KR20130140707A - Laminate body, panel for use in display device with support board, panel for use in display device, and display device - Google Patents

Abstract

The present invention provides a conductive metal oxide film having a support plate, a resin layer, and a conductive metal oxide film including an oxide of at least one metal selected from the group consisting of indium, tin, zinc, titanium, and gallium on the surface of the substrate. The board | substrate provided with the said conductive metal oxide film is arrange | positioned on the said resin layer so that the provided board | substrate may be provided in this order, and the said conductive metal oxide film may contact | tightly contact with said resin layer so that peeling between the said resin layer and the said support plate may be carried out. It is related with the laminated body whose intensity | strength is higher than peeling strength between the said resin layer and the board | substrate provided with the said conductive metal oxide film.

Description

Panel for display device with laminated body, support plate, panel for display device and display device {LAMINATE BODY, PANEL FOR USE IN DISPLAY DEVICE WITH SUPPORT BOARD, PANEL FOR USE IN DISPLAY DEVICE, AND DISPLAY DEVICE}

The present invention relates to a laminate, a display device panel provided with a supporting plate, a display device panel, and a display device.

In recent years, thinning and weight reduction of devices (electronic devices), such as a solar cell PV, a liquid crystal display (LCD), and an organic electroluminescent display (OLED), are progressing, and the thickness of the board | substrate used for these devices is progressing. When the strength of the substrate is insufficient due to the thinning, the handleability of the substrate is reduced in the manufacturing process of the device.

Therefore, conventionally, after forming a device member (for example, a thin film transistor) on the board | substrate thicker than a final thickness, the method of thinning a board | substrate by a chemical etching process is employ | adopted widely. However, in this method, for example, when the thickness of one substrate is thinned from 0.7 mm to 0.2 mm or 0.1 mm, most of the original substrate material is scraped off with an etchant, so that the viewpoint of productivity and use efficiency of raw materials Is not preferred.

In the method of thinning a substrate by chemical etching, when fine scratches are present on the surface of the substrate, fine recesses (etch pits) are formed by etching, starting from scratches, and the optical defects become optical defects. There was.

Recently, in order to cope with the above problems, a method of preparing a laminate in which a substrate and a reinforcement plate are laminated, forming a device member on the substrate of the laminate, and then peeling the reinforcement plate from the substrate has been proposed ( For example, refer patent document 1). The reinforcement plate has a glass plate and a resin layer fixed on the glass plate, and the resin layer and the substrate are in close contact with each other so as to be peelable. After the reinforcing plate is peeled off from the substrate, the reinforcing plate is laminated with a new substrate and can be reused as a laminate.

WO 07/018028

However, in the laminated body of the said conventional structure, when peeling a reinforcement board from a board | substrate, some resin layers may adhere to the board | substrate which is a product side. In particular, after the heat treatment is performed on the laminate under high temperature conditions, it is frequently caused that a part of the resin layer adheres to the substrate on the product side. This is considered to be because a resin layer deteriorates under high temperature conditions, or the adhesive strength of a resin layer and a board | substrate raises.

Therefore, when the said laminated body is applied to the manufacture of the device by which high temperature processing is performed, a part of resin layer adhered to the board | substrate, and there existed a possibility that the yield might fall.

Moreover, after peeling a board | substrate from the said laminated body, particle | grains, dust, etc. are easy to adhere to the surface of a board | substrate, and when a device is manufactured using such a board | substrate, there existed a possibility that a malfunction of a device may arise. It is thought that such adhesion | attachment of particle | grains and dust arises by peeling electrification.

This invention is made | formed in view of the said subject, Even when a high temperature heat processing is performed, when peeling a resin layer and a board | substrate, it can suppress that a part of resin layer adheres to the board | substrate which is a product side, and also the board | substrate which peels An object of the present invention is to provide a laminate that can suppress peeling charge on a surface.

Moreover, an object of this invention is to provide the display apparatus panel and display apparatus which are formed using the display apparatus panel provided with the support plate containing the said laminated body, the display apparatus panel provided with a support plate.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined and completed this invention in order to solve the said subject.

That is, in order to achieve the said objective, the 1st aspect of this invention is an oxide of the at least 1 metal chosen from the group which consists of a support plate, a resin layer, and indium, tin, zinc, titanium, and gallium on the surface of a board | substrate. The board | substrate provided with the said conductive metal oxide film is provided with the board | substrate with a conductive metal oxide film which has a conductive metal oxide film containing in this order, and the said conductive metal oxide film is in close contact with the said resin layer so that peeling is possible. It is a laminated body arrange | positioned above and whose peeling strength between the said resin layer and the said support plate is higher than the peeling strength between the said resin layer and the board | substrate provided with the said conductive metal oxide film.

In a 1st aspect, it is preferable that the said oxide further contains at least 1 sort (s) of element chosen from the group which consists of aluminum, molybdenum, copper, vanadium, niobium, tantalum, boron, and fluorine.

Moreover, in a 1st aspect, it is preferable that the said resin layer is a silicone resin layer.

Moreover, it is preferable that the said resin layer is comprised from the addition reaction type hardened | cured material of organo alkenyl polysiloxane and organohydrogen polysiloxane.

Moreover, it is preferable that the molar ratio of the hydrogen atom couple | bonded with the silicon atom of the said organohydrogenpolysiloxane with respect to the alkenyl group of the said organo alkenyl polysiloxane is 0.5-2.

The 2nd aspect of this invention is a structure of the display apparatus panel provided on the surface on the opposite side to the laminated body of a 1st aspect, and the surface in close contact with the said resin layer of the board | substrate with the said conductive metal oxide film in the said laminated body. It is a panel for display devices provided with a support plate which has a member.

A third aspect of the present invention is a panel for display device, which is formed using a panel for display device provided with a supporting plate of the second aspect.

A 4th aspect of this invention is a display apparatus which has the display apparatus panel of a 3rd aspect.

According to the present invention, even after the high temperature heat treatment is performed, when peeling the resin layer and the substrate, it is possible to suppress the adhesion of a part of the resin layer to the substrate on the product side, and also to suppress the peeling charge on the surface of the substrate to be peeled off. A laminate can be provided.

Moreover, according to this invention, the display apparatus panel and display apparatus which are formed using the display apparatus panel provided with the support plate containing the said laminated body, the display apparatus panel provided with a support plate can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing of one Embodiment of the laminated body which concerns on this invention.
2 is a schematic cross-sectional view of an embodiment of a panel for a display device provided with a supporting plate according to the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, although the form for implementing this invention is demonstrated with reference to drawings, this invention is not limited to the following embodiment, A various deformation | transformation and substitution are added to the following embodiment, without deviating from the range of this invention. Can be.

In addition, in this invention, fixing a resin layer to a support plate means bonding so that the peeling strength between a resin layer and a support plate may become higher than the peeling strength between a resin layer and the board | substrate provided with a conductive metal oxide film.

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

As shown in FIG. 1, the laminated body 10 is a board | substrate 24 with a conductive metal oxide film, the support plate 31, and the laminated body in which the resin layer 32 exists between them.

The substrate 24 provided with the conductive metal oxide film includes a substrate 20 and a conductive metal oxide film 22 provided on the surface of the substrate 20. The substrate 24 with the conductive metal oxide film is disposed on the resin layer 32 such that the conductive metal oxide film 22 is in close contact with the resin layer 32 so as to be peeled off.

In addition, the resin layer 32 is fixed on the support plate 31 and is in close contact with the conductive metal oxide film 22 of the substrate 24 provided with the conductive metal oxide film. The reinforcement board 30 which consists of the support plate 31 and the resin layer 32 reinforces the board | substrate 24 with an electroconductive metal oxide film in the process of manufacturing devices (electronic devices), such as a liquid crystal display.

This laminated body 10 is used until the manufacturing process of a device. That is, this laminated body 10 is used until the member for devices, such as a thin film transistor, is formed on the surface on the opposite side to the resin layer 32 of the board | substrate 24 with a conductive metal oxide film. Thereafter, the reinforcing plate 30 is peeled off from the substrate 24 provided with the conductive metal oxide film, and does not become a member constituting the device. The reinforcement board 30 peeled from the board | substrate 24 with a conductive metal oxide film is laminated | stacked with the board | substrate 24 with a new conductive metal oxide film, and can be reused as the laminated body 10. FIG.

In the present invention, it was found that a desired effect can be obtained by providing the substrate 24 with the conductive metal oxide film on the resin layer 32 so that the conductive metal oxide film 22 and the resin layer 32 are in contact with each other.

Hereinafter, each structure (a board | substrate with a conductive metal oxide film, a support plate, and a resin layer) is demonstrated in detail.

<Substrate with Conductive Metal Oxide Film>

First, the board | substrate 24 provided with the conductive metal oxide film is demonstrated.

The substrate 24 provided with the conductive metal oxide film includes a substrate 20 and a conductive metal oxide film 22 provided on the surface of the substrate 20. The electroconductive metal oxide film 22 is arrange | positioned in the outermost surface of the board | substrate 24 provided with the electroconductive metal oxide film so that it may contact with the resin layer 32 mentioned later so that peeling is possible.

Below, the board | substrate 20 and the conductive metal oxide film 22 are demonstrated in detail.

(Board)

The board | substrate 20 is equipped with the conductive metal oxide film 22 in the 1st main surface 201 on the resin layer 32 side, and a member for devices is provided in the 2nd main surface 202 on the opposite side to the resin layer 32. Are formed to constitute the device. Here, the member for a device means a member which constitutes at least one part of a device like the structural member of the panel for display apparatuses mentioned later. As a specific example, a thin film transistor TFT and a color filter CF are mentioned. Examples of the device include a solar cell (PV), a liquid crystal display (LCD), an organic EL display (OLED), and the like.

The kind of the board | substrate 20 may be common, for example, metal substrates, such as a silicon wafer, a glass substrate, a resin substrate, a SUS substrate, and a copper substrate, may be sufficient. Among these, a glass substrate is preferable. This is because the glass substrate is excellent in chemical resistance, moisture permeability, and low in heat shrinkage. As an index of thermal contraction rate, the linear expansion coefficient prescribed | regulated to JISR3102 (Rev. 1995) is used.

When the coefficient of linear expansion of the board | substrate 20 is large, since the manufacturing process of a device often involves heat processing, various problems tend to arise. For example, in the case of forming the TFT on the substrate 20, if the substrate 20 on which the TFT is formed is cooled under heating, there is a fear that the positional shift of the TFT may be excessive due to thermal contraction of the substrate 20.

The glass substrate is obtained by melting a glass raw material and molding the molten glass into a plate. Such a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a furcol method, a rubber method and the like are used. Moreover, especially a thin glass substrate is obtained by heating the glass once shape | molded to plate shape to the moldable temperature, shaping | molding by the method of extending | stretching and thinning by means, such as extending | stretching (lead furnace method).

Although the glass of a glass substrate is not specifically limited, Oxide type glass which has alkali-free glass, borosilicate glass, soda-lime glass, high silica glass, and other silicon oxide as a main component is preferable. As oxide type glass, glass with a content of 40-90 mass% of the silicon oxide by oxide conversion is preferable.

As glass of a glass substrate, the glass suitable for the kind of device and its manufacturing process is employ | adopted. For example, since the elution of an alkali metal component tends to affect a liquid crystal, the glass substrate for liquid crystal displays consists of glass (alkali free glass) which does not contain an alkali metal component substantially. Thus, the glass of the glass substrate is appropriately selected based on the kind of the applied device and the manufacturing process thereof.

Although the thickness of a glass substrate is not specifically limited, From a viewpoint of thickness reduction and / or light weight of a glass substrate, it is usually less than 0.8 mm, Preferably it is 0.3 mm or less, More preferably, it is 0.15 mm or less. In the case of 0.8 mm or more, it is not possible to satisfy the requirement of thinning and / or lightening the glass substrate. In the case of 0.3 mm or less, it is possible to give favorable flexibility to a glass substrate. When it is 0.15 mm or less, it is possible to wind up a glass substrate in roll shape. Moreover, it is preferable that the thickness of a glass substrate is 0.03 mm or more for the reason of easy manufacture of a glass substrate, easy handling of a glass substrate, etc.

The kind of resin of a resin substrate is not specifically limited. Specifically, polyethylene terephthalate resin, polycarbonate resin, polyimide resin, fluorine resin, polyamide resin, polyaramid resin, polyether sulfone resin, polyether ketone resin, polyether ether ketone resin, polyethylene naphthalate resin, poly Acrylic resins, various liquid crystal polymer resins, cycloolefin resins, silicone resins and the like are exemplified. In addition, the resin substrate may be transparent or opaque. In addition, the resin substrate may be formed by forming functional layers such as a protective layer on the surface.

Although the thickness of a resin substrate is not specifically limited, From a viewpoint of thickness reduction and / or weight reduction, it is preferable that it is 0.7 mm or less, It is more preferable that it is 0.3 mm or less, It is especially preferable that it is 0.1 mm or less. Moreover, it is preferable that it is 1.0 micrometer or more from a viewpoint of handleability.

In addition, the board | substrate 20 may be two or more layers, In this case, the material which forms each layer may be a homogeneous material, or a heterogeneous material may be sufficient as it. In this case, "thickness of the board | substrate 20" shall mean the thickness of the sum total of all the layers.

(Conductive metal oxide film)

The conductive metal oxide film 22 includes an oxide of at least one metal selected from the group consisting of indium, tin, zinc, titanium, and gallium.

For example, when the board | substrate 20 is an alkali free glass substrate, compared with the alkaline earth metal components, such as magnesium, calcium, and barium which exist on the surface of the alkali free glass substrate, it is contained in the conductive metal oxide film 22 The alkaline earth metal component has a low electronegativity. Therefore, compared with the case where the alkali-free glass substrate and the resin layer 32 are directly contacted and exposed to high temperature conditions, even if the laminated body 10 of this invention is exposed to high temperature conditions, the conductive metal oxide film 22 and The progress of the chemical reaction by detachment of the alkaline earth metal component between the resin layers 32 is very small. As a result, the board | substrate 24 with a conductive metal oxide film can be peeled, without sticking to the board | substrate 24 with a conductive metal oxide film of the resin layer 32 by heavy peeling.

Here, the heavy release means that the adhesion strength between the conductive metal oxide film 22 and the resin layer 32 is the adhesion strength between the surface of the support plate 31 and the resin layer 32 and the (bulk) strength of the resin layer 32. It means larger than either.

In addition, the conductive metal oxide film 22 exhibits excellent conductivity. Therefore, peeling charge on the surface of the board | substrate 24 with a conductive metal oxide film peeled can be suppressed. Moreover, peeling charging can be further suppressed when using ionizer or sprayed water together. Or even if the load of ionizer or sprayed water is reduced, the effect of suppression of peeling charge similar to the conventional one can be obtained.

The conductive metal oxide film 22 contains an oxide of at least one metal selected from the group consisting of indium, tin, zinc, titanium, and gallium. In other words, the conductive metal oxide film 22 contains a metal oxide composed of the metal element and the oxygen element.

Specific examples thereof include titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), gallium oxide (Ga ₂ O ₃ ), and the like.

In addition, the conductive metal oxide film 22 may contain an oxide containing two or more kinds of the metals listed above. Specifically, indium tin oxide (ITO), indium zinc oxide (IZO), zinc tin oxide (ZTO), gallium-added zinc oxide (GZO), etc. are mentioned.

The oxide may further contain at least one element selected from the group consisting of aluminum, molybdenum, copper, vanadium, niobium, tantalum, boron, and fluorine. The element serves as a so-called dopant.

Examples of the oxide of the metal containing the element include aluminum-added zinc oxide (AZO), molybdenum-added indium oxide (IMO), niobium-added titanium oxide, tantalum-added titanium oxide, niobium-added tin oxide, and fluorine-containing tin oxide ( FTO), boron-added zinc oxide (BZO), aluminum-copper-added zinc oxide, aluminum vanadium-added zinc oxide, niobium-tantalum-added tin oxide, and the like.

Among them, indium tin oxide (ITO), indium zinc oxide (IZO), aluminum-added zinc oxide (AZO), in terms of better peelability between the substrate with a conductive metal oxide film and the resin layer, and also excellent conductivity. Gallium-added zinc oxide (GZO), fluorine-containing tin oxide (FTO) and niobium-added titanium oxide are preferable, and indium tin oxide (ITO), indium zinc oxide (IZO), and fluorine-containing tin oxide (FTO) are more preferable.

It is preferable that the oxide of the said metal is contained as a main component, and, as for the conductive metal oxide film 22, it is preferable that content of the oxide of the said metal is 98 mass% or more especially with respect to the conductive metal oxide film whole quantity, It is more preferable that it is 99 mass% or more, and it is especially preferable that it is 99.999 mass% or more.

The conductive metal oxide film 22 may contain an oxide of another metal within a range that does not impair the effects of the present invention. In addition, the conductive metal oxide film 22 may contain components (for example, metal) other than the oxide of a metal in the range which does not impair the effect of this invention.

The thickness of the conductive metal oxide film 22 is not particularly limited, but in view of more suppressing adhesion of the resin layer 32 to the substrate 24 provided with the conductive metal oxide film by heavy delamination and maintaining scratch resistance, 5-5000 nm is preferable and 10-500 nm is more preferable.

The conductive metal oxide film 22 containing the oxide of the predetermined metal exhibits excellent conductivity. More specifically, since the peeling charging on the surface of the substrate to be peeled off can be further suppressed, the sheet resistance value of the conductive metal oxide film 22 is preferably 0.1 to 1000 Ω / □, and preferably 1 to 500 Ω / □. More preferred. In addition, as a measuring method, a well-known method (for example, the four probe resistance measuring method prescribed | regulated to JISR1637 (established in 1998)) is employ | adopted.

The proper density of the polar group present on the surface 221 in contact with the resin layer 32 of the conductive metal oxide film 22 is determined by measuring the water contact angle of the surface 221 before close contact. In general, the higher the density of polar groups such as hydrophilicity present on the surface, the smaller the water contact angle tends to be. Here, a water contact angle is a contact angle prescribed | regulated to JISR3257 (established in 1999).

The water contact angle before the surface 221 of the conductive metal oxide film 22 is in close contact with each other is 20 ° because the adhesion of the resin layer 32 to the substrate 24 with the conductive metal oxide film due to heavy peeling is further suppressed. It is preferable that it is the above, It is more preferable that it is 30-90 degrees, It is more preferable that it is 40-70 degrees.

In the surface 221 of the side which contacts the resin layer 32 of the conductive metal oxide film 22, the fine uneven structure may be previously formed. In this case, the degree of the uneven structure is that the surface 221 of the conductive metal oxide film 22 and the contact surface 321 of the resin layer 32 are subjected to heavy peeling due to the anchor effect, so that the conductivity of the resin layer 32 is reduced. It is preferable that it is the range which does not produce excessive adhesion to the board | substrate 24 with a metal oxide film.

Moreover, it is preferable that it is 0.1-50 nm, and, as for the surface roughness Ra of the surface 221 of the conductive metal oxide film 22, it is more preferable that it is 0.5-5 nm. Ra is measured according to JIS B 0601 (revised 2001).

The conductive metal oxide film 22 is preferably transparent in consideration of the use of the substrate 24 having the conductive metal oxide film as a device. Specifically, the transmittance at a wavelength of 380 to 780 nm, that is, the visible light transmittance of the substrate 24 provided with the conductive metal oxide film is preferably 70% or more, and more preferably 80% or more.

Although the conductive metal oxide film 22 is described as a single layer in FIG. 1, two or more layers may be laminated. For example, when the conductive metal oxide film has two layers, the first conductive metal oxide film in contact with the substrate 20 and the second conductive metal oxide layer provided on the first conductive metal oxide film are provided. In the case of two layers, the component of a 1st conductive metal oxide film and a 2nd conductive metal oxide film may differ.

The electroconductive metal oxide film 22 may be provided in part on the surface of the board | substrate 20 in the range which does not impair the effect of this invention. For example, the conductive metal oxide film 22 may be provided in an island shape or a stripe shape on the substrate 20 surface.

More specifically, the coverage on the substrate 20 surface of the conductive metal oxide film 22 further suppresses adhesion of the resin layer 32 to the substrate 24 having the conductive metal oxide film due to heavy peeling. In 50 to 100% is preferable, and 75 to 100% is more preferable.

(Method for producing conductive metal oxide film)

The manufacturing method of the conductive metal oxide film 22 is not specifically limited, A well-known method can be employ | adopted. For example, the method of providing a predetermined metal oxide on the board | substrate 20 by the vapor deposition method or the sputtering method is mentioned.

According to the oxide of the metal used for manufacturing conditions, optimal conditions are selected suitably.

Although the board | substrate 24 provided with the conductive metal oxide film is equipped with the board | substrate 20 mentioned above and the conductive metal oxide film 22, in the range which does not impair the effect of this invention, the board | substrate 20 and the conductive metal oxide film You may have another member between (22).

As another member, the alkali barrier layer which prevents the diffusion of alkali ions from the board | substrate 20 to the conductive metal oxide film 22, the planarization layer which flattens the surface of the conductive metal oxide film 22, etc. are mentioned, for example. .

<Support plate>

The support plate 31 cooperates with the resin layer 32 to support and reinforce the substrate 24 with the conductive metal oxide film, and in the manufacturing process of the device, the deformation of the substrate 24 with the conductive metal oxide film, Prevent scratches, breakage, etc. Moreover, when using the board | substrate 24 provided with the conductive metal oxide film which is thinner than the conventional, it is suitable for the board | substrate of the conventional thickness in the manufacturing process of a device by setting it as the laminated body 10 of the same thickness as the conventional board | substrate. It is also one of the objectives of using the support plate 31 to enable a manufacturing technique or a manufacturing facility.

As the support plate 31, metal plates, such as a glass plate, a resin plate, and a SUS board, etc. are used, for example. When the device manufacturing process involves heat treatment, the support plate 31 is preferably formed of a material having a small difference in coefficient of linear expansion with the substrate 20, and more preferably formed of the same material as the substrate 20. When the board | substrate 20 is a glass substrate, it is preferable that the support plate 31 is a glass plate. In particular, the support plate 31 is preferably a glass plate made of the same glass material as that of the glass substrate of the substrate 20.

The thickness of the support plate 31 may be thicker than the board | substrate 20, and may be thin. Preferably, the thickness of the support plate 31 is selected based on the thickness of the substrate 24 with the conductive metal oxide film, the thickness of the resin layer 32 and the thickness of the laminate 10. For example, when the manufacturing process of the current device is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the substrate 24 having the conductive metal oxide film and the thickness of the resin layer 32 is 0.1 mm, The thickness of the support plate 31 shall be 0.4 mm. It is preferable that the thickness of the support plate 31 is 0.2-5.0 mm normally.

When the support plate 31 is a glass plate, it is preferable that the thickness of a glass plate is 0.08 mm or more for the reason of being easy to handle and hard to break. In addition, it is preferable that the thickness of a glass plate is 1.0 mm or less, for the reason that rigidity like bending suitably without breaking is desired, when peeling after formation of a member for devices.

The difference between the average linear expansion coefficient (hereinafter, simply referred to as "average linear expansion coefficient") at 25 to 300 ° C of the substrate 20 and the support plate 31 is preferably 500 × 10 ^-7 / ° C or less, and more preferably. Preferably it is 300x10 <^-7> / degrees C or less, More preferably, it is 200x10 <^-7> / degrees C or less. If the difference is too large, the laminate 10 may be severely bent at the time of heating and cooling in the manufacturing process of the device, or the substrate 24 and the reinforcing plate 30 provided with the conductive metal oxide film may peel off. When the material of the board | substrate 20 and the material of the support plate 31 are the same, it can suppress that this problem arises.

<Resin Layer>

The resin layer 32 is fixed on the support plate 31 and is in close contact with the substrate 24 provided with the conductive metal oxide film so as to be peelable. The resin layer 32 prevents misalignment of the substrate 24 with the conductive metal oxide film until the peeling operation is performed, and easily peels from the substrate 24 with the conductive metal oxide film by the peeling operation. The substrate 24 provided with the conductive metal oxide film or the like is prevented from being damaged by the peeling operation.

The size of the resin layer 32 is not specifically limited. The size of the resin layer 32 may be larger than the board | substrate 20 or the support plate 31, and may be small.

The surface 321 (hereinafter also referred to as "adhesive surface 321") in contact with the conductive metal oxide film 22 of the resin layer 32 is not an adhesive force that a general pressure-sensitive adhesive has but a half in solid molecules. It is preferable that it adheres to the surface 221 of the conductive metal oxide film 22 by the force resulting from a dervals force. This is because the substrate 24 provided with the conductive metal oxide film can be easily peeled off. In this invention, the property which can peel easily on this resin layer surface is called peelability.

On the other hand, the bonding force with respect to the surface of the support plate 31 of the resin layer 32 is the surface of the board | substrate 24 provided with the conductive metal oxide film of the resin layer 32 (surface 221 of the conductive metal oxide film 22). Is relatively higher than the binding force for. For this reason, the peeling strength between the resin layer 32 and the support plate 31 is higher than the peeling strength between the resin layer 32 and the board | substrate 24 provided with the conductive metal oxide film. In the present invention, the bonding of the resin layer surface to the substrate surface is called adhesion, and the bonding of the resin layer surface and the support plate surface is called fixing. It is preferable to couple between the resin layer 32 and the support plate 31 by adhesive force or adhesive force. However, the present invention is not limited thereto, and as long as the resin layer 32 is relatively higher than the bonding force with respect to the substrate 24 having the conductive metal oxide film, the van der Waals force is between the resin layer 32 and the support plate 31. It may be attached by the force originating in.

Although the thickness of the resin layer 32 is not specifically limited, It is preferable that it is 1-100 micrometers, It is more preferable that it is 5-30 micrometers, It is more preferable that it is 7-20 micrometers. This is because the adhesion between the resin layer 32 and the substrate 24 provided with the conductive metal oxide film becomes sufficient if the thickness of the resin layer 32 is in such a range. This is because generation of distortion defects in the substrate 24 including the conductive metal oxide film can be suppressed even when bubbles or foreign substances are interposed between the resin layer 32 and the substrate 24 including the conductive metal oxide film. In addition, if the thickness of the resin layer 32 is too thick, it is not economical because it requires time and materials to form.

In addition, the resin layer 32 may consist of two or more layers. In this case, "thickness of the resin layer 32" shall mean the thickness of the sum total of all the layers.

In addition, when the resin layer 32 consists of two or more layers, the kind of resin which forms each layer may differ.

It is preferable that the resin layer 32 consists of a material whose glass transition point is lower than room temperature (about 25 degreeC), or does not have a glass transition point. It is because it becomes a non-adhesive resin layer, and it can peel easily with the board | substrate 24 with a conductive metal oxide film, and also the adhesiveness with the board | substrate 24 with a conductive metal oxide film becomes sufficient enough.

In addition, since the resin layer 32 is often heat-processed in the manufacturing process of a device, it is preferable to have heat resistance.

Moreover, when the elasticity modulus of the resin layer 32 is too high, there exists a tendency for the adhesiveness of the board | substrate 24 provided with the conductive metal oxide film to fall. On the other hand, when the elasticity modulus of the resin layer 32 is too low, peelability will become low.

The kind of resin which forms the resin layer 32 is not specifically limited. For example, acrylic resin, polyolefin resin, polyurethane resin or silicone resin can be mentioned. Some types of resins may be mixed and used. Especially, silicone resin is preferable. It is because silicone resin is excellent in heat resistance and peelability. Moreover, when the support plate 31 is a glass plate, it is easy to fix to a glass plate by condensation reaction with the silanol group of the glass plate surface. In the state where the silicone resin layer is interposed between the support plate 31 and the substrate 24 provided with the conductive metal oxide film, even when the silicone resin layer is treated at about 200 ° C. for about 1 hour in the air, the peelability hardly deteriorates. Viscosity is preferred.

It is preferable that the resin layer 32 consists of silicone resin (hardened | cured material) used for release papers among silicone resin. Since the resin layer 32 which hardened | cured the curable resin composition which consists of silicone resin for release papers on the surface of the support plate 31, and formed was excellent, it is preferable. In addition, since the flexibility is high, even if foreign matter such as bubbles or cracks is mixed between the resin layer 32 and the substrate 24 having the conductive metal oxide film, generation of distortion defects in the substrate 24 having the conductive metal oxide film is prevented. It can be suppressed.

Although curable silicone which becomes such a release paper silicone resin is classified into condensation reaction type | mold silicone, addition reaction type | mold silicone, ultraviolet curable silicone, and electron beam curable silicone by the hardening mechanism, all can be used. Of these, addition reaction type silicon is preferable. This is because it is easy to become hardening reaction, when the resin layer 32 is formed, the peelability is favorable and heat resistance is also high.

Addition type | mold silicone is a curable composition containing a main body and a crosslinking agent, and hardening in presence of catalysts, such as a platinum type catalyst. Hardening of addition reaction type silicone is accelerated by heat processing. The main subject of the addition-reactive silicone is an organopolysiloxane having an alkenyl group (vinyl group or the like) bonded to a silicon atom (that is, organoalkenylpolysiloxane, preferably linear), and an alkenyl group or the like It becomes a crosslinking point. The crosslinking agent of the addition-reaction type silicone is preferably an organopolysiloxane having a hydrogen atom (hydrosilyl group) bonded to a silicon atom (i.e., an organohydrogenpolysiloxane, preferably linear), and a hydrosilyl group or the like. It becomes this crosslinking point.

The addition reaction type silicone is cured by addition reaction of the crosslinking point of the main material and the crosslinking agent.

Moreover, curable silicone which becomes a silicone resin for release papers has the form of a solvent type, an emulsion type, and a non-solvent type, and can use any form. Of these, no-solvent formulations are preferred. This is because it is excellent in terms of productivity, safety and environmental characteristics. In addition, since it does not contain the solvent which generate | occur | produces at the time of hardening at the time of forming the resin layer 32, ie, the heat hardening, ultraviolet hardening, or electron beam hardening, it is hard to remain a bubble in the resin layer 32. to be.

Moreover, as curable silicone which becomes a silicone resin for release papers, KNS-320A, KS-847 (all are Shin-Etsu Silicone Co., Ltd.), TPR6700 (all made by Momentive Performance Materials Japan) ), A combination of vinyl silicone `` 8500 '' (manufactured by Arakawa Chemical Co., Ltd.) and methylhydrogenpolysiloxane `` 12031 '' (manufactured by Arakawa Chemical Industries, Ltd.), vinyl silicone `` 11364 '' (manufactured by Arakawa Chemical Industries, Ltd.) And combination of methyl hydrogen polysiloxane "12031" (made by Arakawa Chemical Co., Ltd.), vinyl silicone "11365" (made by Arakawa Chemical Co., Ltd.) and methyl hydrogen polysiloxane "12031" (Arakawa Chemical Co., Ltd. make) ), And the like.

In addition, KNS-320A, KS-847, and TPR6700 are curable silicones containing a main material and a crosslinking agent previously.

Moreover, it is preferable that the silicone resin which forms the resin layer 32 has the property which a component, such as low molecular weight silicon, in a silicone resin layer is hard to transfer to the board | substrate 24 provided with the conductive metal oxide film, ie, low silicon transition property. Do. Moreover, it is preferable that the molar ratio of the hydrogen atom couple | bonded with the silicon atom of organohydrogenpolysiloxane with respect to the alkenyl group of organo alkenyl polysiloxane from the viewpoint of the heat resistance derived from a crosslinked structure is 0.5-2.

(Method for producing resin layer)

Although the method of fixing the resin layer 32 on the support plate 31 is not specifically limited, For example, the method of fixing the film-shaped resin to the surface of the support plate 31 is mentioned. Specifically, in order to give a high fixing force (high peel strength) to the surface of the film on the surface of the support plate 31, a surface modification treatment (priming treatment) is performed on the surface of the support plate 31 to support the support plate 31. The method of fixing on top is mentioned. For example, chemical methods such as silane coupling agents (primer treatment), physical methods of increasing surface active groups such as SiOH groups and SiO groups, such as plasma irradiation or flame (flame) treatment, sandblast treatment and As such, a mechanical treatment method for increasing engagement by increasing the roughness of the surface is exemplified.

For example, the support plate (by a method of forming the layer of curable resin composition which becomes the resin layer 32 on the support plate 31 surface, and then hardening the said curable resin composition and forming the resin layer 32) The resin layer 32 fixed on 31 may be formed. As a method of forming a layer of curable resin composition on the support plate 31 surface, the method of coat | covering curable resin composition on the support plate 31 is mentioned, for example. As a coating method, a spray coating method, the die coating method, the spin coating method, the dip coating method, the roll coating method, the bar coating method, the screen printing method, the gravure coating method, etc. are mentioned. Among these methods, it can select suitably according to the kind of resin composition.

Moreover, when coating curable resin composition used as the resin layer 32 on the support plate 31, it is preferable that it is 1-100 g / m <2>, and it is more preferable that it is 5-20 g / m <2>.

For example, when forming the resin layer 32 from the curable resin composition of addition reaction type silicone, the curable resin composition which consists of a mixture of organo alkenyl polysiloxane, organohydrogen polysiloxane, and a catalyst is mentioned with the said spray coating method, etc. It is apply | coated on the support plate 31 by the well-known method of, and it heat-hardens after that. Although the heat-hardening condition changes also with the compounding quantity of a catalyst, For example, when 2 mass parts of platinum-type catalysts are mix | blended with respect to 100 mass parts of total amounts of organo alkenyl polysiloxane and organohydrogen polysiloxane, it is 50 degreeC in air | atmosphere. To 250 ° C, preferably 100 ° C to 200 ° C. In addition, the reaction time in this case is 5 to 60 minutes, Preferably it is 10 to 30 minutes.

By heat-hardening curable resin composition, a silicone resin couple | bonds with the support plate 31 chemically at the time of hardening reaction. In addition, the silicone resin layer is bonded to the support plate 31 by the anchor effect. By these actions, the silicone resin layer is firmly fixed to the support plate 31. Moreover, also when forming the resin layer which consists of resins other than a silicone resin from curable resin composition, the resin layer fixed to the support plate can be formed by the method similar to the above.

<Laminated body and its manufacturing method>

As mentioned above, the laminated body 10 of this invention is a board | substrate 24 with a conductive metal oxide film, the support plate 31, and the laminated body in which the resin layer 32 exists between them.

Although the manufacturing method of the laminated body of this invention is not specifically limited, Usually, the support plate 31 in which the resin layer 32 was fixed on the surface was produced by the method mentioned above, and after that, a conductive metal oxide is carried out on the resin layer 32. The board | substrate 24 with a film | membrane is arrange | positioned so that the conductive metal oxide film 22 may contact with the resin layer 32 so that peeling is possible.

The method of bringing the resin layer 32 into close contact with the substrate 24 provided with the conductive metal oxide film so that the resin layer 32 can be peeled off is not particularly limited, and a known method may be used. For example, after laminating | stacking the board | substrate 24 with an electroconductive metal oxide film on the peelable surface of the resin layer 32 in an atmospheric pressure environment, the board | substrate with the resin layer 32 and the electroconductive metal oxide film using a roll or a press. The method of crimping | bonding (24) is mentioned. Since the resin layer 32 and the board | substrate 24 with an electroconductive metal oxide film adhere more closely by crimping | bonding by a roll or a press, it is preferable. Moreover, since the bubble mixed in between the resin layer 32 and the board | substrate 24 provided with the conductive metal oxide film is removed comparatively easily by the crimping | rolling by a roll or a press, it is preferable.

When it crimps | bonds by the vacuum lamination method or the vacuum press method, it is more preferable because suppression of mixing of foam | bubble, and ensuring good adhesion are performed more preferable. By pressing under vacuum, even when a minute bubble remains, there is an advantage that the bubble does not grow by heating and is difficult to be connected to the distortion defect of the substrate 24 provided with the conductive metal oxide film.

When the resin layer 32 is brought into close contact with the substrate 24 provided with the conductive metal oxide film, the surfaces of the resin layer 32 and the substrate 24 provided with the conductive metal oxide film in contact with each other are sufficiently washed. It is preferable to laminate in a high clean environment. Even if foreign matter is mixed between the resin layer 32 and the substrate 24 having the conductive metal oxide film, the resin layer 32 is deformed, which affects the flatness of the surface of the substrate 24 with the conductive metal oxide film. However, the higher the cleanliness, the better the flatness becomes, which is preferable.

In addition, there is no restriction | limiting in the order of the process of fixing the resin layer 32 on the support plate 31, and the process of making the resin layer 32 contact | adhesive so that it can peel on the board | substrate 24 provided with a conductive metal oxide film, for example, For example, it may be approximately simultaneous.

The laminated body of this invention can be used for various uses, For example, the manufacture of electronic components, such as a display device panel mentioned later, a PV, a thin film secondary battery, and a semiconductor wafer with a circuit formed in the surface, etc. are mentioned. have. In addition, in the said use, a laminated body is exposed to high temperature conditions (for example, 320 degreeC or more) (for example, 1 hour or more) in many cases.

Here, the panel for a display device includes an LCD, an OLED, an electronic paper, a plasma display panel, a field emission panel, a quantum dot LED panel, a MEMS (Micro Electro Mechanical Systems) panel, and the like.

<Panel for Display Device with Support Plate and Manufacturing Method Thereof>

In this invention, the panel for display apparatus provided with a support plate is manufactured using the laminated body mentioned above.

2 is a schematic cross-sectional view of an example of a panel for a display device provided with a supporting plate according to the present invention.

The display device panel 40 with a supporting plate is composed of the laminate 10 and the constituent members 50 of the display device panel.

(Constituent member of panel for display device)

The structural member 50 of the panel for display devices means the member formed on the glass substrate, or its part in display apparatuses, such as LCD and OLED using a glass substrate, for example. For example, in a display device such as an LCD or an OLED, various circuits such as a TFT array (hereinafter simply referred to as an "array"), a protective layer, a color filter, a liquid crystal, and a transparent electrode including ITO are formed on the surface of a substrate. A member such as a pattern or a combination of these is formed. Moreover, in the display apparatus which consists of OLED, for example, the transparent electrode formed on the board | substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron carrying layer, etc. are mentioned.

The manufacturing method of the display device panel 40 provided with the above-mentioned support plate is not specifically limited, According to the kind of structural member of a display device panel, it is a conventionally well-known method provided with the conductive metal oxide film of the laminated body 10. The structural member 50 of the panel for display apparatuses is formed on the board | substrate 24 surface.

For example, in the case of manufacturing OLED, for example, on the surface on the side opposite to the surface in close contact with the resin layer 32 of the substrate 24 provided with the conductive metal oxide film of the laminate 10 (the second of the substrate) In order to form an organic EL structure on the main surface 202), forming a transparent electrode, or depositing a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. on the surface on which the transparent electrode is formed, the back surface Various layer formation and processes, such as forming an electrode and sealing using a sealing plate, are performed. As these layer formation and processing, a film-forming process, a vapor deposition process, the adhesion process of a sealing plate, etc. are mentioned specifically ,. The formation of these structural members may be part of the formation of all the structural members required for the display device panel. In that case, after peeling the board | substrate 24 provided with the conductive metal oxide film which formed the one structural component with the resin layer 32, the remaining structural member is formed on the board | substrate 24 provided with the conductive metal oxide film, A panel for display device is manufactured.

<Panel for Display Device and Manufacturing Method Thereof>

As shown in FIG. 2, the display device panel 60 according to the present invention is composed of a substrate 24 having a conductive metal oxide film and a constituent member 50 of the panel for display devices.

The display device panel 60 can be obtained by peeling the substrate 24 provided with the conductive metal oxide film and the resin layer 32 fixed to the support plate 31 from the display device panel 40 provided with the support plate. have.

In addition, when the structural member on the board | substrate 24 provided with the conductive metal oxide film at the time of peeling is a part of formation of all the structural members required for the panel for display apparatuses, the remaining structural member is the board | substrate with a conductive metal oxide film after that. It forms on the 24 and manufactures a panel for display devices.

The method of peeling the peelable surface of the electroconductive metal oxide film 22 and the resin layer 32 is not specifically limited. Specifically, for example, a sharp blade-shaped object is inserted into the interface between the conductive metal oxide film 22 and the resin layer 32 to give an opportunity for peeling, and then sprayed by spraying a mixed fluid of water and compressed air, or peeling off. can do.

In addition, after peeling the display device panel 60 from the display device panel 40 provided with a support plate, the electroconductivity of the board | substrate 24 provided with the conductive metal oxide film among the display device panel 60 as needed. A structural member of a panel for a display device may be separately provided on the metal oxide film 22.

<Display device>

In addition, a display device can be obtained from such a panel 60 for display devices. As a display apparatus, LCD and OLED are mentioned. Examples of the LCD include TN type, STN type, FE type, TFT type, and MIM type.

The operation for obtaining the display device is not particularly limited, and for example, the display device can be manufactured by a conventionally known method.

Example

Hereinafter, the present invention will be described in detail by way of examples and the like, but the present invention is not limited to these examples.

In addition, in the Example and comparative example mentioned later, the water contact angle was measured using the contact angle meter (the cross company make, DROP SHAPE ANALYSIS SYSTEM DSA 10Mk2). In addition, surface roughness Ra was measured using the atomic force microscope (The Seiko Instruments company make, SPA300 / SPI3800).

The peelability after the heating of a thin glass laminated body evaluated by peeling a thin glass substrate and a resin layer after heat processing on the predetermined conditions mentioned later, and visually observing the surface image which contacted the resin layer of a thin glass substrate. It is good that there is no residue of a resin layer, and it is bad evaluation that there is a residue of a resin layer.

Moreover, plasma irradiation was performed on the surface which contacted the resin layer of the peeled thin glass substrate using the atmospheric pressure remote plasma apparatus (made by Sekisui Chemical Co., Ltd.), and also the polarizing film (Nitto Denko Corporation make, acrylic adhesive) ) Was attached and the presence or absence of peeling was evaluated. The absence of peeling indicates that there is no residue of the resin layer. Peeling generate | occur | produces that there exists a residue of a resin layer.

&Lt; Example 1 >

First, after purely washing the support glass substrate (alkali-free glass, Asahi Glass Co., Ltd. AN100) of 720 mm long, 600 mm wide, 0.4 mm thick, and a coefficient of linear expansion 38x10 <^-7> / degreeC, UV cleaning to purge.

Next, on a 1st main surface of a support glass substrate, 100 mass parts of silicone for solventless addition reaction type release paper (Shin-Etsu Silicone Co., KNS-320A, viscosity: 0.40 Pa.s, dissolution parameter (SP value): 7.3) And a mixture of 2 parts by mass of a platinum-based catalyst (manufactured by Shin-Etsu Silicone Co., Ltd., CAT-PL-56) were applied in a rectangular screen-printer with a size of 705 mm long and 595 mm wide (coating amount 30 g / m 2). .

Subsequently, this was heat-hardened in air | atmosphere for 30 minutes at 180 degreeC, and the silicone resin layer of 20 micrometers in thickness was formed in the 1st main surface of a support glass substrate.

In addition, the above-mentioned non-solvent addition-reaction type release paper silicone is a linear organoalkenylpolysiloxane having a vinyl group and a methyl group bonded to a silicon atom (topic) and a linear organohydrogenpolysiloxane having a methyl group having a hydrogen atom bonded to a silicon atom. It includes (cross-linking).

Subsequently, the surface of the side which makes contact with the silicone resin of the thin glass substrate (AN100 by Asahi Glass Co., Ltd.) of 720 mm in length, 600 mm in width, 0.3 mm in thickness, and a linear expansion coefficient of 38x10 <^-7> / degreeC is wash | cleaned purely. Then, it was UV-cleaned and cleaned. Further, on the surface to be cleaned, ITO having a thickness of 10 nm was formed by a magnetron sputtering method (heating temperature of 300 ° C., film forming pressure of 5 mTorr, power density of 0.5 W / cm 2) (sheet resistance of 300Ω / □), and a thin glass substrate ( Thin glass substrate provided with a conductive metal oxide film). The water contact angle on the surface of the conductive metal oxide film was 45 degrees. In addition, the surface roughness Ra of the conductive metal oxide film was 0.7 nm.

Then, the ITO film-forming surface of the thin glass substrate and the silicone resin layer surface of the supporting glass substrate were faced by vacuum press at room temperature to obtain a thin glass laminate A1.

In obtained thin glass laminated body A1, both glass substrates were closely_contact | adhered without generating a silicone resin layer and foam | bubble, there was no distortion-like defect, and smoothness was also favorable.

(Evaluation of Peelability after Heating)

About thin glass laminated body A1, heat processing was performed at 320 degreeC for 1 hour in nitrogen atmosphere whose atmospheric oxygen is 0.1% or less.

Subsequently, peeling test was done. Specifically, first, the second main surface of the thin glass in the thin glass laminate A1 was fixed on the fixing table. On the other hand, the 2nd main surface of the support glass substrate was adsorbed by the adsorption pad. Subsequently, as one of four corner parts which thin glass laminated body A1 has, the knife of thickness 0.4mm was inserted in the interface of a thin glass substrate and a resin layer, the thin glass substrate was peeled off slightly, and the opportunity of peeling was given. Next, the adsorption pad was moved in the direction away from the fixing table, and the thin glass substrate and the supporting glass substrate having the resin layer were peeled off.

There was no residue of the resin layer on the surface (on the conductive metal oxide film) that was in contact with the resin layer of the peeled thin glass substrate. In addition, the charging potential on the surface (on the conductive metal oxide film) in contact with the resin layer of the peeled thin glass substrate after peeling was +1.2 kPa by an electrostatic measuring device. Plasma irradiation was performed on the surface (on the conductive metal oxide film) which was in contact with the resin layer of the peeled thin glass substrate using an atmospheric pressure remote plasma apparatus (manufactured by Sekisui Chemical Co., Ltd.), and a polarizing film (Nitto Denko Corporation). When adhesion | attachment of manufacture, an acrylic adhesive agent) was carried out, peeling did not arise.

<Example 2>

In the same manner as in Example 1, the ITO film-forming surface of the thin glass substrate and the silicone resin layer surface of the supporting glass substrate were faced by vacuum press at room temperature to obtain a thin glass laminate A1. Next, the peeling test was done similarly to Example 1, without performing heat processing. There was no residue of the resin layer on the surface (on the conductive metal oxide film) in contact with the resin layer of the peeled thin glass substrate. In addition, the charging potential on the surface (on the conductive metal oxide film) in contact with the resin layer of the peeled thin glass substrate after peeling was +1.3 kV by an electrostatic measuring device. Plasma irradiation was performed on the surface (on the conductive metal oxide film) which was in contact with the resin layer of the peeled thin glass substrate using an atmospheric pressure remote plasma apparatus (manufactured by Sekisui Chemical Co., Ltd.), and a polarizing film (Nitto Denko Corporation). When adhesion | attachment of manufacture, an acrylic adhesive agent) was carried out, peeling did not arise.

<Example 3>

In the same manner as in Example 1, the ITO film-forming surface of the thin glass substrate and the silicone resin layer surface of the supporting glass substrate were faced by vacuum press at room temperature to obtain a thin glass laminate A1. Thereafter, heat treatment was performed on the thin glass laminate A1 in the same manner as in Example 1. Subsequently, peeling test was done. Specifically, first, the second main surface of the thin glass substrate in the thin glass laminate A1 was fixed on the fixing table. On the other hand, the 2nd main surface of the support glass substrate was adsorbed by the adsorption pad. Subsequently, as one of four corner parts which thin glass laminated body A1 has, the knife of thickness 0.4mm was inserted in the interface of a thin glass substrate and a resin layer, the thin glass substrate was peeled off slightly, and the opportunity of peeling was given. Here, the knife was inserted while spraying the antistatic fluid on the interface from the ionizer (manufactured by GEENCE).

Subsequently, the adsorption pad was moved in the direction away from the holder while continuously spraying the antistatic fluid from the ionizer toward the formed voids, and the thin glass substrate and the supporting glass substrate having the resin layer were peeled off.

There was no residue of the resin layer on the surface (on the conductive metal oxide film) that was in contact with the resin layer of the peeled thin glass substrate. In addition, the charging potential on the surface (on the conductive metal oxide film) in contact with the resin layer of the peeled thin glass substrate after peeling was +0.1 kV by an electrostatic measuring device. Plasma irradiation was performed on the surface (on the conductive metal oxide film) which was in contact with the resin layer of the peeled thin glass substrate using an atmospheric pressure remote plasma apparatus (manufactured by Sekisui Chemical Co., Ltd.), and a polarizing film (Nitto Denko Corporation). When adhesion | attachment of manufacture, an acrylic adhesive agent) was carried out, peeling did not arise.

<Example 4>

First, after pure-cleaning the thin glass substrate (alkali-free glass, Asahi Glass Co., Ltd. AN100) of 760 mm in length, 640 mm in width, 0.3 mm in thickness, and a linear expansion coefficient of 38x10 <^-7> / degreeC, furthermore UV cleaning to purge. Furthermore, 10 nm-thick ITO was formed by the magnetron sputtering method (heating temperature 300 degreeC, film-forming pressure 5mTorr, power density 0.5W / cm <2>) on the 1st main surface which was cleaned (sheet resistance 300 (ohm) / square), and thin glass A substrate (thin glass substrate provided with a conductive metal oxide film) was obtained. The water contact angle on the surface of the conductive metal oxide film was 45 degrees. In addition, the surface roughness Ra of the conductive metal oxide film was 0.7 nm. Subsequently, on the conductive metal oxide film surface of the 1st main surface of a thin glass substrate, the linear organo alkenyl polysiloxane (vinyl silicone, Arakawa Chemical Co., Ltd. make, 8500) which has vinyl groups in both terminals similarly to Example 1, A mixture of methylhydrogenpolysiloxane (manufactured by Arakawa Chemical Co., Ltd., 12031) having a hydrosilyl group in the molecule and a platinum-based catalyst (manufactured by Arakawa Chemical Co., Ltd., CAT12070) was 750 mm long and 630 mm wide. Was applied by a screen printing machine in a rectangular shape to form a layer containing uncured curable silicone (coating amount of 35 g / m 2).

Subsequently, the surface (first main surface) of the side which makes contact with the silicone resin of the support glass substrate of length 720mm, width 600mm, and plate thickness 0.4mm was wash | cleaned purely, and it cleaned by UV washing after that. Thereafter, the first main surface of the carrier substrate and the layer containing the uncured curable silicone are bonded by vacuum press at room temperature, and left to stand at 30 kPa for 5 minutes to deflate the layer containing the uncured curable silicone. The process was performed and the laminated body A0 before hardening was obtained. At that time, the carrier substrate was laminated on the layer containing the uncured curable silicone so that the peripheral region not in contact with the carrier substrate remained in the layer containing the uncured curable silicone. In addition, the length from the outer periphery of the carrier substrate to the outer periphery of the uncured curable resin composition layer was about 15 mm or more.

Subsequently, this was heat-hardened at 250 degreeC for 30 minutes in air | atmosphere, and the post-curing laminated body A0 containing the hardened silicone resin layer of thickness 10micrometer was obtained.

Subsequently, the 2nd main surface of a thin glass substrate is fixed to the support glass substrate of laminated body A0 after hardening on the surface plate which mounted the positioning jig, and overlaps one side of the outer periphery of the support glass substrate from the upper surface of the surface plate. After carving a cut line with the diamond wheel cutter on the top, the outside of the cut line of thin glass was pinched | interposed with the pinching jig, and it cut | disconnected. Similarly, after dividing and cutting also about the outer side of the thin glass substrate which overlaps with the remaining three sides of the outer periphery of the support glass substrate, the divided surface of the thin glass substrate is polished with a grindstone having a curved surface, and the chamfering is performed, and the laminated body after cutting A1 was obtained.

Next, the peeling test was done similarly to Example 3. There was no residue of the resin layer on the surface (on the conductive metal oxide film) that was peeled off to the thin glass substrate and the supporting glass substrate having the resin layer and was in contact with the resin layer of the peeled thin glass substrate. In addition, the charging potential on the surface (on the conductive metal oxide film) in contact with the resin layer of the peeled thin glass substrate after peeling was +0.1 kV by an electrostatic measuring device. Plasma irradiation was performed on the surface (on the conductive metal oxide film) which was in contact with the resin layer of the peeled thin glass substrate using an atmospheric pressure remote plasma apparatus (manufactured by Sekisui Chemical Co., Ltd.), and a polarizing film (Nitto Denko Corporation). When adhesion | attachment of manufacture, an acrylic adhesive agent) was carried out, peeling did not arise.

<Example 5>

As a thin glass substrate and a supporting glass substrate, thin glass laminated body B1 was obtained by the method similar to Example 3 except having used the glass plate which consists of soda-lime glass.

Next, the peeling test was done similarly to Example 3. There was no residue of the resin layer on the surface (on the conductive metal oxide film) that was peeled off to the thin glass substrate and the supporting glass substrate having the resin layer and was in contact with the resin layer of the peeled thin glass substrate. In addition, the charging potential on the surface (on the conductive metal oxide film) in contact with the resin layer of the peeled thin glass substrate after peeling was +0.1 kV by an electrostatic measuring device. Plasma irradiation was performed on the surface (on the conductive metal oxide film) in contact with the resin layer of the peeled thin glass substrate by using an atmospheric pressure remote plasma apparatus (manufactured by Sekisui Chemical Co., Ltd.), and a polarizing film (manufactured by Nitto Denko Corporation). And an acrylic pressure sensitive adhesive) were not peeled off.

<Example 6>

As a thin glass substrate and a support glass substrate, thin glass laminated body C1 was obtained by the method similar to Example 3 except having used the chemically strengthened glass plate.

Next, the peeling test was done similarly to Example 3. There was no residue of the resin layer on the surface (on the conductive metal oxide film) that was peeled off to the thin glass substrate and the supporting glass substrate having the resin layer and was in contact with the resin layer of the peeled thin glass substrate. In addition, the charging potential on the surface (on the conductive metal oxide film) in contact with the resin layer of the peeled thin glass substrate after peeling was +0.1 kV by an electrostatic measuring device. Plasma irradiation was performed on the surface (on the conductive metal oxide film) which was in contact with the resin layer of the peeled thin glass substrate using an atmospheric pressure remote plasma apparatus (manufactured by Sekisui Chemical Co., Ltd.), and a polarizing film (Nitto Denko Corporation). When adhesion | attachment of manufacture, an acrylic adhesive agent) was carried out, peeling did not arise.

In addition, about the thin glass laminated body A1 used by the said Examples 1-6, in the said peeling test, not between a silicone resin layer and a support glass substrate, but a silicone resin layer and a thin glass substrate (with a conductive metal oxide film) Peeling occurred between one thin glass substrate). In this respect, the adhesion between the silicone resin layer and the supporting glass substrate is greater than the adhesion between the silicone resin layer and the thin glass substrate, in other words, the peel strength between the silicone resin layer and the supporting glass substrate is greater than that of the silicone resin layer and the thin glass. It was confirmed that it was higher than the peeling strength between board | substrates.

&Lt; Comparative Example 1 &

A thin glass substrate having a length of 720 mm, a width of 600 mm, a sheet thickness of 0.3 mm, and a coefficient of linear expansion of 38 × 10 ⁻⁷ / ° C. instead of the thin glass substrate provided with the conductive metal oxide film used in Example 1 (manufactured by Asahi Glass Co., Ltd.). Except having used AN100), thin glass laminated body C1 was obtained by the same procedure as Example 1. The thin glass laminate C1 does not contain a conductive metal oxide film.

In addition, the surface of the side which contacts a silicone resin of a thin glass substrate was wash | cleaned purely, and UV-cleaned and cleaned after that. The water contact angle of the cleaned thin glass substrate surface was 8 degrees. In addition, the surface roughness Ra of the cleaned thin glass substrate was 0.4 nm.

Next, after heat-processing according to the procedure similar to Example 1, the thin glass substrate and the supporting glass substrate which have a resin layer in the thin glass laminated body C1 were peeled off.

On the surface which was in contact with the resin layer of the peeled thin glass substrate, a part of resin layer adhered and the damage was confirmed by the correspondence part of the resin layer on a support glass substrate. Although the plasma was irradiated with the thin glass substrate with a resin layer using the atmospheric pressure remote plasma apparatus (made by Sekisui Chemical Co., Ltd.), the adhered resin could not be removed and remained. The charging potential on the surface in contact with the resin layer of the peeled thin glass substrate after peeling was -10.5 kPa. Then, peeling generate | occur | produced when the polarizing film (Nitto Denko Corporation make, acrylic adhesive system) was affixed on the surface which carried out the plasma irradiation of the thin glass substrate.

Comparative Example 2

The surface of the side which made contact with the silicone resin of the thin glass substrate (AN100 by Asahi Glass Co., Ltd.) of 720 mm long, 600 mm wide, 0.3 mm thick, and a linear expansion coefficient of 38x10 <^-7> / degreeC was purely washed, It was then cleaned by UV cleaning. Further, on the cleaned side, a chromium oxide film having a thickness of 50 nm and a metal chromium film having a thickness of 100 nm were sequentially formed by a magnetron sputtering method (non-heating, film formation pressure 5 mTorr, power density 5 W / cm 2) to form a thin glass substrate ( Thin glass substrate provided with a metal chromium film). The water contact angle of the surface of the metal chromium film was 25 degrees. In addition, the surface roughness Ra of the metal chromium film was 2.5 nm.

In the same manner as in Example 1, the thin metal glass laminate B1 was obtained by abutting the metal chromium film surface of the thin glass substrate and the silicon resin layer surface of the supporting glass substrate by vacuum pressing at room temperature.

Next, after heat-processing according to the procedure similar to Example 1, the thin glass substrate and the support glass substrate which have a resin layer in thin glass laminated body B1 were peeled off.

In the same manner as in Comparative Example 1, a part of the resin layer adheres to the surface (metal chromium film phase) in contact with the resin layer of the peeled thin glass substrate, and damage to the corresponding portion of the resin layer on the support glass substrate is achieved. Confirmed.

&Lt; Comparative Example 3 &

In the same manner as in Example 1, a silicon resin layer having a thickness of 20 μm was formed on the first main surface of the support glass substrate. Subsequently, the same procedure as in Example 1 was carried out except that a thin glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) having a length of 720 mm, a width of 600 mm, a sheet thickness of 0.3 mm, and a linear expansion coefficient of 38 × 10 ⁻⁷ / ° C. was used. Thus, thin glass laminate C2 was obtained. In addition, the surface of the side which contacts a silicone resin of a thin glass substrate was pure-cleaned and cleaned. The water contact angle of the cleaned thin glass substrate surface was 30 degrees. In addition, the surface roughness Ra of the cleaned thin glass substrate was 0.4 nm. In addition, in the said comparative example, unlike the comparative example 1, UV washing was not performed to the thin glass substrate.

Then, after heat-processing according to the procedure similar to Example 1, the thin glass substrate and the support glass substrate which have a resin layer in thin glass laminated body C2 were peeled.

In the same manner as in Comparative Example 1, a part of the resin layer adheres to the surface (conductive metal oxide film) that has been in contact with the resin layer of the peeled thin glass substrate, and is damaged to a corresponding portion of the resin layer on the support glass substrate. This was confirmed.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various correction and changes can be added without deviating from the range and mind of this invention.

This application is based on the JP Patent application 2010-248294 of an application on November 5, 2010, The content is taken in here with reference.

10:
20: substrate
22: conductive metal oxide film
24: substrate with conductive metal oxide film
201: first major surface of the substrate
202: second main surface of the substrate
221: surface of the conductive metal oxide film
30: gusset
31: support plate
32: resin layer
321: adhesion surface of the resin layer
40: panel for display device with support plate
50: constituent member of the panel for display device
60: panel for display device

Claims (8)

Support plate,
A resin layer,
A substrate having a conductive metal oxide film having a conductive metal oxide film containing an oxide of at least one metal selected from the group consisting of indium, tin, zinc, titanium, and gallium on the surface of the substrate is provided in this order,
A substrate provided with the conductive metal oxide film is disposed on the resin layer so that the conductive metal oxide film is in close contact with the resin layer so that the conductive metal oxide film can be peeled off.
The laminated body whose peeling strength between the said resin layer and the said support plate is higher than the peeling strength between the said resin layer and the board | substrate provided with the said conductive metal oxide film. The laminate according to claim 1, wherein the oxide further contains at least one element selected from the group consisting of aluminum, molybdenum, copper, vanadium, niobium, tantalum, boron, and fluorine. The laminated body of Claim 1 or 2 whose said resin layer is a silicone resin layer. The laminate according to any one of claims 1 to 3, wherein the resin layer is composed of an addition reaction type cured product of organoalkenylpolysiloxane and organohydrogenpolysiloxane. The laminated body of any one of Claims 1-4 whose molar ratio of the hydrogen atom couple | bonded with the silicon atom of the said organohydrogenpolysiloxane with respect to the alkenyl group of the said organoalkenylpolysiloxane is 0.5-2. The laminate according to any one of claims 1 to 5,
A display device panel provided with a supporting plate, comprising a structural member of a panel for display device provided on a surface on the side opposite to the surface in close contact with the resin layer of the substrate provided with the conductive metal oxide film in the laminate. The display device panel formed using the panel for display devices provided with the support plate of Claim 6. The display device which has the panel for display devices of Claim 7.

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