WO2015119210A1 - ガラス積層体 - Google Patents
ガラス積層体 Download PDFInfo
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- WO2015119210A1 WO2015119210A1 PCT/JP2015/053286 JP2015053286W WO2015119210A1 WO 2015119210 A1 WO2015119210 A1 WO 2015119210A1 JP 2015053286 W JP2015053286 W JP 2015053286W WO 2015119210 A1 WO2015119210 A1 WO 2015119210A1
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- WIPO (PCT)
- Prior art keywords
- silicone resin
- resin layer
- glass substrate
- glass
- layer
- Prior art date
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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
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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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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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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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
- B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
- B32B2315/08—Glass
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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
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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 in particular, to a glass laminate provided with a predetermined silicone resin layer.
- 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 silicone resin layer in the glass laminate described in Patent Document 1 decomposes in a short time at 450 ° C., and a large amount of outgas is generated. Generation
- production of such an outgas contaminates the member for electronic devices formed on a glass substrate, and becomes a cause of reducing the productivity of an electronic device as a result.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a glass laminate in which a glass substrate can be easily peeled even after high-temperature heat treatment and decomposition of a silicone resin layer is suppressed.
- the present invention comprises a support substrate layer, a silicone resin layer, and a glass substrate layer in this order, and the silicone resin in the silicone resin layer has an organosiloxy unit represented by T3 described later,
- the molar ratio ((A-1) / (B-1)) to the organosiloxy unit (B-1) as a group is 80/20 to 20/80, and the interface of the silicone resin layer to the glass substrate layer is It is a glass laminate in which the peel strength and the peel strength at the interface of the silicone resin layer with respect to the support base material layer are different.
- the silicone resin preferably further has an organosiloxy unit represented by Q described later.
- the silicone resin is a cured product of a curable organopolysiloxane, and the curable organopolysiloxane has organosiloxy units represented by T1 to T3 described later in terms of the number of units (molar amount).
- the number average molecular weight of the curable organopolysiloxane is preferably 500 to 2,000.
- the weight average molecular weight / number average molecular weight of the curable organopolysiloxane is preferably 1.00 to 2.00.
- the particle size of the curable organopolysiloxane measured by a dynamic light scattering method is preferably 0.5 to 100 nm.
- the curable organopolysiloxane is preferably an organopolysiloxane obtained by hydrolyzing phenyltrichlorosilane and methyltrichlorosilane.
- the thickness of the silicone resin layer is preferably 0.1 to 30 ⁇ m.
- the support substrate is preferably a glass plate.
- the peeling strength of the interface with respect to the layer of the glass substrate of a silicone resin layer is lower than the peeling strength of the interface with respect to the layer of the support base material of a silicone resin layer.
- the present invention of this aspect is also referred to as a first aspect.
- the peeling strength of the interface with respect to the layer of the glass substrate of a silicone resin layer is higher than the peeling strength of the interface with respect to the layer of the support base material of a silicone resin layer.
- the present invention of this aspect is also referred to as a second aspect.
- the present invention it is possible to provide a glass laminate in which the glass substrate can be easily peeled even after high-temperature heat treatment, and decomposition of the silicone resin layer is suppressed.
- the silicone resin in the silicone resin layer contains a predetermined amount of an organosiloxy unit represented by T3 described later, and an organosiloxy unit in which R in T3 is a phenyl group ( A molar ratio ((A-1) / (B-1)) between A-1) and an organosiloxy unit (B-1) in which R in T3 is a methyl group is within a predetermined range.
- an organosiloxy unit represented by T3 an organosiloxy unit represented by T3 described later
- an organosiloxy unit in which R in T3 is a phenyl group A molar ratio ((A-1) / (B-1)) between A-1) and an organosiloxy unit (B-1) in which R in T3 is a methyl group is within a predetermined range.
- the present inventors examined the reason why the glass substrate and the support substrate are difficult to separate in the glass laminate after the high-temperature heat treatment, and the functional group contained on the surface of the silicone resin layer has an effect. I found out. For example, when a Si—Me group is contained on the surface of the silicone resin layer, the group is relatively likely to be a Si—OH group after high-temperature heat treatment at 250 ° C. or higher. Therefore, if the amount of Si—Me groups contained in the silicone resin layer is too large, many Si—OH groups appear on the surface of the silicone resin layer after high-temperature heat treatment, and bond to the adjacent substrate (for example, glass substrate).
- Si—Ph groups are relatively difficult to convert to Si—OH groups.
- the crosslinking curing of the curable organopolysiloxane does not proceed sufficiently due to the steric hindrance of the substituent, and the degree of crosslinking of the silicone resin layer decreases.
- the mechanical strength of the silicone resin layer is reduced, or unreacted Si—OH groups derived from organopolysiloxane remain on the surface of the silicone resin layer, resulting in poor peelability of the glass substrate.
- the present inventor based on the above knowledge, adjusts the molar ratio ((A-1) / (B-1)) to make the silicone resin easy to peel off even after high-temperature heat treatment. The composition of the layer is found.
- the peel strength at the interface of the silicone resin layer with respect to the glass substrate layer and the peel strength at the interface of the silicone resin layer with respect to the layer of the supporting substrate are different.
- the peel strength at the interface between the silicone resin layer and the glass substrate layer is lower than the peel strength at the interface between the silicone resin layer and the support substrate layer, and the silicone resin layer and the glass substrate layer Peels and separates into a laminate of the silicone resin layer and the support substrate and a glass substrate.
- the peel strength at the interface between the silicone resin layer and the glass substrate layer is higher than the peel strength at the interface between the silicone resin layer and the support substrate layer, and the silicone resin layer and the support substrate layer Are separated and separated into a laminate of a glass substrate and a silicone resin layer and a supporting substrate. Below, it divides into 1st embodiment and 2nd embodiment, and demonstrates.
- FIG. 1 is a schematic cross-sectional view of a first embodiment of a glass laminate according to the present invention.
- the glass laminated body 10 is a laminated body in which the layer of the support base material 12, the layer of the glass substrate 16, and the silicone resin layer 14 exist among them.
- One side of the silicone resin layer 14 is in contact with the layer of the support base 12, and the other side is in contact with the first main surface 16 a of the glass substrate 16.
- the two-layer portion including the layer 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 layer of the support base material 12 manufactured previously for manufacture of the glass laminated body 10, and the silicone resin layer 14 is called the support base material 18 with a 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. Then, the glass laminated body in which the member for electronic devices was formed is isolate
- the support substrate 18 with the resin layer is laminated with a new glass substrate 16 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), and when a stress in the peeling direction exceeding the peel strength (y) is applied to the interface between the silicone resin layer 14 and the glass substrate 16, The interface between the silicone resin layer 14 and the glass substrate 16 is peeled off.
- the peel strength (x) is higher than the peel strength (y).
- the glass laminate 10 when a stress is applied to the glass laminate 10 in the direction in which the support base 12 and the glass substrate 16 are peeled off, the glass laminate 10 is peeled off at the interface between the silicone resin layer 14 and the glass substrate 16 and glass It isolate
- the peel strength (x) is preferably sufficiently higher than the peel strength (y). Increasing the peel strength (x) increases the adhesion of the first silicone resin layer 14 to the support base 12 and can maintain a relatively higher adhesion than the glass substrate 16 after the heat treatment. means.
- 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 bonding strength of the silicone resin after cross-linking and curing to the glass substrate 16 is generally lower than the bonding force generated during the cross-linking and curing. Therefore, the glass laminate 10 can be manufactured by forming the silicone resin layer 14 on the support base 12 and then laminating the glass substrate 16 on the surface of the silicone resin layer 14.
- each layer (support base material 12, glass substrate 16, silicone resin layer 14) constituting the glass laminate 10 will be described in detail, and then a method for manufacturing the glass laminate will be described in detail.
- 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 linear expansion coefficient from the glass substrate 16 and more preferably formed of the same material as the glass substrate 16.
- the support base 12 is a glass plate.
- the support base 12 is preferably a glass plate made of the same glass material as the glass substrate 16.
- the support substrate 12 may be a laminate including two or more layers.
- 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 is too large, the glass laminate 10 may be severely warped or the support substrate 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 can suppress that such a problem arises.
- 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.
- As an index of the heat shrinkage rate a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.
- the member forming process often involves 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 an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) 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 0.15 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 16. 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 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.
- a surface 14 a of the silicone resin layer 14 that contacts the glass substrate 16 is in close contact with the first main surface 16 a of the glass substrate 16.
- 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 peeling strength (y) at the interface is the peeling at the interface between the silicone resin layer 14 and the support base 12. Lower than strength (x).
- the bonding force at the interface between the silicone resin layer 14 and the glass substrate 16 may be changed 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.
- the peel strength (y) is preferably lower than the peel strength (x).
- the silicone resin layer 14 and the glass substrate 16 layer are bonded with a bonding force resulting from weak adhesive force or van der Waals force.
- 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 glass laminate 10 after the glass laminate 10 is manufactured, the silicone resin of the silicone resin layer 14 is made of glass by a heating operation or the like.
- the bonding force between the silicone resin layer 14 and the glass substrate 16 increases as it adheres to the surface of the substrate 16.
- 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, and a known method can be adopted as a method for improving the adhesion between the two.
- a strong bonding force such as an adhesive force or an adhesive force
- a known method can be adopted as a method for improving the adhesion between the two.
- the silicone resin layer 14 is formed on the surface of the support base 12 (more specifically, a curable organopolysiloxane capable of forming a predetermined silicone resin is crosslinked and cured on the support base 12. By doing so, the silicone resin in the silicone resin layer 14 can be adhered to the surface of the support substrate 12, and a high bonding strength can be obtained.
- the process for example, process using a coupling agent which produces strong bond strength between the support base material 12 surface and the silicone resin layer 14 is given, and between the support base material 12 surface and the silicone resin layer 14 The binding power of can be increased.
- the fact that the silicone resin layer 14 and the layer of the supporting substrate 12 are bonded with a high bonding force means that the peel strength (x) at the interface between them is high.
- the thickness of the silicone resin layer 14 is not particularly limited, but the upper limit is preferably 30 ⁇ m (that is, 30 ⁇ m or less), more preferably 20 ⁇ m, and even more preferably 8 ⁇ m.
- the lower limit is not particularly limited as long as it is a peelable thickness, but it is often 0.1 ⁇ m or more.
- the above thickness is intended to mean the average thickness, and the thickness of the silicone resin layer 14 at an arbitrary position of five or more points is measured with a contact-type film thickness measuring device, and these are arithmetically averaged.
- the surface roughness Ra of the surface of the silicone resin layer 14 on the glass substrate 16 side is not particularly limited, but is preferably from 0.1 to 20 nm, more preferably from 0.1 to 10 nm, from the viewpoint that the laminateability and peelability of the glass substrate 16 are more excellent. Is more preferable.
- the surface roughness Ra is measured according to JIS B 0601-2001, and an arithmetic average value of Ra measured at any five or more points corresponds to the surface roughness Ra.
- 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 silicone resin layers.
- a curable organopolysiloxane coated on a substrate is cured by heating after drying and removing the solvent contained in the material under a temperature condition from room temperature to a temperature lower than the thermal deformation temperature of the substrate. It becomes a silicone resin.
- silanol groups (—Si—OH) contained in the curable organopolysiloxane undergo a dehydration condensation reaction to form siloxane bonds (—Si—O—Si—), which are crosslinked and cured. It becomes a silicone resin.
- a gel film In the temperature rising process, the gel film becomes dense due to the capillary force generated by evaporation of the solvent and the dehydration condensation reaction that proceeds in the film, and the volume reduction rate of the film reaches several tens of percent.
- a gel film is not a perfect elastic body, but if it is approximated as an elastic body, when the film contracts in a state of being constrained in the in-plane direction by the substrate, strain is accumulated in the in-plane direction of the film. Will be.
- tensile stress hereinafter also referred to as “shrinkage stress” is generated in the in-plane direction of the film.
- the shrinkage stress of the silicone resin layer in the present invention refers to the value of the curvature radius of the silicon wafer before and after the formation of the silicone resin layer, measured by a thin film stress measuring device at an ambient temperature of 25 ° C., and the film thickness of the silicone resin layer. Is a tensile stress value acting in the in-plane direction of the silicone resin layer calculated by the equation represented by the following equation (1) using the value of: The measurement procedure will be described in detail in Examples.
- E / (1- ⁇ ) is the biaxial elastic modulus of the silicon wafer (crystal plane (100): 1.805 ⁇ 10 11 Pa), and h is the thickness [m] of the silicon wafer.
- T is the thickness [m] of the silicone resin layer, and R is the difference between the radius of curvature of the silicon wafer before forming the silicone resin layer and the radius of curvature of the silicon wafer after forming the silicone resin layer. [M].
- the difference R in the radius of curvature of the silicon wafer before and after forming the silicone resin layer is determined by the thickness h of the silicon wafer, the elastic modulus E of the silicon wafer, the Poisson's ratio ⁇ of the silicon wafer, the film thickness t, and the tensile stress ⁇ . . If the tensile stress ⁇ is generated in the in-plane direction of the film formed on one side of the silicon wafer, as the stress ⁇ generated in the in-plane direction of the film is larger as can be read from the above equation (1), the radius of curvature is larger.
- the difference R increases, that is, the warpage of the silicon wafer increases.
- the shrinkage stress of the silicone resin layer can be obtained.
- the radius of curvature R is obtained by forming a silicone resin layer on one surface of a single crystal silicon wafer, scanning the surface of the silicon wafer on which the silicone resin layer is formed with a laser beam using a thin film stress measuring device, and reflecting light. Can be obtained by reading R from the direction of.
- the magnitude of the shrinkage stress of the silicone resin layer 14 is not particularly limited, it is possible to prevent cracks from being formed in the cooling process after the process of forming the silicone resin layer 14 by crosslinking and curing the curable organopolysiloxane. From the point which can suppress further the curvature of the glass laminated body 10, 50 Mpa or less is preferable and 45 Mpa or less is more preferable.
- the lower limit is not particularly limited, but is usually 15 MPa or more in many cases.
- the silicone resin layer 14 is made of a silicone resin containing a predetermined organosiloxy unit.
- the silicone resin is usually obtained by crosslinking and curing a curable organopolysiloxane that can be converted into a silicone resin by a curing treatment.
- the curable organopolysiloxane in the present invention is a partially hydrolyzed condensate (organopolysiloxane) obtained by subjecting a mixture of monomer hydrolyzable organosilane compounds (monomer mixture) to a partial hydrolytic condensation reaction. Moreover, the partial hydrolysis-condensation product may contain the unreacted monomer.
- the curable organopolysiloxane In order to crosslink and cure the curable organopolysiloxane, it is usually cured by proceeding with a crosslinking reaction by heating (that is, thermosetting). And a silicone resin is obtained by thermosetting the curable organopolysiloxane.
- heating is not necessarily required for curing, and room temperature curing can also be performed.
- Common silicone resins are monofunctional organosiloxy units called M units, bifunctional organosiloxy units called D units, trifunctional organosiloxy units called T units, and 4 units called Q units. It is composed of functional organosiloxy units.
- the Q unit is a unit that does not have an organic group bonded to a silicon atom (an organic group having a carbon atom bonded to a silicon atom), but is regarded as an organosiloxy unit (silicon-containing bonded unit) in the present invention.
- the monomer forming the T unit is hereinafter referred to as T monomer.
- Monomers that form M units, D units, and Q units are also referred to as M monomers, D monomers, and Q monomers.
- the siloxane bond is a bond in which two silicon atoms are bonded via one oxygen atom, so that the number of oxygen atoms per silicon atom in the siloxane bond is considered to be 1/2. Expressed as medium O 1/2 . More specifically, for example, in one D unit, one silicon atom is bonded to two oxygen atoms, and each oxygen atom is bonded to a silicon atom of another unit. The formula is -O 1/ 2- (R) 2 Si-O 1/ 2- . Since there are two O 1/2 s , the D unit is usually expressed as (R) 2 SiO 2/2 .
- an oxygen atom O * bonded to another silicon atom is an oxygen atom bonded between two silicon atoms, and is intended to be an oxygen atom in a bond represented by Si—O—Si. To do. Accordingly, one O * exists between the silicon atoms of two organosiloxy units.
- the T unit means an organosiloxy unit represented by R—SiO 3/2 (R represents a hydrogen atom or an organic group).
- R represents a hydrogen atom or an organic group.
- the T unit has one silicon atom, a unit having one hydrogen atom or monovalent organic group bonded to the silicon atom, and three oxygen atoms O * bonded to another silicon atom. It is.
- a case where a functional group that can be bonded to another silicon atom instead of a part or all of the oxygen atom O * bonded to another silicon atom is also regarded as a T unit.
- the functional group that can be bonded to another silicon atom is a hydroxyl group or a group that becomes a hydroxyl group upon hydrolysis (hereinafter referred to as a hydrolyzable group). More specifically, in this specification, the T unit is a total of three oxygen atoms O * bonded to other silicon atoms and functional groups capable of bonding to other silicon atoms, Depending on the difference in the number of functional groups that can be bonded to the bonded oxygen atom O * and other silicon atoms, the T unit is classified into three types of units called T1 unit, T2 unit, and T3 unit.
- the T1 unit has one oxygen atom O * bonded to another silicon atom
- the T2 unit has two oxygen atoms O *
- the T3 unit has three oxygen atoms O * .
- a monovalent functional group that can be bonded to another silicon atom is represented by Z.
- the monomer (hydrolyzable organosilane compound) is usually represented by (R′—) a Si (—Z) 4-a .
- a represents an integer of 0 to 3
- R ′ represents a hydrogen atom or a monovalent organic group
- Z represents a hydroxyl group or a hydrolyzable group.
- the Z group is usually a hydrolyzable group.
- the plurality of R ′ may be different.
- the curable organopolysiloxane which is a partially hydrolyzed condensate is obtained by a reaction in which a part of the Z group of the monomer is converted into an oxygen atom O * .
- the Z group of the monomer is a hydrolyzable group
- the Z group is converted into a hydroxyl group by a hydrolysis reaction, and then two silicon atoms are converted by a dehydration condensation reaction between two hydroxyl groups bonded to separate silicon atoms. Bonded through an oxygen atom O * .
- hydroxyl groups (or Z groups that have not been hydrolyzed) remain, and when the curable organopolysiloxane is cured, these hydroxyl groups and Z groups react and cure as described above.
- a cured product of the curable organopolysiloxane is usually a three-dimensionally crosslinked polymer (silicone resin).
- the Z group of the curable organopolysiloxane is converted to O * , but a part of the Z group (particularly hydroxyl group) remains and is considered to be a cured product having a hydroxyl group.
- the curable organopolysiloxane is cured at a high temperature, it may be a cured product in which almost no hydroxyl groups remain.
- the Z group of the monomer is a hydrolyzable group
- examples of the Z group include an alkoxy group, a chlorine atom, an acyloxy group, and an isocyanate group.
- a monomer in which the Z group is an alkoxy group is used as the monomer.
- the alkoxy group is a hydrolyzable group having a relatively low reactivity as compared with a chlorine atom and the like, and in the curable organopolysiloxane obtained by using a monomer in which the Z group is an alkoxy group, it is not present together with the hydroxyl group as a Z group. Often an alkoxy group of the reaction is present.
- the Z group of the monomer is a hydrolyzable group having a relatively high reactivity (for example, a chlorine atom)
- most of the Z groups in the curable organopolysiloxane obtained using the monomer are hydroxyl groups. Therefore, in a normal curable organopolysiloxane, the Z group in each unit constituting it is often composed of a hydroxyl group or a hydroxyl group and an alkoxy group.
- the silicone resin constituting the silicone resin layer 14 has an organosiloxy unit represented by T3 (hereinafter also simply referred to as T3 unit), and the total ratio of the organosiloxy unit represented by T3 to the total organosiloxy unit is 80.
- T3 unit organosiloxy unit represented by T3
- the silicone resin contains an organosiloxy unit represented by T3 as a main component.
- R represents a phenyl group or a methyl group.
- the organosiloxy unit represented by T3 corresponds to one of the T units described above.
- the silicone resin may contain other units in addition to the organosiloxy unit represented by T3. Examples of other units include M units, D units, T1 units, T2 units, and Q units.
- the organosiloxy unit represented by the following Q is used in that the silicone resin layer 14 does not cohesively break during peeling, the mechanical strength of the silicone resin layer 14 is excellent, and the peelability of the glass substrate 16 is more excellent.
- Q unit The content of the Q unit is not particularly limited, but is preferably 1 mol% or more, and more preferably 5 mol% or more with respect to all organosiloxy units.
- the upper limit is not particularly limited, but the brittleness of the silicone resin layer 14 is reduced by increasing the degree of crosslinking, and the silicone resin layer 14 may cause cohesive failure at the time of peeling. 20 mol% or less is preferable at the point which may cause the curvature of the glass composite by increase.
- Q SiO 4/2
- the said all organosiloxy unit intends the sum total of the M unit contained in a silicone resin, D unit, T unit, and Q unit.
- the ratio of the number of M units, D units, T units (T1 to T3 units), and Q units (molar amount) can be calculated from the value of the peak area ratio by 29 Si-NMR.
- the molar ratio ((A-1) / (B-1)) is preferably 75/25 to 20/80, more preferably 70/30 to 20/80 in that the glass substrate can be more easily peeled off. preferable.
- the organosiloxy unit (A-1) in which R is a phenyl group means an organosiloxy unit represented by PT3 below. Ph represents a phenyl group. P-T3: Ph-SiO 3/2 Further, the organosiloxy unit (B-1) in which R is a methyl group means an organosiloxy unit represented by MT3 below. M-T3: Me-SiO 3/2
- the silicone resin can be manufactured using a known material.
- the curable organopolysiloxane that can be converted into the silicone resin by the curing treatment for example, a partially hydrolyzed condensate obtained by subjecting a mixture of hydrolyzable organosilane compounds as monomers to a partial hydrolytic condensation reaction ( Organopolysiloxanes) are used. More specifically, the monomer includes a hydrolyzable organosilane compound represented by (Me-) Si (-Z) 3 and a hydrolyzability represented by (Ph-) Si (-Z) 3 . Organosilane compounds are used.
- the Z group represents a hydroxyl group or a hydrolyzable group.
- hydrolyzable group examples include a halogen atom such as a chlorine atom, an alkoxy group, an acyl group, an amino group, and an alkoxyalkoxy group.
- the hydrolysis condensation reaction is a reaction in which T1 units are generated from T monomers, T2 units are generated from T1 units, and T3 units are generated from T2 units. Reaction rate of condensation reaction in which T1 unit is generated from T monomer in which one or more hydrolyzable groups are converted to hydroxyl group, condensation reaction in which T2 unit is generated from T1 unit, and condensation reaction in which T2 unit is generated from T2 unit Are considered to be slower in this order.
- the curable organopolysiloxane that can be the silicone resin includes, as described above, a partially hydrolyzed condensate (organopolysiloxane) obtained from a mixture of hydrolyzable organosilane compounds from the aspects of reaction control and handling. Used.
- the partially hydrolyzed condensate is obtained by partially hydrolyzing and condensing a monomer mixture in which a hydrolyzable organosilane compound is mixed so as to have the ratio of each of the above organosiloxy units.
- the method of partially hydrolytic condensation is not particularly limited. Usually, it is produced by reacting a mixture of a hydrolyzable organosilane compound in a solvent in the presence of a catalyst.
- the partial hydrolysis-condensation product used in the present invention is preferably a product produced by reacting a mixture of hydrolyzable organosilane compounds in a solvent in the presence of an acid or alkaline aqueous solution.
- the hydrolyzable organosilane compound used is represented by the above-described hydrolyzable organosilane compound represented by (Me-) Si (-Z) 3 and (Ph-) Si (-Z) 3. Among them, hydrolyzable organosilane compounds are mentioned.
- phenyltrichlorosilane (described below) is excellent in handling property of the resulting curable organopolysiloxane, has high heat resistance, and can easily peel off the glass substrate 16. It is preferable to use a compound represented by the formula (1)) and methyltrichlorosilane (a compound represented by the following formula (2)). In addition, Ph in Formula (1) represents a phenyl group.
- a composition containing a curable organopolysiloxane is used, but the stability of the curable organopolysiloxane in the composition is improved.
- the end of the cured silicone can be capped. More specifically, the terminal Si—OH in the curable organopolysiloxane can be reacted with an alcohol in the presence of an acid catalyst (for example, in the presence of acetic acid) to cap the Si—OH while removing water. it can. For example, when methanol is used, Si-OMe groups are formed.
- the type of alcohol used is not particularly limited, and examples thereof include low boiling point alcohols such as methanol, ethanol, 1-propanol, and 1-butanol. Of these, methanol and ethanol are preferred from the viewpoint of good reactivity with Si—OH groups and good solubility of the curable organopolysiloxane.
- One preferred embodiment of the curable organopolysiloxane has at least one of the organosiloxy units represented by the following T1 to T3, and is represented by the following T1 to T3 with respect to all organosiloxy units.
- organopolysiloxanes having a molar ratio ((A-2) / (B-2)) to the unit (B-2) of 80/20 to 20/80 hereinafter also referred to as organopolysiloxane X). If it is this organopolysiloxane, a desired silicone resin can be obtained easily.
- T1 R—Si (—OX) 2 O 1/2
- T2 R—Si (—OX) O 2/2
- T3 R—SiO 3/2
- R represents a phenyl group or a methyl group.
- X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- R in the above formula is not limited to one type, and R may be different for each of T1, T2, and T3. Further, -OX may be the same or different between the T1 unit and the T2 unit.
- Two —OX in the T1 unit may be different, for example, one may be a hydroxyl group and the other may be an alkoxy group. In addition, when both of the two —OX are alkoxy groups, the alkoxy groups may be different alkoxy groups.
- T0 The T unit having no oxygen atom (O * ) for bonding two silicon atoms and having only three —OX is hereinafter referred to as T0.
- T0 actually corresponds to an unreacted T monomer and is not an organosiloxy unit (silicon-containing bond unit).
- This T0 is measured in the same manner as T1 to T3 in the analysis of units of T1 to T3.
- the units T1 to T3 in the organopolysiloxane X can be analyzed by measuring the bonding state of silicon atoms by nuclear magnetic resonance analysis ( 29 Si-NMR). The ratio of the number of units of T0 to T3 (molar amount) is determined from the peak area ratio of 29 Si-NMR.
- the mass average molecular weight Mw, the number average molecular weight Mn, and the dispersity Mw / Mn of the organopolysiloxane X are values measured by gel permeation chromatography using polystyrene as a standard substance. Such characteristics of organopolysiloxane X do not refer to the characteristics of one molecule, but are determined as the average characteristics of each molecule.
- the total proportion of the organosiloxy units represented by T1 to T3 in the organopolysiloxane X is preferably 80 to 100 mol% with respect to the total organosiloxy units, and the resulting silicone resin In view of excellent heat resistance of the layer 14 and easier peeling of the glass substrate 16, it is preferably 82 to 100 mol%, more preferably 85 to 100 mol%.
- the organopolysiloxane X preferably includes at least the T3 unit, and more preferably includes at least the T2 unit and the T3 unit from the viewpoint of handleability. As a result of various studies, it is known that the proportion of T1 units increases as the number of Ph groups (phenyl groups) increases.
- the organopolysiloxane X may contain other units in addition to the organosiloxy units represented by T1 to T3. Examples of the other units include M units, D units, and Q units.
- T-curing organopolysiloxane polyphenyl polysiloxane, polymethyl polysiloxane, and the like are generally known, but silanol-terminated polyphenyl polysiloxane has a molecular weight of several hundreds of times when PhSiCl 3 is hydrolyzed. Obtained as thousands of oligomers.
- the solubility in a solvent is poor, and a large amount of solvent is required to dissolve the condensate, and a thin film for coating use can be obtained, but a cured product having a certain thickness is obtained due to the occurrence of cracks, etc. It is difficult. Therefore, it is preferable to use the curable organopolysiloxane X having both heat resistance and reactivity and improved solubility.
- the molar ratio ((A-2) / (B-2)) is preferably 75/25 to 20/80, and more preferably 70/30 to 20/80.
- the organosiloxy unit (A-2) in which R is a phenyl group means a T1 unit in which R is a phenyl group (hereinafter referred to as P-T1), a T2 unit in which R is a phenyl group (hereinafter referred to as P-T2), and , R 3 is intended to include a T3 unit (hereinafter referred to as P-T3) in which a phenyl group is included.
- P-T3 T3 unit
- Ph represents a phenyl group.
- the content of the organosiloxy unit (A-2) is represented by the content of the unit represented by the PT, the content of the unit represented by the PT2, and the content of the PT3.
- the total amount of unit content is intended.
- the organosiloxy unit (B-2) in which R is a methyl group is a T1 unit in which R is a methyl group (hereinafter referred to as M-T1), and a T2 unit in which R is a methyl group (hereinafter referred to as M-T2).
- M-T3 T3 unit
- R is a methyl group.
- Me represents a methyl group.
- M-T1 Me-Si (-OX) 2 O 1/2
- M-T2 Me—Si (—OX) O 2/2
- M-T3 Me-SiO 3/2 Therefore, the content of the organosiloxy unit (B-2) is the content of the unit represented by M-T1, the content of the unit represented by M-T2, and the content represented by M-T3. The total amount of unit content is intended.
- the ratio of T1: T2: T3 is, in other words, a ratio of T1 units of 0 to 5 mol%, a ratio of T2 units of 20 to 50 mol%, and a ratio of T3 units of 50 to 80 mol%. I can say that.
- the ratio of the (A-2) unit to the (B-2) unit in the curable organopolysiloxane X ((A-2) /) in that the glass substrate 16 can be easily peeled and the warp of the glass laminate 10 can be reduced.
- the silicone resin layer is formed using the curable organopolysiloxane X, depending on the curing conditions, the methyl group or phenyl group in T1 to T3 may be eliminated and Q units may be formed.
- the number average molecular weight of the curable organopolysiloxane (particularly, the curable organopolysiloxane X) is excellent in solubility of the curable organopolysiloxane, and can produce the silicone resin layer 14 with few foreign matter defects, or the glass substrate 16.
- the number average molecular weight in terms of polystyrene is preferably 500 to 2000, more preferably 600 to 2000, and more preferably 800 to 2000, as measured by GPC (gel permeation chromatography). 1800 is more preferable.
- the mass average molecular weight / number average molecular weight of the curable organopolysiloxane is excellent in solubility of the curable organopolysiloxane, and the silicone resin layer 14 with few foreign matter defects can be produced.
- 1.00 to 2.00 is preferable, 1.00 to 1.70 is more preferable, and 1.00 to 1.50 is further preferable in that the glass substrate 16 can be more easily peeled off.
- the molecular weight of the curable organopolysiloxane (particularly the curable organopolysiloxane X) can be adjusted by controlling the reaction conditions.
- the shape of the curable organopolysiloxane is not particularly limited, and may be granular. That is, when a curable organopolysiloxane (particularly, the curable organopolysiloxane X) is added to a solvent, it may exist as fine particles.
- the particle diameter of the curable organopolysiloxane (particularly the curable organopolysiloxane X) measured by the dynamic light scattering method is not particularly limited, but the silicone resin layer with few foreign matter defects can be produced, or From the viewpoint that the glass substrate 16 can be more easily peeled off, the thickness is preferably from 0.5 to 100 nm, more preferably from 0.5 nm to less than 40 nm.
- a curable organopolysiloxane is added to a PEGMEA solution (propylene glycol-1-monomethyl ether-2-acetate) at 20% by mass.
- a sample is prepared by adjusting so that the histogram average particle size (D50) is obtained using a concentrated particle size analyzer (manufactured by Otsuka Electronics Co., Ltd., FPAR-1000).
- the manufacturing method of the silicone resin layer 14 described above is not particularly limited, and a known method can be adopted.
- a method for producing the silicone resin layer 14, as described later a layer of a curable organopolysiloxane that becomes the silicone resin is formed on the support substrate 12, and the curable organopolysiloxane is crosslinked and cured to form a silicone resin.
- Layer 14 is preferred.
- a solution in which the curable organopolysiloxane is dissolved in a solvent (a composition containing the curable organopolysiloxane) is used.
- the thickness of the curable organopolysiloxane layer can be controlled by adjusting the concentration of the solution.
- the content of the curable organopolysiloxane in the composition containing the curable organopolysiloxane is superior to the handleability and the control of the film thickness of the silicone resin layer 14 is easier.
- the content is preferably 1 to 100% by mass, more preferably 1 to 50% by mass.
- the solvent is not particularly limited as long as it can easily dissolve the curable organopolysiloxane in a working environment and can be easily volatilized and removed.
- Specific examples include butyl acetate, 2-heptanone, 1-methoxy-2-propanol acetate and the like.
- the pH in the composition from the viewpoint of further improving the stability of the curable organopolysiloxane in the composition.
- An acid is preferably used for pH control in terms of further improving the stability of the curable organopolysiloxane and acting as a curing catalyst when the curable organopolysiloxane is cured.
- Additive acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, p-toluene Examples include organic acids such as sulfonic acid, and acetic acid is preferred.
- the amount of acid used is preferably from 0.1 to 50 parts by weight, particularly preferably from 1 to 20 parts by weight, based on 100 parts by weight of the curable organopolysiloxane composition.
- an alcohol having a boiling point higher than that of the coating solvent can be added in order to further improve the stability of the curable organopolysiloxane in the composition.
- the type of alcohol used is not particularly limited, and 1-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-methyl-1-butanol, 1-pentanol, diacetone alcohol, 2- (2 -Ethoxyethoxy) ethanol and the like. Of these, 1-methoxy-2-propanol, diacetone alcohol, and 2- (2-ethoxyethoxy) ethanol are preferred from the viewpoint of good solubility of the curable organopolysiloxane.
- the coating property to the substrate may contain an antifoaming agent and a viscosity modifier, and may further contain additives such as an adhesion-imparting agent for the purpose of improving the adhesion to the substrate.
- a leveling agent may be blended for the purpose of improving the coatability and the smoothness of the resulting coating film.
- the amount of these additives is preferably 0.01 to 2 parts by mass for each component with respect to 100 parts by mass of the curable organopolysiloxane.
- you may add a filler etc. in the range which does not impair the objective of this invention. The procedure for forming the silicone resin layer using the curable organopolysiloxane will be described in detail later.
- 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 of the glass laminated body 10 of this invention is not restrict
- the silicone resin layer 14 is formed on the support base material 12 surface.
- a curable organopolysiloxane is applied to the surface of the support substrate 12 to form a silicone resin layer 14 on the surface of the support substrate 12, and then a glass substrate 16 is laminated on the silicone resin surface of the silicone resin layer 14.
- the method of manufacturing the glass laminated body 10 is preferable.
- a step of forming a curable organopolysiloxane layer on the surface of the support substrate 12 and forming the silicone resin layer 14 on the surface of the support substrate 12 is a resin layer formation step, and a silicone resin surface of the silicone resin layer 14 is formed.
- the process of laminating the glass substrate 16 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 of curable organopolysiloxane is formed on the surface of the support substrate 12, and the silicone resin layer 14 is formed on the surface of the support substrate 12.
- a coating composition in which the curable organopolysiloxane is dissolved in a solvent is prepared.
- the composition is applied onto the support substrate 12 to form a solution layer, and then cured to form the silicone resin layer 14.
- the method for applying the composition containing the curable 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.
- the curable organopolysiloxane on the support substrate 12 is cured 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 surface of the support base 12.
- the curing method is not particularly limited, but is usually performed by a heat curing treatment.
- the temperature condition for thermosetting 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, but is 150 to 550 ° C. Is preferable, and 200 to 450 ° C. is more preferable.
- the heating time is usually preferably 10 to 300 minutes, more preferably 20 to 120 minutes.
- the heating condition may be implemented stepwise by changing the temperature condition.
- the temperature range and the heating time range it is possible to control the generation ratio of T units, T2 units, T3 units, and Q units that are easily generated by heating at 250 ° C. or higher.
- the silicone resin layer 14 excellent in heat resistance can be obtained.
- 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 crosslinked layer and the step of performing precuring.
- the removal of the solvent is preferably performed by heating to 100 ° C. or higher, and precure can be continued by heating to 150 ° C. or higher.
- the temperature at which the solvent is removed and precured and the heating time are preferably 100 to 420 ° C. and 5 to 60 minutes, more preferably 150 to 300 ° C. and 10 to 30 minutes. A silicone resin layer that is easily peeled when the temperature is 420 ° C. or lower is obtained.
- 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 layer of the supporting base 12, the silicone resin layer 14, and the glass substrate 16 are laminated.
- This is a step of obtaining the glass laminate 10 provided in this order. More specifically, as shown in FIG. 2 (B), a glass substrate having a surface 14a opposite to the support base 12 side of the silicone resin layer 14, and a first main surface 16a and a second main surface 16b.
- the silicone resin layer 14 and the glass substrate 16 are laminated by using the first principal surface 16a of 16 as a lamination surface, and the glass laminate 10 is obtained.
- 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 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 silicone resin layer 14 which provided the difference in the peeling strength with respect to the 1st main surface of the glass substrate 16 and the peeling strength with respect to the 1st main surface of the support base material 12 is not restricted to the said method.
- the silicone resin film is cured by curing the curable organopolysiloxane on some peelable surface. The film can be manufactured and interposed between the glass substrate 16 and the support base 12 and laminated simultaneously.
- the adhesiveness by hardening of curable organopolysiloxane when the adhesiveness by hardening of curable 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 product can be cured to form the silicone resin layer 14.
- 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 according to the first aspect of the present invention can be used for various applications.
- the use etc. which manufacture electronic parts, such as these, are mentioned.
- the glass laminate 10 is often exposed (for example, 1 hour or longer) under high temperature conditions (for example, 450 ° 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.
- FIG. 3 is a schematic cross-sectional view of a second embodiment of the glass laminate according to the present invention.
- the glass laminated body 100 is a laminated body in which the layer of the support base material 12, the layer of the glass substrate 16, and the silicone resin layer 14 exist between them.
- the silicone resin layer 14 is fixed on the glass substrate 16, and the glass substrate 20 with a resin layer is a resin layer. It laminates
- the fixing and peelable adhesion have a difference in peeling strength (that is, stress required for peeling), and fixing means that the peeling strength is higher than the adhesion. That is, in the glass laminate 100, the peel strength at the interface between the silicone resin layer 14 and the glass substrate 16 is higher than the peel strength at the interface between the silicone resin layer 14 and the support base 12.
- the interface between the glass substrate 16 and the silicone resin layer 14 has a peel strength (z), and the interface between the glass substrate 16 and the silicone resin layer 14 has a peeling direction exceeding the peel strength (z).
- the interface between the glass substrate 16 and the first silicone resin layer 14 is peeled off.
- the interface between the silicone resin layer 14 and the support substrate 12 has a peel strength (w), and a stress in the peeling direction exceeding the peel strength (w) is applied to the interface between the silicone resin layer 14 and the support substrate 12.
- the interface of the silicone resin layer 14 and the support base material 12 peels.
- the peel strength (z) is higher than the peel strength (w).
- the glass laminate 100 of the present invention peels at the interface between the silicone resin layer 14 and the support substrate 12. And it isolate
- the peel strength (z) is preferably sufficiently higher than the peel strength (w).
- Increasing the peel strength (z) means that the adhesion of the silicone resin layer 14 to the glass substrate 16 can be increased and a relatively higher adhesion can be maintained after the heat treatment than to the support substrate 12. .
- the silicone resin layer 14 bonded to the glass substrate 16 with a high bonding force can be formed by the adhesive force at the time of crosslinking and curing.
- the bonding strength of the silicone resin after cross-linking and curing to the support substrate 12 is usually lower than the bonding force generated during the cross-linking and curing. Therefore, the glass laminate 100 can be manufactured by forming the silicone resin layer 14 on the glass substrate 16 and then laminating the support base 12 on the surface of the silicone resin layer 14.
- each layer (support base material 12, glass substrate 16, silicone resin layer 14) constituting glass laminate 100 is synonymous with each layer constituting glass laminate 10 described above, and description thereof is omitted here.
- the surface roughness Ra of the surface of the silicone resin layer 14 on the support base material 12 side is not particularly limited, but is preferably 0.1 to 20 nm from the viewpoint that the laminateability and peelability of the glass substrate 16 are more excellent. 1 to 10 nm is more preferable.
- the surface roughness Ra is measured according to JIS B 0601-2001, and an arithmetic average value of Ra measured at any five or more points corresponds to the surface roughness Ra. .
- the manufacturing method in particular of the glass laminated body 100 is not restrict
- the glass substrate 16 is used instead of the support base material 12, and the support base material 12 is used instead of the glass substrate 16.
- FIG. the desired glass laminated body 100 can be manufactured. More specifically, the glass laminate 100 can be manufactured by forming the silicone resin layer 14 on the glass substrate 16 and then laminating the support base 12 on the silicone resin layer 14.
- an electronic device can be manufactured using the glass laminated body (glass laminated body 10 or glass laminated body 100) mentioned above.
- the glass laminated body 10 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.
- 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 of separating the manufactured and obtained laminated body with a member for electronic devices into a glass substrate with a member and a supporting substrate with a resin layer by using the glass substrate side interface of the silicone resin layer or the inside of the 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 step of separating the glass substrate with a member and the support base with a resin layer using the side interface as a separation surface is referred to as a separation step, and the step of cleaning the separation surface of the glass substrate with a member is referred to as a cleaning treatment step.
- the cleaning process process is an arbitrary process implemented as needed. 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 22 is formed on the second main surface 16b (exposed surface) of the glass substrate 16 to obtain a laminate 24 with the electronic device member. .
- the electronic device member 22 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 22 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 22, 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 its 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 24 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 22 is formed on the surface 16b surface.
- the electronic device member 22 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 the 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 glass substrate 16 (on which the electronic device member 22 is laminated) with the interface between the silicone resin layer 14 and the glass substrate 16 as the release surface from the laminate 24 with the electronic device member obtained in the member forming step.
- This is a step of obtaining a glass substrate 26 with a member including the electronic device member 22 and the glass substrate 16 by separating the glass substrate with a member), the silicone resin layer 14 and the support base 12.
- the method of peeling the glass substrate 26 with a member and the support base material 18 with a resin layer 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 and given 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 24 is placed on the surface plate so that the support base material 12 is on the upper side and the electronic device member 22 side is on the lower side, and the electronic device member 22 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 at the interface between the silicone resin layer 14 and the glass substrate 16, and the air layer spreads over the entire interface, so that the support substrate 18 with the resin layer can be easily peeled off.
- the support base material 18 with a resin layer can be laminated
- a piece of the silicone resin layer 14 is electrostatically adsorbed to the glass substrate 26 with a member by controlling the spraying and humidity with an ionizer. It can be suppressed more.
- the cleaning treatment step is a step of performing a cleaning treatment on the peeling surface (first main surface 16a) of the glass substrate 16 in the glass substrate with member 26 obtained in the separation step.
- This step it is possible to remove impurities such as silicone resin and silicone resin layer adhering to the release surface, metal pieces and dust generated in the member forming step adhering to the release surface, and cleaning the release surface. Sex can be maintained. As a result, the tackiness of a retardation film, a polarizing film or the like attached to the release surface of the glass substrate 16 is improved.
- the cleaning treatment method is not particularly limited as long as the resin or dust attached to the release surface can be removed.
- a method of thermally decomposing the deposit there are a method of thermally decomposing the deposit, a method of removing impurities on the peeled surface by plasma irradiation or light irradiation (for example, UV irradiation treatment), and a cleaning method using a solvent.
- the above-described method for manufacturing the glass substrate with member 26 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.
- an electronic device can also be manufactured using the glass laminated body 100 according to the procedure similar to the above.
- the support base material 12, the silicone resin layer 14, and the glass substrate 16 are set by making the interface of the support base material 12 and the silicone resin layer 14 into a peeling surface.
- an electronic device including the electronic device member 22.
- the ratio of T1 to T3 was determined from the peak area ratio of the solution 29 Si-NMR.
- the measurement conditions were a pulse width of 20 ⁇ sec, a pulse repetition waiting time of 30 sec, and an integration count of 256 scan.
- Toluene was used as the solvent, and 0.1 wt% of Cr (acac) 3 was added as a relaxation reagent to the one prepared to a concentration of 30 wt%.
- the standard of chemical shift was set to 0 ppm for the peak derived from TMS.
- Analysis of phenyl group mol% / methyl group mol% in the curable organopolysiloxane above (A-2) / (B-2) composition ratio Nuclear magnetic resonance analyzer (solution 1 H-NMR: JEOL RESONANCE)
- the composition ratio of phenyl group mol% / methyl group mol% (above (A-2) / (B-2)) was determined using ECP400 manufactured by Co., Ltd.
- the phenyl group mol% / methyl group mol% (above (A-2) / (B-2)) composition ratio was determined from the peak area of 1 H-NMR.
- the measurement conditions were a pulse width of 6.7 ⁇ sec, a pulse repetition waiting time of 5 sec, and an integration count of 16 scan.
- Deuterated chloroform was used as the solvent, and the concentration was adjusted to 1 wt%.
- the standard for chemical shift was 7.26 ppm with a peak derived from chloroform.
- the chemical shift of 1 H-NMR derived from each structure is as follows.
- a glass plate made of non-alkali borosilicate glass (length 274 mm, width 274 mm, plate thickness 0.2 mm, linear expansion coefficient 38 ⁇ 10 ⁇ 7 / The product name “AN100” manufactured by Asahi Glass Co., Ltd.
- a glass plate made of alkali-free borosilicate glass (length 274 mm, width 274 mm, plate thickness 0.4 mm, linear expansion coefficient 38 ⁇ 10 ⁇ 7 / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) It was used.
- the reaction vessel was immersed in an oil bath at 60 ° C. and heated and stirred for 24 hours. After completion of the reaction, the organic phase was washed until the washing water became neutral, and then the organic phase was dried using a desiccant. Next, after removing the desiccant, the solvent was distilled off under reduced pressure, followed by vacuum drying overnight to obtain a white solid (curable organopolysiloxane (U1)).
- the “phenyl group mol% / methyl group mol%” column shows the organosiloxy unit in which R in T1 to T3 in the obtained curable organopolysiloxane is a phenyl group
- T1 ⁇ Represents a molar ratio with an organosiloxy unit in which R in T3 is a methyl group.
- the “ratio of T units” column indicates the ratio (mol%) of the number of each unit of T1 to T3 in the obtained curable organopolysiloxane, and the total of the ratio of the number of each unit of T1 to T3. Is shown to be 100.
- the “particle diameter” column is the particle size of the curable organopolysiloxane measured by the dynamic light scattering method described above, and “ ⁇ 40” means that the particle size was less than 40 nm, and “> 100 "Is intended to mean that the particle size was greater than 100 nm.
- the content of each unit was calculated from 29 Si-NMR and 1 H-NMR.
- Example 1 The obtained curable organopolysiloxane (U1) was dissolved in PEGMEA to prepare a liquid (solid content concentration: 40% by mass) containing the curable organopolysiloxane (U1). It was present in the liquid as fine particles having the particle sizes shown in Table 1.)
- the support substrate was cleaned with pure water, and further cleaned by UV cleaning.
- a liquid material containing a curable organopolysiloxane (U1) having a size of 278 mm in length and 278 mm in width on the first main surface of the support substrate was applied with a spin coater (coating amount 30 g / m). 2 ). Next, this was heat-cured at 350 ° C.
- the peelable surface of the silicone resin layer of the support A is opposed to the first main surface of a glass substrate (“AN100” manufactured by Asahi Glass Co., Ltd.) having the same size as the silicone resin layer and a thickness of 0.2 mm. Then, the two substrates were superposed at room temperature and atmospheric pressure using a laminating apparatus so that the centers of gravity of both substrates overlapped to obtain a glass laminate S1.
- AN100 manufactured by Asahi Glass Co., Ltd.
- the obtained glass laminate S1 corresponds to the glass laminate 10 shown in FIG. 1 described above, and in the glass laminate S1, the peel strength (x) at the interface between the support substrate layer and the silicone resin layer is silicone. It was higher than the peel strength (y) at the interface between the resin layer and the glass substrate.
- the following measurements were performed using the obtained glass laminate S1. The following evaluation results are summarized in Table 1 described later.
- Examples 2 to 10 In place of the liquid material containing the curable organopolysiloxane (U1), the liquid materials containing the curable organopolysiloxanes (U2) to (U6) shown in Table 2 below were used, respectively, except that the heat curing treatment conditions were changed.
- Table 2 below shows the type of solvent, solid content concentration, and the like used when manufacturing the liquid material.
- the heat curing treatment conditions at the time of heat curing were changed from “350 ° C., 30 minutes” to “150 ° C. for 30 minutes in the atmosphere and then further heated at 350 ° C.
- Example 9 the heat curing treatment condition at the time of heat curing was changed from “350 ° C., 30 minutes” to “150 ° C. for 30 minutes in the air, and then further heated at 350 ° C. for 60 minutes. It was heat-cured in the atmosphere and further changed to “heat-cured in the air at 500 ° C. for 60 minutes”.
- the obtained glass laminates S2 to S10 correspond to the glass laminate 10 shown in FIG. 1 described above, and in the glass laminates S2 to S10, the peel strength at the interface between the support substrate layer and the silicone resin layer (x ) was higher than the peel strength (y) at the interface between the silicone resin layer and the glass substrate. Further, the above [Removability Evaluation] and [Heat Resistance Evaluation] were performed using the obtained glass laminates S2 to S10. The results are summarized in Table 2.
- the “applicability evaluation” column shows “ ⁇ ” when the silicone resin layer can be formed by applying a liquid material containing a curable organopolysiloxane, and “No” when the silicone resin layer cannot be formed. ⁇ ”.
- a stainless steel blade is inserted into the interface between the glass substrate and the silicone resin layer, and when the trigger for peeling is given, most of the glass substrate and the silicone resin layer are peeled off. If the glass substrate can be easily peeled off, the glass substrate cannot be peeled off only by the trigger of peeling, but if the glass substrate can be peeled off, the circle indicates that the glass substrate cannot be peeled or the glass substrate is damaged. Shown as “x”.
- the “silicone resin layer” column shows the mol% of T3 unit and Q unit calculated from the peak area ratio by 29 Si-NMR.
- the analysis of the silicone resin layer was performed by the item and method shown below.
- the contents (mol%) of the T3 unit and the Q unit were obtained from the peak area ratio of solid 29 Si-NMR.
- the silicone resin layer is formed by applying a liquid material containing a curable organopolysiloxane used in each example and comparative example on a glass substrate with a spin coater, and heating and curing under the heating conditions of each example and comparative example. Then, after forming a silicone resin layer on the glass substrate, a solid sample was used in which the silicone resin layer was shaved with a razor blade.
- the measurement method was the DDMAS method, and the measurement conditions were a pulse width of 1.9 ⁇ sec, a pulse repetition waiting time of 300 sec, an integration count of 300 scan or more, and a MAS rotation speed of 10 KHz.
- the silicone resin layer is formed by applying a liquid material containing a curable organopolysiloxane used in each example and comparative example on a glass substrate with a spin coater, and heating and curing under the heating conditions of each example and comparative example. Then, after forming a silicone resin layer on the glass substrate, a solid sample was used in which the silicone resin layer was shaved with a razor blade.
- Depth 2 was used as the measurement method, and the measurement conditions were a pulse width of 2.3 ⁇ sec, a pulse repetition waiting time of 15 sec, an integration count of 16 scan, and a MAS rotation speed of 22 KHz.
- the standard of chemical shift was a peak derived from adamantane at 1.7 ppm.
- the chemical shift of solid 1 H-NMR derived from each structure is as follows. A-1 (Ph group): 18 to 4 ppm B-1 (Me group): 4 to -10 ppm
- the silicone resin layer exhibited excellent heat resistance and was excellent in peelability (separability) of the glass substrate. In particular, in Examples 1 to 9 including the Q unit, the peelability was more excellent. On the other hand, as shown in Comparative Examples 1 and 2, when a silicone resin layer having a predetermined composition ratio was not used, the desired effect was not obtained.
- an OLED is manufactured using the glass laminate S1 obtained in Example 1.
- 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 S1 by plasma CVD.
- low concentration boron is injected into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed for dehydrogenation treatment.
- 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 S1 having an organic EL structure on the glass substrate
- panel A is an electron of the present invention. It is a laminated body with a member for devices.
- a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of panel A, and the glass substrate Gives the interface between the resin layer and the 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 continuing to spray a static eliminating fluid from the ionizer toward the formed gap, and while water is inserted into the peeling front.
- the separated glass substrate is cut using a laser cutter or a scribe-break method and divided into a plurality of cells, and then the glass substrate on which the organic EL structure is formed and the counter substrate are assembled to form a module.
- the process is performed to produce an OLED.
- the OLED obtained in this way does not have a problem in characteristics.
- Example 12 an LCD is manufactured using the glass laminate S1 obtained in Example 1.
- two glass laminates S1 are prepared, and silicon nitride, silicon oxide, and amorphous silicon are sequentially formed on the second main surface of the glass substrate in one glass laminate S1-1 by plasma CVD.
- low concentration boron is implanted into the amorphous silicon layer by an ion doping apparatus, and heat treatment is performed in a nitrogen atmosphere to perform dehydrogenation treatment.
- 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 S1-2 is heat-treated in an air atmosphere.
- a chromium film is formed on the second main surface of the glass substrate in the glass laminate S1 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 sheets S1-1 on which the pixel electrodes are formed are used. The second main surface sides of the glass substrates of the glass laminate S1 are bonded together, and an LCD panel is obtained by ultraviolet curing and thermal curing.
- the second main surface of the supporting substrate of the glass laminate S1-1 is vacuum-adsorbed on a surface plate, and a thickness of 0. 0 is formed at the interface between the glass substrate and the resin layer at the corner of the glass laminate S1-2.
- a 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 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 water is being supplied to the separation front while spraying a static elimination fluid from the ionizer toward the formed gap.
- the suction pad is raised after the second main surface of the supporting base material of the glass laminate S1-2 is sucked by the vacuum suction pad.
- the suction pad is raised after the second main surface of the supporting base material of the glass laminate S1-2 is sucked by the vacuum suction pad.
- the second main surface of the glass substrate on which the color filter is formed on the first main surface is vacuum-sucked on a surface plate, and a thick portion is formed at the interface between the glass substrate and the resin layer at the corner of the glass laminate S1-1.
- a stainless steel knife having a thickness of 0.1 mm is inserted to give an opportunity for peeling between the first main surface of the glass substrate and the peelable surface of the resin layer.
- the suction pad is raised while spraying water between the glass substrate and the resin layer.
- a plurality of LCD cells composed of a glass substrate having a thickness of 0.1 mm are obtained.
- an OLED is manufactured using the glass laminate S1 obtained in Example 1.
- molybdenum was formed into a film by sputtering method on the 2nd main surface of the glass substrate in glass laminated body S1, and the gate electrode was formed by the etching using the photolithographic method.
- an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a gate insulating film, and subsequently an indium gallium zinc oxide film is formed by a sputtering method.
- An oxide semiconductor layer was formed by etching.
- an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a channel protective layer.
- a molybdenum film is formed by a sputtering method, and etching is performed using a photolithography method.
- a source electrode and a drain electrode were formed.
- heat treatment is performed in the atmosphere.
- an aluminum oxide film is further formed on the second main surface side of the glass substrate by a sputtering method to form a passivation layer.
- indium tin oxide is formed by a sputtering method, and etching is performed using a photolithography method.
- a pixel electrode is formed.
- panel B a glass laminate S1 having an organic EL structure on the glass substrate
- panel B is an electronic device according to the present invention. It is a laminated body with a member for devices (panel for display devices with a supporting substrate).
- a stainless steel knife having a thickness of 0.1 mm is inserted into the interface between the glass substrate and the resin layer at the corner of panel B, and the glass substrate Gives the interface between the resin layer and the 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 continuing to spray a static eliminating fluid from the ionizer toward the formed gap, and while water is inserted into the peeling front.
- the separated glass substrate is cut using a laser cutter or a scribe-break method and divided into a plurality of cells, and then the glass substrate on which the organic EL structure is formed and the counter substrate are assembled to form a module.
- the process is performed to produce an OLED.
- the OLED obtained in this way does not have a problem in characteristics.
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Abstract
Description
最近では、上記の課題に対応するため、薄板ガラス基板と補強板とを積層したガラス積層体を用意し、ガラス積層体の薄板ガラス基板上に表示装置などの電子デバイス用部材を形成した後、薄板ガラス基板から支持板を分離する方法が提案されている(例えば、特許文献1参照)。補強板は、支持板と、該支持板上に固定されたシリコーン樹脂層とを有し、シリコーン樹脂層と薄板ガラス基板とが剥離可能に密着される。ガラス積層体のシリコーン樹脂層と薄板ガラス基板の界面が剥離され、薄板ガラス基板から分離された補強板は、新たな薄板ガラス基板と積層され、ガラス積層体として再利用することが可能である。
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に記載のガラス積層体に対して450℃、1時間の処理を行った場合、ガラス基板と支持基板とを分離しようとする際に、ガラス基板がシリコーン樹脂層表面から剥がれず、無理に剥がそうとするとガラス基板の一部が破壊され、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。
また、特許文献1に記載のガラス積層体中のシリコーン樹脂層は、450℃においては短時間のうちに分解が起こり、多量のアウトガスが発生する。このようなアウトガスの発生は、ガラス基板上に形成される電子デバイス用部材を汚染し、結果として電子デバイスの生産性を低下させる原因となる。
すなわち、本発明は、支持基材の層とシリコーン樹脂層とガラス基板の層とをこの順で備え、シリコーン樹脂層中のシリコーン樹脂が、後述するT3で表されるオルガノシロキシ単位を有し、全オルガノシロキシ単位に対するT3で表されるオルガノシロキシ単位の合計割合が80~100モル%であり、T3中のRがフェニル基であるオルガノシロキシ単位(A-1)と、T3中のRがメチル基であるオルガノシロキシ単位(B-1)とのモル比((A-1)/(B-1))が80/20~20/80であり、シリコーン樹脂層のガラス基板の層に対する界面の剥離強度とシリコーン樹脂層の支持基材の層に対する界面の剥離強度とが異なる、ガラス積層体である。
本発明において、シリコーン樹脂が、さらに、後述するQで表されるオルガノシロキシ単位を有することが好ましい。
本発明において、シリコーン樹脂が硬化性オルガノポリシロキサンの硬化物であり、該硬化性オルガノポリシロキサンが、後述するT1~T3で表されるオルガノシロキシ単位を、単位の個数の割合(モル量)で、T1:T2:T3=0~5:20~50:50~80(ただし、T1+T2+T3=100の関係を満たす)の割合で含むオルガノポリシロキサンであることが好ましい。
本発明において、硬化性オルガノポリシロキサンの数平均分子量が500~2000であることが好ましい。
本発明において、硬化性オルガノポリシロキサンの質量平均分子量/数平均分子量が1.00~2.00であることが好ましい。
本発明において、動的光散乱法により測定した硬化性オルガノポリシロキサンの粒子径が0.5~100nmであることが好ましい。
本発明において、硬化性オルガノポリシロキサンが、フェニルトリクロロシランおよびメチルトリクロロシランを、加水分解することにより得られるオルガノポリシロキサンであることが好ましい。
本発明において、シリコーン樹脂層の厚みが0.1~30μmであることが好ましい。
本発明において、支持基材がガラス板であることが好ましい。
本発明において、シリコーン樹脂層のガラス基板の層に対する界面の剥離強度が、シリコーン樹脂層の支持基材の層に対する界面の剥離強度よりも低いことが好ましい。この態様の本発明を、以下、第1の態様ともいう。
また、本発明において、シリコーン樹脂層のガラス基板の層に対する界面の剥離強度が、シリコーン樹脂層の支持基材の層に対する界面の剥離強度よりも高いことが好ましい。この態様の本発明を、以下、第2の態様ともいう。
また、本発明者らは、高温加熱処理後のガラス積層体においてガラス基板と支持基板とが分離しづらくなる理由について検討を行ったところ、シリコーン樹脂層表面上に含まれる官能基が影響していることを見出した。例えば、シリコーン樹脂層表面にSi-Me基が含まれている場合、該基は250℃以上の高温加熱処理後に比較的Si-OH基になりやすい。そのため、シリコーン樹脂層中に含まれるSi-Me基の量が多すぎると、高温加熱処理後に多くのSi-OH基がシリコーン樹脂層表面に現れ、隣接する基板(例えば、ガラス基板)との結合力が増加し、結果としてシリコーン樹脂層と該シリコーン樹脂層に隣接する基板との剥離がしづらくなる。一方、Si-Ph基は比較的Si-OH基への変換が起こりにくい。しかし、Si-Ph基が多すぎると、置換基の立体障害のため、硬化性オルガノポリシロキサンの架橋硬化が十分に進行しづらく、シリコーン樹脂層の架橋度が低下する。そのため、シリコーン樹脂層の機械的強度が低下したり、シリコーン樹脂層の表面にオルガノポリシロキサン由来の未反応Si-OH基が残存したりするので、結果としてガラス基板の剥離性が劣る。本発明者は、上記のような知見をもとに、上記モル比((A-1)/(B-1))を調整することにより、高温加熱処理後もガラス基板が剥離しやすいシリコーン樹脂層の組成を見出している。
以下では、第1の実施態様および第2の実施態様に分けて、説明する。
図1は、本発明に係るガラス積層体の第1の実施態様の模式的断面図である。
図1に示すように、ガラス積層体10は、支持基材12の層とガラス基板16の層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の層に接すると共に、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。
支持基材12の層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の層およびシリコーン樹脂層14からなる2層部分を樹脂層付き支持基材18という。
ガラス積層体10においては、上記剥離強度(x)は上記剥離強度(y)よりも高い。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、ガラス積層体10は、シリコーン樹脂層14とガラス基板16との界面で剥離して、ガラス基板16と樹脂層付き支持基材18とに分離する。
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、後述する硬化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、架橋硬化後のシリコーン樹脂のガラス基板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を積層することにより、ガラス積層体10を製造することができる。
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。
なお、後述するように支持基材12は、2種以上の層からなる積層体であってもよい。
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)に規定されている線膨張係数が用いられる。
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。
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14aは、ガラス基板16の第1主面16aに密着する。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。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。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)よりも低いことが好ましい。
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の層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。
シリコーン樹脂層14と支持基材12の層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。
上記厚さは平均厚さを意図し、5点以上の任意の位置におけるシリコーン樹脂層14の厚みを接触式膜厚測定装置で測定し、それらを算術平均したものである。
シリコーン樹脂層14のガラス基板16側の表面の表面粗さRaは特に制限されないが、ガラス基板16の積層性および剥離性がより優れる点より、0.1~20nmが好ましく、0.1~10nmがより好ましい。
なお、表面粗さRaの測定方法としては、JIS B 0601-2001に準じて行われ、任意の5箇所以上の点において測定されたRaを、算術平均した値が上記表面粗さRaに該当する。
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」は全てのシリコーン樹脂層の合計の厚さを意味するものとする。
本発明における硬化性オルガノポリシロキサンは、モノマーである加水分解性オルガノシラン化合物の混合物(モノマー混合物)を部分加水分解縮合反応させて得られる部分加水分解縮合物(オルガノポリシロキサン)である。また、部分加水分解縮合物は未反応のモノマーを含有していてもよい。
硬化性オルガノポリシロキサンを架橋硬化させるためには、通常加熱により架橋反応を進めて硬化させる(すなわち、熱硬化させる)。そして、硬化性オルガノポリシロキサンを熱硬化させることにより、シリコーン樹脂が得られる。ただし、硬化に必ずしも加熱を必要としない場合もあり、室温硬化させることもできる。
なお、以下の説明において、他のケイ素原子に結合した酸素原子O*は、2個のケイ素原子間を結合する酸素原子であり、Si-O-Siで表される結合中の酸素原子を意図する。したがって、O*は、2つのオルガノシロキシ単位のケイ素原子間に1個存在する。
しかし、本明細書においては、他のケイ素原子に結合した酸素原子O*の一部または全部の代わりに、他のケイ素原子に結合できる官能基を有する場合もT単位とみなす。他のケイ素原子に結合できる官能基は、水酸基または加水分解により水酸基となる基(以下、加水分解性基という)である。より具体的には、本明細書において、T単位は、他のケイ素原子に結合した酸素原子O*と他のケイ素原子に結合できる官能基との合計が3個であり、他のケイ素原子に結合した酸素原子O*と他のケイ素原子に結合できる官能基の数の違いにより、T単位はT1単位、T2単位、T3単位と呼ばれる3種の単位に分類される。T1単位は他のケイ素原子に結合した酸素原子O*の数が1個、T2単位はその酸素原子O*の数が2個、T3単位はその酸素原子O*の数が3個である。なお、本明細書においては、他のケイ素原子に結合できる1価の官能基をZで表す。
シリコーン樹脂層14を構成するシリコーン樹脂は、T3で表されるオルガノシロキシ単位(以後、単にT3単位とも称する)を有し、全オルガノシロキシ単位に対するT3で表されるオルガノシロキシ単位の合計割合が80~100モル%であり、得られるシリコーン樹脂層14の耐熱性が優れ、ガラス基板16の剥離がより容易に進行する点で、82~100モル%が好ましく、85~100モル%がより好ましい。つまり、シリコーン樹脂は、T3で表されるオルガノシロキシ単位を主成分として含む。
T3:R-SiO3/2
式中、Rは、フェニル基またはメチル基を表す。
なかでも、剥離時にシリコーン樹脂層14の凝集破壊がなく、シリコーン樹脂層14の機械的強度に優れ、ガラス基板16の剥離性がより優れる点で、下記のQで表されるオルガノシロキシ単位(いわゆる、Q単位)を含むことが好ましい。Q単位の含有量は特に制限されないが、全オルガノシロキシ単位に対して、1モル%以上が好ましく、5モル%以上がより好ましい。上限は特に制限されないが、架橋度が増すことでシリコーン樹脂層14の脆性が低下し、シリコーン樹脂層14が剥離時に凝集破壊を伴って起こすおそれがある点、また、硬化収縮に伴う収縮応力の増大によるガラス複合体の反りが引き起こされるおそれがある点で、20モル%以下が好ましい。
Q:SiO4/2
なお、上記全オルガノシロキシ単位とは、シリコーン樹脂中に含まれるM単位、D単位、T単位、および、Q単位の合計を意図する。M単位、D単位、T単位(T1~T3単位)、Q単位の数(モル量)の割合は、29Si-NMRによるピーク面積比の値から計算できる。
Rがフェニル基であるオルガノシロキシ単位(A-1)とは、以下P-T3で表されるオルガノシロキシ単位を意図する。Phはフェニル基を表す。
P-T3:Ph-SiO3/2
また、Rがメチル基であるオルガノシロキシ単位(B-1)とは、以下M-T3で表されるオルガノシロキシ単位を意図する。
M-T3:Me-SiO3/2
上述したように、硬化処理により上記シリコーン樹脂となり得る硬化性オルガノポリシロキサンとしては、例えば、モノマーである加水分解性オルガノシラン化合物の混合物を部分加水分解縮合反応させて得られる部分加水分解縮合物(オルガノポリシロキサン)が使用される。該モノマーとしては、より具体的には、(Me-)Si(-Z)3で表される加水分解性オルガノシラン化合物と、(Ph-)Si(-Z)3で表される加水分解性オルガノシラン化合物とが使用される。なお、Z基は水酸基または加水分解性基を示し、例えば、加水分解性基としては、塩素原子などのハロゲン原子、アルコキシ基、アシル基、アミノ基、アルコキシアルコキシ基などが挙げられる。
なお、加水分解縮合反応はTモノマーからT1単位が生成し、T1単位からT2単位が生成し、T2単位からT3単位が生成する反応である。加水分解性基の1個以上が水酸基に変換されたTモノマーからT1単位が生成する縮合反応、T1単位からT2単位が生成する縮合反応、T2単位からT3単位が生成する縮合反応、の反応速度はこの順に遅くなると考えられる。加水分解性基の加水分解反応を考慮しても、反応が進むにしたがって各単位の存在量のピークはTモノマーからT3単位へ移動していくと考えられる。反応条件が比較的温和である場合には存在量のピークの移動は比較的整然と進行すると考えられる。
使用される加水分解性オルガノシラン化合物としては、上述した(Me-)Si(-Z)3で表される加水分解性オルガノシラン化合物と、(Ph-)Si(-Z)3で表される加水分解性オルガノシラン化合物とが挙げられるが、なかでも、得られる硬化性オルガノポリシロキサンの取扱い性に優れ、耐熱性が高く、ガラス基板16をより容易に剥離できる点で、フェニルトリクロロシラン(下記式(1)で表わされる化合物)およびメチルトリクロロシラン(下記式(2)で表わされる化合物)を使用することが好ましい。なお、式(1)中のPhはフェニル基を表す。
上記硬化性オルガノポリシロキサンの好適態様の一つとしては、下記T1~T3で表されるオルガノシロキシ単位の少なくともいずれか1つを有し、全オルガノシロキシ単位に対する下記T1~T3で表されるオルガノシロキシ単位の合計割合が80~100モル%であり、下記T1~T3中のRがフェニル基であるオルガノシロキシ単位(A-2)と、下記T1~T3中のRがメチル基であるオルガノシロキシ単位(B-2)とのモル比((A-2)/(B-2))が80/20~20/80であるオルガノポリシロキサン(以後、オルガノポリシロキサンXとも称する)が挙げられる。該オルガノポリシロキサンであれば、容易に所望のシリコーン樹脂が得られる。
T1:R-Si(-OX)2O1/2
T2:R-Si(-OX)O2/2
T3:R-SiO3/2
なお、式中、Rは、フェニル基またはメチル基を表す。Xは、水素原子または炭素数1~6のアルキル基を表す。
上記式におけるRは1種に限定されず、T1、T2、T3はそれぞれRが異なっていてもよい。
また、-OXはT1単位およびT2単位の間で同一であっても異なっていてもよい。T1単位における2つの-OXは異なっていてもよく、例えば、一方が水酸基で他方がアルコキシ基であってもよい。また、2つの-OXがいずれもアルコキシ基である場合、それらのアルコキシ基は異なるアルコキシ基であってもよい。
オルガノポリシロキサンX中のT1~T3の単位は、核磁気共鳴分析(29Si-NMR)によりケイ素原子の結合状態を測定して解析できる。T0~T3の単位の数(モル量)の比は、29Si-NMRのピーク面積比から求める。
なお、オルガノポリシロキサンXの質量平均分子量Mw、数平均分子量Mn、および分散度Mw/Mnは、ゲルパーミエーションクロマトグラフィー法により、ポリスチレンを標準物質として測定した値をいう。このようなオルガノポリシロキサンXの特性は、分子1個の特性をいうものではなく、各分子の平均の特性として求められるものである。
なお、オルガノポリシロキサンXにおいては、取扱い性の点から、上記T3単位が少なくとも含まれることが好ましく、上記T2単位およびT3単位が少なくとも含まれることがより好ましい。種々検討の結果、Ph基(フェニル基)が多くなると、T1単位の割合が多くなることが分かっている。T1単位が多くなると、シリコーン樹脂層作製過程における硬化時に収縮応力が大きくため、T1単位が少ないほうが、収縮応力が低下でき、より好ましい。
また、オルガノポリシロキサンXは、上記T1~T3で表されるオルガノシロキシ単位以外に他の単位を含んでいてもよく、他の単位としてはM単位、D単位、および、Q単位が挙げられる。
T体の硬化性オルガノポリシロキサンとしては、一般的にポリフェニルポリシロキサン、ポリメチルポリシロキサンなどが知られているが、シラノール末端ポリフェニルポリシロキサンはPhSiCl3を加水分解した時に、分子量数百~数千程度のオリゴマーとして得られる。このオリゴマーを用いて0.1mm厚以上の硬化物を作製すると、非常に脆弱であり使用に耐えない。しかしながら、耐熱性に優れたシリコーン樹脂となる。
一方、ケイ素原子上の置換基がメチル基などの脂肪族炭化水素基の場合には、シラノール末端を与えるRSiZ3タイプのモノマーの反応性が高く、得られる加水分解-縮合物の分子量はほとんどの場合1万以上となってしまう。そのため溶媒への溶解性が悪く、該縮合物を溶解させるには大量の溶媒が必要であり、コーティング用途などの薄膜は得られるが、ある程度厚みを持った硬化物はクラックの発生等のため得ることは困難である。
そこで、耐熱性と反応性を両立させ、溶解性を向上させた、上記硬化性オルガノポリシロキサンXの使用が好ましい。
Rがフェニル基であるオルガノシロキシ単位(A-2)とは、Rがフェニル基であるT1単位(以下のP-T1)、Rがフェニル基であるT2単位(以下のP-T2)、および、Rがフェニル基であるT3単位(以下のP-T3)を含む概念を意図する。以下、式P-T1~P-T3中、Phはフェニル基を表す。
P-T1:Ph-Si(-OX)2O1/2
P-T2:Ph-Si(-OX)O2/2
P-T3:Ph-SiO3/2
従って、上記オルガノシロキシ単位(A-2)の含有量は、上記P-T1で表される単位の含有量、上記P-T2で表される単位の含有量、および、上記P-T3で表される単位の含有量の合計量を意図する。
また、Rがメチル基であるオルガノシロキシ単位(B-2)とは、Rがメチル基であるT1単位(以下のM-T1)、Rがメチル基であるT2単位(以下のM-T2)、および、Rがメチル基であるT3単位(以下のM-T3)を含む概念を意図する。以下、式M-T1~M-T3中、Meはメチル基を表す。
M-T1:Me-Si(-OX)2O1/2
M-T2:Me-Si(-OX)O2/2
M-T3:Me-SiO3/2
従って、上記オルガノシロキシ単位(B-2)の含有量は、上記M-T1で表される単位の含有量、上記M-T2で表される単位の含有量、および、上記M-T3で表される単位の含有量の合計量を意図する。
また、硬化性オルガノポリシロキサン(特に、上記硬化性オルガノポリシロキサンX)の質量平均分子量/数平均分子量は、硬化性オルガノポリシロキサンの溶解性に優れ、異物欠陥の少ないシリコーン樹脂層14が作製できる、または、ガラス基板16をより容易に剥離できる点で、1.00~2.00が好ましく、1.00~1.70がより好ましく、1.00~1.50がさらに好ましい。
硬化性オルガノポリシロキサン(特に、上記硬化性オルガノポリシロキサンX)の分子量の調節は、反応条件を制御することにより行うことができる。例えば、硬化性オリゴマーを製造する際の溶媒量を調節し、加水分解性オルガノシラン化合物の濃度を高くすると高分子量物が得られ、濃度を低くすると低分子量物が得られる。
この場合、動的光散乱法により測定した硬化性オルガノポリシロキサン(特に、上記硬化性オルガノポリシロキサンX)の粒子径は特に制限されないが、異物欠陥の少ない当該シリコーン樹脂層が作製できる、または、ガラス基板16をより容易に剥離できる点で、0.5~100nmが好ましく、0.5nm以上40nm未満がより好ましい。
なお、上記動的光散乱法の測定方法としては、硬化性オルガノポリシロキサン(特に、上記硬化性オルガノポリシロキサンX)をPEGMEA溶液(プロピレングリコール-1-モノメチルエーテル-2-アセタート)に20質量%となるように調整してサンプルを作製し、濃厚系粒径アナライザー(大塚電子社製、FPAR-1000)を用いて、ヒストグラム平均粒子径(D50)を求め、粒子径とする。
なお、硬化性オルガノポリシロキサンを用いてシリコーン樹脂層を形成する手順に関しては、後段において詳述する。
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ないが、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表面上でシリコーン樹脂層14を形成する方法が好ましい。なかでも、硬化性オルガノポリシロキサンを支持基材12の表面に塗布し、支持基材12表面上でシリコーン樹脂層14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を製造する方法が好ましい。
硬化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、硬化性オルガノポリシロキサンの層を支持基材12の表面に形成し、支持基材12表面上でシリコーン樹脂層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。
樹脂層形成工程では、硬化性オルガノポリシロキサンの層を支持基材12の表面に形成し、支持基材12表面上でシリコーン樹脂層14を形成する。
支持基材12上に硬化性オルガノポリシロキサンの層を形成するためには、硬化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(上記硬化性オルガノポリシロキサンを含む組成物に該当)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、次いで硬化処理を施してシリコーン樹脂層14とすることが好ましい。
硬化の方法は特に制限されないが、通常、熱硬化処理により行われる。
熱硬化させる温度条件は、シリコーン樹脂層14の耐熱性を向上し、ガラス基板16と積層後の剥離強度(y)を上記のように制御しうる範囲内で特に制限されないが、150~550℃が好ましく、200~450℃がより好ましい。また、加熱時間は、通常、10~300分が好ましく、20~120分がより好ましい。なお、加熱条件は、温度条件を変えて段階的に実施してもよい。
上記温度範囲および、加熱時間の範囲とすることにより、T1単位、T2単位およびT3単位、さらに250℃以上の加熱によって生成しやすいQ単位の生成割合を制御することができる。
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の層とシリコーン樹脂層14とガラス基板16の層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。
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の層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。
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。
例えば、シリコーン樹脂層14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、上記硬化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、硬化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の間で架橋物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。
本発明の第1の態様であるガラス積層体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、450℃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。
図3は、本発明に係るガラス積層体の第2の実施態様の模式的断面図である。
図3に示すように、ガラス積層体100は、支持基材12の層とガラス基板16の層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。
図3に示すガラス積層体100においては、上述した図1に示すガラス積層体10とは異なり、シリコーン樹脂層14はガラス基板16上に固定されており、樹脂層付きガラス基板20は、樹脂層付きガラス基板20中のシリコーン樹脂層14が支持基材12に直接接するように、支持基材12上に剥離可能に積層(密着)する。該固定と剥離可能な密着は剥離強度(すなわち、剥離に要する応力)に違いがあり、固定は密着に対し剥離強度が高いことを意味する。つまり、ガラス積層体100においては、シリコーン樹脂層14とガラス基板16との界面の剥離強度が、シリコーン樹脂層14と支持基材12との界面の剥離強度よりも高い。
ガラス積層体100においては、上記剥離強度(z)は上記剥離強度(w)よりも高い。したがって、ガラス積層体100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100は、シリコーン樹脂層14と支持基材12との界面で剥離して、樹脂層付きガラス基板20と支持基材12とに分離する。
ガラス基板16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、上述した硬化性オルガノポリシロキサンをガラス基板16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、ガラス基板16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、架橋硬化後のシリコーン樹脂の支持基材12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、ガラス基板16上でシリコーン樹脂層14を形成し、その後シリコーン樹脂層14の面に支持基材12を積層することにより、ガラス積層体100を製造することができる。
ただし、シリコーン樹脂層14の支持基材12側の表面の表面粗さRaは特に制限されないが、ガラス基板16の積層性および剥離性がより優れる点より、0.1~20nmが好ましく、0.1~10nmがより好ましい。
なお、表面粗さRaの測定方法としては、JIS B 0601-2001に準じて行われ、任意の5箇所以上の点において測定されたRaを、算術平均した値が上記表面粗さRaに該当する。
本発明においては、上述したガラス積層体(ガラス積層体10、または、ガラス積層体100)を用いて、電子デバイスを製造することができる。
以下では、上述したガラス積層体10を用いた態様について詳述する。
ガラス積層体10を用いることにより、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または樹脂層内部を剥離面として部材付きガラス基板と樹脂層付き支持基材とに分離する方法が好ましい。なお、必要に応じて、次いで、部材付きガラス基板の剥離面を清浄化することがより好ましい。
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樹脂層付き支持基材とに分離する工程を分離工程、部材付きガラス基板の剥離面を清浄化する工程を清浄化処理工程という。なお、上述したように、清浄化処理工程は、必要に応じて実施される任意の工程である。
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。
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22を形成し、電子デバイス用部材付き積層体24を得る。
まず、本工程で使用される電子デバイス用部材22について詳述し、その後工程の手順について詳述する。
電子デバイス用部材22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22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。
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。
上述した電子デバイス用部材付き積層体24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22を形成する。
なお、電子デバイス用部材22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。
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。
分離工程は、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24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22が積層したガラス基板16(部材付きガラス基板)と、シリコーン樹脂層14および支持基材12とに分離して、電子デバイス用部材22およびガラス基板16を含む部材付きガラス基板26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22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。
また、樹脂層付き支持基材18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。
清浄化処理工程は、上記分離工程で得られた部材付きガラス基板26中のガラス基板16の剥離面(第1主面16a)に清浄化処理を施す工程である。該工程を実施することにより、剥離面に付着したシリコーン樹脂やシリコーン樹脂層、剥離面に付着した上記部材形成工程で発生する金属片やホコリなどの不純物を除去することができ、剥離面の清浄性を維持することができる。結果として、ガラス基板16の剥離面に貼り付けられる位相差フィルムや偏光フィルムなどの粘着性が向上する。
なお、ガラス積層体100を使用した場合は、上記分離工程の際に、支持基材12とシリコーン樹脂層14との界面を剥離面として、支持基材12と、シリコーン樹脂層14、ガラス基板16、および、電子デバイス用部材22を含む電子デバイスとに分離される。
(1)硬化性オルガノポリシロキサン中のケイ素原子の結合状態の解析(T単位の割合)
核磁気共鳴分析装置(溶液29Si-NMR:JEOL RESONANCE株式会社製、ECP400)を用いてT1~T3の比を求めた。
T1(Me基):-44~-49ppm、T1(Ph基):-60~-61ppm
T2(Me基):-50~-60ppm、T2(Ph基):-67~-74ppm
T3(Me基):-61~-67ppm、T3(Ph基):-74~-83ppm
(2)硬化性オルガノポリシロキサン中のフェニル基モル%/メチル基モル%(上記(A-2)/(B-2)組成比の解析
核磁気共鳴分析装置(溶液1H-NMR:JEOL RESONANCE株式会社製、ECP400)を用いてフェニル基モル%/メチル基モル%(上記(A-2)/(B-2)組成比を求めた。
A-2(Ph基):8.2~6.4ppm
B-2(Me基):0.6~-0.7ppm
ゲルパーミエーションクロマトグラフィー(GPC、東ソー社製のHLC8220、RI検出、カラム:TSK-GEL SuperHZ、溶離液:テトラヒドロフラン)によって求めた。
硬化性オルガノポリシロキサンを20質量%のPGMEA(プロピレングリコール-1-モノメチルエーテル-2-アセタート)溶液とし、濃厚系粒径アナライザー(大塚電子社製、FPAR-1000)を用いて、ヒストグラム平均粒子径(D50)を求め、粒子径とした。
還流冷却管、滴下ロート、および攪拌機を備えた反応容器に、炭酸ナトリウム(12.7g、0.12モル)と水(80mL)を入れて撹拌し、その後さらにメチルイソブチルケトン(80mL)を加えて、反応溶液を得た。次いで、メチルトリクロロシラン(7.5g、0.05モル)およびフェニルトリクロロシラン(10.6g、0.05モル)を滴下ロートから30分かけて反応溶液に滴下した。この際、反応溶液の温度を40℃まで上昇させた。次に、滴下終了後、60℃の油浴に反応容器を浸漬し、24時間加熱撹拌した。反応終了後、有機相を洗浄水が中性となるまで洗浄し、次いで、乾燥剤を用いて有機相を乾燥した。次に、乾燥剤を除去した後、溶媒を減圧で留去し、さらに一夜真空乾燥を行い、白色の固体(硬化性オルガノポリシロキサン(U1))を得た。
硬化性オルガノポリシロキサン(U2)~(U8)について、製造例1と同様にして、表1に示す組成比で製造した。なお、(U4)に関しては反応時間を24時間から1時間に、(U6)に関しては反応時間を24時間から3時間に調整した以外は、製造例1と同様の手順で製造した。さらに(U5)は、(U4)を製造したのち、50質量%のメタノール溶液とし、固形分に対して2質量%の酢酸を加えた後、再度溶媒を減圧で留去し、白色の固体として得たものである。
また、「T単位の割合」欄では、得られた硬化性オルガノポリシロキサン中における、T1~T3の各単位の個数の割合(モル%)を示し、T1~T3各単位の個数の割合の合計が100となるように示す。
「粒子径」欄は、上述した動的光散乱法により測定した硬化性オルガノポリシロキサンの粒径であり、「<40」とは粒径が40nm未満であったことを意図し、「>100」とは粒径が100nm超であったことを意図する。
なお、上記各単位の含有量は、29Si-NMRや1H-NMRより算出した。
得られた硬化性オルガノポリシロキサン(U1)をPEGMEAに溶解させて硬化性オルガノポリシロキサン(U1)を含む液状物(固形分濃度:40質量%)を作製した(なお、硬化性オルガノポリシロキサンは表1に示す粒子径の微粒子として液状物中に存在した。)。
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、支持基材の第1主面上に縦278mmおよび横278mmの大きさで、硬化性オルガノポリシロキサン(U1)を含む液状物を、スピンコータにて塗工した(塗工量30g/m2)。
次に、これを350℃にて30分間大気中で加熱硬化して、支持基材の第1主面に厚さ2.8μmのシリコーン樹脂層を形成し、支持体A(樹脂層付き支持基材)を得た。
次に、支持体Aのシリコーン樹脂層の剥離性表面と、該シリコーン樹脂層と同じサイズで厚さ0.2mmのガラス基板(「AN100」。旭硝子株式会社製)の第1主面とを対向させて、室温下、大気圧下、積層装置にて両基板の重心が重なるように両基板を重ね合わせ、ガラス積層体S1を得た。
次に、得られたガラス積層体S1を用いた、以下の測定を実施した。以下の評価結果は、後述する表1にまとめて示す。
ガラス積層体S1から50mm角のサンプルを切り出し、このサンプルを450℃(窒素雰囲気下)に加熱した熱風オーブン内に載置し、60分の放置後、取り出した。次いで、ガラス積層体S1のガラス基板の第2主面を定盤に真空吸着させたうえで、ガラス積層体S1の1つ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、上記ガラス基板の第1主面と上記シリコーン樹脂層の剥離性表面との間に剥離のきっかけを与えた。そして、ガラス積層体S1の支持基材の第2主面を90mmピッチで複数の真空吸着パッドで吸着した上で、上記コーナー部に近い吸着パッドから順に上昇させることにより、ガラス基板の第1主面とシリコーン樹脂層の剥離性表面とを剥離した。
上記結果より、高温加熱処理後もガラス基板が剥離できることが確認された。
なお、シリコーン樹脂層の主要部は支持基材と共にガラス基板から分離され、該結果より、支持基材の層と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。
ガラス積層体S1から50mm角のサンプルを切り出し、このサンプルを450℃(窒素雰囲気下)に加熱した熱風オーブン内に載置し、60分の放置後、取り出してサンプル内に発泡または着色が確認されたかどうか評価した。
硬化性オルガノポリシロキサン(U1)を含む液状物の代わりに、下記表2に示す硬化性オルガノポリシロキサン(U2)~(U6)を含む液状物をそれぞれ使用し、熱硬化処理条件を変更した以外は、実施例1と同様の手順に従って、ガラス積層体S2~S10を製造した。
下記表2では、液状物を製造する際に使用した、溶媒の種類、および、固形分濃度などを示す。また、実施例7および8に関しては、加熱硬化の際の熱硬化処理条件を「350℃、30分」から、「150℃にて30分間大気中で加熱硬化して、その後さらに350℃にて60分間大気中で加熱硬化」に変更した。さらに、実施例9に関しては、加熱硬化の際の熱硬化処理条件を「350℃、30分」から、「150℃にて30分間大気中で加熱硬化して、その後さらに350℃にて60分間大気中で加熱硬化して、さらに500℃にて60分間大気中で加熱硬化」に変更した。
なお、得られたガラス積層体S2~S10は上述した図1のガラス積層体10に該当し、ガラス積層体S2~S10においては、支持基材の層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)よりも高かった。
また、得られたガラス積層体S2~S10を用いて、上記[剥離性評価]および[耐熱性評価]を実施した。結果を表2にまとめて示す。
硬化性オルガノポリシロキサン(U1)を含む液状物の代わりに、下記表2に示す硬化性オルガノポリシロキサン(U8)を含む液状物を使用した以外は、実施例1と同様の手順に従って、ガラス積層体C1の製造を行った。得られたガラス積層体C1を用いて、上記[剥離性評価]および[耐熱性評価]を実施した。結果を表2にまとめて示す。
硬化性オルガノポリシロキサン(U1)を含む液状物の代わりに、無溶媒付加反応型剥離紙用シリコーン(信越シリコーン社製 商品名 KNS-320A)100質量部と白金系触媒(信越シリコーン社製 商品名 CAT-PL-56)2質量部の混合物(U9)を使用した以外は、実施例1と同様の手順に従って、ガラス積層体C2を製造した。得られたガラス積層体C2を用いて、上記[剥離性評価]および[耐熱性評価]を実施した。結果を表2にまとめて示す。
なお、上記ガラス積層体C2の態様は、特許文献1に記載される態様に該当する。
また、「剥離性評価」欄において、ガラス基板とシリコーン樹脂層との界面にステンレス製刃物を差し込み、剥離のきっかけを与えた時点でガラス基板とシリコーン樹脂層との大部分が剥離し、ガラス基板を容易に剥離できた場合を「◎」、剥離のきっかけだけではガラス基板は剥離しないが、ガラス基板を剥離できる場合を「○」、ガラス基板を剥離できない、または、ガラス基板が破損する場合を「×」として示す。
さらに、「耐熱性評価」欄において、「着色」「発泡」がない場合は「なし」、ある場合は「有り」と示す。
また、表2中、「シリコーン樹脂層」欄においては、29Si-NMRによるピーク面積比より算出したT3単位およびQ単位のモル%を示す。
(1)シリコーン樹脂層のケイ素原子の結合状態の解析
核磁気共鳴分析装置(固体29Si-NMR:JEOL RESONANCE株式会社製、ECP600)を用いてT3単位およびQ単位の含有量(モル%)を求めた。
T3:-48~-88ppm
Q:-96~-116ppm
核磁気共鳴分析装置(固体1H-NMR:JEOL RESONANCE株式会社製、ECP600)を用いてPh基およびMe基に由来するピーク面積比から求めた。シリコーン樹脂層は、ガラス基材上に各実施例および比較例で使用する硬化性オルガノポリシロキサンを含む液状物を、スピンコータにて塗工し、各実施例および比較例の加熱条件にて加熱硬化して、ガラス基材にシリコーン樹脂層を形成後、該シリコーン樹脂層をカミソリ刃で削りとった固体サンプルを使用した。測定法にはDepth2を用い、測定条件はパルス幅2.3μsec、パルス繰り返しの待ち時間15sec、積算回数16scan、MAS回転速度22KHzとした。化学シフトの基準はアダマンタン由来のピークを1.7ppmとした。また、各構造に由来する固体1H-NMRの化学シフトは、以下のとおりである。
A-1(Ph基):18~4ppm
B-1(Me基):4~-10ppm
シリコーン樹脂層の膜厚は接触式膜圧装置の表面粗さ・輪郭形状測定機(東京精密社製 サーフコム1400G-12)を用いて測定した。
(4)シリコーン樹脂層の収縮応力
外径が4インチ、厚さが525±25μmのシリコンウエハのオリエンテーションフラットを基準とし、薄膜応力測定装置FLX-2320(KLA Tencor社製)内の所定位置に収容した後、周囲温度25℃で、シリコンウエハの曲率半径を計測した。
次に、シリコンウエハを取り出し、スピンコート法を用いて、シリコンウエハ上に各実施例および比較例で使用する硬化性オルガノポリシロキサンを含む液状物を塗布した後、各実施例および比較例の加熱条件にて加熱硬化して、シリコーン樹脂層を形成した。シリコーン系硬化被膜を形成する前と同様にして、周囲温度25℃で、シリコーン樹脂層が形成されたシリコンウエハの曲率半径を計測した。
なお、ガラス複合体S1~S9中のシリコーン樹脂層のオルガノシロキシ単位は、Q単位とT3単位とで構成されていた。上述した実施例10および比較例1においては、Q単位は検出されなかった(測定限界以下であった)。
一方、比較例1、2に示すように、所定の組成比のシリコーン樹脂層を用いていない場合は、所望の効果が得られなかった。
本例では、実施例1で得たガラス積層体S1を用いてOLEDを製造する。
まず、ガラス積層体S1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、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、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S1(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、かつ、水を剥離前線に差し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、樹脂層付き支持基材を剥離することができる。
続いて、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。
本例では、実施例1で得たガラス積層体S1を用いてLCDを製造する。
まず、2枚のガラス積層体S1を準備して、片方のガラス積層体S1-1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、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、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S1-2を大気雰囲気下、加熱処理する。次に、ガラス積層体S1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S1-1を用いて、2枚のガラス積層体S1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。
本例では、実施例1で得たガラス積層体S1を用いてOLEDを製造する。
まず、ガラス積層体S1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した。次に、スパッタリング法により、ガラス基板の第2主面側にさらに酸化アルミニウム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した。次に、スパッタリング法により、ガラス基板の第2主面側にさらに酸化アルミニウム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した。
次に、大気中で加熱処理を行う。次に、ガラス基板の第2主面側にさらにスパッタリング法により酸化アルミニウム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S1(以下、パネルB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Bの封止体側を定盤に真空吸着させたうえで、パネルBのコーナー部のガラス基板と樹脂層との界面に、厚さ0.1mmのステンレス製刃物を差し込み、ガラス基板と樹脂層の界面に剥離のきっかけを与える。そして、パネルB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、かつ、水を剥離前線に差し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、樹脂層付き支持基材を剥離することができる。
続いて、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。
なお、2014年2月7日に出願された日本特許出願2014-022697号の明細書、特許請求の範囲、要約書および図面の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
12 支持基材
14 シリコーン樹脂層
16 ガラス基板
18 樹脂層付き支持基材
20 樹脂層付きガラス基板
22 電子デバイス用部材
24 電子デバイス用部材付き積層体
26 部材付きガラス基板
Claims (11)
- 支持基材の層とシリコーン樹脂層とガラス基板の層とをこの順で備え、
前記シリコーン樹脂層中のシリコーン樹脂が、下記T3で表されるオルガノシロキシ単位を有し、全オルガノシロキシ単位に対する下記T3で表されるオルガノシロキシ単位の合計割合が80~100モル%であり、
下記T3中のRがフェニル基であるオルガノシロキシ単位(A-1)と、下記T3中のRがメチル基であるオルガノシロキシ単位(B-1)とのモル比((A-1)/(B-1))が80/20~20/80であり、
前記シリコーン樹脂層の前記ガラス基板の層に対する界面の剥離強度と前記シリコーン樹脂層の前記支持基材の層に対する界面の剥離強度とが異なる、ガラス積層体。
T3:R-SiO3/2
(式中、Rは、フェニル基またはメチル基を表す。) - 前記シリコーン樹脂が、さらに、下記Qで表されるオルガノシロキシ単位を有する、請求項1に記載のガラス積層体。
Q:SiO4/2 - 前記シリコーン樹脂が、硬化性オルガノポリシロキサンの硬化物であり、
前記硬化性オルガノポリシロキサンが、下記T1~T3で表されるオルガノシロキシ単位を、前記単位の個数の割合(モル量)で、T1:T2:T3=0~5:20~50:50~80(ただし、T1+T2+T3=100の関係を満たす)の割合で含むオルガノポリシロキサンである、請求項1または2に記載のガラス積層体。
T1:R-Si(-OX)2O1/2
T2:R-Si(-OX)O2/2
T3:R-SiO3/2
(式中、Rは、フェニル基またはメチル基を表す。Xは、水素原子または炭素数1~6のアルキル基を表す。) - 前記硬化性オルガノポリシロキサンの数平均分子量が500~2000である、請求項3に記載のガラス積層体。
- 前記硬化性オルガノポリシロキサンの質量平均分子量/数平均分子量が1.00~2.00である、請求項3または4に記載のガラス積層体。
- 動的光散乱法により測定した前記硬化性オルガノポリシロキサンの粒子径が0.5~100nmである、請求項3~5のいずれか1項に記載のガラス積層体。
- 前記硬化性オルガノポリシロキサンが、フェニルトリクロロシランおよびメチルトリクロロシランを共加水分解縮合することにより得られるオルガノポリシロキサンである、請求項3~6のいずれか1項に記載のガラス積層体。
- 前記シリコーン樹脂層の厚みが0.1~30μmである、請求項1~7のいずれか1項に記載にガラス積層体。
- 前記支持基材がガラス板である、請求項1~8のいずれか1項に記載のガラス積層体。
- 前記シリコーン樹脂層の前記ガラス基板の層に対する界面の剥離強度が、前記シリコーン樹脂層の前記支持基材の層に対する界面の剥離強度よりも低い、請求項1~9のいずれか1項に記載のガラス積層体。
- 前記シリコーン樹脂層の前記ガラス基板の層に対する界面の剥離強度が、前記シリコーン樹脂層の前記支持基材の層に対する界面の剥離強度よりも高い、請求項1~9のいずれか1項に記載のガラス積層体。
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KR20160119080A (ko) | 2016-10-12 |
TWI647114B (zh) | 2019-01-11 |
CN105980150A (zh) | 2016-09-28 |
TW201534480A (zh) | 2015-09-16 |
CN105980150B (zh) | 2018-01-30 |
JP6443350B2 (ja) | 2018-12-26 |
JPWO2015119210A1 (ja) | 2017-03-23 |
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