200940334 六、發明說明· 【發明所屬之技術領域】 本發明係關於使用聚碳酸酯系樹脂作為主材料的樹脂片 材，適於真空成形和壓空成形等熱成形的成形用樹脂片材， 及將此成形用樹脂片材成形而成的成形體。 【先前技術】 聚碳酸酯系樹脂因為不止透明性優良、相較於玻璃不僅加 工性、耐衝擊性優良、且相較於其他塑膝材料亦不必擔心有 毒氣體之危害，故被廣泛使用於各式各樣的領域中，亦被使 用作為真空成形和壓空成形等的熱成形用材料。 但是，聚碳酸酯系樹脂一般因表面硬度低，故具有於聚碳 酸酯系樹脂所構成之成形品表面易造成損傷的問題點。於 是，習知提案有於聚碳酸酯系樹脂層的表面形成丙烯酸系樹 脂所構成的保護層，令製品表面不會受到損傷。 例如於專利文獻1中，提案有於聚碳酸酯系樹脂層的一 面，將厚度50〜120//m之丙烯酸系樹脂層藉由共擠出予以層 合作成總厚度0. 5〜1. 2mm的層合體。 又’於專利文獻2中，揭示有適合作為行動型資訊終端之 顯示窗保護板的耐擦傷性丙烯酸薄膜’其係對於含有使橡膠 粒子分散於甲基丙烯酸樹脂中之丙烯酸系樹脂層的丙烯酸 薄膜’施以硬塗處理而賦予耐擦傷性而成的耐擦傷性丙烯酸 薄膜。 098105231 4 200940334 [專利文獻1]日本專利特開2〇〇6_1〇3169號公報 [專利文獻2]日本專利特開2〇〇4 143365號公報 【發明内容】 (發明所欲解決之問題） 如上述，於聚碳酸酷系樹脂層之表面形成由丙烯酸系樹脂 所構成之保》蔓層的情形，一般而言，因為丙稀酸系樹脂比聚 碳酸醋系樹脂更難延#，故於熱成形時、尤其是深引伸成形 ❹時，於聚碳酸g旨系樹脂層與丙烯酸系樹脂層的界面發生制離 且表面白化，並發生裂痕。又，於熱成形前若未充分乾燥， 則亦發生發泡。 於是’本發明係提供於具備此種層合構造之成形用樹脂片 -材中，即使於熱成形時、尤其是深引伸成形時，亦不會產生 - 白化和裂痕、且不發生發泡之新穎的成形用樹脂片材、及將 其成形而成的成形體。 Ο (解決問題之手段） 本發明係提案一種成形用樹脂片材，其#於以含有芳香族 聚碳酸酯（A1)和其他樹脂（A2)之聚合物舍金的聚碳酸酯系 樹脂組成物（A)作為主成分的基材層的一面’具備以丙婦酸 • 系樹脂（B)作為主成分之被覆層的層合片讨’其特徵為該聚 ^ 碳酸酯系樹脂組成物（A)與該丙烯酸系樹脂（B)之玻璃轉移 溫度之差的絕對值為30°C以内。 本發明之成形用樹脂片材’因為具備以兩烯酸系樹脂（B) 098105231 5 200940334 作為主成分的被覆層，故具備難以對成形用樹脂片材的被覆 層表面、以及將該成形用樹脂片材成形而成的製品表面造成 損傷的特徵。 並且，將屬於基材層主成分之聚碳酸酯系樹脂組成物 (A) 、與屬於被覆層主成分之丙烯酸系樹脂（B)的玻璃轉移溫 度差（絕對值）設定於30。(：以内，藉此可在熱成形時、尤其 是深引伸成形時’不致產生白化和裂痕、或發泡。 因此，若使用本發明之成形用樹脂片材進行熱成形，則不 但可提供創作性優良的成形體，亦可提供例如創作性優良之 模塑成形體等。 另外，作為令聚碳酸酯系樹脂組成物（A)與丙烯酸系樹脂 (B) 之玻璃轉移溫度差（絕對值）為以内的方法，有存在 各式各樣方法的可能性，但本發明係由維持片材透明性等之 觀點而言，採用令芳香族聚碳酸酯（A1)與其他樹脂（A2)進行 聚合物合金化以降低玻璃轉移溫度，藉此使兩者之玻璃轉移 溫度差（絕對值）為30。(：以内的方法。 【實施方式】 其-入，說明本發明之實施形態之一例，但本發明並不限定 於下述實施形態。 本實施形態之成形用樹脂片材（以下稱為r本成形用樹脂 片材」），係於以含有芳香族聚碳酸酯（A1)和其他樹脂（A2) 之聚合物合金的聚碳酸酯系樹脂組成物（A)作為主成分的基 098105231 6 200940334 材層的一面’具備以丙稀酸系樹脂（B)作為主成分之被覆層 的層合片材，其特徵為，該聚碳酸酯系樹脂組成物（A)與該 丙烯酸系樹脂（B)之玻璃轉移溫度（Tg)差的絕對值為3〇。〇 以内，即0t>3(TC、較佳為0〜20°C、特佳為〇〜i(TC。 <基材層〉 ❹ 本成形用樹脂片材之基材層，係以含有芳香族聚碳酸酯 (A1)與其他樹脂（A2)之聚合物合金之聚碳酸酯系樹脂組成 物（A)作為主成分而形成。 [芳香族聚碳酸酯（A1)] 本成形用樹脂片材所狀芳香族聚碳_，若為具有芳香 環之聚碳_則無特別限定。可列舉例如，令芳香族二經基 化合物、或芳香族二祕化合物與少量之多祕化合物經 由與光氣的界面聚合法而取得，或者，藉由前述芳香族二經 =物與碳酸—S日之ga父換反應而得的熱可塑性聚碳酸 聚。物等。更具體而5，可列舉例如以雙紛A作為主原料 的碳酸酯聚合物。 务香族聚碳酸醋的分子量，甚发_p μ ^ 念為可藉通常的擠出成形製造 片材，則無特別限定，由溶液黏 ΓΜ _ 狀黏度所換算之黏度平均分子量 [Μν]為 15, 〇〇〇〜40, 000、特別以？ 2〇, 000〜35, 000、其中特別 以 22, 〇〇〇〜3〇, 〇〇〇 為佳。 另外，亦可混合黏度平均分子番τ π 卞垔不同之二種以上的芳香族 聚碳酸酯。 工刃方货秩 098105231 7 200940334 此處，所謂黏度平均分子量[MV] ’係指使用二氯甲烷作為 溶劑，並使用烏伯類德黏度計求取溫度20Ϊ下之極限黏度 [??](單位dl/g)，且由Schnell之黏度式，即，” =1. 23χ 10-4Μ0. 83所算出之值。極限黏度[π ]為測定各溶液濃度 [C](g/dl)之比黏度[β Sp]所算出之值。 又，芳香族聚碳酸酯之終端羥基濃度為1〇〇〇ppm以下、特 別以800卯m以下、其中特別以6〇〇ppm以下為佳下限值為 lOppm以上、特別為30ppm以上、其中特別以4〇ppm以上為 佳。 此處’上述之終端經基濃度為相對於芳香族聚碳酸酯之質 量，以ppm單位表示終端羥基的質量，例如可依由四氣化鈦 /醋酸法所進行之比色定量（Macrom〇1. Chem 88215〇965) 中記載之方法）予以測定。 [其他樹脂（A2)] 其他樹脂（A2)可與芳香族聚碳酸酯（A1)熔融摻合（；混合 且加熱熔融）並予以聚合物合金化，更再，若可令該聚合物 合金之玻璃轉移溫度（Tg)，比前述芳香族聚碳酸酯（A1)之玻 璃轉移溫度（Tg)更低者即可。 一般而έ，芳香族聚碳酸酯之玻螭轉移溫度口心為15〇t>c 附近，因為比丙烯酸系樹脂之玻璃轉移溫度（Tg)更高約5〇 °c’故令聚碳酸酯系樹脂組成物（人）與丙烯酸系樹脂（B)之玻 璃轉移溫度（Tg)之差（絕對值）為30¾以内時，重要的是將 098105231 8 200940334 芳香族聚碳酸酯（A1)與其他樹脂（A2)予以聚人物入 令該聚合物合金的玻璃轉移溫度（Tg)成為更低溫ς金化’ 可 由此種觀點而言，作為其他樹脂（Α2)，以 佳。於是，接著說明芳香族聚酯。 、聚S曰為 (芳香族聚酯） 使用作為其他樹脂（Α2)的芳香族聚酯，可列舉例如，使「芳 香族一叛酸成为」與「一醇成分」縮聚合而成的樹脂。 ❹ 此處，上述之「芳香族二羧酸成分」之代表者可列舉對苯 二酸、間苯二酸、萘二羧酸等。對苯二酸之一部分亦可經「其 他之二羧酸成分」所取代。 作為「其他之二羧酸成分」可列舉草酸、丙二酸、琥珀酸、 * 己二酸、壬二酸、癸二酸、新戊酸、間苯二酸、萘二羧酸、 二苯醚二羧酸、對-羥基苯甲酸等。其可為一種或二種以上 之混合物，又，所取代之其他二羧酸的份量亦可適當選擇。 ❹ 作為上述「二醇成分」之代表者可列舉乙二醇、二乙二醇、 三乙二醇、環己烷二甲醇等。乙二醇之一部分亦可經「其他 之二醇成分」所取代。 作為「其他之二醇成分」可列舉丙二醇、三亞甲基二醇、 . 丁二醇、己二醇、二乙二醇、新戊二醇、聚伸烷基二元醇、 1，4-環己烷二f醇、甘油、季戊四醇、三羥曱基、甲氧基聚 伸烷基二元醇等。其可為一種或二種以上之混合物，又，所 取代之其他二酵的份量亦可適當選擇。 098105231 9 200940334 作為「芳香族聚醋」之具體例可列舉令對苯二酸與乙 縮聚合的聚對本Hn對苯二酸 醋與α丁二醇縮聚合的聚對笨二甲酸丁二㈣:又勺甲 含對苯H外之其他二賴成分及/或乙二 = 二== 聚合聚ss」亦可列舉作為較佳的芳香族聚: 其中較佳例可列舉具有使聚對苯二甲酸乙二酯中—部八 之乙二醉、較佳為55,莫耳％經環己烧二甲醇取代之構二 的共聚合Μ日’或’具有使聚對笨二甲酸丁二醋中―部分之 料讀、較佳為Π)，莫耳％_苯二酸取代之構造的共 聚合聚酯，或此等共聚合聚酯的混合物。 於上述說明之芳香族聚酉旨中，較佳係選擇藉由與芳香族聚 碳酸醋⑹熔融摻合而聚合物合金化，且該聚合物合金 璃轉移溫度⑽可較該芳香族聚碳酸g旨⑼充分降低者。 由此種觀點而言，最佳例係具有使聚對苯二甲酸乙二听 (PET)之二醇成分的乙二醇之5〇 75莫耳%，經l 環己俨 二甲醇U’4-_〇取代之構造的共聚合聚醋（所； MTG」）’或具有絲對苯二ψ酸丁二自旨卿）之—部分的 對苯二酸、較佳為1G〜3Q莫耳％_笨二酸取代之構造的共 聚合聚醋，或其混合物。此等絲合聚_藉_芳香族^ 碳酸輯融摻合，完全相溶且聚合物合金化，並且可有效降 低玻璃轉移溫度。 另外，聚合物摻合物（混合的樹脂組合物）是否變成聚合物 098105231 200940334 合金，換§之，疋否完全相溶，係例如根據差示掃描熱量測 定以加熱速度1(TC/分鐘所測得之玻璃轉移溫度是否為單 一，而可加以判斷。此處，所謂混合樹脂組成物之玻璃轉移 - 溫度為單一，係指將混合樹脂組成物根據JISK7121，以加 熱速度10°C/分鐘，使用差示掃描熱量計測定玻璃轉移溫度 時’表不玻璃轉移溫度的波峯僅出現1個。 又’亦可由將前述混合樹脂組成物，以應變〇· 、頻率 ❿1〇Hz藉動態黏彈性測定（JISK-7198A法之動態黏彈性測定） 進行測定時，損失正切（tan占）的極大值是否存在i個而加 以判斷。 若聚合物摻合物（混合樹脂組成物）為完全相溶（聚合物合 * 金化），則被摻合的成分呈彼此以奈米等級（分子程度）相溶 的狀態。 另外，作為聚合物合金化的手段，採用下述手段：可使用 ❹相溶化劑、或令其進行二級性分段聚合和接枝聚合、或者令 一者聚合物以籟狀分散。 [混合比率] 方香族聚碳酸酯（A1)與芳香族聚酯（A2)的混合比率，若為 可將忍合所知之聚碳酸醋系樹脂組成物⑴與丙婦酸系樹脂 • (B)的玻璃轉移溫度（Tg)差（絕對值）成為 3〇°C以内之比 率1 特別限制，但由維持透明性的觀點而言，以比 千吞t A1 : Λ 0:80〜75:25為佳’特別以αι·α2 = 098105231 200940334 30:70”，其中特m1:A2==45:55〜55:45 為佳。 〈被覆層〉 本熱成形用樹脂片材的被覆層可由以丙稀酸系樹脂⑻作 為主成分的樹脂組成物所形成。 [丙烯酸系樹脂（B)] 本熱成形用樹脂片材所用的丙稀酸系樹脂，若為具有丙稀 基之樹脂職特職制。可列舉例如，？基糾酸甲醋、與 丙烯酸甲酯或丙烯酸乙酯的共聚合物。其中，亦以主成分為 由曱基丙烯酸甲酯所聚合之曱基丙烯酸甲酯樹脂（亦稱為 PMMA :聚（甲基）丙稀酸甲醋）為佳。 丙烯酸系樹脂的共聚合組成較佳係根據製造條件、例如共 擠出條件而適當選擇為佳。例如，於曱基丙烯酸曱酯、與丙 烯酸曱酯或丙烯酸乙酯之共聚合物的情形，以曱基丙烯酸曱 酯··丙烯酸甲酯或乙酯= 80:204 :99的莫耳比為佳。 又，在可進行擠出成形的範圍中亦可含有交聯成分。 丙烯酸系樹脂的分子量，一般以重量平均分子量計為3 萬〜30萬，但並不限於此範圍。[Technical Field] The present invention relates to a resin sheet using a polycarbonate resin as a main material, and a resin sheet for molding which is suitable for hot forming such as vacuum forming and pressure forming, and A molded body obtained by molding the molding resin sheet. [Prior Art] Polycarbonate-based resins are widely used in various applications because they are not only excellent in transparency, but also excellent in workability and impact resistance compared to glass, and they do not have to worry about toxic gases compared with other plastic knee materials. In various fields, it is also used as a material for thermoforming such as vacuum forming and pressure forming. However, since the polycarbonate resin generally has a low surface hardness, it has a problem that the surface of the molded article composed of the polycarbonate resin is liable to be damaged. Therefore, it has been conventionally proposed to form a protective layer made of an acrylic resin on the surface of the polycarbonate resin layer so that the surface of the product is not damaged. 5〜1. 2mm 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Laminate. Further, Patent Document 2 discloses a scratch-resistant acrylic film which is suitable as a display window protection sheet for an action type information terminal, which is an acrylic film containing an acrylic resin layer in which rubber particles are dispersed in a methacrylic resin. A scratch-resistant acrylic film which is subjected to a hard coating treatment to impart scratch resistance. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. No. Hei. No. Hei. In the case where a vine layer composed of an acrylic resin is formed on the surface of the polycarbonate resin layer, in general, since the acrylic resin is more difficult to extend than the polycarbonate resin, it is thermoformed. In the case of the deep drawing, in particular, the interface between the polycarbonate resin layer and the acrylic resin layer is separated and the surface is whitened and cracked. Further, if it is not sufficiently dried before thermoforming, foaming also occurs. Therefore, the present invention provides a resin sheet for molding having such a laminated structure, and does not cause whitening and cracking, and does not cause foaming even during hot forming, especially deep drawing. A novel resin sheet for molding and a molded body obtained by molding the same. Ο (Means for Solving the Problem) The present invention proposes a resin sheet for molding, which is a polycarbonate resin composition containing a polymer containing an aromatic polycarbonate (A1) and another resin (A2). (A) A laminated sheet having a coating layer containing a propylene glycol resin (B) as a main component on one surface of the base material layer as a main component, which is characterized in that the polycarbonate resin composition (A) The absolute value of the difference from the glass transition temperature of the acrylic resin (B) is within 30 °C. Since the resin sheet for molding of the present invention includes a coating layer containing a bisenoic acid-based resin (B) 098105231 5 200940334 as a main component, it is difficult to form a coating layer on the resin sheet for molding, and the molding resin. The surface of the sheet formed by the sheet is damaged. In addition, the glass transition temperature difference (absolute value) of the polycarbonate resin composition (A) which is a main component of the base material layer and the acrylic resin (B) which is a main component of the coating layer is set to 30. (Inside, it is possible to prevent whitening, cracking, or foaming during hot forming, especially deep drawing. Therefore, if the molding resin sheet of the present invention is used for thermoforming, it is not only possible to provide creation. For the molded article having excellent properties, for example, a molded article having excellent flexibility can be provided. Further, as a glass transition temperature difference (absolute value) between the polycarbonate resin composition (A) and the acrylic resin (B) Although there is a possibility that various methods exist, the present invention employs polymerization of an aromatic polycarbonate (A1) and another resin (A2) from the viewpoint of maintaining transparency of the sheet and the like. The alloy is alloyed to lower the glass transition temperature, whereby the glass transition temperature difference (absolute value) of the two is 30. (Embodiment) [Embodiment] An example of an embodiment of the present invention is described. The present invention is not limited to the following embodiments. The resin sheet for molding of the present embodiment (hereinafter referred to as a resin sheet for forming a r-form) is made of an aromatic polycarbonate (A1) and other resins. A2) Polycarbonate-based resin composition (A) of a polymer alloy as a main component 098105231 6 200940334 A laminated sheet having a coating layer containing a acrylic resin (B) as a main component The material is characterized in that the absolute value of the difference between the glass transition temperature (Tg) of the polycarbonate resin composition (A) and the acrylic resin (B) is 3 〇. Within 〇, that is, 0t > 3 (TC, Preferably, it is 0 to 20 ° C, and particularly preferably 〇~i (TC. <Substrate layer> ❹ The base material layer of the resin sheet for molding is an aromatic polycarbonate (A1) and other resin. The polycarbonate resin composition (A) of the polymer alloy of (A2) is formed as a main component. [Aromatic Polycarbonate (A1)] The aromatic polycarb of the resin sheet for molding is _ The polycarbon having an aromatic ring is not particularly limited, and examples thereof include an aromatic di-based compound or an aromatic di-mystery compound and a small amount of a multi-secret compound obtained by an interfacial polymerization method with phosgene, or Thermoplastic polycarbonate obtained by the above-mentioned reaction of the aromatic di-salt and the carbonic acid-S-day ga parent More specifically, and 5, for example, a carbonate polymer having a double A as a main raw material can be cited. The molecular weight of the fragrant polycarbonate is very low, _p μ ^ can be borrowed by ordinary extrusion molding. The sheet is not particularly limited, and the viscosity average molecular weight [Μν] converted from the viscosity of the solution is 15 , 〇〇〇 〜 40, 000, particularly ? 2 〇 000 to 35,000, which is special. It is preferable to use 22, 〇〇〇~3〇, 〇〇〇. In addition, it is also possible to mix two or more kinds of aromatic polycarbonates having different viscosity average molecular weights τ π 。. The so-called viscosity average molecular weight [MV] ' refers to the use of methylene chloride as a solvent, and the Uberoid viscosity meter is used to determine the ultimate viscosity [??] (in dl / g) at a temperature of 20 ,, and by Schnell Viscosity, ie, =1. 23χ 10-4Μ0. 83 calculated value. The ultimate viscosity [π ] is a value calculated by measuring the specific viscosity [β Sp] of each solution concentration [C] (g/dl). Further, the terminal hydroxyl group concentration of the aromatic polycarbonate is 1 〇〇〇 ppm or less, particularly 800 卯 m or less, and particularly preferably 6 〇〇 ppm or less, preferably a lower limit of 10 ppm or more, particularly 30 ppm or more, particularly It is preferably 4 〇 ppm or more. Here, the terminal concentration of the above terminal is relative to the mass of the aromatic polycarbonate, and the mass of the terminal hydroxyl group is expressed in ppm units, for example, colorimetric quantification according to the titanium tetrachloride/acetic acid method (Macrom〇1) The method described in Chem 88215〇965) was determined. [Other Resin (A2)] The other resin (A2) may be melt-blended with the aromatic polycarbonate (A1) (mixed and heated to melt) and alloyed with the polymer, and further, if the polymer alloy is allowed to be The glass transition temperature (Tg) may be lower than the glass transition temperature (Tg) of the aromatic polycarbonate (A1). In general, the glass transition temperature of the aromatic polycarbonate is 15 〇t>c, because the glass transition temperature (Tg) of the acrylic resin is about 5 ° C. When the difference (absolute value) between the glass transition temperature (Tg) of the resin composition (human) and the acrylic resin (B) is 303⁄4 or less, it is important to use 098105231 8 200940334 aromatic polycarbonate (A1) with other resins ( A2) The glass transition temperature (Tg) of the polymer alloy is made into a lower temperature ruthenium. From this viewpoint, it is preferable as another resin (Α2). Then, the aromatic polyester will be described next. In the case of the aromatic polyester which is used as the other resin (Α2), for example, a resin obtained by polycondensation of "aromatic acid-removing acid" and "monool component" can be mentioned.代表 The representative of the above-mentioned "aromatic dicarboxylic acid component" may, for example, be terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid. One part of terephthalic acid can also be replaced by "other dicarboxylic acid components". Examples of the "other dicarboxylic acid component" include oxalic acid, malonic acid, succinic acid, * adipic acid, sebacic acid, sebacic acid, pivalic acid, isophthalic acid, naphthalene dicarboxylic acid, and diphenyl ether. Dicarboxylic acid, p-hydroxybenzoic acid, and the like. It may be a mixture of one or more kinds, and the amount of the other dicarboxylic acid to be substituted may also be appropriately selected. ❹ As a representative of the above "diol component", ethylene glycol, diethylene glycol, triethylene glycol, cyclohexane dimethanol or the like can be given. One part of the ethylene glycol can also be replaced by "other diol components". Examples of the "other diol component" include propylene glycol, trimethylene glycol, . butylene glycol, hexanediol, diethylene glycol, neopentyl glycol, polyalkylene glycol, and 1,4-ring. Hexanedi-f-ol, glycerin, pentaerythritol, trihydroxyindole, methoxy-polyalkyl diol, and the like. It may be a mixture of one kind or two kinds, and the amount of other yeasts to be substituted may also be appropriately selected. 098105231 9 200940334 As a specific example of "aromatic polyacetic acid", poly(p-phenylene dicarboxylate) which is a polycondensation of terephthalic acid and ethylene condensation polymerization of Hn-terephthalic acid vinegar and α-butanediol can be exemplified: Further, the scooping of the other sub-components other than the benzene H and/or the ethylene==================================================================== In the case of ethylene diester, it is preferably 55, and the mole % of the copolymer of the second is replaced by cyclohexane and dimethanol, and the copolymerization of the second is the same as that of the poly(p-dibenzoic acid). Partial material read, preferably Π), a copolymerized polyester having a % phthalic acid substituted structure, or a mixture of such copolymerized polyesters. In the above-mentioned aromatic polycondensation, it is preferred to select a polymer alloy by melt blending with the aromatic polycarbonate (6), and the polymer alloy glass transition temperature (10) can be compared with the aromatic polycarbonate. The purpose of (9) is to reduce it sufficiently. From this point of view, the preferred embodiment has 5 to 75 mol% of ethylene glycol which is a diol component of polyethylene terephthalate (PET), and is subjected to l-cyclohexamethylene dimethanol U'4. - 〇 〇 之 〇 的 的 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 MT 〇 MT MT MT MT MT MT 〇 〇 a copolymerized polyacetate of the structure of a benzoic acid substitution, or a mixture thereof. These filaments are blended, fully miscible and polymer alloyed, and are effective in reducing the glass transition temperature. In addition, whether the polymer blend (mixed resin composition) becomes the polymer 098105231 200940334 alloy, in other words, is it completely compatible, for example, according to differential scanning calorimetry at a heating rate of 1 (TC/min) Whether or not the glass transition temperature is a single one can be judged. Here, the glass transition-temperature of the mixed resin composition is a single, which means that the mixed resin composition is used at a heating rate of 10 ° C / min according to JIS K7121. When the differential scanning calorimeter measures the glass transition temperature, the peak of the glass transition temperature is only one. It can also be measured by the dynamic viscoelasticity of the mixed resin composition by strain 〇·, frequency ❿1〇Hz (JISK). Dynamic Viscoelasticity Measurement of the -7198A Method) When the measurement is performed, it is judged whether or not the maximum value of the loss tangent (tan) is present. If the polymer blend (mixed resin composition) is completely compatible (polymerization) * Gold), the blended components are in a state of being compatible with each other at a nanometer level (molecular level). In addition, as a means of alloying the polymer, The following means: a ruthenium phase melting agent may be used, or it may be subjected to secondary stage polymerization and graft polymerization, or one polymer may be dispersed in a ruthenium shape. [Mixing ratio] Fangxiang polycarbonate (A1) The mixing ratio of the aromatic polyester (A2) is inferior to the glass transition temperature (Tg) of the polyacetal resin composition (1) and the propylene glycol resin (B). ) is a special limit of 1 to 3 °C, but from the viewpoint of maintaining transparency, it is better than a thousand swollen t A1 : Λ 0: 80 to 75: 25 'specially with αι·α2 = 098105231 200940334 30 In the coating layer of the resin sheet for thermoforming, the resin layer containing the acrylic resin (8) as a main component may be used as the main component. [Acrylic Resin (B)] The acrylic resin used in the resin sheet for thermoforming is a resin-based special product having an acryl group. For example, acetaminoacetate and a copolymer of methyl acrylate or ethyl acrylate, wherein the main component is polymerized by methyl methacrylate A mercapto methacrylate resin (also referred to as PMMA: poly(methyl) methacrylate methyl vinegar) is preferred. The copolymerization composition of the acrylic resin is preferably selected as appropriate according to the production conditions, for example, coextrusion conditions. For example, in the case of a copolymer of decyl acrylate, decyl acrylate or ethyl acrylate, the molar ratio of decyl methacrylate methyl acrylate or ethyl acrylate = 80:204:99 is Further, the crosslinking component may be contained in the range in which extrusion molding is possible. The molecular weight of the acrylic resin is generally 30,000 to 300,000 in terms of weight average molecular weight, but is not limited thereto.
丙烯酸系樹脂亦可使用市售品。例如可使用住友化學工業 (股）公司製.SUMIPEX系列、三菱嫘縈（股）公司製：ACURIpETA commercially available product can also be used for the acrylic resin. For example, it can be made by Sumitomo Chemical Industries Co., Ltd. SUMIPEX series, Mitsubishi 嫘萦 (share) company: ACURIpET
系列、（股）CURALE公司製：PARAPET系列、旭化成製：DELPET 等之甲基丙烯酸甲酯樹脂。但，並非限定於此。 丙烯酸系樹脂（B)係為了長期保持耐候性之目的，亦可含 098105231 12 200940334 有紫外線吸收劑。紫外線吸收劑之含量較佳為丙烯酸系樹脂 之0·0卜3.0質量％。 . 又，共擠出成形時為了防止丙烯酸系樹脂的熱惡化，亦可 • 含有抗氧化劑、著色防止劑等。此時，抗氧化劑之含量較佳 為丙烯酸系樹脂之0. 01〜3質量％，且著色防止劑之含量較佳 為0. 0卜3質量％。 於上述任一種情形中，若未達丙烯酸系樹脂之〇 〇1質量 ❹ ％ ’則預測無法取得充分之效果，相反地即使超過5質量％， 則不僅無法期待進一步之效果，且發生析出而成為白化的原 因，導致密黏性和衝擊強度的降低，故為不佳。 又，為了進一步提高表面硬度，亦可於丙烯酸系樹脂中， • 令高τβ丙烯酸等分散以維持透明性。此外，經由添加甲基 _ 丙烯酸曱酯-苯乙烯共聚合物樹脂（MS樹脂），亦可降低吸水 率並且抑制發泡。 ® 〈片材厚度〉 本成形用樹脂片材之各層及片材全體的厚度’可在表面硬 度及成形性方面不會產生問題的範圍中適當設定。但，一般 而吕，片材全體的厚度係以〇. 2mm〜2_ Omm為佳，且被覆層的 ' 厚度以10以m〜、特別以30/zm〜40/zm為佳。 • 〈製造方法〉 本成形用樹脂片材之製造方法並無特別限制，由生產性的 觀點而言，較佳係藉由共擠出令基材層與被覆層層合。 098105231 13 200940334 可列舉例如’將聚碳酸酯系樹脂組成物（A)及丙烯酸系樹 脂（B)分別以擠出機予以加熱熔融，並由τ字模之狹縫狀吐 出口分別擠出層合’接著使其密黏固化至冷卻輥的製造方 法。 芳香族聚碳酸酯（A1)與其他樹脂（A2)，亦可於將聚碳酸酯 系樹脂組成物（A)以擠出機加熱熔融時予以混合，但較佳係 預先混合熔融（熔融摻合），視需要加入相溶化劑等而調製聚 合物合金。 又，以擠出機進行加熱熔融的溫度，較佳係較各樹脂之玻 璃轉移溫度（Tg)高80〜150。(：之溫度。一般而言，擠出聚碳 酸酯系樹脂組成物（A)之主要擠出機的溫度條件通常為 230〜290 C、較佳為240〜280。(：，擠出丙烯酸系樹脂（B)之主 要擠出機的溫度條件通常為220〜270°C、較佳為230~260。〇。 又，作為將一種熔融樹脂共擠出的方法，可採用進料分段 方式、多岐管方式等之公知方法。 例如若為進料分段方式之情形，可將經進料分段而層合的 溶融樹脂導入T字模等之片材成形模中，成形為片狀後，流 入表面經鏡面處理的成形輥（拋光輥）形成傾斜面（bank)，並 於該成形輥通過中進行鏡面加工和冷卻。 於多岐管方式之情形’可將多岐管模内所層合的熔融樹 脂’於模内部成形為片狀後’以成形輥進行表面加工及冷卻 即可。 098105231 14 200940334 任一處理，均將模之溫度設定為通常23〇〜29〇°c、其中較 佳係设疋於250〜280¾，且成形觀溫度通常設定為1〇〇〜 - °C、其中較佳為設定於i1〇〜i9〇t：。 . 〈特徵及用途〉 本成形用樹脂片材因具備以丙烯酸系樹脂（B)作為主成分 的被覆層，故具備難以對成形用樹脂片材之被覆層表面、及 該成形用樹脂片材成形而成的製品表面造成損傷的特徵。並 ❹且，藉由將屬於基材層主成分之聚碳酸酯系樹脂組成物 (A)、與屬於被覆層主成分之丙烯酸系樹脂的破璃轉移溫 度差的絕對值設定於3(TC以内，則即使在以被覆層侧成為 製品表面的方式進行熱成形時、尤其是進行深引伸成形時， 亦不會產生白化和裂痕以及發泡。 ' 因此，若使用本成形用樹脂片材進行熱成形，則可取得創 作性優良的熱成形體，尤其是進行深引伸成形所得之創作性 ❹ 優良的熱成形體。 另外’於本發明中，係將成形時之深号丨伸高度為3賴以 上、特別為5mm以上之情形稱為深引伸，在本成形用樹脂片 材之情形，深引伸高度即使為7mm以上之深弓丨伸，亦不會產 . 生白化和裂痕、以及發泡。 -又，本成形用樹脂片材因為具備如上述之特徵，例如於成 形用樹脂片材之基材層側形成印刷層並予以熱成形，另一方 面於前述印刷層侧將熔融樹脂進行射出成形並形成襯裡 098105231 15 200940334 層’則可製造創作性優良的模塑成形體。 〈用語之說明〉 本發明中所謂「主成分」，只要未特別記載，則包含在不 妨礙該主成錢能之範圍下容許含有其減分㈣義。此 時，雖然未特定該域分的含有_，但以主成分（於二個 成分以上為域分㈣之㈣，該等的合計量）為佔有 物中之50質《以上、特別為7〇質量％以上、其中特別以 90質量％以上（包含1〇〇%)為佳。 人，一㈣_丨片材」，係指JIS之定義上，薄，且一 般其厚度純於長度和寬料小心平坦的製品，—般所謂 的「薄膜」’係指相較於長度及寬度，厚度極小且最大厚 度為任意岐之薄且平坦的製品，通常係指以滚筒形式供: 者（日本工業規格服6_。但，片材與薄膜的界定並益 一定’於本發財並不必要於文字上將兩者㈣區別，故於 本發明中’稱為「薄膜」之情形亦包含「片材」者，稱為「片 材」之情形亦包含「薄膜」者。 又，於本發明中，以「χ~γ」（χ、γ為任意之數字）表現之 情形，只要無特別指明，則包含「X以上Υ以下」之意義， 同時並包含「較佳為大於X」及「較佳為小於Υ」之^義。 [實施例] ^ 其次說明本發明之實施例，但本發明並不限定於此等實施 例0 098105231 200940334 〈玻璃轉移溫度之測定方法〉 使用Perkin Elmer公司製差示掃描熱量計DSC-7型，於 • 氮環境下，於-40°C保持1分鐘後，以1〇。(：/分鐘之升溫速 .度下進行測定’求出所得DSC曲線之微分最大值的溫度作為 玻璃轉移溫度。 (實施例1) 將聚碳酸酯系樹脂組成物（A)及丙烯酸系樹脂（B)分別以 ❹ 個別的擠出機予以加熱熔融，由T字模之狹縫狀吐出口同時 熔融擠出二種樹脂，並層合為二種2層。 擠出聚碳酸酯系樹脂組成物（A)的主要擠出機，設定成桶 直徑65mm、螺桿之L/D=35、汽缸溫度27(TC。擠出丙烯酸 '系樹脂（B)的次要擠出機，設定成桶直徑32mm、螺桿之 ' L/D=32、汽缸溫度 25(TC。 聚碳酸酯系樹脂組成物（A)係準備將芳香族聚碳酸酯（以 ❹ 界面聚合法所製造之雙酚A型芳香族聚碳酸酯、黏度平均分 子量28000、終端羥基濃度= 150ppm、Tgl45t：)、與聚環己 烷對苯二曱酸二亞甲酯樹脂（具有使PET之乙二醇的65莫耳 %經1，4-CHDM取代之構造的低結晶性共聚合聚酯。Tg86 • °C)，以質量比50:50之比例混合，一邊加熱一邊熔融混練 • 成經聚合物合金化的聚碳酸酯系樹脂組成物。測定此聚碳酸 酯系樹脂組成物之玻璃轉移溫度，結果DSC曲線的微分極大 值為單一（TglliTC)，可確認其為聚合物合金。 098105231 17 200940334 作為丙烯酸系樹脂（B)，係使用丙烯酸系樹脂（三菱嫘縈 (股）製、商品名ACRYPET MD、組成：聚曱基丙烯酸甲酯、 TgllO°C)。 為了層合成二種2層，係使用進料分段。模頭内溫度為 250°C，將於模内層合的樹脂，導入至經鏡面加工之橫型配 置的3根流延輥。此時，設定成第1根輥溫度ll〇°C、第2 根輥溫度140°C、第3根輥溫度185°C。 而且，主要擠出機和次要擠出機迴轉數係設定成吐出量比 為主要/次要=470/30,並且以成為0. 5mm厚度之方式進行共 擠出，取得成形用樹脂片材（片材全體厚度0. 5丽、被覆層 厚度30#m)。 所得成形用樹脂片材的評價結果示於表1。 (實施例2) 除了改變聚碳酸酯系樹脂組成物（A)的種類以外，以實施 例1相同之製造條件，取得成形用樹脂片材（片材全體厚度 0. 5mm、被覆層厚度40从m)。 本實施例所用之聚碳酸酯系樹脂組成物（A )係使用將芳香 族聚碳酸酯（以界面聚合法所製造之雙酚A型芳香族聚碳酸 酯、黏度平均分子量28000、終端經基濃度= 150ppm、Tgl45 °C )、和聚環己烷對笨二曱酸二亞甲酯樹脂（具有使PET之乙 二醇的65莫耳％經1，4-CHDM取代之構造的低結晶性共聚合 聚酯。Tg86°C)，以質量比80:20之比例混合，一邊加熱一 098105231 18 200940334 邊烙融混練變成經聚合物合金化的聚碳酸s旨系樹脂飯成 物。測定此聚碳酸酯系樹脂組成物之玻璃轉移溫度，結果^ DSC曲線的微分極大值為單一（Tgl35°C)，可確認其為聚合 物合金。 所得成形用樹脂片材的評價結果示於表1。 (實施例3) 除了改變聚碳酸酯系樹脂組成物（A)的種類以外，以與實 ❹ 施例1相同之製造條件，取得成形用樹脂片材（片材全體厚 度0. 5mm、被覆層厚度40/zm)。 本實施例所用之聚碳酸酯系樹脂組成物（A )係使用將芳香 族聚碳酸酯（以界面聚合法所製造之雙酚A型芳香族聚碳酸 ' 酯、黏度平均分子量28000、終端羥基濃度= 150ppm、Tgl45 * °c)、和聚環己烷對苯二甲酸二亞甲酯樹脂（具有使PET之乙 二醇的65莫耳％經l，4-CHDM取代之構造的低結晶性共聚合 ❷聚醋。Tg86°C )、和共聚合聚酯（具有使聚對苯二甲酸丁二酯 中之對苯二酸的30莫耳％經間苯二酸取代之構造的共聚合 聚酯。Tg3(Tc)，以質量比70:20:10之比例混合，一邊加熱 一邊熔融混練變成經聚合物合金化的聚碳酸酯系樹脂組成 ' 物。測定此聚碳酸酯系樹脂組成物之玻璃轉移溫度，結果 .DSC曲線的微分極大值為單一（Tgl40〇C)，可確認其為聚合 物合金。 所得成形用樹脂片材的評價結果示於表1。 098105231 19 200940334 (實施例4) 除了改變聚碳酸酯系樹脂組成物（A)的種類以外，以與實 施例1相同之製造條件，取得成形用樹脂片材（片材全體厚 度0.5麵、被覆層厚度30//m)。 本實施例所用之聚碳酸酯系樹脂組成物（A )為使用將芳香 族聚碳酸醋（以界面聚合法所製造之雙酚A型芳香族聚碳酸 醋、黏度平均分子量28000、終端羥基濃度= 150ppm、Tgl45 °C)、和聚環己烷對苯二甲酸二亞甲酯樹脂（具有使PET之乙 二醇的65莫耳％經i，4-CHDM取代之構造的低結晶性共聚合 聚Ss。Tg86 C ) ’以質量比35:65之比例混合，一邊加熱一 邊熔融混練變成經聚合物合金化的聚碳酸酯系樹脂組成 物°測定此聚碳酸酯系樹脂組成物之玻璃轉移溫度，結果 DSC曲線的微分極大值為單一（Tgiost：)，可確認其為聚合 物合金。 所得成形用樹脂片材的評價結果示於表1。 (實施例5) 除了改變聚碳酸酯系樹脂組成物（A)的種類以外，以與實 施例1相同之製造條件，取得成形用樹脂片材（片材全體厚 度0· 5mm、被覆層厚度35// m)。 本實施例所用之聚碳酸酯系樹脂組成物（A)為使用將芳香 族聚碳酸酯（以界面聚合法所製造之雙酚A型芳香族聚碳酸 酯、黏度平均分子量28000、終端羥基濃度= 150ppm、Tgl45 098105231 20 200940334 °C)、和聚環已烷對苯二甲酸二亞甲酯樹脂（具有使PET之乙 二醇的65莫耳％經1，4-CHDM取代之構造的低結晶性共聚合 . 聚醋。Tg86°C)，以質量比25:75之比例混合，一邊加熱一 -邊、溶融渴*練變成經聚合物合金化的聚碳酸酯系樹脂組成 物。測定此聚碳酸酯系樹脂組成物之玻璃轉移溫度，結果 DSC曲線的微分極大值為單一（Tg9(rc)，可確認為聚合物合 金。 ❹ 所得成形用樹脂片材的評價結果示於表1。 (比較例1) 以與實施例1同樣之成形條件，未令丙烯酸系樹脂（B)共 擠出，取得聚碳酸酯系樹脂組成物（A)的單層片材（片材全體 Λ 厚度 〇· 5mm)。 擠出聚碳酸酯系樹脂組成物（A)的擠出機，設定成桶直徑 65mm、螺桿之L/D=35、汽纪溫度270°C。 〇 作為聚碳酸酯系樹脂組成物（A)，係使用芳香族聚碳酸酯 (以界面聚合法所製造之雙酚A型芳香族聚碳酸酯、黏度平 均分子量28000、終端羥基濃度= 15〇ppm、Tgi45^)。 所得成形用樹脂片材之評價結果示於表2。 • (比較例2 ) . 除了改變聚碳酸酯系樹脂組成物（A)的種類以外，以與實 施例1相同之製造條件，取得成形用樹脂片材（片材全體厚 度0. 5mm、被覆層厚度35απ〇。 098105231 21 200940334 本比較例所用之聚碳酸酯系樹脂組成物（A)，係使用芳香 族聚碳酸酯（以界面聚合法所製造之雙酚A型芳香族聚碳酸 醋、黏度平均分子量28000、終端羥基濃度= i5〇ppm、Tgl45 〇C)。 所得成形用樹脂片材之評價結果示於表2。 (比較例3) 除了將成形溫度變更成11 〇°C以外，以與比較例2相同之 製造條件，取得成形用樹脂片材（片材全體厚度〇. 、被 覆層厚度35//m)。 所付成形用樹脂片材之評價結果示於表2。 〈試驗及評價〉 1) 鉛筆硬度 根據JIS K5400，以1公斤荷重，對實施例及比較例所得 之成形用樹脂片材表面（未形成被覆層之情形為被覆層表面） 測定鉛筆硬度。 其次，以實用上無問題之程度「H」作為基準，且其以上 之「Η」「2H」等評價為合格（「〇」），其未滿之「B」評價 為不合格（「X」）。 2) 成形加工性（深引伸性） 將實施例及比較例所得之成形用樹脂片材，裁斷成100_ x200mmx(厚度）0· 5mm，並將所得之樣品片材於120〜150。(：中 預熱，以該溫度（參照表1及表2)經由5MPa之高壓空氣， 098105231 22 200940334 並以表1及表2所示之深引伸高度進行壓空成形。另外，深 引伸高度為以lmm、2丽、…、5mm般，使用以1mm刻度變更 , 深引伸高度之金屬模具進行設定。 k 觀察所得成形體之表面狀態（裂痕、白化、發泡、不均）， 於均未觀察到裂痕、白化、發泡及不均之情形評價為「外觀 無異常」），更且，可依外觀無異常之狀態成形為5mm以上 深引伸高度之成型體者，綜合評價為合格（「〇」）。 ❹Series, (share) CURALE company: PARAPET series, Asahi Kasei system: DELPET and other methyl methacrylate resin. However, it is not limited to this. The acrylic resin (B) may contain an ultraviolet absorber in the form of 098105231 12 200940334 for the purpose of maintaining weather resistance for a long period of time. The content of the ultraviolet absorber is preferably 3.0% by mass of the acrylic resin. In addition, in order to prevent deterioration of heat of the acrylic resin during co-extrusion molding, it is also possible to contain an antioxidant, a coloring inhibitor, and the like. O. 3质量质量。 The content of the anti-oxidant is preferably 0. 01〜3质量%, and the content of the coloring preventive agent is preferably 0. 0 Bu 3% by mass. In any of the above cases, if the 〇〇1 mass ❹ % ' of the acrylic resin is not reached, it is predicted that a sufficient effect cannot be obtained. On the other hand, even if it exceeds 5% by mass, further effects cannot be expected, and precipitation is caused. The reason for whitening leads to a decrease in the adhesion and impact strength, which is not preferable. Further, in order to further increase the surface hardness, it is also possible to disperse high-τβ acrylic acid or the like in the acrylic resin to maintain transparency. Further, by adding a methyl methacrylate-styrene copolymer resin (MS resin), water absorption can be lowered and foaming can be suppressed. ® <Sheet Thickness> The thickness of the entire layer of the resin sheet for molding and the entire sheet can be appropriately set in a range where no problem occurs in terms of surface hardness and formability. However, in general, the thickness of the entire sheet is preferably 2 mm to 2 mm, and the thickness of the coating layer is preferably 10 m or more, particularly preferably 30/zm to 40/zm. <Manufacturing Method> The method for producing the resin sheet for molding is not particularly limited. From the viewpoint of productivity, it is preferred to laminate the base material layer and the coating layer by co-extrusion. 098105231 13 200940334 For example, 'the polycarbonate resin composition (A) and the acrylic resin (B) are respectively heated and melted in an extruder, and extruded and laminated by a slit-shaped discharge port of a τ-shaped mold. Then, it is made to adhere to the manufacturing method of a cooling roll. The aromatic polycarbonate (A1) and the other resin (A2) may be mixed while the polycarbonate resin composition (A) is heated and melted by an extruder, but it is preferably premixed and melted (melt blended). The polymer alloy is prepared by adding a compatibilizing agent or the like as needed. Further, the temperature at which the extruder is heated and melted is preferably 80 to 150 higher than the glass transition temperature (Tg) of each resin. (The temperature of the main extruder in which the polycarbonate resin composition (A) is extruded is generally 230 to 290 C, preferably 240 to 280. (:, extruded acrylic The temperature of the main extruder of the resin (B) is usually 220 to 270 ° C, preferably 230 to 260. Further, as a method of coextruding a molten resin, a feed section method may be employed. For example, in the case of the feed section method, the molten resin laminated by the feed section can be introduced into a sheet forming mold such as a T-shaped mold, and formed into a sheet shape, and then flowed in. The mirror-finished forming roll (buffing roll) forms a bank and is mirror-finished and cooled in the pass of the forming roll. In the case of a multi-tube method, the molten resin laminated in the multi-tube mold can be laminated. 'The inside of the mold is formed into a sheet shape', and the surface is processed and cooled by a forming roll. 098105231 14 200940334 In any treatment, the temperature of the mold is set to 23 〇 to 29 〇 °c, preferably 系At 250~2803⁄4, and the forming temperature is usually set It is set to 1 〇〇 to - ° C, and it is preferable to set it to i1〇~i9〇t: . . . Features and Uses The resin sheet for molding has a coating containing an acrylic resin (B) as a main component. In addition, it is difficult to damage the surface of the coating layer of the resin sheet for molding and the surface of the product formed by molding the resin sheet, and the polycarbonate which is a main component of the substrate layer is contained. When the absolute value of the difference in the glass transition temperature of the ester-based resin composition (A) and the acrylic resin which is the main component of the coating layer is set to 3 (within TC), the thermoforming is performed so that the coating layer side becomes the surface of the product. In the case of deep drawing, in particular, whitening, cracking, and foaming do not occur. Therefore, when the resin sheet for molding is used for hot forming, a thermoformed body excellent in seizure property can be obtained, in particular, In the present invention, the deep extensor height at the time of forming is 3 or more, and particularly 5 mm or more, which is called deep drawing, and is formed in the present invention. In the case of the resin sheet, the deep drawing height is not more than 7 mm, and it does not produce whitening, cracking, and foaming. Further, since the resin sheet for molding has the characteristics as described above, for example A printing layer is formed on the base material layer side of the resin sheet for molding and thermoformed. On the other hand, the molten resin is injection-molded on the printing layer side to form a lining 098105231 15 200940334 layer, which can produce a mold excellent in creativity. (Description of Terms) In the present invention, the term "principal component" is included in the range that does not impede the ability of the main money, and is not limited to the meaning of the term "fourth". The domain contains _, but the main component (in the case of two or more components (4), the total amount of these) is 50 or more of the content, especially 7 7% by mass or more, of which More than 90% by mass (including 1% by weight) is preferred. Person, one (four) _ 丨 sheet, refers to the JIS definition, thin, and generally its thickness is pure and length and the material is carefully flat, the so-called "film" refers to the length and width A product having a very small thickness and a maximum thickness of any crucible and flat, usually referred to as a drum: (Japanese Industrial Standard Service 6_. However, the definition of sheet and film is beneficial) In the present invention, the term "film" also includes "sheet", and the case of "sheet" also includes "film". In the case of "χ~γ" (χ, γ is an arbitrary number), unless otherwise specified, the meaning of "X or more" is included, and "Better than X" and "Compare" are included. [Embodiment] ^ Embodiments of the present invention will be described next, but the present invention is not limited to such an embodiment. 0 098105231 200940334 <Method for Measuring Glass Transition Temperature> Using Perkin Elmer Co., Ltd. Scanning calorimeter DSC-7 type, The temperature was maintained at -40 ° C for 1 minute in a nitrogen atmosphere, and the temperature at which the differential maximum value of the obtained DSC curve was determined was measured as a glass transition temperature at a temperature of 1. (minutes/min.). 1) The polycarbonate resin composition (A) and the acrylic resin (B) are separately heated and melted in an individual extruder, and the two resins are melt-extruded simultaneously from the slit-shaped discharge port of the T-shaped mold. Laminated into two types of two layers. The main extruder for extruding the polycarbonate resin composition (A) was set to a barrel diameter of 65 mm, a screw L/D = 35, and a cylinder temperature of 27 (TC. Extrusion acrylic acid' The secondary extruder of the resin (B) is set to have a barrel diameter of 32 mm, a screw of 'L/D=32, and a cylinder temperature of 25 (TC. The polycarbonate resin composition (A) is prepared to be an aromatic polycarbonate. Ester (bisphenol A type aromatic polycarbonate manufactured by 界面 interfacial polymerization method, viscosity average molecular weight 28000, terminal hydroxyl group concentration = 150 ppm, Tgl45t:), and polycyclohexane terephthalic acid dimethylene methyl ester resin (Low-crystalline copolymerization with a structure in which 65 mol% of ethylene glycol of PET is substituted by 1,4-CHDM Ester. Tg86 • °C), which is mixed at a mass ratio of 50:50, melted and kneaded while heating, and formed into a polycarbonate resin composition alloyed with a polymer. The glass of the polycarbonate resin composition is measured. When the temperature was changed, the differential maximum value of the DSC curve was a single (TglliTC), and it was confirmed that it was a polymer alloy. 098105231 17 200940334 As the acrylic resin (B), an acrylic resin (Mitsubishi) was used. Name ACRYPET MD, composition: polymethyl methacrylate, TgllO ° C). In order to synthesize two of the two layers, a feed section is used. The temperature in the die was 250 ° C, and the resin laminated in the mold was introduced into a mirror-processed horizontally-formed three casting rolls. At this time, the first roll temperature was 11° C., the second roll temperature was 140° C., and the third roll temperature was 185° C. Furthermore, the number of revolutions of the main extruder and the secondary extruder was set so that the discharge ratio was mainly/minor = 470/30, and co-extrusion was performed so as to become a thickness of 0.5 mm to obtain a resin sheet for molding. (The total thickness of the sheet is 0.5 liter, the thickness of the coating layer is 30#m). The evaluation results of the obtained resin sheet for molding are shown in Table 1. (Example 2) The resin sheet for molding was obtained in the same manner as in Example 1 except that the type of the polycarbonate resin composition (A) was changed (the total thickness of the sheet was 0.5 mm, and the thickness of the coating layer was 40). m). The polycarbonate resin composition (A) used in the present Example is an aromatic polycarbonate (bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method, viscosity average molecular weight 28000, terminal base concentration) = 150 ppm, Tgl 45 ° C), and polycyclohexane to diammonium phthalate resin (having a low crystallinity of a structure in which 65 mol% of ethylene glycol of PET is substituted by 1,4-CHDM) The polymerized polyester (Tg86 ° C) was mixed at a mass ratio of 80:20, and heated to a 098105231 18 200940334 while being melted and kneaded into a polymer-alloyed polycarbonate s. The glass transition temperature of this polycarbonate resin composition was measured, and as a result, the differential maximum value of the DSC curve was single (Tgl 35 ° C), which was confirmed to be a polymer alloy. The evaluation results of the obtained resin sheet for molding are shown in Table 1. (3) The coating layer was obtained in the same manner as in the above-mentioned Example 1 Thickness 40/zm). The polycarbonate resin composition (A) used in the present embodiment is an aromatic polycarbonate (bisphenol A type aromatic polycarbonate) produced by interfacial polymerization, viscosity average molecular weight 28000, terminal hydroxyl concentration = 150 ppm, Tgl45 * °c), and polycyclohexane terephthalic acid dimethylene methyl ester resin (having a low crystallinity of a structure in which 65 mol% of ethylene glycol of PET is substituted by 1,4,CHDM) Polymeric ruthenium vinegar. Tg86 ° C), and copolymerized polyester (having a copolymerized polyester having a structure in which 30 mol % of terephthalic acid in polybutylene terephthalate is substituted with isophthalic acid) Tg3 (Tc), which is mixed in a mass ratio of 70:20:10, and melted and kneaded to become a polymerized polycarbonate resin composition while heating. The glass of the polycarbonate resin composition is measured. When the temperature was changed, the differential maximum value of the DSC curve was a single (Tgl40 〇C), and it was confirmed that it was a polymer alloy. The evaluation results of the obtained resin sheet for molding are shown in Table 1. 098105231 19 200940334 (Example 4) In addition to the type of the polycarbonate resin composition (A) The resin sheet for molding (the entire thickness of the sheet was 0.5 surface, and the thickness of the coating layer was 30/m) was obtained under the same production conditions as in Example 1. The polycarbonate resin composition (A) used in the present example was Using aromatic polycarbonate (bisphenol A type aromatic polycarbonate manufactured by interfacial polymerization method, viscosity average molecular weight 28000, terminal hydroxyl group concentration = 150 ppm, Tgl 45 ° C), and polycyclohexane terephthalic acid Dimethyl ester resin (low crystalline copolymerized poly-Ss. Tg86 C having a structure in which 65 mol% of ethylene glycol of PET is substituted by i,4-CHDM) is mixed at a mass ratio of 35:65. The mixture is melted and kneaded by heating to form a polycarbonate resin composition which is alloyed with the polymer. When the glass transition temperature of the polycarbonate resin composition is measured, the differential maximum value of the DSC curve is single (Tgiost:), and it can be confirmed. This is a polymer alloy. The evaluation results of the obtained resin sheet for molding are shown in Table 1. (Example 5) The same production conditions as in Example 1 except that the type of the polycarbonate resin composition (A) was changed. , obtaining a forming tree Sheet (the total thickness of the sheet is 0·5 mm, and the thickness of the coating layer is 35//m). The polycarbonate resin composition (A) used in the present example is an aromatic polycarbonate (manufactured by an interfacial polymerization method). Bisphenol A type aromatic polycarbonate, viscosity average molecular weight 28000, terminal hydroxyl group concentration = 150 ppm, Tgl45 098105231 20 200940334 ° C), and polycyclohexane terephthalic acid dimethylene methyl ester resin (having PET Low crystalline copolymerization of 65 mole % of diol substituted by 1,4-CHDM. Polyacetate. Tg86 ° C), which is mixed at a mass ratio of 25:75, is heated to a side, and thawed into a polycarbonate-based resin composition which is alloyed with a polymer. When the glass transition temperature of the polycarbonate resin composition was measured, the differential maximum value of the DSC curve was a single (Tg9 (rc), which was confirmed to be a polymer alloy. 评价 The evaluation results of the obtained resin sheet for molding are shown in Table 1. (Comparative Example 1) The acrylic resin (B) was not coextruded in the same molding conditions as in Example 1 to obtain a single-layer sheet of the polycarbonate resin composition (A). 〇·5mm) The extruder for extruding the polycarbonate resin composition (A) is set to have a barrel diameter of 65 mm, a screw L/D = 35, and a vaporization temperature of 270 ° C. 〇 as a polycarbonate resin In the composition (A), an aromatic polycarbonate (bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method, a viscosity average molecular weight of 28,000, a terminal hydroxyl group concentration of 15 〇 ppm, and Tgi 45^) was used. The results of the evaluation of the resin sheet are shown in Table 2. (Comparative Example 2) The molding resin sheet was obtained under the same production conditions as in Example 1 except that the type of the polycarbonate resin composition (A) was changed. The thickness of the sheet is 0. 5mm, and the thickness of the coating layer is 35α. 098105231 21 200940334 The polycarbonate resin composition (A) used in the comparative example is an aromatic polycarbonate (bisphenol A type aromatic polycarbonate produced by interfacial polymerization method, viscosity average molecular weight 28000). The terminal hydroxyl group concentration = i5 〇 ppm, Tgl45 〇 C) The evaluation results of the obtained resin sheet for molding are shown in Table 2. (Comparative Example 3) In addition to the molding temperature was changed to 11 〇 ° C, and Comparative Example 2 The resin sheet for molding (the total thickness of the sheet 〇., the thickness of the coating layer is 35/m) was obtained under the same production conditions. The evaluation results of the resin sheet for molding to be applied are shown in Table 2. <Test and Evaluation> 1) The pencil hardness was measured on the surface of the resin sheet for molding obtained in the examples and the comparative examples (the surface of the coating layer in the case where the coating layer was not formed) in accordance with JIS K5400 under a load of 1 kg. Secondly, it was practically problem-free. "H" is used as a benchmark, and the above evaluations of "Η" and "2H" are qualified ("〇"), and the less than "B" is evaluated as unqualified ("X"). 2) Formability (deep) Extension) will be implemented The molding resin sheets obtained in the examples and the comparative examples were cut into 100 mm x 200 mm x (thickness) of 0.5 mm, and the obtained sample sheets were placed at 120 to 150. (: preheating, at this temperature (refer to Table 1 and Table 2) via 5MPa high pressure air, 098105231 22 200940334 and with the deep extension height shown in Table 1 and Table 2. In addition, the deep extension height is In the case of lmm, 2 Li, ..., 5 mm, the mold was changed using a 1 mm scale and a deep extension height. k The surface state of the obtained molded body (crack, whitening, foaming, unevenness) was observed. In the case of cracks, whitening, foaming, and unevenness, it is evaluated as "no abnormality in appearance", and it can be molded into a molded body having a deep drawing height of 5 mm or more depending on the appearance without abnormality, and the overall evaluation is acceptable ("〇 "). ❹
098105231 23 200940334 實施例5 c=) r—H LO CO 〇 10mm 115°C 外觀無異常 〇 實施例4 CD τ-Η in CD T-H 〇 9mm 115°C 外觀無異常 〇 實施例3 Ο o o Μ CO 〇 8 mm 120°C 外觀無異常 〇 實施例2 c=> T"H <=> LO CO 1—H LO X CNI 〇 7mm 125〇C 外觀無異常 〇 實施例1 | o C5 >'1 1 Ο W oa 〇 7 mm 1 120°C | |外觀無異常| 〇 丙烯酸系樹脂（B)之Tg(B) 厚度（V m) 聚碳酸酯系樹脂組成物（A)之Tg(A) bfl ^ ^ Μ W Μ 餿〒 寒Q 爱 片材鉛筆硬度 深引伸高度 成形溫度 外觀觀察 評價 成形加工性（深引伸性） 被覆層 基材層 評價 比較例3 CD τ—Η LO CO LO LO CO C<I 〇 5mm litre I 界面白化 X 比較例2 C5 i—Η LO CO LO 寸 i1 i LO CO tn C<l 〇 5mm 140°C 丙烯基發泡 X 比較例1 1 1 LO 呀 i—Η 1 CO X 8mm 140°C 外觀無異常 〇 丙烯酸系樹脂（Β)之Tg(B) 厚度（/z m) 聚碳酸酯系樹脂組成物（Α)之Tg(A) ^ 0Q 餿V 率Q 载.. 1 片材鉛筆硬度 1_ 深引伸高度 成形溫度 外觀觀察 評價 成形加工性（深引伸性） 被覆層 基材層 評價 ο Ο098105231 23 200940334 Example 5 c=) r-H LO CO 〇10mm 115°C No abnormal appearance 〇 Example 4 CD τ-Η in CD TH 〇9mm 115°C No abnormal appearance 〇 Example 3 oo oo Μ CO 〇 8 mm 120 °C No abnormal appearance. Example 2 c=>T"H<=> LO CO 1—H LO X CNI 〇7mm 125〇C No abnormal appearance 〇Example 1 | o C5 >' 1 1 Ο W oa 〇7 mm 1 120°C | |No abnormalities in appearance | Tg(B) thickness of 〇acrylic resin (B) Thickness (V m) Tg(A) of polycarbonate resin composition (A) Bfl ^ ^ Μ W Μ 馊〒 Cold Q Love Sheet Pencil Hardness Deep Extension Height Forming Temperature Appearance Observation Evaluation Formability (Deep Extensibility) Coating Substrate Layer Evaluation Comparative Example 3 CD τ—Η LO CO LO LO CO C< ;I 〇5mm litre I interface whitening X Comparative Example 2 C5 i-Η LO CO LO inch i1 i LO CO tn C<l 〇5mm 140°C Propylene-based foaming X Comparative Example 1 1 1 LO 呀i-Η 1 CO X 8mm 140°C Appearance is not abnormal TAcrylic resin (Β) Tg(B) Thickness (/zm) Polycarbonate resin composition (Α) Tg(A) ^ 0Q 馊V rate Q Load.. 1Sheet pencil hardness 1_ Deep extension height Forming temperature Appearance observation Evaluation Formability (deep extensibility) Coating layer Substrate layer Evaluation ο Ο
1-S18S 200940334 (考察） 以上之結果’可確認經由以丙烯酸系樹脂（B)作為主成分 形成被覆層，則可充分提高成形用樹脂片材表面（被覆層表 面）的硬度。因此，成形用樹脂片材必然難以於其成形而成 之製品表面造成損傷。 又，可判定經由令屬於基材層主成分之聚碳酸酯系樹脂組 成物（A)、與屬於被覆層主成分之丙烯酸系樹脂（β)之破璃轉 ❹移溫度差之絕對值設定於30°C以内，則即使以深引伸高度 7mm以上予以深引伸成形，亦可取得不會產生裂痕、白化、 發泡、不均等之外觀不良的成形品。 鏖 ❹ 如此’可預測若使用本發明之成形用樹脂片材，不僅可取 得表面難以造成損傷，且成形性優良的成形品，且可製造無 印刷油墨之日照槐色的模塑成型品。 又，若考察上述結果，作為將聚碳酸酯系樹脂組成物（A)、 與丙烯酸系樹脂（幻之玻璃轉移溫度差的絕對值設定於別 C以内的方法’料較佳細芳香躲碳酸自旨⑹與其他樹 脂（A2)製作聚合物合金較聚碳_㈣驗祕⑴之玻 璃轉移溫度降低的方法，獻，此時，作為其他樹脂⑽， 為:香族聚自旨’其中特取料苯二f酸乙二針之一部分 乙一醇以環己燒二甲醇取代而成的共聚合聚自旨、或、聚對苯 部分料二酸―苯二酸取代而成的 /、聚0聚知、或其混合物為佳。 098105231 251-S18S 200940334 (Review) The above results have been confirmed. The hardness of the surface of the resin sheet for molding (the surface of the coating layer) can be sufficiently improved by forming the coating layer with the acrylic resin (B) as a main component. Therefore, the resin sheet for molding is inevitably difficult to cause damage to the surface of the molded article. Further, it can be determined that the absolute value of the temperature difference between the polycarbonate resin composition (A) which is the main component of the base layer and the acrylic resin (β) which is the main component of the coating layer is set to Within 30 ° C, even if deep drawing is carried out with a deep drawing height of 7 mm or more, a molded article which does not cause cracks, whitening, foaming, unevenness, and the like can be obtained. In the case of using the resin sheet for molding of the present invention, it is possible to obtain a molded article which is less likely to cause damage on the surface and which is excellent in moldability, and which can produce a molded article having a sun-free color without a printing ink. In addition, when the polycarbonate resin composition (A) and the acrylic resin (the absolute value of the temperature difference of the glass transition temperature is set to be within the other C), it is preferable to consider the above results. The method of (6) and other resin (A2) to produce a polymer alloy is more than the polycarbon_(4) test (1) method for reducing the glass transition temperature, at this time, as other resin (10), it is: a copolymerization of a part of ethyl benzene diacetate, which is substituted with cyclohexane and dimethanol, or a poly(p-phenylene) dibasic acid-dicarboxylic acid substituted. Or a mixture thereof is preferred. 098105231 25