JPWO2011111611A1 - Method for removing resin film and method for producing laminate - Google Patents

Abstract

The present invention relates to a resin film removing method for removing a resin film adhered on a glass plate, a heat treatment step for heat treating the resin film adhered on the glass plate, and washing for washing off the resin film after the heat treatment And in the heat treatment step, the surface of the resin film opposite to the glass plate is exposed to 300 to 450 ° C. air, 350 to 600 ° C. inert atmosphere, or 150 to 350 ° C. water vapor. The present invention relates to a method for removing a resin film.

Description

  The present invention relates to a resin film removal method and a laminate manufacturing method.

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

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

  Further, in the above-described method for thinning a substrate by chemical etching, when a fine scratch is present on the substrate surface, a fine recess (etch pit) is formed from the scratch by the etching process, resulting in an optical defect. There was a case.

  Recently, in order to address the above problems, a method has been proposed in which a laminate in which a substrate and a reinforcing plate are laminated is prepared, a device member is formed on the substrate of the laminated body, and then the reinforcing plate is peeled from the substrate. (For example, refer to Patent Document 1). The reinforcing 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 peeled off. The reinforcing plate can be reused as a laminate after being peeled from the substrate and laminated with a new substrate.

International Publication No. 07/018028 Pamphlet

  However, the resin layer of the reinforcing plate gradually deteriorates according to the number of times the reinforcing plate is used. The deterioration of the resin layer is caused by heat treatment or liquid treatment in the device manufacturing process, peeling operation between the reinforcing plate and the substrate, or the like. When the resin layer has deteriorated to some extent, a part of the resin layer may adhere to the substrate on the product side when the reinforcing plate and the substrate are peeled off. Therefore, when the resin layer of the reinforcing plate has deteriorated to some extent, it is desirable to laminate the reinforcing plate and the substrate after regenerating the resin layer.

  By the way, in order to regenerate the resin layer (resin film) adhered on the glass plate, it is necessary to first remove the resin film. As a method for removing the resin film, it is possible to use a method of scraping off with a blade or a method of removing with a blast particle (for example, calcium carbonate powder). There is a possibility that a fine crack is generated on the surface and the glass plate is damaged by the influence of the fine crack when the glass plate is reused.

  Therefore, as a method of removing the resin film without damaging the glass plate, a method of heat-treating the resin film in the atmosphere can be considered. In this case, an oxide such as silicon oxide is generated by the oxidation of the resin film. There is. Since the produced oxide adheres to the glass plate, it is difficult to remove.

  In addition, as a method of removing the resin film without damaging the glass plate, a method using a liquid such as an alcohol solution or an alkali solution can be considered. It takes several tens of hours.

  This invention is made | formed in view of the said subject, Comprising: The removal method of the resin film which can remove a resin film efficiently without damaging a glass plate, and the manufacturing method of a laminated body are provided. With the goal.

In order to solve the above object, the method for removing a resin film of the present invention comprises:
A resin film removal method for removing a resin film adhered on a glass plate,
A heat treatment step of heat treating the resin film adhered on the glass plate;
A washing step of washing off the resin film after the heat treatment,
In the heat treatment step, the surface of the resin film opposite to the glass plate is exposed to air at 300 to 450 ° C., an inert atmosphere at 350 to 600 ° C., or water vapor at 150 to 350 ° C.

  In the method for removing a resin film of the present invention, it is preferable that in the heat treatment step, the resin film attached on the glass plate is heated and then cooled.

  In the resin film removing method of the present invention, it is preferable that the resin film is dissolved or swollen using a liquid in the cleaning step.

  In the resin film removal method of the present invention, the solubility parameter of the liquid is preferably 7 to 15.

  In the resin film removal method of the present invention, it is preferable that the resin film is removed using an abrasive in the cleaning step.

  In the method for removing a resin film of the present invention, it is preferable to perform cleaning by ultrasonic cleaning or brush cleaning in the cleaning step.

In addition, the method for producing a laminate of the present invention includes
In a manufacturing method of a laminate including a removing step of removing a resin film adhered on a glass plate, and a laminating step of interposing a resin layer between the glass plate from which the resin film has been removed and a substrate,
The removal step includes
A heat treatment step of heat treating the resin film adhered on the glass plate;
A washing step of washing off the resin film after the heat treatment,
In the heat treatment step, the surface of the resin film opposite to the glass plate is exposed to air at 300 to 450 ° C., an inert atmosphere at 350 to 600 ° C., or water vapor at 150 to 350 ° C.

  In the manufacturing method of the laminated body of this invention, it is preferable to cool, after heating the said resin film adhering on the said glass plate in the said heat processing process.

  In the manufacturing method of the laminated body of this invention, it is preferable to melt | dissolve or swell the said resin film using a liquid in the said washing | cleaning process.

  In the manufacturing method of the laminated body of this invention, it is preferable that the solubility parameter of the said liquid is 7-15.

  In the manufacturing method of the laminated body of this invention, it is preferable to remove the said resin film using an abrasive | polishing agent in the said washing | cleaning process.

  In the manufacturing method of the laminated body of this invention, it is preferable to wash | clean by ultrasonic cleaning or brush cleaning in the said washing | cleaning process.

  In the manufacturing method of the laminated body of this invention, it is preferable to adhere | attach the said resin layer on the said board | substrate so that peeling is possible while fixing the said resin layer to the said glass plate in the said lamination process.

  ADVANTAGE OF THE INVENTION According to this invention, the removal method of the resin film which can remove a resin film efficiently without damaging a glass plate, and the manufacturing method of a laminated body can be provided.

FIG. 1 is a process diagram of a method for manufacturing a laminate in one embodiment of the present invention. FIG. 2 is a partial side view of the laminate obtained by the laminate production method of FIG. FIG. 3 is a process diagram of a resin film removing method according to an embodiment of the present invention.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and the following embodiments are not deviated from the scope of the present invention. Various modifications and substitutions can be made.

  FIG. 1 is a process diagram of a method for manufacturing a laminate in one embodiment of the present invention. As shown in FIG. 1, the manufacturing method of a laminated body has a removal process (step S11) which removes the resin film adhering on a glass plate, and a resin layer is interposed between the glass plate and board | substrate which removed the resin film. And laminating process (step S12).

  FIG. 2 is a partial side view of the laminate obtained by the laminate production method of FIG. As shown in FIG. 2, the laminate 10 has a resin layer 22 interposed between a glass plate 21 and a substrate 30. The resin layer 22 is detachably adhered to the first main surface 301 of the substrate 30 and is fixed on the glass plate 21. The glass plate 21 and the resin layer 22 function as the reinforcing plate 20 that reinforces the substrate 30 in the process of manufacturing a device (electronic device) such as a liquid crystal panel.

  This laminated body 10 is used until the middle of the device manufacturing process. That is, the laminate 10 is used until a device member such as a thin film transistor is formed on the substrate 30. Thereafter, the reinforcing plate 20 is peeled from the substrate 30 and does not become a member constituting the device. The reinforcing plate 20 peeled from the substrate 30 is laminated with a new substrate 30 and can be reused as a new laminate 10. Hereinafter, each configuration will be described in detail.

  In addition, although the laminated body 10 of this embodiment was used until a device member such as a thin film transistor was formed on the substrate 30, it may be used after the device member is formed. For example, when manufacturing a liquid crystal panel, first, a TFT substrate on which a thin film transistor (TFT) is formed and a CF substrate on which a color filter (CF) is formed are stacked via a liquid crystal material. Next, after thinning the TFT substrate (or CF substrate) by chemical etching, the reinforcing plate 20 is laminated on the TFT substrate (or CF substrate). Thereby, the strength of the thinned TFT substrate (or CF substrate) can be increased. The laminate is used halfway through the manufacturing process of the liquid crystal panel, and then the reinforcing plate 20 is peeled off from the TFT substrate (or CF substrate).

  First, the substrate 30 will be described.

  The substrate 30 forms a device by forming a device member on the second main surface 302. Here, the device member refers to a member constituting at least a part of the device. Specific examples include a thin film transistor (TFT) and a color filter (CF). Examples of the device include a solar cell (PV), a liquid crystal panel (LCD), and an organic EL panel (OLED).

  The type of the substrate 30 may be a general one, for example, a silicon wafer, a glass substrate, a resin substrate, or a metal substrate such as a SUS substrate or a copper substrate. Among these, a glass substrate is preferable. This is because the glass substrate is excellent in chemical resistance and moisture permeability resistance and has a low heat shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102-1995 is used.

  If the linear expansion coefficient of the substrate 30 is large, the device manufacturing process often involves heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on the substrate 30, if the substrate 30 on which the TFT is formed is cooled under heating, the TFT may be excessively misaligned due to thermal contraction of the substrate 30.

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

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

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

  The thickness of the glass substrate is not particularly limited, but is usually less than 0.8 mm, preferably 0.3 mm or less, more preferably 0.15 mm or less, from the viewpoint of thinning and / or weight reduction of the glass substrate. It is. In the case of 0.8 mm or more, the demand for reducing the thickness and / or weight of the glass substrate cannot be satisfied. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate. In the case of 0.15 mm or less, the glass substrate can be wound into a roll. Further, the thickness of the glass substrate is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate and easy handling of the glass substrate.

  The kind of resin of the resin substrate is not particularly limited. Specifically, polyethylene terephthalate resin, polycarbonate resin, polyimide resin, fluorine resin, polyamide resin, polyaramid resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, polyethylene naphthalate resin, polyacrylic resin, various types Examples thereof include liquid crystal polymer resins, cycloolefin resins, and polysilicon resins. 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 substrate 30 may be composed of two or more layers. In this case, the material for forming each layer may be the same material or different materials. In this case, the “thickness of the substrate 30” means the total thickness of all the layers.

  Next, the glass plate 21 will be described.

  The glass plate 21 cooperates with the resin layer 22 to support and reinforce the substrate 30 and prevent the substrate 30 from being deformed, scratched or damaged in the device manufacturing process. Further, when the substrate 30 having a thickness smaller than that of the conventional substrate is used, the stacked body 10 having the same thickness as that of the substrate having the conventional thickness is used. One of the purposes of using the glass plate 21 is to make it possible to use manufacturing technology and manufacturing equipment suitable for the substrate.

  The glass plate 21 may be thicker than the substrate 30 or thinner. Preferably, the thickness of the glass plate 21 is selected based on the thickness of the substrate 30, the thickness of the resin layer 22, and the thickness of the laminated body 10. For example, when the current device manufacturing process is designed to process a substrate having a thickness of 0.5 mm and the sum of the thickness of the substrate 30 and the thickness of the resin layer 22 is 0.1 mm, glass The thickness of the plate 21 is 0.4 mm. The thickness of the glass plate 21 is preferably 0.08 mm or more because it is easy to handle and difficult to break.

  The glass of the glass plate 21 may be a common one, for example, the above-described alkali-free glass. When the device manufacturing process involves heat treatment, the glass plate 21 is preferably formed of a material having a small difference in linear expansion coefficient from the substrate 30, and more preferably formed of the same material as the substrate 30.

The difference in average linear expansion coefficient between the substrate 30 and the glass plate 21 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 lower, more preferably 200 × 10 ⁻⁷ / ° C. or lower. If the difference is too large, the laminate 10 may be warped severely or the substrate 30 and the glass plate 21 may be peeled off during heating and cooling in the device manufacturing process. When the material of the substrate 30 and the material of the glass plate 21 are the same, it is possible to suppress the occurrence of such a problem.

  Next, the resin layer 22 will be described.

  The resin layer 22 is fixed on the glass plate 21 and is in close contact with the first main surface 301 of the substrate 30 in a peelable manner. The resin layer 22 prevents displacement of the substrate 30 until the peeling operation is performed, and also easily peels from the substrate 30 by the peeling operation, and prevents the substrate 30 and the like from being damaged by the peeling operation.

  The size of the resin layer 22 is not particularly limited. The size of the resin layer 22 may be larger or smaller than the substrate 30 and the glass plate 21.

  The surface 221 of the resin layer 22 is in close contact with the first main surface 301 of the substrate 30 by a force caused by van der Waals force between solid molecules, not an adhesive force that a general adhesive has. Is preferred. It is because it can peel easily. In this invention, the property which can peel this resin layer surface easily is called peelability.

  On the other hand, the bonding force of the resin layer 22 to the surface of the glass plate 21 is relatively higher than the bonding force of the resin layer 22 to the first main surface 301 of the substrate 30. In the present invention, the bonding of the resin layer surface to the substrate surface is referred to as adhesion, and the bonding to the glass plate surface is referred to as fixation.

  The thickness of the resin layer 22 is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 30 μm, and still more preferably 7 to 20 μm. This is because when the thickness of the resin layer 22 is within such a range, the resin layer 22 and the substrate 30 are sufficiently adhered to each other. In addition, even if air bubbles or foreign matters are interposed between the resin layer 22 and the substrate 30, it is possible to suppress the occurrence of distortion defects of the substrate 30. In addition, if the thickness of the resin layer 22 is too thick, it takes more time and materials to form, which is not economical.

  The resin layer 22 may be composed of two or more layers. In this case, “the thickness of the resin layer 22” means the total thickness of all the layers.

  Moreover, when the resin layer 22 consists of two or more layers, the kind of resin which forms each layer may differ.

  The resin layer 22 is preferably made of a material having a glass transition point lower than room temperature (about 25 ° C.) or having no glass transition point. This is because it becomes a non-adhesive resin layer and can be more easily peeled off from the substrate 30, and at the same time, the adhesion to the substrate 30 is sufficient.

  Moreover, since the resin layer 22 is often heat-treated in the device manufacturing process, the resin layer 22 preferably has heat resistance.

  For example, if the elastic modulus of the resin layer 22 is too high, exceeding 1000 MPa, the adhesion with the substrate 30 tends to be low. On the other hand, if the elastic modulus of the resin layer 22 is too low as less than 1 MPa, the peelability is lowered.

  The kind of resin that forms the resin layer 22 is not particularly limited. For example, acrylic resin, polyolefin resin, polyurethane resin, and silicone resin can be used. Several types of resins can be mixed and used. Of these, silicone resins are preferred. This is because the silicone resin is excellent in heat resistance and peelability. Moreover, it is because it is easy to fix to the glass plate 21 by the condensation reaction with the silanol group which exists on the surface of the glass plate 21. In the state where the silicone resin layer is interposed between the glass plate 21 and the substrate 30, it is also preferable that the peelability does not substantially deteriorate even if the silicone resin layer is processed in the atmosphere at about 200 ° C. for about 1 hour.

  The resin layer 22 is preferably made of a silicone resin (cured product) used for release paper among silicone resins. A resin layer 22 formed by curing a curable resin composition to be a silicone resin for release paper on the surface of the glass plate 21 is preferable because it has excellent peelability. In addition, since the flexibility is high, even if foreign matter such as bubbles or dust is mixed between the resin layer 22 and the substrate 30, the occurrence of the distortion defect of the substrate 30 can be suppressed.

  The curable silicone that becomes the silicone resin for release paper is classified into a condensation reaction type silicone, an addition reaction type silicone, an ultraviolet curable type silicone, and an electron beam curable type silicone depending on its curing mechanism. Can do. Among these, addition reaction type silicone is preferable. This is because the curing reaction is easy and the degree of peelability is good when the resin layer 22 is formed, and the heat resistance is also high.

  The addition-reactive silicone is a curable composition that contains a main agent and a crosslinking agent and cures in the presence of a catalyst such as a platinum-based catalyst. Curing of the addition reaction type silicone is accelerated by heat treatment. The main component of the addition reaction type silicone is composed of a linear organopolysiloxane having an alkenyl group (such as a vinyl group) bonded to a silicon atom (that is, an organoalkenyl polysiloxane). The crosslinking agent of the addition reaction type silicone is composed of a linear organopolysiloxane having hydrogen atoms (hydrosilyl groups) bonded to silicon atoms (that is, organohydrogenpolysiloxane).

  Moreover, the curable silicone used as the silicone resin for the release paper is classified into a solvent type, an emulsion type and a solventless type, and any type can be used. Among these, a solventless type is preferable. This is because productivity, safety, and environmental characteristics are excellent. In addition, it does not contain a solvent that causes foaming at the time of curing when forming the resin layer 22, that is, at the time of heat curing, ultraviolet curing, or electron beam curing, so that bubbles are unlikely to remain in the resin layer 22.

  Moreover, as curable silicone used as the silicone resin for release paper, specifically, KNS-320A, KS-847 (both manufactured by Shin-Etsu Silicone), TPR6700 (manufactured by GE Toshiba Silicone Co., Ltd.) are commercially available as product names or model numbers. ), A combination of vinyl silicone “8500” (Arakawa Chemical Industries) and methyl hydrogen polysiloxane “12031” (Arakawa Chemical Industries), vinyl silicone “11364” (Arakawa Chemical Industries) and methyl hydrogen Combinations with polysiloxane “12031” (Arakawa Chemical Industries), vinyl silicone “11365” (Arakawa Chemical Industries) and methylhydrogen polysiloxane “12031” (Arakawa Chemical Industries), etc. It is done.

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

  Moreover, it is preferable that the silicone resin forming the resin layer 22 has a property that components in the silicone resin layer are difficult to migrate to the substrate 30, that is, low silicone migration.

  Next, the removal process (step S11) of FIG. 1 will be described.

  In the removing step (step S11) of FIG. 1, the resin film attached on the glass plate 21 is removed. The removal process of the present embodiment is performed in a process in which the reinforcing plate 20 peeled from the substrate 30 in the device manufacturing process is stacked with a new substrate 30 and reused as a new stacked body 10. More specifically, the removing step of the present embodiment is performed as a step of removing the resin layer 22 fixed on the glass plate 21 in order to regenerate the resin layer 22 of the reinforcing plate 20.

  FIG. 3 is a process diagram of the method for removing a resin film in one embodiment of the present invention, and is a detailed view of the removal process of FIG. As shown in FIG. 3, the removing step includes a heat treatment step (step S31) for heat-treating the resin layer (resin film) 22 adhered on the glass plate 21, and a washing step for washing off the resin layer (resin film) 22 after the heat treatment. (Step S32).

  In the heat treatment step (step S31) of FIG. 3, the surface 221 opposite to the glass plate 21 of the resin layer 22 is formed on the atmosphere of 300 to 450 ° C., the inert atmosphere of 350 to 600 ° C., or the water vapor of 150 to 350 ° C. Expose to. In the resin layer 22, the bonds of atoms and molecules are broken by a decomposition reaction in a high-temperature ambient atmosphere. When the decomposition reaction proceeds sufficiently, fine cracks and fine holes are formed in the resin layer 22.

  When exposed to air at 300 ° C. to 450 ° C., the decomposition reaction of the resin layer 22 proceeds sufficiently in 1 to 120 minutes. Preferably, when exposed to air at 350 ° C. to 450 ° C., the decomposition reaction of the resin layer 22 proceeds sufficiently in 1 to 30 minutes. When the atmospheric temperature is less than 300 ° C., the decomposition reaction of the resin layer 22 is difficult to proceed. Further, when the atmospheric temperature exceeds 450 ° C., an oxide such as silicon oxide is generated by the oxidation of the resin layer 22. Since the generated oxide adheres to the glass plate 21, it is difficult to remove.

  When exposed to an inert atmosphere at 350 ° C. to 600 ° C., the decomposition reaction of the resin layer 22 proceeds sufficiently in 1 to 120 minutes. Preferably, when exposed to an inert atmosphere at 400 ° C. to 600 ° C., the decomposition reaction of the resin layer 22 proceeds sufficiently in 1 to 30 minutes. When the temperature of the inert atmosphere is less than 350 ° C., the decomposition reaction of the resin layer 22 is difficult to proceed. On the other hand, when the temperature of the inert atmosphere exceeds 600 ° C., the glass plate 21 is thermally deformed or thermally deteriorated.

  Here, the inert atmosphere refers to an atmosphere having an oxygen volume concentration of 5000 ppm or less, and includes a nitrogen atmosphere and an argon atmosphere. In an inert atmosphere, generation of oxide can be suppressed. Therefore, heat treatment can be performed at a temperature exceeding 450 ° C., and the heat treatment time required for the decomposition reaction can be shortened. For example, when heated at 600 ° C., the decomposition reaction of the resin layer 22 proceeds sufficiently in 1 to 3 minutes.

  When exposed to water vapor at 150 ° C. to 350 ° C., the decomposition reaction of the resin layer 22 proceeds sufficiently in 1 to 5 hours. This is due to the hydrolyzability of the resin, and it is desirable to decompose under high pressure, particularly at low temperatures. On the other hand, when the temperature of the water vapor is less than 150 ° C., the decomposition reaction of the resin layer 22 is difficult to proceed. Further, when the temperature of the water vapor exceeds 350 ° C., thermal decomposition becomes dominant as compared with hydrolysis, and therefore, exposure to the atmosphere is advantageous in terms of cost.

  In the heat treatment step, the inside of the heating furnace for heating the resin layer 22 may be a pressurized atmosphere. Here, the pressurized atmosphere means an atmosphere whose atmospheric pressure is higher than atmospheric pressure. Thereby, the decomposition reaction of the resin layer 22 can be promoted.

  When the inside of the heating furnace is not a pressurized atmosphere, the heating furnace may be a batch furnace or a continuous furnace in which a heating zone and a cooling zone are continuously connected in a tunnel shape.

  In the heat treatment step, after heating the resin layer 22 at a predetermined temperature, the resin layer 22 may be cooled from the predetermined temperature in order to promote the formation of cracks. The average cooling rate from the predetermined temperature to 50 ° C. is appropriately set according to the size of the glass plate 21 and the like. For example, when the thickness of the glass plate 21 is 0.4 mm, the short side length is 600 mm or more, and the long side length is 800 mm or less, the average cooling rate from a predetermined temperature to 50 ° C. is 5 to 5 ° C. It is preferably 15 ° C./second. If it exceeds 15 ° C./second, the glass plate 21 tends to break. On the other hand, if it is less than 5 ° C./second, the cooling time becomes long and the productivity is poor.

  In the cleaning step (step S32) of FIG. 3, the resin layer 22 after the heat treatment is washed away. Since the resin layer 22 after the heat treatment has broken bonds of atoms and molecules on the surface 221 opposite to the glass plate 21, the resin layer 22 can be washed off efficiently.

  As the cleaning method, for example, a method of dissolving or swelling the resin layer 22 using a liquid, a method of removing the resin layer 22 using an abrasive, a method of cleaning by ultrasonic cleaning or brush cleaning, and air to the resin layer 22 are used. There are a method of spraying and a chemical cleaning method using a liquid such as an acid solution or an alkali solution. These washing methods are used alone or in combination. The combination is not particularly limited, but for example, a method of washing with a brush while dissolving or swelling the resin layer 22 using a liquid, a method of washing with a brush while shaving the resin layer 22 using a dispersion in which an abrasive is dispersed and so on.

The liquid preferably has a solubility parameter (SP value) of 7 to 15 (unit: cal ^1/2 cm ^−3/2 ). When the SP value is outside the range of 7 to 15, since the affinity between the liquid and the resin layer 22 is low, the liquid is difficult to get wet with the resin layer 22. Specific examples of the liquid having an SP value of 7 to 15 include isoparaffin, xylene, hexane, acetone, dimethylformamide, propanol, ethanol, and methanol. These liquids are used alone or in combination. From the viewpoint of environmental burden, an alcohol solution containing ethanol as a main component is desirable. Furthermore, in view of measures against flammability due to influence on the human body or static electricity, an isoparaffin solution having a flash point of 21 ° C. or higher, more preferably 70 ° C. or higher is desirable.

  The polishing agent only needs to have a hardness higher than that of the resin layer 22 and lower than that of the glass plate 21, and preferably has a hardness close to that of the glass plate 21 in order to shorten the cleaning time. The Mohs hardness of the glass plate 21 is usually 5.5-6. The Mohs hardness of the abrasive is preferably 3-5. If the Mohs hardness is less than 3, the resin layer 22 may not be removed. When the Mohs hardness exceeds 5, fine cracks may be generated on the surface of the glass plate 21. Specific examples of abrasives include cerium oxide (Mohs hardness 5), calcium carbonate (Mohs hardness 4), hard plastic (Mohs hardness 4-5), polyplus (Mohs hardness 4), and peach seed powder (Mohs hardness 4). Etc. These abrasives are used alone or in combination. These abrasives preferably have a number average particle diameter of 1 to 10 μm.

  The brush hair used for brush cleaning is made of a material softer than the glass plate 21 so as not to damage the glass plate 21.

  The resin film removal method of the present embodiment is applied to remove the resin layer 22 fixed on the glass plate 21 in order to regenerate the resin layer 22 of the reinforcing plate 20, but the present invention is It is not limited to this. For example, since the glass plate 21 of the reinforcing plate 20 is reused as the substrate 30, it may be applied to remove the resin layer 22 fixed on the glass plate 21. Thus, the application method of the resin film of the present invention is not particularly limited as long as it is applied to remove the resin film adhered on the glass.

  Next, the lamination process (step S12) in FIG. 1 will be described.

  In the stacking step (step S12) in FIG. 1, the resin layer 22 is interposed between the glass plate 21 from which the resin film has been removed and the substrate 30. Specifically, for example, the resin layer 22 is fixed to the glass plate 21 and the resin layer 22 is detachably adhered to the substrate 30. The resin layer 22 may be formed on the surface on which the resin film is removed, or may be formed on the opposite surface.

  A method for fixing the resin layer 22 on the glass plate 21 is not particularly limited, and for example, a method of fixing a film-like resin on the surface of the glass plate 21 may be mentioned. Specifically, in order to give the surface of the glass plate 21 a high fixing force (high peel strength) to the surface of the film, the surface of the glass plate 21 is subjected to surface modification treatment (priming treatment), and the glass plate 21 The method of fixing on top is mentioned. For example, chemical methods (primer treatment) that improve the fixing force chemically such as silane coupling agents, physical methods that increase surface active groups such as flame (flame) treatment, surface treatments such as sandblast treatment Examples thereof include a mechanical processing method for increasing the catch by increasing the roughness.

  Moreover, the method of coating the curable resin composition used as the resin layer 22 on the glass plate 21, for example is mentioned. Examples of the coating method include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. From such a method, it can select suitably according to the kind of resin composition.

In the case of coating a curable resin composition comprising a resin layer 22 on the glass plate 21, more that its coating amount is preferably from 1 to 100 g / ^{m 2,} it is 5 to 20 g / ^{m 2} preferable.

  For example, when the resin layer 22 is formed from an addition reaction type silicone curable resin composition, a curable resin composition comprising a mixture of an organoalkenylpolysiloxane, an organohydrogenpolysiloxane, and a catalyst is applied to the spray coating method described above. The coating is performed on the glass plate 21 by a known method, followed by heat curing. The heat curing conditions vary depending on the blending amount of the catalyst. For example, when 2 parts by mass of a platinum-based catalyst is blended with respect to 100 parts by mass of the total amount of the organoalkenylpolysiloxane and the organohydrogenpolysiloxane, The reaction is carried out at 50 ° C to 250 ° C, preferably 100 ° C to 200 ° C. In this case, the reaction time is 5 to 60 minutes, preferably 10 to 30 minutes. In order to obtain a silicone resin layer having low silicone migration, it is preferable to proceed the curing reaction as much as possible so that an unreacted silicone component does not remain in the silicone resin layer. It is preferable that the reaction temperature and the reaction time are as described above because no unreacted silicone component remains in the silicone resin layer. If the reaction time is too long or the reaction temperature is too high, the oxidative decomposition of the silicone resin occurs at the same time, and a low molecular weight silicone component is produced, which may increase the silicone transferability. It is preferable to allow the curing reaction to proceed as much as possible so that an unreacted silicone component does not remain in the silicone resin layer in order to improve the peelability after the heat treatment.

  For example, when the resin layer 22 is manufactured using a curable resin composition that becomes a silicone resin for release paper, the curable resin composition coated on the glass plate 21 is cured by heating to form a silicone resin layer. To do. By thermally curing the curable resin composition, the silicone resin is chemically bonded to the glass plate 21 during the curing reaction. Further, the silicone resin layer is bonded to the glass plate 21 by the anchor effect. By these actions, the silicone resin layer is firmly fixed to the glass plate 21.

  The method of sticking the resin layer 22 on the substrate 30 in a peelable manner may be a known method. For example, after the substrate 30 is stacked on the peelable surface 221 of the resin layer 22 under a normal pressure environment, the resin layer 22 and the substrate 30 may be pressure-bonded using a roll or a press. It is preferable because the resin layer 22 and the substrate 30 are more closely adhered by pressure bonding with a roll or a press. Further, it is preferable because bubbles mixed between the resin layer 22 and the substrate 30 are relatively easily removed by pressure bonding with a roll or a press.

  When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because suppression of bubble mixing and securing of good adhesion are more preferably performed. By pressure bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are less likely to cause a distortion defect of the substrate 30.

  When the resin layer 22 is detachably adhered to the substrate 30, it is preferable that the surfaces of the resin layer 22 and the substrate 30 on the side in contact with each other are sufficiently washed and laminated in an environment with a high degree of cleanliness. Even if foreign matter is mixed between the resin layer 22 and the substrate 30, the resin layer 22 is deformed and thus does not affect the flatness of the surface of the substrate 30, but the higher the cleanness, the better the flatness. Therefore, it is preferable.

  In addition, there is no restriction | limiting in the order of the process of fixing the resin layer 22 on the glass plate 21, and the process of closely_contact | adhering the resin layer 22 on the board | substrate 30, and may be substantially simultaneous, for example.

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

[Example 1]
(Production of reinforcing plate)
A glass plate (Asahi Glass Co., Ltd., AN100, alkali-free glass) having a length of 720 mm, a width of 600 mm, and a thickness of 0.4 mm obtained by a float method was used as the glass plate of the reinforcing plate. The average linear expansion coefficient of this glass plate was 38 × 10 ⁻⁷ / ° C.

This glass plate was cleaned with pure water and UV to clean the surface of the glass plate. Thereafter, on the surface of the glass plate, a mixture of 100 parts by mass of solvent-free addition-reactive silicone (manufactured by Shin-Etsu Silicone, KNS-320A) and 5 parts by mass of a platinum-based catalyst (manufactured by Shin-Etsu Silicone, CAT-PL-56). Coating was performed by a spin coater (coating amount 20 g / m ² ).

  The above solvent-free addition reaction type silicone is a linear organoalkenylpolysiloxane (main agent) having a vinyl group and a methyl group bonded to a silicon atom, and a linear chain having a hydrogen atom and a methyl group bonded to a silicon atom. It contains an organohydrogenpolysiloxane (crosslinking agent).

  The mixture coated on the glass plate was heat-cured at 180 ° C. for 10 minutes in the air, and a resin layer having a length of 705 mm × width of 595 mm × thickness of 20 μm was formed and fixed at the center on the glass plate.

  In this way, a reinforcing plate was produced.

(Production of laminate)
As the glass substrate, a glass plate (Asahi Glass Co., Ltd., AN100, alkali-free glass) having a length of 720 mm, a width of 600 mm, and a thickness of 0.4 mm obtained by a float process was used. The average linear expansion coefficient of this glass substrate was 38 × 10 ⁻⁷ / ° C.

  The glass substrate was cleaned with pure water and UV to clean the surface of the glass substrate. Thereafter, the glass substrate and the reinforcing plate were brought into close contact with each other at room temperature in a vacuum using a vacuum press apparatus, and the laminate shown in FIG. 2 was obtained.

(Peeling of glass substrate and reinforcing plate)
The laminate was heat-treated at 250 ° C. for 2 hours in the atmosphere, then cooled to room temperature, and a peeling operation between the glass substrate and the reinforcing plate was performed. Specifically, after a 0.4 mm thick knife is inserted between the glass substrate and the reinforcing plate, the reinforcing plate is bent and deformed sequentially from the insertion position of the knife while supporting the glass substrate flat. It was.

  When the reinforcing plate was observed with a microscope after the peeling operation, scratches due to the insertion of the knife were observed on the peelable surface of the resin layer. Moreover, when the peelable surface of the resin layer was analyzed by infrared absorption, a slight deterioration due to the heat treatment was observed at the outer edge of the peelable surface. In the central part of the peelable surface, no deterioration due to heat treatment was observed.

(Removal of resin layer (resin film))
After the peeling operation, the reinforcing plate was heated in the atmosphere at 370 ° C. for 10 minutes to expose the surface of the resin layer (resin film) opposite to the glass plate to the atmosphere at 370 ° C. for 10 minutes. Thereafter, the reinforcing plate was cooled from 370 ° C. to 50 ° C. at an average cooling rate of 5 ° C./second, and then subjected to ultrasonic cleaning for 5 minutes while being immersed in an alkali solution at 50 ° C.

  The alkaline solution is obtained by diluting a resist stripping solution (manufactured by Parker Corporation, PK-CRD620) to 20% by mass with ion-exchanged water. This resist stripping solution contains 20% by mass of potassium hydroxide as a main component.

  Subsequently, brush washing with the alkaline solution was performed for 1 minute to wash off the resin layer (resin film), and then rinsed with pure water, and water was removed by air blowing.

  When the surface of the glass plate after washing was observed with a microscope, no foreign substances such as oxides and resins and scratches were found.

[Example 2]
In Example 2, as a curable resin composition to be a resin layer, linear polyorganosiloxane having vinyl groups at both ends (Arakawa Chemical Industries, Ltd., 8500) and methyl having a hydrosilyl group in the molecule are used. A reinforcing plate was produced in the same manner as in Example 1 except that a mixture of hydrogenpolysiloxane (Arakawa Chemical Industries, Ltd., 12031) and a platinum catalyst (Arakawa Chemical Industries, Ltd., CAT12070) was used. did.

  Here, the mixing ratio of the linear polyorganosiloxane and the methyl hydrogen polysiloxane was adjusted so that the molar ratio of the vinyl group and the hydrosilyl group was 1: 1. The platinum-based catalyst was 5 parts by mass with respect to a total of 100 parts by mass of the linear polyorganosiloxane and methyl hydrogen polysiloxane.

  Next, in the same manner as in Example 1, the laminated body shown in FIG. 2 was produced, and the laminated body was heat-treated, and then the glass substrate and the reinforcing plate were peeled off.

  After the peeling operation, the reinforcing plate was heated in the atmosphere at 370 ° C. for 5 minutes to expose the surface of the resin layer (resin film) opposite to the glass plate to the atmosphere at 370 ° C. for 5 minutes. Thereafter, the reinforcing plate was cooled from 370 ° C. to 50 ° C. at an average cooling rate of 15 ° C./second, and cooled to room temperature. Subsequently, brush washing with an alcohol solution (Nippon Alcohol Sales Co., Neocor R7, solubility parameter 11.5 to 14.7, flash point 11 to 24 ° C.) is performed for 1 minute, and the resin layer (resin film) is washed off. After that, the solvent was removed by air blowing.

  The alcohol solution contains 86.6% by mass of ethanol, 9.5% by mass of normal propyl alcohol (NPA), 2.6% by mass of methanol, and 1.3% by mass of isopropyl alcohol (IPA).

  When the surface of the glass plate after washing was observed with a microscope, no foreign substances such as oxides and resins and scratches were found.

[Example 3]
In Example 3, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, the reinforcing plate was heated in the atmosphere at 370 ° C. for 5 minutes to expose the surface of the resin layer (resin film) opposite to the glass plate to the atmosphere at 370 ° C. for 5 minutes. Thereafter, the reinforcing plate was cooled from 370 ° C. to 50 ° C. at an average cooling rate of 15 ° C./second, and cooled to room temperature. Subsequently, brush washing with an isoparaffin solution (Idemitsu Kosan Co., Ltd., IP Solvent 2028, solubility parameter 7 and flash point 86 ° C.) is performed for 1 minute to wash off the resin layer (resin film), and then heated to 200 ° C. The solvent was removed by blowing air.

  The isoparaffin solution contains 80.5% by mass of isohexadecane, 3.0% by mass of isotridecane, and 16.5% by mass of isododecane.

  When the surface of the glass plate after washing was observed with a microscope, no foreign substances such as oxides and resins and scratches were observed.

[Example 4]
In Example 4, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, the reinforcing plate was heated in the atmosphere at 350 ° C. for 30 minutes, so that the surface of the resin layer (resin film) opposite to the glass plate was exposed to the atmosphere at 350 ° C. for 30 minutes. Subsequently, the reinforcing plate was cooled from 350 ° C. to 50 ° C. at an average cooling rate of 5 ° C./second, and cooled to room temperature. Subsequently, brush cleaning with a dispersion liquid in which an abrasive was dispersed was performed for 1 minute to wash off the resin layer (resin film), and then rinsed with pure water, and water was removed by air blowing.

  The dispersion is obtained by dispersing fine particles of cerium oxide (number average particle diameter of 3 μm) in water. The content of fine particles of cerium oxide in the dispersion was 10% by mass.

  When the surface of the glass plate after washing was observed with a microscope, no foreign substances such as oxides and resins and scratches were found.

[Example 5]
In Example 5, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, the reinforcing plate is heated at 600 ° C. for 2 minutes in a nitrogen atmosphere having an oxygen volume concentration of 1000 ppm, so that the surface opposite to the glass plate of the resin layer (resin film) is brought into a nitrogen atmosphere at 600 ° C. After exposure for a minute, the resin layer (resin film) was washed off in the same manner as in Example 3, and then the solvent was removed by air blowing.

  When the surface of the glass plate after washing was observed with a microscope, no foreign substances such as oxides and resins and scratches were found.

[Example 6]
In Example 6, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, the reinforcing plate is heated at 400 ° C. for 30 minutes in a nitrogen atmosphere having an oxygen volume concentration of 1000 ppm, so that the surface of the resin layer (resin film) opposite to the glass plate is brought to a nitrogen atmosphere of 400 ° C. After exposure for a minute, the resin layer (resin film) was washed off in the same manner as in Example 2, and then the solvent was removed by air blowing.

  When the surface of the glass plate after washing was observed with a microscope, no foreign substances such as oxides and resins and scratches were found.

[Example 7]
In Example 7, in the same manner as in Example 2, the laminate shown in FIG.

After the peeling operation, the reinforcing plate is placed in a 20 liter pressurized container together with 100 g of water, and heated at 250 ° C. for 1 hour, so that the surface of the resin layer (resin film) opposite to the glass plate is turned into high-temperature and high-pressure steam. After the exposure, the resin layer (resin film) was washed off in the same manner as in Example 2, and then the solvent was removed by air blowing.
The maximum pressure in the pressurized container when heat-treated at 250 ° C. for 1 hour was 0.65 MPa.

  When the surface of the glass plate after washing was observed with a microscope, no foreign substances such as oxides and resins and scratches were found.

[Example 8]
In Example 8, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

After the peeling operation, the reinforcing plate is placed in a 20 liter pressurized container together with 100 g of water and heated at 150 ° C. for 5 hours to expose the surface of the resin layer opposite to the glass plate to high temperature and high pressure steam, In the same manner as in Example 2, after washing off the resin layer, the solvent was removed by air blowing.
The maximum pressure in the pressurized container when heat-treated at 150 ° C. for 5 hours was 0.3 MPa.

  When the surface of the glass plate after washing was observed with a microscope, no foreign substances such as oxides and resins and scratches were found.

[Comparative Example 1]
In Comparative Example 1, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, without performing heat treatment, brush cleaning with an alcohol solution was performed for 20 hours in the same manner as in Example 2, and then the solvent was removed by air blowing.

  When the surface of the glass plate after washing was observed with a microscope, the resin was adhered.

[Comparative Example 2]
In Comparative Example 2, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, the reinforcing plate was heated in the atmosphere at 500 ° C. for 10 minutes to expose the surface of the resin layer (resin film) opposite to the glass plate to the atmosphere at 500 ° C. for 10 minutes. Thereafter, the reinforcing plate was cooled from 500 ° C. to 50 ° C. at an average cooling rate of 5 ° C./second, and cooled to room temperature. Subsequently, it was immersed in ion-exchanged water, subjected to ultrasonic cleaning for 5 minutes, and then water was removed by air blowing.

  When the surface of the glass plate after washing was observed with a microscope, no resin was seen, but an oxide such as silicon oxide was fixed.

[Comparative Example 3]
In Comparative Example 3, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, the reinforcing plate is heated in the atmosphere at 250 ° C. for 30 minutes, so that the surface on the side opposite to the glass plate of the resin layer (resin film) is exposed to the atmosphere at 250 ° C. for 30 minutes. Then, after performing brush cleaning with an alcohol solution for 1 minute, the solvent was removed by air blowing.

  When the surface of the glass plate after washing was observed with a microscope, the resin was adhered. Even when the washing time was extended to 60 minutes, the resin was adhered.

[Comparative Example 4]
In Comparative Example 4, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, the reinforcing plate was heated in a nitrogen atmosphere at 300 ° C. for 30 minutes to expose the surface of the resin layer (resin film) opposite to the glass plate to a 300 ° C. nitrogen atmosphere for 30 minutes. In the same manner as described above, brush cleaning with an alcohol solution was performed for 1 minute, and then the solvent was removed by air blowing.

  When the surface of the glass plate after washing was observed with a microscope, the resin was adhered. Even when the washing time was extended to 60 minutes, the resin was adhered.

[Comparative Example 5]
In Comparative Example 5, the laminated body shown in FIG. 2 was produced in the same manner as in Example 2, and after the laminated body was heat-treated, a peeling operation between the glass substrate and the reinforcing plate was performed.

  After the peeling operation, the reinforcing plate is placed in a 20 liter pressurized container together with 100 g of water and heated at 100 ° C. for 1 hour, so that the surface of the resin layer (resin film) opposite to the glass plate is in high-temperature and high-pressure steam. After exposure to water, brush cleaning with an alcohol solution was performed for 60 minutes in the same manner as in Example 2, and then the solvent was removed by air blowing. The maximum pressure in the pressurized container when heat-treated at 100 ° C. for 1 hour was 0.2 MPa.

  When the surface of the glass plate after washing was observed with a microscope, the resin was adhered.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the scope and spirit of the invention.
This application is based on Japanese Patent Application No. 2010-051092 filed on Mar. 8, 2010, the contents of which are incorporated herein by reference.

DESCRIPTION OF SYMBOLS 10 Laminated body 20 Reinforcement plate 21 Glass plate 22 Resin layer 30 Substrate 301 1st main surface 302 2nd main surface

Claims (13)

A resin film removal method for removing a resin film adhered on a glass plate,
A heat treatment step of heat treating the resin film adhered on the glass plate;
A washing step of washing off the resin film after the heat treatment,
In the heat treatment step, the surface of the resin film opposite to the glass plate is exposed to 300 to 450 ° C. air, 350 to 600 ° C. inert atmosphere, or 150 to 350 ° C. water vapor. .   The method for removing a resin film according to claim 1, wherein in the heat treatment step, the resin film adhered on the glass plate is heated and then cooled.   The method for removing a resin film according to claim 1 or 2, wherein in the cleaning step, the resin film is dissolved or swollen using a liquid.   The method for removing a resin film according to claim 3, wherein the liquid has a solubility parameter of 7 to 15. 5.   The method for removing a resin film according to claim 1, wherein the resin film is removed using an abrasive in the cleaning step.   The method for removing a resin film according to any one of claims 1 to 5, wherein in the cleaning step, cleaning is performed by ultrasonic cleaning or brush cleaning. In a manufacturing method of a laminate including a removing step of removing a resin film adhered on a glass plate, and a laminating step of interposing a resin layer between the glass plate from which the resin film has been removed and a substrate,
The removal step includes
A heat treatment step of heat treating the resin film adhered on the glass plate;
A washing step of washing off the resin film after the heat treatment,
In the heat treatment step, the surface of the resin film opposite to the glass plate is exposed to air at 300 to 450 ° C., an inert atmosphere at 350 to 600 ° C., or water vapor at 150 to 350 ° C. .   The manufacturing method of the laminated body of Claim 7 which cools after heating the said resin film adhering on the said glass plate in the said heat processing process.   The manufacturing method of the laminated body of Claim 7 or 8 which dissolves or swells the said resin film using a liquid in the said washing | cleaning process.   The method for producing a laminate according to claim 9, wherein the liquid has a solubility parameter of 7 to 15.   The manufacturing method of the laminated body as described in any one of Claims 7-10 which removes the said resin film using an abrasive | polishing agent in the said washing | cleaning process.   In the said washing | cleaning process, the manufacturing method of the laminated body as described in any one of Claims 7-11 wash | cleaned by ultrasonic cleaning or brush cleaning.   In the said lamination process, While fixing the said resin layer to the said glass plate, the said resin layer is stuck to the said board | substrate so that peeling is possible, The manufacturing method of the laminated body as described in any one of Claims 7-12.

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