JP2016083926A - Laminate having resin/glass composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of producing a resin/glass composite in which the composite does not be peeled during the manufacture process of an electronic device; a support plate can easily be peeled after the manufacture of the electronic device; and after peeling, the occurrence of cracking and the progress of cracks are remarkably improved.SOLUTION: Laminates 10, 20 each have support plates 11, 21, respectively and resin/glass composites each having at least thin plate glasses 12, 22 having a thickness of 100 μm or less and resin layers 13, 23, respectively. The support plates 11, 21, the resin layers 13, 23 and the thin plate glasses 12, 22 are laminated in this order. In at least one cross-section when the laminates 10, 20 are cut in a lamination direction, the laminates 10, 20 have easily peelable parts 14, 24 and closely adhered parts 15, 25 having peel strength larger than that of the easily peelable parts 14, 24 at the interface between the resin/glass composites and the support plates, 11, 21 so that the closely adhered parts 15, 25 are positioned at both ends of the easily peelable parts 14, 15.SELECTED DRAWING: Figure 2

Description

  In the present invention, when an organic electronic device such as an organic electroluminescent element or an organic photoelectric conversion element is formed, the thin glass and the support plate exhibit good adhesion, and after the organic electronic device is formed, the support plate is easily peeled. The present invention relates to a laminate having a resin / glass composite.

In recent years, electronic devices (electronic parts) in organic EL display devices, solar cells, thin-film secondary batteries, etc. have been made thinner and lighter, and glass substrates used in these electronic devices have been made thinner. Yes. However, when the strength of the glass substrate is reduced due to the thinning, there is a problem that the handling property of the glass substrate is deteriorated.
Therefore, when manufacturing electronic devices using thin glass as a substrate, a method of peeling the carrier substrate after laminating the carrier substrate and thin glass to form an electronic device on the thin glass is proposed to improve handling. Has been.

For example, Patent Document 1 discloses an electronic device in which a glass substrate is peelably laminated on a resin layer surface of a carrier substrate with a resin layer, an electronic device is formed on the surface of the glass substrate, and then the carrier substrate with a resin layer is removed. A manufacturing method is disclosed.
In Patent Document 2, a support plate, a resin layer, and a glass substrate with an inorganic insulating film are laminated in this order, a laminated body in which the inorganic insulating film and the resin layer are in contact with each other, and the glass substrate surface of the laminated body A panel for a display device with a support plate in which a member for a display device is formed, and a panel for a display device from which the support plate with a resin layer is peeled off are disclosed.

JP2013-084526A International Publication No. 2012/144499 Pamphlet

However, in Patent Documents 1 and 2, if the adhesive strength of the peeling interface between the carrier substrate or the support plate and the glass is low, during the process of cleaning the substrate at the time of creating the electronic device, drying, and heat treatment under high temperature conditions If it peels and the adhesive strength is too high, it becomes difficult to peel off the carrier substrate or the support plate after the formation of the electronic device, so adjustment of the adhesive strength between the carrier substrate or the support plate and the glass is important. However, there was a problem that the adjustment was very difficult.
In addition, when a thin glass sheet having low strength is used as a substrate for an electronic device, a stress is applied to the thin glass sheet during peeling, which may cause cracks. Furthermore, since the handling property of the thin glass itself is low, handling of the thin glass provided with the electronic device requires great care.

As a result of intensive studies in view of the above-mentioned problems, the present inventors have laminated a support plate and a thin glass plate with a specific configuration, and without peeling during the process of creating the electronic device, After the creation, it was found that a laminate having a resin / glass composite, which can easily peel the support plate and the thin glass, can be obtained.
Furthermore, since the resin layer is laminated on the surface of the thin glass peeled off from the support plate, there is no fear that cracks will occur in the thin glass upon peeling from the support plate. Moreover, handling of the thin glass is easy even after peeling.
That is, the present invention is as follows.

[1] A laminate comprising a support plate, a thin glass having a thickness of 100 μm or less, and a resin / glass composite having at least a resin layer,
Laminated in the order of support plate, resin layer, and thin glass,
In at least one cross section when the laminate is cut in the laminating direction, the interface between the resin / glass composite and the support plate has an easily peelable portion and an adhesive portion having a peel strength higher than that of the easily peelable portion. A laminate comprising the adhesion portions positioned at both ends of a peeling portion.
[2] The laminate according to [1], wherein the resin layer is provided within an outer range of the support plate.
[3] The laminate according to [1] or [2], wherein the thin glass is provided within an outer shape range of the resin layer.
[4] The laminate according to any one of [1] to [3], wherein the easy-peeling portion is surrounded by the close-contact portion.
[5] The laminate according to any one of [1] to [4], wherein the thin glass is provided on the inner side of the outer shape range of the easily peelable portion.
[6] The laminated body according to any one of [1] to [5], wherein the thin glass is provided on the inner side of the outer shape range of the resin layer.
[7] The laminate according to any one of [1] to [6], wherein the difference between the peel strength at the close contact portion and the peel strength at the easy peel portion is 0.5 N / 25 mm or more.
[8] The laminate according to any one of [1] to [7], wherein the peel strength of the easily peelable portion is 0.5 N / 25 mm or less.
[9] The laminate according to any one of [1] to [8], wherein the 5% weight reduction temperature of the resin layer is 230 ° C. or higher.
[10] The laminate according to any one of [1] to [9], wherein the resin layer is a layer mainly composed of a resin obtained by curing a thermal or active energy ray-curable composition. body.
[11] The laminate according to any one of [1] to [9], wherein the resin layer is a film containing a thermoplastic resin as a main component.
[12] An organic electronic device obtained using the laminate according to any one of [1] to [11].
[13] Resin / glass comprising a step of cutting the laminated body according to any one of [1] to [11] in a laminating direction so as to remove the adhesion portion, and a step of peeling a support plate from the laminated body. A method for producing a composite.
[14] A method for producing an organic electronic device, comprising: cutting the organic electronic device according to [12] in a stacking direction so as to remove the adhesion portion; and peeling a support plate from the organic electronic device.

In the laminate having the resin / glass composite proposed by the present invention, an easily peelable portion and an adhesive portion having a peel strength larger than that of the easily peelable portion are provided at the peel interface between the resin / glass composite and the support plate. Since the close contact portion is located at both ends of the easily peelable portion, it is not peeled off in the process of forming an electronic device using the laminate as a substrate, and the close contact portion is removed after the device is formed. The support plate can be easily peeled by cutting in the stacking direction.
Moreover, in one embodiment of the present invention using a release layer as an easily peelable portion, since a part of the resin layer is in direct contact with the support plate, the material is peeled in the step of forming an electronic device using the material as a substrate. In addition to the thin glass sheet and the resin layer, or only the resin layer, or in addition to the thin glass and resin layer within the outer range of the release layer after the process, by cutting to the release layer and the support plate, A portion of the resin layer that is in direct contact with the support plate is cut off, and the thin glass laminate including the electronic device can be easily peeled off from the support plate.
Moreover, the thin glass laminated body which is a laminated body of thin glass and a resin layer is excellent in handling property, and the crack generation and progress in the thin glass at the time of peeling are also suppressed.

(A)-(d) looked at the laminated body from the lamination direction which shows an example of the lamination | stacking relationship of the mold release layer and resin layer by embodiment of this invention, ie, the relationship of the external shape range of a mold release layer and a resin layer. It is a schematic diagram. (A) (b) is a cross-sectional schematic diagram which shows an example at the time of cut | disconnecting the laminated body by one Embodiment of this invention in the lamination direction. (A) (b) is a cross-sectional schematic diagram which shows an example at the time of cut | disconnecting the laminated body by one Embodiment of this invention in the lamination direction. (A) (b) is a cross-sectional schematic diagram which shows an example at the time of cut | disconnecting the laminated body by one Embodiment of this invention in the lamination direction. It is a cross-sectional schematic diagram which shows an example at the time of cut | disconnecting the laminated body by one Embodiment of this invention to the lamination direction.

The laminate having the resin / glass composite of the present invention (hereinafter also referred to as “the present laminate”) and the materials constituting them will be described in detail below. It is an example (representative example) of embodiment of invention, and this invention is not limited to these content.
Moreover, although drawings are used in the description, any of the drawings used schematically shows a laminate or a component thereof according to a specific embodiment of the present invention, and partial emphasis, expansion, In some cases, reduction or omission is performed, and it does not accurately represent the scale or shape of each component. Furthermore, the various numerical values used in the description with reference to the drawings are only examples, and can be variously changed as necessary.
In the present invention, the outer shape range means the range occupied by each layer when the laminate is viewed from the stacking direction, and being provided within the outer shape range includes the outer frame occupied by a certain layer. It means that another layer is provided in the range, and being provided inside the outer shape range means that another layer is provided in a range occupied by a certain layer and not including the outer frame.

A laminate according to an embodiment of the present invention is a laminate having a resin / glass composite (hereinafter also referred to as a thin glass laminate) including a thin glass having a thickness of 100 μm or less and a resin layer on a support plate. Then, the support plate, the resin layer, and the thin glass are laminated in this order.
2 (a) and 2 (b) are schematic cross-sectional views showing an example of a thin glass laminated body with a support plate that is a specific embodiment of the present invention cut in the laminating direction.
As shown in FIGS. 2A and 2B, the thin glass laminate with a support plate according to the embodiment of the present invention is a laminate having a support plate, a release layer, a resin layer, and a thin glass.
Below, the material etc. which are used for the laminated body which concerns on embodiment of this invention including a support plate, a mold release layer, a resin layer, and a sheet glass first are demonstrated first. These materials and the like are used in a method for manufacturing a laminate described later.

<Support plate>
The support plate used in the present embodiment is a member that supports the resin / glass composite in the formation process of the electronic device. Even if stress is applied to the resin / glass composite during the formation of the electronic device, the support plate is deformed. Prevents scratches and damage.
As the support plate, for example, a metal plate such as a glass plate, a resin plate, or a SUS plate is used. Usually, since the electronic device forming process involves heat treatment, the support plate is preferably formed mainly of a material having a small difference in linear expansion coefficient from that of the thin glass, and is preferably formed of the same material as the thin glass. Is more preferable, and 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 thin glass.
The thickness of the support plate is not particularly limited as long as it can prevent deformation, scratching, breakage, etc. of the resin / glass composite in the electronic device forming step, but is usually 0.01 mm or more and 0.1 mm or more. Is preferred. When the support plate is a glass plate, it is usually 5 mm or less, and preferably 3 mm or less, for the reason that it is desired to bend appropriately after being peeled after the electronic device is formed.

<Resin / Glass Composite>
The resin / glass composite used in the present embodiment includes a thin glass plate and a resin layer, and forms a laminate by being supported by the above-described support plate. And a laminated body is laminated | stacked in order of a support plate, a resin layer, and thin glass.
The resin / glass composite may have other layers as long as it includes a thin glass and a resin layer and is thus laminated as a laminate. For example, a composite laminated with resin / glass / resin may be used.

<Resin layer>
The resin layer used in the present embodiment is laminated with a sheet glass described later to form a composite. In the composite, the resin layer plays a role of improving the strength of the thin glass sheet.
In the specific embodiment shown in FIGS. 2A and 2B, the resin layer is formed on the release layer, and a thin glass sheet is further laminated thereon. Further, a part of the resin layer is in direct contact with the support plate, and at least one section when the laminate is cut in the stacking direction, both ends of the resin layer are located outside the both ends of the release layer. . Since a part of the resin layer is in close contact with the support plate, the support plate and the thin glass are not peeled even in the step of forming the electronic device.
Further, the resin layer plays a role of improving the strength of the thin glass, and can improve the handling properties of the thin glass and suppress the generation and progress of cracks when the support plate is peeled off.

(Composition of resin layer)
The resin composition constituting the resin layer contains a resin and other additives as necessary.
The resin contained in the resin composition is not particularly limited, and may be a thermoplastic resin or a resin obtained by curing a curable composition.
The resin layer used in the embodiment of the present invention may not need to have adhesiveness depending on the embodiment, and may require adhesiveness. For example, in the embodiment shown in FIG. 2 and the embodiment shown in FIG. 5 described later, the resin layer constituting the resin layer is required to have adhesiveness. It is preferable that it is a resin layer which has resin obtained as a main component. Here, the main component refers to a component that is contained in the largest amount among all the components, preferably a component that occupies 50% by mass or more, and more preferably a component that exhibits 80% by mass or more.

  As a thermosetting composition, the curable composition containing an acrylic resin, a urethane resin, an epoxy resin, a silicone resin etc. is mentioned as a hardening component, The curable composition containing a silicone resin is preferable from a heat resistant viewpoint.

A preferable example of the active energy ray-curable composition is a curable composition containing an ultraviolet curable monomer and an oligomer as a curing component because it can be cured relatively easily in a short time.
As the ultraviolet curable monomer and oligomer, a (meth) acrylic monomer and a (meth) acrylic oligomer are preferable from the viewpoints of mechanical properties, transparency and processability.
For example, monomers and oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate are used.
Further, some of these are exemplified by trimethylolpropane triacrylate,
Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, isoamyl acrylate, ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, etc. Examples thereof include monofunctional and polyfunctional acrylic monomers and methacrylic monomers having one or more carbon-carbon double bonds.
In addition, these can be used 1 type or in combination of 2 or more types.

When the active energy ray-curable composition contains an ultraviolet curable monomer and oligomer, a photopolymerization initiator is also included as necessary. The photopolymerization initiator is used for absorbing (activating) and activating (exciting) ultraviolet rays and initiating the reaction via a cleavage reaction or the like.
Examples of the photopolymerization initiator include benzoin, acetophenone, thioxanthone, phosphine oxide, and peroxide. Specific examples include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophene, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl}- 2-methyl-propan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl- [4- (methyl Thio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenyl Examples include phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, and the like. it can. These can be used alone or in combination of two or more.

  The concentration of the photopolymerization initiator in the active energy ray-curable composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass from the viewpoint of reliably proceeding the curing reaction. % Or more. On the other hand, from the viewpoint of preventing outgassing due to unreacted substances of the polymerization initiator, it is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

The curable composition can be used after adding a solvent, if necessary. That is, it can be used as a solution containing the curable composition.
Although it will not specifically limit if it is a solvent which dilutes the component contained in a curable composition uniformly as said solvent, For example, methyl isobutyl ketone, butyl acetate, propylene glycol monomethyl ether etc. are mentioned. These can be used alone or in combination of two or more.

  The total concentration of the resin contained in the resin composition constituting the resin layer is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably, from the viewpoints of viscosity during processing and mechanical properties after processing. 80% by mass or more.

The resin composition constituting the adhesive resin layer is a silane coupling agent, a sensitizer, a crosslinking agent, an ultraviolet absorber, a polymerization inhibitor, a surfactant, and a filler as long as the object of the present invention is not impaired. A mold release agent and a thermoplastic resin can be optionally added. In addition, these can be used 1 type or in combination of 2 or more types as appropriate.
Moreover, in order to adjust the peeling strength of a resin layer, you may add a mold release component suitably. Examples of the mold release component include a fluorine-based internal mold release additive, a surfactant, a silicone-type mold release additive, and the like. From the viewpoint of heat resistance, a fluorine-type mold release additive is preferable.

  On the other hand, in the laminate according to the embodiment of the present invention, for example, in the embodiment shown in FIGS. 3 and 4 to be described later, an additional adhesive layer or the like is provided between the resin layer and the support plate. Adhesiveness is not required. In that case, the resin layer is preferably a film mainly composed of a thermoplastic resin. Here, the main component refers to a component that is contained in the largest amount among all the components, preferably a component that occupies 50% by mass or more, and more preferably a component that exhibits 80% by mass or more.

As the thermoplastic resin, a resin having high heat resistance and high transparency is preferable. For example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyphenylene sulfide resins, polyether sulfone resins, polyetherimide resins, polyimides Resin, polyamide resin, polyamideimide resin, polyether ether ketone resin, polycarbonate resin, fluorine resin, cyclic olefin resin such as cyclic olefin homopolymer and cyclic olefin copolymer.
Among the above thermoplastic resins, a transparent resin having a melting point of 230 ° C. or higher, for example, polyethylene terephthalate (melting point: about 260 ° C.), polyethylene naphthalate (melting point: about 270 ° C.), polyetherimide resin (melting point: about 275) ° C), polyphenylene sulfide resin (melting point approximately 280 ° C), polyethersulfone resin, polyether ether ketone resin (melting point approximately 334 ° C), polyimide resin (melting point approximately 350 ° C), tetrafluoroethylene / ethylene A resin such as a polymer (melting point: about 260 ° C.) is preferable from the viewpoint of optical properties and heat resistance, and polyethylene naphthalate, polyether ether ketone resin, and tetrafluoroethylene / ethylene copolymer are more preferable. Ether ketone resins are particularly preferred. Moreover, these resin can be used 1 type or in combination of 2 or more types.

  The resin film may be a resin obtained by curing a heat or active energy ray curable composition. Examples of such a resin include acrylic resin, urethane resin, epoxy resin, silicone resin, polyimide as a curing component. Examples thereof include resins obtained by curing curable compositions such as precursors. Among the above, preferred examples include a resin obtained by curing a curable composition such as a polyimide precursor, an acrylic resin, or a silicone resin as a curing component. Moreover, you may improve toughness by adding a rubber component to these.

The thickness of the resin layer is preferably 1 μm or more. 3 μm or more is more preferable, and 5 μm or more is particularly preferable. On the other hand, it is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 80 μm or less.
If the thickness of the resin layer is 1 μm or more, the handleability of the thin glass can be improved, and if the thickness is 200 μm or less, the increase in the thickness of the entire electronic device is suppressed, There is a tendency that the outgas generation amount can be suppressed.

(Heat resistance of resin layer)
The resin layer has heat resistance corresponding to the process and application such as the heating temperature during the formation process of the electronic device and the heat to which the electronic device such as organic EL lighting, organic EL display, and organic solar cell is practically exposed. Is desirable. As specific heat resistance, the 5% weight reduction temperature of the resin layer is preferably 230 ° C. or higher, more preferably 250 ° C. or higher, and further preferably 350 ° C. or higher. The heat resistance of the resin layer is determined by measuring the heat loss of the resin layer at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere of 50 mL / min using a thermal analyzer (for example, Thermoplus TG8120 manufactured by RIGAKU). The temperature at which 5% of the sample weight before measurement is taken as the 5% weight reduction temperature of the resin layer.
The heat resistance of the resin layer can be adjusted to the above range by adding transparent inorganic particles, organic particles with high heat resistance, fibrous substances such as glass and cellulose, crosslinking accelerators, etc. You may select suitably resin which has.

(Tensile breaking elongation of resin layer)
When the crack occurs in the thin glass, the resin layer preferably does not follow the crack of the thin glass and extends to some extent. Specifically, in the tensile strength test according to JIS-K-7127-1, the elongation at break (tensile elongation at break) is preferably 20% or more. 30% or more is more preferable, and 40% or more is particularly preferable.

(Tensile modulus of resin layer)
The resin layer desirably has a property of absorbing an impact applied to the thin glass. Specifically, in the tensile strength test according to JIS-K-7127-1, the tensile elastic modulus at 23 ° C. is preferably 10 GPa or less, more preferably 5 GPa or less, and particularly preferably 2 GPa or less. Further, since it is desirable to have a property to counteract the force to separate the broken cross section when a crack occurs in the thin glass, the tensile elastic modulus at 23 ° C. is preferably 0.01 MPa or more. 1 MPa or more is more preferable, and 1 MPa or more is particularly preferable.

(Adhesion between resin layer and thin glass)
Moreover, it is desirable that the resin layer is in close contact with the thin glass in a series of steps and practically after the electronic device is formed. Specifically, after forming the laminate according to the present embodiment, assuming a heat treatment process at the time of the electronic device formation process, the support plate is peeled off after heating for 60 minutes at 200 ° C. under vacuum using a vacuum dryer. When the cross-cut tape peeling test is performed on the resin surface of the resin / glass composite according to JIS DO202-1988, the resin layer does not peel 100/100, and the resin layer completely peels 0 / When expressed as 100, 30/100 or more is preferable. 40/100 or more is more preferable, and 50/100 or more is particularly preferable.

<Thin glass>
The thin glass used in the present embodiment can be laminated with a resin layer to form a resin / glass composite, and an electronic device can be formed on the surface opposite to the surface facing the resin layer.
As the thin glass used in the present embodiment, any appropriate glass can be adopted as long as it has a plate shape with a thickness of 100 μm or less. As materials, for example, almost all glass compositions such as soda lime glass, borosilicate glass, non-alkali glass, etc. can be applied, and those subjected to secondary processing such as tempering and surface treatment can also be applied. Can be used properly. As secondary processing, for example, coupling agent treatment with a silane coupling agent, titanium coupling agent, etc., chemical treatment such as acid treatment, alkali treatment, ozone treatment, ion treatment, plasma treatment, glow discharge treatment, arc discharge treatment, Various surface treatments such as discharge treatment such as corona treatment, ultraviolet ray treatment, X-ray treatment, gamma ray treatment, electromagnetic wave irradiation treatment such as laser treatment, and other surface treatment such as flame treatment can be given. In particular, the surface treatment with a silane coupling agent is preferred from the viewpoint of improving the adhesion with the resin layer.

In principle, a thin glass having a thickness of 100 μm or less can be produced by stretching the glass melt at a temperature higher than the temperature at which the glass melt solidifies. The thickness of the thin glass can be controlled by the glass composition, the thickness of the glass melt, the temperature, and the take-up speed.
The thickness of the thin glass may be 100 μm or less, preferably 1 μm or more and 100 μm or less, more preferably 10 μm or more and 100 μm or less, and further preferably 20 μm or more and 80 μm or less. If thickness is 1 micrometer or more, mechanical strength can be ensured and the damage by the stress by the thermal expansion / contraction of the laminated resin layer can be suppressed. On the other hand, when the thickness is 100 μm or less, it is effective to laminate a resin layer for the purpose of improving handling properties and secondary workability.

The average surface roughness of the thin glass surface is preferably 5 nm or less, more preferably 2 nm or less, and particularly preferably 1 nm or less.
If the average surface roughness of the thin glass is 5 nm or less, when an electronic device is formed on the surface of the thin glass, for example, a very thin (several tens of nm) conductive layer having a low surface resistance value can be formed. The laminate according to this embodiment can be suitably used as a substrate for an electronic device.
The average surface roughness (arithmetic average roughness (Sa)) can be measured using an optical interference type non-contact surface shape measuring instrument, and is measured, for example, as follows.
Surface observation (observation field of view: 93.97 μm × 71.30 μm) of the thin glass was performed using a non-contact surface / layer cross-section measurement system VertScan 2.0 (manufactured by Ryoka System Co., Ltd.). (Arithmetic mean roughness Sa) is calculated.

<Other layers>
The laminated body which concerns on this embodiment may also contain the other layer which does not inhibit the effect of this invention other than a support plate, a resin layer, and a sheet glass. Specifically, the resin layer on the side not facing the support plate when the resin / glass composite structure described above is resin / glass / resin can be mentioned. By providing the resin layer on the surface on the side that does not face the support plate of the thin glass, the handling property of the thin glass can be further improved compared to the case where the resin layer is only one layer, and when the support plate is peeled off Crack generation and crack propagation in the thin glass are further suppressed.

The thickness of the resin layer in this case is desirably the same as that of the resin layer provided on the surface of the thin glass facing the support plate. By providing a resin layer with the same thickness on both sides of the thin glass, the difference in the linear expansion coefficient between the thin glass and the resin layer, the distortion of the laminate due to the stress generated by the curing shrinkage of the resin layer, etc. Can be suppressed.
Moreover, the composition of the resin layer in this case can use the same composition as the resin layer with which the surface of the thin glass facing the support plate is provided. In particular, it is preferable to use the same material provided on the side of the thin glass facing the support plate because the above-described distortion is less likely to occur.

  An adhesive layer for adhering the support plate and the resin layer, or an adhesive layer for adhering the resin layer and the thin glass plate may be provided. As the adhesive layer in this case, the heat or active energy ray-curable composition described in the description of the resin layer can be used as appropriate, and preferably has heat resistance equivalent to that of the resin layer.

  A silane coupling agent may be added to the adhesive layer. The adhesive layer can be improved in adhesion to the support plate and the thin glass by adding a coupling agent.

Furthermore, as described in the following description of the laminate, it may have a release layer or an easily peelable adhesive layer.
Specific examples of the material constituting the release layer include a fluororesin, a silicone resin, a wax resin, and a release agent containing a surfactant. Among these, a release agent containing a fluororesin having high heat resistance, little component transfer to a thin glass or resin layer, and good release properties is more preferable.
Examples of the material constituting the easily peelable adhesive layer include the resin composition described in the description of the adhesive layer, and those obtained by adding a release component for adjusting the peel strength to the resin composition. Specific examples of the mold release component include a fluorine mold release additive, a surfactant, a silicone mold release additive, and the like. From the viewpoint of heat resistance, a fluorine mold release additive is preferable.

<Laminate>
As described above, the laminate according to the present embodiment is a laminate having a resin / glass composite on a support plate. And in at least one section when the laminate is cut in the laminating direction, the interface between the resin / glass composite and the support plate has an easily peelable portion and an adhesive portion having a peel strength larger than the easily peelable portion, The close contact portions are located at both ends of the easily peelable portion.
By making the laminate having such a configuration, the interface between the support plate and the resin / glass composite is easily peeled off by cutting in the laminating direction so as to remove the close contact portions present at both ends of the easily peelable portion. Thus, the support plate can be easily peeled off. Specific embodiments of the laminate having such a configuration will be described below with reference to the drawings.
In the present specification, the “interface between the resin / glass composite and the support plate” means the joint surface when the resin / glass composite and the support plate are in direct contact and laminated, In the case where the resin / glass composite and the support plate are laminated via another layer such as an adhesive layer, it means a bonding region between the resin / glass composite and the support plate. For example, in FIG. 2, a region between the thin glass 12 and the support plate 11, that is, a region where the resin layer 13 and the release layer 14 exist, a bonding surface between the thin glass 12 and the resin layer 13, and the support plate 11 The joint surface with the resin layer 13 and the release layer 14 is included.

  FIG. 2 is a schematic cross-sectional view illustrating a laminate according to an embodiment of the present invention. A laminate 10 shown in FIG. 2A has a resin / glass composite composed of a thin glass 12 and a resin layer 13 on a support plate 11. The laminate 10 has a release layer 14 at the interface between the resin layer 13 and the support plate 11. Since the release layer 14 is in close contact with the support plate 11 and exhibits good release properties with respect to the resin layer 13, the support plate can be easily peeled from the laminate. On the other hand, the release layer 14 is provided inside the both ends of the resin layer, that is, within the outer range of the resin layer. Therefore, a portion represented by a chain line 15 which is an interface where the release layer 14 does not exist is an adhesion portion having a high peel strength, and an interface where the release layer exists is an easy peel portion having a low peel strength. Therefore, the laminate 10 has a structure in which an easily peelable portion and a close contact portion are provided at the interface between the composite and the support plate 11 and the close contact portions are located at both ends of the easily peelable portion.

The release layer 14 is not particularly limited as long as it is in close contact with the support plate 11 and has releasability with respect to the resin layer 13. Therefore, an appropriate material is selected depending on the type of the resin layer 13 selected. However, since heat treatment is often performed in the formation process of the electronic device, it is preferable that heat denaturation and volatilization are not caused during heating.
Specific examples of the material constituting the release layer 14 include a fluorine resin, a silicone resin, a wax resin, and a release agent containing a surfactant. Among these, a release agent containing a fluorine-based resin that has high heat resistance, little component transfer to the thin glass 12 and good release properties is more preferable.

The thickness of the release layer 14 is not particularly limited as long as it can exhibit releasability with respect to the resin layer 13, but is usually 0.1 μm or more, preferably 5 μm or more, and usually 20 μm or less, preferably 10 μm or less.
When the thickness of the release layer 14 is 0.1 μm or more, effective release properties can be expressed, and when the thickness is 20 μm or less, surface smoothness can be ensured and generation of voids due to outgas can be suppressed. Tend.

FIG. 2B shows a laminated body 20 which is a modified example of the laminated body 10, and has a resin / glass composite comprising a thin glass plate 22 and a resin layer 23 on a support plate 21. The laminate 20 has a release layer 24 at the interface between the resin layer 23 and the support plate 21. Here, the laminated body according to the embodiment of the present invention peels the support plate by cutting in the laminating direction so as to remove the adhesion portion before or after placing the organic electronic device on the laminated body. And will be used. That is, it cut | disconnects along XX 'dashed-dotted line in FIG. In that case, in the laminated body 10 shown to Fig.2 (a), since the part which exists outside XX 'dashed-dotted line among the thin glass 12 becomes an unnecessary part, a yield is bad. On the other hand, in the laminate 20, the thin glass 22 is provided on the inner side of the outer shape range of the release layer 24, so there is no unnecessary portion or unnecessary portion when cut along the XX ′ dashed line. The yield is improved. Therefore, in the present invention, a mode in which the thin glass is provided on the inner side of the outer range of the easily peelable portion is preferable.

Hereinafter, other embodiments using a release layer will be described.
FIG. 3 is a schematic cross-sectional view illustrating a laminate according to an embodiment of the present invention. A laminated body 30 shown in FIG. 3A has a resin / glass composite composed of a thin glass 32 and a resin layer 33 on a support plate 31. The laminate 30 is different from the laminates 10 and 20 in that a separate adhesive layer 36 is provided at the interface between the resin layer 33 and the support plate 31. In addition, a release layer 34 is provided between the adhesive layer 36 and the support plate 31, and the release layer 34 is in close contact with the support plate 31 and exhibits good release properties with respect to the adhesive layer 36. In order to show, a support plate can be easily peeled from a laminated body. On the other hand, the release layer 34 is provided on the inner side than both ends of the resin layer 33 and the adhesive layer 36, that is, within the outer shape range of the resin layer. Therefore, a portion represented by a chain line 35 that is an interface where the release layer 34 does not exist is an adhesion portion having a high peel strength, and an interface where the release layer exists is an easy peel portion having a low peel strength. Therefore, the laminate 30 has a structure in which an easily peelable portion and a close contact portion are provided at the interface between the composite and the support plate 31 and the close contact portions are located at both ends of the easily peelable portion.

FIG. 3B shows a laminated body 40 which is a modified example of the laminated body 30, and has a resin / glass composite comprising a thin glass plate 42 and a resin layer 43 on a support plate 41. The laminated body 40 is different from the laminated body 30 in that a separate adhesive layer 46 is provided at the interface between the resin layer 43 and the support plate 41 and a release layer 44 is provided between the adhesive layer 46 and the resin layer 43.
Even if it is such a form, the mold release layer 44 is provided inside the both ends of the resin layer 43 and the contact bonding layer 46, ie, in the external range of the resin layer. Therefore, a portion represented by a chain line 45 which is an interface where the release layer 44 does not exist is an adhesion portion having a high peel strength, and an interface where the release layer exists is an easy peel portion having a low peel strength. Therefore, the laminate 40 has a structure in which an easily peelable portion and a close contact portion are provided at the interface between the composite and the support plate 41, and the close contact portions are located at both ends of the easily peelable portion.

Other embodiments that do not use a release layer are also possible and will be described below.
FIG. 4 is a schematic cross-sectional view illustrating a laminate according to an embodiment of the present invention. A laminated body 50 shown in FIG. 4A has a resin / glass composite composed of a thin glass 52 and a resin layer 53 on a support plate 51. Unlike the laminates 30 and 40, the laminate 50 has an easily peelable adhesive layer 57 at the interface between the resin layer 53 and the support plate 51. That is, the easily peelable adhesive layer exhibits a certain adhesiveness to the support plate 51 and the resin layer 53, while exhibiting a good releasability, so that the support plate can be easily peeled from the laminate. In addition, of the contact surface of the easily peelable adhesive layer 57 with the support plate 51, the portion indicated by hatching in the drawing is subjected to an adhesive treatment. Therefore, the part represented by the chain line 55, which is the interface subjected to the adhesion treatment shown by hatching in the figure, is an adhesive part having a high peel strength, and there is an easily peelable adhesive layer represented by the two-dot chain line 58 in the figure. The interface to be an easily peelable portion having low peel strength. Therefore, the laminate 50 has a structure in which an easily peelable portion and a close contact portion are provided at the interface between the composite and the support plate 51, and the close contact portions are located at both ends of the easily peelable portion.

  Examples of the adhesion treatment applied to the hatched portion of the easily peelable adhesive layer include corona treatment, ozone treatment, and silane coupling treatment on the easily peelable adhesive layer surface and the support plate surface. It is done. Moreover, you may perform an adhesion | attachment process using an adhesive agent.

FIG. 4B shows a laminated body 60 which is a modification of the laminated body 50, and has a resin / glass composite comprising a thin glass 62 and a resin layer 63 on a support plate 61. The laminated body 60 includes a resin layer 63.
In addition, an easily peelable adhesive layer 67 is provided at the interface between the support plate 61 and, in addition, of the contact surface of the easily peelable adhesive layer 67 with the resin layer 63, the portion indicated by hatching in FIG. It differs from the laminate 50 in that it is applied.
Even in such a form, a portion represented by a chain line 65 that is an interface subjected to the adhesion treatment shown by hatching in the figure becomes a close contact portion having a high peel strength, and is represented by a two-dot chain line 68 in the figure. The interface where the easily peelable adhesive layer exists is an easily peelable portion having a small peel strength. Therefore, the laminate 60 has a structure in which an easily peelable portion and a close contact portion are provided at the interface between the composite and the support plate 61, and the close contact portions are located at both ends of the easily peelable portion.

  FIG. 5 is a schematic cross-sectional view illustrating a laminate according to an embodiment of the present invention. A laminated body 70 shown in FIG. 5 has a resin / glass composite composed of a thin glass 72 and a resin layer 73 on a support plate 71. Here, unlike the resin layers 13 and 23 in FIG. 2, the resin layer 73 is an easily peelable resin layer and exhibits a good releasability from the support plate 71. It can be easily peeled off. In addition, of the contact surface between the resin layer 73 and the support plate 71, the portion indicated by hatching in the drawing is subjected to an adhesion treatment. Therefore, a portion represented by a chain line 75 which is an interface subjected to the adhesion treatment shown by hatching in the figure is a close adhesion portion having a high peel strength, and an interface where a resin layer represented by a two-dot chain line 78 is present in the figure is It becomes an easy peeling part with small peeling strength. Therefore, the laminated body 70 has a structure in which an easily peelable portion and a close contact portion are provided at the interface between the composite and the support plate 71, and the close contact portions are located at both ends of the easily peelable portion.

<Laminated body according to this embodiment>
In the embodiment shown in FIG. 2 among the laminates according to the present embodiment, a release layer, a resin layer, and a thin glass plate are provided in this order on the support plate surface, and a part of the resin layer is a support plate. It is a laminate that is in direct contact.
Since the laminate shown in FIG. 2 has high strength and excellent handling properties, it is not damaged even in the process of forming an electronic device, and after the process, within the outer range of the release layer, a thin glass and a resin layer, or By cutting only the resin layer, or thin glass and resin layers, as well as the release layer and support plate, the part of the resin layer that is in direct contact with the support plate, that is, the close contact part, is cut off to form an electronic device on the surface. The laminated body of the thin glass plate and the resin layer can be easily peeled from the support plate. Moreover, the laminated body which concerns on this embodiment may be further equipped with the resin layer on the opposite surface to the resin layer side surface of thin glass.

(Peel strength of close contact and easy peel)
The laminate according to this embodiment has an easily peelable portion and a close contact portion at the interface between the composite and the support plate, and the close contact portion has a peel strength higher than that of the easily peelable portion.
The difference between the peel strength at the close contact portion and the peel strength at the easy peel portion of the laminate according to this embodiment is not limited, but is preferably 0.5 N / 25 mm or more. 1N / 25mm or more is more preferable, and 2N / 25mm or more is particularly preferable.
If the difference between the peel strength at the close contact portion and the peel strength at the easy peel portion is 0.5 N / 25 mm or more, the support plate does not peel off in the device formation step, and after the device formation step, the support plate is removed from the laminate. This is preferable because it can be easily peeled off.

The peel strength of the easily peelable portion is preferably such that the support plate can be easily peeled from the laminate when the close contact portion is removed, and is usually 0.5 N / 25 mm or less and 0.4 N / 25 mm or less. It is preferable that it is 0.3 N / 25 mm or less. Although a minimum is not specifically limited, It is preferable that it is 0.01 N / 25mm or more.
On the other hand, the peel strength at the close contact portion is preferably such a peel strength that the support plate does not peel in the device formation step. The specific numerical value is not particularly limited because it can be dealt with by selecting a suitable structure if the peel strength is higher than the easily peelable portion, but preferably 0.5 N / 25 mm or more, It is preferably 1.0 N / 25 mm or more, and more preferably 2.0 N / 25 mm or more. The upper limit is not particularly limited, but a peel strength that does not allow the composite to peel in the peel test is preferable.
The peel strength can be measured by a 90-degree peel test in accordance with JIS K 6854-1, and is measured by, for example, the method described in the section of Examples.

(Lamination relationship between support plate and resin layer)
Regarding the relationship between the support plate and the resin layer according to the present embodiment, the resin layer is preferably provided within the outer range of the support plate, and more preferably provided inside the outer range. By satisfying such a relationship, it is possible to improve transportability when forming an electronic device.

(Lamination relationship between release layer and resin layer)
In the embodiment shown in FIG. 2 among the laminates according to this embodiment, the relationship between the release layer and the resin layer is such that a part of the resin layer is in direct contact with the support plate and is cut in the lamination direction of the laminate. In at least one cross section at the time, the both end portions of the resin layer are located outside the both end portions of the release layer. By satisfying such a relationship, the resin layer and the thin glass are not peeled off from the support plate in the electronic device forming step, and after the forming step, the thin glass and the resin layer within the outer range of the release layer, or In addition to the resin layer, or in addition to the thin glass or resin layer, the release layer and the support plate can be cut to easily peel from the support plate.
In addition, in the electronic device manufacturing process, from the viewpoint of improving the adhesion between the support plate and the resin layer, the release layer is preferably provided within the outer range of the resin layer. More preferably, it is provided inside.
The release layer and the resin layer are not particularly limited as long as the above relationship is satisfied. For example, an embodiment having a stacking relationship as shown in FIGS. . Among these, in the embodiment of FIG. 1 (a), the release layer that forms the easily peelable portion is provided inside the outer shape range of the resin layer. It becomes an enclosed form.

(Lamination relationship between resin layer and thin glass)
Although the relationship between the resin layer and the thin glass according to the present embodiment is not particularly limited, it is preferable that the thin glass is provided within the outer range of the resin layer. By satisfying such a relationship, since the resin layer is laminated on the entire surface of one surface of the thin glass, the step of forming the electronic device, the step of cutting the laminate according to the present embodiment, and the support plate after peeling In the handling of the resin / glass composite, cracking and breakage of the thin glass can be further suppressed.
Further, from the viewpoint of handling when the support plate is peeled off, it is more preferable that the thin glass plate is provided inside the outer range of the resin layer. Among them, the outer range of the resin layer is large enough to grip the end of the resin layer with respect to the outer range of the thin glass, and when the adhesion strength between the support plate and the resin layer is peeled off, It is particularly preferable that the cohesive failure does not occur in the resin layer, since it can be peeled from the support plate without damaging the thin plate glass by gripping the end of the resin layer and applying a tensile stress.
Moreover, the shape which a resin layer covers to the side surface of a sheet glass may be sufficient like FIG.2 (b). In this case, an effect of preventing the thin glass from cracking against an impact from the side surface can be expected.

(Lamination relationship between release layer and thin glass)
As for the relationship between the release layer and the thin glass according to the present embodiment, it is preferable that the thin glass is provided inside the outer shape range of the release layer as shown in FIG. By satisfying such a relationship, after the formation process of the electronic device, only the resin layer within the outer shape range of the release layer and outside the outer shape range of the thin glass, or in addition to the resin layer, the release layer and By cutting the support plate, the portion of the resin layer bonded to the support plate can be separated, and the resin / glass composite can be easily peeled from the support plate.

<Resin / Glass Composite>
Another embodiment of the present invention is a resin / glass composite obtained by peeling a support plate from the laminate described above, and organic electronic devices such as organic EL lighting, organic EL display devices, and organic solar cells. It can be used as a substrate.
In addition, since the resin layer is laminated on the thin glass, handling and handling are improved as compared with the thin glass alone, and the occurrence of defects during secondary processing of the created electronic device is suppressed.

The resin / glass composite is not particularly limited as long as the resin / glass composite has light transmittance according to the application, but it is usually preferable that the total light transmittance is 80% or more. It is more preferably 85% or more, and particularly preferably 90% or more.
If the total light transmittance is 80% or more, good light transmittance is exhibited, and therefore, it can be suitably used as a substrate of a light emitting device such as an organic EL illumination or an organic EL display device.
The total light transmittance can be measured by a method based on JIS K 7361 using a transmittance meter (for example, “HR-100” manufactured by Murakami Color Research Laboratory).

  The thickness of the resin / glass composite is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less from the viewpoint of flexibility. Further, it is usually preferably 10 μm or more, more preferably 30 μm or more, and particularly preferably 50 μm or more.

<The manufacturing method of the laminated body which concerns on this embodiment>
The method for manufacturing a laminate according to the present embodiment includes a resin / glass composite including a resin layer and a thin glass on the support plate in this order, and an easily peelable portion and the interface at the interface between the composite and the support plate. It will not specifically limit if the laminated body in which an adhesion part is located in the both ends of an easily peelable part can be manufactured. Taking the configuration of FIG. 2A as an example, specifically, a support plate is prepared, and a release layer, a resin layer, and a thin glass plate are sequentially laminated on the surface thereof, whereby the laminate according to the present embodiment. Is obtained. Hereinafter, an embodiment of a method for manufacturing a laminate according to this embodiment will be described in more detail.

Examples of the method for laminating the release layer on the surface of the support plate include a direct coating method and a transfer method using a transfer film.
In the direct coating method, specifically, a coating composition containing at least a resin for forming a release layer, an additive, and a solvent is prepared, and the composition is coated with a die coater, a bar coater, a spin coater, a Mayer bar, This is a method of applying to a support plate by a method such as air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, dip coating or spray coating.
As the solvent, an organic solvent is usually used, and is appropriately selected depending on the type of resin contained in the release layer.
In addition, after application | coating, you may include the process of removing a solvent as needed, and the process of hardening a release layer.
In the case of the direct coating method, the coating speed, the discharge amount, etc. are not particularly limited and can be appropriately adjusted depending on the composition of the resin contained in the release layer and the thickness of the release layer.

  The transfer method using a transfer film is a method in which a transfer film having a release layer laminated on a support film is transferred with the release layer side surface facing the support plate surface, and then the support film is peeled off.

  The resin layer is provided within the outer range of the support plate, a part of the resin layer is in direct contact with the support plate, and at least in one section when the laminate is cut in the stacking direction, In order to satisfy the relationship in which both ends of the resin layer are located outside the both ends, for example, a masking tape is applied to a part of the surface of the support plate, a release layer is formed thereon, and then the masking tape is peeled off. A process may be included.

Examples of the method for laminating the resin layer on the support plate and the release layer include the direct coating method and the transfer method.
The resin composition for forming the resin layer has a mold release within at least one cross section when a part of the resin layer is in direct contact with the support plate and the laminate is cut in the stacking direction within the outer range of the support plate. The resin layer is laminated so that both end portions of the resin layer are located outside the both end portions of the layer. At this time, if necessary, the stacking range may be controlled using the masking tape.
Moreover, the process of removing the solvent contained in the resin composition which forms a resin layer as needed, and the process of hardening the curable composition contained in a resin layer after laminating | stacking thin glass on a resin layer are included. But you can.

  As a method of laminating the thin glass within the outer range of the resin layer, a method in which the thin glass is left on the resin layer so as not to have a gap, and an adhesive film is placed on the opposite side of the surface of the thin glass in contact with the resin layer. There is a method of laminating the adhesive film on the resin layer from the end using a roller while applying a tensile stress so that the thin glass is not bent after being bonded to each other.

Further, in the embodiment of FIG. 4 (a), the end of the surface of the support plate facing the easily peelable adhesive layer, and in the embodiment of FIG. 4 (b), facing the easily peelable adhesive layer of the resin layer. After performing the adhesion treatment on the edge of the surface to be performed, an easily peelable adhesive layer is laminated on the support plate by the method described above. Then, a laminated body can be manufactured by laminating | stacking a resin layer and a sheet glass in order.
Examples of the adhesion treatment include corona treatment, ozone treatment, and silane coupling treatment. Moreover, you may perform an adhesion | attachment process using a well-known adhesive agent.

<Method for producing resin / glass composite>
The method for producing the resin / glass composite is not particularly limited as long as the resin / glass composite can be peeled off from the laminate according to the present embodiment. Usually, an electron is formed on the laminate according to the present embodiment. Peel after forming the device.
Specifically, in the laminate according to the present embodiment shown in FIG. 2, for example, along the XX ′ dashed line, the resin layer and the thin glass, or the resin layer alone, or the thin plate, within the range of the release layer A resin / glass composite can be obtained by cutting the release plate and the support plate in addition to glass and the resin layer, and then peeling the support plate at the interface between the release layer and the resin layer. Hereinafter, an embodiment of a method for producing a resin / glass composite will be described in more detail.

In the laminate according to the present embodiment shown in FIG. 2, the support plate and the thin glass are bonded via a portion in direct contact with the support plate of the resin layer. For this reason, the resin / glass composite can be peeled off from the support plate by separating the portion of the resin layer that is in direct contact with the support plate and peeling off at the interface between the release layer and the resin layer.
When the release layer is within the outer shape range of the thin glass, cut within the outer shape range of the release layer and within the outer shape range of the thin glass, that is, the thin glass and the resin layer, or the thin glass and the resin layer. In addition, the resin / glass composite can be peeled by cutting the release layer and the support plate.
When the thin glass is provided inside the outer shape range of the release layer, the outer shape range of the release glass and the outer side of the outer shape range of the thin glass are cut, that is, only the resin layer or the resin layer. In addition, the resin / glass composite can be peeled by cutting the release layer and the support plate. However, in this case, in addition to the thin glass and the resin layer, or the thin glass and the resin layer, the release layer and the support plate may be cut to peel the resin / glass composite.

(Cutting method)
The method of cutting the release layer and the support plate in addition to the resin layer and thin glass, or the thin glass and resin layer is not particularly limited as long as each layer can be cut, but the surface is cut using a blade such as router processing. Method, scratching the glass surface, then cutting the glass by external stress (scribe method), then cutting the resin by another method, water jet method cutting by high pressure water flow, absorption wavelength region of thin glass A method using a CO ₂ laser or a UV laser having a wavelength is used.
Among these, since the release layer and the support plate can be simultaneously cut in addition to the resin layer and the thin glass or the thin glass and the resin layer, a method of cutting the surface, a water jet method, and a method using a laser are preferable. A method using a laser is particularly preferable because cracks are unlikely to occur on the surface.
In the method using a CO ₂ laser, a laser scribing method is also used in which a glass end face is scratched and the laser is irradiated without being converged to cut by thermal stress. At this time, the resin is cut by melting or evaporation by laser absorption.

  The method of cutting only the resin layer is not particularly limited because it is not necessary to consider the state of the cut surface. For example, in addition to the above cutting method, a method of physically cutting using a sharp blade is used. It is done.

(Support plate peeling method)
The method of peeling the support plate is not particularly limited as long as the support plate can be peeled at the interface between the release layer and the resin layer. For example, after cutting each layer, a sharp blade shape at the interface between the release layer and the resin layer is used. There is a method of separating after inserting the thing, giving a trigger for peeling, and a method of fixing the support plate side and the thin glass laminate side of this laminate to a surface plate etc. by vacuum suction and separating them by pulling them apart It is done.

As described above, the outer range of the resin layer is large enough to grip the edge of the resin layer with respect to the outer range of the thin glass, and the adhesion strength between the support plate and the resin layer peels off the support plate and the resin layer. When the cohesive failure does not occur in the resin layer, it can be peeled from the support plate without damaging the thin glass by gripping the end of the resin layer and applying a tensile stress. .
Although the embodiment shown in FIG. 2 has been described as a specific example for the method for producing the resin / glass composite, the description of the embodiment shown in FIG. 2 can be applied to other embodiments.

As described above, as another embodiment of the present invention, the laminate according to this embodiment described above is cut in the stacking direction so as to remove the adhesion portion, and the support plate is peeled from the stack. A resin / glass composite comprising the steps.
When the organic electronic device is mounted on the laminate, another embodiment of the present invention includes cutting the laminate according to the present embodiment in the stacking direction so as to remove the adhesion portion, and And a step of peeling the support plate from the laminate.

<Application>
The laminated body which concerns on this embodiment can be used as a board | substrate at the time of producing organic electronic devices, such as an organic electroluminescent element and an organic photoelectric conversion element, for example. Furthermore, an organic EL illumination and an organic EL display device can be obtained by using the organic electroluminescence element, and an organic solar cell module can be obtained by using an organic photoelectric conversion element. is not.

(Organic electroluminescence device)
It is an organic electroluminescent element (it is also called an organic EL element and an organic electroluminescent element) obtained by using the laminated body which concerns on this embodiment as a board | substrate at the time of preparation.

  The laminate according to the present embodiment has high strength, excellent handling properties, and the resin / glass composite and the support plate do not peel off even in the electronic device formation process, so that it is suitable as a substrate for forming an organic EL element. Can be used. After the element formation, the resin / glass composite having the organic EL element formed on the surface can be obtained by peeling the support plate.

  An organic EL element has a cathode and an anode, and has an organic compound layer including a light emitting layer between both electrodes. Due to the nature of the light emitting element, at least one of the anode and the cathode is transparent.

  As an aspect of lamination of the organic compound layer, for example, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Further, the light emitting layer may be a single layer, or the light emitting layer may be divided into a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers.

[anode]
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. The anode is usually provided as a transparent anode. The transparent anode is described in detail in Yutaka Sawada's “New Development of Transparent Electrode Film” published by CMC (1999). When using a plastic substrate having low heat resistance as the substrate, a transparent anode formed using a transparent conductive material such as ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

[cathode]
The cathode usually only has to have a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc. It can select suitably from well-known electrode materials.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, lithium-aluminum alloys, magnesium-silver alloys, rare earth metals such as indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

  Among these, as a material constituting the cathode, a material mainly composed of aluminum is preferable. The material mainly composed of aluminum refers to aluminum alone or an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a Group 2 metal (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.). The cathode material is described in detail in JP-A-2-15595 and JP-A-5-121172. Moreover, you may insert the dielectric material layer by the thickness of 0.1-5 nm between the cathode and the organic compound layer by the fluoride, oxide, etc. of an alkali metal or 2 group metals. This dielectric layer can also be regarded as a kind of electron injection layer.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode. Usually, it is about 10 nm-5 micrometers, and 50 nm-1 micrometer are preferable. Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

[Light emitting layer]
The organic EL element has at least one organic compound layer including a light emitting layer. As the organic compound layer other than the light emitting layer, as described above, a hole transport layer, an electron transport layer, a charge block layer, a hole Examples thereof include an injection layer and an electron injection layer.

  The light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer and receives electrons from the cathode, the electron injection layer, or the electron transport layer when an electric field is applied, and recombines holes and electrons. It is a layer having a function of providing a field to emit light. The light emitting layer may be composed of only the light emitting material, or may be a mixed layer of the host material and the light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of the fluorescent light-emitting material include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatics. Compound, perinone derivative, oxadiazole derivative, oxazine derivative, aldazine derivative, pyralidine derivative, cyclopentadiene derivative, bisstyrylanthracene derivative, quinacridone derivative, pyrrolopyridine derivative, thiadiazolopyridine derivative, cyclopentadiene derivative, styrylamine derivative, di Typical examples include ketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives. Various metal complexes are, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

  Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom. Although it does not specifically limit as said transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum. Examples of the lanthanoid atom include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

Examples of the ligand of the complex include “Comprehensive Coordination Chemistry” (Pergamon Press, published in 1987, G. Wilkinson et al.), “Photochemistry and Photophysics of Coordination Compounds” (Springer-Verlag, published in 1987, H. By Yersin),
“Organometallic Chemistry-Fundamentals and Applications” (Takahafusa, published in 1982, Akio Yamamoto) and the like.

  Examples of the host material contained in the light emitting layer include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton. And materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.

[Hole injection layer, hole transport layer]
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.

[Electron injection layer, electron transport layer]
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

[Hole blocking layer]
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. As the organic compound layer adjacent to the light emitting layer on the cathode side, a hole blocking layer can be provided. In addition, the electron transport layer / electron injection layer may also function as a hole blocking layer. Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like. In addition, a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side can be provided at a position adjacent to the light emitting layer on the anode side. The hole transport layer / hole injection layer may also serve this function.

[Method of manufacturing organic EL element]
In order to use the laminated body according to the present embodiment as a substrate for forming such an organic EL element, a known method may be used.

[Uses of organic EL elements]
The organic EL element can be used as an organic EL module, for example. There are no particular restrictions on the type or structure, but for example, a plurality of holes may be arranged in parallel in the crossing direction (usually the orthogonal direction) of the hole transport layer, light emitting layer, hole injection layer, etc. Can do.

The organic EL element can also be used as an organic EL display device or organic EL illumination. There is no restriction | limiting in particular about the type and structure of an organic electroluminescent display apparatus and organic electroluminescent illumination, It can assemble according to a conventional method.
If it is an organic EL display device, for example, it is a method as described in “Organic EL display” (Ohm Co., Ltd., issued on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) An organic EL display device using the organic EL element can be formed.

(Organic photoelectric conversion element)
It is an organic photoelectric conversion element obtained by using the laminated body which concerns on this embodiment as a board | substrate at the time of preparation.

  The laminate according to the present embodiment has high strength, excellent handling properties, and the resin / glass composite does not peel off even in the formation process of the electronic device. Therefore, the laminate is preferably used as a substrate when forming an organic photoelectric conversion element. Can do. After the element formation, the support plate is peeled to obtain a resin / glass composite having an organic photoelectric conversion element formed on the surface.

  The organic photoelectric conversion element is basically composed of a pair of electrodes, at least one of which is transparent or translucent, and a single layer composed of an organic thin film in the case of a bulk heterojunction type disposed between the pair of electrodes. In the case of a heterojunction type, it has a laminated structure including two active layers made of an organic thin film.

  About an electrode, an active layer, and another component which comprise an organic photoelectric conversion element, it selects from a well-known material suitably, and can form an organic photoelectric conversion element with a well-known manufacturing method.

[Uses of organic photoelectric conversion elements]
This organic photoelectric conversion element can be used as an organic solar cell module, for example. There is no restriction | limiting in particular about the model and structure of an organic solar cell module, It can assemble according to a conventional method.

<Explanation of terms>
In this specification, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), “preferably greater than X” or “preferably less than Y”. The intention of the effect is also included.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to description to a following example.

<Evaluation>
(Tensile elastic modulus and tensile elongation at break of resin layer)
About the resin composition which comprises the resin layer obtained by the Example and the comparative example, the tensile elasticity modulus and tensile breaking elongation in 23 degreeC were measured in the tensile strength test based on JIS-K-7127-1. The tensile elastic modulus and tensile elongation at break of the resin layer were used.

(Heat resistance of resin layer and adhesive layer)
About the resin composition which comprises the resin layer and adhesive layer which were obtained in the Example and the comparative example, 5% weight reduction | decrease temperature was measured as follows.
Using RIGAKU Thermo plus TG8120, nitrogen 50 mL / mi
In a n atmosphere, the heat loss was measured for the resin composition constituting the resin layer and the adhesive layer at a heating rate of 20 ° C./min, and the temperature at which the heat loss became 5% of the sample weight before measurement was measured for the resin layer and the adhesive layer. The 5% weight loss temperature was set.

(Cleaning test and heat treatment test)
For the laminates obtained in the examples and comparative examples, an ultrasonic wave is output to 8.9 W / L in a hot water bath heated to 60 ° C., assuming a substrate cleaning step and a heat treatment step in the electronic device formation step. Then, after removing the water by removing it for 3 minutes, it was heated for 60 minutes at 200 ° C. under vacuum using a vacuum dryer, then cooled to room temperature, and the appearance of the laminate was observed.
When peeling occurs at the interface between the support plate and the resin layer, “X” is indicated. When no peeling occurs, “
○ ”.

(Peelability evaluation after cleaning test and heat treatment test)
About the laminated body obtained by the Example, after performing the said washing | cleaning test and heat processing test, only the thin glass and the resin layer, or the resin layer was cut | disconnected, and the peelability of the thin glass laminated body was evaluated.
When it was able to peel at the interface of a support plate and a resin layer, it was set as "(circle)", and when it was not able to peel, it was set as "*".

(Adhesion evaluation of thin glass and resin layer after washing test and heat treatment test)
About the laminated body obtained by the Example, after performing the said washing | cleaning test and heat processing test, a support plate is peeled, and it is based on JIS DO202-1988 with respect to the resin surface of the obtained thin glass laminated body. An eye tape peeling test was conducted to evaluate the adhesion between the thin glass and the resin layer. The case where the resin layer did not peel was 100/100, and the case where it completely peeled was 0/100.

(Peel strength evaluation)
For peel strength evaluation, the peel strength by 90-degree peel according to JIS K 6854-1 was measured. However, since the thin glass breaks when bent at 90 degrees when measured in a state where the thin glass is laminated, the following alternative evaluation was performed.
On the resin layer, a test piece (25 mm in width) having the same configuration as the easily peelable portion and the close contact portion in each Example and Comparative Example, except that the thin glass and the adhesive layer between the thin glass and the resin layer are not formed. Created separately.
About the said test piece, peeling strength was measured by peeling the resin layer 90 degree | times from a support plate, and it was set as peeling strength of an easily peelable part and an adhesion part. The measurement was performed under the conditions of 23 ° C. and a peeling rate of 50 mm / min.
When the resin layer broke during the 90-degree peel test, the maximum load until the resin layer broke was read, and the value divided by the width of 25 mm was taken as the peel strength.

[Example 1]
As a support plate, a glass plate (plate thickness 0.2 mm, manufactured by Asahi Glass Co., Ltd., trade name “AN100”) made of alkali-free borosilicate glass is used, and a masking film is used on the glass plate, and a fluorine-based resin is included. A release agent (trade name “Daifree GA-3000”, manufactured by Daikin Industries, Ltd.) was sprayed uniformly 1 cm inside from each side of the support plate, that is, 13 cm square. Thereafter, the masking film was peeled off, heated in an oven set at 200 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a release layer.
Thereafter, UV and thermosetting epoxy resin (trade name “ADEKA OPTOMER KRX-690-5” manufactured by ADEKA Co., Ltd.) was applied to the entire surface of the support plate as the adhesive layer so that the thickness after curing was 5 μm. Further, as a resin layer, a polyether ether ketone film (trade name “SUPERIO PK”, manufactured by Mitsubishi Plastics Co., Ltd., thickness: 6 μm, size 15 cm square) was covered on the entire surface of the support plate so as to be free of bubbles. Further, a high-pressure mercury lamp (160 W / cm) was irradiated from the support plate side, and these were heated in an oven at 150 ° C. for 60 minutes to cure the adhesive layer. After that, UV and thermosetting epoxy resin (made by ADEKA Co., Ltd., trade name “ADEKA OPTMER KRX-690-5”) is cured on the entire surface of the resin layer as an adhesive layer between the resin layer and the thin glass. The coating was applied so that the subsequent thickness was 5 μm, and a thin plate glass (manufactured by Nippon Electric Glass Co., Ltd., trade name “OA-10G”, thickness: 50 μm, size 10 cm square) was put on the center of the support plate so as not to have bubbles. Furthermore, after irradiating a high pressure mercury lamp (160 W / cm) from the thin glass side, these were heated and cured in an oven at 150 ° C. for 60 minutes to obtain a laminate.
The resin layer had a tensile elastic modulus at 23 ° C. of 2.4 GPa and a tensile elongation at break of 120%.
Each evaluation was implemented about the obtained laminated body. The results are shown in Table 1.
In the peel strength evaluation of the close contact portion, the resin layer was broken because the adhesiveness between the resin layer and the support plate was high, and the resin layer was broken. The maximum load until the resin layer broke was 1.2 N, and the peel strength was 1.2 N / 25 mm.

In the evaluation of peelability after the cleaning test and the heat treatment test, an output of 150 mW, a pulse frequency of 10 KHz, a current value of 63%, and a scanning speed of 20 mm / s using a UV laser system (Takano Co., Ltd., UV LASER SYSTEM “UVTS”). , After cutting the thin glass, the adhesive layer, the resin layer, and the adhesive layer on the inner side of 0.5 cm from each side of the thin glass under the condition of 60 shots, the peeling trigger using the feather blade The resin / glass composite was carefully peeled from the support plate.
The 5% weight reduction temperature of the cured product of ultraviolet and thermosetting resin used as the adhesive layer in this example was 370 ° C., and the 5% weight reduction temperature of the resin layer was 550 ° C.

[Example 2]
Using the same support plate as in Example 1, using a masking film thereon, a surfactant (triclosan, water, sodium laureth sulfate, lauryl ether, POE lauryl ether acetic acid, concentrated glycerin, polyglyceryl laurate) as a release agent , Trimethylammoniohydroxypropylhydroxyethylcellulose chloride, DL-malic acid, benzoate, edetate, sodium hydroxide solution, etc. mixed solution made by Kao Corporation, trade name “Biore u Foam Hand Soap”) It was uniformly applied 1.5 cm inside from the side, that is, in a range of 12 cm square, left to stand for 1 minute, and then the excess release agent was removed using an air gun. Then, it was heated in an oven set at 80 ° C. for 1 minute, allowed to cool to room temperature, and then the masking film was peeled off to obtain a release layer.
Next, a thermosetting silicone rubber (manufactured by Momentive Co., Ltd., a thermosetting composition in which trade names “LSR-7090A” and “LSR-7090B” are mixed in an equal amount), the same size as the support plate, 15 cm square, Apply the coating to a thickness of 5 μm, and then apply a polyether ether ketone film (trade name “SUPERIO PK”, thickness: 6 μm, size 15 cm square, manufactured by Mitsubishi Plastics, Inc.) as a resin layer so that there are no bubbles on the entire surface of the support plate. I covered it. These were heated in an oven at 150 ° C. for 60 minutes to cure the thermosetting silicone rubber, thereby forming an adhesive layer. Thereafter, the same thermosetting silicone rubber as described above was applied to the same size of 15 cm square as the support plate and the thickness after curing was 5 μm, and further thin glass (made by Nippon Electric Glass Co., Ltd., trade name “OA-10G”) , Thickness: 50 μm, size 10 cm square) so as to be free of bubbles. These were heated in an oven at 150 ° C. for 60 minutes to cure the thermosetting silicone rubber, thereby forming an adhesive layer to obtain a laminate.
Each evaluation was implemented about the obtained laminated body. The results are shown in Table 1.

In the evaluation of peelability after the cleaning test and the heat treatment test, the NTA cutter was used to cut the adhesive layer, the resin layer, and the adhesive layer on the outer side of the 1.0 mm from each side of the thin glass, and then feather. The blade was used to create a trigger for peeling, and the resin / glass composite was carefully peeled from the support plate.
The 5% weight reduction temperature of the cured product of the thermosetting silicone rubber used in this example was 375 ° C.

[Example 3]
After forming a laminated body using the same method as in Example 1, ultraviolet and thermosetting epoxy resin (trade name “Adekaoptomer KRX-, manufactured by ADEKA Corporation) was formed on the surface of the thin glass side of the laminated body. 690-5 ") at the same position and in the same area as the thin glass so that the thickness after curing is 5 μm, and further irradiated with a high-pressure mercury lamp (160 W / cm) from the coating side, and these are applied to a 150 ° C. oven. The same resin as the adhesive layer was laminated by heating and curing for 60 minutes, and a laminate having a composite in which the resin was laminated on both surfaces of a thin glass plate was obtained.
Each evaluation was implemented about the obtained laminated body. The results are shown in Table 1.
In the peelability evaluation after the cleaning test and the heat treatment test, the same method as in Example 1 was performed.
In the peel strength evaluation of the close contact portion, the resin layer was broken because the adhesiveness between the resin layer and the support plate was high, and the resin layer was broken. The maximum load until the resin layer broke was 1.2 N, and the peel strength was 1.2 N / 25 mm.

[Example 4]
As a support plate, a glass plate (plate thickness 0.2 mm, manufactured by Asahi Glass Co., Ltd., trade name “AN100”) made of alkali-free borosilicate glass is used, and a masking film is used on the glass plate, and a fluorine-based resin is included. A release agent (trade name “Daifree GA-3000”, manufactured by Daikin Industries, Ltd.) was sprayed uniformly 1 cm inside from each side of the support plate, that is, 13 cm square. Thereafter, the masking film was peeled off, heated in an oven set at 200 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a release layer.
Thereafter, UV and thermosetting epoxy resin (trade name “ADEKA OPTOMER KRX-690-5” manufactured by ADEKA Co., Ltd.) was applied to the entire surface of the support plate as the adhesive layer so that the thickness after curing was 5 μm. Further, a PEN film (trade name “Teonex Q51”, manufactured by Teijin Ltd., thickness: 12 μm, size 15 cm square) as a resin layer was covered on the entire surface of the support plate so as to be free of bubbles. Further, a high-pressure mercury lamp (160 W / cm) was irradiated from the support plate side, and these were heated in an oven at 150 ° C. for 60 minutes to cure the adhesive layer. After that, UV and thermosetting epoxy resin (made by ADEKA Co., Ltd., trade name “ADEKA OPTMER KRX-690-5”) is cured on the entire surface of the resin layer as an adhesive layer between the resin layer and the thin glass. The coating was applied so that the subsequent thickness was 5 μm, and a thin plate glass (manufactured by Nippon Electric Glass Co., Ltd., trade name “OA-10G”, thickness: 50 μm, size 10 cm square) was put on the center of the support plate so as not to have bubbles. Furthermore, after irradiating the high pressure mercury lamp (160 W / cm) from the thin glass side, these were heated for 60 minutes in 150 degreeC oven, and the laminated body was obtained by hardening an adhesive layer.
The tensile modulus at 23 ° C. of the resin layer was 5.9 GPa, and the tensile elongation at break was 85%. The 5% weight reduction temperature of the resin layer was 350 ° C. or higher.
Each evaluation was implemented about the obtained laminated body. The results are shown in Table 1.
In the peel strength evaluation of the close contact portion, the resin layer was broken because the adhesiveness between the resin layer and the support plate was high, and the resin layer was broken. The maximum load until the resin layer broke was 1.8 N, and the peel strength was 1.8 N / 25 mm.

[Example 5]
Using the same material as in Example 1, a laminate was produced by the following method.
The resin layer was cut into a 15 cm square size. A release agent was applied to the surface of the resin layer using a screen printer in the range of 13 cm square at the center of the resin layer. Thereafter, the resin layer was heated in an oven at 150 ° C. for 30 minutes and allowed to cool to room temperature to obtain a resin layer with a release layer.
Then, using a 15 cm square support plate, UV and thermosetting epoxy resin as an adhesive layer was applied to the entire surface of the support plate so that the thickness after curing was 5 μm, and the resin layer with a release layer prepared earlier was The release layer side is directed to the support plate side, the center of the release layer is overlapped with the center of the support plate and covered with no bubbles, and further irradiated with a high-pressure mercury lamp (160 W / cm) from the support plate side, These were heated in an oven at 150 ° C. for 60 minutes to cure the adhesive layer. Thereafter, UV and thermosetting epoxy resin is again applied to the entire surface of the resin layer as an adhesive layer between the resin layer and the thin glass so that the thickness after curing is 5 μm. Then, after irradiating a high-pressure mercury lamp (160 W / cm) from the thin glass side, these were heated in an oven at 150 ° C. for 60 minutes to cure the adhesive layer, thereby obtaining a laminate.
Each evaluation was implemented about the obtained laminated body. The results are shown in Table 1.
In the evaluation of the peel strength at the close contact portion, the resin layer and the adhesive layer, and the adhesive layer and the support plate were both highly adhesive, so that the resin layer was broken. The maximum load until the resin layer broke was 1.2 N, and the peel strength was 1.2 N / 25 mm.

  In the peelability evaluation after the cleaning test and the heat treatment test, the thin glass, the adhesive layer, the resin layer, and the adhesive layer were cut from the sides of the thin glass to the inner side of 0.5 cm by the same method as in Example 1. After the treatment, a peeling edge was created using a feather blade, and the resin / glass composite was carefully peeled from the support plate.

[Example 6]
After using a 15 cm square glass plate made of alkali-free borosilicate glass (plate thickness 0.2 mm, manufactured by Asahi Glass Co., Ltd., trade name “AN100”) as the support plate, after masking the central portion 14 cm with an aluminum plate Then, using an ozone cleaning device (PHOTO SURFACE PROCESSOR model “PM908N-5” manufactured by Sen Special Light Source Co., Ltd.), only the end portion of the support plate was subjected to adhesion treatment under the condition of an irradiation time of 200 seconds.
Thereafter, UV and thermosetting epoxy resin (manufactured by ADEKA Co., Ltd., trade name “Adekaoptomer KRX-690-5”) 99.7% as an adhesive layer, fluorine internal release agent (Daikin Industries, Ltd.) Product name “Die Free FB-962”) 0.3% is mixed while heated to 60 ° C., and is applied to the entire surface of the support plate so that the thickness after curing is 5 μm. A PEN film (manufactured by Teijin Ltd., trade name “Teonex Q51”, thickness: 12 μm, size 15 cm square) was covered on the entire surface of the support plate so that there were no air bubbles. Further, a high-pressure mercury lamp (160 W / cm) was irradiated from the support plate side, and these were heated in an oven at 150 ° C. for 60 minutes to cure the adhesive layer. After that, UV and thermosetting epoxy resin (made by ADEKA Co., Ltd., trade name “ADEKA OPTMER KRX-690-5”) is cured on the entire surface of the resin layer as an adhesive layer between the resin layer and the thin glass. The coating was applied so that the subsequent thickness was 5 μm, and a thin plate glass (manufactured by Nippon Electric Glass Co., Ltd., trade name “OA-10G”, thickness: 50 μm, size 10 cm square) was put on the center of the support plate so as not to have bubbles. Furthermore, after irradiating a high pressure mercury lamp (160 W / cm) from the thin glass side, these were heated and cured in an oven at 150 ° C. for 60 minutes to obtain a laminate.
The tensile modulus at 23 ° C. of the resin layer was 5.9 GPa, and the tensile elongation at break was 85%. The 5% weight reduction temperature of the resin layer was 350 ° C. or higher, and the 5% weight reduction temperature of the adhesive layer between the support plate and the resin layer was 370 ° C.
Each evaluation was implemented about the obtained laminated body. The results are shown in Table 1.
In the evaluation of peelability after the cleaning test and the heat treatment test, an output of 150 mW, a pulse frequency of 10 KHz, a current value of 63%, and a scanning speed of 20 mm / s using a UV laser system (Takano Co., Ltd., UV LASER SYSTEM “UVTS”). , After cutting the thin glass, the adhesive layer, the resin layer, and the adhesive layer on the inner side of 0.5 cm from each side of the thin glass under the condition of 60 shots, the peeling trigger using the feather blade The resin / glass composite was carefully peeled from the support plate.

[Example 7]
A glass plate (thickness 0.7 mm, 100 mm square) is used as a support plate, and an ultraviolet and thermosetting epoxy resin (trade name “Adekaoptomer KRX-690-5” manufactured by ADEKA Corporation) is used as an adhesive layer thereon. ) Was applied to the entire surface of the support plate with a bar coater so that the thickness after curing was 3 μm.
As the resin layer, a tetrafluoroethylene / ethylene copolymer film (manufactured by Asahi Glass Co., Ltd., trade name “Aflex”, single-sided corona treatment, thickness: 25 μm, 100 mm square) is used. After masking, the processing amount is 100 W · min /
Corona treatment was applied only to the end portion under the condition of m2. In the oven at 150 ° C, the corona-treated surface of only the end is the support plate side, and the entire support plate is covered so that there are no air bubbles. Further, a high-pressure mercury lamp (160 W / cm) is irradiated from the support plate side. For 60 minutes to cure the adhesive layer.
Thereafter, after the resin layer and the thin glass glass are cured, UV and thermosetting epoxy resin (made by ADEKA, trade name “ADEKA OPTMER KRX-690-5”) is applied to the entire surface of the resin layer. Is applied to the thickness of 3 μm, and a thin plate glass (trade name “OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 50 μm, size 80 mm square) is put on the center of the support plate so that there is no air bubble. After irradiating a high-pressure mercury lamp (160 W / cm) from the glass side, these were heated and cured in an oven at 150 ° C. for 60 minutes to obtain a laminate.
The tensile modulus at 23 ° C. of the resin layer was 0.8 GPa, the tensile elongation at break was 200%, and the 5% weight reduction temperature of the resin layer was 450 ° C.
Each evaluation was implemented about the obtained laminated body. The results are shown in Table 1.
In the evaluation of peelability after the cleaning test and the heat treatment test, the NTA cutter was used to cut the adhesive layer, the resin layer, and the adhesive layer on the outer side of the 1.0 mm from each side of the thin glass, and then feather. The blade was used to create a trigger for peeling, and the resin / glass composite was carefully peeled from the support plate.

[Comparative Example 1]
Using the same support plate as in Example 1, the same release agent as in Example 1 was uniformly applied to the same 15 cm square area as the support plate and cured in the same manner. Thereafter, an adhesive layer, a resin layer, an adhesive layer, and thin glass were laminated using the same materials and methods as in Example 1. When the obtained laminate was subjected to a cleaning test, a part of the end of the adhesive layer was peeled off at the interface between the adhesive layer and the release layer.

[Comparative Example 2]
Using the same support plate as in Example 2, the same release agent as in Example 2 was uniformly applied to the same 15 cm square range as the support plate and cured in the same manner. Thereafter, an adhesive layer, a resin layer, an adhesive layer, and thin glass were laminated using the same materials and methods as in Example 2. When the obtained laminate was subjected to a cleaning test, a part of the end of the adhesive layer was peeled off at the interface between the adhesive layer and the release layer.

[Comparative Example 3]
Using the same support plate as in Example 5, the same release agent as in Example 5 was uniformly applied in the same 15 cm square range as the support plate and cured in the same manner. Thereafter, an adhesive layer, a resin layer, an adhesive layer, and thin glass were laminated using the same materials and methods as in Example 5. When the obtained laminate was subjected to a cleaning test, a part of the end of the resin layer was peeled off at the interface between the resin layer and the release layer.

[Comparative Example 4]
Example 7 A laminate was obtained.
When the obtained laminate was subjected to a cleaning test, a part of the end of the resin layer was peeled off at the interface between the resin layer and the release layer.

[Comparative Example 5]
In Example 7, the entire corona-treated surface of the tetrafluoroethylene / ethylene copolymer film was subjected to a corona treatment under the condition of a treatment amount of 100 W · min / m ² , and the entire surface subjected to the corona treatment was supported on the support plate. The laminated body was obtained through the process similar to Example 7 except having covered the whole surface so that there might be no bubble on the side.
About the obtained laminated body, peelability evaluation after a washing test and a heat treatment test was performed using the same method as in Example 7, but the peel strength at the interface between the resin / glass composite and the support plate was large. For this reason, the thin glass was damaged during peeling, and the resin / glass composite could not be peeled from the support plate.

[Reference Example 1]
As a support plate, a glass plate (plate thickness: 0.2 mm, manufactured by Asahi Glass Co., Ltd., trade name “AN100”) made of non-alkali borosilicate glass is used, and a masking film is used thereon to form a release agent (Daikin). Kogyo Co., Ltd., trade name “Die Free GA-3000”) was sprayed uniformly 3 cm inside from each side of the support plate, that is, 9 cm square. Thereafter, the masking film was peeled off, heated in an oven set at 200 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a release layer.
Thereafter, 97% by mass of an ultraviolet curable monomer (manufactured by Osaka Gas Chemical Co., Ltd., trade name “Ogsol EA-0300”) and 3% by mass of a photopolymerization initiator (manufactured by BASF, trade name “IRGACURE184”) were added in a hot water bath. The mixed ultraviolet curable composition was applied 1.5 cm inside from each side of the support plate, that is, a size of 12 cm square, so that the thickness after curing was 10 μm, and further thin glass (made by Nippon Electric Glass Co., Ltd., trade name) “OA-10G” (thickness: 50 μm, size 10 cm square) is placed 2.5 cm inside each side of the support plate so that there are no air bubbles. Further, a high-pressure mercury lamp (160 W / cm) is irradiated on the surface of the thin glass, and ultraviolet rays are applied. The resin layer was formed by hardening a curable composition, and the thin glass laminated body with a support plate was obtained.
The tensile modulus at 23 ° C. of the resin layer was 100 MPa, and the tensile elongation at break was 54%.
Each evaluation was implemented about the obtained sheet glass laminated body with a support plate. The results are shown in Table 2.
In the evaluation of the peelability after the cleaning test and the heat treatment test, a laser scribe engine (LEMI SE-1002 manufactured by Remi Co., Ltd.) was used and the output was 60 W and the processing speed was 20.
Under the condition of 0 mm / s, the resin layer and the thin glass were cut to the 1.5 cm inner side from each side of the thin glass, and then the peeling layer was created using a feather blade, and the resin layer was removed from the support plate. And the laminated body which consists of thin glass was peeled carefully.

[Reference Example 2]
A support plate similar to that in Reference Example 1 was used, and a masking film was used thereon, and a surfactant (triclosan, water, sodium laureth sulfate, lauryl ether, POE lauryl ether acetic acid, concentrated glycerin, polyglyceryl laurate) as a release agent. , Trimethylammoniohydroxypropylhydroxyethylcellulose chloride, DL-malic acid, benzoate, edetate, sodium hydroxide solution, etc. mixed solution made by Kao Corporation, trade name “Biore u Foam Hand Soap”) It was uniformly applied 1.5 cm inside from the side, that is, in a range of 12 cm square, left to stand for 1 minute, and then the excess release agent was removed using an air gun. Then, it was heated in an oven set at 80 ° C. for 1 minute, allowed to cool to room temperature, and then the masking film was peeled off to obtain a release layer.
Next, a thermosetting silicone rubber (a thermosetting composition obtained by mixing equal amounts of trade names “LSR-7060A” and “LSR-7060B”, manufactured by Momentive Co., Ltd.), the same size as the support plate, 15 cm square, It was coated to a thickness of 10 μm, and further covered with thin glass (made by Nippon Electric Glass Co., Ltd., trade name “OA-10G”, thickness: 50 μm, size 10 cm square) without bubbles, and these were placed in an oven at 170 ° C. Was heated for 3 minutes to cure the thermosetting silicone rubber, thereby forming a resin layer to obtain a thin glass laminate with a support plate.
The tensile modulus at 23 ° C. of only the resin layer at this time was 4.5 MPa, and the tensile elongation at break was 115%.
Each evaluation was implemented about the obtained sheet glass laminated body with a support plate. The results are shown in Table 2.
In the evaluation of peelability after the cleaning test and the heat treatment test, the NTN cutter was used to cut the resin layer on each side of the 1.0 mm outer side from each side of the thin glass, and then peeled off using the feather blade. A trigger was created, and the laminate composed of the resin layer and the thin glass was carefully peeled from the support plate.

[Reference Example 3]
After forming a thin glass laminate with a support plate using the same method as in Reference Example 1, an ultraviolet curable monomer (made by Osaka Gas Chemical Co., Ltd., trade name “Ogsol EA-” was formed on the thin glass side surface of the laminate. 0300 ") 97% by mass, and a photopolymerization initiator (trade name“ IRGACURE184 ”, manufactured by BASF Corporation) 3% by mass in a hot water bath, an ultraviolet curable composition mixed 1.5 cm inside from each side of the support plate, that is, The resin layer is formed by applying a high-pressure mercury lamp (160 W / cm) from the surface of the thin glass plate and curing the ultraviolet curable composition, with a size of 12 cm square and a thickness of 10 μm after curing. The thin glass laminated body with a support plate in which the resin layer was formed on both surfaces of the thin glass was obtained.
Each evaluation was implemented about the obtained sheet glass laminated body with a support plate. The results are shown in Table 2.
In the peelability evaluation after the cleaning test and the heat treatment test, the same method as in Example 1 was used.

[Reference Comparative Example 1]
Using the same support plate as in Reference Example 1, a release agent (trade name “Biore u Foam Hand Soap” manufactured by Kao Corporation) was uniformly applied to the same 15 cm square range as the support plate. Thereafter, the mixture was allowed to stand for 1 minute, and excess mold release agent was removed using an air gun. Then, the mold release layer was obtained by heating for 1 minute in the oven set to 80 degreeC, and allowing it to cool to room temperature.
Thereafter, a thermosetting silicone rubber (a thermosetting composition obtained by mixing equal amounts of trade names “LSR-7060A” and “LSR-7060B” manufactured by Momentive Co., Ltd.) is 10 cm square in size and 10 μm in thickness after curing. Then, a thin plate glass (manufactured by Nippon Electric Glass Co., Ltd., trade name “OA-10G”, thickness: 50 μm, size 10 cm square) is covered so that there are no bubbles, and these are heated in an oven at 170 ° C. for 3 minutes. The resin layer was formed by curing thermosetting silicone rubber to obtain a thin glass laminate with a support plate.
When the obtained thin glass laminate with a support plate was subjected to a cleaning test, the end portion of the resin layer was peeled off by about 5 mm at the interface between the resin layer and the release layer.

  The thin glass laminate with a support plate represented by the above Reference Example shows good adhesion in the step of forming an electronic device, and within the outer range of the release layer in the subsequent step of peeling the support plate. By cutting at, the thin glass laminate can be easily peeled off from the support plate.

  The laminate having the resin / glass composite of the present invention can be used as a substrate for producing electronic devices such as organic electroluminescent elements and organic photoelectric conversion elements. Organic EL lighting and organic EL using the above elements A display device and an organic solar cell module can be obtained.

1 External range of resin layer (range within bold line frame)
2 Outline range of release layer (shaded area)
10, 20, 30, 40, 50, 60, 70 Laminate 11, 21, 31, 41, 51, 61, 71 Support plate 12, 22, 32, 42, 52, 62, 72 Thin glass 13, 23, 33 , 43, 53, 63, 73 Resin layers 14, 24, 34, 44 Release layers 15, 25, 35, 45, 55, 65, 75 Adhering portions 36, 46 Adhesive layers 57, 67 Easy peelable adhesive layer 58, 68, 78 Easy peeling part

Claims (14)

A laminate comprising a support plate, a thin glass having a thickness of 100 μm or less, and a resin / glass composite having at least a resin layer,
Laminated in the order of support plate, resin layer, and thin glass,
In at least one cross section when the laminate is cut in the laminating direction, the interface between the resin / glass composite and the support plate has an easily peelable portion and an adhesive portion having a peel strength higher than that of the easily peelable portion. A laminate comprising the adhesion portions positioned at both ends of a peeling portion.   The laminate according to claim 1, wherein the resin layer is provided within an outer range of the support plate.   The laminated sheet according to claim 1 or 2, wherein the thin glass is provided within an outer range of the resin layer.   The laminate according to any one of claims 1 to 3, wherein the easily peelable portion is surrounded by the close contact portion.   The laminated body according to any one of claims 1 to 4, wherein the thin glass is provided on the inner side of the outer shape range of the easily peelable portion.   The laminated body according to any one of claims 1 to 5, wherein the thin glass is provided on the inner side of the outer range of the resin layer.   The laminate according to any one of claims 1 to 6, wherein the difference between the peel strength at the close contact portion and the peel strength at the easy peel portion is 0.5 N / 25 mm or more.   The laminate according to any one of claims 1 to 7, wherein the peel strength of the easily peelable portion is 0.5 N / 25 mm or less.   The laminate according to any one of claims 1 to 8, wherein a 5% weight reduction temperature of the resin layer is 230 ° C or higher.   The laminate according to any one of claims 1 to 9, wherein the resin layer is a layer mainly composed of a resin obtained by curing a thermal or active energy ray-curable composition.   The laminate according to any one of claims 1 to 9, wherein the resin layer is a film mainly composed of a thermoplastic resin.   The organic electronic device obtained using the laminated body of any one of Claims 1-11.   A step of cutting the laminated body according to any one of claims 1 to 11 in a laminating direction so as to remove the adhesion portion, and a step of peeling a support plate from the laminated body. Production method. A method for producing an organic electronic device, comprising: cutting the organic electronic device according to claim 12 in a stacking direction so as to remove the adhesion portion; and peeling a support plate from the organic electronic device.