JP2021171954A - Resin substrate laminate and method for manufacturing electronic device - Google Patents

Abstract

To provide a resin substrate laminate in which a resin substrate can easily be removed mechanically from a release layer.SOLUTION: A resin substrate laminate comprises: a support substrate 4 with a release layer, which has a support substrate 1 and a release layer 2; and a resin substrate 3 releasably laminated on a surface of the release layer 2, opposite to the support substrate 1, wherein: when a composition of the surface of the release layer 2 is SixCyOz(x+y+z=1), y/(x+z)≤0.67 is satisfied; adhesive strength between the release layer 2 and the resin substrate 3 is 0.35 N/cm or less; and a vapor-deposited film is used as the release layer 2.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin substrate laminate and a method for manufacturing an electronic device using the resin substrate laminate.

In recent years, electronic devices such as organic EL displays (OLEDs), liquid crystal panels (LCDs), and solar cells (PV) have become thinner and lighter. Further, it is desired to impart the functionality of bending, that is, flexibility, to these electronic devices. Against such a background, a lightweight and flexible resin substrate is used instead of the conventional heavy and inflexible glass substrate.

In the manufacturing process of these electronic devices, a substrate laminate is used in which a release layer made of an inorganic substance or an organic substance is formed on a support substrate, and a glass substrate or a resin substrate is detachably laminated on the release layer. Specifically, an electronic component is formed on a glass substrate or a resin substrate of a substrate laminate, and then the glass substrate or the resin substrate with the electronic component is peeled off from a release layer to manufacture an electronic device.

Patent Document 1 uses a support substrate, a support substrate with an inorganic layer having an inorganic layer arranged on the support substrate, and a glass laminate having a glass substrate detachably laminated on the inorganic layer, and is physically used. Describes a method for manufacturing an electronic device for peeling a glass substrate.

In Patent Document 2, a support substrate with a release layer having a support substrate and a release layer laminated on the support substrate is detachably laminated on a surface of the release layer opposite to the support substrate. and a resin substrate, provided with, the composition of the surface of the release _{layer, Si x C y O z (} 0.05 ≦ x ≦ 0.43,0.27 ≦ y ≦ 0.73,0.22 ≦ z ≦ 0 .30, x + y + z = 1), the release layer is in an amorphous state, and the resin substrate is made of a material that can be separated from the release layer by irradiating a ^{laser beam having a wavelength of 355 nm at an intensity of 60 to 80 mJ / cm 2.} The resin substrate laminate and the method for manufacturing an electronic device using the resin substrate laminate are described.

In Patent Document 3, regarding a device structure using a laminate composed of a support and a polyimide film, a polyimide film in which a surface facing the support is subjected to plasma treatment is used, and the support and the polyimide film are used. On at least one of the surfaces facing each other, a coupling agent is used to perform a patterning treatment to form a good adhesive portion and an easy peeling portion having different adhesive peel strengths and substantially the same surface roughness, and then a support. It is described that the polyimide film is peeled off from the support by making a cut in the polyimide film of the easily peelable portion of the laminated body produced by superimposing the polyimide film and the polyimide film under pressure and heat treatment.

Japanese Patent No. 5991373 Japanese Patent No. 6492140 Japanese Unexamined Patent Publication No. 2013-10342

In the technique described in Patent Document 1, a glass substrate is used, but it is not assumed that a resin substrate is used, and there is a problem that a thin resin substrate is torn when physically peeling by machine. was there.

In the technique described in Patent Document 2, the resin substrate is peeled off by irradiating the laser beam, but there is a problem that the equipment becomes expensive because the pulsed laser beam of high energy is used. Further, in the technique described in Patent Document 2, since the laser is irradiated to the resin substrate side through the support substrate such as the glass substrate, the quality of the back surface side of the support substrate is maintained because it is affected by dirt on the support substrate. It has become important, and there is a problem that it is easily affected by the transmittance of the support substrate.

In the technique described in Patent Document 3, the polyimide used is limited, a solution of the coupling agent is applied to the support or the polyimide film, dried and heat-treated, and a part of the coupling treatment layer is selected by etching or the like. It was necessary to perform inactivation treatment to form a predetermined pattern.

The present invention has been made in view of the above problems, and an object of the present invention is a resin substrate laminate and an electronic device using the resin substrate laminate that enable the resin substrate to be easily mechanically peeled from the release layer. To provide a manufacturing method for.

According to the resin substrate laminate of the present invention, the subject is a support substrate with a release layer having a support substrate and a release layer laminated on the support substrate, and the support substrate of the release layer. and a resin substrate that is releasably laminated on the opposite surface, the composition of the surface of the release layer when the _{Si x C y O z (x} + y + z = 1), y / (x + z) ≦ This is solved by satisfying 0.67, having an adhesive force between the peeling layer and the resin substrate of 0.35 N / cm or less, and the peeling layer being a vapor-deposited film.
With the above configuration, the release layer can be easily formed by the thin-film deposition method, and the resin substrate can be easily mechanically separated from the release layer.
In this case, the composition of the surface of the release _{layer, Si x C y O z (} 0.51 ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0.07 ≦ z ≦ 0.11, x + y + z = 1) is preferable.
In this case, the composition of the surface of the release layer when the _{Si x C y O z (x} + y + z = 1), y / satisfies the (x + z) ≦ 0.48, the adhesive strength is less than or equal to 0.20 N / cm It is preferable to have it.
At this time, the film thickness of the resin substrate is 25 μm or less, and it is preferable that the resin substrate is mechanically peeled off.

According to the method for manufacturing an electronic device of the present invention, the problem is that a release layer is laminated on a support substrate by a vapor deposition method, and a resin substrate is laminated on a surface of the release layer opposite to the support substrate. A step of preparing a resin substrate laminate, a member forming step of forming a member for an electronic device on the surface of the resin substrate of the resin substrate laminate, and a peeling step of mechanically peeling the resin substrate from the peeling layer. And, when the composition of the surface of the peeling layer is Si _{x Cy Oz} (x + y + z = 1), it is solved by satisfying y / (x + z) ≦ 0.67.
In this case, the composition of the surface of the release _{layer, Si x C y O z (} 0.51 ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0.07 ≦ z ≦ 0.11, x + y + z = 1) is preferable.
In this case, the composition of the surface of the release layer when the _{Si x C y O z (x} + y + z = 1), it is preferable to satisfy y / (x + z) ≦ 0.48.
At this time, it is preferable that the film thickness of the resin substrate is 25 μm or less.

In the resin substrate laminate of the present invention, the adhesive force between the release layer, which is a vapor-deposited film, and the resin substrate is equal to or less than a predetermined value, and the resin substrate can be easily peeled from the release layer by mechanical peeling. Peeling can be performed without damaging the substrate. Therefore, when the resin substrate laminate of the present invention is used for manufacturing an electronic device, productivity can be improved, the choice of support substrate can be expanded, and the manufacturing cost can be reduced as compared with the case where laser light is used. It will be possible.

It is a schematic cross-sectional view which shows the resin substrate laminated body which concerns on one Embodiment of this invention. It is a schematic cross-sectional view which shows the laminated body with the electronic device member which formed the electronic device member on the resin substrate laminated body which concerns on one Embodiment of this invention. FIG. 5 is a schematic cross-sectional view showing a state in which an electronic device is peeled from a support substrate with a peeling layer in a laminated body with a member for an electronic device according to an embodiment of the present invention. It is a flow chart of the manufacturing method of the electronic device which concerns on one Embodiment of this invention. It is a graph which plotted C / (Si + O) on the horizontal axis and adhesive force on the vertical axis.

Hereinafter, a resin substrate laminate according to an embodiment of the present invention (the present embodiment) and a method for manufacturing an electronic device using the resin substrate laminate will be described with reference to FIGS. 1 to 5.

<Resin substrate laminate S>
The resin substrate laminate S of the present embodiment has a support substrate 1 and a support substrate 4 with a release layer including a release layer 2 which is a vapor-deposited film, and a resin substrate 3, as shown in a schematic cross-sectional view in FIG. .. In the resin substrate laminate S of the present embodiment, the release layer surface 2a (the surface opposite to the support substrate 1 side) of the release layer 2 of the support substrate 4 with the release layer, and the first surface 3a of the resin substrate 3 The support substrate 4 with a release layer and the resin substrate 3 are laminated so as to be removable. In other words, one surface of the release layer 2 is fixed to the support substrate 1, the other surface of the release layer 2 is in contact with the first surface 3a of the resin substrate 3, and the interface between the release layer 2 and the resin substrate 3 is formed. It is in close contact so that it can be peeled off. That is, the release layer 2 has easy release property with respect to the first surface 3a of the resin substrate 3. Hereinafter, the configuration of the resin substrate laminate S will be described in detail.

(Support substrate 4 with release layer)
The support substrate 4 with a release layer includes a support substrate 1 and a release layer 2 laminated on the surface thereof by a thin-film deposition method. The release layer 2 is arranged on the outermost side of the support substrate 4 with a release layer so as to be in close contact with the resin substrate 3 described later so as to be detachable. Next, the support substrate 1 and the release layer 2 will be described.

(Support board 1)
The support substrate 1 is a substrate that has a first surface 1a and a second surface 1b, and supports the resin substrate 3 together with the release layer 2 arranged on the first surface 1a. As the support substrate 1, for example, a glass plate, a plastic plate, or the like is used, but the support substrate 1 is not limited thereto. It is preferable to use a glass plate as the support substrate 1 because it is easy to handle and inexpensive.

Examples of the glass plate include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pylex (registered trademark)), borosilicate glass (non-alkali), and the like. Borosilicate glass (microsheet), aluminosilicate glass and the like are included. Among these, those having a linear expansion coefficient of 5 ppm / K or less are desirable, and if it is a commercially available product, "Corning (registered trademark) 7059" or "Corning (registered trademark) 1737" manufactured by Corning Inc., which is a glass for liquid crystal, "EAGLE", "AN100" manufactured by Asahi Glass, "OA10" manufactured by Nippon Electric Glass, "AF32" manufactured by SCHOTT, "NA32SG" manufactured by Avant Straight, etc. are desirable.

It is desirable that the flat portion of the support substrate 1 is sufficiently flat. Specifically, the PV value of the surface roughness is 50 nm or less, more preferably 20 nm or less, and further preferably 5 nm or less. If the value of the surface roughness is large, the adhesive strength between the release layer 2 and the support substrate 1 may be insufficient.

The thickness of the support substrate 1 is selected based on the thickness of the resin substrate 3 described later and the final thickness of the resin substrate laminate S. When a glass plate is used as the support substrate 1, the thickness of the support substrate 1 is 10 mm or less in order to have a property of appropriately bending without cracking when peeling after forming the member for an electronic device. Preferably, it is 3 mm or less, more preferably 1.3 mm or less. The lower limit of the thickness is not particularly limited, but from the viewpoint of handleability, it is preferably 0.07 mm or more, more preferably 0.15 mm or more, and further preferably 0.3 mm or more.

The area of the support substrate 1 is preferably large from the viewpoint of production efficiency and cost of the support substrate 4 with a release layer, the resin substrate laminate S, and the flexible electronic device. Specifically, it is preferably 1000 cm ² or more, more preferably 1500 cm ² or more, more preferably 2000 cm ² or more.

(Release layer 2)
Release layer 2 is laminated on the first surface 1a of the supporting substrate 1, a layer in contact with the first surface 3a of the resin substrate 3, the composition of the peeling layer surface _{2a Si x C y O z (} 0.51 ≦ When x ≦ 0.76, 0.17 ≦ y ≦ 0.40, 0.07 ≦ z ≦ 0.11, x + y + z = 1), a thin-film film satisfying y / (x + z) ≦ 0.67 (specifically Specifically, it is a physical vapor deposition film or a chemical vapor deposition film). In this case, the composition of the peeling layer surface _{2a Si x C y O z (} 0.59 ≦ x ≦ 0.76,0.33 ≦ y ≦ 0.40,0.08 ≦ z ≦ 0.11, x + y + z = 1 ), It is preferable that y / (x + z) ≦ 0.48 is satisfied.

The release layer surface 2a of the release layer 2 refers to the outermost surface of the release layer 2 (the outermost surface on the opposite side of the support substrate 1). More specifically, the release layer surface 2a of the release layer 2 refers to a region from the outermost surface to a distance of 10% from the outermost surface toward the support substrate 1 side, where the thickness of the release layer 2 is 100%.

The composition of the release layer surface 2a and other components of the release layer 2 can be measured by X-ray photoelectron spectroscopy (XPS). In the release layer 2, the composition other than the release layer surface 2a may be different from or the same as the composition of the release layer surface 2a.

Peeling layer _2, a _{Si x C y O z (0.51} ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0.07 ≦ z ≦ 0.11, x + y + z = 1) is the main component It is preferable that it is contained. Here, the main component of the entire separation layer 2 is taken as 100 _{mass%, Si x C y O z} (0.51 ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0 It means that the total content of .07 ≦ z ≦ 0.11, x + y + z = 1) is 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass or more.

The release layer _{2, Si x C y O z} (0.51 ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0.07 ≦ z ≦ 0.11 , which is a main component, x + y + z = 1 ), A dopant may be added. Examples of the dopant include, but are not limited to, N (nitrogen), B (boron), Al (aluminum), P (phosphorus), and the like. _{Si x C y O z (0.51} ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0.07 ≦ z ≦ 0.11, x + y + z = 1) content of relative dopant which is the main component Is preferably 10 atomic% or less. When the content ratio of the dopant is within the above range, good peelability can be realized.

The release layer 2 in the present embodiment is a vapor deposition film such as a physical vapor deposition film or a chemical vapor deposition film, and requires a wet process such as separately applying a coupling agent in order to form the release layer surface 2a having a predetermined composition. There is no need to perform surface treatment such as additional patterning treatment. Further, since the dry process called the vapor deposition method is adopted, unlike the wet process, no solvent is used, so that the residual solvent does not affect the manufacturing process of the electronic device.

The thickness of the release layer 2 is preferably about 1 nm to 20 μm, more preferably about 10 nm to 2 μm, and even more preferably about 40 nm to 1 μm. If the thickness of the peeling layer 2 is too thin, the uniformity of the formed film thickness may be lost and uneven peeling may occur.

Although the release layer 2 is shown as a single layer in FIG. 1, it is also possible to stack two or more layers.
Further, the release layer 2 is usually laminated over the entire surface of the first surface 1a of the support substrate 1 as shown in FIG. 1, but if it has appropriate peelability, it is on the first surface 1a of the support substrate 1. It may be laminated on a part of. For example, the release layer 2 may be provided on the first surface 1a of the support substrate 1 in an island shape or a stripe shape.

(Resin substrate 3)
In the resin substrate 3, the first surface 3a is in contact with the release layer 2, and the electronic device member P described later is provided on the second surface 3b on the side opposite to the release layer 2 side. The resin constituting the resin substrate 3 may be either a thermoplastic resin or a thermosetting resin, and for example, polyethylene (high density, medium density or low density), polypropylene (isotactic type or syndiotactic type), Polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-propylene-butene copolymer and other polyolefins, cyclic polyolefins, modified polyolefins, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, Aromatic polyimides such as polyimides, polyamideimides, polyetherimides, and fluorinated polyimides, polyimide resins such as alicyclic polyimides, polycarbonates, polyvinyl alcohols, polyethylene vinyl alcohols, poly- (4-methylbenzene-1), ionomers, and acrylics. Based resin, polymethylmethacrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer, acrylic-styrene copolymer (AS resin), Butadiene-styrene copolymer, ethylene vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, polycyclohexylene dimethylene -Polymer such as terephthalate (PCT), polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester, Polytetrafluoroethylene (PTFE), polyvinylidene fluoride, other fluororesins, styrenes, polyolefins, polyvinyl chlorides, polyurethanes, fluororubbers, chlorinated polyethylenes and other various thermoplastic elastomers, evoxy resins, phenols Resins, urea resins, melamine resins, unsaturated polyesters, silicone resins, polyurethanes, nylons, nitrocelluloses, cellulose acetates, cellulose acetate propionates and other cellulose-based resins, or polymers and blends mainly containing these. Examples include polymer alloys, which are used in combination of one or more of these (for example, as a laminate of two or more layers). Can be

As the resin substrate 3, it is preferable that the resin substrate 3 is a film using a polymer having a heat resistance of 100 ° C. or higher, that is, a film using a so-called engineering plastic. The film using engineering plastic is preferably an aromatic polyester film, and further includes an aromatic polyamide film having a heat resistant temperature of more than 150 ° C., a polyamideimide film, a super engineering plastic film such as a polyimide film, and the like. Can be done. Here, heat resistance refers to the glass transition temperature or the thermal deformation temperature.

The thickness of the resin substrate 3 is not particularly limited, but the thickness can be reduced, and the thickness of the polymer film is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 7 μm or more. .. The upper limit of the thickness of the polymer film is not particularly limited, but from the viewpoint of making the final electronic device thinner and more flexible, it is preferably 250 μm or less, more preferably 150 μm or less, still more preferably 90 μm or less. It is more preferably 40 μm or less, 25 μm or less, and 20 μm or less. The resin substrate 3 may be a laminated body in which two or more resin layers are laminated.

(Adhesive strength between the release layer 2 and the resin substrate 3)
In the resin substrate laminate S of the present embodiment, the adhesive force (adhesive force) between the release layer 2 and the resin substrate 3 is small enough to be easily mechanically peeled off. The adhesive strength can be measured, for example, as the 90 ° peel strength measured in the 90 ° peel test.

Although it depends on the thickness of the resin substrate 3, the adhesive strength between the release layer 2 and the resin substrate 3 is 0.35 N / cm or less, preferably 0.30 N / cm or less, more preferably 0.20 N / cm or less, still more preferable. Is preferably 0.10 N / cm or less.

(About the use of the resin substrate laminate S)
As described above, the resin substrate laminate S of the present embodiment has the release layer surface 2a of the support substrate 4 with the release layer and the first surface 3a of the resin substrate 3 as the laminated surfaces, and the support substrate 4 with the release layer. It is a laminated body formed by laminating the resin substrate 3 so as to be peelable. That is, it is a laminated body in which the release layer 2 is interposed between the support substrate 1 and the resin substrate 3.

The resin substrate laminate S having such a configuration is used in the manufacture of an electronic device as will be described later. Specifically, as shown in FIG. 2, in the resin substrate laminate S, the electronic device member P is formed on the surface of the second surface 3b. After that, as shown in FIG. 3, the support substrate 4 with a release layer is peeled off at the interface with the resin substrate 3, and the support substrate 4 with a release layer does not become a member constituting an electronic device. A new resin substrate 3 is laminated on the support substrate 4 with a release layer from which the resin substrate 3 on which the member P for the electronic device is formed is separated, and can be reused as the support substrate 4 with a release layer.

The resin substrate laminate S of the present invention can be used for various purposes, for example, displaying a liquid crystal panel (LCD), an organic EL display (OLED), electronic paper, a field emission panel, a quantum dot LED panel, a MEMS shutter panel, or the like. Examples include applications for manufacturing electronic devices such as device panels, liquid crystal displays (PV), thin film secondary batteries, and semiconductor wafers having circuits formed on their surfaces.

<Manufacturing method of electronic device D>
In the method for manufacturing an electronic device of the present embodiment, a release layer is laminated on a support substrate by a vapor deposition method, and a resin substrate is laminated on a surface of the release layer opposite to the support substrate to form a resin substrate laminate. A member forming step of forming a member for an electronic device on the surface of the resin substrate of the resin substrate laminate, and a peeling step of mechanically peeling the resin substrate from the peeling layer. When the composition of the surface of the release layer is Si _{x Cy Oz} (x + y + z = 1), y / (x + z) ≦ 0.67 is satisfied.
Hereinafter, each step will be described in detail with reference to FIG.

(Process of preparing resin substrate laminate)
In the step of preparing the resin substrate laminate (step S1), first, the release layer 2 is laminated on the support substrate 1 by a vapor deposition method to obtain a support substrate 4 with a release layer, and the support substrate 4 with the release layer is placed on the support substrate 4. The resin substrate 3 is laminated.
Specifically, the release layer 2 is laminated on the support substrate 1 by a vapor deposition method using a target having a predetermined Si: C ratio to obtain a support substrate 4 with a release layer, and the support substrate 4 with a release layer is obtained. The resin substrate 3 is laminated on the surface 2a on the opposite side of the release layer 2 from the support substrate 1.
In the support substrate 4 with a release layer, the method of forming the release layer 2 on the support substrate 1 may be any method as long as the release layer can be formed with a uniform thickness, depending on various conditions such as the composition and thickness of the release layer 2. It is possible to select as appropriate according to the situation. As a vapor deposition method, physical vapor deposition (PVD) or chemical vapor deposition (CVD) can be used. As the physical vapor deposition, for example, a sputtering method, an electron beam deposition, an ion plating, an ion beam deposition, a molecular beam vapor deposition (MB), a vacuum vapor deposition, or the like can be adopted, but the physical vapor deposition is limited to these methods. is not it. Further, as the chemical vapor deposition, for example, various vapor deposition methods such as thermal CVD, optical CVD, plasma CVD, metalorganic vapor deposition (MOCCVD), low pressure CVD, and ECR-CVD can be adopted. It is possible, but not limited to these methods. Two or more of these methods may be combined.

For example, using a SiC target, _{a mixed gas of an inert gas such as Ar and an oxygen atom-containing gas such as O 2} is introduced, and the first surface 1a of the support substrate 1 is subjected to a vapor deposition method such as a sputtering method or a CVD method. By providing the release layer 2 on the top, the support substrate 4 with the release layer is manufactured. At this time, it is possible to control the amount of oxygen (value of z) on the surface 2a of the peeling layer 2 of the peeling layer 2 by adjusting the composition of the target and the amount of the oxygen atom-containing gas in the mixed gas. The film forming conditions of the release layer 2 may be appropriately selected according to the material to be used and the like.

Targets used when forming the release layer 2 include SiC (silicon carbide), SiCO (silicon carbon oxide), SiO ₂ (silicon oxide), and Si (so that the ratio of Si: C is a predetermined ratio. Substances such as silicon) can be used alone or in combination. At this time, by adjusting the ratio of Si: C of the target, it is possible to control the amount of silicon (value of x) and the amount of carbon (value of y) of the release layer surface 2a of the release layer 2.

In the resin substrate laminate S, the method of laminating the resin substrate 3 on the release layer 2 of the support substrate 4 with the release layer is not particularly limited, but a resin solution or a resin precursor solution constituting the resin substrate 3 is used. A method of applying, drying and forming a film can be used.

The application of the resin solution or resin precursor solution on the release layer 2 includes, for example, spin coating, doctor blade, applicator, comma coater, screen printing method, slit coating, reverse coating, dip coating, curtain coating, slit die coating, etc. , A known solution coating means can be appropriately used.

For example, when the resin substrate 3 is a polyimide resin film, a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent is placed on the release layer 2 with a predetermined thickness. It can be obtained by performing a thermal imidization method in which a dehydration ring-closing reaction is carried out by high-temperature heat treatment after coating and drying, or a chemical imidization method in which acetic anhydride or the like is used as a dehydrating agent and pyridine or the like is used as a catalyst. can.

When the resin substrate 3 is a thermoplastic resin film, a thermoplastic resin film can be obtained by a melt-stretching method. If it is not a thermoplastic resin film, a resin film can be obtained by a solution film forming method.

(Member forming process)
In the member forming step (step S2), a member for an electronic device is formed on the surface of the resin substrate of the resin substrate laminate. Specifically, as shown in FIG. 2, in this step, the electronic device member P is formed on the second surface 3b of the resin substrate 3, and the laminated body SP with the electronic device member is manufactured. First, the member P for an electronic device used in this step will be described, and then this step will be described in detail.

The electronic device member P is a member that constitutes at least a part of the electronic device D formed on the second surface 3b of the resin substrate 3 of the resin substrate laminate S. Specifically, examples of the member P for an electronic device include a member used for a panel for a display device such as an OLED, a solar cell, a thin film secondary battery, and an electronic component such as a semiconductor wafer having a circuit formed on its surface. ..

For example, examples of the OLED member include an electrode, a TFT element formed by laminating an organic material layer and etching, and a drive circuit. Examples of the solar cell member include a transparent electrode such as tin oxide as a positive electrode, a silicon layer represented by a p-layer / i-layer / n-layer, and a metal as a negative electrode in the silicon type. In addition, a compound type member is used. , Various members corresponding to the dye-sensitized type, the quantum dot type, and the like can be mentioned. Further, as the member for the 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 and the like are used. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned. Examples of electronic component members include metals in conductive parts, silicon oxide and silicon nitride in insulating parts in CCD and CMOS, as well as various sensors such as pressure sensors and acceleration sensors, rigid printed circuit boards, and flexible printed circuit boards. , Various members corresponding to rigid flexible printed circuit boards and the like can be mentioned.

The method for manufacturing the laminated body SP with the electronic device member is not particularly limited, and a known method is used depending on the type of the constituent member of the electronic device member P, and the second surface of the resin substrate 3 of the resin substrate laminated body S is used. An electronic device member P is formed on the 3b. The electronic device member P may be a part of the member, not all of the members finally formed on the surface of the second surface 3b of the resin substrate 3. The resin substrate with partial members can also be made into a resin substrate with all members (corresponding to an electronic device described later) in a subsequent step. Further, another electronic device member may be formed on the peeled surface (first surface 3a) of the resin substrate. Further, it is also possible to manufacture the electronic device D by assembling the laminated body with all the members and then peeling the support substrate 4 with the release layer from the resin substrate 3 on which the member P for the electronic device is formed.

For example, in the case of manufacturing an OLED, a transparent electrode is formed in order to form an organic EL structure on the surface of the second surface 3b of the resin substrate 3 of the resin substrate laminate S, and further on the surface on which the transparent electrode is formed. Various layers are formed and treated, such as depositing a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc., forming a back electrode, and sealing using a sealing plate. Specific examples of these layer formations and treatments include a film forming process, a thin film deposition process, and a sealing plate bonding process.

Further, for example, in the case of manufacturing a TFT-LCD, a general film formation such as a CVD method and a sputtering method is performed using a resist liquid on the surface of the second surface 3b of the resin substrate 3 of the resin substrate laminate S. A TFT forming step of forming a thin film transistor (TFT) by forming a pattern on a metal film, a metal oxide film, or the like formed by the method, and a resist on the second surface 3b of the resin substrate 3 of another resin substrate laminate S. It has various steps such as a CF forming step of forming a color filter (CF) by using a liquid for pattern forming, and a bonding step of laminating a device substrate with a TFT and a device substrate with a CF.

In the TFT forming step and the CF forming step, the TFT and CF are formed on the second surface 3b of the resin substrate 3 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist liquid is used as a coating liquid for pattern formation. If necessary, the second surface 3b of the resin substrate 3 may be washed before forming the TFT or CF. As the cleaning method, well-known dry cleaning or wet cleaning can be used. In the bonding step, a liquid crystal material is injected and laminated between the laminate with TFT and the laminate with CF. Examples of the method for injecting the liquid crystal material include a reduced pressure injection method and a dropping injection method.

(Peeling process)
In the peeling step (step S3), the resin substrate is mechanically peeled from the peeling layer of the laminate with the electronic device member obtained in the member forming step, and the electronic device including the electronic device member P and the resin substrate 3 is included. Get D. That is, it is a step of separating the laminated body SP with a member for an electronic device into a support substrate 4 with a release layer and an electronic device D.

More specifically, in the peeling step, the resin substrate 3 is pressed by applying a physical force while holding the peeling layer 2 of the laminated body with a member for an electronic device obtained in the member forming step on the support substrate 1. Separate from the release layer 2. When the electronic device member P on the resin substrate 3 after peeling is a part of all the final constituent members, the remaining constituent members may be formed on the resin substrate 3 after peeling.

The resin substrate 3 can be separated from the peeling layer 2 by peeling the resin substrate 3 from the peeling layer 2 by applying a physical force. The method of separating the resin substrate 3 from the release layer 2 is not particularly limited as long as it is a method of applying a physical force, but for example, a method of winding or peeling with a drive roll, or a method of peeling with an adhesive sheet or an adsorption pad. Examples include a method of peeling off while blowing air from the end face, and a method of peeling off by hand.

The electronic device D obtained by the above step is suitable for manufacturing a small display device used for mobile terminals such as mobile phones, smartphones, PDAs, and tablet PCs. The display device is mainly an LCD or an OLED, and the LCD includes a TN type, an STN type, an FE type, a TFT type, a MIM type, an IPS type, a VA type and the like. Basically, it can be applied to both passive drive type and active drive type display devices.

In the present embodiment, the resin substrate laminate and the method for manufacturing an electronic device using the resin substrate laminate according to the present invention have been mainly described. However, the above-described embodiment is merely an example for facilitating the understanding of the present invention, and does not limit the present invention. The present invention can be modified and improved without departing from the spirit thereof, and it goes without saying that the present invention includes an equivalent thereof.

Hereinafter, specific examples of the resin substrate laminate and the method for manufacturing an electronic device using the resin substrate laminate of the present invention will be described, but the present invention is not limited thereto.

<A. Formation of resin substrate laminate according to Examples and Comparative Examples>
(A-1. Release layer forming step)
Under the following conditions, a release layer was laminated on a glass plate (length 100 mm, width 100 mm, plate thickness 0.7 mm, manufactured by AvanStrate Inc., trade name "NA32SG") as a support substrate to prepare a support substrate with a release layer. At this time, the composition ratio of Si and C contained in the peeling layer was changed, and the influence of the composition ratio of Si and C on the peeling performance was examined. The support substrate with the release layer was subjected to a four-layer batch cleaning of one neutral detergent layer, two pure water layers, and a pure water pulling layer.

Sputtering device: Carousel type batch type sputtering device Target: Two-way sputtering deposition of Si (silicon) and C (carbon) Sputtering method: DC pulse application, magnetron sputtering Exhaust device: Turbo molecular pump Reach vacuum degree: 1.0 x 10 ^-4 Pa (7.5 x ^10-6 Torr)
Base material temperature: 200 ° C
Sputtering power: 0.6 to 2.5 kW / cm ² (value is set according to the ratio of Si and C)
Film thickness: 60-100 nm
Ar flow rate: 330 sccm

(A-2. Resin substrate laminating process)
The polyimide resin substrate (resin substrate) was laminated as follows. Using a solvent-diluted solution of polyimide resin molding material (Toray Industries, Inc., SP030N) with a spin coater (Kyowa Riken, K359S1), predetermined spinner conditions (resin substrate thickness 10 μm: initial speed 300 rpm-10 seconds, second speed 1180 rpm) It was applied on the release layer of the support substrate with the release layer at −20 seconds, resin substrate thickness 20 μm: initial speed 300 rpm-10 seconds, second speed 560 rpm-20 seconds)). Leveling (horizontal flat placement) was carried out for 1 minute for the purpose of making the surface of the substrate uniform after coating. It was prebaked using a hot plate under the conditions of 120 ° C. for 6 minutes. Next, post-baking was performed using an oven at 450 ° C. for 30 minutes, and a polyimide resin substrate (length 100 mm, width 100 mm, thickness 10 μm (Sample No. 1-1-1-7)) or 20 μm (Sample No. 1-1-1-7) or 20 μm (Sample No. 1-1-1-7). 2-1 to 2-8)) were laminated to obtain a resin substrate laminate.

<B. Composition analysis by XPS)>
For each sample, the composition analysis of the surface of the release layer by XPS (device: manufactured by JEOL Ltd., JPS-90000MC) was performed under the following conditions.

(Analysis conditions)
X-ray source: MgKα
X-ray output: 10kV x 10mA (100W)
EPass: 10eV
Step: 0.1 eV
Dwell time x total number of times: 100mS x 8
Measuring elements: Si, C, O

<C. Peeling test (90 ° peel test)>
A 90 ° peel test was carried out by the following method, and the adhesive force between the release layer 2 and the resin substrate 3 was measured. First, a 10 mm wide notch was made in the polyimide film (resin substrate) on the resin substrate laminate to prepare a gripping allowance. It was then dried on a hot plate (150 ° C., 20 minutes). Then, it was pulled upward by 90 ° at a speed of 50 mm / min, and its strength (90 ° peel strength) was measured and used as the adhesive strength. For the measurement, a digital force gauge FGJN-5 and a force gauge stand FGS-50V-H (manufactured by Nippon Densan Symposium Co., Ltd.) were used.

In addition, a sensory evaluation was carried out as to whether or not the thin film portion at the end portion of the polyimide resin substrate was torn during mechanical peeling. The edge of the polyimide resin substrate is thin and easily torn.

The results are shown in Table 1 and FIG. 5 below. In Table 1, the composition ratio is shown by the atomic concentration ratio (at%), and the values of Si, C, and O (at%) divided by 100 correspond to x, y, and z, respectively. Further, C / (Si + O) is synonymous with y / (x + z).

From the above results, as shown in FIG. 5, it was found that when y / (x + z) is equal to or higher than a predetermined value, the adhesive force rapidly increases, and it becomes difficult to mechanically peel the polyimide resin substrate from the peeling layer. rice field. From the results when the thickness of the polyimide resin substrate is 20 μm or more (Sample No. 2-1 to 2-8), the adhesive strength is 0.09 or 0 in the range of 0.20 ≦ y / (x + z) ≦ 0.67. It was 10.10, and it was found that it was easy to mechanically peel the polyimide resin substrate from the peeling layer. From the results when the thickness of the polyimide resin substrate is 10 μm or more (Sample No. 1-1 to 1-7), the adhesive strength is 0.35 or less in the range of 0.20 ≦ y / (x + z) ≦ 0.62. It turned out that there was.

Further, the composition of the peeling layer surface _{2a Si x C y O z (} 0.51 ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0.07 ≦ z ≦ 0.11, x + y + z = 1) It was found that the adhesive strength between the release layer 2 and the resin substrate 3 was 0.35 N / cm or less when y / (x + z) ≦ 0.67 was satisfied.

Compared with the case where the thickness of the polyimide resin substrate is 20 μm or more (Sample No. 2-1 to 2-8), when the thickness is 10 μm (Sample No. 1-1 to 1-7), the release layer 2 The adhesive force with and is increased, and the polyimide resin substrate is less likely to be peeled from the peeling layer. Also the thickness of the polyimide resin substrate is an 10 [mu] m, the composition of the peeling layer surface _{2a, Si x C y O z} (0.59 ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.33,0.07 When ≦ z ≦ 0.08, x + y + z = 1) and 0.20 ≦ y / (x + z) ≦ 0.48 are satisfied, the adhesive force between the release layer 2 and the resin substrate 3 becomes 0.20 N / cm or less. I understand.

S Resin substrate laminate 1 Support substrate 1a 1st surface 1b 2nd surface 2 Peeling layer 2a Peeling layer surface 3 Resin substrate 3a 1st surface 3b 2nd surface 4 Supporting substrate with peeling layer P Electronic device member SP Electronic device member Laminated D electronic device with

Claims (8)

Support board and
A support substrate with a release layer having a release layer laminated on the support substrate, and a support substrate with a release layer.
A resin substrate that is detachably laminated on a surface of the release layer opposite to the support substrate is provided.
The composition of the surface of the release layer when the _{Si x C y O z (x} + y + z = 1), satisfies the y / (x + z) ≦ 0.67,
The adhesive force between the release layer and the resin substrate is 0.35 N / cm or less.
A resin substrate laminate characterized in that the release layer is a vapor-deposited film. The composition of the surface of the release _{layer, Si x C y O z (} 0.51 ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0.07 ≦ z ≦ 0.11, x + y + z = 1) The resin substrate laminate according to claim 1, wherein the resin substrate laminate is characterized by the above. When the composition of the surface of the release layer is Si _{x Cy Oz} (x + y + z = 1), y / (x + z) ≤ 0.48 is satisfied.
The resin substrate laminate according to claim 1, wherein the adhesive strength is 0.20 N / cm or less. The film thickness of the resin substrate is 25 μm or less, and the film thickness is 25 μm or less.
The resin substrate laminate according to any one of claims 1 to 3, wherein the resin substrate laminate is mechanically peeled off. A step of laminating a release layer on a support substrate by a vapor deposition method and laminating a resin substrate on a surface of the release layer opposite to the support substrate to prepare a resin substrate laminate.
A member forming step of forming a member for an electronic device on the surface of the resin substrate of the resin substrate laminate, and
A peeling step of mechanically peeling the resin substrate from the peeling layer is performed.
The composition of the surface of the release layer when the _{Si x C y O z (x} + y + z = 1), a method of manufacturing an electronic device, characterized in that satisfy y / (x + z) ≦ 0.67. The composition of the surface of the release _{layer, Si x C y O z (} 0.51 ≦ x ≦ 0.76,0.17 ≦ y ≦ 0.40,0.07 ≦ z ≦ 0.11, x + y + z = 1) The method for manufacturing an electronic device according to claim 5, wherein the method is characterized by the above. The manufacture of the electronic device according to claim 5, wherein y / (x + z) ≤ 0.48 is satisfied when the surface composition of the release layer is Si _{x Cy Oz (x + y + z = 1).} Method. The resin substrate laminate according to any one of claims 5 to 7, wherein the thickness of the resin substrate is 25 μm or less.

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