TWI357424B - - Google Patents

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TWI357424B
TWI357424B TW93115548A TW93115548A TWI357424B TW I357424 B TWI357424 B TW I357424B TW 93115548 A TW93115548 A TW 93115548A TW 93115548 A TW93115548 A TW 93115548A TW I357424 B TWI357424 B TW I357424B
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TW
Taiwan
Prior art keywords
film
polyester
polyester film
patent application
composition
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TW93115548A
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English (en)
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TW200510471A (en
Inventor
Hiroshi Kusume
Atsushi Oyamatsu
Tetsuo Yoshida
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Teijin Dupont Films Japan Ltd
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Publication of TW200510471A publication Critical patent/TW200510471A/zh
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Publication of TWI357424B publication Critical patent/TWI357424B/zh

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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/08Mirrors
    • G02B5/0816Multilayer mirrors, i.e. having two or more reflecting layers
    • G02B5/0825Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
    • G02B5/0841Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising organic materials, e.g. polymers
    • 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
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin 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
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/08Mirrors
    • 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
    • B32B2250/00Layers arrangement
    • B32B2250/24All layers being polymeric
    • B32B2250/244All polymers belonging to those covered by group B32B27/36
    • 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
    • B32B2264/00Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02Synthetic macromolecular particles
    • 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
    • B32B2264/00Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10Inorganic particles
    • B32B2264/102Oxide or hydroxide
    • 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
    • B32B2264/00Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10Inorganic particles
    • B32B2264/104Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • 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
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/308Heat stability
    • 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
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/416Reflective
    • 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
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/71Resistive to light or to UV
    • 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
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/732Dimensional properties
    • B32B2307/734Dimensional stability
    • 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
    • B32B2457/00Electrical equipment
    • B32B2457/20Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • B32B2509/00Household appliances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254Polymeric or resinous material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256Heavy metal or aluminum or compound thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/256Heavy metal or aluminum or compound thereof
    • Y10T428/257Iron oxide or aluminum oxide
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/258Alkali metal or alkaline earth metal or compound thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/259Silicic material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
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    • Y10T428/266Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
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    • Y10T428/268Monolayer with structurally defined element
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    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31786Of polyester [e.g., alkyd, etc.]

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Description

1357424 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明係有關聚酯薄膜。更詳細說,係有關白色聚酯 薄膜,特別是,適用於反射板之白色聚酯薄膜。 【先前技術】 白色聚酯薄膜,廣泛的使用於噴墨,熱感轉印,平版 印刷等之印刷記錄接收薄片之基材。此白色聚酯薄膜,一 般係由聚酯中含有無機微粒子,或含非相溶樹脂而製造者 〇 近年,印刷精度提高,由於印刷物之鮮明性提高,要 求賦予更高級感之白色聚酯薄膜。爲因應此要求,日本特 開平4-153232號公報及日本特開平6-322153號公報提案 添加複數種類之無機微粒子,或添加倂用無機微粒子及非 相溶樹脂者。但是’相對於此技術,亦要求提高更鮮明性 及高級感。特別是超商等商店之店名顯示,或商品之廣告 所使用之內照式電飾招牌,爲提高宣傳效果以多數之日光 燈爲光源,招牌表面之明度爲1 〇〇〇 1UX以上,或使用色 彩豐富的霓虹燈管’刻意進行提昇招牌所繪之意境,提高 宣傳效果,爲提高相關之內照式電飾招牌之照度而使用反 射板。又液晶顯示器顯示面照明時,由顯示器之背面照 射燈光時一般採用背光方式,近年,日本特開昭63-62104號公報揭示之側光方式,由於薄型且可均勻照明, 廣泛的被使用。此側光方式,係由具有一定程度厚度之亞 -5- (2) (2)1357424 克力板等之邊沿以冷陰極管等賦予照明之方式,由於網點 印刷’照明光均勻的分散,可得到均勻亮度的畫面。依此 方式’由於在側面部份而非畫面之背面設置照明,可比背 光方式更爲薄型化。 爲防止照明光由畫面之背面逸出,畫面之背面必要設 置反射板’此反射板要求薄且高光反射性。合乎此目的之 晶顯示器反射板用白色聚酯薄膜,已知由於作業性容易及 價廉’含有氧化鈦。但是,如日本特公平8 - 1 6 1 7 5號公報 所記載’僅添加非相溶性樹脂,氧化鈦等對反射率之提昇 有限度,畫面之明度不能說已充分。 添加高濃度氧化鈦等之無機微粒子時可期待提高反射 效率。但是,例如添加5 0重量%時,由於粒子濃度非常 高,產生多發性斷裂,製膜非常困難,依狀況有不能製膜 之情形。又,爲降低非常高粒子濃度時之破壞頻率,實施 的手段考慮聚酯樹脂之共聚合化,此時,熱收縮率變爲非 常高,熱尺寸安定性極端惡化,不能得到薄膜。 【發明內容】 (發明之揭示) 本發明之目的爲提供解決相關之問題點’可視光領域 實用上維持充分之反射性能,又’添加高濃度無機微粒子 亦可安定製膜,對光源之熱尺寸變化亦安定之白色聚酯薄 膜。 本發明之他項目的爲’提供具有如上述之特性’最適 -6 - (3) 1357424 合於太陽電池之背膜,液晶顯示器或內照式電飾招牌之反 射板用基材之聚酯薄膜。 本發明之其他目的及益處由以下說明可明朗。 依本發明,本發明之上述目的及益處。第1,
二羧酸主成分爲對苯二甲酸,甘醇主成分爲乙二醇,而共 聚合成分爲間苯二甲酸,萘二羧酸及環己烷二甲醇所成群 中至少選擇1種之共聚合聚酯及相對於此組成物3 0〜5 0 重量%之無機微粒子所成之組成物。 於85 °C之熱收縮率,縱方向,橫方向之任一方向均 爲0·7 %以下且於150°C之熱收縮率,不論縱方向,或橫 方向均爲5.0 %以下,而且, 對波長400〜700 nm之平均反射率爲90%以上爲特 徵,由聚酯薄膜而達成。
由上述組成物,向來延伸製膜不易之含有高濃度無機 微粒子之薄膜可安定製膜,得到具備如上述特性之白色聚 酯薄膜。 (用以實施發明之最佳型態) 本發明之聚酯薄膜,可爲單層之單層薄膜或複數層所 成之層合薄膜。 層合薄膜,至少具有1層上述共聚物與無機微粒子所 成之上述組合物。例如可由上述組成物所成之一層,與上 述共聚聚酯與無機微粒子所成,而該無機微粒子爲組成物 之0〜30重量%所成之一層所成之層合薄膜。 (4) (4)1357424 共聚合聚酯 上述共聚合聚酯’二羧酸主成分爲苯二甲酸’甘醇主 成分爲乙二醇’而共聚合成分爲至少1種由間本二甲酸, 萘二羧酸及己烷二甲醇所成群中所選。 共聚合成分之比例爲全二羧酸成分或全二醇成分之! 〜3 0莫耳%爲理想,更理想爲3〜2 5莫耳%,再理想爲5 ~ 2 0莫耳%,最理想爲7〜1 5莫耳%。低於1莫耳%時含 無機微粒子之層之延伸應力高,不能製膜,超過30莫耳 °/〇時’欠缺熱尺寸安定性,製膜有困難β 共聚合成分’如上述’間苯二甲酸,萘二竣酸,例如 2,6-萘二羧酸或環己烷二甲醇,例如ι,4_環己烷二甲醇。 由使用如此之共聚合聚酯’含高濃度無機微粒子之組成物 亦可安定的的製膜爲理想。共合聚酯之融點理想爲25〇β(: 以下,更理想爲245 °C以下,特別理想爲2401以下。
無機微粒子 組成物中含有30 ~ 50重量%無機微粒子。無機微粒 子低於30重量%時難於得到充分之光線反射率或白度。 超過50重量%時製膜時容易產生斷裂。 無機微粒子平均粒徑理想爲0.1〜3.Ogm,吏 0.2〜2_5ym’待別理想爲0.3〜2.0/zm,低於(^丨以爪時 分散性極端惡化,由於引起粒子凝聚,生產步驟容易發生 問題’薄膜形成粗突起,薄膜有光澤差之可能性,不g想 -8 - (5) 1357424 。超過3.0/zm時薄膜表面粗糙,光澤下降不理想。無機 微粒子,例如以硫酸鋇,氧化鈦,碳酸鈣或二氧化矽爲理 想。此等可1種或2種以上一起使用。氧化鈦,可列舉如 金紅石型氧化鈦及銳鈦鑛型氧化鈦,使用金紅石型氧化鈦 時,聚酯薄膜因光線之變黃少,色差之變化可控制爲理想 。金紅石型氧化鈦,以硬脂酸等之脂肪酸或其衍生物圖謀 提高其分散性時,薄膜之光澤度可提高爲理想。因此金紅 石型氧化鈦在添加至聚酯前,使用精製製程進行調整粒徑 ,除去粗大粒子再使用爲理想。有關此精製製程之工業手 段,粉碎手段可使用噴射硏磨,球磨,又分級手段可使用 乾式或濕式離心分離機。此等之手段亦可2種以上組合, 分段精製亦可。 無機粒子含於共聚合聚酯之方法可列舉如以下之方法 〇 共聚合聚酯合成時於酯交換反應或酯化反應終了前添 加,或聚縮合反應開始前添加之方法。或添加至共聚合聚 酯,依溶融混練之方法,以任一方法製造添加多量惰性粒 子之標準膠粒,此等與不含添加劑之共聚合聚酯焜練使其 含有指定量添加物之方法,或原樣使用上述之標準膠粒之 方法。 又,上述共聚合聚酯合成時添加之無機粒子爲氧化鈦 時,將其分散於乙二醇中成爲漿體,再加入反應系中理想 共聚合聚酯中無機微粒子之粗大凝聚粒子之個數以少 (6) 1357424 者爲理想。爲此目的,製膜時之過濾器以線徑 下之不鏽鋼細線所成,平均網目理想爲10〜 理想爲使用20〜50/zm之不織布型過濾器, 共聚物組成物爲理想。 無機微粒子,如上述亦可倂用複數種類。 型氧化鈦可倂用銳鈦礦型氧化鈦。又,亦可於 硫酸鋇,碳酸鈣,二氧化矽。 此共聚合聚酯組成物亦可含有螢光增白劑 收劑。含有時,螢光增白劑之濃度,依組成 0.005〜0.2重量%,更理想爲0.01〜0.1重矍 白劑可使用如 OB-1 (EASTMAN公司製)’ (CIBA-GEIGY公司製)’ JP-Coiic (日本化學工妻 螢光增白劑之含有量低於0.0005重量%時 板時之照度不能充分提高,添加之效果稀薄, 量%時,由於顯出螢光增白劑持有之特有色澤7 外線吸收劑,其種類無特定者,環狀醯亞 1種由環狀醯亞胺酯所選之化合物,以未反應 理想。相關之環狀醯亞胺酯例如記載於曰本 12952號公報,使用其自體爲紫外線吸收劑之 〇 紫外線吸收劑之添加量’相對於共聚合聚 〜5重量%理想,以〇. 2〜3重量%爲更理想 0.1重量%時防紫外線劣化之效果小,一方面超 時聚酯之製膜特性下降’不理想。 1 1 5 ju m 以 1 〇 0以m,更 過濾溶融之 例如金紅石 氧化鈦倂用 或紫外線吸 物,理想爲 t %。螢光增 U v i t e X - M D _公司製)。 ,作爲反射 超過0.2重 F理想。 胺酯及至少 型態使用爲 特開昭 5 9 -公知化合物 酯,以0.1 。此量低於 丨過5重量% -10- (7) (7)1357424 又,構成本發明之聚酯薄膜之上述組成物,共聚合聚 酯與實質上非相溶性之樹脂成分在實質上以不含有理想。 實質上不含有係意味爲組成物之0〜1重量。/。,更理想爲 〇〜0 · 5重量% β 熱收縮率 本發明之聚酯薄膜,85 °c之熱收縮率縱,橫均爲 0.7%以下,理想爲0.6%以下,更理想爲0.5%以下,而且 150°C之熱收縮率縱,橫均爲5.0%以下,理想爲4.5%以下 ,更理想爲4.0°/。以下。而熱收縮率之平衡(縱方向85°C 熱收縮率)/(橫方向8 5 °C熱收縮率)之比以絕對値1 . 〇〜 3_〇之範圍者爲理想。由於超過此範圍時熱收縮率爲上述 値時亦容易起皺紋不理想。 厚度 本發明之聚酯薄膜之厚度,理想爲25〜250/zm,更 理想爲30〜220"m’特別理想40〜2〇〇ym,低於25/zm 時光線之反射率下降,超過25〇vrn時反射率亦無上昇不 理想。 光學性質 本發明聚酯薄膜之光學反射率,波長400 ~ 700 nrr 之平均反射率爲90%以上’理想爲92%以上,更理想爲 94°/〇以上者。由上述構成可達成此反射率,不具備此反射 -11 - (8) 1357424 率時,使用於反射板時不能得到充分之反射率。 又,本發明聚酯薄膜,光學濃度理想爲1.2以上, 400〜700 nm波長域之絕對正反射率之平均値爲2·0以 上。 層構造
本發明聚酯薄膜,如上述,由單層所成薄膜,或由複 數層所成薄膜均可, 由複數層所成時,例如可由Α層及Β層所構成,或 由A層,B層,A層所成之三層或A層,B層,C層所成 之三層所構成。又,由四層所構成亦可。考慮製作上之難 易度時以單層,2層,A層/ B層/A層所成之三層型態馬 特別理想。又爲賦於薄膜單面或雙面其他機能,更可層合 其他層爲層合薄膜。此處所謂其他層爲透明之聚酯薄膜, 金屬薄瞑,硬塗敷層,油墨接收層等。
製造方法 以下說明以複數層所成之層合薄膜時之製造方法之〜 例。單層薄膜時亦依可此方法爲準製造。 爲製造層合薄膜,使用料口嵌段之同時多層擠壓法製 造未延伸薄膜。即形成A層之聚合物溶融物與形成B層 之溶融物使用料口嵌段層合成爲A層/ B層/ A層,於丰莫 頭實施展開。此時,於料口嵌段層合之聚合物維持層合之 形態。由模頭擠壓之薄片’於鑄膜輥上冷卻,成爲未伸狀 -12- (9) (9)1357424 態之薄膜。此未延伸狀態之可延伸層合薄膜,以輥輪加熱 ,紅外線加熱等加熱縱向延伸得到縱延伸薄膜。此延伸以 利用2輥輪之周速差進行者爲理想。延伸溫度爲比聚酯之 玻璃轉移點(Tg)更高之溫度,理想爲比Tg高20〜40 °C之溫度進行。延伸倍率,可依薄膜要求之特性,理想爲 2.5〜4.0倍,更理想爲2.8 ~ 3.9倍。低於2.5倍薄膜之 厚斑變大不能得到良好的薄膜,超過4.0時製膜中容易產 生斷裂不理想。 縱延伸薄膜,接著依順序施以橫延伸,熱固定,熱無 張力之處理成爲二次配向薄膜。此處理以行走中進行爲有 利。橫延伸之理想處理,係於聚酯薄膜之玻璃轉移點 (Tg) 高10°c以上溫度開始,而昇溫至高於Tg 10〜70°c之溫度 進行。於延伸過程中之昇溫爲連續或階段(逐次)均可, 通常爲逐次昇溫。例如延伸器之橫延伸區沿薄膜行走方向 分爲複數區,每區所定之溫度由流通加熱媒體而昇溫。橫 延伸之倍率,可依薄膜要求之特性,理想爲2.5 ~ 4.5倍 ,更理想爲2.8〜3.9倍。低於2.5倍薄膜之厚斑變大不 能得到良好的薄膜,超過4.5時製膜中容易產生斷裂不理 想》 橫延伸後之薄膜,於兩端原狀挾持下以低於聚酯融點 (Tm) 20〜80°C之溫度 (Tm - 20〜80) °C定幅或減幅 1 0%以下熱處理降低熱收縮率爲佳。高於此溫度時薄膜之 平面性差,厚斑變大。又,熱處理溫度低於 (Tm -80)°C 時收縮率變大。又,爲調整熱固定後薄膜溫度恢復至常溫 -13- (10) 1357424 之過程(Tm -2 0〜80) °C以下之範圍之熱收縮量,切斷薄 膜兩端之挾持,調整薄膜縱方向拖拉速度’縱方向無張力 爲理想。無張力之手段係調整延伸器出口輪群之速度。無 張力之比例,以減低輥輪群相對於延伸器薄膜之速度進行 ,理想爲 0.1〜1.2%,更理想爲0.2〜1.0%,特別理想爲 0.3〜0.8 %之減速,實施無張力。由此無張力可調整縱方向 之熱收縮率。薄膜橫方向,由切斷兩端之過程減輻,可得 到所期望之熱收縮率。 依本發明,可維持可視光領域實用上之反射性能,又 ,添加高濃度無機微粒子亦可製膜,可提供對光源之熱尺 寸變化安定之白色聚酯薄膜。本發明之聚酯薄膜,最適合 於太陽電池之背膜,液晶顯示器或如內照式電飾招牌之平 面顯示反射板,或印刷記錄收片之反射板》 【實施方式】 以下以實施例詳細說明本發明,又,各特性値依以下 的方法測定。 (1 )薄膜厚度 薄膜樣本以電子測微器(ANRITU製 K-402B)測定 10處厚度,以平均値作爲薄膜厚度。 (2 )各層厚度 切取三角形薄膜樣本,固定於包裹膠囊,以環氧樹脂 -14 - (11) 1357424 塡埋。塡埋之樣本以 MICRODOM ( ULTRACUT-S )平行 於縱方向斷面切取50nm厚之薄膜切片’使用穿透型電子 顯微鏡,於1 OOkv加速電壓照相觀察’由照相測定各層之 厚度,求不均値。 (3 )全光線相對反射率 於分光光度計(日本島津製作製UV-3101PC)安裝積 分球,BaS04白板爲全光線反射率 100%時轉換測定 400〜700nm。由所得之測定値讀取每2nm間隔之反射率。 所得値之平均値作爲全光線反射率之平均値。平均値依以 下基準評價之。 〇:全測定範圍之反率爲90%以上。 △:測定範圍之平均反射率爲90 %以上,一部份之反 射率爲低於90%之範圍。 (4 )絕對正反射率 於分光光度計(日本島津製作製UV-3101PC)安裝絕 對反射率測定裝置(日本島津製作製 ASR3105)於入射 5、測定400〜700 nm。由所得之測定値讀取每2 nm間 隔之反射率。所得値之平均値作爲絕對反射率。 (5)光學濃度 使用光學濃度計 (X-Rite公司製,商品名「TR-310 」)測定薄膜3原色相關之V (Visual)光學濃度。 -15- (12) 1357424 (6)延伸性 延伸縱方向3.4倍’橫方向3.6〜3.7倍製膜,以下 述基準評價此時薄膜是否可安定製膜。 〇:可1小時以上安定製膜。 X : 1小時以內發生斷裂,不能安定製膜。
(7)熱收縮 薄膜樣本於各自設定溫度爲85°C,15(TC之烘箱中無 張力狀態下放置3 0分鐘,測定加熱處理前後之標點間距 離,依下式算出熱收縮率 (85°C熱收縮率與150°C熱收縮 率)。 熱收縮率 % = ((L0 - L) / LO ) X 100
L0 :熱收縮前之標點間距離 L :熱收縮後之標點間距離 (Tm) (ΤΑ Instruments 2 100 (8)玻璃轉移點(Tg),融點 使用差示掃瞄熱量測定裝置 DSC)以昇溫速度20 m/分測定 實施例1〜4 如表1所示之各共聚合聚酯添加表1所示無機微粒子 -16- (13) 1357424 ,各自於2 80 °C加熱供給2部擠壓機,A層聚合 聚合物使用3層料口嵌段裝置使A層與B層以A 合流,維持此層合狀態由模頭形成薄片。此薄片 溫度爲2 5 °C之冷卻輥輪冷卻固化得到之未延伸 至加熱至85〜98 °C之輥輪群,長方向(縱方向) 倍,於2 5 °C之輥輪群冷卻。接著,縱延伸之薄 挾具挟持下導至延伸機於120°C加熱之環境中以 方向之方向(橫方向)延伸3.7倍。其後於如表 載之溫度進行熱固定,於表2所記載之溫度進行 張力,橫方向之定幅,冷卻至室溫得到2軸延伸 用此薄膜之反射板之物性如表2所示β 實施例5,6 實施例1 ~ 4,除薄膜層構造爲單層,條件 所記載以外與實施例1同樣得到薄膜。由於層構 ,使用1部擠壓機。 比較例1 依表1,2記載之條件外與實施例丨同樣製 向,橫方向由於未實施無張力,熱收縮率變差。 比較例2 依表1,2記載之條件外與實施例丨同樣製 微粒子之含有量少反射率變差。 物,Β層 ./ B / A 更於表面 薄膜,導 延伸3.4 膜兩端以 垂直於長 2所示記 縱方向無 薄膜。使 【口表1,2 成爲單層 膜。縱方 膜。無機 -17- (14〉 (14〉1357424 比較例3 依表1,2記載之條件外與實施例1同樣製膜。薄膜 厚度不足’反射率變差。 比較例4 依表1,2記載之條件外與實施例1同樣製膜。使用 無共聚合之聚合物,延伸性極低,製膜時多發斷裂,因此 不能製作薄膜 比較例5 依表1,2記載之條件外與實施例1同樣製膜。共聚 合成分之比例低,由於招致延伸性低,製膜時多發斷裂, 因此不能測定物性。 比較例6 除使用聚苯二甲酸乙二醇酯配合14重量%碳酸鈣之 組成物爲A層’聚苯二甲酸乙二醇酯配合非相溶性之聚 甲基戊樹脂1 〇重量% ’聚乙二醇1重量。/。之組成物爲B 層以外’與實施例丨同樣製膜。結果如表1及2所示。反 射率之結果差。 -18- 1357424 I谳 A層薄膜 £ H P Ό (Ν CN 230 j- 223 225 1 1 226 226 225 256 253 255 bD P JO (N OO 1 1 JO VO (Ν OO Γ^- OO 無機微粒子 靼 5Γ M g u -R w 滕 5.0/1.2 5.0/1.2 4.0/1.0 3.0/1.5 1 1 7.5/1.5 3.0/1.5 7.5/1.5 7.5/1.5 3.0/1.5 14/1.5 種類 硫酸鋇 碳酸鈣 二氧化鈦 硫酸鋇 1 1 二氧化欽 硫酸鋇 二氧化欽 二氧化欽 硫酸鋇 碳酸鈣 共聚合 比例% Ο oo CN CM 1 1 Ο (Ν Ο 1 1 成分 1_ ΙΡΑ CHDM NDC IPA 1 1 NDC IPA NDC 1 IPA 1 聚合物 PET [ PET PET PET 1 1 PET PET PET PET PET PET 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 比較例1 比較例2 比較例3 .比較例4 比蛟例5 比較例6 ι@Ε13:Γ^[υ1ϊ:ΙΛΙαΗυ氈ffi-u 擀酲:Vdl 题氍惣 ζ:鄱:οαΜ - Hs
-19 - 1357424 -I A層薄膜 |微粒子之全 含有量 (重量%) m (N cn 〇\ m m CM OO ro CN <N 層構成 層之厚度比例 I A/B/A= 10/80/10 A/B/A=20/60/20 A/B/A= 12/76/12 A/B/A= 12/76/12 〇 II CQ 〇 II CQ A/B/A= 15/70/15 A/B/A= 15/70/15 A/B/A= 15/70/15 A/B/A= 15/70/15 A/B/A=l 2/76/12 A/B/A=6/88/6 B Η P Ο CN CN o cn CM m <N <N (N CN 1 | 224 225 225 226 CN CN 257 CN yr\ rs 253 ^D0 P Ο in oo JO oo CN OO OO OO 無機微粒子 添加量/平均粒子徑 (MS:%/ β m) 40/1.2 50/1.2 50/1.0 45/1.5 45/1.5 i- 45/1.5 30/1.5 10/1.2 30/1.5 50/1.5 45/1.2 添加PMX樹脂 種類 硫酸鋇 碳酸鈣 二氧化鈦 硫酸鋇 二氧化欽 硫酸鋇 二氧化鈦 硫酸鋇 二氧化·駄 二氧化鈦 硫酸鋇 碳酸鈣 共聚合 比例% Ο oo cs (N fN (N Ο <N Ο 1 1 成分 ΙΡΑ CHDM NDC IPA NDC- -IPA NDC IPA NDC 1 IPA 1 聚合物 PET PET PET PET PET PET PET PET PET PET PET PET 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6
遐^:XSCI 鑒&:3遯旧酹:saHu鍫 ώΐ:浒酲:Vdl 觀經斑-3撕:oaz鍫 Ek:I 擀¾¾: HHCI -20- 1357424 (N漱 仲縮率 I (%) CN ψ·^ m r~i 1 1 (N cn m 1 無張力率/ 兩端切除部之溫度 (%/°〇 0.5/130 0.4/120 0.7/150 0.5/150 1.0/150 0.5/120 1 0.5/130 0.5/130 0.5/130 1.5/130 1 熱固定溫度(°c) 〇 210 Ο 210 o 210 〇 〇 (N 210 210 〇 〇 (N I- 橫延伸溫度(。〇 H 1 < § 〇 橫倍率 卜 ro r- γλ m 卜 m o 卜 Γ- γο m 縱延伸溫度(°c) σ\ Os § CN ON 縱倍率 ro 寸 rn 寸 rn 寸 rn 寸 rn r〇 寸 rn 寸 Γ-Ί rn 寸 r〇 5 ^r rn 實施例1 實施例2 實施例3 實施例4 實施例5 1 實施例6 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6
-21 - 1357424
(N谳爾 延伸率 〇 〇 〇 〇 〇 〇 〇 〇 〇 X X 〇 光濃度 (N m ΟΪ CN σ\ o oo 1 1 15〇°C熱收縮率(%) 藤 〇 fN S oo (N κη C\ 00 1 1 00 o 鼙 On co m CN (N ΚΠ CM rs cn m os rsi (N CO 1 1 p 85°C熱收縮率(%) <N o < < \q 1 —> oo c? r 4 -1嶙 1 1 装 (N 〇 d CN 〇 —’ -H oo Ψ 一 r ^ 1 1 ΓΛ 相對反射率 〇 〇 〇 〇 〇 〇 〇 X X 1 1 X 雙軸延伸後 之厚度(Aim) 〇 〇 100 o r—H r · o vn 1 t 伸縮部之溫 度fc) 〇 ΚΤ\ o ΓΛ 130 o 1 0 vy^ 1 1 * % o o 〇 VO 1 < o m t 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 -22 - (19) 1357424 (產業上之利用領域)
本發明聚酯薄膜取代紙,即可適合於卡片、標籤、封 條、宅配傳票、影像印刷用受像紙、噴墨、條碼印刷用受 像紙、海報、地圖、無塵紙、顯示板、白板、熱感轉印、 平版印刷、電話卡、I c卡等各種印刷記錄用途使用。本 發明聚酯薄膜,作爲反射率高創意性優接收薄膜之基材, 又’最適合使用於商品或商店之宣導,或車站之告示顯示 板等使用之內照式電飾招牌,液晶畫面由燈光照明時,可 構成得到更鮮明之畫面之反射板用基材,由於對光源之熱 尺寸變化小,特別可適用於液晶顯示器之反射板用基材或 太陽電池之背膜。
-23-

Claims (1)

1357424
第0931 15548號專利申請案中文申請專利範圍 民國100年 誠'本〜 令 U 日 10 月 26 修i: 觀 拾、申請專利範圍 1. 一種反射板用聚酯薄膜,其包含一共聚合聚酯組成 物,該組成物含有相對於組成物30~50重量%之無機微粒 子,及特徵爲該共聚合聚酯爲二羧酸主成分爲對苯二甲酸 ,甘醇主成分爲乙二醇,而共聚合成分爲間苯二甲酸,萘 春二羧酸及環己烷二甲醇所成群中至少選擇1種之共聚合聚 酯,於85 °C之熱收縮率,縱方向,橫方向之任一方向均 爲0.7 %以下’且於150 °C之熱收縮率,不論縱方向,或 橫方向均爲5.0 °/〇以下,而且, 對波長400〜700 nm之平均反射率爲90%以上, 厚度爲40//m以上者。 2. 如申請專利範圍第1項之反射板用聚酯薄膜,其中 無機微粒子係由,氧化鈦硫酸鋇,碳酸鈣或二氧化矽所成 ♦群中至少選取1種》 3. 如申請專利範圍第1項之反射板用聚酯薄膜,其中 共聚合聚酯組成物最高含1重量%非相溶性之樹脂。 4. 如申請專利範圍第1項之反射板用聚酯薄膜,其爲 2層以上之層合薄膜’其中至少1層爲如申請專利範圍第 1項所定義之共聚合聚酯組成物所成。 5. 如申請專利範圍第4項之反射板用聚酯薄膜,其中 層合薄膜係具有1層由如申請專利範圍第1項所定義之共 聚合聚酯組成物所成及至少1層由如申請專利範圍第1項 1357424 所定義之共聚合聚酯及〇 ~ 30重量%無機微粒子所成之組 成物所形成者。 6. 如申請專利範圍第4項之反射板用聚酯薄膜,其中 光學濃度爲1.2以上’且於400〜700 nm之波長範圍之 絕對正反射率之平均値爲2.0以上者》 7. 如申請專利範圍第1項之反射板用聚酯薄膜,其係 使用於平面顯示器之反射板者。 8. 如申請專利範圍第1項之反射板用聚酯薄膜,其係 使用於印刷記錄接收片者。
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