TW201139532A - Improved light diffusing composition - Google Patents

Abstract

The present invention relates to a light diffusing composition and its use for imparting light diffusing properties to a thermoplastic polymer. The present invention further relates to a polymer composition containing said novel light diffusing composition and to a compounded composition or formed article produced therefrom such as a cover. Said thermoplastic light diffusing composition comprises (a) an inorganic particle, (b) a polymeric particle differs in refractive index n at 589 nm by at least 0.05 from that of the thermoplastic resin polymer, and one or more of (c), (d), or mixtures thereof wherein (c) is a wavelength downshifting material, and (d) is an interference pigment. Further, the present invention relates to a luminous device comprising a light source, preferably one or more LED and a formed cover comprising said light diffusing composition.

Description

201139532 六、發明說明： 【韻^明戶斤屬_^控^奸々貝域^】 發明之技術領域 本發明係有關於一種光擴散組成物，及其用以赋予一 熱塑性聚合物光擴散性質之用途。本發明進一步係有關於 含有該新穎光擴散組成物之一種聚合物組成物，及自其形 成之一種化合組成物或形成物件，諸如，一蓋子。再者， 本發明係有關於一種發光裝置，其包含一光源，較佳係一 或多個LED，及一包含該光擴散組成物之成型蓋子。 發明背景 一照明件號之功能係用以引起客戶、使用者、消費者、 路過者等之注意，因此’係儘可能於白天及夜晚可看到。 因此，於標誌照明時，需使此標誌所含之元件（此等可為字 母、數字、符號、圖形等）於白天及夜晚，或於半黑暗時可 看到。因此’需使標誌於白天及夜晚具有高對比。 一照明標誌係由一光源及一蓋子所組成。傳統光源係 白熾燈及/或霓虹燈管。更具能量/熱效率及更長壽命之發光 二極體(LED)係曰益替代傳統光源。但是，以LED光源替代 傳統光源造成照明標誌、之照明及外觀之修改。即，部份地， 因為LED展現南方向性照明’然而，例如，霓虹燈管之照 明係從0至360°。此外，LED之發射光譜係全然不同於傳統 光光源。發展併納一或多個具有大於3流明之光通量之白色 LED發光裝置已改變適於作為盖子之熱塑性物之需求。 201139532 熱塑性標認蓋子之功能係用以遮蓋及保護光源，而仍 能確保由光源發射的光之良好透射。蓋子亦具有使發射光 散射使得照明均勻及不刺眼之功能。光源發射的光之散射 係藉由使具有機及/或礦物性質之散射顆粒於熱塑性物中 分散而達成。好之熱塑性物可被上色或可具有裝飾性元 件或圖案。蓋子通常亦採用字母或任何其它標滤之裂式。 已知將光擴散劑併納於熱塑性透明聚合物内。光擴散 劑-般係呈白色粉末型式。當光擴散劑併二於_性聚合 物内，聚合物組成物及自其產生之物件具有光擴散性質。 通常此等複合物形成之顏色係稱為乳白色。其對於玎見光 係半透明’即’其散射透射之光，使得光源不可見到。光 擴散聚合物組成物可形成各種不同厚度之片材或膜，或形 成更複雜之形狀，諸如，燈蓋，如球狀物等。光擴散聚合 物組成物係由燈具產業廣泛用於生產顯示面板、發光顯示 益、聚光燈、街燈、照明標誌等。因此，光擴散聚合物組 成物及自其產生之物件之一重要性質係當長時間曝置於高 溫時對熱老化之高耐性，特別是高顏色穩定性。 已知將某些無機添加物併納於聚合物組成物内以赋予 組成物光擴散性質》 USP 6723772揭示一種散射組成物，其包含以甲基丙稀 酸甲酯或苯乙烯為主之一透明塑料，及有機或礦物散射顆 粒。顆粒含量係於0.1與20重量％之間。 US公開第2〇〇4/〇191550號案揭示—種片材，包含一（A) 層，其係由以曱基丙稀酸甲醋為主之—樹脂组成，及一或 201139532 二(B)層’其係由以甲基丙烯酸甲酯為主之一樹脂及以偏二 氟乙烯為主之一樹脂所組成。此片材可於層内含有有機 或礦物散射顆粒’且可以霓虹燈或以LED照明。 US公開第2004/0255497號案揭示一種照明標誌，其 中，此標誌之字母係由使光散射之一透明塑料製成。光源 係LED、霓虹燈管、白熾燈等並不重要。 EP 1369224揭示一種經共同擠塑之片材，其包含至少 二層’一以有機散射顆粒填充之熱塑性物層，及一透熱塑 性物層。此片材可藉由LED照明。 WO 2003/052315揭示一種發光裝置，其係組合由透明 塑料製成之一蓋子，及一彩色LED。透明塑料含有ι·5至2.5 重量％之BaSCU或聚苯乙烯顆粒。於交聯塑料顆粒之情況， 此含量係從0.1至10重量％變化。白色LED未被描述。此外， 此發明之目的係確保一照明標誌於關閉及點亮時具有相同 顏色。 WO 2006/100127揭不"一種發光裝置，包含至少一 LED，其中，蓋子係一單層，其包含用於使光散射之有機 顆粒，諸如，PTFE顆粒之聚醯胺、以甲基丙烯酸曱酯為主 之交聯顆粒、以交聯苯乙烯為主之顆粒或聚矽氧顆粒。另 外，散射顆粒於性質可為礦物’諸如，BaS04、Ti02、ΖηΟ、 CaC〇3 ' MgO，或Α12〇3 ’或中空玻璃微球。 ΕΡ 634445揭示一種光擴散組成物，其包含諸如丁丨〇2、 石夕石凝膠、ZnS、ZnO ’或MgTi〇3之無機顆粒，及具有一芯 /核形態之聚合物顆粒之混合物，其中，芯係橡膠狀之院基 201139532 丙烯酸《合物。該光擴散組成物證實錢射光相似 射光光譜。 1之反 C 明内^^】 發明之概要說明 本發明之一目的係提供一種光擴散熱塑性組成物，包 含-熱塑性聚合物，及a)從0_001至2重量%之—無機顆粒， 其具有0.1至1微米之一平均顆粒尺寸，及19至3 2之—折射 率，b)從0.01至10重量％之一聚合物顆粒，其具有從〇 2至2〇 微米範圍之一平均顆粒尺寸，其於589 nm之折射率n係與熱 塑性樹脂聚合物者差至少0 05，及幻、d)之一或多者，或其 等之混合物’其中’ c)係從(USIOOOppm之一波長下移材 料，且d)係從0.005至2重量❶/。之一干涉色料。 於本發明之一實施例，此處於上揭露之熱塑性光擴散 組成物之無機顆粒a)較佳係二氧化鈦、矽石凝膠、硫化鋅、 氣化鋅、MgTi03，或其等之混合物。 於本發明之另一實施例，此處於上揭露之熱塑性光擴 散組成物之聚合物顆粒b)較佳係一經交聯之丙烯聚合物、 ~經交聯之苯乙烯聚合物、一經交聯之聚矽氧聚合物，或 其等之混合物。 於本發明之另一實施例，此處於上揭露之熱塑性光擴 散組成物之聚合物顆粒b)較佳係具有包含一或多個殼之— 芯/殼形態，其中，芯係一橡膠狀之乙烯基聚合物，其以芯 之重量為基準係包含至少15重量％之經聚合化之烷基丙晞 酸酯或烷基曱基丙烯酸酯。 201139532 於本發明之另一實施例，此處於上揭露之熱塑性光擴 散組成物之波長下移材料c)較佳係選自含有Sm3+、Cr3+、 ZnSe、Eu，或Tb之波長下移材料之一無機波長下移材料， 一量子點材料，選自羅丹寧、香豆素、紅螢烯、雷射染料、 Alqs、TPD、Gaqfl ;茈碳酸或其衍生物、萘碳酸或其衍 生物、紫蒽嗣或異紫蒽酮或其衍生物之一有機下移材料， 或其等之混合物。 於本發明之另一實施例，此處如上揭露之熱塑性光擴 散組成物之干涉色料d)較佳係選自雲母薄片+Ti〇2 ;雲母薄 片 +Zr02 ; Si02 薄片 +Ti02 ; Si〇2 薄片 +Zr02 ; Al2〇3 薄片 +201139532 VI. Description of the invention: [Rhyme ^ Ming jin _ ^ control ^ 々 々 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 Use. The invention further relates to a polymer composition comprising the novel light diffusing composition, and a compound composition or formed article formed therefrom, such as a lid. Furthermore, the present invention relates to a light-emitting device comprising a light source, preferably one or more LEDs, and a shaped cover comprising the light diffusing composition. BACKGROUND OF THE INVENTION The function of a lighting item number is used to draw the attention of customers, users, consumers, passers-by, etc., so that it can be seen as much as possible during the day and night. Therefore, when marking the illumination, the components contained in the logo (these can be letters, numbers, symbols, graphics, etc.) need to be visible during the day and night, or in the dark. Therefore, it is necessary to make the logo highly contrasted during the day and night. A lighting sign consists of a light source and a cover. Traditional light sources are incandescent and/or neon tubes. More energy/thermal efficiency and longer life LEDs are a good alternative to traditional light sources. However, replacing the traditional light source with an LED light source causes modification of the illumination sign, illumination, and appearance. That is, in part, because the LED exhibits south directional illumination' however, for example, the neon tube illumination is from 0 to 360°. In addition, the emission spectrum of LEDs is completely different from conventional light sources. The development of one or more white LED illuminators having a luminous flux of greater than 3 lumens has changed the need for thermoplastics suitable as caps. 201139532 The function of the thermoplastic marking cover is to cover and protect the light source while still ensuring good transmission of light emitted by the light source. The cover also has the function of scattering the emitted light for uniform illumination and no glare. The scattering of light emitted by the source is achieved by dispersing scattering particles having organic and/or mineral properties in the thermoplastic. Preferably, the thermoplastic can be colored or can have decorative elements or patterns. The lid is usually also split with letters or any other standard filter. It is known to incorporate a light diffusing agent into a thermoplastic transparent polymer. The light diffusing agent is generally in the form of a white powder. When the light diffusing agent is in the _ polymer, the polymer composition and the article produced therefrom have light diffusing properties. Usually the color formed by such composites is called milky white. It is semi-transparent for the glimpse of the light, i.e. its scattered transmitted light, so that the light source is not visible. The light diffusing polymer composition can form sheets or films of various thicknesses or form more complex shapes such as lamp covers such as spheres and the like. The light-diffusing polymer composition is widely used in the lighting industry to produce display panels, illuminating displays, spotlights, street lights, and lighting signs. Therefore, one of the important properties of the light-diffusing polymer composition and the article produced therefrom is high resistance to heat aging, especially high color stability, when exposed to high temperatures for a long period of time. It is known to incorporate certain inorganic additives into the polymer composition to impart light diffusing properties to the composition. USP 6,723,772 discloses a scattering composition comprising a transparent one of methyl methacrylate or styrene. Plastic, and organic or mineral scattering particles. The particle content is between 0.1 and 20% by weight. US Publication No. 2/4, 191, 550 discloses a sheet comprising an (A) layer consisting of a resin based on thioglycolic acid methyl vinegar, and one or 201139532 two (B The layer 'is composed of a resin mainly composed of methyl methacrylate and a resin mainly composed of vinylidene fluoride. This sheet may contain organic or mineral scattering particles in the layer' and may be illuminated by neon or LED. US Publication No. 2004/0255497 discloses an illumination sign in which the letter of the mark is made of a transparent plastic that scatters light. Light source LED, neon tube, incandescent lamp, etc. are not important. EP 1 369 224 discloses a coextruded sheet comprising at least two layers of a thermoplastic layer filled with organic scattering particles and a layer of a heat permeable plastic. This sheet can be illuminated by LEDs. WO 2003/052315 discloses a lighting device which is a combination of a cover made of transparent plastic and a colored LED. The transparent plastic contains from 5 to 2.5% by weight of BaSCU or polystyrene particles. In the case of cross-linking plastic granules, this content varies from 0.1 to 10% by weight. White LEDs are not described. Moreover, the purpose of this invention is to ensure that an illumination sign has the same color when turned off and on. WO 2006/100127 discloses a light-emitting device comprising at least one LED, wherein the cover is a single layer comprising organic particles for scattering light, such as polyamide of PTFE particles, strontium methacrylate Ester-based crosslinked particles, crosslinked styrene-based particles or polyfluorene oxide particles. Further, the scattering particles may be minerals such as BaS04, TiO 2 , ΖηΟ, CaC〇 3 'MgO, or Α12〇3' or hollow glass microspheres. 634 634 445 discloses a light diffusing composition comprising inorganic particles such as butyl sulfonate 2, Shishi stone gel, ZnS, ZnO ' or MgTi 〇 3 , and a mixture of polymer particles having a core/core morphology, wherein , core rubber-like yard base 201139532 acrylic "composite. The light diffusing composition confirms that the light is similar to the luminescence spectrum. BRIEF DESCRIPTION OF THE INVENTION One of the objects of the present invention is to provide a light-diffusing thermoplastic composition comprising a thermoplastic polymer, and a) from 0 to 001% by weight of inorganic particles having 0.1 An average particle size of one micron to 1 micron, and a refractive index of 19 to 32, b) from 0.01 to 10% by weight of one of the polymer particles having an average particle size ranging from 〇2 to 2 〇 micrometers, The refractive index n at 589 nm differs from the thermoplastic resin polymer by at least 0 05, and one or more of illusion, d), or a mixture thereof, where 'c' is a material that is shifted from one wavelength of USIOOOppm. And d) is from 0.005 to 2 weight ❶ /. One of the interference pigments. In one embodiment of the invention, the inorganic particles a) of the thermoplastic light-diffusing composition disclosed herein are preferably a mixture of titanium dioxide, vermiculite gel, zinc sulfide, zinc vapor, MgTi03, or the like. In another embodiment of the present invention, the polymer particles b) of the thermoplastic light-diffusing composition disclosed herein are preferably a crosslinked propylene polymer, a crosslinked styrene polymer, and a crosslinked one. A polyoxyl polymer, or a mixture thereof. In another embodiment of the present invention, the polymer particles b) of the thermoplastic light-diffusing composition disclosed herein preferably have a core/shell form comprising one or more shells, wherein the core is a rubbery A vinyl polymer comprising at least 15% by weight, based on the weight of the core, of a polymerized alkyl propionate or alkylmercaptoacrylate. 201139532 In another embodiment of the present invention, the wavelength shifting material c) of the thermoplastic light diffusing composition disclosed above is preferably selected from one of the wavelength shifting materials containing Sm3+, Cr3+, ZnSe, Eu, or Tb. Inorganic wavelength shifting material, a quantum dot material, selected from the group consisting of rhodamine, coumarin, red fluorene, laser dye, Alqs, TPD, Gaqfl; phthalic acid or its derivatives, naphthalene or its derivatives, sable An organically moving material, or a mixture thereof, of hydrazine or isopurinone or a derivative thereof. In another embodiment of the present invention, the interference color material d) of the thermoplastic light diffusing composition disclosed above is preferably selected from the group consisting of mica flakes + Ti〇2; mica flakes + Zr02; SiO 2 flakes + Ti02; Sheet + Zr02 ; Al2〇3 sheet +

Ti02 ; Al2〇3薄片+Zr02 ;玻璃薄片+Ti〇2 ;玻璃薄片+Zr〇2 ; 玻璃薄片+ Si〇2+Ti〇2 ;或其等之組合。 於本發明之另一實施例，此處如上揭露之熱塑性光擴 散組成物之熱塑性聚合物較佳係選自聚碳酸酯、聚甲基丙 烯酸曱酯、聚苯乙烯、聚苯乙烯及丙烯腈之共聚物，或其 等之混合物。 本發明之另一實施例係一單層或多層之熱塑性光擴散 片材，其具有至少一包含此處於上揭露之熱塑性光擴散組 成物之層。 本發明之另一實施例係一種發光裝置，其包含至少一 光源，及由此處於上揭露之熱塑性光擴散組成物製成之一 蓋子，較佳地，此至少一光源係具有大於3Lm之光通量之 一 LED。 圖式簡單說明 201139532 第1圖顯示—燈型式之LED之圖。 子 弟2圖顯示藉由LED照明之 照明標誌之一字母之例 〃第I頁不於白天未點亮時之於—建築物頂部之包含 第2圖之字母之—照明標誌。 第4圖顯示於夜晚點亮時於—建築物頂部之第3圖之照 明標誌、。 【實方方式】 發明之詳細說明 驚人地’發現自聚合物組成⑼包含以所示量之無機 顆㈣、聚合物顆粒b)，及一波長下移材料e)及/或 一干涉色 料之者之組合生產之—物件證明良好之熱老化抗 性、光擴散性質、有關於亮度之良好外觀，及依光源係經 由物件透射或反射而定之外觀差異。 適用於本發明之無機顆粒a)具有從0.1至1微米 ，較佳係 攸0.1至0·8微来K圭係從〇2至〇5微米之一平均顆粒直 徑。此等無機顆粒及其生產方法係此項技藝已知。"平均顆 粒直徑’’一辭係意指數平均。無機顆粒具有從i 9至3 2，較 佳係從2.0至2.9 ’最佳係從2.〇至2 7之一折射率。較佳之無 機顆粒a)係二氧化鈦(Ti〇2) '石夕石凝膠、硫化鋅(ZnS) '氧化 鋅(ZnO)、MgTi〇3顆粒，或其等之浪合物’只要其顆粒尺 寸分佈係於指示之範圍内。最佳之無機顆粒係二氧化鈦顆 粒。無機顆粒可以各種修改使用，例如，銳鈦礦，板鈦礦 或金紅石結構之二氧化鈦係有用。>氧化鈦可以一矽氧烷 201139532 層塗覆。經塗覆之二氧化鈦及其製備方法係已知。 無機顆粒a)係以等於或大於約〇.〇〇1重耋％之量，較佳 係以專於或大於約0.005重量％之量，更值係以專於或大於 約0.01重量％之量，更佳係以等於或大於約〇_05重量％之 里’且更佳係以等於或大於約0.075重量。/。之量存在於本發 明之熱塑性光擴散組成物中，其中，重量有分率係以熱塑 性光擴散組成物之總重量為基準。 無機顆粒a)係以等於或少於約2重量。之量’較佳係以 等於或少於約丨.5重量％之量，更佳係以等於或少於約1重量 /〇之畺更佳係以等於或少於約0.5重量％之量’更佳係以 等於或v於約〇 25重量。/。之量，且更佳係以等於或少於約 0.15重里/0之量存在於本發明之熱塑性光擴散組成物中，其 里百分率係以熱塑性光擴散組成物之總重量計。Ti02; Al2〇3 flakes+Zr02; glass flakes+Ti〇2; glass flakes+Zr〇2; glass flakes+Si〇2+Ti〇2; or combinations thereof. In another embodiment of the present invention, the thermoplastic polymer of the thermoplastic light diffusing composition disclosed herein above is preferably selected from the group consisting of polycarbonate, polymethyl methacrylate, polystyrene, polystyrene, and acrylonitrile. a copolymer, or a mixture thereof. Another embodiment of the invention is a single or multiple layer thermoplastic light diffusing sheet having at least one layer comprising the thermoplastic light diffusing composition disclosed herein above. Another embodiment of the present invention is a light emitting device comprising at least one light source, and thus a cover made of the exposed thermoplastic light diffusing composition, preferably, the at least one light source has a luminous flux greater than 3 Lm One of the LEDs. Brief description of the diagram 201139532 Figure 1 shows the diagram of the LED type of the lamp type. The picture of the child 2 shows one of the letters of the illumination by the LED illumination. The first page is not illuminated during the day—the inclusion of the top of the building—the letter of the second figure—the illumination sign. Figure 4 shows the illuminated sign on Figure 3 at the top of the building when it is lit at night. [Solid mode] Detailed description of the invention surprisingly 'discovered from polymer composition (9) comprising inorganic particles (IV) in the amounts indicated, polymer particles b), and a wavelength down-shifting material e) and/or an interference colorant The combination produced by the object proves good thermal aging resistance, light diffusion properties, good appearance with respect to brightness, and appearance differences depending on the transmission or reflection of the light source. The inorganic particles a) suitable for use in the present invention have an average particle diameter of from 0.1 to 1 μm, preferably from 0.1 to 0.8 μm, from K 2 to 〇 5 μm. Such inorganic particles and methods for their production are known in the art. The "average particle diameter" is the average of the index. The inorganic particles have a refractive index from i 9 to 3 2, preferably from 2.0 to 2.9 Å from 2. 〇 to 27. Preferred inorganic particles a) are titanium dioxide (Ti〇2) 'Shishishi gel, zinc sulfide (ZnS) 'zinc oxide (ZnO), MgTi〇3 particles, or the like thereof, as long as the particle size distribution thereof Within the scope of the instructions. The most preferred inorganic particles are titanium dioxide particles. The inorganic particles can be used in various modifications, for example, an anatase, a brookite or a rutile structure of titanium dioxide is useful. > Titanium oxide can be coated with a layer of monooxane 201139532. Coated titanium dioxide and methods for its preparation are known. The inorganic particles a) are present in an amount equal to or greater than about 5% by weight, preferably in an amount of more than or equal to about 0.005% by weight, more preferably in an amount of about 0.01% by weight or more. More preferably, it is equal to or greater than about 〇055% by weight and more preferably equal to or greater than about 0.075 by weight. /. The amount is present in the thermoplastic light diffusing composition of the present invention wherein the weight fraction is based on the total weight of the thermoplastic light diffusing composition. The inorganic particles a) are equal to or less than about 2% by weight. The amount ' is preferably in an amount equal to or less than about 5% by weight, more preferably equal to or less than about 1% by weight, more preferably equal to or less than about 0.5% by weight' More preferably, it is equal to or v to about 25 weight. /. The amount, and more preferably, is present in the thermoplastic light diffusing composition of the present invention in an amount equal to or less than about 0.15 deg/0, wherein the percentage is based on the total weight of the thermoplastic light diffusing composition.

人適用於本發明之聚合物顆粒b)可為一經交聯之丙烯聚 口物。鉍父聯之苯乙烯聚合物、一經交聯之聚矽氧聚合 =it等之混合物。一較佳之聚合物顆粒具有-芯/核形 八=了有一橡膠狀乙烯基聚合物之芯。橡膠狀乙烯基聚 …β為於水性介質中於乳化聚合條件下進行加成聚合之 ’:’頁技藝者所知之任何具有至少—乙稀不飽和基團之 ° 句I物或共聚物。此等單體係列示於USP 、’ ’ 52〜第3欄’第4〇·62行，其教示内容在此併入本案 以為，考讀^此等單體包括〖，3.丁n曱基4丁二 烯2,3^一曱基]，3_丁二烯、烯丙基笨、二丙嗣丙稀酿胺、 乙稀基萘、氣笨乙稀、4_乙稀基笨甲基醇、笨甲酸乙烯|旨、 201139532 丙酸乙烯酯、己酸乙烯酯、氣乙烯、油酸乙烯酯、馬來酸 二甲酯、馬來酸酐、福馬酸二甲酯、乙烯基磺酸、乙烯基 磺醯胺，及甲基乙烯基磺酸酯。特別佳之單體包括，例如， N-乙烯基吼咯烷酮、乙烯基Dttn定、苯乙烯、心甲基苯乙烯、 第二苯乙烯、乙烯基甲苯、二乙烯基苯、乙酸乙烯、叔碳 酸乙烯酯、烷基丙烯酸酯及曱基丙烯酸酯，諸如，丙烯酸 乙酯、丙烯酸丁酯、1，6-己二醇二丙烯酸酯、曱基丙烯酸乙 基硫基乙酯、丙烯酸甲酯、丙烯酸異冰片酯、丙烯酸2羥 基乙酯、丙烯酸2-苯氧基乙酯、丙烯酸縮水甘油酯、丙烯 酸2-乙基己酯、新戊基二醇二丙烯酸酯、丙烯酸孓乙氧基乙 酯、曱基丙烯酸第三丁基胺基乙酯、丙烯酸2_甲氧基乙酯、 曱基丙烯酸曱酯、曱基丙烯酸縮水甘油酯、曱基丙烯酸苯 甲酯、曱基丙烯酸乙酯、丙烯酸、甲基丙烯酸、Ν_甲基曱 基丙烯醯胺、丙烯腈、曱基丙烯腈、丙烯醯胺、Ν_(異丁氧 基甲基）丙烯醯胺等。以橡膠狀乙烯基聚合物之總重量為基 準，橡膠狀乙烯基聚合物較佳係含有至少15%，更佳係至 少25%，最佳係至少40%之聚合化之丙烯酸酯、甲基丙烯酸 酯、單乙烯基芳烴，或選擇性經取代之丁二烯，及從〇至 85°/。’更佳係從〇至75%，最佳係從〇至60%之一或多種共聚 合之乙烯基單體。 較佳之丙烯酸酯及甲基丙烯酸酯係烷基丙烯酸酯或烧 基曱基丙烯酸酯’其於烷基較佳係含有1至18個，更佳 至8個，最佳係2至8個碳原子，諸如，甲基、乙基、正丙基、 異丙基、正丁基、第二丁基，或第三丁基，或己基，或辛 10 201139532 基基團。烷基可為分支或線性。較佳之烷基丙烯酸酯係丙 烯酸乙i旨、丙稀酸正丁酷、丙烯酸異丁醋，或丙烯酸2-乙 基己酯。最佳之烷基丙烯酸酯係丙烯酸丁酯。 其它有用之丙烯酸酯係，例如，1, 6-己二醇二丙烯酸 酯、甲基丙烯酸乙基硫基乙酯、丙浠酸異冰片酯、丙烯酸 2-經基乙酯、丙稀酸2-笨氧基乙酯、丙烯酸縮水甘油酯 '新 戊基二醇二丙烯酸酯、丙烯酸2-乙氧基乙酯、甲基丙烯酸 第三丁基胺基乙酯、丙烯酸2-甲氧基乙酯、曱基丙烯酸縮 水甘油酯，或甲基丙烯酸苯甲酯。 較佳之單乙烯基芳烴係苯乙烯或α-甲基苯乙烯，其選 擇性於芳香族環以諸如曱基、乙基，或第三丁基之一烷基 基團或以一鹵素取代’諸如，氯苯乙浠。 若被取代’丁二烯較佳係以一或多個含有1至6個碳原 子之烷基基團或以一或多個鹵素取代，最佳係以一或多個 甲基基團及/或一或多個氯取代。較佳之丁二烯係1，3-丁二 烯、異戊二烯、氯丁二烯，或2,3-二甲基-1，3·丁二烯。 橡膠狀之乙烯基聚合物可含有一或多個經（共）聚合之 丙烯酸酯、曱基丙烯酸酯、單乙烯基芳烴，及/或選擇性經 取代之丁二烯。此等單體可與一或多種其它可共聚合之乙 烯基聚合物共聚合，諸如，二丙酮丙烯醯胺、乙烯基萘、 4-乙烯基苯曱基醇、苯曱酸乙烯酯、丙酸乙烯酯、己酸乙 烯酯' 氯乙烯、油酸乙烯酯、馬來酸二曱酯、馬來酸酐、 福馬酸二甲酯、乙烯基磺酸、乙烯基磺醯胺、甲基乙烯基 磺酸酯、Ν-乙烯基吡咯烷酮、乙烯基吡啶、二乙烯基笨、 11 201139532 乙酸乙烯酯、叔碳酸乙烯酯、丙烯酸、甲基丙烯酸、N甲 基甲基丙烯醯胺、丙烯腈、甲基丙烯腈、丙烯醯胺或N (異 丁氧基曱基）丙烯醯胺。 以心之、％、重董為基準，一或多種上述單體係選擇性址 與0至10%，較佳係與0至5%，之一可共聚合之多官能性六 聯劑及/或與0至10%，較佳係與〇至5%之一可共聚人之多— 能性接枝聯接劑反應。若交聯單體被使用，以芯單體總重 量為基準，較佳係以從0.05至5%，更佳係從〇丨至丨。/。之量使 用。交聯單體係此項技藝已知，且一般具有其中乙烯不飽 和基團具有約相等反應性之一聚乙烯不飽和，諸如，二乙 烯基苯、^乙稀基苯、L 3•或M•三醇丙稀酸s旨或甲基丙稀 酸酯、二醇二-或三曱基丙烯酸酯或_丙烯酸酯，諸如，乙二 醇：曱基丙烯酸酷或二丙烯酸醋、丙二醇二甲基丙烯酸能 或一丙烯酸酯、L 3^，4_丁二醇二甲基丙烯酸酯或，最 1’ 3或1，4_丁二醇二丙烯酸酯。若一接枝聯接單體被 使用’以芯單體總重量為基準，較佳係以從G.1至5%，更佳 係〇·5至2.5%之量使用。接枝聯接單體係此項技藝已知，且 一般係具有足夠低之聽和基團反應性之聚乙烯不飽和單 使大里之殘餘不飽和於其聚合化後留於芯中。較佳之 接枝聯接義可共聚合之U·乙稀不飽和賴或二缓酸 之稀丙基、甲基㈣基或丁稀基§旨，諸如，甲基丙稀酸稀 丙醋 '丙烯酸稀㈣、馬來酸二稀丙酿，及丙烯氧基丙基 稀丙Sa，最佳係、甲基丙烯酸烯丙醋。 最佳地’聚合物顆粒b)含有一橡膠狀烧基丙烯酸醋聚The polymer particles b) suitable for use in the present invention may be a crosslinked propylene polymer. A mixture of styrene polymer, a crosslinked polyoxyl polymerization = it, etc. A preferred polymer particle has a core/core shape and a core of a rubbery vinyl polymer. The rubbery vinyl poly(β) is an addition polymerization of any of the at least ethylidene-unsaturated groups known to those skilled in the art as an addition polymerization in an aqueous medium under emulsion polymerization conditions. These monomer series are shown in USP, ''52~3rd column', paragraph 4〇62, the teaching content of which is incorporated herein into the case, and the reading of such monomers includes 〖, 3.丁n曱基4 butadiene 2,3^-mercapto], 3_butadiene, allyl stupid, dipropylene propylene oxide, ethylene naphthalene, gas stupid ethylene, 4_ethylene Alcohol, benzoic acid ethylene|, 201139532 Vinyl propionate, vinyl hexanoate, ethylene ethylene, vinyl oleate, dimethyl maleate, maleic anhydride, dimethyl fumarate, vinyl sulfonic acid, ethylene Sulfosamine, and methyl vinyl sulfonate. Particularly preferred monomers include, for example, N-vinylpyrrolidone, vinyl Dttnidine, styrene, cardiomethylstyrene, second styrene, vinyl toluene, divinylbenzene, vinyl acetate, tertiary carbonic acid Vinyl esters, alkyl acrylates and mercapto acrylates, such as ethyl acrylate, butyl acrylate, 1,6-hexanediol diacrylate, ethyl thioethyl methacrylate, methyl acrylate, acrylic acid Borneol ester, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate, glycidyl acrylate, 2-ethylhexyl acrylate, neopentyl glycol diacrylate, ethoxyethyl acrylate, sulfhydryl Tert-butylaminoethyl acrylate, 2-methoxyethyl acrylate, decyl methacrylate, glycidyl methacrylate, benzyl methacrylate, ethyl methacrylate, acrylic acid, methacrylic acid And Ν_methylmercapto acrylamide, acrylonitrile, mercapto acrylonitrile, acrylamide, hydrazine-(isobutoxymethyl) acrylamide, and the like. The rubbery vinyl polymer preferably contains at least 15%, more preferably at least 25%, most preferably at least 40% of polymerized acrylate, methacrylic acid, based on the total weight of the rubbery vinyl polymer. Ester, monovinyl arene, or selectively substituted butadiene, and from hydrazine to 85°/. More preferably, from 〇 to 75%, the best is from one to six or more of the copolymerized vinyl monomers. Preferred acrylate and methacrylate alkyl acrylate or alkyl acrylate acrylates preferably have from 1 to 18, more preferably up to 8, and most preferably from 2 to 8 carbon atoms in the alkyl group. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, or tert-butyl, or hexyl, or oct 10 201139532 radical. The alkyl group can be branched or linear. Preferred are alkyl acrylate-based acrylic acid, n-butyl acrylate, isobutyl acrylate, or 2-ethylhexyl acrylate. The most preferred alkyl acrylate is butyl acrylate. Other useful acrylates, for example, 1,6-hexanediol diacrylate, ethyl thioethyl methacrylate, isobornyl propionate, 2-ethylidene acrylate, acrylic acid 2- Stupid oxyethyl ester, glycidyl acrylate, neopentyl glycol diacrylate, 2-ethoxyethyl acrylate, t-butylaminoethyl methacrylate, 2-methoxyethyl acrylate, Glycidyl methacrylate, or benzyl methacrylate. Preferred monovinyl arene styrene or alpha-methyl styrene, which is selective for the aromatic ring to be substituted with an alkyl group such as a fluorenyl group, an ethyl group or a third butyl group or with a halogen such as Chlorophenidin. If the substituted butadiene is preferably substituted with one or more alkyl groups having 1 to 6 carbon atoms or substituted with one or more halogens, it is preferred to have one or more methyl groups and/or Or one or more chlorine substitutions. Preferred butadiene is 1,3-butadiene, isoprene, chloroprene, or 2,3-dimethyl-1,3.butadiene. The rubbery vinyl polymer may contain one or more (co)polymerized acrylates, mercapto acrylates, monovinyl arenes, and/or selectively substituted butadienes. These monomers may be copolymerized with one or more other copolymerizable vinyl polymers, such as diacetone acrylamide, vinyl naphthalene, 4-vinylphenylnonanol, vinyl benzoate, propionic acid Vinyl ester, vinyl hexanoate 'vinyl chloride, vinyl oleate, dinonyl maleate, maleic anhydride, dimethyl fumarate, vinyl sulfonic acid, vinyl sulfonamide, methyl vinyl sulfonic acid Ester, fluorene-vinyl pyrrolidone, vinyl pyridine, divinyl stupid, 11 201139532 vinyl acetate, vinyl versatate, acrylic acid, methacrylic acid, N-methyl methacrylamide, acrylonitrile, methacrylonitrile , acrylamide or N (isobutoxyfluorenyl) acrylamide. Based on the heart, %, heavy Dong, one or more of the above single system selective sites and 0 to 10%, preferably 0 to 5%, one of the copolymerizable polyfunctional hexamers and / Or reacting with 0 to 10%, preferably from 5% to 5% of one copolymerizable human-grafting coupling agent. If the crosslinking monomer is used, it is preferably from 0.05 to 5%, more preferably from hydrazine to hydrazine, based on the total weight of the core monomers. /. The amount is used. Crosslinked single systems are known in the art and generally have one of the polyethylene unsaturations in which the ethylenically unsaturated groups have about equal reactivity, such as divinylbenzene, ethylbenzene, L3• or M. • Triol acrylate or methyl acrylate, diol di- or tridecyl acrylate or acrylate, such as ethylene glycol: mercapto acrylate or diacrylate acrylate, propylene glycol dimethyl Acrylic energy or monoacrylate, L 3 , 4 - butanediol dimethacrylate or, most 1 ' 3 or 1,4-butanediol diacrylate. If a graft linking monomer is used, it is preferably used in an amount of from G.1 to 5%, more preferably from 5 to 2.5%, based on the total weight of the core monomers. Graft-linked single systems are known in the art and are generally polyethylene-unsaturated with sufficiently low auditory and group reactivity to leave the residual unsaturation of the residue in the core after polymerization. Preferably, the graft-coupled copolymerizable U·ethyl sulphate or bis-acidic propyl, methyl (tetra) or butyl group, such as methacrylic acid propylene vinegar (4), maleic acid di-propyl propylene, and propylene oxypropyl di-propyl Sa, the best system, methacrylic acid allyl vinegar. Optimally 'polymer particles b) contain a rubbery alkyl acrylate condensate

S 12 201139532 合物之芯，烷基具有2至8個碳原子，以芯之總重量為基準， 選擇性地與從0至5%之交聯劑及從0至5%接枝聯接劑共聚 合。橡膠狀烷基丙烯酸酯較佳係與最高達50。/。之一或多種 可共聚合之乙烯基單體，例如，如上所述者，共聚合。適 合之交聯及接枝聯接單體係熟習此項技藝者所知，且較佳 係於閩開之EP 269324中所揭示者。例如，交聯單體一般係 可與其它芯單體共聚合之單體，且具有其中乙烯不飽和基 團具有約相等反應性之聚乙烯不飽和，例如，- —· C*沛基本、 二醇二-及三甲基丙烯酸醋及丙烯酸酿，及三醇三丙稀酸醋 及甲基丙烯酸酯。接枝單體一般係可與其它芯單體共聚合 之聚乙烯讀和單體’且具有足夠低之不飽和基團反： 性，使足夠之殘餘不飽和於其聚合化後留於芯聚合物中了 例如’甲基丙烯酸烯丙酯、馬來酸二烯 丙酸稀丙自旨。 —Μ烯氧基 I合物顆粒b)之芯可含有用於聚合化方、 物材料以使聚合物顆粒膨脹，但此等寡聚物=== 高之分子量，以避免其擴散或於加 I有足夠 取。 处理或使用期間被萃 聚合物顆粒b)含有一或多個殼。兮一 由-乙烯基均聚物或共聚物製成。用或夕個殼較佳係 單體係列示於USP 4,226,752，第4攔^此等殼之適合 内容在此併入本案以為參考資料。〇·46行，其教示 飽和乙稀基單體，諸如，丨，3丁 讀可包括乙烯不 —烯、2-甲技，， 2’3_二甲基-1，3-丁二烯、稀丙基笨' 153.丁二烯、 一丙鲷丙烯醯胺、乙烯 13 201139532 基萘、氣苯乙烯、4-乙烯基苯甲基醇、苯曱酸乙烯酯、丙 酸乙烯酯、己酸乙烯酯、氣乙烯、油酸乙烯酯、馬來酸二 曱酯、馬來酸酐、福馬酸二曱酯、乙烯基磺酸、乙烯基磺 醯胺、甲基乙烯基磺酸酯，且較佳係N-乙烯基吡咯烷酮、 乙烯基。比啶、苯乙烯、α-曱基苯乙烯、第三丁基苯乙烯、 乙烯基曱苯、二乙烯基苯、乙酸乙烯酯、叔碳酸乙烯酯、 烷基丙烯酸酯及曱基丙烯酸酯，諸如，丙烯酸乙酯、丙烯 酸丁酯、1,6-己二醇二丙烯酸酯、曱基丙烯酸乙基硫基乙 酯、丙烯酸甲酯、丙烯酸異冰片酯、丙烯酸2-羥基乙酯、 丙浠酸2-苯氧基乙醋、丙稀酸縮水甘油醋、丙烯酸2-乙基己 酯、新戊基二醇二丙烯酸酯、丙烯酸2-乙氧基乙酯、甲基 丙烯酸第三丁基胺基乙酯、丙烯酸2-曱氧基乙酯、曱基丙 烯酸曱酯、甲基丙烯酸縮水甘油酯、曱基丙烯酸苯曱酯、 曱基丙烯酸乙酯、丙烯酸、曱基丙烯酸、Ν-曱基曱基丙烯 醯胺、丙烯腈、甲基丙烯腈、丙烯醯胺、Ν-(異丁氧基甲基) 丙烯醯胺等。一或更多之殼較佳係甲基丙烯酸酯、丙烯酸 酯、乙烯基芳烴、羧酸乙烯酯、丙烯酸及/或甲基丙烯酸之 聚合物。 較佳之丙稀酸S旨及甲基丙稀酸S旨係烧基丙烯酸醋或烧 基曱基丙烯酸酯，其於烷基較佳係含有1至18個，更佳係1 至8個，最佳係2至8個碳原子，諸如，甲基、乙基、正丙基、 異丙基、正丁基、異丁基，或第三丁基、2-乙基己基，或 己基、庚基，或辛基基團。烷基基團可為分支或線性。較 佳之烷基丙烯酸酯係丙烯酸乙酯。其它有用之丙烯酸酯及S 12 201139532 The core of the compound, the alkyl group having 2 to 8 carbon atoms, based on the total weight of the core, selectively with from 0 to 5% of the crosslinking agent and from 0 to 5% of the grafting agent polymerization. The rubbery alkyl acrylate is preferably up to 50. /. One or more copolymerizable vinyl monomers, for example, as described above, are copolymerized. Suitable cross-linking and grafting linkage systems are known to those skilled in the art and are preferably disclosed in the pp. EP 269,324. For example, the crosslinking monomer is generally a monomer copolymerizable with other core monomers, and has a polyethylene unsaturation in which the ethylenically unsaturated groups have about equal reactivity, for example, - C. Alcohol di- and trimethacrylic acid vinegar and acrylic acid, and triol triacetic acid vinegar and methacrylate. The grafting monomer is generally a polyethylene read and monomer which can be copolymerized with other core monomers and has a sufficiently low unsaturated group reverse: sufficient residual unsaturated to remain in the core polymerization after polymerization. For example, 'allenyl methacrylate, dimeric acid maleate is used. - the core of the deceneoxy I compound particles b) may contain a material for polymerizing the materials to swell the polymer particles, but such oligomers === high molecular weight to avoid diffusion or addition thereof I have enough to take. The polymer particles b) are extracted during processing or use containing one or more shells.兮 is made of a vinyl homopolymer or copolymer. A preferred series of monomers is shown in USP 4,226,752, and the contents of the fourth block are incorporated herein by reference. 〇·46 lines, which teach saturated ethylenic monomers, such as 丨, 3, can include ethylene non-ene, 2-method, 2'3-dimethyl-1,3-butadiene, Dilute propyl stupid 153. butadiene, propylene propylene amide, ethylene 13 201139532 naphthalene, gas styrene, 4-vinyl benzyl alcohol, vinyl benzoate, vinyl propionate, hexanoic acid Vinyl ester, ethylene ethylene, vinyl oleate, dinonyl maleate, maleic anhydride, dinonyl fumarate, vinyl sulfonic acid, vinyl sulfonamide, methyl vinyl sulfonate, and preferably N-vinylpyrrolidone, vinyl. Pyridin, styrene, α-mercaptostyrene, t-butyl styrene, vinyl fluorene, divinyl benzene, vinyl acetate, vinyl versatate, alkyl acrylate and methacrylate, such as , ethyl acrylate, butyl acrylate, 1,6-hexanediol diacrylate, ethyl thioethyl methacrylate, methyl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, propionic acid 2 -phenoxyacetic acid, propylene glycol acetoacetate, 2-ethylhexyl acrylate, neopentyl glycol diacrylate, 2-ethoxyethyl acrylate, tert-butylaminoethyl methacrylate Ester, 2-methoxyethyl acrylate, decyl methacrylate, glycidyl methacrylate, phenyl decyl acrylate, ethyl methacrylate, acrylic acid, methacrylic acid, fluorenyl-mercapto propylene Guanamine, acrylonitrile, methacrylonitrile, acrylamide, hydrazine-(isobutoxymethyl) acrylamide, and the like. The one or more shells are preferably polymers of methacrylate, acrylate, vinyl arene, vinyl carboxylate, acrylic acid and/or methacrylic acid. Preferably, the acrylic acid S and the methyl methacrylate S are alkyl acrylate or decyl acrylate, and the alkyl group preferably has from 1 to 18, more preferably from 1 to 8, most Preferably 2 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, 2-ethylhexyl, or hexyl, heptyl , or octyl group. The alkyl group can be branched or linear. A preferred alkyl acrylate is ethyl acrylate. Other useful acrylates and

S 14 201139532 甲基丙稀酸_如上對於芯所列示者，較佳係甲基丙稀酸 3-羥基丙自曰。最佳之烷基曱基丙烯酸酯係甲基丙烯酸甲酯。 車乂佳之⑽基芳煙係苯⑽或基苯⑽，其選擇 性地於芳香族環以諸如曱基、乙基或第三丁基—烧基基團 或以齒素取代，諸如，氣苯乙稀。 較佳之羧酸乙烯酯係乙酸乙烯酯。 殼較佳係含有至少15%，更佳係至少25%，最佳係至少 40%之經聚合之甲基丙烯酸自旨、丙稀酸_，或單乙稀基芳 烴，及0至85%，更佳係0至75%，最佳係〇至60%之一或多 種乙稀基共單體’諸如，其它烧基？基丙稀義、芳基甲 基丙烯酸酯、烷基丙烯酸酯、芳基丙烯酸酯、烷基及芳基 丙烯基醯胺、丙烯腈 '曱基丙稀腈、馬來醯亞胺，及/或烷 基及芳基丙烯酸酯及甲基丙烯酸酯，其係以一或多個諸如 ii素、院氧基、烷基硫基、氰烷基或胺基之取代基取代。 適5之乙浠基共單體之例子係如上所列示。二或更多種單 體可被共聚合。 殼聚合物可含有一交聯劑及/或一接枝聯接劑，其係如 上有關於芯聚合物所指示者。 殼聚合物較佳係包含總顆粒重量之從5至40%，更佳係 從15至35%。 以聚合物總重量為基準，聚合物顆粒b)含有至少15%， 較佳係從20至80%，更佳係從25至60%，最佳係從30至 50% ’之聚合化的烷基丙烯酸酯或甲基丙烯酸酯。較佳之 院基丙烯酸醋及甲基丙烯酸醋係如上所列示。炫基丙稀酸 15 201139532 酯或烷基曱基丙烯酸酯組份可包含於聚合物顆粒b)之芯及/ 或殼内。於殼及/或殼内之烧基丙烯酸鲳或甲基丙稀酸醋之 均聚物係有用的；但是，烷基（甲基）丙烯酸g旨較佳係與一或 多種其它型式之烷基（曱基）丙烯酸酯及/或一或多種其它乙 稀基聚合物共聚合，較佳係如上所列示者。 最佳地’聚合物顆粒b)含有一聚（两烯酸丁g旨）芯及一多 個聚（甲基丙烯酸甲酯）殼。 聚合物顆粒b)係用於賦予熱塑性聚合物光擴散性質。 聚合物顆粒b)之芯及殼之折射率n較佳係於熱塑性聚合物 之折射率之+八0.25單位内，更佳係於+/_〇18單位内，最佳 係於仏(U2單位内。Μ殼之折射率與熱塑性聚合物之折 射率不相近係多於+/-0.003單位，更佳地不相近係多於 +/-請單&amp;，最佳㈣相近係多於單位。折射率係 依據ASTM D 542_5〇及/或麵53_。用於比較芯/殼橡膠 之折射率η與熱塑性聚合物之折射率n之—特別有用之波長 係 589 nm。 聚合物顆粒b)通常具有等於或大於約〇2微米之一平均 顆粒直徑，較佳係等於或大於触5微米之—平均顆粒直 徑，更佳係大於或特約丨微米之—平㈣綠錄，且更佳 係等於或大於約丨.5微米之—平均顆粒直徑。 聚合物顆粒b)通常具有等於或少於⑽微米之一平均 顆粒直徑，較佳料於或少於⑽微米之—平均顆粒顆 粒’更佳係少等於或少於約1〇微米之—平均顆粒直徑，更 佳係等於或少於約7.5微米之-平均難直徑，且更佳係等 201139532 於或少於約5微米之一平均顆粒直徑。 聚合物顆粒b)較佳 '•平均顆粒直徑&quot;一辭係意指數平均 係一自由流動之粉末。 聚合物顆粒b)可以-已知方式生產。—般，芯聚人物 之至少—單體組份拉受乳化聚合形成乳化聚合物顆粒。乳 化聚合物娜係以其本身或❹合物之—❹料它單體 組份而膨脹’且此等單體係於乳化聚合物顆粒内聚合。臉 脹及聚合化之步驟可重複至顆粒生長成所欲芯尺寸為止: 怒聚合物顆粒係懸浮於__第二水性單體乳化液，且—聚人 物殼係係自此等單體聚合於第二乳化液内之聚合物顆： 上。二或多個殼可聚合於芯聚合物上。芯/殼聚合物顆粒之 製備係揭示於公開之Ep 269324及usp 3,793,4〇2與usp 3,808,180中，其等在此皆被併入本案以為參考資料。 一般，此方法可包含： A) 選擇作為一橡膠狀芯聚合物組成物之烷基丙烯酸酯 之共聚物，此烷基具有2至8個碳原子，且此共聚物具有熱 塑性基質聚合物之折射率之+/·㈣5單仙，但不相近係多 於約+/-0.003單位之折射率， B) 自或夕種單體之一第一水性乳化液聚合芯聚合物 顆粒，此等單體聚合時，產生選擇之芯聚合物， C) 實施下列之一或多個步驟 1) 使芯聚合物顆粒以一或多種單體膨脹，當此等單體 聚合時，產生選擇之芯聚合物，及 2) 於此等顆粒中，使芯聚合物顆粒内之膨脹單體聚合 17 201139532 至導致選擇之芯聚合物之所有單體已聚合且此等顆粒達成 於從約2至約15 mum範圍内之一所欲尺寸為止，以及 D)實施下列之一或多個步驟 1) 將芯聚合物顆粒懸浮於一第二水性單體乳化液其 之單體係可聚合形成可與基質聚合物相容之一聚合物以 及 2) 於第二乳化液中，自單體將一聚合物殼聚合於聚合 物顆粒上。 聚合物顆粒b)係以等於或大於約〇.〇1重量％之量，較佳 係以4於或大於約〇·〇5重量％之量，更佳係以等於或大於約 0.1重量°/〇之量，更佳係以等於或大於約0 25重量％之量，且 更佳係以等於或大於約〇.5重量％之量存在於本發明之熱塑 性光擴散組成物，其中，重量百分率係以熱塑性光擴散組 成物之總重量為基準。 聚合物顆粒b)係以等於或少於約2〇重量％之量，較佳 係以等於或少於約1〇重量％之量，更佳係以等於或少於約 7.5重量％之量，更佳係以等於或少於約5重量。之量，更佳 係以等於或少於約2.5重量。/。之量，且更佳係以等於或少於 約1重量％之量存在於本發明之熱塑性光擴散組成物，其 中，重量百分率係以熱塑性光擴散組成物之總重量為基準。 適用於本發明之波長下移材料c)可包含一或多種之有 機及/或無機發光材料。因此，單一波長下移材料可被使 用，或另外或此外，一”系列”之波長下移材料可被使用， 例如’以提供一波長下移”串級&quot;。 201139532 較佳地，一或多種下列材料被使用（單獨或以混合物）： 一有機發光材料，較佳係羅丹寧、香豆素、紅螢烯、一雷 射染料、Ah、TPD、Gaqfl ;茈碳酸或其衍生物；萘碳 酸或其衍生物；紫蒽酮或異紫蒽酮或其衍生物；一無機發 光材料’較佳係Sm3、Cr3+、ZnSe、Eu2+、Tb3+下移發光材 料、一半導性量子點材料，或奈米顆粒。其中，係 三-(8-羥喹啉)鋁，TPD係N，N’_二苯基_N，N,_雙_(3甲基苯基 -1，Γ-二苯基_ 4_4，_二胺，且Gaq2C1表示雙_(8_羥基喹啉)_ 氯鎵。 波長下移材料以從1 ppn^2000ppm，更佳係從2〇〇卿 至咖解之量存在已證實於有關於?文良外㈣係展現有 利效果，特別是包含本發明之㈣良的光舰組成物之聚 合物組成物之亮度L精確之最全濃度可依波長下移 材料及/或宿主材料之性質而定。 再者為改良於短波長區域之光譜反應，若波長下移材 料於從3GGS5GG奈米之光譜範圍内，較佳係於伽奈米展 現電磁輻射最大值被證實係有利。再者，較佳地，波長下 移材料可於從榻至奈米之光譜範圍内，較㈣於伽至 5〇〇奈米之範圍内，或於500至_奈来之範圍内且最佳係 於約500奈米，展現最大發射電磁輻射。 ,、 如上所概述，下移材料較佳可包含包含由下列所構成 、群之-或多者之-染料：⑧碳酸或其衍生物、萘碳酸或 其衍生物、紫蒽酮或異紫蒽酮或其衍生物。 作為以⑦碳酸或其衍生物為主之染料(於此後：，，花染 201139532 料）’較佳地’-或多種之下列染料可被使用：花四碳妒 二醯亞胺1四碳酸單料醯亞胺、心俩二奸^ 奴酸醯亞胺1,3,4·二碳酸酐、花二碳酸s旨、$二碳^ 胺。其中’最佳係花二碳酸、花二碳酸醯亞胺，或^酸 酸一醯亞胺，或其等之組合。 厌 其中，茈二碳酸醯亞胺係衍生自苑-3,4-二碳酸，* 一石反酸醋及醯胺係魅自異構物之花_3, 9及 〔 於花碳酸醯亞胺中，氫或CrCl8-院基係特別適於 醯亞胺之氮原子上之取代基。 、下為 茈染料可為未經取代。但是，較佳地，其可以丨至5個（於 茈四碳二醯亞胺之情況，較佳係2至4個）(雜）芳氧基-戈（雜） 芳硫基取代基R取代。 取代基係定義如下： R係芳氧基、芳硫基、雜芳氧基，或雜芳硫基，其係以飽和 或不飽和之5-至7-個成員之環系統環化，其碳原子主鏈可以 —或多個下列之官能基團中斷：-〇_、___NR1-' -N=CR' -CO-、-SO-及/或-so - ’而整個環系統可以一或多個取代基 (i)、（ii)、（iii)、（W)及/或(v)取代： (i)係CrCw烷基，其奴原子鏈可以一或多個下列基團中 斷:-〇-'-S-、-NR1-、-N-CRL、CsC CRl= CR丨、c〇、 -SO-及/或-SO2- ’且可以一或多個下列取代基取代：d- C12_ 烷氧基、CVC6-炫硫基、-CsCRl、_crI=cr12、羥基、綺 基、鹵素、氰基、硝基、-NR2R3、_NR2C〇R3、_C〇NR2r3、 -so2nr2r3、_cook2、-so#2、芳基及/或飽和或不飽和之 20 201139532 C4_C·/-環烧基’其碳原子主鍵可以一或多個下列基團中斷.· -Ο-、-S-、-NR1-、-NsCR1-、-CR1: CR1-、-CO- ' -so-及/ 或-SO2-，而每一芳基-及環烷基取代基可以一或多個如下之 取代基取代.烧基及/或如前作為對於烧基所述取代 基之取代基。 (11)係CrC8-環烷基，其碳原子主鏈可以一或多個下列基團 中斷：-0-、-S-、-NR1-、-NCR1-、-CRi= CR1-、-CO-、-SO- 及/或-SO - ’其係以飽和或不飽和之5_至7_個成員之環系統 環化，.其碳原子主鏈可以一或多個如下官能基團中斷： -Ο-、-S-、-NR1-、-NtCR1-、-CR丨CR1-、-CO-、-SO-及/ 或-SO2-，而整個環系統可以一或多個下列取代基取代： Ci-Cu-烧基 ' crc12-烷氧基、Crc6-烷硫基、-CeCR1、 CrI-=Cr12、羥基、巯基、鹵素、氰基、硝基、-NR2R3、 -NR2COR3、-CONR2R3、_s〇2NR2R3、-COOR2及/或-so3r2 ; (iii)芳基或雜芳基，可可以另外之飽和或不飽和之5_至7個 成員之環環化’其碳原子主鏈可以一或多個下列基團中 斷：-〇-、-S-、_服丨_、一N=CR1_、_CR1= CR1-、-CO-、-S0-及/或-SO2-，而整個環系統可以一或多個下列取代基取代： CrC丨8-烷基、CrC丨2-烷氧基、crC6-烷硫基、-CECR1、 CR^CR、、羥基、鲸基、鹵素、氰基、硝基、_NR2r3、 -NR2COR3、-CONR2R3、_s〇2NR2R3、&quot;C00R2、-SO3R2、芳 基，及/或雜芳基，其本身可以Ci_C|8_烷基、CrC12_烷氧基、 羥基、巯基 '鹵素、氰基、硝基、_NR2R3、_NR2COR3、 -CONR2R3、-S02NR2R3、-COOR2及/或-so3r2取代； 21 201139532 (lv)係一取代基-u-芳基，其可以一或多個如上所述之芳基 取代基(iii)之取代基取代，而U可為下列之_基團：-〇-、- S-、-NR1-、_c〇-、-so-，或 _s〇2-; (V)係CrC丨2-烷氧基' (^(^烷硫基、_CECRi、R1、 CR -CR 2、經基、疏基、鹵素、氰基、石肖基、_nr2R3、 -NR2COR3、-C〇NR2R3、-S02NR2R3、-匸〇〇尺2或_8〇3尺2，而 對於η&gt;1之取代基R可彼此相同或相異；RI氫或CrC8_烷 基’而若出現多次，殘基R1可為相同或相異；r2、R3獨立 地係氫；C^-Cm-烷基，其碳原子鏈可以一或多個下列基團 中斷：-0- ' -S- ' -C0-、-SO-及/或-S〇2-，且可以下列取代 一或多次：Ci-C|2-烧氧基、Ci-C6-炫硫基、經基、疏基、鹵 素、氰基、硝基，及/或-C00R1 ;芳基或雜芳基，其可以另 外之飽和或不飽和之5-至7-個成員之環環化，其碳原子主鏈 可以一或多個下列基團中斷：-〇_、_s_、-CO-及/或-S〇2- ’ 而全部之環系統可以CrCu-烷基及/或前述之烷基的取代 基取代一或多次。 此外，茈染料可以氰基基團取代。此取代對於芘一* 匕--石炭 酸醯亞胺及茈二碳酸酯具重大重要性。 特別適合之茈染料之下列例子需被提及雙(2 6 二異丙基苯基）3£-3,4:9，1〇_四碳酸二醯亞胺、雙6 二曱基苯基）托-3,4:9，l〇-四碳酸二醯亞胺、凡沖、雙(7、十— 烷基）3£-3,4:9,1〇-四碳酸二醯亞胺、队^-雙彳2，心二異丙八 苯基)-1，6,7,12-四(4-第三辛基苯氧基成 醯亞胺、N，N，-雙(2,6_二異丙基苯基儿6,7，12-四笨氣基* 22 201139532 -3,4:9，10-四碳酸二醯亞胺、队：^-雙（2,6-二異丙基苯基)-1,6-及-1,7-雙（4-第三辛基苯氧基）-茈-3,4:9,1 0-四碳酸二醯亞 胺、Ν,Ν’-雙(2,6-二異丙基苯基)-1,6-及-1,7-雙(2,6-二異丙基 苯氧基）3£-3,4:9，10-四碳酸二醯亞胺、乂(2,6-二異丙基苯基) 茈-3,4二碳酸醯亞胺、N-(2,6-二異丙基苯基)-9-苯氧基茈 -3,4-二碳酸醯亞胺、N-(2,6-二異丙基苯基)-9-(2,6-二異丙基 苯氧基）3£-3,4-二碳酸醯亞胺、N-(2,6-二異丙基苯基)-9-氰 基茈-3,4-二碳酸醯亞胺、N-(7-十三烷基)-9-苯氧基茈-3,4-二碳酸醯亞胺、-3,9-及-3,10-二碳酸二異丁基酯、4，10-二娘基花_3,9-及4,9-二氣基花-3,10-二礙酸二異丁基S旨，及 茈-3,9-及-3,10-二碳酸二(2, 6-二異丙基苯基）醯胺。 茈染料係已知，個別描述於USP 2008/0167467(以〇-,〇·-二取代之(硫基）苯氧基取代基R取代），其在此完整併入本案 以為參考資料。其通常於360至630奈米（nm)之波長區域吸 收，且於470至750 nm間發射。 除茈染料外，具有相似結構之其它螢光染料可被使 用，諸如，以紫蒽酮及/或異紫蒽酮為主之染料，諸如，於 US 4,486,587中描述之結構，其在此完整併入本案以為參考 資料。作為充份適合材料之一較佳例子，烷氧基化之紫蒽 酮及/或異紫蒽酮可被使用，諸如，6，15-二（十二烷氧基）異 紫蒽酮二酮-(9，18)。 最後，作為適合螢光染料之另一例子，以萘碳酸衍生 物為基準之染料可被提及。以萘為基準之螢光染料典型上 於約300至420 nm波長之UV範圍内展現吸收，且展現於約 23 201139532 380至520 nm之發射範圍。因此 Γ產生將_有效率轉化成較長波長之光:而1: Μ勿組成物形成對抗uv_之有效率保護。 、 於萘碳酸衍生物内，最佳係酿亞胺類(例如’萃·18.45_ 四碳酸二醯亞胺，且特㈣从：碳軸㈣、，最佳係 -=氧基m碳酸單醢亞賴及4•笨氧基蔡¥ -碳酸早醯亞麵，其於下係縮寫為&quot;萘醯亞胺類&quot;）。蔡酿 亞胺類，特別是萘-l，8:4,5_四碳酸二醯亞胺類，於蔡框架亦 可為未經取代。_，較佳地，特別地，萘二碳酸酿亞胺 類具有-或較佳係二㈣氧基、芳氧基·或氰基基團作為取 代基。 烷氧基基團較佳係包含丨至以個匕原子。於芳氧基基團 内，最佳係苯氧基部份，其可為未經取代或經取代。 作為特別適合之萘醯胺之例子，下列可被提及：Ν·(2_ 乙基己基)-4,5-一甲氧基萘-1,8-二碳酸醯亞胺、ν_(2,6_二異 丙基-本基)-4,5-一曱氧基萘-1,8-二碳酸醯亞胺、队(7_十： 院基)-4,5二甲氧基_蔡_1，8_二碳酸醯亞胺、队(2, 6_二異丙基 本基)-4,5-一苯氧基萘-1,8-二礙酸醯亞胺，及ν，ν'-雙(2 6· 二異丙基苯基)-1,8:4,5-萘四礙酸二醯亞胺。 波長下移材料c)係以等於或大於約0 01份/百萬（ppm) 之量，較佳係以等於或大於約〇_〇5 PPm之量，更佳係以等 於或大於約0.1 ppm之量，更佳係以等於或大於約〇 5 ppm之 量，且更佳係以等於或大於約1 ppm之量存在於本發明之熱 塑性光擴散組成物中，其中ppm係以熱塑性光擴散組成物之 24 201139532 總重量為基準。 波長下移材料c)係以等於或少於約1000 ppm之量，較 佳係以等於或少於約5〇〇 ppm之量，更佳係以等於或少於約 100 ppm之i，更佳係以等於或少於約5〇 口口爪之量，更佳係 以等於或少於約25 ppm之量’且更佳係以等於或少於約1〇 ppm2S存在於本發明之熱塑性光擴散組成物中其中， ppm係以熱塑性光擴散組成物之總重量為基準。若下移材料 之濃度太高，再吸收效果會減少轉化效率。 吾等發現干涉色料d)單獨或與波長下移材料c)組合可 對本發明之熱塑性光擴散組成物進一步提供所欲之光擴散 及顏色性質。干涉色料可用於許多汽車及工業塗料配製 物。此作為部份係由於顏色之交互作用及由於用於其層狀 結構之各種材料之作用。光於此等層及其内之折射及反射 造成干涉，產生選擇之顏色。干涉色料係藉由折射及反射 操綻入射光線，使得形成之折射及反射之光於人類眼睛及 腦部產生顏色感知。 干涉色料可藉由用於其製造而使用之方法或藉由其結 構而分類。具有高折射率之諸如二氧化鈦或氧化鐵之物質 可’例如，沉積於一透明基材上，諸如於IRI〇DINTM情況般 之雲母’如於COLORSTREAMtm情況般之二氧化矽，或如 於XIRALLIC™情況般之氧化紹。此等色料係使用濕式化學 方法生產，而具有作為一内部反射體之一鋁層者 (VARIOCHROM™ 、 CHROMAFLAIR™ ，及 SPECTRAFLAIR™)係於高度真空製造。液晶亦被分類為干 25 201139532 涉色料。 適用於本發明之干涉色料d)係以—或多個薄片型# 透明基材為基準。較佳基㈣片狀卿#。特_^ 然及/或合成之雲母、薄片型式之氧化链、玻璃薄片^&amp; 缚片、™2薄片、合成之無支掠式薄片、·α或其它牙相 比擬之材料。玻璃薄片、八丨2〇3薄片， 及Si〇2溥片亦可被務 雜。 亦可使用不同基材之混合物或具有不同顆粒尺寸之相 同基材之混合物等基材可彼此以任何重量㈣遇合。 較佳係使用1〇:1至1:10之混合物，特別是1:1之混合物^特 別佳係由具有不同顆粒尺寸之雲母薄片所構成之基材浪合 物’特別是N雲母（少於60微米）及F雲母（少於25微米）之混合 物0 基本基材之尺寸本身並不重要’且可與特別應用相配 合0 一般，溥片型式之基材具有〇.〇5與5微米間之厚度，特 另J疋0.1與1微米間。其它一維度之尺寸通常係丨與25〇微米 之間，較佳係2與200微米之間，且特別是5與6〇微米之間。 基本基材上之至少一個別層之厚度對於色料之光學性 質係重要。色料需具有至少一光學活性層，較佳係一高折 射率之層，高折射率之層於此處係意指具有大於15之折射 率η之所有層，較佳係等於或大於2.0之n。 此光學層較佳係由Ti02、Zr02、Sn02、ΖηΟ，或其等 之混合物或組合所構成。此層可為未經摻雜或經摻雜。適S 14 201139532 Methyl acrylate <RTIgt; </ RTI> As indicated above for the core, it is preferred that the methyl methacrylate is 3-hydroxypropyl. The most preferred alkyl methacrylate is methyl methacrylate.车乂佳之(10)-based aromatic benzene (10) or benzene (10), which is optionally substituted with an aromatic ring such as a mercapto group, an ethyl or a tert-butyl group, or a dentate, such as benzene. Ethylene. A preferred vinyl carboxylate is vinyl acetate. Preferably, the shell contains at least 15%, more preferably at least 25%, most preferably at least 40% of the polymerized methacrylic acid, acrylic acid, or monoethylarene, and 0 to 85%, More preferably from 0 to 75%, optimally from about 60% to one or more of ethylene-based comonomers such as other alkyl groups? Propylene, aryl methacrylate, alkyl acrylate, aryl acrylate, alkyl and aryl acrylamide, acrylonitrile 'mercapto acrylonitrile, maleimide, and/or Alkyl and aryl acrylates and methacrylates substituted with one or more substituents such as ii, alkoxy, alkylthio, cyanoalkyl or amine. Examples of suitable conjugated monomers are as listed above. Two or more monomers may be copolymerized. The shell polymer may contain a crosslinking agent and/or a grafting linker as indicated above for the core polymer. The shell polymer preferably comprises from 5 to 40% by weight of the total particles, more preferably from 15 to 35%. The polymer particles b) contain at least 15%, preferably from 20 to 80%, more preferably from 25 to 60%, most preferably from 30 to 50% of the polymerized alkane based on the total weight of the polymer. Acrylate or methacrylate. Preferred hospital based acrylic vinegar and methacrylic acid vinegar are listed above. Heptyl Acrylic Acid 15 201139532 The ester or alkyl methacrylate component can be included in the core and/or shell of the polymer particles b). A homopolymer of ruthenium acrylate or methyl acrylate in the shell and/or shell is useful; however, the alkyl (meth) acrylate is preferably one or more other types of alkyl groups. The (mercapto) acrylate and/or one or more other ethylene-based polymers are copolymerized, preferably as listed above. Preferably, the 'polymer particles b' contain a poly(dienoic acid) core and a plurality of poly(methyl methacrylate) shells. Polymer particles b) are used to impart light diffusing properties to the thermoplastic polymer. The refractive index n of the core and the shell of the polymer particles b) is preferably within + 0.25 units of the refractive index of the thermoplastic polymer, more preferably within +/_ 〇 18 units, preferably in 仏 (U2 unit) The refractive index of the clam shell is not more than +/- 0.003 units of the refractive index of the thermoplastic polymer, and more preferably is not more than +/- the order &amp; the best (four) is more than the unit. The refractive index is based on ASTM D 542_5 and/or face 53. For comparing the refractive index η of the core/shell rubber with the refractive index n of the thermoplastic polymer - a particularly useful wavelength system is 589 nm. The polymer particles b) usually have An average particle diameter equal to or greater than about 2 micrometers, preferably equal to or greater than the average particle diameter of 5 micrometers, more preferably greater than or more than about 10,000 micrometers, and more preferably equal to or greater than About 5 microns - the average particle diameter. The polymer particles b) generally have an average particle diameter equal to or less than (10) micrometers, preferably less than or equal to (10) micrometers - more preferably less than or less than about 1 micron. - average particles The diameter, more preferably equal to or less than about 7.5 microns - average difficult diameter, and more preferably 201139532 or less than one of the average particle diameters of about 5 microns. The polymer particles b) are preferably '•average particle diameter&quot; the average index is a free flowing powder. The polymer particles b) can be produced in a known manner. Typically, at least the monomer component of the core gather is subjected to emulsion polymerization to form emulsified polymer particles. The emulsified polymer is swelled by itself or by the chelating compound, and the single system is polymerized in the emulsified polymer particles. The step of swelling and polymerizing can be repeated until the particles are grown to the desired core size: the anger polymer particles are suspended in the __ second aqueous monomer emulsion, and the polycrystalline shell system is polymerized from the monomers Polymer particles in the second emulsion: top. Two or more shells may be polymerized on the core polymer. The preparation of the core/shell polymer particles is disclosed in the disclosure of Ep 269,324 and U.S. Patent No. 3,793, the entire disclosure of which is incorporated herein by reference. In general, the method may comprise: A) selecting a copolymer of an alkyl acrylate as a rubbery core polymer composition having from 2 to 8 carbon atoms and having a refractive index of the thermoplastic matrix polymer Rate of + / · (four) 5 single cents, but not similar to more than about +/- 0.003 units of refractive index, B) one of the first aqueous emulsion polymer core polymer particles, such monomers During polymerization, a selected core polymer is produced, C) performing one or more of the following steps: 1) expanding the core polymer particles in one or more monomers, and when such monomers are polymerized, producing a selected core polymer, And 2) in such particles, polymerizing the expanded monomer in the core polymer particles 17 201139532 to cause all of the monomers of the selected core polymer to be polymerized and such particles to be in the range of from about 2 to about 15 mum One of the desired dimensions, and D) one or more of the following steps: 1) suspending the core polymer particles in a second aqueous monomer emulsion, the single system of which is polymerizable to form a matrix polymer compatible One of the polymers and 2) in the second emulsion, The polymerization of monomers in a polymer shell polymeric particles. The polymer particles b) are in an amount equal to or greater than about 〇1% by weight, preferably 4 or more than 5% by weight, more preferably equal to or greater than about 0.1% by weight/ The amount of ruthenium, more preferably in an amount equal to or greater than about 0.255% by weight, and more preferably in an amount equal to or greater than about 5% by weight, in the thermoplastic light-diffusing composition of the present invention, wherein the weight percentage Based on the total weight of the thermoplastic light diffusing composition. The polymer particles b) are in an amount equal to or less than about 2% by weight, preferably in an amount equal to or less than about 1% by weight, more preferably in an amount equal to or less than about 7.5% by weight, More preferably, it is equal to or less than about 5 by weight. More preferably, the amount is equal to or less than about 2.5 weight. /. The amount, and more preferably, is present in the thermoplastic light diffusing composition of the present invention in an amount equal to or less than about 1% by weight, wherein the weight percentage is based on the total weight of the thermoplastic light diffusing composition. The wavelength shifting material c) suitable for use in the present invention may comprise one or more organic and/or inorganic luminescent materials. Thus, a single wavelength down-shift material can be used, or in addition or in addition, a "series" of wavelength shifting material can be used, such as 'to provide a wavelength down shift" cascading &quot; 201139532 Preferably, one or A variety of the following materials are used (alone or in a mixture): an organic luminescent material, preferably rhodamine, coumarin, erythroprene, a laser dye, Ah, TPD, Gaqfl; phthalic acid or a derivative thereof; naphthalene Carbonic acid or a derivative thereof; purpurin or isopurinone or a derivative thereof; an inorganic luminescent material 'preferably Sm3, Cr3+, ZnSe, Eu2+, Tb3+ downward luminescent material, half-conductive quantum dot material, or nai Rice granules, among which are tris-(8-hydroxyquinoline)aluminum, TPD is N,N'-diphenyl-N,N,_bis-(3methylphenyl-1, fluorene-diphenyl _ 4_4, _diamine, and Gaq2C1 represents bis(8-hydroxyquinoline)-chlorogallium. The wavelength shifting material from 1 ppn ^ 2000 ppm, more preferably from 2 〇〇 至 to the amount of caffeine has been confirmed The brightness of the polymer composition of the light ship composition comprising the (four) good light of the invention is particularly advantageous. The most complete concentration may depend on the nature of the wavelength shifting material and/or the host material. Further, in order to improve the spectral response in the short wavelength region, if the wavelength shifts the material in the spectral range from 3GGS5GG nm, it is preferably It is believed that the maximum value of the electromagnetic radiation exhibited by the ganami is advantageous. Further, preferably, the wavelength shifting material can be in the range from the couch to the nanometer, and (4) in the range of gamma to 5 Å nanometer, or In the range of 500 to _Nai and preferably about 500 nm, exhibiting maximum emission of electromagnetic radiation. As outlined above, the downwardly moving material preferably comprises or consists of: - Dyes: 8 carbonic acid or its derivatives, naphthalene carbonic acid or its derivatives, purpurin or isopurinone or its derivatives. As a dye based on 7 carbonic acid or its derivatives (after this:,, flowers) Dye 201139532 material) 'preferably'- or more of the following dyes can be used: flower four carbon quinone diimine 1 tetracarbonate monoamide imipenem, heart two traits ^ bismuth iodide 1,3, 4. Dicarbonic anhydride, flower dicarbonate, and di-carbon amine. Among them, 'the best flower bicarbonate , flower bismuth subcarbonate, or bismuth imidate, or a combination thereof, etc. Among them, bismuth subcarbonate is derived from Yuan-3,4-dicarbonic acid, * one stone vinegar and The amines of the amides are derived from the isomers of flowers _3, 9 and [in the yttrium carbonate, the hydrogen or CrCl8-hospital based system is particularly suitable for the substituents on the nitrogen atom of the quinone imine. It may be unsubstituted. However, preferably, it may be up to 5 (in the case of 茈tetracarbodiimide, preferably 2 to 4) (hetero) aryloxy-go (hetero) aryl Substituents for the thio substituent R. The substituents are defined as follows: R is an aryloxy group, an arylthio group, a heteroaryloxy group, or a heteroarylthio group which is a 5- to 7-member of a saturated or unsaturated group. The ring system is cyclized, and its carbon atom backbone can be interrupted by one or more of the following functional groups: -〇_, ___NR1-' -N=CR' -CO-, -SO- and/or -so - 'and the whole The ring system may be substituted with one or more substituents (i), (ii), (iii), (W) and/or (v): (i) a CrCw alkyl group having one or more of the following Group interruption: -〇-'-S-, -NR1-, -N-CRL, CsC CRl=CR丨, c〇, -SO- and/or -SO2-' and may be substituted by one or more of the following substituents: d-C12_alkoxy, CVC6- thiol, -CsCR1, _crI=cr12, hydroxy, thiol, halogen, cyano, Nitro, -NR2R3, _NR2C〇R3, _C〇NR2r3, -so2nr2r3, _cook2, -so#2, aryl and/or saturated or unsaturated 20 201139532 C4_C·/-cycloalkyl group's primary bond of carbon atom Or a plurality of the following groups interrupted: -Ο-, -S-, -NR1-, -NsCR1-, -CR1: CR1-, -CO-'-so-, and/or -SO2-, and each aryl group And the cycloalkyl substituent may be substituted with one or more substituents which may be substituted and/or a substituent as described above for the alkyl group. (11) is a CrC8-cycloalkyl group whose carbon atom backbone can be interrupted by one or more of the following groups: -0-, -S-, -NR1-, -NCR1-, -CRi=CR1-, -CO- , -SO- and/or -SO - ' is cyclized by a ring system of 5 to 7 members of saturated or unsaturated, and its carbon atom backbone may be interrupted by one or more of the following functional groups: Ο-, -S-, -NR1-, -NtCR1-, -CR丨CR1-, -CO-, -SO- and/or -SO2-, and the entire ring system may be substituted with one or more of the following substituents: Ci -Cu-alkyl group crc12-alkoxy, Crc6-alkylthio, -CeCR1, CrI-=Cr12, hydroxy, decyl, halogen, cyano, nitro, -NR2R3, -NR2COR3, -CONR2R3, _s〇2NR2R3 , -COOR2 and/or -so3r2; (iii) an aryl or heteroaryl group which may be cyclized with another 5 to 7 member ring of saturated or unsaturated 'the carbon atom backbone may be one or more of the following The group is interrupted: -〇-, -S-, _service _, one N=CR1_, _CR1=CR1-, -CO-, -S0- and/or -SO2-, and the entire ring system can be one or more Substituted by the following substituents: CrC丨8-alkyl, CrC丨2-alkoxy, crC6-alkylthio, -CECR1, CR^CR, hydroxy, whale, halogen, cyanide , nitro, _NR2r3, -NR2COR3, -CONR2R3, _s〇2NR2R3, &quot;C00R2, -SO3R2, aryl, and/or heteroaryl, which may themselves be Ci_C|8-alkyl, CrC12-alkoxy, hydroxy , fluorenyl-halogen, cyano, nitro, _NR2R3, _NR2COR3, -CONR2R3, -S02NR2R3, -COOR2 and/or -so3r2 substituted; 21 201139532 (lv) is a substituent-u-aryl group which may be one or more Substituted by a substituent of the aryl substituent (iii) as described above, and U may be a group of the following: -〇-, -S-, -NR1-, _c〇-, -so-, or _s 〇2-; (V) is CrC丨2-alkoxy' (^(^ alkylthio, _CECRi, R1, CR-CR 2, thiol, sulfhydryl, halogen, cyano, schwitz, _nr2R3, -NR2COR3) , -C〇NR2R3, -S02NR2R3, -匸〇〇2 or _8〇3 ft 2, and the substituents R for η&gt;1 may be identical or different from each other; RI hydrogen or CrC8_alkyl' Multiple times, the residues R1 may be the same or different; r2, R3 are independently hydrogen; C^-Cm-alkyl, the carbon chain of which may be interrupted by one or more of the following groups: -0- '-S- '-C0-, -SO- and/or -S〇2-, and may be substituted one or more times: Ci-C|2-alkoxy, Ci- C6-thiol, thiol, sulfhydryl, halogen, cyano, nitro, and/or -C00R1; aryl or heteroaryl, which may be additionally saturated or unsaturated, from 5 to 7 members Cyclic cyclization, the carbon atom backbone can be interrupted by one or more of the following groups: -〇_, _s_, -CO- and/or -S〇2-' and all ring systems can be CrCu-alkyl and/or The substituent of the aforementioned alkyl group is substituted one or more times. Further, the anthraquinone dye may be substituted with a cyano group. This substitution is of great importance for 芘一*--carbonic acid imide and bismuth dicarbonate. The following examples of particularly suitable anthraquinone dyes are referred to as bis(2 6 diisopropylphenyl) 3 £-3, 4:9, 1 〇 _ tetradecyl imide, bis 6 decyl phenyl)托-3,4:9, l〇-tetradecyl imide, vanadium, bis(7, deca-alkyl) 3 £-3, 4:9, 1 〇-tetradecyl diimide, team ^-Bisindole 2, diisopropyl octaphenyl)-1,6,7,12-tetrakis(4-trioctylphenoxy quinone imine, N,N,-bis (2,6_II Isopropyl phenyl 6,7,12-four stupid base * 22 201139532 -3,4:9,10-tetradecyl iodide, team: ^-bis (2,6-diisopropylbenzene -1,6- and -1,7-bis(4-trioctylphenoxy)-indole-3,4:9,1 0-tetracarboxylic acid diimine, hydrazine, Ν'-double (2,6-diisopropylphenyl)-1,6- and-1,7-bis(2,6-diisopropylphenoxy)3£-3,4:9,10-tetracarbonate Dimethyleneimine, anthracene (2,6-diisopropylphenyl)indole-3,4 diimide diimide, N-(2,6-diisopropylphenyl)-9-phenoxyhydrazine -3,4-dicarbonate imine, N-(2,6-diisopropylphenyl)-9-(2,6-diisopropylphenoxy) 3 £-3,4-dicarbonate Yttrium, N-(2,6-diisopropylphenyl)-9-cyanoindole-3,4-dicarbonate, N-(7-tridecyl)-9 -phenoxypurine-3,4-dicarbonate imine, -3,9- and -3,10-dicarbonate diisobutyl ester, 4,10-diniethyl flower _3,9- and 4 , 9-di-gas-based flower-3,10-dioxalate diisobutyl S, and bis-3,9- and-3,10-dicarbonate di(2,6-diisopropylphenyl) Anthraquinone dyes are known and described individually in USP 2008/0167467 (substituted with 〇-, 〇·-disubstituted (thio)phenoxy substituents R), which is hereby incorporated by reference in its entirety by reference. It is typically absorbed in the wavelength region of 360 to 630 nanometers (nm) and is emitted between 470 and 750 nm. In addition to anthraquinone dyes, other fluorescent dyes having similar structures can be used, such as purpurin and And/or isoflavone-based dyes, such as those described in U.S. Patent No. 4,486,587, the disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety in its entirety in Ketones and/or isopurinone can be used, for example, 6,15-di(dodecyloxy)isopurinone dione-(9,18). Finally, as another example suitable for fluorescent dyes. A dye based on a naphthalene carbonate derivative can be mentioned. The reference fluorescent dye typically exhibits absorption in the UV range at a wavelength of about 300 to 420 nm and exhibits an emission range of about 23 201139532 380 to 520 nm. Thus, Γ produces light that converts _ efficiency into longer wavelengths: And 1: Do not form an effective protection against uv_. In the naphthalene-carbonic acid derivatives, the best is the imines (for example, 'extracted 18.45_ diimine imide, and the special (four) from: carbon axis (four), the best system - = oxy-m carbonate Yalai and 4 • Stupid Ethoxy Cao ¥ - Carbonate, which is abbreviated as &quot;naphthyl imines&quot; The chlorinated imines, especially naphthalene-l,8:4,5-tetradecyldiamine, can also be unsubstituted in the framework of Cai. Preferably, in particular, the naphthalene dicarbonate-rich imine has - or preferably a di(tetra)oxy, aryloxy or cyano group as a substituent. The alkoxy group preferably comprises fluorene to a fluorene atom. Within the aryloxy group, the most preferred is a phenoxy moiety which may be unsubstituted or substituted. As an example of a particularly suitable naphthylamine, the following may be mentioned: Ν·(2_ethylhexyl)-4,5-monomethoxynaphthalene-1,8-dicarbonate imine, ν_(2,6 _Diisopropyl-benyl)-4,5-monodecyloxynaphthalene-1,8-dicarbonate imine, team (7_10: hospital base)-4,5 dimethoxy_cai_ 1,8-diimide diimide, team (2,6-diisopropyl basic)-4,5-monophenoxynaphthalene-1,8-dioxalate imine, and ν,ν'- Bis(2 6·diisopropylphenyl)-1,8:4,5-naphthyltetramethylene diimide. The wavelength shifting material c) is equal to or greater than about 0.01 parts per million (ppm), preferably equal to or greater than about 〇_〇5 ppm, and more preferably equal to or greater than about 0.1 ppm. More preferably, the amount is present in the thermoplastic light diffusing composition of the present invention in an amount equal to or greater than about 5 ppm, and more preferably in an amount equal to or greater than about 1 ppm, wherein the ppm is composed of thermoplastic light diffusing. 24 of the total weight of 201139532. The wavelength shifting material c) is in an amount equal to or less than about 1000 ppm, preferably in an amount equal to or less than about 5 ppm, more preferably equal to or less than about 100 ppm i, more preferably The amount of the thermoplastic light diffusion present in the present invention is equal to or less than about 5 〇 mouth claws, more preferably equal to or less than about 25 ppm', and more preferably equal to or less than about 1 〇 ppm 2 s. In the composition, ppm is based on the total weight of the thermoplastic light diffusing composition. If the concentration of the material moved down is too high, the resorption effect will reduce the conversion efficiency. We have found that the interference coloring material d) alone or in combination with the wavelength shifting material c) can further provide the desired light diffusion and color properties to the thermoplastic light diffusing composition of the present invention. Interference pigments are used in many automotive and industrial coating formulations. This is partly due to the interaction of colors and the various materials used for its layered structure. The light and the reflections and reflections in the layers cause interference and produce a color of choice. The interference color is caused by the refracting and reflecting of the incident light, so that the refracted and reflected light produces color perception in the human eye and the brain. The interference colorant can be classified by the method used for its manufacture or by its structure. A material having a high refractive index such as titanium dioxide or iron oxide can be deposited, for example, on a transparent substrate such as mica in the case of IRI〇DINTM as in the case of COLORSTREAMtm, or as in the case of XIRALLICTM The same as oxidation. These pigments are produced using a wet chemical process, and those having an aluminum layer as an internal reflector (VARIOCHROMTM, CHROMAFLAIRTM, and SPECTRAFLAIRTM) are manufactured in a high vacuum. LCD is also classified as dry 25 201139532. The interference color d) suitable for use in the present invention is based on - or a plurality of sheet type # transparent substrates. Preferred base (four) flaky clear #. Special _^ and / or synthetic mica, thin-film oxidized chain, glass flakes ^ &amp; ligatures, TM2 flakes, synthetic non-swept flakes, · α or other teeth comparable materials. Glass flakes, gossip 2〇3 flakes, and Si〇2 flakes can also be used. Substrates such as mixtures of different substrates or mixtures of identical substrates having different particle sizes may also be used to meet each other at any weight (four). It is preferred to use a mixture of 1 〇:1 to 1:10, especially a mixture of 1:1. Particularly preferred is a substrate ram consisting of mica flakes having different particle sizes, especially N mica (less than 60). Mixture of micron) and F mica (less than 25 microns) 0 The size of the base substrate itself is not important' and can be combined with special applications. 0. The substrate of the crepe type has a thickness of between 〇5 and 5 microns. Thickness, especially between J疋0.1 and 1 micron. The dimensions of the other dimension are typically between 丨 and 25 〇 microns, preferably between 2 and 200 microns, and especially between 5 and 6 〇 microns. The thickness of at least one of the other layers on the base substrate is important to the optical quality of the colorant. The colorant needs to have at least one optically active layer, preferably a high refractive index layer, and the high refractive index layer herein means all layers having a refractive index η greater than 15, preferably 2.0 or more. n. The optical layer is preferably composed of a mixture or a combination of TiO 2 , ZrO 2 , SnO 2 , Ζ Ο , or the like. This layer can be undoped or doped. suitable

S 26 201139532 合之摻合劑係，例如，驗土金屬或其化合物，特別是奶及 鎂。以個別層為基準，摻合比例一般係至多5重量0/〇。 光學層特別佳係一無色層，特別是一Ti〇2層。Ti〇2於 此處可為金紅石及銳鈦礦修改物，較佳係金紅石。 光學活性層之厚度較佳係30至350nm，特別係5〇至25〇 nm ° 特別較佳之干涉色料係：雲母薄片+ Ti〇2 ;雲母薄片 +Zr〇2，Si〇2薄片 + Ti02 ; Si02薄片 + Zr〇2 ; Al2〇3薄片 + Ti02; A1203薄片+Zr〇2;玻璃薄片+ Ti〇2;玻璃薄片+ Zr〇2 ; 玻璃薄片+ Si02+Ti02 ;或其等之組合。 適合的干涉色料亦可為多層之色料，只要其具有至少 一且至多二個相同之光學活性層。特別較佳係具有 Ti(VSi〇2(光學非活性層）-Ti〇2層順序之多層色料。此種色 料係可自，例如，EP 0882099得知。光學非活性層一般係 具有少於10nm，較佳係少於5nm之層厚度之8丨〇2及/或 Al2〇3層。此外，色料亦可於干涉層之上或之下包含另外之 輔助層，例如，用於控制金紅石化V顆粒生長，或用於抑 制光活性。 干涉色料之製備已多次描述於文獻，且係熟習此項技 藝者所知，例如，見US公開第2008/0210133號案，其在此 完整併入本案以為參考資料。 干涉色料d)係以等於或大於約〇·〇〇 1重量％之量，較佳 係以等於或大於約〇.〇〇5重量％之量，更佳係以等於或大於 約〇·〇1重量％之量，更佳係以等於或大於約〇 〇5重量％之 27 201139532 量，且更佳係以等於或大於約0.075重量°/°之f存在於熱塑 性光擴散組成物中，其中，重量百分率係以熱塑性光擴散 組成物之總重量為基準。 干涉色料d)係以等於或少於約2重量°/。之量，以等於或 少於約1.5重量％之量，更佳係以等於或少於約1重量％之 量，更佳係以等於或少於約0.5重量％之量，更佳係以等於 或少於約0.25重量％之量，且更佳係以等於或少於約0.15重 量〇/〇之量存在於本發明之熱塑性光擴散組成物中，其中， 重量百分率係以熱塑性光擴散組成物之總重量為基準。 本發明之光擴散劑組成物可含有其它無機色料，諸 如，硫酸鋇；但是，含有此等其它無機色料係次佳。本發 明之光擴散劑組成物可含有其它有機光擴散劑，諸如，經 交聯之聚（曱基丙烯酸甲酯）、聚烯烴、MBS-橡膠，或於下 所述之另外光擴散劑。但是，本發明之光擴散劑組成物於 缺乏任何大量之其它色料或光擴散劑時亦極有用。 本發明之光擴散劑組成物可藉由以如上所示之重量比 率摻合無機顆粒a)、聚合物顆粒b)，與波長下移材料幻及/ 或干涉色料d)之一或多種而製備。此摻合可於—有機稀釋 劑中進行。較佳地，乾燥之組份a)、b)，與幻及/或…之一或 多者’及任何另外之組份可被摻合。另外，無機顆粒^及/ 或波長下移材料c)及/或干涉色料句之一或多種可於生產聚 合物顆粒b)之前或期間添加。 摻合溫度不重要。室溫係最方便；但是， 之溫度亦可使用。 3 °S 26 201139532 A blending agent, for example, a soil metal or a compound thereof, especially milk and magnesium. The blending ratio is generally up to 5 wt%/〇 based on the individual layers. The optical layer is particularly preferably a colorless layer, in particular a Ti〇2 layer. Ti〇2 may here be a rutile and anatase modification, preferably rutile. The thickness of the optically active layer is preferably from 30 to 350 nm, in particular from 5 〇 to 25 〇 nm °. Particularly preferred interference color system: mica flakes + Ti 〇 2; mica flakes + Zr 〇 2, Si 〇 2 flakes + Ti02; Si02 sheet + Zr〇2; Al2〇3 sheet + Ti02; A1203 sheet + Zr〇2; glass flake + Ti〇2; glass flake + Zr〇2; glass flake + Si02 + Ti02; Suitable interference pigments can also be multi-layered pigments as long as they have at least one and at most two identical optically active layers. Particularly preferred is a multilayer colorant having a sequence of Ti (VSi〇2 (optical inactive layer)-Ti〇2 layer. Such a colorant is known from, for example, EP 0882099. The optically inactive layer generally has less At 10 nm, preferably 8 丨〇 2 and/or Al 2 〇 3 layers having a layer thickness of less than 5 nm. In addition, the colorant may also include an additional auxiliary layer above or below the interference layer, for example, for control Gold-red petrochemical V particles are grown or used to inhibit photoactivity. The preparation of interference colorants has been described in the literature many times and is known to those skilled in the art, for example, see US Publication No. 2008/0210133, which This is incorporated herein by reference. The interference color d) is equal to or greater than about 重量·〇〇1% by weight, preferably equal to or greater than about 〇.〇〇5 wt%, more preferably Preferably, it is equal to or greater than about 1% by weight of 〇·〇, more preferably equal to or greater than about 5% by weight of 27 201139532, and more preferably equal to or greater than about 0.075 wt/°. In a thermoplastic light diffusing composition, wherein the weight percentage is the total of the thermoplastic light diffusing composition The weight is the benchmark. The interference color d) is equal to or less than about 2 weight %. The amount is, in an amount equal to or less than about 1.5% by weight, more preferably equal to or less than about 1% by weight, more preferably equal to or less than about 0.5% by weight, more preferably equal to Or less than about 0.25 wt%, and more preferably present in the thermoplastic light diffusing composition of the present invention in an amount equal to or less than about 0.15 wt./twist, wherein the weight percentage is a thermoplastic light diffusing composition. The total weight is based on the benchmark. The light diffusing agent composition of the present invention may contain other inorganic colorants such as barium sulfate; however, it is preferred that such other inorganic colorants are contained. The light diffusing agent composition of the present invention may contain other organic light diffusing agents such as crosslinked poly(methyl methacrylate), polyolefin, MBS-rubber, or an additional light diffusing agent as described below. However, the light diffusing agent composition of the present invention is also extremely useful in the absence of any large amount of other colorants or light diffusing agents. The light diffusing agent composition of the present invention can be obtained by blending the inorganic particles a), the polymer particles b), and the wavelength shifting material illusion and/or the interference color d) in a weight ratio as indicated above. preparation. This blending can be carried out in an organic diluent. Preferably, the dried components a), b), and one or more of the phantoms and/or ... and any other components may be blended. Alternatively, one or more of the inorganic particles and/or the wavelength shifting material c) and/or the interference colorant may be added before or during the production of the polymer particles b). The blending temperature is not critical. Room temperature is most convenient; however, the temperature can also be used. 3 °

S 28 201139532 本發明之光擴散劑組成物對於賦予任何適合熱塑性聚 合物，較佳係透明’光擴散性質係極有用。 熱塑性聚合物通常係透明。其可為澄清或具顏色。較 佳地，其係聚丙烯酸酯，諸如，聚甲基丙烯酸甲酯（pMMA)， 聚苯乙烯（ps)，苯乙烯/丙烯腈共聚物（SAN)，聚碳酸酯 (PC)，或其等之摻合物。本發明之光擴散劑組成物對於聚 碳酸酯係特別有用。 於下列段落，主要地，係描述含有聚碳酸酯作為熱塑 性聚合物之聚合物組成物，即使本發明不限於此。適合之 聚碳酸酯係描述於USP 4,722, 955，第2欄，第6-42行，及其 内引述之參考文獻，其在此併入本案以為參考資料。例示 之碳酸酯聚合物可包括三苯曱基二醇碳酸酯；雙(ar_羥基苯 基)亞烧基(通常稱為雙紛-A型二醇之聚碳酸酯，包含其芳香 族及脂族取代之衍生物；及自其它芳香族二醇衍生之碳酸 酯聚合物。於碳酸酯共聚物或異種共聚物係所欲而非均聚 物時，聚碳酸酯亦可衍生自（1)二或更多種不同之二羥基 齡’或(2)—二羥基酚及一二醇或一以羥基或酸終結之聚酯 或一二元酸。如上之碳酸酯聚合物之摻合物亦可使用。碳 酸酯聚合物可包括酯/碳酸酯之共聚物。 聚碳酸S旨一般係可藉由使二紛，諸如，雙紛-A及/或雙 羥基苯基芴’粤光氣反應而獲得之一聚縮合物，或碳酸、 二羥基二芳基烷之二酯，除未經取代之二羥基二芳基烷 外，芳基基團於相對於經基基團呈鄰位及/或間位處載荷一 或多個甲基基團或鹵素原子者亦適合。可作為用於聚礙酸 29 201139532 酯之起始材料之適合二酚之例子係列示於usp 4, 627,949，第2欄，第68行-第3攔，第1-22行，其在此併入本 案以為參考資料。例示之二酚係氫醌、間苯二酚' 4,4，_二 經基聯苯、雙-(經基-苯基)_烷，諸如，CrC8_烷撐基 亞烷基-雙酚，雙-(羥基苯基)-環烷，諸如，C5_C|5_環烷撐 基-或CVCt環亞烷基-雙酚，雙(羥基_苯基)硫化物、醚類、 酮類、亞硬類，或颯類，及進一步之雙（羥基_苯基)_ 一異丙基本及相對應之核-烧基化或核_齒化之化合物。以 2,2·雙-(4_羥基苯基)-丙烧(雙紛Α)、2,2_雙_(4_羥基_3,5_二氯 -苯基)-丙烷（四氣雙酚Α)、2,2-雙-(4-羥基-3,5_二溴基丙烷 (四溴雙酚Α)、2,2-雙-(4-羥基-3,5-二曱基-苯基丙烷（四甲 基雙酚Α)及1，1-雙-(4-經基苯基)-環己烷(雙酚ζ)為基準之聚 碳酸Ϊ旨，及以三核雙紛，諸如，α,α:1-雙-(4-經基苯基)_對_ 二異丙基苯為基準者亦可被使用。最佳地，聚碳酸s旨係自 雙酚-A及光氣製備。 聚碳酸S旨及其生產方法係此項技藝已知。例如，聚碳 酸酯可藉由一已知之界面二相方法、一均質有機溶液方 法，及/或一炫融方法製備。在此併入本案以為參考資料之 USP 4,092,288於第4攔，第4-68行及實施例1中揭示芳香族 聚碳酸酯及其製備方法。如此專利案中所述，芳香族聚碳 酸酯可包含二羥基酚’例如，雙酚類，諸如，雙(4-羥基苯 基）曱烷、2,2·雙(4-羥基苯基）丙烷、2,2-雙(4-羥基-3-曱基苯 基）丙烷、4,4-雙(4-羥基笨基)庚烷等，二羥基酚醚類，諸如， 雙(4-羥基苯基)醚、雙(3,5-二氣-4-羥基苯基)醚等，二羥基S 28 201139532 The light diffusing agent composition of the present invention is extremely useful for imparting any suitable thermoplastic polymer, preferably a transparent 'light diffusing property. Thermoplastic polymers are generally transparent. It can be clarified or colored. Preferably, it is a polyacrylate such as polymethyl methacrylate (pMMA), polystyrene (ps), styrene/acrylonitrile copolymer (SAN), polycarbonate (PC), or the like. Blend. The light diffusing agent composition of the present invention is particularly useful for the polycarbonate system. In the following paragraphs, mainly, a polymer composition containing polycarbonate as a thermoplastic polymer is described, even if the invention is not limited thereto. Suitable polycarbonates are described in U.S. Patent No. 4,722,955, the entire disclosure of which is incorporated herein by reference. Exemplary carbonate polymers may include triphenyl decyl diol carbonate; bis(ar-hydroxyphenyl) alkylene (a polycarbonate commonly referred to as bis-A diol, including aromatics and fats thereof) a substituted derivative of a family; and a carbonate polymer derived from other aromatic diols. When a carbonate copolymer or a heteropolymer is desired rather than a homopolymer, the polycarbonate may also be derived from (1) Or a plurality of different dihydroxy-aged or (2)-dihydroxyphenols and a monoglycol or a polyester or a dibasic acid terminated with a hydroxyl group or an acid. The above blend of carbonate polymers may also be used. The carbonate polymer may include a copolymer of an ester/carbonate. The polycarbonate S is generally obtained by reacting a phosgene such as bis-A and/or bishydroxyphenyl hydrazine. a polycondensate, or a diester of carbonic acid, dihydroxydiarylalkane, in addition to the unsubstituted dihydroxydiarylalkane, the aryl group is ortho and/or relative to the radical group It is also suitable for loading one or more methyl groups or halogen atoms at the position. It can be used as a starting material for the acid 29 201139532 ester. A series of examples suitable for diphenols are shown in usp 4, 627, 949, column 2, line 68-block 3, line 1-22, which is incorporated herein by reference. Illustrated bisphenol hydroquinone, Hydroquinone ' 4,4,-di-biphenyl, bis-(trans-phenyl)-alkane, such as CrC8-alkylene alkylene-bisphenol, bis-(hydroxyphenyl)-ring An alkane such as C5_C|5_cycloalkylene- or CVCt cycloalkylene-bisphenol, bis(hydroxy-phenyl) sulfide, ether, ketone, sub-hard, or anthraquinone, and further A compound of bis(hydroxy-phenyl)-isopropyl as a basic and corresponding core-alkylated or nucleated-toothed. 2,2·bis-(4-hydroxyphenyl)-propanone (double Α ), 2,2_bis-(4-hydroxy-3,5-dichloro-phenyl)-propane (tetra-gas bisphenolphthalein), 2,2-bis-(4-hydroxy-3,5-dibromo Propane (tetrabromobisphenolphthalein), 2,2-bis-(4-hydroxy-3,5-dimercapto-phenylpropane (tetramethylbisphenolphthalein) and 1,1-bis-(4- Polyphenyl carbonate based on phenylphenyl)-cyclohexane (bisphenolphthalein), and trinuclear, such as α,α:1-bis-(4-pyridylphenyl)_pair Diisopropylbenzene can also be used as a benchmark. Optimally, polycarbonate is intended to be -A and phosgene preparation. Polycarbonate S and its production method are known in the art. For example, polycarbonate can be formed by a known interfacial two-phase method, a homogeneous organic solution method, and/or a smelting The method of the present invention is incorporated herein by reference in its entirety by U.S. The carbonate may comprise a dihydric phenol 'for example, a bisphenol such as bis(4-hydroxyphenyl)decane, 2,2.bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyl) -3-mercaptophenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, etc., dihydric phenol ethers, such as bis(4-hydroxyphenyl)ether, bis(3,5- Dioxo-4-hydroxyphenyl)ether, dihydroxy

S 30 201139532 聯苯’ δ者如’ p,p’_二經基聯笨、3,3,二氣·4,4，_二經基聯苯 等’二經基芳基碾類，諸如，雙(4-經基苯基)颯、雙(3,5_ m經基苯基)颯 '雙(3-曱基-5-乙基-4-經基苯基)石風 等’一智基苯類、間苯二g分、氫酿、_基_及烷基_取代之二 經基苯類，諸如，M_二經基_2_氣苯、 苯、1，4-二羥基-3-甲基笨等，及二羥基二苯基亞砜類諸 如，雙(4-減苯基)亞石風、雙(3,5二漠_4_經基苯基)亞職等。 於非均聚物之碳酸酯共聚物或異種共聚物之情況，二或更 多種不同之二羥基酚二羥基酚與二醇之共聚物、以羥基或 自欠終結之聚酷，或二元酸可被使用。 一般，聚碳酸酯可藉由使二羥基酚與碳酸酯先質於分 子量調節劑及酸接受劑存在中反應而製備。碳酸酯先質可 為羰基齒化物、碳酸酯，或_甲酸酯。適合地，羰基鹵化 物係羰基溴化物、羰基氣化物、羰基氟化物等，或其等之 混合物。典型之碳酸酯係二苯基碳酸酯、二_(画苯基)碳酸 S曰，诸如’ _一·（氣本基)碳酸S旨、二-(漠苯基)碳酸g旨、二-(三 氯笨基)碳酸酯、二-(三溴苯基)碳酸酯等，二_(烷基苯基) 碳酸酯’諸如’二-(甲苯基)碳酸酯等 '二萘基)碳酸酯、 二_(氯萘基)碳酸酯、苯基甲苯基碳酸酯、氣苯基氯萘基碳 酸酯等，或其等之混合物。鹵曱酸酯可包括二羥基酚之雙 鹵甲酸酯（氫酿等之雙氯甲酸酯）或二醇類（乙二醇、新戊二 醇、聚乙二醇等之雙鹵曱酸酯）。 反應可於可為有機或無機之化合物之酸接受劑存在中 進行。例如’有機酸接受劑可為三級胺，諸如，α比咬、三 31 201139532 乙基fee、—甲基苯胺、二丁基胺等。無機酸接受劑可為驗 金屬或鹼土金屬之氫氧化物、碳酸鹽、碳酸氫鹽，或磷酸 鹽。另外，聚碳酸酯可自二笨基碳酸酯或二曱基破酸酯藉 由轉酯化而製備。 分支之聚碳酸酯亦適合。若聚碳酸酯係分支，以聚碳 酸酯之重量’其較佳係含有從〇·〇1至3莫耳％，更佳係從〇.05 至2莫耳％之分支劑。分支之聚碳酸酯，其製備方法，及適 合之分支劑係描述於’例如，USP 3,544,514，其在此併入 本案以為參考資料’公開之歐洲專利申請案第Ep 411433號 案及於EP 411433中引述之參考文獻。較佳之分支劑係 三(4羥基苯基）乙烷。 聚碳酸酯較佳係具有從1〇,〇〇〇克/莫耳（g/m〇le)至 200,000克/莫耳’更佳係從15,〇〇〇克/莫耳至1〇〇〇〇〇克/莫 耳’且最佳係從17, 000克/莫耳至45,000克/莫耳之重量平均 分子量。 聚碳酸酯之端基可為相同或相異。最佳之端基係對-第 三丁基苯基、對-辛基苯基，或苯基。可導致聚碳酸酯，諸 如，以芳基環己烯終結之碳酸酯聚合物，交聯之端基係特 別有用。本發明不限於此等例子。 除光散射聚合物顆粒b)外，本發明之聚合物組成物選 擇性地含有有機光擴散劑。若存在，以熱塑性聚合物之重 里，另外之有機光擴散劑之量較佳係從〇〇1至1〇%，更佳係 從0.02至5% ’最佳係從0.5至3%。例示之有用的已知光擴散 劑係具有4至1 〇〇微米平均直徑之丨至9〇重量％之環己基馬S 30 201139532 biphenyl 'δ δ such as 'p, p' _ two-base stupid, 3,3, two gas · 4,4, _ bi-biphenyl and other 'di-aryl aryl mills, such as, Bis(4-phenylphenyl)anthracene, bis(3,5-m-phenylphenyl)anthracene bis(3-indolyl-5-ethyl-4-ylphenyl) stone, etc. Classes, m-phenylene di-g, hydrogen-branched, _yl- and alkyl-substituted di-terminated benzenes, such as M-di-diyl-2-benzene, benzene, 1,4-dihydroxy-3- Methyl stupid and the like, and dihydroxydiphenyl sulfoxides such as bis(4- minus phenyl) stony wind, bis (3,5 di-di- 4-phenyl) sub-sector. In the case of a non-homopolymer carbonate copolymer or a heteropolymer, a copolymer of two or more different dihydric phenol dihydric phenols and a diol, a hydroxyl group or a self-depleting gel, or a binary Acid can be used. In general, polycarbonates can be prepared by reacting a dihydric phenol with a carbonate precursor in the presence of a molecular weight regulator and an acid acceptor. The carbonate precursor can be a carbonyl dentate, a carbonate, or a phthalate. Suitably, the carbonyl halide is a carbonyl bromide, a carbonyl vapor, a carbonyl fluoride, or the like, or a mixture thereof. Typical carbonate-based diphenyl carbonate, bis(phenylene)carbonate, such as ' _ _ (a gas base) carbonic acid, bis-(indiyl) carbonate, g-, Trichlorophenyl)carbonate, di-(tribromophenyl)carbonate, etc., bis(alkylphenyl)carbonate such as 'dinaphthyl) carbonate such as 'di-(tolyl) carbonate, Di-(chloronaphthyl)carbonate, phenyltolyl carbonate, phenylphenylnaphthyl carbonate, and the like, or a mixture thereof. The halophthalic acid ester may include a dihaloformate of a dihydric phenol (a bischloroformate such as hydrogen or a bis-chloroformate) or a glycol (a dihalophthalic acid such as ethylene glycol, neopentyl glycol or polyethylene glycol). ester). The reaction can be carried out in the presence of an acid acceptor which can be an organic or inorganic compound. For example, the organic acid acceptor may be a tertiary amine such as α-bite, tri 31 201139532 ethylfee, -methylaniline, dibutylamine, and the like. The inorganic acid acceptor can be a hydroxide, carbonate, bicarbonate, or phosphate of a metal or alkaline earth metal. Alternatively, the polycarbonate can be prepared by transesterification from diphenyl carbonate or dimercaptocarboxylate. Branched polycarbonate is also suitable. If the polycarbonate is branched, it preferably has a branching agent of from 〇·〇1 to 3 mol%, more preferably from 〇.05 to 2 mol%, based on the weight of the polycarbonate. A branched polycarbonate, a method of making the same, and a suitable branching agent are described in, for example, U.S. Patent No. 3,544,514, the disclosure of which is incorporated herein in References cited. A preferred branching agent is tris(4-hydroxyphenyl)ethane. Preferably, the polycarbonate has from 1 〇, gram/mole (g/m〇le) to 200,000 gram/mole 'better from 15, gram/mole to 1 〇〇〇 〇〇克/莫耳' and preferably from 7,000 g/m to 45,000 g/mole of weight average molecular weight. The end groups of the polycarbonates may be the same or different. The most preferred end groups are p-tert-butylphenyl, p-octylphenyl, or phenyl. It can lead to polycarbonates, such as carbonate polymers terminated with arylcyclohexene, which are particularly useful for cross-linking end groups. The invention is not limited to these examples. In addition to the light-scattering polymer particles b), the polymer composition of the present invention optionally contains an organic light diffusing agent. If present, the amount of the additional organic light diffusing agent is preferably from 〇〇1 to 1% by weight, more preferably from 0.02 to 5% 'from 0.5 to 3%, based on the weight of the thermoplastic polymer. A known known light diffusing agent is a cyclohexyl horse having a mean diameter of 4 to 1 〇〇 micron to 9 〇 by weight.

S 32 201139532 來醯亞胺及99至10重量％之苯乙烯之球狀交聯共聚物。另 一有用之已知光擴散劑係具有0.5至100微米，較佳係1至20 微米之平均直徑之聚（甲基丙烯酸曱酯）脂。最佳之另外光擴 散劑係含有至少15重量％，較佳係從20至80重量％，更佳係 從25至60重量％之聚合物化之選擇性經烷基化之丙烯酸酯 之經交聯之均聚物或共聚物。若選擇性經烷基化之丙烯酸 酯係經共聚合，一或多種下列單體對於共聚合反應係較 佳：乙烯基芳烴，諸如，苯乙烯或烷基苯乙烯，如，曱基 苯乙烯或乙基苯乙烯；烯烴，諸如，丁二烯；丙烯腈或馬 來醯亞胺。二或更多種之選擇性經烷基化之丙烯酸酯亦可 經共聚合。若經烷基化，丙烯酸酯較佳係含有(^.8烷基基 團，更佳係C2-8烧基基團。較佳之烧基丙烯酸S旨係丙烯酸曱 酯、丙烯酸乙酯，及丙烯酸丁酯。此等選擇性之有機光擴 散劑不具有一芯-殼形態。此等有機光擴散劑及其製備方法 係普遍已知。 本發明之聚合物組成物可含有選擇性之添加劑，諸 如，色料或著色劑、增稠劑、脫模劑、衝擊改質劑、填料 等，只要此等選擇性之添加劑對於聚合物組成物之光學性 質不具負面影響。此等選擇性之添加劑係此項技藝普遍已 知。若存在，聚合物組成物含有較佳係從0.01至3重量％之 量的衝擊改質劑。若真有的話，色料或著色劑之量係從 0.0001至5重量％。較佳之脫模劑係已知之長脂肪酸酯，其 較佳量係從0.01至2重量％。較佳之填料係玻璃填料，較佳 含量係從1至20重量％。所有百分率係以熱塑性聚合物之重 33 201139532 ®為基準。 =發明之聚合触成物亦可含切㈣，諸如，抗氧 化劑及/或w穩定劑，諸如，含硫之分子、亞磷酸鹽、位阻 齡、：：酸鹽、亞膦酸鹽及/或二亞膦酸鹽，諸如，四兑4_ 二第三苯基)二苯撑基二亞膦酸鹽等，其可於生產聚碳酸醋 ㈣及/或於生產聚合物顆_期間添加。以聚碳酸醋之重 量’ 一^多種穩定劑較佳係以從〇.〇1至5%，較佳係從〇 〇5 至2%之量包含於聚碳酸酯組成物中。 較佳之穩定劑係，例如，有機亞魏鹽，較佳係化學 式⑴之亞磷酸鹽 R4S 32 201139532 The conjugated spherical copolymer of styrene and 99 to 10% by weight of styrene. Another useful known light diffusing agent is a poly(methacrylate methacrylate) grease having an average diameter of from 0.5 to 100 microns, preferably from 1 to 20 microns. Preferably, the additional light diffusing agent comprises at least 15% by weight, preferably from 20 to 80% by weight, more preferably from 25 to 60% by weight of the polymerized, selectively alkylated acrylate crosslinked. a homopolymer or copolymer. If the selectively alkylated acrylate is copolymerized, one or more of the following monomers are preferred for the copolymerization reaction: a vinyl arene such as styrene or an alkylstyrene such as nonylstyrene or Ethyl styrene; an olefin such as butadiene; acrylonitrile or maleimide. Two or more selectively alkylated acrylates may also be copolymerized. If alkylated, the acrylate preferably contains (^.8 alkyl groups, more preferably C2-8 alkyl groups. Preferred alkyl acrylates are decyl acrylate, ethyl acrylate, and acrylic acid. Butyl esters. These selective organic light diffusing agents do not have a core-shell morphology. Such organic light diffusing agents and methods for their preparation are generally known. The polymer compositions of the present invention may contain optional additives such as , colorants or colorants, thickeners, mold release agents, impact modifiers, fillers, etc., as long as such selective additives do not adversely affect the optical properties of the polymer composition. These optional additives are The art is generally known. If present, the polymer composition contains an impact modifier preferably in an amount of from 0.01 to 3% by weight. If true, the amount of colorant or colorant is from 0.0001 to 5% by weight. Preferred release agents are known long fatty acid esters, preferably in amounts of from 0.01 to 2% by weight. Preferably, the filler is a glass filler, preferably from 1 to 20% by weight. All percentages are based on thermoplastic polymers. The weight 33 201139532 ® based The inventive polymeric contact may also contain cuts (4), such as antioxidants and/or w stabilizers, such as sulfur-containing molecules, phosphites, hindered ages,: acid salts, phosphinates, and / or diphosphinate, such as tetra- 4 - di-t-phenyl) diphenylene diphosphinate, etc., which can be added during the production of polycarbonate (IV) and / or during the production of polymer particles. The weight of the polycarbonate is preferably contained in the polycarbonate composition in an amount of from 1 to 5%, preferably from 5 to 2% by weight. A preferred stabilizer is, for example, an organic sulfite salt, preferably a phosphite R4 of the formula (1).

P (I) 其中，R4及R5每一者獨立地係一C|γ烷基基團、一 基炫基基團，或一Cw烧氧基基團，諸如，甲基、乙基、 正丙基、異丙基、正丁基、異丁基、第三丁基、戊基或己 基基團、經基曱基、經基乙基或經基丙基基團、曱氧基、 乙氧基或丙氧基基團。其較佳係三(2，4-二第三丁基苯基)_ 亞磷酸鹽(IRGAPHOS™ 168)。 另一較佳之穩定劑係位阻酚。位阻酚及其作為抗氧化 劑之用途係描述於 Ullmann's Encyclopedia of industrial Chemistry，第 3冊，&quot;Antioxidants&quot;，第 95-98 頁，第 5版，P (I) wherein R 4 and R 5 are each independently a C | γ alkyl group, a hexyl group, or a Cw alkoxy group such as methyl, ethyl or n-propyl Base, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl or hexyl group, thiol group, benzyl group or propyl group, decyloxy group, ethoxy group Or a propoxy group. It is preferably tris(2,4-di-t-butylphenyl)-phosphite (IRGAPHOSTM 168). Another preferred stabilizer is a hindered phenol. The hindered phenol and its use as an antioxidant are described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 3, &quot;Antioxidants&quot;, pages 95-98, 5th edition,

S 34 201139532 VCH Verlagsgesellschaft mbH 及 Encyclopedia of Polymer Science and Engineering，第 2冊 ’ &quot;Antioxidants&quot;，第 75-91 頁，1985，John Wiley &amp; Sons，Inc。製備位阻酚之方法亦係 此項技藝已知。 較佳之位阻酚係化學式(II)者S 34 201139532 VCH Verlagsgesellschaft mbH and Encyclopedia of Polymer Science and Engineering, Volume 2 ‘ &quot;Antioxidants&quot;, pp. 75-91, 1985, John Wiley &amp; Sons, Inc. Methods of preparing hindered phenols are also known in the art. Preferred hindered phenolic formula (II)

OHOH

其中，R4、R5及R6每一者獨立地係一Cy烷基基團、一C|3_ 經基烧基基團’或一C1-3-烧氧基基團’諸如，曱其、乙美 正丙基、異丙基、正丁基、異丁基、第三丁基、戊基或己 基基團、羥基曱基、羥基乙基或羥基丙基基團，或甲氧其、 乙氧基或丙氧基基團。 一般，至少一個，較佳係至少二個基團需提供化學式 (Π)之分子立體位阻性。R4、R5及R6基團之较佳係至少— 個，更佳係至少二個係異丁基或第三丁基。化學式丨〗〗之位 阻酚之較佳例子係2, 6-二第三丁基-4-甲基酚 Ό·—第二丁 基-4-第二丁基酚、4_(羥基甲基)-2,6-二第三丁基紛，或2 6 二第三丁基-4-甲氧基-酚。 其它較佳之位阻酚係具化學式(III)者 35 201139532Wherein each of R4, R5 and R6 is independently a Cy alkyl group, a C|3_carbyl group or a C1-3-alkoxy group such as 曱, 乙美N-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl or hexyl, hydroxyindenyl, hydroxyethyl or hydroxypropyl groups, or methoxy, ethoxy Or a propoxy group. Generally, at least one, and preferably at least two, groups are required to provide a molecular steric hindrance of the formula (Π). Preferably, the R4, R5 and R6 groups are at least one, more preferably at least two isobutyl or tert-butyl groups. A preferred example of the hindered phenol of the formula is 2,6-di-t-butyl-4-methylphenolphthalein--t-butyl-4-butanol, 4-(hydroxymethyl) -2,6-di-t-butyl butyl, or 2 6 di-t-butyl-4-methoxy-phenol. Other preferred hindered phenolic compounds of formula (III) 35 201139532

OHOH

(HI) 其中’ R7、R8及R9係以與羥基基團呈鄰位及對位而配置， R7係一 C|_6_烷基基團，R8係一 Ck-烷基基團或—含有—咬 多個酯、醚、醢胺、胺、亞膦酸鹽、膦酸鹽、硫酯及/戈碌 醚官能性且含有最高達24個，較佳係最高達12個碳原子之 基團，諸如 ’ -CH2-CH2-C(0)-0-C18H37基團或-(：Η2κ：8ϋ 基團，且R9係一含有一或多個酯、ϋ、醯胺、胺、亞鱗於 鹽、膦酸鹽、硫酯及/或硫醚官能性且含有最高達24個，車交 佳係最高達12個碳原子之基團，諸如， -CH2-CH2-C(0)-0-C|8H37 基團或-CH2-S-C8H|7 基團。當 r7 戈 R8或二者係一C|·6·烧基基團，其較佳係曱基、乙基、正丙 基、異丙基、正丁基、異丁基、第三丁基、戊基，或己基 基團。 化學式(III)之位阻酚之較佳例子係3,5-二第三丁基_4經 基氫肉桂酸十八酯，可以IRGANOX™丨〇76購得，2_甲其 -4,6雙((辛基硫基)-甲基)-酚，可以IRGANOX 1520購得，2 6_ 二第三丁基-4-(二曱基胺基曱基）酚或3,5-二第三丁基·4_經 基苯甲基二-Ο-乙基膦酸酯，可以IRGANOX 1222購得。 其它較佳之位阻酚含有2個酚基團，例如，N，N’- 1，6-六甲撐基-雙-3-(3,5-二第三丁基-4-羥基笨基）丙醯胺，可以(HI) wherein 'R7, R8 and R9 are arranged ortho and para to the hydroxy group, R7 is a C|_6-alkyl group, R8 is a Ck-alkyl group or-containing- Biting a plurality of ester, ether, decylamine, amine, phosphonite, phosphonate, thioester and/or oligoether functional groups and containing up to 24, preferably up to 12 carbon atoms, Such as a '-CH2-CH2-C(0)-0-C18H37 group or a -(:Η2κ:8ϋ group, and R9 contains one or more esters, hydrazine, decylamine, amine, squamous salt, Phosphonate, thioester and/or thioether functional and containing up to 24 groups, up to 12 carbon atoms, such as -CH2-CH2-C(0)-0-C| 8H37 group or -CH2-S-C8H|7 group. When r7 戈R8 or both are a C|·6·alkyl group, it is preferably a decyl group, an ethyl group, a n-propyl group or an isopropyl group. a base, n-butyl, isobutyl, tert-butyl, pentyl, or hexyl group. A preferred example of a hindered phenol of formula (III) is 3,5-di-t-butyl-4-trans-hydrogen Octadecyl cinnamate, available as IRGANOXTM 丨〇76, 2_methyl--4,6-bis((octylthio)-methyl)-phenol, available from IRGANOX 1520 , 2 6_ di-tert-butyl-4-(didecylaminodecyl)phenol or 3,5-di-t-butyl-4-yl-benzoyl-di-indole-ethylphosphonate, Other preferred hindered phenols contain 2 phenolic groups, for example, N,N'- 1,6-hexamethylene-bis-3-(3,5-di-t-butyl-4- Hydroxy stupid) propylamine, can

S 36 201139532 IRGANOX 1098購得，1,6-六曱撐基雙(3,5_二第三丁基_4_ 經基氫肉桂酸酯’可以IRGANOX 259購得，三甘醇雙[3-(3-第三丁基-4-羥基-5甲基苯基)]丙酸酯，可以IRGANOX 24 購得，N，N'-雙（3，5-二第三丁基-4-經基氫肉桂醯基)肼，可 以IRGANOX MD 1024購得，及鎳或約雙[〇_乙基（3,5-二第 三丁基-4-羥基苯曱基)膦酸酯，後者係可以irgANOX 1425 購得。 最佳之位阻酚係四[甲撐基（3,5-二第三丁基-4-羥基氫 肉桂酸酯）]甲烷，可以IRGANOX 1010購得，3,5-二第三丁 基-4-羥基氫肉桂酸酯，可以IRGANOX 1076購得，或 IRGANOX 1010與三（2,4-二第三丁基-苯基）亞磷酸鹽 (IRGAPHOS 168，商標）之1:1摻合物，此摻合物係可以 IRGANOX B 225購得。 位阻酚有利地係與通式PR^i^R^IV)之膦組合使用，其 中，R1、R2及R3彼此獨立地代表一烷基、環烷基、芳基， 或芳基-烷基基團，或於芳香族環以一或多個鹵素及/或一或 多個烷基、羥基，或烷氧基基團取代之一芳基基團。 R1、R2及R3基可為相同或相異。烧基基團中，較佳係 具有1至18個，較佳係1至12個碳原子者，諸如，甲基、乙 基、正丙基、異丙基、正丁基、第二丁基，或第三丁基， 或戊基、己基、辛基、壬基、癸基或十八烷基基團。烷基 基團可為直鏈或分支。環烷基基團中，較佳係具有5或6個 碳原子者，諸如’環戊基或環己基。芳基基團中，較佳係 具有從6至14個碳原子者，苯基或萘基。芳基基團可以一或 37 201139532 多個上述烷基基團及/或以一或多個_素，諸如，氟化物、 氣化物或漠化物，及/或一或多個經基基團及/或一或多個烧 氧基基團取代。若存在，烷氧基基團較佳係含有1至6個碳 原子’諸如，曱氧基、乙氧基、正丙氧基、異丙氧基、正 丁氧基、第二丁氧基，或第三丁氧基基團。若被取代，芳 基基團較佳係以1、2或3個取代基團取代。於芳基-烷基基 團’上述烷基基團係較佳，且芳基基團較佳係苯基。較佳 之芳基-烷基基團係笨甲基、丁基苯基，或曱笨基。三苯基 膦係最佳之化學式（IV)之化合物。 為了製備本發明之聚合物組成物，〇 〇〇1至2重量％之上 述無機顆粒a)，〇.1至10重量％之上述聚合物顆粒b)，選擇性 之0.1至1，GGG ppm之上述波長下移材料e)，選擇性之〇 〇〇5 至2重量％之上述干涉色料句及，若要的話，-或多種上述 之選擇性的添加劑係與熱塑性聚合物混合。此等化合物係 於使此摻合物與熱塑性聚合物摻合前預先混合。另外，此 * σ物可個別與熱塑性聚合物混合。無機顆粒&amp;)、聚合 物顆粒b)，及一或容絲七、丄 一種之波長下移材料c)及/或干涉色料 ，=選擇性之添加劑可同時或依序添加至熱塑性聚合 等：：序及添加期間之溫度不重要。此 其4之未經稀釋之型式人S 36 201139532 IRGANOX 1098, 1,6-hexamethylene bis (3,5-di-t-butyl-4-yl-perfluorohydrocinnamate) can be purchased from IRGANOX 259, triethylene glycol bis [3-( 3-tert-butyl-4-hydroxy-5methylphenyl)]propionate, available as IRGANOX 24, N,N'-bis(3,5-di-tert-butyl-4-yl-hydrogen Cinnamonyl), available as IRGANOX MD 1024, and nickel or about bis[〇-ethyl(3,5-di-t-butyl-4-hydroxyphenylhydrazo)phosphonate, the latter can be irgANOX 1425 The best hindered phenolic tetrakis[Methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane can be purchased from IRGANOX 1010, 3,5-two. Butyl-4-hydroxyhydrocinnamate, available as IRGANOX 1076, or 1:1 blend of IRGANOX 1010 and tris(2,4-di-t-butyl-phenyl)phosphite (IRGAPHOS 168, trademark) The compound is commercially available as IRGANOX B 225. The hindered phenol is advantageously used in combination with a phosphine of the formula PR^i^R^IV), wherein R1, R2 and R3 independently of each other represent an alkane. a cyclyl, cycloalkyl, aryl, or aryl-alkyl group, or one or more halogens and/or one in the aromatic ring A plurality of alkyl, hydroxy, or alkoxy groups substituted with one aryl group. The R1, R2 and R3 groups may be the same or different. The alkyl group preferably has 1 to 18, preferably 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. Or a tert-butyl group, or a pentyl, hexyl, octyl, decyl, decyl or octadecyl group. The alkyl group can be straight or branched. Among the cycloalkyl groups, those having 5 or 6 carbon atoms are preferred, such as 'cyclopentyl or cyclohexyl. Among the aryl groups, those having from 6 to 14 carbon atoms, phenyl or naphthyl are preferred. The aryl group may be one or 37 201139532 of a plurality of the above alkyl groups and/or with one or more molecules, such as fluorides, vapors or deserts, and/or one or more via groups and / or substituted with one or more alkoxy groups. If present, the alkoxy group preferably has from 1 to 6 carbon atoms 'such as decyloxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, Or a third butoxy group. If substituted, the aryl group is preferably substituted with 1, 2 or 3 substituent groups. The above alkyl group is preferred for the aryl-alkyl group, and the aryl group is preferably a phenyl group. Preferred aryl-alkyl groups are methyl, butylphenyl or phenyl. Triphenylphosphine is the most preferred compound of formula (IV). In order to prepare the polymer composition of the present invention, 1 to 2% by weight of the above inorganic particles a), 1 to 10% by weight of the above polymer particles b), selectivity 0.1 to 1, GGG ppm The above-mentioned wavelength shifts the material e), the selectivity of 〇〇〇 5 to 2% by weight of the above-mentioned interference coloring matter and, if desired, - or a plurality of the above-mentioned selective additives are mixed with the thermoplastic polymer. These compounds are premixed prior to blending the blend with the thermoplastic polymer. In addition, this * σ can be individually mixed with the thermoplastic polymer. Inorganic particles &amp;), polymer particles b), and one or seven or one of the wavelengths of the material c) and / or interference color, = selective additives can be added to the thermoplastic polymerization, etc. simultaneously or sequentially :: The temperature during the sequence and addition is not important. This 4 undiluted type of person

見&amp;，或—或多種之此等化合物可 以一水性或有機稀釋 切J 顆粒a)、b)與物或d)之稀—釋’而不是製備含有上述濃度之 較高濃度之無_^ 〇者之—聚合物組祕，含有 及/或干涉色料t r合物顆㈣，與波長下移材叫 s多者之母料可被製備。母料其後可See &amp;, or - or a plurality of such compounds may be used to dilute J particles a), b) with or dilute-releases as an aqueous or organic dilution instead of preparing a higher concentration containing the above concentrations. The master of the polymer-polymer group, containing and/or interfering with the colorant tra- ing (4), and the masterbatch with a wavelength shifting material called s can be prepared. Masterbatch can be followed by

S 38 201139532 ，熱=性聚合物摻合’以製備含有所界定濃度之顆粒a)、 b) ’與c)及’之—或多者之聚合物組成物。適當地係於 ‘、'、』!·生*。物被化合成顆粒或丸粒前使無機顆粒a)、聚 °物顆粒b) ’與波長下移材料⑽或干涉色料d)之-或多 ti及？擇性之添加劑與可含有選擇性之添加劑之熱塑性 聚口物此口。使無機顆粒a)、聚合物顆粒b)，與波長下移材 料c)及/或干涉色料d)之―或多者，及任何選擇性之添加劑 與熱塑=聚合物分散或混合之方式並不重要。但是，選擇 之方法而為使所有添加物於整個熱塑性聚合物造成大的分 散度者。較佳混合設備係混合輥、帶式摻合機、麵團混合 機、Banbury混合機等。 ^ t °物組成物可藉由已知擠塑技術化合成顆粒或丸 ”若4 口物組成物含有聚碳酸醋，擠塑較佳係於從2〇〇0c 至卿卜更佳係從咖㈤㈣’最佳係從雙⑶卿 之溫度進行。混合物被供應至—擠塑機内，且擠塑成股材， 然後’粉碎成丸粒或顆粒。有狀擠塑機係此項技藝普遍 ^叫齊塑機-般具有-單螺桿或—雙螺桿。使用一雙螺 W齊塑麟，螺桿速度較佳係從避：分鐘(RpM)，更 一螺桿速度較佳 佳係從100至350 RPM。使用一單螺桿時， 係從5至250 RPM,更佳係從 丸粒或顆粒可以-普遍已知方式形成模製物件，例 如’藉由射出成型、射出吹塑成型、滾輪研磨加工、旋轉 式模製、擠塑等。若聚合物組成物含有聚碳酸醋，模製較 佳係於從200。(：至380。(：，更佳係從25〇。〇至38〇。€，最佳係 39 201139532 從260°C至380°C之溫度進行。 模製物件之例子係片材、膜、共同材、㈣ «之膜 '包含至少-片材及至少—膜之共同擠塑複合 物、燈益、照明器具、燈具等。模製物件具有—優異表面 外觀。表面可依需特別應用之需求而為平滑或具質地。 一LED 1，第1圖’係—利用電致發光物理原理之光源， 即，當一電位差施加至一p_nS結合時藉由一半導體5發射 光。LED因而包含半導體本身，且亦包含用於操作及處理 LED之其它το件，諸如，_透明保護殼7、供應接觸（陽極2/ 陰極3)、導線4、選擇性之一反射發射光之反射杯6等。依 據本發明，散射顆粒並非分散於透明保護殼内，而係於蓋 子内。於可見光譜發射之LED，於彩色LDE及白色LED間可 作區別。彩色LED之發射光譜係極窄，且具有3〇與ηηι間’ 較佳係於30與50 nm間之中高度之寬度（如第2圖中所見 般）。發射光譜係依p-n接合之性質而定，因此，係依用於此 半導體之材料的化學性質而定。不同於另一光源，諸如， 一白熾燈或一霓虹燈’下列方程式將發射光之波長χ(以nm) 與依使用之半導體材料而定之能帶隙以eV)相連接： E帶 其中，c表示光速(3 X 108 m/s)，且h表示卜朗克常數(4.136 X 10' eV/s)。 例如，若半導體材料係砷化鎵GaAs，能帶隙係1.35 eV，且LED係於約920 nm之近紅外線處發射。磷砷化鎵S 38 201139532, Thermal = Polymer Blend' to prepare a polymer composition containing particles a), b) ' and c) and - or more at a defined concentration. Appropriately tied to ‘, ', 』!·生*. Before the material is synthesized into pellets or pellets, the inorganic particles a), the polyparticles b)' and the wavelength-shifting material (10) or the interference pigment d) are - or more ti? An optional additive and a thermoplastic polyurethane that can contain optional additives. Dispersing or mixing the inorganic particles a), the polymer particles b), the wavelength-shifting material c) and/or the interference color d), and any optional additives and thermoplastics = polymers not important. However, the method of choice is to cause all of the additives to cause large dispersibility throughout the thermoplastic polymer. Preferred mixing equipment is a mixing roll, a belt blender, a dough mixer, a Banbury mixer, and the like. ^ t ° composition can be synthesized into pellets or pellets by known extrusion techniques. If the composition of the mouthpiece contains polycarbonate, the extrusion is preferably from 2〇〇0c to the better. (v) (iv) 'The best line is carried out from the temperature of Shuang (3) Qing. The mixture is supplied to the extruder and extruded into strands and then 'pulverized into pellets or granules. The squeezing machine is a popular technique. The molding machine generally has a single screw or a twin screw. A double screw W is used, and the screw speed is preferably from the avoidance: minute (RpM), and the screw speed is preferably from 100 to 350 RPM. When using a single screw, it is from 5 to 250 RPM, more preferably from pellets or granules - a generally known way to form molded articles, such as 'by injection molding, injection blow molding, roller grinding, rotary Molding, extrusion, etc. If the polymer composition contains polycarbonate, the molding is preferably from 200. (: to 380. (:, better from 25 〇. 〇 to 38 〇. €, the best Department 39 201139532 From 260 ° C to 380 ° C. Examples of molded objects are sheets, films, common materials, (four) «film ' A co-extruded composite comprising at least a sheet and at least a film, a lamp, a lighting fixture, a luminaire, etc. The molded article has an excellent surface appearance. The surface can be smooth or textured depending on the needs of the particular application. LED 1, Fig. 1 is a light source utilizing the principle of electroluminescence physics, that is, when a potential difference is applied to a p_nS bond, light is emitted by a semiconductor 5. The LED thus contains the semiconductor itself, and also includes for operation and Processing other elements of the LED, such as a transparent protective casing 7, a supply contact (anode 2 / cathode 3), a wire 4, a reflective cup 6 that selectively reflects the emitted light, etc. According to the present invention, the scattering particles are not dispersed Inside the transparent protective case, it is inside the cover. The LED emitted in the visible spectrum can be distinguished between the color LDE and the white LED. The emission spectrum of the color LED is extremely narrow and has a relationship between 3〇 and ηηι. The width of the height between 30 and 50 nm (as seen in Figure 2). The emission spectrum depends on the nature of the pn junction and, therefore, on the chemistry of the material used in this semiconductor. One light Source, such as an incandescent lamp or a neon' equation, the wavelength of the emitted light χ (in nm) is connected to the band gap according to the semiconductor material used (eV): E band, where c is the speed of light (3 X 108 m/s), and h represents the Braunk constant (4.136 X 10' eV/s). For example, if the semiconductor material is gallium arsenide GaAs, the band gap is 1.35 eV, and the LED is near 920 nm. Infrared emission. Phosphorus arsenide

S 40 201139532S 40 201139532

GaAsP、鱗化嫁GaP、氮化蘇GaN，及氮化錄姻GalnN係可 用於製造LED之其它金屬間化合物之其它例子。 以LED發射白光係更有問題，因為其需混合白光之三 種基本組份，即，藍、紅，及綠。亦需混合此三種組份以 便獲得具有良好演色性或CR1及良好色溫（以凱氏）之白色 光。現今，具有至少三種獲得發射白光之技術： 第一種係在於將一於藍色發射之LED與一或多種於黃 色再發射之構光化合物組合。此係於現今廣泛使用之一種 方法，但CR1(演色指數)差，少於75，由於藍光及再發射之 黃光不會於各種均勻混合而通常具有暈環問題。 第二種係在於將一於紫外線發射之L E D與一或多種之 每一者於一特定顏色再發射光線之磷光化合物組合◦使用 此技術之白色LED之例子係於US 6,084,250文件中提供β例 如，一於370與410 nm間發射之LED係與磷光化合物，即， Eu: BaMgAlu017、Cu: ZnS及YV04，之混合物組合。此種 LED產生具有接近螢光燈之良好CRI之白光；以及 第三種在於混合藉由數種顏色之LED發射之顏色以獲 得白色光。此技術具有更具變通性之優點，因為無需使用 磷光化合物。藉由個別LED之強度作用，可使色溫細微調 整，因而可獲得一完整範圍之白光（範圍從”熱”白至冷藍 白）。貫際上，為獲得白光，需使LED發射相對應於存在人 類眼睛之每一種錐狀體之敏感性最大值之單色光（於藍色 情況係450 nm，於綠色情況係550 nm，且於紅色情況係 620)。若以此精確頻率發射之LED不可獲得，需藉由調整發 41 201139532 射強度而作補償。 白色LED之發射光譜係比顏色LED者更廣。於白色 之情況，依據本發明之散射塑料能消除與此三種技術有關 之缺點’例如’與第—種技術有關之暈環現象或第三種技 術之不TO i的顏色·$合。依據本發明之散射塑料因而係相 當適於生產併納-或多個白色LED之發光裝置。 具有大於3流明（Lm)之高光通量之LED可有利地作為 照明標瑞之光源。感謝其長的壽命，㈣無需經常替換， 此係-主要優點，特別是位於高處之照明標諸，例如，高 塔或建築物之頂部。另—優點係LED係小的光源，因此， 可製造更小巧之照明標誌、’因此’更易於安裝及拆除。 於一實施例，本發明係一種發光裝置8，第2圖，包含 一光源，較佳係至少一LED丨，較佳係一白色LED，其中， 其光通量料於或大於3 Lm，有繼係料或大於5 Lm， 較佳係等於或大於l〇Lm，更佳係等於或大於5〇Lm，及至 少-蓋子9’蓋子包含此處於上揭露之光擴散組成物。此蓋 子與其它事物能確保LED發射之光透射；遮蔽及保護 LED，提供均勻且不刺眼之照明；降低或甚至去除led之 缺點，特別是於白色LED之暈環作用；及確保於白天及夜 晚良好能見度。 有利地，光通量係於3與1，000 Lm之間，更佳係於3與 500 Lm之間，更佳係於3與2〇〇 Lm之間’更佳係於3與1〇〇 Lm之間，較佳係於5與1〇〇 Lm之間，更佳係於1〇與1〇() 之間，且極佳係於50 and Lm之間。感謝具有高光通量之白 42 201139532 色LED ’可降低用以獲得特定照明之lED數量。與白熾燈 或霓虹燈管相比’可獲得更小巧且消耗較少電力之發光裝 置。此外，當LED點亮時，蓋子看起來係實質上白色，且 以L、a*、b*值，係具有大於55之發光度，於_7 5與十7 5間 之a*值，及於-7.5與+7. 5間之b*值。 於一實施例，蓋子包含一單層之片材或膜。 於另一實施例，蓋子包含一多層片材、多層膜，包含 一或多個片材及一或多個膜之多層複合物。具有一或多層 之多層片材、多層膜，及多層複合物可藉由任何適合手段 製造’且共同擠塑係較佳。一多層片材可包含一或多個片 狀基質層及/或一或多個覆蓋層。 典型上，一片狀基材層可具有等於或大於約〇 5毫米 (mm) ’較佳係等於或大於約丨腿，更佳係等於或大於約2 mm，且更佳係等於或大於約3 mm之厚度。典型上，一片 狀基材層可具有等於或少於約5 mm，較佳係等於或少於約 4.5mm，且更佳係等於或大於約4mm之厚度。典型上，一 片狀覆蓋層係從1微米至_微来，較佳係從職米至微 米。 §蓋子3有夕於一個片材，或多於—個膜時，每一膜 及/或每一片材可包含組份幻、b)、c)，及句之一者或全部， 使得於此多層材、？層膜，❹層複合體之所有層間， 存有組份a)及b)與組份e)及d)之—或多者。舉例鮞言，若蓋 子包含-與覆蓋層共同擠塑之片狀基材，此片狀基材可包 含組份a)+b)+d)，而覆蓋層包含組份c)。 43 201139532 具有數種熟習此項技藝者所知之用以生產本發明之發 光裝置之蓋子的方法。蓋子可具有所有種類之依所欲應用 之性質而定之幾何形狀。例如，其可呈平坦、？曲，或圓 頂狀片材之型式’矩形或圓形，呈圓盤狀等。例如，於第2 圖所例示’於照明標狀情况，其亦可採用字母或任何其 它本似s件之型式。例示料下敎獻中提供：us公開第 衡测m案，其纽完整併人本案以為參考資料。 蓋子具有〇.05與15⑽間，較佳係(U cm與10 cm間，更 佳係(U cm與7⑽間，更佳係ο]⑽與5 em間且更佳係〇 2 cm與4 cm間之厚度。 蓋子與㈣係以1⑽與50⑽間，更佳係2 cm與50 cm 間，較佳係2⑽與20 Cm間，且更佳係3 cm與20 cm間之距 離刀開&amp;光裝置係不同於’例如，於Ep 893似中所述 之邊緣發射褒置。此係因為於依據本發明之發光裝置中， 被照明不是蓋子邊緣，而係蓋子之一面。 依據本發明之發找置具有各種應用 ，諸如，一般照 明、室内照明設備(起居室燈、辦公室燈等）；廣告顯示器、 指不照明设備或逃離路徑標記；照明標誌(於此情況，蓋子 可特別具有字母8 ’第2圖，數字，符號，或任何其它標然 之型式）’交通標誌；汽車照明設備，諸如，車前燈、日間 行車燈、方向指示器、停車燈、霧燈、倒車燈、行動裝置、 LED-TV之背光單元、嵌人式筒燈、工作燈、辦公室層板燈、 廚房櫃底燈、圓球燈、透鏡、光學元件等。 第3圖及第4圖顯示於建築物12頂部之—照明標該u。Other examples of GaAsP, squamous-grained GaP, nitrided GaN, and nitrided GalnN can be used to make other intermetallic compounds for LEDs. It is more problematic to emit white light with LEDs because it requires mixing the three basic components of white light, namely blue, red, and green. It is also necessary to mix these three components in order to obtain white light with good color rendering or CR1 and good color temperature (Kjeldahl). Today, there are at least three techniques for obtaining white light emission: The first is to combine a blue emitting LED with one or more photoluminescent compounds that are re-emitted in yellow. This is a method widely used today, but the CR1 (color rendering index) is poor, less than 75, since the blue light and the re-emitted yellow light do not uniformly mix in various kinds and usually have a halo problem. The second type consists in combining a phosphorescent compound that emits light from an ultraviolet-emitting LED with one or more of them in a particular color. An example of a white LED using this technique is provided in US 6,084,250, for example, An LED system that emits between 370 and 410 nm is combined with a phosphorescent compound, that is, a mixture of Eu: BaMgAlu017, Cu: ZnS, and YV04. Such an LED produces white light having a good CRI close to that of a fluorescent lamp; and a third is to mix colors emitted by LEDs of several colors to obtain white light. This technology has the advantage of being more flexible because there is no need to use phosphorescent compounds. By the intensity of the individual LEDs, the color temperature can be fine-tuned so that a full range of white light (ranging from "hot" white to cool blue-white) is obtained. In order to obtain white light, it is necessary to make the LED emit a monochromatic light corresponding to the maximum sensitivity of each cone of the human eye (450 nm in the blue case and 550 nm in the green case, and In the case of red, 620). If the LED emitted at this precise frequency is not available, it should be compensated by adjusting the intensity of the radiation. The emission spectrum of white LEDs is wider than that of color LEDs. In the case of white, the scattering plastic according to the present invention can eliminate the disadvantages associated with the three techniques, e.g., the halo phenomenon associated with the first technique or the color of the third technique. The scattering plastics according to the invention are thus relatively suitable for the production of light-emitting devices of nano- or multiple white LEDs. An LED having a high luminous flux of more than 3 lumens (Lm) can be advantageously used as a light source for illumination. Thanks to its long life, (iv) no need to replace it frequently, this is the main advantage, especially for lighting fixtures located at high places, for example, on top of tall towers or buildings. Another advantage is that the LED is a small light source, so that a smaller illumination sign can be made, which is therefore easier to install and remove. In one embodiment, the present invention is a light-emitting device 8, and FIG. 2 includes a light source, preferably at least one LED, preferably a white LED, wherein the luminous flux is at or above 3 Lm, and has a successor. The material is greater than 5 Lm, preferably equal to or greater than 10 Lm, more preferably equal to or greater than 5 Lm, and at least the cover 9' cover comprises the light diffusing composition disclosed herein. This cover and other things can ensure the transmission of light emitted by the LED; shield and protect the LED, providing uniform and non-glare illumination; reducing or even eliminating the disadvantages of led, especially the halo effect of white LED; and ensuring day and night Good visibility. Advantageously, the luminous flux is between 3 and 1,000 Lm, more preferably between 3 and 500 Lm, more preferably between 3 and 2 Lm, more preferably between 3 and 1 Lm. Preferably, it is between 5 and 1 〇〇Lm, more preferably between 1 〇 and 1 〇 (), and is preferably between 50 and Lm. Thanks to the white light with high luminous flux 42 201139532 The color LED ’ can be reduced to obtain the number of lEDs for a specific illumination. A lighter device that is smaller and consumes less power can be obtained compared to incandescent or neon tubes. In addition, when the LED is lit, the cover appears to be substantially white, and with L, a*, b* values, has a luminosity greater than 55, an a* value between _75 and 175, and The b* value between -7.5 and +7.5. In one embodiment, the lid comprises a single layer of sheet or film. In another embodiment, the cover comprises a multilayer sheet, a multilayer film, a multilayer composite comprising one or more sheets and one or more films. Multilayer sheets, multilayer films, and multilayer composites having one or more layers can be made by any suitable means and co-extrusion is preferred. A multilayer sheet may comprise one or more sheet substrate layers and/or one or more cover layers. Typically, the sheet-like substrate layer may have a thickness equal to or greater than about 毫米5 mm (mm) preferably equal to or greater than about 丨 leg, more preferably equal to or greater than about 2 mm, and more preferably equal to or greater than about 3 mm thickness. Typically, the sheet-like substrate layer can have a thickness equal to or less than about 5 mm, preferably equal to or less than about 4.5 mm, and more preferably equal to or greater than about 4 mm. Typically, a sheet of cover layer is from 1 micron to _ micro, preferably from the working meter to the micrometer. § When the cover 3 has a sheet, or more than one film, each film and/or each sheet may contain one or all of the components, b), c), and This multilayer material,? The film, the layer of the ruthenium complex, contains components a) and b) and components e) and d) - or more. By way of example, if the cover comprises a sheet-like substrate which is coextruded with the cover layer, the sheet-like substrate may comprise components a) + b) + d) and the cover layer comprises component c). 43 201139532 There are several methods known to those skilled in the art for producing a cover for a light-emitting device of the present invention. The lid can have all kinds of geometric shapes depending on the nature of the application. For example, can it be flat,? The shape of the curved or rounded sheet is 'rectangular or circular, and is disc-shaped. For example, as illustrated in Fig. 2, in the case of an illumination standard, it may also take the form of a letter or any other s. In the example, the offer is provided: us open the case of the first measure, and the new one is considered as the reference material. The lid has between 〇.05 and 15(10), preferably between U cm and 10 cm, better (U cm and 7 (10), better ο) (10) and 5 em and better 〇 2 cm and 4 cm The thickness of the cover. The cover and (4) are between 1 (10) and 50 (10), more preferably between 2 cm and 50 cm, preferably between 2 (10) and 20 Cm, and more preferably between 3 cm and 20 cm. The device is different from the edge emitting device described in, for example, Ep 893. This is because in the illuminating device according to the present invention, the illuminating device is not the edge of the cover, but is one side of the cover. There are various applications, such as general lighting, indoor lighting (living room lights, office lights, etc.); advertising displays, pointing to no lighting or escape path markings; lighting signs (in this case, the cover may have in particular the letter 8 ' Figure 2, numbers, symbols, or any other type of standard) 'traffic signs; automotive lighting equipment, such as headlights, daytime running lights, direction indicators, parking lights, fog lights, backup lights, actions Device, LED-TV backlight unit, embedded downlight, work light, office Room floor lights, kitchen cabinet lights, ball lights, lenses, optical components, etc. Figures 3 and 4 are shown on the top of the building 12 - the lighting standard u.

44 201139532 於構成此標誌之字母間再次地係如上所述之第2圖中之字 母8。第3圖顯示於白天期間未點亮時之標誌。第4圖顯示於 仪晚期間點亮時之標誌、。 於本發明之一實施例，無論光源係led及/或螢光燈及/ 或白熾燈’自本發明之光擴散組成物製成之物件當以反射 光’較佳係太陽光(於白天期間）觀看時出現與自一背光光源 (於夜晚期間）觀看時不同之顏色及/或亮度。色差之程度及 量係與使用之特定波長下移材有關。雖不受任何特別理論 約束，但相信於300 11111至4〇〇 nm範圍之紫外線光係由波長 下移材料吸收，且於可見區域反射，典型上係於4〇〇 nm至 500 nm間之範圍的藍色螢光。 外觀差異係裸眼可看出或可檢測出，但當以點亮然後 關閉之背光LED測量時經由至少50之黃色指數變化量化。 另外，可藉由背光光源於打開及關閉時於至少一色座標(χ, y)以0.01之量的色度變化而檢測。 本發明係藉由下列非限制性之實施例更詳細地進一步 例示。 實施例 實施例1至3及比較例A至F之組成物係列示於第1表，且 除非其它指示’所有量係以聚碳酸輻纟且成物總重量為基準 之重量百分率。 摻合組成物係於一玻璃瓶内預先混合，且混合樣品係 使用Haake PPLYLABTM系統以60分鐘_ι之速度於25〇〇c化 合5分鐘’其後係使用一壓縮機進行快速冷卻處理，產生約 45 201139532 3 mm厚之板材。 _，〇口之板材係使用New Hermes煎切機切成約1 χ 1英寸之讀。帶材被置於一壓縮模具内，以-〖ΑΡΤΟΝ™ 膜覆蓋以提供—平滑表面。模具置於-於25G°C預熱之 Carver壓If目;^製機之平台間。平台於獅㈣之壓力下壓製3 ，其後係以1〇,〇〇〇磅進行3分鐘其後係2〇,〇〇〇磅之壓 力進行2分鐘，且最後於3,〇〇〇磅之壓力下持續3分鐘冷卻至 %境溫度。形成之2.7 mm板材之平滑側被用於光學性質測 試。 下列組份被用於實施例1至3及比較例A至F : PC係具有於300。(：且於1.2公斤之載重下測定為6克 A0分鐘之熔融流之雙酚_A聚碳酸酯均聚物； ”Ti〇2”係二氧化鈦’且可得自 cristal Global之TIONATM RCL-4 ； &quot;C/S-1橡膠”係具有約6微米之平均橡膠顆粒尺寸之芯/ 殼橡膠’其中，殼係MMA/EA共聚物，其包含此橡膠之約 20重量％，具有1.46之折射率（RI)，且芯係BA/ALMA共聚 物，其包含橡膠之剩餘的80重量％，具有1.49之RI，可得自 陶氏化學公司之PARALOID™ EXL 5136 ; &quot;C / S - 2橡膠&quot;係具有約0 · 1至0.2微米之平均橡膠顆粒尺 寸之芯/殼橡膠，其中，殼係MMA/EA共聚物’其包含橡膠 之約20重量％，具有1.46之折射率（RI) ’且芯係BA/ALMA 共聚物，其包含橡膠之剩餘80重量％，具有L49之RI ’可得 自陶氏化學公司之PARALOID PRD 137 ;44 201139532 Again, the letter 8 in Fig. 2 as described above is used between the letters constituting this mark. Figure 3 shows the signs when they are not lit during the day. Figure 4 shows the sign when it is lit during the night of the instrument. In one embodiment of the present invention, regardless of the source of the light and/or the fluorescent lamp and/or the incandescent lamp 'the article made from the light diffusing composition of the present invention, when the reflected light is used, it is preferably sunlight (during the daytime) The color and/or brightness that appears when viewed from a backlight source (during the night) appears. The degree and amount of chromatic aberration is related to the shifting material at a specific wavelength used. Without being bound by any particular theory, it is believed that the UV light in the range of 300 11111 to 4 〇〇 nm is absorbed by the wavelength-shifting material and is reflected in the visible region, typically between 4 〇〇 nm and 500 nm. Blue fluorescent. The difference in appearance is visible or detectable by the naked eye, but is quantified by a yellow index change of at least 50 when measured with a backlight LED that is illuminated and then turned off. In addition, the backlight source can be detected by changing the chromaticity of at least one color coordinate (χ, y) by 0.01 when the backlight source is turned on and off. The invention is further illustrated in more detail by the following non-limiting examples. EXAMPLES The composition series of Examples 1 to 3 and Comparative Examples A to F are shown in Table 1, and unless otherwise indicated, all amounts are based on the weight percentage of the polycarbonate and the total weight of the product. The blended composition was pre-mixed in a glass vial and the mixed sample was compounded using a Haake PPLYLABTM system at 25 ° C for 5 minutes at a rate of 60 minutes _ followed by rapid cooling with a compressor. Approximately 45 201139532 3 mm thick sheet. _, the plate of the mouth is cut into about 1 χ 1 inch using the New Hermes frying machine. The strip is placed in a compression mold covered with a ΑΡΤΟΝTM film to provide a smooth surface. The mold is placed in a pre-heated Carver press at 25G °C; The platform is pressed under the pressure of the lion (four), followed by 1 〇, 〇〇〇 pound for 3 minutes and then 2 〇, 〇〇〇 pound pressure for 2 minutes, and finally 3, 〇〇〇 pound Cool down to % ambient temperature for 3 minutes under pressure. The smooth side of the formed 2.7 mm sheet was used for optical property testing. The following components were used for Examples 1 to 3 and Comparative Examples A to F: The PC system had 300. (: and a bisphenol_A polycarbonate homopolymer having a melt flow of 6 g A0 minutes under a load of 1.2 kg; "Ti〇2" is a titanium dioxide' and available from Cristal Global's TIONATM RCL-4; &quot;C/S-1 rubber&quot; is a core/shell rubber having an average rubber particle size of about 6 microns. wherein the shell is an MMA/EA copolymer comprising about 20% by weight of the rubber having a refractive index of 1.46. (RI), and a core BA/ALMA copolymer comprising 80% by weight of the remainder of the rubber, having an RI of 1.49, available from The Dow Chemical Company's PARALOIDTM EXL 5136; &quot;C / S - 2 Rubber &quot a core/shell rubber having an average rubber particle size of from about 0. 1 to 0.2 microns, wherein the shell MMA/EA copolymer 'containing about 20% by weight of rubber has a refractive index (RI) of 1.46 and Core BA/ALMA copolymer comprising 80% by weight of rubber, RI' with L49 available from Dow Chemical Company PARALOID PRD 137;

S 46 201139532 &quot;LDSM”係可得自 BASF之LUMOGENTM Violet 570之 波長下移材料；且 ’’IFP&quot;係可得自 Merck Chemicals之IRIODIN™ 97225 Ultra Rutile Blue Pearl SW之包含塗覆於黏土上之Ti02之干 涉色料。 包含實施例1至3及比較例A至F之組成物之經製縮成型 之板材接受下列光學性質評估，且結果係列示於第1表： % T&quot;係藉由使用 BYK Gardner(Haze-Gard 5 Plus)依據 ASTM D-1003測量之光透射百分率，且測得之透射率係總 透射率。測試樣本係使用Hunterlab Colorquest以透射模 式’使用C光源(模擬日光），2。之觀察角及400-700 nm之波 長而測量； ”D50”係自一光學測角光度計（型號：GP-200)測定，且 係指可透射為於透射模式時於〇度視角的光強度之5〇%的 光強度時之角度0 ’且係測量樣品之光擴散能力。光學測 角光度計具有一鹵素光源，且樣品支撐器可從_9〇至90度旋 轉。不同樣品旋轉角度之光強度可以一極軸圖繪製，且光 強度分佈亦可轉移成一X-Y轴圖。半增益角或D50係用以評 估光擴散性質。 ”L*、a* ’及b*”值係用以依據ASTM E 308以反射率（黑 色）描述於 Commission Internationale d'Eclairage 系統(CIE-系統）之主要顏色。L*表示從〇(黑色）至ι〇〇(白色）之發光 度。a*值係測量顏色之紅及綠：易趨向綠色之顏色具有負 的a*值，而易趨向紅色之顏色具有正的a*值。b*值係測量 47 201139532 顏色之藍及黃：易趨向黃色之顏色具有正的b*值，而易趨 向藍色之顏色具有負的b*值。L*、a*、b*值係使用反射模 式依據八3丁1\4£313測量； ΗΥΓ係黃色指數，且係依據ASTM E313測定；且 ”顏色變化&quot;係色差是否能被察覺之視覺測定。一板材 以LED光源（USLED之MWL-4-12-W4)施以背光，且於二條 件下觀看：（1)當LED打開時，及⑺當LED關閉時。若於此 二條件間於任何角度之任何顏色變化可被察覺，樣品被認 為係顯不顏色變化。若於任何角度未察覺顏色變化，此樣 品被認為係未顯示顏色變化。 本發明之實施例，實施例1、2及3，顯示於反射及透射 光觀看時之顏色變化’而非本發明實施例之比較例A、B、 E及F未顯不顏色變化。雖然比較例c顯示顏色變化， 其具有不可接光透射率，因為高IFP量使其於LED光擴 散應用係不可接受。S 46 201139532 &quot;LDSM" is a wavelength shifting material available from BASF's LUMOGENTM Violet 570; and ''IFP&quot; is available from Merck Chemicals' IRIODINTM 97225 Ultra Rutile Blue Pearl SW, which is coated on clay. Interference colorant of Ti02. The shrink-formed sheet comprising the compositions of Examples 1 to 3 and Comparative Examples A to F was subjected to the following optical property evaluation, and the result series is shown in Table 1: % T&quot; The percentage of light transmission measured by BYK Gardner (Haze-Gard 5 Plus) according to ASTM D-1003, and the measured transmittance is the total transmittance. The test sample is in the transmission mode using the Hunterlab Colorquest 'using C light source (analog daylight), 2 The observation angle is measured at a wavelength of 400-700 nm; the "D50" is measured from an optical goniophotometer (Model: GP-200) and refers to light that is transmissive to the viewing angle in the transmission mode. The angle of light intensity of 5〇% of intensity is 0' and the light diffusing ability of the sample is measured. The optical goniophotometer has a halogen light source, and the sample holder can be rotated from _9 〇 to 90 degrees. Different sample rotation angles It The intensity can be plotted on a polar plot, and the light intensity distribution can also be transferred to an XY-axis plot. The half-gain angle or D50 is used to evaluate the light diffusion properties. The "L*, a*' and b*" values are used in accordance with ASTM. E 308 is described in the main color of the Commission Internationale d'Eclairage system (CIE-System) in reflectance (black). L* represents the luminosity from 〇 (black) to ι (white). Red and green: the color tending to green has a negative a* value, while the color tending to red has a positive a* value. b* value is measured 47 201139532 Color blue and yellow: easy to yellow color has positive The b* value, while the blue color tends to have a negative b* value. The L*, a*, b* values are measured using the reflection mode according to 八三丁1\4£313; Determined according to ASTM E313; and "color change" is a visual measurement of whether the color difference can be perceived. A panel is backlit with an LED source (USLED's MWL-4-12-W4) and viewed under two conditions: (1) when the LED is on, and (7) when the LED is off. If any color change at any angle between the two conditions is detectable, the sample is considered to exhibit no color change. If the color change is not perceived at any angle, the sample is considered to have no color change. Embodiments of the present invention, Examples 1, 2, and 3, show color changes upon viewing of reflected and transmitted light', and Comparative Examples A, B, E, and F of the embodiments of the present invention show no color change. Although Comparative Example c shows a color change, it has a non-light transmittance, because the high IFP amount makes it unacceptable for LED light diffusion applications.

S 48 201139532 ΠΊ Ο 0.00001 ο ο 0.005 〇\ (Ν o (N cn 1 s oi 1 \ό 1 (N Ο τ—Η 0.000014 ο ο r*H 0.005 1 ιη m ON 'S 〇 1 cn 1 1 &lt; Ο 1 0.000014 Η ο ο ο ι—Η 0.002 1 m νη OO 'sd CN vd pUi ο 0.00001 S ο 0.002 CN (Ν as 〇\ s 1 Os r-H K〇 ω ο 0.00001 ο 0.005 ιη οο ψ&lt;1 Η c\ 〇〇 卜 m o 1 g i—H ί—H K〇 Q ο 0.000014 ο ο 0.005 On in iTi 00 i—H O) H o in 14.46 K〇 U ο I 0.000014 ο ο ο τ-Η 0.025 1 Os in g m 00 咖 PQ ο 0.000014 ο &lt;Ν yn κη in 1 00 寸· (N K〇 &lt; ο 〇\ 00 ，叫 O 卜 cK Γ- Γη 〇 1 ON o 1 卜 Os 1 K〇 £ 組份 υ PLh C/S-1橡膠 C/S-2橡膠 ε &amp; Q τ,% cf * % 顏色變化 49 201139532 L圖式簡單說明3 第1圖顯示一燈型式之LED之圖。 第2圖顯示藉由LED照明之一照明標誌之一字母之例 子。 第3圖顯示於白天未點亮時之於一建築物頂部之包含 第2圖之字母之一照明標誌。 第4圖顯示於夜晚點亮時於一建築物頂部之第3圖之照 明標認。S 48 201139532 ΠΊ Ο 0.00001 ο ο 0.005 〇\ (Ν o (N cn 1 s oi 1 \ό 1 (N Ο τ—Η 0.000014 ο ο r*H 0.005 1 ιη m ON 'S 〇1 cn 1 1 &lt; Ο 1 0.000014 Η ο ο ο ι—Η 0.002 1 m νη OO 'sd CN vd pUi ο 0.00001 S ο 0.002 CN (Ν as 〇\ s 1 Os rH K〇ω ο 0.00001 ο 0.005 ιη οο ψ&lt;1 Η c\ Mo mo mo 1 gi—H ί—HK〇Q ο 0.000014 ο ο 0.005 On in iTi 00 i—HO) H o in 14.46 K〇U ο I 0.000014 ο ο ο τ-Η 0.025 1 Os in gm 00 Coffee PQ ο 0.000014 ο &lt;Ν yn κη in 1 00 寸 · (NK〇&lt; ο 〇\ 00 , called O 卜 cK Γ- Γη 〇1 ON o 1 卜 Os 1 K〇£ Component υ PLh C/S-1 Rubber C/S-2 rubber ε &amp; Q τ,% cf * % Color change 49 201139532 L-mode simple description 3 Figure 1 shows a diagram of a lamp type LED. Figure 2 shows one illumination by LED illumination An example of a letter in one of the signs. Figure 3 shows an illumination sign containing the letter of Figure 2 at the top of a building when it is not lit during the day. Illumination at night to recognize the scale of FIG. 3, the top of a building during lighting.

S 【主要元件符號說明】 1..LED 7...透明保護殼 2...陽極 8...字母 3...陰極 9...蓋子 4...導線 11...照明標誌 5...半導體 12...建築物 6...反射杯 50S [Description of main component symbols] 1..LED 7...transparent protective case 2...anode 8...letter 3...cathode 9...cover 4...wire 11...illumination sign 5 ...semiconductor 12...building 6...reflecting cup 50

Claims (1)

201139532 七、申請專利範圍： l —種光擴散熱塑性組成物，包含一熱塑性聚入物，以及 a) 從0.001至2重量％之一無機顆粒，其具有從〇丨至丨微米 之—平均顆粒直徑及從1_9至3.2之一折射率， b) 從0.01至1〇重量％之一聚合物顆粒，其具有從至 微米範圍之-平均顆粒尺寸，於589⑽之折射率η係與 該熱塑性樹脂聚合物者差至少〇〇5， 以及c)' d)之一或多者，或其等之混合物，其中， e)係從0·1至1，〇〇〇 ppm之一波長下移材料， 且 d)係從0.005至2重量％之一干涉色料。 2·如申請專利範圍第丨項之光擴散熱塑性組成物，其中， 该無機顆粒a)係二氧化鈦、石夕石凝膠、硫化鋅、氧化辞、 MgTi〇3，或其等之混合物。 3·如申請專利範圍第丨項之光擴散熱塑性組成物，其中， =聚合物顆粒b)係一經交聯之丙烯聚合物、一經交聯之 求乙稀聚合物、-經交聯之㈣氧聚合物，或其等之混 合物。 汝申。月專利範圍第i項之光擴散熱塑性組成物，其中， 該聚合物顆粒b)具有包含-或多個殼之一以殼形態，其 中，該芯係、-橡膠狀之乙烯基聚合物，其以該怒之重量 為基準係包含至少15重量％之_經聚合化之减丙稀酸 酸或烷基甲基丙烯酸酯。 士申明專利範圍第1項之光擴散熱塑性組成物，其中， 51 201139532 該波長下移材料C)係選自含有Sm3+、Cr3+、ZnSe、Eu， 或Tb之波長下移材料之一無機波長下移材料，一量子點 材料，選自羅丹寧、香豆素、紅螢烯、一雷射染料、Alq3、 TPD、Gaq2Cl ;茈碳酸或其衍生物、萘碳酸或其衍生物、 紫蒽酮或異紫蒽酮或其衍生物之一有機下移材料，或其 等之混合物。 6. 如申請專利範圍第1項之光擴散熱塑性組成物，其中， 該干涉色料d)係選自雲母薄片+Ti02 ;雲母薄片+Zr02 ; Si02 薄片 +Ti02 ; Si02 薄片 +Zr02 ; Al2〇3 薄片 + Ti02 ; Al2〇3薄片+Zr02 ;玻璃薄片+Ti02 ;玻璃薄片+Zr02 ;玻 璃薄片+ Si02+Ti02 ;或其等之組合。 7. 如申請專利範圍第1項之光擴散熱塑性組成物，其中， 該熱塑性聚合物係選自聚碳酸酯、聚曱基丙烯酸曱酯、 聚苯乙烯、聚苯乙烯及丙烯腈之共聚物，或其等之混合 物。 8. —種單層或多層之熱塑性光擴散片材，其具有至少一包 含申請專利範圍第1項之熱塑性光擴散組成物之層。 9. 一種發光裝置，包含至少一光源，及由申請專利範圍第 1項之組成物製成之一蓋子。 10.如申請專利範圍第9項之發光裝置，其中，該至少一光 源係具有大於3Lm的光通量之一 LED。 52201139532 VII. Patent application scope: l - a light-diffusing thermoplastic composition comprising a thermoplastic agglomerate, and a) from 0.001 to 2% by weight of one inorganic particle having an average particle diameter from 〇丨 to 丨 micron And a refractive index from 1_9 to 3.2, b) from 0.01 to 1% by weight of the polymer particles having an average particle size ranging from the micron range to a refractive index η of 589 (10) and the thermoplastic resin polymer a difference of at least ,5, and c)' d), or a mixture thereof, wherein e) is a material that moves from one wavelength of 0·1 to 1, 〇〇〇ppm, and d ) is an interfering colorant from 0.005 to 2% by weight. 2. The light-diffusing thermoplastic composition of claim </ RTI> wherein the inorganic particles a) are titanium dioxide, shisha gel, zinc sulfide, oxidized, MgTi〇3, or a mixture thereof. 3. The light-diffusing thermoplastic composition of claim </ RTI> wherein the polymer particles b) are a crosslinked propylene polymer, a crosslinked ethylene polymer, and a crosslinked (tetra) oxygen a polymer, or a mixture thereof. Shen Shen. The light-diffusing thermoplastic composition of the invention of claim i, wherein the polymer particles b) have a shell form comprising one or more shells, wherein the core, a rubbery vinyl polymer, Based on the weight of the anger, at least 15% by weight of the polymerized acrylic acid or alkyl methacrylate is included. The light-diffusing thermoplastic composition of claim 1 of the patent scope, wherein, 51 201139532, the wavelength shifting material C) is selected from the group consisting of Sm3+, Cr3+, ZnSe, Eu, or Tb. Material, a quantum dot material selected from the group consisting of rhodamine, coumarin, erythroprene, a laser dye, Alq3, TPD, Gaq2Cl; phthalic acid or its derivatives, naphthaleneic acid or its derivatives, asterone or different One of the purpurone or one of its derivatives is an organically moved material, or a mixture thereof. 6. The light-diffusing thermoplastic composition of claim 1, wherein the interference color d) is selected from the group consisting of mica flakes + Ti02; mica flakes + Zr02; SiO 2 flakes + Ti02; SiO 2 flakes + Zr02; Al2 〇 3 Sheet + Ti02; Al2〇3 sheet + Zr02; glass flakes + Ti02; glass flakes + Zr02; glass flakes + Si02 + Ti02; or a combination thereof. 7. The light-diffusing thermoplastic composition of claim 1, wherein the thermoplastic polymer is selected from the group consisting of polycarbonate, polydecyl methacrylate, polystyrene, polystyrene, and acrylonitrile. Or a mixture thereof. A single-layer or multi-layer thermoplastic light-diffusing sheet having at least one layer comprising the thermoplastic light-diffusing composition of claim 1 of the patent application. 9. A light-emitting device comprising at least one light source and a cover made of the composition of claim 1 of the patent application. 10. The illuminating device of claim 9, wherein the at least one light source has one of the luminous fluxes greater than 3 Lm. 52