WO2014103678A1 - Glass laminate, method for producing same, and supporting base with silicone resin layer - Google Patents
Glass laminate, method for producing same, and supporting base with silicone resin layer Download PDFInfo
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- WO2014103678A1 WO2014103678A1 PCT/JP2013/082947 JP2013082947W WO2014103678A1 WO 2014103678 A1 WO2014103678 A1 WO 2014103678A1 JP 2013082947 W JP2013082947 W JP 2013082947W WO 2014103678 A1 WO2014103678 A1 WO 2014103678A1
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- silicone resin
- resin layer
- glass substrate
- glass
- substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10798—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing silicone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10697—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being cross-linked
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a glass laminate and a method for producing the same, and more particularly to a glass laminate having a silicone resin layer exhibiting a predetermined elastic modulus and a method for producing the same.
- the present invention also relates to a support base material with a silicone resin layer, and more particularly, to a support base material with a silicone resin layer on which a glass substrate is releasably laminated and a manufacturing method thereof.
- devices such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) have been made thinner and lighter, and the glass substrates used in these devices have been made thinner. Progressing. If the strength of the glass substrate is insufficient due to the thinning, the handling property of the glass substrate is lowered in the device manufacturing process.
- PV solar cells
- LCD liquid crystal panels
- OLED organic EL panels
- a method of forming a device member for example, a thin film transistor
- a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching is widely used.
- this method for example, when the thickness of one glass substrate is reduced from 0.7 mm to 0.2 mm or 0.1 mm, most of the original glass substrate material is scraped off with an etching solution. Therefore, it is not preferable from the viewpoint of productivity and use efficiency of raw materials.
- the method of thinning a glass substrate by the above chemical etching if a fine scratch exists on the surface of the glass substrate, a fine recess (etch pit) is formed from the scratch by the etching process, resulting in an optical defect. There was a case.
- Patent Document 1 A method of separating a support plate from a thin glass substrate has been proposed (for example, Patent Document 1).
- the reinforcing plate has a support plate and a silicone resin layer fixed on the support plate, and the silicone resin layer and the thin glass substrate are in close contact with each other in a peelable manner.
- the reinforcing plate separated from the thin glass substrate is peeled off from the interface between the silicone resin layer of the glass laminate and the thin glass substrate, and can be reused as a glass laminate by being laminated with a new thin glass substrate.
- the glass substrate is When peeling from the surface of the silicone resin layer, the glass substrate is not peeled off from the surface of the resin layer, but part of it is destroyed, or part of the resin of the resin layer remains on the glass substrate, resulting in an electronic device. In some cases, the productivity of the product was reduced.
- the present invention has been made in view of the above problems, and even after high-temperature heat treatment, the increase in peel strength between the glass substrate and the silicone resin layer is suppressed, and the glass substrate can be easily peeled off. It aims at providing a glass laminated body and its manufacturing method. Another object of the present invention is to provide a support substrate with a silicone resin layer used in the production of the glass laminate.
- the first aspect of the present invention includes a support base material, a silicone resin layer, and a glass substrate in this order, and the peel strength at the interface between the support base material and the silicone resin layer is between the silicone resin layer and the glass substrate.
- the glass laminate is larger than the peel strength at the interface, and the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the elastic modulus of the silicone resin layer measured by the nanoindentation method is 0.
- the crosslinked product of the crosslinkable organopolysiloxane is preferably a crosslinked product obtained by reacting an organopolysiloxane having an alkenyl group and an organopolysiloxane having a hydrosilyl group.
- the mixing molar ratio of alkenyl group to hydrosilyl group is preferably 1/1 to 1 / 0.8.
- the silicone resin layer preferably further contains silicone oil.
- the thickness of the silicone resin layer is preferably 2 to 100 ⁇ m. 1st aspect WHEREIN: It is preferable that a support base material is a glass plate.
- a layer containing a crosslinkable organopolysiloxane is formed on one side of a support substrate, and the silicone resin layer is formed by crosslinking the crosslinkable organopolysiloxane on the support substrate surface. It is a method for producing a glass laminate of the first embodiment in which a glass substrate is laminated on the surface of a silicone resin layer.
- a support substrate with a silicone resin layer having a support substrate and a silicone resin layer provided on the support substrate surface, wherein the silicone resin of the silicone resin layer is crosslinkable.
- a support substrate with a silicone resin layer which is a crosslinked product of an organopolysiloxane and has an elastic modulus of 0.5 to 2.5 MPa as measured by a nanoindentation method.
- the support base material with a silicone resin layer used for manufacture of this glass laminated body can also be provided.
- FIG. 1 is a schematic cross-sectional view of an embodiment of a glass laminate according to the present invention.
- 2 (A) to 2 (D) are schematic cross-sectional views showing an embodiment of a method for producing a glass substrate with a member according to the present invention in the order of steps.
- the glass laminated body of this invention is equipped with a support base material, a silicone resin layer, and a glass substrate in this order. That is, it has a silicone resin layer between a support base material and a glass substrate, therefore, one side of the silicone resin layer is in contact with the support base material, and the other side is in contact with the glass substrate.
- One of the characteristic points of the glass laminate of the present invention is that the elastic modulus of the silicone resin layer measured by the nanoindentation method is within a predetermined range.
- the elastic modulus of the silicone resin layer formed on the support substrate is within a predetermined range.
- a silicone resin layer having an elastic modulus within a predetermined range is softer than a conventional silicone resin layer.
- the glass substrate can be peeled relatively easily while being in close contact with the glass substrate disposed on the silicone resin layer to a certain degree to prevent positional displacement.
- the silicone resin layer is soft so that it deforms to follow the shape of the glass substrate surface without causing a gap or the like between the silicone resin layer and the glass substrate. The silicone resin layer and the glass substrate adhere well.
- the silicone resin layer is easily deformed, so that it is possible to suppress stress from being locally applied to the glass substrate, and as a result, the glass substrate is easily peeled off. be able to.
- FIG. 1 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.
- the glass laminated body 10 is a laminated body in which the support base material 12, the glass substrate 16, and the silicone resin layer 14 exist among them.
- the silicone resin layer 14 has one surface in contact with the support base 12 and the other surface in contact with the first main surface 16 a of the glass substrate 16. In other words, the silicone resin layer 14 is in contact with the first major surface 16 a of the glass substrate 16.
- the two-layer portion composed of the support base 12 and the silicone resin layer 14 reinforces the glass substrate 16 in a member forming process for manufacturing a member for an electronic device such as a liquid crystal panel.
- the two-layer part which consists of the support base material 12 manufactured in advance for manufacture of the glass laminated body 10 and the silicone resin layer 14 is called the support base material 18 with a silicone resin layer.
- the glass laminate 10 is used until a member forming step described later. That is, the glass laminate 10 is used until a member for an electronic device such as a liquid crystal display device is formed on the surface of the second main surface 16b of the glass substrate 16. Thereafter, the glass laminate on which the electronic device member is formed is separated into a supporting substrate 18 with a silicone resin layer and a glass substrate with an electronic device member, and the supporting substrate 18 with a silicone resin layer is a portion constituting an electronic device. It will not be. A new glass substrate 16 is laminated on the support base material 18 with the silicone resin layer, and can be reused as a new glass laminate 10.
- the interface between the support substrate 12 and the silicone resin layer 14 has a peel strength (x), and when a stress in the peeling direction exceeding the peel strength (x) is applied to the interface between the support substrate 12 and the silicone resin layer 14, The interface between the support base 12 and the silicone resin layer 14 is peeled off.
- the interface between the silicone resin layer 14 and the glass substrate 16 has a peel strength (y).
- the peel strength (x) is greater (higher) than the peel strength (y).
- the glass laminate 10 of the present invention peels off at the interface between the silicone resin layer 14 and the glass substrate 16.
- the substrate is separated into a glass substrate 16 and a support substrate 18 with a silicone resin layer. That is, the silicone resin layer 14 is fixed on the support substrate 12 to form a support substrate 18 with a silicone resin layer, and the glass substrate 16 is in close contact with the silicone resin layer 14 so as to be peeled off.
- the peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the silicone resin layer 14 to the support base 12 can be increased, and a relatively higher adhesion to the glass substrate 16 can be maintained after the heat treatment. .
- the silicone resin layer 14 bonded to the support substrate 12 with a high bonding force can be formed by the adhesive force at the time of crosslinking and curing.
- the bond strength of the cured product of the crosslinkable organopolysiloxane after the crosslink curing to the glass substrate 16 is usually lower than the bond strength generated at the time of the crosslink curing. Therefore, the crosslinkable organopolysiloxane is crosslinked and cured on the support base 12 to form the silicone resin layer 14, and then the glass substrate 16 is laminated on the surface of the silicone resin layer 14 to produce the glass laminate 10. Is preferred.
- the glass laminate according to the first aspect of the present invention includes a support base, a silicone resin layer, and a glass substrate in this order, and the peel strength at the interface between the support base and the silicone resin layer is the silicone resin layer and the glass.
- the glass laminate is larger than the peel strength at the interface with the substrate, and the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the elasticity of the silicone resin layer measured by the nanoindentation method A glass laminate having a rate of 0.5 to 2.5 MPa.
- each layer (support base material 12, glass substrate 16, silicone resin layer 14) which comprises the glass laminated body 10 is explained in full detail first, About the manufacturing method of a glass laminated body and the glass substrate with a member for electronic devices after that. Detailed description.
- the support base material 12 supports and reinforces the glass substrate 16, and the glass substrate 16 is deformed and scratched when the electronic device member is manufactured in a member forming step (step of manufacturing an electronic device member) described later. Prevent damage.
- the support substrate 12 for example, a metal plate such as a glass plate, a plastic plate, or a SUS plate is used.
- the support base 12 is preferably formed of a material having a small difference in average linear expansion coefficient from the glass substrate 16, and may be formed of the same material as the glass substrate 16. More preferably, the support substrate 12 is preferably a glass plate.
- the support base 12 is preferably a glass plate made of the same glass material as the glass substrate 16.
- the thickness of the support base 12 may be thicker or thinner than the glass substrate 16.
- the thickness of the support base 12 is selected based on the thickness of the glass substrate 16, the thickness of the silicone resin layer 14, and the thickness of the glass laminate 10.
- the thickness of the support base 12 is set to 0.4 mm. In general, the thickness of the support base 12 is preferably 0.2 to 5.0 mm.
- the thickness of the glass plate is preferably 0.08 mm or more for reasons such as being easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.
- the difference in average linear expansion coefficient between the support base 12 and the glass substrate 16 at 25 to 300 ° C. is preferably 500 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 300 ⁇ 10 ⁇ 7 / ° C. or less. More preferably, it is 200 ⁇ 10 ⁇ 7 / ° C. or less. If the difference in the average linear expansion coefficient is too large, the glass laminate 10 may be warped severely or the support base 12 and the glass substrate 16 may be peeled off during heating and cooling in the member forming process. When the material of the support base material 12 is the same as the material of the glass substrate 16, it is possible to suppress the occurrence of such a problem, and therefore the support base material is preferably a glass plate.
- the 1st main surface 16a touches the silicone resin layer 14, and the member for electronic devices is provided in the 2nd main surface 16b on the opposite side to the silicone resin layer 14 side.
- the glass substrate 16 may be of a general type, and examples thereof include a glass substrate for a display device such as an LCD or an OLED.
- the glass substrate 16 is excellent in chemical resistance and moisture permeability and has a low heat shrinkage rate.
- an index of the heat shrinkage rate an average linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.
- the member forming process is often accompanied by heat treatment, and various inconveniences are likely to occur.
- the TFT may be displaced excessively due to thermal contraction of the glass substrate 16.
- the glass substrate 16 is obtained by melting a glass raw material and molding the molten glass into a plate shape.
- a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used.
- the glass substrate 16 having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature and then stretching it by means of stretching or the like to make it thin (redraw method).
- the type of glass of the glass substrate 16 is not particularly limited, but non-alkali borosilicate glass, borosilicate glass, soda lime glass, high silica glass, and other oxide-based glasses mainly composed of silicon oxide are preferable.
- oxide-based glass a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.
- glass suitable for the type of electronic device member and the manufacturing process thereof is employed.
- a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of the alkali metal component easily affects the liquid crystal. Ingredients are included).
- the glass of the glass substrate 16 is appropriately selected based on the type of device to be applied and its manufacturing process.
- the thickness of the glass substrate 16 is preferably 0.3 mm or less, more preferably 0.20 mm or less, and further preferably 0.15 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. Especially preferably, it is 0.10 mm or less. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 16. In the case of 0.15 mm or less, the glass substrate 16 can be rolled up. Further, the thickness of the glass substrate 16 is preferably 0.03 mm or more for reasons such as easy manufacture of the glass substrate 16 and easy handling of the glass substrate 16.
- the glass substrate 16 may be composed of two or more layers.
- the material forming each layer may be the same material or a different material.
- the thickness of the glass substrate 16 means the total thickness of all the layers.
- the silicone resin layer is substantially composed of a silicone resin, and the silicone resin is a crosslinked product of a crosslinkable organopolysiloxane and has an elastic modulus of 0.5 to 2.5 MPa measured by a nanoindentation method.
- the peel strength at the interface between the support substrate and the silicone resin layer is greater than the peel strength at the interface between the silicone resin layer and the glass substrate.
- the silicone resin layer 14 prevents the glass substrate 16 from being displaced until the operation for separating the glass substrate 16 and the support base 12 is performed, and prevents the glass substrate 16 and the like from being damaged by the separation operation.
- the surface (first main surface of the silicone resin layer) 14a of the silicone resin layer 14 in contact with the glass substrate 16 is in close contact with the first main surface 16a of the glass substrate 16 in a peelable manner.
- the silicone resin layer 14 is fixed on the support substrate 12. Therefore, the silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a weak bonding force, and the peel strength (y) at the interface is the interface between the silicone resin layer 14 and the support base 12. Lower than the peel strength (x). That is, when separating the glass substrate 16 and the support base material 12, the glass substrate 16 is peeled off at the interface between the first main surface 16 a of the glass substrate 16 and the silicone resin layer 14, and the support base material 12 and the silicone resin layer 14 are separated.
- the silicone resin layer 14 is in close contact with the first main surface 16a of the glass substrate 16, but has a surface characteristic that allows the glass substrate 16 to be easily peeled off. That is, the silicone resin layer 14 is bonded to the first main surface 16a of the glass substrate 16 with a certain amount of bonding force to prevent the glass substrate 16 from being displaced, and at the same time, when the glass substrate 16 is peeled off.
- the glass substrate 16 is bonded with a bonding force that can be easily peeled without breaking the glass substrate 16.
- peelability the property which can peel this silicone resin layer 14 surface easily is called peelability.
- the 1st main surface of the support base material 12 and the silicone resin layer 14 are couple
- the bonding force at the interface between the silicone resin layer 14 and the glass substrate 16 may change before and after the electronic device member is formed on the surface (second main surface 16b) of the glass substrate 16 of the glass laminate 10. (That is, the peel strength (x) and peel strength (y) may change). However, even after the electronic device member is formed, the peel strength (y) is lower than the peel strength (x).
- the silicone resin layer 14 and the glass substrate 16 are considered to be bonded with a bonding force resulting from a weak adhesive force or van der Waals force.
- a weak adhesive force or van der Waals force When the glass substrate 16 is laminated on the surface after the silicone resin layer 14 is formed, if the silicone resin of the silicone resin layer 14 is sufficiently cross-linked so as not to exhibit an adhesive force, the binding force due to van der Waals force It is thought that it is combined with.
- the silicone resin of the silicone resin layer 14 often has a certain weak adhesive force. Even when the adhesiveness is extremely low, when the electronic device member is formed on the laminated body after the glass laminated body 10 is manufactured, the silicone resin of the silicone resin layer 14 is removed from the glass substrate 16 by a heating operation or the like.
- the bonding force between the silicone resin layer 14 and the glass substrate 16 is increased by adhering to the surface.
- the surface of the silicone resin layer 14 before lamination or the first main surface 16a of the glass substrate 16 before lamination can be laminated by performing a treatment for weakening the bonding force between them.
- the bonding strength at the interface between the silicone resin layer 14 and the glass substrate 16 can be weakened, and the peel strength (y) can be lowered.
- the silicone resin layer 14 is bonded to the surface of the support base 12 with a strong bonding force such as an adhesive force or an adhesive force.
- a strong bonding force such as an adhesive force or an adhesive force.
- the elastic modulus of the silicone resin layer 14 measured by the nanoindentation method is 0.5 to 2.5 MPa. Among these, 0.5 to 2.0 MPa is preferable and 0.5 to 1.2 MPa is more preferable in terms of more excellent peelability of the glass substrate 16.
- the elastic modulus is an average value obtained by arithmetically averaging the elastic modulus measured at any five or more points on the surface of the silicone resin layer 14.
- the silicone resin layer should be a predetermined silicone resin layer, the silicone resin layer contains silicone oil, It can be controlled by the forming method or the like.
- the elastic modulus (Young's modulus) can be obtained by combining JKR (Johnson-Kendall-Roberts) analysis with force measurement using an atomic force microscope as a method of measuring elastic modulus by the nanoindentation method.
- JKR Johnson-Kendall-Roberts
- the cantilever is moved perpendicularly to the sample surface, and the load is measured with respect to the position of the cantilever.
- Samples that are sufficiently hard with respect to the spring constant of the cantilever do not cause sample deformation, but soft samples can also be used to obtain a relationship between the load and the amount of sample deformation by utilizing the deformation of the sample according to the load.
- JKR analysis is optimal when the indentation is small and the sample is soft.
- the thickness of the silicone resin layer 14 is not particularly limited, but is preferably 2 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, and even more preferably 7 to 20 ⁇ m. When the thickness of the silicone resin layer 14 is within such a range, even if air bubbles or foreign matter may be present between the silicone resin layer 14 and the glass substrate 16, the occurrence of distortion defects in the glass substrate 16 is suppressed. can do. In addition, if the thickness of the silicone resin layer 14 is too thick, it takes time and materials to form it, which is not economical and the heat resistance may decrease. Moreover, when the thickness of the silicone resin layer 14 is too thin, the adhesiveness of the silicone resin layer 14 and the glass substrate 16 may fall.
- the silicone resin layer 14 may be composed of two or more layers. In this case, “the thickness of the silicone resin layer 14” means the total thickness of all the layers. Moreover, when the silicone resin layer 14 consists of two or more layers, the crosslinked silicone resin from which resin which forms each layer differs may be sufficient.
- the silicone resin contained in the silicone resin layer 14 is a crosslinked product of a crosslinkable organopolysiloxane and usually forms a three-dimensional network structure.
- the type of the crosslinkable organopolysiloxane is not particularly limited, and the structure is not particularly limited as long as it is cross-linked and cured through a predetermined cross-linking reaction to obtain a cross-linked product (cured product) constituting the silicone resin. What is necessary is just to have sex.
- the form of crosslinking is not particularly limited, and a known form can be appropriately employed depending on the kind of the crosslinkable group contained in the crosslinkable organopolysiloxane.
- Examples thereof include a hydrosilylation reaction, a condensation reaction, a heat treatment, a high energy ray treatment, or a radical reaction using a radical polymerization initiator. More specifically, when the crosslinkable organopolysiloxane has a radical reactive group such as an alkenyl group or an alkynyl group, the cured product (crosslinked silicone resin) is crosslinked by a reaction between the radical reactive groups via the radical reaction. ) Moreover, when crosslinkable organopolysiloxane has a silanol group, it crosslinks by the condensation reaction of silanol groups, and it becomes a hardened
- a radical reactive group such as an alkenyl group or an alkynyl group
- the crosslinkable organopolysiloxane has an organopolysiloxane having an alkenyl group (such as a vinyl group) bonded to a silicon atom (ie, an organoalkenylpolysiloxane) and a hydrogen atom bonded to a silicon atom (hydrosilyl group).
- an organopolysiloxane having that is, organohydrogenpolysiloxane
- it is crosslinked by a hydrosilylation reaction in the presence of a hydrosilylation catalyst (for example, a platinum-based catalyst) to form a cured product.
- a hydrosilylation catalyst for example, a platinum-based catalyst
- the crosslinkable organopolysiloxane is an organopolysiloxane having alkenyl groups at both ends and / or side chains (hereinafter referred to as appropriate) because the silicone resin layer 14 can be easily formed and is excellent in releasability of the glass substrate 16.
- An embodiment including an organopolysiloxane A) and an organopolysiloxane having hydrosilyl groups at both ends and / or side chains (hereinafter also referred to as organopolysiloxane B as appropriate) is preferred.
- the alkenyl group is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, and a hexynyl group. Among them, the heat resistance is excellent. A vinyl group is preferred. Examples of the group other than the alkenyl group contained in the organopolysiloxane A and the group other than the hydrosilyl group contained in the organopolysiloxane B include an alkyl group (particularly an alkyl group having 4 or less carbon atoms).
- the position of the alkenyl group in the organopolysiloxane A is not particularly limited. However, when the organopolysiloxane A is linear, the alkenyl group may be present in any one of the M unit and D unit shown below. And D units may be present. From the viewpoint of curing speed, it is preferably present at least in M units, and preferably present in both two M units.
- the M unit and D unit are examples of basic structural units of organopolysiloxane.
- the M unit is a monofunctional siloxane unit in which three organic groups are bonded.
- the D unit is bonded to two organic groups. Bifunctional siloxane unit.
- the siloxane bond is a bond in which two silicon atoms are bonded through one oxygen atom, so that the oxygen atom per silicon atom in the siloxane bond is regarded as 1 ⁇ 2, Expressed as O 1/2 .
- the number of alkenyl groups in organopolysiloxane A is not particularly limited, but is preferably 1 to 3 and more preferably 2 per molecule.
- the preferred structure of the organopolysiloxane A is linear or cyclic, has two or more alkenyl groups in one molecule, and one or more alkenyl groups are present in both of two M units. Is.
- the position of the hydrosilyl group in the organopolysiloxane B is not particularly limited. However, when the organopolysiloxane A is linear, the hydrosilyl group may be present in either the M unit or the D unit. It may be present in both D units. It is preferable that it exists in at least D unit from the point of a cure rate.
- the number of hydrosilyl groups in the organopolysiloxane B is not particularly limited, but it is preferably at least 3 per molecule, and more preferably 3.
- the organopolysiloxane B when the organopolysiloxane A is linear or cyclic, it has two or more hydrosilyl groups in one molecule, and the molar content of hydrosilyl groups is 30% or more. It is preferable.
- the mixing ratio of the organopolysiloxane A and the organopolysiloxane B is not particularly limited, but the organopolysiloxane A and the organopolysiloxane B are used in order to keep the elastic modulus of the resulting silicone resin layer by the nanoindentation method within a predetermined range.
- the mixing ratio can be adjusted.
- the molar ratio (number of moles of alkenyl group / number of moles of hydrosilyl group) of all alkenyl groups in organopolysiloxane A and hydrosilyl groups (hydrogen atoms bonded to silicon atoms) in organopolysiloxane B is glass. It is preferable to adjust so that it may become 1/1 to 1 / 0.8 at the point which the peelability of a board
- the organopolysiloxane A is linear or cyclic, has two or more alkenyl groups in one molecule, and two alkenyl groups. It is preferable that at least one of both M units is present, and the organopolysiloxane B has two or more hydrosilyl groups in one molecule, and the molar content of hydrosilyl groups is 30% or more.
- the molar ratio (number of moles of alkenyl group / number of moles of hydrosilyl group) of all alkenyl groups in organopolysiloxane A and hydrosilyl groups (hydrogen atoms bonded to silicon atoms) in organopolysiloxane B is It is preferable to adjust so that 1/1 to 1 / 0.8.
- a platinum group metal catalyst is preferably used as the hydrosilylation catalyst.
- the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use as a platinum-based catalyst from the viewpoint of economy and reactivity.
- known catalysts can be used. Specifically, platinum fine powder, platinum black, chloroplatinic acid such as chloroplatinic acid, chloroplatinic acid, platinum tetrachloride, alcohol compounds of chloroplatinic acid, aldehyde compounds, platinum olefin complexes, alkenyls Examples thereof include siloxane complexes and carbonyl complexes.
- the amount of the hydrosilylation catalyst used is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total mass of organopolysiloxane A and organopolysiloxane B.
- the platinum component is preferably 2 to 400 ppm, more preferably 2 to 300 ppm, based on 100 parts by mass of the total mass of organopolysiloxane A and organopolysiloxane B.
- the weight-average molecular weight of the crosslinkable organopolysiloxane is not particularly limited, but it is excellent in handleability, excellent in film formability, and GPC (gel permeation) in that the decomposition of the silicone resin under high temperature processing conditions is further suppressed.
- the weight average molecular weight in terms of polystyrene as measured by chromatography is preferably 1,000 to 5,000,000, and more preferably 2,000 to 3,000,000.
- the viscosity of the crosslinkable organopolysiloxane is preferably 10 to 5000 mPa ⁇ s, more preferably 15 to 3000 mPa ⁇ s.
- a viscosity is a value when it measures at 25 degreeC.
- an activity inhibitor (compound also called a reaction inhibitor, a retarder, etc.) having an action of suppressing the catalyst activity is used together with the catalyst for the purpose of adjusting the catalyst activity.
- the activity inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, and organic chloro compounds.
- Specific examples of the acetylene compound include 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 4-ethyl-1-octyn-3-ol, and the like.
- inorganic fillers such as various silicas, calcium carbonates, iron oxides and the like may be contained within a range not impairing the effects of the present invention.
- metal compounds such as a metal oxide, may be included as a heat resistance improvement agent.
- organic solvents such as hexane, heptane, octane, toluene and xylene, and dispersion media such as water are components that do not constitute a cured silicone resin, but include improved workability for application of the curable silicone resin composition. For the purpose, it can be used by blending with the curable silicone resin composition of the present invention.
- the silicone resin layer 14 may contain silicone oil. Even when silicone oil is contained in the silicone resin layer, the elastic modulus of the silicone resin layer measured by the nanoindentation method can be controlled to a predetermined value.
- silicone oil is a non-crosslinkable (nonreactive) organopolysiloxane that does not react with the crosslinkable organopolysiloxane and does not have crosslinkability.
- the type of silicone oil is not particularly limited, but straight silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc., modified silicone oils in which polyether groups, halogen groups, etc.
- silicone oil having an aromatic group (for example, phenyl group), KTSF433 (manufactured by Momentive Performance Materials Japan GK), KF -50, KF-53, KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH550 (manufactured by Toray Dow Corning), and the like.
- silicone oil having no aromatic group examples include SH200 (manufactured by Toray Dow Corning), KNS-330 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
- the viscosity of the silicone oil is not particularly limited, but it is 100 to 100 in that it is easy to bleed out on the surface of the silicone resin layer 14 and the peelability of the glass substrate 16 is more excellent, and the transparency of the peeled glass substrate 16 is more excellent. 6000 mm 2 / s is preferable, 100 to 3000 mm 2 / s is more preferable, and 125 to 1000 mm 2 / s is more preferable.
- the content ratio of the silicone oil in the silicone resin layer 14 is not particularly limited, but with respect to 100 parts by mass of the silicone resin in terms of excellent peelability of the glass substrate 16 and more excellent transparency of the peeled glass substrate. 6 to 20 parts by mass is preferable, 6 to 15 parts by mass is more preferable, and 8 to 15 parts by mass is even more preferable.
- the glass laminate 10 of the present invention is a laminate in which the support base 12, the glass substrate 16, and the silicone resin layer 14 exist between them.
- the manufacturing method in particular of the glass laminated body 10 of this invention is not restrict
- immobilized on the support base material 12 is preferable.
- a predetermined crosslinkable organopolysiloxane is crosslinked and cured on the surface of the support substrate 12 to form the silicone resin layer 14.
- the method is preferred. That is, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, and the crosslinkable organopolysiloxane is crosslinked on the surface of the support substrate 12 to form a silicone resin layer 14 (crosslinked silicone resin).
- the glass substrate 16 is manufactured by laminating the glass substrate 16 on the silicone resin surface of the silicone resin layer 14.
- the elastic modulus by the nanoindentation method can be controlled within a predetermined range by crosslinking and curing a predetermined crosslinkable organopolysiloxane on the surface of the support substrate 12.
- a predetermined crosslinkable organopolysiloxane on the surface of the support substrate 12.
- the crosslinkable organopolysiloxane adheres due to the interaction with the surface of the support substrate 12 during the curing reaction, and the peel strength between the silicone resin and the surface of the support substrate 12 increases. . Therefore, even if the glass substrate 16 and the support base 12 are made of the same material, a difference can be provided in the peel strength between the silicone resin layer 14 and the both.
- a step of forming a silicone resin layer 14 by forming a layer containing a crosslinkable organopolysiloxane on the surface of the support substrate 12 and crosslinking the crosslinkable organopolysiloxane on the surface of the support substrate 12 is a resin layer forming step.
- the process of laminating the glass substrate 16 on the silicone resin surface of the silicone resin layer 14 to form the glass laminate 10 is referred to as a lamination process, and the procedure of each process will be described in detail.
- a layer containing a crosslinkable organopolysiloxane is formed on the surface of the support substrate 12, and the crosslinkable organopolysiloxane is crosslinked on the surface of the support substrate 12 to form the silicone resin layer 14.
- a coating composition in which the crosslinkable organopolysiloxane is dissolved in a solvent is used, and this composition is formed on the support substrate 12. It is preferable to form a solution layer by coating, and then remove the solvent to form a layer containing a crosslinkable organopolysiloxane.
- the thickness of the layer containing the crosslinkable organopolysiloxane can be controlled by adjusting the concentration of the crosslinkable organopolysiloxane in the composition.
- the solvent is not particularly limited as long as it can easily dissolve the crosslinkable organopolysiloxane in a working environment and can be easily volatilized and removed. Specific examples include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF, chloroform and the like.
- the method for applying the composition containing the crosslinkable organopolysiloxane on the surface of the support substrate 12 is not particularly limited, and a known method can be used. Examples thereof include spray coating, die coating, spin coating, dip coating, roll coating, bar coating, screen printing, and gravure coating. Then, if necessary, a drying process for removing the solvent may be performed.
- the method for the drying treatment is not particularly limited, and examples thereof include a method of removing the solvent under reduced pressure conditions and a method of heating at a temperature at which the curing of the crosslinkable organopolysiloxane does not proceed.
- the crosslinkable organopolysiloxane on the support substrate 12 is crosslinked to form the silicone resin layer 14. More specifically, as shown in FIG. 2A, in this step, a silicone resin layer 14 is formed on the surface of at least one side of the support base 12.
- the curing (crosslinking) method is appropriately selected according to the crosslinking type of the crosslinkable organopolysiloxane, and examples thereof include heat treatment and exposure treatment.
- the crosslinkable organopolysiloxane is crosslinked by a hydrosilylation reaction, a condensation reaction, or a radical reaction, a silicone resin having excellent adhesion and heat resistance to the glass substrate 16 can be obtained. It is preferable to manufacture.
- the aspect of thermosetting is explained in full detail.
- the temperature condition for thermosetting the crosslinkable organopolysiloxane is not particularly limited as long as the heat resistance of the silicone resin layer 14 is improved and the peel strength (y) after lamination with the glass substrate 16 can be controlled as described above.
- 150 to 300 ° C is preferable, and 180 to 250 ° C is more preferable.
- the heating time is usually preferably 10 to 120 minutes, more preferably 30 to 60 minutes.
- the temperature of thermosetting is too low, the heat resistance and the flatness of the silicone resin layer 14 are lowered.
- the peel strength (y) is too low, both of which are the glass substrate 16 and the silicone resin layer 14. Adhesiveness may be weakened.
- the crosslinkable organopolysiloxane may be cured by precuring (precuring) and then by postcuring (main curing).
- Precuring is preferably performed following the removal of the solvent. In that case, there is no particular distinction between the step of removing the solvent from the layer to form a layer containing a crosslinkable organopolysiloxane and silicone oil and the step of performing precuring.
- the glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14 obtained in the resin layer forming step, and the support base 12, the silicone resin layer 14, and the glass substrate 16 are provided in this order.
- the glass laminate 10 is obtained by laminating the silicone resin layer 14 and the glass substrate 16 with the first principal surface 16a of the glass substrate 16 having the second principal surface 16b as a lamination surface.
- stacking the glass substrate 16 on the silicone resin layer 14 is not restrict
- a well-known method is employable.
- a method of stacking the glass substrate 16 on the surface of the silicone resin layer 14 under a normal pressure environment can be mentioned.
- the glass substrate 16 may be pressure-bonded to the silicone resin layer 14 using a roll or a press. Air bubbles mixed between the silicone resin layer 14 and the glass substrate 16 can be removed relatively easily by pressure bonding using a roll or a press, which is preferable.
- the surface of the glass substrate 16 in contact with the silicone resin layer 14 is sufficiently washed and laminated in an environment with a high degree of cleanliness.
- pre-annealing process heat processing
- the adhesion of the laminated glass substrate 16 to the silicone resin layer 14 can be improved, and an appropriate peel strength (y) can be obtained. Misalignment of members is less likely to occur, and the productivity of electronic devices is improved.
- the conditions for the pre-annealing treatment are appropriately selected according to the type of the silicone resin layer 14 to be used, but the peel strength (y) between the glass substrate 16 and the silicone resin layer 14 is more appropriate. In view of this, it is preferable to perform heat treatment at 300 ° C. or higher (preferably 300 to 400 ° C.) for 5 minutes or longer (preferably 5 to 30 minutes).
- the formation of the silicone resin layer 14 is not limited to the above method.
- a crosslinkable organopolysiloxane is cured on some peelable surface to produce a silicone resin film, This film can be interposed between the glass substrate 16 and the support base 12 and laminated simultaneously.
- the adhesiveness by hardening of crosslinkable organopolysiloxane is low enough with respect to the glass substrate 16, and the adhesiveness is high enough with respect to the support base material 12, it bridge
- the silicone resin layer 14 can be formed by curing the functional organopolysiloxane.
- the support base 12 is made of the same glass material as that of the glass substrate 16, it is possible to increase the peel strength with respect to the silicone resin layer 14 by performing a process for improving the adhesion of the support base 12 surface.
- a chemical method that improves the fixing force chemically such as a silane coupling agent
- a physical method that increases surface active groups such as a flame (flame) treatment
- a surface such as a sandblast treatment
- a mechanical processing method increase the catch by increasing the roughness of the material.
- the glass laminate 10 of the present invention can be used for various applications, for example, manufacturing electronic parts such as a display device panel, PV, a thin film secondary battery, and a semiconductor wafer having a circuit formed on the surface, which will be described later. The use to do is mentioned.
- the glass laminate 10 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 360 ° C. or higher).
- the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.
- the glass substrate with a member (glass substrate with a member for electronic devices) containing a glass substrate and the member for electronic devices is manufactured using the laminated body mentioned above.
- the manufacturing method of this glass substrate with a member is not specifically limited, From the point which is excellent in productivity of an electronic device, the member for electronic devices is formed on the glass substrate in the said glass laminated body, and the laminated body with an electronic device member is used.
- a method in which the manufactured and obtained laminate with a member for electronic devices is separated into a glass substrate with a member and a supporting substrate with a silicone resin layer by using the glass substrate side interface of the silicone resin layer as a release surface is preferable.
- the step of forming a member for an electronic device by forming a member for an electronic device on the glass substrate in the glass laminate is a member forming step, and the glass substrate for the silicone resin layer from the laminate with the member for an electronic device.
- the process of separating into a glass substrate with a member and a supporting substrate with a silicone resin layer using the side interface as a release surface is called a separation process. The materials and procedures used in each process are described in detail below.
- a member formation process is a process of forming the member for electronic devices on the glass substrate 16 in the glass laminated body 10 obtained in the said lamination process. More specifically, as shown in FIG. 2C, the electronic device member 20 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain the laminate 22 with the electronic device member. .
- the electronic device member 20 used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.
- the electronic device member 20 is a member that is formed on the glass substrate 16 in the glass laminate 10 and constitutes at least a part of the electronic device. More specifically, as the electronic device member 20, a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on the surface (for example, Display member, solar cell member, thin film secondary battery member, electronic component circuit).
- a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
- a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer, etc.
- various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
- a circuit for an electronic component in a CCD or CMOS, a metal of a conductive part, a silicon oxide or a silicon nitride of an insulating part, and the like, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board And various members corresponding to a rigid flexible printed circuit board.
- the manufacturing method of the laminated body 22 with the member for electronic devices mentioned above is not specifically limited, According to the conventionally well-known method according to the kind of structural member of the member for electronic devices, the 2nd main of the glass substrate 16 of the glass laminated body 10 is used.
- the electronic device member 20 is formed on the surface 16b.
- the electronic device member 20 is not all of the members finally formed on the second main surface 16b of the glass substrate 16 (hereinafter referred to as “all members”), but a part of all members (hereinafter referred to as “parts”). May be referred to as a member.
- the glass substrate with a partial member peeled from the silicone resin layer 14 can be used as a glass substrate with an all member (corresponding to an electronic device described later) in the subsequent steps.
- the other electronic device member may be formed in the peeling surface (1st main surface 16a) in the glass substrate with all the members peeled from the silicone resin layer 14.
- FIG. Moreover, an electronic device can also be manufactured by assembling a laminate with all members and then peeling the support substrate 12 from the laminate with all members. Furthermore, it is also possible to assemble using two laminates with all members, and then peel off the two support bases 12 from the laminate with all members to produce a glass substrate with a member having two glass substrates. it can.
- an organic EL is formed on the surface of the glass laminate 10 opposite to the silicone resin layer 14 side of the glass substrate 16 (corresponding to the second main surface 16b of the glass substrate 16).
- a transparent electrode is formed, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc. are deposited on the surface on which the transparent electrode is formed, a back electrode is formed, and sealing is performed.
- Various layers are formed and processed, such as sealing with a plate. Specific examples of the layer formation and processing include film formation processing, vapor deposition processing, sealing plate adhesion processing, and the like.
- a resist film is used on the second main surface 16b of the glass substrate 16 of the glass laminate 10 by a general film forming method such as a CVD method or a sputtering method.
- a TFT forming step of forming a thin film transistor (TFT) by patterning the formed metal film, metal oxide film, etc., and patterning a resist solution on the second main surface 16b of the glass substrate 16 of another glass laminate 10 Various processes such as a CF forming step for forming a color filter (CF) to be used for forming, a laminating step for laminating a laminated body with TFT obtained in the TFT forming step and a laminated body with CF obtained in the CF forming step, etc. Process.
- the TFT and the CF are formed on the second main surface 16b of the glass substrate 16 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
- a cleaning method known dry cleaning or wet cleaning can be used.
- the thin film transistor forming surface of the laminated body with TFT and the color filter forming surface of the laminated body with CF are opposed to each other, and are bonded using a sealant (for example, an ultraviolet curable sealant for cell formation).
- a sealant for example, an ultraviolet curable sealant for cell formation.
- a liquid crystal material is injected into a cell formed by the laminate with TFT and the laminate with CF.
- the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.
- the separation step is performed by using the electronic device member-attached laminate 22 obtained in the member formation step, with the interface between the silicone resin layer 14 and the glass substrate 16 as a release surface.
- This is a step of separating the glass substrate 16 (member-attached glass substrate 24) on which the member 20 for use is laminated and the support base material 12 to obtain the member-equipped glass substrate 24 including the electronic device member 20 and the glass substrate 16. .
- the electronic device member 20 on the glass substrate 16 at the time of peeling is a part of the formation of all the necessary constituent members, the remaining constituent members can be formed on the glass substrate 16 after separation.
- the method of peeling the glass substrate 16 and the support base material 12 is not specifically limited. Specifically, for example, a sharp blade-like object is inserted into the interface between the glass substrate 16 and the silicone resin layer 14 to give a trigger for peeling, and then a mixed fluid of water and compressed air is sprayed. Can be peeled off.
- the electronic device member-attached laminate 22 is placed on the surface plate so that the support substrate 12 is on the upper side and the electronic device member 20 side is on the lower side, and the electronic device member 20 side is vacuumed on the surface plate. In this state, the blade is first allowed to enter the interface between the glass substrate 16 and the silicone resin layer 14.
- the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted.
- an air layer is formed on the interface between the silicone resin layer 14 and the glass substrate 16 and on the cohesive failure surface of the silicone resin layer 14, and the air layer spreads over the entire interface and cohesive failure surface, so that the supporting substrate 12 can be easily peeled off. can do.
- the support base material 12 can be laminated
- a piece of the silicone resin layer 14 is electrostatically adsorbed to the glass substrate 24 with a member by controlling the spraying and humidity with an ionizer. It can be suppressed more.
- the above-described method for manufacturing the glass substrate with member 24 is suitable for manufacturing a small display device used for a mobile terminal such as a mobile phone or a PDA.
- the display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like.
- the present invention can be applied to both passive drive type and active drive type display devices.
- a panel for a display device having a glass substrate and a member for a display device a solar cell having a glass substrate and a member for a solar cell, a glass substrate and a member for a thin film secondary battery.
- a thin film secondary battery an electronic component having a glass substrate and an electronic device member.
- the display device panel include a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.
- the support base material with a silicone resin layer is a support base material with a silicone resin layer, which has a support base material and a silicone resin layer provided on the support base material surface.
- a support substrate with a silicone resin layer wherein the silicone resin of the resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the elastic modulus of the silicone resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa. It is.
- the support substrate with the silicone resin layer is such that the same silicone resin layer as described in the first embodiment is formed on the same surface of the support substrate as described in the first embodiment.
- Such a support substrate with a silicone resin layer can be obtained by forming a silicone resin layer on the surface of the support substrate or by peeling a glass substrate or a glass substrate with a member from the laminate.
- a glass plate made of non-alkali borosilicate glass (200 mm long, 200 mm wide, 0.2 mm thick, average linear expansion coefficient 38 ⁇ 10 ⁇ 7) is used as the glass substrate. / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.).
- a glass plate (240 mm long, 240 mm wide, 0.5 mm thick, average linear expansion coefficient 38 ⁇ 10 ⁇ 7 / ° C., made by Asahi Glass Co., Ltd., also made of non-alkali borosilicate glass. ”)It was used.
- a supporting substrate having a thickness of 0.5 mm was cleaned with pure water, and further cleaned by UV cleaning.
- Arakawa Chemical Co., Ltd. main agent (ASA-V01) 100 parts by mass
- Arakawa Chemical Co., Ltd. curing agent (ASA-X01) 13 parts by mass) were blended.
- Arakawa Chemical's catalyst (ASA-C01) was added in an amount of 5 parts by weight per 100 parts by weight of (ASA-V01).
- a solution X containing a crosslinkable organopolysiloxane was prepared by adding heptane.
- This solution X was applied onto the first main surface of the supporting substrate with a spin coater (rotation speed: 300 rpm, 15 seconds), and a layer containing an uncured crosslinkable organopolysiloxane was provided on the supporting substrate. (Coating amount 20 g / m 2 ).
- the glass substrate A and the silicone resin layer surface of the supporting substrate were bonded together by vacuum pressing at room temperature to obtain a glass laminate A.
- the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
- the glass laminate A was heated at 360 ° C. for 60 minutes in a nitrogen atmosphere and cooled to room temperature.
- the glass substrate A was separated from the supporting substrate and the glass substrate, and the silicone resin layer was foamed or whitened. No change in appearance was observed.
- glass The vacuum suction pad was adsorbed on the surface of the substrate and the supporting base that were not the release surfaces, and an external force was applied in the direction in which the glass substrate and the supporting base were separated from each other, thereby separating the glass substrate and the supporting base without being damaged.
- the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Specifically, the vacuum suction pad was pulled up while spraying a static eliminating fluid continuously from the ionizer toward the formed gap.
- the silicone resin layer is separated from the glass substrate together with the supporting base material. From the result, the peeling strength (x) at the interface between the supporting base material and the silicone resin layer is determined as the peeling strength (y at the interface between the silicone resin layer and the glass substrate). ) was confirmed. Moreover, it was 2.36 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
- the measurement conditions of the nanoindentation method were as follows. Various physical property values of the silicone resin layer were measured using TI-950 Tribo Indenter manufactured by Omicron Nanotechnology Japan Co., Ltd. That is, a Conical 5um type triangular pyramid indenter is used as the working indenter, a pushing load is applied to the constant displacement speed mode 30 nm / sec, and after reaching the maximum load of 2 ⁇ N, the pushing load is gradually reduced stepwise. The measurement is performed under a constant temperature condition of 25 ° C., and after sufficiently stabilizing the temperature of the measuring apparatus and the sample, the elastic modulus at a depth of 200 nm is measured with an indentation strength of 0.2 ⁇ N, and five continuous measurements are performed. The average value was taken as the measured value.
- Example 2 Glass laminates were prepared in the same manner as in Example 1 except that methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s) was added to solution X containing a crosslinkable organopolysiloxane. Body B was obtained. In addition, the usage-amount of methylphenyl silicone oil was 5 mass parts with respect to 100 mass parts of silicone resins.
- methylphenyl silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s
- the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
- the glass laminate B was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate B and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
- the glass base material B was isolate
- the silicone resin layer was separated from the glass substrate together with the supporting base material.
- Example 3 A glass laminate in the same manner as in Example 2, except that the amount of methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s) was changed from 5 parts by mass to 15 parts by mass. C was obtained.
- methylphenyl silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s
- the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
- the glass laminate C was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate C and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
- the glass substrate C was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged.
- the silicone resin layer was separated from the glass substrate together with the supporting base material.
- Example 4 A glass laminate in the same manner as in Example 2 except that the amount of methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s) was changed from 5 parts by mass to 20 parts by mass. D was obtained.
- methyl phenyl silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s
- the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
- the glass laminate D was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate D and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
- the glass base material D was isolate
- the silicone resin layer was separated from the glass substrate together with the supporting base material.
- Example 5 Instead of methylphenyl silicone oil (Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s), methylphenyl silicone oil (Toray Dow Corning, SH200, viscosity 200 mm 2 / s) was used. A glass laminate E was obtained in the same manner as in Example 2.
- the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
- the glass laminate E was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate E, foaming and whitening of the silicone resin layer were observed. There wasn't.
- the glass substrate E was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged.
- the silicone resin layer was separated from the glass substrate together with the supporting base material.
- Example 6 The glass laminate F was prepared in the same manner as in Example 5 except that the amount of methyl phenyl silicone oil (Toray Dow Corning, SH200, viscosity 200 mm 2 / s) was changed from 5 parts by mass to 10 parts by mass. Obtained.
- methyl phenyl silicone oil Toray Dow Corning, SH200, viscosity 200 mm 2 / s
- the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
- the glass laminate F was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate F, foaming or whitening of the silicone resin layer were observed. There wasn't.
- the glass laminate F was separated from the support base material and the glass substrate by the same method as in Example 1, the glass substrate and the support base material were separated without being damaged.
- the silicone resin layer was separated from the glass substrate together with the supporting base material.
- Example 7 The glass laminate G was prepared in the same manner as in Example 5 except that the amount of methyl phenyl silicone oil (Toray Dow Corning, SH200, viscosity 200 mm 2 / s) was changed from 5 parts by mass to 15 parts by mass. Obtained.
- methyl phenyl silicone oil Toray Dow Corning, SH200, viscosity 200 mm 2 / s
- the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
- the glass laminate G was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate G and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
- the glass substrate G was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged.
- the silicone resin layer was separated from the glass substrate together with the supporting base material.
- Example 8> A glass laminate H was obtained in the same manner as in Example 1 except that the solution Y containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.
- a solution Y containing a crosslinkable organopolysiloxane was prepared by adding heptane.
- the molar ratio of the vinyl group of the main agent to the hydrogen group of the curing agent is 1 mole: 0.8 mole.
- the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
- the glass laminate H was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate H, foaming and whitening of the silicone resin layer were recognized. There wasn't.
- the glass substrate H was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged.
- the silicone resin layer was separated from the glass substrate together with the supporting base material.
- Example 9 A glass laminate I was obtained in the same manner as in Example 1 except that the solution Z containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.
- the supporting substrate and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and there was no distortion defect and smoothness was good.
- the glass laminate I was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate I, foaming and whitening of the silicone resin layer were observed. There wasn't.
- the glass substrate I was separated from the supporting base material and the glass substrate by the same method as in Example 1, the glass substrate and the supporting base material were separated without being damaged.
- the silicone resin layer was separated from the glass substrate together with the supporting base material.
- Example 1 A glass laminate J was obtained in the same manner as in Example 1, except that the solution W containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.
- Example 2 A glass laminate K was obtained in the same manner as in Example 1, except that the solution V containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.
- the silicone resin layer and the glass substrate were difficult to peel off, and the glass substrate was broken, or The silicone resin layer was destroyed, and most of it was deposited on the glass substrate.
- it was 3.15 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
- the following peel test was performed on the glass laminates A to K after the heat treatment at 360 ° C. for 60 minutes, and the peel strength (N / 25 mm) of the glass substrate was measured.
- Glass laminates A to K having a width of 25 mm and a length of 70 mm were prepared, and the glass substrate was peeled off using Autograph AG-20 / 50kNXDplus (Shimadzu Corporation).
- the peeling speed was 30 mm / min.
- the point where the load was detected was set to 0, and the peel strength at a position 1.5 mm away from the position was taken as the measured value.
- Example 10 an OLED is manufactured using the glass laminate A obtained in Example 1. First, silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in the glass laminate A by plasma CVD. Next, low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and a dehydrogenation process is performed by heating at 450 ° C. for 60 minutes in a nitrogen atmosphere. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus.
- low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas.
- a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, then molybdenum is formed by a sputtering method, and etching is performed using a photolithography method.
- a gate electrode is formed.
- high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area.
- an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography.
- a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method.
- an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography.
- a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
- panel A a glass laminate A having the organic EL structure on the glass substrate is used for the electronic device of the present invention. It is a laminated body with a member (panel for display apparatuses with a supporting base material).
- a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner portion of the panel A, and glass Provides a trigger for peeling at the interface between the substrate and the silicone resin layer.
- a suction pad is raised.
- the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation).
- the vacuum suction pad is pulled up while the static elimination fluid is continuously sprayed from the ionizer toward the formed gap.
- the separation surface of the glass substrate separated by the same method as in Example 1 was cleaned, the separated glass substrate was cut using a laser cutter or a scribe-break method, and divided into a plurality of cells.
- the glass substrate on which the EL structure is formed and the counter substrate are assembled, and a module forming process is performed to manufacture an OLED.
- the OLED obtained in this way does not have a problem in characteristics.
- Example 11 an LCD is manufactured using the glass laminate A obtained in Example 1.
- two glass laminates A are prepared, and silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in one glass laminate A1 by plasma CVD.
- low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and a dehydrogenation process is performed by heating at 450 ° C. for 60 minutes in a nitrogen atmosphere.
- the amorphous silicon layer is crystallized by a laser annealing apparatus.
- low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas.
- a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method and a gate insulating film is formed, molybdenum is formed by a sputtering method, and the gate is etched by photolithography. An electrode is formed.
- high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area.
- an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography.
- a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method.
- an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography.
- a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
- the other glass laminate A2 is heat-treated at 450 ° C. for 60 minutes in an air atmosphere.
- a chromium film is formed on the second main surface of the glass substrate in the glass laminate A by a sputtering method, and a light shielding layer is formed by etching using a photolithography method.
- a color resist is applied to the second main surface side of the glass substrate by a die coating method, and a color filter layer is formed by a photolithography method and heat curing.
- a film of indium tin oxide is formed by a sputtering method to form a counter electrode.
- an ultraviolet curable resin liquid is applied to the second main surface side of the glass substrate by a die coating method, and columnar spacers are formed by a photolithography method and thermal curing.
- a polyimide resin solution is applied by a roll coating method, an alignment layer is formed by thermosetting, and rubbing is performed.
- a sealing resin liquid is drawn in a frame shape by the dispenser method, and after dropping the liquid crystal in the frame by the dispenser method, two glass layers are laminated using the glass laminate A1 in which the pixel electrodes are formed as described above.
- the second main surface sides of the glass substrate of the body A are bonded together, and an LCD panel is obtained by ultraviolet curing and thermal curing.
- the second main surface of the glass laminate A1 is vacuum-adsorbed on a surface plate, and a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner of the glass laminate A2. Triggering the peeling between the first main surface of the glass substrate and the peelable surface of the silicone resin layer.
- the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation).
- the vacuum suction pad is pulled up while the static elimination fluid is continuously sprayed from the ionizer toward the formed gap.
- the second main surface of the glass substrate on which the color filter is formed on the first main surface is vacuum-adsorbed on a surface plate, and the thickness is formed at the interface between the glass substrate and the silicone resin layer at the corner portion of the glass laminate A1.
- a 0.1 mm stainless steel blade is inserted to give a trigger for peeling between the first main surface of the glass substrate and the peelable surface of the silicone resin layer.
- sucking the 2nd main surface of the support base material of glass laminated body A1 with a vacuum suction pad a suction pad is raised.
- only the LCD cell is left on the surface plate, and the supporting substrate to which the silicone resin layer is fixed can be peeled off.
- a plurality of LCD cells composed of a glass substrate having a thickness of 0.1 mm are obtained.
- Example 12 an OLED is manufactured using the glass laminate A obtained in Example 1.
- molybdenum is deposited on the second main surface of the glass substrate in the glass laminate A by a sputtering method, and a gate electrode is formed by etching using a photolithography method.
- a silicon nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then an indium gallium zinc oxide film is formed by a sputtering method to perform a photolithography method.
- An oxide semiconductor layer is formed by the etching used.
- a silicon nitride film is further formed on the second main surface side of the glass substrate by plasma CVD to form a channel protective layer, and then molybdenum is formed by sputtering and etching using a photolithography method is performed. Thus, a source electrode and a drain electrode are formed. Next, heat treatment is performed in the atmosphere at 450 ° C. for 60 minutes. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a passivation layer, followed by an indium tin oxide film formed by a sputtering method and etching using a photolithography method. Thus, a pixel electrode is formed.
- panel A a glass laminate A having the organic EL structure on the glass substrate is used for the electronic device of the present invention. It is a laminated body with a member (panel for display apparatuses with a supporting base material).
- a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner portion of the panel A, and glass Provides a trigger for peeling at the interface between the substrate and the silicone resin layer.
- a suction pad is raised.
- the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation).
- the vacuum suction pad is pulled up while the static elimination fluid is continuously sprayed from the ionizer toward the formed gap.
- the separation surface of the glass substrate separated by the same method as in Example 1 was cleaned, the separated glass substrate was cut using a laser cutter or a scribe-break method, and divided into a plurality of cells.
- the glass substrate on which the EL structure is formed and the counter substrate are assembled, and a module forming process is performed to manufacture an OLED.
- the OLED obtained in this way does not have a problem in characteristics.
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Abstract
Description
また、本発明はシリコーン樹脂層付き支持基材に係り、特に、ガラス基板がその表面に剥離可能に積層されるシリコーン樹脂層付き支持基材およびその製造方法に関する。 The present invention relates to a glass laminate and a method for producing the same, and more particularly to a glass laminate having a silicone resin layer exhibiting a predetermined elastic modulus and a method for producing the same.
The present invention also relates to a support base material with a silicone resin layer, and more particularly, to a support base material with a silicone resin layer on which a glass substrate is releasably laminated and a manufacturing method thereof.
しかし、この方法では、例えば、1枚のガラス基板の厚さを0.7mmから0.2mmや0.1mmに薄板化する場合、元々のガラス基板の材料の大半をエッチング液で削り落とすことになるので、生産性や原材料の使用効率という観点では好ましくない。また、上記の化学エッチングによるガラス基板の薄板化方法においては、ガラス基板表面に微細な傷が存在する場合、エッチング処理によって傷を起点として微細な窪み(エッチピット)が形成され、光学的な欠陥となる場合があった。 Therefore, conventionally, a method of forming a device member (for example, a thin film transistor) on a glass substrate thicker than the final thickness and then thinning the glass substrate by chemical etching is widely used.
However, in this method, for example, when the thickness of one glass substrate is reduced from 0.7 mm to 0.2 mm or 0.1 mm, most of the original glass substrate material is scraped off with an etching solution. Therefore, it is not preferable from the viewpoint of productivity and use efficiency of raw materials. In addition, in the method of thinning a glass substrate by the above chemical etching, if a fine scratch exists on the surface of the glass substrate, a fine recess (etch pit) is formed from the scratch by the etching process, resulting in an optical defect. There was a case.
特許文献1に記載のガラス積層体は大気中300℃、1時間の処理に耐えうる。しかし、本発明者らの検討によれば、特許文献1を参照して、より厚みの薄いガラス基板を使用したガラス積層体に対して360℃、1時間の処理を行った場合、ガラス基板をシリコーン樹脂層表面から剥離する際に、ガラス基板が樹脂層表面から剥がれずにその一部が破壊されたり、樹脂層の樹脂の一部がガラス基板上に残存したりして、結果として電子デバイスの生産性の低下を招く場合があった。 In recent years, higher heat resistance has been required for the glass laminate described in Patent Document 1. As the electronic device members formed on the glass substrate of the glass laminate become more functional and complex, the temperature at which the electronic device members are formed becomes even higher, and the time exposed to the high temperatures also increases. It often takes a long time. Moreover, the glass substrate used is also made thinner, making it difficult to handle.
The glass laminate described in Patent Document 1 can withstand treatment at 300 ° C. for 1 hour in the air. However, according to studies by the present inventors, referring to Patent Document 1, when a glass laminate using a thinner glass substrate is treated at 360 ° C. for 1 hour, the glass substrate is When peeling from the surface of the silicone resin layer, the glass substrate is not peeled off from the surface of the resin layer, but part of it is destroyed, or part of the resin of the resin layer remains on the glass substrate, resulting in an electronic device. In some cases, the productivity of the product was reduced.
また、本発明は、該ガラス積層体の製造に使用されるシリコーン樹脂層付き支持基材を提供することも目的とする。 The present invention has been made in view of the above problems, and even after high-temperature heat treatment, the increase in peel strength between the glass substrate and the silicone resin layer is suppressed, and the glass substrate can be easily peeled off. It aims at providing a glass laminated body and its manufacturing method.
Another object of the present invention is to provide a support substrate with a silicone resin layer used in the production of the glass laminate.
すなわち、本発明の第1の態様は、支持基材とシリコーン樹脂層とガラス基板とをこの順で備え、支持基材とシリコーン樹脂層との界面の剥離強度がシリコーン樹脂層とガラス基板との界面の剥離強度よりも大きい、ガラス積層体であって、シリコーン樹脂層のシリコーン樹脂が、架橋性オルガノポリシロキサンの架橋物であり、ナノインデンテーション法により測定したシリコーン樹脂層の弾性率が0.5~2.5MPaである、ガラス積層体である。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the first aspect of the present invention includes a support base material, a silicone resin layer, and a glass substrate in this order, and the peel strength at the interface between the support base material and the silicone resin layer is between the silicone resin layer and the glass substrate. The glass laminate is larger than the peel strength at the interface, and the silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the elastic modulus of the silicone resin layer measured by the nanoindentation method is 0. A glass laminate having a pressure of 5 to 2.5 MPa.
第1の態様において、アルケニル基とハイドロシリル基との混合モル比(アルケニル基のモル数/ハイドロシリル基のモル数)が1/1~1/0.8であることが好ましい。
第1の態様において、シリコーン樹脂層が、さらにシリコーンオイルを含むことが好ましい。
第1の態様において、シリコーン樹脂層の厚さが2~100μmであることが好ましい。
第1の態様において、支持基材がガラス板であることが好ましい。 In the first embodiment, the crosslinked product of the crosslinkable organopolysiloxane is preferably a crosslinked product obtained by reacting an organopolysiloxane having an alkenyl group and an organopolysiloxane having a hydrosilyl group.
In the first embodiment, the mixing molar ratio of alkenyl group to hydrosilyl group (number of moles of alkenyl group / number of moles of hydrosilyl group) is preferably 1/1 to 1 / 0.8.
In the first aspect, the silicone resin layer preferably further contains silicone oil.
In the first embodiment, the thickness of the silicone resin layer is preferably 2 to 100 μm.
1st aspect WHEREIN: It is preferable that a support base material is a glass plate.
また、本発明によれば、該ガラス積層体の製造に使用されるシリコーン樹脂層付き支持基材を提供することもできる。 ADVANTAGE OF THE INVENTION According to this invention, even after high temperature heat processing, the raise of the peeling strength of a glass substrate and a silicone resin layer is suppressed, and the glass laminated body which can peel a glass substrate easily, and its manufacturing method are provided. be able to.
Moreover, according to this invention, the support base material with a silicone resin layer used for manufacture of this glass laminated body can also be provided.
本発明のガラス積層体の特徴点の一つは、ナノインデンテーション法により測定されるシリコーン樹脂層の弾性率が所定の範囲内にある点が挙げられる。特に、支持基材上に形成したシリコーン樹脂層の弾性率が所定の範囲内にある。弾性率が所定の範囲内にあるシリコーン樹脂層は、従来のシリコーン樹脂層と比較して柔らかい。このような柔軟なシリコーン樹脂層を使用すると、このシリコーン樹脂層上に配置されるガラス基板とある程度密着してその位置ズレを防止すると共に、比較的容易にガラス基板を剥離することができる。上記のような特性が得られる詳細な理由は不明だが、以下のように推測される。まず、ガラス基板がシリコーン樹脂層上に積層された場合、シリコーン樹脂層が柔らかいためガラス基板表面の形状に追随するように変形し、シリコーン樹脂層とガラス基板との間に空隙などを生じることなく、シリコーン樹脂層とガラス基板とが良好に密着する。また、高温加熱処理後にガラス基板をシリコーン樹脂層から剥離する際には、シリコーン樹脂層が変形しやすいため局所的にガラス基板に応力が加わることも抑制でき、結果としてガラス基板を容易に剥離することができる。 The glass laminated body of this invention is equipped with a support base material, a silicone resin layer, and a glass substrate in this order. That is, it has a silicone resin layer between a support base material and a glass substrate, therefore, one side of the silicone resin layer is in contact with the support base material, and the other side is in contact with the glass substrate.
One of the characteristic points of the glass laminate of the present invention is that the elastic modulus of the silicone resin layer measured by the nanoindentation method is within a predetermined range. In particular, the elastic modulus of the silicone resin layer formed on the support substrate is within a predetermined range. A silicone resin layer having an elastic modulus within a predetermined range is softer than a conventional silicone resin layer. When such a flexible silicone resin layer is used, the glass substrate can be peeled relatively easily while being in close contact with the glass substrate disposed on the silicone resin layer to a certain degree to prevent positional displacement. Although the detailed reason for obtaining the above characteristics is unknown, it is presumed as follows. First, when the glass substrate is laminated on the silicone resin layer, the silicone resin layer is soft so that it deforms to follow the shape of the glass substrate surface without causing a gap or the like between the silicone resin layer and the glass substrate. The silicone resin layer and the glass substrate adhere well. Further, when the glass substrate is peeled from the silicone resin layer after the high-temperature heat treatment, the silicone resin layer is easily deformed, so that it is possible to suppress stress from being locally applied to the glass substrate, and as a result, the glass substrate is easily peeled off. be able to.
図1に示すように、ガラス積層体10は、支持基材12とガラス基板16とそれらの間にシリコーン樹脂層14が存在する積層体である。シリコーン樹脂層14は、その一方の面が支持基材12に接すると共に、その他方の面がガラス基板16の第1主面16aに接している。言い換えると、シリコーン樹脂層14はガラス基板16の第1主面16aに接している。
支持基材12およびシリコーン樹脂層14からなる2層部分は、液晶パネルなどの電子デバイス用部材を製造する部材形成工程において、ガラス基板16を補強する。なお、ガラス積層体10の製造のためにあらかじめ製造される支持基材12およびシリコーン樹脂層14からなる2層部分をシリコーン樹脂層付き支持基材18という。 FIG. 1 is a schematic cross-sectional view of an example of a glass laminate according to the present invention.
As shown in FIG. 1, the glass laminated
The two-layer portion composed of the
ガラス積層体10(後述の電子デバイス用部材付き積層体も意味する)においては、上記剥離強度(x)は上記剥離強度(y)よりも大きい(高い)。したがって、ガラス積層体10に支持基材12とガラス基板16とを引き剥がす方向の応力が加えられると、本発明のガラス積層体10は、シリコーン樹脂層14とガラス基板16の界面で剥離してガラス基板16とシリコーン樹脂層付き支持基材18に分離する。
つまり、シリコーン樹脂層14は支持基材12上に固定されてシリコーン樹脂層付き支持基材18を形成し、ガラス基板16はシリコーン樹脂層14上に剥離可能に密着している。 The interface between the
In the glass laminate 10 (which also means a laminate with an electronic device member described later), the peel strength (x) is greater (higher) than the peel strength (y). Therefore, when a stress is applied to the
That is, the
支持基材12に対するシリコーン樹脂層14の付着力を高めるためには、後述するように、架橋性オルガノポリシロキサンを支持基材12上で架橋硬化させてシリコーン樹脂層14を形成することが好ましい。架橋硬化の際の接着力で、支持基材12に対して高い結合力で結合したシリコーン樹脂層14を形成することができる。
一方、架橋硬化後の架橋性オルガノポリシロキサンの硬化物のガラス基板16に対する結合力は、上記架橋硬化時に生じる結合力よりも低いのが通例である。したがって、支持基材12上で架橋性オルガノポリシロキサンを架橋硬化させてシリコーン樹脂層14を形成し、その後シリコーン樹脂層14の面にガラス基板16を積層して、ガラス積層体10を製造することが好ましい。 The peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) means that the adhesion of the
In order to increase the adhesion of the
On the other hand, the bond strength of the cured product of the crosslinkable organopolysiloxane after the crosslink curing to the
支持基材12は、ガラス基板16を支持して補強し、後述する部材形成工程(電子デバイス用部材を製造する工程)において電子デバイス用部材の製造の際にガラス基板16の変形、傷付き、破損などを防止する。
支持基材12としては、例えば、ガラス板、プラスチック板、SUS板などの金属板などが用いられる。通常、部材形成工程が熱処理を伴うため、支持基材12はガラス基板16との平均線膨張係数の差の小さい材料で形成されることが好ましく、ガラス基板16と同一材料で形成されることがより好ましく、支持基材12はガラス板であることが好ましい。特に、支持基材12は、ガラス基板16と同じガラス材料からなるガラス板であることが好ましい。 [Supporting substrate]
The
As the
ガラス基板16は、第1主面16aがシリコーン樹脂層14と接し、シリコーン樹脂層14側とは反対側の第2主面16bに電子デバイス用部材が設けられる。
ガラス基板16の種類は、一般的なものであってよく、例えば、LCD、OLEDといった表示装置用のガラス基板などが挙げられる。ガラス基板16は耐薬品性、耐透湿性に優れ、且つ、熱収縮率が低い。熱収縮率の指標としては、JIS R 3102(1995年改正)に規定されている平均線膨張係数が用いられる。 [Glass substrate]
As for the
The
また、ガラス基板16の厚さは、ガラス基板16の製造が容易であること、ガラス基板16の取り扱いが容易であることなどの理由から、0.03mm以上であることが好ましい。 The thickness of the
Further, the thickness of the
シリコーン樹脂層は実質的にシリコーン樹脂からなり、該シリコーン樹脂は架橋性オルガノポリシロキサンの架橋物であり、ナノインデンテーション法により測定した弾性率が0.5~2.5MPaである。支持基材とシリコーン樹脂層との界面の剥離強度は、シリコーン樹脂層とガラス基板との界面の剥離強度よりも大きい。
シリコーン樹脂層14は、ガラス基板16と支持基材12とを分離する操作が行われるまでガラス基板16の位置ずれを防止すると共に、ガラス基板16などが分離操作によって破損するのを防止する。シリコーン樹脂層14のガラス基板16と接する表面(シリコーン樹脂層の第1主面)14aは、ガラス基板16の第1主面16aに剥離可能に密着する。一方、シリコーン樹脂層14は支持基材12上に固定されている。そのため、シリコーン樹脂層14はガラス基板16の第1主面16aに弱い結合力で結合しており、その界面の剥離強度(y)は、シリコーン樹脂層14と支持基材12との間の界面の剥離強度(x)よりも低い。
すなわち、ガラス基板16と支持基材12とを分離する際には、ガラス基板16の第1主面16aとシリコーン樹脂層14との界面で剥離し、支持基材12とシリコーン樹脂層14との界面では剥離し難い。このため、シリコーン樹脂層14はガラス基板16の第1主面16aと密着するが、ガラス基板16を容易に剥離することができる表面特性を有する。すなわち、シリコーン樹脂層14は、ガラス基板16の第1主面16aに対してある程度の結合力で結合してガラス基板16の位置ずれなどを防止していると同時に、ガラス基板16を剥離する際には、ガラス基板16を破壊することなく、容易に剥離できる程度の結合力で結合している。本発明では、このシリコーン樹脂層14表面の容易に剥離できる性質を剥離性という。一方、支持基材12の第1主面とシリコーン樹脂層14とは相対的に剥離しがたい結合力で結合している。
なお、シリコーン樹脂層14とガラス基板16の界面の結合力は、ガラス積層体10のガラス基板16の面(第2主面16b)上に電子デバイス用部材を形成する前後に変化してもよい(すなわち、剥離強度(x)や剥離強度(y)が変化してもよい)。しかし、電子デバイス用部材を形成した後であっても、剥離強度(y)は、剥離強度(x)よりも低い。 [Silicone resin layer]
The silicone resin layer is substantially composed of a silicone resin, and the silicone resin is a crosslinked product of a crosslinkable organopolysiloxane and has an elastic modulus of 0.5 to 2.5 MPa measured by a nanoindentation method. The peel strength at the interface between the support substrate and the silicone resin layer is greater than the peel strength at the interface between the silicone resin layer and the glass substrate.
The
That is, when separating the
The bonding force at the interface between the
場合により、積層前のシリコーン樹脂層14の表面や積層前のガラス基板16の第1主面16aに両者間の結合力を弱める処理を行って積層することもできる。積層する面に非接着性処理などを行い、その後積層することにより、シリコーン樹脂層14とガラス基板16の界面の結合力を弱め、剥離強度(y)を低くすることができる。 The
In some cases, the surface of the
シリコーン樹脂層14と支持基材12とが高い結合力で結合していることは、両者の界面の剥離強度(x)が高いことを意味する。 The
The fact that the
シリコーン樹脂層14の弾性率が0.5MPa未満の場合、および、シリコーン樹脂層14の破壊が生じ、2.5MPa超の場合、ガラス基板16とシリコーン樹脂層14とが剥離し難くなる。なお、上記弾性率は、シリコーン樹脂層14表面の任意の5箇所以上の点で測定した弾性率を算術平均して得られる平均値である。 The elastic modulus of the
When the elastic modulus of the
上記弾性率測定方法の詳細については、高分子論文集Vol.69,No.7,435~442に開示される。なお、弾性率の測定手順に関しては、後述する実施例欄において詳述する。 In the present invention, the elastic modulus (Young's modulus) can be obtained by combining JKR (Johnson-Kendall-Roberts) analysis with force measurement using an atomic force microscope as a method of measuring elastic modulus by the nanoindentation method. In this method, the cantilever is moved perpendicularly to the sample surface, and the load is measured with respect to the position of the cantilever. Samples that are sufficiently hard with respect to the spring constant of the cantilever do not cause sample deformation, but soft samples can also be used to obtain a relationship between the load and the amount of sample deformation by utilizing the deformation of the sample according to the load. JKR analysis is optimal when the indentation is small and the sample is soft.
For details of the above elastic modulus measurement method, see Polymer Journal Vol. 69, no. 7, 435-442. The procedure for measuring the elastic modulus will be described in detail in an example section described later.
なお、シリコーン樹脂層14は2層以上からなっていてもよい。この場合「シリコーン樹脂層14の厚さ」は全ての層の合計の厚さを意味するものとする。
また、シリコーン樹脂層14が2層以上からなる場合は、各々の層を形成する樹脂が異なる架橋シリコーン樹脂であってもよい。 The thickness of the
The
Moreover, when the
架橋性オルガノポリシロキサンの種類は特に制限されず、所定の架橋反応を介して、架橋硬化し、シリコーン樹脂を構成する架橋物(硬化物)となれば特にその構造は限定されず、所定の架橋性を有していればよい。架橋の形式は特に制限されず、架橋性オルガノポリシロキサン中に含まれる架橋性基の種類に応じて適宜公知の形式を採用できる。例えば、ヒドロシリル化反応、縮合反応、または、加熱処理、高エネルギー線処理若しくはラジカル重合開始剤によるラジカル反応などが挙げられる。
より具体的には、架橋性オルガノポリシロキサンがアルケニル基またはアルキニル基などのラジカル反応性基を有する場合、上記ラジカル反応を介したラジカル反応性基同士の反応により架橋して硬化物(架橋シリコーン樹脂)となる。
また、架橋性オルガノポリシロキサンがシラノール基を有する場合、シラノール基同士の縮合反応により架橋して硬化物となる。
さらに、架橋性オルガノポリシロキサンが、ケイ素原子に結合したアルケニル基(ビニル基など)を有するオルガノポリシロキサン(すなわち、オルガノアルケニルポリシロキサン)、および、ケイ素原子に結合した水素原子(ハイドロシリル基)を有するオルガノポリシロキサン(すなわち、オルガノハイドロジェンポリシロキサン)を含む場合、ヒドロシリル化触媒(例えば、白金系触媒)の存在下、ヒドロシリル化反応により架橋して硬化物となる。 The silicone resin contained in the
The type of the crosslinkable organopolysiloxane is not particularly limited, and the structure is not particularly limited as long as it is cross-linked and cured through a predetermined cross-linking reaction to obtain a cross-linked product (cured product) constituting the silicone resin. What is necessary is just to have sex. The form of crosslinking is not particularly limited, and a known form can be appropriately employed depending on the kind of the crosslinkable group contained in the crosslinkable organopolysiloxane. Examples thereof include a hydrosilylation reaction, a condensation reaction, a heat treatment, a high energy ray treatment, or a radical reaction using a radical polymerization initiator.
More specifically, when the crosslinkable organopolysiloxane has a radical reactive group such as an alkenyl group or an alkynyl group, the cured product (crosslinked silicone resin) is crosslinked by a reaction between the radical reactive groups via the radical reaction. )
Moreover, when crosslinkable organopolysiloxane has a silanol group, it crosslinks by the condensation reaction of silanol groups, and it becomes a hardened | cured material.
In addition, the crosslinkable organopolysiloxane has an organopolysiloxane having an alkenyl group (such as a vinyl group) bonded to a silicon atom (ie, an organoalkenylpolysiloxane) and a hydrogen atom bonded to a silicon atom (hydrosilyl group). In the case of containing the organopolysiloxane having (that is, organohydrogenpolysiloxane), it is crosslinked by a hydrosilylation reaction in the presence of a hydrosilylation catalyst (for example, a platinum-based catalyst) to form a cured product.
なお、アルケニル基としては特に限定されないが、例えば、ビニル基(エテニル基)、アリル基(2-プロペニル基)、ブテニル基、ペンテニル基、ヘキシニル基などが挙げられ、なかでも耐熱性に優れる点から、ビニル基が好ましい。
また、オルガノポリシロキサンAに含まれるアルケニル基以外の基、および、オルガノポリシロキサンBに含まれるハイドロシリル基以外の基としては、アルキル基(特に、炭素数4以下のアルキル基)が挙げられる。 Among these, the crosslinkable organopolysiloxane is an organopolysiloxane having alkenyl groups at both ends and / or side chains (hereinafter referred to as appropriate) because the
The alkenyl group is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, and a hexynyl group. Among them, the heat resistance is excellent. A vinyl group is preferred.
Examples of the group other than the alkenyl group contained in the organopolysiloxane A and the group other than the hydrosilyl group contained in the organopolysiloxane B include an alkyl group (particularly an alkyl group having 4 or less carbon atoms).
なお、M単位およびD単位とは、オルガノポリシロキサンの基本構成単位の例であり、M単位とは有機基が3つ結合した1官能性のシロキサン単位、D単位とは有機基が2つ結合した2官能性のシロキサン単位である。シロキサン単位において、シロキサン結合は2個のケイ素原子が1個の酸素原子を介して結合した結合であることより、シロキサン結合におけるケイ素原子1個当たりの酸素原子は1/2個とみなし、式中O1/2と表現される。 The position of the alkenyl group in the organopolysiloxane A is not particularly limited. However, when the organopolysiloxane A is linear, the alkenyl group may be present in any one of the M unit and D unit shown below. And D units may be present. From the viewpoint of curing speed, it is preferably present at least in M units, and preferably present in both two M units.
The M unit and D unit are examples of basic structural units of organopolysiloxane. The M unit is a monofunctional siloxane unit in which three organic groups are bonded. The D unit is bonded to two organic groups. Bifunctional siloxane unit. In the siloxane unit, the siloxane bond is a bond in which two silicon atoms are bonded through one oxygen atom, so that the oxygen atom per silicon atom in the siloxane bond is regarded as ½, Expressed as O 1/2 .
オルガノポリシロキサンAの好適な構造としては、直鎖状または環状であり、1分子中に2個以上のアルケニル基を有し、該アルケニル基が2個のM単位の両方に1つ以上存在するものである。
オルガノポリシロキサンB中におけるハイドロシリル基の位置は特に制限されないが、オルガノポリシロキサンAが直鎖状の場合、ハイドロシリル基はM単位およびD単位のいずれかに存在してもよく、M単位とD単位の両方に存在していてもよい。硬化速度の点から、少なくともD単位に存在していることが好ましい。
オルガノポリシロキサンB中におけるハイドロシリル基の数は特に制限されないが、1分子中に少なくとも3個有することが好ましく、3個がより好ましい。
オルガノポリシロキサンBの好適な構造としては、オルガノポリシロキサンAが直鎖状または環状の場合、ハイドロシリル基を1分子中に2個以上有し、ハイドロシリル基のモル含有率が30%以上あることが好ましい。 The number of alkenyl groups in organopolysiloxane A is not particularly limited, but is preferably 1 to 3 and more preferably 2 per molecule.
The preferred structure of the organopolysiloxane A is linear or cyclic, has two or more alkenyl groups in one molecule, and one or more alkenyl groups are present in both of two M units. Is.
The position of the hydrosilyl group in the organopolysiloxane B is not particularly limited. However, when the organopolysiloxane A is linear, the hydrosilyl group may be present in either the M unit or the D unit. It may be present in both D units. It is preferable that it exists in at least D unit from the point of a cure rate.
The number of hydrosilyl groups in the organopolysiloxane B is not particularly limited, but it is preferably at least 3 per molecule, and more preferably 3.
As a preferred structure of the organopolysiloxane B, when the organopolysiloxane A is linear or cyclic, it has two or more hydrosilyl groups in one molecule, and the molar content of hydrosilyl groups is 30% or more. It is preferable.
ヒドロシリル化触媒の使用量としては、オルガノポリシロキサンAとオルガノポリシロキサンBとの合計質量100質量部に対して、0.1~20質量部が好ましく、1~10質量部がより好ましい。白金成分としては、オルガノポリシロキサンAとオルガノポリシロキサンBとの合計質量100質量部に対して2~400ppmが好ましく、2~300ppmがより好ましい。 As the hydrosilylation catalyst, a platinum group metal catalyst is preferably used. Examples of the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use as a platinum-based catalyst from the viewpoint of economy and reactivity. As the platinum group metal catalyst, known catalysts can be used. Specifically, platinum fine powder, platinum black, chloroplatinic acid such as chloroplatinic acid, chloroplatinic acid, platinum tetrachloride, alcohol compounds of chloroplatinic acid, aldehyde compounds, platinum olefin complexes, alkenyls Examples thereof include siloxane complexes and carbonyl complexes.
The amount of the hydrosilylation catalyst used is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total mass of organopolysiloxane A and organopolysiloxane B. The platinum component is preferably 2 to 400 ppm, more preferably 2 to 300 ppm, based on 100 parts by mass of the total mass of organopolysiloxane A and organopolysiloxane B.
架橋性オルガノポリシロキサンの粘度は10~5000mPa・sが好ましく、15~3000mPa・sがより好ましい。なお本明細書において、特に断りのない場合は、粘度は25℃で測定した時の値である。 The weight-average molecular weight of the crosslinkable organopolysiloxane is not particularly limited, but it is excellent in handleability, excellent in film formability, and GPC (gel permeation) in that the decomposition of the silicone resin under high temperature processing conditions is further suppressed. The weight average molecular weight in terms of polystyrene as measured by chromatography is preferably 1,000 to 5,000,000, and more preferably 2,000 to 3,000,000.
The viscosity of the crosslinkable organopolysiloxane is preferably 10 to 5000 mPa · s, more preferably 15 to 3000 mPa · s. In addition, in this specification, unless there is particular notice, a viscosity is a value when it measures at 25 degreeC.
また、ヘキサン、ヘプタン、オクタン、トルエン、キシレンなどの有機溶媒や水などの分散媒は、硬化シリコーン樹脂を構成しない成分であるが、硬化性シリコーン樹脂組成物の塗布のための作業性向上などの目的で本発明における硬化性シリコーン樹脂組成物に配合して使用することができる。 In the curable silicone resin composition of the present invention, an activity inhibitor (compound also called a reaction inhibitor, a retarder, etc.) having an action of suppressing the catalyst activity is used together with the catalyst for the purpose of adjusting the catalyst activity. Is preferred. Examples of the activity inhibitor include various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, and organic chloro compounds. Specific examples of the acetylene compound include 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 4-ethyl-1-octyn-3-ol, and the like. Furthermore, if necessary, inorganic fillers such as various silicas, calcium carbonates, iron oxides and the like may be contained within a range not impairing the effects of the present invention. Moreover, metal compounds, such as a metal oxide, may be included as a heat resistance improvement agent.
In addition, organic solvents such as hexane, heptane, octane, toluene and xylene, and dispersion media such as water are components that do not constitute a cured silicone resin, but include improved workability for application of the curable silicone resin composition. For the purpose, it can be used by blending with the curable silicone resin composition of the present invention.
シリコーンオイルの種類は特に限定されないが、ジメチルポリシロキサン、メチルフェニルポリシロキサン、ジフェニルポリシロキサンなどのストレートシリコーンオイル、ストレートシリコーンオイルの側鎖または末端にポリエーテル基、ハロゲン基等を導入した変性シリコーンオイルが例示される。
なお、シリコーンオイルの具体的に市販されている商品名または型番としては、芳香族基(例えば、フェニル基)を有するシリコーンオイルとして、KTSF433(モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製)、KF-50、KF-53、KF-54(信越化学工業社製)、SH550(東レダウコーニング社製)などが挙げられる。
芳香族基を有さないシリコーンオイルとしては、SH200(東レダウコーニング社製)、KNS-330(信越化学社製)などが挙げられる。 The
The type of silicone oil is not particularly limited, but straight silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc., modified silicone oils in which polyether groups, halogen groups, etc. are introduced into the side chain or terminal of straight silicone oil Is exemplified.
In addition, as a trade name or model number of silicone oil specifically marketed, as silicone oil having an aromatic group (for example, phenyl group), KTSF433 (manufactured by Momentive Performance Materials Japan GK), KF -50, KF-53, KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH550 (manufactured by Toray Dow Corning), and the like.
Examples of the silicone oil having no aromatic group include SH200 (manufactured by Toray Dow Corning), KNS-330 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
シリコーン樹脂層14中におけるシリコーンオイルの含有割合は特に制限されないが、ガラス基板16の剥離性が優れると共に、剥離されたガラス基板の透明性がより優れる点で、シリコーン樹脂100質量部に対して、6~20質量部が好ましく、6~15質量部がより好ましく、8~15質量部がさらに好ましい。 The viscosity of the silicone oil is not particularly limited, but it is 100 to 100 in that it is easy to bleed out on the surface of the
The content ratio of the silicone oil in the
本発明のガラス積層体10は、上述したように、支持基材12とガラス基板16とそれらの間にシリコーン樹脂層14が存在する積層体である。
本発明のガラス積層体10の製造方法は特に制限されず、公知の方法を採用し得る。例えば、支持基材12上にシリコーン樹脂層14が固定化されたシリコーン樹脂層付き支持基材18のシリコーン樹脂層14上にガラス基板16を積層する方法が好ましい。なかでも、剥離強度(x)が剥離強度(y)よりも高い積層体を得るために、支持基材12表面上で所定の架橋性オルガノポリシロキサンを架橋硬化させてシリコーン樹脂層14を形成する方法が好ましい。すなわち、架橋性オルガノポリシロキサンを含む層を支持基材12の表面に形成し、支持基材12表面上で架橋性オルガノポリシロキサンを架橋させてシリコーン樹脂層14(架橋シリコーン樹脂)を形成し、次いで、シリコーン樹脂層14のシリコーン樹脂面にガラス基板16を積層して、ガラス積層体10を製造する方法である。また、支持基材12表面上で所定の架橋性オルガノポリシロキサンを架橋硬化させることによっても、ナノインデンテーション法による弾性率を所定の範囲に制御することができる。
架橋性オルガノポリシロキサンを支持基材12表面で硬化させると、硬化反応時の支持基材12表面との相互作用により接着し、シリコーン樹脂と支持基材12表面との剥離強度は高くなると考えられる。したがって、ガラス基板16と支持基材12とが同じ材質からなるものであっても、シリコーン樹脂層14と両者間の剥離強度に差を設けることができる。
以下、架橋性オルガノポリシロキサンを含む層を支持基材12の表面に形成し、支持基材12表面上で架橋性オルガノポリシロキサンを架橋させてシリコーン樹脂層14を形成する工程を樹脂層形成工程、シリコーン樹脂層14のシリコーン樹脂面にガラス基板16を積層してガラス積層体10とする工程を積層工程といい、各工程の手順について詳述する。 [Glass laminate and manufacturing method thereof]
As described above, the
The manufacturing method in particular of the glass laminated
When the crosslinkable organopolysiloxane is cured on the surface of the
Hereinafter, a step of forming a
樹脂層形成工程では、架橋性オルガノポリシロキサンを含む層を支持基材12の表面に形成し、支持基材12表面上で架橋性オルガノポリシロキサンを架橋させてシリコーン樹脂層14を形成する。
支持基材12上に架橋性オルガノポリシロキサンを含む層を形成するためには、架橋性オルガノポリシロキサンを溶媒に溶解させたコーティング用組成物を使用し、この組成物を支持基材12上に塗布して溶液の層を形成し、次いで溶媒を除去して架橋性オルガノポリシロキサンを含む層とすることが好ましい。組成物中における架橋性オルガノポリシロキサンの濃度の調整などにより、架橋性オルガノポリシロキサンを含む層の厚さを制御することができる。
溶媒としては、作業環境下で架橋性オルガノポリシロキサンを容易に溶解でき、かつ、容易に揮発除去させることのできる溶媒であれば、特に限定されるものではない。具体的には、例えば、酢酸ブチル、ヘプタン、2-ヘプタノン、1-メトキシ-2-プロパノールアセテート、トルエン、キシレン、THF、クロロホルム等を例示することができる。 (Resin layer forming process)
In the resin layer forming step, a layer containing a crosslinkable organopolysiloxane is formed on the surface of the
In order to form a layer containing a crosslinkable organopolysiloxane on the
The solvent is not particularly limited as long as it can easily dissolve the crosslinkable organopolysiloxane in a working environment and can be easily volatilized and removed. Specific examples include butyl acetate, heptane, 2-heptanone, 1-methoxy-2-propanol acetate, toluene, xylene, THF, chloroform and the like.
その後、必要に応じて、溶媒を除去するための乾燥処理が実施されてもよい。乾燥処理の方法は特に制限されないが、例えば、減圧条件下で溶媒を除去する方法や、架橋性オルガノポリシロキサンの硬化が進行しないような温度で加熱する方法などが挙げられる。 The method for applying the composition containing the crosslinkable organopolysiloxane on the surface of the
Then, if necessary, a drying process for removing the solvent may be performed. The method for the drying treatment is not particularly limited, and examples thereof include a method of removing the solvent under reduced pressure conditions and a method of heating at a temperature at which the curing of the crosslinkable organopolysiloxane does not proceed.
硬化(架橋)の方法は、上述したように、架橋性オルガノポリシロキサンの架橋形式に応じて適宜最適な方法が選択され、例えば、加熱処理や露光処理が挙げられる。なかでも、架橋性オルガノポリシロキサンがヒドロシリル化反応、縮合反応、ラジカル反応により架橋する場合、ガラス基板16に対する密着性および耐熱性に優れるシリコーン樹脂が得られる点で、熱硬化によりシリコーン樹脂層14を製造することが好ましい。
以下、熱硬化の態様について詳述する。 Next, the crosslinkable organopolysiloxane on the
As described above, the curing (crosslinking) method is appropriately selected according to the crosslinking type of the crosslinkable organopolysiloxane, and examples thereof include heat treatment and exposure treatment. In particular, when the crosslinkable organopolysiloxane is crosslinked by a hydrosilylation reaction, a condensation reaction, or a radical reaction, a silicone resin having excellent adhesion and heat resistance to the
Hereinafter, the aspect of thermosetting is explained in full detail.
積層工程は、上記の樹脂層形成工程で得られたシリコーン樹脂層14のシリコーン樹脂面上にガラス基板16を積層し、支持基材12とシリコーン樹脂層14とガラス基板16とをこの順で備えるガラス積層体10を得る工程である。より具体的には、図2(B)に示すように、シリコーン樹脂層14の支持基材12側とは反対側の表面(シリコーン樹脂層の第1主面)14aと、第1主面16aおよび第2主面16bを有するガラス基板16の第1主面16aとを積層面として、シリコーン樹脂層14とガラス基板16とを積層し、ガラス積層体10を得る。 (Lamination process)
In the laminating step, the
例えば、常圧環境下でシリコーン樹脂層14の表面上にガラス基板16を重ねる方法が挙げられる。なお、必要に応じて、シリコーン樹脂層14の表面上にガラス基板16を重ねた後、ロールやプレスを用いてシリコーン樹脂層14にガラス基板16を圧着させてもよい。ロールまたはプレスによる圧着により、シリコーン樹脂層14とガラス基板16との間に混入している気泡が比較的容易に除去されるので好ましい。 The method in particular of laminating | stacking the
For example, a method of stacking the
プレアニール処理の条件は使用されるシリコーン樹脂層14の種類に応じて適宜最適な条件が選択されるが、ガラス基板16とシリコーン樹脂層14の間の剥離強度(y)をより適切なものとする点から、300℃以上(好ましくは、300~400℃)で5分間以上(好ましく、5~30分間)加熱処理を行うことが好ましい。 In addition, after laminating | stacking the
The conditions for the pre-annealing treatment are appropriately selected according to the type of the
例えば、シリコーン樹脂表面に対する密着性がガラス基板16よりも高い材質の支持基材12を用いる場合には、架橋性オルガノポリシロキサンを何らかの剥離性表面上で硬化してシリコーン樹脂のフィルムを製造し、このフィルムをガラス基板16と支持基材12との間に介在させ同時に積層することができる。
また、架橋性オルガノポリシロキサンの硬化による接着性がガラス基板16に対して充分低くかつその接着性が支持基材12に対して充分高い場合は、ガラス基板16と支持基材12の間で架橋性オルガノポリシロキサンを硬化させてシリコーン樹脂層14を形成することができる。
さらに、支持基材12がガラス基板16と同様のガラス材料からなる場合であっても、支持基材12表面の接着性を高める処理を施してシリコーン樹脂層14に対する剥離強度を高めることもできる。例えば、シランカップリング剤のような化学的に固定力を向上させる化学的方法(プライマー処理)や、フレーム(火炎)処理のように表面活性基を増加させる物理的方法、サンドブラスト処理のように表面の粗度を増加させることにより引っかかりを増加させる機械的処理方法などが例示される。 The formation of the
For example, in the case of using a
Moreover, when the adhesiveness by hardening of crosslinkable organopolysiloxane is low enough with respect to the
Furthermore, even when the
本発明のガラス積層体10は、種々の用途に使用することができ、例えば、後述する表示装置用パネル、PV、薄膜2次電池、表面に回路が形成された半導体ウェハ等の電子部品を製造する用途などが挙げられる。なお、該用途では、ガラス積層体10が高温条件(例えば、360℃以上)で曝される(例えば、1時間以上)場合が多い。
ここで、表示装置用パネルとは、LCD、OLED、電子ペーパー、プラズマディスプレイパネル、フィールドエミッションパネル、量子ドットLEDパネル、MEMS(Micro Electro Mechanical Systems)シャッターパネル等が含まれる。 (Glass laminate)
The
Here, the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.
本発明においては、上述した積層体を用いて、ガラス基板と電子デバイス用部材とを含む部材付きガラス基板(電子デバイス用部材付きガラス基板)が製造される。
該部材付きガラス基板の製造方法は特に限定されないが、電子デバイスの生産性に優れる点から、上記ガラス積層体中のガラス基板上に電子デバイス用部材を形成して電子デバイス用部材付き積層体を製造し、得られた電子デバイス用部材付き積層体からシリコーン樹脂層のガラス基板側界面を剥離面として部材付きガラス基板とシリコーン樹脂層付き支持基材とに分離する方法が好ましい。
以下、上記ガラス積層体中のガラス基板上に電子デバイス用部材を形成して電子デバイス用部材付き積層体を製造する工程を部材形成工程、電子デバイス用部材付き積層体からシリコーン樹脂層のガラス基板側界面を剥離面として部材付きガラス基板とシリコーン樹脂層付き支持基材とに分離する工程を分離工程という。
以下に、各工程で使用される材料および手順について詳述する。 [Glass substrate with member and method for producing the same]
In this invention, the glass substrate with a member (glass substrate with a member for electronic devices) containing a glass substrate and the member for electronic devices is manufactured using the laminated body mentioned above.
Although the manufacturing method of this glass substrate with a member is not specifically limited, From the point which is excellent in productivity of an electronic device, the member for electronic devices is formed on the glass substrate in the said glass laminated body, and the laminated body with an electronic device member is used. A method in which the manufactured and obtained laminate with a member for electronic devices is separated into a glass substrate with a member and a supporting substrate with a silicone resin layer by using the glass substrate side interface of the silicone resin layer as a release surface is preferable.
Hereinafter, the step of forming a member for an electronic device by forming a member for an electronic device on the glass substrate in the glass laminate is a member forming step, and the glass substrate for the silicone resin layer from the laminate with the member for an electronic device. The process of separating into a glass substrate with a member and a supporting substrate with a silicone resin layer using the side interface as a release surface is called a separation process.
The materials and procedures used in each process are described in detail below.
部材形成工程は、上記積層工程において得られたガラス積層体10中のガラス基板16上に電子デバイス用部材を形成する工程である。より具体的には、図2(C)に示すように、ガラス基板16の第2主面16b(露出表面)上に電子デバイス用部材20を形成し、電子デバイス用部材付き積層体22を得る。
まず、本工程で使用される電子デバイス用部材20について詳述し、その後工程の手順について詳述する。 (Member formation process)
A member formation process is a process of forming the member for electronic devices on the
First, the
電子デバイス用部材20は、ガラス積層体10中のガラス基板16上に形成され電子デバイスの少なくとも一部を構成する部材である。より具体的には、電子デバイス用部材20としては、表示装置用パネル、太陽電池、薄膜2次電池、または、表面に回路が形成された半導体ウェハ等の電子部品などに用いられる部材(例えば、表示装置用部材、太陽電池用部材、薄膜2次電池用部材、電子部品用回路)が挙げられる。 (Electronic device components (functional elements))
The
また、薄膜2次電池用部材としては、リチウムイオン型では、正極および負極の金属または金属酸化物等の透明電極、電解質層のリチウム化合物、集電層の金属、封止層としての樹脂等が挙げられ、その他に、ニッケル水素型、ポリマー型、セラミックス電解質型などに対応する各種部材等を挙げることができる。
また、電子部品用回路としては、CCDやCMOSでは、導電部の金属、絶縁部の酸化ケイ素や窒化珪素等が挙げられ、その他に圧力センサ・加速度センサなど各種センサやリジッドプリント基板、フレキシブルプリント基板、リジッドフレキシブルプリント基板などに対応する各種部材等を挙げることができる。 For example, as a member for a solar cell, a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
Further, as a member for a thin film secondary battery, in the lithium ion type, a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer, etc. In addition, various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
In addition, as a circuit for an electronic component, in a CCD or CMOS, a metal of a conductive part, a silicon oxide or a silicon nitride of an insulating part, and the like, various sensors such as a pressure sensor and an acceleration sensor, a rigid printed board, a flexible printed board And various members corresponding to a rigid flexible printed circuit board.
上述した電子デバイス用部材付き積層体22の製造方法は特に限定されず、電子デバイス用部材の構成部材の種類に応じて従来公知の方法にて、ガラス積層体10のガラス基板16の第2主面16b表面上に、電子デバイス用部材20を形成する。
なお、電子デバイス用部材20は、ガラス基板16の第2主面16bに最終的に形成される部材の全部(以下、「全部材」という)ではなく、全部材の一部(以下、「部分部材」という)であってもよい。シリコーン樹脂層14から剥離された部分部材付きガラス基板を、その後の工程で全部材付きガラス基板(後述する電子デバイスに相当)とすることもできる。
また、シリコーン樹脂層14から剥離された、全部材付きガラス基板には、その剥離面(第1主面16a)に他の電子デバイス用部材が形成されてもよい。また、全部材付き積層体を組み立て、その後、全部材付き積層体から支持基材12を剥離して、電子デバイスを製造することもできる。さらに、全部材付き積層体を2枚用いて組み立て、その後、全部材付き積層体から2枚の支持基材12を剥離して、2枚のガラス基板を有する部材付きガラス基板を製造することもできる。 (Process procedure)
The manufacturing method of the
The
Moreover, the other electronic device member may be formed in the peeling surface (1st
なお、TFTやCFを形成する前に、必要に応じて、ガラス基板16の第2主面16bを洗浄してもよい。洗浄方法としては、周知のドライ洗浄やウェット洗浄を用いることができる。 In the TFT formation process and the CF formation process, the TFT and the CF are formed on the second
In addition, before forming TFT and CF, you may wash | clean the 2nd
分離工程は、図2(D)に示すように、上記部材形成工程で得られた電子デバイス用部材付き積層体22から、シリコーン樹脂層14とガラス基板16との界面を剥離面として、電子デバイス用部材20が積層されたガラス基板16(部材付きガラス基板24)と、支持基材12とに分離して、電子デバイス用部材20およびガラス基板16を含む部材付きガラス基板24を得る工程である。
剥離時のガラス基板16上の電子デバイス用部材20が必要な全構成部材の形成の一部である場合には、分離後、残りの構成部材をガラス基板16上に形成することもできる。 (Separation process)
As shown in FIG. 2 (D), the separation step is performed by using the electronic device member-attached
When the
また、支持基材12は、新たなガラス基板と積層して、本発明のガラス積層体10を製造することができる。 The method of peeling the
Moreover, the
シリコーン樹脂層付き支持基材は、第1の態様で述べたのと同様のシリコーン樹脂層が第1の態様で述べたのと同様の支持基材の表面に形成されたものである。このようなシリコーン樹脂層付き支持基材は、支持基材表面にシリコーン樹脂層を形成することや、前記積層体からガラス基板または部材付きガラス基板を剥離することにより得られる。 The support base material with a silicone resin layer according to the third aspect of the present invention is a support base material with a silicone resin layer, which has a support base material and a silicone resin layer provided on the support base material surface. A support substrate with a silicone resin layer, wherein the silicone resin of the resin layer is a crosslinked product of a crosslinkable organopolysiloxane, and the elastic modulus of the silicone resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa. It is.
The support substrate with the silicone resin layer is such that the same silicone resin layer as described in the first embodiment is formed on the same surface of the support substrate as described in the first embodiment. Such a support substrate with a silicone resin layer can be obtained by forming a silicone resin layer on the surface of the support substrate or by peeling a glass substrate or a glass substrate with a member from the laminate.
初めに、板厚0.5mmの支持基材を純水洗浄した後、さらにUV洗浄して清浄化した。
次に、荒川化学社製主剤(ASA-V01)(100質量部)と、荒川化学社製硬化剤(ASA-X01)(13質量部)と配合した。荒川化学社製触媒(ASA-C01)は、(ASA-V01)100質量部に対し5重量部添加した。さらに、ヘプタンを添加して架橋性オルガノポリシロキサンを含む溶液Xを作製した。この溶液Xをスピンコーター(回転数:300rpm、15秒)にて支持基材の第1主面上に塗布して、未硬化の架橋性オルガノポリシロキサンを含む層を支持基材上に設けた(塗工量20g/m2)。 <Example 1>
First, a supporting substrate having a thickness of 0.5 mm was cleaned with pure water, and further cleaned by UV cleaning.
Next, Arakawa Chemical Co., Ltd. main agent (ASA-V01) (100 parts by mass) and Arakawa Chemical Co., Ltd. curing agent (ASA-X01) (13 parts by mass) were blended. Arakawa Chemical's catalyst (ASA-C01) was added in an amount of 5 parts by weight per 100 parts by weight of (ASA-V01). Further, a solution X containing a crosslinkable organopolysiloxane was prepared by adding heptane. This solution X was applied onto the first main surface of the supporting substrate with a spin coater (rotation speed: 300 rpm, 15 seconds), and a layer containing an uncured crosslinkable organopolysiloxane was provided on the supporting substrate. (Coating amount 20 g / m 2 ).
その後、ガラス基板と、支持基材のシリコーン樹脂層面とを、室温下で真空プレスにより貼り合わせ、ガラス積層体Aを得た。
得られたガラス積層体Aにおいては、支持基材とガラス基板は、シリコーン樹脂層と気泡を発生することなく密着しており、歪み状欠点もなく、平滑性も良好であった。 Next, it was heated and cured at 230 ° C. for 10 minutes in the air to form a silicone resin layer having a thickness of 10 μm on the first main surface of the support base.
Then, the glass substrate A and the silicone resin layer surface of the supporting substrate were bonded together by vacuum pressing at room temperature to obtain a glass laminate A.
In the obtained glass laminate A, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
そして、ガラス積層体Aの4箇所のうち1箇所のコーナー部におけるガラス基板と支持シリコーン樹脂層の界面に厚さ0.1mmのステンレス製刃物を挿入させて剥離の切欠部を形成しながら、ガラス基板と支持基材それぞれの剥離面でない面に真空吸着パッドを吸着させ、互いにガラス基板と支持基材が分離する方向に外力を加えて、ガラス基板と支持基材を破損すること無く分離した。ここで刃物の差し込みは、イオナイザ(キーエンス社製)から除電性流体を当該界面に吹き付けながら行った。具体的には、形成した空隙へ向けてイオナイザからは引き続き除電性流体を吹き付けながら真空吸着パッドを引き上げた。
なお、シリコーン樹脂層は支持基材と共にガラス基板から分離され、該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、2.36MPaであった。 Next, the glass laminate A was heated at 360 ° C. for 60 minutes in a nitrogen atmosphere and cooled to room temperature. As a result, the glass substrate A was separated from the supporting substrate and the glass substrate, and the silicone resin layer was foamed or whitened. No change in appearance was observed.
And while forming the notch part of peeling by inserting the stainless steel cutting tool of thickness 0.1mm in the interface of the glass substrate and support silicone resin layer in the corner part of one place among four places of the glass laminated body A, glass The vacuum suction pad was adsorbed on the surface of the substrate and the supporting base that were not the release surfaces, and an external force was applied in the direction in which the glass substrate and the supporting base were separated from each other, thereby separating the glass substrate and the supporting base without being damaged. Here, the cutter was inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Specifically, the vacuum suction pad was pulled up while spraying a static eliminating fluid continuously from the ionizer toward the formed gap.
The silicone resin layer is separated from the glass substrate together with the supporting base material. From the result, the peeling strength (x) at the interface between the supporting base material and the silicone resin layer is determined as the peeling strength (y at the interface between the silicone resin layer and the glass substrate). ) Was confirmed.
Moreover, it was 2.36 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
オミクロンナノテクノロジージャパン株式会社製のTI-950 Tribo Indenterを用いて、シリコーン樹脂層の諸物性値の測定を行った。すなわち、使用圧子としてConical 5um型の三角錐圧子を用い、変位速度一定モード30nm/secに押し込み荷重を加え、最大荷重の2μNに到達後、同様にステップ状に押し込み荷重を徐荷していく。測定は25℃の恒温条件下で行い、測定装置とサンプルの温度を十分に安定させた後に、押し込みの強さ0.2μNで、深さ200nmでの弾性率を測定し、5回の連続測定の平均値をもって測定値とした。 The measurement conditions of the nanoindentation method were as follows.
Various physical property values of the silicone resin layer were measured using TI-950 Tribo Indenter manufactured by Omicron Nanotechnology Japan Co., Ltd. That is, a Conical 5um type triangular pyramid indenter is used as the working indenter, a pushing load is applied to the constant displacement speed mode 30 nm / sec, and after reaching the maximum load of 2 μN, the pushing load is gradually reduced stepwise. The measurement is performed under a constant temperature condition of 25 ° C., and after sufficiently stabilizing the temperature of the measuring apparatus and the sample, the elastic modulus at a depth of 200 nm is measured with an indentation strength of 0.2 μN, and five continuous measurements are performed. The average value was taken as the measured value.
架橋性オルガノポリシロキサンを含む溶液Xに、さらにメチルフェニルシリコーンオイル(信越化学工業社製、KF-50、粘度100mm2/s)を加えた以外は、実施例1と同様の方法で、ガラス積層体Bを得た。
なお、メチルフェニルシリコーンオイルの使用量は、シリコーン樹脂100質量部に対して、5質量部であった。 <Example 2>
Glass laminates were prepared in the same manner as in Example 1 except that methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s) was added to solution X containing a crosslinkable organopolysiloxane. Body B was obtained.
In addition, the usage-amount of methylphenyl silicone oil was 5 mass parts with respect to 100 mass parts of silicone resins.
次に、ガラス積層体Bを実施例1と同様の加熱処理をおこなったところ、ガラス積層体Bの支持基材とガラス基板の分離やシリコーン樹脂層の発泡や白化など外観上の変化は認められなかった。
そして、ガラス積層体Bを実施例1と同様の方法で支持基材とガラス基板との分離を行ったところ、ガラス基板と支持基材とが破損すること無く分離した。なお、シリコーン樹脂層は支持基材と共にガラス基板から分離された。該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、2.29MPaであった。 In the obtained glass laminate B, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate B was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate B and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
And when the glass base material B was isolate | separated from the support base material and the glass substrate by the method similar to Example 1, it isolate | separated, without damaging a glass substrate and a support base material. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.29 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
メチルフェニルシリコーンオイル(信越化学工業社製、KF-50、粘度100mm2/s)の使用量を5質量部から15質量部に変更した以外は、実施例2と同様の方法で、ガラス積層体Cを得た。 <Example 3>
A glass laminate in the same manner as in Example 2, except that the amount of methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s) was changed from 5 parts by mass to 15 parts by mass. C was obtained.
次に、ガラス積層体Cを実施例1と同様の加熱処理をおこなったところ、ガラス積層体Cの支持基材とガラス基板の分離やシリコーン樹脂層の発泡や白化など外観上の変化は認められなかった。
そして、ガラス積層体Cを実施例1と同様の方法で支持基材とガラス基板との分離を行ったところ、ガラス基板と支持基材とが破損すること無く分離した。なお、シリコーン樹脂層は支持基材と共にガラス基板から分離された。該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、2.09MPaであった。 In the obtained glass laminate C, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate C was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate C and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
Then, when the glass substrate C was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.09 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
メチルフェニルシリコーンオイル(信越化学工業社製、KF-50、粘度100mm2/s)の使用量を5質量部から20質量部に変更した以外は、実施例2と同様の方法で、ガラス積層体Dを得た。 <Example 4>
A glass laminate in the same manner as in Example 2 except that the amount of methyl phenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s) was changed from 5 parts by mass to 20 parts by mass. D was obtained.
次に、ガラス積層体Dを実施例1と同様の加熱処理をおこなったところ、ガラス積層体Dの支持基材とガラス基板の分離やシリコーン樹脂層の発泡や白化など外観上の変化は認められなかった。
そして、ガラス積層体Dを実施例1と同様の方法で支持基材とガラス基板との分離を行ったところ、ガラス基板と支持基材とが破損すること無く分離した。なお、シリコーン樹脂層は支持基材と共にガラス基板から分離された。該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、1.15MPaであった。 In the obtained glass laminate D, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate D was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate D and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
And when the glass base material D was isolate | separated from the support base material and the glass substrate by the method similar to Example 1, it isolate | separated, without damaging a glass substrate and a support base material. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 1.15 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
メチルフェニルシリコーンオイル(信越化学工業社製、KF-50、粘度100mm2/s)の代わりに、メチルフェニルシリコーンオイル(東レダウコーニング社製、SH200、粘度200mm2/s)を使用した以外は、実施例2と同様の方法で、ガラス積層体Eを得た。 <Example 5>
Instead of methylphenyl silicone oil (Shin-Etsu Chemical Co., Ltd., KF-50, viscosity 100 mm 2 / s), methylphenyl silicone oil (Toray Dow Corning, SH200, viscosity 200 mm 2 / s) was used. A glass laminate E was obtained in the same manner as in Example 2.
次に、ガラス積層体Eを実施例1と同様の加熱処理をおこなったところ、ガラス積層体Eの支持基材とガラス基板の分離やシリコーン樹脂層の発泡や白化など外観上の変化は認められなかった。
そして、ガラス積層体Eを実施例1と同様の方法で支持基材とガラス基板との分離を行ったところ、ガラス基板と支持基材とが破損すること無く分離した。なお、シリコーン樹脂層は支持基材と共にガラス基板から分離された。該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、2.34MPaであった。 In the obtained glass laminate E, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate E was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate E, foaming and whitening of the silicone resin layer were observed. There wasn't.
Then, when the glass substrate E was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.34 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
メチルフェニルシリコーンオイル(東レダウコーニング社製、SH200、粘度200mm2/s)の使用量を5質量部から10質量部に変更した以外は、実施例5と同様の方法で、ガラス積層体Fを得た。 <Example 6>
The glass laminate F was prepared in the same manner as in Example 5 except that the amount of methyl phenyl silicone oil (Toray Dow Corning, SH200, viscosity 200 mm 2 / s) was changed from 5 parts by mass to 10 parts by mass. Obtained.
次に、ガラス積層体Fを実施例1と同様の加熱処理をおこなったところ、ガラス積層体Fの支持基材とガラス基板の分離やシリコーン樹脂層の発泡や白化など外観上の変化は認められなかった。
そして、ガラス積層体Fを実施例1と同様の方法で支持基材とガラス基板との分離を行ったところ、ガラス基板と支持基材とが破損すること無く分離した。なお、シリコーン樹脂層は支持基材と共にガラス基板から分離された。該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、2.31MPaであった。 In the obtained glass laminate F, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate F was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate F, foaming or whitening of the silicone resin layer were observed. There wasn't.
Then, when the glass laminate F was separated from the support base material and the glass substrate by the same method as in Example 1, the glass substrate and the support base material were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.31 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
メチルフェニルシリコーンオイル(東レダウコーニング社製、SH200、粘度200mm2/s)の使用量を5質量部から15質量部に変更した以外は、実施例5と同様の方法で、ガラス積層体Gを得た。 <Example 7>
The glass laminate G was prepared in the same manner as in Example 5 except that the amount of methyl phenyl silicone oil (Toray Dow Corning, SH200, viscosity 200 mm 2 / s) was changed from 5 parts by mass to 15 parts by mass. Obtained.
次に、ガラス積層体Gを実施例1と同様の加熱処理をおこなったところ、ガラス積層体Gの支持基材とガラス基板の分離やシリコーン樹脂層の発泡や白化など外観上の変化は認められなかった。
そして、ガラス積層体Gを実施例1と同様の方法で支持基材とガラス基板との分離を行ったところ、ガラス基板と支持基材とが破損すること無く分離した。なお、シリコーン樹脂層は支持基材と共にガラス基板から分離された。該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、2.09MPaであった。 In the obtained glass laminate G, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate G was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate of the glass laminate G and the glass substrate, foaming or whitening of the silicone resin layer were observed. There wasn't.
And when the glass substrate G was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 2.09 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
架橋性オルガノポリシロキサンを含む溶液Xの代わりに、以下の架橋性オルガノポリシロキサンを含む溶液Yを使用した以外は、実施例1と同様の方法で、ガラス積層体Hを得た。 <Example 8>
A glass laminate H was obtained in the same manner as in Example 1 except that the solution Y containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.
主剤として、両末端にビニル基を1つずつ導入したジメチルシリコーン(56mPa・s)(100質量部)と、硬化剤として、メチルヒドロジェンシリコーン(メチル:ヒドロジェン(モル比)=2:1、ハイドロシリル基のモル含有率は33.3%、104mPa・s)(10質量部)とを配合した。カールステット触媒を樹脂成分に対して、白金換算で3ppm添加した。遅延剤として、1-エチニル-1-シクロヘキサノールを樹脂成分に対して、0.2質量部添加した。さらに、ヘプタンを添加して架橋性オルガノポリシロキサンを含む溶液Yを作製した。主剤のビニル基と硬化剤のヒドロジェン基とのモル比(アルケニル基のモル数/ハイドロシリル基のモル数)は、1モル:0.8モルになるように配合されている。 (Solution Y containing crosslinkable organopolysiloxane)
As the main agent, dimethyl silicone (56 mPa · s) (100 parts by mass) with one vinyl group introduced at both ends, and as the curing agent, methyl hydrogen silicone (methyl: hydrogen (molar ratio) = 2: 1, hydro The molar content of the silyl group was 33.3%, 104 mPa · s) (10 parts by mass). The Karlstedt catalyst was added at 3 ppm in terms of platinum with respect to the resin component. As a retarder, 1 part by mass of 1-ethynyl-1-cyclohexanol was added to the resin component. Further, a solution Y containing a crosslinkable organopolysiloxane was prepared by adding heptane. The molar ratio of the vinyl group of the main agent to the hydrogen group of the curing agent (number of moles of alkenyl group / number of moles of hydrosilyl group) is 1 mole: 0.8 mole.
次に、ガラス積層体Hを実施例1と同様の加熱処理をおこなったところ、ガラス積層体Hの支持基材とガラス基板の分離やシリコーン樹脂層の発泡や白化など外観上の変化は認められなかった。
そして、ガラス積層体Hを実施例1と同様の方法で支持基材とガラス基板との分離を行ったところ、ガラス基板と支持基材とが破損すること無く分離した。なお、シリコーン樹脂層は支持基材と共にガラス基板から分離された。該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、0.65MPaであった。 In the obtained glass laminate H, the supporting base material and the glass substrate were in close contact with the silicone resin layer without generating bubbles, there were no distortion defects, and the smoothness was good.
Next, when the glass laminate H was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate H, foaming and whitening of the silicone resin layer were recognized. There wasn't.
Then, when the glass substrate H was separated from the supporting substrate and the glass substrate by the same method as in Example 1, the glass substrate and the supporting substrate were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 0.65 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
架橋性オルガノポリシロキサンを含む溶液Xの代わりに、以下の架橋性オルガノポリシロキサンを含む溶液Zを使用した以外は、実施例1と同様の方法で、ガラス積層体Iを得た。 <Example 9>
A glass laminate I was obtained in the same manner as in Example 1 except that the solution Z containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.
荒川化学社製主剤(A78)(100質量部)と、荒川化学社製硬化剤(ASA-X01)(15質量部)と配合した。荒川化学社製触媒(ASA-C01)は、(A78)100質量部に対し5重量部添加した。さらに、ヘプタンを添加して架橋性オルガノポリシロキサンを含む溶液Zを作製した。 (Solution Z containing crosslinkable organopolysiloxane)
Arakawa Chemical Co., Ltd. main agent (A78) (100 parts by mass) and Arakawa Chemical Co., Ltd. curing agent (ASA-X01) (15 parts by mass) were blended. Arakawa Chemical's catalyst (ASA-C01) was added in an amount of 5 parts by weight per 100 parts by weight of (A78). Furthermore, a solution Z containing a crosslinkable organopolysiloxane was prepared by adding heptane.
次に、ガラス積層体Iを実施例1と同様の加熱処理をおこなったところ、ガラス積層体Iの支持基材とガラス基板の分離やシリコーン樹脂層の発泡や白化など外観上の変化は認められなかった。
そして、ガラス積層体Iを実施例1と同様の方法で支持基材とガラス基板との分離を行ったところ、ガラス基板と支持基材とが破損すること無く分離した。なお、シリコーン樹脂層は支持基材と共にガラス基板から分離された。該結果より、支持基材とシリコーン樹脂層の界面の剥離強度(x)が、シリコーン樹脂層とガラス基板の界面の剥離強度(y)よりも高いことが確認された。
また、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、1.10MPaであった。 In the obtained glass laminate I, the supporting substrate and the glass substrate were in close contact with the silicone resin layer without generating bubbles, and there was no distortion defect and smoothness was good.
Next, when the glass laminate I was subjected to the same heat treatment as in Example 1, changes in appearance such as separation of the support substrate and glass substrate of the glass laminate I, foaming and whitening of the silicone resin layer were observed. There wasn't.
Then, when the glass substrate I was separated from the supporting base material and the glass substrate by the same method as in Example 1, the glass substrate and the supporting base material were separated without being damaged. The silicone resin layer was separated from the glass substrate together with the supporting base material. From the results, it was confirmed that the peel strength (x) at the interface between the support substrate and the silicone resin layer was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate.
Moreover, it was 1.10 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
架橋性オルガノポリシロキサンを含む溶液Xの代わりに、以下の架橋性オルガノポリシロキサンを含む溶液Wを使用した以外は、実施例1と同様の方法で、ガラス積層体Jを得た。 <Comparative Example 1>
A glass laminate J was obtained in the same manner as in Example 1, except that the solution W containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.
ADEKA社製 FX-T153Vi-5K(900mPa・s)(100質量部)と、ADEKA社製硬化剤FX-T153H-5K(1240mPa・s)(10質量部)とを配合した。さらに、ドデカンを添加して架橋性オルガノポリシロキサンを含む溶液Wを作製した。アルケニル基とハイドロシリル基のモル比が1:1となるように配合した。 (Solution W containing crosslinkable organopolysiloxane)
FX-T153Vi-5K (900 mPa · s) (100 parts by mass) manufactured by ADEKA and a curing agent FX-T153H-5K (1240 mPa · s) (10 parts by mass) manufactured by ADEKA were blended. Further, dodecane was added to prepare a solution W containing a crosslinkable organopolysiloxane. The alkenyl group and the hydrosilyl group were blended so that the molar ratio was 1: 1.
なお、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、0.23MPaであった。 When the obtained glass laminate J was separated from the supporting base material and the glass substrate in the same manner as in Example 1, it was difficult for the silicone resin layer and the glass substrate to peel off, and the glass substrate was cracked, or The silicone resin layer was destroyed, and most of it was deposited on the glass substrate.
In addition, it was 0.23 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
架橋性オルガノポリシロキサンを含む溶液Xの代わりに、以下の架橋性オルガノポリシロキサンを含む溶液Vを使用した以外は、実施例1と同様の方法で、ガラス積層体Kを得た。 <Comparative Example 2>
A glass laminate K was obtained in the same manner as in Example 1, except that the solution V containing the following crosslinkable organopolysiloxane was used instead of the solution X containing the crosslinkable organopolysiloxane.
荒川化学社製主剤(A41)(100質量部)と、荒川化学社製硬化剤(ASA-X01)(13質量部)とを、アルケニル基とハイドロシリル基のモル比が1:1となるように配合した。荒川化学社製触媒(ASA-C01)は、(A41)100質量部に対し5重量部添加した。さらに、ドデカンを添加して架橋性オルガノポリシロキサンを含む溶液Vを作製した。 (Solution V containing crosslinkable organopolysiloxane)
Arakawa Chemical Co., Ltd. main agent (A41) (100 parts by mass) and Arakawa Chemical Co., Ltd. curing agent (ASA-X01) (13 parts by mass) so that the molar ratio of alkenyl group to hydrosilyl group is 1: 1. Blended into Arakawa Chemical's catalyst (ASA-C01) was added in an amount of 5 parts by weight per 100 parts by weight of (A41). Further, a solution V containing a crosslinkable organopolysiloxane was prepared by adding dodecane.
なお、ガラス基板剥離後の支持基材上のシリコーン樹脂層の弾性率をナノインデンテーション法で測定したところ、3.15MPaであった。 When the obtained glass laminate K was separated from the supporting base material and the glass substrate in the same manner as in Example 1, the silicone resin layer and the glass substrate were difficult to peel off, and the glass substrate was broken, or The silicone resin layer was destroyed, and most of it was deposited on the glass substrate.
In addition, it was 3.15 MPa when the elasticity modulus of the silicone resin layer on the support base material after glass substrate peeling was measured by the nanoindentation method.
なお、表1中、「剥離性」は、ガラス基板およびシリコーン樹脂層の破壊がなく、ガラス基板をガラス積層体から剥離できた場合を「○」、ガラス基板の剥離の際に、ガラス基板またはシリコーン樹脂層の破壊が生じた場合を「×」とした。 The results of the above examples and comparative examples are summarized below.
In Table 1, “Peelability” means “◯” when the glass substrate can be peeled from the glass laminate without breaking the glass substrate and the silicone resin layer, and when the glass substrate is peeled, The case where the silicone resin layer was broken was indicated as “x”.
幅25mm・長さ70mmのガラス積層体A~Kを用意し、オートグラフAG-20/50kNXDplus(島津製作所)を用いてガラス基板の剥離を行った。なお、剥離速度は30mm/minあった。荷重を検知した地点を0とし、その位置から1.5mm離れた位置での剥離強度を測定値とした。 Further, the following peel test was performed on the glass laminates A to K after the heat treatment at 360 ° C. for 60 minutes, and the peel strength (N / 25 mm) of the glass substrate was measured.
Glass laminates A to K having a width of 25 mm and a length of 70 mm were prepared, and the glass substrate was peeled off using Autograph AG-20 / 50kNXDplus (Shimadzu Corporation). The peeling speed was 30 mm / min. The point where the load was detected was set to 0, and the peel strength at a position 1.5 mm away from the position was taken as the measured value.
一方、シリコーン樹脂層の弾性率が低すぎる比較例1、および、高すぎる比較例2においては、ガラス基板の剥離性が劣っていた。 As can be seen from Table 1 above, it was confirmed that the peelability of the glass substrate was excellent when the elastic modulus of the silicone resin layer was in a predetermined range (0.5 to 2.5 MPa).
On the other hand, in Comparative Example 1 in which the elastic modulus of the silicone resin layer was too low and in Comparative Example 2 that was too high, the peelability of the glass substrate was inferior.
本例では、実施例1で得たガラス積層体Aを用いてOLEDを製造する。
まず、ガラス積層体Aにおけるガラス基板の第2主面上に、プラズマCVD法により窒化シリコン、酸化シリコン、アモルファスシリコンの順に成膜する。次に、イオンドーピング装置により低濃度のホウ素をアモルファスシリコン層に注入し、窒素雰囲気下450℃60分間加熱処理し脱水素処理をおこなう。次に、レーザアニール装置によりアモルファスシリコン層の結晶化処理をおこなう。次に、フォトリソグラフィ法を用いたエッチングおよびイオンドーピング装置より、低濃度のリンをアモルファスシリコン層に注入し、N型およびP型のTFTエリアを形成する。次に、ガラス基板の第2主面側に、プラズマCVD法により酸化シリコン膜を成膜してゲート絶縁膜を形成した後に、スパッタリング法によりモリブデンを成膜し、フォトリソグラフィ法を用いたエッチングによりゲート電極を形成する。次に、フォトリソグラフィ法とイオンドーピング装置により、高濃度のホウ素とリンをN型、P型それぞれの所望のエリアに注入し、ソースエリアおよびドレインエリアを形成する。次に、ガラス基板の第2主面側に、プラズマCVD法による酸化シリコンの成膜で層間絶縁膜を、スパッタリング法によりアルミニウムの成膜およびフォトリソグラフィ法を用いたエッチングによりTFT電極を形成する。次に、水素雰囲気下450℃60分間加熱処理し水素化処理をおこなった後に、プラズマCVD法による窒素シリコンの成膜で、パッシベーション層を形成する。次に、ガラス基板の第2主面側に、紫外線硬化性樹脂を塗布し、フォトリソグラフィ法により平坦化層およびコンタクトホールを形成する。次に、スパッタリング法により酸化インジウム錫を成膜し、フォトリソグラフィ法を用いたエッチングにより画素電極を形成する。
続いて、蒸着法により、ガラス基板の第2主面側に、正孔注入層として4,4’,4”-トリス(3-メチルフェニルアミノ)トリフェニルアミン、正孔輸送層としてビス[(N-ナフチル)-N-フェニル]ベンジジン、発光層として8-キノリノールアルミニウム錯体(Alq3)に2,6-ビス[4-[N-(4-メトキシフェニル)-N-フェニル]アミノスチリル]ナフタレン-1,5-ジカルボニトリル(BSN-BCN)を40体積%混合したもの、電子輸送層としてAlq3をこの順に成膜する。次に、スパッタリング法によりアルミニウムを成膜し、フォトリソグラフィ法を用いたエッチングにより対向電極を形成する。次に、ガラス基板の第2主面側に、紫外線硬化型の接着層を介してもう一枚のガラス基板を貼り合わせて封止する。上記手順によって、ガラス基板上に有機EL構造体を形成する。ガラス基板上に有機EL構造体を有するガラス積層体A(以下、パネルAという。)が、本発明の電子デバイス用部材付き積層体(支持基材付き表示装置用パネル)である。
続いて、パネルAの封止体側を定盤に真空吸着させたうえで、パネルAのコーナー部のガラス基板とシリコーン樹脂層との界面に、厚さ0.1mmのステンレス製刃物を差し込み、ガラス基板とシリコーン樹脂層の界面に剥離のきっかけを与える。そして、パネルAの支持基材表面を真空吸着パッドで吸着した上で、吸着パッドを上昇させる。ここで刃物の差し込みは、イオナイザ(キーエンス社製)から除電性流体を当該界面に吹き付けながら行う。次に、形成した空隙へ向けてイオナイザからは引き続き除電性流体を吹き付けながら真空吸着パッドを引き上げる。その結果、定盤上に有機EL構造体が形成されたガラス基板のみを残し、シリコーン樹脂層付き支持基材を剥離することができる。
続いて、実施例1と同様の方法で分離したガラス基板の剥離面を清浄化し、分離されたガラス基板をレーザーカッタまたはスクライブ-ブレイク法を用いて切断し、複数のセルに分断した後、有機EL構造体が形成されたガラス基板と対向基板とを組み立てて、モジュール形成工程を実施してOLEDを作製する。こうして得られるOLEDは、特性上問題は生じない。 <Example 10>
In this example, an OLED is manufactured using the glass laminate A obtained in Example 1.
First, silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in the glass laminate A by plasma CVD. Next, low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and a dehydrogenation process is performed by heating at 450 ° C. for 60 minutes in a nitrogen atmosphere. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, then molybdenum is formed by a sputtering method, and etching is performed using a photolithography method. A gate electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after heat treatment is performed at 450 ° C. for 60 minutes in a hydrogen atmosphere, a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Subsequently, by a vapor deposition method, 4,4 ′, 4 ″ -tris (3-methylphenylamino) triphenylamine as a hole injection layer and bis [(( N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq 3 ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene -1,5-dicarbonitrile (BSN-BCN) mixed by 40% by volume, and Alq 3 as an electron transport layer are formed in this order, and then aluminum is formed by a sputtering method. Next, another glass substrate is bonded to the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate A (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is used for the electronic device of the present invention. It is a laminated body with a member (panel for display apparatuses with a supporting base material).
Subsequently, after vacuum-adsorbing the sealing body side of the panel A to the surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner portion of the panel A, and glass Provides a trigger for peeling at the interface between the substrate and the silicone resin layer. And after adsorb | sucking the support base material surface of the panel A with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while the static elimination fluid is continuously sprayed from the ionizer toward the formed gap. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate is left, and the supporting base material with the silicone resin layer can be peeled off.
Subsequently, the separation surface of the glass substrate separated by the same method as in Example 1 was cleaned, the separated glass substrate was cut using a laser cutter or a scribe-break method, and divided into a plurality of cells. The glass substrate on which the EL structure is formed and the counter substrate are assembled, and a module forming process is performed to manufacture an OLED. The OLED obtained in this way does not have a problem in characteristics.
本例では、実施例1で得たガラス積層体Aを用いてLCDを製造する。
まず、2枚のガラス積層体Aを準備して、片方のガラス積層体A1におけるガラス基板の第2主面上に、プラズマCVD法により窒化シリコン、酸化シリコン、アモルファスシリコンの順に成膜する。次に、イオンドーピング装置により低濃度のホウ素をアモルファスシリコン層に注入し、窒素雰囲気下450℃60分間加熱処理し脱水素処理をおこなう。次に、レーザアニール装置によりアモルファスシリコン層の結晶化処理をおこなう。次に、フォトリソグラフィ法を用いたエッチングおよびイオンドーピング装置より、低濃度のリンをアモルファスシリコン層に注入し、N型およびP型のTFTエリアを形成する。次に、ガラス基板の第2主面側に、プラズマCVD法により酸化シリコン膜を成膜しゲート絶縁膜を形成した後に、スパッタリング法によりモリブデンを成膜し、フォトリソグラフィ法を用いたエッチングによりゲート電極を形成する。次に、フォトリソグラフィ法とイオンドーピング装置により、高濃度のホウ素とリンをN型、P型それぞれの所望のエリアに注入し、ソースエリアおよびドレインエリアを形成する。次に、ガラス基板の第2主面側に、プラズマCVD法による酸化シリコンの成膜で層間絶縁膜を、スパッタリング法によりアルミニウムの成膜およびフォトリソグラフィ法を用いたエッチングによりTFT電極を形成する。次に、水素雰囲気下450℃60分間加熱処理し水素化処理をおこなった後に、プラズマCVD法による窒素シリコンの成膜で、パッシベーション層を形成する。次に、ガラス基板の第2主面側に、紫外線硬化性樹脂を塗布し、フォトリソグラフィ法により平坦化層およびコンタクトホールを形成する。次に、スパッタリング法により酸化インジウム錫を成膜し、フォトリソグラフィ法を用いたエッチングにより画素電極を形成する。
次に、もう片方のガラス積層体A2を大気雰囲気下450℃60分間加熱処理する。次に、ガラス積層体Aにおけるガラス基板の第2主面上に、スパッタリング法によりクロムを成膜し、フォトリソグラフィ法を用いたエッチングにより遮光層を形成する。次に、ガラス基板の第2主面側に、ダイコート法によりカラーレジストを塗布し、フォトリソグラフィ法および熱硬化によりカラーフィルタ層を形成する。次に、スパッタリング法により酸化インジウム錫を成膜し、対向電極を形成する。次に、ガラス基板の第2主面側に、ダイコート法により紫外線硬化樹脂液を塗布し、フォトリソグラフィ法および熱硬化により柱状スペーサを形成する。次に、ロールコート法によりポリイミド樹脂液を塗布し、熱硬化により配向層を形成し、ラビングをおこなう。
次に、ディスペンサ法によりシール用樹脂液を枠状に描画し、枠内にディスペンサ法により液晶を滴下した後に、上記で画素電極が形成されたガラス積層体A1を用いて、2枚のガラス積層体Aのガラス基板の第2主面側同士を貼り合わせ、紫外線硬化および熱硬化によりLCDパネルを得る。 <Example 11>
In this example, an LCD is manufactured using the glass laminate A obtained in Example 1.
First, two glass laminates A are prepared, and silicon nitride, silicon oxide, and amorphous silicon are formed in this order on the second main surface of the glass substrate in one glass laminate A1 by plasma CVD. Next, low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and a dehydrogenation process is performed by heating at 450 ° C. for 60 minutes in a nitrogen atmosphere. Next, the amorphous silicon layer is crystallized by a laser annealing apparatus. Next, low concentration phosphorus is implanted into the amorphous silicon layer by an etching and ion doping apparatus using a photolithography method, thereby forming N-type and P-type TFT areas. Next, after a silicon oxide film is formed on the second main surface side of the glass substrate by a plasma CVD method and a gate insulating film is formed, molybdenum is formed by a sputtering method, and the gate is etched by photolithography. An electrode is formed. Next, high concentration boron and phosphorus are implanted into desired areas of the N-type and P-type by photolithography and an ion doping apparatus, thereby forming a source area and a drain area. Next, an interlayer insulating film is formed on the second main surface side of the glass substrate by silicon oxide film formation by plasma CVD, and a TFT electrode is formed by aluminum film formation by sputtering and etching using photolithography. Next, after heat treatment is performed at 450 ° C. for 60 minutes in a hydrogen atmosphere, a passivation layer is formed by film formation of nitrogen silicon by a plasma CVD method. Next, an ultraviolet curable resin is applied to the second main surface side of the glass substrate, and a planarization layer and a contact hole are formed by photolithography. Next, a film of indium tin oxide is formed by a sputtering method, and a pixel electrode is formed by etching using a photolithography method.
Next, the other glass laminate A2 is heat-treated at 450 ° C. for 60 minutes in an air atmosphere. Next, a chromium film is formed on the second main surface of the glass substrate in the glass laminate A by a sputtering method, and a light shielding layer is formed by etching using a photolithography method. Next, a color resist is applied to the second main surface side of the glass substrate by a die coating method, and a color filter layer is formed by a photolithography method and heat curing. Next, a film of indium tin oxide is formed by a sputtering method to form a counter electrode. Next, an ultraviolet curable resin liquid is applied to the second main surface side of the glass substrate by a die coating method, and columnar spacers are formed by a photolithography method and thermal curing. Next, a polyimide resin solution is applied by a roll coating method, an alignment layer is formed by thermosetting, and rubbing is performed.
Next, a sealing resin liquid is drawn in a frame shape by the dispenser method, and after dropping the liquid crystal in the frame by the dispenser method, two glass layers are laminated using the glass laminate A1 in which the pixel electrodes are formed as described above. The second main surface sides of the glass substrate of the body A are bonded together, and an LCD panel is obtained by ultraviolet curing and thermal curing.
本例では、実施例1で得たガラス積層体Aを用いてOLEDを製造する。
まず、ガラス積層体Aにおけるガラス基板の第2主面上に、スパッタリング法によりモリブデンを成膜し、フォトリソグラフィ法を用いたエッチングによりゲート電極を形成する。次に、プラズマCVD法により、ガラス基板の第2主面側にさらに窒化ケイ素を成膜してゲート絶縁膜を形成し、続いてスパッタリング法により酸化インジウムガリウム亜鉛を成膜してフォトリソグラフィ法を用いたエッチングにより酸化物半導体層を形成する。次に、プラズマCVD法により、ガラス基板の第2主面側にさらに窒化ケイ素を成膜してチャネル保護層を形成し、続いてスパッタリング法によりモリブデンを成膜してフォトリソグラフィ法を用いたエッチングによりソース電極およびドレイン電極を形成する。次に、大気中で450℃にて60分間加熱処理を行う。次に、ガラス基板の第2主面側にさらにプラズマCVD法により窒化ケイ素を成膜してパッシベーション層を形成し、続いてスパッタリング法により酸化インジウム錫を成膜してフォトリソグラフィ法を用いたエッチングにより、画素電極を形成する。
続いて、蒸着法により、ガラス基板の第2主面側に、正孔注入層として4,4’,4”-トリス(3-メチルフェニルアミノ)トリフェニルアミン、正孔輸送層としてビス[(N-ナフチル)-N-フェニル]ベンジジン、発光層として8-キノリノールアルミニウム錯体(Alq3)に2,6-ビス[4-[N-(4-メトキシフェニル)-N-フェニル]アミノスチリル]ナフタレン-1,5-ジカルボニトリル(BSN-BCN)を40体積%混合したもの、電子輸送層としてAlq3をこの順に成膜する。次に、スパッタリング法によりアルミニウムを成膜し、フォトリソグラフィ法を用いたエッチングにより対向電極を形成する。次に、ガラス基板の第2主面側に、紫外線硬化型の接着層を介してもう一枚のガラス基板を貼り合わせて封止する。上記手順によって、ガラス基板上に有機EL構造体を形成する。ガラス基板上に有機EL構造体を有するガラス積層体A(以下、パネルAという。)が、本発明の電子デバイス用部材付き積層体(支持基材付き表示装置用パネル)である。
続いて、パネルAの封止体側を定盤に真空吸着させたうえで、パネルAのコーナー部のガラス基板とシリコーン樹脂層との界面に、厚さ0.1mmのステンレス製刃物を差し込み、ガラス基板とシリコーン樹脂層の界面に剥離のきっかけを与える。そして、パネルAの支持基材表面を真空吸着パッドで吸着した上で、吸着パッドを上昇させる。ここで刃物の差し込みは、イオナイザ(キーエンス社製)から除電性流体を当該界面に吹き付けながら行う。次に、形成した空隙へ向けてイオナイザからは引き続き除電性流体を吹き付けながら真空吸着パッドを引き上げる。その結果、定盤上に有機EL構造体が形成されたガラス基板のみを残し、シリコーン樹脂層付き支持基材を剥離することができる。
続いて、実施例1と同様の方法で分離したガラス基板の剥離面を清浄化し、分離されたガラス基板をレーザーカッタまたはスクライブ-ブレイク法を用いて切断し、複数のセルに分断した後、有機EL構造体が形成されたガラス基板と対向基板とを組み立てて、モジュール形成工程を実施してOLEDを作製する。こうして得られるOLEDは、特性上問題は生じない。 <Example 12>
In this example, an OLED is manufactured using the glass laminate A obtained in Example 1.
First, molybdenum is deposited on the second main surface of the glass substrate in the glass laminate A by a sputtering method, and a gate electrode is formed by etching using a photolithography method. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a gate insulating film, and then an indium gallium zinc oxide film is formed by a sputtering method to perform a photolithography method. An oxide semiconductor layer is formed by the etching used. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by plasma CVD to form a channel protective layer, and then molybdenum is formed by sputtering and etching using a photolithography method is performed. Thus, a source electrode and a drain electrode are formed. Next, heat treatment is performed in the atmosphere at 450 ° C. for 60 minutes. Next, a silicon nitride film is further formed on the second main surface side of the glass substrate by a plasma CVD method to form a passivation layer, followed by an indium tin oxide film formed by a sputtering method and etching using a photolithography method. Thus, a pixel electrode is formed.
Subsequently, by a vapor deposition method, 4,4 ′, 4 ″ -tris (3-methylphenylamino) triphenylamine as a hole injection layer and bis [(( N-naphthyl) -N-phenyl] benzidine, 8-quinolinol aluminum complex (Alq 3 ) as a light emitting layer, 2,6-bis [4- [N- (4-methoxyphenyl) -N-phenyl] aminostyryl] naphthalene -1,5-dicarbonitrile (BSN-BCN) mixed by 40% by volume, and Alq 3 as an electron transport layer are formed in this order, and then aluminum is formed by a sputtering method. Next, another glass substrate is bonded to the second main surface side of the glass substrate through an ultraviolet curable adhesive layer. According to the above procedure, an organic EL structure is formed on a glass substrate, and a glass laminate A (hereinafter referred to as panel A) having the organic EL structure on the glass substrate is used for the electronic device of the present invention. It is a laminated body with a member (panel for display apparatuses with a supporting base material).
Subsequently, after vacuum-adsorbing the sealing body side of the panel A to the surface plate, a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the silicone resin layer at the corner portion of the panel A, and glass Provides a trigger for peeling at the interface between the substrate and the silicone resin layer. And after adsorb | sucking the support base material surface of the panel A with a vacuum suction pad, a suction pad is raised. Here, the blade is inserted while spraying a static eliminating fluid on the interface from an ionizer (manufactured by Keyence Corporation). Next, the vacuum suction pad is pulled up while the static elimination fluid is continuously sprayed from the ionizer toward the formed gap. As a result, only the glass substrate on which the organic EL structure is formed on the surface plate is left, and the supporting base material with the silicone resin layer can be peeled off.
Subsequently, the separation surface of the glass substrate separated by the same method as in Example 1 was cleaned, the separated glass substrate was cut using a laser cutter or a scribe-break method, and divided into a plurality of cells. The glass substrate on which the EL structure is formed and the counter substrate are assembled, and a module forming process is performed to manufacture an OLED. The OLED obtained in this way does not have a problem in characteristics.
12 支持基材
14 シリコーン樹脂層
14a シリコーン樹脂層の第1主面
16 ガラス基板
16a ガラス基板の第1主面
16b ガラス基板の第2主面
18 シリコーン樹脂層付き支持基材
20 電子デバイス用部材
22 電子デバイス用部材付き積層体
24 部材付きガラス基板 DESCRIPTION OF
Claims (8)
- 支持基材とシリコーン樹脂層とガラス基板とをこの順で備え、前記支持基材と前記シリコーン樹脂層との界面の剥離強度が前記シリコーン樹脂層と前記ガラス基板との界面の剥離強度よりも大きい、ガラス積層体であって、
前記シリコーン樹脂層のシリコーン樹脂が、架橋性オルガノポリシロキサンの架橋物であり、
ナノインデンテーション法により測定した前記シリコーン樹脂層の弾性率が0.5~2.5MPaである、ガラス積層体。 A support base material, a silicone resin layer, and a glass substrate are provided in this order, and the peel strength at the interface between the support base material and the silicone resin layer is greater than the peel strength at the interface between the silicone resin layer and the glass substrate. A glass laminate,
The silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane,
A glass laminate in which the elastic modulus of the silicone resin layer measured by a nanoindentation method is 0.5 to 2.5 MPa. - 前記架橋性オルガノポリシロキサンの架橋物が、アルケニル基を有するオルガノポリシロキサンと、ハイドロシリル基を有するオルガノポリシロキサンとを反応させて得られる架橋物である、請求項1に記載のガラス積層体。 The glass laminate according to claim 1, wherein the cross-linked product of the crosslinkable organopolysiloxane is a cross-linked product obtained by reacting an organopolysiloxane having an alkenyl group with an organopolysiloxane having a hydrosilyl group.
- 前記アルケニル基と前記ハイドロシリル基との混合モル比(アルケニル基のモル数/ハイドロシリル基のモル数)が1/1~1/0.8である、請求項2に記載のガラス積層体。 The glass laminate according to claim 2, wherein a mixing molar ratio of the alkenyl group to the hydrosilyl group (number of moles of alkenyl group / number of moles of hydrosilyl group) is 1/1 to 1 / 0.8.
- 前記シリコーン樹脂層が、さらにシリコーンオイルを含む、請求項1~3のいずれか一項に記載のガラス積層体。 The glass laminate according to any one of claims 1 to 3, wherein the silicone resin layer further contains silicone oil.
- 前記シリコーン樹脂層の厚さが2~100μmである、請求項1~4のいずれか一項に記載のガラス積層体。 The glass laminate according to any one of claims 1 to 4, wherein the silicone resin layer has a thickness of 2 to 100 µm.
- 前記支持基材がガラス板である、請求項1~5のいずれか一項に記載のガラス積層体。 The glass laminate according to any one of claims 1 to 5, wherein the supporting substrate is a glass plate.
- 支持基材の片面に架橋性オルガノポリシロキサンを含む層を形成し、前記支持基材面上で前記架橋性オルガノポリシロキサンを架橋させてシリコーン樹脂層を形成し、次いで前記シリコーン樹脂層の表面にガラス基板を積層する、請求項1~6のいずれか一項に記載のガラス積層体を製造する方法。 A layer containing a crosslinkable organopolysiloxane is formed on one side of the support substrate, the silicone resin layer is formed by crosslinking the crosslinkable organopolysiloxane on the surface of the support substrate, and then on the surface of the silicone resin layer The method for producing a glass laminate according to any one of claims 1 to 6, wherein a glass substrate is laminated.
- 支持基材と前記支持基材面上に設けられたシリコーン樹脂層とを有する、シリコーン樹脂層付き支持基材であって、
前記シリコーン樹脂層のシリコーン樹脂が、架橋性オルガノポリシロキサンの架橋物であり、
ナノインデンテーション法により測定した前記シリコーン樹脂層の弾性率が0.5~2.5MPaである、シリコーン樹脂層付き支持基材。
A support substrate with a silicone resin layer, comprising a support substrate and a silicone resin layer provided on the support substrate surface,
The silicone resin of the silicone resin layer is a crosslinked product of a crosslinkable organopolysiloxane,
A support substrate with a silicone resin layer, wherein the silicone resin layer has an elastic modulus of 0.5 to 2.5 MPa measured by a nanoindentation method.
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