JP6350164B2 - Glass laminate - Google Patents

Description

  The present invention relates to a glass laminate having a configuration in which an active energy ray-curable resin layer is laminated on a substrate made of a glass plate.

  In recent years, electronic devices (electronic components) such as organic EL panels, solar cells, and thin film secondary batteries have been made thinner and lighter, and glass substrates used in these electronic devices have been made thinner. . 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. Also, from the viewpoint of handling properties, a resin substrate can be used instead of the glass substrate, but the resin substrate has problems in chemical resistance, moisture resistance, heat resistance, and the like.

  Therefore, recently, a glass laminate in which a transparent resin is laminated on a thin glass plate to improve handling properties has been proposed.

Examples of the glass laminate having improved handling properties include the following disclosure.
Patent Document 1 discloses a substrate in which a synthetic resin having a thickness smaller than that of a glass sheet of 100 μm or less is laminated.
Patent Document 2 discloses a glass-plastic composite in which a polymer layer of 200 μm or less is directly attached to at least one of a glass film having a thickness of 500 μm or less, and at least one side of the surface has low undulation and low roughness. A film is disclosed and described for use in electronic device substrates.
Patent Document 3 discloses a transparent substrate provided with a resin layer having a specific elastic modulus and fracture toughness value on one side or both sides of glass, and the thickness of the resin layer is specified with respect to the thickness of the glass. It is described that a thermoplastic resin is preferable.
Patent Document 4 discloses a transparent substrate having a transparent resin layer on one side or both sides of a glass, which has a shrinkage stress with respect to glass of 5 MPa or more and exhibits a high glass transition temperature. The resin used is thermoplastic. It is stated that resins are preferred.

JP 2002-521234 Gazette Special Table 2002-542971 JP 2010-132526 A JP 2011-088789 A

However, Patent Document 1 does not suggest any mechanical strength of the resin layer, and is insufficient for providing a glass laminate having excellent handling properties.
In patent document 2, although there exists description regarding the surface roughness of a glass-plastic composite film, when using as a board | substrate of an electronic device, for example, the glass laminated body which was excellent in planar smoothness is desired.
In Patent Document 3, although the mechanical strength of the resin layer is mentioned, since the laminate is composed of a very brittle resin, once the laminate is cracked, it propagates in the surface direction, and the film There is a concern that the shape cannot be maintained.
In patent document 4, since the shrinkage stress with respect to the glass of a resin layer is large, when a resin layer is provided in the single side | surface of glass, there exists a concern that a laminated body will warp and handling property will fall.

  The thin film glass laminate having improved handling properties by being laminated with the resin layer can be rolled by reducing the thickness of the thin film glass, which is advantageous in production. On the other hand, a roll-shaped laminate is generally used as a substrate for a device or the like after being unwound from a roll and cut into a desired size. However, even in the case of a glass laminate having improved handling properties, cracks may propagate from the cut location during cutting. The present invention solves such a problem.

As a result of intensive investigations in view of the above problems, the inventors of the present invention have made it possible to significantly prevent the progress of cracks and breakage by laminating an active energy ray-curable resin layer having a specific mechanical strength on a glass plate. It discovered that the glass laminated body which has a prevention function was obtained. Moreover, it discovered that it was excellent in surface smoothness by making surface roughness into a specific value, and the glass laminated body used suitably as a board | substrate of an electronic device was obtained, and came to complete this invention.
That is, the present invention is as follows.

[1] A glass laminate having an active energy ray-curable resin layer on at least one surface of a glass plate having a thickness of 100 μm or less, wherein the active energy ray-curable resin layer has a tensile elongation at break of 10% or more and 500% or less. An average surface roughness of at least one of the active energy ray-curable resin layer side surface of the glass laminate is 10 nm or less.
[2] The glass laminate according to [1], wherein the active energy ray-curable resin layer has a tensile elastic modulus of 10 MPa to 2000 MPa.
[3] The ratio of the total thickness of the active energy ray-curable resin layer to the thickness of the glass plate (the total thickness of the active energy ray-curable resin layer / the thickness of the glass plate) is 5% or more and less than 10%. The glass laminate according to [1] or [2].
[4] A step of preparing a laminate in which a layer containing an active energy ray-curable composition and a protective film having active energy ray permeability are laminated in this order from the glass plate on at least one side of the glass plate; The laminated body is irradiated with an active energy ray, the layer containing the active energy ray curable composition is cured to form an active energy ray curable resin layer, and the cured resin layer and the protective film, The glass laminated body in any one of [1]-[3] manufactured by the manufacturing method including the process of peeling.
[5] The glass laminate according to any one of [1] to [4], which has active energy ray-curable resin layers on both surfaces of the glass plate.
[6] An organic EL device using the glass laminate according to any one of [1] to [5] as a substrate.

  According to the present invention, it is possible to provide a glass laminate that significantly prevents the development and breakage of cracks compared to conventional methods, has a function of preventing breakage, and is excellent in surface smoothness. Therefore, a glass laminate suitable as a substrate for electronic devices is provided. Furthermore, the organic EL element which used such a laminated body as the base material can be provided.

  The present invention includes a glass laminate according to the first embodiment and an organic EL device characterized by using the glass laminate according to the second embodiment as a base material.

The present invention will be described in detail below, but the following description is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents.
In the present specification, for the sake of simplicity, the “active energy ray-curable composition” is referred to as the “curable composition”, the “active energy ray-curable resin” as the “curable resin”, and the “active energy”. The “line curable resin layer” may be referred to as a “cured resin layer”.

  A first embodiment of the present invention is a glass laminate having an active energy ray-curable resin layer on at least one side of a glass plate having a thickness of 100 μm or less, and the tensile break elongation of the active energy ray-curable resin layer is The glass laminate is characterized by being 10% or more and 500% or less, and having an average surface roughness of at least one of the active energy ray-curable resin layer side surface of the glass laminate of 10 nm or less.

<1. Glass>
Any appropriate glass plate can be adopted as long as the glass plate used in the first embodiment of the present invention is a plate having a thickness of 100 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 strengthening and surface treatment are also possible. It is properly used by.
As a specific example marketed, “OA-10G” manufactured by Nippon Electric Glass Co., Ltd., which is an alkali-free glass, can be mentioned.

  Glass having a thickness of 100 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 plate can be controlled by the glass composition, the thickness of the glass melt, the temperature, and the take-up speed.

The thickness of the glass is preferably 0.1 μm or more, more preferably 10 μm or more, and further 20 μm or more. On the other hand, it is usually 100 μm or less, preferably 90 μm or less, more preferably 80 μm or less. By setting the thickness to 0.1 μm or more, extreme reduction in mechanical strength can be prevented, and damage due to stress such as when a cured resin layer is formed can be prevented. On the other hand, by setting the thickness to 100 μm or less, it is possible to efficiently laminate a cured resin layer for the purpose of improving the secondary workability, having excellent handling properties without deteriorating the production efficiency of a single glass.
As a specific example marketed, “OA-10G” manufactured by Nippon Electric Glass Co., Ltd. having a thickness of 50 μm can be mentioned.

<1-1. Total light transmittance of glass plate>
The total light transmittance of the glass plate is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. If it is 80% or more, the light transmittance of a glass laminated body is securable. Such a glass plate 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 plate>
When the active energy ray curable resin layer is formed on one side of the glass plate, the average surface roughness of the other side, that is, the side where the cured resin layer is not formed is preferably 10 nm or less, more preferably 5 nm or less. More preferably, it is 2 nm or less. If it is 10 nm or less, a thin film of carbon and various metals, and oxides and nitrides thereof are laminated on the surface with a thickness of about 0.1 nm to several tens of nm for the purpose of imparting conductivity and gas barrier properties. In the case of a thin film device such as an organic EL. The lower limit is not particularly limited, but is preferably 0.1 nm or more. As such a glass plate, 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):
Surface observation (observation field of view: 93.97 μm × 71.30 μm) of the glass plate was performed using a non-contact surface / layer cross-section measurement system VertScan 2.0 (manufactured by Ryoka System Co., Ltd.). Roughness (arithmetic mean roughness Sa) is calculated.

<2. Active energy ray>
The active energy ray in the first embodiment of the present invention is not particularly limited as long as it is an energy ray that induces a polymerization reaction, and is suitable for the composition, properties, etc. of the curable composition that is cured by irradiation with the active energy ray. Active energy rays can be used. For example, energy rays that affect the electron orbit of the irradiated object, such as electron beams, ultraviolet rays, and infrared rays, and can trigger polymerization reactions such as radicals, cations, and anions. These can be used alone or in combination of two or more.
Specific examples include ultraviolet rays emitted from a high-pressure mercury lamp.

<3. Active energy ray curable resin layer>
The active energy ray-curable resin layer in the glass laminate according to the first embodiment of the present invention is a layer obtained by curing an active energy ray-curable composition described later by irradiating active energy rays.

  The glass laminate according to the first embodiment of the present invention has this active energy ray-curable resin layer, so that when a crack occurs in the glass laminate, the crack does not propagate and the shape on the film Can be held.

  Moreover, in the glass laminated body which concerns on 1st embodiment of this invention, it generate | occur | produces by secondary processes, such as protecting a glass plate from a damage | wound of a surface, and a damage | wound, a glass plate surface, a hole, and a cutting | disconnection. In order to prevent contamination by cutting powder, an active energy ray-curable resin layer may be laminated on both surfaces of the glass plate.

<3-1. Layer containing energy ray curable composition>
The layer containing the active energy ray-curable composition is a layer that is cured by the energy ray and becomes an active energy ray-curable resin layer. If the said layer hardens | cures when irradiated with an active energy ray, it may contain components other than an active energy ray curable composition. Examples of such components include thermoplastic resins, fillers, ultraviolet absorbers, polymerization inhibitors, and the like.

<3-1-1. Energy ray curable composition>
The active energy ray-curable composition is not particularly limited as long as the active energy ray-curable composition is a composition in which a polymerization reaction is induced and cured by the active energy ray, but includes at least an active energy ray-curable resin. In addition, you may include the other component which does not inhibit the effect of the 1st embodiment of this invention, and the other component which improves this effect. Such components will be described later.

<3-1-1-1. Active energy ray curable resin>
The curable resin contained in the active energy ray-curable composition is not particularly limited as long as it is a resin that induces a polymerization reaction by the active energy ray and cures, but can be cured in a short time and relatively easily. Therefore, 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, monomers and oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate are used.
Furthermore, some of these are exemplified by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipenta Examples thereof include monofunctional and polyfunctional acrylic monomers and methacrylic monomers having one or more carbon-carbon double bonds, such as erythritol hexamethacrylate, isoamyl acrylate, ethoxydiethylene glycol acrylate, and methoxydiethylene glycol acrylate.
In addition, these can be used 1 type or in combination of 2 or more types.
Specific examples that are commercially available include, for example, a product name “NK Oligo UA-122P” manufactured by Shin-Nakamura Chemical Co., Ltd., which is a urethane acrylate oligomer, a product name “New Frontier R-1303” manufactured by Daiichi Kogyo Seiyaku, and acrylate. A trade name “Ogsol EA-0300” manufactured by Osaka Gas Chemical, which is a monomer, may be used.

  The total concentration of the curable resin in the active energy ray-curable composition is preferably 30% by mass or more, more preferably because it has a certain degree of viscosity and is easier to process and mechanical properties after processing are improved. Is 65% by mass or more, more preferably 80% by mass or more.

<3-1-1-2. Photopolymerization initiator>
When the curable resin is an ultraviolet curable monomer or oligomer, the active energy ray 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. 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 E) Phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 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.
Specific examples that are commercially available include 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF, trade name “IRGACURE184”).

The concentration of the polymerization 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 surely proceeding the curing reaction. That's it. 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.

<3-1-1-3. Other ingredients>
In addition to the above, for example, in order to adjust physical properties such as curability, water absorption and hardness of the curable resin, any polymer component such as poly (meth) acrylic acid ester, epoxy resin, polyurethane resin, and polyester resin may be arbitrarily selected. To obtain the curable composition. 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, thermoplastic resins, etc. are optional as long as they do not interfere with physical properties such as curability, transparency, and water absorption. Can be added. In addition, these can be used 1 type or in combination of 2 or more types as appropriate.

<3-1-1-4. Solvent>
The active energy ray-curable composition can be used after adding a solvent, if necessary. That is, it can be used as a solution containing the curable composition.
The solvent is not particularly limited as long as it is a solvent that uniformly dilutes the active energy curable resin, and examples thereof include methyl isobutyl ketone, butyl acetate, and propylene glycol monomethyl ether. These can be used alone or in combination of two or more. In addition, since workability is good, after forming an active energy ray-curable composition layer on glass or a protective film, a solvent is used when forming a glass / resin / protective film laminate after drying. It is preferable to add, and when a glass / resin / protective film laminate is formed at a time and a solvent drying step is not included, it is preferable not to add a solvent. The kind and addition amount of a solvent can be suitably selected according to the various coating system mentioned later.

<3-1-2. Thickness of layer containing active energy ray-curable composition>
The thickness of the layer containing the active energy ray-curable composition used in the first embodiment of the present invention depends on the thickness of the cured resin layer formed by irradiation with active energy rays and various coating methods described later. It can be set appropriately.

<3-2. Tensile elongation at break of cured resin layer>
The tensile breaking elongation of the cured resin layer of the glass laminate according to the first embodiment of the present invention is usually 10% or more and 500% or less. Further, it is preferably 15% or more, more preferably 20% or more, preferably 400% or less, more preferably 300% or less.
When the tensile elongation at break has a value in the above range, propagation of cracks from the cut portion can be suppressed during cutting. In addition, even if the glass plate is broken inside the glass laminate, the cured resin layer does not break and maintains its shape as the glass laminate, thereby preventing the glass from scattering.

The tensile elongation at break of the cured resin layer can be measured by the following method.
A strip-shaped resin sample having a thickness of 200 μm, a width of 10 mm, and a length of 100 mm is prepared, and the tensile breaking elongation of the strip-shaped resin sample can be measured using a tensile tester (manufactured by Shimadzu Corporation, AGS-X). The test conditions are such that the distance between chucks is 40 mm, the pulling speed is 50 mm / min, and measurement can be performed at 25 ° C.

<3-3. Average surface roughness of active energy ray-curable resin layer side surface of glass laminate>
The average surface roughness of the active energy ray-curable resin layer side surface of the glass laminate is 10 nm or less. Moreover, it is preferable that it is 5 nm or less, and it is more preferable that it is 3 nm or less. By having such an average surface roughness, the cured resin layer surface of the glass laminate becomes smooth, so that when a thin film is further laminated on the surface, a uniform film is likely to be formed. It can be suitably used as a substrate.
The average surface roughness can be calculated by the same method as described above.
In order to adjust the average surface roughness of the cured resin layer, it is necessary to appropriately adjust the air volume, temperature, and processing time during coating and drying, or to manufacture using a protective film having a predetermined average surface roughness described later. It can be adjusted with.

<3-4. Tensile modulus of cured resin layer>
The tensile elastic modulus of the cured resin layer is preferably 10 MPa or more, more preferably 20 MPa or more, further preferably 25 MPa or more, and particularly preferably 30 MPa or more. On the other hand, it is preferably 2000 MPa or less, more preferably 1800 MPa or less, further preferably 1500 MPa or less, and particularly preferably 400 MPa or less.
By having a tensile elastic modulus of 10 MPa or more, when an impact is applied to the glass laminate from the outside, the cured resin layer can absorb the impact, so that the glass laminate can be prevented from being damaged. In addition, for example, when the glass laminate is used as a substrate for a device or the like, blocking does not occur even when rolled or the like, and the cured resin layer can be prevented from peeling from the glass plate. On the other hand, by setting the tensile elastic modulus to 2000 MPa or less, it is possible to prevent an impact applied to the glass laminate from being applied to the glass plate and to prevent breakage of the glass plate. Furthermore, the shrinkage stress when the curable resin is cured and the stress when the curable resin is thermally expanded after the curable resin is cured can be relaxed, and the deformation of the glass plate and the warp of the glass laminate can be prevented.

The tensile elastic modulus of the cured resin layer can be measured by the following method.
A strip-shaped resin sample having a thickness of 200 μm, a width of 2 cm, and a length of 150 mm is prepared, and using a tensile tester (manufactured by Shimadzu Corp., AGS-X), the tensile elastic modulus is calculated from the elongation and stress in the longitudinal direction of the strip-shaped resin sample. It can be measured. The test conditions can be measured at 25 ° C. with a distance between chucks of 10 cm, a pulling speed of 10 mm / min.

<3-5. Thickness of cured resin layer>
The thickness of the cured resin layer is preferably 1 μm or more, more preferably 3 μm or more, and further preferably 6 μm or more. On the other hand, it is particularly preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less.
When the thickness of the cured resin layer is 1 μm or more, the impact applied to the glass plate can be sufficiently relaxed, and the excellent handling property of the glass laminate can be realized. On the other hand, by setting the thickness of the cured resin layer to 100 μm or less, deformation when a load is applied from the thickness direction of the glass laminate can be prevented, and blocking can be prevented. Also, when the glass laminate is applied to a vacuum process, the amount of outgas composed of moisture and low molecular weight components can be kept within the allowable range in the process.
The thickness of the cured resin layer can be appropriately set according to the thickness of the layer containing the active energy ray-curable resin composition and various coating methods described later.

<3-6. Total light transmittance of cured resin layer>
The total light transmittance of the cured 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 light transmittance of a glass laminated body is securable.
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.
In order to adjust the total light transmittance of the cured resin layer, a curable resin having a short conjugated system molecular skeleton or a molecular skeleton having low crystallinity may be appropriately selected.

<4. Glass laminate>
The glass laminate according to the first embodiment of the present invention comprises an active energy ray-curable resin layer on at least one surface of a glass plate.
Whether the active energy ray-curable resin layer is laminated on at least one side of the glass plate, that is, one side or both sides of the glass plate, can be properly used depending on the purpose and application. When forming a thin film device such as an EL, for example, by laminating only on one side opposite to the device surface, the strength of the glass plate having a thickness of 100 μm or less is improved, and at the same time, the handling property is imparted. Device characteristics similar to those of a conventional glass substrate can be exhibited.
On the other hand, in order to protect the glass plate from scratches and damages on the surface, and to prevent contamination of the glass plate surface and contamination by cutting powder generated in secondary processing such as drilling and cutting, the active energy ray-curable resin layer is made of glass. You may laminate | stack on both surfaces of a board.

<4-1. Ratio of total thickness of cured resin layer and thickness of glass plate in glass laminate>
The ratio of the total thickness of the cured resin layer and the thickness of the glass plate (total thickness of the cured resin layer / thickness of the glass plate) in the glass laminate according to the first embodiment of the present invention is such that the cured resin layer is a glass laminate. Since the impact applied to the film can be relaxed and the handleability of the laminate can be improved, it is preferably at least 5%, more preferably at least 8%, and even more preferably at least 10%. On the other hand, the visible light permeability of the glass laminate can be kept high, and when the laminate is applied to a vacuum process, the amount of outgas consisting of moisture and low molecular weight components can be suppressed. , Preferably less than 100%, more preferably less than 60%, still more preferably less than 50%.
The ratio can be realized by preparing a cured resin layer and a glass plate having a desired thickness by a method that has already been described in detail.

<4-2. Total light transmittance of glass laminate>
The total light transmittance of the glass laminate according to the first embodiment of the present invention is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. If it is 80% or more, it can be used suitably as a base material of light emitting elements, such as organic EL.
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.
In order to adjust the total light transmittance of the glass laminate, for example, an appropriate glass plate is selected, and a curable resin having a short conjugated system molecular skeleton or a molecular skeleton having low crystallinity is appropriately selected. Good.

<4-3. Glass haze haze>
The haze of the glass laminate according to the first embodiment of the present invention is preferably 10% or less, more preferably 5% or less, from the viewpoint of reducing loss due to light scattering.
In addition, haze can be measured by the method based on JISK7136, for example. At this time, for example, a transmittance meter (“HR-100” manufactured by Murakami Color Research Laboratory) can be used.

<4-4. Average surface roughness of active energy ray-curable resin layer side surface of glass laminate>
The average surface roughness of the active energy ray-curable resin layer side surface of the glass laminate according to the first embodiment of the present invention is as described above.

<5. Manufacturing method of glass laminate>
Although the manufacturing method of the glass laminated body which concerns on 1st embodiment of this invention will not be specifically limited if the above-mentioned glass laminated body is obtained, since workability is favorable, at least of the said glass plate A laminate preparation step for preparing a laminate in which a layer containing an active energy ray-curable composition is laminated on one side, an active energy ray irradiation to the laminate, and a layer containing the active energy ray-curable composition It is preferable that it is a manufacturing method including the cured resin layer formation process which hardens | cures and forms an active energy ray cured resin layer.

  Moreover, as described later, it is more preferable to use a protective film having active energy ray permeability. That is, in the laminate preparation step, on at least one surface of the glass plate, a layer containing an active energy ray-curable composition and a protective film having active energy ray permeability are laminated in this order from the glass plate, It is more preferable that the production method includes a peeling step of peeling the cured resin layer and the protective film after forming the cured resin layer.

<5-1. Laminate preparation process>
It is preferable that a laminated body preparation process is a process of preparing the laminated body which laminated | stacked the layer containing an active energy ray curable composition on the at least single side | surface of the said glass plate.
Moreover, as another embodiment, a laminate comprising an active energy ray-curable composition layer and an active energy ray-permeable protective film laminated in this order from the glass plate on at least one side of the glass plate. More preferably, it is a step of preparing a body.

In the glass laminate according to the first embodiment of the present invention, the glass plate is protected from scratches and damages on the surface, or the surface of the glass plate is soiled, or by cutting powder generated by secondary processing such as drilling and cutting. In order to prevent contamination, an active energy ray-curable resin layer may be formed on both surfaces of the glass plate. Therefore, in this process, you may laminate | stack the layer containing an active energy ray curable composition on both surfaces of a glass plate.
Further, in the embodiment in which the laminate is prepared using the protective film having active energy ray permeability, for the same reason, the active energy ray is cured between the glass plate and the protective film on both sides of the glass plate. You may laminate | stack the layer containing an adhesive composition.

<5-1-1. Layer containing active energy ray-curable composition>
Details of the layer containing the active energy ray-curable composition are as described above.

<5-1-2. Protective film>
The protective film is peeled off for the first time in the peeling step when the glass laminate is used as a base material such as an organic EL element. Therefore, when a protective film is laminated on the glass plate, it is possible to prevent foreign matters from being mixed on the surface having the protective film.

  Also, by preparing a laminate in which a layer containing a curable composition is sandwiched between a glass plate and a protective film, the curable composition does not come into contact with oxygen when irradiated with active energy rays in the next step. The polymerization reaction proceeds. Therefore, it is possible to prevent inhibition of curing due to oxygen, and it can be sufficiently cured in a short time to obtain a cured resin layer having a uniform thickness.

<5-1-2-1. Material of protective film>
When using a protective film, it is preferable that a protective film is a protective film which has a property which permeate | transmits an active energy ray mentioned above. The material is not particularly limited, and can be arbitrarily selected from resins such as polyethylene, polypropylene, cyclic polyolefin, polyethylene terephthalate, polyethylene naphthalate, and polyimide. From the viewpoint of applying a curing process by ultraviolet rays that can be cured in a short time, it is preferable to select from polyethylene, polypropylene, cyclic polyolefin, and polyethylene terephthalate that transmit a wavelength region of 250 to 350 nm, from the viewpoint of mechanical strength. It is preferable to select from polyethylene terephthalate, polyethylene naphthalate, and polyimide. In view of the above, it is particularly preferable to use a protective film containing a polyethylene terephthalate resin.
A commercially available protective film may be used as it is, or may be used after subjecting a commercially available protective film to surface treatment as necessary.
Specific examples that are commercially available include “A4100” manufactured by Toyobo, which is a polyethylene terephthalate film.

<5-1-2-2. Surface treatment of protective film>
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. However, the average surface roughness tends to increase by performing the mold release treatment as described above.

<5-1-2-3. Average surface roughness of the layer-side surface containing the active energy ray-curable composition in the protective film>
The average surface roughness of the surface on the layer side containing the active energy ray-curable composition in the protective film is preferably 10 nm or less, more preferably 5 nm or less, and particularly preferably 3 nm or less.
When the average surface roughness is within this range, the surface of the cured resin layer side in the glass laminate after the peeling step becomes smooth, so that when a thin film is further laminated on the surface, a uniform film is easily formed. It can use suitably, when producing thin film devices, such as.
The average surface roughness can be calculated by the same method as described above.

The layer containing the curable composition is laminated so as to be sandwiched between a glass plate and a protective film, and is cured by irradiation with active energy rays to form a cured resin layer. Thereafter, in the peeling step, the protective film is peeled off. Therefore, the average surface roughness of the cured resin layer side surface in the glass laminate after the peeling step depends to some extent on the average surface roughness of the layer side surface containing the active energy ray-curable composition in the protective film.
What is necessary is just to select a well-known thing suitably as such a protective film. Specific examples that are commercially available include “A4100” manufactured by Toyobo, which has an average surface roughness of 0.7 nm.

<5-1-2-4. Protective film thickness>
Although the thickness of a protective film is not specifically limited, It is preferable that it is 25-150 micrometers from a viewpoint of handling property.
What is necessary is just to select a well-known thing suitably as such a protective film. Specific examples that are commercially available include “A4100” manufactured by Toyobo with a thickness of 125 μm.

<5-1-3. Lamination on one side of glass plate>
A preferred embodiment of this step is a form of preparing a laminate in which a layer containing an active energy ray-curable composition is laminated on one side of a glass plate having a thickness of 100 μm or less.
If the layer containing an active energy ray curable composition can be laminated | stacked on the single side | surface of an above described glass plate, the method will not be specifically limited.
For example, it is preferable to laminate a layer containing a curable composition directly on a glass plate.
As a lamination method, a known method can be used. For example, die coating, bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, dip coating and the like can be mentioned.

  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 containing the curable composition, and the desired thickness of the cured resin layer formed by active energy ray irradiation. .

  Moreover, when the solvent is added to the active energy ray curable composition, after laminating | stacking the layer containing a curable composition, the process of drying and removing a solvent may be included.

Further, an embodiment in which a layer containing an active energy ray-curable composition and a protective film having active energy ray permeability are laminated in this order from the glass plate side on one side of the glass plate is also preferable.
Although the method is not particularly limited, for example, after laminating a layer containing an active energy ray-curable composition on a protective film, it is preferably bonded to one side of a glass plate. After laminating the layer containing the curable composition, it is also preferable to attach the protective film. When imparting functionality to the surface shape of the cured resin layer, such as smoothness, slipperiness, and light diffusibility, the former can be transferred to the active energy ray-curable composition because the surface shape of the protective film can be transferred. More preferred.
In any case, the laminating method is not particularly limited, and examples thereof include the method described above.

  Moreover, it is also preferable to laminate | stack the layer containing a curable composition, a protective film, and a glass plate at once. For example, it is also preferable to form a layer containing the curable composition into a sheet in a state of being sandwiched between a glass plate and a protective film, and to laminate the layer containing the curable composition. Although the method of forming in a sheet form is not specifically limited, For example, well-known methods, such as a press and rolling, are mentioned.

  When the solvent is added to the active energy ray-curable composition, a step of drying and removing the solvent after laminating a layer containing the curable composition on the protective film may be included.

<5-1-4. Lamination on both sides of glass plate>
Other preferable embodiment of this process is a form which prepares the laminated body which laminated | stacked the layer containing an energy-beam curable composition on both surfaces of the glass plate of thickness 100 micrometers or less.
A layer containing the active energy ray-curable composition may be laminated on both surfaces of the glass plate, and the method is not particularly limited. At this time, it may be laminated one side at a time, or may be laminated on both sides at once. Moreover, when laminating | stacking one surface each, you may laminate | stack on the other surface, after the layer containing the curable composition of the laminated surface dries.
In any case, the laminating method is not particularly limited, and examples thereof include the method described above.

  Moreover, when the solvent is added to the active energy ray curable composition, after laminating | stacking the layer containing a curable composition, the process of drying and removing a solvent may be included.

Moreover, it is also preferable to laminate | stack the layer containing an active energy ray curable composition and the protective film which has active energy ray permeability | transmittance in this order from the glass plate side on both surfaces of a glass plate.
The method is not particularly limited, but when imparting functionality to the surface shape of the cured resin layer, such as smoothness, slipperiness, and light diffusibility, the surface shape of the protective film is transferred to the active energy ray-curable composition. Therefore, for example, it is preferable to laminate a layer containing the active energy ray-curable composition on the protective film and bond them to both surfaces of the glass plate.
In addition, after laminating a layer containing the active energy ray-curable composition on both surfaces of the glass plate, it is also preferable to attach a protective film. In this case, the layer containing the curable composition on the laminated surface is dried. Then, it may be laminated on the other surface.
In any case, the laminating method is not particularly limited, and examples thereof include the method described above.

  Moreover, it is also preferable to laminate | stack the layer containing a curable composition, a protective film, and a glass plate at once. For example, it is also preferable to form a layer containing the curable composition by forming a layer containing the curable composition into a sheet shape in a state of being sandwiched between the protective film on both surfaces of the glass plate. Examples of the method for forming a sheet include known methods such as pressing and rolling.

  When the solvent is added to the active energy ray-curable composition, a step of drying and removing the solvent after laminating a layer containing the curable composition on the protective film may be included.

<5-2. Cured resin layer forming step>
The cured resin layer forming step is a step of irradiating the laminated body prepared in the above “laminated body preparing step” with active energy ray irradiation and curing a layer containing the curable composition to form a cured resin layer.

  In this step, the irradiation direction of the active energy ray irradiation for curing the layer containing the curable composition is not particularly limited. For example, even when a protective film is used, it may be irradiated from the protective film side. You may irradiate from other directions, such as from the side.

The light source of active energy rays, its arrangement, the amount of light, and the like are not particularly limited as long as the layer containing the curable composition can be cured. As an example, in the case of curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or the like can be mentioned, and the light amount, the arrangement of the light source, etc. are adjusted as necessary.
Moreover, when using a high pressure mercury lamp, it is preferable to harden at the conveyance speed of 5-60 m / min with respect to 1 lamp | ramp which has the light quantity of 80-160 W / cm.

<5-3. Peeling process>
If a protective film is used, a peeling step is included. In this step, the active energy ray-curable resin layer formed in the “cured resin layer forming step” is peeled off from the protective film.
The protective film usually has good releasability, and the peeling method is not particularly limited.
By performing the peeling step after irradiation of the active energy ray in the cured resin layer forming step, the curing reaction of the curable composition can be sufficiently cured in a short time without being inhibited by oxygen. Moreover, it is possible to prevent dust from adhering to the surface of the cured resin layer.

<6. Organic EL device>
In a second embodiment of the present invention, an organic EL device (also referred to as an organic electroluminescence device or an organic electroluminescence device) is characterized in that the glass laminate according to the first embodiment of the present invention is used as a substrate. It is.

  The glass laminate according to the first embodiment of the present invention is suitable as a substrate for a thin film device such as an organic EL, for example, because a uniform film is easily formed when a thin film is further laminated on a smooth surface. Can be used.

  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.

<6-1. 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 with low heat resistance as the substrate, ITO or IZO is used, and a transparent anode formed at a low temperature of 150 ° C. or lower is preferable.

<6-2. Cathode>
The cathode usually has 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., depending on the use and purpose of the light-emitting element, 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 (for example, 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 a cathode and an organic compound layer with 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.

<6-3. 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 the dopant 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 G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha.

  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.

<6-4. 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.

<6-5. 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.

<6-6. 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.

<6-7. Manufacturing method of organic EL element>
In order to use the glass laminate according to the first embodiment as a substrate of such a thin film device of an organic EL element, a known method may be used, for example, batch processing by a single wafer form or winding in a roll shape. From the taken state, it can be processed by a roll-to-roll manufacturing method. When batch processing is performed on a single sheet, it can be processed after being attached to a support plate having no flexibility, and then peeled off from the support plate for use.

<6-8. Applications of organic EL devices>
The organic EL device according to the second embodiment of the present invention can be used as, for example, an organic EL module. 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. on the substrate. Can do.

Moreover, the organic EL element which concerns on the 2nd embodiment of this invention can also be used as an organic EL display apparatus 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 according to the second embodiment of the present invention can be formed.

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

<Evaluation>
The tensile modulus of elasticity and the elongation at break of the resin constituting the ultraviolet curable resin layer of the glass laminate obtained in Examples and Comparative Examples were measured by the following methods.

(Tensile modulus of UV curable resin layer)
A strip-shaped resin sample having a thickness of 200 μm, a width of 2 cm, and a length of 150 mm is prepared, and using a tensile tester (manufactured by Shimadzu Corp., AGS-X), the tensile elastic modulus is calculated from the elongation and stress in the longitudinal direction of the strip-shaped resin sample. It was measured. The test conditions were a distance between chucks of 10 cm, a pulling speed of 10 mm / min, and measurement at 25 ° C.

(Tensile rupture elongation of UV curable 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 the tensile breaking elongation of the strip-shaped resin sample was measured using a tensile tester (manufactured by Shimadzu Corporation, AGS-X). The test conditions were a chuck distance of 40 mm, a pulling speed of 50 mm / min, and measurement at 25 ° C.

(Total light transmittance, haze)
The total light transmittance and haze of the glass laminates obtained in the examples and comparative examples were measured using a transmittance meter (“HR-100” manufactured by Murakami Color Research Laboratory), and JIS K 7361 and JIS K, respectively. It was measured by a method based on 7136.

(Crack propagation of glass laminate)
The glass laminate was cut 5 cm with scissors (“Hasa 151B” manufactured by KOKUYO S & T) from the end face, and the condition of cracks propagating from the cutting direction was evaluated according to the following criteria.
○: Propagation of crack from cutting direction is less than 5 mm Δ: Propagation of crack from cutting direction is from 5 mm to less than 10 mm ×: Propagation of crack from cutting direction is 10 mm or more

(Average surface roughness)
In the cured resin layers of the glass laminates obtained in Examples and Comparative Examples, the average surface roughness of the surface on the side opposite to the glass plate, or the surface on which the protective film is peeled off when the protective film is attached is as follows. It is measured by.
That is, surface observation (observation field of view: 93.97 μm × 71.30 μm) of the glass laminate was performed using a non-contact surface / layer cross-section measurement system VertScan 2.0 (manufactured by Ryoka System Co., Ltd.), and glass The average surface roughness (arithmetic average roughness Sa) is calculated for the cured resin layer of the laminate.

[Example 1]
97% by mass of UV curable monomer (trade name “NK Oligo UA-122P” manufactured by Shin-Nakamura Chemical Co., Ltd.), 1-hydroxy-cyclohexyl-phenyl-ketone (product name “IRGACURE184” manufactured by BASF) as a photopolymerization initiator 3 Mass% was uniformly diluted with a solvent (methyl isobutyl ketone) to obtain an ultraviolet curable composition 1 (paint A). The paint A prepared above was applied to one side of a glass substrate (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 50 μm) using a wire bar coater so that the thickness after curing was 3 μm. Thereafter, the solvent was dried and removed. Further, the coated surface was irradiated with a high-pressure mercury lamp (160 W / cm) to obtain a laminate having an ultraviolet curable resin layer on one side. And the glass laminated body 1 by which the ultraviolet curable resin layer was formed in both surfaces was obtained by apply | coating the coating material A similarly to the above and hardening | curing with respect to the surface in which the ultraviolet curable resin layer of the said laminated body is not formed. It was.

[Example 2]
A glass laminate 2 was obtained in the same manner as in Example 1 except that the ultraviolet curable monomer was changed to “New Frontier R-1303” manufactured by Daiichi Kogyo Seiyaku.

[Example 3]
A glass laminate 3 was obtained in the same manner as in Example 1 except that the ultraviolet curable monomer was changed to the product name “Ogsol EA-0300” manufactured by Osaka Gas Chemical.

[Example 4]
The paint A used in Example 1 is applied to the plain surface (average surface roughness 0.7 nm) of a PET film (Toyobo “A4100, thickness 125 μm”) used as a protective film so that the thickness after curing is 3 μm. It apply | coated using the wire bar coater, it was made to dry and the solvent was removed. Next, the surface of the PET film coated with the coating A and one side of a glass substrate (“OA-10G” manufactured by Nippon Electric Glass Co., Ltd., thickness: 50 μm) are bonded together. By irradiating a lamp (160 W / cm), a glass laminate was obtained in which an ultraviolet curable resin layer and a PET film were laminated in this order from the glass substrate side. And the PET film of the obtained glass laminated body was peeled, and the glass laminated body 4 by which the ultraviolet resin cured layer was laminated | stacked on the glass plate was obtained.

[Comparative Example 1]
A glass laminate 5 was obtained in the same manner as in Example 1 except that the ultraviolet curable monomer was changed to a product name “NK Oligo U-10PA” manufactured by Shin-Nakamura Chemical Co., Ltd.

[Comparative Example 2]
In Example 4, the UV curable resin layer and the PET film were used in the same order from the glass substrate side, except that the PET film “T100-100, thickness 100 μm”, average surface roughness 16 nm) was used. A laminated glass laminate was obtained. And the PET film of the obtained glass laminated body was peeled, and the glass laminated body 6 by which the ultraviolet resin cured layer was laminated | stacked on the glass plate was obtained.

  Tensile elastic modulus (MPa), tensile elongation at break (%), total resin thickness / glass thickness (%), total light transmittance (%), haze (%), glass lamination of the obtained glass laminates 1 to 6 Table 1 shows the results of crack propagation of the body and average surface roughness Sa (nm).

The glass laminate according to the first embodiment of the present invention is excellent in handling properties without propagation of cracks, and excellent in surface smoothness, so that it is easy to form a uniform film when a thin film is laminated thereon, When electronic device elements are formed, performance is unlikely to deteriorate. Therefore, it is suitable as a substrate for electronic devices. Moreover, the organic EL element which concerns on the 2nd embodiment of this invention is useful for an organic EL module, an organic EL display apparatus, and organic EL illumination.

Claims (5)

A glass laminate comprising an active energy ray-curable resin layer directly on at least one surface of a glass plate having a thickness of 100 μm or less,
The tensile breaking elongation of the active energy ray-curable resin layer is 10% or more and 500% or less,
Ri at least one of the average surface roughness is 10nm der following active energy ray curable resin layer side surface of the glass laminate,
Tensile modulus of the active energy ray curable resin layer is more than 10 MPa, the glass laminate according to claim der Rukoto below 2000 MPa. The ratio of the total thickness of the active energy ray-curable resin layer and the thickness of the glass plate (the total thickness of the active energy ray-curable resin layer / the thickness of the glass plate) is 5% or more and less than 10%, The glass laminate according to claim 1 . A step of preparing a laminate in which an active energy ray-curable composition-containing layer and an active energy ray-permeable protective film are laminated in this order from the glass plate on at least one surface of the glass plate;
Irradiating the laminate with active energy rays, curing the layer containing the active energy ray-curable composition, and forming an active energy ray-curable resin layer; and
The glass laminated body of Claim 1 or 2 manufactured by the manufacturing method including the process of peeling this cured resin layer and this protective film. It has an active energy ray hardening resin layer on both surfaces of the said glass plate, The glass laminated body of any one of Claims 1-3 characterized by the above-mentioned. An organic EL device using the glass laminate according to any one of claims 1 to 4 as a substrate.