JPWO2011142280A1 - LAMINATE MANUFACTURING METHOD AND LAMINATE - Google Patents

Abstract

The present invention is a method for producing a laminate having a substrate, a support plate, and a resin layer existing between them, the step of forming the resin layer on the support plate, and the resin layer on the substrate Or a step of releasably adhering to the substrate, including a step of treating at least one of the substrate surface and the resin layer surface to be adhered with a silicone oil or a silane coupling agent in advance before the adhering step. Or a laminate in which the resin layer is formed from a resin containing silicone oil or a silane coupling agent in the step of forming the resin layer, and then the substrate and the resin layer are stacked and adhered in the step of closely contacting. A manufacturing method is provided.

Description

  The present invention relates to a method for manufacturing a laminate, and a laminate.

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

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

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

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

International Publication No. 07/018028

  However, in the laminate having the conventional configuration, when the reinforcing plate is peeled from the substrate, the resin layer of the reinforcing plate may be coherently broken, and a part of the resin layer may adhere to the substrate on the product side. It was. This is presumably because the resin layer deteriorates or the adhesion strength between the resin layer and the substrate increases depending on the conditions of the heat treatment or chemical treatment in the device manufacturing process.

  The present invention has been made in view of the above-described problem, and provides a method for manufacturing a laminate and a laminate that can suppress the cohesive failure of the resin layer when peeling the resin layer and the substrate. The purpose is to provide.

In order to solve the above-mentioned object, the method for producing a laminate of the present invention includes
A method of manufacturing a laminate having a substrate, a support plate, and a resin layer existing between them, the step of forming the resin layer on the support plate, and the resin layer closely attached to the substrate A method comprising the steps of:
Before the step of closely contacting, including a step of previously treating at least one of the substrate surface and the resin layer surface to be closely contacted with silicone oil or a silane coupling agent, or
A method of manufacturing a laminate, wherein the resin layer is formed from a resin containing silicone oil or a silane coupling agent in the step of forming the resin layer, and then the substrate and the resin layer are overlapped and adhered in the step of adhering. It is.

In the method for producing a laminate of the present invention, a step of applying a silicone oil or a silane coupling agent to at least one of the substrate surface and the resin layer surface to be adhered,
When applying silicone oil, it has a step of performing a treatment for lowering the molecular weight of silicone oil, and when applying a silane coupling agent, it has a step of performing a treatment of reacting the silane coupling agent,
Thereafter, it is preferable that the substrate and the resin layer are stacked and adhered in the step of closely contacting. Further, it is preferable that the surface of the substrate to be adhered is surface-treated with silicone oil or a silane coupling agent, and the water contact angle of the substrate surface subjected to the treatment is 90 ° or more.

  In the method for producing a laminate of the present invention, in the step of forming the resin layer on the support plate, a curable resin composition layer is formed on the surface of the support plate, and then the curable resin composition is cured. It is preferable to form the resin layer.

  Moreover, in the manufacturing method of the laminated body of this invention, it is preferable that the said resin layer consists of silicone resins.

  Furthermore, in the manufacturing method of the laminated body of this invention, it is preferable that the said resin layer consists of the reaction hardened | cured material of organoalkenyl polysiloxane and organohydrogen polysiloxane.

The laminate of the present invention is
A substrate, a support plate, and a resin layer existing between them; the resin layer and the substrate are in close contact with each other so as to be peelable; and the resin layer is on the support plate and the peel strength between them is the resin. A laminate that is fixed to be higher than the peel strength between the layer and the substrate,
At least one of the substrate surface and the resin layer surface in close contact with each other consists of a surface previously treated with silicone oil or a silane coupling agent, or the resin layer is made of a resin containing silicone oil or a silane coupling agent. It is a laminated body which is a formed resin layer.

  In the laminate of the present invention, it is preferable that the substrate surface that is in close contact with the surface of the resin layer is a surface that has been surface-treated with silicone oil or a silane coupling agent. The water contact angle on the surface-treated substrate surface is preferably 90 ° or more.

  In the laminate of the present invention, it is preferable that the resin layer is made of a silicone resin.

  Furthermore, in the laminate of the present invention, the resin layer is preferably made of a reaction cured product of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a laminated body which can suppress that a resin layer cohesively breaks when peeling a resin layer and a board | substrate, and a laminated body can be provided.

FIG. 1 is a partial side view of an example of a laminate according to the present invention.

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

  In the present invention, the resin layer being fixed on 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. To do.

(First embodiment)
FIG. 1 is a partial side view of an example of a laminate according to the present invention. As shown in FIG. 1, the laminate 10 is a laminate in which a substrate 20, a support plate 31, and a resin layer 32 exist between them. The resin layer 32 is fixed on the support plate 31 and is in close contact with the first main surface 201 of the substrate 20 in a peelable manner. The support plate 31 and the resin layer 32 function as a reinforcing plate 30 that reinforces the substrate 20 in a process of manufacturing a device (electronic device) such as a liquid crystal panel.

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

  First, the substrate 20 will be described.

  The substrate 20 forms a device by forming a device member on the second main surface 202. Here, the device member refers to a member constituting at least a part of the device. Specific examples of the device member include a thin film transistor (TFT) and a color filter (CF). Examples of the device include a solar cell (PV), a liquid crystal panel (LCD), and an organic EL panel (OLED).

  The type of the substrate 20 may be a general one, for example, a silicon 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. This is because the glass substrate is excellent in chemical resistance and moisture permeability resistance and has a low heat shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102-1995 is used.

  If the linear expansion coefficient of the substrate 20 is large, the device manufacturing process often involves heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on the substrate 20, if the substrate 20 on which the TFT is formed is cooled under heating, the TFT may be excessively misaligned due to thermal contraction of the substrate 20.

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

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

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

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

  The kind of resin of the resin substrate is not particularly limited. Specifically, polyethylene terephthalate resin, polycarbonate resin, polyimide resin, fluorine resin, polyamide resin, polyaramid resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, polyethylene naphthalate resin, polyacrylic resin, various types Examples thereof include liquid crystal polymer resins, cycloolefin resins, and silicone resins. The resin substrate may be transparent or opaque. Further, the resin substrate may have a functional layer such as a protective layer formed on the surface.

  The substrate 20 may be composed of two or more layers. In this case, the material for forming each layer may be the same material or different materials. Further, 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, more preferably 0.3 mm or less, from the viewpoint of reducing the thickness and / or weight of the substrate. Moreover, it is preferable that it is 0.01 mm or more from the reason of manufacture of a board | substrate being easy and handling of a board | substrate being easy.

  Next, the support plate 31 will be described.

  The support plate 31 cooperates with the resin layer 32 to support and reinforce the substrate 20, and prevents deformation, scratching, breakage, and the like of the substrate 20 in the device manufacturing process. In addition, when using the substrate 20 having a thickness smaller than that of the conventional substrate, by using the laminated body 10 having the same thickness as that of the conventional substrate, in the device manufacturing process, Making the manufacturing equipment usable is one of the purposes of using the support plate 31.

  As the support plate 31, for example, a glass plate, a resin plate, or a metal plate such as a stainless steel (SUS) plate is used. When the device manufacturing process involves heat treatment, the support plate 31 is preferably formed of a material having a small difference in linear expansion coefficient from the substrate 20, and more preferably formed of the same material as the substrate 20. When the substrate 20 is a glass substrate, the support plate 31 is preferably a glass plate. In particular, a glass plate made of the same glass material as the glass substrate is preferable.

  The support plate 31 may be thicker than the substrate 20 or thinner. Preferably, the thickness of the support plate 31 is selected based on the thickness of the substrate 20, the thickness of the resin layer 32, and the thickness of the laminated body 10. For example, if the current device manufacturing process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the substrate 20 and the thickness of the resin layer 32 is 0.1 mm, then The thickness of the plate 31 is 0.4 mm. In general, the thickness of the support plate 31 is preferably 0.08 to 5.0 mm, more preferably 0.2 to 5.0 mm, and preferably 0.2 to 1.0 mm. Further preferred.

  When the support plate 31 is a glass plate, the thickness of the glass plate is preferably 0.08 mm or more because it is easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled after the device member is formed.

The difference in average linear expansion coefficient between the substrate 20 and the support plate 31 at 25 to 300 ° C. (hereinafter simply referred to as “average linear expansion coefficient”) is preferably 500 × 10 ⁻⁷ / ° C. or less, more preferably 300 × 10 ⁻⁷ / ° C. or lower, more preferably 200 × 10 ⁻⁷ / ° C. or lower. If the difference is too large, the laminate 10 may be warped severely or the substrate 20 and the reinforcing plate 30 may be peeled off during heating and cooling in the device manufacturing process. When the material of the board | substrate 20 and the material of the support plate 31 are the same, it can suppress that such a problem arises.

  Next, the resin layer 32 will be described.

  The resin layer 32 is fixed on the support plate 31 and is in close contact with the substrate 20 in a peelable manner. The resin layer 32 prevents displacement of the substrate 20 until the peeling operation is performed, and also easily peels from the substrate 20 by the peeling operation, and prevents the substrate 20 and the like from being damaged by the peeling operation.

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

  The surface 321 on the substrate side of the resin layer 32 (hereinafter, also referred to as “adhesion surface 321”) is not an adhesive force that a general adhesive has, but a force caused by van der Waals force between solid molecules. The substrate 20 is preferably attached to the surface 201 (hereinafter also referred to as “contact surface 201”). It is because it can peel easily. In this invention, the property which can peel this resin layer surface easily is called peelability.

  On the other hand, the bonding force of the resin layer 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. For this reason, the peel strength between the resin layer 32 and the support plate 31 is higher than the peel strength between the resin layer 32 and the substrate 20. In the present invention, the bonding of the resin layer surface to the substrate surface is referred to as adhesion, and the bonding to the support plate surface is referred to as fixation. It is preferable that 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 to this, and as long as it is relatively higher than the bonding force of the resin layer 32 to the adhesion surface 201, the resin layer 32 and the support plate 31 are attached by a force due to the van der Waals force. It may be attached.

  Although the thickness of the resin layer 32 is not specifically limited, It is preferable that it is 1-100 micrometers, It is more preferable that it is 5-30 micrometers, It is further more preferable that it is 7-20 micrometers. This is because when the thickness of the resin layer 32 is within such a range, the resin layer 32 and the substrate 20 are sufficiently adhered to each other. In addition, even if bubbles or foreign substances are present between the resin layer 32 and the substrate 20, the occurrence of the distortion defect of the substrate 20 can be suppressed. If the thickness of the resin layer 32 is too thick, it takes time and materials to form the resin layer, which is not economical.

  The resin layer 32 may be composed of two or more layers. In this case, “the thickness of the resin layer 32” means the total thickness of all the resin layers.

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

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

  Moreover, since the resin layer 32 is often heat-treated in the device manufacturing process, it is preferable to have heat resistance.

  Moreover, when the elasticity modulus of the resin layer 32 is too high, it exists in the tendency for adhesiveness with the board | substrate 20 to become low. On the other hand, if the elastic modulus of the resin layer 32 is too low, the peelability is lowered.

  The kind of resin that forms the resin layer 32 is not particularly limited. For example, acrylic resin, polyolefin resin, polyurethane resin, and silicone resin can be used. Several types of resins can be mixed and used. Of these, silicone resins are preferred. This is because the silicone resin is excellent in heat resistance and peelability. Further, when the support plate 31 is a glass plate, it is easy to fix to the glass plate by a condensation reaction with a silanol group on the surface of the glass plate. In the state where the silicone resin layer is interposed between the support plate 31 and the substrate 20, it is also preferable that the peelability does not substantially deteriorate even if the silicone resin layer is processed in the atmosphere at about 200 ° C. for about 1 hour.

  The resin layer 32 is preferably made of a silicone resin (cured product) used for release paper among silicone resins. A resin layer 32 formed by curing a curable resin composition to be a silicone resin for release paper on the surface of the support plate 31 is preferable because it has excellent peelability. Moreover, since the flexibility is high, even if foreign matters such as bubbles and dust are mixed between the resin layer 32 and the substrate 20, it is possible to suppress the occurrence of the distortion defect of the substrate 20.

  The curable silicone that becomes the silicone resin for release paper is classified into a condensation reaction type silicone, an addition reaction type silicone, an ultraviolet curable type silicone, and an electron beam curable type silicone depending on its curing mechanism. Can do. Among these, addition reaction type silicone is preferable. This is because the curing reaction is easy and the degree of peelability is good when the resin layer 32 is formed, and the heat resistance is also high.

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

  Moreover, the curable silicone used as the silicone resin for the release paper is classified into a solvent type, an emulsion type and a solventless type, and any type can be used. Among these, a solventless type is preferable. This is because productivity, safety, and environmental characteristics are excellent. In addition, it does not contain a solvent that causes foaming at the time of curing when forming the resin layer 32, that is, at the time of heat curing, ultraviolet curing, or electron beam curing, so that bubbles are unlikely to remain in the resin layer 32.

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

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

  Moreover, it is preferable that the silicone resin forming the resin layer 32 has a property that the components in the silicone resin layer are difficult to migrate to the substrate 20, that is, low silicone migration.

  A method for fixing the resin layer 32 on the support plate 31 is not particularly limited, and for example, a method of fixing a film-like resin on the surface of the support plate 31 may be mentioned. Specifically, in order to give a high fixing force (high peel strength) to the surface of the film, a surface modification treatment (priming treatment) is performed on the surface of the support plate 31 to fix the resin layer 32 on the support plate 31. The method of doing is mentioned. For example, chemical methods (primer treatment) that improve the fixing force chemically such as silane coupling agents, physical methods that increase surface active groups such as flame (flame) treatment, surface treatments such as sandblast treatment Examples thereof include a mechanical processing method for increasing the catch by increasing the roughness.

  Further, for example, a layer of a curable resin composition that becomes the resin layer 32 is formed on the surface of the support plate 31, and then fixed on the support plate 31 by a method of forming the resin layer 32 by curing the curable resin composition. The formed resin layer 32 can also be formed. Examples of the method for forming a layer of the curable resin composition on the surface of the support plate 31 include a method of coating the curable resin composition on the support plate 31. Examples of the coating method include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. From such a method, it can select suitably according to the kind of resin composition.

In the case of coating a curable resin composition comprising a resin layer 32 on the support plate 31, it is preferable that the coating amount is 1 to 100 g / ^{m 2,} and more preferably 5 to 20 g / ^{m 2} .

  For example, when the resin layer 32 is formed from an addition reaction type silicone curable resin composition, a curable resin composition comprising a mixture of an organoalkenylpolysiloxane, an organohydrogenpolysiloxane, and a catalyst is applied to the spray coating method described above. Is applied onto the support plate 31 by a known method, and then cured by heating. The heat curing conditions vary depending on the blending amount of the catalyst. For example, when 2 parts by mass of a platinum-based catalyst is blended with respect to 100 parts by mass of the total amount of the organoalkenylpolysiloxane and the organohydrogenpolysiloxane, The reaction is carried out at 50 ° C to 250 ° C, preferably 100 ° C to 200 ° C. In this case, the reaction time is 5 to 60 minutes, preferably 10 to 30 minutes.

  By curing the curable resin composition by heating, the silicone resin is chemically bonded to the support plate 31 during the curing reaction, and / or the silicone resin layer is bonded to the support plate 31 by an anchor effect. By these actions, the silicone resin layer is firmly fixed to the support plate 31. In addition, also when forming the resin layer which consists of resin other than a silicone resin from a curable resin composition, the resin layer fixed to the support plate by the method similar to the above can be formed.

  The method of sticking the resin layer 32 on the substrate 20 in a peelable manner may be a known method. For example, there is a method in which the substrate 20 is stacked on the peelable surface of the resin layer 32 under a normal pressure environment, and then the resin layer 32 and the substrate 20 are pressure-bonded using a roll or a press. It is preferable because the resin layer 32 and the substrate 20 are more closely adhered by pressure bonding with a roll or a press. Further, it is preferable because bubbles mixed between the resin layer 32 and the substrate 20 are relatively easily removed by pressure bonding with a roll or a press.

  When pressure bonding is performed by a vacuum laminating method or a vacuum pressing method, it is more preferable because suppression of bubble mixing and securing of good adhesion are more preferably performed. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are less likely to cause a distortion defect of the substrate 20.

  When the resin layer 32 is detachably adhered to the substrate 20, it is preferable that the surfaces of the resin layer 32 and the substrate 20 on the side in contact with each other are sufficiently washed and laminated in a high clean environment. Even if a foreign substance is mixed between the resin layer 32 and the substrate 20, the resin layer 32 is deformed and thus does not affect the flatness of the surface of the substrate 20. However, the higher the cleanness, the better the flatness. Therefore, it is preferable.

  In addition, there is no restriction | limiting in the order of the process of fixing the resin layer 32 on the support plate 31, and the process of closely_contact | adhering the resin layer 32 on the board | substrate 20, and may be substantially simultaneous, for example.

  In the present invention, at least one of the contact surface 201 and the contact surface 321 is previously treated with silicone oil or a silane coupling agent, or the resin layer 32 is formed of a resin containing silicone oil or a silane coupling agent. . The first embodiment is the former surface treatment. It is possible to appropriately adjust the density of polar groups present on the contact surfaces 201 and 321 by subjecting at least one of the contact surface 201 and the contact surface 321 to surface treatment with a silicone oil or a silane coupling agent in advance before the contact. it can. In the present embodiment, the adhesion surface 201 on the substrate 20 side may be surface-treated in advance, the adhesion surface 321 on the resin layer 32 side may be surface-treated in advance, and the adhesion surfaces 201 and 321 on both sides may be treated in advance. Surface treatment may be performed in advance. It should be noted that the density of polar groups present on the adhesion surface 321 can be appropriately adjusted similarly by forming the resin layer 32 from a resin containing silicone oil or a silane coupling agent (second embodiment). .

  Here, as a polar group which exists on the surface of a glass substrate, a hydroxyl group (-OH) etc. are mentioned, for example. 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.

  Appropriate density of the polar groups present on the contact surfaces 201 and 321 between the substrate 20 and the resin layer 32 is determined by measuring the water contact angle of the surfaces that become the contact surfaces 201 and 321 before the contact. In general, the higher the density of hydrophilic polar groups present on the surface, the smaller the water contact angle. Here, the water contact angle is a contact angle defined in JIS R 3257-1999.

  The water contact angle before the adhesion of the surface-treated adhesion surfaces 201 and 321 is preferably 90 ° or more, more preferably 90 to 120 °, and still more preferably 90 to 110 °. If the water contact angles before the contact between both the contact surfaces 201 and 321 are smaller than 90 °, the density of polar groups present on the surface of the substrate 20 or the resin layer 32 is too high. Therefore, in the device manufacturing process, when the temperature of the laminated body 10 exceeds 250 ° C., chemical bonding between the substrate 20 and the resin layer 32 is promoted, and the substrate 20 and the resin layer 32 (reinforcing plate 30) are separated. Becomes difficult.

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

  A fine concavo-convex structure may be formed in advance on the adhesion surface 201 of the substrate 20 by surface treatment before adhesion. In this case, due to the anchor effect of the concavo-convex structure, the contact surface 201 of the substrate 20 and the contact surface 321 of the resin layer 32 are in close contact with each other with a sufficient bonding force, and the laminate 10 can be easily handled. When a 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 on which the surface treatment is performed is preferably a sufficiently clean surface, and is preferably a surface immediately after cleaning. If the cleanliness (activity) is too low, uniform surface treatment cannot be performed. As a cleaning method, a general method used for cleaning a glass surface or a resin surface is used.

  The surface not subjected to the surface treatment is desirably protected in advance with a protective film such as a mask. This is because it is difficult to form a device member on the surface to which the surface treatment material is mistakenly attached in the device manufacturing process.

  Silicone oil and silane coupling agent, which are surface treatment materials, are used alone or in combination. When used in combination, the surface treatment may be performed with a silicone oil after the surface treatment with a silane coupling agent, or the surface treatment with a silane coupling agent may be performed after the surface treatment with a silicone oil.

  The type of silicone oil is not particularly limited, but straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, alkyl group, hydrogen group, epoxy group, amino group, carboxyl at the side chain or terminal. Examples thereof include modified silicone oil into which a group, a polyether group, a halogen group and the like are introduced. Specific examples include methylhydrogenpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylsiloxane, and the like. The heat resistance increases in the order listed, and diphenylsiloxane has the highest heat resistance. These silicone oils are generally used for water repellent treatment of the surface of a substrate such as a glass substrate or a primer-treated metal substrate.

  The surface treatment method using silicone oil may be a general method. In the treatment that simply applies silicone oil, the silicone oil is less bound to the surface to be treated, and the effect of the treatment may not be fully exhibited. It is preferable to add a treatment for binding to the. The treatment for bonding the silicone oil to the surface to be treated is a treatment that cleaves the molecular chain of the silicone oil, and it is considered that the cleaved fragments bind to the surface to be treated (this treatment is hereinafter referred to as lowering the molecular weight of the silicone oil). Called).

  As a surface treatment method using silicone oil, a method in which silicone oil is applied to the adhesion surface 201 of the substrate 20 or the adhesion surface 321 of the resin layer 32 to reduce the molecular weight is preferable. The density of polar groups present on the contact surface 201 of the substrate 20 and the contact surface 321 of the resin layer 32 can be optimized by adjusting the amount of silicone oil applied and the processing conditions for lowering the molecular weight. Therefore, when the resin layer 32 and the board | substrate 20 are peeled, it can suppress that the resin layer 32 is destroyed by aggregation.

  The application method of silicone oil may be a general method. For example, spray coating method, die coating method, spin coating method, dip coating method, roll coating method, bar coating method, screen printing method, gravure coating method, etc. are selected as appropriate according to the type and application amount of silicone oil. Is done. As the coating solution, it is desirable to use a solution obtained by diluting silicone oil to 1% by mass or less with a solvent such as hexane, heptane, or xylene. If it exceeds 1% by mass, the treatment time for lowering the molecular weight is too long. It is desirable to use a solution diluted to 0.01% by mass or more. If it is less than 0.01% by mass, it is insufficient for optimizing the density of polar groups.

  As a method for reducing the molecular weight of the silicone oil, a general method is used. For example, there is a method of breaking a siloxane bond of the silicone oil by photolysis or thermal decomposition. For photolysis, ultraviolet rays irradiated from a low-pressure mercury lamp, a xenon arc lamp, or the like are used, and ozone generated by ultraviolet irradiation in the atmosphere may be used in combination. Pyrolysis may be performed in a batch furnace, a conveyor furnace, or the like, or plasma or arc discharge may be used. In the case of thermal decomposition in a batch furnace or a conveyor furnace, treatment at 250 ° C. to 400 ° C. is desirable, depending on the type and concentration of the silicone oil in the coating solution. When the temperature is lower than 250 ° C., the molecular weight reduction of the silicone becomes insufficient, and when the temperature exceeds 400 ° C., the silicone becomes markedly silicified and becomes insufficient as a molecular weight reduction treatment.

  When the siloxane bond of the silicone oil is cleaved, the density of hydrophobic functional groups such as methyl groups increases, and the density of hydrophilic polar groups present on the adhesion surface 201 of the substrate 20 and the adhesion surface 321 of the resin layer 32 is increased. Decrease. In addition, when the siloxane bond of silicone oil is cut too much, the density of hydrophilic polar groups tends to increase again.

  The type of the silane coupling agent is not particularly limited. For example, hexamethyldisilazane (HMDS), 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- Aminosilanes such as {N- (2-aminoethyl) -2-aminoethyl} -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) epoxysilanes such as ethyltrimethoxysilane, chlorosilanes and fluorosilanes such as 3-chloropropyltrimethoxysilane, mercaptosilanes such as 3-mercaptotrimethoxysilane, vinyltrimethoxysilane N-2- (N-vinylbenzyl- - aminoethyl) -3-vinylsilane such as aminopropyltrimethoxysilane, 3-methacryloxypropyl trimethoxy silane having 1 or more species selected from acrylic silanes such as can be preferably used.

  A surface treatment method using a silane coupling agent may be a general method. For example, the adhesion surface 201 of the substrate 20 and the adhesion surface 321 of the resin layer 32 are exposed to an atmosphere containing a gas obtained by vaporizing a silane coupling agent, and the hydrophilicity existing on the adhesion surface 201 of the substrate 20 and the adhesion surface 321 of the resin layer 32. There is a method of substituting a polar functional group with a hydrophobic functional group such as a methyl group. By adjusting the concentration, temperature, treatment time, etc. of the silane coupling agent in the atmosphere, the density of polar groups present on the adhesion surface 201 of the substrate 20 and the adhesion surface 321 of the resin layer 32 can be optimized. Therefore, when the resin layer 32 and the board | substrate 20 are peeled, it can suppress that the resin layer 32 is destroyed by aggregation.

  The contact surfaces 201 and 321 can be returned to the state before the surface treatment by a predetermined treatment after being peeled from each other during the device manufacturing process. For example, a surface that has been surface-treated with silicone oil or a silane coupling agent can be returned to the state before the surface treatment by photolysis or thermal decomposition. Thus, if the surface 201 of the substrate 20 is returned to the state before the surface treatment, for example, when an optical film (for example, a polarizing film) is attached to the surface 201, the attaching strength can be increased. Incidentally, if importance is attached to reworkability, an optical film may be attached to the surface 201 of the substrate 20 in the state after the surface treatment.

(Second Embodiment)
Since the structure of the laminated body of this embodiment is substantially the same as FIG. 1, illustration is abbreviate | omitted.

  In the present embodiment, the resin layer 32 is formed from a resin containing silicone oil or a silane coupling agent. The resin layer 32 is preferably formed by curing a curable resin composition containing silicone oil or a silane coupling agent. Although it does not specifically limit as a curable resin composition, For example, the curable resin composition used as the silicone resin for release paper is used. The contact surfaces 201 and 321 of the substrate 20 and the resin layer 32 do not have to be subjected to the surface treatment before the contact.

  The silicone oil and the silane coupling agent are used alone or in combination, and it is preferable to use one that does not have a functional group that reacts with a component of the curable resin composition. For example, when the resin layer 32 is formed from the curable resin composition of the addition reaction type silicone, the silicone oil or the silane coupling agent does not have a functional group (for example, vinyl group or hydrosilyl group) serving as a crosslinking point. Is used. Moreover, when forming the resin layer 32 from the curable resin composition of a condensation reaction type silicone, the silicone oil which does not have a functional group (hydrolyzable group, silanol group, etc.) which can be co-condensed is used.

  In this resin layer 32, silicone oil is dispersed and contained without crosslinking when the curable resin composition is cured. Moreover, the silane coupling agent is usually condensed when the curable resin composition is cured, and is contained in the cured resin as a condensate of the silane coupling agent. Therefore, the condensate of silicone oil or silane coupling agent is dispersed and contained in the adhesion surface 321 of the resin layer 32.

  For example, when silicone oil is contained in the adhesion surface 321 of the resin layer 32, the silicone oil has a low molecular weight when the temperature of the laminate 10 is increased in the device manufacturing process. As a result, the density of hydrophilic polar groups present on both adhesion surfaces 201 and 321 is reduced, and the density of hydrophobic functional groups such as methyl groups is increased.

  When the adhesion surface 321 of the resin layer 32 contains a silane coupling agent condensate, the hydrophilic polar group present on both adhesion surfaces 201 and 321 is replaced with a hydrophobic functional group such as a methyl group. The

  For this reason, the density of polar groups existing on both adhesion surfaces 201 and 321 is optimized by adjusting the content and type of silicone oil or silane coupling agent contained in the curable resin composition to be the resin layer 32. Can be

  Therefore, also in the present embodiment, as in the first embodiment, the resin layer 32 can be prevented from being coherently broken when the resin layer 32 and the substrate 20 are peeled off. In addition, since the step of lowering the molecular weight of the silicone oil is performed in combination with other steps, and since there is no step of vaporizing the silane coupling agent, the number of steps can be reduced.

  Content of the silicone oil and silane coupling agent contained in the curable resin composition used as the resin layer 32 is 0.1-5 mass% with respect to solid content of the curable resin composition containing these. Is desirable. When the amount is less than 0.1% by mass, a sufficient effect cannot be obtained. On the other hand, when it exceeds 5 mass%, the heat resistance of the resin layer 32 becomes too low.

  In the case of the second embodiment, the close contact surface 201 of the substrate 20 may not be subjected to the surface treatment in the first embodiment. When the substrate 20 is a glass substrate, since the surface is a highly hydrophilic surface, the close-contact surface 201 may be subjected to the surface treatment in the first embodiment before the close contact.

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

[Example 1]
As the substrate and the support plate, a glass plate (Asahi Glass Co., Ltd., AN100, alkali-free glass) having a length of 720 mm and a width of 600 mm obtained by a float method was used. The thickness of the substrate was 0.4 mm, and the thickness of the support plate was 0.3 mm. The average linear expansion coefficients of the substrate and the support plate were 38 × 10 ⁻⁷ / ° C., respectively.

(Production of reinforcing plate)
The support plate was cleaned with pure water and UV to clean the surface of the support plate. Thereafter, the curable resin composition was applied to one side of the support plate by screen printing (application amount 30 g / m ² ).

  In the curable resin composition, a mixture of 100 parts by mass of a solventless addition reaction type silicone (manufactured by Shin-Etsu Silicone, KNS-320A) and 2 parts by mass of a platinum-based catalyst (manufactured by Shin-Etsu Silicone, CAT-PL-56) is used. Using.

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

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

(Surface treatment of substrate)
The substrate was cleaned with pure water and UV to clean the surface of the substrate. Then, after masking the 2nd main surface which is the single side | surface of a board | substrate, the 1st main surface of the other side was spray-coated with the heptane solution whose silicone oil content is 0.5 mass%, and it dried. Dimethylpolysiloxane (manufactured by Dow Corning Toray, SH200) was used as the silicone oil. Subsequently, in order to reduce the molecular weight of the silicone oil, ultraviolet treatment with a low-pressure mercury lamp was performed in air for 2 minutes.

  Then, when the water contact angle of the 1st main surface of a board | substrate was measured using the contact angle meter (The Cruz company make, DROP SHAPE ANALYSIS SYSTEM DSA 10Mk2), it was 100 degrees.

(Production of laminate)
After the ultraviolet treatment, a silicone resin layer was stacked on the first main surface of the substrate, and the substrate and the silicone resin layer were brought into close contact with each other by a vacuum press at room temperature to obtain a laminate composed of the substrate and the reinforcing plate.

(Heat resistance test of laminate)
This laminate was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere having an oxygen volume concentration of 1000 ppm or less. Then, after cooling to room temperature, insert a peeling blade between the substrate and the silicone resin layer, while holding the substrate side flat, the silicon resin layer side is sequentially bent and deformed from the vicinity of the insertion position, The substrate and the silicone resin layer were peeled off.

  No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 100 degrees.

[Example 2]
The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(Production of reinforcing plate)
In Example 2, as the curable resin composition, linear organoalkenylpolysiloxane having vinyl groups at both ends (vinyl silicone, manufactured by Arakawa Chemical Industries, Ltd., 8500) and methylhydro having a hydrosilyl group in the molecule are used. A reinforcing plate was produced in the same manner as in Example 1 except that a mixture of Genpolysiloxane (Arakawa Chemical Industries, 12031) and a platinum catalyst (Arakawa Chemical Industries, CAT12070) was used.

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

(Surface treatment of substrate)
In Example 2, the surface treatment of the substrate was performed in the same manner as in Example 1 except that plasma treatment was performed with an atmospheric pressure remote plasma apparatus (RT series, manufactured by Sekisui Chemical Co., Ltd.) in order to reduce the molecular weight of the silicone oil. went.

  Here, the processing conditions of the plasma treatment were an output of 3 kW, a nitrogen / air flow ratio = 600 slm / 750 sccm, and a conveyance speed of 5 m / min. The surface temperature of the substrate at the time of plasma irradiation was 50 ° C. or less. The water contact angle of the first main surface of the substrate after the surface treatment was 95 °.

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

(Heat resistance test of laminate)
The laminate was heat treated in the same manner as in Example 1, and then the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 100 degrees.

[Example 3]
The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

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

(Surface treatment of substrate)
In Example 3, the surface treatment of the substrate was performed in the same manner as in Example 1 except that heat treatment was performed at 400 ° C. for 10 minutes in the atmosphere in order to reduce the molecular weight of the silicone oil. The water contact angle of the first main surface of the substrate after the surface treatment was 105 °.

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

(Heat resistance test of laminate)
The laminate was heat treated in the same manner as in Example 1, and then the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 105 degrees.

[Example 4]
The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

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

(Surface treatment of substrate)
In Example 4, in order to reduce the molecular weight of silicone oil, the first main surface of the substrate was spray-coated with a heptane solution having a silicone oil content of 0.1% by mass, dried, and heated in the atmosphere at 250 ° C. for 10 minutes. A substrate surface treatment was performed in the same manner as in Example 1 except that the treatment was performed. The water contact angle of the first main surface of the substrate after the surface treatment was 98 °.

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

(Heat resistance test of laminate)
The laminate was heat treated in the same manner as in Example 1, and then the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 98 degrees.

[Example 5]
As the substrate and the support plate, a glass plate (AS, soda lime glass, manufactured by Asahi Glass Co., Ltd.) having a length of 720 mm and a width of 600 mm obtained by the float method was used. The thickness of the substrate was 0.4 mm, and the thickness of the support plate was 0.3 mm. The average linear expansion coefficients of the substrate and the support plate were 85 × 10 ⁻⁷ / ° C., respectively.

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

(Surface treatment of substrate)
In Example 5, in order to reduce the molecular weight of the silicone oil, the first main surface of the substrate was spray-coated with a heptane solution having a silicone oil content of 0.5% by mass, dried, and heated at 350 ° C. for 10 minutes in the atmosphere. The substrate was subjected to surface treatment in the same manner as in Example 1 except that. The water contact angle of the first main surface of the substrate after the surface treatment was 102 °.

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

(Heat resistance test of laminate)
The laminate was heat treated in the same manner as in Example 1, and then the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 102 degrees.

[Example 6]
As the substrate and the support plate, the same glass plates as in Example 5 were used except that they were chemically strengthened.

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

(Surface treatment of substrate)
In Example 6, the surface treatment of the substrate was performed in the same manner as in Example 5 in order to reduce the molecular weight of the silicone oil. The water contact angle of the first main surface of the substrate after the surface treatment was 102 °.

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

(Heat resistance test of laminate)
The laminate was heat treated in the same manner as in Example 1, and then the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 102 degrees.

[Example 7]
The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

(Production of reinforcing plate)
The support plate was cleaned with pure water and UV 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 silicone oil was applied to one side of the support plate by screen printing (application amount: 30 g / m ² ). Here, the same curable resin composition as that in Example 2 was used, and dimethylpolysiloxane (SH200, manufactured by Toray Dow Corning Co., Ltd.) was used as the silicone oil.

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

(Production of laminate)
After production of the reinforcing plate, a silicone resin layer was layered on the cleaned surface of the substrate, and the substrate and the silicone resin layer were brought into close contact with each other by a vacuum press at room temperature to obtain a laminate composed of the substrate and the reinforcing plate.

(Heat resistance test of laminate)
The laminate was heat treated in the same manner as in Example 1, and then the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no resin transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 102 degrees.

[Example 8]
As the substrate and the support plate, a polyimide resin plate (manufactured by Toray DuPont, Kapton 200HV) having a length of 720 mm and a width of 600 mm was used. The substrate thickness was 0.05 mm, and the support plate thickness was 0.5 mm.

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

(Surface treatment of substrate)
In Example 8, the surface treatment of the substrate was performed in the same manner as in Example 2. The water contact angle of the first main surface of the substrate after the surface treatment was 100 °.

(Production of laminate)
After the surface treatment, a silicone resin layer was stacked on the first main surface of the substrate, and the substrate and the silicone resin layer were brought into close contact with each other by a vacuum press at room temperature to obtain a laminate composed of the substrate and the reinforcing plate.

(Heat resistance test of laminate)
After heat-treating this laminate in the same manner as in Example 1, the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 100 degrees.

[Example 9]
The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

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

(Surface treatment of substrate)
The substrate was cleaned with pure water and UV to clean the surface of the substrate. Then, after masking the second main surface, which is one side of the substrate, the first main surface on the opposite side is saturated with a gas obtained by vaporizing a silane coupling agent (manufactured by Toray Dow Corning, Z6040). Exposure to a maintained atmosphere for 10 minutes. The surface temperature of the substrate at the time of exposure was 25 ° C. The water contact angle of the 1st main surface of the board | substrate after exposure was 100 degrees.

(Production of laminate)
After the surface treatment with the silane coupling agent, a silicone resin layer was stacked on the first main surface of the substrate, and the substrate and the silicone resin layer were brought into close contact with each other by a vacuum press at room temperature to obtain a laminate composed of the substrate and the reinforcing plate. .

(Heat resistance test of laminate)
The laminate was heat treated in the same manner as in Example 1, and then the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. No cohesive failure was observed in the peeled silicone resin layer by observation with an optical microscope, and no transfer from the silicone resin layer was found on the peeled substrate. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 100 degrees.

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

(Production of laminate)
In Comparative Example 1, a reinforcing plate was produced in the same manner as in Example 2, and after cleaning the first main surface of the substrate with pure water cleaning and UV cleaning, a silicone resin layer was overlaid on the first main surface of the substrate. The substrate and the silicone resin layer were brought into close contact with each other by a vacuum press at room temperature to obtain a laminate composed of the substrate and the reinforcing plate. The water contact angle before the close contact of the substrate (first main surface) was 7 °.

(Heat resistance test of laminate)
After heat-treating this laminate in the same manner as in Example 1, the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. As a result, the silicone resin layer was agglomerated and destroyed, and part of the silicone resin layer was on the substrate side. Adhered to.

[Comparative Example 2]
The same glass plate as in Example 1 was used for the substrate and the support plate, respectively.

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

(Production of laminate)
A reinforcing plate was produced in the same manner as in Example 2, and the first main surface of the substrate was cleaned with pure water and cleaned, and then a silicone resin layer was stacked on the first main surface of the substrate, and the substrate and the silicone resin layer were bonded together. The laminated body which consists of a board | substrate and a reinforcement board was made to contact | adhere with the vacuum press under room temperature. In addition, the water contact angle before the close_contact | adherence of the 1st main surface of a board | substrate was 40 degrees.

(Heat resistance test of laminate)
After heat-treating this laminate in the same manner as in Example 1, the substrate and the silicone resin layer were peeled off in the same manner as in Example 1. As a result, the silicone resin layer was agglomerated and destroyed, and part of the silicone resin layer was on the substrate side. Adhered to.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application 2010-108952 filed on May 11, 2010, the contents of which are incorporated herein by reference.

10 Laminate 20 Substrate 201 Adhesive surface (first main surface)
202 Second main surface 30 Reinforcing plate 31 Support plate 32 Resin layer 321 Adhering surface

Claims (11)

A method of manufacturing a laminate having a substrate, a support plate, and a resin layer existing between the substrate, the step of forming the resin layer on the support plate, and the resin layer being peelable from the substrate In the method comprising the step of adhering,
Before the step of closely contacting, including a step of previously treating at least one of the substrate surface and the resin layer surface to be closely contacted with silicone oil or a silane coupling agent, or
A method of manufacturing a laminate, wherein the resin layer is formed from a resin containing silicone oil or a silane coupling agent in the step of forming the resin layer, and then the substrate and the resin layer are overlapped and adhered in the step of adhering. . Applying silicone oil or a silane coupling agent to at least one of the substrate surface and the resin layer surface to be adhered; and
A process of reducing the molecular weight of the silicone oil when applying silicone oil, a process of reacting the silane coupling agent when applying a silane coupling agent,
Then, the manufacturing method of the laminated body of Claim 1 which piles up and adhere | attaches the said board | substrate and the said resin layer in the said close_contact | adhering process.   3. The laminate according to claim 2, wherein the substrate surface to be adhered is surface-treated with a silicone oil or a silane coupling agent, and a water contact angle of the treated substrate surface is 90 ° or more. Method.   In the step of forming the resin layer on the support plate, a curable resin composition layer is formed on the surface of the support plate, and then the curable resin composition is cured to form the resin layer. The manufacturing method of the laminated body of any one of -3.   The manufacturing method of the laminated body of any one of Claims 1-4 in which the said resin layer consists of silicone resins.   The manufacturing method of the laminated body of any one of Claims 1-5 in which the said resin layer consists of reaction hardened | cured material of organoalkenyl polysiloxane and organohydrogen polysiloxane. A substrate, a support plate, and a resin layer existing between them; the resin layer and the substrate are in close contact with each other so as to be peelable; and the resin layer is on the support plate and the peel strength between them is the resin. A laminate that is fixed to be higher than the peel strength between the layer and the substrate,
At least one of the substrate surface and the resin layer surface that are in close contact with each other consists of a surface that has been previously treated with silicone oil or a silane coupling agent, or
A laminate in which the resin layer is a resin layer formed from a resin containing silicone oil or a silane coupling agent.   The laminate according to claim 7, wherein the substrate surface that is in close contact with the resin layer surface is a surface that has been surface-treated with silicone oil or a silane coupling agent.   The laminate according to claim 8, wherein a water contact angle of the surface-treated substrate surface is 90 ° or more.   The laminate according to any one of claims 7 to 9, wherein the resin layer is made of a silicone resin.   The laminate according to any one of claims 7 to 10, wherein the resin layer comprises a reaction cured product of an organoalkenylpolysiloxane and an organohydrogenpolysiloxane.

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