JPWO2013054792A1 - Manufacturing method of electronic device with adhesive resin layer - Google Patents

Abstract

  The present invention is a method for manufacturing an electronic device with an adhesive resin layer, which has an adhesive resin layer, a substrate, and an electronic device member in this order. The first lamination step, the first separation step, the second The present invention relates to a production method including the laminating step and the second separation step.

Description

  The present invention relates to a method for manufacturing an electronic device with an adhesive resin layer.

  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 glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.

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

  In addition, in the method of thinning a glass substrate by the above chemical etching, if a fine scratch exists on the surface of the glass substrate, 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 cope with the above problems, a laminate in which a glass substrate and a reinforcing plate are laminated is prepared, and a member for an electronic device such as a display device is formed on the glass substrate of the laminate, and then reinforced from the glass substrate. A method for separating plates has been proposed (see, for example, Patent Document 1). The reinforcing plate has a support plate and a resin layer fixed on the support plate, and the resin layer and the glass substrate are in close contact with each other in a peelable manner. The reinforcing plate separated from the glass substrate after the interface between the resin layer and the glass substrate of the laminate is peeled off can be laminated with a new glass substrate and reused as a laminate.

International Publication No. 07/018028

On the other hand, in recent years, as ubiquitous devices and the like have attracted attention, it is necessary to improve the attachment of the electronic device itself, such as wearing the electronic device itself to make it easy to carry or attaching the electronic device such as a display to a desired position. It has been.
As one of countermeasures for such a demand, there is a method of providing an electronic device having a resin layer on the surface that shows adhesion to an attachment target. According to the electronic device, the electronic device can be detachably attached to a desired position such as a wall, skin, or clothing via the adhesive resin layer.

  On the other hand, when an adhesive resin layer such as a silicone resin is formed on the exposed surface of a glass substrate on which an electronic device member such as a display device obtained in Patent Document 1 described above is formed, it is already formed. There is a possibility that the material of the adhesive resin layer adheres to the existing electronic device member, thereby reducing the performance of the electronic device and reducing the productivity of the electronic device.

Then, the present inventors tried manufacture of an electronic device using the glass substrate with a resin layer with which the adhesive silicone resin layer was fixed on the glass substrate with reference to invention of patent document 1. FIG. Specifically, as shown in FIG. 5, after the silicone resin layer 102 is cured and formed on one surface of the glass substrate 100 and the glass substrate 104 with a resin layer to which the silicone resin layer 102 is fixed is manufactured (FIG. 5). (A)), a laminated body 108 was obtained by closely laminating the glass substrate with a resin layer and the support plate with the surface of the silicone resin layer 102 and the surface of the support plate 106 as a laminate surface (FIG. 5B). Then, after forming the electronic device member 110 on the glass substrate 100 in the laminate under a high temperature condition (FIG. 5C), the interface between the support plate 106 and the silicone resin layer 102 is used as a release surface, and the electronic device is formed. The electronic device 114 with the resin layer in which the silicone resin layer 102 was fixed to the electronic device 112 including the member 110 for use and the glass substrate 100 was separated from the laminate (FIG. 5D).
However, the obtained electronic device 114 with a resin layer may have inferior performance. For example, when an OLED panel is manufactured, display unevenness may occur in the drive region of the panel.

The inventors of the present invention have examined the above cause and found that the thickness unevenness of the resin layer 102 in the laminated body 108 (particularly, a convex portion at the peripheral portion) is one of the causes.
FIG. 6A shows an enlarged side view of the glass substrate 104 with a resin layer, which is used when the laminated body 108 is manufactured. As shown in FIG. 6A, the silicone resin layer 102 in the glass substrate 104 with a resin layer has thickness unevenness. In particular, the thickness unevenness is remarkable in the vicinity of the outer peripheral edge of the silicone resin layer 102, and the convex portion 114 is formed in the vicinity of the outer peripheral edge. When the silicone resin layer 102 having such thickness unevenness is laminated on the support plate 106, the glass substrate 100 is bent so that the central portion is recessed, and the flatness of the glass substrate 100 is impaired (see FIG. 6B). . As a result, the position where the electronic device member formed on the glass substrate 100 is arranged may be shifted, and there is a concern that the productivity of the electronic device itself may be reduced.

As shown in FIG. 6B, when such a glass substrate 104 with a resin layer is laminated on the support plate 106, a gap 116 is formed between the support plate 106 and the silicone resin layer 102. End up. The laminate is subjected to a manufacturing process of the electronic device member, and a functional layer such as a conductive layer is formed on the exposed surface of the glass substrate 106. At that time, various solutions such as a resist solution are used.
If there are voids 116 in the laminate, various solutions will enter by capillary action. The material that has entered the gap 116 is difficult to remove even by washing, and tends to remain as a foreign substance after drying. Since the foreign matter becomes a contamination source that contaminates the electronic device member by heat treatment or the like, the yield of the electronic device is reduced. In addition, the adhesion of the silicone resin layer 102 to the object may be reduced.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing an electronic device having an adhesive resin layer that exhibits excellent productivity and exhibits detachable adhesion to an object. And

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the first aspect of the present invention is a method for manufacturing an electronic device with an adhesive resin layer having an adhesive resin layer, a substrate, and an electronic device member in this order,
An auxiliary substrate preparation step of preparing a peelable auxiliary substrate having a surface exhibiting easy peelability;
A curable resin composition layer forming step of forming an uncured curable resin composition layer by applying a curable resin composition on the surface showing the easy releasability of the peelable auxiliary substrate;
A substrate having an outer dimension smaller than the outer dimension of the uncured curable resin composition layer is left in the uncured curable resin composition layer so that a peripheral region that does not contact the substrate remains in the uncured curable resin composition layer. Laminating on the curable resin composition layer to obtain a laminate before curing,
A curing step of curing the uncured curable resin composition in the pre-cured laminate and obtaining a post-cured laminate having an adhesive resin layer;
A first separation step obtained by separating a substrate with an adhesive resin layer having the substrate and an adhesive resin layer in contact with the surface of the substrate from the post-curing laminate;
Second laminate for obtaining a laminate by laminating the substrate with an adhesive resin layer on the support plate so that the adhesive resin layer in the substrate with the adhesive resin layer comes into contact with the support plate. Process,
Forming a member for an electronic device on the surface of the substrate in the laminate and obtaining a laminate with the member for an electronic device; and
A second separation step of removing the support plate from the laminate with the electronic device member and obtaining an electronic device with an adhesive resin layer having the adhesive resin layer, the substrate, and the electronic device member in this order. And a method for producing an electronic device with an adhesive resin layer.

In the first aspect, the substrate is preferably a glass substrate.
1st aspect WHEREIN: It is preferable to further provide the defoaming process of carrying out the defoaming process of the said uncured curable resin composition layer after the said 1st lamination process and before the said hardening process.
1st aspect WHEREIN: It is preferable that the said auxiliary substrate preparation process is a process of processing the surface of an auxiliary substrate using a peeling agent, and obtaining the peelable auxiliary substrate which has the surface which shows easy peelability.

The release agent preferably contains a compound having a methylsilyl group or a fluoroalkyl group.
Alternatively, the release agent preferably contains silicone oil or a fluorine compound.
1st aspect WHEREIN: It is preferable that the said adhesive resin layer contains a silicone resin.

In the first embodiment, the adhesive resin layer is a cured product of an addition reaction type silicone comprising a combination of an organoalkenylpolysiloxane having an alkenyl group and an organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom. Preferably there is.
It is preferable that the molar ratio of the hydrogen atom bonded to the silicon atom of the organohydrogenpolysiloxane to the alkenyl group of the organoalkenylpolysiloxane is 0.5 to 2.
1st aspect WHEREIN: It is preferable that the said adhesive resin layer contains 5 mass% or less of non-curable organopolysiloxane.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the electronic device with an adhesive resin layer which has the adhesive resin layer which is excellent in productivity and shows the adhesiveness which can be attached or detached with respect to object can be provided.
In the method for manufacturing an electronic device with an adhesive resin layer according to the present invention, the resin layer can be formed on the surface of the thin glass substrate on which the device is not formed without touching the device forming surface. The risk of contamination of device components can be reduced.

FIG. 1 is a flowchart showing a manufacturing process of an embodiment of a method for manufacturing an electronic device with an adhesive resin layer of the present invention. FIG. 2: is typical sectional drawing which shows one Embodiment of the manufacturing method of the electronic device with an adhesive resin layer concerning this invention in order of a process. FIG. 3A is a top view of the pre-cured laminate obtained in the lamination step. FIG. 3B is a partial cross-sectional view illustrating a state before the substrates are stacked. FIG. 3C is a partial cross-sectional view showing a state after the substrates are stacked. FIG. 4 is a flowchart showing manufacturing steps of another embodiment of the method for manufacturing an electronic device with an adhesive resin layer of the present invention. FIG. 5: is typical sectional drawing which shows one Embodiment of the manufacturing method of an electronic device based on a prior art in order of a process. FIG. 6A is an enlarged side view of the end portion of the glass substrate with a resin layer based on the conventional technology. FIG. 6B is an enlarged side view of the end portion of the laminate based on the prior art.

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 adhesive resin has a higher peel strength at the interface between the adhesive resin layer and the substrate layer than the peel strength at the interface between the peelable auxiliary substrate layer and the adhesive resin layer. It is also said that the layer is fixed to the substrate and the adhesive resin layer is detachably attached to the peelable auxiliary substrate.

The present inventors have studied the problems of the invention of Patent Document 1, and found that the resin layer surface is uneven due to the influence of the surface tension at the air interface when the resin layer is cured. It was.
Therefore, paying attention to the order of the manufacturing process of the laminate, a peelable auxiliary substrate having a peelable surface is used, and a substrate having a smaller outer dimension than the uncured curable resin composition layer on the peelable auxiliary substrate is used. Adhesive resin that is excellent in flatness by maintaining contact with the uncured curable resin composition layer at a predetermined position and curing, so that the adhesiveness of the surface is not impaired even after peeling from the peelable auxiliary substrate. An electronic device with an adhesive resin layer having a layer is obtained.

[First Embodiment]
FIG. 1 is a flowchart showing manufacturing steps in an embodiment of a method for manufacturing an electronic device with an adhesive resin layer of the present invention. As shown in FIG. 1, the manufacturing method of the electronic device with an adhesive resin layer includes an auxiliary substrate preparation step S102, a curable resin composition layer formation step S104, a first lamination step S106, a curing step S108, and a first separation. It includes a step S110, a second stacking step S112, a member forming step S114, and a second separation step S116.
Moreover, FIG. 2 is typical sectional drawing which shows each manufacturing process in order in the manufacturing method of the electronic device with an adhesive resin layer of this invention.
Hereinafter, the materials used in each step and the procedure thereof will be described in detail with reference to FIG. First, the auxiliary substrate preparation step S102 will be described in detail.

[Auxiliary board preparation process]
The auxiliary substrate preparation step S102 is a step of preparing a peelable auxiliary substrate having a surface exhibiting easy peelability. The peelable auxiliary substrate 10 shown in FIG. 2 (A) means a support plate having a surface 10a showing easy peelability with respect to the adhesive resin layer to be described later, and the peelable auxiliary substrate 10 is an adhesive resin layer. It can adhere in a peelable manner. In FIG. 2A, the surface 10a showing easy peelability is formed only on one main surface of the peelable auxiliary substrate 10, but the other surface may show easy peelability.
Below, the aspect of the peelable auxiliary substrate used at this process S102 is explained in full detail.

(Peelable auxiliary substrate)
The peelable auxiliary substrate supports and reinforces the uncured curable resin composition layer and the substrate described later. Further, the peelable auxiliary substrate is a substrate used for enhancing the flatness of the surface of the adhesive resin layer obtained by curing the uncured curable resin composition layer, and is curable in an uncured state. In contact with the resin composition layer, the surface of the layer is flattened, and thickness unevenness of the adhesive resin layer is suppressed. The easy releasability of the surface of the peelable auxiliary substrate refers to the interface between the substrate and the adhesive resin layer and the inside of the resin layer when an external force for peeling the peelable auxiliary substrate is applied to the post-curing laminate described below. It means the property of peeling at the interface between the peelable auxiliary substrate and the adhesive resin layer without peeling.
The water contact angle of the surface showing the easy peelability of the peelable auxiliary substrate is preferably 90 ° or more from the viewpoint that peeling at the interface between the peelable auxiliary substrate and the adhesive resin layer is more likely to proceed. More preferably, it is -120 degrees, and it is still more preferable that it is 90-110 degrees.

  The material which comprises a peelable auxiliary substrate will not be restrict | limited especially if the surface shows easy peelability with respect to the adhesive resin layer. For example, a glass plate, a plastic plate (for example, a silicone substrate), a metal plate such as a SUS plate, or a substrate in which these are laminated (a laminated substrate having a silicone substrate as an upper layer and a glass substrate as a lower layer) is used.

  The thickness of the peelable auxiliary substrate is not particularly limited, and may be thicker or thinner than the laminated substrate. The thickness of the peelable auxiliary substrate is preferably 0.3 to 3.0 mm from the viewpoint that the current manufacturing apparatus can be used and the handleability.

The surface roughness (Ra) indicating the easy releasability of the releasable auxiliary substrate is preferably 2.0 nm or less in that the flatness of the adhesive resin layer obtained in the curing step S108 described later is more excellent. 0 nm or less is more preferable, and 0.5 nm or less is more preferable. The lower limit is not particularly limited, but 0 nm is particularly preferable.
In addition, the measurement of surface roughness (Ra) is performed by atomic force microscope (Pacific Nanotechnology, Nano Scope IIIa; Scan Rate 1.0 Hz, Sample Lines 256, Off-line Modification Flatten order-2, Plane-2 etc.). Can be performed based on JIS B 0601 (2001).

(Preferred embodiment)
A preferred embodiment of the auxiliary substrate preparation step is preferably a step of treating the surface of the auxiliary substrate with a release agent to obtain a peelable auxiliary substrate having a surface exhibiting easy peelability. By performing this step, a peelable auxiliary substrate having a surface exhibiting easy peelability can be obtained regardless of the type of the auxiliary substrate.
First, the auxiliary substrate and the release agent used in this process aspect will be described in detail, and then the procedure of the process will be described in detail.

(Auxiliary board)
The auxiliary substrate supports and reinforces the uncured curable resin composition layer and the substrate described later.
The type of the auxiliary substrate is not particularly limited, and for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. When the curing step S108 involves heat treatment, the auxiliary substrate is preferably formed of a material having a small difference in linear expansion coefficient from the substrate, more preferably formed of the same material as the substrate, and the substrate is a glass substrate. In some cases, the auxiliary substrate is preferably a glass plate. In particular, the auxiliary substrate is preferably a glass plate made of the same glass material as the substrate.

  The external dimension of the auxiliary substrate is not particularly limited, but is usually the same as the external dimension of the uncured curable resin composition layer to be laminated or larger than the external dimension of the uncured curable resin composition layer.

(paint remover)
As the release agent, a known release agent can be used. For example, a silicone-based compound (for example, silicone oil), a silylating agent (for example, hexamethyldisilazane), a fluorine-based compound (for example, fluorine resin) ) And the like. The release agent can be used as an emulsion type, a solvent type, or a solventless type. As a preferable example from the viewpoint of peeling force, safety, cost, etc., a methylsilyl group (any one of ≡SiCH ₃ , ═Si (CH ₃ ) ₂ , —Si (CH ₃ ) ₃ ) or a fluoroalkyl group (—C _m F _{2m + 1} ) (m is preferably an integer of 1 to 6), and other suitable examples include silicone compounds or fluorine compounds, with silicone oils being particularly preferred.

The type of silicone oil is not particularly limited, but is straight silicone oil such as methyl hydrogen silicone oil, dimethyl silicone oil, methyl phenyl silicone oil, etc., alkyl group, hydrogen group, epoxy group, amino group at the side chain or terminal of straight silicone oil Examples thereof include modified silicone oil into which a group, a carboxyl group, a polyether group, a halogen group and the like are introduced.
Specific examples of straight silicone oils include methyl hydrogen polysiloxane, dimethyl polysiloxane, methylphenyl polysiloxane, and diphenyl polysiloxane. The heat resistance increases in the order listed, and the most heat resistant is diphenyl polysiloxane. Siloxane.
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.
Silicone oil, from the viewpoint of the efficiency of the process to be bound to the treated surface of the auxiliary substrate, kinematic viscosity is preferably from 5000 mm ² / s at 25 ° C., more preferably at most 500 mm ² / s. The lower limit of the kinematic viscosity is not particularly limited, but is preferably 0.5 mm ² / s or more in consideration of handling and cost.
Of the above silicone oils, straight silicone oils are preferable in terms of good releasability from the adhesive resin layer, and dimethylpolysiloxane is particularly preferable in terms of providing high releasability. In addition, methylphenylpolysiloxane or diphenylpolysiloxane is preferred when particularly heat resistance is required along with peelability.

In the case of a fluorine-based compound, the type is not particularly limited, but perfluoroalkyl ammonium salt, perfluoroalkyl sulfonic acid amide, perfluoroalkyl sulfonate (for example, sodium perfluoroalkyl sulfonate), perfluoroalkyl potassium salt, perfluoroalkyl potassium salt, perfluoroalkyl sulfonate. Fluoroalkylcarboxylates, perfluoroalkylethylene oxide adducts, perfluoroalkyltrimethylammonium salts, perfluoroalkylaminosulfonates, perfluoroalkyl phosphates, perfluoroalkyl compounds, perfluoroalkyl betaines, perfluoroalkyl halogen compounds, etc. Is mentioned.
As the compound containing a fluoroalkyl group _{(-C m F 2m + 1)} , for example, compounds having a fluoroalkyl group in the exemplified compounds of the fluorine-based compounds. The upper limit of m is not particularly limited in terms of peeling performance, but m is preferably an integer of 1 to 6 in terms of better handling safety.

(Process procedure)
As the method for treating the surface of the auxiliary substrate, an optimum method is appropriately selected according to the release agent used. Usually, the treatment is performed by applying (for example, applying) a release agent to the surface of the auxiliary substrate. In addition, this process should just be made | formed with respect to the surface on which the uncured curable resin composition layer mentioned later is laminated | stacked, and surface treatment may be given to the other surface. Usually, the auxiliary substrate is a plate-like body having a first main surface and a second main surface, and it is preferable that the treatment is performed on at least one of the main surfaces.
For example, when silicone oil is used, a method of applying silicone oil to the surface of the auxiliary substrate can be mentioned. Especially, after apply | coating silicone oil, it is preferable to perform the process which couple | bonds silicone oil with the to-be-processed surface of an auxiliary substrate. The treatment for bonding the silicone oil to the surface to be treated is a treatment for breaking the molecular chain of the silicone oil, and the cut fragments are bound to the surface to be treated (hereinafter, this treatment is referred to as lowering the molecular weight of the silicone oil). ).

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 5% by mass or less with a solvent such as hexane, heptane, xylene, or isoparaffin. If it exceeds 5% by mass, the treatment time for reducing the molecular weight is too long.
The solvent contained in the coating solution is removed by a method such as heating and / or drying under reduced pressure as necessary. It may be removed by heating in the molecular weight reduction step.
The amount of silicone oil applied is preferably 0.1 to 10 μg / cm ² . When it is 0.1 μg / cm ² or more, it is preferable from the viewpoint that the releasability is more excellent, and when it is 10 μg / cm ² or less, it is preferable from the viewpoint that the coating property of the coating liquid and the low molecular weight treatment property are more excellent.

As a method for reducing the molecular weight of silicone oil, a general method is used. For example, there is a method of cutting a siloxane bond of 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. Thermal decomposition may be performed in a batch furnace, a conveyor furnace, or the like, or plasma or arc discharge may be used.
When the siloxane bond of the silicone oil or the bond between the silicon atom and the carbon atom is broken, the generated active site reacts with an active group such as a hydroxyl group on the surface to be treated. As a result, the density of hydrophobic functional groups such as methyl groups on the surface to be treated increases, the density of hydrophilic polar groups decreases, and as a result, easy peelability is imparted to the surface to be treated.

Note that the surface of the reinforcing substrate to be surface-treated is preferably a sufficiently clean surface, and is preferably a surface immediately after cleaning. 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.

When a silylating agent such as hexamethyldisilazane is used, it is preferable that the vapor of the silylating agent is brought into contact with the auxiliary substrate surface. In addition, you may make it contact with the vapor | steam of a silylating agent in the state which heated the auxiliary substrate.
A higher silylating agent vapor concentration, that is, closer to the saturated concentration is preferable because the treatment time can be shortened.
The contact time between the silylating agent and the auxiliary substrate can be shortened as long as the function of the peelable auxiliary substrate is not impaired.

  A water repellent group (hydrophobic group) derived from silicone oil, a silylating agent or the like is introduced on the surface of the peelable auxiliary substrate obtained in the above step.

[Curable resin composition layer forming step]
In the curable resin composition layer forming step S104, the curable resin composition is applied on the surface showing the easy peelability of the peelable auxiliary substrate obtained in the auxiliary substrate preparing step S102, and the uncured curability is applied. This is a step of forming a resin composition layer. More specifically, as shown in FIG. 2B, the uncured curable resin composition layer 12 is formed on the surface 10a showing the peelability of the peelable auxiliary substrate 10 by this step S104. .

The uncured curable resin composition layer is in contact with the surface showing the peelability of the peelable auxiliary substrate without leaving a gap. Therefore, when the curable resin composition layer is cured in the curing step S108 described later, an adhesive resin layer to which the flat surface of the peelable auxiliary substrate is transferred can be obtained. As a result, the distortion of the board | substrate in the laminated body mentioned later is suppressed.
First, the curable resin composition used at this process is explained in full detail, and the procedure of this process S104 is explained in full detail after that.

(Curable resin composition)
The curable resin composition used in this step S104 is a composition that can form an adhesive resin layer in the curing step S108 described later.
The curable resin contained in the curable resin composition may be any known curable resin (for example, thermosetting) as long as the cured film has an adhesive property capable of being peelably adhered to an object. Curable compositions, photocurable compositions, etc.) can be used. For example, curable acrylic resin, curable urethane resin, curable silicone, and the like can be given. Several kinds of curable resins can be mixed and used. Among these, curable silicone is preferable. This is because the silicone resin obtained by curing the curable silicone is excellent in heat resistance and peelability. In addition, when curable silicone is used, when the substrate to be described later is a glass substrate, it is easily fixed to the glass substrate by a condensation reaction with a silanol group on the surface of the glass substrate.

  As the curable resin composition, a curable silicone resin composition (in particular, a curable silicone resin composition used for release paper is preferable) is preferable. The adhesive resin layer formed using this curable silicone resin composition is preferable because it adheres to the substrate surface and its free surface has excellent easy peelability.

  Such a curable silicone 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 the curing mechanism, and any of them can be used. Among these, addition reaction type silicone is preferable. This is because the curing reaction is easy, the degree of peelability is good when the adhesive resin layer is formed, and the heat resistance is also high.

The addition reaction type silicone resin composition 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 resin composition is accelerated by heat treatment. The main component in the addition reaction type silicone resin composition is preferably an organopolysiloxane having an alkenyl group (such as a vinyl group) bonded to a silicon atom (that is, an organoalkenylpolysiloxane, preferably a straight chain). An alkenyl group or the like serves as a crosslinking point. The crosslinking agent in the addition reaction type silicone resin composition is an organopolysiloxane having a hydrogen atom (hydrosilyl group) bonded to a silicon atom (that is, an organohydrogenpolysiloxane, preferably a straight chain). Is preferred, and a hydrosilyl group or the like serves as a crosslinking point.
The addition reaction type silicone resin composition is cured by an addition reaction between the crosslinking points of the main agent and the crosslinking agent. In addition, the molar ratio of the hydrogen atom bonded to the silicon atom of the organohydrogenpolysiloxane to the alkenyl group of the organoalkenylpolysiloxane is 0.5 to 2 in that the heat resistance derived from the crosslinked structure is more excellent. preferable.

  Moreover, the curable silicone resin composition used for forming a release layer such as a release paper has 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, since it does not contain a solvent that causes foaming during curing when forming the adhesive resin layer described later, that is, heat curing, ultraviolet curing, or electron beam curing, bubbles are unlikely to remain in the adhesive resin layer. It is.

  Moreover, as a curable silicone resin composition used for forming a release layer such as release paper, specifically, KNS-320A and KS-847 (both Shin-Etsu Silicone Co., Ltd.) are used as commercially available product names or model numbers. ), TPR6700 (made by Momentive Performance Materials Japan LLC), a combination of vinyl silicone “8500” (made by Arakawa Chemical Industries) and methylhydrogenpolysiloxane “12031” (made by Arakawa Chemical Industries), Combination of vinyl silicone “11364” (Arakawa Chemical Industries) and methyl hydrogen polysiloxane “12031” (Arakawa Chemical Industries), vinyl silicone “11365” (Arakawa Chemical Industries) and methyl hydrogen polysiloxane "12031" (Arakawa Chemical Industries) Combination and the like.

  KNS-320A, KS-847, and TPR6700 are addition reaction type curable silicone resin compositions containing a main agent and a crosslinking agent in advance.

(Process procedure)
The method in particular of apply | coating curable resin composition on the surface which shows the easy peelability of a peelable auxiliary substrate is not restrict | limited, A well-known method can be employ | adopted. 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 curable resin composition.

Although not coated amount particularly limited curable resin composition, from the viewpoint that a suitable thickness of the adhesive resin layer is obtained, is preferably from 1 to 100 g / m ^2, is 5 to 20 g / m ² It is more preferable.

  In addition, when the solvent is contained in the curable resin composition, you may volatilize a solvent by performing the heat processing to such an extent that a curable resin does not harden | cure as needed.

  The thickness of the uncured curable resin composition layer obtained by applying the curable resin composition onto the peelable auxiliary substrate is not particularly limited, so that an adhesive resin layer having a suitable thickness described later can be obtained. Adjust as appropriate.

  The outer dimension of the uncured curable resin composition layer to be formed is the same as or smaller than the outer dimension of the peelable auxiliary substrate.

[First laminating step]
In the first lamination step S106, a substrate having an outer dimension smaller than the outer dimension of the uncured curable resin composition layer is applied to the uncured curable resin obtained in the curable resin composition layer forming step S104. Laminating on an uncured curable resin composition layer so that a peripheral region that does not come into contact with the substrate remains in the resin composition layer to obtain a pre-cured laminate (laminate before being subjected to curing treatment) It is. In other words, the substrate is laminated on the uncured curable resin composition layer such that the uncured curable resin composition layer is exposed on the outer periphery of the substrate.
More specifically, as shown in FIG. 2 (C), the substrate 14 smaller than the outer dimensions of the uncured curable resin composition layer 12 is replaced with an uncured curable resin composition layer by this step S106. 12 is laminated on the uncured curable resin composition layer 12 so that a peripheral region 12a that does not come into contact with the substrate 14 is formed. 3A is a top view of the uncured laminate 16, and as shown in the figure, the peripheral region 12a of the uncured curable resin composition layer 12 is not in contact with the substrate 14. FIG. .

  Usually, on the exposed surface of the uncured curable resin composition layer 12, a convex portion is likely to be formed near the peripheral edge due to the influence of the coating method and the influence of the surface tension of the layer itself (see FIG. 3B). . When the substrate 14 is laminated, contact with such a convex portion may cause a gap 36 or the like between the substrate 14 and the uncured curable resin composition layer 12. As a result, the substrate 14 and the uncured layer are uncured. There may be a region where the curable resin composition layer 12 is not in contact. If there is such a region, the adhesion of the adhesive resin layer obtained in the curing step S108 to the substrate 14 may decrease. Moreover, the thickness nonuniformity of an adhesive resin layer may arise, and it may become a cause of surface unevenness | corrugation on the exposed surface of the adhesive resin layer of a board | substrate with an adhesive resin layer. Further, a foreign substance enters the gap 36 and becomes a contamination source that contaminates the electronic device member, which may cause a reduction in the yield of the electronic device.

Therefore, by using the substrate 14 having an outer dimension smaller than the outer dimension of the uncured curable resin composition layer 12, the substrate 14 is not cured with the uncured curable resin composition without being brought into contact with the convex portion. It can be in contact with layer 12. As a result, the occurrence of a region where the substrate 14 and the uncured curable resin composition layer 12 do not contact is further suppressed, the adhesion of the adhesive resin layer obtained in the curing step S108 to the substrate 14 is further improved, and the adhesion Occurrence of uneven thickness of the conductive resin layer is further suppressed.
Moreover, according to this method, the pre-curing laminate can be obtained without damaging the surface of the substrate on which the electronic device member is formed.
First, the board | substrate used at this process is explained in full detail, and the procedure of this process is explained in full detail after that.

(substrate)
The substrate is a plate-like substrate having a first main surface and a second main surface, an adhesive resin layer is fixed to the first main surface, and an electron is formed on the second main surface opposite to the adhesive resin layer side. A device member is provided.
The type of the substrate used is not particularly limited. For example, a resin substrate (in terms of heat resistance, a polyimide resin plate, a polyamide resin plate, a polyamideimide resin plate, a polyether ether ketone resin plate, a liquid crystal polyester resin plate, Polycarbonate resin plate, polyethersulfone resin plate, polyethylene naphthalate resin plate, polyarylate resin plate, fluorine-containing resin plate such as ethylene-tetrafluoroethylene copolymer, silicon-containing resin such as acrylic-silsesquioxane copolymer Plate, etc.), a resin plate containing inorganic fine particles such as silica, a glass cloth substrate impregnated with resin, a glass substrate, a metal substrate, and the like. Especially, it is preferable to use a glass substrate at the point which adhesiveness with an adhesive resin layer (especially adhesive resin layer containing silanol resin) is more excellent. Moreover, in order to ensure adhesiveness with the adhesive resin layer, primer treatment such as plasma treatment, ultraviolet treatment or silane coupling agent may be performed on the substrate surface alone or in combination.
Hereinafter, the aspect of a glass substrate is explained in full detail.

  The kind of glass substrate may be a common one, and examples thereof include glass substrates for display devices such as LCD and OLED. The glass substrate is excellent in chemical resistance and moisture permeability resistance and has a low thermal shrinkage rate. As an index of the heat shrinkage rate, a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.

  When the linear expansion coefficient of the glass substrate is large, the member forming step S114 is often accompanied by heat treatment, and various inconveniences are likely to occur. For example, when a TFT is formed on a glass substrate, if the glass substrate on which the TFT is formed is cooled under heating, the TFT may be displaced excessively due to thermal contraction of the glass substrate.

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

  The glass of the glass substrate is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide glass mainly containing 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, a glass suitable for the type of electronic device member and its manufacturing process is employed. 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 the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included). 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 from the viewpoint of reducing the thickness and / or weight of the glass substrate, it is usually preferably 0.8 mm or less, more preferably 0.3 mm or less, and further preferably It is 0.15 mm or less. If it exceeds 0.8 mm, the glass substrate cannot be made thinner and / or lighter. 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.

Note that the glass substrate may be composed of two or more layers. In this case, the material forming each layer may be the same material or different materials. In this case, “the thickness of the glass substrate” means the total thickness of all the layers.
Further, another substrate may be laminated on one surface of the glass substrate. For example, a resin substrate or the like may be laminated to reinforce the strength of the glass substrate.

(Process procedure)
The method in particular of laminating | stacking a board | substrate on an uncured curable resin composition layer is not restrict | limited, A well-known method is employable.
For example, the method of laminating | stacking a board | substrate on the surface of an uncured curable resin composition layer under a normal pressure environment is mentioned. If necessary, after the substrate is stacked on the surface of the uncured curable resin composition layer, the substrate may be pressure-bonded to the uncured curable resin composition layer using a roll or a press. It is preferable because air bubbles mixed between the uncured curable resin composition layer and the substrate layer 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 it suppresses mixing of bubbles and secures good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are not likely to cause a distortion defect of the substrate.

  When laminating the substrates, it is preferable that the surface of the substrate in contact with the uncured curable resin composition layer is sufficiently washed and laminated in an environment with a high degree of cleanliness. The higher the degree of cleanness, the better the flatness of the substrate.

  In addition, in order to further strengthen the adhesion between the substrate and the adhesive resin layer described later, a treatment for strengthening the adhesion such as plasma treatment or silane coupling agent treatment in advance on the contact surface of the substrate with the adhesive resin layer. You may give it.

  The layer of the peelable auxiliary substrate, the uncured curable resin layer, and the layer of the substrate are included in this order in the pre-cured laminate obtained by the above process.

  In this embodiment, the outer dimension of the uncured curable resin composition layer is larger than the outer dimension of the substrate, but the area A of the region of the uncured curable resin composition layer in contact with the substrate and the uncured curable property. The ratio (area A / total area B) to the total area B of the resin composition layer is preferably 0.98 or less, and more preferably 0.95 or less. If it is in the said range, the flatness of the board | substrate in the laminated body mentioned later becomes higher, and the productivity of an electronic device improves more. Although a minimum in particular is not restrict | limited, From points, such as productivity, it is preferable that it is 0.75 or more, and it is more preferable that it is 0.80 or more.

  Moreover, 10 mm or more is preferable and, as for the length from the outer periphery of a board | substrate to the outer periphery of an uncured curable resin composition layer, 15 mm or more is more preferable. If it is in the said range, generation | occurrence | production of the thickness nonuniformity of an adhesive resin layer will be suppressed more. The upper limit is not particularly limited, but is preferably 100 mm or less from the viewpoint of productivity.

[Curing process]
In the curing step S108, the pre-cured laminate obtained in the first lamination step S106 is cured to cure the uncured curable resin composition in the pre-cured laminate, and the adhesive resin layer. This is a step of obtaining a post-curing laminate (a laminate subjected to curing treatment) having More specifically, as shown in FIG. 2D, by performing the step S108, the uncured curable resin composition layer 12 is cured to obtain the adhesive resin layer 18, and the peelability is obtained. A post-curing laminate 20 having the auxiliary substrate 10 layer, the adhesive resin layer 18 and the substrate 14 layer in this order is obtained.
Below, the procedure of the process implemented at this process is explained in full detail, and the structure of the laminated body obtained after that is explained in full detail.

(Process procedure)
As the curing treatment performed in this step, an optimum method is appropriately selected depending on the type of the curable resin to be used, but usually a heat treatment or an exposure treatment is performed.

  When the curable resin contained in the curable resin composition is thermosetting, the layer can be cured by heat-treating the uncured curable resin composition layer. The optimum conditions for the heat treatment are appropriately selected according to the type of the thermosetting resin used. From the viewpoint of the curing speed of the curable resin and the heat resistance of the adhesive resin layer to be formed, 150 Heat treatment is preferably performed at ˜300 ° C. (preferably 180 to 250 ° C.) for 10 to 120 minutes (preferably 30 to 60 minutes).

  When the curable resin contained in the curable resin composition is a photocurable resin, the layer can be cured by performing an exposure treatment on the uncured curable resin composition layer. Although the kind of light irradiated in the case of an exposure process is suitably selected according to the kind of photocurable resin, an ultraviolet light, visible light, infrared light etc. are mentioned, for example. Moreover, the irradiation time in the case of an exposure process is 0.1 to 10 minutes (preferably 0.5 to 5 minutes) from points, such as the hardening rate of curable resin, and the light resistance of the adhesive resin layer formed. preferable.

(Adhesive resin layer)
Next, the adhesive resin layer in the laminate after curing will be described in detail.
The thickness of the adhesive resin layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 30 μm, and even more preferably 7 to 20 μm. This is because when the thickness of the adhesive resin layer is in such a range, the adhesive resin layer and the support plate described later are sufficiently adhered. In addition, even if bubbles or foreign matter may be present between the adhesive resin layer and the support plate, it is possible to suppress the occurrence of distortion defects of the substrate. On the other hand, if the thickness of the adhesive resin layer is too thick, it takes time and materials to form, and this is not economical.

The adhesive resin layer may be composed of two or more layers. In this case, “the thickness of the adhesive resin layer” means the total thickness of all the layers.
Moreover, when the adhesive resin layer is composed of two or more layers, the type of resin forming each layer may be different.

  The adhesive resin layer 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 can be easily peeled off from the support plate, and at the same time, the contact with the support plate is sufficient.

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

  Moreover, when the elasticity modulus of an adhesive resin layer is too high, it exists in the tendency for adhesiveness with a support plate to become low. On the other hand, if the elastic modulus of the adhesive resin layer is too low, the peelability from the support plate is lowered.

  The type of resin that forms the adhesive resin layer is not particularly limited, and varies depending on the type of resin contained in the curable resin composition described above. For example, acrylic resin, polyolefin resin, polyurethane resin, or silicone resin can be used. Among these, as described above, a silicone resin is preferable.

In addition, the adhesive resin layer may contain a non-curable organopolysiloxane as necessary, and the content thereof is specifically preferably 5% by mass or less (0 to 5% by mass), more Preferably 0.01-1 mass% is mentioned. When the non-curable organopolysiloxane is contained in the adhesive resin layer, peeling at the interface between the peelable auxiliary substrate and the adhesive resin layer in the first separation step S110 described later proceeds more efficiently.
The method for adding the non-curable organopolysiloxane to the adhesive resin layer is not particularly limited, and examples thereof include a method of adding the above-described curable resin composition.
Examples of the non-curable organopolysiloxane include silicone oils that do not contain Si—H bonds, specifically, polydimethylsiloxane-based or polymethylphenylsiloxane-based silicone oils.

(Laminated body after curing)
The post-curing laminate obtained by the curing step S108 includes a peelable auxiliary substrate layer, an adhesive resin layer, and a substrate layer in this order.
In the obtained laminated body after curing, the adhesive resin layer is fixed on the substrate and is in close contact with the peelable auxiliary substrate in a peelable manner. The adhesive resin layer prevents displacement of the substrate until an operation of separating the peelable auxiliary substrate and the substrate with the adhesive resin layer is performed in a first separation step S110 described later.
The surface in contact with the adhesive resin layer of the peelable auxiliary substrate is in close contact with the surface of the adhesive resin layer so as to be peelable. In the present invention, the easily peelable property of the peelable auxiliary substrate is called easy peelability.

In the present invention, the above-mentioned fixing and (separable) adhesion have a difference in peeling strength (that is, stress required for peeling), and fixing means that the peeling strength is larger than the adhesion. Specifically, the peel strength at the interface between the adhesive resin layer and the substrate layer in the laminate after curing is higher than the peel strength at the interface between the peelable auxiliary substrate layer and the adhesive resin layer.
Further, the peelable adhesion means that it can be peeled at the same time that it can be peeled without causing peeling of the fixed surface.
Specifically, in the laminated body after curing, when an operation of separating the substrate and the peelable auxiliary substrate is performed, it means that the peeled surface is peeled off and the fixed surface is not peeled off. Therefore, when the operation of separating the cured laminate into a substrate and a peelable auxiliary substrate is performed, the cured laminate is separated into two substrates, a substrate with an adhesive resin layer and a peelable auxiliary substrate.

  As described above, since the uncured curable resin composition is reactively cured while being in contact with the substrate surface, the formed adhesive resin layer strongly adheres to the substrate surface. On the other hand, the uncured curable resin composition is reactively cured in contact with the peelable auxiliary substrate. However, the formed adhesive resin layer is formed because of the easy peelability (non-adhesiveness) of the peelable auxiliary substrate surface. Adheres to the peelable auxiliary substrate with weak bonding force such as bonding force caused by van der Waals force between solid molecules.

[First separation step]
The first separation step S110 is obtained by separating the substrate with the adhesive resin layer having the substrate and the adhesive resin layer in contact with the surface of the substrate from the post-curing laminate obtained in the curing step S108. It is a process. That is, in this step, the peelable auxiliary substrate and the peripheral region of the adhesive resin layer that is not in contact with the substrate are removed from the cured laminate, and the adhesive resin layer that is in contact with the substrate and the surface of the substrate. A substrate with an adhesive resin layer is obtained.
More specifically, as shown in FIG. 2E, in step S110, the peelable auxiliary substrate from the post-cured laminate 20 with the interface between the peelable auxiliary substrate 10 and the adhesive resin layer 18 as a peeled surface. 10 and the peripheral region 18a of the adhesive resin layer 18 that does not contact the substrate are removed, and the substrate 22 with the adhesive resin layer having the adhesive resin layer 18 fixed on the substrate 14 is obtained.

By performing this process S110, the board | substrate with an adhesive resin layer laminated | stacked on a support plate by 2nd lamination process S112 mentioned later is obtained. The surface (exposed surface) of the adhesive resin layer of the obtained substrate with the adhesive resin layer is excellent in flatness. Therefore, in the second laminating step S112 described later, the adhesive resin layer in the substrate with the adhesive resin layer and the support plate can be laminated without a gap. As a result, the flatness of the substrate in the laminate is also excellent, which contributes to improving the productivity of electronic devices.
In addition, the perimeter of each outer periphery of the board | substrate in the board | substrate with an adhesive resin layer and an adhesive resin layer is equal. In other words, the substrate and the adhesive resin layer have the same outer dimensions.

The method for obtaining the substrate with the adhesive resin layer from the laminate after curing is not particularly limited.
For example, a sharp blade-like object is inserted into the interface between the peelable auxiliary substrate and the adhesive resin layer near the outer periphery of the substrate, and a fluid mixture of water and compressed air is sprayed after triggering the peeling. And can be peeled off. Preferably, the cured auxiliary substrate in the laminate after curing is placed on the surface plate so that the substrate is on the upper side and the substrate is on the lower side, and the substrate side is vacuum-adsorbed on the surface plate. A cutter is made to enter the interface between the peelable auxiliary substrate and the adhesive resin layer near the outer periphery. After that, the peelable auxiliary substrate side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. Then, an air layer is formed at the interface between the peelable auxiliary substrate and the adhesive resin layer, the air layer spreads over the entire interface, and the peelable auxiliary substrate can be easily peeled off. Moreover, if it is this method, a board | substrate with an adhesive resin layer can be obtained, without removing separately the peripheral area | region of the adhesive resin layer which is not in contact with the board | substrate on a peelable auxiliary substrate.

  The adhesive resin layer in the substrate with the adhesive resin layer obtained by the manufacturing method described above has an adhesive surface whose exposed surface can be attached to and detached from the object. This is because cohesive peeling of the adhesive resin layer is suppressed at the time of peeling from the peelable auxiliary substrate, and the peeled surface of the adhesive resin layer can maintain a state having sufficient adhesiveness.

If the peripheral region that does not come into contact with the substrate of the adhesive resin layer in the laminate after curing is removed, the fragments of the adhesive resin layer are electrostatically adsorbed to the substrate and the like, and a support plate and the like to be described later are laminated. In some cases, the piece may enter between the support plate and the adhesive resin layer.
Therefore, it is preferable to separate the substrate with an adhesive resin layer from the laminated body after curing without removing the peripheral region.

When the substrate with the adhesive resin layer is separated from the laminate after curing without removing the peripheral region, a burr-like resin is formed near the peripheral edge of the adhesive resin layer of the substrate with the adhesive resin layer. May be attached. In this case, it is preferable to remove the fragments within a range that does not damage the adhesive resin layer such as scratches. More specifically, the entire circumference of each outer peripheral edge of the substrate and the adhesive resin layer in the substrate with the adhesive resin layer between the first separation step S110 and the second lamination step S112 described later. It is preferable to provide a step of aligning the above.
The method of this step is not particularly limited, but for example, removal with high-pressure water having a charge eliminating effect is preferable, and water attached to the adhesive resin layer after removal is preferably removed by air blowing or the like.

  In addition, when removing the substrate with the adhesive resin layer from the laminate after curing, the fragments of the adhesive resin layer can be electrostatically adsorbed to the substrate with the adhesive resin layer by controlling the spraying and humidity with an ionizer. Can be further suppressed.

[Second laminating step]
In the second stacking step S112, the substrate with the adhesive resin layer is peeled off on the support plate so that the adhesive resin layer of the substrate with the adhesive resin layer obtained in the first separation step S110 is in contact with the support plate. This is a process of stacking possible. More specifically, as shown in FIG. 2 (F), a laminate 26 is obtained by laminating the support plate 24 on the surface of the adhesive resin layer 18 of the substrate 22 with the adhesive resin layer in this step S112. It is done. In addition, when peelable is applied external force to peel the support plate to the laminate with the electronic device member described later, without peeling at the interface between the substrate and the adhesive resin layer and inside the adhesive resin layer, It means the property of peeling at the interface between the support plate and the adhesive resin layer.

As shown in FIG. 2F, the laminate 26 is a laminate in which the layer of the substrate 14, the layer of the support plate 24, and the adhesive resin layer 18 exist between them. One surface of the adhesive resin layer 18 is fixed to the layer of the substrate 14, and the other surface is in contact with the support plate 24, and the interface between the support plate 24 and the adhesive resin layer 18 is peelably adhered. Has been. In other words, the peel strength at the interface between the adhesive resin layer 18 and the substrate 14 in the laminate 26 is higher than the peel strength at the interface between the support plate 24 layer and the adhesive resin layer 18.
The support plate 24 reinforces the substrate 22 with an adhesive resin layer in a member forming step S114 for manufacturing a member for an electronic device such as a liquid crystal panel.

  This laminated body 26 is used until a member forming step S114 described later. That is, the stacked body 26 is used until an electronic device member 28 such as a liquid crystal display device is formed on the surface of the second main surface 14b of the substrate 14 (see FIG. 2G). Thereafter, the layer of the support plate 24 is peeled off at the interface with the adhesive resin layer 18, and the layer of the support plate 24 does not become a part constituting the electronic device. The separated support plate 24 is laminated with a new substrate with an adhesive resin layer, and can be reused as a laminate.

  Below, the support plate used at this process is explained in full detail, and the procedure of this process S112 is explained in full detail after that.

(Support plate)
The support plate supports and reinforces the substrate with the adhesive resin layer, and when the electronic device member is manufactured in the member forming step S114 (step of manufacturing the electronic device member) described later, the substrate is deformed, scratched, It is a substrate that prevents damage and the like.
As the support plate, for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used. When the member forming step S114 involves heat treatment, the support plate is preferably formed of a material having a small difference in linear expansion coefficient from the substrate, more preferably formed of the same material as the substrate, and the substrate is a glass substrate. In this case, the support plate is preferably a glass plate. In particular, the support plate is preferably a glass plate made of the same glass material as the substrate.

  The thickness of the support plate may be thicker or thinner than the substrate. Preferably, the thickness of the support plate is selected based on the thickness of the substrate, the thickness of the adhesive resin layer, and the thickness of the laminate described later. For example, the current member formation process is designed to perform a process (eg, heating, cleaning, film formation, exposure, development, inspection, etc.) for forming a member on a 0.5 mm thick substrate. When the sum of the thickness of the substrate and the thickness of the adhesive resin layer is 0.1 mm, the thickness of the support plate is set to 0.4 mm. In general, the thickness of the support plate is preferably 0.2 to 5.0 mm.

  When the support plate 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 off after forming the electronic device member.

The difference in average linear expansion coefficient between the substrate and the support plate 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 may warp severely during heating and cooling in the member forming step S114. When the material of the substrate and the material of the support plate are the same, occurrence of such a problem can be suppressed.

(Process procedure)
In this step S112, the above-mentioned substrate with an adhesive resin layer and a support plate are prepared, and both are adhered and laminated using the adhesive resin layer surface and the support plate surface of the substrate with an adhesive resin layer as a laminate surface. The laminated surface of the adhesive resin layer has easy releasability, and can be easily and removably adhered by normal superposition and pressurization.
Specifically, for example, there is a method in which the adhesive resin layer and the support plate are pressure-bonded using a roll or a press after the easily peelable surface of the adhesive resin layer and the support plate are stacked under an atmospheric pressure environment. Can be mentioned. It is preferable that the adhesive resin layer and the support plate are more closely adhered by pressure bonding with a roll or a press. Further, it is preferable because air bubbles mixed between the adhesive resin layer and the support plate 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 it suppresses mixing of bubbles and secures good adhesion. By press-bonding under vacuum, even if minute bubbles remain, there is an advantage that the bubbles do not grow by heating and are not likely to cause a distortion defect of the substrate.

  When the adhesive resin layer is detachably adhered to the support plate, it is preferable that the adhesive resin layer and the surface of the support plate on the side in contact with each other are sufficiently washed and laminated in an environment with a high degree of cleanliness.

[Member forming process]
Member formation process S114 is a process of forming the member for electronic devices on the surface of the board | substrate in the laminated body obtained in said 2nd lamination | stacking process S112.
More specifically, as shown in FIG. 2G, in this step S114, the electronic device member 28 is formed on the second main surface 14b of the substrate 14 to obtain the laminated body 30 with the electronic device member. .

  First, the electronic device member used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

(Electronic device components (functional elements))
The electronic device member is a member that is formed on the substrate in the laminate and constitutes at least a part of the electronic device. More specifically, examples of the member for an electronic device include a member used for a display panel, a solar cell, a thin film secondary battery, a sensor, or an electronic component such as a semiconductor wafer having a circuit formed on the surface. It is done. Examples of the display device panel include an organic EL panel, electronic paper, a plasma display panel, a field emission panel, and the like.

For example, as a member for a solar cell, a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
Further, as a member for a thin film secondary battery, in the lithium ion type, a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
Examples of the sensor member include various members used in various sensors such as a biosensor formed with a circuit using an OLED or an inorganic LED as a light emitting element and a photodiode as a light receiving element.
In addition, as a member for electronic components, in CCD and CMOS, metal of conductive part, silicon oxide and silicon nitride of insulating part, etc., other various sensors such as pressure sensor and acceleration sensor, rigid printed board, flexible printed board And various members corresponding to a rigid flexible printed circuit board.

(Process procedure)
The manufacturing method of the laminated body with the member for electronic devices mentioned above is not specifically limited, According to the kind of structural member of the member for electronic devices, it is a member for electronic devices on the surface of the board | substrate of a laminated body by a conventionally well-known method. Form.
The electronic device member is not all of the members finally formed on the surface of the substrate (hereinafter referred to as “all members”), but a part of all the members (hereinafter referred to as “partial members”). May be. In the subsequent steps, a substrate with all members (corresponding to an electronic device described later) can be used.

For example, taking the case of manufacturing an OLED as an example, in order to form an organic EL structure on the surface of the laminate opposite to the adhesive resin layer side of the substrate (corresponding to the second main surface of the substrate) Forming a transparent electrode, depositing a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. on the surface on which the transparent electrode is formed, forming a back electrode, and sealing with a sealing plate Various layer formation and processing such as. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.
In the case of manufacturing an LCD, for example, a TFT device is formed on the surface opposite to the adhesive resin layer side of the laminate substrate (corresponding to the second main surface of the substrate), and the color filter The formed substrate can be bonded through a seal so that the TFT device and the color filter face each other. Furthermore, a TFT device is formed on the surface opposite to the adhesive resin layer side of the substrate of the laminate (corresponding to the second main surface of the substrate), and the adhesive resin layer side of the substrate of the other laminate is Can form a color filter on the opposite surface (corresponding to the second main surface of the substrate), and both laminates can be bonded together via a seal so that the TFT device and the color filter face each other (obtained). The laminated body thus obtained is called a laminated body X).
Taking the case of manufacturing electronic paper as an example, a TFT device is formed on the surface opposite to the adhesive resin layer side of the substrate of the laminate (corresponding to the second main surface of the substrate). The substrate on which the element is formed can be attached through a seal.
In the case of manufacturing a biosensor, for example, a light emitting element such as an OLED and light on the surface opposite to the adhesive resin layer side of the substrate of the laminate (corresponding to the second main surface of the substrate). A circuit including a light receiving element such as a diode can be formed, and a cover glass can be attached.

[Second separation step]
In the second separation step S116, an adhesive resin layer having an adhesive resin layer, a substrate, and an electronic device member is removed from the laminate with the electronic device member obtained in the member forming step S114. This is a step of obtaining an attached electronic device. More specifically, as shown in FIG. 2 (H), in step S116, the support plate 24 is separated and removed from the laminate 30 with the electronic device member, and the substrate 14, the electronic device member 28, The electronic device 32 with an adhesive resin layer including the electronic device 32 including the adhesive resin layer 18 is obtained.

When the electronic device member on the substrate at the time of peeling is a part of the formation of all necessary constituent members, the remaining constituent members can be formed on the substrate after separation.
Hereinafter, the procedure of this process S116 is explained in full detail.

A method for peeling the support plate and the peelable surface of the adhesive resin layer is not particularly limited. For example, the procedure described in the first separation step described above can be performed.
Specifically, for example, a sharp blade-like object is inserted into the interface between the support plate and the adhesive resin layer, giving a trigger for peeling, and then peeling off by spraying a mixed fluid of water and compressed air. can do.

  Moreover, when removing a support plate from the laminated body with a member for electronic devices, the static electricity which may affect an electronic device can be suppressed by controlling spraying and humidity with an ionizer. Alternatively, a circuit that consumes static electricity may be incorporated into the electronic device, or a sacrificial circuit may be incorporated to establish conduction from the terminal portion to the outside of the stacked body.

The adhesive resin layer in the electronic device with an adhesive resin layer obtained by the above-described manufacturing method has an adhesive surface whose exposed surface is detachable from an object. This is because cohesive peeling of the adhesive resin layer is suppressed at the time of peeling from the peelable auxiliary substrate, and the peeled surface of the adhesive resin layer can maintain a state having sufficient adhesiveness.
Moreover, the electronic device with an adhesive resin layer can be used for various applications, and examples thereof include a biosensor and a wall-mounted display device (wall-mounted display). In addition, use of optical film such as polarizing plate, microlens array, active shutter panel, touch panel and other devices (second device) bonded to electronic devices with adhesive resin layer and removability The second device can be replaced and the device can be reused. For example, in an electronic device having a color filter and a TFT device in which adhesive resin layers are arranged on both sides, obtained by removing the support plate from the laminate X described above, the adhesive resin layer on the color filter side is described above. The second device thus bonded can be bonded, and the adhesive resin layer on the TFT substrate side can be bonded to the wall surface. Furthermore, in a see-through double-sided display using a transparent oxide TFT substrate, both the TFT substrate and the color filter substrate can be attached to the wall surface.
The display device is mainly an LCD, an OLED, or an electronic paper. Examples of the LCD include a TN type, an STN type, an FE type, a TFT type, an MIM type, an IPS type, and a VA type. Basically, the present invention can be applied to both passive drive type and active drive type display devices. As the electronic paper, any of a microcapsule electrophoresis type, a cholesteric liquid crystal type, a polymer network liquid crystal type, an electronic powder flow type, an electrowetting type, and the like can be applied.

[Second Embodiment]
FIG. 4 is a flowchart showing manufacturing steps in another embodiment of the method for manufacturing an electronic device with an adhesive resin layer of the present invention. As shown in FIG. 4, the manufacturing method of the electronic device with an adhesive resin layer includes an auxiliary substrate preparation step S102, a curable resin composition layer formation step S104, a first lamination step S106, a defoaming step S118, and a curing step S108. The first separation step S110, the second lamination step S112, the member formation step S114, and the second separation step S116.
Each step shown in FIG. 4 is the same procedure as the step shown in FIG. 1 except that it includes a defoaming step S118. The same steps are denoted by the same reference numerals, and the description thereof is omitted. The defoaming step S118 will be mainly described.

[Defoaming process]
The defoaming step S118 is a step of defoaming the uncured curable resin composition layer after the laminating step S106 and before the curing step S108. By providing this step S118, bubbles and easily volatile components are removed from the uncured curable resin composition layer, and the adhesion between the resulting adhesive resin layer and the substrate is further enhanced.

  As the processing method of the defoaming step, an optimum method is appropriately selected depending on the material of the uncured curable resin composition layer to be used. For example, vacuum defoaming using a vacuum pump or centrifugation using centrifugal force is performed. Examples thereof include separation defoaming and ultrasonic defoaming using an ultrasonic defoaming apparatus. From the viewpoint of productivity and the like, vacuum defoaming in which defoaming treatment is performed under reduced pressure is preferable, and as the condition, defoaming treatment is preferably performed at 1000 Pa or less (preferably 100 Pa or less) for about 1 to 30 minutes.

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

In the following Examples 1 and 5 to 9 and Comparative Examples 1 and 2, a glass plate made of non-alkali borosilicate glass (vertical 720 mm, horizontal 600 mm, plate thickness 0.3 mm, linear expansion coefficient 38 × 10 ⁻⁷⁾ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.). Further, as an auxiliary substrate, a glass plate made of alkali-free borosilicate glass (length 760 mm, width 640 mm, plate thickness 0.7 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) As a support plate, a glass plate (also made of alkali-free borosilicate glass (length 720 mm, width 600 mm, thickness 0.4 mm, linear expansion coefficient 38 × 10 ⁻⁷ / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) ")It was used.

(Example 1)
The auxiliary substrate was cleaned with pure water and UV to clean the surface. Thereafter, a mask was applied to the second main surface, which is one side of the auxiliary substrate, and a heptane solution having a silicone oil content of 1 mass% was spray-coated on the first main surface on the opposite side and dried. Dimethylpolysiloxane (manufactured by Dow Corning Toray, SH200, kinematic viscosity 190-210 mm ² / s) was used as the silicone oil. Subsequently, in order to reduce the molecular weight of the silicone oil, a heat treatment at 350 ° C. was performed for 5 minutes to obtain a peelable auxiliary substrate.

Thereafter, the water contact angle of the first main surface of the peelable auxiliary substrate was measured using a contact angle meter (manufactured by Cruz, DROP SHAPE ANALYSIS SYSTEM DSA 10Mk2), and found to be 100 °.
In addition, using an atomic force microscope (Pacific Nanotechnology, Nano Scope IIIa; Scan Rate 1.0 Hz, Sample Lines 256, Off-line Modify Flatten order-2, Planfit order-2), the first auxiliary substrate is used. The surface roughness Ra of the main surface was measured and found to be 0.5 nm. The surface roughness Ra was calculated from measured values in a measuring range of 10 μm square.

Next, on the first main surface of the peelable auxiliary substrate, linear organoalkenylpolysiloxane having vinyl groups at both ends (vinyl silicone, manufactured by Arakawa Chemical Industries, Ltd., 8500), and hydrosilyl group in the molecule A liquid mixture of methylhydrogenpolysiloxane (Arakawa Chemical Industries, Ltd., 12031) and a platinum-based catalyst (Arakawa Chemical Industries, Ltd., CAT12070) is 750 mm in length and 630 mm in width into a rectangular screen printer. Then, a layer containing uncured curable silicone was provided on the peelable auxiliary substrate (coating amount 35 g / m ² ). 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.

Next, the surface (first main surface) of the substrate having a thickness of 0.3 mm that was brought into contact with the silicone resin was cleaned with pure water and then cleaned by UV cleaning. Thereafter, the first main surface of the substrate and the layer containing uncured curable silicone are bonded together by a vacuum press at room temperature, and allowed to stand at 30 Pa for 5 minutes. A defoaming treatment was performed to obtain a laminate A0 before curing. The length from the outer peripheral edge of the substrate to the outer peripheral edge of the uncured curable resin composition layer was about 15 mm. The ratio (area A / total area B) of the area A of the region in contact with the substrate of the uncured curable resin composition layer to the total area B of the uncured curable resin composition layer is 0.91. Met.
Next, the pre-cured laminate A0 was heat-cured in the air at 250 ° C. for 30 minutes to obtain a post-cured laminate A1 including a cured silicone resin layer having a thickness of 10 μm.

Subsequently, after the surface (second main surface) opposite to the contact surface with the silicone resin of the substrate in the laminated body A1 after curing is vacuum-adsorbed to the surface plate, one of the four corner portions of the substrate is A stainless steel knife having a thickness of 0.1 mm was inserted into the interface between the peelable auxiliary substrate and the silicone resin layer in the corner portion, and a trigger for peeling was given to the interface between the peelable auxiliary substrate and the silicone resin layer. Then, after the surface of the peelable auxiliary substrate was sucked by 24 vacuum suction pads, it was raised in order from the suction pad near the corner portion into which the blade was inserted. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad was pulled up while spraying a static eliminating fluid continuously from the ionizer toward the formed gap. As a result, only the glass substrate A3 (substrate with an adhesive resin layer) having a silicone resin layer formed on the first main surface was left on the surface plate, and the peelable auxiliary substrate could be peeled off. At this time, the adhesion of the silicone resin was not visually observed on the surface (first main surface) that was in close contact with the silicone resin layer of the peelable auxiliary substrate. From the results, it was confirmed that the peel strength at the interface between the silicone resin layer and the substrate layer was larger than the peel strength at the interface between the peelable auxiliary substrate layer and the adhesive resin layer.
Next, the burr-like silicone resin adhering to the periphery of the glass substrate A3 was removed with high-pressure water, and water was removed by air blowing. Next, on the silicone resin layer of the glass substrate A3, the surface to be brought into contact with the silicone resin (first main surface) is cleaned with pure water, and then the support plate cleaned by UV cleaning is vacuum-pressed at room temperature. Bonding was performed to obtain a glass laminate A2. Next, the support plate was peeled off from the glass laminate A2 in the same manner as the above-mentioned cured laminate A1. At this time, adhesion of the silicone resin was not visually observed on the surface (first main surface) that was in close contact with the silicone resin layer of the support plate.
Next, after the silicone resin layer formed on the first main surface of the glass substrate A3 is adsorbed onto a glass plate having a thickness of 2 mm, one corner portion of the four corner portions is peeled off as a trigger. I was able to. At this time, no silicone resin was visually observed on the surface of the glass plate having a thickness of 2 mm. Furthermore, when adsorbed and peeled once again, no silicone resin was visually observed on the surface of a 2 mm thick glass plate.
From the results, it was confirmed that the adhesive resin layer exhibits removable adhesiveness without causing destruction of the layer at the time of peeling from the object.

(Example 2)
A glass laminate B2 was obtained in the same manner as in Example 1 except that a glass plate made of soda lime glass was used as the auxiliary substrate, the support plate, and the substrate. The sizes of the auxiliary substrate, the support plate, and the substrate used were the same as those of the auxiliary substrate, the support plate, and the substrate used in Example 1.
Next, the support plate was peeled from the glass laminate B2 by the same method as in Example 1 to obtain a soda lime glass substrate B3 having a silicone resin layer formed on the first main surface. At this time, adhesion of the silicone resin was not visually observed on the surface (first main surface) that was in close contact with the silicone resin layer of the support plate.
Next, by the same method as in Example 1, the soda lime glass substrate B3 could be adsorbed onto a 2 mm thick glass plate and peeled off. At this time, no silicone resin was visually observed on the surface of the glass plate having a thickness of 2 mm.
From the results, it was confirmed that the adhesive resin layer exhibits removable adhesiveness without causing destruction of the layer at the time of peeling from the object.

(Example 3)
A glass laminate C2 was obtained in the same manner as in Example 1 except that a chemically strengthened glass plate was used as the auxiliary substrate, the support plate, and the substrate. The sizes of the auxiliary substrate, the support plate, and the substrate used were the same as those of the auxiliary substrate, the support plate, and the substrate used in Example 1.
Next, by the same method as in Example 1, the support plate was peeled from the glass laminate C2, and a chemically strengthened glass substrate C3 having a silicone resin layer formed on the first main surface was obtained. At this time, adhesion of the silicone resin was not visually observed on the surface (first main surface) that was in close contact with the silicone resin layer of the support plate.
Next, the glass substrate C3 was adsorbed onto a glass plate having a thickness of 2 mm and peeled by the same method as in Example 1. At this time, no silicone resin was visually observed on the surface of the glass plate having a thickness of 2 mm.

Example 4
A laminate D2 having a support plate layer, an adhesive resin layer and a polyimide resin plate tank in the same manner as in Example 1 except that a polyimide resin plate (manufactured by Toray DuPont, Kapton 200HV) is used as the substrate. Got. In addition, the thickness of the substrate was 0.05 mm, and the thickness of the support plate was 0.7 mm.
Next, by the same method as in Example 1, the support plate was peeled from the laminate D2, and a polyimide resin substrate D3 having a silicone resin layer formed on the first main surface was obtained. At this time, adhesion of the silicone resin was not visually observed on the surface (first main surface) that was in close contact with the silicone resin layer of the support plate.
Next, by the same method as in Example 1, the polyimide resin substrate D3 could be adsorbed onto a 2 mm thick glass plate and peeled off. At this time, no silicone resin was visually observed on the surface of the glass plate having a thickness of 2 mm.

(Example 5)
In this example, an OLED was produced using the glass laminate A2 obtained in Example 1.
More specifically, a molybdenum film was formed by sputtering on the second main surface of the substrate in the glass laminate A2, and a gate electrode was formed by etching using photolithography. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, the gate insulating film, the semiconductor element portion, and the source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the substrate by plasma CVD, indium tin oxide is formed by sputtering, and etching using a photolithography method is performed. Thus, a pixel electrode was formed.
Subsequently, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer were formed in this order, and then aluminum was formed on the second main surface side of the substrate by sputtering. A counter electrode was formed by etching using a photolithography method, and then an ultraviolet curable adhesive layer was formed on the second main surface of the substrate on which the counter electrode was formed. Then, another separately prepared glass plate was bonded and sealed, and the laminate A2 having the organic EL structure on the substrate obtained by the above procedure was used as a display device panel with a support plate (panel It corresponds to A2) (laminated body with electronic device member).
Subsequently, after the panel A2 sealing body side is vacuum-adsorbed to the surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the support plate at the corner portion of the panel A2 and the silicone resin layer. The plate was separated to obtain an OLED panel (corresponding to an electronic device with an adhesive resin layer; hereinafter referred to as panel A) having a silicone resin layer formed on the first main surface. When an IC driver was connected to the manufactured panel A and driven, no display unevenness was observed in the driving region.
Next, after adsorbing the silicone resin layer on the first main surface of the panel A onto a glass plate having a thickness of 2 mm, the panel A is peeled off without being damaged by using one of the four corners as a trigger. I was able to. Furthermore, another adsorption and peeling could be performed without damaging the panel.
From the results, it was confirmed that the adhesive resin layer exhibits removable adhesiveness without causing destruction of the layer at the time of peeling from the object.

(Example 6)
In this example, electronic paper was produced using the glass laminate A2 obtained in Example 1.
On the second main surface of the substrate in the glass laminate A2, molybdenum was deposited by a sputtering method, and a gate electrode was formed by etching using a photolithography method. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, the gate insulating film, the semiconductor element portion, and the source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the substrate by plasma CVD, indium tin oxide is formed by sputtering, and etching using a photolithography method is performed. Thus, a pixel electrode was formed.
Next, indium tin oxide was formed by sputtering on the surface (first main surface) of a separately prepared glass plate, and a counter electrode was formed by etching using photolithography. Next, an adhesive resin liquid in which microcapsules were further dispersed was applied on the first main surface of the glass plate by printing. In the microcapsules, white particles made of titanium oxide and black particles made of carbon black were dispersed in silicone oil in a wall film made of a composite film of gum arabic and gelatin having an average diameter of 50 micrometers. What was enclosed in the state was used. The white particles of titanium oxide were positively charged, while the black particles of carbon black were negatively charged.
Next, the surface on the second main surface side of the glass laminate A2 provided with the pixel electrodes by the above procedure and the surface on the first main surface side of the glass plate coated with the adhesive resin liquid were bonded together. By the above procedure, an electronic paper panel with a support plate (a laminate with electronic device members) was obtained.
Subsequently, the support plate was peeled off by the same method as in Example 5 to obtain an electronic paper panel (corresponding to an electronic device with an adhesive resin layer, hereinafter referred to as panel B) having a silicone resin layer formed on the first main surface. It was.
When an IC driver was connected to the manufactured panel B and driven, display unevenness was not observed in the driving region.
Next, after the silicone resin layer on the first main surface of panel B was adsorbed onto a glass plate having a thickness of 2 mm by the same method as in Example 5, it was possible to peel the panel without damaging the panel.

(Example 7)
In this example, a blood flow sensor was produced using the glass laminate A2 obtained in Example 1.
First, indium tin oxide was formed by sputtering on the second main surface of the substrate in the glass laminate A2, and a transparent electrode was formed by etching using a photolithography method. Next, a p-type amorphous silicon layer, an i-type amorphous silicon layer, and an n-type amorphous silicon layer are formed in this order on the second main surface side of the substrate provided with the gate electrode by plasma CVD, and molybdenum is formed by sputtering. After the film was formed, etching using a photolithography method was performed to form an upper electrode from the photoelectric conversion layer. Next, a silicon nitride film was further formed on the second main surface side of the substrate by plasma CVD, an insulating layer was formed by etching using photolithography, and a photodiode array as a light receiving element was formed.
Subsequently, by vapor deposition, on the second main surface side of the substrate, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine as a hole injection layer and bis [ (N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] A mixture of 40% by volume of naphthalene-1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer were formed in this order, and then aluminum was formed by a sputtering method. A counter electrode was formed by etching using an organic EL array as a light emitting element, and prepared separately through an ultraviolet curable adhesive layer. Another laminate obtained by the above procedure was laminated with a blood flow sensor element on the substrate, the blood flow sensor element with a support plate (laminate with electronic device member). )
Subsequently, the support plate was peeled off in the same manner as in Example 5 to obtain a plurality of blood flow sensor element assemblies in which a silicone resin layer was formed on the first main surface. Each blood flow sensor element was divided from the integrated body, and a support band was attached to obtain a blood flow sensor.
When an IC driver was connected to the manufactured blood flow sensor and driven, no drive unevenness was observed in the drive region.
Next, the blood flow sensor was attached so that the silicone resin layer of the first main surface of the blood flow sensor element was in close contact with the back of the human hand, and the sensor could be detached without damaging the sensor.

(Example 8)
In this example, an LCD with a touch panel was produced using the glass laminate A2 obtained in Example 1.
Two glass laminates A2 were prepared. First, a molybdenum film was formed by sputtering on the second main surface of the substrate in one glass laminate A2, and a gate electrode was formed by etching using photolithography. . Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering. Then, the gate insulating film, the semiconductor element portion, and the source / drain electrodes were formed by etching using a photolithography method. Next, after forming a passivation layer by further forming silicon nitride on the second main surface side of the substrate by plasma CVD, indium tin oxide is formed by sputtering, and etching using a photolithography method is performed. Thus, a pixel electrode was formed. Next, a polyimide resin liquid was applied on the second main surface of the substrate on which the pixel electrode was formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed. The obtained glass laminate A2 is referred to as a glass laminate A2-1.
Next, a chromium film was formed by sputtering on the second main surface of the substrate in the other glass laminate A2, and a light-shielding layer was formed by etching using photolithography. Next, a color resist was further applied by a die coating method to the second main surface side of the substrate provided with the light shielding layer, and a color filter layer was formed by a photolithography method and thermal curing. Next, an indium tin oxide film was further formed on the second main surface side of the substrate by sputtering to form a counter electrode. Next, an ultraviolet curable resin liquid was applied by die coating on the second main surface of the substrate provided with the counter electrode, and columnar spacers were formed by photolithography and thermal curing. Next, a polyimide resin solution was applied by roll coating on the second main surface of the substrate on which the columnar spacers were formed, an alignment layer was formed by thermosetting, and rubbing was performed. Next, on the second main surface side of the substrate, the sealing resin liquid is drawn in a frame shape by the dispenser method, and after the liquid crystal is dropped in the frame by the dispenser method, using the above-described glass laminate A2-1, The 2nd main surface side of the board | substrate of two glass laminated bodies A2 was bonded together, and the laminated body which has an LCD panel by ultraviolet curing and thermosetting was obtained. Hereinafter, the laminate having the LCD panel is referred to as a laminate C2 with a panel.
Next, in the same manner as in Example 1, the support plates on both sides were peeled from the paneled laminate C2, and an LCD panel C (hereinafter referred to as panel C) in which a silicone resin layer was formed on the first main surface of each of the TFT array substrate and the color filter substrate. )
When an IC driver was connected to the manufactured panel C and driven, no display unevenness was observed in the driving region.
Next, a touch panel was attached to the silicone resin layer on the first main surface of the color filter substrate of panel C. Further, after the silicone resin layer on the first main surface of the TFT array substrate of panel C was adsorbed on a glass plate having a thickness of 2 mm by the same method as in Example 1, it could be peeled off without damaging the panel. Furthermore, the touch panel affixed to the silicone resin layer on the first main surface of the color filter substrate of panel C could be peeled off without any damage.

Example 9
In this example, a see-through OLED was produced using the glass laminate A2 obtained in Example 1.
First, a film of molybdenum was formed by sputtering on the second main surface of the substrate in the glass laminate A2, and a gate electrode was formed by etching using a photolithography method. Next, a gate insulating film was formed by further forming aluminum oxide on the second main surface side of the substrate by sputtering, and then indium gallium zinc oxide was formed by sputtering and photolithography was used. An oxide semiconductor layer was formed by etching. Next, an aluminum oxide film is further formed on the second main surface side of the substrate by a sputtering method to form a channel protective layer. Subsequently, molybdenum is formed by a sputtering method, and etching is performed using a photolithography method to form a source. An electrode and a drain electrode were formed. Next, an aluminum oxide film is further formed on the second main surface side of the substrate by a sputtering method to form a passivation layer, and then indium tin oxide is formed by a sputtering method and etched by photolithography. A pixel electrode was formed.
Subsequently, by vapor deposition, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine is further formed on the second main surface side of the substrate as a hole injection layer, and bis [(( N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq ₃ ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene A mixture of 40% by volume of 1,5-dicarbonitrile (BSN-BCN) and Alq ₃ as an electron transport layer were formed in this order, and then aluminum was formed by a sputtering method. A counter electrode was formed by the etching used.
Next, another laminate A2 in which a sealing layer is formed on the second main surface of the substrate to be a sealing body is prepared, and bonded to the surface on which the above-described see-through organic EL structure is formed, and sealed. A laminated body D2 was obtained.
Next, in the same manner as in Example 1, the support plates on both sides were peeled from the paneled laminate D2 to obtain a see-through OLED panel (hereinafter referred to as panel D).
When an IC driver was connected to the manufactured panel D and driven, no display unevenness was observed in the driving region.
Next, the silicone resin layer formed on the first main surface of the TFT array substrate of panel D is adsorbed on a glass plate having a thickness of 2 mm in the same manner as in Example 1, and then peeled off without damaging the panel. I was able to. Further, after the silicone resin layer formed on the first main surface of the sealing substrate of panel D is adsorbed on a glass plate having a thickness of 2 mm in the same manner as in Example 1, it can be peeled off without damaging the panel. did it.

(Comparative Example 1)
In the same manner as in Example 1, the first main surface of the substrate was cleaned by pure water cleaning and UV cleaning.
Next, 99.5 parts by mass of a mixed solution of a linear organoalkenylpolysiloxane having a vinyl group at the terminal, a methylhydrogenpolysiloxane having a hydrosilyl group in the molecule, and a platinum catalyst in Example 1. And 0.5 parts by mass of silicone oil (manufactured by Toray Dow Corning, SH200) were applied onto the first main surface of the substrate by screen printing. Next, this was heat-cured at 250 ° C. for 30 minutes in the air to form a cured silicone resin layer having a thickness of 10 μm.
Subsequently, after cleaning the first main surface of the support plate with pure water, UV cleaning and cleaning, the first main surface of the support plate is brought into close contact with the silicone resin layer formed on the first main surface of the substrate by a vacuum press at room temperature, and the laminate P1 Got.
Then, an OLED was produced on the substrate of the laminate P1 by the same procedure as in Example 5, and then the support plate was peeled off, and an organic EL panel in which a silicone resin layer was formed on the first main surface of the substrate (hereinafter referred to as panel P). I got).
When an IC driver was connected to the manufactured panel P and driven, display unevenness was observed in the driving region, and the defective portion was present in a portion corresponding to the vicinity of the end of the multilayer body P1.

(Comparative Example 2)
A laminate P1 was obtained in the same manner as in Comparative Example 1.
And after producing an electronic paper panel on the board | substrate of the laminated body P1 by the procedure similar to Example 6, the support plate was peeled and the electronic paper panel (henceforth the silicon resin layer was formed in the 1st main surface of a board | substrate) Panel Q).
When an IC driver was connected to the manufactured panel Q and driven, display unevenness was observed in the drive region, and the defective portion was present in a portion corresponding to the vicinity of the end portion of the multilayer body P1.

(Comparative Example 3)
Except for changing to a glass substrate having a length of 760 mm, a width of 640 mm, and a plate thickness of 0.3 mm, the glass substrate and the resin layer surface of the support plate were vacuum-pressed at room temperature in the same manner as in Example 1. The gap between the end portion (peripheral portion) and the central portion of the resin layer surface of the support plate was not eliminated, and further, when a heat treatment was performed at 350 ° C. for 10 minutes in an environment of pressure 10 Pa, the glass substrate was damaged.

As shown in Examples 5 to 9, according to the electronic device manufacturing method of the present invention, it is possible to manufacture an electronic device excellent in performance with a high yield.
On the other hand, in the conventional method described in Patent Document 1 in which there is no auxiliary substrate preparation step, as shown in Comparative Examples 1 and 2, the performance of the obtained electronic device may be degraded. In Comparative Examples 1 and 2, display unevenness was observed near the end (periphery) of the electronic device. This is because, as described above, a gap is generated between the support plate and the adhesive resin layer due to thickness unevenness in the adhesive resin layer (particularly in the vicinity of the outer peripheral edge of the adhesive resin layer) obtained by the curing treatment, It is thought that foreign matter entered the voids and caused the performance degradation of the electronic device.
Moreover, in Comparative Example 3 using a substrate having the same outer dimensions as the uncured curable resin composition layer, voids were generated at the end (periphery) and the center.

  This application is based on Japanese Patent Application No. 2011-225255 filed on Oct. 12, 2011, the contents of which are incorporated herein by reference.

DESCRIPTION OF SYMBOLS 10 Peelable auxiliary substrate 12 Uncured curable resin composition layer 12a Peripheral region of uncured curable resin composition layer 14 Substrate 16 Pre-cured laminate 18 Adhesive resin layer 18a Peripheral region of adhesive resin layer 20 Cured Rear laminated body 22 Substrate with adhesive resin layer 24 Support plate 26 Laminated body 28 Electronic device member 30 Laminated body with electronic device member 32 Electronic device 34 Electronic device with adhesive resin layer 36, 118 Void 100 Glass substrate 102 Silicone resin layer 104 Substrate with resin layer 106 Support plate 108 Laminate 110 Electronic device member 112 Electronic device 114 Electronic device with resin layer 116 Convex part

Claims (10)

A method for producing an electronic device with an adhesive resin layer having an adhesive resin layer, a substrate and an electronic device member in this order,
An auxiliary substrate preparation step of preparing a peelable auxiliary substrate having a surface exhibiting easy peelability;
A curable resin composition layer forming step of forming an uncured curable resin composition layer by applying a curable resin composition on the surface showing the easy releasability of the peelable auxiliary substrate;
A substrate having an outer dimension smaller than the outer dimension of the uncured curable resin composition layer is left in the uncured curable resin composition layer so that a peripheral region that does not contact the substrate remains in the uncured curable resin composition layer. Laminating on the curable resin composition layer to obtain a laminate before curing,
A curing step of curing the uncured curable resin composition in the pre-cured laminate and obtaining a post-cured laminate having an adhesive resin layer;
A first separation step obtained by separating a substrate with an adhesive resin layer having the substrate and an adhesive resin layer in contact with the surface of the substrate from the post-curing laminate;
Second laminate for obtaining a laminate by laminating the substrate with an adhesive resin layer on the support plate so that the adhesive resin layer in the substrate with the adhesive resin layer comes into contact with the support plate. Process,
Forming a member for an electronic device on the surface of the substrate in the laminate and obtaining a laminate with the member for an electronic device; and
Second separation to obtain the electronic device with an adhesive resin layer having the adhesive resin layer, the substrate, and the electronic device member in this order by removing the support plate from the laminate with the electronic device member A process for producing an electronic device with an adhesive resin layer.   The method for manufacturing an electronic device with an adhesive resin layer according to claim 1, wherein the substrate is a glass substrate.   The adhesive resin according to claim 1, further comprising a defoaming step of performing a defoaming treatment of the uncured curable resin composition layer after the first laminating step and before the curing step. Manufacturing method of electronic device with layer.   The said auxiliary substrate preparation process is a process of processing the surface of an auxiliary substrate using a peeling agent, and obtaining the peelable auxiliary substrate which has the surface which shows easy peelability. Of manufacturing an electronic device with an adhesive resin layer.   The manufacturing method of the electronic device with an adhesive resin layer according to claim 4, wherein the release agent includes a compound having a methylsilyl group or a fluoroalkyl group.   The manufacturing method of the electronic device with an adhesive resin layer according to claim 4, wherein the release agent contains silicone oil or a fluorine-based compound.   The manufacturing method of the electronic device with an adhesive resin layer according to claim 1, wherein the adhesive resin layer contains a silicone resin.   The adhesive resin layer is a cured product of an addition reaction type silicone composed of a combination of an organoalkenylpolysiloxane having an alkenyl group and an organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom. 8. A method for producing an electronic device with an adhesive resin layer according to any one of 7 above.   The electronic device with an adhesive resin layer according to claim 8, wherein a molar ratio of hydrogen atoms bonded to silicon atoms of the organohydrogenpolysiloxane to alkenyl groups of the organoalkenylpolysiloxane is 0.5 to 2. Production method.   The manufacturing method of the electronic device with an adhesive resin layer of any one of Claims 1-9 in which the said adhesive resin layer contains 5 mass% or less of non-curable organopolysiloxane.

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