TWI441733B - Method for manufacturing multilayer laminated film - Google Patents

Method for manufacturing multilayer laminated film Download PDF

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Publication number
TWI441733B
TWI441733B TW96121454A TW96121454A TWI441733B TW I441733 B TWI441733 B TW I441733B TW 96121454 A TW96121454 A TW 96121454A TW 96121454 A TW96121454 A TW 96121454A TW I441733 B TWI441733 B TW I441733B
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TW
Taiwan
Prior art keywords
film
elastic roller
resin
angle
laminated film
Prior art date
Application number
TW96121454A
Other languages
English (en)
Other versions
TW200817181A (en
Inventor
Yutaka Fujita
Kazuki Tsuchimoto
Morimasa Wada
Tomoyuki Senoo
Takafumi Ooura
Kentarou Ikeshima
Tomoaki Masuda
Original Assignee
Nitto Denko Corp
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Publication date
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Publication of TW200817181A publication Critical patent/TW200817181A/zh
Application granted granted Critical
Publication of TWI441733B publication Critical patent/TWI441733B/zh

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/40General 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
    • B29C66/41Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45Joining of substantially the whole surface of the articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805Joining 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
    • B29C65/481Non-reactive adhesives, e.g. physically hardening adhesives
    • B29C65/4825Pressure sensitive adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52Joining 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/05Particular design of joint configurations
    • B29C66/10Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11Joint 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
    • B29C66/112Single lapped joints
    • B29C66/1122Single lap to lap joints, i.e. overlap joints
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/342Preventing air-inclusions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/72General 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 structure of the material of the parts to be joined
    • B29C66/723General 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 structure of the material of the parts to be joined being multi-layered
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/73General 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
    • B29C66/733General 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
    • B29C66/7332General 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 coloured
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/73General 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
    • B29C66/733General 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
    • B29C66/7336General 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
    • B29C66/73365General 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
    • B29C66/73366General 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 both parts to be joined being transparent or translucent to visible light
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/73General 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
    • B29C66/733General 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
    • B29C66/7338General 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 polarising
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/73General 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
    • B29C66/737General 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 state of the material of the parts to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/73General 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
    • B29C66/739General 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
    • B29C66/7392General 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/80General aspects of machine operations or constructions and parts thereof
    • B29C66/83General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834General 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
    • B29C66/8341Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83411Roller, cylinder or drum types
    • B29C66/83413Roller, cylinder or drum types cooperating rollers, cylinders or drums
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/80General aspects of machine operations or constructions and parts thereof
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    • B29C66/83411Roller, cylinder or drum types
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B32B37/0007Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
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    • GPHYSICS
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    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
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Description

多層層疊膜之製造方法
本發明係關於一種於水分率為10~60重量%之樹脂薄膜之兩面,經由接著層或黏著層而貼合水分率為0.5~5重量%之第一及第二透明薄膜之多層層疊膜之製造方法。
本發明之製造方法可應用於各種多層層疊膜之製造,例如可於使用偏光膜作為樹脂薄膜、使用偏光膜用之透明保護薄膜作為透明薄膜來製造偏光板之方法中使用。此外,亦可用於製造食品、醫療儀器等之包裝中所使用之多層層疊膜。
自先前以來,於樹脂薄膜之兩面貼合透明薄膜而製造多層層疊膜時,通常使用水系接著劑或黏著劑。作為於樹脂薄膜之兩面貼合透明薄膜之方法,例如可採用於一對輥間輸送樹脂薄膜,並且向其兩面上輸送並同時貼合透明薄膜之同時層疊法;於一對輥間輸送透明薄膜,並且向其一面上輸送並貼合透明薄膜後,接著於樹脂薄膜之另一面上貼合透明薄膜之逐次層疊法。
然而,利用上述層疊法,於貼合樹脂薄膜與透明薄膜時,所獲得之多層層疊膜中之樹脂薄膜與透明薄膜之間會產生氣泡。另外,會產生皺褶或生成條紋狀之凹凸不均。
針對上述皺褶之產生等相關課題,提出有以特定之夾持壓而貼合樹脂薄膜(含水率為0.1~20重量%之聚乙烯醇系薄膜)與透明薄膜(纖維素系薄膜)之方法(專利文獻1)。然而,即使利用該方法,亦無法充分地抑制於多層層疊膜中之樹脂薄膜與透明薄膜之間所產生之氣泡。
專利文獻1:日本專利特開平10-166519號公報
本發明之目的在於提供一種多層層疊膜之製造方法,其係於樹脂薄膜上貼合透明薄膜之多層層疊膜之製造方法,其可抑制於樹脂薄膜與透明薄膜之間所產生之氣泡,並且可抑制皺褶或條紋狀凹凸不均之產生。
本發明人等為了解決上述課題而進行積極研究,結果發現利用以下所示之多層層疊膜之製造方法可實現上述目的,以至完成本發明。
本發明係關於一種多層層疊膜之製造方法,其係於水分率為10~60重量%之樹脂薄膜之兩面,經由接著層或黏著層而貼合水分率為0.5~5重量%之第一透明薄膜及第二透明薄膜之多層層疊膜之製造方法,其特徵在於,按照第一透明薄膜位於第一金屬輥側之方式使樹脂薄膜於第一透明薄膜通過第一金屬輥與第一彈性輥該一對輥間,藉此壓接而形成層疊膜之後,並不捲取該層疊膜,按照第二透明薄膜位於第二金屬輥側之方式使該層疊膜與第二透明薄膜通過第二金屬輥與第二彈性輥該一對輥間,藉此壓接而形成多層層疊膜。
上述多層層疊膜之製造方法中,較好的是第一金屬輥與第二金屬輥之至少任一者為鐵輥或不銹鋼輥。
上述多層層疊膜之製造方法中,較好的是第一彈性輥及第二彈性輥均為於金屬製芯部上塗佈橡膠層或樹脂層而獲得之彈性輥。上述第一彈性輥及第二彈性輥較好的是橡膠層或樹脂層之硬度為70以上100以下。
上述多層層疊膜之製造方法中,較好的是第一彈性輥之變形凹部端點處之切線與樹脂薄膜之輸送線所成之角度(θ1a)、和第一彈性輥之變形凹部端點處之切線與第一透明薄膜之輸送線所成之角度(θ1b),相對於第一彈性輥之變形凹部端點處之切線為相反方向。
其中,第一彈性輥之變形凹部端點係指由第一金屬輥接觸擠壓第一彈性輥而產生之第一彈性輥之變形凹部處的第一彈性輥與第一金屬輥之最開始接觸點。
樹脂薄膜之輸送線係指樹脂薄膜與第一彈性輥之最開始接觸點處之切線。
第一透明薄膜之輸送線係指第一透明薄膜與第一金屬輥之最開始接觸點處之切線。
上述多層層疊膜之製造方法中可具有如下機構,該機構於將樹脂薄膜向第一金屬輥與第一彈性輥該一對輥間輸送之前,改變第一彈性輥之變形凹部端點處之切線與樹脂薄膜之輸送線所成之角度(θ1a)。
上述多層層疊膜之製造方法中,較好的是第二彈性輥之變形凹部端點處之切線與層疊膜之輸送線所成之角度(θ2a)、和第二彈性輥之變形凹部端點處之切線與第二透明薄膜之輸送線所成之角度(θ2b),相對於第二彈性輥之變形凹部端點處之切線為相反方向。
其中,第二彈性輥之變形凹部端點係指由第二金屬輥接觸擠壓第二彈性輥而產生之第二彈性輥之變形凹部處的第二彈性輥與第二金屬輥之最開始接觸點。
層疊膜之輸送線係指層疊膜與第二彈性輥之最開始接觸點處之切線。
第二透明薄膜之輸送線係指第二透明薄膜與第二金屬輥之最開始接觸點處之切線。
上述多層層疊膜之製造方法中具有如下機構,該機構於將層疊膜向第二金屬輥與第二彈性輥該一對輥間輸送之前,改變第二彈性輥之變形凹部端點處之切線與層疊膜之輸送線所成之角度(θ2a)者。
上述多層層疊膜之製造方法中,較好的是第一金屬輥與第一彈性輥間之層疊壓力及第二金屬輥與第二彈性輥間之層疊壓力之至少任一者為2 MPa以上5 MPa以下。
上述本發明之多層層疊膜之製造方法採用逐次層疊法,並於貼合各薄膜時使用組合彈性輥與金屬輥該一對輥。並且,於貼合樹脂薄膜與透明薄膜時,或者將貼合有樹脂薄膜與透明薄膜之層疊膜中之樹脂薄膜側與透明薄膜進行貼合時,均以透明薄膜位於金屬輥側之方式使之通過。利用該輥之組合,金屬輥不會接觸含水之樹脂薄膜,並且利用彈性輥之彈性力使樹脂薄膜與透明薄膜貼合,因此可抑制於樹脂薄膜與透明薄膜之間所產生之氣泡,且可製造多層層疊膜。另外,亦可抑制產生皺褶或生成條紋狀之凹凸不均。
於上述本發明之多層層疊膜之製造方法中,對所輸送之各薄膜之角度進行控制,使樹脂薄膜之輸送角度(θ1a)與第一透明薄膜之輸送角度(θ1b)相對於第一彈性輥之變形凹部端點處之切線成為相反方向,另外使層疊膜之輸送角度(θ2a)與第二透明薄膜之輸送角度(θ2b)相對於第二彈性輥之變形凹部端點處之切線成為相反方向,藉此可將樹脂薄膜與第一透明薄膜之最開始接觸時期或層疊膜與第二透明薄膜之最開始接觸時期、各薄膜由輥進行壓接之時期的時間控制成較短,可進一步抑制於樹脂薄膜與透明薄膜之間所產生之氣泡。
上述多層層疊膜之製造方法適用於使用偏光膜作為樹脂薄膜、使用偏光膜用之透明保護薄膜作為透明薄膜來製造偏光板之方法中。可獲得各薄膜間不會產生氣泡,另外不會產生皺褶或條紋狀凹凸不均之外觀良好之偏光板。該偏光板之面內均勻性優良,析像度高,並且可實現高對比度之液晶顯示裝置(LCD)、電致發光顯示裝置(ELD)等圖像顯示裝置。
以下參照圖式,說明本發明之多層層疊膜之製造方法。圖1為表示本發明之多層層疊膜之製造方法之一例之圖,首先,使樹脂薄膜A與第一透明薄膜B1通過第一彈性輥a1與第一金屬輥b1該一對輥間,藉此壓接而形成層疊膜L1。於上述一對輥中,樹脂薄膜A位於第一彈性輥a1側,另外,第一透明薄膜B1位於第一金屬輥b1側。接著,不捲取層疊膜,而使層疊膜L1(樹脂薄膜A側)與第二透明薄膜B2通過第二金屬輥b2與第二彈性輥a2該一對輥間,藉此壓接而形成多層層疊膜L2。多層層疊膜L2於樹脂薄膜A之兩面具有第一透明薄膜B1及第二透明薄膜B2。於上述一對輥中,層疊膜L1位於第二彈性輥a2側,另一方面,第二透明薄膜B2位於第二金屬輥b2側。
另外,於圖1中,於向第一彈性輥a1與第一金屬輥b1該一對輥間輸送樹脂薄膜A之前,設置有樹脂薄膜A之角度改變機構M1。另外,於向第二彈性輥a2與第二金屬輥b2該一對輥間輸送層疊膜L1之前,設置有層疊膜L1之角度改變機構M2。利用角度改變機構M1可控制進入第一彈性輥a1與第一金屬輥b1之間之樹脂薄膜A之角度。另外,利用角度改變機構M2可控制進入第二彈性輥a2與第二金屬輥b2之間之樹脂薄膜L1之角度。角度改變機構M1、M2於圖1中顯示為一對輥,於圖1中可藉由使其左右移動而控制上述進入角度。
再者,於第一彈性輥a1與第一金屬輥b1該一對輥間,經由接著層或黏著劑(未圖示)而貼合樹脂薄膜A與第一透明薄膜B1。上述接著層或黏著層可設置於樹脂薄膜A與第一透明薄膜B1之至少任一者一側,另外,亦可於貼合樹脂薄膜A與第一透明薄膜B1臨前,與已調節濃度或黏度之接著劑(溶液)或黏著劑(溶液)一起,通過第一彈性輥a1與第一金屬輥b1該一對輥間,藉此壓接。同樣,於第二彈性輥a2與第二金屬輥b2該一對輥間,經由接著層或黏著劑(未圖示)而貼合層疊膜L1與第二透明薄膜B2。上述接著層或黏著層既可設置於第二透明薄膜B2上,另外,亦可於貼合層疊膜L1與第二透明薄膜B2臨前,與己調節濃度或黏度之接著劑(溶液)或黏著劑(溶液)一起,通過第二彈性輥a2與第二金屬輥b2該一對輥間,藉此壓接。
再者,對輥之材質、輥直徑、貼合時之輸送速度等進行適當調節,另外,亦可適當調節接著層或黏著層之厚度。
作為上述第一彈性輥a1、第二彈性輥a2,例如可較好地使用於金屬製造之芯部塗佈有橡膠層或樹脂層之彈性輥。作為該橡膠層或樹脂層之硬度,較好的是使用70以上者,更好的是使用80以上者,進而較好的是使用85以上者。另外,為了防止薄膜表面受到損傷,較好的是100以下,更好的是95以下。作為此時之硬度,例如可利用JIS K6253(1997)中所揭示之方法,使用市售之硬度計(A型)來測定。再者,就表面壓力分布之均勻性方面而言,橡膠層或樹脂層之厚度較好的是1~15 mm左右,進而較好的是3~10 mm左右。第一彈性輥a1、第二彈性輥a2既可相同亦可不同。
作為上述第一金屬輥b1、第二金屬輥b2之材料,例如可列舉鐵、不銹鋼、鈦、鋁等。作為金屬輥,就相對費用效果及耐腐蝕性方面而言,較好的是鐵輥或不銹鋼輥。第一金屬輥b1、第二金屬輥b2既可相同亦可不同。
進而,作為上述各輥之直徑,由於直徑越小,樹脂薄膜A與第一透明薄膜B1或第二透明薄膜B2接觸之面積越小,故而對薄膜面施加之壓力相對變高。因此,作為輥之直徑,較好的是使用250 mm以下者,進而更好的是使用200 mm以下者。其中,若該直徑過小,則輥之耐久性會變弱,而無法施加充分之力,故而較好的是使用50 mm以上之輥,更好的是使用100 mm以上之輥。
另外,對貼合時之輸送速度並無特別限制,通常較好的是於2 m/分鐘~50 m/分鐘左右調節。
另外,對貼合時之輥間之層疊壓力並無特別限制,可適當設定。就調節之容易度或多層層疊膜之生產率方面而言,層疊壓力較好的是2 MPa以上5 MPa以下左右,更好的是3 MPa以上4 MPa以下。若層疊壓力小於2 MPa,則無法充分地擠壓,故而會於薄膜間產生氣泡。另外,若層疊壓力大於5 MPa,則對輥或裝置施加之負荷會過大,而成為破損之原因。層疊壓力之測定係使用富士膠片公司製造之感壓紙「Prescale」,藉由計算機圖像處理使該感壓紙之顏色變化二值化,而對於其顯色面積及濃度,根據所製作之壓力標準線之近似式進行求得。
如圖2A所示,於上述多層層疊膜之製造方法中,較好的是將樹脂薄膜A之輸送角度(θ1a)與第一透明薄膜B1之輸送角度(θ1b)控制成,相對於第一彈性輥a1之變形凹部端點x1處之切線y1為相反方向。即,較好的是第一彈性輥a1之變形凹部端點x1處之切線y1與樹脂薄膜A之輸送線所成之角度(θ1a)和切線y1與第一透明薄膜B1之輸送線所成之角度(θ1b),相對於切線y1為相反方向。藉此,可以將樹脂薄膜A與第一透明薄膜B1之最開始接觸時期和該等薄膜由第一彈性輥a1及第一金屬輥壓接之時期的時間控制為較短,藉此,可進一步抑制於樹脂薄膜A與第一透明薄膜B1之間所產生的氣泡。上述角度(θ1a)之控制可利用圖1之角度控制機構M1進行。
圖2A中,第一彈性輥a1之變形凹部端點x1係指第一彈性輥a1由第一金屬輥b1接觸擠壓而產生之第一彈性輥之變形凹部z1處的第一彈性輥a1與第一金屬b1之最開始接觸點(旋轉方向之最開始之接觸點)。另外,樹脂薄膜A之輸送線係指樹脂薄膜A與第一彈性輥a1之最開始接觸點處之切線(所輸送之樹脂薄膜A之延長線上之線)。第一透明薄膜B1之輸送線係指第一透明薄膜B1與第一金屬輥b1之最開始接觸點處之切線(所輸送之第一透明薄膜B1之延長線上之線)。
圖2A中,關於角度(θ1a)、角度(θ1b),若以切線y1為基準右旋表示為「+」、左旋表示為「-」,則角度(θ1a)若為「-」之角度,則並無特別限制。角度(θ1b)若為「+」之角度,則並無特別限制。
於上述中,關於圖2A,提及有樹脂薄膜A之輸送角度(θ1a)與第一透明薄膜B1之輸送角度(θ1b),同樣,如圖2B所示,亦可對層疊膜L1之輸送角度(θ2a)與第二透明薄膜B2之輸送角度(θ2b)加以控制,藉此進一步抑制層疊膜L1中之樹脂薄膜A與第二透明薄膜B2之間所產生之氣泡。上述角度(θ2a)之控制可利用圖1之角度控制機構M2進行。
圖2B中,關於角度(θ2a)、角度(θ2b),若以切線y2為基準右旋表示為「+」、左旋表示為「-」,則角度(θ2a)若為「+」,則並無特別限制。角度(θ2b)若為「-」之角度,則並無特別限制。
本發明之多層層疊膜之製造方法中所使用之樹脂薄膜水分率為10~60重量%。本發明中較好的是所應用之樹脂薄膜之水分率為15~50重量%,更好的是20~40重量%。另一方面,第一及第二透明薄膜之水分率為0.5~5重量%。本發明較好的是所應用之上述透明薄膜之水分率為1~3重量%。再者,第一及第二透明薄膜之材料既可相同亦可不同。另外,水分率既可相同亦可不同。再者,於多層層疊膜之製造方法中,形成接著層或黏著層之材料可根據所使用之樹脂薄膜、透明薄膜而適當確定。
以下,就使用偏光膜作為樹脂薄膜,使用偏光膜用之透明保護薄膜作為透明薄膜,經由接著層或黏著層將其貼合,從而製造偏光板之情況加以說明。
作為上述偏光膜,通常使用對聚乙烯醇(PVA)系薄膜等聚合物薄膜以碘或二色性染料等二色性物質進行染色並單軸拉伸之薄膜。對此種偏光膜之厚度並無特別限制,通常使用5~80 μm左右、較好的是為40 μm以下者。
作為偏光膜之特性,用偏光膜單體測定時之單體透過率較好的是40%以上,更好的是處於42~45%之範圍。另外,準備兩張上述偏光膜,以兩張偏光膜之吸收軸相互呈90°之方式進行重疊所測定之正交透過率較好的是更小,實際使用時較好的是0.00%以上0.050%以下,更好的是0.030%以下。作為偏光度,實際使用時較好的是99.90%以上100%以下,特別好的是99.93%以上100%以下。作為偏光板進行測定時,亦較好的是獲得與其大致相同之光學特性。
作為形成偏光膜之聚合物薄膜,並無特別限制,可使用各種薄膜。例如,可列舉對聚乙烯醇(PVA)系薄膜、聚對苯二甲酸乙二醇酯(PET)系薄膜、乙烯.乙酸乙烯酯共聚物系薄膜或該等之部分皂化薄膜、纖維素系薄膜等親水性高分子薄膜進行PVA之脫水處理物或聚氯乙烯之脫鹽酸處理物等多烯系配向薄膜等。其中,就利用碘等二色性物質所進行之染色性優良方面而言,較好的是使用PVA系薄膜。
作為上述聚合物薄膜之材料的聚合物之聚合度通常為500~10,000,較好的是1000~6000之範圍,更好的是1400~4000之範圍。進而,於皂化薄膜之情形時,例如就對水之溶解性方面而言,其皂化度較好的是75莫耳%以上,更好的是98莫耳%以上,進而較好的是處於98.3~99.8莫耳%之範圍。
於使用PVA系薄膜作為上述聚合物薄膜之情形時,作為PVA系薄膜之製造方法,可適當使用將溶解於水或有機溶劑中之原液進行流延成膜之流延法、澆鑄法、擠出法等任意方法成膜之薄膜。較好的是使用此時之相位差值為5 nm~100 nm之薄膜。另外,為了獲得面內均勻之偏光膜,較好的是PVA系薄膜面內之相位差不均盡可能小者,PVA系薄膜之面內相位差不均於檢測波為1000 nm時較好的是10 nm以下,更好的是5 nm以下。
作為貼合偏光膜與透明保護薄膜時之偏光膜之水分率,若水分率為10~60重量%,則並無特別限定,若過低,則製成偏光板時容易產生條紋狀之凹凸不均或氣泡,相反,若過高,則需要長時間之乾燥時間,要求過大之乾燥設備。因此,作為於偏光膜上貼合透明保護薄膜時之偏光膜之水分率,較好的是15~50重量%,更好的是20~40重量%。此種偏光膜之水分率通常可利用偏光膜製造步驟中之乾燥處理之條件進行調節,亦可根據需要另外設置調濕處理步驟,實施向水浴中之浸漬或水滴之噴霧或者再次加熱乾燥或減壓乾燥。
作為偏光膜之製造方法,並非限定於此,通常可大致分為乾式拉伸法與濕式拉伸法。作為利用濕式拉伸法所進行之偏光膜之製造步驟,可根據其條件,使用適當之方法,通常為藉由例如包括膨潤、染色、交聯、拉伸、水洗以及乾燥處理步驟之一系列製造步驟而製造上述偏光膜之方法。除了乾燥處理步驟以外,於該等各處理步驟中,一邊於浸漬於包含各種溶液之浴中,一邊進行處理。對此時之各處理步驟中之膨潤、染色、交聯、水洗以及乾燥之各處理之順序、次數以及實施之有無並無特別限定,既可於一個處理步驟中同時進行幾個處理,亦可不進行幾個處理。例如,拉伸處理既可於染色處理之後進行,亦可與膨潤或染色處理同時進行,或者亦可於拉伸處理之後進行染色處理。進而,亦較好的是使用於拉伸處理之前後進行交聯處理之方法。另外,作為拉伸處理,並無特別限定,可使用適當之方法,例如於輥拉伸之情形時,可使用利用輥間之輥的圓周速度差進行拉伸之方法。進而,於各處理中亦可添加適當之硼酸、硼砂或碘化鉀等添加劑。因此,於偏光膜中,根據需要亦可含有硼酸、硫酸鋅、氯化鋅或碘化鉀等。進而,於該等幾個處理中既可適當向縱向或寬度方向拉伸,亦可於各處理中進行水洗處理。
作為膨潤處理步驟,例如將上述聚合物薄膜浸漬於以水注滿之處理浴(膨潤浴)中。藉此,水洗聚合物薄膜,可清洗聚合物薄膜表面之污垢或抗黏連劑,並且可期待藉由使聚合物薄膜膨潤而防止染色不均等不均勻性之效果。於該膨潤浴中,亦可適當添加甘油或碘化鉀等,添加之濃度較好的是甘油為5重量%以下、碘化鉀為10重量%以下。膨潤浴之溫度為20~50℃左右,於膨潤浴中之浸漬時間為2~180秒左右。另外,亦可於該膨潤浴中拉伸聚合物薄膜,此時之拉伸倍率為1.1~3.5倍左右。
作為染色處理步驟,例如可列舉藉由將上述聚合物薄膜浸漬於含有碘等二色性物質之處理浴(染色浴)中而進行染色之方法。作為上述二色性物質,可使用先前眾所周知之物質,例如可列舉碘或有機染料等。作為有機染料,例如可使用紅BR、紅LR、紅R、粉LB、玉紅BL、棗紅GS、天藍LG、檸檬黃、藍色BR、藍色2R、藏青RY、綠色LG、紫色LB、紫色B、黑色H、黑色B、黑色GSP、黃色3G、黃色R、橙色LR、橙色3R、猩紅GL、猩紅KGL、剛果紅、亮紫BK、蘇普拉藍G、蘇普拉藍GL、蘇普拉橙GL、直接天藍、直接永固橙S、永固黑等。該等二色性物質既可使用一種,亦可併用兩種以上。其中,於本發明中,就偏光度等光學特性優良、容易獲得本發明之條紋狀凹凸不均之降低效果方面而言,較好的是使用碘。
作為染色浴之溶液,可使用將上述二色性物質溶解於溶劑中之溶液。作為溶劑,通常使用純水等水,亦可進一步添加與水有相溶性之有機溶劑。作為二色性物質之濃度,為0.010~10重量%左右。對聚合物薄膜於該染色浴中之浸漬時間並無特別限定,為0.5~20分鐘左右,染色浴之溫度為5~42℃左右。於該染色浴中亦可拉伸聚合物薄膜,與前面之處理步驟中之拉伸倍率累計之累積拉伸倍率為1.1~3.5倍左右。
另外使用碘作為上述二色性物質時,就可進一步提高染色效率方面而言,較好的是於染色浴中進一步添加碘化物。作為該碘化物,例如可列舉碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鐵等。該等碘化物之添加比例於上述染色浴中為0.010~10重量%左右即可。其中,較好的是添加碘化鉀,碘與碘化鉀之比例(重量比)較好的是於1:5~1:100之範圍。進而,以提高薄膜面內之均勻性為目的,亦可適當添加硼化合物等交聯劑。
另外,作為染色處理,除了浸漬於如上所述之染色浴中之方法以外,例如既可使用將含有二色性物質之水溶液塗佈或噴霧於上述聚合物薄膜上之方法,亦可使用於上述聚合物薄膜製膜時預先混合二色性物質之方法。
作為交聯處理步驟,例如於含有交聯劑之處理浴(交聯浴)中浸漬處理聚合物薄膜而進行處理。作為交聯劑,可使用先前眾所周知之物質。例如可列舉硼酸、硼砂等硼化合物或乙二醛、戊二醛等。該等既可為一種,亦可併用兩種以上。併用兩種以上時,例如較好的是硼酸與硼砂之組合,另外,其添加比例(莫耳%比)為4:6~9:1左右。作為交聯浴之溶劑,通常使用純水等水,亦可含有與水有相溶性之有機溶劑。交聯浴中之交聯劑濃度為1~10重量%左右。
就可獲得偏光膜之面內均勻特性方面而言,亦可於上述交聯劑中添加碘化物。作為該碘化物,例如可列舉碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鐵,其含量為0.05~15重量%,更好的是0.5~8重量%。其中,較好的是硼酸與碘化鉀之組合,硼酸與碘化鉀之比例(重量比)較好的是於1:0.1~1:3.5之範圍,更好的是於1:0.5~1:2.5之範圍。交聯浴之溫度通常為20~70℃,浸漬時間通常為1秒~15分鐘左右。進而,交聯處理與染色處理同樣,既可使用塗佈或噴霧含交聯劑溶液之方法,亦可與交聯處理同時實施拉伸處理。此時之累積拉伸倍率為1.1~3.5倍左右。
作為拉伸處理步驟,於濕式拉伸法之情形時,於浸漬於處理浴(拉伸浴)中之狀態下,拉伸到累積拉伸倍率為2~7倍左右。作為拉伸浴之溶液,較好的是使用於水、乙醇或各種有機溶劑等溶劑中添加有各種金屬鹽、碘、硼或鋅之化合物之溶液。其中,較好的是使用分別以2~18重量%左右添加硼酸及/或碘化鉀之溶液。於同時使用該硼酸與碘化鉀之情形時,其含有比例(重量比)較好的是1:0.1~1:4左右。該拉伸浴之溫度較好的是40~67℃左右。
作為水洗處理步驟,例如藉由於處理浴(水洗浴)中浸漬聚合物薄膜,可洗去於前面之處理中附著之硼酸等不需要之殘存物。於上述水溶液中亦可添加碘化物,例如較好的是使用碘化鈉或碘化鉀。水洗浴之溫度為10~60℃左右。該水洗處理之次數並無特別限定,可實施複數次,較好的是適當調節各水洗浴中之添加物之種類或濃度。
再者,自各處理浴中提出聚合物薄膜時,為了防止液體滴落之發生,既可使用先前眾所周知之夾送輥等除液輥,亦可藉由以氣刀去除液體等之方法除去多餘之水分。
作為乾燥處理步驟,可使用自然乾燥、送風乾燥、加熱乾燥等先前眾所周知之乾燥方法。例如,於加熱乾燥中,加熱溫度為20~80℃左右,乾燥時間為1~10分鐘左右。另外,於該乾燥處理步驟中,亦可適當進行拉伸。
進而,藉由上述處理步驟而獲得之偏光膜之最終拉伸倍率(總拉伸倍率)較好的是3~7倍。總拉伸倍率未滿3倍時,難以獲得高偏光度之偏光膜,若超過7倍,則薄膜容易破裂。
另外,偏光膜之製造方法並不限定於上述製造方法,若滿足水分率為10~60重量%,則亦可使用其它製造方法製造偏光膜。例如,亦可為乾式拉伸法,或於聚對苯二甲酸乙二醇酯(PET)等聚合物薄膜中攪入二色性物質後進行製膜、拉伸之方法,可列舉將於單軸方向配向之液晶作為主(host)、於其中將二色性物質作為賓(guest)之類之O型方法(美國專利5,523,863號,日本專利特表平3-503322號公報),使用二色性溶致液晶等之E型方法(美國專利6,049,428號公報)。
作為上述透明保護薄膜,以保護偏光膜為目的,故而較好的是透明性、機械強度、熱穩定性、各向同性等方面優良之薄膜。透明保護薄膜之厚度通常較好的是1~300 μm左右,更好的是5~100 μm左右。另外,就提高偏光特性或耐久性以及接著特性等方面而言,亦可藉由電暈處理、電漿處理、火焰處理、臭氧處理、底塗處理、輝光處理、皂化處理對透明保護薄膜表面進行表面改性處理。該等表面改性處理中,較好的是用鹼等進行皂化處理。若按照溫度40℃、相對濕度90%下之JIS Z0208(杯式法)測定此種透明保護薄膜之透濕率,則為0.5~5000 g/m2 .24 h左右。
作為形成透明保護薄膜之材料,例如可列舉聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等聚酯系聚合物,二乙醯纖維素或三乙醯纖維素等纖維素系聚合物,聚甲基丙烯酸甲酯等丙烯酸系聚合物,聚苯乙烯或丙烯睛-苯乙烯共聚物(AS樹脂)等苯乙烯系聚合物,聚碳酸酯系聚合物。另外,作為形成上述保護薄膜之聚合物之例,亦可舉例聚乙烯、聚丙烯、具有環系或降冰片烯結構之聚烯烴、乙烯-丙烯共聚物之類之聚烯烴系聚合物,氯乙烯系聚合物,尼龍或芳香族聚醯胺等醯胺系聚合物,醯亞胺系聚合物,碸系聚合物,聚醚碸系聚合物,聚醚醚酮系聚合物,聚苯硫醚系聚合物,乙烯基醇系聚合物,偏氯乙烯系聚合物,乙烯丁醛系聚合物,芳酯系聚合物,聚甲醛系聚合物,環氧系聚合物,或者上述聚合物之摻合物等。透明保護薄膜中亦可含有1種以上任意之適當添加劑。作為添加劑,例如可列舉紫外線吸收劑、抗氧化劑、潤滑劑、可塑劑、脫模劑、著色防止劑、阻燃劑、成核劑、抗靜電劑、顏料、著色劑等。透明保護薄膜中之上述熱塑性樹脂之含量較好的是50~100重量%,更好的是50~99重量%,進而較好的是60~98重量%,特別好的是70~97重量%。透明保護薄膜中之上述熱塑性樹脂之含量為50重量%以下之情形時,可能無法充分地表現出熱塑性樹脂本來具有之高透明性等。
另外,作為透明保護薄膜,可列舉如日本專利特開2001-343529號公報(WO 01/37007)中揭示之上述聚合物薄膜,例如可列舉包含(A)側鏈上具有取代及/或未取代醯亞胺基之熱塑性樹脂、以及(B)側鏈上具有取代及/或未取代苯基及腈基之熱塑性樹脂的樹脂組合物。作為具體例,可列舉含有包含異丁烯與N-甲基順丁烯二醯亞胺之交替共聚物及丙烯腈-苯乙烯共聚物的樹脂組合物之薄膜。薄膜可使用由樹脂組合物之混合擠壓製品等構成之薄膜。該等薄膜之相位差較小,且光彈性模量較小,故而能夠消除偏光板之應變所造成之不均等不良情況,另外因其透濕度較小,故加濕耐久性優良。
將該保護薄膜貼合於偏光膜之兩面時,亦可於其每一面上使用具有彼此不同之特性之保護薄膜。作為其特性,例如可列舉厚度、材質、透光率、拉伸彈性模量或光學功能層之有無等。
作為本發明之透明保護薄膜,較好的是使用自纖維素樹脂(聚合物)、聚碳酸酯樹脂(聚合物)、環狀聚烯烴樹脂(具有環系或降冰片烯結構之聚烯烴)及(甲基)丙烯酸樹脂中選擇之至少一種。使用包含三乙醯纖維素之保護薄膜之情形時,本發明之效果特別顯著。
纖維素樹脂為纖維素與脂肪酸之酯。作為此種纖維素酯系樹脂之具體例,可列舉三乙醯纖維素、二乙醯纖維素、三丙醯纖維素、二丙醯纖維素等。其中,特別好的是三乙醯纖維素。三乙醯纖維素有很多製品出售,於容易獲得或成本方面亦較為有利。作為三乙醯纖維素之市售品之例,可列舉富士膠片公司製造之商品名「UV-50」、「UV-80」、「SH-80」、「TD-80U」、「TD-TAC」、「UZ-TAC」或KONICA公司製造之「KC系列」等。通常該等三乙醯纖維素,面內相位差(Re)大致為0,厚度方向相位差(Rth)具有約60 nm左右。
再者,厚度方向相位差較小之纖維素樹脂,例如可藉由處理上述纖維素樹脂而獲得。例如可列舉將塗佈有環戊酮、甲基乙基酮等溶劑之聚對苯二甲酸乙二醇酯、聚丙烯、苯乙烯等基材薄膜貼合於通常之纖維素系薄膜上,加熱乾燥(例如於80~150℃加熱3~10分鐘左右)後,剝離基材薄膜之方法;將於環戊酮、甲基乙基酮等溶劑中溶解有降冰片烯系樹脂、(甲基)丙烯酸系樹脂等之溶液塗佈於通常之纖維素樹脂薄膜上,加熱乾燥(例如於80~150℃加熱3~10分鐘左右)後,剝離塗佈薄膜之方法等。
另外,作為厚度方向相位差較小之纖維素樹脂,可使用控制了脂肪取代度之脂肪酸纖維素系樹脂薄膜。於通常使用之三乙醯纖維素中,通過乙酸取代度為2.8左右,較好的是控制為1.8~2.7,藉此可以減小Rth。藉由於上述脂肪酸取代纖維素系樹脂中添加鄰苯二甲酸二丁酯、對甲苯磺醯苯胺、檸檬酸乙醯三乙酯等可塑劑,可以控制Rth為較小值。相對於100重量份脂肪酸纖維素系樹脂,可塑劑之添加量較好的是40重量份以下,更好的是1~20重量份,進而較好的是1~15重量份。
作為環狀聚烯烴樹脂之具體例,較好的是降冰片烯系樹脂。環狀聚烯烴系樹脂係將環狀烯烴作為聚合單元而聚合之樹脂之總稱,例如,可列舉日本專利特開平1-240517號公報、日本專利特開平3-14882號公報、日本專利特開平3-122137號公報等所揭示之樹脂。作為具體例,可列舉環狀烯烴之開環(共)聚合物、環狀烯烴之加聚物、環狀烯烴與乙烯、丙烯等a-烯烴之共聚物(代表性的為無規共聚物)及用不飽和羧酸或其衍生物使該等改性之接枝共聚物、以及該等之氫化物等。作為環狀烯烴之具體例,可列舉降冰片烯系單體。
作為環狀聚烯烴樹脂,有多種製品出售。作為具體例,可列舉日本Zeon股份有限公司製造之商品名「ZEONEX」、「ZEONOR」、JSR股份有限公司製造之商品名「ARTON」、TICONA公司製造之商品名「TOPAS」、三井化學股份有限公司製造之商品名「APEL」。
作為(甲基)丙烯酸系樹脂,Tg(玻璃轉移溫度)較好的是115℃以上,更好的是120℃以上,進而較好的是125℃以上,特別好的是130℃以上。藉由使Tg為115℃以上,可使偏光板之耐久性優良。對上述(甲基)丙烯酸系樹脂之Tg之上限值並無特別限定,就成形性之觀點而言,較好的是170℃以下。由(甲基)丙烯酸系樹脂,可獲得面內相位差(Re)、厚度方向相位差(Rth)大致為0之薄膜。
作為(甲基)丙烯酸系樹脂,於不損及本發明之效果之範圍內,可採用任意適當之(甲基)丙烯酸系樹脂。例如可列舉聚甲基丙烯酸甲酯等聚(甲基)丙烯酸酯、甲基丙烯酸甲酯-(甲基)丙烯酸共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚物、甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚物、(甲基)丙烯酸甲酯-苯乙烯共聚物(MS樹脂等)、具有脂環族烴基之聚合物(例如甲基丙烯酸甲酯-甲基丙烯酸環已酯共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸降冰片烯酯共聚物等)。較好的是列舉聚(甲基)丙烯酸甲酯等聚(甲基)丙烯酸C1~6烷基酯。更好的是列舉以甲基丙烯酸甲酯為主要成分(50~100重量%,較好的是70~100重量%)之甲基丙烯酸甲酯系樹脂。
作為(甲基)丙烯酸系樹脂之具體例,例如可列舉三菱RAYON股份有限公司製造之Acrypet VH或Acrypet VRL 20A、日本專利特開2004-70296號公報中揭示之分子內具有環結構之(甲基)丙烯酸系樹脂、利用分子內交聯或分子內環化反應而獲得之高Tg(甲基)丙烯酸樹脂系。
作為(甲基)丙烯酸系樹脂,亦可使用具有內酯環結構之(甲基)丙烯酸系樹脂。其原因在於,具有高耐熱性、高透明性、利用雙軸拉伸之高機械強度。
作為具有內酯環結構之(甲基)丙烯酸系樹脂,可列舉日本專利特開2000-230016號公報、日本專利特開2001-151814號公報、日本專利特開2002-120326號公報、日本專利特開2002-254544號公報、日本專利特開2005-146084號公報等中揭示之具有內酯環結構之(甲基)丙烯酸系樹脂。
具有內酯環結構之(甲基)丙烯酸系樹脂,較好的是具有以下述通式(化1)表示之環結構。
[化1] 式中,R1 、R2 及R3 分別獨立,表示氫原子或碳原子數為1~20之有機殘基。再者,有機殘基亦可包括氧原子。
具有內酯環結構之(甲基)丙烯酸系樹脂之結構中,以通式(化1)表示之內酯環結構之含有比例較好的是5~90重量%,更好的是10~70重量%,進而較好的是10~60重量%,特別好的是10~50重量%。具有內酯環結構之(甲基)丙烯酸系樹脂之結構中,以通式(化1)表示之內酯環結構之含有比例若小於5重量%,則耐熱性、耐溶劑性、表面硬度可能會變得不充分。具有內酯環結構之(甲基)丙烯酸系樹脂之結構中,以通式(化1)表示之內酯環結構之含有比例若多於90重量%,則可能會變得缺乏成形加工性。
具有內酯環結構之(甲基)丙烯酸系樹脂之質量平均分子量(有時亦稱為重量平均分子量)較好的是1000~2000000,更好的是5000~1000000,進而較好的是10000~500000,特別好的是50000~500000。若質量平均分子量超出上述範圍,則就成型加工性方面而言,並非較好。
具有內酯環結構之(甲基)丙烯酸系樹脂,Tg較好的是115℃以上,更好的是120℃以上,進而較好的是125℃以上,特別好的是130℃以上。由於Tg為115℃以上,故而例如作為透明保護薄膜組入至於偏光板之情形時,則成為耐久性優良之偏光板。對上述具有內酯環結構之(甲基)丙烯酸系樹脂之Tg之上限值並無特別限定,就成形性等觀點而言,較好的是170℃以下。
具有內酯環結構之(甲基)丙烯酸系樹脂藉由射出成形而獲得之成形品,利用基於ASTM-D-1003之方法所測定之總光線透過率越高越好,較好的是85%以上,更好的是88%以上,進而較好的是90%以上。總光線透過率為透明性之基準,若總光線透過率未滿85%,則透明性可能會降低。
上述透明保護薄膜通常使用正面相位差未滿40 nm且厚度方向相位差未滿80 nm者。正面相位差Re以Re=(nx-ny)×d表示。厚度方向相位差Rth以Rth=(nx-nz)×d表示。另外,Nz係數以Nz=(nx-nz)/(nx-ny)表示。[其中,薄膜之滯相軸方向、進向軸方向以及厚度方向之折射率分別為nx、ny、nz、d(nm)為薄膜之厚度;滯相軸方向為薄膜面內之折射率最大之方向]。再者,透明保護薄膜較好的是盡可能不著色。可較好地使用厚度方向之相位差值為-90 nm~+75 nm之保護薄膜。藉由使用該厚度方向之相位差值(Rth)為-90 nm~+75 nm之保護薄膜,可基本消除透明保護薄膜引起之偏光板之著色(光學性著色)。厚度方向相位差值(Rth)進而較好的是-80 nm~+60 nm,特別好的是-70 nm~+45 nm。
另一方面,作為上述透明保護薄膜,可使用具有正面相位差為40 nm以上及/或厚度方向相位差為80 nm以上的相位差之相位差板。正面相位差通常控制於40~200 nm之範圍,厚度方向相位差通常控制於80~300 nm之範圍。使用相位差板作為透明保護薄膜之情形時,該相位差板亦起到透明保護薄膜之功能,故而可實現薄型化。
作為相位差板,可列舉對高分子素材實施單軸或雙軸拉伸處理而成之雙折射性薄膜、液晶聚合物之配向薄膜、以薄膜支持液晶聚合物之配向層之相位差板等。對相位差板之厚度並無特別限制,一般為20~150 μm左右。
作為高分子材料,例如可列舉聚乙烯醇、聚乙烯醇縮丁醛、聚甲基乙烯醚、聚丙烯酸羥乙酯、羥乙基纖維素、羥丙基纖維素、甲基纖維素、聚碳酸酯、聚芳酯、聚碸、聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚醚碸、聚苯硫醚、聚苯醚、聚烯丙基碸、聚醯胺、聚醯亞胺、聚烯烴、聚氯乙烯、纖維素樹脂、環狀聚烯烴樹脂(降冰片烯系樹脂)或該等之二元系、三元系各種共聚物、接枝共聚物、摻合物等。該等高分子材料可藉由拉伸等而成為配向物(拉伸薄膜)。
作為液晶聚合物,例如可列舉於聚合物之主鏈或側鏈中導入有賦予液晶配向性之共軛性直線狀原子團(液晶原基)之主鏈型或側鏈型各種液晶聚合物等。作為主鏈型液晶聚合物之具體例,可列舉具有以賦予彎曲性之間隔部而結合液晶原基之構造之聚合物,例如向列配向性之聚酯系液晶性聚合物、圓盤狀液晶聚合物或膽固醇型液晶聚合物等。作為側鏈型液晶聚合物之具體例,可列舉如下化合物等,即,將聚矽氧烷、聚丙烯酸酯、聚甲基丙烯酸酯或聚丙二酸酯作為主鏈骨架,作為側鏈利用由共軛性原子團構成之間隔部而具有由賦予向列配向性之對位取代環狀化合物單元構成之液晶原基部之聚合物等。該等液晶聚合物例如通過以下方法進行處理,即,於對形成於玻璃板上之聚醯亞胺或聚乙烯醇等薄膜之表面進行摩擦處理者、斜向蒸鍍有氧化矽者等之配向處理面上,鋪展液晶性聚合物之溶液並進行熱處理。
相位差板例如既可為各種波長板或以補償液晶層之雙折射所造成之著色或視角等為目的者等具有對應於使用目的適當相位差者,亦可為層疊2種以上之相位差板而控制相位差等光學特性者。
相位差板可根據各種用途而選擇使用滿足nx=ny>nz、nx>ny>nz、ny>ny=nz、nx>nz>ny、nz=nx>ny、nz>nx>ny、nz>nx=ny之關係者。再者,ny=nz不僅包括ny與nz完全相同之情況,亦包括ny與nz實質上相同之情況。
例如,滿足nx>ny>nz之相位差板,較好的是使用滿足正面相位差滿足40~100 nm、厚度方向相位差滿足100~320 nm、Nz係數滿足1.8~4.5者。例如,滿足nx>ny=nz之相位差板(正性A板),較好的是使用正面相位差滿足100~200 nm者。例如滿足nz=nx>ny之相位差板(負性A板),較好的是使用正面相位差滿足100~200 nm者。例如,滿足nx>nz>ny之相位差板,較好的是使用正面相位差滿足150~300 nm、Nz係數滿足0~0.7者。另外,如上所述,例如可使用滿足nx=ny>nz、nz>nx>ny或nz>nx=ny之相位差板。
透明保護薄膜可根據所應用之液晶顯示裝置進行適當選擇。例如為VA(垂直排列)(Vertical Alignment,包括MVA、PVA)之情形時,期望偏光板之至少一者(單元側)之透明保護薄膜具有相位差。作為具體之相位差,期望於Re=0~240 nm、Rth=0~500 nm之範圍。至於三維折射率,期望nx>ny=nz、nx>ny>nz、nx>nz>ny、nx=ny>nz(單軸、雙軸、Z化、負性C板)之情況。於液晶單元之上下使用偏光板時,既可為液晶單元之上下均具有相位差,或者亦可為上下任一之透明保護薄膜具有相位差。
例如為IPS(In-Plane Switing(板內轉換),包括FFS)之情形時,於偏光板之一方之透明保護薄膜具有相位差之情況、不具有之情況,均可使用。例如,於不具有相位差之情形時,期望於液晶單元之上下(單元側)均不具有相位差之情況。於具有相位差之情形時,期望於液晶單元之上下均具有相位差之情況、上下任一者具有相位差之情況(例如上側Z化、下側無相位差之情況,或上側A-板、下側正性C-板之情況)。具有相位差之情形時,期望於Re=-500~500 nm、Rth=-500~500 nm之範圍。至於三維折射率,期望nx>ny=nz、nx>nz>ny、nz>nx=ny、nz>nx>ny(單軸、Z化、正性C板、正性A板)。
再者,上述具有相位差之薄膜,可於不具有相位差之透明保護薄膜上另外貼合,從而賦予上述功能。
貼合上述偏光膜與透明保護薄膜時所使用之接著層或黏著層若光學上透明,則並無特別限制,可使用水系、溶劑系、熱熔系、自由基硬化型之各種形態者,較好的是水系接著劑或自由基硬化型接著劑。
作為形成接著層之水系接著劑,並無特別限制,例如可例示乙烯基聚合物系、明膠系、乙烯系乳膠系、聚胺酯系、異氰酸酯系、聚酯系、環氧系等。包含此種水系接著劑之接著層可作為水溶液之塗佈乾燥層等而形成,於製備該水溶液時,根據需要,亦可調配交聯劑或其他添加劑、酸等催化劑。作為上述水系接著劑,較好的是使用含有乙烯基聚合物之接著劑等,作為乙烯基聚合物,較好的是聚乙烯醇系樹脂。另外,亦可於聚乙烯醇系樹脂中含有硼酸或硼砂、戊二醛或三聚氰胺、草酸等水溶性交聯劑。特別是於使用聚乙烯醇系之聚合物薄膜作為偏光膜之情形時,就接著性方面而言,較好的是使用含有聚乙烯醇系樹脂之接著劑。進而,就提高耐久性方面而言,更好的是含有具有乙醯乙醯基之聚乙烯醇樹脂之接著劑。
對上述聚乙烯醇系樹脂並無特別限定,就接著性方面而言,較好的是平均聚合度為100~3000左右、平均皂化度為85~100莫耳%左右。另外,作為接著劑水溶液之濃度,可根據目標接著層之厚度而適當確定,故而並無特別限定,較好的是0.1~15重量%,更好的是0.5~10重量%。若該溶液濃度過高,則黏度過於上升,故而容易產生條紋狀之凹凸不均,若溶液濃度過低,則塗佈性變差,容易成為不均。
聚乙烯醇系樹脂可列舉使聚乙酸乙烯酯皂化而獲得之聚乙烯醇;其衍生物;進而可列舉乙酸乙烯酯與具有共聚合性之單體之共聚物之皂化物;使聚乙烯醇縮醛化、胺基甲酸酯化、醚化、接枝化、磷酸酯化等獲得之改性聚乙烯醇。作為上述單體,可列舉順丁烯二酸(酐)、反丁烯二酸、丁烯酸、衣康酸、(甲基)丙烯酸等不飽和羧酸及其酯類;乙烯、丙烯等α-烯烴,(甲基)烯丙基磺酸(鈉)、磺酸鈉(順丁烯二酸單烷基酯)、烷基順丁烯二酸二磺酸鈉、N-羥甲基丙烯醯胺、丙烯醯胺烷基磺酸鹼鹽、N-乙烯基吡咯烷酮、N-乙烯基吡咯烷酮衍生物等。該等聚乙烯醇系樹脂可單獨使用一種,或併用兩種以上。
含有乙醯乙醯基之聚乙烯醇系樹脂,係利用眾所周知之方法使聚乙烯醇系樹脂與二乙烯酮發生反應獲得。例如,可列舉使聚乙烯醇系樹脂分散於乙酸等溶劑中後,向其中添加二乙烯酮之方法;預先使聚乙烯醇系樹脂溶解於二甲基甲醯胺或二噁烷等溶劑後,向其中添加二乙烯酮之方法等。另外,亦可列舉使二乙烯酮氣體或液狀二乙烯酮直接接觸聚乙烯醇之方法。
含有乙醯乙醯基之聚乙烯醇系樹脂之乙醯乙醯基改性度若為0.1莫耳%以上,則並無特別限定。當未滿0.1莫耳%時,接著層之耐水性不充分,故而不適合。乙醯乙醯基改性度較好的是0.1~40莫耳%左右,進而較好的是1~20莫耳%,特別好的是2~7莫耳%。乙醯乙醯基改性度若超過40莫耳%,則與交聯劑之反應點變少,耐水性之提高效果較小。此種乙醯乙醯基改性度可利用核磁共振裝置(NMR:Nuclear Magnetic Resonance)測定。
作為交聯劑,可並無特別限制地使用通常於接著劑中使用者,例如使用如上所述之聚乙烯醇系樹脂之接著劑之情形時,可較好地使用至少具有2個與聚乙烯醇系樹脂具有反應性之官能團之化合物。例如,可列舉乙二胺、三伸乙二胺、己二胺等具有伸烷基與兩個胺基之烷基二胺類;甲苯二異氰酸酯、氫化甲苯二異氰酸酯、三羥甲基丙烷甲苯二異氰酸酯加合物、三苯基甲烷三異氰酸醋、亞甲基雙(4-苯基甲烷三異氰酸酯)、異佛爾酮二異氰酸酯以及該等之酮肟嵌段物或苯酚嵌段物等異氰酸酯類;乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、甘油二或三縮水甘油醚、1,6-己二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、二縮水甘油基苯胺、二縮水甘油基胺等環氧類;甲醛、乙醛、丙醛、丁醛等單醛類;乙二醛、丙二醛、丁二醛、戊二醛、順丁烯二醛、鄰苯二甲醛等二醛類;羥甲基尿素、羥甲基三聚氰胺、烷基化羥甲基尿素、烷基化羥甲基三聚氰胺、乙胍、苯代三聚氰胺與甲醛之縮合物等胺基-甲醛樹脂;進而可列舉鈉、鉀、鎂、鈣、鋁、鐵、鎳等二價金屬或三價金屬之鹽及其氧化物。其中,較好的是胺基-甲醛樹脂,特別好的是具有羥甲基之羥甲基化合物。
交聯劑之調配量相對於100重量份樹脂,通常為0.1~35重量份左右,較好的是使用10~25重量份者,於強調接著劑之耐久性之情形時,與從製備接著劑到成為接著層之時間(使用時間)變短相反,調配30重量份以上46重量份以下、更好的是32重量份以上40重量份以下之交聯劑亦較為有效。
作為自由基硬化型接著劑,可例示電子射線硬化型、紫外線硬化型等活化能量線硬化型,熱硬化型等各種接著劑,較好的是短時間內可硬化之活化能量線硬化型。特別好的是電子射線硬化型。
作為硬化性成分,可列舉具有(甲基)丙烯醯基之化合物、具有乙烯基之化合物。該等硬化性成分可使用單官能或二官能以上之任意一種。另外,該等硬化性成分可單獨使用一種或組合使用兩種以上。作為該等硬化性成分,例如較好的是具有(甲基)丙烯醯基之化合物,例如可列舉各種環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、聚酯(甲基)丙烯酸酯或各種(甲基)丙烯酸酯系單體等。
於上述硬化性成分中,較好的是環氧(甲基)丙烯酸酯、特別好的是具有芳香環及羥基之單官能之(甲基)丙烯酸酯。(甲基)丙烯酸酯表示丙烯酸酯及/或甲基丙烯酸酯。於本發明中(甲基)丙烯酸酯為該含義。
具有芳香環及羥基之單官能之(甲基)丙烯酸酯可使用具有芳香環及羥基之各種單官能之(甲基)丙烯酸酯。羥基亦可作為芳香環之取代基而存在,於本發明中較好的是作為使芳香環與(甲基)丙烯酸酯鍵結之有機基團(鍵結於羥基、尤其是伸烷基者)而存在。
作為上述具有芳香環及羥基之單官能之(甲基)丙烯酸酯,例如可列舉具有芳香環之單官能之環氧化合物與(甲基)丙烯酸之間之反應物。作為具有芳香環之單官能之環氧化合物,例如可列舉苯基縮水甘油醚、第三丁基苯基縮水甘油醚、苯基聚乙二醇縮水甘油醚等。作為具有芳香環及羥基之單官能之(甲基)丙烯酸酯之具體例,例如可列舉(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-羥基-3-第三丁基苯氧基丙酯、(甲基)丙烯酸2-羥基-3-苯基聚乙二醇丙酯等。
另外,作為具有(甲基)丙烯醯基之化合物,可較好地使用含氮單體及/或羧基單體。該等單體於接著性方面較好。
作為含氮單體,例如可列舉N-丙烯醯嗎啉、N-丙烯醯哌啶、N-甲基丙烯醯哌啶、N-丙烯醯吡咯啶等具有嗎啉環、哌啶環、吡咯啶環、哌嗪等雜環之含雜環丙烯酸單體。另外,作為含氮單體,例如可列舉順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯基順丁烯二醯亞胺;(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、N-甲基(甲基)丙烯酞胺、N-丁基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺或N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺、N-異丙基丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸胺基丙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯、(甲基)丙烯酸3-(3-pyrinidyl)丙酯等(甲基)丙烯酸烷基胺基烷基酯系單體;N-(甲基)丙烯醯氧基亞甲基丁二醯亞胺或N-(甲基)丙烯醯基-6-氧基六亞甲基丁二醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基丁二醯亞胺等丁二醯亞胺系單體等。含氮單體例如較好的是含雜環丙烯酸單體,特別好的是N-丙烯醯嗎啉。
作為羧基單體,例如可列舉(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯等。其中,較好的是丙烯酸。
除此以外,作為具有(甲基)丙烯醯基之化合物,亦可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基已酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸月桂酯等碳數為1~12之(甲基)丙烯酸烷基酯;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系單體;(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲墓)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酯或(4-羥甲基環已基)-甲基丙烯酸酯等含羥基單體;順丁烯二酸酐、衣康酸酐等含酸酐基單體;丙烯酸之已內酯加成物;苯乙烯磺酸或烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙烷磺酸、(甲基)丙烯醯胺丙烷磺酸、磺基丙基(甲基)丙烯酸酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基單體;2-羥乙基丙烯醯基磷酸酯等含磷酸基單體等。
作為上述硬化性成分,可較好地使用具有芳香環及羥基之單官能之(甲基)丙烯酸酯、含氮單體、羧基單體。就可以獲得相對於偏光膜及透明保護薄膜接著性良好之接著層之偏光板方面而言,較好的是含有50重量%以上之該等成分作為硬化性成分。進而,就塗佈性、加工性等方面而言亦較好。上述硬化性成分之比例較好的是含有60重量%以上,更好的是70重量%以上,進而較好的是80重量%以上。
作為上述硬化性成分,可使用二官能以上之硬化性成分。作為二官能以上之硬化性成分,較好的是二官能以上之(甲基)丙烯酸酯、特別好的是二官能以上之環氧(甲基)丙烯酸酯。二官能以上之環氧(甲基)丙烯酸酯可藉由單官能之環氧化合物與(甲基)丙烯酸之之反應而獲得。多官能之環氧化合物可例示各種環氧化合物。作為多官能之環氧化合物,例如可列舉芳香族環氧樹脂、脂環式環氧樹脂、脂肪族環氧樹脂。
作為芳香族環氧樹脂,例如可列舉雙酚A之二縮水甘油醚、雙酚F之二縮水甘油醚、雙酚S之二縮水甘油醚之類之雙酚型環氧樹脂;苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、羥基苯甲醛苯基酚醛清漆環氧樹脂之類之酚醛清漆型環氧樹脂;四羥基苯基甲烷之縮水甘油醚、四羥基二苯甲酮之縮水甘油醚、環氧化聚乙烯基苯酚之類之多官能型環氧樹脂等。
作為脂環式環氧樹脂,可列舉上述芳香族環氧樹脂之氫化物、環己烷系、環已基甲基酯系、環已基甲醚系、螺系、三環癸烷系等環氧樹脂。
作為脂肪族環氧樹脂,可列舉脂肪族多元醇或其環氧烷加成物之聚縮水甘油醚。作為該等之例,可列舉藉由使1,4-丁二醇之二縮水甘油醚、1,6-己二醇之二縮水甘油醚、甘油之三縮水甘油醚、三羥甲基丙烷之三縮水甘油醚、聚乙二醇之二縮水甘油醚、丙二醇之二縮水甘油醚、乙二醇或丙二醇、甘油之類之脂肪族多元醇加成1或2種以上之環氧烷(環氧乙烷或環氧丙烷)而獲得之聚醚多元醇之聚縮水甘油醚等。
上述環氧樹脂之環氧當量通常於30~3000 g/當量之範圍,較好的是於50~1500 g/當量之範圍。
上述二官能以上之環氧(甲基)丙烯酸酯較好的是脂肪族環氧樹脂之環氧(甲基)丙烯酸酯。特別好的是二官能之脂肪族環氧樹脂之環氧(甲基)丙烯酸酯。
於上述硬化性成分中,具有(甲基)丙烯醯基之化合物、特別是具有芳香環及羥基之單官能之(甲基)丙烯酸酯、含氮(甲基)丙烯酸酯、含羧基(甲基)丙烯酸酯適合作為電子射線型接著劑,藉由使用該接著劑,可獲得相對於偏光膜及透明保護薄膜具有良好之接著性之偏光板。例如使用低水分率之偏光膜之情形時,以及使用透濕度低之材料作為透明保護薄膜之情形時,本發明之接著劑對該等顯示出良好之接著性,其結果可獲得寸法穩定性良好之偏光板。
硬化型接著劑含有硬化性成分,除了上述成分以外,根據硬化之類型而添加自由基起始劑。以電子射線硬化型使用上述接著劑之情形時,並非必須於上述接著劑中含義自由基起始劑,以紫外線硬化型、熱硬化型使用之情形時使用自由基起始劑。自由基起始劑之使用量,每100重量份硬化性成分,通常為0.1~10重量份左右,較好的是0.5~3重量份。
另外,上述接著劑中亦可含有金屬化合物填充劑。利用金屬化合物填充劑,可控制接著層之流動性,可獲得使膜厚穩定化、具有良好之外觀、面內均勻且無接著性不均之偏光板。
可使用各種金屬化合物填充劑。作為金屬化合物,例如可列舉氧化鋁、氧化矽、氧化鋯、氧化鐵、矽酸鋁、碳酸鈣、矽酸鎂等金屬氧化物;碳酸鋅、碳酸鋇、磷酸鈣等金屬鹽;氟鎂石、滑石、黏土、高嶺土等礦物。另外,該等金屬化合物填充劑可使用已進行表面改性之金屬化合物填充劑。
金屬化合物填充劑之平均粒徑通常為1~1000 nm左右,較好的是1~500 nm,進而較好的是10~200 nm,進而更好的是10~100 nm。金屬化合物填充劑之平均粒徑若於上述範圍內,則可於接著層中大致均勻地分散金屬化合物,可確保接著性且獲得外觀良好之、面內均勻之接著性。
金屬化合物填充劑之調配量,相對於100重量份接著劑成分,較好的是以100重量份以下之比例調配。另外,藉由使金屬化合物填充劑之調配比例於上述範圍內,能夠確保偏光膜與透明保護薄膜之接著性,且同時可獲得外觀良好、面內均勻之接著性。金屬化合物填充劑之調配比例較好的是1~100重量份,進而較好的是2~50重量份,進而更好的是5~30重量份。金屬化合物填充劑之調配比例,相對於100重量份接著劑成分,若超過100重量份,則接著劑中之接著劑成分之比例變小,就接著性方面而言並非較好。再者,對金屬化合物填充劑之調配比例並無特別限制,為了確保接著性且同時獲得外觀良好之、面內均勻之接著性,而使其為上述範圍之下限值。
另外,接著層或黏著層之形成,可較好地使用能夠於無溶劑或低溶劑狀態下進行貼合之乾式層壓法。作為該乾式層壓法,使用先前眾所周知之乾式層壓用接著劑及貼合方法即可,除了本發明以外,亦可使用該方法。藉此,具有進一步減少條紋狀凹凸不均等之效果。
作為上述乾式層壓用接著劑,可列舉二液硬化型接著劑、二液溶劑型接著劑、一液無溶劑型接著劑。作為二液硬化型接著劑,可使用丙烯酸系樹脂,作為二液溶劑型接著劑,可使用聚酯系、芳香族聚酯系、脂肪族聚酯系、聚酯/聚胺酯系、聚醚/聚胺酯系樹脂,作為一液無溶劑型接著劑(濕硬化型類型),可使用聚醚/聚胺酯系等樹脂。
上述接著層或黏著劑,必要時亦可含有適當之添加劑。作為添加劑之例,可列舉以羰基化合物等為代表之利用電子射線提高硬化速度或靈敏度之增感劑、矽烷偶合劑、鈦偶合劑等偶合劑,以環氧乙烷為代表之助黏劑,提高與透明保護薄膜之潤濕性之添加劑,以丙烯醯氧基化合物或烴系(天然、合成樹脂)等為代表、提高機械強度或加工性等之添加劑,紫外線吸收劑,抗老化劑,染料,加工助劑,離子捕集劑,抗氧化劑,增黏劑,填充劑(除了金屬化合物填充劑以外),可塑劑,均化劑,發泡抑制劑,抗靜電劑,耐熱穩定劑,耐水解穩定劑等穩定劑等。
藉由於上述偏光膜之兩面經由接著層或黏著層貼合透明保護薄膜,可獲得偏光板,亦可於接著層或黏著層與透明保護薄膜或偏光膜之間設置底塗層或易接著處理層等。
利用上述製造方法而形成之接著層由水系接著劑等形成之情形時,上述接著層之厚度較好的是30~300 nm。上述接著層之厚度進而較好的是60~250 nm。另一方面,接著層由硬化型接著劑形成之情形時,上述接著層之厚度較好的是0.1~200 μm。更好的是0.5~50 μm,進而較好的是0.5~10 μm。
上述偏光板進而可製成至少層疊有1層各種光學功能層之光學薄膜而使用。作為該光學功能層,例如可列舉硬塗處理層或抗反射處理層、防黏處理層、或者擴散層或防眩處理層等表面處理層、或者以視角補償或光學補償為目的之配向液晶層。進而亦可列舉層疊有1或2層以上偏光轉換元件、反射板或半透過板、相位差板(包括1/2或1/4等波長板(λ板))、視角補償薄膜、亮度提昇薄膜等於圖像顯示裝置等之形成中所使用之光學薄膜的光學功能層。特別好的是使用於上述偏光板上層疊反射板或半透過反射板而成之反射型偏光板或半透過型偏光板;於偏光板上層疊相位差板而成之橢圓偏光板或圓偏光板;於偏光板上層疊視角補償層或視角補償薄膜而成之寬視角偏光板;或者於偏光板上層疊亮度提昇薄膜而成之偏光板。
層疊上述光學功能層之情形時,通常上述表面處理層或配向液晶層直接層疊於偏光板等薄膜上即可,由各種薄膜構成之光學功能層較好的是使用經由上述接著層或黏著層層疊之方法。作為此時之接著層或黏著層,特別好的是使用包含黏著劑之黏著層。
作為包含黏著劑之黏著層,例如可利用丙烯酸系、矽酮系、聚酯系、聚胺酯系、聚醚系、橡膠系等基於先前之適當黏著劑而形成。作為該黏著劑,自防止因吸濕所造成之發泡現象或剝離現象、防止因熱膨脹差等所引起之光學特性下降或液晶單元翹曲、並且品質高且耐久性優良之液晶顯示裝置之形成性等觀點而言,較好的是吸濕率低且耐熱性優良之黏著層,進而,就防止偏光板等之光學特性變化方面而言,較好的是於硬化或乾燥時不需要高溫之製程之黏著層,不需要長時間之硬化處理或乾燥處理之黏著層。就此種觀點而言,於偏光板或光學薄膜上較好的是使用丙烯酸系黏著劑。另外,亦可於上述黏著劑中添加微粒子,製成顯示光擴散性之黏著層等。
該接著層或黏著層根據需要設置於必要之面上即可,例如若提及如本發明之包含偏光膜與保護薄膜之偏光板,則根據需要於偏光板之一面或兩面、即若為保護薄膜則於與偏光膜貼合之相反側之面設置接著層或黏著層即可。作為用於如此層疊光學功能層之情形時的包含黏著劑之接著層或黏著層之乾燥後之厚度,並無特別限定,通常為1~500 μm左右,較好的是5~200 μm,更好的是10~100 μm。藉由使接著層或黏著層之厚度於該範圍內,可緩和偏光板或光學功能層之尺寸變動所伴隨之應力。
於包含黏著劑之黏著層露出於表面之情形時,較好的是於供於使用前以防止該黏著層受到污染等為目的,而利用隔離件進行臨時黏貼覆蓋。作為隔離件,較好的是使用於適於上述保護薄膜等之薄膜上,根據需要設置利用矽酮系或長鏈烷基系、氟系或硫化鉬等適宜之剝離劑所實施之剝離塗層者。
實施硬塗處理之目的在於防止偏光板表面之損傷等,例如可藉由如下方式形成,即,於保護薄膜之表面上附加由丙烯酸系、矽酮系等適當之紫外線硬化型樹脂所形成之硬度、滑移特性等良好之硬化被膜。實施抗反射處理之目的在於防止外光偏光板表面之反射,可藉由形成基於先前之抗反射膜等來實現。再者,實施防黏處理之目的在於防止與鄰接層密接。
實施防眩處理之目的在於防止外光於偏光板表面反射而干擾偏光板透射光之辨識等,例如,可藉由利用噴砂方式或壓花加工方式所進行之粗面化方式或調配透明微粒子之方式等適當之方式,對保護薄膜表面賦予微細凹凸結構,藉此形成。作為用以形成上述表面微細凹凸結構而含有之微粒,例如,可使用平均粒徑為0.5~50 μm之包含二氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻等之有時具有導電性之無機系微粒子、包含交聯或者末交聯之聚合物等之有機系微粒子等透明微粒子。當形成表面微細凹凸結構時,微粒子之使用量相對於100重量份形成表面微細凹凸結構之透明樹脂,通常為2~70重量份左右。防眩層亦可兼作用以使偏光板透射光擴散而擴大視角等之擴散層(視角擴大功能等)。
再者,上述抗反射層、防黏層、擴散層或防眩層等光學功能層除了可直接設置於偏光板上以外,亦可作為其他之光學薄膜與偏光板分開設置。
反射型偏光板係於偏光板上設置反射層者,其用以形成反射來自辨識側(顯示側)之入射光而進行顯示之類型的液晶顯示裝置等,並且可省略背光燈等光源,具有易於使液晶顯示裝置薄型化等優點。形成反射型偏光板時,可利用根據需要經由保護薄膜等於偏光板之一面上附設由金屬等構成之反射層的方式等適當之方式進行。
再者,半透過型偏光板可藉由製成於上述中以反射層反射光之同時使光透過的半透半反鏡等半透過型反射層而獲得。半透過型偏光板通常設置於液晶單元之內側,可形成如下類型之液晶顯示裝置等,即,於比較明亮之環境中使用液晶顯示裝置等之情形時,反射來自辨識側(顯示側)之入射光而顯示圖像,於比較暗之環境中,使用內置於半透過型偏光板之背面之背光燈等內置光源來顯示圖像。
對偏光板上進一步層疊相位差板而構成之橢圓偏光板或圓偏光板進行說明。於將直線偏光改變為橢圓偏光或圓偏光,或將橢圓偏光或圓偏光改變為直線偏光,或者改變直線偏光之偏振方向之情形時,可使用相位差板等。特別是,作為將直線偏光改變為圓偏光或將圓偏光改變為直線偏光之相位差板,可使用所謂之1/4波長板(亦稱為λ/4板)。1/2波長板(亦稱為λ/2板)通常用於改變直線偏光之偏振方向之情形。
橢圓偏光板可有效地用於以下情形等,即補償(防止)超扭曲向列(STN)型液晶顯示裝置因液晶層之雙折射而產生之著色(藍或黃),從而進行無上述著色之白黑顯示。另外,控制三維折射率之偏光板亦可補償(防止)自斜向觀察液晶顯示裝置之畫面時產生之著色,故而較好。圓偏光板可有效地用於例如對以彩色顯示圖像之反射型液晶顯示裝置之圖像之色調進行調整之情形等,而且亦具有防止反射之功能。
作為相位差板,可列舉對聚合物薄膜進行單軸或雙軸拉伸處理而形成之雙折射性薄膜,使液晶單體發生配向之後使其交聯、聚合而成之配向薄膜,液晶聚合物之配向薄膜,以薄膜支持液晶聚合物之配向層者等眾所周知之薄膜。
相位差板既可為例如各種波長板或以補償由液晶層之雙折射所造成之著色或視角等為目的者等具有對應於使用目的之適當相位差者,亦可為層疊2種以上之相位差板而控制相位差等光學特性者等。
視角補償薄膜係於自不垂直於畫面而稍微傾斜之方向觀察液晶顯示裝置之畫面時亦使圖像看起來比較鮮明之、用於擴大視角之薄膜。可使用具有如下目的之適當者,即,防止基於由液晶單元所造成之相位差而形成的辨識角之變化所帶來之著色等或擴大辨識度良好之視角等。另外,就實現辨識度良好之寬視角方面等而言,可較好地使用以三乙醯纖維素薄膜支持包含液晶聚合物之配向層、特別是圓盤狀液晶聚合物之傾斜配向層的光學各向異性層之光學補償相位差板。
作為偏光轉換元件,例如可列舉各向異性反射型偏光元件或各向異性散射型偏光元件等。例如可列舉日東電工製造之PCF系列或3M公司製造之DBEF系列等。另外,作為各向異性反射型偏光元件,亦可較好地使用反射型柵式偏光子。作為該例,可列舉Moxtek製造之MicroWires等。另一方面,作為各向異性散射型偏光元件,例如可列舉3M公司製造之DRPF等。
貼合有偏光板與亮度提昇薄膜之偏光板通常設置於液晶單元之內側而加以使用。亮度提昇薄膜係顯示如下特性之薄膜,即,當因液晶顯示裝置等之背光燈式來自內側之反射等而自然光入射時,會反射特定偏光軸之直線偏光或特定方向之圓偏光,而使其他光透過,因此將亮度提昇薄膜與偏光板層疊而成之偏光板可使來自背光燈等光源之光入射,而獲得特定偏光狀態之透過光,並且上述特定偏光狀態以外之光無法透過而被反射。進而經由設置於其後側之反射層等使於該亮度提昇薄膜面上反射之光反轉,再次入射至亮度提昇薄膜上,使其一部分或全部作為特定偏光狀態之光透過,從而增加透過亮度提昇薄膜之光,同時提供偏光薄膜難以吸收之偏光,從而增大可用於液晶顯示圖像之顯示等之光量,藉此可提高亮度。
另外,本發明之偏光板如同上述偏光分離型偏光板,可由層疊有偏光板與2或3層以上之光學功能層者構成。因此,亦可為組合上述反射型偏光板或半透過型偏光板與相位差板而成之反射型橢圓偏光板或半透過型橢圓偏光板等。
於偏光板上層疊有上述光學功能層之光學薄膜,亦可利用於液晶顯示裝置等之製造過程中依次獨立層疊之方式而形成,但預先經層疊而製成光學薄膜者具有品質之穩定性或組裝作業等優良、可改善液晶顯示裝置等之製造步驟的優點。於層疊中可使用接著層等適當之接著手段。於接著上述偏光板與其他光學功能層時,彼等之光學軸可根據目標之相位差特性等而設為適當之配置角度。
再者,上述偏光板、光學功能層或接著劑、黏著層等各層亦可為例如藉由如下適當方式而使之具有紫外線吸收能力者,該方式為利用水楊酸醋系化合物或二苯甲酮系化合物、苯幷三唑系化合物或氰基丙烯酸酯系化合物、鎳錯鹽系化合物等紫外線吸收劑進行處理之方式等。
本發明之偏光板可較好地用於液晶顯示裝置(LCD)、電致發光顯示裝置(ELD)等圖像顯示裝置之形成。
偏光板可較好地用於液晶顯示裝置之形成等,例如可用在於液晶單元之一側或兩側配置偏光板而成之反射型或半透過型或者透過反射兩用型等之液晶顯示裝置。液晶單元基板可為塑膠基板、玻璃基板之任一種。形成液晶顯示裝置之液晶單元可為任意類型,例如可使用以薄膜晶體管型為代表之主動矩陣驅動型液晶單元、以扭曲向列型或超扭曲向列型為代表之單純矩陣驅動型之液晶單元等適當類型之液晶單元。
另外,當於液晶單元之兩側設置偏光板或光學薄膜時,彼等既可相同亦可不同。進而,於形成液晶顯示裝置時,可於適當位置上配置1或2層以上之例如稜鏡陣列板、透鏡陣列板、光擴散板、背光燈等適當之部件。
[實施例]
以下利用實施例及比較例對本發明進一步具體說明,但本發明不受該等實施例及比較例限定。
(偏光膜之水分率測定方法)自所獲得之偏光膜切下180 mm×500 mm之樣品,測定其初始重量(W(g))。將該樣品於120℃之乾燥機內放置2小時,然後測定乾燥後重量(D(g))。根據下述式,自該等測定值求得水分率。
水分率(%)={(W-D)/W}×100
(偏光膜之製作)使用厚度為75 μm之聚乙烯醇薄膜((株)Kuraray製:VF-PS7500,寬1000 mm),將其於30℃之純水中浸漬60秒,同時拉伸至拉伸倍率為2.5,於30℃之碘水溶液(重量比:純水/碘(I)/碘化鉀(KI)=100/0.01/1)中染色45秒,於4重量%之硼酸水溶液中拉伸至拉伸倍率為5.8倍,於純水中浸漬10秒後,於保持薄膜之張力之狀態下於40℃乾燥3分鐘,獲得偏光膜。該偏光膜之厚度為25 μm,水分率為30重量%。
(附有接著層之透明保護薄膜之製作)於3760重量份純水中溶解100重量份PVA樹脂(日本合成化學工業(株)製:Gosenol)及35重量份交聯劑(大日本油墨化學工業(株)製:Watersol),製備接著劑。以槽模將該接著劑塗佈於厚度為80 μm之三乙醯纖維素(TAC)薄膜(富士膠片公司製:UZ-80T,水分率為1.4重量%)之一面側後,於85℃乾燥1分鐘,獲得具有厚度為0.1 μm之接著層之附有接著層之TAC薄膜。
實施例1
(偏光板之製作)利用圖1所示之方法,製作偏光板。樹脂薄膜A使用上述偏光膜,第一透明薄膜B1及第二透明薄膜B2使用上述附有接著層之TAC薄膜。以TAC薄膜側成為第一金屬輥b1、第二金屬輥b2側之方式輸送附有接著層之TAC薄膜。使用直徑200 mm之鐵輥作為第一金屬輥b1、第二金屬輥b2。使用於鐵芯之周圍具有橡膠層(硬度90度,厚度3 mm)之結構之直徑200 mm之輥作為第一彈性輥a1、第二彈性輥a2。
向第一彈性輥與第一金屬輥之輥間,輸送偏光膜與附有接著層之TAC薄膜,對該等進行壓接,使TAC薄膜貼合於偏光膜之一面,獲得層疊膜(圖1之層疊膜L1)。此時,第一彈性輥與第一金屬輥之層疊壓力為3.5 MPa,第一彈性輥因與第一金屬輥之擠壓而發生凹變形。確認如圖2A所示之凹部端點(x1)。以第一彈性輥之變形凹部端點處之切線(y1)與偏光膜之輸送線所成之角度(θ1a)成為-11.1°之方式輸送偏光膜。另一方面,以凹部端點(x1)與第一透明薄膜之輸送線所成之角度(θ1b)成為+94°之方式輸送第一透明薄膜。再者,上述角度係以切線(y1)為基準,右旋為「+」,左旋為「-」之角度。
其後,不捲取層疊膜,而向第二彈性輥與第二金屬輥之輥間輸送層疊膜與附有接著層之TAC薄膜,對該等進行壓接,獲得於偏光膜之兩面貼合有TAC薄膜之偏光板(相當於圖1之多層層疊膜L2)。此時,第二彈性輥與第二金屬輥之層疊壓力為3.5 MPa,第二彈性輥因與第二金屬輥之間之擠壓而發生凹變形。確認如圖2B所示之凹部端點(x2)。以第二彈性輥之變形凹部端點處之切線(y2)與層疊膜之輸送線所成之角度(θ2a)成為+11.1°之方式輸送層疊膜。另一方面,以凹部端點(x2)與第二透明薄膜之輸送線所成之角度(θ2b)成為-94°之方式輸送第二透明薄膜。再者,上述角度係以切線(y2)為基準,右旋為「+」,左旋為「-」之角度。
於上述中,各薄膜之輸送速度為30 m/分鐘。再者,於上述中所獲得之偏光板,貼合後於80℃乾燥2分鐘。
實施例2~18
於實施例1中,將各薄膜之輸送線相對於切線(y1)所成之角度(θ1a)、(θ1b)、各薄膜之輸送線相對於切線(y2)所成之角度(θ2a)、(θ2b)或層疊壓力如表1所示加以改變,除此以外,以與實施例1同樣之方式獲得偏光板。
實施例19
於實施例16中,將第一及第二彈性輥之橡膠層之硬度改變為65度,除此以外,以與實施例16同樣之方式獲得偏光板。
實施例20
於實施例16中,將第一及第二彈性輥之橡膠層之硬度改變為75度,除此以外,以與實施例16同樣之方式獲得偏光板。
比較例1~9
於實施例1中,如表1所示,替代圖1之方法,採用圖3~6中揭示之方法,改變各輥與各薄膜之間之關係,將各薄膜之輸送線相對於切線(y1)所成之角度(θ1a)、(θ1b)、各薄膜之輸送線相對於切線(y2)所成之角度(θ2a)、(θ2b)或層疊壓力如表1所示加以改變,除此以外,以與實施例1同樣之方式獲得偏光板。
對實施例及比較例中製作之偏光板進行下述評價。結果示於表1。
(氣泡之確認)自所獲得之偏光板切下500 mm×300 mm之樣品,確認偏光膜與TAC薄膜之間之氣泡數目。
表1中,* 1表示氣泡被帶入、輸送到偏光膜與第一金屬輥之間,形成帶有氣泡之凹凸痕跡之偏光板,* 2表示無法製備正確之線壓,而形成帶有皺褶之偏光板。
由上述表1之結果可知,藉由本發明之實施例,可抑制樹脂薄膜(偏光膜)與透明薄膜(透明保護薄膜)之間所產生之氣泡,製造多層層疊膜。另外,由實施例1~7與實施例8~15之比較可知,藉由控制各薄膜之輸送線相對於切線(y1)所成之角度(θ1a)、(θ1b)、各薄膜之輸送線相對於切線(y2)所成之角度(θ2a)、(θ2b),可以進一步抑制氣泡。
A...樹脂薄膜
B1...第一透明薄膜
B2...第二透明薄膜
a1...第一彈性輥
a2...第二彈性輥
b1...第一金屬輥
b2...第二金屬輥
M1、M2...角度改變機構
圖1為表示本發明之多層層疊膜之製造方法之示意圖。
圖2A為表示於本發明之多層層疊膜之製造方法中薄膜進入輥間之角度的關係之示意圖。
圖2B為表示於本發明之多層層疊膜之製造方法中薄膜進入輥間之角度的關係之示意圖。
圖3為表示比較例之多層層疊膜之製造方法之示意圖。
圖4為表示比較例之多層層疊膜之製造方法之示意圖。
圖5為表示比較例之多層層疊膜之製造方法之示意圖。
圖6為表示比較例之多層層疊膜之製造方法之示意圖。
a1...第一彈性輥
a2...第二彈性輥
b1...第一金屬輥
b2...第二金屬輥
A...樹脂薄膜
B1...第一透明薄膜
B2...第二透明薄膜
M1、M2...角度改變機構
L1...層疊膜
L2...多層層疊膜

Claims (9)

  1. 一種多層層疊膜之製造方法,其係於水分率為10~60重量%之樹脂薄膜之兩面,經由接著層或黏著層而貼合水分率為0.5~5重量%之第一透明薄膜及第二透明薄膜,該製造方法之特徵在於,以第一透明薄膜位於第一金屬輥側之方式,使樹脂薄膜與第一透明薄膜通過第一金屬輥與第一彈性輥此等一對輥間,藉此壓接而形成層疊膜之後,並不捲取該層疊膜,以第二透明薄膜位於第二金屬輥側之方式,使該層疊膜與第二透明薄膜通過第二金屬輥與第二彈性輥此等一對輥間,藉此壓接而形成多層層疊膜。
  2. 如請求項1之多層層疊膜之製造方法,其中第一金屬輥及第二金屬輥之至少任一者為鐵輥或不銹鋼輥。
  3. 如請求項1之多層層疊膜之製造方法,其中第一彈性輥及第二彈性輥均為於金屬製造之芯部塗佈有橡膠層或樹脂層之彈性輥。
  4. 如請求項3之多層層疊膜之製造方法,其中第一彈性輥及第二彈性輥之橡膠層或樹脂層之硬度為70以上100以下。
  5. 如請求項1之多層層疊膜之製造方法,其中第一彈性輥之變形凹部端點處之切線與樹脂薄膜之輸送線所成之角度(θ1a)、和第一彈性輥之變形凹部端點處之切線與第一透明薄膜 之輸送線所成之角度(θ1b),若角度(θ1a)、角度(θ1b)以第一彈性輥之變形凹部端點處之切線為基準右旋表示為「+」、左旋表示為「-」,則角度(θ1a)及角度(θ1b)為「-」及「+」之關係中,相對於第一彈性輥之變形凹部端點處之切線係為相反方向,其中,第一彈性輥之變形凹部端點係指:由第一金屬輥接觸擠壓第一彈性輥而產生之第一彈性輥之變形凹部處的、第一彈性輥與第一金屬輥之最開始接觸點,樹脂薄膜之輸送線係指樹脂薄膜與第一彈性輥之最開始接觸點處之切線,第一透明薄膜之輸送線係指第一透明薄膜與第一金屬輥之最開始接觸點處之切線。
  6. 如請求項1之多層層疊膜之製造方法,其具有如下機構:於將樹脂薄膜向第一金屬輥與第一彈性輥該一對輥間輸送之前,改變第一彈性輥之變形凹部端點處之切線與樹脂薄膜之輸送線所成之角度(θ1a)者。
  7. 如請求項1之多層層疊膜之製造方法,其中第二彈性輥之變形凹部端點處之切線與層疊膜之輸送線所成之角度(θ2a)、和第二彈性輥之變形凹部端點處之切線與第二透明薄膜之輸送線所成之角度(θ2b),若角度(θ2a)、角度(θ2b)以第二彈性輥之變形凹部端點處之切線為基準右旋表示為「+」、左旋表示為「-」,則角度(θ2a)及角度(θ2b)為「+」及「-」之關係中,相對於 第二彈性輥之變形凹部端點處之切線係為相反方向,其中,第二彈性輥之變形凹部端點係指:由第二金屬輥接觸擠壓第二彈性輥而產生之第二彈性輥之變形凹部處的、第二彈性輥與第二金屬輥之最開始接觸點,層疊膜之輸送線係指層疊膜與第二彈性輥之最開始接觸點處之切線,第二透明薄膜之輸送線係指第二透明薄膜與第二金屬輥之最開始接觸點處之切線。
  8. 如請求項1之多層層疊膜之製造方法,其具有如下機構:於將層疊膜向第二金屬輥與第二彈性輥此等一對輥間輸送之前,改變第二彈性輥之變形凹部端點處之切線與層疊膜之輸送線所成之角度(θ2a)者。
  9. 如請求項1~8中任一項之多層層疊膜之製造方法,其中第一金屬輥與第一彈性輥間之層疊壓力及第二金屬輥與第二彈性輥間之層疊壓力之至少任一者為2MPa以上5MPa以下。
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