TWI647114B - Glass laminate - Google Patents

Abstract

The present invention provides a glass base layer which can be easily peeled off even after high-temperature heat treatment, and decomposition of the silicone resin layer is suppressed.

A glass laminate comprising a support substrate layer, a silicone resin layer and a glass substrate layer in sequence; the epoxy resin in the epoxy resin layer has an organic phosphonium unit represented by the following T3, and is relatively organic The total ratio of the organic methoxy unit represented by T3 in the decyloxy unit is 80 to 100 mol%; in T3, R is an organic decyl unit (A-1) of a phenyl group and R is a methyl group in T3. The molar ratio of the organic methoxy unit (B-1) ((A-1): (B-1)) is 80 to 20: 20 to 80; and, the predetermined peel strength relationship is satisfied; T3: R-SiO _3/2 (wherein R represents a phenyl group or a methyl group).

Description

Glass laminate Field of invention

The present invention relates to a glass laminate, and more particularly to a glass laminate having a predetermined silicone resin layer.

Background of the invention

In recent years, thinner devices and electronic devices such as solar cells (PV), liquid crystal panels (LCDs), and organic EL panels (OLEDs) have been thinner and lighter, and the thinning of glass substrates used in such devices has also been made. Continue to progress. However, if the strength of the glass substrate is insufficient due to thinning, the rationality of the glass substrate is lowered in the manufacturing process of the device.

Recently, in order to cope with the above-mentioned problems, there has been proposed a method of preparing a glass laminate having a laminated glass substrate and a reinforcing plate, and forming a member for an electronic device such as a display device on a thin glass substrate of a glass laminate. Thereafter, the support sheets are separated from the thin glass substrate (for example, refer to Patent Document 1). The reinforcing plate has a support plate and a silicone resin layer fixed to the support plate, and the silicone resin layer and the thin glass substrate are detachably adhered to each other. The interface between the epoxy resin layer of the glass laminate and the thin glass substrate is peeled off, and the reinforcing plate separated from the thin glass substrate can be combined with the new thin glass substrate. The sheets are laminated and reused as a glass laminate.

Advanced technical literature Patent literature

Patent Document 1: International Publication No. 2007/018028

Summary of invention

In the glass laminate described in Patent Document 1, in recent years, higher heat resistance has been demanded. With the high functionality and complication of the components for electronic devices formed on the glass substrate of the glass laminate, the temperature becomes higher than the temperature at which the components for the electronic device are formed, and the time required for exposure to the high temperature takes a long time. There are also many situations.

The glass laminate described in Patent Document 1 is resistant to atmospheric treatment at 300 ° C for 1 hour. However, when the glass laminate disclosed in Patent Document 1 is treated at 450 ° C for one hour, the glass substrate cannot be self-deoxidized when the glass substrate and the support substrate are to be separated. When the surface of the resin layer is peeled off, if a part of the glass substrate is to be peeled off, the glass substrate may be damaged, and as a result, the productivity of the electronic device may be lowered.

Further, the epoxy resin layer described in the glass laminate of Patent Document 1 is decomposed in a short time at 450 ° C, and a large amount of outgas is generated. On the other hand, the generation of the exhaust gas contaminates the member for an electronic device formed on the glass substrate, and as a result, the productivity of the electronic device is lowered.

The present invention has been made in view of the above problems, and it is an object of the invention to provide a glass laminate which can easily peel off a glass substrate even after high-temperature heat treatment, and the decomposition of the silicone resin layer is also suppressed.

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

That is, the present invention is a glass laminate comprising a support substrate layer, a silicone resin layer, and a glass substrate layer in this order, wherein the epoxy resin in the epoxy resin layer has an organic phosphonium unit represented by T3 described later. And the total ratio of the organic decyloxy units represented by T3 is 80 to 100 mol% with respect to all the organic decyloxy units; and in the T3, R is an organic decyloxy unit (A-1) of the phenyl group and The molar ratio ((A-1)/(B-1)) of the organic decyloxy unit (B-1) wherein R is a methyl group in T3 is 80/20 to 20/80; and the epoxy resin layer is The interfacial peel strength of the glass substrate layer is different from the interfacial peel strength of the silicone resin layer to the support substrate layer.

In the present invention, the oxime resin preferably further has an organic decyloxy unit represented by Q described later.

In the present invention, the oxime resin is a hardened organic polyfluorene oxide, and the curable organic polyfluorene is preferably an organic polyoxygen oxide containing an organic decyloxy unit represented by T1 to T3 described later in the following ratio: The ratio of the number of cells (mole amount), T1: T2: T3 = 0 to 5: 20 to 50: 50 to 80 (however, the relationship of T1 + T2 + T3 = 100 is satisfied).

In the present invention, the number average molecular weight of the curable organopolyfluorene is preferably from 500 to 2,000.

In the present invention, the mass average molecular weight/number average molecular weight of the curable organopolyfluorene is preferably from 1.00 to 2.00.

In the present invention, the particle diameter of the curable organopolyphosphonium oxide measured by the dynamic light scattering method is preferably from 0.5 to 100 nm.

In the present invention, the curable organopolyfluorene is preferably an organic polyfluorene obtained by hydrolyzing phenyltrichloromethane and methyltrichloromethane.

In the present invention, the thickness of the silicone resin layer is preferably from 0.1 to 30 μm.

In the present invention, the support substrate is preferably a glass plate.

In the present invention, the interfacial peel strength of the silicone resin layer to the glass substrate layer is preferably lower than the interfacial peel strength of the silicone resin layer to the support substrate layer. Hereinafter, the present invention is also referred to as "the first aspect".

Further, in the present invention, the interfacial peeling strength of the silicone resin layer to the glass substrate layer is preferably higher than the interfacial peel strength of the silicone resin layer to the supporting substrate layer. Hereinafter, the present invention is also referred to as "the second aspect".

According to the present invention, it is possible to provide a glass laminate which can easily peel off the glass substrate even after the high-temperature heat treatment, and the decomposition of the silicone resin layer is also suppressed.

10,100,200‧‧‧glass laminate

12‧‧‧Support substrate

14‧‧‧Oxygenated resin layer

14a‧‧‧ surface of the epoxy resin layer and the glass substrate

16‧‧‧ glass substrate

16a‧‧‧1st main surface of the glass substrate

16b‧‧‧2nd main surface of the glass substrate

18‧‧‧Support substrate with resin layer

20‧‧‧ glass substrate with resin layer

22‧‧‧Members for electronic devices

24‧‧‧Laminated body of components for electronic devices

26‧‧‧ Glass substrate with attached components

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a first embodiment of a glass laminate according to the present invention.

Fig. 2 is a schematic cross-sectional view showing an embodiment of a method for producing a glass substrate according to the attachment member of the present invention in order of steps.

Figure 3 is a schematic cross-sectional view showing a second embodiment of the glass laminate of the present invention. Surface map.

Form for implementing the invention

In the following, the embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the embodiments described below, and various modifications and substitutions can be made to the following embodiments without departing from the scope of the invention. .

The glass laminate of the present invention is characterized in that the oxime resin in the oxime resin layer contains not only a predetermined amount of an organic oxime unit represented by T3 described later, but also an organic ruthenium in which T is a phenyl group. The molar ratio ((A-1) / (B-1)) of the oxy group (A-1) to the organomethoxy unit (B-1) wherein R is a methyl group in T3 is within a predetermined range. More specifically, the heat resistance of the silicone resin layer can be improved by the fact that the silicone resin contains a predetermined amount of the organic phosphonium oxygen unit represented by T3.

Moreover, the inventors of the present invention examined the reason why the glass substrate and the support substrate were difficult to separate in the glass laminate after the high-temperature heat treatment, and found that it was an influence of the functional group contained on the surface of the epoxy resin layer. For example, in the case where the surface of the epoxy resin layer contains a Si-Me group, it is more likely to become a Si-OH group after heat treatment at a high temperature of 250 ° C or higher. Therefore, once the amount of the Si-Me group contained in the silicone resin layer is excessive, many Si-OH groups appear on the surface of the silicone resin layer after the high-temperature heat treatment, and the adjacent substrate (for example, a glass substrate). As a result, the bonding force increases, and as a result, the epoxy resin layer and the substrate adjacent to the epoxy resin layer become difficult to peel off. On the other hand, the Si-Ph group is more difficult to convert to a Si-OH group. However, once there are too many Si-Ph groups, Due to the steric hindrance of the base, the cross-linking hardening of the hardening organic polyoxygen will be difficult to proceed sufficiently, so that the degree of crosslinking of the silicone resin layer is lowered. Therefore, since the mechanical strength of the silicone resin layer is lowered or the unreacted Si-OH group derived from the organic polyfluorene remains on the surface of the silicone resin layer, the peeling property of the glass substrate is deteriorated. The inventors of the present invention have found that the composition of the silicone resin layer which is easily peeled off even after the high-temperature heat treatment is obtained by adjusting the aforementioned molar ratio ((A-1)/(B-1)) based on the above findings. .

Further, in the case of a glass laminate, the interfacial peel strength of the silicone resin layer to the glass substrate layer is different from the interfacial peel strength of the silicone resin layer to the support substrate layer. For example, in the first embodiment, the interfacial peel strength of the silicone resin layer to the glass substrate layer is lower than the interfacial peel strength of the epoxy resin layer to the support substrate layer, and the epoxy resin layer and the glass substrate layer are peeled off. The laminate is separated into a laminate of a silicone resin layer and a support substrate, and a glass substrate. Further, in the second embodiment, the interface peeling strength of the silicone resin layer with respect to the glass substrate layer is higher than the interface peeling strength of the silicone resin layer with respect to the supporting substrate layer, so that the epoxy resin layer and the supporting substrate layer are peeled off. And separated into a laminate of a glass substrate and a silicone resin layer, and a support substrate.

Hereinafter, the first embodiment and the second embodiment will be described.

<First embodiment>

Fig. 1 is a schematic cross-sectional view showing a first embodiment of the glass laminate of the present invention.

As shown in FIG. 1, the glass laminate 10 is a laminate having a layer supporting the substrate 12, a layer of the glass substrate 16, and a layer of the epoxy resin layer 14 present between the layers. body. On the other hand, the surface of the silicone resin layer 14 is in contact with the layer of the support substrate 12, and the other surface is in contact with the first main surface 16a of the glass substrate 16.

The two-layer portion composed of the layer of the support substrate 12 and the epoxy resin layer 14 is used to reinforce the glass substrate 16 in the member forming step of manufacturing the member for an electronic device such as a liquid crystal panel. In addition, the two-layer portion composed of the layer of the support substrate 12 and the silicone resin layer 14 which are previously manufactured to produce the glass laminate 10 is referred to as "the support substrate 18 with the resin layer".

This glass laminate 10 is used until the member forming step described later. In other words, the glass laminate 10 is formed such that a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 16b of the glass substrate 16. Thereafter, the glass laminate in which the member for electronic device is formed is separated into the glass substrate supporting the substrate 12 and the attached member, and the support substrate 18 with the resin layer does not become a part constituting the electronic device. The support substrate 18 with the resin layer can be laminated with the new glass substrate 16 and reused as a new glass laminate 10.

The interface between the support substrate 12 and the silicone resin layer 14 has a peel strength (x), and when a stress exceeding the peeling strength (x) in the peeling direction is applied to the interface between the support substrate 12 and the silicone resin layer 14, the support base The interface between the material 12 and the silicone resin layer 14 is peeled off. The interface between the silicone resin layer 14 and the glass substrate 16 has a peeling strength (y), and when a stress exceeding the peeling strength (y) in the peeling direction is applied to the interface between the silicone resin layer 14 and the glass substrate 16, the silicone resin layer 14 is applied. The interface with the glass substrate 16 is peeled off.

In the glass laminate 10, the peel strength (x) is higher than the peel strength (y). Therefore, the support substrate 12 and the glass are pulled apart from the glass laminate 10 In the direction of the glass substrate 16, the glass laminate 10 is peeled off from the interface between the silicone resin layer 14 and the glass substrate 16, and is separated into the glass substrate 16 and the support substrate 18 with the resin layer.

The peel strength (x) is preferably higher than the peel strength (y). Increasing the peel strength (x) means increasing the adhesion of the first silicone resin layer 14 to the support 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 silicone resin layer 14 to the support substrate 12, it is preferable to form a silicone resin layer by crosslinking and curing the curable organopolysiloxane described later on the support substrate 12. The epoxy resin layer 14 bonded to the support substrate 12 with high bonding force can be formed by the adhesive force at the time of crosslinking hardening.

On the other hand, the bonding strength of the glass substrate 16 of the cross-linking hardened epoxy resin is lower than that of the bonding force generated at the time of the crosslinking hardening. Therefore, the epoxy resin layer 14 is formed on the support substrate 12, and then the glass substrate 16 is laminated on the surface of the epoxy resin layer 14, whereby the glass laminate 10 can be produced.

Hereinafter, the respective layers (the support substrate 12, the glass substrate 16, and the epoxy resin layer 14) constituting the glass laminate 10 will be described in detail, and then the method for producing the glass laminate will be described in detail.

[Support substrate]

The support substrate 12 can support and reinforce the glass substrate 16 and prevent deformation, damage, breakage, and the like of the glass substrate 16 when the electronic device member is manufactured in the member forming step (step of manufacturing the electronic device).

As the support base material 12, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. Generally, since the member forming step is accompanied by heat treatment, the support substrate 12 is preferably made of a material having a small difference in linear expansion coefficient from the glass substrate 16. It is preferably formed and formed in the same material as the glass substrate 16, and the support substrate 12 is preferably a glass plate. In particular, the support substrate 12 is preferably a glass plate composed of the same glass material as the glass substrate 16.

Further, the support base material 12 to be described later may be a laminate body composed of two or more layers.

The thickness of the support substrate 12 can be thicker than the glass substrate 16, and can also be thin. It is desirable to select the thickness of the support substrate 12 in accordance with 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, a current member forming step is designed to treat a substrate having a thickness of 0.5 mm, and 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 supporting substrate 12 is set to 0.4mm. The thickness of the support substrate 12 is usually 0.2 to 5.0 mm in the usual case.

When the support substrate 12 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for the reason that it is easy to handle and is not easily cracked. In addition, when the member for an electronic device is formed and peeled off, it is desirable to have a rigidity that can be flexed without being cracked, and the thickness of the glass plate is preferably 1.0 mm or less.

The difference between the average linear expansion coefficient of the support substrate 12 and the glass substrate 16 at 25 to 300 ° C is preferably 500 × 10 ^-7 / ° C or less, preferably 300 × 10 ^-7 / ° C or less, and 200 × 10 ^{- 7} / ° C or less is better. When the difference is too large, when the member is heated and cooled in the member forming step, there is a possibility that the glass laminate 10 is strongly warped or the substrate 12 and the glass substrate 16 are peeled off. When the material of the support substrate 12 is the same as the material of the glass substrate 16, the occurrence of the problem can be suppressed.

[glass substrate]

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

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

When the linear expansion coefficient of the glass substrate 16 is large, since the member forming step is often accompanied by heat treatment, various defects are likely to occur. For example, when a TFT is formed on the glass substrate 16, if the glass substrate 16 on which the TFT is formed is cooled by heating, there is a fear that the positional deviation of the TFT becomes excessive due to thermal contraction of the glass substrate 16. .

The glass substrate 16 can be obtained by melting a glass raw material and forming the molten glass into a plate shape. The forming method may be a general method, for example, a floating glass plate method, a melting method, a flow hole down-draw method, a Fourcault process, a Lubbers method, or the like may be used. . Further, in particular, the glass substrate 16 having a small thickness can be formed by heating a glass which has been temporarily formed into a plate shape to a moldable temperature, and stretching it to be thinned by means of stretching or the like (re-drawing method). To form it.

The type of the glass of the glass substrate 16 is not particularly limited, but an alkali-free borosilicate glass, a borosilicate glass, a soda-lime glass, a sorghum glass, and other oxide-based glass containing cerium oxide as a main component are used. should. As oxidation The glass of the system is preferably a glass having a cerium oxide content of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate 16, a glass suitable for the type of the member for electronic devices and the manufacturing steps thereof is used. For example, a glass substrate for a liquid crystal panel is easily formed by an alkali metal component, and therefore is made of a glass (alkali-free glass) which does not substantially contain an alkali metal component (except for an alkaline earth metal component). As described, the glass of the glass substrate 16 can be appropriately selected depending on the kind of the apparatus to be applied and the manufacturing steps thereof.

The thickness of the glass substrate 16 is preferably 0.3 mm or less, and preferably 0.15 mm or less, from the viewpoint of thinning and/or weight reduction of the glass substrate 16. When it is 0.3 mm or less, the glass substrate 16 can be provided with favorable flexibility. On the other hand, in the case of 0.15 mm or less, the glass substrate 16 can be wound into a roll shape.

Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for the reason that the glass substrate 16 and the disposable glass substrate 16 are easily produced.

Further, the glass substrate 16 may be composed of two or more layers, and in this case, the materials forming the respective layers may be the same material or different materials. In this case, the "thickness of the glass substrate 16" means the total thickness of all the layers.

[矽 树脂 resin layer]

The epoxy resin layer 14 can prevent the positional deviation of the glass substrate 16 from the operation of separating the glass substrate 16 and the support substrate 12, and can prevent the glass substrate 16 and the like from being damaged by the separation operation. The surface 14a of the epoxy resin layer 14 that is in contact with the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16. The epoxy resin layer 14 is weakly bonded to the first main glass substrate 16 The face 16a is bonded such that its interfacial peel strength (y) is lower than the interfacial peel strength (x) between the silicone resin layer 14 and the support substrate 12. The bonding force between the epoxy resin layer 14 and the glass substrate 16 may be changed before and after the electronic device member is formed on the surface (the second main surface 16b) of the glass substrate 16 of the glass laminate 10. However, even after forming the member for an electronic device, the peel strength (y) is preferably lower than the peel strength (x).

It is assumed that the silicone resin layer 14 and the glass substrate layer 16 are bonded by a weak bonding force or a combination of van der Waals forces. When the glass substrate 16 is formed on the surface layer of the epoxy resin layer 14 after the formation of the epoxy resin layer 14, when the epoxy resin of the epoxy resin layer 14 is sufficiently crosslinked to exhibit no adhesion, it is presumed that The combination of the power of the tile to combine. However, it is not the case that the epoxy resin of the silicone resin layer 14 has a certain degree of weak adhesion. In the case where the adhesiveness of the glass laminate 10 is to be formed on the glass laminate 10 after the production of the glass laminate 10, it is presumed that the epoxy resin layer 14 is caused by a heating operation or the like. The epoxy resin adheres to the surface of the glass substrate 16 so that the bonding force between the epoxy resin layer 14 and the glass substrate layer 16 rises.

Further, depending on the case, the surface of the epoxy resin layer 14 before the deposition or the first main surface 16a of the glass substrate 16 before the deposition may be subjected to a process of weakening the bonding force therebetween. By performing non-adhesion treatment on the surface to be laminated, and then laminating, the bonding strength between the interface between the silicone resin layer 14 and the glass substrate layer 16 can be weakened, and the peel strength (y) can be lowered.

The epoxy resin layer 14 is bonded to the surface of the support substrate 12 by a strong bonding force such as an adhesive force or an adhesive force, thereby improving the adhesion between the two. A well-known method can be employed. For example, as described later, the epoxy resin layer 14 is formed on the surface of the support substrate 12 (more specifically, the hardenable organic polyoxyl which can form a predetermined epoxy resin is formed on the support substrate 12). The co-hardening) causes the epoxy resin in the silicone resin layer 14 to adhere to the surface of the support substrate 12 to obtain high bonding force. Further, a treatment for generating a strong bonding force between the surface of the support substrate 12 and the silicone resin layer 14 (for example, treatment using a coupling agent) can improve the bonding between the surface of the support substrate 12 and the silicone resin layer 14. force.

The layer of the silicone resin layer 14 and the support substrate 12 are bonded with a high bonding force, which means that the interface peel strength (x) of both is high.

The thickness of the silicone resin layer 14 is not particularly limited, but the upper limit is preferably 30 μm (that is, 30 μm or less), preferably 20 μm, and more preferably 8 μm. The lower limit is not particularly limited as long as it is a peelable thickness, but is usually 0.1 μm or more. When the thickness of the silicone resin layer 14 is within the above range, cracking of the epoxy resin layer 14 is difficult, and even if bubbles or foreign matter are present between the silicone resin layer 14 and the glass substrate 16, deformation of the glass substrate 16 can be suppressed. The occurrence of defects.

The thickness means the average thickness, and the thickness of the epoxy resin layer 14 at any position of 5 points or more is measured by a contact type film thickness measuring apparatus, and arithmetic average is performed.

The surface roughness Ra of the surface of the surface of the glass substrate 16 of the silicone resin layer 14 is not particularly limited, but is preferably 0.1 to 20 nm and 0.1 to 10 nm from the viewpoint of excellent laminate property and releasability of the glass substrate 16 . Preferably.

In addition, the method of measuring the surface roughness Ra is performed in accordance with JIS B 0601-2001, and the Ra measured by an arbitrary five or more points is arithmetically averaged. The value is the aforementioned surface roughness Ra.

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

Usually, the curable organic polyfluorene coated on the substrate is subjected to heat hardening by heating after drying and removing the solvent contained in the material at a temperature from a normal temperature to a temperature lower than a heat distortion temperature of the substrate. And become a silicone resin. In the process of thermal hardening, the sterol groups (-Si-OH) contained in the hardenable organopolyoxygen will undergo dehydration condensation reaction with each other to form a siloxane chain (-Si-O-Si-). It will harden into a silicone resin at the same time as crosslinking. During the heating process, the gel film is densified due to the capillary force generated by evaporation of the solvent and the dehydration condensation reaction in the film, so that the volume reduction rate of the film is several tens of%. Although the gel film is not completely elastic, once the gel film is similar to the elastomer, when the film is shrunk in the in-plane direction depending on the substrate, strain accumulation occurs in the in-plane direction of the film. situation. As a result, tensile stress (hereinafter also referred to as "shrinkage stress") occurs in the in-plane direction of the film.

The "shrinkage stress of the silicone resin layer" of the present invention is a tensile stress value acting in the direction of the layer of the epoxy resin, which is measured by a film stress measuring device at a peripheral temperature of 25 ° C before and after the formation of the silicone resin layer. The value of the radius of curvature of the wafer and the value of the film thickness of the silicone resin layer are calculated by the equation shown in the following formula (1). In addition, the measurement procedure will be described in detail in the examples.

[Number 1]

Where E/(1-ν) is the biaxial elastic modulus of the tantalum wafer (crystal face (100): 1.805×10 ¹¹ Pa), h is the thickness of the tantalum wafer [m], and t is the thickness of the tantalum oxide layer [m], R is the difference [m] between the radius of curvature of the tantalum wafer before the formation of the tantalum resin layer and the radius of curvature of the tantalum wafer after the formation of the tantalum oxide layer.

Further, the difference R in the radius of curvature of the tantalum wafer before and after the formation of the tantalum resin layer depends on the thickness h of the tantalum wafer, the elastic modulus E of the tantalum wafer, the Pason ratio ν of the tantalum wafer, the film thickness t, and the tensile stress σ. As long as the tensile stress σ is generated in the in-plane direction of the film formed on one side of the tantalum wafer, as can be understood from the above formula (1), the larger the stress σ generated in the in-plane direction of the film, the aforementioned radius of curvature The difference R will become larger, that is, the warpage of the wafer will become larger.

Therefore, the shrinkage stress of the silicone resin layer can be determined by investigating the difference R between the curvature radii of the tantalum wafer before and after the formation of the silicone resin layer and the thickness t of the tantalum oxide layer. Further, the radius of curvature R can be obtained by forming a silicone resin layer on one side of the single crystal germanium wafer, and scanning the surface of the germanium wafer on which the tantalum resin layer is formed by laser light using a film stress measuring device. And read R from the direction of the reflected light.

Although the size of the shrinkage stress of the silicone resin layer 14 is not particularly limited, it is prevented from occurring in the cooling process based on the process of forming the epoxy resin layer 14 by hardening the curable organic polyfluorene. The warpage of the glass laminate 10 to be produced can be further suppressed, and it is preferably 50 MPa or less and 45 MPa or less. The lower limit is not particularly limited, but Usually more than 15MPa.

The epoxy resin layer 14 is composed of a silicone resin containing a predetermined organic methoxy group. Further, the epoxy resin can be obtained by crosslinking and hardening the curable organopolyoxygen which can be the epoxy resin by a hardening treatment.

The curable organic polyfluorene oxygen of the present invention is a partially hydrolyzed condensate (organic polyoxygen) obtained by subjecting a mixture (monomer mixture) of a monomeric hydrolyzable organodecane compound to a partial hydrolysis condensation reaction. Further, the partially hydrolyzed condensate may also contain unreacted monomers.

In order to harden the curable organopolyfluorene cross-linking, it is usually hardened by heat-crosslinking reaction (that is, it is thermally hardened). Further, a silicone resin can be obtained by thermally curing the curable organopolysiloxane. However, hardening does not necessarily require heating, and it can harden the room temperature.

The general oxime resin (organopolyoxyl) is a monofunctional organic decyloxy unit called M unit, a bifunctional organic decyloxy unit called D unit, and a trifunctional organic compound called a T unit. A decyloxy unit or a tetrafunctional organomethoxy unit called a Q unit. Further, although the Q unit is a unit having no organic group bonded to a ruthenium atom (an organic group having a carbon atom bonded to a ruthenium atom), it is still regarded as an organic oxime unit (including a fluorene bond unit) in the present invention. ). Hereinafter, the monomer forming the T unit will be referred to as "T monomer". The monomers forming the M unit, the D unit, and the Q unit are also referred to as "M monomer", "D monomer", and "Q monomer".

In the organic decyloxy unit, since the ruthenium atom bonds two 矽 atoms through a bond of one oxygen atom, the oxygen atom per 矽 atom in the siloxane bond is regarded as 1/2. In the formula, it is represented by O _1/2 . More specifically, for example, in one D unit, one of its ruthenium atoms is bonded to two oxygen atoms, and each oxygen atom is bonded to a ruthenium atom of another unit, so that the formula is -O _{1 /2} -(R) ₂ Si-O _1/2 -. Since there are two O _1/2 , the D unit is generally represented by (R) ₂ SiO _2/2 .

Further, in the following description, the oxygen atom O ^* bonded to another germanium atom is used to bond an oxygen atom between two germanium atoms, and means an oxygen atom in the bond shown by Si-O-Si. Therefore, O ^* exists between the ruthenium atoms of the two organic methoxy units.

In general, "T unit" means an organic decyloxy unit represented by R-SiO _3/2 (R represents a hydrogen atom or an organic group). That is, the T unit is a unit having one deuterium atom and having one hydrogen atom or a monovalent organic group bonded to the deuterium atom, and three oxygen atoms O ^* bonded to the other deuterium atom.

However, in the present specification, when a part or all of the oxygen atom O ^* bonded to another germanium atom is replaced by a functional group which may be bonded to another germanium atom, it is also regarded as a T unit. A functional group-based hydroxyl group which may be bonded to another germanium atom or a group which is hydrolyzed to a hydroxyl group (hereinafter referred to as "hydrolyzable group"). More specifically, in the present specification, the T unit is based on a total of three oxygen atoms O ^* bonded to other deuterium atoms and functional groups that can be bonded to other deuterium atoms, and is bonded to other deuterium atoms. The oxygen atom O ^* differs from the number of functional groups that can be bonded to other germanium atoms, and the T unit can be classified into three units of a so-called T1 unit, a T2 unit, and a T3 unit. T1 unit number bonded to a silicon atom of the other oxygen atom O ^* is a sum, T2 means the oxygen atom O ^* is the number 2, and T3 means the oxygen atom O ^* 3 compared to the number. Further, in the present specification, a monovalent functional group which may be bonded to another deuterium atom is represented by Z.

The monomer (hydrolyzable organodecane compound) is usually represented by (R'-) _a Si(-Z) _4-a . However, a is an integer of 0 to 3, R' is a hydrogen atom or a monovalent organic group, and Z represents a hydroxyl group or a hydrolyzable group. In the formula, the compound of a=3 is an M monomer, the compound of a=2 is a D monomer, the compound of a=1 is a T monomer, and the compound of a=0 is a Q monomer. Among the monomers, the Z group is a general hydrolyzable group. Further, if there are two or three R's (a is 2 or 3), most of the R's may be different.

The sclerosing organopolyfluorene which partially hydrolyzes the condensate can be obtained by a reaction of converting a part of the Z group of the monomer into an oxygen atom O ^* . When the Z group of the monomer is a hydrolyzable group, the Z group is converted into a hydroxyl group by a hydrolysis reaction, and then by a dehydration condensation reaction between two hydroxyl groups bonded to an individual germanium atom, two germanium atoms pass through the oxygen atom. O ^* and bonding. When a hydroxyl group (or an unhydrolyzed Z group) remains in the curable organic polyfluorene, the hydroxyl group or the Z group is reacted and hardened in the same manner as described above in the curing of the curable organopolysiloxane. The hardened organic polyfluorene hardened material usually becomes a three-dimensional crosslinked polymer (oxygenated resin). At the time of hardening, the Z group of the curable organopolyoxygen is converted into O ^* , but it is presumed that a part of the Z group (particularly a hydroxyl group) remains and becomes a cured product having a hydroxyl group. On the other hand, when the curable organic polyfluorene is hardened at a high temperature, there is a case where a cured product of a hydroxyl group hardly remains.

When the Z group of the monomer is a hydrolyzable group, the Z group may, for example, be an alkoxy group, a chlorine atom, a decyloxy group or an isocyanate group. In many cases, a single system uses a monomer having a Z group as an alkoxy group. The alkoxy group is a less reactive hydrolyzable group than the chlorine atom and the like, and is hardened by using the Z group as an alkoxy group. In the organopolyorganosiloxane, the Z group is mostly a hydroxyl group which is present together with the unreacted alkoxy group. On the other hand, when the Z group of the monomer is a highly reactive hydrolyzable group (for example, a chlorine atom), the Z group in the curable organopolysiloxane obtained by using the monomer is almost a hydroxyl group. Therefore, in the general hardening organic polyfluorene oxide, the Z group in each of the units constituting it is mostly composed of a hydroxyl group or a hydroxyl group and an alkoxy group.

(oxygenated resin)

The oxime resin constituting the oxime resin layer 14 has an organic decyloxy unit represented by T3 (hereinafter, also referred to as "T3 unit"), and an organic oxime represented by T3 with respect to all the organic decyloxy units. The total ratio of the base units is from 80 to 100 mol%, and is preferably from 82 to 100 mol%, more preferably from the viewpoint that the heat resistance of the obtained epoxy resin layer 14 is excellent and the peeling of the glass substrate 16 is easier. It is 85~100% by mole. In summary, the epoxy resin contains an organic decyloxy unit represented by T3 as a main component.

T3: R-SiO _3/2

(wherein R represents a phenyl group or a methyl group).

Further, the organic decyloxy unit represented by T3 corresponds to one of the aforementioned T units. Further, the epoxy resin may contain other units in addition to the organic decyloxy unit represented by T3, and examples of other units include M unit, D unit, T1 unit, T2 unit, and Q unit.

In addition, the silicone resin layer 14 does not undergo cohesive failure at the time of peeling, and the mechanical strength of the silicone resin layer 14 is excellent and the peeling property of the glass substrate 16 is more excellent, and it is represented by the following Q. An organic decyloxy unit (so-called Q unit) is preferred. The content of the Q unit is not particularly limited, but is preferably 1 mol% or more and 5 mol% or more based on the total of the organic decyloxy unit. The upper limit is not particularly limited, but is preferably 20 mol% or less from the viewpoint of the fact that the brittleness of the epoxy resin layer 14 is lowered due to an increase in the degree of crosslinking, and there is a fear that the epoxy resin layer 14 is peeled off. The enthalpy of causing cohesive failure; and fear of causing warpage of the glass composite due to an increase in shrinkage stress accompanying hardening shrinkage.

Q: SiO _4/2

In addition, the "all organic methoxy group" means the total of the M unit, the D unit, the T unit, and the Q unit contained in the oxime resin. The ratio of the number of M units, D units, T units (T1 to T3 units), and Q units (molar amount) can be calculated from the value of the peak area ratio of ²⁹ Si-NMR.

In the epoxy resin in the epoxy resin layer 14, in the T3, R is an organic decyloxy unit (A-1) of a phenyl group and an organic decyloxy unit (B-1) wherein T is a methyl group in T3. The ear ratio ((A-1)/(B-1)) is 80/20 to 20/80 (in addition, the relationship of (A-1) + (B-1) = 100 is satisfied). Among them, in terms of making it easier to peel off the glass substrate, the molar ratio ((A-1)/(B-1)) is preferably 75/25 to 20/80, and 70/30 to 20/80 is more good.

The "organomethoxy group (A-1) wherein R is a phenyl group" means an organic decyloxy unit represented by the following P-T3. Ph represents a phenyl group.

P-T3: Ph-SiO _3/2

Further, "organic methoxy unit (B-1) wherein R is a methyl group" means an organic decyloxy unit represented by the following M-T3.

M-T3: Me-SiO _3/2

The aforementioned silicone resin can be produced using well-known materials.

As described above, the curable organic polyfluorene which can be the above-described oxime resin by the curing treatment is, for example, a partially hydrolyzed condensate obtained by subjecting a mixture of a monomeric hydrolyzable organodecane compound to a partial hydrolysis condensation reaction. (organic polyoxo). More specifically, as the monomer, a hydrolyzable organodecane compound represented by (Me-)Si(-Z) ₃ and a hydrolyzable organodecane compound represented by (Ph-)Si(-Z) ₃ are used. In addition, the Z group represents a hydroxyl group or a hydrolyzable group, and examples of the hydrolyzable group include a halogen atom such as a chlorine atom, an alkoxy group, a mercapto group, an amine group, and an alkoxyalkoxy group.

Further, the hydrolysis condensation reaction is a reaction in which a T1 unit is generated from a T monomer, a T2 unit is generated from a T1 unit, and a T3 unit is generated from a T2 unit. It is presumed that the reaction rate of the condensation reaction is slowed down in the following order: a condensation reaction of T1 units from one or more hydrolyzable groups converted to hydroxyl groups; a condensation reaction of T2 units from T1 units; from T2 The unit generates a condensation reaction of the T3 unit. Considering the hydrolysis reaction of the hydrolyzable group, it is presumed that as the reaction proceeds, the peak of the amount of each unit will also move from the T monomer to the T3 unit. In the case where the reaction conditions are mild, it is presumed that the movement of the amount spikes will proceed neatly.

As the curable organic polyfluorene which can be the above-mentioned oxime resin, as described above, a partial hydrolysis condensate (organic polymerization) obtained by using a mixture of hydrolyzable organodecane compounds is used from the viewpoint of control and treatment of the reaction. Oxygen). The partially hydrolyzed condensate is obtained by mixing a hydrolyzable organodecane compound into a ratio of each of the above organic decyloxy units to obtain a monomer mixture, and then partially hydrolyzing and condensing the monomer mixture. The method of partially hydrolyzing and condensing is not particularly limited. It is usually produced by reacting a mixture of hydrolyzable organodecane compounds in a solvent in the presence of a catalyst. Catalyst An acid catalyst or a base catalyst can be used. Further, it is preferred to use water for the hydrolysis reaction. The partially hydrolyzed condensate used in the present invention is preferably produced by reacting a mixture of hydrolyzable organodecane compounds in the presence of an acid or an aqueous alkali solution in a solvent.

The hydrolyzable organodecane compound (Me-)Si(-Z) _{3 and} the hydrolyzable organodecane compound represented by (Ph-)Si(-Z) _{3 may be} mentioned. However, in view of the fact that the obtained curable organic polyfluorene is excellent in practicability, high in heat resistance, and the glass substrate 16 can be more easily peeled off, phenyltrichloromethane is preferably used (shown by the following formula (1)). The compound) and methyltrichloromethane (a compound represented by the following formula (2)). Further, Ph in the formula (1) represents a phenyl group.

Further, as described later, in the case of forming a curable organic polyfluorene oxide layer, a composition containing a curable organic polyfluorene oxide is used, but the stability of the curable organic polyfluorene in the composition can be further improved. In addition, the end of the hardened polyoxyl oxide can also be blocked. More specifically, the terminal Si-OH in the hardenable organopolyoxygen is reacted with an alcohol under an acid catalyst (for example, in the presence of acetic acid), and the Si-OH protective seal can be removed while removing water. end. For example, when methanol is used, a Si-OMe group is formed. Further, the type of the alcohol to be used is not particularly limited, and examples thereof include low-boiling alcohols such as methanol, ethanol, 1-propanol, and 1-butanol. Among these, methanol and ethanol are preferred from the viewpoints of good reactivity with the Si-OH group and solubility of the curable organic polyfluorene.

(suitable form of hardening organic polyfluorene)

One of the suitable aspects of the curable organic polyfluorene oxide is an organic polyfluorene oxide (hereinafter also referred to as "organic polyxylene oxide X") having an organic decyloxy group represented by the following T1 to T3. At least one of the units, and the total ratio of the organic decyloxy units represented by the following T1 to T3 is 80 to 100 mol% with respect to all of the organic decyloxy units; R in the following T1 to T3 is The molar ratio of the organic decyloxy unit (A-2) of the phenyl group to the organic decyloxy unit (B-2) wherein R is a methyl group in the following T1 to T3 ((A-2)/(B-2) )) is 80/20~20/80. As long as it is the organic polyfluorene, the desired epoxy resin can be easily obtained.

T1: R-Si(-OX) ₂ O _1/2

T2: R-Si(-OX)O _2/2

T3: R-SiO _3/2

Further, in the formula, R represents a phenyl group or a methyl group. X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the above formula, R is not limited to one type, and R of each of T1, T2 and T3 may be different.

Further, -OX may be the same or different between the T1 unit and the T2 unit. Further, two of the T1 units may be different from each other. For example, one of them may be a hydroxyl group and the other may be an alkoxy group. Further, when both -OX are alkoxy groups, the alkoxy groups may be different alkoxy groups.

Hereinafter, a T unit having no oxygen atom (O ^* ) in which two deuterium atoms are bonded and having only three -OX is referred to as "T0". T0 is actually equivalent to an unreacted T monomer, not an organodecyloxy unit (containing a fluorene bond unit). The T0 can be measured in the same manner as T1~T3 in the unit analysis of T1~T3.

The unit of T1 to T3 in the organic polyoxo X can be determined by nuclear magnetic resonance analysis ( ²⁹ Si-NMR) and the bonding state of the deuterium atom is analyzed. The ratio of the number of units (molar amount) of T0 to T3 was obtained from the peak area ratio of ²⁹ Si-NMR.

Further, the mass average molecular weight Mw, the number average molecular weight Mn, and the dispersity Mw/Mn of the organopolyxylene X are values measured by gel permeation chromatography using polystyrene as a standard substance. The characteristics of the organopolyoxygen X described above do not refer to the characteristics of one molecule, but to the average characteristics of each molecule.

The total ratio of the organic decyloxy units represented by the above T1 to T3 in the organic polyoxo X is as described above, and is preferably from 80 to 100 mol% based on the total of the organic decyloxy units, and the obtained oxirane resin layer 14 is used. The heat resistance is excellent, and from the viewpoint that the peeling of the glass substrate 16 can be easily performed, it is preferably 82 to 100 mol%, and more preferably 85 to 100 mol%.

Further, in the organopolyoxygen X, it is preferred to contain at least the above T3 unit from the viewpoint of handleability, and more preferably at least the above T2 unit and T3 unit. As a result of various reviews, it is known that as the number of Ph groups (phenyl groups) increases, the ratio of T1 units increases. When the number of T1 units is increased, the shrinkage stress is increased during hardening of the silicone resin layer, so that the shrinkage stress of the T1 unit is less, which is preferable.

Further, the organopolyoxygen X may also contain the above-mentioned organic oxime represented by T1 to T3. Other units than the base unit, and other units include M units, D units, and Q units.

The sclerosing organic polyfluorene of the T body is generally known as polyphenyl polyfluorene oxide and polymethyl polyfluorene, and the sterol terminal polyphenyl polyoxyl is obtained by hydrolyzing PhSiCl ₃ . An oligomer having a molecular weight of several hundred to several thousand. When the oligomer is used to produce a cured product having a thickness of 0.1 mm or more, it is extremely weak and can be used. However, it can be a silicone resin having excellent heat resistance.

On the other hand, when the substituent on the ruthenium atom is an aliphatic hydrocarbon group such as a methyl group, the reactivity of the monomer of the RSiZ ₃ type which can provide a sterol terminal is high, and the molecular weight of the obtained hydrolysis-condensate is almost It becomes 10,000 or more. Therefore, the solubility in a solvent is inferior, and a large amount of solvent is required to dissolve the condensate. Therefore, a film for coating or the like can be obtained, but a cured product having a certain thickness is difficult to be obtained due to cracks or the like.

Therefore, it is preferable to use the above-mentioned curable organopolyoxyxene X which has been considered to have both heat resistance and reactivity and has improved solubility.

In the sclerosing organopolyoxyxylene X, in the T1 to T3, R is an organic decyloxy unit (A-2) of a phenyl group and an organic decyloxy unit (B-2) wherein T is a methyl group in T1 to T3. The molar ratio ((A-2)/(B-2)) is preferably 80/20 to 20/80 (in addition, the relationship of (A-2) + (B-2) = 100 is satisfied). Among them, the solubility of the curable organic polyfluorene is excellent, and a coating liquid having a moderate surface tension (that is, good coatability) to the washed glass substrate can be prepared, and the viewpoint of shrinkage stress at the time of hardening can be reduced. For example, Mobi ((A-2)/(B-2)) should be 75/25~20/80, and 70/30~20/80 is better.

"R is an organic decyloxy unit (A-2) of a phenyl group" means a concept including a unit in which R is a T1 unit of a phenyl group (hereinafter P-T1), and R is a T2 unit of a phenyl group (hereinafter) P-T2), and R is a T3 unit of a phenyl group (hereinafter P-T3). Hereinafter, in the formulae P-T1 to P-T3, Ph represents a phenyl group.

P-T1: Ph-Si(-OX) ₂ O _1/2

P-T2: Ph-Si(-OX)O _2/2

P-T3: Ph-SiO _3/2

Therefore, the content of the above-mentioned organomethoxy group (A-2) means the total amount of the unit represented by the above P-T1, the content of the unit represented by the above P-T2, and the total content of the unit represented by the above P-T3. .

Further, "organic methoxy unit (B-2) in which R is a methyl group" means a concept including a unit in which R is a T1 unit of a methyl group (hereinafter, M-T1), and R is a T2 unit of a methyl group. (M-T2 below), and T is a T3 unit of methyl group (hereinafter M-T3). Hereinafter, in the formulae M-T1 to M-T3, Me represents a methyl group.

M-T1: Me-Si(-OX) ₂ O _1/2

M-T2: Me-Si(-OX)O _2/2

M-T3: Me-SiO _3/2

Therefore, the content of the above-mentioned organomethoxy group (B-2) means the total amount of the unit represented by the above M-T1, the content of the unit represented by the above M-T2, and the total content of the unit represented by the above M-T3. .

The curable organopolyoxygen (especially the aforementioned curable organopolyoxygen X) preferably contains the above-mentioned organic decyloxy unit represented by T1 to T3 in the following ratio: in terms of the number of units (molar amount), T1 :T2: T3=0~5:20~50:50~80 (otherly, the relationship of T1+T2+T3=100 is satisfied). As long as it is within the aforementioned range, The glass substrate 16 can be peeled off more easily. In other words, the ratio of the above T1:T2:T3 may also be referred to as the ratio of the T1 unit being 0 to 5 mol%, the ratio of the T2 unit being 20 to 50 mol%, and the ratio of the T3 unit being 50 to 80 mol%.

The ratio of the (A-2) unit to the (B-2) unit in the curable organopolysiloxane X from the viewpoint that the glass substrate 16 can be easily peeled off and the warpage of the glass laminate 10 can be reduced. -2)/(B-2)) should be 80/20~20/80, and the ratio of the number of T1~T3 units (mole amount) should be T1:T2:T3=0~5:20 ~50:50~80.

Further, when the epoxy resin layer is formed using the curable organopolyoxygen X, the methyl group or the phenyl group in T1 to T3 may be desorbed depending on the curing conditions to form a Q unit.

The number average molecular weight of the curable organopolyfluorene (especially the above-mentioned curable organopolyoxygen X) is such that the epoxy resin layer 14 which is excellent in solubility to the curable organic polyfluorene and has few foreign matter defects can be produced, or In view of the fact that the glass substrate 16 can be more easily peeled off, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is preferably 500 to 2,000, preferably 600 to 2,000. And 800~1800 is better.

Further, the mass average molecular weight/number average molecular weight of the curable organopolyfluorene (particularly the curable organopolyoxygen X) is such that it is excellent in solubility to curable organopolyfluorene and has less foreign matter defects. The resin layer 14 or the viewpoint of more easily peeling off the glass substrate 16 is preferably 1.00 to 2.00, preferably 1.00 to 1.70, and more preferably 1.00 to 1.50.

The adjustment of the molecular weight of the curable organopolyfluorene (especially the aforementioned curable organopolyoxygen X) can be carried out by controlling the reaction conditions. For example, tune When the amount of the solvent in the production of the curable oligomer is increased and the concentration of the hydrolyzable organodecane compound is increased, a high molecular weight substance can be obtained, and if the concentration is lowered, a low molecular weight substance can be obtained.

The shape of the curable organopolyfluorene (particularly the above-mentioned curable organopolyoxygen X) is not particularly limited, and may be in the form of particles. In other words, when the curable organic polyfluorene oxide (especially the curable organopolyoxygen X) is added to a solvent, it may be present in a fine particle state.

In this case, the particle size of the curable organopolyfluorene (especially the curable organopolyoxygen X) measured by the dynamic light scattering method is not particularly limited, but the niobium resin having less foreign matter defects can be produced. The layer or the viewpoint that the glass substrate 16 can be more easily peeled off is preferably 0.5 to 100 nm, and more preferably 0.5 nm or more and less than 40 nm.

Further, the method for measuring the dynamic light scattering method is to use a curable organic polyfluorene oxide (particularly, the aforementioned curable organopolyoxygen X) in a PEGMEA solution (propylene glycol-1-monomethyl ether-2-acetate). The sample was prepared by adjusting it to 20% by mass, and a histogram average particle diameter (D50) was determined as a particle diameter using a thick particle size analyzer (manufactured by OTSUKA ELECTRONICS Co., Ltd., FPAR-1000).

The method for producing the above-described silicone resin layer 14 is not particularly limited, and a well-known method can be employed. As a method for producing the epoxy resin layer 14, as described later, a curable organic polyfluorene oxide layer which becomes the above-described epoxy resin is formed on the support substrate 12, and the curable organic polyfluorene is cross-linked and hardened. The epoxy resin layer 14. In order to form a hardenable organopolyfluorene layer on the support substrate 12, it is preferred to use a solution in which the curable organopolysiloxane is dissolved in a solvent. (Constituent containing a curable organopolyoxygen), and the solution is applied onto a support substrate 12 to form a solution layer, followed by removal of the solvent to form a curable organopolysiloxane layer. The thickness of the hardenable organopolysiloxane layer can be controlled by adjusting the concentration of the solution. Among them, the content of the hardening organic polyfluorene in the composition containing the hardening organic polyfluorene is relative to the composition from the viewpoint of having superiority and controlling the film thickness of the epoxy resin layer 14 to be easier. The total mass of the material is preferably from 1 to 100% by mass, and more preferably from 1 to 50% by mass.

The solvent is not particularly limited as long as it can easily dissolve the curable organic polyfluorene in an operating environment and is a solvent which can be easily removed by volatilization. Specific examples thereof include butyl acetate, 2-heptanone, and 1-methoxy-2-propanol acetate.

Further, from the viewpoint of further improving the stability of the curable organopolyfluorene in the composition, it is preferred to control the pH in the composition. In general, the pH at which the sterol group can be stably present has a certain range, and it is known that gelation can be easily performed in the vicinity of neutral, and on the acidic side (pH 2 to 4) or the alkaline side (pH 11 to 14). It can exist more stably. From the viewpoint of further improving the stability of the curable organic polyfluorene and acting as a curing catalyst in the curing of the curable organopolysiloxane, it is suitable to use an acid for controlling the pH. The acid to be added may be an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid or sulfamic acid; and formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluene An organic acid such as an acid; and acetic acid is preferred. The amount of use of the acid is preferably from 0.1 to 50 parts by mass, and particularly preferably from 1 to 20 parts by mass, per 100 parts by mass of the curable organopolyfluorene composition.

Moreover, in order to further improve the hardening organic polyoxygen in the composition From the standpoint of stability, it is also possible to add an alcohol having a higher boiling point than the coating solvent. The type of the alcohol to be used is not particularly limited, and examples thereof include 1-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-methyl-1-butanol, and 1-pentanol. Acetyl alcohol, 2-(2-ethoxyethoxy)ethanol, and the like. Among these, from the viewpoint of good solubility of the curable organopolyfluorene, 1-methoxy-2-propanol, diacetone alcohol, and 2-(2-ethoxyethoxy) are used. Ethanol is preferred.

In addition, an antifoaming agent and a viscosity adjusting agent may be contained for the purpose of improving the coating property to the substrate, and an additive such as an adhesion imparting agent may be further contained for the purpose of improving the adhesion to the substrate. The leveling agent may also be blended for the purpose of improving the applicability and the smoothness of the resulting coating film. The blending amount of the additives is preferably 0.01 to 2 parts by mass per 100 parts by mass of the curable organopolyfluorene. Further, a filler or the like may be added to the extent that the object of the present invention is not impaired.

Further, the procedure for forming the epoxy resin layer using the curable organopolysiloxane will be described in detail later.

[Glass laminate and its manufacturing method]

The glass laminate 10 of the present invention is a laminate having the support substrate 12, the glass substrate 16, and the epoxy resin layer 14 present between them, as described above.

The method for producing the glass laminate 10 of the present invention is not particularly limited. However, in order to obtain a laminate having a peel strength (x) higher than the peel strength (y), a silicone resin layer is formed on the surface of the support substrate 12. The method of 14 is suitable. Further, it is preferable to apply the curable organic polyfluorene oxide to the surface of the support substrate 12, and form the epoxy resin layer 14 on the surface of the support substrate 12, followed by the oxygenation on the surface of the silicone resin layer 14. The glass substrate 16 is laminated on the resin surface A glass laminate 10 is provided.

It is assumed that once the surface of the support substrate 12 is hardened by the curable organopolysiloxane, the peel strength of the surface of the support resin substrate 12 is followed by the interaction with the surface of the support substrate 12 during the hardening reaction. Will become higher. Therefore, even if the glass substrate 16 and the support base material 12 are made of the same material, the difference in peel strength between the glass substrate 16 and the silicone resin layer 14 can be set.

Hereinafter, the step of forming the curable organic polyfluorene oxide on the surface of the support substrate 12 and forming the epoxy resin layer 14 on the surface of the support substrate 12 is referred to as "resin layer formation step", and the epoxy resin layer 14 will be formed. The step of laminating the glass substrate 16 on the epoxy resin surface to form the glass laminate 10 is referred to as "layering step", and the procedure of each step will be described in detail.

(Resin layer forming step)

In the resin layer forming step, a curable organic polyfluorene oxide layer is formed on the surface of the support substrate 12, and a silicone resin layer 14 is formed on the surface of the support substrate 12.

In order to form the curable organic polyfluorinated layer on the support substrate 12, it is preferable to use a coating composition (corresponding to the composition containing the curable organic polyfluorene) in which the curable organopolysiloxane is dissolved in a solvent. The composition is applied onto the support substrate 12 to form a solution layer, and then subjected to a hardening treatment to form the epoxy resin layer 14.

The method of applying the composition containing the curable organopolyfluorene on the surface of the support substrate 12 is not particularly limited, and a well-known method can be used. For example, spraying, die coating, spin coating, dip coating, roller Coating method, stick coating method, screen printing method, gravure coating method, and the like.

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

Although the method of hardening is not particularly limited, it is usually carried out by a heat hardening treatment.

The temperature condition for thermally hardening is not particularly limited as long as the peeling strength (y) after laminating the glass substrate 16 can be controlled within a range as long as the heat resistance of the epoxy resin layer 14 can be improved, but it is preferably 150~550°C, and 200~450°C is better. Moreover, the heating time is usually preferably from 10 to 300 minutes, and more preferably from 20 to 120 minutes. Further, the heating conditions may be carried out stepwise by changing the temperature conditions.

By setting the temperature range and the heating time range, the T1 unit, the T2 unit, and the T3 unit can be controlled, and the generation ratio of the Q unit which is easily generated by heating at 250 ° C or higher can be further controlled.

Further, in the heat hardening treatment, it is preferable to perform hardening (formal hardening) after performing PRECURE (pre-hardening) to harden it. The epoxy resin layer 14 having excellent heat resistance can be obtained by performing pre-hardening. The pre-hardening is preferably carried out by removing the solvent, and at this time, the step of removing the solvent from the layer and forming the layer of the cross-linking is not particularly different from the step of performing the pre-hardening. The solvent removal is preferably carried out by heating to 100 ° C or higher, and pre-curing can be carried out by heating to 150 ° C or higher. The temperature for removing the solvent and pre-hardening and the heating time are preferably 100 to 420 ° C and 5 to 60 minutes, and 150 to 300 ° C and 10 to 30 minutes are more preferable. If it is 420 ° C or less, an epoxy resin layer which is easily peeled off can be obtained.

(layering step)

The layering step is to laminate the glass substrate 16 on the surface of the epoxy resin layer of the epoxy resin layer 14 obtained by the resin layer forming step, thereby obtaining a layer having the support substrate 12, the epoxy resin layer 14 and the glass substrate. The step of the layered glass laminate 10 of 16. More specifically, as shown in FIG. 2(B), the surface 14a of the side of the silicone resin layer 14 opposite to the support substrate 12 side, and the glass substrate having the first main surface 16a and the second main surface 16b are shown. The first main surface 16a of the 16 is used as an accumulation layer to laminate the silicone resin layer 14 and the glass substrate 16 to obtain a glass laminate 10.

The method of laminating the glass substrate layer 16 on the epoxy resin layer 14 is not particularly limited, and a well-known method can be employed.

For example, a method of laminating a glass substrate 16 on the surface of the epoxy resin layer 14 under a normal pressure environment can be mentioned. Alternatively, after the glass substrate 16 is laminated on the surface of the silicone resin layer 14, the glass substrate 16 may be pressure-bonded to the silicone resin layer 14 by using a roll or a press. It is preferable that the air bubbles mixed between the epoxy resin layer 14 and the glass substrate layer 16 can be easily removed by pressure bonding using a roll or a press.

When the pressure bonding is carried out by a vacuum lamination method or a vacuum pressing method, it is more preferable because the mixing of bubbles can be suppressed and a good adhesion can be ensured. When the pressure is applied under vacuum, even if fine bubbles remain, there is no possibility that the bubbles grow due to heating, and there is an advantage that the glass substrate 16 is not easily deformed.

When laminating the glass substrate 16, it should be sufficiently washed with the epoxy resin. The layer 14 is in contact with the surface of the glass substrate 16, and is laminated in an environment of high cleanliness. The higher the degree of cleanliness, the better the flatness of the glass substrate 16 becomes.

Further, after the laminated glass substrate 16, the pre-annealing treatment (heat treatment) may be performed as needed. By performing the pre-annealing treatment, the adhesion of the laminated glass substrate 16 to the silicone resin layer 14 is improved, and an appropriate peel strength (y) can be obtained, so that it is difficult to occur in the member forming step described later. The positional deviation of the manufacturing member or the like improves the productivity of the electronic device.

Although the conditions for the pre-annealing treatment are appropriately selected depending on the type of the epoxy resin layer 14 to be used, the peel strength (y) between the glass substrate 16 and the silicone resin layer 14 can be made more suitable. From the point of view of the person, it is preferable to carry out heat treatment for more than 5 minutes (preferably 5 to 30 minutes) at 300 ° C or higher (preferably at 300 to 400 ° C).

Further, the formation of the silicone resin layer 14 having a difference in peel strength between the first main surface of the glass substrate 16 and the first main surface of the support substrate 12 is not limited to the above method.

For example, when the support substrate 12 having a higher adhesion to the surface of the silicone resin layer 14 than the material of the glass substrate 16 is used, the curable organic polyfluorene can be cured on a peelable surface to produce A film of a silicone resin is laminated while the film is interposed between the glass substrate 16 and the support substrate 12.

Moreover, when the adhesion is sufficiently low to the glass substrate 16 by the curing of the curable organopolysiloxane, and the adhesion is sufficiently high for the support substrate 12, The crosslinked material is hardened between the glass substrate 16 and the support substrate 12 to form the epoxy resin layer 14.

Further, even when the support base material 12 is made of the same glass material as the glass substrate 16, the treatment for improving the adhesion of the surface of the support substrate 12 can be performed to improve the peel strength against the silicone resin layer 14. For example, the following method can be exemplified: a chemical method (primer treatment) which chemically raises the fixing force like a decane coupling agent; a physical method of increasing a surface active group as in the case of FLAME (flame) treatment; A mechanical treatment method or the like which increases the thickness by increasing the surface roughness as in the case of sand blasting.

(glass base layer)

The glass substrate 10 according to the first aspect of the present invention can be used for various applications, and examples thereof include the use of an electronic component such as a panel for a display device to be described later, a PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed thereon. Further, in this application, the glass base layer 10 is often exposed to high temperature conditions (for example, 450 ° C or higher) (for example, 1 hour or longer).

Here, the "display panel panel" includes an LCD, an OLED, an electronic paper, a plasma display, a field emission display, a quantum dot LED display, and a MEMS (Micro Electro Mechanical Systems) shutter display (SHUTTER PANEL). Wait.

<Second embodiment>

Fig. 3 is a schematic cross-sectional view showing a second embodiment of the glass laminate of the present invention.

As shown in FIG. 3, the glass substrate 100 is a layer having a layer supporting the substrate 12, a layer of the glass substrate 16, and a layer of the epoxy resin layer 14 present between the layers. body.

The glass substrate 100 shown in FIG. 3 is different from the glass substrate 10 shown in FIG. 1 in that the epoxy resin layer 14 is fixed on the glass substrate 16, and the glass substrate 20 with the resin layer is The epoxy resin layer 14 in the glass substrate 20 with the resin layer can be peelably laminated (adhered) to the support substrate 12 so as to be in direct contact with the support substrate 12. The fixing is different from the peelable adhesion to the peeling strength (that is, the stress required for peeling), and the fixing means that the peeling strength is high with respect to the adhesion. That is, in the glass base layer 100, the interfacial peel strength between the silicone resin layer 14 and the glass substrate 16 is higher than the interfacial peel strength of the silicone resin layer 14 and the support substrate 12.

More specifically, the interface between the glass substrate 16 and the silicone resin layer 14 has a peeling strength (z), and once the interface between the glass substrate 16 and the silicone resin layer 14 is subjected to a stress exceeding the peeling strength (z) peeling direction, The interface between the glass substrate 16 and the first epoxy resin layer 14 is peeled off. The interface between the silicone resin layer 14 and the support substrate 12 has a peel strength (w), and when a stress exceeding the peel strength (w) peeling direction is applied to the interface between the silicone resin layer 14 and the support substrate 12, the oxygen is removed. The interface between the resin layer 14 and the support substrate 12 is peeled off.

In the glass laminate 100, the peel strength (z) is higher than the peel strength (w). Therefore, when the glass laminate 100 is subjected to the stress in the direction in which the support substrate 12 and the glass substrate 16 are peeled off, the glass laminate 100 of the present invention is peeled off at the interface between the silicone resin layer 14 and the support substrate 12, and is separated into attached. The glass substrate 20 of the resin layer and the support substrate 12.

The peel strength (z) is preferably sufficiently high compared to the peel strength (w). Increasing the peel strength (z) means increasing the adhesion of the silicone resin layer 14 to the glass substrate 16. The force, and after the heat treatment, maintains a relatively high adhesion to the support substrate 12.

In order to increase the adhesion of the silicone resin layer 14 to the glass substrate 16, the curable organic polyfluorene oxide is preferably cross-linked and hardened on the glass substrate 16 to form the epoxy resin layer 14. The epoxy resin layer 14 bonded to the glass substrate 16 with high bonding force can be formed by the adhesion force at the time of crosslinking hardening.

On the other hand, the bonding strength of the cross-linking hardened epoxy resin to the support substrate 12 is lower than that of the above-mentioned cross-linking hardening. Therefore, the glass laminate 100 can be produced by forming the epoxy resin layer 14 on the glass substrate 16 and then laminating the support substrate 12 on the surface of the epoxy resin layer 14.

The respective layers (the support substrate 12, the glass substrate 16, and the epoxy resin layer 14) constituting the glass laminate 100 are synonymous with the layers constituting the glass laminate 10, and thus will not be described here.

However, the surface roughness Ra of the side surface of the supporting substrate 12 of the silicone resin layer 14 is not particularly limited, but is preferably 0.1 to 20 nm from the viewpoint of further excellent lamination property and releasability of the glass substrate 16. ~10nm is better.

In addition, the method of measuring the surface roughness Ra is performed in accordance with JIS B 0601-2001, and the value obtained by arithmetic mean of Ra measured at any five or more points is the surface roughness Ra.

The method for producing the glass laminate 100 is not particularly limited. However, in the method for producing the glass laminate 10, the glass substrate 16 may be used instead of the support substrate 12, and the support substrate 12 may be used instead of the glass substrate 16 to manufacture the glass substrate 16. The desired glass laminate 100. More specifically, the epoxy resin layer 14 can be formed on the glass substrate 16, followed by laminating the layer on the silicone resin layer 14. The glass laminate 100 is produced by holding the substrate 12.

[Glass substrate with attached member and method of manufacturing the same]

In the present invention, the above-described glass laminate (glass laminate 10 or glass laminate 100) can be used to manufacture an electronic device.

Hereinafter, the aspect of the glass laminate 10 will be described in detail.

By using the glass laminate 10, a glass substrate (a glass substrate with a member for an electronic device) including a member for a glass substrate and a member for an electronic device can be manufactured.

The method for producing the glass substrate of the member is not particularly limited. However, from the viewpoint of excellent productivity of the electronic device, it is preferable to form a member for an electronic device on the glass substrate in the glass composite. And the laminated body of the member for electronic devices is manufactured, and the laminated body of the member for electronic devices obtained is separated into the glass substrate of the attached member by using the glass substrate side interface of the oxime resin layer or the inside of the resin layer as a peeling surface. A support substrate with a resin layer. Further, it is more preferable to clean the peeled surface of the glass substrate of the attached member as needed.

In the following, a step of forming a laminate for a member for an electronic device on a glass substrate in the glass laminate to produce a laminate for a member for an electronic device is referred to as a "member forming step", and a laminate of a member for an electronic device is used as a laminate. The glass substrate side interface of the oxygen resin layer is a peeling surface, and the step of separating the glass substrate of the attached member and the supporting substrate with the resin layer is referred to as a "separation step"; the step of cleaning the peeling surface of the glass substrate of the attached member is called "Kilution process steps". In addition, as described above, the cleaning process step can be implemented as needed Optional steps.

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

(component forming step)

The member forming step is a step of forming a member for an electronic device on the glass substrate 16 in the glass composite 10 obtained in the above-described lamination step. More specifically, as shown in FIG. 2(C), the electronic device member 22 is formed on the second main surface 16b (exposed surface) of the glass substrate 16, and the laminated body 24 for the electronic device is produced.

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

(Mechanical components (functional components))

The electronic device member 22 is a member for constituting at least a part of the electronic device formed on the glass substrate 16 in the glass laminate 10. More specifically, the electronic device member 22 can be used as a member for a display device panel, a solar cell, a thin film secondary battery, or an electronic component such as a semiconductor wafer on which a circuit is formed (for example, a member for a display device) , a member for a solar cell, a member for a thin film secondary battery, and a circuit for an electronic component).

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

In addition, as a member for a thin film secondary battery, a lithium ion type may be a transparent electrode or an electrolyte layer such as a metal or a metal oxide of a positive electrode or a negative electrode. The lithium compound, the metal of the collector layer, and the resin as the sealing layer may be various members such as a nickel-hydrogen type, a polymer type, and a ceramic electrolyte type.

Further, as the circuit for the electronic component, the CCD and the CMOS include a metal of a conductive portion, a ruthenium oxide or a tantalum nitride of an insulating portion, and the like, and may correspond to a pressure sensor. Various sensors such as an acceleration sensor or various components such as a rigid printed circuit board, a flexible printed circuit board, and a rigid flexible printed circuit board.

(procedure of steps)

The method of manufacturing the laminated body 24 of the electronic device-attached member is not particularly limited, and may be applied to the second main surface 16b of the glass substrate 16 of the glass laminate 10 according to a conventionally known method depending on the type of the constituent member of the electronic device member. A member 22 for an electronic device is formed on the surface.

Further, the electronic device member 22 is not the entire member (hereinafter referred to as "all members") formed on the second main surface 16b of the glass substrate 16, and may be one part of the entire member (hereinafter referred to as "partial member"). The glass substrate with the part of the member which has been peeled off from the epoxy resin layer 14 may be formed into a glass substrate (corresponding to an electronic device described later) in which all the members are attached.

Further, other electronic device members may be formed on the peeling surface (first main surface 16a) of the glass substrate having all the members which have been peeled off from the silicone resin layer 14. Further, the laminate of all the members may be combined, and then the laminate of all the members may be peeled off from the support substrate 12 to manufacture an electronic device. Further, it is also possible to use and combine two laminated bodies with all the members, and then peel the two supporting substrates 12 from the laminated body of all the members, and to manufacture two glass substrates. A glass substrate attached to the board.

For example, a case where the OLED is manufactured is formed on the surface of the glass laminate 10 on the side opposite to the side of the epoxy resin layer 14 (corresponding to the second main surface 16b of the glass substrate 16). The organic EL structure is formed and processed by forming a transparent electrode, and further depositing a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and the like on a surface on which the transparent electrode is formed; The back electrode; and sealing using a sealing plate. The layer formation and treatment are specifically, for example, a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate.

Further, for example, when manufacturing a TFT-LCD, there are various steps such as a step of forming a TFT on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by using a photoresist solution and using a CVD method and sputtering. A metal film, a metal oxide film or the like formed by a general film forming method such as plating is patterned to form a thin film transistor (TFT), and a CF forming step is performed on the second main surface of the glass substrate 16 of the other glass laminate 10. 16b, a photoresist solution is used for pattern formation to form a color filter (CF); and a bonding step is performed on the laminate of the TFT obtained by the TFT forming step and the CF-attached layer obtained by the CF forming step. Laminated.

In the TFT formation step and the CF formation step, TFTs and CFs are formed on the second main surface 16b of the glass substrate 16 by using well-known lithography and etching techniques. At this time, the coating liquid for pattern formation uses a photoresist liquid.

Further, before forming the TFT and the CF, the second main surface 16b of the glass substrate 16 may be cleaned as needed. The method of washing can be carried out using a well-known dry cleaning or wet washing.

In the bonding step, the thin film transistor forming surface of the laminated body with the TFT is opposed to the color filter forming surface of the laminated body with CF, and is bonded by using an adhesive (for example, an ultraviolet curing adhesive for cell formation). Thereafter, a liquid crystal material is injected into a cell formed of a laminate body with TFTs and a laminate body with CF. The method of injecting the liquid crystal material is, for example, a vacuum injection method and a dropping injection method.

(separation step)

The separation step is a laminate body 24 of the member for an electronic device obtained by the member forming step, and the interface between the silicone resin layer 14 and the glass substrate 16 is a peeling surface, and is separated into a glass substrate 16 in which the electronic device member 22 is laminated ( The glass substrate of the member, the epoxy resin layer 14 and the support substrate 12 are obtained, and the glass substrate 26 containing the member for the electronic device 22 and the member of the glass substrate 16 is obtained.

On the other hand, when the electronic device member 22 on the glass substrate 16 is part of all the constituent members to be formed when peeling, the remaining constituent members may be formed on the glass substrate 16 after separation.

The method of peeling off the glass substrate 26 of the attachment member and the support substrate 18 with the resin layer is not particularly limited. Specifically, for example, a sharp blade can be inserted into the interface between the glass substrate 16 and the silicone resin layer 14, and after the peeling start is applied, a mixed fluid of water and compressed air is blown and peeled off. In addition, it is preferable that the support substrate 12 of the laminated body 24 of the member for electronic device is placed on the upper side and the electronic device member 22 is on the lower side, and the electronic device member 22 side is provided. The vacuum is adsorbed on the fixed plate (sequentially when the supporting substrate is laminated on both sides), and in this state, the tool is first introduced. The glass substrate 16 is placed in the interface of the silicone resin layer 14. Then, the support substrate 12 side is adsorbed by a plurality of vacuum adsorption pads thereafter, and the vacuum adsorption pad is sequentially raised in the vicinity of the inserted tool. As a result, an air layer is formed at the interface between the epoxy resin layer 14 and the glass substrate 16, and the air layer diffuses over the entire surface of the interface, and the support substrate 18 with the resin layer can be easily peeled off.

Further, the support substrate 18 with the resin layer can be laminated with a new glass substrate to produce the glass base layer 10 of the present invention.

Further, when the laminated body 24 of the member for electronic device is separated from the glass substrate 26 of the attached member, the electrode of the epoxy resin layer 14 can be more electrostatically adsorbed to the attached member by the blowing of the ionizing agent or the humidity control. The glass substrate 26 is.

[cleaning process steps]

The cleaning treatment step is a step of performing a cleaning treatment on the peeling surface (first main surface 16a) of the glass substrate 16 in the glass substrate 26 of the member obtained by the separation step. By performing this step, it is possible to remove impurities such as metal sheets and dust generated in the above-described member forming step of the epoxy resin adhered to the peeling surface or adhered to the epoxy resin layer and the peeling surface, thereby maintaining the cleansing of the peeling surface. degree. As a result, the adhesion of the retardation film or the polarizing film adhered to the peeling surface of the glass substrate 16 is improved.

The method of the cleaning treatment is not particularly limited as long as the resin, dust, and the like adhering to the peeling surface can be removed. For example, a method of thermally decomposing a deposit, a method of removing impurities on a peeling surface by irradiation with plasma or irradiation light (for example, a UV irradiation treatment), a method of performing a clean treatment using a solvent, and the like may be mentioned.

The manufacturing method of the glass substrate 26 of the above-mentioned attached member is suitable for the manufacture of a small display device for use in a mobile terminal like a mobile phone and a PDA. Further, the display device is mainly an LCD or an OLED, and the LCD includes a TN type, an STN type, an FE type, a TFT type, an MIM type, an IPS type, and a VA type. Basically, any of the passive driving type and the active driving type can be applied.

The glass substrate 26 of the member which is produced by the above-mentioned method is a panel for a display device which has a glass substrate and the member for display devices, the solar cell which has the member of the glass substrate and solar cell, and the glass substrate and the thin film secondary battery. A thin film secondary battery using a member, an electronic component having a glass plate and a member for an electronic device, and the like. The panel for a display device includes a liquid crystal panel, an organic EL panel, a plasma display panel, and a field emission panel.

Although the above description has been made in detail using the glass laminate 10, the glass laminate 100 can be used and the electronic device can be manufactured in accordance with the same procedure as described above.

Further, when the glass laminate 100 is used, in the separation step, the interface between the support substrate 12 and the epoxy resin layer 14 is a release surface, and is separated into a support substrate 12, a silicone resin layer 14, and a glass substrate. 16 and an electronic device including the member 22 for an electronic device.

Example

Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples. Further, in the present production example, the evaluation of the curable organopolyoxygen was carried out in accordance with the items and methods shown below.

(1) Analysis of the bonding state of the ruthenium atom in the sclerosing organic polyfluorene (T unit ratio)

The ratio of T1 to T3 was determined using a nuclear magnetic resonance analyzer (solution ²⁹ Si-NMR: manufactured by JEOL RESONANCE Co., Ltd., ECP400).

The ratio of T1 to T3 was determined from the peak area ratio of solution ²⁹ Si-NMR. The measurement conditions were set to a pulse width of 20 μsec, a waiting time for pulse wave recovery of 30 sec, and a cumulative number of times of 256 scan. Toluene was used as the solvent, and a relaxation reagent, that is, 0.1 wt% of Cr(acac) ₃ was added to a concentration of 30% by weight. The basis for the chemical shift is to set the peak from TMS to 0 ppm.

The integral calculation range of each structure is as follows: T1 (Me base): -44 to -49 ppm, T1 (Ph base): -60 to -61 ppm

T2 (Me base): -50~-60ppm, T2 (Ph base): -67~-74ppm

T3 (Me base): -61~-67ppm, T3 (Ph base): -74~-83ppm

(2) Analysis of the composition ratio of phenyl mole %/methyl mole % (the aforementioned (A-2) / (B-2)) in the curable organopolyoxygen

The composition ratio of phenyl mole % / methyl mole % (the above (A-2) / (B-2)) was determined using a nuclear magnetic resonance analyzer (solution ¹ H-NMR: manufactured by JEOL RESONANCE Co., Ltd., ECP400). .

The phenyl mole % / methyl mole % (the above (A-2) / (B-2)) composition ratio was determined from the peak area of ¹ H-NMR. The measurement conditions were set to a pulse width of 6.7 μsec, a waiting time for pulse wave recovery of 5 sec, and a cumulative number of 16 scans. The solvent was prepared by deuterated chloroform to a concentration of 1% by weight. The basis for the chemical shift is to set the peak from chloroform to 7.26 ppm. Further, the chemical shifts from ¹ H-NMR of each structure are as follows: A-2 (Ph group): 8.2 to 6.4 ppm

B-2 (Me base): 0.6 to -0.7 ppm.

(3) Evaluation of number average molecular weight Mn, mass average molecular weight Mw, and dispersity Mw/Mn

It was determined by gel permeation chromatography (GPC, HLC8220 manufactured by Tosoh Corporation, RI detection, column: TSK-GEL SuperHZ, eluent: tetrahydrofuran).

(4) Evaluation of particle size by dynamic light scattering method

The curable organic polyfluorene was made into a 20% by mass solution of PGMEA (propylene glycol-1-monomethyl ether-2-acetate), and a thick particle size analyzer (OTSUKA ELECTRONICS Co., Ltd., FPAR-1000) The histogram average particle diameter (D50) was determined as the particle diameter.

In the following Examples 1 to 10 and Comparative Examples 1 and 2, a glass plate composed of alkali-free borosilicate glass (274 mm in length, 274 mm in width, 0.2 mm in plate thickness, and linear expansion coefficient 38 × 10 ^{-7 was used.} /°C, the product name "AN100" manufactured by Asahi Glass Co., Ltd.) is used as a glass substrate. In addition, the support plate uses a glass plate which is composed of alkali-free borosilicate glass (transformation 274 mm, transverse 274 mm, plate thickness 0.4 mm, linear expansion coefficient 38×10 ^-7 /°C, manufactured by Asahi Glass Co., Ltd., The name "AN100").

<Production Example 1: Production of Curable Organic Polyoxane>

Sodium carbonate (12.7 g, 0.12 mol) and water (80 mL) were placed in a reaction vessel equipped with a reflux condenser, a dropping funnel, and a stirrer, and stirred, and then methyl isobutyl ketone (80 mL) was added thereto. The reaction solution was obtained. Next, methyltrichloromethane (7.5 g, 0.05 mol) and phenyltrichlorodecane (10.6 g, 0.05 mol) were dropped from the dropping funnel into the reaction solution for 30 minutes. At this time, The temperature of the reaction solution was raised to 40 °C. Next, after the completion of the dropwise addition, the reaction vessel was immersed in an oil bath of 60 ° C, and heated and stirred for 24 hours. After completion of the reaction, the organic phase is washed until the washing water becomes neutral, and then the organic phase is dried using a drying agent. Next, after removing the desiccant, the solvent was distilled off under reduced pressure, and vacuum drying was performed overnight to obtain a white solid (curable organic polyfluorene (U1)).

<Manufacturing Example 2 to 8>

The curable organic polysiloxanes (U2) to (U8) were produced in the same manner as in Production Example 1 according to the composition ratio shown in Table 1. In addition, (U4) except that the reaction time was adjusted from 24 hours to 1 hour, and (U6) was carried out in the same procedure as in Production Example 1 except that the reaction time was adjusted from 24 hours to 3 hours. Manufacturing. (U5), after (U4) was produced, it was made into a 50 mass % methanol solution, and after adding the acetic acid of 2 mass % with respect to a solid content, it was obtained by extracting the solvent under reduced pressure again. White solid.

In addition, the column "Phenyl mole % / methyl mole %" in Table 1 below is shown in the obtained curable organopolyfluorene oxide, and R is a phenyl group-containing oxy group unit in T1 to T3. And the molar ratio of the decyloxy unit in which R is a methyl group in T1 to T3.

In the column of "T unit ratio", the ratio of the number of units of T1 to T3 in the obtained curable organopolyfluorinated oxygen (% by mole) is shown, and the number of each unit of T1 to T3 is made. The total of the ratios is expressed as 100.

The "particle size" column is the particle size of the sclerosing organic polyfluorene oxide measured by the above dynamic light scattering method, and "<40" means that the particle diameter is less than 40 nm, and ">100" means that the particle diameter exceeds 100 nm. .

Further, the content of each of the above units was calculated by ²⁹ Si-NMR or ¹ H-NMR.

<Example 1>

The obtained curable organopolyfluorene (U1) was dissolved in PEGMEA to prepare a liquid material containing a curable organopolyfluorene (U1) (solid content concentration: 40% by mass) (in addition, curable organic polyoxyl The fine particles having the particle diameters shown in Table 1 were present in the liquid).

The support substrate is washed with pure water, and then washed with UV to be cleaned.

Next, a liquid material containing a curable organic polyfluorene oxide (U1) (coating amount: 30 g/m ² ) was applied to the first main surface of the support substrate by a spin coater at a length of 278 mm and a width of 278 mm.

Then, it was heat-hardened at 350 ° C for 30 minutes in the atmosphere, and a tantalum resin layer having a thickness of 2.8 μm was formed on the first main surface of the supporting substrate to obtain a support A (supporting substrate with a resin layer).

Then, the peeling surface of the epoxy resin layer of the support A and the crucible The first main surface of the glass substrate ("AN100", manufactured by Asahi Glass Co., Ltd.) having the same size and a thickness of 0.2 mm is opposed to each other, and a stacking device is used at room temperature and atmospheric pressure to overlap the center of gravity of the two substrates. The two substrates are laminated to obtain a glass laminate S1.

Further, the obtained glass laminate S1 corresponds to the glass laminate 10 of Fig. 1 described above, and in the glass laminate S1, the interfacial peel strength (x) of the layer of the support substrate and the epoxy resin layer is higher than that of the epoxy resin layer. Interfacial peel strength (y) from the glass substrate.

Next, the following measurement was carried out using the obtained glass laminate S1. The results of the following evaluations are shown in Table 1 below.

[Peeability evaluation]

A 50 mm square sample was cut out from the glass laminate S1, and the sample was placed in a hot air oven heated to 450 ° C (under a nitrogen atmosphere), and taken out after leaving for 60 minutes. Next, after the second main surface of the glass substrate in the glass laminate S1 is vacuum-adsorbed on the fixed plate, a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at one corner of the glass laminate S1. And a peeling opening is provided between the first main surface of the glass substrate and the peelable surface of the silicone resin layer. Then, after adsorbing the second main surface of the support substrate of the glass laminate S1 at a pitch of 90 mm and a plurality of vacuum adsorption pads, the adsorption pads from the corner portions are sequentially raised to thereby increase the first of the glass substrates. The main surface is peeled off from the peeling surface of the silicone resin layer.

From the above results, it was confirmed that the glass substrate could be peeled off even after the high-temperature heat treatment.

In addition, the main part of the silicone resin layer will be self-glassed together with the support substrate. The glass substrate was separated, and based on the results, it was confirmed that the interfacial peel strength (x) of the layer of the support substrate and the epoxy resin layer was higher than the interfacial peel strength (y) between the silicone resin layer and the glass substrate.

[Heat resistance evaluation]

A 50 mm square specimen was cut out from the glass laminate S1, and the sample was placed in a hot air oven heated to 450 ° C (under a nitrogen atmosphere), and after being left for 60 minutes, it was taken out and the sample was evaluated. Whether it is confirmed to be foaming or coloring.

<Examples 2 to 10>

The liquid material containing the curable organopolyfluorene (U1) was replaced with a liquid material containing a curable organic polyfluorene (U2) to (U6) as shown in Table 2 below, and the thermosetting was changed. The glass laminates S2 to S10 were produced in the same manner as in Example 1 except for the treatment conditions.

The types of the solvent used in the production of the liquid material, the solid content concentration, and the like are shown in Table 2 below. Further, in Examples 7 and 8, the heat curing treatment conditions at the time of heat curing were changed from "350 ° C and 30 minutes" to "heat curing at 150 ° C for 30 minutes in the atmosphere, and then at 350 ° C in the atmosphere. Heat hardened for 60 minutes". Further, in the ninth embodiment, the thermosetting treatment conditions at the time of heat curing were changed from "350 ° C and 30 minutes" to "heat curing at 150 ° C for 30 minutes in the atmosphere, and then heat-hardening at 350 ° C in the atmosphere. After 60 minutes, and further heat-hardened in the atmosphere at 500 ° C for 60 minutes.

Further, the obtained glass laminates S2 to S10 correspond to the glass laminate 10 of Fig. 1 described above, and in the glass laminates S2 to S10, the interface peeling strength (x) between the layer of the support substrate and the silicone resin layer is high. On the epoxy resin layer and the glass substrate Interface peel strength (y).

Moreover, the above-mentioned [peelability evaluation] and [heat resistance evaluation] were carried out using the obtained glass laminates S2 to S10. The results are shown in Table 2.

<Comparative Example 1>

The same procedure as in Example 1 was followed except that the liquid material containing the curable organopolyfluorene (U1) was replaced with the liquid material containing the curable organopolyfluorene (U8) shown in Table 2 below. The manufacture of the glass laminate C1 is carried out. The above-mentioned [peelability evaluation] and [heat resistance evaluation] were carried out using the obtained glass laminate C1. The results are shown in Table 2.

<Comparative Example 2>

100 parts by mass of polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KNS-320A) and platinum-based catalyst (Shin-Etsu Chemical Co., Ltd.) were used except for the solvent-free additional reaction type release paper. Manufactured, product name: CAT-PL-56) 2 parts by mass of the mixture (U9) was replaced with the liquid material containing the curable organopolyfluorene (U1), and the same procedure as in Example 1 was followed to produce a glass laminate. Body C2. The above-mentioned [peelability evaluation] and [heat resistance evaluation] were carried out using the obtained glass laminate C2. The results are shown in Table 2.

Further, the aspect of the glass laminate C2 corresponds to the aspect of Patent Document 1.

In Table 2, the "Applicability Evaluation" column is treated as "○" when a liquid material containing a curable organic polyfluorene is applied, and when the epoxy resin layer is formed, "X" is not formed when the epoxy resin layer cannot be formed. "."

Also, in the "peelability evaluation" column, the glass substrate and the enamel tree will be A stainless steel cutter is inserted into the interface of the grease layer, and when the peeling opening is applied, most of the glass substrate and the silicone resin layer are peeled off, and the glass substrate can be easily peeled off by "◎"; only the peeling start is provided. In the case where the glass substrate is not peeled off, the glass substrate may be peeled off by "○"; the glass substrate may not be peeled off, or the glass substrate may be broken by "x".

In addition, in the "heat resistance evaluation" column, "no" is indicated when there is no "coloring" and "bubble", and "yes" is indicated when there is such a case.

Further, in Table 2, in the column of "oxygenated resin layer", the molar percentage of the T3 unit and the Q unit calculated from the peak area ratio of ²⁹ Si-NMR was shown.

Further, in the present production examples and comparative examples, the analysis of the silicone resin layer was carried out in accordance with the items and methods shown below.

(1) Analysis of bonding state of germanium atoms in the epoxy resin layer

The content (% by mole) of the T3 unit and the Q unit was determined using a nuclear magnetic resonance analyzer (solid ²⁹ Si-NMR: manufactured by JEOL RESONANCE Co., Ltd., ECP600).

The content (% by mole) of the T3 unit and the Q unit was determined from the peak area ratio of the solid ²⁹ Si-NMR. As the epoxy resin layer, a solid sample containing the curable organopolyxylene-containing liquid used in each of the examples and the comparative examples was applied onto a glass substrate by a spin coater, and each of the examples was used. The heating conditions of the comparative examples were heat-hardened to form a silicone resin layer on the glass substrate, and the epoxy resin layer was obtained by cutting with a razor blade. The measurement method was performed by the DDMAS method, and the measurement conditions were set to be 1.9 μsec in pulse width, 300 sec in pulse wave recovery, 300 scan or more in cumulative number, and 10 KHz in MAS rotation speed. The basis for the chemical shift is to set the peak derived from polydimethyl oxime to -22 ppm. Further, the chemical shift of the solid ²⁹ Si-NMR derived from each structure was as follows: T3: -48 to -88 ppm

Q: -96~-116ppm.

(2) Analysis of (A-1)/(B-1) ratio of the epoxy resin layer

Using a nuclear magnetic resonance analyzer (solid ¹ H-NMR: manufactured by JEOL RESONANCE Co., Ltd., ECP600), the peak area ratio derived from the Ph group and the Me group was determined. As the epoxy resin layer, a solid sample containing the curable organopolyxylene-containing liquid used in each of the examples and the comparative examples was applied onto a glass substrate by a spin coater, and each of the examples was used. The heating conditions of the comparative examples were heat-hardened to form a silicone resin layer on the glass substrate, and the epoxy resin layer was obtained by cutting with a razor blade. In the measurement method, Depth2 was used, and the measurement conditions were set to be 2.3 μsec in pulse width, 15 sec in pulse wave recovery, 16 scan in cumulative number, and 22 KHz in MAS rotation speed. The basis for the chemical shift is to set the peak derived from adamantane to 1.7 ppm. Further, the chemical shift of the solid ¹ H-NMR derived from each structure is as follows: A-1 (Ph group): 18 to 4 ppm

B-1 (Me base): 4 to -10 ppm.

(3) Film thickness of the epoxy resin layer

The film thickness of the epoxy resin layer is the surface roughness of the contact membrane pressure device. The contour shape measuring machine (SURFCOM 1400G-12 manufactured by Tokyo Seimitsu Co., Ltd.) was measured.

(4) Shrinkage stress of the epoxy resin layer

After being placed in a predetermined position in the film stress measuring device FLX-2320 (manufactured by KLA Tencor Corporation), the measurement was performed at an ambient temperature of 25 ° C, based on the orientation of the wafer having an outer diameter of 4 吋 and a thickness of 525 ± 25 μm. The radius of curvature of the wafer.

Next, the ruthenium wafer was taken out, and the curable organic polyfluorene-containing liquid material used in each of the examples and the comparative examples was applied onto the ruthenium wafer by spin coating, and heated under the heating conditions of the respective examples and comparative examples. It is hardened to form a layer of a silicone resin. The radius of curvature of the tantalum wafer on which the tantalum oxide layer had been formed was measured in the same manner as before the formation of the tantalum-based coating film at an ambient temperature of 25 °C.

From (where E/(1-ν) is the biaxial elastic coefficient of the tantalum wafer (crystal face (100): 1.805×10 ¹¹ Pa), h is the thickness of the tantalum wafer [m], t is the epoxy resin The thickness [m] of the layer, R is the difference [v] between the radius of curvature of the tantalum wafer before the formation of the tantalum resin layer and the radius of curvature of the tantalum oxide layer, and the shrinkage stress of the tantalum resin layer at 25 ° C was calculated.

Further, the organic methoxy unit of the oxime resin layer in the glass composites S1 to S9 is composed of a Q unit and a T3 unit. In the above-described Example 10 and Comparative Example 1, the Q unit was not detected (below the measurement limit).

As shown in the above-mentioned Table 2, in the glass laminate of the present invention, the epoxy resin layer exhibits excellent heat resistance and is excellent in peelability (separability) on a glass substrate. In particular, in Examples 1 to 9 containing Q units, the releasability was more excellent.

On the other hand, as shown in Comparative Examples 1 and 2, when the silicone resin layer having a predetermined composition ratio was not used, the desired effect was not obtained.

<Example 11>

In this example, the OLED was produced using the glass laminate S1 obtained in Example 1.

First, tantalum nitride, hafnium oxide, and amorphous germanium are sequentially formed by the plasma CVD method on the second main surface of the glass substrate in the glass laminate S1. Next, a low concentration of boron is implanted into the amorphous germanium layer by an ion doping apparatus, and heat treatment is performed and dehydrogenation treatment is performed. Next, the crystallization treatment of the amorphous germanium layer is performed by a laser annealing apparatus. Then, by using an etching and ion doping apparatus which is performed by photolithography, a low concentration of phosphorus is implanted into the amorphous germanium layer to form N-type and P-type TFT regions. Next, on the second main surface side of the glass substrate, a ruthenium oxide film is formed by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by sputtering, and photolithography is used. Etching forms a gate electrode. Then, by using a photolithography method and an ion doping apparatus, a high concentration of boron and phosphorus is implanted into an N-type and a P-type desired region 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 plasma CVD method, and aluminum is formed by sputtering and etching is performed by photolithography. electrode. Secondly, in a hydrogen gas environment, after heat treatment and hydrogenation treatment, nitriding by plasma CVD The film formation of ruthenium forms a protective layer. Then, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, indium tin oxide is formed into a film by sputtering, and a pixel electrode is formed by etching using photolithography.

Next, the following film formation was sequentially performed on the second main surface side of the glass substrate by a vapor deposition method: 4,4',4"-parameter (3-methylphenylanilinyl group) as a hole injection layer Triphenylamine; as a hole transport layer is bis[(N-naphthyl)-N-phenyl]benzidine; as a light-emitting layer, 40% by volume is mixed in 8-quinolinol aluminum complex (Alq ₃ ) 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl]naphthalene-1,5-dicarbonitrile (BSN-BCN); And the electron transport layer is Alq ₃ . Next, aluminum is formed into a film by sputtering, and a counter electrode is formed by etching by photolithography. Then, on the second main surface side of the glass substrate, ultraviolet light is hardened. The other layer of the glass substrate is bonded to another glass substrate, and the organic EL structure is formed on the glass substrate by the above-described procedure. The glass laminate S1 having an organic EL structure on the glass substrate (hereinafter referred to as "panel A") That is, it is a laminate of the member for an electronic device of the present invention.

Next, in a state where the sealing body side of the panel A is vacuum-adsorbed on the fixing plate, a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of the panel A, and the glass substrate and the resin are imparted. The interface of the layer is peeled off at the beginning. Then, the adsorption pad is raised in a state where the surface of the support substrate of the panel A has been adsorbed by the vacuum adsorption pad. Here, the insertion of the cutter is performed while blowing a static eliminating fluid from the static eliminator (manufactured by KEYENCE CORPORATION) toward the interface. Next, while continuing to blow the destaticizing fluid from the static eliminator toward the formed void, and water the side The vacuum adsorption pad is raised while peeling off the front line. As a result, only the glass substrate on which the organic EL structure was formed was left on the plate, and the support substrate with the resin layer was peeled off.

Next, the separated glass substrate is cut by a laser cutter or a scribe breaking method, and after being divided into a plurality of cells, the glass substrate and the counter substrate are formed with the organic EL structure, and The module forming step is performed to fabricate an OLED. The OLED characteristics thus obtained do not cause problems.

<Example 12>

In this example, an LCD was produced using the glass laminate S1 obtained in Example 1.

First, two glass laminates S1 are prepared, and on the second main surface of the glass substrate of one of the glass laminates S1-1, tantalum nitride, tantalum oxide, and amorphous germanium are sequentially formed by plasma CVD. . Next, a low concentration of boron is injected into the amorphous germanium layer by an ion doping apparatus, and heat treatment is performed in a nitrogen gas atmosphere to perform dehydrogenation treatment. Next, the crystallization treatment of the amorphous germanium layer is performed by a laser annealing apparatus. Then, by using an etching and ion doping apparatus which is performed by photolithography, a low concentration of phosphorus is implanted into the amorphous germanium layer to form N-type and P-type TFT regions. Next, on the second main surface side of the glass substrate, a ruthenium oxide film is formed by a plasma CVD method to form a gate insulating film, and then molybdenum is formed by sputtering, and etching is performed by photolithography. Gate electrode. Next, a high concentration of boron and phosphorus is implanted into the N-type and P-type regions as desired by photolithography and an ion doping apparatus to form a source region and a drain region. Then, on the second main surface side of the glass substrate, the ruthenium oxide formed by the plasma CVD method forms a layer between the layers. The film is formed by sputtering, and aluminum is formed by sputtering and etching is performed by photolithography to form a TFT electrode. Next, after heat treatment and hydrogenation treatment in a hydrogen gas atmosphere, a protective layer is formed by film formation of tantalum nitride by a plasma CVD method. 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 photolithography. Then, indium tin oxide is formed into a film by sputtering, and a pixel electrode is formed by etching by photolithography.

Next, another glass laminated body S1-2 is heat-treated under an atmospheric environment. Next, chromium is formed on the second main surface of the glass substrate in the glass laminate S1 by sputtering, and a light shielding layer is formed by etching by photolithography. Then, a color resist is applied by a die coating method on the second main surface side of the glass substrate, and a color filter layer is formed by photolithography and thermal curing. Next, indium tin oxide is formed into a film by sputtering to form a counter electrode. Then, on the second main surface side of the glass substrate, the ultraviolet curable resin liquid was applied by a die coating method, and a columnar spacer was formed by photolithography and thermal curing. Next, the polyimide solvent solution was applied by a roll coating method, and an alignment layer was formed by thermal hardening, and rubbing was performed.

Next, the sealing resin liquid is drawn into a frame shape by a dispenser method, and the liquid crystal is dropped by a dispenser in a frame, and then the glass laminated body S1-1 having the pixel electrode formed thereon is used. The second main surface side of the glass substrate of the glass laminate S1 is bonded to each other, and an LCD panel is produced by ultraviolet curing and heat curing.

Then, the second main surface of the support substrate of the glass laminate S1-1 is vacuum-adsorbed on the fixed plate, and the glass at the corner of the glass laminate S1-2 A stainless steel cutter having a thickness of 0.1 mm was inserted into the interface between the substrate and the resin layer, and the first main surface of the glass substrate was peeled off from the peeling surface of the resin layer. Here, the inserting of the cutter was performed while blowing a static eliminating fluid to the interface from a static eliminator (manufactured by KEYENCE CORPORATION). Next, while continuing to eject the destaticizing fluid from the static eliminator toward the formed void, the water is supplied to the peeling front line to raise the vacuum suction pad. Then, when the second main surface of the support substrate of the glass laminate S1-2 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised. As a result, only the empty cells of the LCD with the support substrate of the glass laminate S1-1 are left on the fixed plate, and the support substrate with the resin layer can be peeled off.

Next, the second main surface of the glass substrate on which the color filter is formed on the first main surface is vacuum-adsorbed to the fixed plate, and the thickness of the interface between the glass substrate and the resin layer at the corner portion of the glass laminate S1-1 is 0.1 mm. The stainless steel cutter is provided with a peeling open end of the first main surface of the glass substrate and the peeling surface of the resin layer. Then, when the second main surface of the support substrate of the glass laminate S1-1 is adsorbed by the vacuum adsorption pad, the adsorption pad is raised while spraying water between the glass substrate and the resin layer. As a result, only the LCD unit is left on the fixing plate, and the supporting substrate to which the resin layer is fixed can be peeled off. In this way, a plurality of LCD units composed of a glass substrate having a thickness of 0.1 mm can be produced.

Then, it is divided into a plurality of LCD units by a cutting step. An LCD is prepared by performing a step of applying a polarizing plate to each of the completed LCD units, and then performing a module forming step. There is no problem in the LCD characteristics thus obtained.

<Example 13>

In this example, an OLED was produced using the glass laminate S1 obtained in Example 1.

First, molybdenum is formed on the second main surface of the glass substrate in the glass laminate S1 by sputtering, and a gate electrode is formed by etching by photolithography. Next, a sputtering film is formed on the second main surface side of the glass substrate by a sputtering method to form a gate insulating film, and then indium gallium zinc oxide is formed by sputtering and photolithography is used. The etching forms an oxide semiconductor layer. Then, by a sputtering method, an aluminum oxide is formed on the second main surface side of the glass substrate to form a channel protective layer, and then molybdenum is formed by sputtering and formed by etching by photolithography. Source and bungee.

Next, heat treatment is performed in the atmosphere. Then, a film is formed by sputtering on the second main surface side of the glass substrate to form a protective layer, and then indium tin oxide is formed by sputtering and etched by photolithography. Form a pixel electrode.

Next, the following film formation was performed on the second main surface side of the glass substrate by a vapor deposition method: 4,4′,4′′-para (3-methylphenylanilinyl) as a hole injection layer. Triphenylamine; as a hole transport layer is bis[(N-naphthyl)-N-phenyl]benzidine; as a light-emitting layer, 40% by volume is mixed in the 8-quinolinol aluminum complex (Alq ₃ ) 2,6-bis[4-[N-(4-methoxyphenyl)-N-phenyl]aminostyryl]naphthalene-1,5-dicarbonitrile (BSN-BCN); and The electron transporting layer is Alq ₃ . Next, aluminum is formed into a film by a sputtering method, and a counter electrode is formed by etching by photolithography. Then, the second main surface side of the glass substrate is passed through an ultraviolet curing type. Then, the other glass substrate is bonded to the other layer, and the organic EL structure is formed on the glass substrate by the above procedure. The glass laminate S1 (hereinafter referred to as "panel B") having the organic EL structure on the glass substrate is A laminated body of a member for an electronic device according to the invention (a panel for a display device with a supporting substrate).

Then, in a state where the sealing body side of the panel B is vacuum-adsorbed on the fixing plate, a stainless steel cutter having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of the panel B to impart a glass substrate and a resin. The interface of the layer is peeled off at the beginning. Then, the adsorption pad is raised in a state where the surface of the support substrate of the panel B has been adsorbed by the vacuum adsorption pad. Here, the inserting of the cutter was performed while blowing a static eliminating fluid to the interface from a static eliminator (manufactured by KEYENCE CORPORATION). Next, the destaticizing fluid is continuously blown from the static eliminator toward the formed void, and the vacuum adsorption pad is raised while supplying water to the peeling front line. As a result, only the glass substrate on which the organic EL structure was formed was left on the plate, and the support substrate with the resin layer was peeled off.

Then, the separated glass substrate is cut by a laser cutting machine or a scribing splicing method, and after being divided into a plurality of units, the glass substrate and the opposite substrate on which the organic EL structure is formed are assembled, and the module is implemented. The formation step produces an OLED. The OLED characteristics thus obtained do not cause problems.

In addition, the entire contents of the specification, the scope of the application, the abstract and the drawings of the Japanese Patent Application No. 2014-022697, filed on Feb. 7, 2014, the entire contents of .

Claims (13)

A glass laminate comprising a support base layer, a silicone resin layer and a glass substrate layer; wherein the epoxy resin in the epoxy resin layer has an organic phosphonium unit represented by the following T3, and is relative to all The organic decyloxy unit, the total ratio of the organic decyloxy unit represented by the following T3 is 80 to 100 mol%; and in the following T3, R is a phenyl organic decyloxy unit (A-1) and the following The molar ratio ((A-1)/(B-1)) of the organic decyloxy unit (B-1) wherein R is a methyl group in T3 is 80/20 to 20/80; and the above-mentioned epoxy resin layer The interfacial peel strength of the glass substrate layer is different from the interfacial peel strength of the above-mentioned niobium oxide layer to the support substrate layer; T3: R-SiO _3/2 (wherein R represents a phenyl group or a methyl group). The glass laminate according to claim 1, wherein the above-mentioned oxime resin further has an organic decyloxy unit represented by Q: Q: SiO _4/2 . The glass laminate according to claim 1, wherein the oxime resin is a cured product of a curable organopolyfluorene; and the curable organopolysiloxane contains the organic methoxy unit represented by the following T1 to T3 in the following ratio; Organic polyfluorene: in terms of the number of units (molar amount), T1: T2: T3 = 0 to 5: 20 to 50: 50 to 80 (however, the relationship of T1 + T2 + T3 = 100 is satisfied) ): T1: R-Si(-OX) ₂ O _1/2 T2: R-Si(-OX)O _2/2 T3: R-SiO _3/2 (wherein R represents a phenyl group or a methyl group; X It means a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The glass laminate according to claim 2, wherein the oxime resin is a cured organic sulfonate; and the sclerosing organopolyoxygen contains the following organic methoxy unit represented by T1 to T3 in the following ratio; Organic polyfluorene: based on the number of units (molar amount), T1: T2: T3 = 0 to 5: 20 to 50: 50 to 80 (however, the relationship of T1 + T2 + T3 = 100 is satisfied) ): T1: R-Si(-OX) ₂ O _1/2 T2: R-Si(-OX)O _2/2 T3: R-SiO _3/2 (wherein R represents a phenyl group or a methyl group; X It means a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The glass laminate according to claim 3, wherein the hardening organic polyfluorene has a number average molecular weight of 500 to 2,000. The glass laminate according to claim 4, wherein the hardening organic polyfluorene has a number average molecular weight of 500 to 2,000. The glass laminate according to claim 3, wherein the mass average molecular weight/number average molecular weight of the hardenable organopolyfluorene is from 1.00 to 2.00. The glass laminate according to any one of claims 3 to 7, which is characterized by dynamic light dispersion The particle size of the aforementioned curable organic polyfluorene oxide measured by the sputtering method is 0.5 to 100 nm. The glass laminate according to any one of claims 3 to 7, wherein the curable organopolyfluorene is an organopolyoxygen obtained by cohydrolyzing and condensing phenyltrichloromethane with methyltrichloromethane. The glass laminate according to any one of claims 1 to 7, wherein the thickness of the above-mentioned silicone resin layer is 0.1 to 30 μm. The glass laminate according to any one of claims 1 to 7, wherein the aforementioned support substrate is a glass plate. The glass laminate according to any one of claims 1 to 7, wherein the interfacial peel strength of the silicone resin layer to the glass substrate layer is lower than the interfacial peel strength of the epoxy resin layer to the support substrate layer. The glass laminate according to any one of claims 1 to 7, wherein the interfacial peel strength of the epoxy resin layer to the glass substrate layer is higher than the interfacial peel strength of the epoxy resin layer to the support substrate layer.