TW201442859A - 積層體 - Google Patents

積層體 Download PDF

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Publication number
TW201442859A
TW201442859A TW103126680A TW103126680A TW201442859A TW 201442859 A TW201442859 A TW 201442859A TW 103126680 A TW103126680 A TW 103126680A TW 103126680 A TW103126680 A TW 103126680A TW 201442859 A TW201442859 A TW 201442859A
Authority
TW
Taiwan
Prior art keywords
thermoplastic resin
solvent
transparent substrate
layer
inorganic glass
Prior art date
Application number
TW103126680A
Other languages
English (en)
Inventor
Daisuke Hattori
Takeshi Murashige
Tadayuki Kameyama
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of TW201442859A publication Critical patent/TW201442859A/zh

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/481—Non-reactive adhesives, e.g. physically hardening adhesives
    • B29C65/482—Drying adhesives, e.g. solvent based adhesives
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73117—Tg, i.e. glass transition temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7318—Permeability to gases or liquids
    • B29C66/73181—Permeability to gases or liquids permeable
    • B29C66/73183—Permeability to gases or liquids permeable to liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/733—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence
    • B29C66/7336—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence at least one of the parts to be joined being opaque, transparent or translucent to visible light
    • B29C66/73365—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the optical properties of the material of the parts to be joined, e.g. fluorescence, phosphorescence at least one of the parts to be joined being opaque, transparent or translucent to visible light at least one of the parts to be joined being transparent or translucent to visible light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/735—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the extensive physical properties of the parts to be joined
    • B29C66/7352—Thickness, e.g. very thin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/74—Joining plastics material to non-plastics material
    • B29C66/746—Joining plastics material to non-plastics material to inorganic materials not provided for in groups B29C66/742 - B29C66/744
    • B29C66/7465—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83421—Roller, cylinder or drum types; Band or belt types; Ball types band or belt types
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83421—Roller, cylinder or drum types; Band or belt types; Ball types band or belt types
    • B29C66/83423—Roller, cylinder or drum types; Band or belt types; Ball types band or belt types cooperating bands or belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91431—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being kept constant over time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9161—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux
    • B29C66/91641—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time
    • B29C66/91643—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time following a heat-time profile
    • B29C66/91645—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux the heat or the thermal flux being non-constant over time following a heat-time profile by steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/94—Measuring or controlling the joining process by measuring or controlling the time
    • B29C66/944—Measuring or controlling the joining process by measuring or controlling the time by controlling or regulating the time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/94—Measuring or controlling the joining process by measuring or controlling the time
    • B29C66/949—Measuring or controlling the joining process by measuring or controlling the time characterised by specific time values or ranges
    • 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
    • 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
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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Abstract

本發明提供一種彎曲性、可撓性、耐衝擊性以及外觀優異之透明基板之製造方法。本發明之透明基板之製造方法包含：步驟A，於具有溶劑透過性之支撐基材上塗佈熱塑性樹脂(A)組合物溶液而形成塗佈層；步驟B，將無機玻璃之至少一個面與該塗佈層經由接著劑組合物而貼合，形成積層體；步驟C，對該積層體實施第1熱處理，使該塗佈層中之殘存溶劑量減少至特定量；及步驟D，將該支撐基材自該積層體上剝離後，進行第2熱處理，使該塗佈層乾燥而形成熱塑性樹脂層。

Description

積層體
本發明係關於一種透明基板之製造方法。
近年來，由於影像通信技術之發展，如平面顯示器(FPD；例如液晶顯示裝置、有機EL顯示裝置)這樣的顯示裝置以及太陽電池不斷推進輕量、薄型化。於先前，於顯示裝置以及太陽電池中所使用之基板中，在多數情況下使用玻璃基板。玻璃基板之透明性或耐溶劑性、阻氣性、耐熱性優異。然而，若實現構成玻璃基板之玻璃的薄型化，則雖然輕量化之同時可撓性亦優異，但產生如下之問題：耐衝擊性變得不充分，操作變困難。
為了使薄型玻璃基板之操作性提高，提出了：於玻璃表面塗佈樹脂溶液後加以乾燥而所得之可撓性基板(例如參照專利文獻1、2)，於玻璃表面貼附有樹脂膜之可撓性基板(例如參照專利文獻3)。然而，即使使用該等技術，於要求高溫高濕下之較高之可靠性的顯示裝置之製造步驟中，亦無法獲得滿足充分之耐衝擊性之可撓性基板。
又，於玻璃表面塗佈樹脂溶液後加以乾燥而所得之可撓性基板存在如下之問題：樹脂溶液於塗佈步驟以及乾燥步驟時發泡，外觀變差。另一方面，於玻璃表面貼附有樹脂膜之可撓性基板存在如下之問題：並未對玻璃充分附加為了提高玻璃之耐衝擊性所必須之應力，因此並未獲得充分之耐衝擊性。進而，為了貼附樹脂膜，使用樹脂溶液或者溶劑作為接著劑之情形時，容易於膜上產生皺褶。膜之皺褶除了 成為可撓性基板之外觀上之問題以外，若實施不使該皺褶產生之處置，則產生膜破斷之問題。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開平11-329715號公報
[專利文獻2]日本專利特開2008-107510號公報
[專利文獻3]日本專利特開2007-010834號公報
本發明係為了解決上述先前之問題而成者，其目的在於提供一種彎曲性、可撓性、耐衝擊性以及外觀優異之透明基板之製造方法。
本發明之透明基板之製造方法包含：步驟A，於具有溶劑透過性之支撐基材上塗佈熱塑性樹脂(A)組合物溶液而形成塗佈層；步驟B，將無機玻璃之至少一個面與該塗佈層經由接著劑組合物而貼合，形成積層體；步驟C，對該積層體實施第1熱處理，使該塗佈層中之殘存溶劑量減少至特定量；步驟D，將該支撐基材自該積層體上剝離後，進行第2熱處理，使該塗佈層乾燥而形成熱塑性樹脂層。
於較佳之實施形態中，上述塗佈層形成時之該塗佈層中之溶劑量為7重量%以上。
於較佳之實施形態中，藉由上述第1熱處理，使上述塗佈層中之殘存溶劑量減少至15重量%以下。
於較佳之實施形態中，將上述支撐基材剝離時之上述塗佈層之收縮應力為10MPa以下。
於較佳之實施形態中，於上述第2熱處理後對無機玻璃所附加之應力為10MPa~30MPa。
於較佳之實施形態中，上述第1熱處理之溫度相對於上述熱塑性樹脂(A)組合物溶液中所含最多之溶劑之沸點(bpA)而言為(bpA-60)℃~(bpA+40)℃。
於較佳之實施形態中，上述第2熱處理之溫度相對於上述熱塑性樹脂(A)組合物溶液中所含最多之溶劑之沸點(bpA)而言為(bpA-20)℃~250℃。
於較佳之實施形態中，上述接著劑組合物包含溶劑，該接著劑層中之溶劑之沸點係上述熱塑性樹脂(A)組合物溶液中所含之溶劑之沸點以上。
於較佳之實施形態中，上述接著劑組合物包含溶劑，該接著劑層中之溶劑對於熱塑性樹脂(A)組合物溶液中所含之熱塑性樹脂(A)顯示出溶解性。
於較佳之實施形態中，上述接著劑組合物包含與熱塑性樹脂(A)組合物溶液中所含之熱塑性樹脂(A)顯示出相溶性的成分。
於較佳之實施形態中，上述接著劑組合物包含溶劑、與上述熱塑性樹脂(A)組合物溶液顯示出相溶性之熱塑性樹脂(B)、熱固性單體以及硬化反應觸媒。
於較佳之實施形態中，上述熱塑性樹脂(B)於末端具有反應基。
於較佳之實施形態中，上述支撐基材於90℃下之儲藏彈性模數為1.0×107Pa以上。
於較佳之實施形態中，上述無機玻璃之厚度為100μm以下。
藉由本發明，對將於具有溶劑透過性之支撐基材上所形成之包含溶劑之塗佈層(亦即半乾燥狀態之塗佈層)與無機玻璃經由接著劑組合物而貼合所得的積層體實施熱處理，使塗佈層中之殘存溶劑量減少至特定量，其後將支撐基材自該積層體上剝離，再次進行熱處理而使 塗佈層乾燥，藉此可獲得具有充分附加應力之無機玻璃以及發泡得到抑制之熱塑性樹脂層，且彎曲性、可撓性、耐衝擊性以及外觀優異之透明基板。
10‧‧‧支撐基材
20‧‧‧塗佈層
21‧‧‧熱塑性樹脂層
30‧‧‧無機玻璃
40‧‧‧接著劑組合物
41‧‧‧接著劑層
100、100'‧‧‧烘箱
200‧‧‧透明基板
圖1係模式性表示本發明之較佳之實施形態的透明基板之製造方法之概略圖。
圖2係模式性表示本發明之其他較佳之實施形態的透明基板之製造方法之概略圖。
圖3係藉由本發明之製造方法而所得之透明基板之概略截面圖。
圖1係模式性表示本發明之較佳之實施形態的透明基板之製造方法之概略圖。本發明之製造方法包含：步驟A，於支撐基材10上塗佈熱塑性樹脂(A)組合物溶液而形成塗佈層20；步驟B，將無機玻璃30之至少一個面(於圖示例中為無機玻璃30之兩個面)與塗佈層20經由接著劑組合物40而貼合，形成積層體；步驟C，對該積層體實施第1熱處理，使上述塗佈層中之殘存溶劑減少至特定量；步驟D，將支撐基材10自該積層體上剝離後，進行第2熱處理，使塗佈層20乾燥而形成熱塑性樹脂層21。於本發明之製造方法中，塗佈層20於步驟A~步驟C中為包含溶劑之半乾燥狀態，於其後之步驟D中，為剝離了支撐基材10之狀態，溶劑之乾燥結束後形成熱塑性樹脂層21。藉由本發明之製造方法，可獲得具有無機玻璃30、使接著劑組合物40乾燥而所得之接著劑層41、使包含熱塑性樹脂(A)之塗佈層20乾燥而所得之熱塑性樹脂層21的透明基板。
圖2係模式性表示本發明之其他較佳之實施形態的透明基板之製造方法之概略圖。圖2係表示將無機玻璃30之單面與塗佈層20經由接著劑組合物40而貼合之情形時的實施形態。
A.步驟A
步驟A係於支撐基材上塗佈熱塑性樹脂(A)組合物溶液而形成塗佈層的步驟。
上述支撐基材較佳的是對於上述熱塑性樹脂(A)組合物溶液之溶劑以及後述之接著劑組合物中所含之溶劑而言具有耐溶劑性。作為構成此種支撐基材之材料，例如可列舉聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)等。
上述支撐基材具有溶劑透過性。較佳的是上述支撐基材對於上述熱塑性樹脂(A)組合物溶液之溶劑而言具有溶劑透過性。更佳的是對於上述熱塑性樹脂(A)組合物溶液之溶劑以及後述之接著劑組合物中所含之溶劑而言具有溶劑透過性。若使用此種支撐基材，則於後製程(步驟C)中進行第1熱處理而使溶劑揮發時，溶劑透過支撐基材，因此可於第1熱處理時防止塗佈層發泡。作為構成此種支撐基材之材料，例如可列舉未實施矽處理等表面處理的聚對苯二甲酸乙二酯(PET)。再者，於本說明書中，「溶劑透過性」之有無例如可藉由以下方式而判斷。亦即，對裝入有10g溶劑之玻璃瓶(直徑3.5cm×高度7.5cm)內進行氮氣置換，將該玻璃瓶之口以支撐基材封住之後，將該放入有溶劑之玻璃瓶於((溶劑之沸點)-(35~45))℃之加熱板上進行2小時之加熱時，於該玻璃瓶以及/或者支撐基材之內側不產生冷凝之情形時，判斷為該支撐體對於該溶劑而言具有「溶劑透過性」。
上述支撐基材於90℃下之儲藏彈性模數較佳的是1.0×107Pa以上，更佳的是1.0×107Pa~1.0×1010Pa。若為該範圍，則可良好地保持上述塗佈層，可獲得無外觀上之不均的透明基板。
上述支撐基材之厚度較佳的是25μm~120μm，更佳的是50μm~100μm。若為該範圍，則可良好地保持上述塗佈層，可獲得無外觀上之不均的透明基板。
上述熱塑性樹脂(A)組合物溶液包含熱塑性樹脂(A)以及溶劑。
作為上述熱塑性樹脂(A)，可列舉聚醚碸系樹脂、聚碳酸酯系樹脂、環氧系樹脂、丙烯酸系樹脂、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂；聚烯烴系樹脂、降冰片烯系樹脂等環烯系樹脂；聚醯亞胺系樹脂、聚醯胺系樹脂、聚醯亞胺醯胺系樹脂、聚芳酯系樹脂、聚碸系樹脂、聚醚醯亞胺系樹脂等。
上述熱塑性樹脂(A)之玻璃轉移溫度較佳的是150℃~350℃，更佳的是170℃~330℃，特佳的是190℃~300℃。
上述熱塑性樹脂(A)組合物溶液中所含之溶劑只要可溶解熱塑性樹脂(A)則可採用任意之適宜之溶劑。作為該溶劑，例如可列舉甲苯、二甲苯等芳香族系溶劑；環戊酮、甲基異丁基酮等酮系溶劑；四氫呋喃、丙二醇甲醚等醚系溶劑；二氯甲烷、三氯乙烷等鹵素系溶劑。該等溶劑可單獨使用或者將2種以上組合使用。
上述熱塑性樹脂(A)組合物溶液之熱塑性樹脂(A)濃度，可於良好地進行塗佈作業之範圍內而設定為任意之適宜濃度。
作為於上述支撐基材上塗佈熱塑性樹脂(A)組合物溶液之方法，例如可列舉空氣刮刀塗佈、刮塗、刀塗、反塗、傳送輥塗佈、凹版輥式塗佈、吻合式塗佈、鑄塗、噴灑式塗佈、孔縫式塗佈、壓光塗佈、電鍍塗佈、浸塗、模塗法等塗佈法；軟版印刷等凸版印刷法、直接凹板印刷法、間接凹版印刷法等凹版印刷法、平板印刷法等平版印刷法、絲網印刷法等孔版印刷法等印刷法等。
步驟A中之塗佈層之厚度較佳的是15μm~40μm，更佳的是20μm~30μm。
上述塗佈層形成時之塗佈層中之溶劑量(亦即步驟A中之塗佈層中之溶劑量)較佳的是7重量%以上，更佳的是7重量%~50重量%，特佳的是8重量%~40重量%，最佳的是11重量%~30重量%。於步驟A中 之塗佈層中之溶劑量少於7重量%之情形時，於後製程(步驟C)之第1熱處理時，存在由於接觸接著劑組合物中之溶劑而於塗佈層上產生溶劑裂痕之虞。又，於多於50重量%之情形時，存在塗佈層之流動性變高，於後製程(步驟B)中將塗佈層與無機玻璃貼合時之作業性變差之虞。
步驟A中之塗佈層中之溶劑量例如可控制熱塑性樹脂(A)組合物溶液中之溶劑之種類以及溶劑量而進行調整。又，亦可視需要而塗佈熱塑性樹脂(A)組合物溶液後，使特定量之溶劑揮發而調整塗佈層中之溶劑量。於一實施形態中，將塗佈有溶劑量為70重量%以上之熱塑性樹脂(A)組合物溶液的支撐基材，於20℃~100℃之環境溫度下放置30秒~10分鐘，可形成溶劑量為7重量%以上之塗佈層。
B.步驟B
步驟B係將無機玻璃之至少一個面與上述塗佈層經由接著劑組合物而貼合，形成積層體的步驟。
上述無機玻璃若為板狀者，則可採用任意之適宜之無機玻璃。上述無機玻璃可為長條狀，亦可為單片狀。上述無機玻璃根據組成之分類，例如可列舉鈉鈣玻璃、硼酸玻璃、鋁矽酸鹽玻璃、石英玻璃等。又，根據鹼成分之分類，可列舉無鹼玻璃、低鹼玻璃。上述無機玻璃之鹼金屬成分(例如Na2O、K2O、Li2O)之含量較佳的是15重量%以下，更佳的是10重量%以下。
上述無機玻璃之厚度較佳的是100μm以下，更佳的是20μm~90μm，特佳的是30μm~80μm。於本發明中，藉由於無機玻璃之單側或者兩側形成熱塑性樹脂層，可使無機玻璃之厚度變薄。
上述無機玻璃之波長550nm下的透射率較佳的是85%以上。上述無機玻璃之波長550nm下的折射率ng較佳的是1.4~1.65。
上述無機玻璃之密度較佳的是2.3g/cm3~3.0g/cm3，更佳的是2.3 g/cm3~2.7g/cm3。若為上述範圍之無機玻璃，則可獲得輕量之透明基板。
上述無機玻璃之成形方法可採用任意之適宜之方法。代表性的是上述無機玻璃可藉由如下方式而製作：將包含二氧化矽或氧化鋁等主原料、芒硝或氧化銻等消泡劑、碳等還原劑之混合物於1400℃~1600℃之溫度下熔融，成形為薄板狀之後，加以冷卻而製作。作為上述無機玻璃之薄板成形方法，例如可列舉流孔下引法(slot down draw)、熔融法、浮法等。藉由該等方法而成形為板狀之無機玻璃為了薄板化或提高平滑性，亦可視需要而藉由氫氟酸等溶劑進行化學研磨。
上述無機玻璃可直接使用市售之無機玻璃，或者將市售之無機玻璃研磨為所期望之厚度而使用。作為市售之無機玻璃，例如可列舉Corning公司製造之「7059」、「1737」或者「EAGLE2000」、旭硝子公司製造之「AN100」、NH TECHNO GLASS公司製造之「NA-35」、日本電氣硝子公司製造之「OA-10」、SCHOTT公司製造之「D263」或者「AF45」等。
上述無機玻璃較佳的是預先對單面或者兩個面實施偶合處理。若對無機玻璃進行了偶合處理，則可獲得無機玻璃與接著劑層之密接性優異之透明基板。作為偶合處理中所使用之偶合劑，可列舉環氧末端偶合劑、含有胺基之偶合劑、含有甲基丙烯基之偶合劑、含有巰基之偶合劑等。
上述接著劑組合物較佳的是包含與上述熱塑性樹脂(A)顯示出相溶性之成分。若使用此種接著劑組合物，則可獲得接著劑層與熱塑性樹脂層之密接性優異之透明基板。
上述接著劑組合物較佳的是包含與熱塑性樹脂(A)顯示出相溶性之熱塑性樹脂(B)。作為熱塑性樹脂(B)之具體例，可列舉聚醚碸系樹 脂、聚碳酸酯系樹脂、環氧系樹脂、丙烯酸系樹脂、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂；聚烯烴系樹脂、降冰片烯系樹脂等環烯系樹脂；聚醯亞胺系樹脂、聚醯胺系樹脂、聚醯亞胺醯胺系樹脂、聚芳酯系樹脂、聚碸系樹脂、聚醚醯亞胺系樹脂等樹脂。再者，作為上述熱塑性樹脂(B)，較佳的是使用與上述熱塑性樹脂(A)不同之樹脂。
上述熱塑性樹脂(B)較佳的是於末端具有反應性高之官能基。例如可列舉羥基、酚性羥基、丙烯基、甲基丙烯基、烯丙基、乙烯基、巰基、烷氧基矽烷基、異氰酸酯基、胺基、羧酸基等。其中較佳的是酚性羥基。
上述熱塑性樹脂(B)之含量可根據所期望之接著劑組合物之黏度而設定為任意之適宜之值。上述接著劑組合物於25℃下之黏度較佳的是0.1mPa‧s~1000000mPa‧s，更佳的是0.2mPa‧s~500000mPa‧s，特佳的是0.3mPa‧s~300000mPa‧s。若為此種範圍，則將無機玻璃與上述塗佈層經由接著劑組合物而貼合時之作業性優異。
上述接著劑組合物較佳的是包含熱固性單體以及硬化反應觸媒。若包含熱固性單體以及硬化反應觸媒，則可獲得無機玻璃與接著劑層、以及接著劑層與熱塑性樹脂層之密接性更優異之透明基板。
上述熱固性單體例如可列舉環氧系單體、環氧丙烷系單體、丙烯酸系單體、聚矽氧系單體等。該等熱固性單體可單獨使用或者將2種以上組合使用。其中較佳的是環氧系單體或者環氧丙烷系單體。若為此種熱固性單體，則例如於上述熱塑性樹脂(B)具有酚性羥基之情形時，可形成與該熱塑性樹脂(B)之鞏固之相互作用，且可獲得無機玻璃與接著劑層、以及接著劑層與熱塑性樹脂層之密接性更優異之透明基板。
上述熱固性單體之含有比例相對於上述熱塑性樹脂(B)而言較佳 的是10重量%~50重量%，更佳的是12重量%~40重量%，特佳的是15重量%~35重量%。若為此種範圍，則可獲得無機玻璃與接著劑層、以及接著劑層與熱塑性樹脂層之密接性更優異，且著色較少之透明基板。
上述硬化反應觸媒較佳的是咪唑系觸媒、錫系觸媒或者鈦系觸媒。該等觸媒可單獨使用或者將2種以上組合使用。
作為上述咪唑系觸媒之具體例，可列舉2-甲基咪唑、1,3-二甲基咪唑、2-乙基4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基4-甲基咪唑等。
作為上述錫系觸媒之具體例，可列舉二丁基二月桂酸錫、二丁基二乙酸錫、二辛基二月桂酸錫、雙(乙醯氧基二丁基錫)氧化物等。
作為上述鈦系觸媒之具體例，可列舉松本精密化學公司製造之「TA-25」、「TC-750」等。
上述硬化反應觸媒之含有比例相對於熱塑性樹脂(B)而言較佳的是1重量%~10重量%，更佳的是2重量%~8重量%，特佳的是3重量%~5重量%。若為此種範圍，則可獲得無機玻璃與接著劑層、以及接著劑層與熱塑性樹脂層之密接性更優異，且著色較少之透明基板。
上述接著劑組合物較佳的是包含溶劑。接著劑組合物中所含之溶劑較佳的是對於上述熱塑性樹脂(A)亦顯示出溶解性。若接著劑組合物包含此種溶劑，則接著劑組合物變得容易浸透至上述塗佈層中，可獲得接著劑層與熱塑性樹脂層之密接性優異之透明基板。作為接著劑組合物中所含之溶劑，較佳的是可使用與上述熱塑性樹脂(A)組合物溶液中所含之溶劑同樣之溶劑。
上述接著劑組合物中所含之溶劑之沸點較佳的是與上述熱塑性樹脂(A)組合物溶液中所含之溶劑之沸點為同等以上。若接著劑組合 物中所含之溶劑之沸點與上述熱塑性樹脂(A)組合物溶液中所含之溶劑之沸點為同等以上，則於後製程(步驟C以及D)之第1熱處理以及第2熱處理時，接著劑組合物中所含之溶劑之揮發難以受熱塑性樹脂(A)組合物溶液中所含之溶劑妨礙，因此可防止接著劑組合物之發泡，獲得外觀優異之透明基板。
作為將上述無機玻璃與上述塗佈層經由接著劑組合物而貼合之方法，可採用任意之適宜之方法。作為該貼合之方法，例如可列舉：使形成有塗佈層之支撐基材與無機玻璃，一面於該等之間供給接著劑組合物，一面使其通過以一定之間隙而設置之2個輥之間的方法。所供給之接著劑組合物可為溶液狀態亦可為薄板狀態。
C.步驟C
步驟C係對步驟B中所得之積層體實施第1熱處理之步驟。藉由第1熱處理，可使上述塗佈層中之殘存溶劑減少至特定量。又，同時接著劑組合物中之溶劑亦減少。進而，於接著劑組合物包含熱固性單體之情形時，進行該熱固性單體之硬化反應。
作為上述第1熱處理之方法，可採用任意之適宜之方法。第1熱處理例如可列舉使用如下裝置之熱處理：空氣循環式恆溫烘箱、利用微波或者遠紅外線等之加熱器、溫度調節用中得到加熱之輥、熱管輥或者金屬帶等。
上述第1熱處理之溫度相對於上述熱塑性樹脂(A)組合物溶液中所含最多之溶劑之沸點(bpA)而言較佳的是(bpA-60)℃~(bpA+40)℃，更佳的是(bpA-60)℃~(bpA+20)℃，特佳的是(bpA-50)℃~(bpA+20)℃，最佳的是(bpA-45)℃~(bpA)℃。若為此種溫度範圍，則於第1熱處理時，可防止上述塗佈層以及接著劑組合物發泡。再者，於第1熱處理中，亦可階段性地提高溫度。
上述第1熱處理之時間較佳的是1分鐘~30分鐘，更佳的是5分鐘 ~20分鐘。
較佳的是藉由上述第1熱處理，使上述塗佈層中之殘存溶劑量減少至15重量%以下。更佳的是減少至3重量%~15重量%，特佳的是減少至4重量%~14重量%，最佳的是減少至5重量%~13重量%。於第1熱處理後之塗佈層中之殘存溶劑量多於15重量%之情形時，上述積層體存在如下之虞：於後製程(步驟D)中，搬送中之積層體變得不耐對該積層體所施加之張力而破斷。
D.步驟D
步驟D係將上述支撐基材自上述積層體上剝離後，進行第2熱處理之步驟。藉由第2熱處理，可使塗佈層乾燥而形成熱塑性樹脂層。又，同時可使接著劑組合物之乾燥以及/或者硬化結束而形成接著劑層。
對於上述積層體之上述塗佈層，藉由上述步驟C中之第1熱處理而使塗佈層中之溶劑揮發，藉此而施加收縮應力。將上述支撐基材剝離時之上述塗佈層之收縮應力較佳的是10MPa以下，更佳的是8MPa以下。若為此種範圍，可防止於基材上產生皺褶。再者，於基材上產生皺褶之情形時，存在皺褶被轉印至塗佈層上，獲得外觀上欠佳之透明基板之虞。
上述第2熱處理之方法可採用與上述第1熱處理同樣之方法。
上述第2熱處理之溫度相對於上述熱塑性樹脂(A)組合物溶液所含最多之溶劑之沸點(bpA)而言較佳的是(bpA-20)℃~250℃，更佳的是(bpA-10)℃~200℃，特佳的是(bpA)℃~180℃。上述第2熱處理之時間可設定為與上述第1熱處理之時間同樣之時間。
藉由進行上述第2熱處理，可將使塗佈層乾燥而所得之熱塑性樹脂層之收縮應力附加於無機玻璃上。具有如此而附加有應力之無機玻璃的透明基板之彎曲性、可撓性以及耐衝擊性優異。
於上述第2熱處理後附加於無機玻璃上之應力(亦即藉由本發明之製造方法而所得之透明基板之無機玻璃上所附加之應力)較佳的是10MPa~30MPa，更佳的是12MPa~30MPa，特佳的是15MPa~30MPa。若為此種範圍，則可獲得無機玻璃與接著劑層充分密接，且彎曲性、可撓性以及耐衝擊性優異之透明基板。更詳細而言，於無機玻璃受到拉伸方向之外力之情形時，由於在裂痕上集中拉伸應力而產生無機玻璃之破斷，但藉由本發明之製造方法而所得之透明基板之無機玻璃附加有塗佈層以及接著劑層之收縮所造成之應力，因此裂痕所受到之拉伸應力減低。其結果，即使對於更大之拉伸方向之外力，亦可防止無機玻璃之裂痕之進展以及破斷，可獲得彎曲性、可撓性以及耐衝擊性優異之透明基板。
E.透明基板
圖3係藉由本發明之製造方法而所得之透明基板之概略截面圖。該透明基板200具有無機玻璃30、於無機玻璃30之單側或者兩側(較佳的是如圖示例那樣為兩側)所配置之熱塑性樹脂層21，且於無機玻璃30與熱塑性樹脂層21之間進而具有接著劑層41。
本發明之透明基板可視需要於上述熱塑性樹脂層之與無機玻璃為相反側處具有任意之適宜之其他層。作為上述其他層，例如可列舉透明導電性層、硬塗層等。
上述透明基板之總厚較佳的是150μm以下，更佳的是140μm以下，特佳的是80μm~130μm。
於上述透明基板上放入裂痕而使其彎曲時之破斷直徑較佳的是40mm以下，更佳的是30mm以下。
上述透明基板之波長550nm下之透光率較佳的是80%以上，更佳的是85%以上。較佳的是上述透明基板於以180℃而實施2小時之加熱處理後的透光率之減少率為5%以內。其原因在於：若為此種減少 率，則即使於FPD之製造製程中實施必要之加熱處理，亦可確保實用上所許可之透光率。
上述透明基板之表面粗度Ra(實質上為上述熱塑性樹脂層或者上述其他層之表面粗度Ra)較佳的是50nm以下，更佳的是30nm以下、特佳的是10nm以下。上述透明基板之起伏較佳的是0.5μm以下，更佳的是0.1μm以下。
作為上述透明基板，其線膨脹係數較佳的是15ppm/℃以下，更佳的是10ppm/℃以下，特佳的是1ppm/℃~10ppm/℃。上述透明基板由於具有上述無機玻璃而顯示出優異之尺寸穩定性(例如如上所示之範圍的線膨脹係數)。更具體而言，除了上述無機玻璃自身剛直以外，由於上述熱塑性樹脂層受到該無機玻璃拘束而亦可抑制熱塑性樹脂層之尺寸變動。其結果，上述透明基板整體顯示出優異之尺寸穩定性。
上述熱塑性樹脂層之於波長550nm下之透光率較佳的是80%以上。上述熱塑性樹脂層之於波長550nm下之折射率(nr)較佳的是1.3~1.7。
上述熱塑性樹脂層之厚度較佳的是5μm~80μm，更佳的是8μm~60μm，特佳的是10μm~50μm。若為此種範圍，則熱塑性樹脂層可充分地強化無機玻璃。
上述熱塑性樹脂層之彈性模數較佳的是1.5GPa~10GPa以上，更佳的是1.8GPa~9GPa，特佳的是2GPa~8GPa。
上述熱塑性樹脂層之破壞韌性值較佳的是1.5MPa‧m1/2~10MPa‧m1/2，更佳的是2MPa‧m1/2~6MPa‧m1/2，特佳的是2.5MPa‧m1/2~8MPa‧m1/2。若為此種範圍，則形成具有充分之黏著強度之熱塑性樹脂層，由該熱塑性樹脂層而防止無機玻璃之裂痕之進展或破斷，可獲得具有良好之彎曲性的透明基板。又，將此種包含熱塑性樹 脂(A)之熱塑性樹脂層形成於無機玻璃兩個面之情形時，即使於假設無機玻璃於透明基板內部破斷之情形時，熱塑性樹脂層亦難以破斷，因此由於熱塑性樹脂層而防止無機玻璃之飛散，且保持透明基板之形狀，因此可防止顯示元件以及太陽電池之製造步驟中的設施之污染，可提高良率。
上述接著劑層之厚度較佳的是0.001μm~20μm，更佳的是0.001μm~15μm，特佳的是0.01μm~10μm。若為此種範圍，則對透明基板之透明性的影響少，且即使於高溫高濕之狀況下亦可表現出充分之接著力。
於將上述透明基板作為照明元件、顯示元件或者太陽電池之基板而使用之情形時，上述透明導電性層可作為電極或者電磁波遮罩等而發揮功能。
作為可用於上述透明導電性層之材料，例如可列舉銅、銀等金屬；氧化銦錫(ITO)、氧化銦鋅(IZO)等金屬氧化物；聚噻吩、聚苯胺等導電性高分子；包含碳奈米管之組合物等。
上述硬塗層具有賦予上述透明基板耐化學品性、耐擦傷性以及表面平滑性之功能。
作為構成上述硬塗層之材料，可採用任意之適宜之材料。作為構成上述硬塗層之材料，例如可列舉環氧系樹脂、丙烯酸系樹脂、聚矽氧系樹脂以及該等之混合物。其中較佳的是耐熱性優異之環氧系樹脂。上述硬塗層可藉由熱或者活性能量線而使該等樹脂硬化。
[實施例]
以下，藉由實施例對本發明加以具體之說明，但本發明並不受該等實施例任何限定。再者，厚度係使用安立公司製造之數位式測微計「KC-351C型」而測定。又，於實施例以及比較例中，作為支撐基材而使用之PET基材之溶劑透過性係如下所述而判斷。
(PET基材之溶劑透過性)
於螺旋管瓶(As One公司製造、型號「No.7L」、件號「5-098011」、直徑3.5cm×高度7.5cm)中放入環戊酮10g。其後，對該螺旋管瓶內進行氮氣置換，將該螺旋管瓶以5cm見方之PET基材封住。此時，藉由接著劑(Cemedine Co.,Ltd.製造、件號「AX-083」)使螺旋管瓶與PET基材接著。其次，將該螺旋管瓶放置於加熱為90℃之加熱板上，進行2小時之加熱。於加熱結束後，目視觀察PET基材以及螺旋管瓶之內側之狀態。
目視觀察之結果，於PET基材以及/或者螺旋管瓶之內側產生溶劑之冷凝之情形時，判斷為該PET基材無溶劑透過性。另一方面，於不產生冷凝之情形時，判斷為該PET基材具有溶劑透過性。
[製造例1]
於具有攪拌裝置之反應容器中，使4,4'-(1,3-二甲基亞丁基)雙酚7.65g(0.028mol)、4,4'-(1-苯基亞乙基)雙酚12.35g(0.043mol)、苄基三乙基氯化銨0.444g、對第三丁基苯酚0.022g溶解於1M氫氧化鈉溶液185g中。於該溶液中一面攪拌一面一次性添加於氯仿246g中溶解有對苯二甲醯氯14.4g(0.071mol)之溶液，於室溫下攪拌120分鐘。其後，對聚合溶液進行靜置分離而分離包含聚合物之氯仿溶液，其次以乙酸水溶液加以清洗，並以離子交換水加以清洗後，投入至甲醇中而使聚合物析出。對析出之聚合物進行過濾，於減壓下進行乾燥而獲得白色之聚合物27g。
[實施例1]
將經末端羥基改性之聚醚碸(SUMIKAEXCEL 5003P：住友化學公司製造)10g加熱溶解於環戊酮90g中，獲得10重量%之溶液。於所得之溶液中添加3-乙基-3{[(3-乙基環氧丙烷-3-基)甲氧基]甲基}環氧丙烷(ARONE OXETANE OXT-221：東亞合成公司製造)0.6g、1,2-二 甲基咪唑0.4g、以及環氧末端偶合劑(KBM403：信越化學工業公司製造)2.5g，獲得接著劑組合物。
另外，將無機玻璃(厚度50μm、長度10cm×寬度4cm)之單面表面以丁酮加以清洗後，進行電暈處理，塗佈環氧偶合劑(KBM403：信越化學工業公司製造)2%水溶液，於100℃下乾燥10分鐘。關於無機玻璃之另一面，亦進行同樣之處理。
其後，將於環戊酮90g中溶解有製造例1中所得之聚合物10g的10重量%之熱塑性樹脂(A)溶液，塗佈於具有溶劑透過性之PET(Lumirror：日本東麗股份有限公司製造、厚度75μm)基材上，於90℃下使溶劑揮發8分鐘而形成塗佈層。塗佈層中之溶劑量為23重量%(熱塑性樹脂(A)之濃度：77重量%)。
一面於上述無機玻璃與上述PET基材上所形成之塗佈層之間供給上述接著劑組合物，一面將無機玻璃與塗佈層貼合。於無機玻璃之兩個面進行此種操作，獲得積層體(PET基材/塗佈層/接著劑組合物/無機玻璃/接著劑組合物/塗佈層/PET基材)。
對所得之積層體，於90℃下進行4分鐘之熱處理，於130℃下進行4分鐘之熱處理，於150℃下進行4分鐘之熱處理。該熱處理後之塗佈層中之殘留溶劑量為6重量%。
其後，將兩個面之PET基材剝離，進而於150℃下進行12分鐘之熱處理，獲得總厚度為115μm之透明基板(熱塑性樹脂層(30μm)/接著劑層(2.5μm)/無機玻璃(50μm)/接著劑層(2.5μm)/熱塑性樹脂層(30μm))。再者，於上述透明基板之寬度方向端部(長度10cm×寬度1cm)露出無機玻璃。
[實施例2]
於接著劑組合物中進而添加二丁基二月桂酸錫0.05g，除此以外與實施例1同樣地進行而獲得透明基板。
[比較例1]
將形成塗佈層時之塗佈層中之溶劑量設為6重量%(熱塑性樹脂層(A)之濃度為94重量%)，除此以外與實施例1同樣地進行而獲得透明基板。
[比較例2]
使用進行了矽處理之不具溶劑透過性之PET(MRF：三菱樹脂股份有限公司製造、厚度38μm)基材而代替具有溶劑透過性之PET(Lumirror：日本東麗股份有限公司製造、厚度75μm)基材，除此以外與實施例1同樣地進行而獲得透明基板。
[比較例3]
於形成積層體形成之後(亦即於熱處理前)將PET基材剝離，除此以外與實施例1同樣地進行而獲得透明基板。
[比較例4]
將於環戊酮600g中溶解有製造例1中所得之聚合物90g之鑄塑溶液塗佈於PET(Lumirror：日本東麗股份有限公司製造、厚度75μm)基材上，進而進行乾燥直至殘存溶劑量成為5%以下，然後將基材剝離，獲得聚芳酯膜。
另外，將無機玻璃(厚度50μm、長度10cm×寬度4cm)之單面表面以丁酮加以清洗後，進行電暈處理，藉由環氧偶合劑(KBM403：信越化學工業公司製造)進行處理。關於無機玻璃之另一面，亦進行同樣之處理。
於上述無機玻璃之兩個面，使用包含3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯(Celloxide 2021P：DAICEL CHEMICAL INDUSTRIES,LTD.製造)8g、3-乙基-3{[(3-乙基環氧丙烷-3-基)甲氧基]甲基}環氧丙烷(ARONE OXETANE OXT-221：東亞合成公司製造)2g、光聚合起始劑(SP-170：ADEKA公司製造)0.4g之接著劑組合 物而貼合上述聚芳酯膜後，進行UV照射而使接著劑組合物硬化，獲得透明基板(聚芳酯膜層/接著劑層/無機玻璃/接著劑層/聚芳酯膜層)。再者，於上述透明基板之寬度方向端部(長度10cm×寬度1cm)露出無機玻璃。
[比較例5]
將經末端羥基改性之聚醚碸(SUMIKAEXCEL 5003P：住友化學公司製造)36.2g溶解於環戊酮172g以及N,N-二甲基甲醯胺10.8g之混合溶劑中，獲得聚醚碸為16.5重量%之溶液。進而於該溶液中添加均化劑(BYK307，BYK Chemie公司製造)0.027g、3,4-環氧環己烯基甲基-3',4'-環氧環己烯甲酸酯(Celloxide 2021P：DAICEL CHEMICAL INDUSTRIES,LTD.製造)1.81g、3-乙基-3{[(3-乙基環氧丙烷-3-基)甲氧基]甲基}環氧丙烷(ARONE OXETANE OXT-221：東亞合成公司製造)1.45g、2-甲基咪唑1.09g、環氧末端偶合劑(KBM403：信越化學工業公司製造)9.05g，獲得第1鑄塑溶液。
另外，將無機玻璃(厚度50μm、長度10cm×寬度4cm)之單面表面以丁酮加以清洗後，進行電暈處理，塗佈添加有偶合劑等之鑄塑溶液，於100℃下乾燥10分鐘，進而於170℃下乾燥20分鐘，形成厚度為1μm之第1熱塑性樹脂層。關於無機玻璃之另一面，亦進行同樣之處理。
其後，將於環戊酮600g中溶解有製造例1中所得之聚合物90g之第2鑄塑溶液塗佈於第1熱塑性樹脂層上，於90℃下乾燥15分鐘。進而於背面亦將第2鑄塑溶液塗佈於第1熱塑性樹脂層上，於85℃下乾燥10分鐘，其後使兩個面於130℃下乾燥10分鐘，進而於170℃下乾燥20分鐘，獲得單側之厚度為36.5μm之第2熱塑性樹脂，獲得總厚度為125μm之透明基板(第2熱塑性樹脂層/第1熱塑性樹脂層/無機玻璃/第1熱塑性樹脂層/第2熱塑性樹脂層)。再者，於上述透明基板之寬度方向端 部(長度10cm×寬度1cm)露出無機玻璃。
<評價>
藉由下述方法而評價上述所得之透明基板。將結果示於表1。
(1)密接性試驗
藉由JIS K 5400之網格剝離試驗而進行評價。亦即，於所得之透明基板以及積層體之單面最外層之表面上之10mm見方中，以1mm之間隔藉由切割機劃入縫隙，製作100個網格，於其上貼附黏著帶後進行剝離，根據自無機玻璃上剝離之樹脂層之網格數而評價密接性。
(2)外觀
目視確認所得之透明基板之外觀。於透明基板上確認不到發泡、裂痕、皺褶之情形時記為合格(於表1中以○表示)。
(3)破斷直徑
(a)準備實施例以及比較例中所得之透明基板作為評價用試樣。
(b)於薄板玻璃露出部分之長邊中央切入5mm以下之裂痕。
(c)使評價用試樣之長邊彎曲，觀察裂痕之進展，將玻璃破斷時的以彎曲之邊(長邊)為圓周之圓的直徑作為破斷直徑。
(4)收縮應力
於寬度30mm×長度125mm之帶狀無機玻璃(厚度100μm)之單面，藉由與實施例以及比較例同樣之方法而形成樹脂層，測定捲曲之樣本之曲率半徑R。
於導入有校正項之Stonry之下述式(C.A.Klien,J.Appl.Phys.,885487(2000))中代入曲率半徑R；薄板玻璃之楊氏模量(70GPa)、帕松比(0.2)以及厚度(100μm)；樹脂之楊氏模量、帕松比以及厚度，求出樹脂層之收縮應力(亦即於無機玻璃上所附加之應力)。
[數l]σ=((1+χδ3)/(1+δ))*(E's＊ts 2/(6＊R＊tf)) ~(1/(1+δ))＊(E's＊ts 2/(6＊R＊tf))
σ：收縮應力(MPa) σ：tf/ts
χ：E'f/E's tf：玻璃之厚度(μm)
E'f：Ef/(1-γf) ts：樹脂層之厚度(μm)
E's：Es/(1-γs) R：曲率半徑(μm)
Ef：樹脂之楊氏模量(MPa)
γf：樹脂之帕松比
Es：玻璃之楊氏模量(MPa)
γs：玻璃之帕松比
根據表1可知：實施例1以及2之透明基板由於對具有支撐基材、接著劑組合物、包含有特定量之溶劑之塗佈層的積層體進行第1熱處理，其後將支撐基材剝離而進行第2熱處理，因此密接性優異、樹脂層之收縮應力較大、破斷直徑較小。該等表示藉由本發明之製造方法而所得之透明基板之彎曲性、可撓性以及耐衝擊性優異。另一方面，比較例4之透明基板之樹脂層(聚芳酯膜層)之收縮應力較小。此種透 明基板並未對無機玻璃附加充分之應力，彎曲性、耐衝擊性差。
又，藉由實施例1以及2之製造方法而獲得外觀優異之透明基板。另一方面，於塗佈層中之溶劑量較少之狀態下進行了第1熱處理的透明基板(比較例1)產生裂痕。又，於形成積層體之後(亦即熱處理前)而將PET基材剝離之情形時，於步驟中破斷而無法製作透明基板(比較例3)。進而，於使用不具溶劑透過性之PET基材作為支撐基材之情形時(比較例2)、以及藉由並不使用支撐基材之先前方法之直接塗佈而形成熱塑性樹脂層之情形時，確認到發泡(比較例5)。
[產業上之可利用性]
藉由本發明之製造方法而所得之透明基板可用於顯示元件、太陽電池或者照明元件中。作為顯示元件，例如可列舉液晶顯示器、電漿顯示器、有機EL顯示器、電子紙等。作為照明元件，例如可列舉有機EL元件等。
10‧‧‧支撐基材
20‧‧‧塗佈層
21‧‧‧熱塑性樹脂層
30‧‧‧無機玻璃
40‧‧‧接著劑組合物
41‧‧‧接著劑層
100、100'‧‧‧烘箱

Claims (2)

  1. 一種積層體，其包含無機玻璃及塗佈熱塑性樹脂(A)組合物溶液而形成之塗佈層，該塗佈層中之殘存溶劑量為3重量%~15重量%。
  2. 如請求項1之積層體，其係於具有溶劑透過性之支撐基材上塗佈熱塑性樹脂(A)組合物溶液使形成塗佈層，之後將無機玻璃之至少一個面與該塗佈層經由接著劑組合物而貼合後，對該積層體實施第1熱處理，使該塗佈層中之殘存溶劑量減少至特定量所形成者。
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JP2011245843A (ja) 2011-12-08
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EP2565170A1 (en) 2013-03-06
US20150072155A1 (en) 2015-03-12
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EP2565170A4 (en) 2014-06-18
TW201218147A (en) 2012-05-01
TWI496124B (zh) 2015-08-11
CN104589736A (zh) 2015-05-06
US20130032277A1 (en) 2013-02-07
WO2011136327A1 (ja) 2011-11-03
JP5615134B2 (ja) 2014-10-29
CN102869632B (zh) 2015-05-06
CN102869632A (zh) 2013-01-09
KR20130024902A (ko) 2013-03-08

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