JP5615134B2 - 透明基板の製造方法 - Google Patents
透明基板の製造方法 Download PDFInfo
- Publication number
- JP5615134B2 JP5615134B2 JP2010252704A JP2010252704A JP5615134B2 JP 5615134 B2 JP5615134 B2 JP 5615134B2 JP 2010252704 A JP2010252704 A JP 2010252704A JP 2010252704 A JP2010252704 A JP 2010252704A JP 5615134 B2 JP5615134 B2 JP 5615134B2
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- JP
- Japan
- Prior art keywords
- thermoplastic resin
- solvent
- transparent substrate
- coating layer
- layer
- Prior art date
- Legal status (The legal status 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 status listed.)
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Classifications
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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
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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
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- B29C66/70—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
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- 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
- B29C66/70—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
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- 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
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- 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
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C66/80—General aspects of machine operations or constructions and parts thereof
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- G—PHYSICS
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Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Theoretical Computer Science (AREA)
- Laminated Bodies (AREA)
- Liquid Crystal (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
好ましい実施形態においては、上記塗布層形成時における該塗布層中の溶剤量が、7重量%以上である。
好ましい実施形態においては、上記第1の熱処理により、上記塗布層中の残存溶剤量を15重量%以下まで減少させる。
好ましい実施形態においては、上記支持基材を剥離する際の上記塗布層の収縮応力が、10MPa以下である。
好ましい実施形態においては、上記第2の熱処理後に無機ガラスに付加される応力が、10MPa〜30MPaである。
好ましい実施形態においては、上記第1の熱処理の温度が、上記熱可塑性樹脂(A)組成物溶液に最も多く含まれる溶剤の沸点(bpA)に対して、(bpA−60)℃〜(bpA+40)℃である。
好ましい実施形態においては、上記第2の熱処理の温度が、上記熱可塑性樹脂(A)組成物溶液に最も多く含まれる溶剤の沸点(bpA)に対して、(bpA−20)℃〜250℃である。
好ましい実施形態においては、上記接着剤組成物が溶剤を含み、該接着剤層中の溶剤の沸点が、上記熱可塑性樹脂(A)組成物溶液に含まれる溶剤の沸点以上である。
好ましい実施形態においては、上記接着剤組成物が溶剤を含み、該接着剤層中の溶剤が、熱可塑性樹脂(A)組成物溶液に含まれる熱可塑性樹脂(A)に対して溶解性を示す。
好ましい実施形態においては、上記接着剤組成物が、熱可塑性樹脂(A)組成物溶液に含まれる熱可塑性樹脂(A)と相溶性を示す成分を含む。
好ましい実施形態においては、上記接着剤組成物が、溶剤、上記熱可塑性樹脂(A)組成物溶液と相溶性を示す熱可塑性樹脂(B)、熱硬化性モノマーおよび硬化反応触媒を含む。
好ましい実施形態においては、上記熱可塑性樹脂(B)が、末端に反応基を有する。
好ましい実施形態においては、上記支持基材の90℃における貯蔵弾性率が、1.0×107Pa以上である。
好ましい実施形態においては、上記無機ガラスの厚みが、100μm以下である。
工程Aは、支持基材上に熱可塑性樹脂(A)組成物溶液を塗布して、塗布層を形成する工程である。
工程Bは、無機ガラスの少なくとも一方の面と上記塗布層とを、接着剤組成物を介して貼り合わせて、積層体を形成する工程である。
工程Cは、工程Bで得られた積層体に第1の熱処理を施す工程である。第1の熱処理により、上記塗布層中の残存溶剤を所定量まで減少させることができる。また、同時に、接着剤組成物中の溶剤も減少する。さらに、接着剤組成物が熱硬化性モノマーを含む場合、当該熱硬化性モノマーの硬化反応が進む。
工程Dは上記積層体から、上記支持基材を剥離した後、第2の熱処理を行う工程である。第2の熱処理により、塗布層を乾燥して、熱可塑性樹脂層を形成させることができる。また、同時に、接着剤組成物の乾燥および/または硬化が完了して、接着剤層を形成させることができる。
図3は、本発明の製造方法により得られる透明基板の概略断面図である。この透明基板200は、無機ガラス30と、無機ガラス30の片側または両側(好ましくは図示例のように両側)に配置された熱可塑性樹脂層21とを備え、無機ガラス30と熱可塑性樹脂層21との間に接着剤層41をさらに備える。
スクリュー管瓶(アズワン社製、型番「No.7L」、品番「5−098011」、直径3.5cm×高さ7.5cm)にシクロペンタノン10gを入れた。その後、当該スクリュー管瓶内を窒素置換し、当該スクリュー管瓶を5cm角のPET基材で封をした。このとき、スクリュー管瓶とPET基材とは、接着剤(セメダイン社製、品番「AX−083」)で接着させた。次いで、当該スクリュー管瓶を90℃に加熱したホットプレート上に置き、2時間加熱した。加熱終了後、PET基材およびスクリュー管瓶の内側の状態を目視観察した。
目視観察の結果、PET基材および/またはスクリュー管瓶の内側に溶剤の結露が生じていた場合は、当該PET基材は溶剤透過性がないと判断した。一方、結露が生じなかった場合は、当該PET基材は溶剤透過性があると判断した。
攪拌装置を備えた反応容器中、4,4’−(1,3−ジメチルブチリデン)ビスフェノール7.65g(0.028mol)、4,4’−(1−フェニルエチリデン)ビスフェノール12.35g(0.043mol)、ベンジルトリエチルアンモニウムクロライド0.444g、p−ターシャリーブチルフェノール0.022gを1M水酸化ナトリウム溶液185gに溶解させた。この溶液に、テレフタル酸クロライド14.4g(0.071mol)をクロロホルム246gに溶解させた溶液を攪拌しながら一度に加え、室温で120分間攪拌した。その後、重合溶液を静置分離してポリマーを含んだクロロホルム溶液を分離し、ついで酢酸水で洗浄し、イオン交換水で洗浄した後、メタノールに投入してポリマーを析出させた。析出したポリマーを濾過し、減圧下で乾燥することで、白色のポリマー27gを得た。
末端水酸基変性されたポリエーテルサルホン(スミカエクセル 5003P:住友化学社製)10gをシクロペンタノン90gに加熱して溶かし、10重量%の溶液を得た。得られた溶液に、3−エチル−3{[(3−エチルオキセタン−3−イル)メトキシ]メチル}オキセタン(アロンオキセタン OXT−221:東亞合成社製)0.6g、1、2−ジメチルイミダゾール0.4g、およびエポキシ末端カップリング剤(KBM403:信越化学工業社製)2.5g添加し、接着剤組成物を得た。
別途、無機ガラス(厚み50μm、長さ10cm×幅4cm)の片面表面をメチルエチルケトンで洗浄後、コロナ処理を行い、エポキシカップリング剤(KBM403:信越化学工業社製)2%水溶液を塗布し、100℃で10分間乾燥させた。同様の処理を無機ガラスのもう一方の面についても行った。
その後、製造例1で得られたポリマー10gをシクロペンタノン90gに溶かした10重量%の熱可塑性樹脂(A)溶液を、溶剤透過性を有するPET(ルミラー:東レ株式会社製、厚み75μm)基材上に塗布し、90℃で8分間溶剤を揮発させて塗布層を形成させた。塗布層中の溶剤量は、23重量%(熱可塑性樹脂(A)の濃度:77重量%)であった。
上記無機ガラスと上記PET基材上に形成された塗布層との間に上記接着剤組成物を供給しながら、無機ガラスと塗布層とを貼り合わせた。このような操作を無機ガラスの両面に行って、積層体(PET基材/塗布層/接着剤組成物/無機ガラス/接着剤組成物/塗布層/PET基材)を得た。
得られた積層体に、90℃で4分間、130℃で4分間、150℃で4分間の熱処理を行った。当該熱処理後の塗布層中の残存溶剤量は6重量%であった。
その後、両面のPET基材を剥離して、さらに150℃で12分間の熱処理を行い、総厚み115μmの透明基板(熱可塑性樹脂層(30μm)/接着剤層(2.5μm)/無機ガラス(50μm)/接着剤層(2.5μm)/熱可塑性樹脂層(30μm))を得た。なお、上記透明基板の幅方向端部(長さ10cm×幅1cm)は無機ガラスを露出させた。
接着剤組成物にジブチル錫ジラウレート0.05gをさらに加えた以外は、実施例1と同様にして透明基板を得た。
塗布層形成時における、塗布層中の溶剤量を、6重量%(熱可塑性樹脂層(A)の濃度94重量%)とした以外は、実施例1と同様にして透明基板を得た。
溶剤透過性を有するPET(ルミラー:東レ株式会社製、厚み75μm)基材に代えて、シリコン処理された溶剤透過性を有さないPET(MRF:三菱樹脂株式会社製、厚み38μm)基材を用いた以外は、実施例1と同様にして透明基板を得た。
積層体形成直後に(すなわち、熱処理前に)、PET基材を剥離した以外は、実施例1と同様にして透明基板を得た。
製造例1で得られたポリマー90gをシクロペンタノン600gに溶かしたキャスティング溶液を、PET(ルミラー:東レ株式会社製、厚み75μm)基材上に塗布し、さらに残存溶剤量が5%以下になるまで乾燥した後、基材を剥離して、ポリアリレートフィルムを得た。
別途、無機ガラス(厚み50μm、長さ10cm×幅4cm)の片面表面をメチルエチルケトンで洗浄後、コロナ処理を行い、エポキシカップリング剤(KBM403:信越化学工業社製)で処理した。同様の処理を無機ガラスのもう一方の面についても行った。
上記無機ガラスの両面に、上記ポリアリレートフィルムを、3,4−エポキシシクロヘキセニルメチル−3´,4´−エポキシシクロヘキセンカルボキシレート(セロキサイド2021P:ダイセル化学工業社製)8g、3−エチル−3{[(3−エチルオキセタン−3−イル)メトキシ]メチル}オキセタン(アロンオキセタン OXT−221:東亞合成社製)2g、光重合開始剤(SP−170:アデカ社製)0.4gを含む接着剤組成物を用いて貼り合わせた後、UV照射して接着剤組成物を硬化させて、透明基板(ポリアリレートフィルム層/接着剤層/無機ガラス/接着剤層/ポリアリレートフィルム層)を得た。なお、上記透明基板の幅方向端部(長さ10cm×幅1cm)は無機ガラスを露出させた。
末端水酸基変性されたポリエーテルサルホン(スミカエクセル 5003P:住友化学社製)36.2gをシクロペンタノン172gおよびN,N−ジメチルホルムアミド10.8gの混合溶剤に溶かし、ポリエーテルサルホンが16.5重量%の溶液を得た。さらに該溶液にレベリング剤(BYK307 ビックケミー社製)0.027g、3,4−エポキシシクロヘキセニルメチル−3´,4´−エポキシシクロヘキセンカルボキシレート(セロキサイド2021P:ダイセル化学工業社製)1.81g、3−エチル−3{[(3−エチルオキセタン−3−イル)メトキシ]メチル}オキセタン(アロンオキセタン OXT−221:東亞合成社製)1.45g、2−メチルイミダゾール1.09g、エポキシ末端カップリング剤(KBM403:信越化学工業社製)9.05g添加し、第1のキャスティング溶液を得た。
別途、無機ガラス(厚み50μm、長さ10cm×幅4cm)の片面表面をメチルエチルケトンで洗浄後、コロナ処理を行い、カップリング剤等を添加したキャスティング溶液を塗布し、100℃で10分間、さらに170℃で20分間乾燥させ、厚みが1μmの第1の熱可塑性樹脂層を形成した。同様の処理を無機ガラスのもう一方の面についても行った。
その後、製造例1で得られたポリマー90gをシクロペンタノン600gに溶かした第2のキャスティング溶液を、第1の熱可塑性樹脂層上に塗布し、90℃で15分間乾燥させた。さらに裏面にも第2のキャスティング溶液を第1の熱可塑性樹脂層上に塗布し、85℃で10分間乾燥させ、その後、両面を130℃で10分間、さらに170℃で20分間乾燥させ、片側の厚みが36.5μmの第2の熱可塑性樹脂を得て、総厚み125μmの透明基板(第2の熱可塑性樹脂層/第1の熱可塑性樹脂層/無機ガラス/第1の熱可塑性樹脂層/第2の熱可塑性樹脂層)を得た。なお、上記透明基板の幅方向端部(長さ10cm×幅1cm)は無機ガラスを露出させた。
上記で得られた透明基板を下記の方法で評価した。結果を表1に示す。
(1)密着性試験
JIS K 5400の碁盤目剥離試験により評価した。すなわち、得られた透明基板および積層体の片面最外層の表面上10mm角中に1mm間隔にカッターで切れ目を入れ、100個の碁盤目を作り、粘着テープをその上に貼り付けた後、剥離し、無機ガラスから剥離した樹脂層の碁盤目の数により密着性を評価した。
(2)外観
得られた透明基板の外観を目視にて確認した。透明基板に、発泡、クラック、シワが確認されない場合は合格(表1中、○で示す)とした。
(3)破断直径
(a)実施例および比較例で得られた透明基板を評価用試料として準備した。
(b)薄板ガラス露出部分の長辺中央に5mm以下のクラックを入れた。
(c)評価用試料の長辺を屈曲させ、クラックの進展を観察し、ガラスが破断した際の、屈曲した辺(長辺)を円周とする円の直径を破断直径とした。
(4)収縮応力
幅30mm×長さ125mmの短冊状無機ガラス(厚み100μm)の片面に、実施例および比較例と同様の方法で樹脂層を形成させ、カールしたサンプルの曲率半径Rを測定した。
補正項を導入したStonryの下記式(C.A.Klien,J.Appl.Phys., 88 5487 (2000))に、曲率半径R;薄板ガラスのヤング率(70GPa)、ポアソン比(0.2)および厚み(100μm);樹脂のヤング率、ポアソン比および厚みを代入して、樹脂層の収縮応力(すなわち、無機ガラスに付加される応力)を求めた。
20 塗布層
30 無機ガラス
40 接着剤組成物
21 熱可塑性樹脂層
41 接着剤層
100、100´ オーブン
200 透明基板
Claims (13)
- 溶剤透過性を有する支持基材上に熱可塑性樹脂(A)組成物溶液を塗布して、塗布層を形成する工程Aと、
無機ガラスの少なくとも一方の面と該塗布層とを、接着剤組成物を介して貼り合わせて、積層体を形成する工程Bと、
該積層体に第1の熱処理を施し、該塗布層中の残存溶剤量を所定量まで減少させる工程Cと、
該積層体から該支持基材を剥離した後、第2の熱処理を行い、該塗布層を乾燥して、熱可塑性樹脂層を形成する工程Dとを含み、
該工程Aにおける塗布層形成時に、該塗布層中の溶剤量が、7重量%以上である、
透明基板の製造方法。 - 前記第1の熱処理により、前記塗布層中の残存溶剤量を15重量%以下まで減少させる、請求項1記載の透明基板の製造方法。
- 前記支持基材を剥離する際の前記塗布層の収縮応力が、10MPa以下である、請求項1または2に記載の透明基板の製造方法。
- 前記第2の熱処理後に無機ガラスに付加される応力が、10MPa〜30MPaである、請求項1から3のいずれかに記載の透明基板の製造方法。
- 前記第1の熱処理の温度が、前記熱可塑性樹脂(A)組成物溶液に最も多く含まれる溶剤の沸点(bpA)に対して、(bpA−60)℃〜(bpA+40)℃である、請求項1から4のいずれかに記載の透明基板の製造方法。
- 前記第2の熱処理の温度が、前記熱可塑性樹脂(A)組成物溶液に最も多く含まれる溶剤の沸点(bpA)に対して、(bpA−20)℃〜250℃である、請求項1から5のいずれかに記載の透明基板の製造方法。
- 前記接着剤組成物が溶剤を含み、該接着剤層中の溶剤の沸点が、前記熱可塑性樹脂(A)組成物溶液に含まれる溶剤の沸点以上である、請求項1から6のいずれかに記載の透明基板の製造方法。
- 前記接着剤組成物が溶剤を含み、該接着剤層中の溶剤が、前記熱可塑性樹脂(A)組成物溶液に含まれる熱可塑性樹脂(A)に対して溶解性を示す、請求項1から7のいずれかに記載の透明基板の製造方法。
- 前記接着剤組成物が、前記熱可塑性樹脂(A)組成物溶液に含まれる熱可塑性樹脂(A)と相溶性を示す成分を含む、請求項1から8のいずれかに記載の透明基板の製造方法。
- 前記接着剤組成物が、溶剤、前記熱可塑性樹脂(A)組成物溶液と相溶性を示す熱可塑性樹脂(B)、熱硬化性モノマーおよび硬化反応触媒を含む、請求項1から9のいずれかに記載の透明基板の製造方法。
- 前記熱可塑性樹脂(B)が、末端に反応基を有する、請求項10に記載の透明基板の製造方法。
- 前記支持基材の90℃における貯蔵弾性率が、1.0×107Pa以上である、請求項1から11のいずれかに記載の透明基板の製造方法。
- 前記無機ガラスの厚みが、100μm以下である、請求項1から12のいずれかに記載の透明基板の製造方法。
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010252704A JP5615134B2 (ja) | 2010-04-30 | 2010-11-11 | 透明基板の製造方法 |
| PCT/JP2011/060367 WO2011136327A1 (ja) | 2010-04-30 | 2011-04-28 | 透明基板の製造方法 |
| CN201180021854.2A CN102869632B (zh) | 2010-04-30 | 2011-04-28 | 透明基板的制造方法 |
| KR1020127028339A KR101381087B1 (ko) | 2010-04-30 | 2011-04-28 | 투명 기판의 제조 방법 |
| US13/640,444 US9254627B2 (en) | 2010-04-30 | 2011-04-28 | Manufacturing method for transparent substrate |
| KR1020137032933A KR20140005376A (ko) | 2010-04-30 | 2011-04-28 | 투명 기판의 제조 방법 |
| EP14197914.6A EP2899169A1 (en) | 2010-04-30 | 2011-04-28 | Manufacturing method for transparent substrate |
| CN201410746255.2A CN104589736A (zh) | 2010-04-30 | 2011-04-28 | 透明基板的制造方法 |
| EP11775108.1A EP2565170A4 (en) | 2010-04-30 | 2011-04-28 | PROCESS FOR PRODUCING TRANSPARENT SUBSTRATE |
| TW103126680A TW201442859A (zh) | 2010-04-30 | 2011-04-29 | 積層體 |
| TW100115238A TWI496124B (zh) | 2010-04-30 | 2011-04-29 | Method of manufacturing transparent substrate |
| US14/542,138 US20150072155A1 (en) | 2010-04-30 | 2014-11-14 | Manufacturing method for transparent substrate |
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| CN (2) | CN102869632B (ja) |
| TW (2) | TW201442859A (ja) |
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| JP5883333B2 (ja) * | 2012-04-02 | 2016-03-15 | 日東電工株式会社 | 透明シートおよびその製造方法 |
| CN104350122A (zh) * | 2012-05-29 | 2015-02-11 | 日东电工株式会社 | 粘合剂和使用所述粘合剂的透明基板 |
| US20150140343A1 (en) * | 2012-05-29 | 2015-05-21 | Nitto Denko Corporation | Adhesive, and transparent substrate using same |
| JP6170288B2 (ja) * | 2012-09-11 | 2017-07-26 | 富士フイルム株式会社 | 転写材料、静電容量型入力装置の製造方法および静電容量型入力装置、並びに、これを備えた画像表示装置 |
| KR102147509B1 (ko) | 2013-03-14 | 2020-08-25 | 코닝 인코포레이티드 | 연성 유리 및 고분자 복합 구조의 제조 및 절단을 위한 방법 및 장치 |
| JP6530582B2 (ja) * | 2013-05-21 | 2019-06-12 | 大日本印刷株式会社 | 保護板用基板、電極付き表示装置用前面保護板、及び表示装置 |
| DE102013214422A1 (de) * | 2013-07-24 | 2015-01-29 | Schott Ag | Verbundelement und dessen Verwendung |
| KR102355043B1 (ko) * | 2014-03-28 | 2022-01-25 | 엘지디스플레이 주식회사 | 디스플레이 장치 및 이를 제조하는 벤딩 장치 |
| JP2016105183A (ja) * | 2016-01-07 | 2016-06-09 | 大日本印刷株式会社 | 薄膜素子用基板、薄膜素子、有機エレクトロルミネッセンス表示装置、および電子ペーパー |
| JP6170224B1 (ja) * | 2016-05-10 | 2017-07-26 | 住友化学株式会社 | 透明樹脂フィルムの製造方法、及び透明樹脂フィルムを有する積層体の製造方法 |
| KR102696454B1 (ko) * | 2016-12-02 | 2024-08-22 | 삼성디스플레이 주식회사 | 저곡률로 굽힘이 가능한 플렉시블 글라스 물품 및 그 제조 방법 |
| JP7268445B2 (ja) * | 2019-03-29 | 2023-05-08 | 大日本印刷株式会社 | フロストガラス調有機ガラスの製造方法。 |
| US12434265B2 (en) | 2019-07-19 | 2025-10-07 | Tokuyama Corporation | Coating method |
| JP2021154664A (ja) * | 2020-03-30 | 2021-10-07 | 日東電工株式会社 | 複層構造体 |
| WO2022186529A1 (ko) * | 2021-03-05 | 2022-09-09 | 주성엔지니어링(주) | 탠덤 태양 전지 및 그 제조방법 |
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2010
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2011
- 2011-04-28 EP EP14197914.6A patent/EP2899169A1/en not_active Withdrawn
- 2011-04-28 CN CN201180021854.2A patent/CN102869632B/zh not_active Expired - Fee Related
- 2011-04-28 US US13/640,444 patent/US9254627B2/en not_active Expired - Fee Related
- 2011-04-28 EP EP11775108.1A patent/EP2565170A4/en not_active Withdrawn
- 2011-04-28 KR KR1020137032933A patent/KR20140005376A/ko not_active Withdrawn
- 2011-04-28 WO PCT/JP2011/060367 patent/WO2011136327A1/ja not_active Ceased
- 2011-04-28 KR KR1020127028339A patent/KR101381087B1/ko not_active Expired - Fee Related
- 2011-04-28 CN CN201410746255.2A patent/CN104589736A/zh active Pending
- 2011-04-29 TW TW103126680A patent/TW201442859A/zh unknown
- 2011-04-29 TW TW100115238A patent/TWI496124B/zh not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2011136327A1 (ja) | 2011-11-03 |
| KR20130024902A (ko) | 2013-03-08 |
| KR101381087B1 (ko) | 2014-04-02 |
| US20130032277A1 (en) | 2013-02-07 |
| EP2899169A1 (en) | 2015-07-29 |
| JP2011245843A (ja) | 2011-12-08 |
| CN102869632A (zh) | 2013-01-09 |
| TW201442859A (zh) | 2014-11-16 |
| US9254627B2 (en) | 2016-02-09 |
| EP2565170A4 (en) | 2014-06-18 |
| CN104589736A (zh) | 2015-05-06 |
| EP2565170A1 (en) | 2013-03-06 |
| TWI496124B (zh) | 2015-08-11 |
| KR20140005376A (ko) | 2014-01-14 |
| US20150072155A1 (en) | 2015-03-12 |
| TW201218147A (en) | 2012-05-01 |
| CN102869632B (zh) | 2015-05-06 |
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