JP6551151B2 - Glass laminate, substrate for electronic device, and electronic device - Google Patents

Description

  The present invention relates to a glass laminate that includes a support layer that can be used as a substrate for electronic devices. More specifically, the present invention relates to a glass laminate in which peeling and bubbles do not easily occur in the step of forming an electronic device on a glass laminate, and the support layer can be easily peeled even after the formation of the electronic device.

  In recent years, thickness reduction and weight reduction of electronic devices (electronic parts) such as organic EL panels, solar cells, thin film secondary batteries, etc. have been progressing, and thinning of glass layers used in these electronic devices has progressed . However, when the strength of the glass layer is reduced by thinning, there is a problem that the handling property of the glass layer is deteriorated. In addition, although it is possible to use a resin substrate instead of the glass layer from the viewpoint of handling property, the resin substrate has problems in chemical resistance, moisture permeation resistance, heat resistance and the like.

Therefore, in recent years, a glass laminate excellent in visible light transmittance, in which the handling property is improved by laminating a transparent resin on a thin glass layer, has been used.
On the other hand, it is difficult to apply an electronic device forming process based on the use of a normal glass layer because the glass laminate has insufficient rigidity. Therefore, attempts have been proposed to improve rigidity by laminating a support and a glass laminate.

For example, Patent Document 1 discloses a substrate for an element manufacturing process having a rigid plate, a hard coat layer, and at least one flexible sheet in this order, and is less damaged and contaminated during element manufacturing, and is transported. There is disclosed a laminated substrate excellent in the properties.
Patent Document 2 discloses a laminated structure having a support substrate, a peelable silicone resin, and a flexible base material, and is excellent in heat resistance and can easily separate the closely attached flexible base material and the support body. The body is disclosed.

JP 2009-265215 A International Publication No. 2011/024690

  By laminating a thin glass layer and a support layer, it becomes possible to adapt the electronic device formation process on the premise of a normal glass layer to the thin glass layer, but on the other hand, the support layer is formed after the electronic device formation process. It is necessary to peel off. Although the above-mentioned document discloses a technique using a resin or the like having peelability in order to facilitate peeling of the support, the resin layer is peeled off by heat treatment or the like in forming an electronic device, The present inventors have found that new problems such as generation of air bubbles, peeling of the glass substrate from the support due to in-process washing, and inability to peel the support after forming the electronic device occur. The present invention solves such problems.

As a result of intensive investigations in view of the above problems, the present inventors set a glass laminate including a resin layer between a glass layer to be an electronic device substrate and a support layer, and the resin layer has specific physical properties. So, I found that I could solve the above problems.
That is, the present invention is as follows.

(1) A glass laminate comprising a support layer, a release resin layer A, and a glass layer having a thickness of 10 μm to 200 μm in this order, and the storage elastic modulus (E ′ ₆₀ ) of the release resin layer A at a temperature of 60 ° C. The ratio (E ′ ₆₀ / E ′ ₂₃ ) of the storage elastic modulus (E ′ ₂₃ ) at a temperature of 23 ° C. is 8.0 × 10 ⁻¹ or less, and E ′ ₂₃ is 10 MPa or more. Glass laminate.
(2) The glass laminate according to (1), wherein a 5% mass loss temperature of the release resin layer A is 250 ° C. or higher.
(3) The glass laminate according to (1) or (2), wherein the release resin layer A is a layer obtained by curing a curable resin composition.
(4) The glass laminate according to any one of (1) to (3), further comprising a protective resin layer B between the glass layer and the release resin layer A.
(5) The glass laminate according to (4), wherein the protective resin layer B is a film composed of a thermoplastic resin.
(6) The peel strength between the release resin layer A and the protective resin layer B under conditions of a temperature of 60 ° C. and a relative humidity of 30% is 0.3 N / 50 mm or more (4) or (5) The glass laminated body as described in).
(7) The manufacturing method of the board | substrate for electronic devices including the step which peels peeling resin layer A and a support layer from the glass laminated body in any one of (1)-(6).
(8) The electron from which the release resin layer A and the support layer were peeled from the glass laminate according to any one of (1) to (6) or the glass laminate according to any one of (1) to (6). Electronic device including substrate for device.

  According to the present invention, in the electronic device formation process, even if there is physical stimulation due to high temperature conditions or washing, etc., peeling of the resin layer and generation of air bubbles can be suppressed, and the laminated structure of the glass laminate can be maintained. And it can have favorable peelability even after the electronic device is formed.

It is a cross-sectional schematic diagram of the glass laminated body which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram of the glass laminated body which concerns on one Embodiment of this invention.

  Hereinafter, the glass laminates according to an embodiment of the present invention and the materials constituting them will be described in detail, but the description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention. The present invention is not limited to these contents. Further, the drawings are schematic views, and there are cases where the scale, shape, and the like of each component are not accurately represented. Moreover, in this invention, all the aspects can be used together.

The glass laminate according to one embodiment of the present invention comprises at least a support layer, a release resin layer A, and a glass layer having a thickness of 10 μm to 200 μm in this order. FIG. 1: is a cross-sectional schematic diagram of the glass laminated body 100 provided with the support layer 1, peeling resin layer A2, and the glass layer 3 in this order.
Hereinafter, each material which comprises a glass laminated body is demonstrated.

<Support layer>
The support layer in the present invention improves the handling of the glass layer in the process of forming the electronic device, and suppresses deformation and breakage.
As a material constituting the support layer, for example, glass, resin, metal such as SUS, or the like is used. In general, since the electronic device forming process involves heat treatment, the support layer is preferably formed mainly from a material having a small difference in linear expansion coefficient from the glass layer, and is preferably formed from the same material as the glass layer. Is more preferable, and the material constituting the support layer is preferably glass.

  The thickness of the support layer is not particularly limited as long as it can prevent deformation, damage, breakage, etc. of the glass layer and the release resin layer A in the electronic device forming step, but is usually 0.1 mm or more, 0.3 mm or more Preferably there is. When the support layer is made of glass, it is usually 5 mm or less, preferably 3 mm or less, because it is desired that the support layer be suitably bent without breaking when it is peeled off after the formation of the electronic device.

<Peeling resin layer A>
The release resin layer A is a resin layer that is provided between the glass layer and the support layer, adheres to the support layer, and has a release function capable of being peeled off from the glass layer, and has a storage elastic modulus (E ′ ₆₀ at 60 ° C. ) And a storage elastic modulus (E ′ ₂₃ ) ratio at 23 ° C. (E ′ ₆₀ / E ′ ₂₃ ) is 8.0 × 10 ⁻¹ or less and E ′ ₂₃ is 10 MPa or more. By having such properties, it is possible to suppress the generation of bubbles in the resin layer in the washing process using ultrasonic waves in warm water, and the separation of the glass layer from the support layer, and the electronic device is placed on the glass layer. The release resin layer A and the support layer can be easily peeled off from the glass layer at room temperature after having been formed into, i.e., subjected to an electronic device formation step including a heating step.
From the viewpoint of achieving both suppression of peeling in the cleaning step and peelability at room temperature, E ′ ₆₀ / E ′ ₂₃ is 8.0 × 10 ⁻¹ or less and E ′ ₂₃ is 10 MPa or more. is important.
In substrates for electronic devices, it is generally known that ultrasonic cleaning is performed using a cleaning liquid or pure water before forming an electronic device. In ultrasonic cleaning, a cleaning liquid is used to enhance the cleaning effect. It is known that pure water or the like is adjusted to a temperature higher than room temperature (for example, 60 ° C.).
In the release resin layer A, the storage elastic modulus at a temperature (for example, 60 ° C.) at which ultrasonic cleaning is performed is lower than that at room temperature (for example, 23 ° C.), that is, E ′ ₆₀ / E ′ ₂₃ is 8. Since the adhesiveness between the glass layer and the release resin layer A can be improved by being 0 × 10 ⁻¹ or less, moisture can be prevented from entering from the side surface of the glass laminate in ultrasonic cleaning. Bubble generation and peeling of the glass layer from the support layer can be suppressed.
Furthermore, in the peeling resin layer A, by the storage elastic modulus upon peeling is somewhat is ensured, i.e. the storage modulus at 23 ° C. E _'23 is 10MPa or more, the heating step in an electronic device formation (e.g., 230 C) for 1 hour, it is possible to prevent a situation in which the peeling resin layer A and the glass layer etc. are in close contact with each other and can not be peeled.
E ′ ₆₀ / E ′ ₂₃ is preferably 7.0 × 10 ⁻¹ or less, and 6.0 × 10 ⁻¹ or less from the viewpoint of coexistence of suppression of peeling in the washing step and peelability at room temperature. Is more preferably 5.8 × 10 ⁻¹ or less, and particularly preferably 4.0 × 10 ⁻¹ or less. The lower limit of E ′ ₆₀ / E ′ ₂₃ is not particularly limited, but is usually 1.0 × 10 ⁻² .
Further, E ′ ₂₃ is preferably 20 MPa or more, more preferably 35 MPa or more, still more preferably 50 MPa or more, and particularly preferably 500 MPa or more. The upper limit of E ′ ₂₃ is not particularly limited, but is usually 10 GPa or less.
In addition, the storage elastic modulus of the release resin layer A can be measured by a dynamic viscoelasticity measurement method described in JISK-7244-1, and is a dynamic viscoelasticity measuring device (for example, manufactured by IT Measurement Control Co., Ltd.). Visco-elasticity measurement device "DVA-200").
The storage elastic modulus of the release resin layer A can be adjusted to the above range by adding a monomer or an oligomer or a crosslinking agent, and a resin exhibiting the storage elastic modulus in the above range may be appropriately selected.
The release resin layer A preferably has a glass transition temperature (Tg) in the range of 100 ° C. or lower. If the glass transition temperature is too high, the adhesion between the release resin layer A obtained and the glass layer tends to be poor.

The thickness of the release resin layer A 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 release resin layer A is 0.5 μm or more, it can be sufficiently adhered to the support layer, and if the thickness is 10 μm or less, the increase in the thickness of the entire electronic device is suppressed, and the release resin layer at the time of manufacturing the electronic device There is a tendency to be able to suppress the amount of outgassing from A.

The water absorption of the release resin layer A is preferably 5% or less, more preferably 3% or less, and still more preferably 2% or less. If the water absorption is 5% or less, generation of bubbles due to moisture in the resin layer is suppressed during the heating step, and there is a tendency that peeling of the glass layer from the support layer can be suppressed. The water absorption rate of the resin layer can be measured according to JIS K7209.
The water absorption rate of the release resin layer A can be adjusted to the above range by the addition of a hydrophobic monomer or a hydrophobic oligomer, and a resin having such characteristics may be appropriately selected.

The release resin layer A preferably has a 5% mass loss temperature of 250 ° C. or higher, more preferably 280 ° C. or higher, from the viewpoint of heat resistance. The upper limit is not particularly limited, but is usually 650 ° C. or less. If the 5% mass loss temperature is 250 ° C. or more, the amount of outgas generation from the release resin layer A at the heating step tends to be suppressed. The 5% mass reduction temperature of the resin layer is determined by using a thermal analyzer (for example, “Thermoplus TG8120” manufactured by RIGAKU) and a resin layer at a temperature rising rate of 20 ° C./min in an atmosphere of nitrogen of 50 mL / min. The heat loss is measured for, and the temperature at which the heat loss is 5% is defined as the 5% mass reduction temperature of the release resin layer A.
The 5% mass decrease temperature of the release resin layer A can be adjusted to the above range by addition of a monomer or oligomer having high heat resistance, and a resin having such characteristics may be appropriately selected.

As a resin composition which comprises peeling resin layer A, curable resin composition is preferable, ie, it is preferable that peeling resin layer A is the layer which hardened | cured curable resin composition. The curable resin composition used in the present invention is not particularly limited as long as it is a component that induces a polymerization reaction by curing treatment and is cured. However, heat and active energy can be easily achieved in a short period of time. The curable resin composition containing the hardening component hardened | cured by line irradiation is mentioned as a preferable example.
The active energy ray is not particularly limited as long as it is an energy ray that induces a polymerization reaction, and an active energy ray suitable for the composition and properties of the resin component that is cured by irradiation with the active energy ray 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 light emitted from a high pressure mercury lamp.
As a hardening component hardened | cured by said heat | fever or active energy ray irradiation, curable resin of an acryl type, a urethane type, an epoxy type, and a silicone type is mentioned.
Among these, a urethane curable resin or an epoxy curable resin having a flexible skeleton is preferable.
Since the urethane-based curable resin exhibits flexibility even after the curing treatment by having a urethane bond in the molecule, it is easy to adjust the storage elastic modulus of the release resin layer A to the above range. Further, among the epoxy resins, it is easy to adjust the storage elastic modulus of the release resin layer A to the above-mentioned range in the same manner for the epoxy-based curable resin having a flexible skeleton.
As an epoxy-based curable resin having a flexible skeleton, for example, a hydrogenated bisphenol A-type epoxy resin, an aliphatic epoxy resin, an epoxy resin having a silicone skeleton as a main chain and an epoxy group (hereinafter, also referred to as epoxy-modified silicone resin) Etc.
As a commercial item of an epoxy modified silicone resin, the brand name "UV9430" by Momentive Co., Ltd. which is a type which carries out cationic polymerization of an epoxy group and hardens it, etc. are mentioned.

Further, as the curing component, (meth) acrylic monomers and (meth) acrylic oligomers are preferable from the viewpoint of mechanical physical properties, transparency and processability etc. Specifically, (meth) acrylates and urethane (meth) acrylates And monomers (such as polyester (meth) acrylate) and oligomers. Among them, urethane (meth) acrylate is preferred because it can be easily adjusted to the elastic modulus range as described above.
Furthermore, the urethane (meth) acrylate is more preferably 1 to 4 functional, further preferably 1 or 2 functional, and particularly preferably 2 functional.
The weight average molecular weight of the curable oligomer is usually 1,000 or more, preferably 1,000 to 1,000,000, and more preferably 1,000 to 100,000, 1,000. It is further more preferable that it is-50,000, and it is especially preferable that it is 2,000-20,000. If it is the said range, coating property will also be favorable and it will become easy to satisfy | fill ratio of a specific storage elastic modulus.
Examples of commercially available products include New Frontier "R1303" and "R1304" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., which contain urethane acrylate oligomers.

When the curable resin composition contains an ultraviolet-curable resin, or an ultraviolet-curable monomer or oligomer, it also contains a photopolymerization initiator, if necessary. The photopolymerization initiator is used to absorb and activate (excitation) ultraviolet light and to initiate a reaction via a cleavage reaction or the like.
Examples of the photopolymerization initiator include benzoin type, acetophenone type, thioxanthone type, phosphine oxide type and peroxide type. 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 Phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, methyl benzoyl formate, etc. it can. These can be used singly or in combination of two or more.

  The concentration of the photopolymerization initiator in the curable resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more from the viewpoint of reliably advancing the curing reaction. It is. On the other hand, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, from the viewpoint of preventing the generation of outgassing due to the unreacted material of the polymerization initiator.

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

  The resin composition constituting the peeling resin layer A may be a silane coupling agent, a sensitizer, a crosslinking agent, an ultraviolet absorber, a polymerization inhibitor, a surfactant, a filler, to the extent that the object of the present invention is not impaired. A mold release agent, an antioxidant, a leveling agent, a slip agent, a dispersant and the like can be optionally added. In addition, these can be used 1 type or in combination of 2 or more types as appropriate.

  The total concentration of the resin contained in the release resin layer A is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably 80% by mass or more from the viewpoint of viscosity at processing and mechanical properties after processing. It is.

<Glass layer>
The glass layer can be a substrate of the electronic device. In the present embodiment, an electronic device can be formed on the surface opposite to the surface facing the release resin layer A by laminating the release resin layer A.
The material of the glass layer is not particularly limited. For example, almost all glass compositions such as soda lime glass, borosilicate glass and alkali-free glass can be applied, and those subjected to secondary processing such as tempering and surface treatment can also be applied. And both can be used properly depending on the application. As secondary processing, for example, coupling agent treatment with a silane coupling agent, titanium coupling agent, etc., acid treatment, alkali treatment, ozone treatment, chemical treatment such as 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 treatments such as flame treatment may be mentioned. In particular, from the viewpoint of improving the adhesion to the resin layer, it is preferable that the surface is treated with a silane coupling agent.

The glass layer has a thickness of 10 μm to 200 μm. If thickness is this range, a shape will not be specifically limited, However, Usually, it is a plate-shaped thin plate glass. When the thickness is 10 μm or more, mechanical strength can be secured, and damage due to stress due to thermal expansion and contraction of the laminated resin layers can be suppressed. In addition, when the thickness is 200 μm or less, lamination of a resin layer for the purpose of improving handling property and secondary processability is effective.
The glass layer can in principle be produced by stretching the glass melt at a temperature above the solidification temperature of the glass melt. The thickness of the glass layer can be controlled by the glass composition, the thickness of the glass melt, the temperature, and the take-up speed.

The average surface roughness of the glass layer surface is preferably 5 nm or less, more preferably 2 nm or less, and particularly preferably 1 nm or less. In particular, the average surface roughness of the surface opposite to the surface facing the resin layer, that is, the average surface roughness of the surface capable of forming an electronic device is preferably 5 nm or less, more preferably 2 nm or less, and particularly preferably 1 nm or less. preferable.
If the average surface roughness of the glass layer is 5 nm or less, when an electronic device is formed on the surface of the glass layer, for example, a very thin (several tens of nm) conductive layer having a low surface resistance value can be formed. The glass laminate according to the present embodiment can be suitably used as a substrate of an electronic device.
In addition, average surface roughness (arithmetic average roughness (Sa)) can be measured using an optical interference type non-contact shape measuring instrument. For example, the surface observation (observation visual field: 93.97 μm × 71.30 μm) of the glass layer is carried out 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.

<Other layers>
The glass laminate according to this embodiment has a support layer, a release resin layer A, and a thickness of 10 μm or more.
In addition to the glass layer of 200 μm or less, other layers that do not hinder the effects of the present invention may be included. The other layers will be described below.

<Protective resin layer B>
In the embodiment, the glass laminate preferably further includes a protective resin layer B having a protective function on the side of the release resin layer A of the glass layer. By providing the protective resin layer B, the glass layer after peeling of the support layer is protected by the protective resin layer B. The protective resin layer B provided between the release resin layer A and the glass layer is not particularly limited as long as the glass layer can be protected, and a thermoplastic resin or a heat or active energy ray-curable resin composition is used. A film containing as a main component a resin obtained by curing is used. As the thermoplastic resin, a resin having high heat resistance and transparency is preferable.

The thickness of the protective resin layer B is preferably 5 μm or more. 10 micrometers or more are further preferable, and 15 micrometers or more are especially preferable. On the other hand, it is preferably 100 μm or less, more preferably 50 μm or less, and particularly preferably 30 μm or less.
If the thickness of the protective resin layer B is 5 μm or more, the handling property of the thin glass layer can be improved, and if the thickness is 100 μm or less, the thickness increase of the entire electronic device is suppressed, and the electronic device is manufactured. There is a tendency that the amount of outgassing from the resin layer of can be suppressed.

The protective resin layer B preferably has a 5% mass loss temperature of 250 ° C. or higher, more preferably 300 ° C. or higher, and still more preferably 400 ° C. or higher from the viewpoint of heat resistance. If the 5% mass reduction temperature is less than 250 ° C., the glass laminate may float during the heating process. The 5% mass reduction temperature of the resin layer can be measured in the same manner as in the case of the release resin layer A.
The 5% mass decrease temperature of the protective resin layer B can be adjusted to the above range by adding a material having high heat resistance, and a resin having such characteristics may be appropriately selected.

The water absorption rate of the protective resin layer B is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less. If the water absorption rate is more than 3%, bubbles may be generated in the glass laminate during the heating step, which may cause the glass layer to peel off from the support layer. The water absorption rate of the protective resin layer B can be measured according to JIS K7209.
The water absorption of the protective resin layer B can be adjusted to the above range by adding a resin having a hydrophobic skeleton, and a resin having such characteristics may be appropriately selected.

It is preferable that at least one surface of the protective resin layer B have releasability, and in particular, the surface facing the release resin layer A preferably has releasability. It can be said that the water contact angle is large so that it has good releasability. Specifically, at least one surface of the protective resin layer B preferably has a water contact angle of 90 ° or more, more preferably 100 ° or more. is there. If the contact angle is 90 ° or more, the adhesion between the release resin layer A and the protective resin layer B can be easily adjusted, which is preferable. The water contact angle can be measured using a contact angle meter. For example, using a contact angle meter “Drop Master 500” manufactured by Kyowa Interface Science Co., Ltd., the contact angle between the sample film and distilled water can be measured under conditions of a temperature of 23 ° C. and a relative humidity of 50%.
In addition to using an existing film having the above-mentioned releasability, releasability can be imparted to the surface of the protective resin layer B by the existing method such as addition of a release agent or coating. .

The material constituting the protective resin layer B preferably satisfies the above physical properties such as heat resistance, and any suitable resin can be adopted as long as the effects of the present invention are not impaired. Examples of the resin include thermoplastic resins, heat or active energy ray curable resins, and the like.
Specific examples of the thermoplastic resin include fluorine resin, polyether sulfone resin, polycarbonate resin, acrylic resin, silicone resin, cycloolefin resin, thermoplastic polyimide resin, polyamide resin, polyamideimide Resin, polyarylate resin, polysulfone resin, polyetherimide resin, polyether ether ketone resin, polyether silicone resin, polyester resin, polyphenylene sulfide resin and the like.
The thermoplastic resin is preferably a thermoplastic polyimide resin, a silicone resin, and a fluorine resin from the viewpoint of elastic modulus and heat resistance, and more preferably a silicone resin and a fluorine resin from the viewpoint of releasability, In particular, fluorine resins are preferable.
Specific examples of the heat or active energy ray curable resin include epoxy resins, silicone resins, acrylic resins, urethane resins, polyimide resins and the like.

  In addition to the above resins, the protective resin layer B may be a silane coupling agent, a sensitizer, a crosslinking agent, an ultraviolet absorber, a polymerization inhibitor, a surfactant, a filler, to the extent that the object of the present invention is not impaired. A mold release agent, an antioxidant, a leveling agent, a slip agent, a dispersant and the like can be optionally added. In addition, these can be used 1 type or in combination of 2 or more types as appropriate.

When the glass laminate according to the present embodiment includes the protective resin layer B, the compositions of the release resin layer A and the protective resin layer B may be the same or different. From the viewpoint of adjusting the releasability, the release resin layer A and the protective resin layer B preferably have different compositions. Here, that the compositions are different means that the components constituting the resin A and the resin B are different or that the ratio of the components constituting them is different.
More preferably, the main components constituting the release resin layer A and the protective resin layer B are different. The term "main component" as used herein refers to the component contained in the largest amount among the components forming each layer, which may occupy 50% by mass or more in each layer, or 80% by mass or more. The main component may be 90% by mass or more.

As a combination of preferable compositions of the peeling resin layer A and the protective resin layer B, it is preferable that at least one of the layers is made of a resin having peelability.
For example, when the curable resin composition constituting the peeling resin layer A contains (meth) acrylate monomers and oligomers, the protective resin layer B is a silicone resin, a fluorine resin, etc. from the viewpoint of peelability before and after heat treatment. It is preferable that it is comprised with the thermosetting resin which has releasability like a thermoplastic resin which has releasability, or a polyimide. Moreover, it is also preferable to be comprised with the thermoplastic resin or thermosetting resin surface-treated by the mold release agent of a silicone type or a fluorine type.
Moreover, when the curable resin composition which comprises the peeling resin layer A contains a silicone resin, it is preferable to be similarly comprised from fluorine resin from the viewpoint of the peelability before and behind heat processing.

When the glass laminate according to this embodiment includes the protective resin layer B, the peel strength between the protective resin layer B and the release resin layer A is lower than the peel strength between the glass layer and the protective resin layer B. Is preferred. By doing so, the glass laminate according to the present embodiment can be easily peeled off between the protective resin layer B and the peeling resin layer A. Moreover, it is also preferable that the peeling strength between the peeling resin layer A and the protective resin layer B is lower than the peeling strength between the support layer and the peeling resin layer A.
Although the peel strength according to the glass laminate satisfies the above requirements, the specific numerical range is not particularly limited, but the peel strength between the protective resin layer B and the peel resin layer A is usually 0.1 N / 50 mm or more It is preferably 0.2 N / 50 mm or more, while it is usually less than 2.0 N / 50 mm, preferably 1.5 N / 50 mm or less, and more preferably 1.0 N / 50 mm or less. preferable.

When the glass laminate according to the present embodiment includes the protective resin layer B, the laminate having the protective resin layer B and the glass layer (hereinafter sometimes referred to as a protective resin layer B / glass layer laminate), It is preferable that the peeling resin layer A be provided with easy peelability. Since the protective resin layer B is opposed to the peeling resin layer A in the protective resin layer B / glass layer laminate, the peeling resin layer A has easy peelability to the protective resin layer B. For this reason, the release resin layer A is in close contact with the protective resin layer B / glass layer laminate, but the surface from which the protective resin layer B / glass layer laminate can be easily released from the glass laminate according to this embodiment. It is preferable to have the characteristics. That is, the peeling resin layer A is bonded to the protective resin layer B / glass layer laminate with a certain degree of bonding force, and at the same time, when peeling the protective resin layer B / glass layer laminate, the protective resin The layers B and the glass layer are bonded with a bonding force that can be easily peeled without breaking. In the present invention, the property of being able to peel the surface of the peeling resin layer A and the protective resin layer B / glass layer laminate without peeling the glass layer is called easy peeling.
If easy peelability is expressed by specific numerical values, the peel strength between the release resin layer A and the protective resin layer B may be expressed as 0.1 N / 50 mm or more and less than 2.0 N / 50 mm. it can. However, the present numerical range is an example, and is not limited to the above numerical range as long as the above-described easily peelable property is satisfied.

  In the glass laminate according to the present embodiment, the peel strength between the release resin layer A and the protective resin layer B under the conditions of a temperature of 60 ° C. and a relative humidity of 30% is preferably 0.3 N / 50 mm or more. The cleaning temperature in the cleaning process of the electronic device forming process is usually around 60 ° C. By setting the peeling strength between the peeling resin layer A and the protective resin layer B in this range, the peeling resin layer and the protective resin layer are difficult to peel in the cleaning step of the electronic device formation step, and the separation of the thin sheet glass laminate is suppressed be able to. The peel strength between the peeling resin layer A and the protective resin layer B under the conditions of temperature 60 ° C. and relative humidity 30% is 0.3 N / 50 mm from the viewpoint of coexistence of suppression of peeling in the washing step and peelability at room temperature. It is preferable that it is above, more preferably 0.4 N / 50 mm or more.

In addition, before and after heat treatment of the glass laminate according to the present embodiment at 230 ° C. for 1 hour, the rate of change in peel strength between the release resin layer A and the protective resin layer B (= peel strength after heat treatment / before heat treatment (Peeling strength) is preferably 4 or less. By setting it as this range, the glass laminate according to the present embodiment has a change in peel strength between the release resin layer A and the protective resin layer B even after an electronic device formation step having a heating step. The rate is small, and the support layer can be easily peeled from the glass laminate after forming the electronic device.
The rate of change is preferably 4 or less, more preferably 3 or less. On the other hand, if the rate of change is too small, ie, far below 1, the adhesion between the release resin layer A and the protective resin layer B will be significantly lost, so it is usually 1 or more, 1.2 It is preferable that it is more than.
The peel strength is measured by the same method as the method of delamination strength at 23 ° C. described in the examples.
Furthermore, the peel strength between the release resin layer A and the protective resin layer B after heat treatment at 230 ° C. for 1 hour is preferably 0.1 N / 50 mm or more, more preferably 0.2 N / 50 mm or more. On the other hand, it is preferably less than 2.0 N / 50 mm, more preferably 1.5 N / 50 mm or less, and particularly preferably 1.0 N / 50 mm or less. By satisfying the above range, the support layer can be easily peeled off from the glass laminate even after the electronic device formation step.

In the glass laminated body concerning this embodiment, you may have a resin layer further in the surface of the side which does not oppose peeling resin layer A of the glass layer mentioned above. By further providing a resin layer on the surface of the glass layer that does not face the release resin layer A, the handling of the glass layer can be further improved compared to the case where the resin layer is only one layer, Crack generation and crack propagation in the glass layer at the time of peeling are further suppressed.

The thickness of the resin layer in this case is desirably about the same as the thickness of the release resin layer A provided between the glass layer and the support layer. When the protective resin layer B is provided, a thickness similar to that of the protective resin layer B is more desirable. By providing a resin layer having a similar thickness on both sides of the glass layer, distortion of the glass laminate due to a stress generated due to a difference in linear expansion coefficient between the glass layer and the resin layer or curing shrinkage of the resin layer. Can be suppressed.
Moreover, as for the composition of the resin layer in this case, when the protective resin layer B is provided, the same composition as the protective resin layer B can also be used. In particular, providing the resin layer having the same composition on both sides of the glass layer is preferable because the above-mentioned distortion is less likely to occur.

Moreover, you may have an adhesive layer for making a support layer and the peeling resin layer A adhere, and an adhesive layer for making the protective resin layer B and a glass layer adhere. As a material for forming the adhesive layer in this case, the heat or active energy ray curable resin composition described in the description of the release resin layer A and the protective resin layer B can be appropriately used. The thickness, heat resistance, and water absorption of the adhesive layer are preferably in the same range as the release resin layer A for the same reason as the release resin layer A.
Moreover, when the linear expansion coefficient of the protective resin layer B is high, there is a possibility that the protective resin layer B may be peeled off by heat treatment or the like when forming an electronic device, so that the protective resin layer B and the glass layer are bonded. The storage elastic modulus at 23 ° C. of the adhesive layer is preferably 1 GPa or more.

  In the present embodiment, as a method of adjusting the peel strength between the layers in the glass laminate, the method of adjusting the adhesive strength according to the type of resin, monomer or oligomer used, etc., and surface treatment of each layer separately from the above-mentioned adhesive layer. A method for adjusting the adhesive force is given. As the surface treatment for adjusting the adhesion, coupling agent treatment with a silane coupling agent, titanium coupling agent, etc., acid treatment, alkali treatment, ozone treatment, chemical treatment such as ion treatment, plasma treatment, glow discharge treatment, arc Discharge treatment, discharge treatment such as corona treatment, ultraviolet ray treatment, electromagnetic wave irradiation treatment such as ultraviolet ray treatment, X-ray treatment, gamma ray treatment, laser treatment, etc., other flame treatment, release by release agent containing fluorine resin, silicone resin, wax resin For example, mold processing.

<Manufacturing method>
The method for producing a glass laminate according to this embodiment is not particularly limited as long as it can produce a glass laminate having a support layer, a peeling resin layer A, and a glass layer having a thickness of 10 μm or more and 200 μm or less in this order. Examples thereof include a method of directly laminating the release resin layer A on the support layer by a direct coating method and a method of using a transfer film.
The direct coating method specifically prepares a coating composition containing at least a resin composition and a solvent, and the composition is die-coated, bar coater coated, spin coater coated, mayer bar coated, air knife coated, gravure coated, reverse It is a technique of applying to a support layer by methods such as gravure coating, offset printing, flexographic printing, screen printing, dip coating and the like.
As the solvent, an organic solvent is usually used, and is appropriately selected depending on the type of resin contained in the release resin layer A.
In addition, after application | coating, you may also include the process of removing the solvent, and the process of hardening with respect to peeling resin layer A as needed.
In the case of direct application, the application speed, the discharge amount, and the like are not particularly limited, and can be appropriately adjusted from the composition and thickness of the resin composition contained in the release resin layer A.
After forming the release resin layer A, a glass laminate is obtained by laminating a glass layer on the release resin layer A side.

When using a transfer film, it is preferable to include the process of the following (1)-(4).
(1) A step of forming a release resin layer A on a support film to produce a transfer film,
(2) A step of transferring the release resin layer A formed in the previous step to the surface of the support layer and peeling the support film after transfer,
(3) laminating a glass layer on the side of the transferred separated oil layer A,
(4) A step of performing a curing treatment on the release resin layer A transferred in the previous step as necessary.

When the glass laminate according to the present embodiment includes the protective resin layer B, after forming the release resin layer A on the support layer, the protective resin layer B is laminated on the release resin layer A side, and further the glass layer is laminated. A method in which the peeling resin layer A is formed on the support layer and a method in which the protective resin layer B is laminated on the glass layer are prepared and the peeling resin layer A side and the protective resin layer B side are bonded It can be mentioned.
In the manufacturing method of the said glass laminated body, you may provide an adhesive layer other than peeling resin layer A and protective resin layer B, and may carry out the hardening process of each layer as needed.

<Peeling of support layer>
The substrate for an electronic device according to an embodiment of the present invention is in a state in which the peeling resin layer A and the support layer are peeled from the glass laminate according to the embodiment of the present invention. That is, the manufacturing method of the substrate for electronic devices which is one embodiment of the present invention includes the step of peeling off the peeling resin layer A and the support layer from the glass laminate which is one embodiment of the present invention. Moreover, the manufacturing method of the electronic device which is one Embodiment of this invention includes the step which peels peeling resin layer A and a support layer from the glass laminated body which is one Embodiment of this invention.
It will not specifically limit, if it can peel between a support layer and peeling resin layer A, and a glass layer as a method of peeling a support layer from a glass laminated body. For example, a sharp blade-like thing is inserted between the release resin layer A and the glass layer, and the peeling is performed after giving a trigger for peeling, or the support layer side and the glass layer side of the glass laminate are vacuum-adsorbed. There is a method of fixing on a surface plate or the like and peeling it apart.

<Applications of Glass Laminates>
The glass laminate according to an embodiment of the present invention can be suitably used, for example, as a substrate of an electronic device such as an organic EL element. When it is used as a substrate of an electronic device such as an organic EL element, a flexible electronic device can be obtained by forming an electronic device member on a glass layer of a glass laminate and then peeling off a support layer, so that it is flexible. It can be used for 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.

As a member used for an organic EL element, 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, an electron injection layer etc. are mentioned.
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, as a member used for a liquid crystal display element, a transparent electrode layer, a liquid-crystal layer, etc. are mentioned.
Moreover, as a member for thin film secondary batteries, in the case of lithium ion type, a transparent electrode layer, an electrolyte layer containing a lithium compound, and a current collecting layer containing a metal can be mentioned. 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, an electroconductive part, an insulation part, etc. are mentioned, In addition, the various members corresponding to various sensors, such as a pressure sensor and an acceleration sensor, etc. are mentioned.

The glass laminated body which concerns on specific embodiment of this invention is demonstrated in detail using drawing.
FIG. 2 is a schematic cross-sectional view of a glass laminate 10 provided with a support layer 11, a peeling resin layer A12, a protective resin layer B13, an adhesive layer 15, and a glass layer 14 in this order.
The glass laminate 10 is usually used as a substrate for forming an electronic device (not shown) on the glass layer 14. And after forming an electronic device, the support layer 11 can be removed from the glass laminated body 10 by peeling along an AA 'chain line in the figure. Therefore, the release resin layer A has a ratio (E ′ ₆₀ / E ′ ₂₃ ) of the storage elastic modulus (E ′ ₆₀ ) at ₆₀ ° C. to the storage elastic modulus (E ′ ₂₃ ) at 23 ° C. of 8.0 × 10 It is necessary to be ⁻¹ or less and E ′ _{23 to} be 10 MPa or more. In order to satisfy such requirements, the glass laminate 10 can suppress the generation of bubbles in the resin layer and the peeling of the support layer from the glass layer in the cleaning process using ultrasonic waves, and the release resin at room temperature after the electronic device is formed. The layer A and the support layer can be easily peeled along the AA ′ chain line in the figure.

Before and after the glass laminate is treated at 230 ° C. for 1 hour, the rate of change in peel strength between the release resin layer A and the protective resin layer B (= peel strength after heat treatment / peeling before heat treatment) The strength is preferably 4 or less. In the process of forming an electronic device on a glass layer, for example, there is a process in which a glass laminate is exposed to a high temperature, such as a deposition process when forming a metal thin film. Even when exposed to such a process, when the rate of change in peel strength between the release resin layer A and the protective resin layer B at 230 ° C. is small, good peelability is obtained after the electronic device is formed. Can be maintained.
The release resin layer A satisfying such conditions is preferably a resin having a high storage elastic modulus, a high heat resistance, and a low water absorption. The protective resin layer B is preferably a resin having high heat resistance, a large contact angle, and a low water absorption rate.

An adhesive layer 15 may be provided between the protective resin layer B13 and the glass layer 14 in order to increase the peel strength between the protective resin layer B13 and the glass layer 14. The adhesive layer 15 can be used without particular limitation as long as it is a layer having an adhesive force. Further, as an alternative to the adhesive layer 15, the surface of the protective resin layer B13 facing the glass layer 14 may be subjected to an adhesive treatment. Adhesive treatment for adjusting the adhesive strength includes coupling agent treatment with a silane coupling agent, titanium coupling agent, acid treatment, alkali treatment, ozone treatment, chemical treatment such as ion treatment, plasma treatment, glow discharge treatment, arc Examples include discharge treatment, discharge treatment such as corona treatment, ultraviolet light treatment, X-ray treatment, gamma ray treatment, electromagnetic wave irradiation treatment such as laser treatment, and flame treatment.
In addition, in order to satisfy | fill the relationship of the said peeling strength, when providing the protective resin layer B, in the protective resin layer B and the peeling resin layer A, it is preferable not to perform an adhesion | attachment process on the surface facing each other layer. Moreover, it is preferable not to have an adhesive layer between the protective resin layer B and the release resin layer A.

  Hereinafter, the present invention will be described in more detail by way of examples, but it goes without saying that the scope of the present invention is not limited to the following examples.

<Measurement of physical properties of resin layer>
Physical properties of the release resin layer A of this example were measured by the following method.
(Storage elastic modulus)
A strip-shaped resin sample having a thickness of 50 μm, a width of 4 mm, and a length of 50 mm was prepared for the release resin layer A, and the dynamic viscoelasticity measurement manufactured by IT Measurement Control Co., Ltd. was performed by the dynamic viscoelasticity measurement method described in the JISK-7198A method. Using the apparatus “DVA-200”, the distance between chucks is 25 mm, the vibration frequency is 10 Hz, the strain is 0.3%, and the temperature rise rate is 3 ° C./min. The storage elastic modulus (E ′) of the resin layer A at a temperature of 23 ° C. and a temperature of 60 ° C. was determined.
Further, log (tan δ) = log (loss elastic modulus E ′ ′ / storage elastic modulus E ′) at each temperature was calculated, and the peak temperature of tan δ was taken as the Tg of the release resin layer A.
(Heat resistance: 5% mass loss temperature)
Using a thermal analyzer “Thermoplus TG8120” manufactured by RIGAKU, the thermal loss is measured for the release resin layer A at a heating rate of 20 ° C./min under a nitrogen atmosphere of 50 mL / min, and the temperature at which the thermal loss is 5% (originally The temperature at which the mass becomes 100% by mass is 95% by mass) is defined as the 5% mass reduction temperature (heat loss). The higher the 5% mass loss temperature, the higher the heat resistance.

Example 1
A glass laminate having the layer configuration shown in FIG. 2 was produced.
100 parts by mass of an ultraviolet curable resin composition (made by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "New Frontier R1303") containing a urethane acrylate oligomer, 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator (manufactured by BASF Co., Ltd.) Three parts by mass of the name “IRGACURE 184” were uniformly mixed to obtain an ultraviolet curable resin composition 1 (paint A).
Paint A is applied as an uncured product of release resin layer A so that the thickness after curing is 3 μm on a support layer (Floattech float glass thickness 0.7 mm) by a bar coater, and a protective resin Layer B is a hand roll (hardness: 90 °) with the corona-untreated surface of the ETFE film (trade name “Aflex”, manufactured by Asahi Glass Co., Ltd., thickness: 25 μm, single-sided corona treated) facing the coated surface of the release resin layer A Laminated on the support layer.
The ultraviolet curable resin composition 1 was cured by irradiation with a high pressure mercury lamp (irradiation intensity: 370 mJ / cm ² ) to obtain a peeling resin layer A.
On the corona-treated surface side of the ETFE film, UV and thermosetting epoxy resin (trade name “KRX-690-5” manufactured by ADEKA Co., Ltd.) as an uncured product of the adhesive layer is cured to 3 μm with a bar coater. After being coated, 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 match the center of the support layer, and a high-pressure mercury lamp ( Irradiation intensity: 370 mJ / cm ² ), and then heat treated at 150 ° C. for 1 hour with a hot air circulation drier to cure the ultraviolet ray and the thermosetting resin composition.
Thus, from the support layer side, the glass laminated body laminated | stacked in order of the peeling resin layer A, the protective resin layer B, the contact bonding layer, and the glass layer was obtained.

Example 2
100 parts by mass of an ultraviolet curable resin composition (made by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "New Frontier R1304") containing a urethane acrylate oligomer, 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator (manufactured by BASF Co., Ltd.) Three parts by mass of the name “IRGACURE 184” were uniformly mixed to obtain an ultraviolet curable resin composition 2 (paint B).
Coating B is applied as an uncured product of release resin layer A onto the support layer, and after laminating the ETFE film used in Example 1 in the same manner as in Example 1, a high pressure mercury lamp (irradiation intensity: 370 mJ / cm ² ) Was applied to cure the ultraviolet curable resin composition 2 to obtain a release resin layer A.
The release resin layer A, the protective resin layer B, and the adhesion are performed from the support layer side in the same manner as in Example 1 except that the paint B is applied on the support layer instead of the paint A as the uncured material of the adhesive layer. The glass laminated body laminated | stacked in order of the layer and the glass layer was obtained.

Example 3
UV curable resin composition containing urethane acrylate oligomer (Daiichi Kogyo Seiyaku Co., Ltd. trade name "New Frontier R1303") 50 parts by mass, UV curable resin composition containing urethane acrylate oligomer (Daiichi Kogyo Seiyaku Co., Ltd.) 50 parts by mass of trade name "New Frontier R1304", 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name "IRGACURE 184" manufactured by BASF as a photopolymerization initiator) are uniformly mixed, and an ultraviolet curable resin composition Object 3 (paint C) was obtained.
Coating C is applied as a non-cured product of release resin layer A on the support layer, and after laminating the ETFE film used in Example 1 in the same manner as Example 1, a high pressure mercury lamp (irradiation intensity: 370 mJ / cm ² ) Was applied to cure the ultraviolet curable resin composition 3 to obtain a release resin layer A.
The release resin layer A, the protective resin layer B, and the adhesion are performed from the support layer side in the same manner as in Example 1 except that the paint C is applied on the support layer instead of the paint A as the uncured material of the adhesive layer. The glass laminated body laminated | stacked in order of the layer and the glass layer was obtained.

Example 4
100 parts by mass of an epoxy-modified silicone resin (manufactured by Momentive, trade name "UV9430"), 3 parts by mass of bis (dodecylphenyl) iodonium hexafluoroantimonate (trade name "UV9380c", manufactured by Momentive) as a catalyst, and uniformly mixed A curable resin composition 4 (paint D) was obtained.
After coating D as an uncured material of release resin layer A on the support layer and laminating the ETFE film used in Example 1 in the same manner as in Example 1, a high pressure mercury lamp (irradiation intensity: 370 mJ / cm ² ) Was applied to cure the ultraviolet curable resin composition 4 to obtain a release resin layer A.
The release resin layer A, the protective resin layer B, and the adhesion are performed from the support layer side in the same manner as in Example 1 except that the paint D is applied on the support layer instead of the paint A as the uncured material of the adhesive layer. The glass laminated body laminated | stacked in order of the layer and the glass layer was obtained.

Comparative Example 1
On the support layer, UV and thermosetting epoxy resin (trade name “KRX-690-5” manufactured by ADEKA Corporation) was applied as an uncured product of the release resin layer A, and the ETFE film used in Example 1 was applied. After laminating in the same manner as in Example 1, the composition was irradiated with a high-pressure mercury lamp (irradiation intensity: 370 mJ / cm ² ), and then heat treated at 150 ° C. for 1 hour with a hot air circulating drier to obtain an ultraviolet and thermosetting resin composition. Were cured to obtain a release resin layer A.
On the support layer, the release resin layer A, the protective resin layer B, from the support layer side in the same manner as in Example 1 except that the epoxy resin was applied instead of using the coating material A as the uncured product of the adhesive layer. The glass laminated body laminated | stacked in order of the contact bonding layer and the glass layer was obtained.

Comparative Example 2
Liquid A and liquid B of a silicone resin (trade name "LSR 7060" manufactured by Momentive Co., Ltd.) were uniformly mixed in a ratio of 1: 1 to obtain a thermosetting resin composition 5 (paint E).
After coating E as a non-cured material of release resin layer A on the support layer and laminating the ETFE film used in Example 1 in the same manner as Example 1, a high pressure mercury lamp (irradiation intensity: 370 mJ / cm ² ) The cured resin composition was cured to obtain a release resin layer A.
On the support layer, from the support layer side, the release resin layer A, the protective resin layer B, and the adhesion were applied in the same manner as in Example 1 except that the paint E was applied instead of using the paint A as an uncured product of the adhesive layer. The glass laminated body laminated | stacked in order of the layer and the glass layer was obtained.

(Ultrasonic test)
The glass laminates obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were subjected to ultrasonic cleaning in warm water at 60 ° C. for 30 minutes, and foaming and peeling phenomena in the glass laminate were visually confirmed. The results are shown in Table 1.
The evaluation criterion is the time until bubbles of 1 mm ² or more are generated in the glass laminate during ultrasonic cleaning of the glass laminate in warm water at 60 ° C., and is as follows.
○: No foaming was observed in 30 minutes, and no peeling was observed in the glass laminate.
X: It foamed in less than 5 minutes and some peeling was seen in the glass laminated body.

(Measurement of Peeling Strength Between Peeling Resin Layer A and Protective Resin Layer B)
In the same manner as in Examples 1 to 4 and Comparative Examples 1 and 2, a release resin layer A of each example or comparative example having a thickness of 10 μm and a protective resin layer B having a thickness of 25 μm are formed on a glass plate having a thickness of 2 mm. Were laminated in this order to prepare a test piece (width 50 mm) for measuring peel strength.
For this test piece, using a tensile compression tester “INTESCO 200X” manufactured by Intesco Co., Ltd., the peeling rate was set at 23 ° C. and 50 mm / min, and the protective resin layer B was peeled off from the glass plate by a 90 ° peeling method. The tensile strength at that time was defined as the delamination strength at 23 ° C. between the release resin layer A and the protective resin layer B.
Using a tensile compression tester “INTESCO 200X” manufactured by Intesco Co., Ltd., in a constant temperature and humidity chamber set to a temperature of 60 ° C. and a relative humidity of 30%, the peel rate was set to 50 mm / min. The tensile strength at the time of setting and peeling the protective resin layer B from the peeling resin layer A by the 90 ° peeling method was taken as the delamination strength between the peeling resin layer A and the protective resin layer B at a temperature of 60 ° C. and a relative humidity of 30%. . The results are shown in Table 1.
In the evaluation of peel strength, the peel resin layer A did not peel from the support layer, and the protective resin layer B did not peel from the glass plate.

(Heating test: Foaming)
The evaluation standard of the heating test (foaming) is the time until bubbles of 1 mm ² or more are generated in the glass laminate when the glass laminate is placed in an oven at 230 ° C., and is as follows. The results are shown in Table 1.
○: 1 hour or more Δ: 5 minutes or more and less than 1 hour ×: 5 minutes or less (peeling evaluation)
The evaluation criteria for the peelability after heat treatment of the glass laminate is that the glass laminate is heat-treated in an oven at 230 ° C. for 1 hour and left for 1 hour under conditions of a temperature of 23 ° C. and a humidity of 50% RH, and then the protective resin is removed from the support layer. It is whether it can peel, without damaging a glass layer, and a layer B / glass layer laminated body is as follows. The results are shown in Table 1.
:: The glass layer can be peeled off from the support layer without breakage.
X: When it is going to peel from a support layer, a glass layer will be damaged.

(Discussion)
From the results of Examples 1-4 and Comparative Examples 1-2, the ratio of the storage elastic modulus (E ′ ₆₀ ) at a temperature of ₆₀ ° C. to the storage elastic modulus (E ′ ₂₃ ) at a temperature of 23 ° C. ( E ′ ₆₀ / E ′ ₂₃ ) is 8.0 × 10 ⁻¹ or less, and E ′ ₂₃ is 10 MPa or more, so that foaming and peeling in the glass laminate are not caused even when ultrasonic cleaning is performed. Even if a heating test is performed, generation of air bubbles in the glass laminate is suppressed, and even after the heating test, the protective resin layer B / glass layer laminate can be peeled off from the support layer without breakage of the glass layer. It was found that a glass laminate was obtained.

  According to the present invention, in the electronic device formation step, peeling of the resin layer and the generation of air bubbles are suppressed and the laminated structure is maintained even if there is a physical stimulus such as a change in external environment such as vacuum or heating or washing. The present invention also provides a glass laminate suitable as a substrate for an electronic device, capable of maintaining good releasability even after formation of the electronic device.

10, 100 Glass laminate 1, 11 Support layer 2, 12 Peeling resin layer A
13 Protective resin layer B
3, 14 Glass layer 15 Adhesive layer

Claims (8)

A glass laminate comprising a support layer, a release resin layer A, and a glass layer having a thickness of 10 μm or more and 200 μm or less in this order, and the storage elastic modulus (E ′ ₆₀ ) of the release resin layer A at 60 ° C. and the temperature 23 Glass laminate characterized in that the ratio of storage elastic modulus (E ′ ₂₃ ) at E ° C. (E ′ ₆₀ / E ′ ₂₃ ) is 8.0 × 10 ⁻¹ or less and E ′ ₂₃ is 10 MPa or more. body.   The 5% mass loss temperature of the said peeling resin layer A is 250 degreeC or more, The glass laminated body of Claim 1 characterized by the above-mentioned.   The said peeling resin layer A is a layer which hardened | cured the curable resin composition, The glass laminated body of Claim 1 or 2 characterized by the above-mentioned.   The glass laminate according to any one of claims 1 to 3, further comprising a protective resin layer B between the glass layer and the peeling resin layer A.   The said protective resin layer B is a film comprised with a thermoplastic resin, The glass laminated body of Claim 4 characterized by the above-mentioned.   The glass according to claim 4 or 5, characterized in that the peel strength between the release resin layer A and the protective resin layer B at a temperature of 60 ° C and a relative humidity of 30% is 0.3 N / 50 mm or more. Laminated body.   The manufacturing method of the board | substrate for electronic devices including the step which peels peeling resin layer A and a support layer from the glass laminated body of any one of Claims 1-6.   Forming an electronic device member on the glass layer of the glass laminate according to any one of claims 1 to 6, and
  And peeling the release resin layer A and the support layer from the glass laminate.

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