TW200930758A - Transparent thermoplastic resin and method for preparing the same - Google Patents

Abstract

Disclosed herein is a transparent thermoplastic resin comprising a rubber phase including an aromatic rubbery block copolymer resin, and a resin phase including a terpolymer comprising an aromatic vinyl compound, a vinyl cyanide compound and an unsaturated alkyl ester compound, wherein the rubber phase and the resin phase have a co-continuous phase structure.

Description

200930758 六、發明說明： 【發明所屬之技術領域】 本發明是關於一種锈日日办& 方法。 透月熱塑性樹月旨以及-種其製造 【先前技術】 通常’用於需要透明度 ❺ φ 射率之單組份材料。然而，單二脂包3有單-折 應用中受到限制。最近， 77材料之用途在各種複雜 維持各種㈣之所_麵^=製造具有透明度同時 研4二:=具有增強之衝擊強度以及硬度之材料的 樹月曰或本乙料合物_旨來進行。然‘於 烯之聚合物樹脂與㈣_樹 ς ^ ^ 的差異相當大，因而f要且古/本6職口物樹月曰之間 、#B日勒滿祕似要/、有與早聚物相同之高透明度之 透月,、，、塑性树月曰以彌補折射率之間的差里 以滿足良好透明度以及改良之如仍= 性以及耐化學性。 两划w單预度机動 料_^下，已知有多種方法 使丙烤，糸職與不透明梅樹脂共聚合 國專利第4,113,798號是釙斟—從立， ^ 十對—種利用熔融擠壓藉由使用 71 BS樹脂以及SAN #丨脂來製造透明 的ABS树月曰之方法。然而，因為添加過量調節劑以製造初 始樹脂’所輯述縣擠_由使时批製 枝 ABS麟以湖_旨的核之齡在 ❹200930758 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a rust day & method. The purpose of the monthly thermoplastic tree and its manufacture [Prior Art] is generally used for a one-component material requiring transparency ❺ φ radiance. However, single-lipid packs 3 are limited in single-fold applications. Recently, the use of 77 materials has been carried out in various complexes to maintain various (4) aspects. = 制造 制造 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = . However, the difference between the polymer resin of the ene and the (4) _ tree ς ^ ^ is quite large, so f and the ancient / this 6 job mouth between the tree and the moon, #B日勒满秘要要/,有早早The same high transparency transparency of the polymer, the plastic tree, to compensate for the difference between the refractive indices to meet the good transparency and improved such as still = sex and chemical resistance. Under the two-way pre-motorized material _^, there are known a variety of methods for making B-baked, the patent for the co-polymerization of defamation and opaque plum resin is No. 4,113,798, which is 钋斟-立立, ^十对- A method of manufacturing a transparent ABS tree by using 71 BS resin and SAN #Rouge. However, because of the addition of an excess of the regulator to make the initial resin, the counted villages are squeezed by the time of the batching of ABS Lin to the core of the lake.

G 200930758 物獲得所需顏色，… 另—製造透明ΓΓ其應用。 程。然而，此方 、Ai3s樹脂之方法使用單一連續製 受限使用之橡膠可由於用於進行連續製程之裝置而 滑劑之添加劑的使’合物的限制。所述裝置亦限制諸如潤 定。因此，报難籍用，其視所用添加劑之量以及類型而 此外，所述方、、/π此方法獲得良好衝擊強度以及流動性。 <万去不適於批量生產。 為克服上述Πθ§ 、，座 5,252,664號揭’吳國專利第5,079,296號以及第 共聚物舆具有^ ^度可11由混合具雜雜質之嵌段 橡膠狀顆粒以增加樹脂以賦予透明度，且添加少量 有習知橡膠性強ί來獲得。然而，僅用具 度，且所仍售難以獲収夠的衝擊強 、，I橡勝狀顆粒會降低透明度。 美國專利第5,237,007號、第5,2%,862號、第5 344 878 號以及第6,734,247號揭露透明度以及所需性可 由使用兩種射不同橡膠含量之不同橡膠狀共 衝擊強度且亦藉由使用具有良好硬度之共聚細 的硬度來獲得。然而，此等方法之賴在於耐 化學性由於橡膠含量大而降低。 f 【發明内容】 本發明是針對一種具有良好透明度之熱塑性樹脂，发 中所述熱塑性樹脂包括包含芳族橡膠狀嵌段共聚物9樹二 (aromatic rubbery block copolymer resin)之橡膠相以及 ^ 含三共聚合物（terpolymer)之樹脂相，且亦針對其擎$方 4 200930758 法 三共聚合物可具有良好耐化學性，從叫予透明 :』性树脂良好耐化學性。透明熱 ==狀嵌段共聚物樹脂以及三共心 林士刀子量而具有良好衝擊強度以及流動性。此 夂藉由匹配三共聚合物樹脂以及芳族橡膠錢 又/、澉物樹知之折射率（或換言之藉由調整折射率之差里G 200930758 Get the desired color,... Another – make transparent ΓΓ its application. Cheng. However, the method of this and Ai3s resin uses a single continuous process. The limited use of the rubber can be limited by the additive of the additive for the continuous process. The device also limits such as lubrication. Therefore, it is reported that it is difficult to use, depending on the amount and type of the additive used. Further, the method of the square, / π obtains good impact strength and fluidity. < Wan is not suitable for mass production. In order to overcome the above Πθ§, Block 5, 252, 664, 'Wu Guo Patent No. 5, 079, 296 and the copolymer 舆 have a ^ ^ degree 11 by mixing the rubber particles with impurity impurities to increase the resin to impart transparency, and add a small amount It is known that rubber is strong. However, only the degree of use, and the impact is still difficult to obtain enough impact, I rubber particles will reduce the transparency. U.S. Patent Nos. 5,237,007, 5,2%, 862, 5,344,878, and 6,734,247 disclose the transparency and the sufficiency of the use of two different rubber-like co-impact strengths of different rubber contents and also by use A fine hardness of copolymerization with good hardness is obtained. However, these methods depend on the fact that the chemical resistance is lowered due to the large rubber content. f [ SUMMARY OF THE INVENTION The present invention is directed to a thermoplastic resin having good transparency, wherein the thermoplastic resin comprises a rubber phase comprising an aromatic rubbery block copolymer resin and The polymer phase of the polymer (terpolymer), and also for its engine, can have good chemical resistance, and it is called transparent: the resin has good chemical resistance. The transparent heat == block copolymer resin and the three concentric knives have good impact strength and fluidity. This is achieved by matching the tri-copolymer resin with the aromatic rubber and/or the refractive index of the sputum tree (or in other words, by adjusting the refractive index difference)

❹ 以，供約_8歧小讀料差_使透明熱塑性樹脂 、一月度最大本發明之其他態樣特點以及優點將自隨後 揭示内容以及附加申請專利範圍而顯而易見。 根據本發明之例示性實施例，透明熱塑性樹脂包含包 括芳族橡膠狀嵌段共聚物樹脂之橡膠相；以及包括包含芳 族乙烯基化合物（aromatic vinyl compound)、氰化乙烯化 合物（vinyl cyanide compound)以及不飽和烷基醋化合物 (unsaturated alkyl ester compound)之三共聚合物的樹脂 相，其中所述橡膠相以及所述樹脂相具有共連續相結構 (co-continuous phase structure ) 〇 在本發明之一些實施例中，橡膠相之一部分以及樹脂 相之一部分可形成不連續結構（discontinuous structure )。 在本發明之一些實施例中，熱塑性樹脂可包括約20% 至約80% (以重量百分比計）之量的橡膠相以及約20%至 約80% (以重量百分比計）之量的樹脂相。 三共聚合物可包含約50%至約95%(以重量百分比計） 之芳族乙烯基化合物、約0.1%至約30%(以重量百分比計） 之氰化乙烯化合物以及約0.1%至約45% (以重量百分比 5 200930758 計）之不飽和烧基酯化合物。 芳族橡膠狀嵌段共聚物樹脂可包含約10%至約50% (以重量百分比計）之橡膠狀聚合物以及約50%至約90% (以重量百分比計）之芳族乙稀基化合物。 三共聚合物與芳族橡膠狀嵌段共聚物樹脂之折射率 之間的差異可小於約0.008。 在本發明之一些實施例中，三共聚合物之重量平均分 子量可為約140,000至約350,000。 ® 透明熱塑性樹脂可進一步包含選自由下列各物組成 之群組的添加劑：阻燃劑、抗生素劑、釋放劑、熱穩定劑、 抗氧化劑、光穩定劑、配伍劑、染料、無機填充劑、界面 活性劑、成核劑、偶合劑、填充劑、增塑劑、抗衝擊改質 劑、混雜劑（admixing agent )、著色劑、穩定劑、潤滑劑、 抗靜電劑、顏料、防火劑以及其組合。 在本發明之一些實施例中，透明熱塑性樹脂可包含： (A)約20%至約80% (以重量百分比計）之三共聚合物， 〇 其包含約50%至約95% (以重量百分比計）之芳族乙烯基 化合物、約0.1%至約30% (以重量百分比計）之氰化乙烯 化合物以及約0.1%至約45% (以重量百分比計）之不飽和 烷基酯化合物；以及（B)約20至約80% (以重量百分比 計）之芳族橡膠狀嵌段共聚物樹脂，其包含約10%至約50% (以重量百分比計）之橡膠狀聚合物以及約50%至約90% (以重量百分比計）之芳族乙稀基化合物。 所述樹脂亦可具有下列性質之一或多者：於23°C下根 200930758 ^y y i. 據ASTM-D256對1/8”試樣所量測到之約10公斤力·公分/ 公分或更大的伊佐德氏衝擊強度（Izod impact strength); 根據ASTM D-1238所量測到之約45公克/10分鐘或更大 的溶體流動速率（melt flow rate，MFR ) ( 220°C，10 公斤）； 約2.5或更小之濁度（haze)以及約88%或更大之透明度， 其是使用Nippon Denshoku濁度計對3毫米厚試樣所量 測’約10%或更小之重量增加以及約80%或更小之拉伸強 度變化，其是根據ASTM D-543 (浸沒測試）在將試樣浸 0 沒於甲醇中7天後所量測；約5%或更小之重量增加以及 約40°/。或更小之拉伸強度變化，其是根據ASTM D-543(浸 沒測試）在將試樣浸沒於乙醇中7天後所量測；以及約15% 或更小之重量增加以及約45%或更小之拉伸強度變化，其 是根據ASTM D-543 (浸沒測試）在將試樣浸沒於汽油中 7天後所量測。 根據本發明之另一態樣，提供一種製造透明熱塑性樹 脂之方法。所述方法包含製造具有約10%至約50% (以重 Ο 量百分比計）之橡膠狀聚合物的芳族橡膠狀嵌段共聚物樹 脂；藉由聚合芳族乙烯基化合物、氰化乙烯化合物以及不 飽和烧基酯化合物來製造具有約140,000至約350,000之 重量平均分子量的芳族乙烯基-氰化乙烯·不飽和烷基酯三 共聚合物以具有約0.008或更小之所述芳族橡膠狀嵌段共 聚物樹脂與所述三共聚合物之間的折射率差異；以及將芳 族橡膠狀嵌段共聚物樹脂與芳族乙烯基·氰化乙烯_不飽和 烷基酯三共聚合物混合並熔融擠壓。 7 ΟFurther, other aspects and advantages of the invention will be apparent from the following disclosure and the appended claims. According to an exemplary embodiment of the present invention, the transparent thermoplastic resin comprises a rubber phase including an aromatic rubbery block copolymer resin; and includes an aromatic vinyl compound, a vinyl cyanide compound And a resin phase of a tri-copolymer of an unsaturated alkyl ester compound, wherein the rubber phase and the resin phase have a co-continuous phase structure 〇 in some embodiments of the invention In one example, a portion of the rubber phase and a portion of the resin phase may form a discontinuous structure. In some embodiments of the invention, the thermoplastic resin may comprise from about 20% to about 80% by weight of the rubber phase and from about 20% to about 80% by weight of the resin phase. . The tricopolymer may comprise from about 50% to about 95% by weight of the aromatic vinyl compound, from about 0.1% to about 30% by weight of the vinyl cyanide compound, and from about 0.1% to about 45% % (in weight percent 5 200930758) of unsaturated alkyl ester compounds. The aromatic rubbery block copolymer resin may comprise from about 10% to about 50% by weight of the rubbery polymer and from about 50% to about 90% by weight of the aromatic vinyl compound. . The difference between the refractive indices of the tricopolymer and the aromatic rubbery block copolymer resin may be less than about 0.008. In some embodiments of the invention, the tri-copolymer may have a weight average molecular weight of from about 140,000 to about 350,000. The ® transparent thermoplastic resin may further comprise an additive selected from the group consisting of flame retardants, antibiotic agents, release agents, heat stabilizers, antioxidants, light stabilizers, compatibilizers, dyes, inorganic fillers, interfaces. Active agents, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, admixing agents, colorants, stabilizers, lubricants, antistatic agents, pigments, fire retardants, and combinations thereof . In some embodiments of the invention, the transparent thermoplastic resin may comprise: (A) from about 20% to about 80% by weight of the tri-copolymer, which comprises from about 50% to about 95% by weight An aromatic vinyl compound, from about 0.1% to about 30% by weight of the vinyl cyanide compound, and from about 0.1% to about 45% by weight of the unsaturated alkyl ester compound; (B) from about 20 to about 80% by weight of the aromatic rubbery block copolymer resin comprising from about 10% to about 50% by weight of the rubbery polymer and about 50% Up to about 90% (by weight percent) of the aromatic vinyl compound. The resin may also have one or more of the following properties: at 23 ° C, 200930758 ^ yy i. According to ASTM-D256, about 10 kg force · cm / cm or as measured by 1 / 8" sample or Greater Izod impact strength; melt flow rate (MFR) of about 45 g/10 min or more as measured by ASTM D-1238 (220 ° C, 10 kg); haze of about 2.5 or less and transparency of about 88% or more, measured by a Nippon Denshoku turbidity meter to a sample of 3 mm thick 'about 10% or less An increase in weight and a change in tensile strength of about 80% or less, measured according to ASTM D-543 (Immersion Test) after immersing the sample in methanol for 7 days; about 5% or less An increase in weight and a change in tensile strength of about 40° or less, measured after immersing the sample in ethanol for 7 days according to ASTM D-543 (immersion test); and about 15% or less The increase in weight and the change in tensile strength of about 45% or less, measured after immersing the sample in gasoline for 7 days according to ASTM D-543 (Immersion Test) According to another aspect of the present invention, there is provided a method of producing a transparent thermoplastic resin, the method comprising producing an aromatic rubber-like inlay having from about 10% to about 50% by weight of the rubbery polymer. a segmental copolymer resin; an aromatic vinyl-cyanide-ethylene-unsaturated alkyl having a weight average molecular weight of from about 140,000 to about 350,000 by polymerizing an aromatic vinyl compound, a vinyl cyanide compound, and an unsaturated alkyl ester compound The ester triester has a refractive index difference between the aromatic rubbery block copolymer resin having a thickness of about 0.008 or less and the tricopolymer; and the aromatic rubbery block copolymer resin and aromatic The vinyl group-vinyl cyanide-unsaturated alkyl ester tri-copolymer is mixed and melt extruded.

200930758 曰在本發明之—些實施例中，可將約20%至約80% (以 重量百分比計）之芳族橡膠狀嵌段共聚物樹脂與約20%至 約80/。（以重量百分比計）之芳族乙稀基-氰化乙稀-不飽 和烷基酯三共聚合物混合且經由習知擠壓機熔融擠壓。 芳無乙歸基-I化乙稀-不飽和烧基酯三共聚合物可夢 由共聚合約50%至約95% (以重量百分比計）之芳族乙^ 基化合物、約0.1%至約30% (以重量百分比計）之氰化乙 烯化合物以及約〇·1%至約45% (以重量百分比計）之不飽 和炫基S旨化合物來製造。 【實施方式】 •本發明現在將在下文隨後實施方式中更充分地加以 描述，在實施方式中描述本發明L非所有實施例。 實際上’本發明可以許多*_式體現且不應理解為限於 本文所述之#施例；更確㈣言，提供此#實_以致本 揭示案將符合適用的法律要求。 本發明之態樣提供-種透明熱雖樹脂。所述透明熱 塑性樹脂包含橡膠相與樹脂相，且所述橡膠相以及 脂相具有共連續相結構。 ^、 在本發明之例示性實施例中，橡膠相之一部分以及樹 脂相之一部分可形成不連續結構。在下文中，術ς “共連 續相結構（co-continuous phase structure )，，音袖取人 形成連續邊界（線）而不形成聚合物相之—者 之其他者中的分離區域之結構。在下文中，術组 鍵構（discontinuous structure)，，意謂一個相包圍其他相而 8 200930758 由其所形成的分離區域之結構。 圖1說明根據本發明之一例示性實施例之形成共連續 結構的透明熱塑性樹脂。所述共連續結構可由試樣之具有 約30,000放大倍數的透射電子顯微鏡（transmissi〇n electronmicroscope，TEM)圖像來鑑別。在圖1中白色部 分表示樹脂相且黑色部分表示橡膠相。如圖1中所示，橡 膠相與樹脂相具有共連續相結構且同時確定橡膠之一部分 〇 以及樹脂相之一部分形成不連續結構。橡膠相與樹脂相具 有非晶形不規則結構。 在本發明之一例示性實施例中，橡膠相形成連續相且 樹脂相與一些橡膠相可形成不連續結構。在本發明之另一 例示性貫施例中，樹脂相形成連續相且橡膠相與另一些樹 脂相可形成不連續結構。 、樹脂相包含包括芳族乙烯基化合物、氰化乙烯化合物 Μ及不飽和絲|旨化合物之三絲合物。三共聚合物可藉 ^聚合芳族乙烯基化合物、氰化乙齡合物以及不飽和炫 基醋化合物來製造以料樹脂良好耐化學性。 橡膠相包含芳族橡膠狀嵌段共聚物樹脂。 μ 發r ’ _嗅_目讀料之_差異小 於，.、勺’例如小於約Q•⑻4，200930758 In some embodiments of the invention, from about 20% to about 80% by weight of the aromatic rubbery block copolymer resin can be from about 20% to about 80%. The (in weight percent) aromatic vinyl-cyanoacetate-unsaturated alkyl ester tricopolymer is mixed and melt extruded by a conventional extruder.芳无乙基基-I-ethylene-unsaturated alkyl ester tri-copolymer can dream from the copolymer contract 50% to about 95% (by weight percent) of aromatic ethyl compound, about 0.1% to about 30 % (by weight percent) of the vinyl cyanide compound and from about 1% to about 45% (by weight percent) of the unsaturated sulfo S compound. [Embodiment] The present invention will now be more fully described in the following embodiments, in which all embodiments of the invention are described. In fact, the present invention may be embodied in a number of ways and should not be construed as being limited to the embodiment described herein; more precisely (d), providing such a fact that the disclosure will comply with applicable legal requirements. Aspects of the invention provide a transparent heat resin. The transparent thermoplastic resin comprises a rubber phase and a resin phase, and the rubber phase and the fat phase have a co-continuous phase structure. ^, In an exemplary embodiment of the invention, a portion of the rubber phase and a portion of the resin phase may form a discontinuous structure. In the following, the structure of the separation region in the "co-continuous phase structure", the sound sleeve is taken to form a continuous boundary (line) without forming a polymer phase. , a discontinuous structure, means a structure in which a phase surrounds other phases and 8 200930758 is formed by a separate region. Figure 1 illustrates the formation of a co-continuous structure in accordance with an exemplary embodiment of the present invention. Thermoplastic Resin The co-continuous structure can be identified by a transmission electron microscope (TEM) image of the sample having a magnification of about 30,000. In Figure 1, the white portion indicates the resin phase and the black portion indicates the rubber phase. As shown in Fig. 1, the rubber phase and the resin phase have a co-continuous phase structure and simultaneously determine that one part of the rubber and one part of the resin phase form a discontinuous structure. The rubber phase and the resin phase have an amorphous irregular structure. In an exemplary embodiment, the rubber phase forms a continuous phase and the resin phase and some rubber phases form a discontinuous junction In another exemplary embodiment of the present invention, the resin phase forms a continuous phase and the rubber phase forms a discontinuous structure with other resin phases. The resin phase comprises an aromatic vinyl compound, a vinyl cyanide compound, and Unsaturated silk|The tri-complex of the compound. The tri-copolymer can be made by polymerizing an aromatic vinyl compound, a cyanated ethylene compound, and an unsaturated sulfoacetate compound to produce a good chemical resistance of the resin. Contains an aromatic rubbery block copolymer resin. μ r r ' _ sniffing _ reading material _ difference is less than, ., spoon 'for example less than about Q • (8) 4,

於約0.001。 貝她例Y /、J 至約中，組合物包括約2〇% 三共聚合物 約ecmunbh :之㈣橡膠独及約20%至 里買白刀比叶）之量的樹脂相 200930758 可以約35%至約70% (以重量百分比計）之量使用。若〜 共聚合物之含量小於約2〇%，則可能難以獲得本發明所= 之高於一定程度的耐化學性，且若三共聚合物之含量大^ 約80〇/。，則可能難以獲得本發明所需之高於一定 浐 衝擊性。 又机 在本發明之例示性實施例中，本發明之透明熱塑性樹 脂可包含約20%至約80% (以重量百分比計）之包含芳族 ❹ 乙烯基化合物、氰化乙烯化合物以及不飽和烷基酯化合物 的二共聚合物；以及約20%至約80% (以重量百分比計） 之芳族橡膠狀嵌段共聚物樹脂。 本發明之各組份將在下文更充分地描述。 方族乙炼基-氰化乙烯-不餘知烧^酷三共聚奋物 本發明之三共聚合物（A)是藉由聚合芳族乙烯基化 合物、氰化乙烯化合物以及不飽和烷基酯化合物來製造以 賦*予樹脂良好财化學性。 在本發明之一例示性實施例中，三共聚合物（A)是 ® 藉由共聚合約50%至約95% (以重量百分比計）之芳族乙 烯基化合物、約0.1%至約30% (以重量百分比計）之氰化 乙烯化合物以及約0.1%至約45% (以重量百分比計）之不 餘和统基酯化合物來製造。在本發明之另一例示性實施例 中，三共聚合物（A)是藉由共聚合約65%至約85% (以 重量百分比計）之芳族乙烯基化合物、約2%至約7% (以 重量百分比計）之氰化乙烯化合物以及約10%至約30%(以 重量百分比計）之不飽和烷基酯化合物來製造。 10 ❹ ❹ 200930758 某之結構或芳族結構的氫 基之‘可經C1_C8院基取代。芳族 == 限於)笨乙稀;經_二= 4甲本乙稀、2·甲基笨乙稀，基苯乙浠、 嫌、4土正苯乙烯、3_乙絲W、4·乙基苯乙 烯-正丙基本乙稀、4·第三丁基苯 乙烯基萘，諸如1·乙烯基萘以及2_乙烯 以及其類似基團。芳族乙烯基化合物 ==;，膠狀嵌段共聚物樹脂之== 之量，但芳族乙稀基化合物可以職 里刀比计）二共聚合物（A)計以約5〇〇/0至約95% ==)之量存在。若三共聚合物包括小心About 0.001. In the case of Y /, J to about, the composition comprises about 2〇% of the tri-copolymer about ecmunbh: (4) rubber alone and about 20% to buy white knife than the leaf) the amount of resin phase 200930758 can be about 35% Use up to about 70% (in weight percent). If the content of the ~copolymer is less than about 2%, it may be difficult to obtain a chemical resistance higher than a certain degree of the present invention, and if the content of the tri-copolymer is as large as about 80 Å. It may be difficult to obtain a higher than a certain impact required for the present invention. Further, in an exemplary embodiment of the present invention, the transparent thermoplastic resin of the present invention may comprise from about 20% to about 80% by weight of the aromatic fluorene-containing vinyl compound, the vinyl cyanide compound, and the unsaturated alkane. a dicopolymer of a base ester compound; and from about 20% to about 80% by weight of the aromatic rubbery block copolymer resin. The components of the invention will be described more fully below. The tri-copolymer (A) of the present invention is obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound, and an unsaturated alkyl ester compound. To make a good chemical and chemical properties. In an exemplary embodiment of the invention, the tri-copolymer (A) is an aromatic vinyl compound from about 50% to about 95% by weight of the copolymer, from about 0.1% to about 30% ( It is produced in a percentage by weight of the vinyl cyanide compound and from about 0.1% to about 45% by weight of the total alkyl ester compound. In another exemplary embodiment of the invention, the tri-copolymer (A) is from 65% to about 85% (by weight percent) of the aromatic vinyl compound by copolymerization, from about 2% to about 7% ( It is produced by weight percent of the vinyl cyanide compound and from about 10% to about 30% by weight of the unsaturated alkyl ester compound. 10 ❹ ❹ 200930758 The hydrogen radical of a structure or aromatic structure can be replaced by a C1_C8 yard. Aromatic == limited to) stupid ethylene; by _ two = 4 Abenz, 2, methyl stupid, styrene, susceptibility, 4 soil styrene, 3 _ wire W, 4 · B Styrene-n-propylethylene, 4·t-butylstyryl naphthalene, such as 1·vinylnaphthalene and 2-vinylidene and the like. The aromatic vinyl compound ==;, the amount of the gelatinous block copolymer resin ==, but the aromatic vinyl compound can be measured by the ratio of the ruthenium (A) to about 5 〇〇 / The amount from 0 to about 95% ==) exists. If the tri-copolymer includes caution

Si 分比計）或大於約挪之量的芳族乙烯基 化&物’則可能難以匹配芳族橡膠狀嵌段共聚物樹脂之折 射率以提供所fit财。 # 氰化乙烯化合物可為具有可共聚合不飽和烴以及氰 化物取代基之材料，且不飽和結構之氫基之一部分可經 C1-C8烷基取代。氰化乙烯化合物之實例可包括（但不限 於^丙烯腈、甲基丙烯腈、乙基丙烯腈以及其類似基團。 此等氰化乙烯化合物可單獨或相互組合使用。氰化乙烯化 合物可以100% (以重量百分比計）三共聚合物（A)計以 約0.1 /〇至約30% (以重量百分比計）之量使用。若氰化乙 稀化合物之量小於約0.1% (以重量百分比計），則可能不 會獲得所需耐化學性，且若氰化乙烯化合物之量大於約 200930758 30% (以重量百分比計）’則可能難㈣配料橡膠狀嵌段 共奇&物树月曰（B)之折射率以提供所需透明度。 不飽和烧絲化合物可為具討絲合讀和煙以 及基於烧基醋之取代基的材料。基於燒基醋之取代基的烧 基Z呈C1-C8絲或絲狀形式。獨和絲§|化合物 之貫例可包括（但不限於）甲基丙烯酸燒基醋或經C1_C12 烧基取代之（曱基）丙烯酸酯，諸如丙烯酸烧基酯、曱基 〇 丙烯酸曱醋、甲基丙烯酸乙醋、甲基丙稀酸2_乙基己醋、 丙烯酸曱酯、丙烯酸乙酯、丙烯酸丁醋、丙烯酸2_乙基己 酯以及其類似基團。此等化合物可單獨或相互組合使用。 不飽和烧基醋化合物可以1 〇〇% (以重量百分比計）三共 聚合物（A)計以約〇.1%至約45% (以重量百分比計）^ i使用。若不飽和燒基酯化合物之量大於約45% (以重量 百分比計）’則可能難以匹配芳族橡膠狀嵌段共聚物樹脂 (B)之折射率以提供所需透明度。 用於本發明之三共聚合物（A)之各組份的量可藉由 D 下文所述之橡膠共聚物化合物的折射率來控制。當化合物 之各組份具有不同光學折射率以便獲得透明度時，極重要 的是藉由調整其各組份之量而儘可能緊密地匹配共聚物之 折射率。 根據本發明，良好透明度可藉由使用芳族乙烯基化合 物·氮化乙烯化合物·不飽和烷基酯化合物之三共聚合物來 獲得。本發明之發明者已令人驚訝地發現，使用所述三共 聚合物以替代習知SAN樹脂更容易彌補芳族橡膠狀嵌段 12 200930758 共聚物與樹脂之折射率之間的差異。折射率之間的差異可 藉由控制芳族乙烯基化合物、氰化乙烯化合物以及不飽和 烷基酯三共聚合物化合物中各組份之組成來彌補。 芳族乙烯基化合物-氰化乙烯化合物-不飽和烷基酯化 合物之三共聚合物（A)與芳族橡膠狀嵌段共聚物樹脂（B) 之折射率之間的差異可調整至約〇.〇〇8或更小，例如約 0.004或更小，且在另一實施例中，其約〇 〇〇1或更小。 二共聚合物（A)可具有約140,000至約350,000、例 如約200,000至約3〇〇,〇〇〇之重量平均分子量（Mw)。若 重量平均分子量小於約140,000,則可能不會獲得本發明 所需之良好衝擊強度，且若重量平均分子量大於約 350,000 ’則可能降低流動性。 百分比計）具有良好耐化學性之三共聚合物約1% (以重 在三共聚合物（A)之製造中，可按每1〇〇% (以重 劑、有機以及無機顏料、染料、 以及其組合。 篁百分比計）之餘加f知添加舰舒抗氧化劑性 改良流動性、衝擊強度以及其他物理性質。所述添加劑可 ❹ 找（但祕於）阻_、熱狀劑、抗氧侧、光稃定 無ϊ、七城t、； η紜j办女《Γ心 . υ ^ ^ 、無機填充劑以及其類似物，The Si vinylation & matter or greater than the amount of aromatic vinylation &' may be difficult to match the refractive index of the aromatic rubbery block copolymer resin to provide a good margin. The cyanide vinyl compound may be a material having a copolymerizable unsaturated hydrocarbon and a cyanide substituent, and a part of the hydrogen group of the unsaturated structure may be substituted with a C1-C8 alkyl group. Examples of the vinyl cyanide compound may include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. These vinyl cyanide compounds may be used singly or in combination with each other. The vinyl cyanide compound may be 100. % (by weight percent) triaconomer (A) is used in an amount of from about 0.1 /〇 to about 30% by weight. If the amount of ethylene cyanide compound is less than about 0.1% by weight ), the required chemical resistance may not be obtained, and if the amount of the vinyl cyanide compound is greater than about 200930758 30% (in weight percent), then it may be difficult. (4) Ingredients rubbery block common & (B) The refractive index to provide the desired transparency. The unsaturated calcined compound may be a material having a silky read and smoke and a base based on a burnt vinegar. The base Z based on the substituent of the burnt vinegar is C1. -C8 silk or filament form. Monofilament §|Company examples of compounds may include, but are not limited to, methacrylic acid methacrylate or (meth) acrylate substituted with C1_C12 alkyl group, such as alkyl acrylate,曱基〇Acrylic vinegar, A Ethyl acrylate, methyl acrylate 2-ethyl hexanoic acid, decyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. These compounds can be used singly or in combination with each other. The unsaturated alkyl vinegar compound may be used in an amount of from about 1% to about 45% by weight of the tri-copolymer (A) in an amount of from 1% by weight to about 4% by weight. The amount of the ester compound is greater than about 45% (by weight percent) 'it may be difficult to match the refractive index of the aromatic rubbery block copolymer resin (B) to provide the desired transparency. The tri-copolymer used in the present invention (A) The amount of each component can be controlled by the refractive index of the rubber copolymer compound described below. When the components of the compound have different optical refractive indices in order to obtain transparency, it is extremely important to adjust each of them. The refractive index of the copolymer is matched as closely as possible in the amount of the component. According to the present invention, good transparency can be obtained by using a tricopolymer of an aromatic vinyl compound, a vinyl nitride compound, and an unsaturated alkyl ester compound. The inventors of the present invention have surprisingly found that the use of the tri-copolymer to replace the conventional SAN resin makes it easier to compensate for the difference between the refractive index of the aromatic rubber-like block 12 200930758 copolymer and the resin. The difference can be compensated by controlling the composition of each component in the aromatic vinyl compound, the vinyl cyanide compound, and the unsaturated alkyl ester tri-copolymer compound. Aromatic vinyl compound-vinyl cyanide compound-unsaturated alkyl group The difference between the refractive index of the triester of the ester compound (A) and the aromatic rubbery block copolymer resin (B) can be adjusted to about 〇〇.〇〇8 or less, for example, about 0.004 or less, and In another embodiment, it is about 1 or less. The dicopolymer (A) may have a weight average molecular weight (Mw) of from about 140,000 to about 350,000, for example from about 200,000 to about 3 Torr. ). If the weight average molecular weight is less than about 140,000, good impact strength required by the present invention may not be obtained, and if the weight average molecular weight is more than about 350,000 ', the fluidity may be lowered. Percentage) about 1% of the tri-copolymer with good chemical resistance (in terms of weight in the manufacture of the tri-copolymer (A), it can be used per 1% (by heavy, organic and inorganic pigments, dyes, and The combination of 篁% meter) plus the addition of the sulphate antioxidant to improve fluidity, impact strength and other physical properties. The additive can be found (but secret) resistance _, thermal agent, anti-oxidation side, The light is determined to be innocent, the seven cities t,; η纭j office female "Γ心. υ ^ ^, inorganic fillers and their analogues,

具有良好耐化學性之三 之二共聚合物（Α)可按總樹脂以 200930758 /以至約8G%(以重量百分比計）、例如約35%至約70% 於約2!=比計）之量使用。若三共聚合物⑷之量小 兩之——(以重量百分比計），則可能難以獲得本發明所 ^ 度的耐化學性，且若三絲合物（A)之量大 需之衝擊^重量百分比計），則可能難以獲得本發明所 狀嵌段共聚物接f賠 ❹ 至纟ί!，明之芳族橡膠狀嵌段共聚物樹脂（Β)包含約10〇/〇 。（以重量百分比計）之橡膠狀聚合物與約50。/〇至 、’、' 以重量百分比計）之芳族乙烯基化合物。在一些 例不性實施例中，芳族橡膠狀嵌段共聚物樹脂包含約14% 至約40%(以重量百分比計）之橡膠組份與約6〇%至約85% (以重量百分比計）之絲乙稀基化合物。 橡膠狀聚合物可為基於共輛二烯之橡膠且可具有每 分子4-12個、例如4_8個碳原子。橡膠組份之實例包括（但 不限於）1,3-丁二烯、異戊二烯、2_甲基—1,3-丁二烯、2_ 乙基-1，3-丁二烯、2,3_二曱基_〗，3_丁二烯、i，3-戊二烯、3 _ 丁基-1,3-辛二烯以及其類似基團，以及其缉合。 用於芳族橡膠狀嵌段共聚物樹脂（B)中之橡膠狀聚 合物的量可為每100% (以重量百分比計）芳族橡膠狀嵌 段共聚物樹脂約1〇%至約5〇% (以重量盲分比計），例如 約15%至約35% (以重量百分比計）。當橡膠狀聚合物之 含量為約10%至約50% (以重量百分比計）時’有可能獲 得本發明所需之良好衝擊強度與透明度。 14 200930758 芳族乙烯基化合物之實例可包括（但不限於）笨 烯、α·曱基苯乙烯、2-甲基笨乙烯、3_甲基笨乙烯、 苯乙烯、2_乙基苯乙烯、3-乙基苯乙烯、4-乙基笨乙烯、 4-正丙基苯乙烯、4-第三丁基苯乙烯、卜乙烯基萘、孓乙 基萘以及其類似基團，且此等芳族乙烯基化合物可單 相互組合使用。The diterpene copolypolymer (Α) having good chemical resistance may be in the total resin at 200930758 / to about 8G% (in weight percent), for example, about 35% to about 70% in about 2! = ratio The amount is used. If the amount of the tri-copolymer (4) is small (in terms of weight percent), it may be difficult to obtain the chemical resistance of the present invention, and if the amount of the triple-filament (A) is large, the impact is required. In terms of percentage, it may be difficult to obtain the block copolymer of the present invention, and the aromatic rubbery block copolymer resin (Β) contains about 10 Å/〇. (by weight percent) of a rubbery polymer with about 50. /〇 to , ', 'by weight percent) of an aromatic vinyl compound. In some exemplary embodiments, the aromatic rubbery block copolymer resin comprises from about 14% to about 40% by weight of the rubber component and from about 6% to about 85% by weight percent ) a silky compound. The rubbery polymer may be a rubber based on a total of diene and may have 4 to 12, for example 4 to 8, carbon atoms per molecule. Examples of the rubber component include, but are not limited to, 1,3-butadiene, isoprene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2 , 3_dimercapto-_, 3-butadiene, i, 3-pentadiene, 3-butyl-1,3-octadiene and the like, and the like. The amount of the rubbery polymer used in the aromatic rubbery block copolymer resin (B) may be from about 1% to about 5% per 100% by weight of the aromatic rubbery block copolymer resin. % (by weight blind ratio), for example from about 15% to about 35% (in weight percent). When the content of the rubbery polymer is from about 10% to about 50% by weight, it is possible to obtain the good impact strength and transparency required by the present invention. 14 200930758 Examples of aromatic vinyl compounds may include, but are not limited to, olefin, α-mercapto styrene, 2-methyl styrene, 3-methyl styrene, styrene, 2-ethyl styrene, 3-ethylstyrene, 4-ethylidene ethylene, 4-n-propylstyrene, 4-tert-butylstyrene, vinylnaphthalene, anthranylnaphthalene, and the like, and such aromatic groups The group vinyl compounds can be used in combination with each other.

本發明之芳族橡膠狀嵌段共聚物樹脂（B)可選擇性 地包括（需要時）可與芳族乙烯基化合物共聚合之單體。 ^與芳族乙烯基化合物共聚合之單體可包括（但不限於） 氰化乙烯化合物、丙烯酸、甲基丙烯酸、順丁烯二酸酐、 N-取代之順丁烯二醯亞胺以及其類似物，以及其組合。 芳族橡膠狀嵌段共聚物樹脂可以錐形（橡膠 聚合物-不飽和單體）共聚物、線性共聚物、二敌段共^ (不飽和單體橡縣聚合物）或三紐絲物（不飽和 體-橡膠狀聚合物_讀和單體）以及其組合之形式製迭。 芳族橡膠狀嵌段共聚齡m (b)可藉由諸如活㈣ 合之f知方法來製造。用於本發明之芳族橡膠狀嵌 U物樹脂（B)包括可購自Daelim H&amp;L、KUmho =ch簡cal、Chevr〇n_phmips、Krat〇n 以及 a刷⑽之樹 曰 α舌^^橡、膠狀敗段共聚物樹脂⑻可以約2G%至約80% 計）之里旦H比t·)、例如約4〇%至約7〇% (以重量百分比 ?〇〇/〈、里去旦。右芳族橡膠狀嵌段共聚物樹脂之量小於約 0 里百分比計），則可能難以獲得本發明所需之一 15 200930758 定程度的抗衝擊性，且若装 大於約_ (以重f百八=橡膠狀嵌段共聚物樹脂之量 所需之良好耐化學性。㈣）’則可能難以獲得本發明 對於透明熱塑性椒 ASTM-D256對1/8,4樣所旦曰而言，於23t下根據 為約】〇公斤力.公分/公分之伊佐德氏衝擊強度可 旦…以 刀A刀或更大；根據ASTMD_1238所 里測到之雜流動速率（MFR)(22(rc，心斤）可為約The aromatic rubber-like block copolymer resin (B) of the present invention may optionally include, if necessary, a monomer copolymerizable with the aromatic vinyl compound. The monomer copolymerized with the aromatic vinyl compound may include, but is not limited to, a vinyl cyanide compound, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like. Things, and combinations thereof. The aromatic rubbery block copolymer resin may be a tapered (rubber polymer-unsaturated monomer) copolymer, a linear copolymer, a disulfide group (unsaturated monomer rubber polymer) or a triplex material ( The formation of the unsaturated body-rubbery polymer_read and monomer) and combinations thereof. The aromatic rubber-like block copolymerization age m (b) can be produced by a method such as living (four). The aromatic rubber-like embedded resin (B) used in the present invention includes a tree 曰α tongue ^^ rubber which is commercially available from Daelim H&amp;L, KUmho=ch Jane cal, Chevr〇n_phmips, Krat〇n, and a brush (10). The colloidal segment copolymer resin (8) may be from about 2G% to about 80% by weight of the base H to t·), for example from about 4% to about 7% by weight (in weight percent? 〇〇/<, Once the amount of the right aromatic rubbery block copolymer resin is less than about 0 percent, it may be difficult to obtain the impact resistance of one of the requirements of the present invention 15 200930758, and if the loading is greater than about _ (by weight) f hundred eight = good chemical resistance required for the amount of rubbery block copolymer resin. (d)) 'It may be difficult to obtain the present invention for transparent thermoplastic pepper ASTM-D256 for 1/8, 4 sample, At 23t, the Izod impact strength can be as high as 〇 力 力 公 公 公 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米 厘米Jin) can be about

45公克/10分鐘或更大；使用NiPpon Densh〇ku蜀度計對3 毫米厚試樣所量測到之濁度可為約2.5或更小；透明度可 為約88%或更大；重量增加可為約1()%或更小且拉伸強度 變化可為約80%或更小，其是根據A· D_543 (浸沒測 試）在將試樣浸沒於曱醇中7天後所量測；重量增加可為 約5%或更小且拉伸強度變化可為約4〇%或更小，其是根 據ASTM D-543 (浸沒測試）在將試樣浸沒於乙醇中7天 後所量測；以及重量增加可為約15q/g或更小且拉伸強度變 化可為約45%或更小，其是根據ASTMD-543 (浸沒測試） 在將試樣浸沒於汽油中7天後所量測。 在本發明之例示性實施例中，對於透明熱塑性樹脂而 言’於23°C下根據ASTM-D256對1/8&quot;試樣所量測到之伊 佐德氏衝擊強度可為約10公斤力.公分/公分至約5〇公斤 力.公分/公分；根據ASTM D-1238所量測到之炫體流動速 率（MFR)(220t：，10公斤）可為約45公克/10分鐘至約 65公克/10分鐘；使用Nippon Denshoku濁度計對3毫米 厚試樣所量測到之濁度可為約1.0至約2.3 ;透明度可為約 16 200930758 88%至約95%;重量增加可為約3%至約10〇/。且拉伸強度變 化可為約20°/。至約80%，其是根據ASTM D_543 (浸沒測 试）在將試樣浸沒於曱醇中7天後所量測；重量增加可為 約1%至約5%且拉伸強度變化可為約15%至約4〇%，其是 根據ASTM D-543 (浸沒測試）在將試樣浸沒於乙醇中7 天後所量測；以及重量增加可為約5%至約15%且拉伸強 度變化可為約25至約43%，其是根據ASTM d_543 (浸沒 測試）在將試樣浸沒於汽油中7天後所量測。 根據本發明之另-悲樣，提供一種製造透明執塑性樹 紅方法。所述方法包含縣捏合（A)芳族⑽基氮化 =不，和絲紅絲合物與（B)芳族_狀紐共 物树脂。 在本發明之例示性實施例中，所述方法包含製造具有 約10%至約50% (以重量百分比計）之橡膠 ❹45 g/10 min or more; the turbidity measured on a 3 mm thick sample using a NiPpon Densh〇ku oximeter may be about 2.5 or less; the transparency may be about 88% or more; weight increase It may be about 1 (%) or less and the tensile strength change may be about 80% or less, which is measured after immersing the sample in sterol for 7 days according to A·D_543 (immersion test); The weight gain may be about 5% or less and the tensile strength change may be about 4% or less, which is measured after immersing the sample in ethanol for 7 days according to ASTM D-543 (Immersion Test). And the weight increase may be about 15q/g or less and the tensile strength change may be about 45% or less, which is according to ASTM D-543 (immersion test) after immersing the sample in gasoline for 7 days. Measurement. In an exemplary embodiment of the present invention, for a transparent thermoplastic resin, the Izod impact strength measured at 1/8&quot; according to ASTM-D256 at 23 ° C may be about 10 kg. Centimeters/cm to approximately 5〇Kg. centimeters/cm; the glare flow rate (MFR) (220t:, 10kg) measured according to ASTM D-1238 can range from approximately 45g/10min to approximately 65g /10 minutes; the turbidity measured on a 3 mm thick sample using a Nippon Denshoku turbidity meter may be from about 1.0 to about 2.3; the transparency may be from about 16 200930758 88% to about 95%; the weight increase may be about 3 % to about 10 〇 /. And the tensile strength change can be about 20 ° /. Up to about 80%, measured according to ASTM D_543 (Immersion Test) after immersing the sample in sterol for 7 days; weight gain may be from about 1% to about 5% and tensile strength change may be about 15% to about 4% by weight, measured according to ASTM D-543 (Immersion Test) after immersing the sample in ethanol for 7 days; and weight gain may be from about 5% to about 15% and tensile strength The change can range from about 25 to about 43%, which is measured after immersing the sample in gasoline for 7 days according to ASTM d_543 (immersion test). According to another embodiment of the present invention, a method of manufacturing a transparent plastic tree is provided. The method comprises county kneading (A) aromatic (10)-based nitridation = no, and silk red silk compound and (B) aromatic _-shaped neo-copolymer. In an exemplary embodiment of the invention, the method comprises making from about 10% to about 50% (by weight percent) of rubber ❹

聚物樹脂，藉由聚合芳族乙_二二“ 乙烯化δ物以及不飽和烷基酯化合 140,000至約350,000之重量平 衣&quot;―、U 所u二，、聚合物與所料雜·嵌段妓 卿咖鳩翻綱乙 2基-威乙烯残和料§|三料合物混合並溶融擠 在本發明之例示性實施例中，可 重量百分輯）之芳麵雜歧絲物 17 200930758 80% (以重量百分比計）之芳族乙稀基-戴化 基酯三共聚合物混合並熔融擠壓。 ^和烷 芳=橡膠狀毅共聚物樹脂與芳族乙絲. =二共聚合物之適用化合物的特定組份：實 在? 界面活性劑、成核劑、偶合劑、i充;枓劑、 改質劑、混雜劑、著色劑、充士增塑劑、抗衝擊 顏料、防火劑:及劑，^ 擊強度，且n之透明熱塑性樹月旨維持高流動性與衝 於时好=耐化學性與透明度以致其充分適合 物品1=1:可能需要透明度以及耐化學性之模製 ❹ 設備以外部部件與用於汽車、玩具、衛生 及其類似物之精密部件。 音欲藉由參考下財例錢好_解，所述實例 的且不理解為以任何方式限制本文所附 申關巾職叙本發明的範嘴。 聚（甲基丙稀酸曱醋_丙烯重量α平均分子量（Mw)的 合時間為4小時之日本2乙烯單體)共聚物’其藉由聚 本體连π衣程，且藉由將曱基丙烯酸甲 18 200930758 酯之含量調整至22.8%並將苯乙烯單體之含量調整至 74.2°/〇以便獲得I.5655之折射率以及3。/。（以重旦百八 計）之丙烯腈來製造。 里刀比 (a2)使用具有202，·之重量平均分子量（Mw 聚(甲基丙稀酸曱醋-丙稀笨乙稀單體)共聚物，里藉: 合時間為4小時之本體連續製程’且藉由將甲基 酯之含量調整至21.3。/。並將苯乙烯單體之含量調整 ❹ ❹ 73.7%以便獲得1.5655之折射率以及5% (以重量百= 計）之丙烯腈來製造。 I β tb (B)芳族橡膠狀嵌段共聚物~^ 使用由Che—Phillips Co.製造、具有3〇% (以重旦 百分比計）之丁二烯以及1.5655之折射率的笨乙稀_丁 = 烯嵌段共聚物樹脂（KK-38級）。 一 (.C)基於苯乙烯之共聚物檄脂 (cl)使用聚合時間為4小時之本體連續製程製 具有212,000公克/莫耳之重量平均分子量以及】％ 射率的聚笨乙烯聚合物。 n (c2)使用具有2〇5,〇〇〇之重量平均分子量以 :5:之 1?率的聚(甲基丙烯酸甲醋-苯乙烯單體)共 小物其藉由聚合時間為4小時之本體連續製程製造。 實例1-6 、 。將如表1中所示之組份添加至習知混合器中，且於220 ^之溫度下經由雙螺桿擠壓機（L/D=29，（D=45mm)擠壓 此合物以製造呈雜形式之絲。接著將所賴粒於80t： 19 200930758 乾燥3小時且於18〇-28(TC下使用6盎斯射出成形機以 40-80°C之模製溫度模製成試樣以評估其性質。 比較實例1-9 將如表1中所示之組份添加至習知混合器中，且藉由 與上述實例相同之方法製造顆粒以及試樣以獲得性質。 表1 (Α)三 物 -共聚合 (B)橡膠狀 山 d t 1 ·〇 一 * . (cl ) 聚苯乙烯 (c2) MMA-SMco- 聚合物 al — a2 甘欠丰又共聚物 1 50 - 50 參 2 55 - 45 • 實例 3 4 60 —·_ · 40 亀 50 50 输 〜55 45 嫌 t) - 60 40 丄 - 一 ~ 50 50 _ 2 45 55 3 —_ 40 60 比較 4 c 一 麵 「50 50 實例 6 η ~~ ， 45 55 ~~—~ 40 60 / Q 1 π7Γ^~ 一 100 _ Ο 9 1UU 100 - - - m (1)伊佐德氏衝擊強度：於下根據ASTMD256 對=試樣量測凹口伊佐德氏衝擊強/公分）。 旦（2 )抓動性（熔體流動指數：):根據 里'貝&quot;1L動性（公克/10分鐘，10公斤，220°C )。 (丄3 )濁度-使用 Nippon Denshoku 濁度計（NDH 2000 ) '皆3宅米厚試樣量測濁度。 20 200930758 (4)透明度.使用Nippon Denshoku濁度計（NDH 2000)對3毫米厚試樣量測透明度。 物理·性貝之結果在以下表2中展示。 表2Polymer resin, by polymerizing aromatic B-dioxin "ethylated δ" and unsaturated alkyl esters to form a weight of 140,000 to about 350,000 jersey, "," U, the polymer and the impurities Block 妓 鸠 鸠 乙 2 2 2 2 2 2 2 § 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三17 200930758 80% (by weight percent) of aromatic vinyl-terminated triesters mixed and melt extruded. ^ and alkane = rubbery copolymer resin and aromatic ethyl wire. Specific components of the applicable compound of the polymer: actual? Surfactant, nucleating agent, coupling agent, i charge; tincture, modifier, mixture, colorant, plasticizer, impact paint, fire protection Agent: and agent, ^ impact strength, and n transparent thermoplastic tree to maintain high fluidity and good time = chemical resistance and transparency so that it is fully suitable for articles 1 = 1: may require transparency and chemical resistance The equipment is made up of external parts and precision parts for cars, toys, hygiene and the like. The sound of the vocabulary is to be understood by reference to the following example, and the example is not to be construed as limiting the scope of the invention in any way. Poly(methyl acrylate vinegar _ The propylene weight α average molecular weight (Mw) is 4 hours of the Japanese 2 ethylene monomer) copolymer 'by the bulk of the π coating process, and by adjusting the content of the thiol methacrylate 18 200930758 ester to 22.8 % and the content of styrene monomer is adjusted to 74.2 ° / 〇 in order to obtain the refractive index of I.5655 and 3% (by weight) of acrylonitrile. The inner knife ratio (a2) has 202, · Weight average molecular weight (Mw poly(methyl acrylate vinegar - propylene vinyl monomer) copolymer, borrowed: 4 hours of bulk continuous process ' and by methyl ester The content was adjusted to 21.3%, and the content of the styrene monomer was adjusted to ❹ 73.7% in order to obtain a refractive index of 1.5655 and 5% (by weight) of acrylonitrile. I β tb (B) Fang Group rubber block copolymer ~^ used by Che-Phillips Co., with 3〇% (in percent of denier) a diene and a refractive index of 1.5655 stupid ethylene-butadiene block copolymer resin (KK-38 grade). One (.C) styrene-based copolymer resin (cl) using a polymerization time of 4 hours The bulk continuous process produces a polystyrene polymer having a weight average molecular weight of 212,000 g/mole and a [%] rate. n (c2) uses a weight average molecular weight of 2〇5, 〇〇〇: 5:1? The rate of poly(methyl methacrylate-styrene monomer) co-work was produced by a bulk continuous process with a polymerization time of 4 hours. Examples 1-6, . The components as shown in Table 1 were added to a conventional mixer, and the mixture was extruded through a twin-screw extruder (L/D = 29, (D = 45 mm) at a temperature of 220 °. The yarn is in the form of a mixture. The granules are then dried at 80t: 19 200930758 for 3 hours and molded at a molding temperature of 40-80 ° C using a 6 oz injection molding machine at 18 〇 28 (TC). To evaluate the properties thereof. Comparative Examples 1 to 9 The components as shown in Table 1 were added to a conventional mixer, and pellets and samples were produced by the same method as the above examples to obtain properties. Tri-copolymerization (B) rubbery mountain dt 1 ·〇一* . (cl ) polystyrene (c2) MMA-SMco- polymer al — a2 tributary copolymer 1 50 - 50 gin 2 55 - 45 • Example 3 4 60 —·_ · 40 亀50 50 Loss~55 45 Suppose t) - 60 40 丄- One ~ 50 50 _ 2 45 55 3 —_ 40 60 Compare 4 c One side “50 50 Example 6 η ~~ , 45 55 ~~-~ 40 60 / Q 1 π7Γ^~ A 100 _ Ο 9 1UU 100 - - - m (1) Izod impact strength: under ASTM D256 pair = sample Measuring notch Izod impact / cm). (2) Grip (melt flow index:): According to the 'Bei' &quot; 1L dynamic (g / 10 min, 10 kg, 220 ° C). (丄3) Turbidity - Use Nippon Denshoku Turbidity Meter (NDH 2000) 'Measure the turbidity for all 3 house meters thick samples. 20 200930758 (4) Transparency. Use Nippon Denshoku Turbidity Meter (NDH 2000) for 3 mm Thick samples were measured for transparency. The results of physical and sexual properties are shown in Table 2 below.

如表2中所示’即時使用相同量之橡膠共聚物樹脂， ❹ 當使用三共聚合物翻旨時，可製造出與不制三共聚合物 之實例相，，良衝擊強度且亦顯示衝擊強度_生 之各方面協5周性貝的材料〇另々k /5 ώ !用作組份之不同聚合物樹脂之折二二彌 件。 在兵來獲 對·耐化學性之測詁 使用實例⑷X及比較實例卜6中財 二對在表3情述之化學_巾之 :7樣進 餘水、甲醇(一，9%)、乙醇(一^ 2] 200930758 =油（GSCaltex，“Kixx”無鉛汽油）、清潔齊 Tn〇)以及橄欖油（CJ，100%撖欖油）用作化學試劑。 ❹ =樣浸沒於上軌學試射糾7天且接著錢 =(浸沒賴）量啦量增加以及拉伸财變化。 ^性ί測試結果在以下表3中展示，且相_在圖2以 及圖3中展不。圖2展示在化學試射之重量增加，且 顯不在化學試财之拉伸強錢化。在目2及圖 根據化學f舖之各餘财自纟絲 比較實例1-6之結果。 曰⑽i 6以及 表3As shown in Table 2, 'the same amount of rubber copolymer resin is used immediately, ❹ When using a tri-copolymer, an example phase with and without tri-copolymer can be produced, good impact strength and also shows impact strength _ In all aspects of life, the materials of the 5-week shell are 々k /5 ώ ! In the case of the soldier's test of chemical resistance, use examples (4) X and comparative examples, and the second paragraph of the chemical analysis of the chemical in the table 3: 7 samples of residual water, methanol (1, 9%), ethanol (1^2] 200930758 = Oil (GSCaltex, "Kixx" unleaded gasoline), clean Tn〇) and olive oil (CJ, 100% eucalyptus oil) used as a chemical reagent. ❹ = immersed in the upper track test and corrected for 7 days and then the money = (immersion) amount increased and stretched financial changes. The results of the ί ί test are shown in Table 3 below, and the phase _ is shown in Figure 2 and Figure 3. Figure 2 shows the increase in the weight of the chemical test, and it is not in the chemical test. In the head 2 and the figure, according to the chemical f shop, the balance of the results of Examples 1-6.曰(10)i 6 and Table 3

如表3以及圖i與圖2中所示，可見使^ ^As shown in Table 3 and Figure i and Figure 2, it can be seen that ^ ^

=製造出之試樣與知其他聚合物樹脂製造 比展現改㈣耐化學性。尤其 2；式樣4 造出之試樣相比，針對諸4 /、他聚s物樹脂| 了每如醇類、油類 ^= The manufactured sample is known to be modified (4) chemical resistance. In particular 2; compared with the sample made by the model 4, for the 4 /, he poly s resin | for every alcohol, oil ^

試劑的财化學性得到改良。 、 /、釗之化S _共連_續相鐘構之笔I 對於實例4-6中所劁、皮b , 顯微鏡（TEM)在放大^ ^樣而言’藉由透射電: °數30,〇〇〇下鑑別共連續相結 22 200930758 實例4-6之試樣的TEM表面圖像在圖4(a)、圖4(b)以 及圖4 (c)中展示。比較實例4-6之試樣的TEM表面圖 像在圖5 (a)、圖5 (b)以及圖5 (c)中展示。所有實例 4-6以及比較實例4-6均包括包含芳族橡膠狀嵌段共聚物 樹脂之橡膠相且具有共連縯結構。然而，如表2以及3中 所示，除衝擊強度以及流動性外’比較實例中之樹脂The chemical properties of the reagents have been improved. , /, 钊化化 S _ _ _ continuous phase clock pen I For the example 4-6, 皮, skin b, microscope (TEM) in the magnification ^ ^ sample 'by transmission: ° 30 Subgingival identification of co-continuous phase junctions 22 200930758 The TEM surface images of the samples of Examples 4-6 are shown in Figures 4(a), 4(b) and 4(c). The TEM surface images of the samples of Comparative Examples 4-6 are shown in Figures 5(a), 5(b) and 5(c). All of Examples 4 to 6 and Comparative Examples 4 to 6 each included a rubber phase containing an aromatic rubbery block copolymer resin and had a co-intercalation structure. However, as shown in Tables 2 and 3, in addition to impact strength and fluidity, the resin in the comparative example

相因為未使用二共^^合物而展現顯著退化的透明度以及耐 化學性。 圖6是在放大倍數30,000下展示使用透明的ABS樹 脂（產品名稱：UT0100，Korea 之 Jeil industrial c〇，Ltd.) 製造出之試樣表面的TEM圖像。如圖6中所示，習知透 明的ABS樹月旨並不具有共連續結構。事實上，樹脂相具有 連續相結構且橡膠相具有分散相結構。 具有以上描述中所呈現之教示的㈣之^^本發明 所屬技術者將想起本㈣之許多修⑽及其他實施例。因 =應，解本㈣並祕於·露之較實施取修改以 欲包括在附加申請專利範圍之㈣内。儘 =用於關之目的，本_之㈣料料郷 【圖式簡單說明】 圖1說明根據本發明夕.,_ .. _ 結構的透明熱塑性樹脂从—例讀實施例之形成共連續 圖2是說明根據用於實例W以及比較實例卜6之化 200930758 予试劑之重量變化的圖。 凤」3疋明根於實例卜6以及比較實例1-6之化 予试劑之拉伸強度變化的圖。 圖4 “）、圖4(b)以及圖4(c)是實例4、5以及 6所衣4出之試樣的透射電子顯微鏡（TEM)圖像。 圖5 (a)、圖5 (b)以及圖5 (c)是比較實例4、5 以及6中所製造出之試樣的TEM圖像。 ❹ 圖6是透明的ABS樹脂之TEM圖像。 【主要元件符號說明】 »、、、 ❹ 24Significantly degraded transparency and chemical resistance are exhibited because the two complexes are not used. Fig. 6 is a TEM image showing the surface of a sample produced using a transparent ABS resin (product name: UT0100, Jeil industrial c〇, Ltd. of Korea) at a magnification of 30,000. As shown in Fig. 6, the conventional transparent ABS tree does not have a co-continuous structure. In fact, the resin phase has a continuous phase structure and the rubber phase has a dispersed phase structure. The present invention having the teachings presented in the above description will recognize many of the modifications (10) and other embodiments of the present invention. Because = should, the solution (4) and the secret of the dew is better than the implementation of the modification to be included in the scope of the additional patent application (4). ____________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________ 2 is a graph illustrating the change in weight of the reagent according to Example W and Comparative Example 200930758. Fig. 3 is a diagram showing the change in tensile strength of the reagents in the example of Example 6 and Comparative Examples 1-6. Figure 4 "), Figure 4 (b) and Figure 4 (c) are transmission electron microscope (TEM) images of the samples of Examples 4, 5 and 6. Figure 5 (a), Figure 5 (b) Fig. 5(c) is a TEM image of the sample produced in Comparative Examples 4, 5, and 6. ❹ Fig. 6 is a TEM image of a transparent ABS resin. [Explanation of main component symbols] », ,, ❹ 24

Claims (1)

200930758 七、申請專利範圍： 1. 一種透明熱塑性樹脂，其包含： 一橡膠相，其包括芳族橡膠狀嵌段共聚物樹脂；以及 一樹脂相，其包括包含芳族乙烯基化合物、氰化乙烯 化合物以及不飽和烷基酯化合物之三共聚合物， 其中’該橡膠相以及該樹腊相具有共連續相結構。 2. 如申請專利範圍第丨項戶斤述之透明熱塑性樹脂，其 中該橡膠相之一部分以及該樹脂相之一部分形成不連續結 構0 3. 如申請專利範圍第1項所述之透明熱塑性樹脂，其 包含實質上含量為以重量百分比計至80%的該橡膠相 以及實質上含量為以重量百分比計20%至80%的該樹脂 相。 4. 如申請專利範圍第1頊所述之透明熱塑性樹脂，其 中所述三共聚合物包含以重量百分比計50%至95%之芳族 乙烯基化合物、以重量百分比計0.1%至30%之氰化乙烯化 合物以及以重量百分比計Oj%至45%之不飽和烷基酯化 合物。 5. 如申請專利範圍第1項所述之透明熱塑性樹脂，其 中所述芳族橡膠狀嵌段共聚物樹脂包含以重量百分比計 10%至50°/❶之橡膠狀聚合物以及以重量百分比計5〇q/〇至 90%之方族乙稀基化合物。 6. 如申請專利範圍第1項所述之透明熱塑性樹脂，其 中所述二共聚合物與所述芳族橡膠狀嵌段共聚物樹脂之折 25 200930758 — — f 一— 射率之問的差異小於等於0.008。 7. 妒申凊專利範圍第1項所述之透明熱塑性樹脂，其 中所述彡共聚合物具有140,000至350,000之重量平均&amp; 子量。 刀 8. 妒申凊專利範圍第4項所述之透明熱塑性樹脂，其 中： 所述芳族乙烯基化合物包括苯乙烯、經C1_C8取代之 苯乙烯、乙烯基萘、乙烯基甲苯或其组合；所述氰化乙烯 ❹ 化合物包括丙烯腈、曱基丙烯腈、乙基丙稀腈或其組合. 且所述不飽和烷基酯化合物包括經C1-C12烷基取代之（曱 基）丙烯酸酯或其組合。 9. 如申請專利範圍第5項所述之透明熱塑性樹脂，其 中所述橡膠狀聚合物是基於二烯之橡朦。 10. 如申請專利範圍第1項所述之透明熱塑性樹脂，其 更包含一添加劑，其中該添加劑選自由下列各物所組成之 群組：阻燃劑、抗生素劑、釋放劑、熱穩定劑、抗氧化劑、 ❹ 光穩定劑、配伍劑、染料、無機填充劑、界面活性劑、成 核劑、偶合劑、填充劑、增塑劑、抗衝擊改質劑、混雜劑、 著色劑、穩定劑、潤滑劑、抗靜電劑、顏料、防火劑以及 其組合。 11. 一種透明熱塑性樹脂，其包含·· (A) —以重量百分比計20%至80%之三共聚合物，其 中該三共聚合物包含以重量百分比計5〇至95%之芳族乙 烯基化合物、以重量百分比計0.1%至3〇%之氰化乙烯化合 26 200930758 物以及以重量百分比計〇.1%至45%之不飽和燒基醋化合 物；以及 (B)—以重量百分比計2〇%至8〇%之芳族橡膠狀嵌段 共聚物樹脂，其中該芳族橡膠狀嵌段共聚物樹脂包含以重 量百分比計10 %至5 0 %之橡膠狀聚合物以及以重量;分比 計50%至90%之芳族乙烯基化合物， 其中’該透明熱塑性樹脂具有於23。(：下根據 ASTM-D256對1/8”試樣所量測到之1〇公斤力·公分/公分 或更大的伊佐德氏衝擊強度（IZO(j impact strength)，根據 ASTMD-1238所量測到之45公克/1()分鐘或更大的溶體流 動速率（melt flow rate，MFR) (220°C，10 公斤），使用 Nippon Denshoku濁度計對3毫米厚試樣所量測到之實質 上小於等於2.5的濁度以及大於等於88%的透明度，根據 ASTM D-543 (浸沒測試）在將試樣浸入曱醇中7天後戶斤 量測到之10%或更小的重量增加以及80%或更小的拉伸強 度變化，根據ASTM D-543 (浸沒測試）在將試樣浸入乙 Ο 醇中7天後所量測到之5%或更小的重量增加以及40%或 更小的拉伸強度變化，以及根據ASTMD-543 (浸沒測試） 在將試樣浸入汽油中7天後所量測到之15%或更小的重量 增加以及45%或更小的拉伸強度變化。 12.—種透明熱塑性樹脂的製造方法，所述方法包含： 製造具有以重量百分比計10%至50%之橡膠狀聚合物 的一芳族橡膠狀嵌段共聚物樹脂； 藉由聚合芳族乙烯基化合物、氰化乙烯化合物以及不 27 200930758 餘和烧絲化合物來製造—騎H0，_ i 35G,_之重 =分子量的芳族乙烤基·氰化乙烯-不飽和烷基醋的三 物，以付到具有〇._或更小之該三共聚合物與該 芳族橡膠狀嵌段共聚物樹脂之間的折射率差異；以及 將該芳族橡膠狀嵌段共聚物樹脂與該芳族乙稀基_氮 化乙稀-不飽和院基醋的三共聚合物混合並溶融擠壓。 13.如申請專利範圍第12項所述之透明熱塑性樹脂的 製^方法，其包含將以重量百分比計20%至80%之該芳族 橡膠狀嵌^又共聚物與以重量百分比計至之該芳族 乙晞基敦化乙埽_不飽和烧基酯的三共聚合物混合並炼融 擠壓。 14·如申凊專利範圍弟12項所述之透明熱塑性樹脂的 製造方法’其中該芳族乙烯基_氰化乙烯_不飽和烷基酯的 二共聚合物是藉由共聚合以重量百分比計50%至95%之一 芳族乙烯基化合物、以重量百分比計0.1%至30%之一氰化 乙稀化合物以及以重量百分比計0.1%至45%之一不飽和 ❹ 烧基酯化合物來製造。 28200930758 VII. Patent Application Range: 1. A transparent thermoplastic resin comprising: a rubber phase comprising an aromatic rubbery block copolymer resin; and a resin phase comprising an aromatic vinyl compound, vinyl cyanide a terpolymer of a compound and an unsaturated alkyl ester compound, wherein 'the rubber phase and the wax phase have a co-continuous phase structure. 2. A transparent thermoplastic resin according to the scope of the patent application, wherein one part of the rubber phase and a part of the resin phase form a discontinuous structure. 3. 3. The transparent thermoplastic resin according to claim 1 of the patent application, It comprises substantially the content of the rubber phase in an amount of up to 80% by weight and the resin phase in an amount of from 20% to 80% by weight. 4. The transparent thermoplastic resin according to claim 1, wherein the tri-copolymer comprises 50% to 95% by weight of an aromatic vinyl compound, and 0.1% to 30% by weight of cyanide. The ethylene compound and the Oj% to 45% unsaturated alkyl ester compound in weight percentage. 5. The transparent thermoplastic resin according to claim 1, wherein the aromatic rubbery block copolymer resin comprises 10% to 50% by weight of a rubbery polymer and is in weight percent 5〇q/〇 to 90% of the family of ethylenic compounds. 6. The transparent thermoplastic resin according to claim 1, wherein the difference between the dicopolymer and the aromatic rubbery block copolymer resin is 25, 2009, 758, y, f, y Less than or equal to 0.008. 7. The transparent thermoplastic resin according to claim 1, wherein the bismuth copolymer has a weight average &amp; quantity of from 140,000 to 350,000. The transparent thermoplastic resin according to claim 4, wherein: the aromatic vinyl compound comprises styrene, C1_C8 substituted styrene, vinyl naphthalene, vinyl toluene or a combination thereof; The vinyl cyanide compound includes acrylonitrile, mercapto acrylonitrile, ethyl acrylonitrile or a combination thereof. And the unsaturated alkyl ester compound includes a C1-C12 alkyl-substituted (mercapto) acrylate or combination. 9. The transparent thermoplastic resin according to claim 5, wherein the rubbery polymer is a diene-based rubber. 10. The transparent thermoplastic resin according to claim 1, further comprising an additive, wherein the additive is selected from the group consisting of a flame retardant, an antibiotic agent, a release agent, a heat stabilizer, Antioxidants, ray stabilizers, compatibility agents, dyes, inorganic fillers, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, hybrids, colorants, stabilizers, Lubricants, antistatic agents, pigments, fire retardants, and combinations thereof. A transparent thermoplastic resin comprising: (A) - 20% to 80% by weight of a tri-copolymer, wherein the tri-copolymer comprises from 5 to 95% by weight of an aromatic vinyl compound , from 0.1% to 3% by weight of the cyanide ethylene compound 26 200930758 and from 1% to 45% by weight of the unsaturated alkyl vinegar compound; and (B) - 2% by weight From 8% to 8% by weight of the aromatic rubbery block copolymer resin, wherein the aromatic rubbery block copolymer resin comprises from 10% to 50% by weight of the rubbery polymer and by weight; 50% to 90% of an aromatic vinyl compound, wherein 'the transparent thermoplastic resin has 23'. (: IZO (j impact strength) measured according to ASTM-D256 for 1/8" sample, 1 〇 kg force · cm / cm or more, according to ASTM D-1238 The melt flow rate (MFR) (220 ° C, 10 kg) was measured at 45 g / 1 () minutes or more, measured on a 3 mm thick sample using a Nippon Denshoku turbidimeter. The turbidity of substantially less than or equal to 2.5 and the transparency of 88% or more, according to ASTM D-543 (immersion test), the weight of 10% or less after 7 days of immersing the sample in sterol An increase and a change in tensile strength of 80% or less, a weight gain of 5% or less measured after 7 days of immersing the sample in acetol in accordance with ASTM D-543 (Immersion Test) and 40% Or less change in tensile strength, and a weight gain of 15% or less and a stretch of 45% or less after 7 days of immersing the sample in gasoline according to ASTM D-543 (immersion test) Change in strength 12. A method of producing a transparent thermoplastic resin, the method comprising: manufacturing having 10% to 50% by weight An aromatic rubbery block copolymer resin of a rubbery polymer; manufactured by polymerizing an aromatic vinyl compound, a vinyl cyanide compound, and a compound and a calcining compound - riding H0, _i 35G, _ a weight=molecular weight of an aromatic ethyl bake-vinyl cyanide-unsaturated alkyl vinegar for the addition of the tri-copolymer having 〇._ or less and the aromatic rubbery block copolymer resin a difference in refractive index; and mixing the aromatic rubbery block copolymer resin with the triethylene terpolymer of the aromatic vinylidene-ethylidene-unsaturated vinegar and melt-squeezing. The method for producing a transparent thermoplastic resin according to claim 12, which comprises, by weight percentage, 20% to 80% by weight of the aromatic rubber-like copolymer and the aromatic B in weight percentage三基敦化乙埽_Unsaturated alkyl ester of the tri-copolymer is mixed and smelted and extruded. 14. The method for producing a transparent thermoplastic resin as described in claim 12, wherein the aromatic vinyl-cyanide Diethylene polymer of ethylene-unsaturated alkyl ester By copolymerization, 50% to 95% by weight of one aromatic vinyl compound, 0.1% to 30% by weight of one of the cyanide compounds, and 0.1% to 45% by weight of one percent by weight Manufactured by saturating sulfonate ester compound.