JP6477279B2 - Method for peeling glass laminate and method for manufacturing electronic device - Google Patents

Description

  The present invention relates to a method for peeling a support layer and a glass laminate, and a method for manufacturing an electronic device.

In recent years, electronic devices in organic EL display devices, solar cells, thin film secondary batteries, and the like have been made thinner and lighter, and glass layers used in these electronic devices have been made thinner. However, when the strength of the glass layer is lowered due to the thin plate, there is a problem that the handling property of the glass layer is deteriorated.
Therefore, a method has been proposed in which a laminated body in which a support layer is detachably attached to the back surface of the glass layer is formed, an electronic device member is formed on the surface of the glass layer, and then the glass layer and the support layer are peeled off. .

  For example, Patent Document 1 discloses a thin glass laminate obtained by laminating a thin glass substrate and a supporting glass substrate, and the thin glass and the supporting glass have easy peelability and non-adhesiveness. The thin glass laminated body characterized by laminating | stacking through the silicone resin layer which has is described. And, to separate the thin glass substrate and the supporting glass substrate, it can be done by manual peeling, but it is easier by giving the edge of peeling with a razor blade or by injecting air to the lamination interface. It is described that it can be peeled off.

Patent Document 2 discloses a peeling device that peels off a reinforcing sheet attached to a substrate. A flexible member is disposed between a laminate and a pad so that a rod connected to the pad rotates. It is described that the reinforcing sheet attached to the substrate can be easily peeled off by being provided.

International Publication No. 2007/018028 Pamphlet International Publication No. 2011/024689 Pamphlet

However, in Patent Document 1, if the thin glass substrate is manually peeled from the supporting glass substrate, there is a concern that the thin glass substrate is damaged due to low strength. In addition, when air is injected into the laminated interface, there is a concern that stress is locally generated on the thin glass substrate and is damaged.
In Patent Document 2, there is a concern that a large-scale device is required to peel the substrate and the reinforcing sheet, and that the glass substrate size applicable to the device is also limited.

  The present invention has been made in order to solve the above-described conventional problems, and the object of the present invention is to peel off a glass laminate that is simple and can suppress breakage of the glass layer in a glass laminate with a support layer. It is to provide a method and a method for manufacturing an electronic device.

As a result of earnestly examining the above problems, the inventors of the present invention have at least a part of the resin layer that exceeds the outer shape range of the glass layer when laminating at least the support layer, the resin layer, and the glass layer having a specific thickness. A glass laminate that can be easily formed and peels off a part of the resin layer that is formed beyond the outer shape range from the support layer, and grips the peeled part and peels it from the support layer, thereby preventing damage to the glass layer. Found that it can provide a peeling method

That is, the present invention is as follows.
[1] A glass laminate with a support layer, which includes at least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less, and at least a part of the resin layer is formed to exceed the outer shape range of the glass layer. A method of peeling a glass laminate including a resin layer and a glass layer from a body,
A glass laminate with a support layer is prepared, which includes at least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less, and at least a part of the resin layer is formed to exceed the outer range of the glass layer. The process of
A step of peeling at least a part of the resin layer formed beyond the outer shape range of the glass layer from the support layer; and gripping the peeled resin layer to remove the glass laminate including the resin layer and the glass layer from the support layer. The peeling method of a glass laminated body provided with the process to peel.
[2] The method for peeling a glass laminate according to [1], wherein an outer range of the resin layer is larger than an outer range of the glass layer.
[3] The method for peeling a glass laminate according to [1] or [2], wherein the resin layer has a tensile strength at break of 10 MPa or more and 300 MPa or less.
[4] The method for peeling a glass laminate according to any one of [1] to [3], wherein the resin layer has a tensile elongation at break of 5% or more and 500% or less.
[5] The method for peeling a glass laminate according to any one of [1] to [4], wherein the resin layer has a tensile elastic modulus of 50 MPa or more and 2500 MPa or less.
[6]
The method for peeling a glass laminate according to any one of [1] to [5], wherein the peel strength between the resin layer and the support layer is 0.1 N / 50 mm or more and 5 N / 50 mm or less.
[7] The method for peeling a glass laminate according to any one of [1] to [6], wherein the resin layer includes a thermoplastic resin.
[8] The method for peeling a glass laminate according to any one of [1] to [6], wherein the resin layer is formed by curing a curable resin composition.
[9] A glass laminate with a support layer, which includes at least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less, and at least a part of the resin layer is formed beyond the outer shape range of the glass layer. Preparing the body,
A step of forming an electronic device member on the glass layer of the prepared glass laminate with a support layer,
A step of peeling at least a part of the resin layer formed beyond the outer shape range of the glass layer from the support layer; and gripping the peeled resin layer to remove the glass laminate including the resin layer and the glass layer from the support layer. A method for manufacturing an electronic device, comprising the step of peeling.

  By the peeling method of this invention, the peeling method of the glass laminated body which can suppress the damage of a glass layer easily can be provided. Moreover, the manufacturing method of an electronic device using the said technique can be provided.

It is a cross-sectional schematic diagram which shows the laminated structure of one Embodiment of the glass laminated body with a support layer. It is a figure which shows the external shape range in this invention. It is a cross-sectional schematic diagram which shows one Embodiment of the peeling method. It is a cross-sectional schematic diagram which shows the laminated structure of another embodiment of the glass laminated body with a support layer.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below, but the following descriptions will explain examples (representative examples) of embodiments of the present invention, and the present invention is not limited to these contents. Absent.

FIG. 1 is a schematic cross-sectional view showing an embodiment of a glass laminate with a support layer used in the present invention. The glass laminate 100 with a support layer includes a support layer 12, a release layer 19, a resin layer 11, and a glass layer 10 in this order.
Moreover, FIG. 4 is a cross-sectional schematic diagram which shows another embodiment of the glass laminated body with a support layer used for this invention. The glass laminate 200 with a support layer includes a support layer 22, an adhesion layer 26, a resin layer 21, an adhesive layer 25, and a glass layer 20 in this order.
Below, first, the material etc. which are used for the glass laminated body with a support layer used for this invention including a glass layer, a resin layer, and a support layer are demonstrated. These materials and the like are used in the method for producing a glass laminate described later.

<1. Glass layer>
As the glass layer used in the present invention, any appropriate one can be adopted as long as it has a plate shape with a thickness of 10 μm or more and 200 μm or less. As the material, for example, almost any glass composition 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 used. It is properly used depending on the application. As a specific example marketed, trade name “OA-10G” manufactured by Nippon Electric Glass Co., Ltd., which is alkali-free glass, can be mentioned.

  Glass having a thickness of 10 μm or more and 200 μm or less can in principle be produced by stretching the glass melt at a temperature above the temperature at which the glass melt solidifies. The thickness of the glass layer can be controlled by the glass composition, the thickness of the glass melt, the temperature, and the take-off speed.

  The thickness of the glass layer is preferably 15 μm or more, more preferably 20 μm or more, and further preferably 25 μm or more. On the other hand, Preferably it is 100 micrometers or less, More preferably, it is 80 micrometers or less, More preferably, it is 75 micrometers or less. By setting the thickness to 10 μm or more, it is possible to prevent an extreme decrease in mechanical strength and prevent breakage due to stress such as when a cured resin layer is formed. On the other hand, by setting the thickness to 200 μm or less, it is possible to efficiently perform lamination of a cured resin layer for the purpose of improving the secondary workability with excellent handling properties without deteriorating the production efficiency of a single glass.

As the glass layer used in the present invention, those subjected to surface treatment can be used. As the surface treatment, for example, a coupling agent treatment with a silane coupling agent, a 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, for the purpose of improving adhesion with the resin layer and preventing peeling during handling, the surface on the resin layer side described later may be subjected to some surface treatment.
The surface treatment agent is not particularly limited, and examples thereof include derivatives such as methoxysilane, ethoxysilane, chlorosilane, and silazane. In particular, a methoxysilane derivative having an amino group, an acrylic group, or a methacryl group at the terminal is preferably used.

<1-1. Total light transmittance of glass layer>
The total light transmittance of the glass layer is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. If it is 80% or more, the higher light transmittance of a glass laminated body can be achieved. Such a glass layer can be obtained by appropriately selecting a known one or by producing it by a known method.
The total light transmittance can be measured by a method based on JIS K 7361, for example. At this time, for example, a transmittance meter (“HR-100” manufactured by Murakami Color Research Laboratory) can be used.

<1-2. Average surface roughness of glass layer>
When the resin layer is formed on one surface of the glass layer, the average surface roughness of the other surface, that is, the surface where the resin layer is not formed is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 2 nm. It is as follows. If it is 10 nm or less, it is easy to form a uniform film when a thin film is further laminated on the surface. For example, a glass laminate is used as a substrate, and a conductive layer such as an ITO film is used as an electronic device member on the glass layer surface. When formed, a conductive layer having a very thin thickness (several tens of nm) and a low surface resistance can be formed. Therefore, the glass layer having the above average surface roughness can be suitably used as a substrate for electronic devices. The lower limit is not particularly limited, but is preferably 0.1 nm or more. As such a glass layer, it can obtain by selecting a well-known thing suitably or producing by a well-known method.

The average surface roughness (arithmetic average roughness (Sa)) can be calculated by the following measuring method.
Method for measuring arithmetic average roughness (Sa):
The average surface roughness (arithmetic average roughness (Sa)) can be measured using an optical interference type non-contact surface shape measuring instrument. For example, surface observation (observation field of view: 93.97 μm × 71.30 μm) of the glass layer was performed using a non-contact surface / layer cross-sectional measurement system VertScan 2.0 (manufactured by Ryoka System Co., Ltd.), and the surface of the glass layer was averaged. The surface roughness (arithmetic average roughness Sa) is calculated.

<1-3. Flexibility of glass layer>
Since the glass laminated body in this invention peels in the state bent when peeling from a support layer, it is necessary for a glass layer not to be damaged in that case. The glass layer is preferably not damaged by deformation with a curvature radius of 200 mm or more, and particularly preferably not damaged by deformation of 100 mm or more.

<2. Support layer>
The support layer used in the present invention improves the handleability of the glass layer and suppresses deformation and breakage of the glass layer when forming the electronic device member.
As a support layer used for this invention, metal materials, such as glass, resin, or SUS, are used, for example. Usually, since an electronic device member is formed with heat treatment, it is preferable to use a material mainly having a small difference in linear expansion coefficient from the glass layer, and the same material as the glass layer, that is, the support layer is used as the support layer. More preferably, it is a glass material. In particular, the glass material is preferably the same as the glass layer.

  The thickness of the support layer is preferably 0.2 mm or more, more preferably 0.3 mm or more, and still more preferably 0.5 mm or more. On the other hand, it is preferably 5 mm or less, more preferably 2 mm or less. By setting the thickness to 0.2 mm or more, bending does not occur when the glass laminate is conveyed, and it is easy to handle when forming the electronic device member. On the other hand, when the thickness is 5 mm or less, it is possible to reduce the weight of the glass laminate and increase the efficiency of packaging.

The support layer used in the present invention may be subjected to a release treatment on the surface of the resin layer described later, if necessary. By performing the mold release treatment, the peelability from the resin layer is improved, and it becomes easy to prevent breakage of the resin layer when the resin layer is peeled from the support layer.
Although it does not specifically limit as a mold release process, Treating the surface by the side of the resin layer of a support layer with a mold release agent is mentioned.
The release agent is not particularly limited, and silicone compounds (for example, silicone oil, thermosetting silicone, ultraviolet curable silicone, modified silicone, etc.), fluorine compounds (for example, fluorine resin, etc.), olefin resins, alkyd resins, etc. In particular, silicone compounds are preferably used.

<3. Resin layer>
The resin layer used in the present invention is provided between the support layer and the glass layer, protects the glass layer, and improves the handling properties of the glass layer. After the electronic device member is formed on the glass laminate with the support layer, the support layer can be peeled between the resin layer and the support layer. When the support layer is peeled off or after peeling, it becomes possible to prevent the occurrence of cracks in the glass layer and propagation of cracks by covering the glass layer with a thin thickness and poor impact resistance with a resin layer, Improve handling.

The resin layer may be a resin layer containing a thermoplastic resin, or may be a resin layer obtained by curing a curable resin composition, and is not limited as long as the effects of the present invention are obtained, but is not curable. The resin composition is preferably a resin layer obtained by curing the curable resin composition in terms of easy blending design that induces chemical bonding to the glass layer surface during the curing reaction.
On the other hand, since a thermoplastic resin is generally excellent in toughness with respect to a curable resin, it is preferable in that the breakage of the resin layer at the time of peeling is suppressed.

<3-1. Thermoplastic resin>
Thermoplastic resins include fluororesins, polyethersulfone resins, polycarbonate resins, acrylic resins, silicone resins, cycloolefin resins, thermoplastic polyimide resins, polyamide resins, polyamideimide resins, polyresins. Examples include arylate-based resins, polysulfone-based resins, polyetherimide-based resins, polyetheretherketone-based resins, polyether silicon-based resins, polyester-based resins, and polyphenylene sulfide-based resins.
Of these, fluororesins, silicone resins, polyimide resins, and polyester resins are preferred in that they can maintain the required mechanical strength during peeling after the heating step and the cleaning step in the formation of electronic devices. Fluorine-based resins are particularly preferable because the adhesion with the support layer is easy to adjust.

<3-2. Curable resin composition>
The component contained in the composition is not particularly limited as long as the curable resin composition is a resin composition that is cured by a curing treatment. For example, the curable resin composition is cured by heat treatment or active energy ray irradiation. Is mentioned. Especially, since a hardening process process is simple, it is preferable that it is a thermosetting resin composition or an ultraviolet curable resin composition.

  The curable resin composition contains a curable resin and, if necessary, a polymerization initiator. In addition, you may contain the other component which does not inhibit the effect of this invention, and the other component which improves the effect of this invention. Such components will be described later.

  The curable resin contained in the curable resin composition is not particularly limited as long as it is a component that induces a polymerization reaction by the curing process and cures, but it can be cured easily in a short time, and thus is ultraviolet curable. Monomers and oligomers can be mentioned as preferred examples.

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, epoxy (meth) acrylate, urethane (meta ) Monomers and oligomers such as acrylate and polyester (meth) acrylate are preferred examples.
Further, some examples are trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate. Examples thereof include monofunctional or polyfunctional acrylic monomers or methacrylic monomers having one or more carbon-carbon double bonds, such as methacrylate, isoamyl acrylate, ethoxydiethylene glycol acrylate, and methoxydiethylene glycol acrylate.

  As the (meth) acrylic monomer and (meth) acrylic oligomer, a functional group equivalent, that is, a (meth) acrylic monomer and a (meth) acrylic oligomer having a molecular weight / functional group number in the range of 500 or more and 5000 or less are more preferable. More preferably, the (meth) acrylic monomer and the (meth) acrylic oligomer having a group equivalent in a range include 70% by mass or more and 100% by mass or less with respect to the entire curable resin contained in the curable resin composition. By using (meth) acrylic monomers and (meth) acrylic oligomers in a range that requires a functional group equivalent, it becomes possible to suppress cracking and breakage of the resin layer and to express adhesiveness with the glass layer. When the amount is 70% by mass or more, it becomes possible to further suppress the cracking or breaking of the resin layer.

  Further, for the purpose of adjusting the heat resistance and mechanical strength of the resin layer, a (meth) acryl monomer and a (meth) acryl oligomer having a functional group equivalent in the range of 100 or more and 300 or less are more preferable, and the functional group equivalent is applied. More preferably, the range of (meth) acrylic monomer and (meth) acrylic oligomer is contained in an amount of 0.1% by mass or more and 30% by mass or less based on the entire curable resin contained in the curable resin composition. When the (meth) acrylic monomer and (meth) acrylic oligomer having a functional group equivalent in a range have a high crosslinking density, it is possible to impart good heat resistance to the resin layer, and the content is 30% by mass or less. Further, it is more preferable because the crosslink density of the resin layer does not become excessively high and good heat resistance can be imparted while suppressing cracking and breakage of the resin layer.

Moreover, it is especially preferable that 70 mass% or more and 100 mass% or less of urethane acrylate whose functional group equivalent is the range of 500-5000 are included with respect to the whole curable resin contained in curable resin composition. By using an acrylate having a urethane bond and having a functional group equivalent within this range, the toughness and impact resistance of the resin layer are improved, so that it is possible to particularly suppress the breakage and breakage of the glass layer.
In addition, these can be used 1 type or in combination of 2 or more types.
As a commercial item, the brand name "NK oligo UA-122P" by Shin-Nakamura Chemical Co., Ltd. which is urethane acrylate, etc. are mentioned, for example.

  The total concentration of the curable resin in the curable resin composition is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably 80% by mass, from the viewpoints of viscosity during processing and mechanical properties after processing. That's it.

When the curable resin is an ultraviolet curable monomer or oligomer, the curable composition contains a photopolymerization initiator. The photopolymerization initiator is used to absorb (activate) active energy rays and activate (excited), and to initiate the reaction via a cleavage reaction or the like.
Examples of the photopolymerization initiator include benzoin, acetophenone, thioxanthone, phosphine oxide, and peroxide photopolymerization initiators. 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.
Examples of commercially available products include 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, trade name “IRGACURE184”).

  The concentration of the polymerization initiator in the curable resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more from the viewpoint of more reliably performing the curing reaction. It is. On the other hand, from the viewpoint of suppressing generation of outgas due to the unreacted product 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.

In addition to the above, in order to adjust physical properties such as curability, water absorption, adhesion, hardness, heat resistance, and mechanical strength of the curable resin, (meth) acrylic acid ester, phosphoric acid (meth) Monomer components such as acrylate, (meth) acrylamide, vinyl ether, and thiol compound, and polymer components such as acrylic resin, epoxy resin, polyurethane resin, and polyester resin can be optionally added to obtain the curable resin composition. Among these, it is particularly preferable to add a thiol compound because heat resistance and mechanical strength are improved. Examples of the thiol compound include pentaerythritol tetrakisthioglycolate and pentaerythritol tetrakisthiopropionate. In addition, these can be used 1 type or in combination of 2 or more types as appropriate.
In addition, silane coupling agents, sensitizers, crosslinking agents, UV absorbers, polymerization inhibitors, fillers, antioxidants, leveling agents, slip agents, fine particles, dispersants, thermoplastic resins, etc. Can be optionally added as long as physical properties such as properties and water absorption are not hindered.
In addition, these can be used 1 type or in combination of 2 or more types as appropriate.

<3-3. Surface treatment of resin layer>
The resin layer may be subjected to a surface treatment for the purpose of improving the adhesion with the glass layer or adjusting the adhesion with the support layer. Examples of the surface treatment include a mold release treatment in which a silicone resin, an alkyd resin, a fluororesin, or the like is applied to the surface in advance, or a discharge treatment such as corona or plasma, which can be appropriately performed as necessary.

<3-4. Resin layer thickness>
The thickness of the resin layer is preferably 1 μm or more, more preferably 5 μm or more, and further preferably 10 μm or more. On the other hand, it is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.
It is preferable for the thickness of the resin layer to be 1 μm or more because the impact applied to the glass layer can be reduced, and more excellent handling properties of the glass laminate including the resin layer and the glass layer can be realized. On the other hand, by setting the thickness of the resin layer to 200 μm or less, even when the glass laminate is applied to a vacuum process, the amount of outgas consisting of moisture and low molecular weight components can be within a preferable range in the process.
The thickness of the resin layer can be appropriately adjusted depending on the coating thickness of the resin composition and various coating methods described later.

<3-5. Total light transmittance of resin layer>
The total light transmittance of the resin layer is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. If it is 80% or more, the higher light transmittance of the glass laminated body containing a resin layer and a glass layer can be achieved.
The total light transmittance can be measured by a method based on JIS K 7361, for example. At this time, for example, a transmittance meter (“HR-100” manufactured by Murakami Color Research Laboratory) can be used.
The total light transmittance of the resin layer can be adjusted by appropriately selecting a resin having a short conjugated system molecular skeleton or a molecular skeleton with low crystallinity.

<3-6. Tensile modulus of resin layer>
The tensile elastic modulus of the resin layer is preferably 50 MPa or more, more preferably 250 MPa or more, further preferably 500 MPa or more, and particularly preferably 700 MPa or more. On the other hand, it is preferably 2500 MPa or less, more preferably 2300 MPa or less, still more preferably 2100 MPa or less, and particularly preferably 2000 MPa or less.
By having a tensile elastic modulus of 50 MPa or more, when peeling between the resin layer and the support layer, excessive deformation of the resin layer is suppressed, and peeling can be performed without breaking.
On the other hand, by setting the tensile modulus to 2500 MPa or less, when peeling between the resin layer and the support layer, it is possible to suppress excessive bending stress on the glass layer and prevent breakage of the glass layer. It becomes possible.

  As a method for adjusting the tensile modulus of the resin layer, for example, a method for adjusting the molecular weight and the number of functional groups of monomers and oligomers as raw materials for the resin to be contained, a method for adjusting to an appropriate crosslinking density, and a method for appropriately adding a filler Or a method of appropriately adjusting the irradiation amount of the active energy ray, and the like.

The tensile elastic modulus of the resin layer can be measured by the following method.
For example, a curable resin composition is cured to prepare a strip-shaped resin sample having a thickness of 200 μm, a width of 2 cm, and a length of 150 mm, and a universal testing machine (for example, Autograph AGS-X manufactured by Shimadzu Corporation) can be mentioned. ) Was used to measure the elongation and stress in the longitudinal direction of the strip-shaped resin sample, and the tensile elastic modulus was calculated from these values to obtain the tensile elastic modulus of the resin layer. The test conditions were a distance between chucks of 10 cm, a tensile speed of 10 mm / min, and measurement at 25 ° C.

<3-7. Tensile elongation at break of resin layer>
The tensile elongation at break of the resin layer is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more. On the other hand, it is preferably 500% or less, more preferably 400% or less, and still more preferably 300% or less.
By having a tensile elongation at break of 5% or more, propagation of cracks from the cut portion can be suppressed when a glass laminate including a resin layer and a glass layer is cut. In addition, even if the glass layer is broken inside the glass laminate, the glass layer is maintained in its shape without breaking the resin layer, so that the glass can be prevented from scattering. Furthermore, when peeling between the resin layer and the support layer, the resin layer can be peeled without breaking.

As a method of adjusting the tensile elongation at break of the resin layer, for example, a method of adjusting the appropriate crosslinking density by appropriately selecting the molecular weight and the number of functional groups of the monomers and oligomers that are the raw materials of the resin contained, and a filler is added as appropriate. And a method of appropriately adjusting the irradiation amount of the active energy ray and the like.

The tensile breaking elongation of the resin layer can be measured by the following method.
For example, a curable resin composition is cured to prepare a strip-shaped resin sample having a thickness of 200 μm, a width of 10 mm, and a length of 100 mm, and a universal testing machine (for example, Autograph AGS-X manufactured by Shimadzu Corporation) can be mentioned. ) Was used to measure the tensile elongation at break of the strip-shaped resin sample, and was used as the tensile elongation at break of the resin layer. The test conditions were a distance between chucks of 40 mm, a pulling speed of 50 mm / min, and measurement at 25 ° C.

<3-8. Tensile strength at break of resin layer>
The tensile strength at break of the resin layer is preferably 10 MPa or more, more preferably 12 MPa or more, further preferably 15 MPa or more, and particularly preferably 30 MPa or more.
When the tensile breaking strength has a value of 10 MPa or more, it is possible to suppress breakage during the peeling of the resin layer when peeling between the resin layer and the support layer. In addition, although an upper limit is not specifically limited, Usually, it is 300 Mpa or less.

The tensile breaking strength of the resin layer can be measured by the following method.
For example, a curable resin composition is cured to produce a strip-shaped resin sample having a thickness of 200 μm, a width of 10 mm, and a length of 100 mm, and a universal testing machine (for example, Autograph AGS-X manufactured by Shimadzu Corporation) is used. Then, the tensile breaking strength of the strip-shaped resin sample was measured to obtain the tensile breaking strength of the resin layer. The test conditions were a distance between chucks of 40 mm, a pulling speed of 50 mm / min, and measurement at 25 ° C.

<3-9. 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. Specifically, the 5% weight loss temperature is preferably 250 ° C. or higher, and more preferably 280 ° C. or higher.
The 5% weight loss temperature of the resin layer was determined by measuring the thermal loss of the resin layer at a temperature rising rate of 20 ° C./min under a nitrogen atmosphere of 50 mL / min using a thermal analyzer, for example, Thermoplus TG8120 manufactured by RIGAKU. The temperature at which the weight loss is 5% is defined 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.

<3-10. Adhesion layer>
In order to adjust the peel strength between the resin layer and the support layer to a range as described later, an adhesion layer may be provided between the support layer and the resin layer as necessary.
The adhesion layer is a layer that sufficiently adheres to one of the resin layer and the support layer and exhibits easy peelability to the other layer.
Note that if easy peelability is expressed by specific numerical values, it can also be expressed that the peel strength is 0.1 N / 50 mm or more and less than 5 N / 50 mm. However, this numerical range is an example, and it is not limited to the above numerical range as long as it satisfies the easily peelable property described above.

The resin composition constituting the adhesion layer contains a resin and other additives as necessary.
As the resin contained in the resin composition constituting the adhesion layer, a resin obtained by curing the curable resin composition is preferable.
The curable resin composition is not particularly limited as long as it is a component in which a polymerization reaction is induced by the curing treatment and cures, but since it can be cured easily in a short time, an ultraviolet curable resin or a thermosetting resin is possible. Or, a curable resin composition containing ultraviolet rays and a thermosetting resin can be cited as a preferred example.

The ultraviolet curable resin, the thermosetting resin, or the ultraviolet and thermosetting resin is appropriately selected depending on the material of the adhesion layer. For example, the curable resin such as an acrylic resin, a urethane resin, an epoxy resin, or a silicone resin. From the viewpoints of heat resistance, mechanical properties, workability, and the like, an epoxy curable resin is preferable.
Examples of the epoxy curable resin include an epoxy resin having an alicyclic compound group, an epoxy resin having a glycidyl ether group, an epoxy resin having an aromatic group, and more specifically, bisphenol A type and bisphenol. Although F type is mentioned, it is not limited only in particular to this.
As a commercial item, the brand name "KRX-690-5" by ADEKA Co., Ltd. which is an ultraviolet-ray and a thermosetting epoxy resin is mentioned, for example.

  In the resin composition constituting the adhesion layer, a silane coupling agent, a sensitizer, a crosslinking agent, an ultraviolet absorber, a polymerization inhibitor, a surfactant, a filler, a mold release, as long as the object of the present invention is not impaired. An 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.

The thickness of the adhesion layer is preferably 0.5 μm or more. 1 μm or more is more preferable. On the other hand, it is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less.
If the thickness of the adhesion layer is 0.5 μm or more, it can sufficiently adhere to the support layer or the resin layer, and if the thickness is 10 μm or less, the increase in the thickness of the entire electronic device is suppressed, and the adhesion layer at the time of creating the electronic device There is a tendency that the outgas generation amount from can be suppressed.

<3-11. Adhesive layer>
In order to adjust the peel strength between the resin layer and the glass layer to a range as described later, an adhesive layer may be provided between the glass layer and the resin layer as necessary.
An adhesive layer is a layer which shows sufficient adhesiveness with respect to a resin layer and a glass layer.
The material constituting the adhesive layer is not particularly limited as long as it exhibits the properties described above, and the curable resin composition described in the description of the resin layer and the adhesion layer can be used as appropriate.

<3-12. Release layer>
In order to adjust the peel strength between the resin layer and the support layer to a range as described later, a release layer may be provided between the support layer and the resin layer as necessary.
Examples of the release layer include a layer formed by the release treatment on the surface of the support layer and the resin layer described above.

<4. Glass laminate with support layer>
Since the glass laminate with a support layer used in the present invention has a configuration in which the glass layer is laminated on the support layer, the handling property of the glass layer can be improved, and there is a problem in forming an electronic device member on the glass layer. Applicable without any problem.

In the glass laminate with a support layer used in the present invention, at least a part of the resin layer is formed so as to exceed the outer range of the glass layer.
Here, FIG. 2 shows the outline range of the glass layer (solid line range of 13) and the outline range of the resin layer (14
Is a diagram showing an example of (solid line range). That is, in this specification, the outer shape range means a range occupied by each layer when the laminate is viewed from the stacking direction (thickness direction), and the formation within the outer shape range means that an outer layer is occupied by a certain layer. It means that another layer is formed in the range including the frame, and exceeding the outer range means that another layer is formed in the range that occupies one layer and extends outside the outer frame. Yes.
As for the glass layer and resin layer which comprise the glass laminated body with a support layer used for this invention, as shown to FIG. 1 and 2, at least one part of the resin layer is formed exceeding the external shape range of a glass layer.

  By forming such a laminate, a portion where the glass layer is not laminated on the resin layer is formed, so that only the resin layer can be used as a starting point of peeling, and when peeling from the support layer, the resin Only the layer can be gripped, and the glass layer can be peeled off without applying an excessive load, and breakage of the glass layer can be remarkably prevented.

The resin layer is formed so that at least a part thereof is larger than the outer range of the glass layer, and then a part of the resin layer formed to be larger than the outer range of the glass layer is peeled off, Since the step of grasping the peeled portion and peeling the glass laminate having the resin layer and the glass from the support layer becomes easy, a resin layer is formed in a part of which is 1 mm or more larger than the outer shape range of the glass layer. It is more preferable to form a resin layer 5 mm larger.
Moreover, it is more preferable that the glass layer is formed within the outer shape range of the resin layer from the reason of protecting the resin layer side surface and the end surface of the glass layer and suppressing cracking during the process.

The glass laminate with a support layer used in the present invention preferably has a ratio (d1 / d2) of the glass layer thickness (d1) to the resin layer thickness (d2) of 0.3 to 3. Moreover, it is preferable that ratio (d3 / (d1 + d2)) of the total thickness (d1 + d2) of a glass layer and a resin layer and the thickness (d3) of a support layer is 1-25.
If the ratio of the thickness (d1) of the glass layer and the thickness (d2) of the resin layer is in the range of 0.3 to 3, it is possible to prevent warping and the like while significantly improving the cracking and scattering of the glass layer. It becomes possible. Further, when the ratio (d3 / (d1 + d2)) of the total thickness (d1 + d2) of the glass layer and the resin layer to the thickness (d3) of the support layer is in the range of 1 to 25, the handling property of the glass laminate is maintained. In this state, since the thickness does not become excessively large, there is no possibility of impairing the packaging efficiency and the operability in the electronic device member forming step.

The glass laminate with a support layer that satisfies the above two thickness ratios does not bend when forming an electronic device member, and further, as described later, by peeling the glass laminate from the support layer, It is possible to obtain a glass laminate including a glass layer and a resin layer in which generation and crack propagation are remarkably improved.
Moreover, the glass laminated body containing the obtained glass layer and resin layer can be used suitably as a board | substrate for electronic devices, or a board | substrate for flexible devices.

The ratio (d1 / d2) between the thickness (d1) of the glass layer and the thickness (d2) of the resin layer is 0.4 to 2 from the viewpoint of preventing warpage while significantly improving the cracking and scattering of the glass layer. .5 is preferable, and 0.5 to 2.0 is more preferable.
The ratio (d3 / (d1 + d2)) of the total thickness (d1 + d2) of the glass layer and the resin layer to the thickness (d3) of the support layer is such that the glass laminate is excessively thick while maintaining the handling properties of the glass laminate. From the viewpoint of not increasing the thickness, 3 to 20 is preferable, and 5 to 15 is more preferable.
Ratio (d1 / d2) of glass layer thickness (d1) and resin layer thickness (d2), ratio of total thickness of glass layer and resin layer (d1 + d2) and support layer thickness (d3) (d3 / ( In order to adjust d1 + d2)), it can be adjusted by appropriately using a glass layer or a support layer having a preferable thickness range.

  In the glass laminate with a support layer, the peel strength between the support layer and the resin layer is preferably lower than the peel strength between the resin layer and the glass layer. The peel strength between the support layer and the resin layer is preferably 0.1 N / 50 mm or more and 5 N / 50 mm or less, more preferably 0.1 N / 50 mm or more and 2 N / 50 mm or less. On the other hand, the peel strength between the glass layer and the resin layer is preferably 10 N / 50 mm or more.

By satisfying this peel strength and its magnitude relationship, the glass layer can follow the resin layer and be easily peeled between the resin layer and the support layer by applying a stress by gripping the resin layer. It becomes. Moreover, the glass laminated body containing the resin layer and glass layer excellent in handling property after support layer peeling can be provided.
In order to adjust the peel strength between the support layer and the resin layer and between the resin layer and the glass layer, the surface of the support layer on the resin layer side is subjected to release treatment (including the release treatment described above). It can be adjusted with.
The peel strength can be measured by a 90 degree peel method. At this time, for example, a universal testing machine (INTESCO 200X manufactured by Intesco) can be used.

  The glass laminate with a support layer includes at least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less, and may optionally include other layers. Specific examples include an adhesive layer for adhering the glass layer and the resin layer, an adhesive layer for adhering the support layer and the resin layer, a release layer formed by surface treatment, and the like. These layers can be laminated by a known method using a known material.

<5. Glass laminate including resin layer and glass layer>
In this invention, the glass laminated body containing a resin layer and a glass layer can be obtained by peeling a support layer from the glass laminated body with a support layer. A glass laminate including a resin layer and a glass layer is excellent in handling properties even after the support layer is peeled off because the resin layer is laminated on the glass layer, and is suitably used as an electronic device substrate or a flexible device substrate. be able to.

  When used as an electronic device substrate or a flexible device substrate, the total light transmittance of the glass laminate including the resin layer and the glass layer is preferably 80% or more, and more preferably 85% or more. 90% or more is particularly preferable. If it is 80% or more, it can be suitably used as a substrate for a display element or the like.

  When used as an electronic device substrate or a flexible device substrate, the thickness of the glass laminate including the resin layer and the glass layer is preferably 5 μm or more and 300 μm or less, and more preferably 10 μm or more and 200 μm or less. It is particularly preferably 30 μm or more and 100 μm or less. When the thickness is 5 μm or more and 300 μm or less, a substrate suitable for an electronic device or a flexible device having excellent flexibility can be provided without impairing handling properties.

<6. Manufacturing method of glass laminate including resin layer and glass layer>
In this invention, the glass laminated body containing a resin layer and a glass layer is obtained by peeling a support body from the glass laminated body with a support layer. That is, a specific embodiment of the present invention includes at least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less, and at least a part of the resin layer is formed beyond the outer range of the glass layer. A step of preparing a glass laminate with a supporting layer, a step of peeling at least a part of the resin layer formed beyond the outer shape range of the glass layer from the supporting layer, and a resin by gripping the peeled resin layer A method for peeling a glass laminate, and a method for producing a glass laminate, comprising a step of peeling a glass laminate including a layer and a glass layer from a support layer. Hereinafter, these steps will be described in order with reference to FIG.

<6-1. Process for preparing glass laminate with support layer>
This step is shown in FIG. 3 (a), and prepares a glass laminate 100 with a support layer in which a support layer 12, a release layer 19, a resin layer 11, and a glass layer 10 having a thickness of 10 μm or more and 200 μm or less are laminated in this order. It is a process. The release layer 19 is an arbitrarily provided layer and is not an essential component in the present invention.

In this step, for example, when a cured resin layer is used as the resin layer, a layer made of the curable resin composition is formed on the glass layer or the support layer, and then the other glass layer or support layer is laminated.
As a method for forming a layer made of the curable resin composition on the glass layer or the support layer, a known method can be used. Examples include spin coater coating, die coater coating, bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and dip coating. .
There are no particular limitations on the coating speed, discharge rate, etc. in the coating, and it can be appropriately adjusted from the composition and coating speed of the layer made of the curable resin composition and the desired thickness of the cured resin layer after curing.
Moreover, when a curable resin composition contains a solvent, after forming the layer which consists of a curable resin composition, the process of drying and removing a solvent may be included.
In addition, a release layer may be formed between the support layer and the resin layer by performing a release treatment on the surface of the support layer facing the resin layer, and a known method is used as the method. .

  When forming a layer made of a resin composition, it is necessary to make the range for forming the resin composition larger than the glass layer so that at least a part of the resin layer is formed beyond the outer range of the glass layer. is there. Thus, in order to form a resin layer, it is preferable to form the layer which consists of a resin composition on a support layer larger than a glass layer, and to laminate | stack a glass layer on the layer which consists of a resin composition after that.

At this time, as described above, the resin composition is formed so that a part thereof is larger than the outer shape range of the glass layer, and a process of peeling a part of the subsequent resin layer and gripping the part. Since it becomes easy, in one part, it is preferable to form a resin layer 1 mm or more larger than the external range of a glass layer, and it is more preferable to form a resin layer larger than 5 mm.
Moreover, it is preferable that the glass layer is formed in the external range of the resin layer from the reason of protecting the resin layer side surface and end surface of a glass layer, and preventing scattering of glass.
The method of laminating the glass layer or the support layer on the layer composed of the resin composition is not particularly limited, and examples thereof include a method of laminating through a press, a hand roll, and a nip roll.

In this step, the layer composed of the resin composition, the glass layer, and the support layer may be laminated at a time. By using such a laminating method, the process is simpler than the laminating method in which the resin composition is applied onto the support layer and bonded to the glass layer, and the application surface of the resin composition is exposed to the outside air. Therefore, mixing of foreign matters and generation of bubbles can be suppressed, and a good glass laminate with a support layer with few optical defects can be produced.
The method of laminating these members at a time is not particularly limited, and examples thereof include a method of rolling the resin composition by simultaneously passing the glass layer, the resin composition, and the support layer through a press or nip roll.

In this step, when a curable resin layer is used as the resin layer, the curable resin composition is irradiated with active energy rays, for example, on the laminate including the support layer prepared above, the layer made of the curable resin composition, and the glass layer. A layer made of a product can be cured to obtain a cured resin layer.
The method for curing the layer made of the curable resin composition is not particularly limited, and examples thereof include a method of curing by irradiation with active energy rays such as ultraviolet rays and visible rays, or a method of curing by heat treatment. Among the above, from the simplicity of the process, active energy ray irradiation in which the curing reaction is performed in a short time is preferably used.

The light source of the active energy ray, its arrangement, the amount of light and the like are not particularly limited as long as the layer containing the curable resin composition can be cured. For example, in the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like as a light source is used, and the light amount, the arrangement of the light sources, etc. are adjusted as necessary.
When a high-pressure mercury lamp is used, it is preferable to cure at a conveyance speed of 5 to 60 m / min for one lamp having an output of 80 to 160 W / cm.

On the other hand, when the resin layer contains a thermoplastic resin, a coating solution containing a known solvent and thermoplastic resin in the resin composition that can form the resin layer is applied to the support layer or glass layer by the method described above. After processing, creating a laminate including a support layer, a layer containing a thermoplastic resin, and a glass layer, the solvent contained in the resin composition is removed by heating to prepare a glass laminate with a support layer In addition, after the coating and the solvent are removed from the support layer or the glass layer, the glass laminate with the support layer can be prepared by a hot press or a heat laminating method.
The heating temperature for removing the solvent is not particularly limited as long as it is a temperature sufficient to dry the solvent.

Furthermore, a method of previously forming a resin layer containing a thermoplastic resin into a film shape and directly laminating it with a support layer and a glass layer, or a method of laminating with a support layer and a glass layer via an adhesion layer or an adhesive layer And the glass laminated body with a support layer can also be prepared.
As a method for laminating, the above-mentioned press, nip roll, thermal laminating method and the like can be appropriately selected.
When the adhesion layer or the adhesive layer is a layer made of a curable resin composition, a curing step may be appropriately included.

<6-2. Step of peeling at least part of resin layer from support layer>
This step is shown in FIG. 3 (b), and the blade tool 17 is inserted between the release layer 19 and the resin layer 11 formed on the support layer 12, and the outer layer is formed beyond the outer range of the glass layer. At least a part of the obtained resin layer is peeled off from the support layer.
Any blade-shaped tool may be used in the glass laminate 100 with a support layer as long as a part of the resin layer 11 can be peeled off from the support layer 12, and is preferably a blade-shaped tool with a sharp tip. Specific examples include blades such as knives, cutter knives, and scrapers. Furthermore, if the tip is sharp, a polyester resin film or the like can be used.

<6-3. Process of peeling glass laminate from support layer>
This process is shown in FIG. 3 (c). The peeled portion of the resin layer 11 peeled in the process is gripped by the gripping tool 18, and the glass laminate including the glass layer 10 and the resin layer 11 is removed from the support layer 12. Peel off.
The gripping tool 18 is not particularly limited as long as it can grip the peeled portion of the resin layer 11, and when the peeled portion has a sufficient size, it may be picked up with a finger and peeled off. Also, suction / sticking jigs such as vacuum pads and adhesive rolls, and gripping jigs such as clamps are preferably used. At the time of peeling, an attractive force may be applied upward in the drawing, and an attractive force may be applied obliquely upward in the drawing according to the degree of adhesion between the resin layer 11 and the support layer 12.

At the time of peeling, if the radius of curvature of the glass layer is excessively small, the glass layer may be damaged. Therefore, it is preferable to peel the glass layer while keeping the radius of curvature of 30 mm or more. Is particularly preferably maintained at 50 mm or more.
The speed at the time of peeling (the length of the support layer peeled per unit time) is not particularly limited, but is usually 0.01 m / min to 100 m / min, and 1 m / min to 50 m in view of productivity and stability. Peeling at / min is preferable.
By passing through these steps, the glass laminate including the glass layer 10 and the resin layer 11 can be easily and easily peeled from the glass laminate 100 with a support layer without using a large-scale apparatus.

  In addition, normally after forming an electronic device member on the glass layer of the glass laminated body with a support layer, a support layer is peeled. As an embodiment in this case, at least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less are included, and at least a part of the resin layer is formed to exceed the outer range of the glass layer. The step of preparing a glass laminate with a support layer, the step of forming an electronic device member on the glass layer of the prepared glass laminate with a support layer, at least a part of the resin layer formed beyond the outer shape range of the glass layer And a step of holding the peeled resin layer part and peeling the glass laminate including the resin layer and the glass layer from the support layer.

<7. Applications of glass laminates>
In the present invention, a glass laminate including a resin layer and a glass layer can be suitably used as a substrate for electronic devices such as organic EL elements. When used as a substrate for an electronic device such as an organic EL element, a flexible electronic device is obtained by forming an electronic device member on the glass layer of the glass laminate and then peeling between the resin layer and the support layer. Therefore, it can be used for flexible displays and flexible lighting.
As an electronic device, a solar cell element, a thin film secondary battery element, a liquid crystal display element, etc. other than an organic EL element are mentioned.
The electronic device member is a member that is formed on the glass layer and constitutes at least a part of the electronic device, and specifically includes an organic EL element, a solar cell element, a thin film secondary battery element, and a liquid crystal display element. Or the member used for various electronic components etc. is mentioned.

Examples of the member used in the organic EL element include a transparent electrode, a metal electrode, an insulating layer, a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, and an electron injection layer.
Examples of the member used for the solar cell element include an organic semiconductor layer composed of an organic electron donor and an organic electron acceptor, a transparent electrode layer, a metal electrode layer, etc. Various members corresponding to the type, the dye-sensitized type, the quantum dot type solar cell element and the like can be mentioned.
Moreover, a transparent electrode layer, a liquid crystal layer, etc. are mentioned as a member used for a liquid crystal display element.
Moreover, as a member for thin film secondary batteries, a lithium ion type includes a transparent electrode layer, an electrolyte layer containing a lithium compound, and a current collecting layer containing a metal. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
Moreover, as a member for electronic components, in CCD and CMOS, a conductive part, an insulating part, etc. are mentioned, In addition, various members etc. corresponding to various sensors, such as a pressure sensor and an acceleration sensor, are mentioned.

If an electronic device is to be formed using only a glass layer having a thickness of 10 μm or more and 200 μm or less, the glass layer is very fragile, and the process of forming the electronic device member on the substrate becomes difficult. In addition, when a resin layer is laminated on the glass layer in advance, cracking and the like are improved, but since the substrate itself is flexible, the substrate is bent when the substrate is fixed in the formation process of the electronic device member. In addition, defects in the thickness and position accuracy of the electronic device are likely to occur.
Therefore, by fixing the glass layer to the support layer via a resin layer or the like, the handling property during the process of forming the electronic device member is remarkably improved, and a good electronic device can be formed.
However, if the support layer is peeled off at the interface between the glass layer and the resin layer after the electronic device member is formed, the glass layer itself is very easy to break, so there are concerns about the occurrence of cracks after peeling and the scattering of the glass.
In this invention, the handleability in the creation process of an electronic device member can be improved by fixing the glass layer coat | covered with the resin layer to a support layer.

Moreover, when peeling a support layer from a glass laminated body after electronic device member formation, since the resin layer has coat | covered the glass layer, a support layer can be peeled easily, without damaging a glass layer.
The electronic device or flexible device obtained by peeling the support layer from the glass laminate to the resin layer covers the glass layer with the resin layer, so it is possible to prevent breakage and scattering of the glass layer. It becomes.

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

<Evaluation>
The glass laminate with a support layer obtained in the production example was evaluated by the following method.
(Tensile modulus of resin layer)
A strip-shaped resin sample having a thickness of 200 μm, a width of 2 cm, and a length of 150 mm was prepared, and from the elongation and stress in the longitudinal direction of the strip-shaped resin sample using a universal testing machine (manufactured by Shimadzu Corporation, Autograph AGS-X). The tensile elastic modulus was measured and used as the tensile elastic modulus of the resin layer. The test conditions were a chuck distance of 10 cm, a pulling speed of 10 mm / min, and measurement at 25 ° C.

(Tensile elongation at break and tensile strength of resin layer)
A strip-shaped resin sample having a thickness of 200 μm, a width of 10 mm, and a length of 100 mm was prepared, and using a universal testing machine (manufactured by Shimadzu Corporation, Autograph AGS-X), the tensile fracture elongation and tensile fracture of the strip-shaped resin sample were measured. The strength was measured and used as the tensile elongation at break and tensile strength of the resin layer. The test conditions were a distance between chucks of 40 mm, a pulling speed of 50 mm / min, and measurement at 25 ° C.

(Measurement of peel strength between resin layer and support layer)
On the support layer, in the case of Production Examples 1 and 3, a release layer and a resin layer are laminated in this order, and in the case of Production Example 2, an adhesion layer and a resin layer are laminated in this order, and a test piece for measuring peel strength (width 50 mm) is obtained. Produced.
The tensile strength when the resin layer was peeled from the support layer by a 90 degree peel method was set at 23 ° C. and the peel rate was set to 50 mm / min using an Intesco tensile test machine INTESCO 200X. The peel strength was determined.

(Measurement of peel strength between resin layer and glass layer)
On a 2 mm thick glass plate, in the case of Production Examples 1 and 3, a resin layer is laminated in this order, and in the case of Production Example 2, an adhesive layer and a resin layer are laminated in this order to produce a test piece (width 50 mm) for measuring peel strength. did.
The tensile strength when the resin layer was peeled from the glass plate by a 90 degree peeling method was set at 23 ° C. and a peeling speed of 50 mm / min using an Intesco tensile compression tester INTESCO 200X. The peel strength was determined. In addition, when the resin layer did not peel and was broken, the tensile strength at the time of the break was defined as the peel strength between the glass layer and the resin layer.

[Production Example 1]
The glass laminated body with a support layer which has a layer structure shown in FIG. 1 was manufactured.
UV curable urethane acrylate monomer having a functional group equivalent of about 550 (Shin Nakamura Chemical Co., Ltd., trade name “NK Oligo UA-122P”) 54% by mass, functional group equivalent of about 800 UV curable urethane acrylate monomer ( Shin-Nakamura Chemical Co., Ltd., trade name “NK Oligo UA-160TM”) 27 mass%, UV curable acrylate monomer having functional group equivalent of about 150 (Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester A- DCP ") 9% by mass, thiol monomer (manufactured by SC Organic Chemical Co., Ltd., trade name" PEMP ") 9% by weight, 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Corp., trade name" IRGACURE 184 ") 1) 1% by mass was uniformly mixed to obtain an ultraviolet curable resin composition 1 (paint A).
Further, 97% by mass of silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KS-847”) and 3% by mass of a platinum catalyst are provided on one side of a support layer (clean glass, float glass, thickness: 0.7 mm). A silicone paint diluted with methyl ethyl ketone (MEK) was coated with a bar coater and then heat-treated at 150 ° C. for 10 minutes to give a release treatment to form a release layer on the support layer.

Then, after sandwiching the coating material A between the glass layer (manufactured by Nippon Electric Glass Co., Ltd., trade name “OA-10G”, thickness: 50 μm) and the release layer forming side of the support layer, by passing a nip roll, The glass layer, paint A, release layer, and support layer were laminated at once. Further, the used glass layer is 70 mm × 80 mm, the resin layer, the release layer, and the support layer are 100 mm × 100 mm in size, the resin layer and the support layer are arranged so that the outer shape ranges match, and the glass layer is It arrange | positioned so that it might be located inside 5 mm or more from the edge part of the resin layer.
Further, by irradiating a high-pressure mercury lamp (integrated light amount: 580 mJ / cm ² ) from the glass layer side, the layer made of the coating A is cured, and from the support layer side, a support layer, a release layer, a resin layer having a thickness of 50 μm, The glass laminated body 1 with a support layer laminated | stacked in order of the glass layer was obtained. Various evaluation was performed about the obtained glass laminated body 1 with a support layer. The results are shown in Table 1.

[Production Example 2]
The glass laminated body with a support layer which has a layer structure shown in FIG. 4 was manufactured.
Specifically, UV and thermosetting epoxy systems are used as the uncured adhesive layer so that the thickness after curing with a bar coater is 3 μm on the support layer (Clean Tech float glass thickness 0.7 mm). Resin (made by ADEKA, trade name “KRX-690-5”) was applied, and a thermoplastic ETFE film (trade name “Aflex”, made by Asahi Glass Co., Ltd., thickness: 25 μm, single-sided corona treated) as a resin layer The untreated corona surface was laminated on the support layer with a hand roll (hardness: 90 °) with the coated surface of the adhesion layer applied.
Irradiation with a high-pressure mercury lamp (integrated light quantity: 370 mJ / cm ² ), followed by heat treatment at 150 ° C. for 30 minutes with a hot air circulation dryer, the ultraviolet ray and the thermosetting resin composition were cured to obtain an adhesion layer .

On the corona-treated surface side of the ETFE film, the thickness after curing the above-mentioned ultraviolet and thermosetting epoxy resin (made by ADEKA, trade name “KRX-690-5”) as an uncured product of the adhesive layer with a bar coater After coating to 3 μm, a glass layer (trade name “OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 50 μm) is laminated on the coated surface so as to be aligned with the center of the glass plate, and a high-pressure mercury lamp (Integrated light quantity: 370 mJ / cm ² ) was irradiated, and then the ultraviolet ray and the thermosetting resin composition were cured by heat treatment at 150 ° C. for 1 hour with a hot air circulation dryer.

Thus, the glass laminated body 2 with a support layer laminated | stacked in order of the contact | adherence layer, the resin layer, the contact bonding layer, and the glass layer from the support layer side was obtained. The used glass layer has a size of 70 mm × 80 mm, the adhesive layer, the resin layer, the adhesion layer, and the support layer have a size of 100 mm × 100 mm. It arrange | positioned so that it might correspond and arrange | positioned so that a glass layer might be located inside 5 mm or more from the edge part of a resin layer. Various evaluation was performed about the obtained glass laminated body 2 with a support layer. The results are shown in Table 1.
In the measurement of the peel strength between the resin layer and the glass layer, the resin layer was broken before peeling from the glass. The tensile strength when the resin layer broke was 28 N / 50 mm or more.

[Production Example 3]
The glass layer, the resin layer, the release layer, and the support layer are 100 mm × 100 mm in size, and are manufactured in the same manner as in Production Example 1 except that they are laminated so that the outer shape ranges of all the layers match. A laminate 3 was obtained.
Various evaluation was performed about the obtained glass laminated body 3 with a support layer. The results are shown in Table 1.

[Example]
About the glass laminated body 1 and 2 with a support layer obtained by the said manufacture examples 1 and 2, the support layer was peeled by the method shown in FIG. At this time, as a blade-like tool, a part of the resin layer was peeled off using a cutter knife, and peeling was attempted by gripping the peeled portion with a finger.
As a result, both of the glass laminates 1 and 2 with the support layer could be peeled from the support layer without breaking the glass layer in the middle and without cracking.

[Comparative example]
About the glass laminated body 3 with a support layer obtained by the said manufacture example 3, the cutter knife was inserted between the resin layer and the support layer, and a part of resin layer was peeled. Further, when the peeled portion was grasped with a finger, the glass layer was broken.

100, 200 Glass laminate 10 with support layer, 20 Glass layer 11, 21 Resin layer 12, 22 Support layer 13 Outline range of glass layer (solid line range)
14 External range of resin layer (solid line range)
17 Cutting tool 18 Grasping tool 19 Release layer 25 Adhesive layer 26 Adhesive layer

Claims (8)

At least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less formed in the outer range of the resin layer are provided in this order, and at least a part of the resin layer has an outer range of the glass layer. A method of peeling a glass laminate including a resin layer and a glass layer from a glass laminate with a support layer formed beyond,
At least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less formed in the outer range of the resin layer are provided in this order, and at least a part of the resin layer has an outer range of the glass layer. A step of preparing a glass laminate with a support layer formed beyond,
A step of peeling from the support layer at least a part of the resin layer formed beyond the outer diameter range of the glass layer, and a glass laminate having the resin layer and the glass layer from the support layer by grasping the peeled resin layer. The peeling method of a glass laminated body provided with the process to peel. The method for peeling a glass laminate according to claim 1 , wherein the resin layer has a tensile breaking strength of 10 MPa or more and 300 MPa or less. The method for peeling a glass laminate according to claim 1 or 2 , wherein the resin layer has a tensile elongation at break of 5% or more and 500% or less. The method for peeling a glass laminate according to any one of claims 1 to 3 , wherein the resin layer has a tensile elastic modulus of 50 MPa or more and 2500 MPa or less. The method for peeling a glass laminate according to any one of claims 1 to 4 , wherein a peel strength between the resin layer and the support layer is 0.1 N / 50 mm or more and 5 N / 50 mm or less. . The said resin layer contains a thermoplastic resin, The peeling method of the glass laminated body of any one of Claims 1-5 characterized by the above-mentioned. The method for peeling a glass laminate according to any one of claims 1 to 5 , wherein the resin layer is formed by curing a curable resin composition. At least a support layer, a resin layer, and a glass layer having a thickness of 10 μm or more and 200 μm or less formed in the outer range of the resin layer are provided in this order, and at least a part of the resin layer has an outer range of the glass layer. A step of preparing a glass laminate with a support layer formed beyond,
A step of forming an electronic device member on the glass layer of the prepared glass laminate with a support layer,
A step of peeling at least a part of the resin layer formed beyond the outer shape range of the glass layer from the support layer; and gripping the peeled resin layer to remove the glass laminate including the resin layer and the glass layer from the support layer. A method for manufacturing an electronic device, comprising the step of peeling.

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