TWI505933B - The manufacturing method and the layered body of the layered body - Google Patents

Description

Method for manufacturing laminated body and laminated body

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

In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCDs), and organic EL panels (OLEDs) have been thinned and lightened, and thinning of substrates for such devices has been carried out. On the other hand, if the strength of the substrate is insufficient due to the thinning, the handleability of the substrate is lowered in the manufacturing process of the device.

Therefore, a method of thinning a substrate by a chemical etching process after forming a device member (for example, a thin film transistor) on a substrate thicker than the final thickness has been widely used. However, in this method, for example, when the thickness of one substrate is reduced from 0.7 mm to 0.2 mm or 0.1 mm, the etching material is used to cut the material of the original substrate by a large part, so that productivity or The use efficiency of raw materials is not good.

Further, in the thinning method of the substrate by chemical etching, when there is a fine damage on the surface of the substrate, a fine recess (corrosion pit) is formed from the damage as a starting point due to the etching treatment, thereby forming an optical defect.

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

Prior technical literature Patent literature

Patent Document 1: International Publication No. 07/018028

However, in the laminate of the above-described prior art, when the reinforcing plate is peeled off from the substrate, the resin layer of the reinforcing plate is agglomerated and the resin layer is partially adhered to the substrate on the product side. The reason for this is considered to be that the resin layer is deteriorated or the adhesion strength between the resin layer and the substrate is increased depending on the conditions of the heat treatment or the chemical liquid treatment in the manufacturing steps of the apparatus.

The present invention has been made in view of the above-described problems, and an object of the invention is to provide a method for producing a laminate which can suppress aggregation failure of a resin layer when a resin layer and a substrate are peeled off, and a laminate.

In order to achieve the above object, a method for producing a laminate according to the present invention is a method for producing a laminate comprising a substrate, a support plate, and a resin layer present between the substrate, and a method of forming the resin layer. a step of the support plate and a step of adhering the resin layer to the substrate in a peelable manner, and comprising: before the bonding step, preliminarily contacting the surface of the substrate to be adhered with a polyoxygenated oil or a decane coupling agent a step of treating at least one of the surface of the resin layer or a step of forming the resin layer, wherein the resin layer is formed of a resin containing a polysiloxane or a decane coupling agent, and thereafter, the substrate and the substrate are adhered in the adhesion step The above resin layers are overlapped and adhered.

In the method for producing a laminate according to the present invention, preferably, the method comprises the steps of: coating a surface of the substrate to be adhered and at least one of the surface of the resin layer with a polyoxygenated oil or a decane coupling agent; In the case of oil, a treatment for lowering the molecular weight of the polyoxyxene oil is carried out; in the case of coating the decane coupling agent, a treatment for reacting the decane coupling agent is carried out; thereafter, the substrate and the resin are subjected to the adhesion step Layers overlap and close. Further, it is preferable that the surface of the substrate to be adhered is surface-treated with a polyoxygen oxyhydroxide or a decane coupling agent, and the water contact angle of the surface of the substrate subjected to the above treatment is 90 or more.

In the method for producing a laminate according to the present invention, it is preferable that a step of forming the resin layer on the support sheet forms a curable resin composition layer on the surface of the support sheet, and then the curable resin composition is formed. The resin layer is formed by hardening.

Further, in the method for producing a laminate according to the present invention, it is preferable that the resin layer contains a polyoxyn resin.

Further, in the method for producing a laminate according to the present invention, it is preferable that the resin layer contains a reaction cured product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene.

Further, the laminated system of the present invention includes a substrate, a support plate, and a resin layer interposed therebetween, wherein the resin layer is detachably adhered to the substrate, and the resin layer is on the support plate. The peeling strength between the resin layer and the substrate is fixed, and at least one of the surface of the substrate and the surface of the resin layer which are in contact with each other includes a polyoxygenated oil or a decane coupling agent. The surface to be treated, or the above resin layer, is formed of a resin containing a polyoxygenated oil or a decane coupling agent.

In the laminate of the present invention, it is preferred that the surface of the substrate which is in close contact with the surface of the resin layer is a surface which is surface-treated with a polyoxygenated oil or a decane coupling agent. Further, it is preferable that the water contact angle of the surface of the surface-treated substrate is 90 or more.

Further, in the laminate of the present invention, it is preferable that the resin layer contains a polyfluorene oxide resin.

Further, in the laminate of the present invention, it is preferred that the resin layer contains a reaction cured product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene.

According to the present invention, it is possible to provide a method for producing a laminate which can suppress aggregation damage of the resin layer when the resin layer and the substrate are peeled off, and a laminate.

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

Further, in the present invention, the fact that the resin layer is fixed to the support plate means that the peel strength between the resin layer and the support plate is higher than the peel strength between the resin layer and the substrate.

(First embodiment)

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial side elevational view showing an example of a laminate of the present invention. As shown in FIG. 1, the laminated body 10 is a laminated body in which the resin layer 32 exists between the board|substrate 20, the support board 31, etc.. The resin layer 32 is fixed to the support plate 31 and is detachably adhered to the first main surface 201 of the substrate 20. The support plate 31 and the resin layer 32 function as the reinforcing plate 30 of the reinforcing substrate 20 in the manufacturing process of a device (electronic device) such as a liquid crystal panel.

This laminated body 10 is used until the middle of the manufacturing process 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 20. Thereafter, the reinforcing plate 30 is peeled off from the substrate 20 so as not to become a member constituting the device. The reinforcing plate 30 peeled off from the substrate 20 can be laminated with the new substrate 20 and reused as the laminated body 10. Hereinafter, each configuration will be described in detail.

First, the substrate 20 will be described.

The substrate 20 forms a device member on the second main surface 202 to constitute a device. Here, the means for the device means a member constituting at least a part of the device. Specific examples of the member for the device include a thin film transistor (TFT, Thin Film Transistor) and a color filter (CF, Color Filter). As the device, a solar cell (PV), a liquid crystal panel (LCD), an organic EL panel (OLED), or the like can be exemplified.

The type of the substrate 20 may be a general one, for example, a germanium wafer, a glass substrate, a resin substrate, or a metal substrate such as a stainless steel (SUS) 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. As an index of the heat shrinkage rate, the linear expansion coefficient specified in JIS R 3102-1995 can be used.

When the linear expansion coefficient of the substrate 20 is large, since the manufacturing process of the apparatus is often accompanied by heat treatment, various problems are likely to occur. For example, when a TFT is formed on the substrate 20, if the substrate 20 on which the TFT is formed by heating is cooled, there is a thermal contraction of the substrate 20, and the positional shift of the TFT is excessively large.

The glass substrate can be obtained by melting a glass raw material and forming the molten glass into a plate shape. The above-mentioned forming method may be a general one, and for example, a floating method, a fusion method, a flow hole down-draw method, a rich method, a Luber method, or the like may be used. Further, the glass substrate having a particularly small thickness can be obtained by heating a glass which has been temporarily formed into a plate shape to a temperature at which it can be formed, and stretching it by means of stretching or the like (re-drawing method).

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

As the glass of the glass substrate, a glass suitable for the type of the device or a manufacturing step thereof can be used. For example, the glass substrate for a liquid crystal panel contains a glass (alkali-free glass) which does not substantially contain an alkali metal component because the elution of an alkali metal component is easy to influence a liquid crystal. In this manner, the glass of the glass substrate can be appropriately selected depending on the type of the apparatus to be applied and the manufacturing steps thereof.

The thickness of the glass substrate is not particularly limited, and is usually less than 0.8 mm, preferably 0.3 mm or less, and more preferably 0.15 mm or less from the viewpoint of thickness reduction and/or weight reduction of the glass substrate. When the thickness is 0.8 mm or more, the requirements for thinning and/or weight reduction of the glass substrate are not satisfied. When the thickness is 0.3 mm or less, good flexibility can be imparted to the glass substrate. When the thickness is 0.15 mm or less, the glass substrate can be wound into a roll 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. Specific examples thereof include polyethylene terephthalate resin, polycarbonate resin, polyimide resin, fluororesin, polyamide resin, aromatic polyamide resin, polyether oxime resin, polyether ketone resin, Polyetheretherketone resin, polyethylene naphthalate resin, polyacrylic resin, various liquid crystal polymer resins, cycloolefin resins, polyoxyxylene resins, and the like. Further, the resin substrate may be transparent or opaque. Further, the resin substrate may be formed by forming a functional layer such as a protective layer on the surface.

Furthermore, the substrate 20 may include two or more layers. In this case, the materials forming the layers may be the same material or different materials. Moreover, in this case, "the thickness of the substrate 20" means the total thickness of all the layers in the substrate. The thickness of the substrate 20 is usually less than 1.0 mm, preferably 0.5 mm or less, and more preferably 0.3 mm or less from the viewpoint of thinning and/or weight reduction of the substrate. Further, it is preferably 0.01 mm or more depending on the ease of production of the substrate and the ease of handling of the substrate.

Next, the support board 31 will be described.

The support plate 31 cooperates with the resin layer 32 to support and reinforce the substrate 20, thereby preventing deformation, damage, breakage, and the like of the substrate 20 in the manufacturing steps of the device. Moreover, when a substrate 20 having a thinner thickness than the previous one is used, by forming the laminated body 10 having the same thickness as the previous substrate, a manufacturing technique or manufacturing apparatus suitable for the substrate of the previous thickness can be used in the manufacturing steps of the device. It is also one of the purposes of using the support board 31.

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

The thickness of the support plate 31 may be thicker than the substrate 20 or thinner than the substrate 20. It is preferable to select the thickness of the support plate 31 in accordance with the thickness of the substrate 20, the thickness of the resin layer 32, and the thickness of the laminated body 10. For example, in the case where the manufacturing process of the current apparatus is designed to handle a substrate having a thickness of 0.5 mm, and the sum of the thickness of the substrate 20 and the thickness of the resin layer 32 is 0.1 mm, the thickness of the support plate 31 is used. Set to 0.4 mm. In the usual case, the thickness of the support plate 31 is preferably 0.08 to 5.0 mm, more preferably 0.2 to 5.0 mm, and still more preferably 0.2 to 1.0 mm.

In the case where the support plate 31 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more for reasons of easy handling, difficulty in breaking, and the like. Moreover, the thickness of the glass plate is preferably 1.0 mm or less, depending on the reason why the member for the device is peeled off after formation and can be expected to be moderately bent without being broken.

The difference between the average linear expansion coefficient of the substrate 20 and the support plate 31 at 25 to 300 ° C (hereinafter referred to as "average linear expansion coefficient") is preferably 500 × 10 ^-7 / ° C or less, more preferably 300 × 10 ^{- 7} / ° C or less, and more preferably 200 × 10 ^-7 / ° C or less. If the difference is too large, there is a possibility that the laminate 10 is severely warped during heating and cooling in the manufacturing process of the apparatus, and the substrate 20 and the reinforcing plate 30 are peeled off. When the material of the substrate 20 is the same as the material of the support plate 31, the above problem can be suppressed.

Next, the resin layer 32 will be described.

The resin layer 32 is fixed to the support plate 31, and is detachably adhered to the substrate 20. The resin layer 32 prevents the positional deviation of the substrate 20 before performing the peeling operation, and is easily peeled off from the substrate 20 by the peeling operation, thereby preventing the substrate 20 or the like from being damaged by the peeling operation.

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

The surface 321 of the substrate side of the resin layer 32 (hereinafter also referred to as "adhesive surface 321") is preferably not by the adhesive force as a general adhesive, but by the vanadium caused by the solid molecules. The force of the Van Der Waals force is attached to the surface 201 of the substrate 20 (hereinafter also referred to as "the contact surface 201"). The reason for this is that it can be easily peeled off. In the present invention, the property of the surface of the resin layer which can be easily peeled off is referred to as peelability.

On the other hand, the bonding strength of the resin layer 32 to the surface of the support plate 31 is relatively higher than the bonding force of the resin layer 32 to the surface 201 of the substrate 20. Therefore, the peeling strength between the resin layer 32 and the support sheet 31 is higher than the peel strength between the resin layer 32 and the substrate 20. In the present invention, the bonding of the surface of the resin layer to the surface of the substrate is referred to as adhesion, and the bonding of the surface of the resin layer to the surface of the support plate is referred to as fixation. Preferably, the resin layer 32 and the support plate 31 are bonded by an adhesive force or an adhesive force. However, the present invention is not limited thereto, and as long as it is relatively higher than the bonding strength of the resin layer 32 to the adhesion surface 201, the resin layer 32 and the support plate 31 may be caused by the force due to the above-described van der Waals force. Attached.

The thickness of the resin layer 32 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. The reason for this is that when the thickness of the resin layer 32 is in the above range, the adhesion between the resin layer 32 and the substrate 20 is sufficient. Moreover, the reason is that even if air bubbles or foreign matter are interposed between the resin layer 32 and the substrate 20, the occurrence of strain defects of the substrate 20 can be suppressed. Moreover, when the thickness of the resin layer 32 is too thick, it takes time and material to form a resin layer, and it is economically disadvantageous.

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

Moreover, when the resin layer 32 contains two or more layers, the kind of the resin which forms each layer may differ.

The resin layer 32 preferably contains a material having a glass transition point lower than room temperature (about 25 ° C) or having no glass transition point. This is because the resin layer 32 is a non-adhesive resin layer, and can be more easily peeled off from the substrate 20, and the adhesion to the substrate 20 is also sufficient.

Further, since the resin layer 32 is often subjected to heat treatment in the manufacturing process of the apparatus, it is preferably heat-resistant.

Further, when the elastic modulus of the resin layer 32 is too high, the adhesion to the substrate 20 tends to be low. On the other hand, if the elastic modulus of the resin layer 32 is too low, the peelability becomes low.

The kind of the resin forming the resin layer 32 is not particularly limited. For example, an acrylic resin, a polyolefin resin, a polyurethane resin, and a polyoxyl resin can be mentioned. It can also be used by mixing several kinds of resins. Among them, polyfluorene oxide resin is preferred. The reason for this is that the polyoxynoxy resin is excellent in heat resistance and peelability. Further, the reason is that when the support plate 31 is a glass plate, it is easily fixed to the glass plate by a condensation reaction with a stanol group on the surface of the glass plate. Even if the polyoxynoxy resin layer is interposed between the support plate 31 and the substrate 20, for example, in the atmosphere, it is treated at about 200 ° C for about 1 hour, and the peeling property is hardly deteriorated. Preferably.

The resin layer 32 is preferably a polyoxyl resin (hardened product) for use in a release paper in a polyoxyxylene resin. The resin layer 32 formed by curing the surface of the support sheet 31 as a curable resin composition for a release resin for a release paper has excellent releasability, which is preferable. Moreover, since the flexibility is high, even if foreign matter such as bubbles or dust is mixed between the resin layer 32 and the substrate 20, the occurrence of strain defects of the substrate 20 can be suppressed.

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

The addition reaction type polyoxo oxygen-based 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 polyoxane is promoted by heat treatment. The main component of the addition reaction type polyoxane includes a linear organopolyoxyalkylene (ie, an organic alkenyl polyoxyalkylene) having an alkenyl group (vinyl group or the like) bonded to a ruthenium atom, and a vinyl group or the like Cross-linking point. The addition reaction type polyfluorene crosslinking agent comprises a linear organopolyoxane (i.e., an organic hydrogen polyoxyalkylene) having a hydrogen atom (hydroalkylene group) bonded to a halogen atom, a hydroquinone group, or the like. Become a cross-linking point.

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 can be used. Among these, a solventless type is preferred. The reason is excellent in terms of productivity, safety, and environmental characteristics. Moreover, when curing the resin layer 32, that is, when heat curing, ultraviolet curing, or electron beam curing is performed, the solvent that causes foaming is not contained, so that it is difficult to leave bubbles in the resin layer 32.

In addition, as a commercially available product name or model, KNS-320A and KS-847 (both manufactured by Shin-Etsu Silicone Co., Ltd.) are specifically mentioned as a curable polyfluorene which is a polyoxyl resin for a release paper. ), TPR6700 (manufactured by GE Toshiba Silicone Co., Ltd.), vinyl polyoxylium "8500" (manufactured by Arakawa Chemical Industries, Ltd.), and methyl hydrogen polyoxyalkylene "12031" (manufactured by Arakawa Chemical Industries, Ltd.), vinyl polymerization a combination of "11364" (manufactured by Arakawa Chemical Industries Co., Ltd.) and methyl hydrogen polyoxyalkylene "12031" (manufactured by Arakawa Chemical Industries, Ltd.), vinyl polyoxylium "11365" (manufactured by Arakawa Chemical Industries, Ltd.) and A A combination of a base hydrogen polyoxane "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 32 preferably has a property that it is difficult to transfer the components in the polyoxynoxy resin layer to the substrate 20, that is, oligomeric oxygen transfer property.

The method of fixing the resin layer 32 to the support plate 31 is not particularly limited, and examples thereof include a method of fixing a film-like resin to the surface of the support plate 31. Specifically, in order to impart a high fixing force (high peel strength) to the surface of the film, the surface of the support plate 31 is subjected to a surface modification treatment (primer treatment) to fix the resin layer 32 to the resin layer 32. Support plate 31. For example, a chemical method such as a chemical reaction for increasing the fixing force of a decane coupling agent (underlayer treatment), a physical method of increasing a surface active group such as a flame treatment, and an increase in surface roughness by sandblasting may be exemplified. Mechanical handling methods for holding power, etc.

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

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

For example, when the resin layer 32 is formed of a curable resin composition of an addition reaction type polyoxymethylene, the organic alkenyl polysiloxane or the organic hydrogen polyoxygen oxide is contained by a known method such as the above-described spraying method. The curable resin composition of the mixture of the alkane and the catalyst is applied onto the support sheet 31, and then heat-hardened. The heat-hardening conditions are also different depending on the amount of the catalyst to be mixed. For example, 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 organohydrogenpolyoxyalkylene. In the case of the reaction, the reaction is carried out at 50 ° C to 250 ° C, preferably at 100 ° C to 200 ° C in the atmosphere. Further, the reaction time in this case is set to 5 to 60 minutes, preferably 10 to 30 minutes.

By curing the curable resin composition by heat hardening, the polyoxyxylene resin is chemically bonded to the support sheet 31 at the time of the hardening reaction, and/or the polyoxyxylene resin layer is bonded to the support sheet 31 by the anchoring effect. By these actions, the polyoxyxene resin layer is firmly fixed to the support plate 31. In the case where a resin layer containing a resin other than the polyfluorene resin is formed from the curable resin composition, the resin layer fixed to the support sheet may be formed by the same method as described above.

The method of adhering the resin layer 32 to the substrate 20 in a peelable manner can be a well-known method. For example, a method in which the resin layer 32 and the substrate 20 are pressure-bonded by using a roll or a press after the substrate 20 is superposed on the peeling surface of the resin layer 32 in a normal pressure environment. The resin layer 32 and the substrate 20 can be more cryptographically bonded by pressure bonding using a roll or a press, which is preferable. Further, since the air bubbles mixed between the resin layer 32 and the substrate 20 can be relatively easily removed by pressure bonding using 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 crimping under vacuum, there is also an advantage that even in the case where fine bubbles remain, the bubbles are not grown by heating, and it is difficult to cause strain defects of the substrate 20.

When the resin layer 32 is peelably adhered to the substrate 20, it is preferable to sufficiently clean the surface of the resin layer 32 and the substrate 20 on the side in contact with each other, and to laminate the layer in a highly clean environment. That is, it is easy to mix foreign matter between the resin layer 32 and the substrate 20, and the flatness of the surface of the substrate 20 is not affected by the deformation of the resin layer 32. The higher the cleanliness, the better the flatness, which is preferable.

Further, the order of the step of fixing the resin layer 32 to the support plate 31 and the step of adhering the resin layer 32 to the substrate 20 in a peelable manner are not limited, and for example, they may be performed substantially simultaneously.

In the present invention, at least one of the adhesion surface 201 and the adhesion surface 321 is previously treated with a polyoxygenated oil or a decane coupling agent, or the resin layer 32 is formed of a resin containing a polyoxygenated oil or a decane coupling agent. In the first embodiment, the surface treatment of the former is performed. By subjecting at least one of the adhesion surface 201 and the adhesion surface 321 to surface treatment with a polyoxygenated oil or a decane coupling agent before the adhesion, the density of the polar groups existing on the adhesion surfaces 201 and 321 can be appropriately adjusted. Furthermore, in the present embodiment, the adhesion surface 201 on the substrate 20 side may be subjected to surface treatment in advance, or the adhesion surface 321 on the resin layer 32 side may be surface-treated in advance, and the adhesion surfaces 201 on both sides may be previously provided. 321 is surface treated. In addition, by forming the resin layer 32 from the resin containing a polysiloxane or a decane coupling agent (second embodiment), the density of the polar group existing on the adhesion surface 321 can be appropriately adjusted in the same manner.

Here, examples of the polar group present on the surface of the glass substrate include a hydroxyl group (-OH). Moreover, examples of the polar group present on the surface of the resin layer include a carbonyl group (-CO) and a carboxyl group (-COOH). These polar groups are all hydrophilic groups.

The density of the polar groups existing on the adhesion surfaces 201 and 321 of the substrate 20 and the resin layer 32 is appropriate, and the water contact angle of the surfaces of the adhesion surfaces 201 and 321 can be measured before the adhesion. Generally, the higher the density of the hydrophilic polar groups present on the surface, the smaller the water contact angle. Here, the water contact angle means a contact angle defined in JIS R 3257-1999.

The water contact angle of the surface-treated adhesive surfaces 201, 321 before the adhesion is preferably 90 or more, more preferably 90 to 120, and still more preferably 90 to 110. If the water contact angles before the close contact between the two adjacent surfaces 201 and 321 are less than 90, the density of the polar groups present on the surface of the substrate 20 or the resin layer 32 is too high. Therefore, if the temperature of the laminated body 10 exceeds 250 ° C in the manufacturing process of the apparatus, chemical bonding between the substrate 20 and the resin layer 32 can be promoted, and it is difficult to separate the substrate 20 from the resin layer 32 (the reinforcing plate 30).

The surface having a water contact angle of 90 or more before the adhesion is preferably the adhesion surface 201 of the substrate 20. When the water contact angle of the adhesion surface 201 is 90° or more, even if the water contact angle before the adhesion of the adhesion surface 321 is less than 90°, the resin layer 32 and the substrate can be easily peeled off as long as the resin is not particularly hydrophilic. 20. In particular, when the resin layer 32 is a hydrophobic resin such as a polysiloxane resin, even if the water contact angle before the adhesion of the adhesion surface 321 is less than 90°, the resin layer 32 can be easily peeled off.

The fine surface 201 of the substrate 20 may be previously formed with a fine uneven structure by surface treatment before the adhesion. In this case, by the anchoring effect of the uneven structure, the bonding surface 201 of the substrate 20 can be brought into close contact with the adhesion surface 321 of the resin layer 32 with sufficient bonding force, and the laminated body 10 can be easily handled. Further, when the fine uneven structure is formed by the surface treatment, the water contact angle tends to increase, and the water contact angle may exceed 120°.

The surface to be surface-treated is preferably a sufficiently clean surface, preferably a surface just after washing. If the cleanliness (activity) is too low, uniform surface treatment cannot be performed. As the washing method, a usual method used for washing the glass surface or the resin surface can be used.

The surface which is not subjected to the surface treatment is preferably protected by a protective film such as a mask in advance. The reason for this is that in the manufacturing step of the device, it is difficult to form the member for the device on the surface on which the surface-treated material is erroneously adhered.

The polyoxygenated oil and the decane coupling agent which are materials for surface treatment may be used singly or in combination. In the case of combined use, the surface treatment may be carried out after the surface treatment of the decane coupling agent, or the surface treatment may be carried out by polyoxygenated oil, followed by surface treatment with a decane coupling agent.

The type of the polyoxygenated oil is not particularly limited, and examples thereof include straight silicone oil such as dimethylpolyphthalic acid oil, methylphenyl polyfluorene oxide oil, and methyl hydrogen polyoxygenated oil. A modified polyoxyxylene oil having an alkyl group, a hydrogen group, an epoxy group, an amine group, a carboxyl group, a polyether group, a halogen group or the like introduced into the side chain or the terminal. Specific examples thereof include methyl hydrogen polyoxyalkylene oxide, dimethyl polyoxyalkylene oxide, methylphenyl polyoxyalkylene oxide, and diphenyl polyoxyalkylene. The heat resistance is gradually increased in the order listed. The highest heat resistance is diphenyl polysiloxane. These polyoxygenated oils are generally used for water repellent treatment on the surface of a substrate such as a glass substrate or a metal substrate subjected to an underlayer treatment.

The surface treatment method using polyoxygenated oil can be a general method. In the treatment of coating only the polyoxygenated oil, there is a possibility that the polyoxyphthalocene oil is bonded to the surface to be treated to a low extent and the treatment effect cannot be sufficiently exerted. Therefore, it is preferred to apply the polyfluorene oxide after the coating. The polyoxygenated oil is combined with the treatment of the treated surface. The treatment of binding the polyoxyxene oil to the surface to be treated is a treatment such as cutting the molecular chain of the polyoxygenated oil, and it is considered that the cut segment is bonded to the surface to be treated (hereinafter, the treatment is referred to as a low concentration of polyoxygenated oil). Molecular weight).

As a surface treatment method using polyoxyxylene oil, a method of applying a polyoxyxylene oil to the adhesion surface 201 of the substrate 20 or the adhesion surface 321 of the resin layer 32 is preferably carried out to reduce the molecular weight. The density of the polar groups existing on the adhesion surface 201 of the substrate 20 or the adhesion surface 321 of the resin layer 32 can be adjusted to be optimized by adjusting the coating amount of the polyoxygenated oil or the processing conditions for lowering the molecular weight. Therefore, when the resin layer 32 and the substrate 20 are peeled off, the resin layer 32 can be prevented from being agglomerated and destroyed.

The coating method of the polyoxygenated oil can be a general method. For example, depending on the type or coating amount of the polyoxygenated oil, self-spraying method, die coating method, spin coating method, dip coating method, roll coating method, bar coating method, screen printing method, gravure coating method, etc. Appropriately selected. As the coating liquid, it is preferred to use a solution in which the polyfluorene oxide oil is diluted to 1% by mass or less with a solvent such as hexane, heptane or xylene. When it exceeds 1 mass%, the processing time of low molecular weight is too long. Further, it is preferred to use a solution diluted to 0.01% by mass or more. If it is less than 0.01% by mass, it is not sufficient to optimize the density of the polar group.

A method of lowering the molecular weight of the polyoxygenated oil can be carried out by a general method such as a method of cutting the oxygen bond of the polyoxygenated oil by photolysis or thermal decomposition. In the photolysis, ultraviolet rays irradiated from a low-pressure mercury lamp or a xenon arc lamp or the like may be used, and ozone generated by ultraviolet irradiation in the atmosphere may be used in combination. The thermal decomposition can be carried out in a batch furnace, a conveyor furnace, or the like, or a plasma or an arc discharge or the like can be used. In the case of thermal decomposition using a batch furnace or a conveyor furnace, it is also preferably treated at a temperature of from 250 ° C to 400 ° C depending on the type or concentration of the polyoxygenated oil of the above coating liquid. When the temperature is less than 250 ° C, the molecular weight of polyoxymethylene is insufficient, and when it exceeds 400 ° C, the cerium oxide of polyoxymethylene is remarkable, and it is insufficient as a low molecular weight treatment.

When the oxygen bond of the polyoxygenated oil is cut, the density of the hydrophobic functional group such as a methyl group becomes high, and the density of the hydrophilic polar group existing on the adhesion surface 201 of the substrate 20 or the adhesion surface 321 of the resin layer 32 is lowered. . Further, if the oxygen bond of the polyoxygenated oil is excessively cleaved, the density of the hydrophilic polar group tends to increase again.

The type of the decane coupling agent is not particularly limited, and for example, hexamethyldiaziridine (HMDS), 3-aminopropyltriethoxydecane, and N-(2-aminoethyl) can be preferably used. --3-aminopropyltrimethoxydecane, N-{N-(2-aminoethyl)-2-aminoethyl}-3-aminopropyltrimethoxydecane, 3-anilino An alkyl decane such as propyltrimethoxydecane; or an epoxy decane such as 3-glycidoxypropyltrimethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; Such as 3-chloropropyltrimethoxydecane chlorodecane or fluorodecane; 3-mercaptotrimethoxydecane and other decyl decane; vinyl trimethoxy decane, N-2-(N-vinylbenzyl-2 One or more of a vinyl decane such as an aminoethyl)-3-aminopropyltrimethoxy decane or an acrylonitrile decane such as 3-methylpropenyloxypropyltrimethoxydecane.

The surface treatment method using a decane coupling agent can be a general method. For example, in a case where the adhesion surface 201 of the substrate 20 or the adhesion surface 321 of the resin layer 32 is exposed to a gas containing a gas obtained by vaporizing a decane coupling agent, it may exist on the adhesion surface 201 of the substrate 20 or the adhesion surface of the resin layer 32. A method in which a hydrophilic polar group of 321 is substituted with a hydrophobic functional group such as a methyl group. By adjusting the concentration, temperature, treatment time, and the like of the decane coupling agent in the environment, the density of the polar groups existing on the adhesion surface 201 of the substrate 20 or the adhesion surface 321 of the resin layer 32 can be optimized. Therefore, when the resin layer 32 and the substrate 20 are peeled off, the resin layer 32 can be suppressed from being agglomerated and destroyed.

Further, the adhesion surfaces 201 and 321 are mutually peeled off in the middle of the manufacturing process of the apparatus, and can be restored to the state before the surface treatment by a specific treatment. For example, a surface subjected to surface treatment using a polyoxygenated oil or a decane coupling agent can be restored to a state before surface treatment by photolysis or thermal decomposition. In this manner, for example, when the surface 201 of the substrate 20 is returned to the state before the surface treatment, when the optical film (for example, a polarizing film) is attached to the surface 201, the adhesion strength can be improved. Further, if the reworkability is emphasized, the optical film may be attached to the surface 201 of the substrate 20 in the state after the surface treatment.

(Second embodiment)

The configuration of the laminated body of the present embodiment is substantially the same as that of Fig. 1, and therefore the illustration thereof is omitted.

In the present embodiment, the resin layer 32 is formed of a resin containing a polyoxygenated oil or a decane coupling agent. The resin layer 32 is preferably formed by curing a curable resin composition containing a polyoxygenated oil or a decane coupling agent. The curable resin composition is not particularly limited, and for example, a curable resin composition which is a polyfluorene resin for release paper can be used. Further, the adhesion surfaces 201 and 321 of the substrate 20 and the resin layer 32 may not be subjected to the surface treatment before the adhesion.

The polyoxygenated oil and the decane coupling agent may be used singly or in combination, and it is preferred to use a functional group which does not have a reaction with a component of the curable resin composition, respectively. For example, when the resin layer 32 is formed of the above-described addition reaction type polyoxyl curable resin composition, as the polyoxygenated oil or the decane coupling agent, a functional group which does not have a crosslinking point (for example, ethylene) can be used. Or a hydroquinone group. In the case where the resin layer 32 is formed of the condensation reaction type polyfluorene-based curable resin composition, a polyoxygenated oil which does not have a co-condensable functional group (hydrolyzable group or stanol group or the like) can be used.

The polyoxygenated oil is dispersed in the resin layer 32 without being crosslinked at the time of curing of the curable resin composition. Further, the decane coupling agent is usually condensed at the time of curing of the curable resin composition, and is contained in the cured resin in the form of a condensate of a decane coupling agent. Therefore, a condensate containing a polyoxygenated oil or a decane coupling agent is dispersed on the adhesion surface 321 of the resin layer 32.

For example, when the adhesion surface 321 of the resin layer 32 contains a polyoxygenated oil, if the temperature of the laminated body 10 becomes high in the manufacturing process of the apparatus, the polyoxygenated oil is reduced in molecular weight. As a result, the density of the hydrophilic polar group existing in the two close contact faces 201 and 321 is lowered, and the density of the hydrophobic functional group such as a methyl group is increased.

In the case where the adhesion surface 321 of the resin layer 32 contains a decane coupling agent condensate, the hydrophilic polar group of the two adhesion surfaces 201 and 321 is substituted with a hydrophobic functional group such as a methyl group.

Therefore, by adjusting the content or type of the polyoxygenated oil or the decane coupling agent contained in the curable resin composition to be the resin layer 32, the density of the polar groups existing on the two closely-bonded surfaces 201 and 321 can be adjusted to the maximum. Jiahua.

Therefore, in the present embodiment, similarly to the first embodiment, the resin layer 32 can be prevented from being agglomerated and broken when the resin layer 32 and the substrate 20 are peeled off. Further, since the step of lowering the molecular weight of the polyoxygenated oil is carried out together with the steps of other purposes, and there is no step of vaporizing the decane coupling agent, the number of operations can be reduced.

The content of the polyoxygenated oil and the decane coupling agent to be contained in the curable resin composition of the resin layer 32 is preferably 0.1 to 5% by mass based on the solid content of the curable resin composition. When the content is less than 0.1% by mass, sufficient effects cannot be obtained. On the other hand, when the content exceeds 5% by mass, the heat resistance of the resin layer 32 becomes too low.

In the case of the second embodiment, the surface 201 of the substrate 20 may not be subjected to the surface treatment in the first embodiment. In the case where the substrate 20 is a glass substrate, since the surface thereof is a surface having high hydrophilicity, the surface of the first embodiment can be preliminarily performed before the adhesion surface 201 is adhered.

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples.

[Example 1]

As the substrate and the support plate, a glass plate (manufactured by Asahi Glass Co., Ltd., AN100, alkali-free glass) which is obtained by a floating method and has a length of 720 mm × a width of 600 mm is used. Further, the thickness of the substrate was set to 0.4 mm, and the thickness of the support plate was set to 0.3 mm. The average linear expansion coefficients of the substrate and the support plate were 38 × 10 ^-7 / ° C, respectively.

(production of reinforcing board)

The support plate is washed with pure water and UV (ultraviolet) to clean the surface of the support plate. Thereafter, a curable resin composition (coating amount: 30 g/m ² ) was applied to one side of the support sheet by screen printing.

The curable resin composition was 100 parts by mass of a solvent-free addition-reactive polyfluorene (Kn-Etsu Silicone Co., Ltd., KNS-320A) and a platinum-based catalyst (manufactured by Shin-Etsu Silicone Co., Ltd., CAT-PL-56) 2 a mixture of parts by mass.

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

The mixture coated on the support plate was heat-hardened at 180 ° C for 30 minutes in the atmosphere, and a polyoxynitride resin layer having a length of 705 mm × a width of 595 mm × a thickness of 20 μm was formed in the center of the support plate and fixed.

(surface treatment of the substrate)

The substrate is washed with pure water and UV washed to clean the surface of the substrate. Thereafter, after the second main surface of the single surface of the substrate was masked, a heptane solution having a polyoxygenated oil content of 0.5% by mass was sprayed on the first main surface on the opposite side, and dried. As the polyoxygenated oil, dimethylpolysiloxane (manufactured by Dow Corning Toray Co., Ltd., SH200) was used. Then, in order to lower the molecular weight of the polyoxygenated oil, ultraviolet treatment with a low pressure mercury lamp was carried out for 2 minutes in the air.

Thereafter, using a contact angle meter (Kr Manufactured by Ss Corporation, DROP SHAPE ANALYSIS SYSTEM DSA 10Mk2), the water contact angle of the first main surface of the substrate was measured and found to be 100°.

(production of laminated body)

After the ultraviolet treatment, the polyoxyxylene resin layer was placed on the first main surface of the substrate, and the substrate and the polyoxyxylene resin layer were adhered to each other at room temperature by a vacuum press to obtain a laminate including the substrate and the reinforcing plate.

(heat test of laminate)

The laminate was heat-treated at 350 ° C for 1 hour in a nitrogen atmosphere having a volume concentration of oxygen of 1000 ppm or less. Thereafter, after cooling to room temperature, a peeling blade is pierced between the substrate and the polyoxynitride resin layer to keep the substrate side flat, and the side of the polyoxyxylene resin layer is sequentially bent and deformed from the vicinity of the piercing position, and the substrate is peeled off. With a layer of polyoxymethylene resin.

No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer material from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 100°.

[Embodiment 2]

The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(production of reinforcing board)

In Example 2, a linear organoalkenyl polyoxyalkylene having a vinyl group at both ends (vinyl polyfluorene, manufactured by Arakawa Chemical Industries, Ltd., 8500) and a methyl hydrogen group having a hydroquinone group in the molecule were used. A mixture of a siloxane (manufactured by Arakawa Chemical Industry Co., Ltd., 12031) and a platinum-based catalyst (manufactured by Arakawa Chemical Industries, Ltd., CAT 12070) was used as a curable resin composition, and was reinforced in the same manner as in Example 1. board.

Here, the mixing ratio of the linear organic alkenyl polyoxyalkylene to the methylhydrogenpolyoxyalkylene is adjusted so that the molar ratio of the vinyl group to the hydrofluorenyl group becomes 1:1. In addition, the platinum-based catalyst is used in an amount of 5 parts by mass based on 100 parts by mass of the total of the linear organic alkenyl polysiloxane and the methylhydrogenpolyoxyalkylene.

(surface treatment of the substrate)

In the second embodiment, in order to carry out the low molecular weight of the polyoxygenated oil, the plasma treatment is carried out using a remote plasma device (RT series manufactured by Sekisui Chemical Co., Ltd., RT series), in addition to The surface treatment of the substrate was carried out in the same manner as in Example 1.

Here, the processing conditions of the plasma treatment were set to output 3 kw, nitrogen/air flow ratio = 600 slm/750 sccm, and conveying speed of 5 m/min. The surface temperature of the substrate when the plasma is irradiated is 50 ° C or lower. The water contact angle of the first main surface of the surface-treated substrate was 95°.

(production of laminated body)

After the surface treatment, a laminate including the substrate and the reinforcing plate was obtained in the same manner as in Example 1.

(heat test of laminate)

After the laminate was heat-treated in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer material from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 100°.

[Example 3]

The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(production of reinforcing board)

In Example 3, a reinforcing plate was produced in the same manner as in Example 2.

(surface treatment of the substrate)

In the third embodiment, the surface treatment of the substrate was carried out in the same manner as in Example 1 except that the polyoxymethane oil was reduced in molecular weight and heat-treated at 400 ° C for 10 minutes in the air. The water contact angle of the first main surface of the surface-treated substrate was 105°.

(production of laminated body)

After the surface treatment, a laminate including the substrate and the reinforcing plate was obtained in the same manner as in Example 1.

(heat test of laminate)

After the laminate was heat-treated in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer material from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 105°.

[Example 4]

The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(production of reinforcing board)

In Example 4, a reinforcing plate was produced in the same manner as in Example 2.

(surface treatment of the substrate)

In Example 4, in order to reduce the molecular weight of the polyoxygenated oil, a heptane solution having a polyoxyxane content of 0.1% by mass was sprayed on the first main surface of the substrate, and dried in the atmosphere at 250. The surface treatment of the substrate was carried out in the same manner as in Example 1 except that the temperature was heated for 10 minutes at °C. The water contact angle of the first main surface of the surface-treated substrate was 98°.

(production of laminated body)

After the surface treatment, a laminate including the substrate and the reinforcing plate was obtained in the same manner as in Example 1.

(heat test of laminate)

After the laminate was heat-treated in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer material from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 98°.

[Example 5]

The substrate and the support plate were each made of a glass plate (manufactured by Asahi Glass Co., Ltd., AS, soda lime glass) having a length of 720 mm × a width of 600 mm obtained by a floating method. Further, the thickness of the substrate was set to 0.4 mm, and the thickness of the support plate was set to 0.3 mm. The average linear expansion coefficients of the substrate and the support plate were 85×10 ^-7 /°C, respectively.

(production of reinforcing board)

In Example 5, a reinforcing plate was produced in the same manner as in Example 2.

(surface treatment of the substrate)

In the fifth embodiment, in order to reduce the molecular weight of the polyoxygenated oil, a heptane solution having a polyoxyxane content of 0.5% by mass is sprayed on the first main surface of the substrate, and dried in the atmosphere at 350. The surface treatment of the substrate was carried out in the same manner as in Example 1 except that the temperature was heated for 10 minutes at °C. The water contact angle of the first main surface of the surface-treated substrate was 102°.

(production of laminated body)

After the surface treatment, a laminate including the substrate and the reinforcing plate was obtained in the same manner as in Example 1.

(heat test of laminate)

After the laminate was heat-treated in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer material from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 102°.

[Embodiment 6]

The same glass plate as in Example 5 except for chemical strengthening was used for the substrate and the support plate, respectively.

(production of reinforcing board)

In Example 6, a reinforcing plate was produced in the same manner as in Example 2.

(surface treatment of the substrate)

In Example 6, the surface treatment of the substrate was carried out in the same manner as in Example 5 in order to reduce the molecular weight of the polyoxygenated oil. The water contact angle of the first main surface of the surface-treated substrate was 102°.

(production of laminated body)

After the surface treatment, a laminate including the substrate and the reinforcing plate was obtained in the same manner as in Example 1.

(heat test of laminate)

After the laminate was heat-treated in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer material from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 102°.

[Embodiment 7]

The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(production of reinforcing board)

The support plate is washed with pure water and UV washed to clean the surface of the support plate. Thereafter, a mixture of 99.5 parts by mass of the curable resin composition and 0.5 parts by mass of the polyoxyxylene oil (coating amount: 30 g/m ² ) was applied to one side of the support sheet by screen printing. Here, as the curable resin composition, the same as in Example 2 was used, and dimethylpolysiloxane (manufactured by Dow Corning Toray Co., Ltd., SH200) was used.

The mixture coated on the support plate was heat-hardened at 180 ° C for 30 minutes in the atmosphere, and a polyoxynitride resin layer having a length of 705 mm × a width of 595 mm × a thickness of 20 μm was formed in the center of the support plate and fixed.

(production of laminated body)

After the preparation of the reinforcing plate, the surface of the substrate is washed with a polysilicon oxide resin layer, and the substrate is adhered to the polyoxyn resin layer by a vacuum press at room temperature to obtain a laminate comprising the substrate and the reinforcing plate. body.

(heat test of laminate)

After the laminate was heat-treated in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer of the resin from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 102°.

[Embodiment 8]

A substrate of 720 mm × 600 mm in width was used for the substrate and the support plate (Toray‧Dupont, Kapton 200HV). Further, the thickness of the substrate was set to 0.05 mm, and the thickness of the support plate was set to 0.5 mm.

(production of reinforcing board)

In Example 8, a reinforcing plate was produced in the same manner as in Example 2.

(surface treatment of the substrate)

In Example 8, the surface treatment of the substrate was carried out in the same manner as in Example 2. The water contact angle of the first main surface of the surface-treated substrate was 100°.

(production of laminated body)

After the surface treatment, the polyoxyxylene resin layer was placed on the first main surface of the substrate, and the substrate was adhered to the polyoxymethylene resin layer by a vacuum press at room temperature to obtain a laminate including the substrate and the reinforcing plate.

(heat test of laminate)

After the laminate was heat-treated in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer material from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 100°.

[Embodiment 9]

The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(production of reinforcing board)

In Example 9, a reinforcing plate was produced in the same manner as in Example 2.

(surface treatment of the substrate)

The substrate is washed with pure water and UV washed to clean the surface of the substrate. Thereafter, after the second main surface of the single surface of the substrate is masked, the first main surface on the opposite side is maintained in a saturated state in a gas obtained by vaporizing a decane coupling agent (manufactured by Dow Corning Toray Co., Ltd., Z6040). Exposure for 10 minutes in the environment. The surface temperature of the substrate when exposed was 25 °C. The water contact angle of the first main surface of the exposed substrate was 100°.

(production of laminated body)

After surface treatment with a decane coupling agent, the polyoxyxylene resin layer is superposed on the first main surface of the substrate, and the substrate and the polyoxynoxy resin layer are adhered to each other by a vacuum press at room temperature to obtain a substrate and a reinforcing plate. Laminated body.

(heat test of laminate)

After the laminate was heat-treated in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the polyoxyxene resin layer after peeling observed by an optical microscope, and no transfer material from the polyoxyxylene resin layer was observed on the substrate after peeling. Further, the water contact angle of the first main surface of the substrate after peeling was 100°.

[Comparative Example 1]

The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(production of laminated body)

In Comparative Example 1, a reinforcing plate was produced in the same manner as in Example 2, and the first main surface of the substrate was washed with pure water and UV-cleaned to be cleaned, and then laminated on the first main surface of the substrate. The oxygen resin layer was adhered to the polyoxynitride resin layer by a vacuum press at room temperature to obtain a laminate including the substrate and the reinforcing plate. Further, the water contact angle before the adhesion of the adhesion surface (first main surface) of the substrate was 7°.

(heat test of laminate)

After the laminate was subjected to a heat treatment in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. As a result, the polyoxyxylene resin layer was agglomerated and a part of the polyoxynitride resin layer was adhered to the substrate. side.

[Comparative Example 2]

The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(production of reinforcing board)

In Comparative Example 2, a reinforcing plate was produced in the same manner as in Example 2.

(production of laminated body)

A reinforcing plate was produced in the same manner as in Example 2, and the first main surface of the substrate was washed with pure water to be cleaned, and then the polyoxyalkyl resin layer was laminated on the first main surface of the substrate, and the mixture was allowed to stand at room temperature. The substrate was adhered to the polyoxymethylene resin layer by a vacuum press to obtain a laminate including the substrate and the reinforcing plate. Further, the water contact angle before the first main surface of the substrate was in contact with each other was 40°.

(heat test of laminate)

After the laminate was subjected to a heat treatment in the same manner as in Example 1, the substrate and the polyoxyalkylene resin layer were peeled off in the same manner as in Example 1. As a result, the polyoxyxylene resin layer was agglomerated and a part of the polyoxynitride resin layer was adhered to the substrate. side.

The present invention has been described in detail with reference to the preferred embodiments thereof.

The present application is based on Japanese Patent Application No. 2010-108952, filed on Jan.

10. . . Laminated body

20. . . Substrate

30. . . Reinforcing plate

31. . . Support board

32. . . Resin layer

201. . . Close contact surface (1st main surface)

202. . . Second main face

321. . . Close contact

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial side elevational view showing an example of a laminate of the present invention.

10. . . Laminated body

20. . . Substrate

30. . . Reinforcing plate

31. . . Support board

32. . . Resin layer

201. . . Close contact surface (1st main surface)

202. . . Second main face

321. . . Close contact

Claims (11)

A method for producing a laminate comprising a method of producing a laminate of a substrate, a support plate, and a resin layer present between the substrate, and a method of forming the resin layer on the support plate, and a step of adhering the resin layer to the substrate in a peelable manner, and comprising the step of treating at least one of the surface of the substrate to be adhered and the surface of the resin layer to be closely adhered by a polyoxygenated oil or a decane coupling agent before the adhesion step Or, in the step of forming the resin layer, the resin layer is formed of a resin containing a polysiloxane or a decane coupling agent, and thereafter, the substrate and the resin layer are adhered to each other in the adhesion step. The method for producing a laminate according to claim 1, comprising the steps of: coating a surface of the substrate to be adhered and at least one of the surface of the resin layer with a polyoxygenated oil or a decane coupling agent; and coating the polyoxygenated oil. In the case of performing the treatment of lowering the molecular weight of the polyoxygenated oil; in the case of applying the decane coupling agent, performing a treatment for reacting the decane coupling agent; thereafter, in the adhesion step, the substrate and the substrate are The resin layers are overlapped and adhered. The method for producing a laminate according to claim 2, wherein the surface of the substrate to be adhered is surface-treated with a polyoxygen oxyhydroxide or a decane coupling agent, and a water contact angle of the surface of the substrate subjected to the above treatment is 90° or more. The method for producing a laminate according to any one of claims 1 to 3, wherein in the step of forming the resin layer on the support sheet, the support is A curable resin composition layer is formed on the surface of the sheet, and then the curable resin composition is cured to form the above resin layer. The method for producing a laminate according to any one of claims 1 to 3, wherein the resin layer comprises a polyoxyxylene resin. The method for producing a laminate according to claim 5, wherein the resin layer comprises a reaction hardened product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene. A laminate comprising a substrate, a support plate, and a resin layer present between the substrate, the resin layer being detachably adhered to the substrate, and the resin layer having a high peeling strength between the layers on the support plate Fixing the peeling strength between the resin layer and the substrate, and at least one of the surface of the substrate and the surface of the resin layer that are in close contact with each other includes a surface previously treated with a polyoxygenated oil or a decane coupling agent, or The resin layer is formed of a resin containing a polyoxygenated oil or a decane coupling agent. The laminate according to claim 7, wherein the surface of the substrate which is in close contact with the surface of the resin layer is a surface which has been surface-treated with a polyoxygenated oil or a decane coupling agent. The laminate according to claim 8, wherein the surface of the surface-treated substrate has a water contact angle of 90 or more. The laminate according to any one of claims 7 to 9, wherein the resin layer comprises a polysiloxane resin. The laminate according to claim 10, wherein the resin layer comprises a reaction hardened product of an organic alkenyl polysiloxane and an organic hydrogen polyoxyalkylene.