TWI526306B - A laminated body, a panel for a display device with a support plate, a display panel, and a display device - Google Patents

Description

Multilayer body, panel for display device with support plate, panel for display device, and display device

The present invention relates to a laminated body, a panel for a display device with a support plate, a panel for a display device, and a display device.

In recent years, thinner and lighter devices (electronic devices) such as solar cells (PV), liquid crystal displays (LCDs), and organic EL displays (OLEDs) have been developed, and substrates used in such devices have been continuously thinned. If the strength of the substrate is insufficient due to thinning, the handleability of the substrate is lowered in the manufacturing process of the device.

Therefore, a method of thinning a substrate by a chemical etching treatment after forming a device member (for example, a thin film transistor) on a substrate thicker than the final thickness has been widely used. 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 material of the original substrate needs to be removed by the etching liquid, so that the use of productivity or raw materials is required. The point of view of efficiency is not good.

Further, in the method of thinning the substrate by chemical etching, when there is a fine scratch on the surface of the substrate, a fine concave portion (etching hole) is formed by scratching from the etching process to become an optical defect. The situation.

Recently, in order to cope with the above-mentioned problem, a method of forming a laminate for a substrate and a reinforcing plate, and forming a member for a device on a substrate of a laminate, and then peeling the reinforcing plate from the substrate has been proposed (for example, see Patent Document 1). The reinforcing plate includes a glass plate and a resin layer fixed to the glass plate, and the resin layer and the substrate are detachably adhered to each other. After the reinforcing plate is peeled off from the substrate, it can be laminated with a new substrate to be reused as a laminate.

Prior technical literature Patent literature

Patent Document 1: International Publication No. 07/018028

However, in the laminated body of the above-described prior art, when the reinforcing plate is peeled off from the substrate, one of the resin layers may be partially adhered to the substrate on the product side. In particular, after the laminate is subjected to heat treatment under high temperature conditions, a part of the resin layer is frequently attached to the substrate on the product side. The reason for this is considered to be that the resin layer is deteriorated under high temperature conditions, or the adhesion strength between the resin layer and the substrate is increased.

Therefore, when the laminated body is applied to the device manufacturing for performing high-temperature processing, one of the resin layers is partially adhered to the substrate, and as a result, the yield is lowered.

Further, after the substrate is peeled off from the laminated body, dirt, dust, or the like easily adheres to the surface of the substrate, and when such a substrate is used to manufacture the device, the device may be defective or the like. It is considered that the adhesion of the above-mentioned dirt or dust is caused by peeling electrification.

The present invention has been made in view of the above-described problems, and it is an object of the invention to provide a method of preventing adhesion of a part of a resin layer to a substrate side when a resin layer and a substrate are peeled off even after high-temperature heat treatment. A stripped charged laminate on the surface of the substrate.

Further, an object of the present invention is to provide a panel for a display device including a support sheet including the laminate, a panel for a display device formed using a panel for a display device with a support panel, and a display device.

The present inventors have made intensive studies to solve the above problems, and have completed the present invention.

That is, in order to achieve the above object, a first aspect of the present invention is a laminate comprising, in order, a support plate, a resin layer, and a substrate with a conductive metal oxide film attached to the surface of the substrate. a conductive metal oxide film containing an oxide of at least one selected from the group consisting of indium, tin, zinc, titanium, and gallium; and the substrate with the conductive metal oxide film oxidized by the conductive metal The material film is disposed on the resin layer so as to be in close contact with the resin layer, and the peeling strength between the resin layer and the support sheet is higher than between the resin layer and the substrate with the conductive metal oxide film. Peel strength.

In the first aspect, it is preferable that the oxide further contains at least one element selected from the group consisting of aluminum, molybdenum, copper, vanadium, niobium, tantalum, boron, and fluorine.

Further, in the first aspect, it is preferable that the resin layer is a polyoxynitride resin layer.

Further, it is preferable that the resin layer contains an addition reaction type cured product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene.

Further, it is preferred that the molar ratio of the hydrogen atom bonded to the ruthenium atom of the organohydrogenpolyoxyalkylene to the alkenyl group of the above organic alkenyl polyoxyalkylene is 0.5 to 2.

A second aspect of the present invention is a panel for a display device with a support plate, comprising: a laminate according to the first aspect; and a constituent member of the panel for a display device, which is provided in the laminate The substrate on which the conductive metal oxide film is attached is on the surface opposite to the surface on which the resin layer is adhered.

According to a third aspect of the invention, there is provided a panel for a display device which is formed by using a panel for a display device with a support plate as in the second aspect.

A fourth aspect of the invention is a display device comprising the panel for a display device according to the third aspect.

According to the present invention, it is possible to prevent a part of the resin layer from adhering to the substrate on the side of the product when the resin layer is peeled off from the substrate even after the high-temperature heat treatment is performed, and the peeling electrification on the surface of the substrate after peeling can be suppressed. The layered body.

Further, according to the present invention, it is possible to provide a panel for a display device including a support plate including the laminate, and a panel for a display device and a display device which are formed by using a panel for a display device with a support plate.

In the following, the embodiments of the present invention are described with reference to the accompanying drawings. However, the present invention is not limited by the following embodiments, and various modifications and substitutions are possible in the following embodiments without departing from the scope of the invention.

Further, in the present invention, the fixing of the resin layer to the support plate means that the peeling strength between the resin layer and the support plate is higher than the peel strength between the resin layer and the substrate with the conductive metal oxide film. Combine the way.

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

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

The substrate 24 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 and the resin layer 32 are in close contact with each other.

Further, the resin layer 32 is fixed to the support plate 31, and is in close contact with the conductive metal oxide film 22 of the substrate 24 to which the conductive metal oxide film is attached. The reinforcing plate 30 including the support plate 31 and the resin layer 32 reinforces the substrate 24 with the conductive metal oxide film in the step of manufacturing a device (electronic device) such as a liquid crystal display.

This laminated body 10 is used until the middle of the manufacturing process of the device. In other words, the laminated body 10 is used until a device member such as a thin film transistor is formed on the surface of the substrate 24 with the conductive metal oxide film on the side opposite to the resin layer 32. Thereafter, the reinforcing plate 30 is peeled off from the substrate 24 to which the conductive metal oxide film is attached, and does not become a member constituting the device. The reinforcing plate 30 peeled off from the substrate 24 to which the conductive metal oxide film is attached can be laminated with the new substrate 24 with the conductive metal oxide film, and reused as the laminated body 10.

In the present invention, it has been found that the substrate 24 with the conductive metal oxide film attached thereon is provided on the resin layer 32 so that the conductive metal oxide film 22 is in contact with the resin layer 32, whereby a desired effect can be obtained.

Hereinafter, each configuration (substrate, support plate, and resin layer with a conductive metal oxide film) will be described in detail.

<Substrate with conductive metal oxide film>

First, the substrate 24 with the conductive metal oxide film attached will be described.

The substrate 24 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 conductive metal oxide film 22 is disposed on the outermost surface of the substrate 24 on which the conductive metal oxide film is attached so as to be in close contact with the resin layer 32 to be described later.

The substrate 20 and the conductive metal oxide film 22 will be described in detail below.

(substrate)

The substrate 20 has a conductive metal oxide film 22 on the first main surface 201 on the resin layer 32 side, and a device member is formed on the second main surface 202 on the opposite side to the resin layer 32 to form a device. Here, the member for a device refers to a member constituting at least a part of a device such as a constituent member of a panel for a display device to be described later. Specific examples include a thin film transistor (TFT) and a color filter (CF). As the device, a solar cell (PV), a liquid crystal display (LCD), an organic EL display (OLED), or the like can be exemplified.

The type of the substrate 20 may be a general substrate, and may be, for example, a metal substrate such as a germanium wafer, a glass substrate, a resin substrate, an SUS substrate, or a copper substrate. Among these, a glass substrate is preferred. The glass substrate is excellent in chemical resistance and moisture permeability, and has a low heat shrinkage rate. As an index of the heat shrinkage rate, it can be used for the coefficient of linear expansion specified in JIS R 3102 (1995 Revision).

When the linear expansion coefficient of the substrate 20 is large, since the manufacturing process of the device is accompanied by heat treatment, various defects are likely to occur. For example, when a TFT is formed on the substrate 20, when the substrate 20 on which the TFT is formed under heating is cooled, there is a possibility that the position of the TFT is excessively shifted due to thermal contraction of the substrate 20.

The glass substrate can be obtained by melting a glass raw material and forming the molten glass into a plate shape. Such a forming method can be carried out by a usual method, for example, a floating method, a melting method, a flow hole down method, a rich method, a Luber method, or the like. Further, the glass substrate having a particularly small thickness can be obtained by heating a glass which is temporarily formed into a plate shape to a moldable temperature, and stretching and thinning by a method such as stretching (re-drawing method).

The glass of the glass substrate is not particularly limited, and is preferably an alkali-free glass, a borosilicate glass, a soda lime glass, a sorghum glass, or another oxide-based glass containing cerium oxide as a main component. The oxide-based glass is preferably a glass having a content of cerium oxide in an amount of 40 to 90% by mass in terms of oxide.

As the glass of the glass substrate, a glass suitable for the kind of the device or a manufacturing step thereof is used. For example, in a glass substrate for a liquid crystal display, since the elution of an alkali metal component is likely to affect the liquid crystal, it is a glass (alkali-free glass) which does not substantially contain an alkali metal component. As described above, the glass of the glass substrate is appropriately selected depending on the type of the device to be used and the manufacturing steps thereof.

The thickness of the glass substrate is not particularly limited, and is usually less than 0.8 mm, preferably 0.3 mm or less, and more preferably 0.15 mm or less from the viewpoint of thickness reduction and/or weight reduction of the glass substrate. When the thickness is 0.8 mm or more, the requirements for thinning and/or weight reduction of the glass substrate cannot be satisfied. When it is 0.3 mm or less, good flexibility can be imparted to the glass substrate. When it is 0.15 mm or less, the glass substrate can be wound into a reel shape. Further, the thickness of the glass substrate is preferably 0.03 mm or more for the reason that the glass substrate is easily produced and the glass substrate is easily handled.

The type of the resin of the resin substrate is not particularly limited. Specific examples thereof include polyethylene terephthalate resin, polycarbonate resin, polyimide resin, fluororesin, polyamide resin, aromatic polyamide resin, polyether oxime resin, polyether ketone resin, Polyetheretherketone resin, polyethylene naphthalate resin, polyacrylic resin, various liquid crystal polymer resins, cycloolefin resins, polyoxyxylene resins, and the like. Further, the resin substrate may be transparent or opaque. Further, the resin substrate may have a functional layer such as a protective layer formed on the surface.

The thickness of the resin substrate is not particularly limited, and is preferably 0.7 mm or less, more preferably 0.3 mm or less, and particularly preferably 0.1 mm or less from the viewpoint of thickness reduction and/or weight reduction. Further, from the viewpoint of workability, it is preferably 1.0 μm or more.

Furthermore, the substrate 20 may comprise two or more layers. In this case, the materials forming the layers may be the same material or different materials. Moreover, in this case, "the thickness of the substrate 20" means the total thickness of all the layers.

(conductive metal oxide film)

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

For example, when the substrate 20 is an alkali-free glass substrate, the above-described conductive metal oxide film 22 is contained in comparison with an alkaline earth metal component such as magnesium, calcium or barium present on the surface of the alkali-free glass substrate. The alkaline earth metal component has a small electronegativity. Therefore, the conductive metal oxide film 22 and the resin layer 32 are exposed even when the laminated body 10 of the present invention is exposed to high temperature conditions as compared with the case where the alkali-free glass substrate is directly contacted with the resin layer 32 and exposed to high temperature conditions. It is also less likely that a chemical reaction will occur due to the detachment of the above alkaline earth metal component. As a result, the substrate 24 with the conductive metal oxide film attached thereto is peeled off from adhesion of the resin layer 32 to the substrate 24 with the conductive metal oxide film due to heavy peeling.

Here, the term "removal" refers to directing the adhesion strength between the electric metal oxide film 22 and the resin layer 32 to be greater than the adhesion strength between the surface of the support plate 31 and the resin layer 32, and the (main body) strength of the resin layer 32. One.

Further, the conductive metal oxide film 22 exhibits excellent conductivity. Therefore, peeling electrification on the surface of the substrate 24 with the conductive metal oxide film attached after peeling can be suppressed. Further, when an ionizer or spray water is used in combination, peeling electrification can be further suppressed. Alternatively, even if the load of the static eliminator or the spray water is reduced, the same peeling electrification suppression effect as before can be obtained.

The conductive metal oxide film 22 contains an oxide of at least one selected from the group consisting of indium, tin, zinc, titanium, and gallium. That is, the conductive metal oxide film 22 contains a metal oxide containing the above-described metal element and oxygen element.

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

Further, the conductive metal oxide film 22 may contain an oxide containing two or more kinds of the above-exemplified metals. Specific examples thereof include indium tin oxide (ITO), indium zinc oxide (IZO), zinc tin oxide (ZTO), and gallium-doped zinc oxide (GZO).

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

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

Among them, in the case where the substrate with the conductive metal oxide film and the resin layer are more excellent in peelability, and the conductivity is more excellent, indium tin oxide (ITO), indium zinc oxide (IZO), and doping are preferable. Aluminum zinc oxide (AZO), gallium-doped zinc oxide (GZO), fluorine-doped tin oxide (FTO), antimony-doped titanium oxide, more preferably indium tin oxide (ITO), indium zinc oxide (IZO), fluorine-doped tin oxide ( FTO).

The conductive metal oxide film 22 preferably contains the oxide of the above metal as a main component. Specifically, the content of the oxide of the metal is preferably 98% by mass or more based on the total amount of the conductive metal oxide film. Preferably, it is 99% by mass or more, and particularly preferably 99.999% by mass or more.

The conductive metal oxide film 22 may contain an oxide of another metal in a range that does not impair the effects of the present invention. Further, the conductive metal oxide film 22 may contain a component (for example, a metal) other than the oxide of the metal within a range that does not impair the effects of the present invention.

The thickness of the conductive metal oxide film 22 is not particularly limited, and the adhesion of the resin layer 32 to the substrate 24 with the conductive metal oxide film attached thereto due to heavy peeling is further suppressed, and the wear resistance is maintained. In terms of, it is preferably 5 to 5000 nm, more preferably 10 to 500 nm.

The conductive metal oxide film 22 containing the oxide of the above specific metal exhibits excellent conductivity. More specifically, from the viewpoint of further suppressing the peeling electrification on the surface of the substrate after peeling, the surface resistance value of the conductive metal oxide film 22 is preferably from 0.1 to 1000 Ω/□, more preferably from 1 to 500. Ω/□. Further, the measurement method is a known method (for example, a four-probe resistance measurement method prescribed in JIS R 1637 (established in 1998)).

Whether or not the density of the polar group present on the surface 221 of the conductive metal oxide film 22 in contact with the resin layer 32 is appropriate can be judged by measuring the water contact angle of the surface 221 before the adhesion. Generally, the higher the density of the polar group such as the hydrophilicity of the surface, the lower the water contact angle. Here, the water contact angle means a contact angle defined in JIS R 3257 (established in 1999).

The water contact angle before the adhesion of the surface 221 of the conductive metal oxide film 22 to the viewpoint of 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 preferably 20 or more, more preferably 30 to 90, and still more preferably 40 to 70.

A fine uneven structure may be formed in advance on the surface 221 of the conductive metal oxide film 22 on the side in contact with the resin layer 32. In this case, the degree of the uneven structure is preferably within a range in which the surface 221 of the conductive metal oxide film 22 and the adhesion surface 321 of the resin layer 32 are not peeled off by the anchoring effect, thereby producing a resin. The layer 32 is in the range of excessive adhesion on the substrate 24 to which the conductive metal oxide film is attached.

Further, the surface roughness (Ra) of the surface 221 of the conductive metal oxide film 22 is preferably from 0.1 to 50 nm, more preferably from 0.5 to 5 nm. The Ra system was measured in accordance with JIS B 0601 (corrected in 2001).

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

The conductive metal oxide film 22 is described as a single layer in FIG. 1, but may be a laminate of two or more layers. For example, when the conductive metal oxide film is two layers, the first conductive metal oxide film that is in contact with the substrate 20 and the second conductive metal that is provided on the first conductive metal oxide film are provided. Oxide layer. In the case of two layers, the components of the first conductive metal oxide film and the second conductive metal oxide film may be different.

The conductive metal oxide film 22 may be provided on one portion of the surface of the substrate 20 within a range that does not impair the effects of the present invention. For example, the conductive metal oxide film 22 may be provided in an island shape or a stripe shape on the surface of the substrate 20.

More specifically, the coverage of the conductive metal oxide film 22 on the surface of the substrate 20 further suppresses adhesion of the resin layer 32 to the substrate 24 with the conductive metal oxide film due to heavy peeling. From the viewpoint, it is preferably 50 to 100%, more preferably 75 to 100%.

(Method of Manufacturing Conductive Metal Oxide Film)

The method for producing the conductive metal oxide film 22 is not particularly limited, and a known method can be employed. For example, a method of providing a specific metal oxide on the substrate 20 by a vapor deposition method or a sputtering method can be cited.

The manufacturing conditions are appropriately selected depending on the oxide of the metal to be used.

The substrate 24 with the conductive metal oxide film includes the substrate 20 and the conductive metal oxide film 22, but the substrate 20 and the conductive metal oxide film may be formed within a range that does not impair the effects of the present invention. 22 rooms contain other components.

The other member may, for example, be a flattening layer that prevents alkali ions from diffusing from the substrate 20 into the conductive metal oxide film 22, and a flattening layer that planarizes the surface of the conductive metal oxide film 22.

<Support Board>

The support plate 31 cooperates with the resin layer 32 to support and reinforce the substrate 24 with the conductive metal oxide film, and prevents deformation, damage, breakage, and the like of the substrate 24 with the conductive metal oxide film attached in the manufacturing process of the device. Further, in the case where the substrate 24 with the conductive metal oxide film having a smaller thickness than the previous one is used, by forming the laminated body 10 having the same thickness as the previous substrate, it is possible to use it in the manufacturing steps of the device. The manufacturing technique or manufacturing equipment of the substrate of the previous thickness is also one of the purposes of using the support plate 31.

As the support plate 31, for example, a metal plate such as a glass plate, a resin plate, or a SUS plate can be used. When the manufacturing process of the device is accompanied by heat treatment, the support plate 31 is preferably formed of a material having a small difference in linear expansion coefficient from the substrate 20, and more preferably formed of the same material as the substrate 20. In the case where the substrate 20 is a glass substrate, the support plate 31 is preferably a glass plate. More preferably, the support plate 31 is a glass plate formed of the same glass material as the glass substrate of the substrate 20.

The thickness of the support plate 31 may be thicker or thinner than the substrate 20. It is preferable to select the thickness of the support plate 31 in accordance with 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, the manufacturing process of the current device is designed to process a substrate having a thickness of 0.5 mm, and the support plate is used when the sum of the thickness of the substrate 24 with the conductive metal oxide film and the thickness of the resin layer 32 is 0.1 mm. The thickness of 31 is set to 0.4 mm. In the usual case, the thickness of the support plate 31 is preferably 0.2 to 5.0 mm.

In the case where the support plate 31 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons of easy handling and difficulty in cracking. In addition, when the member for a device is formed and peeled off, the thickness of the glass plate is preferably 1.0 mm or less for the reason that the rigidity of the member can be appropriately bent without being broken.

The difference between the average linear expansion coefficient of the substrate 20 and the support plate 31 at 25 to 300 ° C (hereinafter simply referred to as "average linear expansion coefficient") is preferably 500 × 10 ^-7 / ° C or less, more preferably 300 × 10 ^{-7 .} / ° C or less, further preferably 200 × 10 ^-7 / ° C or less. If the difference is too large, the laminate 10 is warped sharply when heated or cooled in the manufacturing step of the device, or the substrate 24 with the conductive metal oxide film is peeled off from the reinforcing plate 30. When the material of the substrate 20 is the same as the material of the support plate 31, the occurrence of such problems can be suppressed.

<Resin layer>

The resin layer 32 is fixed to the support plate 31, and is detachably adhered to the substrate 24 to which the conductive metal oxide film is attached. The resin layer 32 can prevent the position of the substrate 24 with the conductive metal oxide film attached from being displaced until the peeling operation is performed, and can be easily attached to the substrate 24 on which the conductive metal oxide film is attached by the peeling operation. The peeling prevents the substrate 24 or the like with the conductive metal oxide film attached from being damaged by the peeling operation.

The size of the resin layer 32 is not particularly limited. The resin layer 32 may be larger or smaller than the substrate 20 or the support plate 31.

The surface 321 of the resin layer 32 that is in contact with the conductive metal oxide film 22 (hereinafter also referred to as the "adhesive surface 321") is preferably not adhered by a usual adhesive, but by solids. The force generated by the intrinsic van der Waals force is adhered to the surface 221 of the conductive metal oxide film 22. The reason for this is that the substrate 24 with the conductive metal oxide film attached can be easily peeled off. In the present invention, the property of easily peeling off the surface of the resin layer is referred to as peelability.

On the other hand, the bonding force of the resin layer 32 to the surface of the support plate 31 is relatively higher than the surface of the resin layer 32 to the substrate 24 to which the conductive metal oxide film is attached (corresponding to the surface 221 of the conductive metal oxide film 22) The binding force. Therefore, the peeling strength between the resin layer 32 and the support sheet 31 is higher than the peel strength between the resin layer 32 and the substrate 24 with the conductive metal oxide film attached thereto. In the present invention, the bonding of the surface of the resin layer to the surface of the substrate is referred to as adhesion, and the bonding of the surface of the resin layer to the surface of the support plate is referred to as fixation. Preferably, the resin layer 32 and the support plate 31 are bonded by an adhesive force or an adhesive force. However, the present invention is not limited thereto, and as long as it is relatively higher than the bonding force of the resin layer 32 to the substrate 24 to which the conductive metal oxide film is attached, the resin layer 32 and the support plate 31 may be generated by using the above-described van der Waals force. The force sticks.

The thickness of the resin layer 32 is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 30 μm, still more preferably 7 to 20 μm. The reason for this is that if the thickness of the resin layer 32 is within the above range, the adhesion between the resin layer 32 and the substrate 24 with the conductive metal oxide film is sufficient. Further, even if bubbles or impurities are interposed between the resin layer 32 and the substrate 24 with the conductive metal oxide film, strain defects can be suppressed from occurring on the substrate 24 with the conductive metal oxide film. Further, if the thickness of the resin layer 32 is too thick, it takes time and material to form the resin layer 32, which is uneconomical.

Further, the resin layer 32 may also contain two or more layers. In this case, the "thickness of the resin layer 32" means the total thickness of all the layers.

Further, when the resin layer 32 contains two or more layers, the types of the resins forming the respective layers may be different.

The resin layer 32 is preferably formed of a material having a glass transition point lower than room temperature (about 25 ° C) or having no glass transition point. This is because the non-adhesive resin layer can be more easily peeled off from the substrate 24 with the conductive metal oxide film, and the adhesion to the substrate 24 with the conductive metal oxide film is also formed. full.

Further, since the heat treatment is often performed in the manufacturing steps of the device, the resin layer 32 preferably has heat resistance.

When the elastic modulus of the resin layer 32 is too high, the adhesion to the substrate 24 with the conductive metal oxide film tends to be low. On the other hand, if the elastic modulus of the resin layer 32 is too low, the peelability becomes low.

The kind of the resin forming the resin layer 32 is not particularly limited. For example, an acrylic resin, a polyolefin resin, a polyurethane resin, or a polyoxyl resin can be mentioned. It can also be mixed with several types of resins. Among them, a polyoxyxylene resin is preferred. The heat resistance or peelability of the polyoxymethylene resin is excellent. Further, when the support plate 31 is a glass plate, it is easily fixed to the glass plate by a condensation reaction with a stanol group on the surface of the glass plate. In a state in which the polyoxyxylene resin layer is interposed between the support sheet 31 and the substrate 24 with the conductive metal oxide film, for example, even if it is treated in the air at about 200 ° C for about 1 hour, the peeling property hardly deteriorates. From the viewpoint of the polyoxyalkylene resin layer, it is also preferred.

The resin layer 32 is preferably a polyoxyl resin (hardened product) for use in a release paper in a polyoxyxylene resin. The resin layer 32 formed by curing the surface of the support sheet 31 as a curable resin composition for a release resin for a release paper has excellent releasability, which is preferable. Further, since the flexibility is high, even if foreign matter such as bubbles or dust is mixed between the resin layer 32 and the substrate 24 with the conductive metal oxide film, the substrate 24 with the conductive metal oxide film can be prevented from being generated. Strain defects.

The above-mentioned curable polyfluorene oxide which is a polyoxyxylene resin for release paper is classified into a condensation reaction type polyoxane, an addition reaction type polyoxane, an ultraviolet curing type polyfluorene oxygen, and an electron beam hardening type polycondensation according to the curing mechanism. Oxygen can be used. Among these, an addition reaction type polyoxane is preferred. Since the resin layer 32 is formed, the degree of peeling property is good and the heat resistance is also high because the curing reaction is easy.

The addition reaction type polyfluorene is a curable composition containing a main component and a crosslinking agent and hardened in the presence of a catalyst such as a platinum-based catalyst. The hardening of the addition reaction type polyoxygen can be promoted by heat treatment. The main component of the addition reaction type polyoxo is preferably an organic polyoxyalkylene having an alkenyl group (vinyl group or the like) bonded to a ruthenium atom (i.e., an organic alkenyl polysiloxane). Further, preferably, A linear form, an alkenyl group or the like becomes a crosslinking point. The addition reaction type polyfluorene crosslinking agent is preferably an organic polyoxyalkylene having a hydrogen atom (hydroalkylene group) bonded to a halogen atom (i.e., an organic hydrogen polyoxyalkylene. Further, preferably, Straight chain), hydroquinone or the like becomes a crosslinking point.

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

Further, the curable polyfluorene oxide which is a polyoxyxylene resin for release paper has a solvent type, an emulsion type, and a solventless type, and any of them may be used. Among these, a solventless type is preferred. The reason for this is that the solvent-free type is superior in terms of productivity, safety, and environmental characteristics. Further, in the case of curing at the time of forming the resin layer 32, that is, heat curing, ultraviolet curing, or electron beam curing, since the solvent for foaming is not contained, bubbles are less likely to remain in the resin layer 32.

In addition, as a commercially available product name or model, KNS-320A and KS-847 (all manufactured by Shin-Etsu Silicones Co., Ltd.) are exemplified as the curable polyfluorene which is a polyoxyl resin for a release paper. , TPR6700 (manufactured by Momentive Performance Materials Japan Co., Ltd.), a combination of ethylene polyoxylium "8500" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogen polyoxyalkylene "12031" (manufactured by Arakawa Chemical Industries, Ltd.), ethylene polymerization A combination of "11364" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogen polyoxyalkylene "12031" (manufactured by Arakawa Chemical Industries, Ltd.), ethylene polyoxylium "11365" (manufactured by Arakawa Chemical Industries, Ltd.) and methyl A combination of hydrogen polyoxyalkylene "12031" (manufactured by Arakawa Chemical Industries, Ltd.).

Further, KNS-320A, KS-847, and TPR6700 are hardening polyfluorenes containing a main component and a crosslinking agent in advance.

Further, the polyfluorene-oxygen resin forming the resin layer 32 is preferably one having a low molecular weight polyfluorene oxide or the like in the polyoxynoxy resin layer, which is not easily transferred to the substrate 24 with the conductive metal oxide film, that is, low. Polyoxygen transferability. Further, from the viewpoint of heat resistance derived from the crosslinked structure, it is preferred that the hydrogen atom bonded to the ruthenium atom of the organohydrogenpolyoxyalkylene has a molar ratio to the alkenyl group of the organic alkenyl polyoxyalkylene. It is 0.5~2.

(Method of Manufacturing Resin Layer)

The method of fixing the resin layer 32 to the support plate 31 is not particularly limited, and examples thereof include a method of fixing a film-like resin to the surface of the support plate 31. Specifically, in order to impart a high fixing force (high peeling strength) to the surface of the support sheet 31 on the surface of the support sheet 31, surface modification treatment (primer treatment) is performed on the surface of the support sheet 31, and then A method of fixing to the support board 31. For example, a chemical method (primer treatment) for chemically raising a fixing force such as a decane coupling agent; a physical method of increasing a surface active group such as a SiOH group or an SiO group such as plasma irradiation or flame treatment; A mechanical treatment method or the like which increases the grip by increasing the roughness of the surface.

In addition, for example, a layer of the curable resin composition to be the resin layer 32 is formed on the surface of the support sheet 31, and then the curable resin composition is cured to form the resin layer 32, and is formed to be fixed to the support sheet 31. The resin layer 32 thereon. As a method of forming a layer of the curable resin composition on the surface of the support sheet 31, for example, a method of applying the curable resin composition onto the support sheet 31 can be mentioned. Examples of the coating method include a spray coating method, a die coating method, a spin coating method, a dip coating method, a roll coating method, a bar coating method, a screen printing method, and a gravure coating method. It can be suitably selected among these methods according to the kind of resin composition.

Further, when the curable resin composition to be the resin layer 32 is applied onto the support sheet 31, the coating amount thereof is preferably from 1 to 100 g/m ² , more preferably from 5 to 20 g/m ^{2 .} .

For example, in the case where the resin layer 32 is formed of an addition reaction type polyoxyl curable resin composition, the curability of a mixture containing an organic alkenyl polysiloxane, an organic hydrogen polyoxyalkylene, and a catalyst is used. The resin composition is applied onto the support sheet 31 by a known method such as the above-described spraying method, and then heat-hardened. The heat-hardening conditions are also different depending on the amount of the catalyst to be mixed. For example, when 100 parts by weight of the platinum-based catalyst is blended with respect to 100 parts by weight of the total of the organic alkenyl polysiloxane and the organohydrogenpolyoxyalkylene. It is reacted in the atmosphere at 50 ° C to 250 ° C, preferably at 100 ° C to 200 ° C. Further, the reaction time in this case is set to 5 to 60 minutes, preferably 10 to 30 minutes.

By heat-hardening the curable resin composition, the polyoxymethylene resin is chemically bonded to the support plate 31 at the time of the hardening reaction. Further, the polyoxymethylene resin layer is bonded to the support plate 31 by the anchoring effect. By these effects, the polyoxyphthalide resin layer is firmly fixed to the support plate 31. In the case where a resin layer containing a resin other than the polyoxyn resin is formed from the curable resin composition, the resin layer fixed to the support sheet can be formed by the same method as described above.

<Laminated body and its manufacturing method>

As described above, the laminated body 10 of the present invention includes the laminated body in which the substrate 24 with the conductive metal oxide film and the support plate 31 are present and the resin layer 32 is present between them.

The method for producing the laminate of the present invention is not particularly limited. Usually, the support sheet 31 having the resin layer 32 fixed on its surface is formed by the above method, and then the substrate 24 with the conductive metal oxide film is attached to conduct electricity. The metal oxide film 22 is disposed on the resin layer 32 so as to be in close contact with the resin layer 32.

The method in which the resin layer 32 is peelably adhered to the substrate 24 to which the conductive metal oxide film is attached is not particularly limited, and may be a known method. For example, a method in which a substrate 24 having a conductive metal oxide film is adhered to a peelable surface of a resin layer 32 under a normal pressure environment, and a resin layer 32 and a conductive property are bonded using a roll or a press. A substrate 24 of a metal oxide film. It is preferable that the resin layer 32 is further adhered to the substrate 24 with the conductive metal oxide film by pressure bonding by a roll or a press. Further, it is preferable to perform pressure bonding by a roll or a press, and it is relatively easy to remove air bubbles mixed between the resin layer 32 and the substrate 24 with the conductive metal oxide film.

When the pressure bonding is carried out by a vacuum lamination method or a vacuum press method, it is more preferable to suppress the incorporation of air bubbles or to ensure good adhesion. Further, by pressure bonding under vacuum, there is an advantage that even if minute bubbles remain, the bubbles do not grow due to heating, and it is difficult to cause strain defects in the substrate 24 with the conductive metal oxide film.

When the resin layer 32 is detachably adhered to the substrate 24 to which the conductive metal oxide film is attached, it is preferable that the surface of the resin layer 32 and the substrate 24 with the conductive metal oxide film are in contact with each other. Wash the floor and laminate it in a clean environment. That is, the foreign matter is mixed between the resin layer 32 and the substrate 24 with the conductive metal oxide film, and the resin layer 32 is deformed, so that the flatness of the surface of the substrate 24 with the conductive metal oxide film is not caused. The effect is better, but the higher the cleanliness, the better the flatness is.

Further, the step of fixing the resin layer 32 to the support plate 31 and the step of adhering the resin layer 32 to the substrate 24 with the conductive metal oxide film adhered thereto are not limited, and may be, for example, substantially Simultaneously.

The laminate of the present invention can be used for various applications, and examples thereof include the use of a panel for a display device to be described later, a PV, a thin film secondary battery, and an electronic component such as a semiconductor wafer on which a circuit is formed. Further, in this application, the laminate is often exposed to high temperature conditions (for example, 320 ° C or higher) (for example, 1 hour or longer).

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

<Panel for display device with support plate and method for manufacturing the same>

In the present invention, the above-mentioned laminated body is used to manufacture a panel for a display device with a support plate.

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

The display device panel 40 with the support plate includes the laminated body 10 and the constituent member 50 of the display device panel.

(constituting members of the panel for display device)

The constituent member 50 of the panel for a display device is, for example, a display device such as an LCD or an OLED using a glass substrate, or a member formed on the glass substrate or a part thereof. For example, in a display device such as an LCD or an OLED, a TFT array (hereinafter simply referred to as an "array"), a protective layer, a color filter, a liquid crystal, a transparent electrode including ITO, and the like, and various circuit patterns are formed on the surface of the substrate. Or combine them. Further, examples of the display device including the OLED include a transparent electrode formed on a substrate, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and the like.

The manufacturing method of the display device panel 40 with the above-mentioned support plate is not particularly limited, and the conductive metal oxide film may be attached to the laminated body 10 by a conventionally known method depending on the type of the constituent members of the display device panel. A constituent member 50 of a panel for a display device is formed on the surface of the substrate 24.

For example, in the case of manufacturing an OLED, the surface of the substrate 24 with the conductive metal oxide film on the laminate 10 on the opposite side to the surface of the adhesion resin layer 32 (corresponding to the second main surface of the substrate) 202) forming an organic EL structure, and performing various layer formation or treatment of forming a transparent electrode; and further depositing a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, etc. on a surface on which the transparent electrode is formed Forming a back electrode; sealing using a sealing plate. Specific examples of the formation or treatment of the layers include a film formation treatment, a vapor deposition treatment, and a subsequent treatment of a sealing plate. The formation of the constituent members may also be part of the formation of all the constituent members required for the panel for the display device. In this case, after the substrate 24 with the conductive metal oxide film formed with a part of the constituent members is peeled off from the resin layer 32, the remaining constituent members are formed on the substrate 24 to which the conductive metal oxide film is attached. , manufacturing panels for display devices.

<Panel for display device and method of manufacturing the same>

As shown in FIG. 2, the panel 60 for a display device of the present invention includes a substrate 24 with a conductive metal oxide film and a constituent member 50 of a panel for a display device.

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

In addition, when the constituent member on the substrate 24 to which the conductive metal oxide film is attached at the time of peeling is a part of the formation of all the constituent members required for the panel for a display device, the conductive metal oxide film is attached thereto. The remaining constituent members are formed on the substrate 24 to manufacture a panel for a display device.

The method of peeling off the peelable surface of the conductive metal oxide film 22 and the resin layer 32 is not specifically limited. Specifically, for example, a sharp cutter can be inserted into the interface between the conductive metal oxide film 22 and the resin layer 32 to form a starting point of peeling, and then a mixed fluid of water and compressed air is blown and peeled off.

In addition, after the display device panel 60 is detached from the display device panel 40 with a support plate, the substrate 24 with the conductive metal oxide film attached to the display device panel 60 may be used as needed. Further, a constituent member of the panel for a display device is provided on the conductive metal oxide film 22.

<display device>

Moreover, the display device can be obtained by such a display device panel 60. Examples of the display device include an LCD and an OLED. Examples of the LCD include a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an FE (Field Emission) type, and a TFT (Thin Film Transistor) type. , MIM (Metal-Insulator-Metal, metal-insulator-metal) type.

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

Example

Hereinafter, the present invention will be specifically described by way of Examples and the like, but the invention is not limited thereto.

In the following examples and comparative examples, the water contact angle was measured using a contact angle meter (manufactured by Kruss Corporation, droplet shape analysis system DSA 10Mk2). Further, the surface roughness Ra was measured using an atomic force microscope (Seiko Instruments, SPA300/SPI3800).

The peeling property after heating of the thin-plate glass laminate was subjected to heat treatment under the following specific conditions, and then the thin glass substrate and the resin layer were peeled off, and evaluated on the surface of the thin glass substrate in contact with the resin layer. . The residue of the resin layer was not evaluated as being good, and the residue of the resin layer was evaluated as being unsatisfactory.

Further, on the surface of the thin glass substrate after peeling, which is in contact with the resin layer, plasma irradiation is carried out using a normal-pressure remote plasma device (manufactured by Sekisui Chemical Co., Ltd.), and then a polarizing film is adhered thereto (made by Nitto Denko Co., Ltd., acrylic adhesive) The agent was evaluated for the presence or absence of peeling. The absence of peeling indicates that there is no residue of the resin layer. The occurrence of peeling indicates that there is a residue of the resin layer.

<Example 1>

First, after supporting a glass substrate (an alkali-free glass, AN100 manufactured by Asahi Glass Co., Ltd.) having a length of 720 mm, a width of 600 mm, a thickness of 0.4 mm, and a linear expansion coefficient of 38 × 10 ^-7 /°C, pure water is washed. Further, it is washed by UV and cleaned.

Then, on the first main surface of the supporting glass substrate, a non-solvent addition reaction type release paper for polyether (for use by Shin-Etsu Silicones Co., Ltd., KNS-320A, viscosity: 0.40 Pa‧s) was used by a screen printing machine. Solubility parameter (SP value): 7.3) 100 parts by weight of a mixed solution of a platinum-based catalyst (manufactured by Shin-Etsu Silicones Co., Ltd., CAT-PL-56) of 2 parts by weight was coated to a size of 705 mm and a width of 595 mm. Rectangular (application amount 30 g/m ² ).

Then, it was heat-hardened in the air at 180 ° C for 30 minutes to form a polyoxyxylene resin layer having a thickness of 20 μm on the first main surface of the supporting glass substrate.

Further, the polyoxosiloxane for the solventless addition reaction type release paper contains a linear organic alkenyl polyoxyalkylene (main component) having a vinyl group and a methyl group bonded to a ruthenium atom, and has a bond. A linear organohydrogenpolyoxyalkylene (crosslinking agent) which is bonded to a hydrogen atom and a methyl group on a halogen atom.

Then, on the side of the thin glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) having a length of 720 mm, a width of 600 mm, a thickness of 0.3 mm, and a coefficient of linear expansion of 38 × 10 ^-7 /°C, which is in contact with the polyoxyxene resin It is washed with pure water and then washed with UV to clean it. Further, on the cleaned surface, ITO (surface resistance 300 Ω/□) having a thickness of 10 nm was formed by magnetron sputtering (heating temperature 300 ° C, film formation pressure 5 mTorr, power density 0.5 W/cm ² ). ), a thin glass substrate (a thin glass substrate with a conductive metal oxide film) was obtained. The water contact angle of the surface of the conductive metal oxide film was 45°. Further, the surface roughness Ra of the conductive metal oxide film was 0.7 nm.

Thereafter, the ITO film-forming surface of the thin glass substrate was bonded to the layer of the polyoxyl resin supporting the glass substrate by a vacuum press at room temperature to obtain a thin-plate glass laminate A1.

In the obtained thin plate glass laminate A1, the two glass substrates were in close contact with the polyoxymethylene resin layer without generating bubbles, and there was no strain-like defect, and the smoothness was also good.

(evaluation of peelability after heating)

The thin-plate glass laminate A1 was heat-treated at 320 ° C for 1 hour in a nitrogen atmosphere having an atmospheric oxygen content of 0.1% or less.

Then, a peeling test was performed. Specifically, first, the second main surface of the thin plate glass in the thin plate glass laminate A1 is fixed to the fixing table. On the other hand, the second main surface of the supporting glass substrate is adsorbed by the adsorption pad. Then, at the interface between the thin glass substrate and the resin layer at one of the four corner portions of the thin plate glass laminate A1, a blade having a thickness of 0.4 mm was inserted to slightly peel the thin glass substrate to form a starting point of peeling. Then, the adsorption pad is moved away from the fixing table to peel the thin glass substrate from the supporting glass substrate having the resin layer.

There is no residue of the resin layer on the surface of the thin plate glass substrate after contact with the resin layer (on the conductive metal oxide film). Further, the charged potential of the surface of the thin glass substrate which was peeled off after peeling (on the conductive metal oxide film) was measured by an electrostatic measuring device to be +1.2 kV. On the surface of the thin glass substrate after contact with the resin layer (on the conductive metal oxide film), the plasma is irradiated with a normal pressure remote plasma device (manufactured by Sekisui Chemical Co., Ltd.), and the polarizing film is adhered (Nitto Produced by an electrician company, an acrylic adhesive), and no peeling occurred.

<Example 2>

In the same manner as in Example 1, the ITO film formation surface of the thin glass substrate and the polyoxyl resin layer of the support glass substrate were bonded together at room temperature by a vacuum press to obtain a thin glass laminate. Then, the peeling test was performed in the same manner as in Example 1 without performing heat treatment. There is no residue of the resin layer on the surface of the thin plate glass substrate after contact with the resin layer (on the conductive metal oxide film). Further, the charged potential of the surface of the thin glass substrate which was peeled off and peeled off from the resin layer (on the conductive metal oxide film) was measured to be +1.3 kV by an electrostatic measuring device. On the surface of the thin glass substrate after contact with the resin layer (on the conductive metal oxide film), the plasma is irradiated with a normal pressure remote plasma device (manufactured by Sekisui Chemical Co., Ltd.), and the polarizing film is adhered (Nitto Produced by an electrician company, an acrylic adhesive), and no peeling occurred.

<Example 3>

In the same manner as in Example 1, the ITO film formation surface of the thin glass substrate and the polyoxyl resin layer of the support glass substrate were bonded together at room temperature by a vacuum press to obtain a thin glass laminate. Thereafter, the thin-plate glass laminate A1 was heat-treated in the same manner as in the first embodiment. Then, a peeling test was performed. Specifically, first, the second main surface of the thin glass substrate in the thin plate glass laminate A1 is fixed to the fixing table. On the other hand, the second main surface of the supporting glass substrate is adsorbed by the adsorption pad. Then, at the interface between the thin glass substrate and the resin layer at one of the four corner portions of the thin plate glass laminate A1, a blade having a thickness of 0.4 mm was inserted to slightly peel the thin glass substrate to form a starting point of peeling. Here, the blade is inserted while the static eliminator (manufactured by Keyence Corporation) is blown to the interface.

Then, while the static eliminator is continuously ejected from the static eliminator to remove the electrostatic fluid, the adsorption pad is moved away from the fixing table to peel the thin glass substrate from the supporting glass substrate having the resin layer.

There is no residue of the resin layer on the surface of the thin plate glass substrate after contact with the resin layer (on the conductive metal oxide film). Further, the charged potential of the surface of the thin glass substrate which was peeled off after peeling (on the conductive metal oxide film) was measured to be +0.1 kV by an electrostatic measuring device. On the surface of the thin glass substrate after contact with the resin layer (on the conductive metal oxide film), the plasma is irradiated with a normal pressure remote plasma device (manufactured by Sekisui Chemical Co., Ltd.), and the polarizing film is adhered (Nitto Produced by an electrician company, an acrylic adhesive), and no peeling occurred.

<Example 4>

First, a thin glass substrate (an alkali-free glass, AN100 manufactured by Asahi Glass Co., Ltd.) having a length of 760 mm, a width of 640 mm, a thickness of 0.3 mm, and a linear expansion coefficient of 38 × 10 ^-7 /°C is washed with pure water. Further, it is washed by UV and cleaned. Further, on the first main surface to be cleaned, ITO (surface resistance 300 Ω) having a thickness of 10 nm was formed by magnetron sputtering (heating temperature 300 ° C, film formation pressure 5 mTorr, power density 0.5 W/cm ² ). /□), obtaining a thin glass substrate (a thin glass substrate with a conductive metal oxide film). The water contact angle of the surface of the conductive metal oxide film was 45°. Further, the surface roughness Ra of the conductive metal oxide film was 0.7 nm. Then, in the same manner as in the first embodiment, a linear organic alkenyl group having a vinyl group at both ends was formed by a screen printing machine on the surface of the conductive metal oxide film on the first main surface of the thin glass substrate. Alkane (ethylene polyfluorene, manufactured by Arakawa Chemical Industries, Ltd., 8500), methylhydrogenated polyoxyalkylene having a hydroquinone group in the molecule (manufactured by Arakawa Chemical Industries, Ltd., 12031), platinum-based catalyst (manufactured by Arakawa Chemical Industries, Ltd.) The mixture of CAT12070) was coated with a rectangle having a size of 750 mm and a width of 630 mm to form a layer containing uncured hardened polyfluorene (coating amount: 35 g/m ² ).

Then, the surface of the supporting glass substrate having a length of 720 mm, a width of 600 mm, and a thickness of 0.4 mm and the contact side of the polyoxyxylene resin (the first main surface) is washed with pure water, and then cleaned by UV cleaning. . Thereafter, the first main surface of the carrier substrate was bonded to the layer containing the uncured curable polyfluorinated oxygen at room temperature by a vacuum press, and allowed to stand at 30 Pa for 5 minutes to contain unhardened. The layer of the hardenable polyfluorene is subjected to a defoaming treatment to obtain a layered body A0 before hardening. At this time, the carrier substrate is laminated on the layer containing the uncured curable polyfluorene so that the peripheral layer region which is not in contact with the carrier substrate is left on the layer containing the uncured curable polyfluorene oxide. Further, the length from the outer periphery of the carrier substrate to the outer periphery of the uncured curable resin composition layer is about 15 mm or more.

Then, it was heat-hardened in the air at 250 ° C for 30 minutes to obtain a cured laminated body A0 containing a hardened polyoxyn resin layer having a thickness of 10 μm.

Then, the supporting glass substrate of the laminated body A0 after hardening is fixed on the pressure plate on which the positioning jig is mounted, and the diamond grinding wheel blade is used to overlap the one side of the outer periphery of the supporting glass substrate by the diamond grinding wheel cutter. After the tangential line is drawn on the second main surface of the thin glass substrate, the tangential side of the thin glass is sandwiched by a clamp to be cut. In the same manner, the outer side of the thin glass substrate and the remaining three sides of the outer periphery of the supporting glass substrate are also cut, and then the cut surface of the thin glass substrate is ground by a vermiculite having a curved surface, and chamfering is performed to obtain a laminated body after cutting. A1.

Then, a peeling test was performed in the same manner as in Example 3. The thin glass substrate and the supporting glass substrate having the resin layer are peeled off, and the residue of the resin layer is not present on the surface of the thin glass substrate after peeling (on the conductive metal oxide film). Further, the charged potential of the surface of the thin glass substrate which was peeled off after peeling (on the conductive metal oxide film) was measured to be +0.1 kV by an electrostatic measuring device. On the surface of the thin glass substrate after contact with the resin layer (on the conductive metal oxide film), the plasma is irradiated with a normal pressure remote plasma device (manufactured by Sekisui Chemical Co., Ltd.), and the polarizing film is adhered (Nitto Produced by an electrician company, an acrylic adhesive), and no peeling occurred.

<Example 5>

A thin plate glass laminate B1 was obtained by the same method as in Example 3 except that a glass plate containing soda lime glass was used as the thin glass substrate and the support glass substrate.

Then, a peeling test was performed in the same manner as in Example 3. The thin glass substrate and the supporting glass substrate having the resin layer are peeled off, and the residue of the resin layer is not present on the surface of the thin glass substrate after peeling (on the conductive metal oxide film). Further, the charged potential of the surface of the thin glass substrate which was peeled off after peeling (on the conductive metal oxide film) was measured to be +0.1 kV by an electrostatic measuring device. On the surface of the thin glass substrate after contact with the resin layer (on the conductive metal oxide film), the plasma is irradiated with a normal pressure remote plasma device (manufactured by Sekisui Chemical Co., Ltd.), and the polarizing film is adhered (Nitto Produced by an electrician company, an acrylic adhesive), and no peeling occurred.

<Example 6>

A thin plate glass laminate C1 was obtained by the same method as in Example 3 except that a chemically strengthened glass plate was used as the thin glass substrate and the support glass substrate.

Then, a peeling test was performed in the same manner as in Example 3. The thin glass substrate and the supporting glass substrate having the resin layer are peeled off, and the residue of the resin layer is not present on the surface of the thin glass substrate after peeling (on the conductive metal oxide film). Further, the charged potential of the surface of the thin glass substrate which was peeled off after peeling (on the conductive metal oxide film) was measured to be +0.1 kV by an electrostatic measuring device. On the surface of the thin glass substrate after contact with the resin layer (on the conductive metal oxide film), the plasma is irradiated with a normal pressure remote plasma device (manufactured by Sekisui Chemical Co., Ltd.), and the polarizing film is adhered (Nitto Produced by an electrician company, an acrylic adhesive), and no peeling occurred.

Further, in the above peeling test, the thin plate glass laminate A1 used in the above Examples 1 to 6 is not between the polyoxynated resin layer and the supporting glass substrate, but is bonded to the polyoxyxene resin layer and the thin plate glass. Peeling occurs between the substrate (thin glass substrate with a conductive metal oxide film). According to this, it is confirmed that the adhesion between the polyoxyxylene resin layer and the supporting glass substrate is greater than the adhesion between the polyoxynoxy resin layer and the thin glass substrate, in other words, the peeling strength between the polyoxy-resin layer and the supporting glass substrate is higher than Peel strength between the polyoxymethylene resin layer and the thin glass substrate.

<Comparative Example 1>

Instead of the thin-plate glass substrate with the conductive metal oxide film used in Example 1, a thin-plate glass substrate having a length of 720 mm, a width of 600 mm, a thickness of 0.3 mm, and a coefficient of linear expansion of 38 × 10 ^-7 /°C was used ( A thin plate glass laminate C1 was obtained in the same manner as in Example 1 except that AN100 manufactured by Asahi Glass Co., Ltd. was used. The conductive metal oxide film is not contained in the thin plate glass laminate C1.

Further, the surface of the thin glass substrate on the side in contact with the polyoxymethylene resin was washed with pure water, and then subjected to UV cleaning to be cleaned. The water contact angle of the surface of the cleaned sheet glass substrate was 8°. Further, the surface roughness Ra of the cleaned thin glass substrate was 0.4 nm.

Then, after the heat treatment was carried out in the same manner as in Example 1, the thin glass substrate in the thin plate glass laminate C1 was peeled off from the support glass substrate having the resin layer.

One portion of the resin layer was adhered to the surface of the thin glass substrate after contact with the resin layer, and the portion corresponding to the resin layer on the supporting glass substrate was damaged. The thin-plate glass substrate to which the resin layer was adhered was irradiated with a plasma using a normal-pressure remote plasma device (manufactured by Sekisui Chemical Co., Ltd.), but the adhered resin could not be removed and remained. The charged potential on the surface of the thin glass substrate which was peeled off after peeling and the resin layer was -10.5 kV. Thereafter, a polarizing film (manufactured by Nitto Denko Corporation, an acrylic adhesive) was adhered to the surface of the thin glass substrate subjected to the plasma irradiation, and peeling occurred.

<Comparative Example 2>

For the side of the thin plate glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) having a length of 720 mm, a width of 600 mm, a thickness of 0.3 mm, and a linear expansion coefficient of 38 × 10 ^-7 /°C, which is in contact with the side of the polyoxyxylene resin, is pure. Wash with water, then clean with UV and clean. Further, on the cleaned surface, a chromium oxide film having a thickness of 50 nm and a thickness of 100 nm were sequentially formed by magnetron sputtering (no heating, film formation pressure: 5 mTorr, power density: 5 W/cm ² ). A metal chromium film is obtained as a thin glass substrate (a thin glass substrate with a metallic chromium film). The water contact angle of the surface of the metal chromium film is 25°. Further, the surface roughness Ra of the metallic chromium film was 2.5 nm.

In the same manner as in the first embodiment, the metal chromium film surface of the thin glass substrate and the polyoxyxene resin layer of the supporting glass substrate were bonded together at room temperature in a vacuum press to obtain a thin glass laminated body B1.

Then, after the heat treatment was carried out in the same manner as in Example 1, the thin glass substrate in the thin plate glass laminate B1 was peeled off from the support glass substrate having the resin layer.

In the same manner as in the case of the comparative example 1, a part of the resin layer was adhered to the surface of the thin glass substrate after contact with the resin layer (on the metal chromium film), and the portion corresponding to the resin layer on the supporting glass substrate was confirmed. damaged.

<Comparative Example 3>

In the same manner as in Example 1, a polyoxynoxy resin layer having a thickness of 20 μm was formed on the first main surface of the supporting glass substrate. Then, except that a thin plate glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) having a length of 720 mm, a width of 600 mm, a thickness of 0.3 mm, and a coefficient of linear expansion of 38 × 10 ^-7 /° C. was used, the same as in Example 1. In the process, a thin plate glass laminate C2 is obtained. Further, the surface of the thin glass substrate which is in contact with the polyoxyxene resin is washed with pure water and cleaned. The water contact angle of the surface of the cleaned sheet glass substrate was 30°. Further, the surface roughness Ra of the cleaned thin glass substrate was 0.4 nm. Further, in this comparative example, unlike Comparative Example 1, the thin glass substrate was not subjected to UV cleaning.

Thereafter, the heat treatment was carried out in the same manner as in Example 1, and then the thin glass substrate in the thin glass laminated body C2 was peeled off from the supporting glass substrate having the resin layer.

In the same manner as in Comparative Example 1, a part of the resin layer was adhered to the surface of the thin glass substrate after contact with the resin layer (on the conductive metal oxide film), and the portion corresponding to the resin layer on the supporting glass substrate Confirmed damage.

The present invention has been described in detail above with reference to the specific embodiments thereof. It is understood that various modifications and changes may be made without departing from the scope and spirit of the invention.

The present application is based on Japanese Patent Application No. 2010-248294 filed on Nov. 5, 2010, the content of

10. . . Laminated body

20. . . Substrate

twenty two. . . Conductive metal oxide film

twenty four. . . Substrate with conductive metal oxide film

30. . . Reinforcing plate

31. . . Support board

32. . . Resin layer

40. . . Panel for display device with support plate

50. . . Component of panel for display device

60. . . Display panel

201. . . First main surface of the substrate

202. . . Second main surface of the substrate

221. . . Surface of conductive metal oxide film

321. . . Adhesive layer

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

Fig. 2 is a schematic cross-sectional view showing an embodiment of a panel for a display device with a support plate according to the present invention.

10. . . Laminated body

20. . . Substrate

twenty two. . . Conductive metal oxide film

twenty four. . . Substrate with conductive metal oxide film

30. . . Reinforcing plate

31. . . Support board

32. . . Resin layer

201. . . First main surface of the substrate

202. . . Second main surface of the substrate

221. . . Surface of conductive metal oxide film

321. . . Adhesive layer

Claims (9)

A laminated body comprising: a support plate; a resin layer; and a substrate with an indium tin oxide (ITO) film attached to the surface of the substrate and having an indium tin oxide (ITO) film; The substrate of the (ITO) film is disposed on the resin layer such that the indium tin oxide (ITO) film is detachably adhered to the resin layer, and the peel strength between the resin layer and the support sheet is higher than the resin layer. Peel strength between the substrate with the indium tin oxide (ITO) film described above. The laminate according to claim 1, wherein the indium tin oxide (ITO) further contains at least one element selected from the group consisting of aluminum, molybdenum, copper, vanadium, niobium, tantalum, boron, and fluorine. The laminate of claim 1, wherein the resin layer is a polyoxynitride resin layer. The laminate according to claim 2, wherein the resin layer is a polyoxymethylene resin layer. The laminate according to any one of claims 1 to 4, wherein the resin layer comprises an addition reaction type hardened material of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene. The laminate according to claim 5, wherein the molar ratio of the hydrogen atom bonded to the ruthenium atom of the above organohydrogenpolyoxyalkylene to the alkenyl group of the above organic alkenyl polyoxyalkylene is 0.5 to 2. A panel for a display device with a support plate, comprising: a laminate according to any one of claims 1 to 6; and a constituent member of a panel for a display device, which is provided in the laminate and oxidized The substrate of the indium tin (ITO) film is on the surface opposite to the surface on which the resin layer is adhered. A panel for a display device which is formed using a panel for a display device with a support plate as claimed in claim 7. A display device comprising a panel for a display device as claimed in claim 8.