TW200936373A - Multilayer film - Google Patents

Abstract

Disclosed is a multilayer film composed of a polyester film and a coating layer formed thereon and containing a phosphor. The multilayer film is characterized in that the phosphor in the coating layer is composed of an inorganic material, and the phosphor content in the coating layer is within the range of 5-80% by weight. The multilayer film is suppressed in yellowing over time, while having high luminance and less color shift. The multilayer film is suitable for reflector plates.

Description

200936373 九、發明說明 【發明所屬之技術領域】 本發明係關於一種由聚酯薄膜及設置於其上之塗佈層 構成之層合薄膜。 【先前技術】 近年來’以液晶電視爲代表之液晶顯示裝置快速普及 Q 。液晶顯示裝置通常具備側邊型發光方式或垂直型發光方 式之背光元件。液晶電視之背光元件係採用垂直型發光方 式。該方式係在液晶元件與配置在其深處之反射板之間並 列設置冷陰極射線管。液晶顯示裝置之背光元件中使用之 反射板要求有高的反射性能。過去，該反射板係使用含有 白色顏料之薄膜，或內部含有細微氣泡之薄膜。內部含有 白色顏料之薄膜由於可獲得高亮度及均勻亮度而被廣泛使 用，例如特開2004-050479號公報、特開2004-330727號 〇 公報中之揭示。又，內部含有細微氣泡之薄膜係揭示於例 如特開平6-322 1 53號公報、特開平7-1 1 8433號公報中。 提升背光元件亮度之方法，除了提高反射板所使用之 薄膜本身之反射率以外，亦提出在薄膜上塗佈螢光增白劑 (特開2002-402 1 4號公報）。但是，當塗佈螢光增白劑 時，由於自冷陰極射線管發射之紫外光使螢光增白劑劣化 ，結果使薄膜變成隨時間而變黃。 【發明內容】 -5- 200936373 〔發明欲解決之課題〕 本發明之課題係提供一種抑制經時變黃之層合薄膜。 本發明之另一課題爲提供一種作爲液晶顯示裝置之背光元 件之構件使用時可獲得高亮度之層合薄膜。本發明又一課 題係提供一種得以抑制經時變黃、可獲得高亮度、色彩不 均較少、適用作反射板之層合薄膜。 〔解決課題之方法〕 @ 亦即本發明爲一種層合薄膜，其係由聚酯薄膜以及設 於其上之含有螢光體之塗佈層所組成之層合薄膜，其特徵 爲該塗佈層之螢光體係由無機物質所組成，且該螢光體於 該塗佈層中之含有量爲5~80重量％。 以下詳細說明本發明。 (塗佈層）BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film composed of a polyester film and a coating layer provided thereon. [Prior Art] In recent years, liquid crystal display devices represented by liquid crystal televisions have rapidly spread Q. The liquid crystal display device usually has a backlight element of a side type light emitting mode or a vertical type light emitting mode. The backlight unit of the LCD TV adopts a vertical type of illumination. In this method, a cold cathode ray tube is arranged in parallel between the liquid crystal element and a reflecting plate disposed at a depth thereof. A reflector used in a backlight element of a liquid crystal display device requires high reflection performance. In the past, the reflecting plate used a film containing a white pigment or a film containing fine bubbles inside. A film containing a white pigment in the interior is widely used because it can obtain high brightness and uniform brightness, and is disclosed in, for example, JP-A-2004-050479, JP-A-2004-330727. Further, a film containing fine bubbles in the inside is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. In addition to improving the reflectance of the film itself used for the reflecting plate, it is also proposed to apply a fluorescent whitening agent to the film (JP-A-2002-402-14). However, when the fluorescent whitening agent is applied, the fluorescent whitening agent is deteriorated by the ultraviolet light emitted from the cold cathode ray tube, and as a result, the film becomes yellowish with time. SUMMARY OF THE INVENTION - 5 - 200936373 [Problem to be Solved by the Invention] An object of the present invention is to provide a laminated film which suppresses yellowing over time. Another object of the present invention is to provide a laminated film which can obtain high luminance when used as a member of a backlight element of a liquid crystal display device. Still another subject of the present invention is to provide a laminated film which is capable of suppressing yellowing over time, obtaining high luminance, and having less color unevenness, and is suitable as a reflecting plate. [Means for Solving the Problem] @ That is, the present invention is a laminated film which is a laminated film composed of a polyester film and a coating layer containing a phosphor provided thereon, which is characterized by the coating The phosphor system of the layer is composed of an inorganic substance, and the content of the phosphor in the coating layer is 5 to 80% by weight. The invention is described in detail below. (coating layer)

本發明中重要的是塗佈層之螢光體係由無機物質所組 Q 成。藉使用由無機物質組成之螢光體作爲螢光體，可獲得 顏色不均較少之層合薄膜。另一方面，當使用由有機物質 組成之螢光體作爲螢光體時，螢光體因紫外線而分解，結 果是長期使用下層合薄膜因紫外線而變黃。 塗佈層爲每100重量％之塗佈層組成物含有5~80重量 % ’較好15〜50重量％之由無機物質組成之螢光體。若未 達5重量％，則使用白色薄膜作爲反射板用途中使用之薄 膜時無法維持足夠高之亮度。另一方面，若超過80重量％ -6 - 200936373 則無法獲得均勻之塗佈層，難以使薄膜整體無斑點地抑制 變黃。 就有效抑制薄膜變黃之觀點而言，塗佈層較好爲含有 具有紫外線吸收能之化合物。塗佈層爲含有具有紫外線吸 收能之化合物時，其含有量爲每100重量％之塗佈層組成 物爲例如20~95重量％，較好爲20〜50重量％。具有紫外 線吸收能之化合物可爲低分子二聚物，亦可爲高分子二聚 〇 物。至於高分子二聚物者可使用在高分子之主鏈或側鏈上 聚合具有紫外線吸收能之低分子者。該高分子二聚物之具 有紫外線吸收能之化合物較好具備有作爲結合劑功能者。 塗佈層除具有紫外線吸收能之化合物以外，較好含有 作爲結合劑之樹脂。當塗佈層含有結合劑樹脂時，結合劑 之樹脂可佔據塗佈層組成物中由無機物質組成之螢光體以 外之部分’或者’可佔據塗佈層組成物中之由無機物質組 成之螢光體及具有紫外線吸收能之化合物以外之部分。 ❹ 構成塗佈層之該等成分係以溶解或分散於溶劑中之塗 佈液而使用。 至於結合劑樹脂可使用例如聚酯、聚胺基甲酸酯、丙 嫌酸、聚醯胺、聚乙烯、聚丙烯、聚氯乙烯、聚偏氯乙烯 、聚苯乙烯' 聚乙酸乙烯酯、氟系樹脂、及該等之共聚物 、二種以上之混合物等。另外，亦可使用使作爲共聚合成 分之具有紫外線吸收能之化合物共聚合之結合劑樹脂。 塗佈層厚度較好爲2~10μπι。藉由使厚度在該範圍之 內’無機螢光體不會脫落，且可獲得具備良好滑動性之層 200936373 合薄膜。 (由無機物質組成物之螢光體） 本發明中由無機物質構成之螢光體較好爲激發波長爲 40 0~4 5 0nm者。藉由使用由在該範圍激發波長之無機物質 構成之螢光體可獲得可作爲反射板用時之高亮度，且可獲 得不會因吸收而變色之層合薄膜。以下，有時將「由無機 物質構成之螢光體」簡稱爲「無機螢光體」。 本發明之無機螢光體以發光峰値波長在500〜600nm者 較佳。當發光波長未達500nm或超過600nm時，作爲反 射板用時之亮度改善效果少而不佳。 至於滿足上述激發波長及發光峰値波長要件之無機螢 光體，可使用以具有岩鹽型結晶構造之鹼土類金屬硫化物 、鹼土類金屬複合氧化物或磷酸緬化合物作爲母體，含有 賦活物質之無機螢光體。 鹼土類金屬硫化物可使用例如硫化鋅（ZnS )、硫化 緦（SrS )、氧化釔（Y202 )。 鹼土類金屬複合氧化物可使用例如鋇·鎂·鋁複合氧 化物（BaMgAli〇〇i7)。 至於賦活物質可使用例如Eu、Cu、Μη、Al、Ce、Tb 、Ba、Sr、Ag。至於進一步之組合可使用例如Eu、Cu與 A1之組合，Ce與Tb之組合，Ba與Eu之組合Ba與Sr及It is important in the present invention that the phosphor system of the coating layer is composed of an inorganic substance. By using a phosphor composed of an inorganic substance as a phosphor, a laminated film having less uneven color can be obtained. On the other hand, when a phosphor composed of an organic substance is used as the phosphor, the phosphor is decomposed by ultraviolet rays, and as a result, the underlying film is yellowed by ultraviolet rays for a long period of time. The coating layer contains 5 to 80% by weight, preferably 15 to 50% by weight, of the phosphor composed of an inorganic substance per 100% by weight of the coating layer composition. If it is less than 5% by weight, a sufficiently high brightness cannot be maintained when a white film is used as a film for use in a reflector. On the other hand, if it exceeds 80% by weight -6 - 200936373, a uniform coating layer cannot be obtained, and it is difficult to suppress the yellowing of the entire film without spots. The coating layer preferably contains a compound having ultraviolet absorbing energy from the viewpoint of effectively suppressing yellowing of the film. When the coating layer contains a compound having ultraviolet absorbing energy, the coating layer composition is, for example, 20 to 95% by weight, preferably 20 to 50% by weight, per 100% by weight of the coating layer composition. The compound having ultraviolet absorption energy may be a low molecular dimer or a polymer dimer. As for the polymer dimer, those having a low molecular weight of ultraviolet absorbing energy can be polymerized on the main chain or the side chain of the polymer. The compound having ultraviolet absorbing energy of the polymer dimer preferably has a function as a binder. The coating layer preferably contains a resin as a binder in addition to the compound having ultraviolet absorbing energy. When the coating layer contains a binder resin, the resin of the binder may occupy a portion other than the phosphor composed of the inorganic substance in the coating layer composition or may be composed of an inorganic substance which may occupy the coating layer composition. A phosphor and a part other than a compound having ultraviolet absorbing energy. These components constituting the coating layer are used as a coating liquid dissolved or dispersed in a solvent. As the binder resin, for example, polyester, polyurethane, acrylic acid, polyamine, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene' polyvinyl acetate, fluorine can be used. A resin, a copolymer of the above, a mixture of two or more, or the like. Further, a binder resin which copolymerizes a compound having ultraviolet absorbing energy as a copolymerization component can also be used. The thickness of the coating layer is preferably from 2 to 10 μm. By making the thickness within this range, the inorganic phosphor does not fall off, and a layer having good slidability can be obtained. (Fluorescent body composed of inorganic substance composition) The phosphor composed of the inorganic substance in the present invention preferably has an excitation wavelength of 40 0 to 450 nm. By using a phosphor composed of an inorganic substance having an excitation wavelength in the range, a high-brightness which can be used as a reflecting plate can be obtained, and a laminated film which does not discolor by absorption can be obtained. Hereinafter, "a phosphor composed of an inorganic substance" may be simply referred to as an "inorganic phosphor". The inorganic phosphor of the present invention is preferably one having a luminescence peak wavelength of 500 to 600 nm. When the emission wavelength is less than 500 nm or exceeds 600 nm, the effect of improving the brightness as a reflector is small and not preferable. As the inorganic phosphor satisfying the excitation wavelength and the luminescence peak wavelength requirement, an alkaline earth metal sulfide, an alkaline earth metal composite oxide or a phosphoric acid-based compound having a rock salt type crystal structure may be used as a precursor, and an inorganic substance containing an active substance may be used. Fluorescent body. As the alkaline earth metal sulfide, for example, zinc sulfide (ZnS), strontium sulfide (SrS), or cerium oxide (Y202) can be used. As the alkaline earth metal composite oxide, for example, barium magnesium complex aluminum oxide (BaMgAli〇〇i7) can be used. As the activating material, for example, Eu, Cu, Μη, Al, Ce, Tb, Ba, Sr, Ag can be used. For further combinations, for example, a combination of Eu, Cu and A1, a combination of Ce and Tb, a combination of Ba and Eu, Ba and Sr and

Eu之組合。 最佳之無機螢光體爲含有以硫化緦（SrS )或氧化釔 -8 - 200936373 (Υ2〇2 )作爲母體，以含有銪（Eu )及/或銅（Cu )作爲 賦活物質之無機螢光體；以鋇.鎂·鋁複合氧化物（ BaMgAl1()017)作爲母體，且含有銪（Eu)及/或錳（Μη) 作爲賦活物質之無機螢光體；以磷酸鑭（LaP04 )作爲母 體且含有Ce及/或Tb作爲賦活物質之無機螢光體。 賦活物質爲Eu時，可使用例如Eu203作爲賦活劑。 此時，無機螢光體中之賦活劑Eu203之含有量以無機螢光 φ 體之總重量作爲基準爲例如0.0 1 ~ 1 0重量％。 賦活物質爲Μη時，可使用例如MnO作爲賦活劑。此 時，無機螢光體中之賦活劑MnO之含有量以無機螢光體 之總重量作爲基準爲例如0.0 1 ~ 1重量％。 賦活物質爲Ce時，可使用例如CeP04作爲賦活劑。 此時，無機螢光體中之賦活劑CeP04之含有量以無機螢光 體之總重量作爲基準爲例如0.0 1 ~3 5重量％。 賦活物質爲Tb時，可使用例如Tb407作爲賦活劑。 φ 此時，無機螢光體中之賦活劑Tb4o7之含有量以無機螢光 體之總重量作爲基準爲例如0.0 1〜2 5重量％。 賦活物質爲Cu時，可使用例如Cu2S作爲賦活劑。此 時，無機螢光體中之賦活劑CuzS之含有量以無機螢光體 之總重量作爲基準爲例如〇.〇1 ~1重量％。 賦活物質爲A1時，可使用例如Al2〇3作爲賦活劑。 此時，無機螢光體中之賦活劑Ah〇3之含有量以無機螢光 體之總重量作爲基準爲例如〇.〇1〜1重量％。 無機螢光體係使用例如粒子狀者，且不論粒子形狀， 200936373 可使用例如球狀者。粒子之平均粒徑爲例如2〜1〇μιη，較 好爲3~7μιη。藉由使用該範圍之平均粒徑之粒子形狀無機 螢光體，可均勻地分散於塗佈液中，可獲得螢光體均勻分 布之塗佈層。 無機螢光體爲市售者，例如可使用以下者。 綠色發光無機螢光體可使用2210(化成OPTRONICS 公司製造’以ZnS作爲母體，以Cu作爲賦活物質）、 E703 1-2 (根本特殊化學公司製造，以La2〇2S作爲母體， ❹ 以Eu作爲賦活物質）、E4011-1 (根本特殊化學公司製造 ’以SrAl2〇4作爲母體，以Eu作爲賦活物質）。 紅色無機螢光體可使用D1110(根本特殊化學公司製 造，以Y2〇3作爲母體，以Eu作爲賦活物質）。 藍色螢光體可使用D1230 (根本特殊化學公司製造，Eu combination. The most preferred inorganic phosphor is inorganic fluorite containing strontium sulfide (SrS) or yttrium oxide-8 - 200936373 (Υ2〇2) as a precursor, and containing europium (Eu) and/or copper (Cu) as a living substance. Body; an inorganic phosphor containing lanthanum-magnesium-aluminum composite oxide (BaMgAl1() 017) as a precursor and containing lanthanum (Eu) and/or manganese (Μη) as a living substance; lanthanum phosphate (LaP04) as a parent And an inorganic phosphor containing Ce and/or Tb as an activating substance. When the activating substance is Eu, for example, Eu203 can be used as the activator. In this case, the content of the activator Eu203 in the inorganic phosphor is, for example, 0.01 to 10% by weight based on the total weight of the inorganic fluorescent φ body. When the activating substance is Μη, for example, MnO can be used as the activator. In this case, the content of the activator MnO in the inorganic phosphor is, for example, 0.01 to 1% by weight based on the total weight of the inorganic phosphor. When the activating substance is Ce, for example, CeP04 can be used as an activator. In this case, the content of the activator CeP04 in the inorganic phosphor is, for example, 0.01 to 35 % by weight based on the total weight of the inorganic phosphor. When the activating substance is Tb, for example, Tb407 can be used as an activator. φ In this case, the content of the activator Tb4o7 in the inorganic phosphor is, for example, 0.01 to 25 wt% based on the total weight of the inorganic phosphor. When the activating substance is Cu, for example, Cu2S can be used as an activator. In this case, the content of the activator CuzS in the inorganic phosphor is, for example, 〇1 to 1% by weight based on the total weight of the inorganic phosphor. When the activating substance is A1, for example, Al2?3 can be used as an activator. In this case, the content of the activator Ah 〇 3 in the inorganic phosphor is, for example, 1 to 1% by weight based on the total weight of the inorganic phosphor. The inorganic fluorescent system uses, for example, a particulate shape, and regardless of the particle shape, for example, a spherical shape can be used for 200936373. The average particle diameter of the particles is, for example, 2 to 1 μmηη, preferably 3 to 7 μmη. By using the particle-shaped inorganic phosphor having an average particle diameter in this range, it can be uniformly dispersed in the coating liquid, and a coating layer in which the phosphor is uniformly distributed can be obtained. The inorganic phosphor is commercially available, and for example, the following can be used. The green-emitting inorganic phosphor can be used in 2210 (manufactured by OCTRONIC, Inc., with ZnS as the parent and Cu as the active material), E703 1-2 (manufactured by the fundamental special chemical company, with La2〇2S as the parent, ❹ with Eu as the living body) Substance), E4011-1 (manufactured by Basic Specialty Chemicals Co., Ltd. with SrAl2〇4 as the parent and Eu as the activating substance). The red inorganic phosphor can be produced using D1110 (manufactured by Basic Specialty Chemical Co., Ltd., with Y2〇3 as the parent and Eu as the activating substance). Blue phosphors can be made with D1230 (manufactured by Basic Specialty Chemicals,

以SrS作爲母體，以Eu作爲賦活物質）、E203 1 -2 (根本 特殊化學公司製造，以BaMgAl1G017作爲母體，以Eu作 爲賦活物質）。 Q 綠色螢光體可使用KX732A (化成OPTRONICS公司 製造，以鋇·鎂·鋁複合氧化物（BaMgAl1Q017 )作爲母 體，以Eu及Μη作爲賦活物質）。 黃綠色螢光體可使用P22-GN4 (化成OPTRONICS公 司製造，以ZnS作爲母體，以Cu、A1作爲賦活物質）、 LP-G2 (化成OPTRONICS公司製造，以LaP04作爲母體 ，以Ce、Tb作爲賦活物質）。 -10- 200936373 (具有紫外線吸收能之化合物） 具有紫外線吸收能之化合物可使用例如二 苯并***系、氰基丙烯酸酯系、水楊酸系、三 酸酯系、草酸苯胺系等有機系者，另外，可使 無機系者。有機系之具有紫外線吸收能之化合 聚合成聚合物之形態使用。 具有紫外線吸收能之化合物例示於下： 〇 二苯甲酮系者可例示爲2,4-二羥基二苯甲 4 -甲氧基二苯甲酮、2-羥基-4 -甲氧基-5-磺基 2,2’-4,4’-四羥基二苯甲酮、2,2’-二羥基-4-甲 酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、雙 4-羥基-5-苯甲醯基苯基）甲烷。 苯并***系者例示爲2- (2，-羥基-5’-甲基 ***、2- (2，-羥基- 5，-第三丁基苯基）苯并三 羥基-3’，5’-二第三丁基苯基）苯并***、2-( ® 第三丁基- 5，-甲基苯基）-5-氯苯并***、2-3’，5’-二第三丁基苯基）-5-氯苯并***、2-( 第三辛基苯基）苯并***、2- (2，-羥基-3’，5’-苯基）苯并***、2,2’-亞甲基雙〔4- ( 1，1，3, 基）-6- ( 2H-苯并***-2-基）酚〕、2- ( 2’-湾 丙烯醯氧基苯基）-2H-苯并***、2-〔 2’-3”，4”，5”，6”-四氫苯二醯亞胺基甲基）-5’-甲基 三哩。 氰基丙烯酸酯系者可例示爲丙烯酸乙基 苯甲酮系、 嗪系、苯甲 用溶凝膠等 物亦可以共 酮、2 -經基- 二苯甲酮、 氧基二苯甲 (2-甲氧基- 苯基）苯并 唑、2- ( 2，-2’·羥基-3’-(2’-羥基-2’-羥基-5’-二第三戊基 3-四甲基丁 i基-5’-甲基 羥基-3’-( 苯基〕苯并 N氰基-3,3’- -11 - 200936373 二苯酯。 水楊酸系者可例示爲對-第三丁基苯基水楊酸酯、對-辛基苯基水楊酸酯。 (聚酯薄膜） 聚酯薄膜係使用由熱可塑性芳香族聚酯構成之薄膜。 至於熱可塑性芳香族聚酯可舉例爲例如聚對苯二甲酸乙二 酯、聚萘二羧酸乙二酯、聚對苯二甲酸丁二酯。亦可於該 等聚酯中共聚合有共聚合成分。該情況下，共聚合成分之 比例以全部二羧酸成分爲基準爲例如20莫耳％以下之比例 〇 使用本發明之層合薄膜作爲反射板時以使用白色聚酯 薄膜作爲聚酯薄膜較佳。 白色聚酯薄膜可使用例如將顆粒添加於聚酯中之組成 物或於聚酯中添加不相溶樹脂而成之組成物之薄片加以延 伸，且延伸時於聚酯與顆粒之界面，或聚酯與不相溶樹脂 之界面產生剝離而在薄膜內部形成細微空隙而成之白色聚 酯薄膜。作爲粒子可使用例如無機粒子、有機粒子、該等 之複合粒子。 至於白色聚酯薄膜較好使用由反射層與支撐該反射層 之支撐層構成之白色層合薄膜。該情況下，此反射層上可 有用以抑制反射層變黃之塗佈層。 白色層合薄膜中之反射層之空隙體積率較好爲 3 0〜8 0%，更好爲35〜75%，最好爲38〜70%。該空隙體積率 200936373 可藉由延伸時使聚酯與粒子或不相溶樹脂之界面剝離 生空隙而獲得。 使用作爲形成空隙之物質之粒子時，粒子之平均 較好爲0.3〜3·0μιη，更好爲0.4〜2.5μιη，最好爲0.5~2 。若平均粒徑未達〇.3μηι，則容易產生凝聚而不佳， 過3.0 μιη，則可能引起薄膜破裂而較不佳。粒子對每 重量份之反射層之聚酯組成物較好爲31〜60重量份， ❹ 爲35~55重量份，最好爲37〜50重量份。若未達31重 則反射率下降，因紫外線引起之劣化將變劇烈而不佳 超過60重量％則薄膜容易破裂而不佳。至於粒子較好 機粒子。 就獲得特別高之反射性能之觀點而言之無機粒子 使用白色顏料。至於白色顏料係使用例如氧化鈦、硫 、碳酸鈣、二氧化矽之粒子，且較好使用硫酸鋇粒子 由使用硫酸鋇粒子可獲得特別良好之反射率。硫酸鋇 〇 可爲板狀、球狀之任一種形狀。 又，有機粒子可使用例如下列說明之不相溶樹脂 〇 使用不相溶樹脂作爲空隙形成物質時，不相溶樹 使用例如聚烯烴樹脂、聚苯乙烯樹脂。具體而言可使 如聚-3-甲基丁-1-烯、聚-4-甲基戊-1-烯、聚乙烯、聚 、聚乙烯基·第三丁烷、1,4-反式-聚-2,3-二甲基丁二 聚乙烯基環己烷、聚苯乙烯、聚氟苯乙烯、纖維素乙 纖維素丙酸酯、聚氯三氟乙烯，且最好使用聚丙烯、 而產 粒徑 .0 μιη 若超 100 更好 量％ 。若 爲無 較好 酸鋇 。藉 粒子 粒子 脂可 用例 丙烯 烯、 酸酯 聚甲 -13- 200936373 基戊烯。聚丙烯、聚甲基戊烯由於樹脂本身爲高透明，因 此可抑制光吸收而改善反射率故而最適用。SrS is used as the parent, Eu is used as the activating substance), E203 1 -2 (manufactured by the Basic Chemical Company, BaMgAl1G017 is used as the parent, and Eu is used as the activating substance). Q Green phosphor can be made of KX732A (manufactured by OCTRONIC, Inc., with BaMgAl1Q017 as the parent and Eu and Μ as the active material). The yellow-green phosphor can be made of P22-GN4 (manufactured by OCTRONIC, ZnS as the parent, Cu and A1 as the activating substances), LP-G2 (manufactured by OPTRONICS, with LaP04 as the parent and Ce and Tb as the living). substance). -10- 200936373 (Compound having ultraviolet absorbing energy) For the compound having ultraviolet absorbing energy, for example, an organic system such as a dibenzotriazole system, a cyanoacrylate system, a salicylic acid system, a tricarboxylic acid ester system or an oxalic acid aniline system can be used. In addition, inorganics can be used. The organic system is used in the form of a combination of ultraviolet absorbing energy and polymerization into a polymer. The compound having ultraviolet absorbing energy is exemplified below: benzophenone can be exemplified as 2,4-dihydroxydibenzoyl 4-methoxybenzophenone, 2-hydroxy-4-methoxy-5 - sulfo 2,2'-4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4-ketone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, bis 4-hydroxy-5-benzimidylphenyl)methane. The benzotriazole system is exemplified by 2-(2,-hydroxy-5'-methyltriazole, 2-(2,-hydroxy-5,-tert-butylphenyl)benzotrihydroxy-3', 5'-di-t-butylphenyl)benzotriazole, 2-( ® tert-butyl-5,-methylphenyl)-5-chlorobenzotriazole, 2-3', 5'- Di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(third octylphenyl)benzotriazole, 2-(2,-hydroxy-3',5'-phenyl)benzene And triazole, 2,2'-methylenebis[4-(1,1,3,yl)-6-(2H-benzotriazol-2-yl)phenol], 2- (2'-bay Propylene methoxy phenyl)-2H-benzotriazole, 2-[ 2'-3",4",5",6"-tetrahydrophenyldiimide iminomethyl)-5'-methyl Three. Examples of the cyanoacrylate may be exemplified by ethyl benzophenone acrylate, azine or benzoate, or may be ketone, 2-pyridyl-benzophenone or oxybenzophenone (2). -Methoxy-phenyl)benzoxazole, 2-( 2,-2'-hydroxy-3'-(2'-hydroxy-2'-hydroxy-5'-di-p-pentyl 3--4-methyl Butyl i--5'-methylhydroxy-3'-(phenyl)benzo N-cyano-3,3'--11 - 200936373 diphenyl ester. Salicylic acid can be exemplified as p-third Phenylphenyl salicylate, p-octylphenyl salicylate (polyester film) The polyester film is a film composed of a thermoplastic aromatic polyester. The thermoplastic aromatic polyester can be exemplified as For example, polyethylene terephthalate, polyethylene naphthalate or polybutylene terephthalate. Copolymerization may also be copolymerized in the polyesters. In this case, the copolymerization component The ratio is, for example, 20 mol% or less based on the entire dicarboxylic acid component. When the laminated film of the present invention is used as a reflecting plate, it is preferred to use a white polyester film as the polyester film. The white polyester film can be used. Extending with a sheet of a composition obtained by adding particles to a polyester or a composition in which an incompatible resin is added to a polyester, and extending at the interface between the polyester and the particles, or incompatible with the polyester A white polyester film in which a fine void is formed in the film by peeling off the interface of the resin, and as the particles, for example, inorganic particles, organic particles, or composite particles thereof can be used. As for the white polyester film, it is preferably used by a reflective layer and a support. The support layer of the reflective layer comprises a white laminated film. In this case, a coating layer for suppressing yellowing of the reflective layer can be used on the reflective layer. The reflective layer in the white laminated film preferably has a void volume ratio of 3 0 to 8 0%, more preferably 35 to 75%, most preferably 38 to 70%. The void volume ratio 200936373 can be obtained by peeling the gap between the polyester and the particles or the incompatible resin at the time of stretching. When the particles as the substance forming the voids are used, the average particle diameter is preferably from 0.3 to 3·0 μm, more preferably from 0.4 to 2.5 μm, and most preferably from 0.5 to 2. If the average particle diameter is less than 〇.3 μη, the particles are likely to be produced. Cohesive If it exceeds 3.0 μm, the film may be broken and it is less preferable. The polyester composition of the particles per part by weight of the reflective layer is preferably 31 to 60 parts by weight, and ❹ is 35 to 55 parts by weight, preferably 37 to 50. If the weight is less than 31, the reflectance will decrease, and the deterioration due to ultraviolet rays will become severe. If the temperature exceeds 60% by weight, the film will be easily broken. As for the particles, the particles are better. The viewpoint of obtaining particularly high reflection performance is obtained. In the case of the inorganic pigment, a white pigment is used. As the white pigment, particles such as titanium oxide, sulfur, calcium carbonate, and ceria are used, and it is preferred to use barium sulfate particles to obtain a particularly good reflectance by using barium sulfate particles. Barium sulfate 〇 can be any shape of a plate or a sphere. Further, as the organic particles, for example, an immiscible resin described below can be used. When an immiscible resin is used as the void-forming material, for example, a polyolefin resin or a polystyrene resin is used as the immiscible tree. Specifically, for example, poly-3-methylbut-1-ene, poly-4-methylpent-1-ene, polyethylene, poly, polyvinyl·third butane, 1,4-trans - poly-2,3-dimethylbutanepolyvinylcyclohexane, polystyrene, polyfluorostyrene, cellulose ethylcellulose propionate, polychlorotrifluoroethylene, and preferably polypropylene, And the particle size of .0 μιη is more than 100%. If there is no better acid 钡. By particle particle grease, propylene olefin, acid ester polymethyl-13-200936373 pentene. Polypropylene and polymethylpentene are most suitable because they are highly transparent, so that light absorption can be suppressed and the reflectance is improved.

使用不相溶樹脂時，較好以對每100重量份之反射層 之聚酯組成物使用5~30重量份之比例，更好爲8~25重量 份，最好爲1〇~20重量份。若反射層中添加超過30重量 份，則薄膜極容易破裂而不佳，若未達5重量份，則無法 形成足夠之空隙，會有薄膜反射率降低之情況而不佳，又 對紫外線之抗性會劣化而不佳。 Q 支撐層係由聚酯組成物構成，每100重量份之該聚酯 組成物較好含有〇 . 5 ~3 0重量％，更好1〜2 7重量％，最好 2〜25重量％之無機粒子。若未達0.5重量％則無法獲得足 夠之滑動性而不佳，若超過3 0重量％，則無法確保作爲支 撐反射層之支撐層之強度，薄膜可能破裂而不佳。 無機粒子之平均粒徑較好爲 〇.1~5μπι，更好爲 0.5〜3μιη，最好爲0.6〜2μιη。若未達Ο.ΐμπι，則容易造成粒 子凝聚而不佳，若超過5μπι則變成粗大突起而有可能使薄 © 膜破裂故而不佳。 (製造方法） 以下，以由含有硫酸鋇粒子之反射層與支撐層構成之 白色聚酯薄膜上設置塗佈層而成層合薄膜，例示性說明本 發明之製造層合薄膜之方法。 硫酸鋇粒子添加於聚酯組成物中可在聚酯聚合時進行 ，亦可在聚合後進行。於聚合時進行之情況，可在酯交換 -14- 200936373 反應或酯化反應結束前添加，亦可在聚縮合反應開始前添 加。 聚合後進行之情況，較好在聚合後添加聚酯並熔融混 練。此時，以較高濃度含有硫酸鋇粒子製造主顆粒，且將 其添加於不含硫酸鋇粒子之聚酯顆粒中，可獲得以所需含 有率含有硫酸鋇粒子之聚酯組成物。 較好使用線徑15 μιη以下之不鏽鋼細線構成之平均網 〇 目爲10〜ΙΟΟμιη，較好平均網目20~50μιη之不織布型過濾 器作爲製膜時之過濾器，過濾聚酯組成物。藉由進行該過 濾，可抑制一般容易凝聚成粗大凝聚顆粒之粒子之凝聚， 可獲得粗大異物少之薄膜。 使用供料套管，藉由同時多層押出法自模嘴押出熔融 聚酯組成物，製造層合未延伸之薄片。亦即使用供料套管 ，將構成反射層之聚酯組成物之熔融物與構成支撐層之聚 酯組成物之熔融物以成爲反射層/支撐層之方式加以層合 © ，且於模嘴中進行展開押出。此時，以供料套管層合之聚 酯組成物維持層合之形態。 由模嘴押出之未延伸薄片以澆鑄桶冷卻固化成爲未延 伸薄膜。 用於塗設塗佈層之塗佈液較好對於該未延伸之薄膜， 或者對於隨後經縱向延伸之縱向延伸薄膜塗佈。 使未延伸狀薄膜經輥加熱、紅外線加熱等加熱，獲得 縱向延伸之縱向延伸薄膜。該延伸較好利用兩個以上之輥 之周速差進行。延伸溫度較好爲聚酯之玻璃轉移點（Tg) -15- 200936373 以上之溫度，進而更好爲Tg〜（Tg + 70°c )之溫度。延伸 倍率係依據用途之要求特性而定，但縱向、與縱向正交之 方向（以下稱爲橫向）均較好爲2.2〜4.0倍，更好爲 2 ·3~3.9倍。若未達2.2倍，則薄膜厚度斑變惡化而無法獲 得良好之薄膜，若超過4.0倍，則製膜中容易產生破裂而 不佳。 縱向延伸薄膜接著依序進行橫向延伸、熱固定、熱鬆 弛之處理成爲二軸配向之薄膜，該等處理係使薄膜邊前進 Q 邊進行。橫向延伸之處理係自比聚酯之玻璃轉移點（Tg) 高之溫度開始，邊升溫至（Tg + 5 ) ~ ( Tg + 70°C )之溫度邊 進行。橫向延伸過程中之升溫可爲連續，亦可分階段（逐 次）進行，但通常係逐次升溫。例如沿著薄膜行進方向將 張布機之橫向延伸區分成複數區，使特定溫度之加熱介質 流過每一區域而升溫。橫向延伸之倍率較好爲2.5〜4.5倍 ，更好爲2.8〜3.9倍。若未達2.5倍，則薄膜之厚度斑惡 化無法獲得良好薄膜而不佳，若超過4.5倍，則容易在製 © 膜中產生破裂而不佳。 夾住橫向延伸後之薄膜兩端且在（Tm-20 )〜（Tm-1〇〇) °C下在固定寬度或在10%以下之寬度減少下進行熱 處理使熱收縮率下降較佳。在比該溫度更高之溫度下薄膜 之平面性變差，且厚度斑變大而不佳。熱處理溫度若低於 (Tm_10 0 ) °C則熱收縮率有變大之情況。 熱處理後，使薄膜溫度恢復至常溫之過程中在（Tm-2〇 )〜（Tm-100 ) °C之溫度領域中，爲了調整薄膜熱收縮 -16- 200936373 量，將夾住之薄膜兩端切落，調整薄膜縱向之拉伸速 使於縱方向鬆弛亦可。鬆弛較好調整張布機出口端之 速度。鬆弛係針對張布機之薄膜直線速度進行輥群之 降低，較好以 0.1-1.5%，更好以 0.2-1.2%，最 0.3〜1.0%之速度降低率實施並進行。如此般使薄膜鬆 調整縱向之熱收縮率。另外，薄膜橫向在切落兩端之 過程中使寬度減少，亦可獲得所需熱收縮率。 φ 本文中雖然例示性詳細說明藉由逐次二軸延伸法 之情況，但本發明之層合薄膜以逐次二軸延伸法、二 時延伸法之任一方法延伸均可。 本發明中之塗佈層雖可直接設置在基材之聚酯薄 ’但當接著性不足時，較好對聚酯薄膜之表面進行電 電處理或底塗處理。底塗處理可設在聚酯薄膜之製造 內進行（線上塗佈法）、亦可在製造聚酯薄膜後另外 (製程外塗佈法）。底塗處理所用之材料可適當的選 Φ 但較適用者可使用共聚合聚酯、聚胺基甲酸酯、丙烯 、各種偶合劑。 含有無機螢光體之塗佈層可以任意方法塗佈。例 使用凹版印刷塗佈、輥塗、旋塗、逆輥塗、桿塗、網 # '浸漬塗佈等方法。塗佈後之硬化方法可使用習知 。例如可適當地使用熱硬化、紫外線、電子束、輻射 Μ性線之方法。塗佈可在製造聚酯薄膜時於薄膜之結 向化完成前進行，亦可在薄膜結晶配向化完成後進行 度， 輥群 速度 好以 弛可 前之 延伸 軸同 膜上 暈放 步驟 塗佈 擇， 酸系 如可 板塗 方法 線等 晶配 -17- 200936373 【實施方式】 實施例 以下，以實施例詳述本發明。 又，測定及評估係以下列方法進行。 (1 )薄膜厚度 以電子微米計（ANRITSU製造之K-402B)測定薄膜 樣品1 〇點之厚度求得平均値作爲薄膜厚度。 (2)塗佈層厚度 將樣品切成三角形，固定於包埋囊之後，以環氧樹脂 包埋。接著，以切片機（Microtome ) ( ULTRACUT-S ) 將包埋之樣品依縱向平行剖面切成薄膜切片後，使用光學 顯微鏡觀察攝影，由照片測定塗佈層與薄膜厚度之比，由 薄膜整體厚度計算求得塗佈層之厚度。 (3 )激發波長自400至45 Οποί下之發光及發光峰値波長 使用螢光分光光度計F-4 5 00 (日立製），取得激發波 長自400至450nm之範圍以及發光波長自300至800nm 之範圍中之激發發光光譜，以下列基準評估是否有螢光發 光。測定係針對設置含有螢光體之塗佈層之面進行。對於 有螢光發光者，係由激發發光光譜求得發光峰値波長。 ◎:有螢光發光 X :沒有螢光發光 -18- 200936373 (4 )經時性變黃 以高壓水銀燈（HALISON東芝 Lighting製造之「 TOSCURE 401」：加裝玻璃濾光片）照光50小時，觀察 照光前後之顏色變化。光照射之輻射照度爲18m W/cm2。 當薄膜之構成爲反射層/支撐層兩層時’自反射層面進行 照光測定。 φ 以色差計（日本電色工業製造之SZS-S90色彩測量系 統）測定初期薄膜色柑（L，、a"、tu* )與照射後之薄膜 色相（L2*、a2*、b2* ) ’算出以下式表示之色相變化dE* ，且以下述基準評估。 dE* = {(Li*-L2*)2+(ai -a2 )2+(bi -b2 )2}1/2 ◎ : dE* 〇 ： 5 < dE* ^10 △ : 10 < dE+ ^ 1 5 φ x ： 15 < dE* (5 )平均粒徑 將添加於聚酯中之前之粉體狀態之粒子’在掃描電子 顯微鏡（SEM )試料台上貼上雙面膠帶，且於其上薄薄鋪 上粒子，經碳蒸鍍後，使用掃描電子顯微鏡（SEM ) ’依 據粒子之大小改變適當倍率進行照相攝影。以畫像處理裝 置求得至少1〇〇點以上之粒子之相當於圓之直徑，除以顆 粒之個數求得個數基準之平均粒徑（μπι)。 -19- 200936373 (6)亮度及色度 關於測定對象爲白色聚酯薄膜之情況（實施例1〜5及 比較例1〜3 )，以下述（6-1 )至（6-5 )所述之方法評估 (6-1 )評估用背光單元之作成 自評估用所準備之液晶電視（SHARP公司製造之 Q AQUOS LC-20S4 )取出垂直型背光單元（20吋），且以 組裝測定對象之薄膜代替原先組裝之背光單元之光反射薄 片，製作成評估用背光單元。 將評估用背光單元之背光面分區分成2x2之4畫面， 使用TOPCON公司製造之BM-7亮度計，以1°之測定角， 及亮度計與背光板之距離爲50cm測定背光板經點燈1小 時後之正面亮度及色度。測定係針對背光板面之4畫面分 別進行，求得亮度之單純平均作爲平均亮度，且求得色度 〇 之單純平均作爲平均亮度。 (6-2)亮度提高率 以含有螢光體塗佈層之塗佈前薄膜做爲測定對象，以 上述（6-1)之方法測定塗佈前之平均亮度。其次，以含 有螢光體塗佈層之塗佈後薄膜做爲測定對象，以上述（6-1)之方法測定塗佈後之平均亮度。使用下式自所得之平 均亮度計算出亮度提高率。 -20- 200936373 亮度提高率（％)=(塗佈後之平均亮度）/(塗佈前 之平均亮度）x 1 〇〇 (6-3 )色度差 以含有螢光體塗佈層之塗佈前薄膜做爲測定對象，以 上述（6-1)之方法測定塗佈前之平均色度（X，y)。其次 ，以含有螢光體塗佈層之塗佈後薄膜做爲測定對象，以上 0 述（6-1)之方法測定塗佈後之平均色度（X，y)。使用下 式自所得之平均色度（x，y)計算出色度差Axy。When the immiscible resin is used, it is preferably used in an amount of 5 to 30 parts by weight, more preferably 8 to 25 parts by weight, more preferably 1 to 20 parts by weight per 100 parts by weight of the polyester layer of the reflective layer. . When more than 30 parts by weight is added to the reflective layer, the film is liable to be broken easily. If it is less than 5 parts by weight, sufficient voids cannot be formed, and the film reflectance is lowered, which is not preferable, and the ultraviolet resistance is resistant. Sex will deteriorate. The Q supporting layer is composed of a polyester composition, and the polyester composition preferably contains 〇. 5 to 30% by weight, more preferably 1 to 27% by weight, most preferably 2 to 25% by weight, per 100 parts by weight of the polyester composition. Inorganic particles. If it is less than 0.5% by weight, sufficient slidability cannot be obtained, and if it exceeds 30% by weight, the strength of the support layer as the supporting reflection layer cannot be ensured, and the film may be broken. The average particle diameter of the inorganic particles is preferably from 〇.1 to 5 μm, more preferably from 0.5 to 3 μm, most preferably from 0.6 to 2 μm. If it does not reach Ο.ΐμπι, it is easy to cause particle aggregation to be poor. If it exceeds 5μπι, it will become coarse protrusions, which may make the thin film rupture. (Manufacturing Method) Hereinafter, a method of producing a laminated film according to the present invention will be exemplarily described by providing a coating film on a white polyester film comprising a reflective layer containing barium sulfate particles and a support layer. The addition of the barium sulfate particles to the polyester composition can be carried out during the polymerization of the polyester or after the polymerization. The polymerization may be carried out before the end of the transesterification -14-200936373 reaction or the esterification reaction, or may be added before the start of the polycondensation reaction. In the case where the polymerization is carried out, it is preferred to add a polyester after the polymerization and melt-knead. At this time, the main particles are produced by containing barium sulfate particles at a relatively high concentration, and are added to the polyester particles containing no barium sulfate particles, whereby a polyester composition containing barium sulfate particles at a desired content can be obtained. It is preferable to use a non-woven fabric of an average mesh size of 10 to 50 μm, which is composed of a stainless steel wire having a wire diameter of 15 μm or less, as a filter for film formation, and to filter the polyester composition. By carrying out this filtration, aggregation of particles which are generally easily aggregated into coarse aggregated particles can be suppressed, and a film having a small amount of foreign matter can be obtained. Using a feed sleeve, the melted polyester composition was extruded from the die by simultaneous multi-layer extrusion to produce a laminate unstretched sheet. That is, using a supply sleeve, the melt of the polyester composition constituting the reflective layer and the melt of the polyester composition constituting the support layer are laminated as a reflective layer/support layer, and are applied to the mold. In the middle of the expansion. At this time, the polyester composition laminated with the supply sleeve was maintained in a laminated form. The unstretched sheet extruded from the die is cooled in a casting bucket to form an unstretched film. The coating liquid for applying the coating layer is preferably applied to the unstretched film or to the longitudinally extending film which is subsequently longitudinally stretched. The unstretched film is heated by roll heating, infrared heating or the like to obtain a longitudinally extending longitudinally stretched film. This extension is preferably carried out using the peripheral speed difference of two or more rolls. The elongation temperature is preferably a temperature at which the glass transition point (Tg) of the polyester is -15-200936373 or higher, and more preferably a temperature of Tg~(Tg + 70 °c). The stretching ratio is determined according to the required characteristics of the application, but the direction perpendicular to the longitudinal direction (hereinafter referred to as the lateral direction) is preferably 2.2 to 4.0 times, more preferably 2 to 3 to 3.9 times. If it is less than 2.2 times, the film thickness is deteriorated and a good film cannot be obtained. If it exceeds 4.0 times, cracking is likely to occur in the film formation, which is not preferable. The longitudinally stretched film is then subjected to lateral stretching, heat setting, and thermal relaxation to form a film which is biaxially aligned, and the treatment is carried out while advancing the film edge Q. The lateral stretching treatment is carried out at a temperature higher than the glass transition point (Tg) of the polyester, and is raised to a temperature of (Tg + 5 ) ~ (Tg + 70 ° C). The temperature rise during the lateral extension can be continuous or can be carried out in stages (successively), but usually it is sequentially heated. For example, the lateral extension of the machine is divided into a plurality of zones along the direction of travel of the film, and a heating medium of a specific temperature flows through each zone to raise the temperature. The lateral extension ratio is preferably from 2.5 to 4.5 times, more preferably from 2.8 to 3.9 times. If it is less than 2.5 times, it is not preferable that the thickness of the film is deteriorated, and if it is more than 4.5 times, it is liable to cause cracking in the film. The heat shrinkage is preferably reduced by sandwiching both ends of the film after the lateral stretching and heat treatment at a fixed width or a width reduction of 10% or less at (Tm-20) to (Tm-1 〇〇) °C. At a temperature higher than the temperature, the planarity of the film deteriorates, and the thickness spot becomes large, which is not preferable. If the heat treatment temperature is lower than (Tm_10 0 ) °C, the heat shrinkage rate may become large. After the heat treatment, in the temperature range of (Tm-2〇)~(Tm-100) °C during the recovery of the film temperature to the normal temperature, in order to adjust the heat shrinkage of the film-16-200936373, the film ends will be clamped. The cutting is performed to adjust the stretching speed in the longitudinal direction of the film to relax in the longitudinal direction. The slack is better to adjust the speed of the exit end of the cloth machine. The relaxation is carried out by reducing the roll speed of the film linear speed of the sheeting machine, and is preferably carried out at a speed reduction rate of 0.1 to 1.5%, more preferably 0.2 to 1.2%, and most 0.3 to 1.0%. The film is loosened to adjust the thermal shrinkage in the longitudinal direction. In addition, the film is reduced in width during the process of cutting both ends, and the desired heat shrinkage rate can be obtained. φ Although the case of the sequential biaxial stretching method is exemplarily described in detail herein, the laminated film of the present invention may be extended by either the sequential biaxial stretching method or the two-time stretching method. The coating layer in the present invention may be directly disposed on the polyester of the substrate. However, when the adhesion is insufficient, the surface of the polyester film is preferably subjected to electro-treatment or primer treatment. The primer treatment can be carried out in the production of a polyester film (on-line coating method) or in addition to the production of a polyester film (external coating method). The material used for the primer treatment may be appropriately selected from Φ, but a copolymerized polyester, a polyurethane, a propylene, and various coupling agents may be used as appropriate. The coating layer containing the inorganic phosphor can be applied by any method. Examples are gravure coating, roll coating, spin coating, reverse roll coating, rod coating, web dipping coating, and the like. A hardening method after coating can be used. For example, a method of thermosetting, ultraviolet rays, electron beam, or radiation enthalpy can be suitably used. The coating can be carried out before the completion of the formation of the film in the production of the polyester film, or after the completion of the crystallization of the film, the roll group speed is good, and the stretching axis before the relaxation is coated with the film on the film. Alternatively, an acid system such as a plate coating method line or the like -17-200936373 [Embodiment] Hereinafter, the present invention will be described in detail by way of examples. Further, the measurement and evaluation were carried out in the following manner. (1) Film thickness The thickness of the film sample 1 was measured by an electron micrometer (K-402B manufactured by ANRITSU) to obtain an average 値 as the film thickness. (2) Coating layer thickness The sample was cut into a triangle shape, fixed in an embedding capsule, and embedded in an epoxy resin. Next, the embedded sample was cut into thin film sections by a longitudinal parallel section using a microtome (ULTRACUT-S), and the photograph was observed using an optical microscope, and the ratio of the thickness of the coating layer to the film thickness was measured from the photograph, and the thickness of the entire film was measured. The thickness of the coating layer was calculated. (3) The excitation wavelength is from 400 to 45 Οπί, and the luminescence peak and the luminescence peak wavelength are obtained by using a fluorescence spectrophotometer F-4 5 00 (manufactured by Hitachi Ltd.), and the excitation wavelength is from 400 to 450 nm and the emission wavelength is from 300 to 800 nm. The excitation luminescence spectrum in the range was evaluated for the presence of fluorescent luminescence on the following basis. The measurement was performed on the surface on which the coating layer containing the phosphor was provided. For those who have fluorescent light, the luminescence peak wavelength is obtained from the excitation luminescence spectrum. ◎: Fluorescent X: No Fluorescent -18- 200936373 (4) Time-lapse yellowing with high-pressure mercury lamp ("TOSCURE 401" manufactured by HALISON Toshiba Lighting: Adding a glass filter) for 50 hours, observe The color changes before and after illumination. The illuminance of the light irradiation was 18 mW/cm2. When the composition of the film is two layers of the reflective layer/support layer, the light is measured from the reflective layer. φ The initial film color orange (L, a", tu*) and the film color after irradiation (L2*, a2*, b2*) were measured by a color difference meter (SZS-S90 color measurement system manufactured by Nippon Denshoku Industries Co., Ltd.). The hue change dE* represented by the following formula was calculated and evaluated on the basis of the following criteria. dE* = {(Li*-L2*)2+(ai -a2 )2+(bi -b2 )2}1/2 ◎ : dE* 〇: 5 < dE* ^10 △ : 10 < dE+ ^ 1 5 φ x : 15 < dE* (5 ) Particles of the powder state before the average particle diameter is added to the polyester 'on the scanning electron microscope (SEM) sample table, and on the double-sided tape The particles were thinly coated, and after carbon deposition, a scanning electron microscope (SEM) was used to perform photogrammetry according to the size of the particles. The image processing apparatus obtains a diameter corresponding to a circle of at least one point or more, and divides the number of particles to obtain an average particle diameter (μπι) based on the number of particles. -19- 200936373 (6) Luminance and chromaticity In the case where the measurement target is a white polyester film (Examples 1 to 5 and Comparative Examples 1 to 3), the following (6-1) to (6-5) are described. Method evaluation (6-1) Evaluation of the backlight unit for the evaluation of the liquid crystal television (Q AQUOS LC-20S4 manufactured by SHARP) for taking out the vertical type backlight unit (20 turns), and assembling the film of the measurement object Instead of the light-reflecting sheet of the originally assembled backlight unit, a backlight unit for evaluation is produced. The backlight surface division of the evaluation backlight unit is divided into 2 screens of 2x2, using the BM-7 luminance meter manufactured by TOPCON Co., Ltd., and measuring the angle of 1°, and the distance between the luminance meter and the backlight panel is 50 cm. Front brightness and chromaticity after hours. The measurement was performed on the four screens of the backlight panel, and the simple average of the luminance was obtained as the average luminance, and the simple average of the chromaticity 〇 was obtained as the average luminance. (6-2) Brightness improvement rate The pre-coating film containing the phosphor coating layer was used as a measurement target, and the average brightness before coating was measured by the method of the above (6-1). Next, the coated film containing the phosphor coating layer was used as a measurement object, and the average brightness after coating was measured by the method (6-1) above. The brightness improvement rate was calculated from the average luminance obtained by the following formula. -20- 200936373 Brightness improvement rate (%) = (average brightness after coating) / (average brightness before coating) x 1 〇〇 (6-3) chromaticity difference with a coating containing a phosphor coating layer The pre-cloth film was used as a measurement object, and the average color (X, y) before coating was measured by the method of the above (6-1). Next, the coated film containing the phosphor coating layer was used as a measurement target, and the average color (X, y) after coating was measured by the method described in (6-1) above. The excellentness difference Axy is calculated from the obtained average chromaticity (x, y) using the following formula.

Axy = ( Δχ2 + Δγ2 ) 1/2 Δχ=(塗佈後之平均色度之x成分）-(塗佈前之平均 色度之X成分）Axy = ( Δχ2 + Δγ2 ) 1/2 Δχ = (x component of average chromaticity after coating) - (X component of average chromaticity before coating)

Ay =(塗佈後之平均色度之y成分）-(塗佈前之平均 色度之y成分） 使用所得之Axy，以下述基準評估色度差Axy : ❿ ◎ : Axy < 0.05 〇 ： 0.05 S Axy < 0.10 χ ： 0.10^ Axy (6-4)耐久性試驗之亮度維持率 以含有螢光體塗佈層塗佈後之薄膜（耐久性試驗前之 薄膜）做爲測定對象，以上述（6- 1 )之方法測定平均亮 度。其次，對經過點燈約3000小時之背光板進行耐久性 試驗。以上述（6-1)之方法，對經歷耐久性試驗之薄膜 -21 - 200936373 測定耐久性試驗後之平均亮度。 以下式計算出亮度維持率： 亮度維持率（％)=(耐久性試驗後之平均亮度）/ ( 耐久性試驗前之平均亮度）χίοο (6-5)耐久性試驗之色度變化 以含有螢光體塗佈層塗佈後之薄膜（耐久性試驗前之 薄膜）作爲測定對象，以上述（6-1 )之方法測定平均色 q 度（x,y)。其次，對經過點燈約3000小時之背光板進行 耐久性試驗。以上述（6-3 )之方法，對經歷耐久性試驗 之薄膜測定耐久性試驗後之平均色度（x，y)。使用下式 自所得之平均色度（x，y )計算出Axy。 △ xy = ( Δχ2 + Δγ2 ) 1/2 Δχ=(耐久性試驗後之平均色度之x成分）-(耐久性 試驗前之平均色度之X成分）Ay = (y component of average chromaticity after coating) - (y component of average chromaticity before coating) Using the obtained Axy, the chromaticity difference Axy is evaluated by the following criteria: ❿ ◎ : Axy < 0.05 〇: 0.05 S Axy < 0.10 χ : 0.10^ Axy (6-4) The brightness retention rate of the durability test is measured by the film (the film before the durability test) which is coated with the phosphor coating layer, and The method of the above (6-1) measures the average brightness. Next, the durability test was performed on the backlight panel which was lit for about 3,000 hours. The average brightness after the durability test was measured for the film subjected to the durability test -21 - 200936373 by the method of the above (6-1). The brightness maintenance rate is calculated by the following formula: brightness maintenance rate (%) = (average brightness after durability test) / (average brightness before durability test) χίοο (6-5) chromaticity change of durability test to contain firefly The film after the application of the light-coated layer (film before the durability test) was used as a measurement object, and the average color q degree (x, y) was measured by the method of the above (6-1). Next, the durability test was performed on the backlight panel which was lit for about 3,000 hours. The film subjected to the durability test was measured for the average chromaticity (x, y) after the durability test by the method (6-3) above. Axy was calculated from the obtained average chromaticity (x, y) using the following formula. △ xy = ( Δχ2 + Δγ2 ) 1/2 Δχ = (x component of average chromaticity after durability test) - (endurance X component of average chromaticity before test)

Ay=(耐久性試驗後之平均色度之y成分）-(耐久性 Q 試驗前之平均色度之y成分） 使用所得之Axy，以下述基準評估色度差Axy : ◎ ·· Axy < 0.05 〇：0.05 SAxy< 0.10 χ ： 0.10^ Δχγ (7)亮度及色度 測定對象爲透明聚酯薄膜時（實施例6及比較例4 ) -22- 200936373 ，係以下述（7-1 )至（7-5 )中所 (7-1 )評估用背光單元之作成 自評估用所準備之液晶電市 AQUOS LC-20S4 )取出垂直型背 組裝測定對象之薄膜代替光原先組 薄片，製作成評估用背光單元。 φ 將評估用背光單元之背光面分 用TOPCON公司製造之BM-7亮度 亮度計與背光板之距離爲50cm測 後之正面亮度及色度。測定係針對 進行，求得亮度之單純平均作爲平 純平均作爲平均亮度。 (7-2 )亮度提高率 φ 以含有螢光體塗佈層塗佈前之 上述（7-1)之方法測定塗佈前之 有螢光體塗佈層塗佈後之薄膜作爲 1 )之方法測定塗佈後之平均亮度 均亮度計算出亮度提高率。 亮度提商率（％)=(塗佈後 之平均亮度）χΙΟΟ (7-3 )色度差 之方法評估。 (SHARP公司製造之 單元（20吋），且以 裝之背光單元之光擴散 成2x2之4畫面，且使 計，以1°之測定角，及 定背光板經點燈1小時 背光板面之4畫面分別 均亮度，求得色度之單 薄膜作爲測定對象，以 平均亮度。其次，以含 .測定對象，以上述（7_ 。使用下式自所得之平 之平均亮度）/(塗佈前 -23- 200936373 以含有螢光體塗佈層塗佈前之薄膜作爲測定對象，以 上述（7-1)之方法測定塗佈前之平均色度（x，y)。其次 ，以含有螢光體塗佈層塗佈後之薄膜作爲測定對象，以上 述（7-1)之方法測定塗佈後之平均色度（x，y)。使用下 式自所得之平均色度（X，y )計算出色度差Axy。 △ xy= ( Δχ2 + Δγ2) 1/2 △x=(塗佈後之平均色度之x成分）-(塗佈前之平均 色度之X成分） △ y=(塗佈後之平均色度之y成分）-(塗佈前之平均 色度之y成分） 使用所得之Axy，以下述基準評估色度差Axy: ◎ : Axy< 0.05 〇：0.05^ Axy <0.10 x : 0 · 1 0 g Axy (7-4 )耐久性試驗之亮度維持率 以含有螢光體塗佈層塗佈後之薄膜（耐久性試驗前之 薄膜）作爲測定對象，以上述（7-1 )之方法測定平均亮 度。其次，對經過點燈約3000小時之背光板進行耐久性 試驗。以上述（7-1)之方法，對經歷耐久性試驗之薄膜 測定耐久性試驗後之平均亮度。 以下式計算出亮度維持率： 亮度維持率（％)=(耐久性試驗後之平均亮度）/ ( 耐久性試驗前之平均亮度）xl00 -24- 200936373 (7-5 )耐久性試驗之色度變化 以含有螢光體塗佈層塗佈後之薄膜（耐久性試驗前之. 薄膜）作爲測定對象，以上述（7-1 )之方法測定平均色 度（x，y)。其次，對經過點燈約3 000小時之背光板進行 耐久性試驗。以上述（7-3 )之方法，對經歷耐久性試驗 之薄膜測定耐久性試驗後之平均色度（x，y)。使用下式 φ 自所得之平均色度（x，y)計算出Axy。Ay = (y component of average chromaticity after durability test) - (y component of average chromaticity before durability Q test) Using the obtained Axy, the chromaticity difference Axy was evaluated by the following criteria: ◎ ·· Axy < 0.05 〇: 0.05 SAxy<0.10 χ : 0.10^ Δχγ (7) When the brightness and chromaticity measurement target is a transparent polyester film (Example 6 and Comparative Example 4) -22- 200936373, the following (7-1) is used. (7-5) (7-1) Evaluation of the backlight unit for evaluation The liquid crystal market AQUOS LC-20S4 prepared for evaluation) Take out the film of the vertical back assembly measurement object instead of the original light sheet, and make an evaluation. Use a backlight unit. φ The backlight surface of the evaluation backlight unit is divided into the front brightness and chromaticity of the BM-7 brightness meter and the backlight from TOPCON. For the measurement, the simple average of the luminance was obtained as the average average luminance. (7-2) Brightness improvement rate φ The film after coating with the phosphor coating layer before coating is measured as 1) by the method (7-1) before coating with the phosphor coating layer. Method The brightness improvement rate was calculated by measuring the average brightness after coating. Brightness quotient rate (%) = (average brightness after coating) χΙΟΟ (7-3) Method evaluation of chromaticity difference. (The unit manufactured by SHARP (20吋), and the light of the backlight unit is diffused into a 2x2 picture, and the measurement is made at a measurement angle of 1°, and the backlight is lit for 1 hour. The brightness of each of the four screens is determined by the average brightness of the single film of the chromaticity as the measurement target. Secondly, the above-mentioned (7_. The average brightness obtained from the following formula is used) / (before coating) -23- 200936373 The film before coating with the phosphor coating layer was used as the measurement target, and the average color (x, y) before coating was measured by the method of the above (7-1). The film after the application of the body coating layer was used as a measurement object, and the average color chromaticity (x, y) after coating was measured by the method of the above (7-1). The average color chromaticity (X, y) obtained from the following formula was used. Calculate the excellentness difference Axy. △ xy= ( Δχ2 + Δγ2) 1/2 △x=(x component of the average chromaticity after coating)-(X component of the average chromaticity before coating) △ y=(coating The y component of the average chromaticity after the cloth) - (y component of the average chromaticity before coating) Using the obtained Axy, the chromaticity difference Axy was evaluated by the following criteria: : Axy< 0.05 〇: 0.05^ Axy <0.10 x : 0 · 1 0 g Axy (7-4) Brightness maintenance rate of durability test film after coating with a phosphor coating layer (before durability test) The film was measured for the average brightness by the method of the above (7-1). Next, the durability test was performed on the backlight plate which was lit for about 3,000 hours. The method of (7-1) above was used for durability. The film was tested for the average brightness after the durability test. The following formula calculates the brightness maintenance rate: brightness maintenance rate (%) = (average brightness after durability test) / (average brightness before durability test) xl00 -24 - 200936373 (7-5) The change in chromaticity of the durability test was carried out by measuring the film containing the phosphor coating layer (film before the durability test) and measuring it by the method of (7-1) above. Average chromaticity (x, y). Secondly, durability test was performed on a backlight panel that was lit for about 3,000 hours. After the durability test of the film subjected to the durability test by the method of the above (7-3) Average color (x, y). Use the following formula φ to get it. Average chromaticity (x, y) is calculated Axy.

Axy= ( Ax2 + Ay2 ) 1/2 Δχ=(耐久性試驗後之平均色度之χ成分）-(耐久 性試驗前之平均色度之X成分） △ y=(耐久性試驗後之平均色度之y成分）-(耐久性 試驗前之平均色度之y成分） 使用所得之Axy，以下述之基準評估色度差Axy: ◎ : Axy < 0.05 ❹ 〇 ： 0.05 ^ Axy <0.10 χ ： 0.10^ Axy 參考例1(白色聚酯薄膜之製造）Axy= ( Ax2 + Ay2 ) 1/2 Δχ = (χ component of average chromaticity after durability test) - (X component of average chromaticity before durability test) △ y = (average color after durability test) y component) - (y component of average chromaticity before durability test) Using the obtained Axy, the chromaticity difference Axy was evaluated on the basis of the following: ◎ : Axy < 0.05 ❹ 〇: 0.05 ^ Axy < 0.10 χ : 0.10^ Axy Reference Example 1 (Manufacture of White Polyester Film)

將132重量份之對苯二甲酸二甲酯、18重量份之間苯 二甲酸二甲酯（以聚酯之全部二羧酸成分爲準爲12莫耳％ )、96重量份之乙二醇、3.0重量份之二乙二醇、〇.〇5重 量份之乙酸錳、0.012重量份之乙酸鋰饋入配置有精餾塔 、餾出冷凝器之燒瓶中，一邊攪拌一邊加熱至150~ 235 °C -25- 200936373 使甲醇餾出進行酯交換反應。甲醇餾出後’添加〇·〇3重 量份之磷酸三甲酯、0.0 4重量份之二氧化鍺’將反應產物 移到反應器中。接著一邊攪拌且使反應器內部緩慢減壓至 0.5mmHg之同時升溫至290°C進行聚縮合反應。所得共聚 合聚酯之二乙二醇成分量爲2.5重量％，鍺元素含有量爲 50ppm，鋰元素之含有量爲5ppm。 於該聚酯中添加50重量％之平均粒徑1.5μηι之硫酸鋇 粒子獲得反射層用聚酯組成物。又，於該聚酯中添加5重 q 量％之平均粒徑1 . 5 μιη之硫酸鋇粒子獲得支撐層用聚酯組 成物。將各組成物供給至加熱至280°C之兩台押出機中， 以使反射層/支撐層之厚度比率爲3/1之方式使用兩層進料 套管裝置合流而層合成二層，維持在該層合狀態由模嘴押 出成形爲兩層薄片狀。以表面溫度25°C之冷卻筒使之冷卻 固化成未延伸薄膜，進而加熱至95 °C於長度方向（縱向） 延伸，且以25 °C之輥群冷卻。接著，一邊以夾子夾住縱向 延伸薄膜兩端一邊引導至張布機在加熱至12〇°C之氛圍氣 〇 體中以與長度方向垂直之方向（橫向）延伸。隨後在張布 機內以20(TC之溫度進行熱固定，且在130°C之溫度下分別 以平均0.5%、1 %進行縱向之鬆弛及橫向之加寬，冷卻至 室溫，獲得總厚度爲188μιη之雙軸延伸之聚酯薄膜。 參考例2(透明聚酯薄膜之製造） 將96重量份之對苯二甲酸二甲酯、58重量份之乙二 醇及0.0 3重量份之乙酸錳分別饋入反應器中，在攪拌下 -26- 200936373 一邊使內溫上升至240 °C—邊使甲醇餾出進行酯交換反應 ，該酯交換反應結束後，添加0.097重量份之磷酸三甲醋 及0.041重量份之二氧化鍊，接著使反應產物升溫’最終 在高度真空下280°C之條件進行聚縮合’獲得固有黏度（ 〔η〕）0.64之聚酯顆粒。 使所得聚酯顆粒在160°C下乾燥3小時後，於280°C下 熔融押出，且以表面溫度20 °C之冷卻筒冷卻固化成未延伸 φ 薄膜。接著，加熱至95 °C以長度方向（縱向）延伸3.2倍 ，且以2 5 °C之輥群冷卻後，一邊以夾子夾住縱向延伸薄膜 兩端一邊引導至張布機，在加熱至120 °C之氛圍氣體中以 與長度方向垂直之方向（橫向）延伸3.6倍後’在220 °C 之溫度下進行熱固定。隨後，在張布機內130 °C之溫度下 分別以平均0.5 %、1 %進行縱向之鬆驰及橫向之加寬，冷 卻至室溫，獲得二軸延伸之薄膜。 Ο 實施例1(白色聚酯薄膜之例） 將下列組成物溶解於甲苯/乙酸丁酯之混合溶液中， 作成45重量％固成分濃度之塗佈液。使用重量比爲1:1 之混合溶液作爲甲苯/乙酸丁酯之混合溶液。 (塗佈液固成分組成） .綠色發光無機螢光體2210(化成OPHTRONICS公 司製造） 3 0重量份 •紫外線吸收物質 YUTABL UV6010 (曰本觸媒公司 -27- 200936373 製） 15重量份 以乾燥後之厚度成爲5 μιη之方式，將該塗佈液塗佈在 參考例1中獲得之白色聚酯薄膜之反射層上，在150°C下 熱風乾燥2分鐘，獲得塗佈之薄膜。 所得塗佈薄膜之亮度上升率爲1〇4%。其他評估結果 列於表1。132 parts by weight of dimethyl terephthalate, 18 parts by weight of dimethyl phthalate (12 mol% based on the total dicarboxylic acid component of the polyester), and 96 parts by weight of ethylene glycol 3.0 parts by weight of diethylene glycol, 〇. 〇 5 parts by weight of manganese acetate, and 0.012 parts by weight of lithium acetate are fed into a flask equipped with a rectification column and a distillation condenser, and heated to 150 to 235 while stirring. °C -25- 200936373 Distillation of methanol for transesterification. After the methanol was distilled off, 3 parts by weight of trimethyl phosphate and 0.04 parts by weight of cerium oxide were added, and the reaction product was transferred to the reactor. Subsequently, the inside of the reactor was gradually stirred under reduced pressure to 0.5 mmHg while the temperature was raised to 290 ° C to carry out a polycondensation reaction. The amount of the diethylene glycol component of the obtained copolymerized polyester was 2.5% by weight, the content of the lanthanum element was 50 ppm, and the content of the lithium element was 5 ppm. To the polyester, 50% by weight of barium sulfate particles having an average particle diameter of 1.5 μm was added to obtain a polyester composition for a reflective layer. Further, a polyester composition of a support layer was obtained by adding 5 wt% of an average particle diameter of 1.5 μm of barium sulfate particles to the polyester. Each composition was supplied to two extruders heated to 280 ° C so that the thickness ratio of the reflective layer / the support layer was 3/1, and the two layers of the feeding device were joined to form a layer to form a layer to maintain In this laminated state, the die is extruded into a two-layered sheet shape. The film was cooled to a non-stretched film by a cooling cylinder having a surface temperature of 25 ° C, further heated to 95 ° C in the longitudinal direction (longitudinal direction), and cooled at 25 ° C. Next, while sandwiching the both ends of the longitudinally extending film with a clip, it is guided to the spreader to extend in a direction perpendicular to the longitudinal direction (lateral direction) in the atmosphere of the heating to 12 °C. Then, it was heat-fixed in a cloth machine at a temperature of 20 (TC temperature, and longitudinal relaxation and lateral width were respectively performed at an average of 0.5% and 1% at a temperature of 130 ° C, and cooled to room temperature to obtain a total thickness. A biaxially stretched polyester film of 188 μm. Reference Example 2 (Production of Transparent Polyester Film) 96 parts by weight of dimethyl terephthalate, 58 parts by weight of ethylene glycol, and 0.03 parts by weight of manganese acetate Feeding into the reactor separately, raising the internal temperature to 240 ° C while stirring - 26-200936373 - distilling the methanol for transesterification reaction, after the end of the transesterification reaction, adding 0.097 parts by weight of trimethyl citrate and 0.041 parts by weight of the dioxygen chain, followed by heating the reaction product to 'finally polycondensate under conditions of 280 ° C under high vacuum' to obtain polyester particles having an intrinsic viscosity ([η]) of 0.64. The obtained polyester particles were made at 160°. After drying for 3 hours at C, it was melted and extruded at 280 ° C, and cooled to a film of unstretched φ by a cooling cylinder having a surface temperature of 20 ° C. Then, it was heated to 95 ° C to extend 3.2 times in the longitudinal direction (longitudinal direction). And after cooling at 2 5 °C While holding the both ends of the longitudinally extending film with a clip, it is guided to the spreader, and is extended 3.6 times in the direction perpendicular to the longitudinal direction (lateral direction) in an atmosphere heated to 120 ° C, and then carried out at a temperature of 220 ° C. Heat-fixed. Subsequently, longitudinal relaxation and lateral broadening were carried out at an average temperature of 130 ° C in a cloth machine at an average of 0.5% and 1%, and cooled to room temperature to obtain a biaxially stretched film. 1 (Example of white polyester film) The following composition was dissolved in a mixed solution of toluene/butyl acetate to prepare a coating liquid having a solid concentration of 45% by weight. A mixed solution having a weight ratio of 1:1 was used as toluene/ Mixed solution of butyl acetate. (Solid composition of coating liquid). Green luminescent inorganic phosphor 2210 (manufactured by OPHTRONICS) 30 parts by weight • UV absorbing material YUTABL UV6010 (曰本触媒公司-27- 200936373 15 parts by weight of the coating liquid was applied to the reflective layer of the white polyester film obtained in Reference Example 1 in such a manner that the thickness after drying became 5 μm, and dried by hot air at 150 ° C for 2 minutes to obtain a coating. Cloth Film. The resulting coated film of the luminance increase rate 1〇4% other evaluation results are shown in Table 1.

又，綠色發光無機螢光體2210(化成OPHTRONICS 公司製造），爲以ZnS爲母體、以Cu作爲賦活物質之無 機螢光體。 實施例2(白色聚酯薄膜之例） 除將塗佈液之螢光物質改變成紅色無機螢光體D1110 (根本特殊化學公司製造）以外，其餘與實施例1相同， 獲得塗佈之薄膜。評估結果列於表1。 又，紅色無機螢光體D1110 (根本特殊化學公司製造 )爲以Y2〇3爲母體、以Eu作爲賦活物質之無機螢光體。 實施例3 (白色聚酯薄膜之例） 除將塗佈液之螢光物質改變成藍色無機螢光體D1230 (根本特殊化學公司製造）以外，其餘與實施例1相同， 獲得塗佈之薄膜。評估結果列於表1。 又，藍色無機螢光體D1 23 0(根本特殊化學公司製造 )爲以SrS爲母體、以Eu作爲賦活物質之無機螢光體。 200936373 實施例4(白色聚酯薄膜之例） 除將塗佈液之螢光物質改變成綠色無機螢光體 KX732A (化成OPHTRONICS公司製造）以外，其餘與實 施例1相同，獲得塗佈之薄膜。評估結果列於表1。 又，綠色無機螢光體KX732A (化成OPHTRONICS公 司製造）爲以鋇·鎂·鋁複合氧化物（BaMgAl1Q017 )爲 母體、以Eu及Μη作爲賦活物質之無機螢光體。 實施例5 (白色聚酯薄膜之例） 除將紫外線吸收物質改變成丙烯酸系結合劑YUTABL S-2 840 (日本觸媒公司製造）以外，其餘與實施例1相同 ，獲得塗佈之薄膜。亮度提高率爲1 〇4%。評估結果列於 表1。 比較例1 (白色聚酯薄膜之例） Φ 將下列組成物溶解於甲苯/乙酸丁酯之混合溶液中， 製作成45重量％固成分濃度之塗佈液。又，使用重量比爲 1 : 1之混合溶液作爲甲苯/乙酸丁酯混合溶液。 (塗佈液固成分組成） •有機螢光增白劑OB-1 (Eastman公司製造）5重量份 •紫外線吸收物質YUTABL UV6010 (日本觸媒公司 製造） 1 5重量份 以乾燥後之厚度成爲5μιη之方式將所得塗佈液塗佈在 -29- 200936373 參考例1中獲得之白色聚酯薄膜之反射層上，且在150°C 下熱風乾燥2分鐘，獲得塗佈之薄膜。 儘管所得塗佈薄膜之亮度上升率顯示爲105%，但因 濁色使色度差變大，又耐久性試驗後之亮度下降亦大，使 薄膜在實用上難以使用。評估結果列於表1。 比較例2(白色聚酯薄膜之例） 除將表1中所示之螢光物質改變成有機螢光增白劑 UVITEX-OB (汽巴特用化學品公司製造），且其添加量成 爲5重量份以外，其餘使實施例1相同獲得塗佈之薄膜。 此時之亮度上升率爲10 0%左右，未確認到亮度提高。該 薄膜爲因變色使色度差變大且耐久性試驗後之亮度降低亦 大之薄膜，在實用上無法被使用。評估結果列於表1。 比較例3 (白色聚酯薄膜之例） 除將有機螢光增白劑OB-1之添加量變更成30重量份 以外，其餘與比較例1相同，獲得塗佈之薄膜。評估結果 列於表1。 實施例6 (透明聚酯薄膜之例） 將下列組成物溶解於乙酸丁酯中，製作成45重量°/。固 成分濃度之塗佈液。 (塗佈液固成分組成） -30- 200936373 •無機螢光體（2210化成OPHTRONICS公司製造） 1 〇重量份 •丙烯酸珠粒（MBX-15，積水化成品工業公司製造 ) 60重量份 •丙烯酸系結合劑（YUTABL S2740日本觸媒公司製 造） 25重量份 •交聯劑（CORONET HL，曰本胺基甲酸酯工業公司 〇 製造） 5重量份 除以固化後成爲8g/m2之方式塗佈作爲塗佈液之該塗 佈液之外，其餘與實施例1相同，獲得塗佈之薄膜。評估 結果列於表1。Further, the green light-emitting inorganic phosphor 2210 (manufactured by OPHTRONICS Co., Ltd.) is an inorganic phosphor using ZnS as a precursor and Cu as an activating substance. Example 2 (Example of White Polyester Film) A coated film was obtained in the same manner as in Example 1 except that the fluorescent substance of the coating liquid was changed to the red inorganic phosphor D1110 (manufactured by Basic Specialty Chemical Co., Ltd.). The evaluation results are shown in Table 1. Further, the red inorganic phosphor D1110 (manufactured by Basic Specialty Chemical Co., Ltd.) is an inorganic phosphor having Y2〇3 as a matrix and Eu as an activating substance. Example 3 (Example of a white polyester film) A coated film was obtained in the same manner as in Example 1 except that the fluorescent substance of the coating liquid was changed to the blue inorganic phosphor D1230 (manufactured by Basic Specialty Chemical Co., Ltd.). . The evaluation results are shown in Table 1. Further, the blue inorganic phosphor D1 23 0 (manufactured by Basic Specialty Chemical Co., Ltd.) is an inorganic phosphor having SrS as a matrix and Eu as an activating material. 200936373 Example 4 (Example of a white polyester film) A coated film was obtained in the same manner as in Example 1 except that the fluorescent substance of the coating liquid was changed to a green inorganic phosphor KX732A (manufactured by Chemical Industries, Inc.). The evaluation results are shown in Table 1. In addition, the green inorganic phosphor KX732A (manufactured by the company of OPHTRONICS Co., Ltd.) is an inorganic phosphor having a ruthenium-magnesium-aluminum composite oxide (BaMgAl1Q017) as a precursor and Eu and Μη as an activating substance. Example 5 (Example of white polyester film) A coated film was obtained in the same manner as in Example 1 except that the ultraviolet absorbing material was changed to an acrylic binder YUTABL S-2 840 (manufactured by Nippon Shokubai Co., Ltd.). The brightness improvement rate is 1 〇 4%. The results of the assessment are listed in Table 1. Comparative Example 1 (Example of White Polyester Film) Φ The following composition was dissolved in a mixed solution of toluene/butyl acetate to prepare a coating liquid having a solid concentration of 45% by weight. Further, a mixed solution having a weight ratio of 1:1 was used as a mixed solution of toluene/butyl acetate. (Coating liquid solid content composition) • Organic fluorescent whitening agent OB-1 (manufactured by Eastman Co., Ltd.) 5 parts by weight • UV absorbing material YUTABL UV6010 (manufactured by Nippon Shokubai Co., Ltd.) 1 5 parts by weight, the thickness after drying is 5 μm The resulting coating liquid was applied onto a reflective layer of a white polyester film obtained in Reference Example 1 of -29-200936373, and dried by hot air at 150 ° C for 2 minutes to obtain a coated film. Although the brightness increase rate of the obtained coated film was 105%, the difference in chromaticity was caused by the turbid color, and the brightness after the durability test was also lowered, making the film difficult to use practically. The evaluation results are shown in Table 1. Comparative Example 2 (Example of White Polyester Film) The fluorescent substance shown in Table 1 was changed to an organic fluorescent whitening agent UVITEX-OB (manufactured by Kabate Chemicals Co., Ltd.), and the amount thereof was changed to 5 weights. The coated film was obtained in the same manner as in Example 1 except for the remainder. At this time, the brightness increase rate was about 10%, and the brightness improvement was not confirmed. This film is a film in which the chromaticity difference is large due to discoloration and the brightness after the durability test is also lowered, and it is practically impossible to use. The evaluation results are shown in Table 1. Comparative Example 3 (Example of White Polyester Film) A coated film was obtained in the same manner as in Comparative Example 1, except that the amount of the organic fluorescent whitening agent OB-1 was changed to 30 parts by weight. The results of the assessment are listed in Table 1. Example 6 (Example of transparent polyester film) The following composition was dissolved in butyl acetate to prepare 45 wt%. A coating solution having a solid concentration. (Coating liquid solid content composition) -30- 200936373 • Inorganic phosphor (manufactured by OPHTRONICS Co., Ltd.) 1 〇 by weight • Acrylic beads (MBX-15, manufactured by Sekisui Chemicals Co., Ltd.) 60 parts by weight • Acrylic Binding agent (manufactured by YUTABL S2740, Nippon Shokubai Co., Ltd.) 25 parts by weight of a cross-linking agent (CORONET HL, manufactured by Nippon Nippon Chemical Co., Ltd.) 5 parts by weight divided by 8 g/m 2 after curing The coated film was obtained in the same manner as in Example 1 except for the coating liquid of the coating liquid. The results of the evaluation are shown in Table 1.

又，綠色發光無機螢光體22 10(化成OPHTRONICS 公司製造）爲以ZnS作爲母體、以Cu作爲賦活物質之無 機螢光體。MBX-15爲平均粒徑15μπι之丙烯酸系粒子。 以使乾燥後之厚度成爲5 μπι之方式將該塗佈液塗佈於 〇 參考例2中所得之透明聚酯薄膜上，且在150°c下乾燥2 分鐘，獲得塗佈之薄膜。評估結果列於表1。 比較例4 (透明聚酯薄膜之例） 將下列組成物溶解於乙酸丁酯中，製作成45重量％固 成分濃度之塗佈液。 (塗佈液固成分組成） •丙烯酸珠粒（MBX-1 5，積水化成品工業公司製造 -31 - 200936373 •丙烯酸 製造） •交聯劑 製造） 除以固化 佈液之外，其 結果列於表1 60重量份 系結合劑（YUTABL S2740，日本觸媒公司 32重量份 (CORONET HL，日本胺基甲酸酯工業公司 8重量份 後成爲8g/m2之方式塗佈作爲塗佈液之該塗 餘與實施例6相同，獲得塗佈之薄膜。評估 。 ❹Further, the green light-emitting inorganic phosphor 22 10 (manufactured by OPHTRONICS Co., Ltd.) is an inorganic phosphor using ZnS as a precursor and Cu as an activating substance. MBX-15 is an acrylic-based particle having an average particle diameter of 15 μm. This coating liquid was applied onto the transparent polyester film obtained in Reference Example 2 so that the thickness after drying became 5 μm, and dried at 150 ° C for 2 minutes to obtain a coated film. The evaluation results are shown in Table 1. Comparative Example 4 (Example of transparent polyester film) The following composition was dissolved in butyl acetate to prepare a coating liquid having a solid concentration of 45% by weight. (Coating liquid solid content composition) • Acrylic beads (MBX-1 5, manufactured by Sekisui Kogyo Seiki Co., Ltd. -31 - 200936373 • Made of acrylic acid) • Crosslinker manufacturing) Divided by curing liquid, the results are listed in Table 1 60 parts by weight of a binder (YUTABL S2740, 32 parts by weight of Nippon Shokubai Co., Ltd. (CORONET HL, 8 parts by weight of Nippon Amino Acid Industry Co., Ltd., and 8 g/m 2 was applied as a coating liquid) The coated film was obtained in the same manner as in Example 6. Evaluation.

-32- 200936373 表1-32- 200936373 Table 1

螢光體 之種類 塗佈層之螢 光體含有量 (莆景％Ί 激發波長 400~450nm 之發光 發光峰値 波長(nm) 經時 變黃 亮度提 nm(%) 色度 差 耐久性試驗 之亮度維持 率(％) 耐久性試驗 之色度變化 實施 例1 無機螢 光體 2210 30 ◎ 535 ◎ 104.0 〇 99.6 ◎ 實施 例2 無機笛 光體 D1110 40 ◎ 650 ◎ 101.8 ◎ 99.5 〇 實施 例3 無機螢 光體 D1230 40 ◎ 440 ◎ 101.1 ◎ 99.5 ◎ 實施 例4 無機營 光體 KX732 A 30 ◎ 510 ◎ 101.2 ◎ 99.5 ◎ 實施 例5 無機$ 光體 2210 30 ◎ 535 〇 104.0 〇 96.4 〇 比較 例1 有機螢 光體OB-1 5 ◎ 550 X 105.2 X 94.3 X 比較 例2 有機螢 光體 UVITEX -OB 5 ◎ 440 X 100.0 〇 95.2 X 比較 例3 有機螢 光體OB-1 30 ◎ 550 X 108.2 X 94.2 X 實施 例6 無機$ 光體 2210 10 ◎ 535 〇 103.8 〇 99.1 〇 比較 例4 - 0 X - 〇 100.0 ◎ 99.0 〇 -33- 200936373 發明之效果 依據本發明，可提供一種經時變黃得以受到抑制之層 合薄膜，又，可提供一種作爲液晶顯乎裝置之背光元件之 構件用時可獲得闻亮度之層合薄膜。依據本發明，又提供 一種經時變黃受到抑制、可獲得高亮度、色彩不均少而適 用作爲反射板之層合薄膜。 產業上利用之可能性 本發明之層合薄膜可用於廣泛的光學用途中，例如作 爲液晶顯示裝置之背光板單元之構件，尤其是可適用作液 晶顯不裝置之背光板單元之反射板。 -34-Phosphor content of the coating layer of the phosphor type (luminescence % Ί excitation wavelength 400~450nm luminescence luminescence peak ( wavelength (nm) over time yellow brightness enhancement nm (%) chromaticity difference durability test Luminance maintenance ratio (%) Chromaticity change in durability test Example 1 Inorganic phosphor 2210 30 ◎ 535 ◎ 104.0 〇 99.6 ◎ Example 2 Inorganic fluoroton D1110 40 ◎ 650 ◎ 101.8 ◎ 99.5 〇 Example 3 Inorganic fluorite Light body D1230 40 ◎ 440 ◎ 101.1 ◎ 99.5 ◎ Example 4 Inorganic camping body KX732 A 30 ◎ 510 ◎ 101.2 ◎ 99.5 ◎ Example 5 Inorganic $ Light body 2210 30 ◎ 535 〇104.0 〇96.4 〇Comparative example 1 Organic fluorescing OB-1 5 ◎ 550 X 105.2 X 94.3 X Comparative Example 2 Organic phosphor UVITEX - OB 5 ◎ 440 X 100.0 〇 95.2 X Comparative Example 3 Organic phosphor OB-1 30 ◎ 550 X 108.2 X 94.2 X Example 6 Inorganic $ Light Body 2210 10 ◎ 535 〇103.8 〇99.1 〇Comparative Example 4 - 0 X - 〇100.0 ◎ 99.0 〇-33- 200936373 Effect of the Invention According to the present invention, it is possible to provide a laminate which is inhibited by yellowing over time. film Moreover, it is possible to provide a laminated film which can obtain a brightness when used as a member of a backlight element of a liquid crystal display device. According to the present invention, it is also provided that the yellowing over time is suppressed, high luminance is obtained, and color unevenness is small. It is suitable for laminated film as a reflecting plate. Industrial Applicability The laminated film of the present invention can be used in a wide range of optical applications, for example, as a member of a backlight unit of a liquid crystal display device, and particularly suitable for use as a liquid crystal display device. The reflector of the backlight unit. -34-

Claims (1)

200936373 十、申請專利範園 1·—種層合薄膜，係由聚酯薄膜以及設於其上之含 有螢光體之塗佈層所構成之層合薄膜，其特徵爲該塗佈層 之螢光體係由無機物質所構成且該螢光體於該塗佈層中之 含有量爲5〜80重量％。 2.如申請專利範圍第1項之層合薄膜，其係使用作 爲液晶顯示裝置之背光單元構件。 Φ 3.如申請專利範圍第1項之層合薄膜，其中該聚酯 薄膜爲白色聚酯薄膜且係使用作爲液晶顯示裝置之背光單 元之反射板。 ❿ -35- 200936373 七 明 說 單 簡 號 為符 圖件 表元 代之 定圖 指表 :案代 圖本本 表、、 代 定一二 指c C 無 無 ❹ 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式·無 ◎ -4-200936373 X. Applying for a patented film, a laminated film comprising a polyester film and a coating layer containing a phosphor disposed thereon, characterized in that the coating layer is fired. The optical system is composed of an inorganic substance and the content of the phosphor in the coating layer is 5 to 80% by weight. 2. A laminated film according to claim 1 which is a backlight unit member for use as a liquid crystal display device. Φ 3. The laminated film of claim 1, wherein the polyester film is a white polyester film and is used as a reflecting plate of a backlight unit of a liquid crystal display device. ❿ -35- 200936373 The syllabus of the seven-speaking syllabary is the map of the map. The table of the map is represented by the map: the table of the case, the table of the case, and the c/c of the C 2 without ❹ VIII. If there is a chemical formula in this case, please reveal The chemical formula that best shows the characteristics of the invention·No ◎ -4-