KR20130097069A - Process for producing laminate, and laminate - Google Patents

Abstract

The present invention provides a method of manufacturing a laminate having a substrate, a support plate, and a resin layer present therebetween, wherein the resin layer is formed on the support plate, and the resin layer is in close contact with the substrate. The method which has a process WHEREIN: The process of processing the at least one of the surface of the said board | substrate and the said resin layer to adhere previously with a silicone oil or a silane coupling agent before the said process to adhere | attach, or the process of forming the said resin layer The method of manufacturing the laminated body which forms the said resin layer from resin containing a silicone oil or a silane coupling agent, and makes the said board | substrate and the said resin layer overlap and adhere | attaches in the said step of contact | adherence after that, is provided.

Description

Manufacturing method and laminated body of a laminated body {PROCESS FOR PRODUCING LAMINATE, AND LAMINATE}

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

In recent years, thinning and weight reduction of devices (electronic devices), such as a solar cell PV, a liquid crystal panel (LCD), and an organic EL panel (OLED), are progressing, and the thickness of the board | substrate used for these devices is progressing. On the other hand, when the strength of the substrate is insufficient due to the thinning, the handling property of the substrate is lowered in the manufacturing process of the device.

Therefore, conventionally, after forming a device member (for example, a thin film transistor) on the board | substrate thicker than a final thickness, the method of thinning a board | substrate by a chemical etching process is employ | adopted widely. However, in this method, for example, when the thickness of one substrate is reduced to 0.7 mm to 0.2 mm or 0.1 mm, most of the material of the original substrate is scraped off with an etching solution. It is not preferable from a viewpoint.

In the method of thinning a substrate by chemical etching, in the case where minute scratches are present on the surface of the substrate, fine recesses (etch pits) are formed at the scratches by etching, resulting in optical defects. There was.

Recently, in order to cope with the above problem, a method of preparing a laminate in which a substrate and a reinforcement plate are laminated, forming a device member on the substrate of the laminate, and then peeling the reinforcement plate from the substrate has been proposed (for example, See 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 peelable. After the reinforcing plate is peeled off from the substrate, the reinforcing plate can be laminated with a new substrate and reused as a laminate.

WO 07/018028

However, in the above-mentioned laminated body of the conventional structure, when peeling a reinforcement board from a board | substrate, the resin layer of a reinforcement board may cohesively break and a part of resin layer may adhere to the board | substrate which is a product side. This is considered to be because the resin layer deteriorates or the adhesion strength between the resin layer and the substrate increases depending on the conditions of heat treatment and chemical liquid treatment in the device manufacturing process.

This invention is made | formed in view of the said subject, Comprising: It aims at providing the manufacturing method and laminated body which can suppress that a resin layer coagulates and breaks when peeling a resin layer and a board | substrate.

MEANS TO SOLVE THE PROBLEM In order to solve the said objective, the manufacturing method of the laminated body of this invention is a method of manufacturing the laminated body which has a board | substrate, a support plate, and the resin layer which exists between them, The process of forming the said resin layer in the said support plate, In the method which has a process of making the said resin layer adhere to the said board | substrate so that peeling is possible,

Before the close contacting step, a step of treating at least one of the closely contacted substrate surface and the resin layer surface with a silicone oil or a silane coupling agent in advance; or

The manufacturing method of the laminated body which forms the said resin layer from resin containing a silicone oil or a silane coupling agent in the process of forming the said resin layer, and overlaps and adhere | attaches the said board | substrate and the said resin layer in the said step of making it contact thereafter. to be.

In the manufacturing method of the laminated body of this invention, the process of apply | coating a silicone oil or a silane coupling agent to at least one of the said board | substrate surface and the said resin layer surface made to adhere,

When apply | coating a silicone oil, it has a process of performing the process which makes silicone oil low molecular weight, and when apply | coating a silane coupling agent, the process of making the process which makes a silane coupling agent react,

After that, in the step of adhering, it is preferable that the substrate and the resin layer are overlapped and adhered. Moreover, it is preferable that the surface of the said board | substrate adhere | attached is surface-treated with silicone oil or a silane coupling agent, and the water contact angle of the surface of the board | substrate to which the said process was performed is 90 degrees 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 to form the resin layer. It is preferable to form.

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

Moreover, in the manufacturing method of the laminated body of this invention, it is preferable that the said resin layer contains the reaction hardened | cured material of organo alkenyl polysiloxane and organohydrogen polysiloxane.

In addition, the laminate of the present invention,

It has a board | substrate, a support plate, and the resin layer which exists between them, The said resin layer and the said board | substrate adhere | attach so that peeling is possible, The said resin layer is on the said support plate, The peeling strength between them is between the said resin layer and the said board | substrate. As a laminated body fixed so that it may become higher than the peeling strength of,

At least one of the surface of the substrate and the surface of the resin layer in close contact is made of a surface previously treated with a silicone oil or a silane coupling agent, or the resin layer is a resin layer formed from a resin containing a silicone oil or a silane coupling agent. It is a laminated body.

In the laminate of the present invention, it is preferable that the surface of the substrate in close contact with the surface of the resin layer is a surface treated with a silicone oil or a silane coupling agent. Moreover, it is preferable that the water contact angle of the surface-treated board | substrate surface is 90 degrees or more.

Moreover, in the laminated body of this invention, it is preferable that the said resin layer contains a silicone resin.

Moreover, in the laminated body of this invention, it is preferable that the said resin layer contains the reaction hardened | cured material of organo alkenyl polysiloxane and organohydrogen polysiloxane.

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

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

EMBODIMENT OF THE INVENTION Hereinafter, although the form for implementing this invention is demonstrated with reference to drawings, this invention is not limited to the following embodiment, A various deformation | transformation and substitution are added to the following embodiment, without deviating from the range of this invention. Can be.

In addition, in this invention, that the resin layer is being fixed on the support plate means that the peeling strength between a resin layer and a support plate is higher than the peeling strength between a resin layer and a board | substrate.

(1st embodiment)

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 so as to be peeled off. The support plate 31 and the resin layer 32 function as a reinforcing plate 30 for reinforcing the substrate 20 in the process of manufacturing a device (electronic device) such as a liquid crystal panel.

This laminated body 10 is used until the middle of the manufacturing process of a device. In other words, the laminate 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 from the substrate 20 and does not become a member constituting the device. The reinforcement board 30 peeled from the board | substrate 20 can be laminated | stacked with the new board | substrate 20, and can be reused as the laminated body 10. FIG. Hereinafter, each structure is demonstrated in detail.

First, the substrate 20 will be described.

In the substrate 20, a device member is formed on the second main surface 202 to constitute a device. Here, the member for a device means the member which comprises at least one part of a 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), an organic EL panel (OLED), and the like.

The kind of the board | substrate 20 may be general, for example, a silicon wafer, a glass substrate, a resin substrate, or metal substrates, such as a stainless steel (SUS) substrate and a copper substrate, may be sufficient. Among these, a glass substrate is preferable. This is because the glass substrate is excellent in chemical resistance, moisture permeability, and low in heat shrinkage. As an index of thermal contraction rate, the linear expansion coefficient prescribed in JIS R 3102-1995 is used.

When the coefficient of linear expansion of the board | substrate 20 is large, since the manufacturing process of a device often involves heat processing, various problems are likely to arise. For example, when forming a TFT on the substrate 20, if the substrate 20 on which the TFT is formed is cooled under heating, there is a fear that the positional shift of the TFT is excessive due to thermal contraction of the substrate 20.

A glass substrate is obtained by melting a glass raw material and shaping molten glass into 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 laver method, or the like is used. Moreover, especially thin glass substrate is obtained by shape | molding the glass once shape | molded in plate shape by the method (stretch method) which stretches and thins by the means, such as extending | stretching, by extending | stretching temperature.

Although the glass of a glass substrate is not specifically limited, Oxide type glass which has alkali-free glass, borosilicate glass, soda-lime glass, high silica glass, chemically strengthened glass, and other silicon oxide as a main component is preferable. As oxide type glass, glass with a content of 40-90 mass% of the silicon oxide by oxide conversion is preferable.

As glass of a glass substrate, the glass suitable for the kind of device and its manufacturing process is employ | adopted. For example, the glass substrate for liquid crystal panels consists of glass (alkali free glass) which does not substantially contain an alkali metal component from the point that elution of an alkali metal component tends to affect a liquid crystal. Thus, the glass of a glass substrate is suitably selected based on the kind of device applied, and its manufacturing process.

Although the thickness of a glass substrate is not specifically limited, From a viewpoint of thickness reduction and / or light weight of a glass substrate, it is usually less than 0.8 mm, Preferably it is 0.3 mm or less, More preferably, it is 0.15 mm or less. In the case of 0.8 mm or more, the demand for thinning and / or lightening the glass substrate cannot be satisfied. When it is 0.3 mm or less, it is possible to give favorable flexibility to a glass substrate. When it is 0.15 mm or less, it is possible to wind up a glass substrate in roll shape. Moreover, it is preferable that the thickness of a glass substrate is 0.03 mm or more from the reasons which manufacture of a glass substrate is easy, the point which is easy to handle a glass substrate, etc.

The kind of resin of a resin substrate is not specifically limited. Specifically, polyethylene terephthalate resin, polycarbonate resin, polyimide resin, fluorine resin, polyamide resin, polyaramid resin, polyether sulfone resin, polyether ketone resin, polyether ether ketone resin, polyethylene naphthalate resin, polyacryl Resin, various liquid crystal polymer resin, cycloolefin resin, silicone resin, etc. are illustrated. In addition, the resin substrate may be transparent or may be opaque. In addition, the resin substrate may be formed by forming a functional layer such as a protective layer on the surface.

In addition, the board | substrate 20 may consist of two or more layers, In this case, the material which forms each layer may be a homogeneous material, or a heterogeneous material may be sufficient as it. In this case, "thickness of the board | substrate 20" shall mean the thickness of the sum total of all the layers in a board | substrate. The thickness of the board | substrate 20 is normally less than 1.0 mm, Preferably it is 0.5 mm or less, More preferably, it is 0.3 mm or less from a viewpoint of thinning and / or lightening of a board | substrate. Moreover, it is preferable that it is 0.01 mm or more from the reason which manufacture of a board | substrate is easy, the point which is easy to handle a board | substrate, and the like.

Next, the supporting 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, damage, breakage, etc. of the substrate 20 in the device manufacturing process. In addition, when using the board | substrate 20 which is thinner than the conventional, when it is set as the laminated body 10 of the same thickness as the conventional board | substrate, the manufacturing technique and manufacturing equipment suitable for the board | substrate of a conventional thickness in the manufacturing process of a device The use of the support plate 31 is also one of the purposes of using.

As the support plate 31, metal plates, such as a glass plate, a resin plate, or a stainless steel (SUS) board, etc. are used, for example. When the device manufacturing process involves heat treatment, the support plate 31 is preferably formed of a material having a small difference in coefficient of linear expansion with the substrate 20, and more preferably formed of the same material as the substrate 20. When the board | substrate 20 is a glass substrate, it is preferable that the support plate 31 is a glass plate. It is especially preferable that it is a glass plate which consists of the same glass material as a glass substrate.

The thickness of the support plate 31 may be thicker or thinner than the substrate 20. Preferably, the thickness of the support plate 31 is selected based on the thickness of the board | substrate 20, the thickness of the resin layer 32, and the thickness of the laminated body 10. FIG. For example, when the current device manufacturing process is designed to process a substrate having a thickness of 0.5 mm, and the sum of the thickness of the substrate 20 and the thickness of the resin layer 32 is 0.1 mm, the thickness of the supporting plate 31 is Is 0.4mm. 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, still more preferably 0.2 to 1.0 mm.

When the support plate 31 is a glass plate, it is preferable that the thickness of a glass plate is 0.08 mm or more from the reasons of being easy to handle and hard to break. Moreover, it is preferable that the thickness of a glass plate is 1.0 mm or less from the reason why the rigidity which makes it bend properly, without breaking, when peeling after formation of a member for devices is calculated | required.

The difference between the average linear expansion coefficient (hereinafter, simply referred to as "average linear expansion coefficient") at 25 to 300 ° C of the substrate 20 and the support plate 31 is preferably 500 × 10 ^-7 / ° C or less, and more preferably. Preferably it is 300x10 <^-7> / degrees C or less, More preferably, it is 200x10 <^-7> / degrees C or less. If the difference is too large, there is a possibility that the laminate 10 is vigorously bent or the substrate 20 and the reinforcing plate 30 are 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 this problem arises.

Next, the resin layer 32 is demonstrated.

The resin layer 32 is fixed on the support plate 31 and is in close contact with the substrate 20 so as to be peeled off. The resin layer 32 prevents the positional shift of the board | substrate 20 until peeling operation is performed, and it peels easily from the board | substrate 20 by peeling operation, and the board | substrate 20 etc. are damaged by peeling operation. Prevent it.

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

The base material side surface 321 of the resin layer 32 (hereinafter also referred to as the "adhesive surface 321") is not a cohesive force of a general adhesive but a force due to van der Waals forces between solid molecules, It is preferable to adhere to the surface 201 of the board | substrate 20 (henceforth an "adhesion surface 201"). It is because it can peel easily. In this invention, the property which can peel easily on this resin layer surface is called peelability.

On the other hand, the bonding force to the surface of the support plate 31 of the resin layer 32 is relatively higher than the bonding force to the surface 201 of the substrate 20 of the resin layer 32. For this reason, the peeling strength between the resin layer 32 and the support plate 31 is higher than the peeling strength between the resin layer 32 and the board | substrate 20. FIG. In the present invention, bonding of the resin layer surface to the substrate surface is called adhesion, and bonding of the support plate surface is called fixing. It is preferable to couple between the resin layer 32 and the support plate 31 by adhesive force or adhesive force. However, the present invention is not limited thereto, and the force between the resin layer 32 and the support plate 31 is due to the van der Waals force as long as the bonding force to the adhesion surface 201 of the resin layer 32 is relatively higher. It may be sticking by.

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. It is because the adhesiveness of the resin layer 32 and the board | substrate 20 becomes enough that the thickness of the resin layer 32 is such a range. This is because generation of deformation defects in the substrate 20 can be suppressed even when bubbles or foreign substances are interposed between the resin layer 32 and the substrate 20. In addition, if the thickness of the resin layer 32 is too thick, it is not economical because it requires time and materials to form the resin layer.

In addition, the resin layer 32 may consist of two or more layers. In this case, "thickness of the resin layer 32" shall mean the thickness of the sum total of all the layers of a resin layer.

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

It is preferable that the resin layer 32 consists of a material whose glass transition point is lower than room temperature (about 25 degreeC), or does not have a glass transition point. It is because it becomes a non-adhesive resin layer, and it can peel easily with the board | substrate 20, and also the adhesiveness with the board | substrate 20 also becomes enough.

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

Moreover, when the elasticity modulus of the resin layer 32 is too high, there exists a tendency for adhesiveness with the board | substrate 20 to become low. On the other hand, when the elasticity modulus of the resin layer 32 is too low, peelability will become low.

The kind of resin which forms the resin layer 32 is not specifically limited. For example, an acrylic resin, a polyolefin resin, a polyurethane resin, and a silicone resin is mentioned. You may mix and use various types of resin. Especially, silicone resin is preferable. It is because silicone resin is excellent in heat resistance and peelability. Moreover, when the support plate 31 is a glass plate, it is easy to fix to a glass plate by condensation reaction with the silanol group of the glass plate surface. In the state where the silicone resin layer is interposed between the supporting plate 31 and the substrate 20, it is also preferable that the peelability hardly deteriorates even if the silicone resin layer is treated at about 200 ° C. for about one hour, for example.

It is preferable that the resin layer 32 consists of silicone resin (hardened | cured material) used for release papers among silicone resin. Since the resin layer 32 which hardened | cured the curable resin composition used as a peeling paper silicone resin on the surface of the support plate 31, and had excellent peelability is preferable. In addition, since the flexibility is high, generation of deformation defects in the substrate 20 can be suppressed even when foreign matter such as bubbles or dust is mixed between the resin layer 32 and the substrate 20.

Curable silicone used as such a release paper silicone resin is classified into condensation reaction type | mold silicone, addition reaction type | mold silicone, ultraviolet ray curable silicone, and electron beam curable silicone according to the hardening mechanism, and can use all. Of these, addition reaction type silicon is preferable. This is because the degree of peelability is good and the heat resistance is high when the curing reaction is easy and the resin layer 32 is formed.

The addition reaction type silicone is a curable composition containing a main material and a crosslinking agent and curing in the presence of a catalyst such as a platinum-based catalyst. Curing of the addition-reactive silicone is promoted by heat treatment. The main component of the addition-reactive silicon is composed of linear organopolysiloxanes (ie, organoalkenylpolysiloxanes) having alkenyl groups (such as vinyl groups) bonded to silicon atoms, and vinyl groups and the like as crosslinking points. The crosslinking agent of the addition-reactive silicone consists of a linear organopolysiloxane (that is, an organohydrogenpolysiloxane) having a hydrogen atom (hydrosilyl group) bonded to a silicon atom, and a hydrosilyl group or the like becomes a crosslinking point.

Moreover, curable silicone used as a release paper silicone resin has a solvent type, an emulsion type, and a non-solvent type in form, and can use any type. Of these, no-solvent formulations are preferred. This is because it is excellent in terms of productivity, safety and environmental characteristics. In addition, since it does not contain the solvent which generate | occur | produces at the time of hardening at the time of forming the resin layer 32, ie, heat hardening, ultraviolet curing, or electron beam hardening, since a bubble is hard to remain in the resin layer 32, to be.

Moreover, as curable silicone used as a silicone resin for release papers, KNS-320A, KS-847 (all are Shin-Etsu Silicone Co., Ltd.), TPR6700 (GE Toshiba Silicone Co., Ltd.), vinyl silicone specifically, as a brand name or model number marketed 8500 "(made by Arakawa Chemical Co., Ltd.) and methylhydrogen polysiloxane" 12031 "(made by Arakawa Chemical Co., Ltd.), vinyl silicone" 11364 "(made by Arakawa Chemical Co., Ltd.), and methylhydrogen polysiloxane" 12031 "(made by Arakawa Chemical Co., Ltd.) And combinations of vinyl silicone "11365" (manufactured by Arakawa Chemical Co., Ltd.) and methylhydrogenpolysiloxane "12031" (manufactured by Arakawa Chemical Co., Ltd.).

In addition, KNS-320A, KS-847, and TPR6700 are curable silicones containing a main material and a crosslinking agent previously.

Moreover, it is preferable that the silicone resin which forms the resin layer 32 has the property which the component in a silicone resin layer is hard to transfer to the board | substrate 20, ie, low silicone transferability.

Although the method of fixing the resin layer 32 on the support plate 31 is not specifically limited, For example, the method of fixing the film-shaped resin to the surface of the support plate 31 is mentioned. Specifically, in order to give a high fixing force (high peel strength) to the surface of the film, surface modification treatment (priming treatment) is performed on the surface of the support plate 31, and the resin layer 32 is placed on the support plate 31. The method of fixing is mentioned. For example, chemical methods such as silane coupling agents (primer treatment), physical methods of increasing surface active groups such as flame (flame) treatment, and roughness by increasing surface roughness such as sandblast treatment. Mechanical treatment methods for increasing the temperature and the like are exemplified.

For example, the support plate 31 is formed by forming a layer of the curable resin composition to be the resin layer 32 on the surface of the support plate 31, and subsequently curing the curable resin composition to form the resin layer 32. The resin layer 32 fixed on () may also be formed. As a method of forming the layer of curable resin composition on the support plate 31 surface, the method of coating curable resin composition on the support plate 31 is mentioned, for example. Examples of the coating method include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. Among these methods, it can select suitably according to the kind of resin composition.

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

For example, in the case of forming the resin layer 32 from the curable resin composition of addition-reaction type silicone, the above-mentioned spray coating method is used for the curable resin composition composed of a mixture of an organoalkenylpolysiloxane, an organohydrogenpolysiloxane, and a catalyst. It apply | coats on the support plate 31 by the well-known method of, and it heat-hardens after that. Although the heat-hardening conditions differ also with the compounding quantity of a catalyst, when 2 mass parts of platinum-type catalysts are mix | blended with respect to 100 mass parts of total amounts of organo alkenyl polysiloxane and organohydrogen polysiloxane, it is 50 degreeC in air | atmosphere. To 250 ° C, preferably 100 ° C to 200 ° C. In addition, the reaction time in this case is 5 to 60 minutes, Preferably it is 10 to 30 minutes.

By heat-hardening curable resin composition, a silicone resin couple | bonds with the support plate 31 chemically at the time of hardening reaction, and / or a silicone resin layer couple | bonds with the support plate 31 by an anchor effect. By these actions, the silicone resin layer is firmly fixed to the support plate 31. Moreover, also when forming the resin layer which consists of resin other than silicone resin from curable resin composition, the resin layer fixed to the support plate can be formed by the method similar to the above.

The method of bringing the resin layer 32 into close contact with the substrate 20 so that it can be peeled off may be a known method. For example, after wrapping the board | substrate 20 on the peelable surface of the resin layer 32 in an atmospheric pressure environment, the method of crimping | bonding the resin layer 32 and the board | substrate 20 using a roll or a press is mentioned. Since the resin layer 32 and the board | substrate 20 adhere more closely by crimping | bonding with a roll or a press, it is preferable. Moreover, since the bubble mixed in between the resin layer 32 and the board | substrate 20 is removed comparatively easily by the crimping | bonding by a roll or a press, it is preferable.

When it crimps | bonds by the vacuum lamination method or the vacuum press method, it is more preferable because suppression of mixing of foam | bubble, and ensuring good adhesion are performed more preferable. By pressing under vacuum, even when a minute bubble remains, there is also an advantage that the bubble does not grow by heating and is hard to lead to deformation defects of the substrate 20.

When the resin layer 32 is brought into close contact with the substrate 20 so that the resin layer 32 can be peeled off, it is preferable that the surfaces of the resin layer 32 and the substrate 20 in contact with each other are sufficiently washed and laminated in a high clean environment. . Even if foreign matter is mixed between the resin layer 32 and the substrate 20, since the resin layer 32 deforms, the flatness of the surface of the substrate 20 is not affected. It is preferable because it becomes good.

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 making the resin layer 32 adhere | attach so that peeling on the board | substrate 20 is possible, for example, it is substantially simultaneous. It may be.

In the present invention, at least one of the contact surface 201 and the contact surface 321 is previously treated with a silicone oil or a silane coupling agent, or the resin layer 32 is formed from a resin containing a silicone oil or a silane coupling agent. Formed. 1st Embodiment is the surface treatment of the former among them. By surface-treating with silicone oil or a silane coupling agent before contacting at least one of the contact surface 201 and the contact surface 321 in advance, the density of the polar groups present on the contact surfaces 201 and 321 can be appropriately adjusted. In addition, in this embodiment, the contact surface 201 of the side of the board | substrate 20 may be surface-treated previously, the contact surface 321 of the side of the resin layer 32 may be surface-treated previously, and the contact | adherence of both sides may be carried out. The surfaces 201 and 321 may be surface-treated in advance. Moreover, also by forming the resin layer 32 from resin containing a silicone oil or a silane coupling agent (2nd Embodiment), the density of the polar group which exists in the contact surface 321 similarly can be adjusted suitably.

Here, as a polar group which exists on the surface of a glass substrate, a hydroxyl group (-OH) etc. are mentioned, for example. Moreover, as a polar group which exists on the surface of a resin layer, a carbonyl group (-CO), a carboxyl group (-COOH), etc. are mentioned, for example. These polar groups are all hydrophilic groups.

The proper density of the polar groups present on the contact surfaces 201 and 321 of the substrate 20 and the resin layer 32 is determined by measuring the water contact angle of the surface serving as the contact surfaces 201 and 321 before adhesion. In general, the higher the density of the hydrophilic polar group present on the surface, the smaller the water contact angle tends to be. Here, a water contact angle means the contact angle prescribed | regulated to JISR3257-1999.

It is preferable that the water contact angle before the close_contact | adherence of the contact surface 201,321 which was surface-treated is 90 degrees or more, It is more preferable that it is 90-120 degrees, It is still more preferable that it is 90-110 degrees. If the water contact angles before the adhesion between both of the adhesion surfaces 201 and 321 are both smaller 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, in the manufacturing process of a device, when the temperature of the laminated body 10 exceeds 250 degreeC, the chemical bonding of the board | substrate 20 and the resin layer 32 is accelerated | stimulated, and the board | substrate 20 and the resin layer 32 (Reinforcing plate 30) becomes difficult to separate.

It is preferable that the surface whose water contact angle before contact | adherence is 90 degrees or more is the contact surface 201 of the board | substrate 20. FIG. If the water contact angle of the adhesion surface 201 is 90 degrees or more, even if the water contact angle before adhesion of the adhesion surface 321 is less than 90 degrees, the resin layer 32 and the board | substrate 20 may be made, unless resin is especially high hydrophilicity. It can peel easily. In particular, when the resin layer 32 is hydrophobic resin, such as a silicone resin, even if the water contact angle before contact | adherence of the adhesion surface 321 is less than 90 degrees, it can peel easily.

In the adhesion surface 201 of the board | substrate 20, the fine uneven structure may be previously formed by the surface treatment before adhesion. In this case, due to the anchoring effect of the uneven structure, the adhesion surface 201 of the substrate 20 and the adhesion surface 321 of the resin layer 32 can be brought into close contact with sufficient bonding force to easily handle the laminate 10. have. Moreover, when a fine uneven structure is formed by surface treatment, there exists a tendency for a water contact angle to increase and a water contact angle may exceed 120 degrees.

It is preferable that the surface which surface-treats is a surface sufficiently clean, and it is preferable that it is a surface immediately after washing | cleaning. If the cleanliness (activity) is too low, uniform surface treatment cannot be performed. As the washing method, a general method used for washing the glass surface or the resin surface is used.

It is preferable to protect the surface which does not surface-treat previously with protective films, such as a mask. It is because it is difficult to form a member for devices in the manufacturing process of a device in the surface to which the material of surface treatment was affixed incorrectly.

Silicone oil and silane coupling agents which are materials for surface treatment are used alone or in combination. When using in combination, it may be surface-treated with a silicone oil after surface treatment with a silane coupling agent, or may be surface-treated with a silane coupling agent after surface treatment with a silicone oil.

Although the kind of silicone oil is not specifically limited, Straight silicone oil, such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, alkyl group, hydrogen group, epoxy group, amino group, carboxyl group, polyether group, halogen in a side chain or terminal The modified silicone oil which introduce | transduced group etc. is illustrated. As a specific example, methylhydrogen polysiloxane, dimethyl polysiloxane, methylphenyl polysiloxane, diphenylsiloxane, etc. are mentioned, heat resistance increases in order of hot air, and diphenylsiloxane is the highest heat resistance. These silicone oils are generally used for water repellent treatment of substrate surfaces such as glass substrates and primer-treated metal substrates.

The surface treatment method using silicone oil may be a general method. In the treatment only by simply applying the silicone oil, since the silicone oil is less likely to bind to the surface to be treated and the effect of the treatment may not be sufficiently exhibited, the silicone oil is applied to the surface after the silicone oil is applied. It is preferable to add a treatment to combine. The process of bonding the silicone oil to the surface to be treated is a process of breaking the molecular chain of the silicone oil, and it is thought that the cut fragments bind to the surface to be treated (hereinafter, this treatment is referred to as low molecular weight of the silicone oil. ).

As a surface treatment method with silicone oil, the method of apply | coating silicone oil to the contact surface 201 of the board | substrate 20, or the contact surface 321 of the resin layer 32, and lowering the molecular weight is preferable. By adjusting the application amount of silicone oil, the processing conditions of low molecular weight, etc., the density of the polar group which exists in the contact surface 201 of the board | substrate 20, or the contact surface 321 of the resin layer 32 can be optimized. Therefore, when peeling the resin layer 32 and the board | substrate 20, cohesion failure of the resin layer 32 can be suppressed.

The coating method of silicone oil may be a general method. For example, the spray coating method, the die coating method, the spin coating method, the dip coating method, the roll coating method, the bar coating method, the screen printing method, the gravure coating method, and the like are appropriately selected depending on the type and application amount of the silicone oil. . As a coating liquid, it is preferable to use the solution which diluted the silicone oil to 1 mass% or less with solvents, such as hexane, heptane, and xylene. When it exceeds 1 mass%, the processing time of low molecular weightization is too long. Moreover, it is preferable to use the solution diluted to 0.01 mass% or more. If it is less than 0.01 mass%, it becomes insufficient in order to optimize the density of a polar group.

As a method for lowering the molecular weight of silicone oil, a general method is used, for example, there is a method of cleaving the siloxane bond of the silicone oil by photolysis or pyrolysis. Ultraviolet light irradiated from a low pressure mercury lamp, a xenon arc lamp, etc. is used for photolysis, and ozone generated by ultraviolet light irradiation in air | atmosphere may be used together. Pyrolysis may be performed in a batch, a conveyor furnace, etc., and a plasma, an arc discharge, etc. may be used. In the case of thermal decomposition in a batch furnace or a conveyor furnace, although it changes also with the kind and density | concentration of the silicone oil of said coating liquid, the process in 250 degreeC-400 degreeC is preferable. If it is less than 250 degreeC, the low molecular weightization of silicon will become inadequate, and if it exceeds 400 degreeC, silicaization of silicon will become remarkable and it will become inadequate as a low molecular weightization process.

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 the hydrophilic polar groups present on the contact surface 201 of the substrate 20 or the contact surface 321 of the resin layer 32 is small. Lose. In addition, when the siloxane bond of the silicone oil is excessively broken, the density of the hydrophilic polar group tends to increase again.

Although the kind of silane coupling agent is not specifically limited, For example, hexamethyldisilazane (HMDS), 3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, Aminosilanes such as N- {N- (2-aminoethyl) -2-aminoethyl} -3-aminopropyltrimethoxysilane and 3-anilinopropyltrimethoxysilane, and 3-glycidoxypropyltrime Epoxysilanes, such as a methoxysilane, 2- (3, 4- epoxycyclohexyl) ethyltrimethoxysilane, chlorsilanes, such as 3-chloropropyl trimethoxysilane, fluorosilanes, and 3-mercaptotrimethoxy Vinylsilanes such as mercaptosilanes such as silane, vinyltrimethoxysilane, N-2- (N-vinylbenzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-methacryloxypropyltri One or more types selected from acrylic silanes such as methoxysilane can be preferably used.

The surface treatment method by a silane coupling agent should just 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 vaporized silane coupling agent, and the adhesion surface of the substrate 20 ( 201) and the hydrophilic polar group which exists in the contact surface 321 of the resin layer 32, etc. are substituted with hydrophobic functional groups, such as a methyl group. By adjusting the concentration, temperature, processing time and the like of the silane coupling agent in the atmosphere, the density of the polar group present on the contact surface 201 of the substrate 20 or the contact surface 321 of the resin layer 32 can be optimized. . Therefore, when peeling the resin layer 32 and the board | substrate 20, cohesion failure of the resin layer 32 can be suppressed.

In addition, the adhesion surfaces 201 and 321 can be returned to the state before surface treatment by a predetermined process after peeling each other during the manufacturing process of a device. For example, the surface on which the surface treatment by the silicone oil or the silane coupling agent was given can be returned to the state before surface treatment by photolysis or thermal decomposition. Thus, when the surface 201 of the board | substrate 20 is returned to the state before surface treatment, for example, when sticking an optical film (for example, a polarizing film) to the surface 201, the adhesive strength can be improved. have. Moreover, when reworkability is important, an optical film can also be stuck to the surface 201 of the board | substrate 20 as it is 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 this embodiment, the resin layer 32 is formed from resin containing a silicone oil or a silane coupling agent. It is preferable that the resin layer 32 is formed by hardening curable resin composition containing a silicone oil or a silane coupling agent. Although it does not specifically limit as curable resin composition, For example, curable resin composition used as a silicone resin for release papers is used. In addition, the contact surfaces 201 and 321 of the substrate 20 and the resin layer 32 may not have been subjected to the surface treatment before the contact.

Silicone oil and a silane coupling agent are used individually or in combination, It is preferable to use what does not have a functional group reacting with the component of curable resin composition, respectively. For example, when forming the resin layer 32 from the curable resin composition of the said addition reaction type silicone, what does not have a functional group (for example, vinyl group or hydrosilyl group) which becomes a crosslinking point as a silicone oil or a silane coupling agent is used. Is used. In addition, when forming the resin layer 32 from the curable resin composition of condensation reaction type silicone, the silicone oil which does not have a functional group (hydrolysable group, a silanol group, etc.) which can be condensed is used.

Silicone resin is dispersed and contained in this resin layer 32, without crosslinking at the time of hardening of the said curable resin composition. In addition, a silane coupling agent is condensed at the time of hardening of the said curable resin composition normally, and is contained as a condensate of a silane coupling agent in hardened resin. Therefore, the condensate of silicone oil or a silane coupling agent is disperse | distributed and contained in the contact surface 321 of the resin layer 32. As shown in FIG.

For example, when silicone oil is contained in the contact surface 321 of the resin layer 32, when the temperature of the laminated body 10 becomes high in a manufacturing process of a device, silicone oil will become low molecular weight. As a result, the density of the hydrophilic polar groups present on both of the adhesion surfaces 201 and 321 decreases, and the density of hydrophobic functional groups such as methyl groups increases.

In addition, when the silane coupling agent condensate is contained in the contact surface 321 of the resin layer 32, the hydrophilic polar group which exists in both adhesion surfaces 201 and 321 is substituted by hydrophobic functional groups, such as a methyl group.

For this reason, the density of the polar group which exists in both contact surfaces 201 and 321 can be optimized by adjusting content and the kind of silicone oil or silane coupling agent which are contained in curable resin composition used as the resin layer 32. FIG.

Therefore, also in this embodiment, when peeling the resin layer 32 and the board | substrate 20 like 1st Embodiment, it can suppress that the resin layer 32 is cohesive-broken. In addition, since the process of lowering the molecular weight of the silicone oil is performed together with the process for other purposes, there is no process of vaporizing the silane coupling agent, so that the number of steps can be reduced.

It is preferable that 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. When it is less than 0.1 mass%, sufficient effect is not acquired. On the other hand, when it exceeds 5 mass%, the heat resistance of the resin layer 32 becomes low too much.

In the case of the second embodiment, the adhesion surface 201 of the substrate 20 may not be subjected to the surface treatment in the first embodiment. When the board | substrate 20 is a glass substrate, since the surface is a surface with high hydrophilicity, the contact surface 201 may be previously surface-treated in the said 1st Embodiment before contact | adherence.

<Examples>

Although an Example etc. demonstrate this invention concretely below, this invention is not limited by these examples.

Example 1

As a board | substrate and a support plate, the glass plate (Asahi Glass Co., Ltd. product, AN100, alkali free glass) of 720 mm long x 600 mm obtained by the float method was used. In addition, the thickness of the board | substrate was 0.4 mm and the thickness of the support plate was 0.3 mm. The average coefficient of linear expansion of the board | substrate and the support plate was 38x10 <^-7> / degreeC, respectively.

(Production of reinforcement board)

The support plate was cleaned purely and UV-cleaned to clean the surface of the support plate. Then, the curable resin composition was apply | coated to the single side | surface of the support plate by screen printing (coating amount 30g / m <^2> ).

The mixture of 100 mass parts of solventless addition reaction type silicone (Shin-Etsu Silicone Co., KNS-320A) and 2 mass parts of platinum-type catalysts (Shin-Etsu Silicone Co., CAT-PL-56) was used for curable resin composition.

The solvent-free addition silicone is a linear organoalkenylpolysiloxane (topic) having a vinyl group and a methyl group bonded to a silicon atom, and a linear organohydrogenpolysiloxane (crosslinking agent) having a hydrogen atom and a methyl group bonded to a silicon atom. It is to include.

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

(Surface treatment of board)

The surface of the substrate was cleaned by pure cleaning and UV cleaning. Thereafter, a mask was applied to the second main surface, which is one side of the substrate, and then spray-coated and dried a heptane solution having a silicon oil content of 0.5% by mass on the first main surface on the opposite side. Dimethyl polysiloxane (made by Toray Dow Corning, SH200) was used for 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, it was 100 degrees when the water contact angle of the 1st main surface of the board | substrate was measured using the contact angle meter (Drop SHAPE ANALYSIS SYSTEM DSA 10Mk2 by the cross company).

(Preparation of laminate)

After the ultraviolet treatment, the 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.

(Heat test of laminated body)

This laminated body was heat-processed at 350 degreeC for 1 hour in nitrogen atmosphere whose oxygen volume concentration is 1000 ppm or less. Thereafter, after cooling to room temperature, a peeling knife is inserted between the substrate and the silicone resin layer, and the substrate and the silicone resin layer are sequentially bent and deformed from the vicinity of the position where the silicone resin layer side is inserted while supporting the substrate side flatly. Peeled off.

Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and the transfer product from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 100 degrees.

[Example 2]

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

(Production of reinforcement board)

In Example 2, as a curable resin composition, linear organo alkenyl polysiloxane (vinyl silicone, Arakawa Chemical Co., Ltd., 8500) which has a vinyl group at both ends, and methylhydrogen polysiloxane (Arakawa Chemical Co., Ltd.) which have a hydrosilyl group in a molecule | numerator A reinforcing plate was produced in the same manner as in Example 1 except that a mixture of Manufacture 12031 and a platinum catalyst (Arakawa Chemical Co., Ltd., CAT12070) was used.

Here, the mixing ratio of the linear organoalkenylpolysiloxane and the methylhydrogenpolysiloxane was adjusted so that the molar ratio of the vinyl group and the hydrosilyl group was 1: 1. In addition, the platinum catalyst was 5 mass parts with respect to a total of 100 mass parts of linear organo alkenyl polysiloxane and methylhydrogen polysiloxane.

(Surface treatment of board)

In Example 2, the surface treatment of the board | substrate was performed similarly to Example 1 except having performed the plasma process by the atmospheric pressure remote plasma apparatus (The Sekisui Chemical Co., Ltd., RT series) in order to reduce the molecular weight of silicone oil.

Here, the processing conditions of the plasma treatment were an output of 3kw, a nitrogen / air flow rate ratio of 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 degrees C or less. The water contact angle of the 1st main surface of the board | substrate after surface treatment was 95 degrees.

(Preparation of laminate)

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

(Heat test of laminated body)

After heat-processing this laminated body similarly to Example 1, the board | substrate and the silicone resin layer were peeled similarly to Example 1. Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and the transfer product from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 100 degrees.

[Example 3]

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

(Production of reinforcement board)

In Example 3, the reinforcement board was produced like Example 2.

(Surface treatment of board)

In Example 3, the surface treatment of the board | substrate was performed like Example 1 except having carried out 10 minute heat processing at 400 degreeC in air | atmosphere for the low molecular weight of silicone oil. The water contact angle of the 1st main surface of the board | substrate after surface treatment was 105 degrees.

(Preparation of laminate)

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

(Heat test of laminated body)

After heat-processing this laminated body similarly to Example 1, the board | substrate and the silicone resin layer were peeled similarly to Example 1. Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and the transfer product from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 105 degrees.

Example 4

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

(Production of reinforcement board)

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

(Surface treatment of board)

In Example 4, in order to reduce the molecular weight of the silicone oil, the first main surface of the substrate was spray-coated and dried with a heptane solution having a silicon oil content of 0.1% by mass, and then heated for 10 minutes at 250 ° C in the air. In the same manner as in 1, the substrate was subjected to surface treatment. The water contact angle of the 1st main surface of the board | substrate after surface treatment was 98 degrees.

(Preparation of laminate)

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

(Heat test of laminated body)

After heat-processing this laminated body similarly to Example 1, the board | substrate and the silicone resin layer were peeled similarly to Example 1. Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and the transfer product from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 98 degrees.

[Example 5]

As a board | substrate and a support plate, the glass plate (Asahi Glass Co., AS, soda-lime glass) of 720 mm long x 600 mm obtained by the float method was used, respectively. In addition, the thickness of the board | substrate was 0.4 mm and the thickness of the support plate was 0.3 mm. The average coefficient of linear expansion of the board | substrate and the support plate was respectively 85x10 <^-7> / degreeC.

(Production of reinforcement board)

In Example 5, the reinforcement board was produced like Example 2.

(Surface treatment of board)

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

(Preparation of laminate)

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

(Heat test of laminated body)

After heat-processing this laminated body similarly to Example 1, the board | substrate and the silicone resin layer were peeled similarly to Example 1. Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and the transfer product from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 102 degrees.

[Example 6]

The glass plate similar to Example 5 was used for the board | substrate and the support plate except having chemically strengthened, respectively.

(Production of reinforcement board)

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

(Surface treatment of board)

In Example 6, the surface treatment of the board | substrate was performed similarly to Example 5, in order to reduce the molecular weight of silicone oil. The water contact angle of the 1st main surface of the board | substrate after surface treatment was 102 degrees.

(Preparation of laminate)

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

(Heat test of laminated body)

After heat-processing this laminated body similarly to Example 1, the board | substrate and the silicone resin layer were peeled similarly to Example 1. Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and the transfer product from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 102 degrees.

[Example 7]

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

(Production of reinforcement board)

The support plate was cleaned purely and UV-cleaned to clean the surface of the support plate. Then, the mixture of 99.5 mass parts of curable resin compositions and 0.5 mass parts of silicone oil was apply | coated to the single side | surface of a support plate by screen printing (coating amount 30g / m <^2> ). Here, the same thing as Example 2 was used for curable resin composition, and dimethyl polysiloxane (made by Toray Dow Corning, SH200) was used for silicone oil.

The mixture applied on the support plate was heat-cured at 180 ° C. for 30 minutes in the air to form a silicone resin layer having a length of 705 mm × 595 mm × 20 μm in the center on the support plate and fixed.

(Preparation of laminate)

After preparation of the reinforcing plate, the silicone resin layer was superimposed on the surface after washing of the substrate, and the substrate and the silicone resin layer were brought into close contact with each other by vacuum press at room temperature to obtain a laminate composed of the substrate and the reinforcing plate.

(Heat test of laminated body)

After heat-processing this laminated body similarly to Example 1, the board | substrate and the silicone resin layer were peeled similarly to Example 1. Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and transfer of resin from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 102 degrees.

[Example 8]

As a board | substrate and a support plate, the polyimide resin board (Toray DuPont company make, Kafuton 200HV) of length 720mm x width 600mm was used for both. In addition, the thickness of the board | substrate was 0.05 mm and the thickness of the support plate was 0.5 mm.

(Production of reinforcement board)

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

(Surface treatment of board)

In Example 8, the substrate was subjected to the surface treatment in the same manner as in Example 2. The water contact angle of the 1st main surface of the board | substrate after surface treatment was 100 degrees.

(Preparation of laminate)

After the surface treatment, the silicone resin layer was superposed 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 vacuum press at room temperature to obtain a laminate composed of the substrate and the reinforcing plate.

(Heat test of laminated body)

After heat-processing this laminated body similarly to Example 1, the board | substrate and the silicone resin layer were peeled similarly to Example 1. Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and the transfer product from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 100 degrees.

[Example 9]

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

(Production of reinforcement board)

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

(Surface treatment of board)

The surface of the substrate was cleaned by pure cleaning and UV cleaning. Subsequently, after masking on the 2nd main surface which is the single side | surface of a board | substrate, the 1st main surface on the opposite side was exposed to the atmosphere which kept the gas which vaporized the silane coupling agent (made by Toray Dow Corning, Z6040) for 10 minutes in saturated state. I was. The surface temperature of the board | substrate at the time of exposure was 25 degreeC. The water contact angle of the 1st main surface of the board | substrate after exposure was 100 degrees.

(Preparation of laminate)

After the surface treatment with a silane coupling agent, the silicone resin layer was superimposed 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 vacuum press at room temperature to obtain a laminate composed of the substrate and the reinforcing plate.

(Heat test of laminated body)

After heat-processing this laminated body similarly to Example 1, the board | substrate and the silicone resin layer were peeled similarly to Example 1. Cohesive failure was not seen in the silicone resin layer after peeling by observation with an optical microscope, and the transfer product from the silicone resin layer was not seen in the substrate after peeling. In addition, the water contact angle of the 1st main surface of the board | substrate after peeling was 100 degrees.

Comparative Example 1

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

(Preparation of laminate)

In Comparative Example 1, a reinforcing plate was fabricated in the same manner as in Example 2, and the first main surface of the substrate was cleaned by pure and UV cleaning, and then cleaned. Then, the silicone resin layer was superimposed on the first main surface of the substrate, and the substrate and the silicone resin layer were formed. It adhered by the vacuum press at room temperature, and the laminated body which consists of a board | substrate and a reinforcement board was obtained. In addition, the water contact angle before adhesion of the contact surface (first main surface) of the substrate was 7 °.

(Heat test of laminated body)

After heat-processing this laminated body like Example 1, the board | substrate and silicone resin layer were peeled like Example 1, and as a result, a silicone resin layer was cohesive-broken and a part of silicone resin layer adhered to the board | substrate side.

Comparative Example 2

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

(Production of reinforcement board)

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

(Preparation of laminate)

In the same manner as in Example 2, a reinforcing plate was produced, the first main surface of the substrate was purely washed and cleaned, and then the silicone resin layer was overlaid 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 vacuum press at room temperature. To obtain a laminate comprising a substrate and a reinforcing plate. In addition, the water contact angle before adhesion of the 1st main surface of a board | substrate was 40 degrees.

(Heat test of laminated body)

After heat-processing this laminated body like Example 1, the board | substrate and silicone resin layer were peeled like Example 1, and as a result, a silicone resin layer was cohesive-broken and a part of silicone resin layer adhered to the board | substrate side.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various corrections and changes can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application 2010-108952 of an application on May 11, 2010, The content is taken in here as a reference.

10: laminate
20: substrate
201: adhesion surface (first principal surface)
202: second principal plane
30: reinforcement plate
31: support plate
32: resin layer
321: contact surface

Claims (11)

A method of manufacturing a laminate having a substrate, a support plate, and a resin layer present therebetween, comprising: forming the resin layer on the support plate; and adhering the resin layer to the substrate so as to be peeled off. In the method,
Before the close contacting step, a step of treating at least one of the closely contacted substrate surface and the resin layer surface with a silicone oil or a silane coupling agent in advance; or
The manufacturing method of the laminated body which forms the said resin layer from resin containing a silicone oil or a silane coupling agent in the process of forming the said resin layer, and makes the said board | substrate and the said resin layer overlap and adhere | attach in the said step of making it contact thereafter. . The process of Claim 1 which apply | coats a silicone oil or a silane coupling agent to at least one of the said board | substrate surface and the said resin layer surface to adhere | attach,
In the case of applying the silicone oil, the process of lowering the molecular weight of the silicone oil is carried out. In the case of applying the silane coupling agent, the process of reacting the silane coupling agent is carried out.
The manufacturing method of the laminated body which overlaps and adhere | attaches the said board | substrate and the said resin layer in the said step of making contact after that. The manufacturing method of the laminated body of Claim 2 whose surface of the said board | substrate which adhere | attaches is surface-treated with silicone oil or a silane coupling agent, and the water contact angle of the surface of the board | substrate to which the said process was performed is 90 degrees or more. The process of forming a said resin layer on the said support plate WHEREIN: The curable resin composition layer is formed in the said support plate surface, Then, the said curable resin composition is hardened | cured by the said The manufacturing method of the laminated body which forms a resin layer. The manufacturing method of the laminated body of any one of Claims 1-4 in which the said resin layer contains a silicone resin. The manufacturing method of the laminated body in any one of Claims 1-5 in which the said resin layer contains the reaction hardened | cured material of organo alkenyl polysiloxane and organohydrogen polysiloxane. It has a board | substrate, a support plate, and the resin layer which exists between them, The said resin layer and the said board | substrate adhere | attach so that peeling is possible, The said resin layer is on the said support plate, The peeling strength between them is between the said resin layer and the said board | substrate. As a laminated body fixed so that it may become higher than the peeling strength of,
At least one of the surface of the substrate and the surface of the resin layer in close contact is made of a surface previously treated with a silicone oil or a silane coupling agent, or
The laminated body whose said resin layer is a resin layer formed from resin containing a silicone oil or a silane coupling agent. The laminated body of Claim 7 whose surface of the board | substrate which adhering to the said resin layer surface is the surface surface-treated with the silicone oil or the silane coupling agent. The laminated body of Claim 8 whose water contact angle of the said surface-treated board | substrate surface is 90 degrees or more. The laminated body of any one of Claims 7-9 in which the said resin layer contains a silicone resin. The laminated body of any one of Claims 7-10 in which the said resin layer contains the reaction hardened | cured material of organo alkenyl polysiloxane and organohydrogen polysiloxane.

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