TWI526316B - A method for removing the resin film and a method for producing the layered product - Google Patents

Description

Method for removing resin film and method for producing laminated body

The present invention relates to a method for removing a resin film and a method for producing a laminate.

In recent years, devices such as solar cells (PV, Photovoltaic), liquid crystal panels (LCD), and organic light emitting panels (OLEDs) have been thinned and lightened, and Thinning of the substrate for such devices is underway. If the strength of the substrate is insufficient due to thinning, the substrate is rationally lowered in the manufacturing process of the device.

Therefore, the following method has been widely used in the prior art: after forming a device member (for example, a thin film transistor) on a substrate thicker than the final thickness, the substrate is thinned by a chemical etching process. 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, since most of the material of the original substrate is removed by the etching liquid, productivity or raw material is used. Not good from the point of view of efficiency.

Further, in the thinning method of the substrate by chemical etching, when fine scratches are present on the surface of the substrate, fine pits (etch pits) are formed as scratches due to the etching process, and optical defects are caused.

Recently, in order to cope with the above-mentioned problems, a laminate in which a substrate and a reinforcing plate are laminated is prepared, and a device member is formed on a substrate of a laminate, and then the reinforcing plate is peeled off from the substrate (for example, refer to the patent document) 1). The reinforcing plate has 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 is laminated with the new substrate, and can be reused as a laminated body.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 07/018028

However, the resin layer of the reinforcing plate is gradually deteriorated according to the number of times of use of the reinforcing plate. The deterioration of the resin layer is caused by heat treatment or liquid treatment in the manufacturing steps of the apparatus, peeling operation of the reinforcing plate and the substrate, and the like. When the resin layer is deteriorated to some extent, when the reinforcing plate and the substrate are peeled off, there is a case where one of the resin layers is partially adhered to the substrate on the product side. Therefore, when the resin layer of the reinforcing plate is deteriorated to some extent, it is desirable to laminate the reinforcing plate and the substrate after the resin layer is regenerated.

However, in order to regenerate the resin layer (resin film) attached to the glass plate, it is first necessary to remove the resin film. As a method of removing the resin film, a method of cutting by a cutter or a method of removing by spraying particles (for example, calcium carbonate powder) may be used, but the surface of the glass plate is caused by contact with the cutter or impact of the sprayed particles. Fine cracks are generated, and when the glass sheet is used again, there is a flaw in the glass sheet due to the influence of fine cracks.

Therefore, a method of heat-treating the resin film in the air is considered as a method of removing the resin film without damaging the glass sheet. However, in this case, an oxide such as ruthenium oxide is formed by oxidation of the resin film. The generated oxide is difficult to remove because it is fixed to the glass plate.

Further, as a method of removing the resin film without damaging the glass plate, a method of using a liquid such as an alcohol solution or an alkaline solution is considered. However, in this case, even if ultrasonic cleaning is used in combination, the resin film is removed for several tens of hours. the above.

The present invention has been made in view of the above problems, and an object of the invention is to provide a method for removing a resin film which can effectively remove a resin film without damaging a glass sheet, and a method for producing a laminate.

In order to achieve the above object, the method for removing a resin film of the present invention is a method of removing a resin film attached to a glass plate, comprising a heat treatment step of heat-treating the resin film attached to the glass plate, and a heat treatment step after heat treatment. In the step of washing the resin film, in the heat treatment step, the surface of the resin film opposite to the glass plate is exposed to an atmosphere of 300 to 450 ° C, an inert atmosphere of 350 to 600 ° C, or 150 to 350 ° C. In water vapor.

In the method for removing a resin film of the present invention, preferably, in the heat treatment step, the resin film adhered to the glass plate is heated and then cooled.

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

In the method for removing a resin film of the present invention, it is preferred that the solubility parameter of the liquid is 7 to 15.

In the method for removing a resin film of the present invention, it is preferred that the resin film is removed by using an abrasive in the washing step.

In the method for removing a resin film of the present invention, it is preferred that the cleaning is carried out by ultrasonic cleaning or brush cleaning in the cleaning step.

Moreover, the method for producing a laminate according to the present invention includes a step of removing a resin film attached to a glass plate, and a step of laminating a resin layer between the glass plate and the substrate from which the resin film is removed, the removing step a heat treatment step of heat-treating the resin film attached to the glass plate, and a cleaning step of the resin film after the heat treatment is performed, wherein in the heat treatment step, the resin film is opposite to the glass plate The surface is exposed to an atmosphere of 300 to 450 ° C, an inert atmosphere of 350 to 600 ° C, or water vapor of 150 to 350 ° C.

In the method for producing a laminate according to the present invention, preferably, in the heat treatment step, the resin film adhered to the glass plate is heated and then cooled.

In the method for producing a laminate according to the present invention, it is preferred that the resin film is dissolved or swollen using a liquid in the washing step.

In the method for producing a laminate according to the present invention, it is preferred that the solubility parameter of the liquid is 7 to 15.

In the method for producing a laminate according to the present invention, it is preferred that the resin film is removed by using an abrasive in the cleaning step.

In the method for producing a laminate according to the present invention, it is preferred that the cleaning is performed by ultrasonic cleaning or brush cleaning in the cleaning step.

In the method for producing a laminate according to the present invention, preferably, in the stacking step, the resin layer is fixed to the glass plate, and the resin layer is detachably adhered to the substrate.

According to the invention, it is possible to provide a method for removing a resin film which can effectively remove a resin film without damaging the glass sheet, and a method for producing the laminate.

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

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the steps of a method for producing a laminate according to an embodiment of the present invention. As shown in FIG. 1, the method for producing a laminated body includes a step of removing a resin film attached to a glass plate (step S11), and a step of laminating a resin layer between the glass plate from which the resin film is removed and the substrate ( Step S12).

Fig. 2 is a partial side view showing a laminate obtained by the method for producing a laminate of Fig. 1. As shown in FIG. 2, the laminated body 10 is formed by interposing the resin layer 22 between the glass plate 21 and the board|substrate 30. The resin layer 22 is adhered to the first main surface 301 of the substrate 30 in a peelable manner, and is fixed to the glass plate 21. In the step of manufacturing a device (electronic device) such as a liquid crystal panel, the glass plate 21 and the resin layer 22 function as the reinforcing plate 20 of the reinforcing substrate 30.

This laminated body 10 is used halfway through the manufacturing steps of the apparatus. In other words, the laminated body 10 is used until a member for a device such as a thin film transistor is formed on the substrate 30. Thereafter, the reinforcing plate 20 is peeled off from the substrate 30 and is no longer a member constituting the device. The reinforcing plate 20 peeled off from the substrate 30 is laminated with the new substrate 30, and can be reused as the new laminated body 10. Hereinafter, each configuration will be described in detail.

In addition, the laminated body 10 of the present embodiment is used until a member for a device such as a thin film transistor is formed on the substrate 30, but it may be used after forming a member for a device. For example, in the case of 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 laminated via a liquid crystal material. Then, the TFT substrate (or CF substrate) is thinned by chemical etching, and then 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 improved. Further, the laminated body is used in the middle of the manufacturing process of the liquid crystal panel, and thereafter, the reinforcing plate 20 is peeled off from the TFT substrate (or the CF substrate).

First, the substrate 30 will be described.

The substrate 30 forms a device member on the second main surface 302 to constitute a device. Here, the means for a device means a member constituting at least a part of the device. Specific examples include a thin film transistor (TFT) and a color filter (CF). As the device, a solar cell (PV), a liquid crystal panel (LCD), an organic electroluminescence panel (OLED), or the like can be exemplified.

The type of the substrate 30 may be a normal type, and may be, for example, a germanium wafer, a glass substrate, a resin substrate, or a metal substrate such as a SUS (Steel Use Stainless) substrate or a copper substrate. Among these, a glass substrate is preferable. The reason for this is that the glass substrate is excellent in chemical resistance and moisture permeability resistance, and has a low heat shrinkage rate. The standard of heat shrinkage rate is the coefficient of linear expansion specified in JIS R 3102-1995.

If the linear expansion coefficient of the substrate 30 is large, the manufacturing steps of the device are often accompanied by heat treatment, which is liable to cause various problems. For example, when a TFT is formed on the substrate 30, if the substrate 30 on which the TFT is formed under heating is cooled, the positional shift of the TFT becomes excessive 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 forming method can be a usual method, for example, a floating method, a melting method, a flow down method, a Fourcault method, a Lubbers method, or the like. Further, in particular, a glass substrate having a small thickness is obtained by the following method (re-draw method): heating a glass temporarily formed into a plate shape to a temperature at which it can be formed, and then stretching and deforming it by stretching or the like thin.

The glass of the glass substrate is not particularly limited, but 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.

The glass of the glass substrate is made of glass suitable for the type of device or its manufacturing steps. For example, since the elution of the alkali metal component is liable to affect the liquid crystal, the glass substrate for the liquid crystal panel contains glass (alkali-free glass) which does not substantially contain an alkali metal component. Thus, the glass of the glass substrate is suitably selected based on the kind of apparatus used and the manufacturing process of it.

The thickness of the glass substrate is not particularly limited, but 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 it is 0.8 mm or more, the requirements for thinning and/or weight reduction of the glass substrate are not satisfied. When it is 0.3 mm or less, the glass substrate can be imparted with good flexibility. When it is 0.15 mm or less, the glass substrate can be wound into a cylindrical shape. Further, the thickness of the glass substrate is preferably 0.03 mm or more for the reason that the production of the glass substrate is easy and the operation of the glass substrate is easy.

The type of the resin of the resin substrate is not particularly limited. Specifically, a polyethylene terephthalate resin, a polycarbonate resin, a polyimide resin, a fluororesin, a polyamide resin, an aromatic polyamide resin, a polyether oxime resin, and a polyether ketone can be exemplified. Resin, polyetheretherketone resin, polyethylene naphthalate resin, polyacrylic resin, various liquid crystal polymer resins, cycloolefin resins, polycrystalline germanium 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.

Furthermore, the substrate 30 may include two or more layers. In this case, the material forming the layers may be the same material or a different material. Further, in this case, "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 functions together with the resin layer 22 to support and strengthen the substrate 30, thereby preventing deformation, damage, breakage, and the like of the substrate 30 in the manufacturing process of the device. Further, one of the purposes of using the glass plate 21 is to form a laminate 10 having the same thickness as that of the substrate of the previous thickness when the thickness is thinner than the previous substrate 30, whereby the device can be used. Manufacturing techniques or manufacturing equipment suitable for substrates of the previous thickness are used in the manufacturing steps.

The glass plate 21 may be thicker than the substrate 30 and may be thinner than it. It is preferable to select the thickness of the glass plate 21 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, the manufacturing process of the current device is designed to treat a substrate having a thickness of 0.5 mm. When the sum of the thickness of the substrate 30 and the thickness of the resin layer 22 is 0.1 mm, the thickness of the glass plate 21 is set to 0.4 mm. The thickness of the glass plate 21 is preferably 0.08 mm or more for reasons of easy handling, difficulty in cracking, and the like.

The glass of the glass plate 21 may be a usual glass, and may be, for example, the above-described alkali-free glass or the like. When the manufacturing process of the apparatus is accompanied by heat treatment, the glass sheet 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 between the average linear expansion coefficient (hereinafter simply referred to as "average linear expansion coefficient") of the substrate 30 and the glass plate 21 at 25 to 300 ° C 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, there is a possibility that the laminated body 10 is strongly warped or the substrate 30 and the glass sheet 21 are peeled off during heating and cooling in the manufacturing process of the apparatus. When the material of the substrate 30 is the same as the material of the glass plate 21, such problems can be suppressed.

Next, the resin layer 22 will be described.

The resin layer 22 is fixed to the glass plate 21, and is detachably adhered to the first main surface 301 of the substrate 30. The resin layer 22 prevents the position of the substrate 30 from shifting until the peeling operation is performed, and is easily peeled off from the substrate 30 by the peeling operation, thereby preventing the substrate 30 or the like from being damaged by the peeling operation.

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

The surface 221 of the resin layer 22 is preferably adhered to the first main surface 301 of the substrate 30 by the force of the vantage force between the solid molecules, and is not adhered by an adhesive such as a usual adhesive. The reason for this is that it can be peeled off relatively easily. 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 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 surface of the resin layer to the surface of the substrate is referred to as adhesion, and the bonding to the surface of the glass plate 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, still more preferably 7 to 20 μm. The reason for this is that if the thickness of the resin layer 22 is within this range, the adhesion between the resin layer 22 and the substrate 30 becomes sufficient. Moreover, the reason is that even if air bubbles or impurities are interposed between the resin layer 22 and the substrate 30, the occurrence of strain defects of the substrate 30 can be suppressed. Further, if the thickness of the resin layer 22 is too thick, it takes less time and material to form, which is uneconomical.

Further, the resin layer 22 may include 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 contains two or more layers, the kind of the resin which forms each layer may differ.

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

Further, since the resin layer 22 is often subjected to heat treatment in the manufacturing process of the apparatus, it is preferably heat-resistant.

Further, for example, when the elastic modulus of the resin layer 22 is too high and exceeds 1000 MPa, the adhesion to the substrate 30 tends to decrease. On the other hand, if the elastic modulus of the resin layer 22 is too low and is less than 1 MPa, the peeling property is lowered.

The kind of the resin forming the resin layer 22 is not particularly limited. For example, an acrylic resin, a polyolefin resin, a polyurethane resin, and a polyoxyl resin can be mentioned. Several resins can also be used in combination. Among them, a polyoxyxylene resin is preferred. The reason for this is that the polyoxynoxy resin is excellent in heat resistance and peelability. Further, the reason for this is that it is easily fixed to the glass plate 21 by a condensation reaction with a stanol group present on the surface of the glass plate 21. In the state in which the polyoxyxylene resin layer is interposed between the glass plate 21 and the substrate 30, the peeling property is not deteriorated, for example, even if it is treated at about 200 ° C for about 1 hour in the air.

The resin layer 22 is preferably a polyoxynoxy resin (cured product) for use in release paper among polyoxyphthalic resins. The resin layer 22 formed by curing the curable resin composition which is a polyoxyxylene resin for release paper on the surface of the glass plate 21 is preferable because it has excellent releasability. Moreover, since the flexibility is high, even if impurities such as bubbles or dust are mixed between the resin layer 22 and the substrate 30, the occurrence of strain defects of the substrate 30 can be suppressed.

The curable polyfluorene oxide which is a polyoxyxylene resin for the release paper is classified into a condensation reaction type polyfluorene oxygen, an addition reaction type polyfluorene oxygen, an ultraviolet curing type polyfluorene oxygen, and an electron beam curing type according to the curing mechanism. Polyoxyl, any of them can be used. Among these, an addition reaction type polyoxane is preferred. This is because the hardening reaction is easy, and the degree of peeling property is good when the resin layer 22 is formed, and the heat resistance is also high.

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 polyxylene is promoted by heat treatment. The main component of the addition reaction type polyoxane includes a linear organopolyoxane (i.e., an organic alkenyl polyoxyalkylene) having an alkenyl group (vinyl group or the like) bonded to a ruthenium atom. The addition reaction type polyfluorene crosslinking agent contains a linear organopolyoxane (i.e., an organic hydrogenated polyoxyalkylene) having a hydrogen atom (hydrazine group) bonded to a halogen atom.

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 type can be used. Among these, it is preferably a solventless type. The reason is excellent in terms of productivity, safety, and environmental characteristics. Moreover, this is because when the resin layer 22 is cured, that is, when heat curing, ultraviolet curing, or electron beam curing, since the solvent which causes foaming is not contained, it is difficult for the bubbles to remain in the resin layer 22.

In addition, as a commercially available product name or model, KNS-320A and KS-847 (both manufactured by Shin-Etsu Silicone Co., Ltd.) and TPR6700 are mentioned as a commercially available product of a poly-oxygen resin for a release paper. (a combination of GE Toshiba Silicone Co., Ltd.), vinyl polyoxylium "8500" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogenated polyoxyalkylene "12031" (manufactured by Arakawa Chemical Industries, Ltd.), vinyl polyoxyl 11364" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogenated polyoxane "12031" (manufactured by Arakawa Chemical Industries, Ltd.), vinyl polyoxylium "11365" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogenated polymer A combination of aerobicane "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 oxide resin forming the resin layer 22 preferably has a property that it is difficult to transfer the components in the polyoxynitride resin layer to the substrate 30, that is, oligomeric oxygen transfer property.

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

In the removal step (step S11) of Fig. 1, the resin film attached to the glass plate 21 is removed. The removal step of the present embodiment is carried out in the following process: in the manufacturing step of the apparatus, the reinforcing plate 20 peeled off from the substrate 30 is laminated with the new substrate 30, and reused as the new laminated body 10. More specifically, the removal step of the present embodiment is carried out in order to remove the resin layer 22 of the reinforcing plate 20 as a step of removing the resin layer 22 fixed to the glass plate 21.

Fig. 3 is a process chart showing a method of removing a resin film in an embodiment of the present invention, and is a detailed view of the removal step of Fig. 1. As shown in FIG. 3, the removing step includes a heat treatment step of heat-treating the resin layer (resin film) 22 attached to the glass plate 21 (step S31), and a washing step of the resin layer (resin film) 22 after the heat treatment is washed away. (step S32).

In the heat treatment step (step S31) of FIG. 3, the surface 221 of the resin layer 22 opposite to the glass plate 21 is exposed to an atmosphere of 300 to 450 ° C, an inert atmosphere of 350 to 600 ° C, or 150 to 350 ° C. In water vapor. The resin layer 22 breaks bonds of atoms or molecules by a decomposition reaction caused by a surrounding atmosphere at a high temperature. When the decomposition reaction proceeds sufficiently, fine cracks, fine pores, and the like are formed in the resin layer 22.

When exposed to the atmosphere of 300 ° C to 450 ° C, the decomposition reaction of the resin layer 22 is sufficiently carried out for 1 to 120 minutes. Preferably, when exposed to an atmosphere of 350 ° C to 450 ° C, the decomposition reaction of the resin layer 22 is sufficiently performed in 1 to 30 minutes. If the temperature of the atmosphere is less than 300 ° C, the decomposition reaction of the resin layer 22 is difficult to proceed. Further, when the temperature of the atmosphere exceeds 450 ° C, an oxide such as cerium oxide is formed by oxidation of the resin layer 22 . Since the generated oxide is fixed to the glass plate 21, it is difficult to remove.

When exposed to an inert atmosphere of 350 ° C to 600 ° C, the decomposition reaction of the resin layer 22 is sufficiently carried out for 1 to 120 minutes. Preferably, when exposed to an inert atmosphere of 400 ° C to 600 ° C, the decomposition reaction of the resin layer 22 is sufficiently carried out for 1 to 30 minutes. If the temperature of the inert atmosphere is less than 350 ° C, the decomposition reaction of the resin layer 22 is difficult to proceed. Further, when the temperature of the inert atmosphere exceeds 600 ° C, the glass sheet 21 is thermally deformed or thermally deteriorated.

Here, the inert atmosphere means 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, the formation of oxides can be suppressed. Therefore, the 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 heating at 600 ° C, the decomposition reaction of the resin layer 22 is sufficiently performed for 1 to 30 minutes.

When it is exposed to water vapor of 150 ° C to 350 ° C, the decomposition reaction of the resin layer 22 is sufficiently performed for 1 to 5 hours. This is due to the hydrolysis of the resin, especially in the low temperature domain. On the other hand, if the temperature of the water vapor is less than 150 ° C, the decomposition reaction of the resin layer 22 is difficult to proceed. Further, if the temperature of the water vapor exceeds 350 ° C, thermal decomposition is advantageous as compared with hydrolysis, so that it is advantageous to be exposed to the atmosphere at a cost.

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

Further, in the case where the inside of the heating furnace is not made into a pressurized atmosphere, the heating furnace may be a batch furnace or a continuous furnace in which the heating belt and the cooling belt are continuously connected and connected in a tunnel shape.

In the heat treatment step, since the resin layer 22 is heated at a specific temperature to promote the formation of cracks, it can be cooled from a specific temperature. The average cooling rate from a specific temperature to 50 ° C is appropriately set depending on the size of the glass plate 21 or the like. For example, when the thickness of the glass plate 21 is 0.4 mm, the length of the short side is 600 mm or more, and the length of the long side is 800 mm or less, the average cooling rate from a specific temperature to 50 ° C is preferably 5 to 15 °C / sec. If it exceeds 15 ° C / sec, the glass plate 21 is easily broken. On the other hand, if it is less than 5 ° C / sec, the cooling time becomes long and the productivity is inferior.

In the cleaning step (step S32) of Fig. 3, the heat-treated resin layer 22 is washed away. Since the resin layer 22 after the heat treatment is broken by atoms and molecules in the surface 221 on the side opposite to the glass plate 21, the resin layer 22 can be efficiently washed away.

Examples of the cleaning method include 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 blowing air to the resin layer 22. The method is a method of chemically cleaning using a liquid such as an acidic solution or an alkaline solution. These cleaning methods can be used singly or in combination. The combination is not particularly limited, and for example, a method in which the resin layer 22 is dissolved or swelled with a liquid while being washed with a brush, and the resin layer 22 is polished with a dispersion in which the polishing agent is dispersed while being washed with a brush.

The liquid desired solubility parameter (SP value) is 7 to 15 (unit: cal ^1/2 cm ^-3/2 ). When the SP value is outside the range of 7 to 15, the liquid is less likely to be wet to the resin layer 22 because the affinity between the liquid and the resin layer 22 is low. Specific examples of the liquid having an SP value of 7 to 15 include isoalkane, xylene, hexane, acetone, dimethylformamide, propanol, ethanol, methanol, and the like. These liquids can be used singly or in combination. From the viewpoint of environmental load, it is desirable to use an alcohol solution containing ethanol as a main component. Further, in view of the influence on the human body or the viewpoint of the ignition caused by static electricity or the like, an isoparaffin solution having a firing point of 21 ° C or higher, more preferably 70 ° C or higher is desired.

The abrasive may have a hardness higher than that of the resin layer 22 and lower than the glass plate 21. In order to shorten the cleaning time, it is desirable that the hardness is close to the glass plate 21. The glass sheet 21 has a Mohs hardness of usually 5.5 to 6. The Mohs hardness of the abrasive is preferably from 3 to 5. When the Mohs hardness is less than 3, there is a possibility that the resin layer 22 cannot be removed. When the Mohs hardness exceeds 5, there is a flaw in the surface of the glass plate 21 to cause fine cracks. Specific examples of the polishing agent include cerium oxide (Mohs hardness 5), calcium carbonate (Mohs hardness 4), hard plastic (Mohs hardness 4 to 5), POLY-PLUS (Mohs hardness 4), green. Mudstone schist powder (Mohs hardness 4) and the like. These abrasives can be used singly or in combination. The number average particle diameter of the abrasives is preferably from 1 to 10 μm.

In order to not scratch the glass plate 21, the hair of the brush for brush cleaning is made of a material softer than the glass plate 21.

Further, in order to regenerate the resin layer 22 of the reinforcing plate 20, the method of removing the resin film of the present embodiment is applied to the removal of the resin layer 22 fixed to the glass plate 21, but the present invention is not limited thereto. For example, in order to reuse the glass plate 21 of the reinforcing plate 20 as the substrate 30, it may be applied to remove the resin layer 22 fixed to the glass plate 21. As described above, the method for removing the resin film of the present invention is not particularly limited as long as it is applied to remove the resin film adhering to the glass.

Next, the lamination step (step S12) of Fig. 1 will be described.

In the lamination step (step S12) of FIG. 1, the resin layer 22 is interposed between the glass sheets 21 from which the resin film is removed, between the substrates 30. Specifically, for example, the resin layer 22 is fixed to the glass plate 21, and the resin layer 22 is peelably adhered to the substrate 30. Further, the resin layer 22 may be formed on the side on which the resin film is removed, or may be formed on the opposite side.

The method of fixing the resin layer 22 to the glass plate 21 is not particularly limited, and for example, a method of fixing the film-like resin to the surface of the glass plate 21 is exemplified. Specifically, a method of imparting a surface modification treatment (initiation treatment) to the surface of the glass sheet 21 to impart a high fixing force (high peel strength) to the surface of the glass sheet 21 is given. And fixed to the glass plate 21. For example, a chemical method (primer treatment) which chemically increases the fixing force like a decane coupling agent, a physical method of increasing a surface active group such as a flame treatment, such as a sandblasting treatment can be exemplified by A mechanical treatment method in which the roughness is increased to increase the friction.

Moreover, the method of apply|coating the hardening resin composition which becomes the resin layer 22 on the glass plate 21 is mentioned, for example. 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 22 is applied to the glass plate 21, 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 22 is formed of a curable resin composition of an addition reaction type polyoxymethylene, a curable resin containing a mixture of an organic alkenyl polysiloxane, an organic hydrogenated polyoxane and a catalyst is used. The composition is applied to the glass plate 21 by a known method such as the above-described spraying method, and thereafter heat-hardened. The heat-hardening condition varies depending on the amount of the catalyst to be mixed. For example, when the platinum-based catalyst is blended in an amount of 2 parts by mass based on 100 parts by mass of the total of the organic alkenyl polysiloxane and the organic hydrogenated polyoxyalkylene. It is reacted in the atmosphere at 50 ° C to 250 ° C, preferably 100 ° C to 200 ° C. Further, the reaction time in this case is set to 5 to 60 minutes, preferably 10 to 30 minutes. In order to produce a polyoxyxylene resin layer having an oligomeric oxime oxygen transfer property, it is preferred to carry out a hardening reaction as much as possible, so that no unreacted polyfluorene oxide component remains in the polyoxynoxy resin layer. If the reaction temperature and the reaction time are as described above, it is preferred that the unreacted polyfluorene oxide component does not remain in the polyoxynated resin layer. When the reaction time is too long or the reaction temperature is too high, oxidative decomposition of the polyfluorene oxide resin may occur at the same time, and a low molecular weight polyfluorene oxygen component may be formed, and the polyoxane oxygen transfer property may become high. In order to prevent the unreacted polyfluorene oxide component from remaining in the polyoxymethylene resin layer, the curing reaction is carried out as much as possible, and it is also preferable in terms of good releasability after heat treatment.

In the case where the resin layer 22 is produced by using a curable resin composition which is a polyoxyxylene resin for release paper, the curable resin composition applied to the glass sheet 21 is heat-cured to form a polyoxyn resin. Floor. By heat-hardening the curable resin composition, the polyfluorene oxide resin and the glass plate 21 are chemically bonded at the time of the hardening reaction. Further, the polyoxyxylene resin layer is bonded to the glass plate 21 by the anchoring effect. By these actions, the polyoxyphthalide resin layer is firmly fixed to the glass plate 21.

The method of allowing the resin layer 22 to be peelably adhered to the substrate 30 can be a well-known method. For example, a method in which the substrate 30 is superposed on the peelable surface 221 of the resin layer 22 in a normal pressure environment, and then the resin layer 22 is pressed against the substrate 30 by a roll or a press. Since the resin layer 22 and the substrate 30 are more closely bonded by pressure bonding by a roll or a press, it is preferable. Further, since the bubbles mixed between the resin layer 22 and the substrate 30 are easily removed by pressure bonding by a roll or a press, it is preferable.

When the pressure bonding is carried out by a vacuum lamination method or a vacuum pressing method, it is more preferable to suppress the incorporation of air bubbles or to ensure good adhesion. By performing pressure bonding under vacuum, even in the case where minute bubbles remain, bubbles do not grow due to heating, and the advantage of strain defects of the substrate 30 is less likely to occur.

When the resin layer 22 is peelably adhered to the substrate 30, it is preferable to sufficiently clean the surface of the resin layer 22 and the substrate 30 on the side in contact with each other, and to laminate the layer in an environment having high cleanliness. Even if impurities are mixed between the resin layer 22 and the substrate 30, the resin layer 22 is not deformed, and the flatness of the surface of the substrate 30 is not affected. However, since the flatness is higher as the degree of cleanliness is higher, it is preferable.

Further, the order of the step of fixing the resin layer 22 to the glass plate 21 and the step of adhering the resin layer 22 to the substrate 30 in a peelable manner is not limited, and for example, it can be performed substantially simultaneously.

[Examples]

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

[Example 1]

(production of reinforcing board)

Regarding the glass plate of the reinforcing plate, a glass plate (manufactured by Asahi Glass Co., Ltd., AN100, alkali-free glass) obtained by a floating method was used. The average expansion coefficient of the glass plate was 38 × 10 ^-7 / ° C.

The glass plate was subjected to pure water washing and UV cleaning to purify the surface of the glass plate. Thereafter, 100 parts by mass of a solvent-free addition-reactive polyfluorene (KNS-320A, manufactured by Shin-Etsu Silicone Co., Ltd.) and a platinum-based catalyst (manufactured by Shin-Etsu Silicone Co., Ltd., CAT-PL-56) were mixed by 5 parts by mass. The coater was applied to the surface of the glass plate (coating amount was 20 g/m ² ).

The solventless addition reaction type polyoxosiloxane includes a linear organic alkenyl polyoxyalkylene (main component) having a vinyl group and a methyl group bonded to a ruthenium atom, and a hydrogen atom having a bond to a ruthenium atom. A linear organic hydrogenated polyoxyalkylene (crosslinking agent) with a methyl group.

The mixture applied to the glass plate was heat-hardened at 180 ° C for 10 minutes in the atmosphere, and a resin layer of 705 mm in length × 595 mm in width × 20 μm in thickness was formed at the center of the glass plate, and fixed.

A reinforcing plate is produced in this way.

(production of laminated body)

As the glass substrate, a glass plate (manufactured by Asahi Glass Co., Ltd., AN100, alkali-free glass) obtained by a floating method of 720 mm × 600 mm × 0.4 mm thick was used. The glass substrate had an average linear expansion coefficient of 38 × 10 ^-7 / ° C.

The glass substrate was subjected to pure water washing and UV cleaning to purify the surface of the glass substrate. Thereafter, the glass substrate and the reinforcing plate were adhered to each other in a vacuum at room temperature using a vacuum pressing device to obtain a laminate shown in Fig. 2.

( peeling of glass substrate and reinforcing plate)

The laminate was heat-treated at 250 ° C for 2 hours in the air, and then cooled to room temperature to carry out a peeling operation between the glass substrate and the reinforcing plate. Specifically, after the blade having a thickness of 0.4 mm is inserted between the glass substrate and the reinforcing plate, the glass substrate is supported flatly, and the reinforcing plate is sequentially flexed and deformed from the piercing position of the blade.

After the peeling operation, the reinforcing plate was observed with a microscope, and as a result, a scratch caused by the blade penetration was found on the peeling surface of the resin layer. Further, the peeling surface of the resin layer was analyzed by an infrared absorption method, and as a result, deterioration due to heat treatment was found only at the outer edge portion of the peelable surface. Further, in the central portion of the peelable surface, deterioration due to heat treatment was not observed.

(Removal of resin layer (resin film))

After the peeling operation, the reinforcing plate was heated at 370 ° C for 10 minutes in the atmosphere, whereby the surface of the resin layer (resin film) opposite to the glass plate was exposed 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 / sec, and then immersed in an alkaline solution at 50 ° C for 5 minutes of ultrasonic cleaning.

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

Then, the alkaline solution was washed with a brush for 1 minute, the resin layer (resin film) was washed away, and then rinsed with pure water, and water was removed by blowing air.

The surface of the cleaned glass plate was observed under a microscope, and as a result, impurities such as oxides or resins and scratches were not observed.

[Embodiment 2]

In Example 2, a linear polyorganosiloxane having a vinyl group at the ends (manufactured by Arakawa Chemical Industries Co., Ltd., 8500) and a methyl hydrogenated polyoxyalkylene having a hydrazine group in the molecule (Arakawa) were used. The mixture of the chemical industry company, 12031) and the platinum-based catalyst (manufactured by Arakawa Chemical Industries Co., Ltd., CAT12070) is the same as that of the first embodiment except that it is a curable resin composition which is a resin layer. Way to make a reinforcement board.

Here, the mixing ratio of the linear polyorganosiloxane and the methylhydrogenated polyoxyalkylene was adjusted so that the molar ratio of the vinyl group to the hydrazine group was 1:1. In addition, the platinum-based catalyst is 5 parts by mass based on 100 parts by mass of the total of the linear polyorganosiloxane and the methylhydrogenated polyoxyalkylene.

Next, the laminated body shown in FIG. 2 was produced in the same manner as in Example 1, and the peeling operation of the glass substrate and the reinforcing plate was performed after heat-treating the laminated body.

After the peeling operation, the reinforcing plate was heated at 370 ° C for 5 minutes in the atmosphere, whereby the surface of the resin layer (resin film) on the opposite side to the glass plate was exposed 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 / sec, and cooled at room temperature. Then, the alcohol solution (manufactured by Japan Alcohol Trading Co., Ltd., Neocol R7, solubility parameter: 11.5 to 14.7, ignition point: 11 to 24 ° C) was subjected to brush cleaning for 1 minute, and after washing off the resin layer (resin film) Air is blown to remove the solvent.

The alcohol solution contained 86.6 mass% of ethanol, 9.5% by mass of normal propanol (NPA), 2.6% by mass of methanol, and 1.3% by mass of isopropyl alcohol (IPA, Isopropyl Alcohol).

The surface of the cleaned glass plate was observed under a microscope, and as a result, impurities such as oxides or resins and scratches were not observed.

[Example 3]

In the third embodiment, the laminate shown in Fig. 2 was produced in the same manner as in the example 2, and the peeling operation of the glass substrate and the reinforcing plate was performed after the laminate was heat-treated.

After the peeling operation, the reinforcing plate was heated at 370 ° C for 5 minutes in the atmosphere, whereby the side of the resin layer (resin film) opposite to the glass plate was exposed 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 / sec, and cooled to room temperature. Then, it was subjected to brush cleaning for 1 minute by an isoalkane solution (manufactured by Idemitsu Kosan Co., Ltd., IP Solvent 2028, solubility parameter of 7, and a fire point of 86 ° C), and was blown off after washing off the resin layer (resin film). The solvent was removed by heating to 200 ° C of air.

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

The surface of the cleaned glass plate was observed under a microscope, and as a result, impurities such as oxides or resins and scratches were not observed.

[Example 4]

In the fourth embodiment, the laminate shown in Fig. 2 was produced in the same manner as in the example 2, and the peeling operation of the glass substrate and the reinforcing plate was performed after the laminate was heat-treated.

After the peeling operation, the reinforcing plate was heated at 350 ° C for 30 minutes in the atmosphere, whereby the side of the resin layer (resin film) opposite to the glass plate was exposed to the atmosphere at 350 ° C for 30 minutes. Then, the reinforcing plate was cooled from 350 ° C to 50 ° C at an average cooling rate of 5 ° C / sec, and cooled to room temperature. Then, the resin was dispersed for 1 minute by a dispersion in which the polishing agent was dispersed, the resin layer (resin film) was washed away, and then rinsed with pure water, and the water was removed by blowing air.

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

The surface of the cleaned glass plate was observed under a microscope, and as a result, impurities such as oxides or resins and scratches were not observed.

[Example 5]

In Example 5, the laminate shown in Fig. 2 was produced in the same manner as in Example 2, and after the laminate was heat-treated, the peeling operation of the glass substrate and the reinforcing sheet was performed.

After the stripping operation, the reinforcing plate was heated at 600 ° C for 2 minutes in a nitrogen atmosphere having an oxygen volume concentration of 1000 ppm, whereby the side of the resin layer (resin film) opposite to the glass plate was placed in a nitrogen atmosphere at 600 ° C. After the exposure for 2 minutes, the resin layer (resin film) was washed away in the same manner as in Example 3, and then the solvent was removed by blowing air.

The surface of the cleaned glass plate was observed under a microscope, and as a result, impurities such as oxides or resins and scratches were not observed.

[Embodiment 6]

In the sixth embodiment, the layered body shown in Fig. 2 was produced in the same manner as in the example 2, and after the layered body was subjected to heat treatment, the peeling operation of the glass substrate and the reinforcing plate was performed.

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

The surface of the cleaned glass plate was observed under a microscope, and as a result, impurities such as oxides or resins and scratches were not observed.

[Embodiment 7]

In the seventh embodiment, the laminate shown in Fig. 2 was produced in the same manner as in the example 2, and after the laminate was subjected to heat treatment, the peeling operation of the glass substrate and the reinforcing plate was performed.

After the stripping operation, the reinforcing plate was placed in a 20-liter pressurized container together with 100 g of water, and heated at 250 ° C for 1 hour, thereby exposing the side of the resin layer (resin film) opposite to the glass plate to the side. After the high-temperature high-pressure steam was applied, the resin layer (resin film) was washed away in the same manner as in Example 2, and then the solvent was removed by blowing air.

Further, the maximum pressure in the pressurized vessel after heat treatment at 250 ° C for 1 hour was 0.65 MPa.

The surface of the cleaned glass plate was observed under a microscope, and as a result, impurities such as oxides or resins and scratches were not observed.

[Embodiment 8]

In the eighth embodiment, the laminate shown in Fig. 2 was produced in the same manner as in the example 2, and after the laminate was subjected to heat treatment, the peeling operation of the glass substrate and the reinforcing plate was performed.

After the stripping operation, the reinforcing plate was placed in a 20-liter pressurized container together with 100 g of water, and heated at 150 ° C for 5 hours, thereby exposing the surface of the resin layer opposite to the glass plate to high temperature and high pressure water. After the vapor, the resin layer was washed away in the same manner as in Example 2, and then the solvent was removed by blowing air. Further, the maximum pressure in the pressurized vessel after heat treatment at 150 ° C for 5 hours was 0.3 MPa.

The surface of the cleaned glass plate was observed under a microscope, and as a result, impurities such as oxides or resins and scratches were not observed.

[Comparative Example 1]

In Comparative Example 1, the laminate shown in Fig. 2 was produced in the same manner as in Example 2, and after the laminate was subjected to heat treatment, the glass substrate and the reinforcing sheet were peeled off.

After the peeling operation, heat treatment was not carried out, and after washing with an alcohol solution for 20 hours in the same manner as in Example 2, the solvent was removed by blowing air.

The surface of the cleaned glass plate was observed under a microscope, and it was found that a resin was attached.

[Comparative Example 2]

In Comparative Example 2, the laminate shown in Fig. 2 was produced in the same manner as in Example 2, and after the laminate was heat-treated, the glass substrate and the reinforcing sheet were peeled off.

After the peeling operation, the reinforcing plate was heated at 500 ° C for 10 minutes in the atmosphere, whereby the surface of the resin layer (resin film) opposite to the glass plate was exposed 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 / sec, and cooled to room temperature. Then, after immersing in ion-exchange water and performing ultrasonic cleaning for 5 minutes, water was removed by blowing air.

The surface of the glass plate after the cleaning was observed with a microscope, and as a result, no resin was found, but an oxide such as cerium oxide was fixed.

[Comparative Example 3]

In Comparative Example 3, the laminate shown in Fig. 2 was produced in the same manner as in Example 2, and after the laminate was subjected to heat treatment, the glass substrate and the reinforcing sheet were peeled off.

After the peeling operation, the reinforcing plate was heated at 250 ° C for 30 minutes in the atmosphere, whereby the surface of the resin layer (resin film) opposite to the glass plate was exposed to an atmosphere of 250 ° C for 30 minutes, and then with the examples. 2 In the same manner, the alcohol solution was washed by a brush for 1 minute, and then the solvent was removed by blowing air.

The surface of the cleaned glass plate was observed under a microscope, and it was found that a resin was attached. Even if the cleaning time is extended to 60 minutes, the resin is attached.

[Comparative Example 4]

In Comparative Example 4, the laminate shown in Fig. 2 was produced in the same manner as in Example 2, and after the laminate was subjected to heat treatment, the glass substrate and the reinforcing sheet were peeled off.

After the stripping operation, the reinforcing plate was heated at 300 ° C for 30 minutes in a nitrogen atmosphere, whereby the surface of the resin layer (resin film) opposite to the glass plate was exposed to a nitrogen atmosphere at 300 ° C for 30 minutes, and then In the same manner as in Example 2, the brush solution was washed by an alcohol solution for 1 minute, and then the solvent was removed by blowing air.

The surface of the cleaned glass plate was observed under a microscope, and it was found that a resin was attached. Even if the cleaning time is extended to 60 minutes, the resin is attached.

[Comparative Example 5]

In Comparative Example 5, the laminate shown in Fig. 2 was produced in the same manner as in Example 2, and after the laminate was subjected to heat treatment, the glass substrate and the reinforcing sheet were peeled off.

After the peeling operation, the reinforcing plate was placed in a 20-liter pressurized container together with 100 g of water, and heated at 100 ° C for 1 hour, thereby exposing the side of the resin layer (resin film) opposite to the glass plate. After the high-temperature and high-pressure water vapor, the solvent was washed by an alcohol solution for 60 minutes in the same manner as in Example 2, and then the solvent was removed by blowing air. Further, the maximum pressure in the pressurized vessel after heat treatment at 100 ° C for 1 hour was 0.2 MPa.

The surface of the cleaned glass plate was observed under a microscope, and it was found that a resin was attached.

The present invention has been described in detail with reference to the specific embodiments thereof, and it is obvious that various modifications and changes may be added without departing from the scope and spirit of the invention.

The present application is based on Japanese Patent Application No. 2010-051092, filed on Mar.

10. . . Laminated body

20. . . Reinforcing plate

twenty one. . . glass plate

twenty two. . . Resin layer

30. . . Substrate

301. . . First main face

302. . . Second main face

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the steps of a method for producing a laminate according to an embodiment of the present invention.

Fig. 2 is a partial side view showing a laminate obtained by the method for producing a laminate of Fig. 1.

Fig. 3 is a flow chart showing a method of removing a resin film in an embodiment of the present invention.

(no component symbol description)

Claims (13)

A method for removing a resin film, which comprises removing a resin film attached to a glass plate, and comprising a heat treatment step of heat-treating the resin film attached to the glass plate, and cleaning the resin film after heat treatment after washing away In the above heat treatment step, the surface of the resin film opposite to the glass plate is exposed to an inert atmosphere of 350 to 600 ° C. The method for removing a resin film according to claim 1, wherein in the heat treatment step, the resin film adhered to the glass plate is heated and then cooled. The method for removing a resin film according to claim 1 or 2, wherein in the washing step, the resin film is dissolved or swollen using a liquid. The method for removing a resin film according to claim 3, wherein the solubility parameter of the liquid is 7 to 15. The method for removing a resin film according to claim 1 or 2, wherein in the washing step, the resin film is removed using an abrasive. A method of removing a resin film according to claim 1 or 2, wherein in the washing step, washing is performed by ultrasonic cleaning or brush cleaning. A method for producing a laminate comprising a step of removing a resin film attached to a glass plate, and a step of laminating a resin layer between the glass plate and the substrate from which the resin film is removed, wherein the removing step comprises Heat treatment of the above resin film attached to the above glass plate The treatment step and the step of washing the resin film after the heat treatment are performed, and in the heat treatment step, the surface of the resin film opposite to the glass plate is exposed to an inert atmosphere at 350 to 600 °C. The method for producing a laminate according to claim 7, wherein in the heat treatment step, the resin film adhered to the glass plate is heated and then cooled. The method for producing a laminate according to claim 7 or 8, wherein in the washing step, the resin film is dissolved or swollen using a liquid. The method for producing a laminate according to claim 9, wherein the solubility parameter of the liquid is 7 to 15. The method for producing a laminate according to claim 7 or 8, wherein in the washing step, the resin film is removed using an abrasive. The method for producing a laminate according to claim 7 or 8, wherein in the cleaning step, the cleaning is performed by ultrasonic cleaning or brush cleaning. The method for producing a laminate according to claim 7 or 8, wherein in the stacking step, the resin layer is fixed to the glass plate, and the resin layer is detachably adhered to the substrate.