1298733 九、發明說明： 【發明所屬之技術領域】 本發明係關於丙烯系聚合物及含有該聚合物之樹脂組 合物，以及由該等所形成之片材及熱成形體。 【先前技術】 聚丙烯片材係因具有高剛性、高耐熱性及回收性等特 性，因此廣泛用於以食品容器為首之産業材料、醫藥品等 之各種包裝材料。 近年，片材製品係之現狀係隨著對環境保護、輕量化及 降低成本等方面開始，薄化、降低填充量、或發泡化等各 種檢討之發展，因而要求其材料性可更進一步高剛性化。 改進片材剛性之方法，已知有使用提高整規中間五價元 素 （isotacticmesopentad)分率之聚丙婦樹月旨之方法及使 用添加了造核劑之聚丙烯樹脂組合物之方法等（例如，參照 日本專利特開平7 - 3 3 9 2 0號、特開2 0 0 1 - 0 8 9 1 2 2號）。 然而，上述方法係間接使熔點增高，結果使得熱成形 中，片材之預熱時間延長，而給予生産性不良之影響。 【發明内容】 本發明之目的在於提供一種具有優良剛性及耐熱性，並 具有優良熱成形性之聚丙烯樹脂，以及由該樹脂所形成之 片材及熱成形體。 本發明人等為解決上述問題而進行深入研究關於聚丙 烯樹脂，結果發現，整合特定範圍之共聚單體含量、特定 範圍之熔體流動速率、特定之分子量分佈以及特定之立體 5 312XP/發明說明書(補件)/93-12/93124531 1298733 規則性之丙烯系聚合物所構成之片材，以及含有特定量之 該丙烯系聚合物及聚乙烯之聚丙烯樹脂組合物，具有極好 之剛性及对熱性，而熱成形性亦佳，且由該片材所製得之 熱成形體之剛性及耐熱性均較習知之熱成形體有著極大之 改善，從而完成本發明。 亦即，本發明係關於下述丙烯系聚合物（A )、（ A ’）及 (A ’，），含有上述聚合物之樹月旨組合物（B )[以下之說明中， (A )、（ A ’）、（ A ’ ’）、（ B )統稱為聚丙烯樹脂]、以及由該等 所形成之片材及熱成形體（C 1 )及（C 2 )。 (A)為丙烯、與乙烯或碳數4〜20之烯烴之丙烯共聚 物，係同時滿足下述條件[1 ]〜[4 ]。 [1]由乙烯或碳數4〜20之〇:_烯烴所衍生之構成單元之 含量在0.1〜2. Omol%之範圍内； [2 ]熔體流動速率（2 3 0 °C，負重2 · 1 6 k g )爲0 · ：1〜5 · 0 g / 1 0 分鐘； [3] 用GPC法戶斤測量之Mw/Mn爲5.0〜20 ; [4] 由13C-NMR光譜中Pmmmm及Pw之吸收強度，利用下 式（Eq-1 )求得立體規則性指標[Ms]之值爲0· 9 6 0〜0· 9 9 0之 範圍， mmm Μ m] (Eq-1) (式中，[Pmmmm]表示來自5個連續丙烯單元所整規 (isotactic)鍵結部位中，第3個單元之曱基之吸收強度， [Pw]表示來自丙烯單元之曱基之吸收強度。） 6 312XP/發明說明書(補件)/93-12/93124531 1298733 (A ’）爲上述丙烯系聚合物（A )，係由D S C所測得之熔點 爲150.0〜163.0°〇，230 °(：之熔融張力爲80〜18011^之丙烯 系聚合物。[以下之說明中，此二條件分別稱為條件[5 ]及 條件[6 ]。] (A ’ ’）爲上述丙烯系聚合物（A ’），係按照A S T Μ - D - 8 8 2之 標準，所測量厚度為0 . 6 m m之片材的拉伸彈性率爲 1 5 0 0〜1 9 Ο Ο Μ P a之丙烯系聚合物。[以下之說明中，此條件 稱為條件[7 ]。] (B)爲由70〜98重量％之上述丙烯系聚合物（A)、（A’）及 (A ’’），以及2〜3 0重量％之不同於該丙烯系聚合物之聚合物 (Q )所構成之聚丙婦樹脂組合物。 (C 1 )爲由上述聚丙烯樹脂（A )、（ A ’）及（A ’ ’）所形成之聚 丙烯片材，或由該片材熱成形所得到之成形體。 (C 2 )爲由上述聚丙烯樹脂組合物（B )所形成之聚丙烯片 材，或由該片材熱成形得到之成形體。 由本發明之丙烯系聚合物或樹脂組合物所形成之片 材，具有優良之剛性、而ί熱性及熱成形性，適合使用作為 熱成形製品之材料。 【實施方式】 本發明之聚丙烯樹脂係丙烯系聚合物（A)以至含有該丙 烯系聚合物（A )之樹脂組合物（B )。 本發明之丙烯系聚合物（A)爲含有以丙烯爲構成單元之 聚合物，係丙婦、與乙嫦或碳數4〜2 0之α -稀烴之共聚物。 此處之碳數4〜20之α-烯烴，可舉出有1-丁烯、1-戊烯、 7 312ΧΡ/發明說明書(補件)/93-12/93124531 1298733 1 -己烯、4 -曱基-1-戊烯、1-辛烯、1-癸烯、1-十二碳烯、 1 —h四碳烯、1 —h六碳稀、1 —("八碳稀、1-二十碳稀等。 其中，較佳爲乙烯或碳數4〜1 0之α -烯烴。聚丙烯樹脂中， 該等α-婦烴所衍生之構成單元之含量，爲0.1〜2. Omol%， 較佳爲0.2〜0.8niol%。 本發明之丙烯系聚合物之熔體流動速率（M F R )係 0. ：1〜5. 0g/10分鐘，較佳爲0. 3〜1. 0g/10分鐘。因MFR在 此範圍内，故片材成形時之擠出性佳。 接著，本發明之丙稀系聚合物（A )之由G P C法所測量之 Mw/Mn爲5.0〜20，較佳爲7.0〜14。Mw/Mn爲表示分子量分 佈之指標，當該值在上述範圍内時，聚合物具有較廣泛之 分子量分佈，因而熔融張力高，熱成形時之下引性 (drawdown)良好 。 由本發明之丙烯系聚合物（A)之13C-NMR光譜中之Pmmmm 及P w吸收強度，利用下述式（E q - 1 )所求得之立體規則性指 標[Μ 5 ]之值爲0 . 9 6 0〜0 . 9 9 0，較佳爲0 . 9 7 0〜0 . 9 9 0。在該範 圍内即可獲得高剛性、高耐熱性之片材及熱戍形體。[Technical Field] The present invention relates to a propylene-based polymer and a resin composition containing the polymer, and a sheet and a thermoformed body formed therefrom. [Prior Art] Polypropylene sheets are widely used in various packaging materials such as industrial materials and pharmaceuticals including food containers because of their high rigidity, high heat resistance and recyclability. In recent years, the status quo of the sheet products industry has started to develop, reduce the amount of filling, or foaming, etc., with the development of environmental protection, light weight, and cost reduction. Therefore, the material properties can be further improved. Rigid. As a method of improving the rigidity of a sheet, there is known a method of using a polypropylene-acrylic resin composition which improves the fraction of an isotactic meso-messue element and a method of using a polypropylene resin composition to which a nucleating agent is added (for example, Refer to Japanese Patent Laid-Open No. 7 - 3 3 9 2 0, Special Opening 2 0 0 1 - 0 8 9 1 2 2). However, the above method indirectly increases the melting point, and as a result, the preheating time of the sheet is prolonged in the thermoforming, which gives an influence of poor productivity. DISCLOSURE OF THE INVENTION An object of the present invention is to provide a polypropylene resin which has excellent rigidity and heat resistance and which has excellent thermoformability, and a sheet and a thermoformed body formed of the resin. The inventors of the present invention conducted intensive studies on polypropylene resins in order to solve the above problems, and found that integration of a specific range of comonomer content, a specific range of melt flow rate, a specific molecular weight distribution, and a specific stereoscopic 5 312XP/invention specification (Repair)/93-12/93124531 1298733 A sheet composed of a regular propylene-based polymer, and a polypropylene resin composition containing a specific amount of the propylene-based polymer and polyethylene, having excellent rigidity and The heat is excellent, and the thermoformability is also good, and the rigidity and heat resistance of the hot formed body obtained from the sheet are greatly improved as compared with the conventional hot formed body, thereby completing the present invention. That is, the present invention relates to the following propylene-based polymers (A), (A') and (A',), and the composition of the polymer (B) containing the above polymer [in the following description, (A) (A '), (A ' '), (B) are collectively referred to as polypropylene resin, and sheets and thermoforms (C 1 ) and (C 2 ) formed therefrom. (A) is a propylene copolymer of propylene, ethylene or an olefin having 4 to 20 carbon atoms, which simultaneously satisfies the following conditions [1] to [4]. [1] The content of the constituent unit derived from ethylene or a carbon number of 4 to 20: olefin is in the range of 0.1 to 2. Omol%; [2] melt flow rate (2 3 0 ° C, load 2) · 1 6 kg ) is 0 · :1~5 · 0 g / 10 0 minutes; [3] Mw/Mn measured by GPC method is 5.0~20; [4] Pmmmm and Pw from 13C-NMR spectrum The absorption intensity is obtained by the following formula (Eq-1). The value of the stereoregularity index [Ms] is 0·9 6 0~0· 9 9 0, mmm Μ m] (Eq-1) [Pmmmm] represents the absorption strength of the thiol group of the third unit from the isotactic bonding sites of the five consecutive propylene units, and [Pw] represents the absorption strength of the thiol group derived from the propylene unit.) 6 312XP /Invention Manual (Supplement)/93-12/93124531 1298733 (A ') is the above propylene-based polymer (A), which has a melting point of 150.0 to 163.0 ° 〇, 230 ° (measured by melt pressure) measured by DSC It is a propylene-based polymer of 80 to 18011. [In the following description, these two conditions are respectively referred to as conditions [5] and conditions [6].] (A ' ') is the above-mentioned propylene-based polymer (A '), According to the standard of AST Μ - D - 8 8 2 The sheet having a thickness of 0.6 mm has a tensile modulus of 1 500 to 1 9 Ο Μ P a of a propylene-based polymer. [In the following description, this condition is called a condition [7].] (B) is 70 to 98% by weight of the above propylene-based polymers (A), (A') and (A ''), and 2 to 30% by weight of a polymer different from the propylene-based polymer ( Q) A polypropylene resin composition composed of (C 1 ) is a polypropylene sheet formed of the above polypropylene resins (A), (A ') and (A ' '), or is thermoformed from the sheet The obtained molded body (C 2 ) is a polypropylene sheet formed of the above polypropylene resin composition (B), or a molded body obtained by thermoforming the sheet. The propylene-based polymer or resin of the present invention. The sheet formed of the composition has excellent rigidity, heat resistance and thermoformability, and is suitable as a material for a thermoformed product. [Embodiment] The polypropylene resin of the present invention is a propylene-based polymer (A) to contain The resin composition (B) of the propylene-based polymer (A). The propylene-based polymer (A) of the present invention contains C. The polymer constituting the unit is a copolymer of propylene, acetonitrile or an α-dilute hydrocarbon having a carbon number of 4 to 20%. Here, the α-olefin having a carbon number of 4 to 20 may be exemplified by 1-butene. Alkene, 1-pentene, 7 312 ΧΡ / invention specification (supplement) / 93-12/93124531 1298733 1 -hexene, 4-mercapto-1-pentene, 1-octene, 1-decene, 1- Dodecene, 1-h tetraene, 1-h six carbon, 1 - (" eight carbon thin, 1- 20 carbon thin, etc. Among them, ethylene or an α-olefin having 4 to 10 carbon atoms is preferred. In the polypropylene resin, the content of the constituent units derived from the α-cationic hydrocarbon is 0.1 to 2. Omol%, preferably 0.2 to 0.8 niol%. The propylene polymer of the present invention has a melt flow rate (M F R ) of 0. 3g/10 minutes, preferably 0. 3~1. 0g/10 minutes. Since the MFR is within this range, the sheet is excellent in extrudability during molding. Next, the Mw/Mn of the propylene polymer (A) of the present invention measured by the G P C method is 5.0 to 20, preferably 7.0 to 14. Mw/Mn is an index indicating the molecular weight distribution. When the value is within the above range, the polymer has a broad molecular weight distribution, so that the melt tension is high and the drawdown is good at the time of thermoforming. From the absorption density of Pmmmm and Pw in the 13C-NMR spectrum of the propylene-based polymer (A) of the present invention, the value of the stereoregularity index [Μ 5 ] obtained by the following formula (E q - 1 ) is 0. 9 6 0~0 . 9 9 0, preferably 0. 9 7 0~0 . 9 9 0. Within this range, a sheet having high rigidity and high heat resistance and a hot 戍 shape can be obtained.
Wsh Μ .· · · ( E q - 1 ) 且在上述式（Eq - 1)中，[Pmmmm]表示來自5個連續丙婦 單元所整規（isotactic)鍵結部位中，第3個單元之甲基之 吸收強度，[Pw]表示來自丙烯單元之甲基之吸收強度。 本發明之丙烯系聚合物（A )之較佳態樣，係由D S C所測 得之熔點（Tm)爲150〜163°C ，較佳爲157〜162°C (條件 8 312XP/發明說明書(補件)/93-12/93124531 1298733 [5 ])。因習知所用之聚丙烯片材之Tm爲1 6 3 °C左右，所以 熱成形時，片材預熱時間不會長於習知技術。 又，本發明之丙烯系聚合物（A)之另一較佳態樣，係2 3 0 °C時之熔融張力爲8 0〜1 8 0 m N，較佳爲9 0〜1 8 0 m N (條件 [6 ])。當熔融張力在該範圍内時，熱成形時之片材下引小， 且深拉延性（deep drawability)良好。 本發明之丙烯系聚合物（A)除上述熔點及熔融張力之條 件[5]及[6]外，還具有根據AST M_D_ 8 8 2之標準（拉伸速度 爲1 0 m m / m i η )所測得之厚度為0 . 6 m m之片材之拉伸彈性率 爲1 5 0 0〜1 9 0 0 MPa，較佳爲1 6 0 0〜1 9 0 0 MPa之特性（條件 [7 ])。當在該範圍時，可有效地得到高剛性、高耐熱性之 片材及熱成形體。 上述滿足乙烯或碳數4〜20之α -烯烴之含量、MFR、 M w / Μ η、[ Μ 5 ]、T m等條件之丙烤系聚合物，係可使用載體 型鈦系觸媒，例如鎂載體型鈦系觸媒，使丙烯與上述單體 之共聚合以兩階段以上之多段聚合方式進行而製得。 鎂載體型鈦系觸媒可舉出有包括例如含有鎂、鈦、_素 及電子供應體（donor)之固體狀鈦系觸媒成分、與含有有機 金屬化合物與電子供應體之觸媒等。 丙烯系聚合物之立體規則性受到電子供應體種類之影 響很大，可得到高立體規則性之電子供應體係以有機矽化 合物為佳，控制聚合時之立體障礙化之單體插入方向，以 提高立體規則性。 本發明所用之有機矽化合物，係如下述一般式（I )所示。 9 312XP/發明說明書(補件)/93-12/93124531 1298733Wsh Μ ·· · · ( E q - 1 ) and in the above formula (Eq - 1), [Pmmmm] represents the isotactic bond from the five consecutive women's units, the third unit The absorption strength of the methyl group, [Pw] represents the absorption strength of the methyl group derived from the propylene unit. A preferred aspect of the propylene-based polymer (A) of the present invention is a melting point (Tm) measured by DSC of from 150 to 163 ° C, preferably from 157 to 162 ° C (condition 8 312 XP / invention specification ( Supplement) /93-12/93124531 1298733 [5 ]). Since the Tm of the polypropylene sheet used in the prior art is about 163 ° C, the sheet preheating time is not longer than the conventional technique at the time of thermoforming. Further, in another preferred embodiment of the propylene-based polymer (A) of the present invention, the melt tension at 20 ° C is from 80 to 180 m N, preferably from 90 to 180 m. N (condition [6]). When the melt tension is within this range, the sheet at the time of thermoforming is small and the deep drawability is good. The propylene-based polymer (A) of the present invention has a standard according to AST M_D_ 8 8 2 (tensile speed of 10 mm / mi η ) in addition to the above conditions of melting point and melt tension [5] and [6]. The measured tensile modulus of the sheet having a thickness of 0.6 mm is from 1 500 to 190 MPa, preferably from 1 600 to 190 MPa (condition [7]). . When it is in this range, a sheet having high rigidity and high heat resistance and a thermoformed body can be obtained efficiently. The above-mentioned acrylic-type catalyst which satisfies the conditions of ethylene or a carbon number of 4 to 20 α-olefin, MFR, M w / Μ η, [ Μ 5 ], T m and the like can be used as a carrier-type titanium-based catalyst. For example, a magnesium carrier type titanium catalyst is obtained by copolymerizing propylene with the above monomer in a multistage polymerization method of two or more stages. The magnesium-supporting titanium-based catalyst includes, for example, a solid titanium-based catalyst component containing magnesium, titanium, and an electron donor, and a catalyst containing an organometallic compound and an electron donor. The stereoregularity of the propylene-based polymer is greatly affected by the type of the electron donor, and the electron supply system with high stereoregularity is preferably an organic ruthenium compound, and the monomer insertion direction for controlling the steric hindrance during polymerization is improved. Stereo regularity. The organic hydrazine compound used in the present invention is represented by the following general formula (I). 9 312XP/Invention Manual (supplement)/93-12/93124531 1298733
RanSi (0Rb)4-n ......... ( I ) 在上述一般式（I)中，n爲1、2或3，當n爲1時，Ra 爲二級或三級之烴基；當η爲2或3時，至少1個Ra爲二 級或三級之烴基；Ra既可相同，亦可相異；Rb爲碳數1〜4 之烴基；4 - η爲2或3時，Rb可相同，亦可相異。 當η爲1時，上述一般式（I )所示之有機矽化合物可例 舉有：環戊基三曱氧基矽烷、2 -曱基環戊基三曱氧基矽烷、 2，3 -二曱基環戊基三曱氧基矽烷、環戊基三乙氧基矽烷、 異丁基三乙氧基矽烷、第三丁基三乙氧基矽烷、環己基三 甲氧基矽烷、環己基三乙氧基矽烷、2 -降冰片烷基三甲氧 基碎烧、2 -降冰片烧基三乙氧基石夕烧等三烧氧基碎烧類。 當上述一般式（I )中之η爲2時，可例舉有··二環戊基 二乙氧基矽烷、第三丁基曱基二曱氧基矽烷、第三丁基曱 基二乙氧基碎烧、第三戊基曱基二乙氧基石夕烧、二環己基 二曱氧基矽烷、環己基甲基二甲氧基矽烷、環己基甲基二 乙氧基矽烷、2_降冰片烷基曱基二曱氧基矽烷等二烷氧基 石夕烧類。 當上述一般式（I )中之η爲3時，可列舉有：三環戊基 曱氧基矽烷、三環戊基乙氧基矽烷、二環戊基曱基甲氧基 矽烷、二環戊基乙基甲氧基矽烷、二環戊基甲基乙氧基矽 烷、環戊基二曱基甲氧基矽烷、環戊基二乙基甲氧基矽烷、 環戊基二甲基乙氧基矽烷、三甲基曱氧基矽烷等單烷氧基 石夕烧類等。 其中，較佳爲二甲氧基矽烷類，具體言之，較佳爲二環 10 312ΧΡ/發明說明書(補件)/93-12/93124531 1298733 戊基二甲氧基矽烷、二第三丁基二曱氧基矽烷、二（2 -曱基 環戊基）二曱氧基矽烷、二（3-曱基環戊基）二曱氧基矽烷、 二第三戊基曱氧基矽烷。 多段聚合係指例如在前段聚合中，製造相對較高分子量 之聚丙烯，而在後段聚合中，製造相對較低分子量之聚丙 烯，以擴展分子量分佈之聚合方法。 具體而言，當採用兩段聚合時，在第一階段中，使極限 黏度[7?1以]爲3.0〜4.5(11/运，較佳爲3.5〜4.5(11/8之聚丙 烯，在最終所得聚丙烯中之含量達到1 0〜6 0重量％之量來製 造，然後，在第二階段中，使極限黏度[?? 2nd ]爲 0.；!〜5dl/g，較佳爲0.3〜3dl/g之聚丙烯，在最終所得聚丙 稀中之含量達到90〜40重量％之量來製造。在此情況下，在 全段或任一段中進行共聚合。 如上所述，當前段聚合而得之聚丙烯之極限黏度[7? ! s t ] 為上述範圍内時，可抑制白點（丙烯塊狀物等）之發生量， 而能得到外觀良好之片材或熱成形體。 本發明中，還可將上述丙烯系聚合物（A )〜（A 與不同 於該聚合物之其他聚合物（Q)組合。亦即，既可單獨使用上 述之丙婦系聚合物（A)〜（A’’），也可在混合有聚合物（Q)之 樹脂組合物之態樣下使用[以下稱此類樹脂組合物爲聚丙 烯樹脂組合物（B )]。 本發明之聚丙烯樹脂組合物（B)係上述丙烯系聚合物 (A )〜（A ’ ’）與聚合物（Q )之樹脂組合物，其構成比例係該聚 丙烯系聚合物爲7 0〜9 8重量％，較佳爲8 0〜9 0重量％，聚合 11 312XP/發明說明書(補件)/93-12/93124531 1298733 物（Q )爲2〜3 0重量％，較佳爲· 1 0〜2 0重量％。由於處於該混 合比率範圍之樹脂組合物，在熱成形性中之下引性可進一 步提高，其結果係可擴展片材之寬度等，在提高生産性之 同時也提高了耐衝擊性，因此較佳。 聚合物（Q )可舉出有：聚乙烯；聚-1 - 丁烯、聚異丁烯、 聚-1 -戊烯、聚曱基-1 -戊烯等聚α -烯烴；丙烯含量小於 7 5重量％之乙烯·丙烯共聚物、乙烯· 1 - 丁烯共聚物、丙烯 含量小於7 5重量％之丙烯· 1 - 丁烯共聚物等乙烯或α -烯 烴· α -烯烴共聚物；丙烯含量小於7 5重量％之乙烯·丙烯· 5 -亞乙基-2 -降冰片烯共聚物等乙烯或α -烯烴· α -烯烴· 二烯單體之共聚物；苯乙烯·丁二烯無規共聚物等乙烯單 體·二烯單體之無規共聚物；苯乙烯·丁二烯·苯乙烯嵌段共 聚物等乙稀單體·二稀單體·乙烯單體之喪段共聚物；氫化 (苯乙烯·丁二烯無規共聚物）等氫化（乙烯單體·二烯單體 無規共聚物）；氫化（苯乙烯· 丁二烯·苯乙烯嵌段共聚物） 等氫化（乙烯單體·二烯單體·乙烯單體嵌段共聚物）等。 在該等聚合物（Q )中，較佳爲聚乙烯。可用之聚乙烯爲 MFR(19(TC ，負重2. 16kg)爲0. 1〜10g/10分鐘，較佳爲 0 . 1〜5 g / 1 0分鐘之聚乙烯。具體而言，可適合使用高壓法 所製造之具有長鏈分支之低密度聚乙烯、具有直鏈狀分子 構造之低密度聚乙烯、高密度聚乙烯、或該等兩種以上之 混合物。 當聚合物（Q )使用除聚乙烯之外之樹脂或橡膠時，其添 加量係隨所添加樹脂之種類及橡膠之種類而異，在無損於 12 312XP/發明說明書(補件)/93-】2/93】2453】 1298733 上述本發明之目的之範圍内，通常在上述丙烯系聚合物 (A )〜（A ’ ’）中之含量約在1 0重量％以下。 又，在以本發明之聚丙烯樹脂爲原料加工成形爲片材 (C1)或（C2)時，在不超出本發明之目的之範圍内，還可添 加填充材料。填充材料可例舉有：滑石、碳酸鈣、黏土、 雲母、玻璃纖維、玻璃片、玻璃珠、矽酸鈣、二氧化矽、 矽藻土、氧化鋁、氧化鈦、氧化鎂、浮石粉、浮石球、氫 氧化铭、氫氧化鎮、驗性碳酸鎮、白雲石、硫酸辦、鈦酸 鉀、硫酸鋇、亞硫酸鈣、蒙脫石、膨潤土、石墨、鋁粉、 硫化鉬、硼纖維、碳化矽纖維、聚酯纖維及聚醯胺纖維等。 填充材料之添加量隨所添加之填充材料之種類而不 同，在無損於上述本發明之目的之範圍内，通常在丙烯系 聚合物或樹脂組合物中之含量約在3 0重量％以下。 而且，在以本發明之丙烯系聚合物或其樹脂組合物爲原 料加工成形爲片材（C 1 )或（C 2 )時，在不超出本發明之目的 之範圍内，還可添加抗氧化劑、紫外線吸收劑、金屬皂類、 鹽酸吸收劑等穩定劑、滑劑、難燃劑、抗靜電劑、發泡劑 等添加劑。 添加劑之添加量隨添加劑之種類而不同，在無損於上述 本發明之目的之範圍内，通常在丙烯系聚合物（A)〜（A’’） 或樹脂組合物（B)中之含量約在3重量％以下。 由具有上述物性及組成之丙烯系聚合物或樹脂組合物 所形成之片材，係剛性，对熱性提升之同時，熱成形性也 變佳。通常供給於擠出機之丙烯系聚合物及樹脂組合物， 13 312XP/發明說明書(補件)/93-12/93124531 1298733 係將樹脂溫度調整到1 7 0〜2 8 0 °C (較佳爲2 Ο 0〜2 5 0 °C )，由裝 配在擠出機前端之T形模具擠出，一邊利用溫度調整到3 Ο °C以上（較佳爲6 0〜9 0 °C )之冷卻親冷卻，一邊拉伸。拉伸 速度爲0 . 2〜1 0 m /分，通過冷卻輥之片材厚度以達到 0 . 1〜1 0 mm為佳。另外，本發明還包括以上述丙烯系聚合物 及上述聚丙烤樹脂組合物之混合物爲原料之丙烯片材。 上述聚丙烯片材係包括未延伸片材、多層片材、單軸及 雙軸延伸片材。進行拉伸之方法可舉出有拉幅式逐步雙軸 延伸法及藉由管式之同步雙軸延伸法。 當上述聚丙烯片材爲多層片材時，對各層構造並無限 定，即使僅含有一層本發明之丙浠系聚合物及樹脂組合物 所形成之層，熱成形性即可變佳。多層片材可例舉有··於 芯（c 〇 r e )層使用本發明之聚丙稀樹脂及樹脂組合物，於皮 (s k i η )層使用低溶點之無規P P，使熱密封性得到改善者、 或於最内層使用乙烯·乙烯醇樹脂等阻氣性樹脂之高性能 片材等。 由於上述聚丙烯片材在真空成形及壓空成形等熱成形 中，下引小且加熱時間短，因此生産性良好。所得到之熱 成形體可廣泛用於以食品容器為首之産業材料、醫藥品等 之各種包裝材料。 接著根據實施例詳細說明本發明，但本發明不受限於該 等實施例。實施例中之物性測量方法如下所述。 1 )熔體流動速率（M F R ) 按照ASTM-D 1 2 3 8之標準，在2 3 0 °C 、負重2. 1 6kg下進 14 312XP/發明說明書(補件)/93-12/93124531 1298733 行測量。 2 )熔融張力 使用東洋精機公司製CAPILOGRAPH 1C，將在2 3 0 °C 、 1 5 m m /分條件下擠出之線料以1 5 m /分之速度拉伸時之張力 作爲溶融張力測量之。 毛細管形狀：L=8mm， D=2.095mm 3 ) M w 及 Μ η 利用GPC法在下述條件下進行測量。 裝置：Waters 公司製 150Cvtype;樣品濃度·· 7.5mg/4ml ; 管柱：昭和電工（股）製Shodex AD - 806ms; 測量溫度：1 3 5 °C ;溶劑：鄰二氣苯，按聚苯乙烯換算。 4 )極限黏度[??] 在1 3 5 °C之四氫化萘溶劑中測量。 5 )整規中間五價元素分率（[M5 ]) 由13C-NMR光譜中Pmmmm及Pw之吸收強度，利用上述式（Eq-1 ) 決定。但是，峰歸屬係按照 Polymer，1993, Vo 134, No 14,3129-3131 進行。 6 )溶點 以使用D S C在1 0 °C /分鐘之升溫速度下的熔融熱量之峰 爲炫點。 7 )拉伸彈性率 按照A S T Μ _ D - 8 8 2之標準，在如下條件下測量。 試片形狀：1號型（厚度0.6mm)，鏈距：100mm，拉伸速 度：10mm/分鐘。 15 312XP/發明說明書(補件)/93-12/93124531 1298733 8 )杜邦衝擊強度RanSi (0Rb)4-n (I) In the above general formula (I), n is 1, 2 or 3, and when n is 1, Ra is a secondary or tertiary a hydrocarbon group; when η is 2 or 3, at least one Ra is a secondary or tertiary hydrocarbon group; Ra may be the same or different; Rb is a hydrocarbon group having 1 to 4 carbon atoms; 4 - η is 2 or 3 When Rb is the same, it can be different. When η is 1, the above organic oxime compound represented by the general formula (I) may, for example, be: cyclopentyltrimethoxy decane, 2-nonylcyclopentyltrimethoxy decane, 2,3 - two. Indenylcyclopentyltrimethoxy decane, cyclopentyltriethoxydecane, isobutyltriethoxydecane, tert-butyltriethoxydecane, cyclohexyltrimethoxynonane, cyclohexyltriethyl Alkoxylated calcined oxoxane, 2-norbornyltrimethoxysulfonate, 2-norbornyl triethoxycarbazone. When η in the above general formula (I) is 2, there may be mentioned dicyclopentyldiethoxydecane, tert-butyldecyldimethoxy decane, and tert-butyldecyldiethyl Alkyl calcination, third amyl decyl diethoxy sulphur, dicyclohexyl decyloxy decane, cyclohexylmethyl dimethoxy decane, cyclohexylmethyl diethoxy decane, 2 _ drop A dialkoxy group such as borneol alkyl decyl decyloxy decane. When η in the above general formula (I) is 3, there may be mentioned: tricyclopentyl decyloxydecane, tricyclopentylethoxy decane, dicyclopentyl decyl methoxy decane, and dicyclopentane. Ethyl methoxy decane, dicyclopentylmethyl ethoxy decane, cyclopentyl dimethyl methoxy decane, cyclopentyl diethyl methoxy decane, cyclopentyl dimethyl ethoxy a monoalkoxy group such as decane or trimethyldecyloxydecane. Among them, dimethoxydecane is preferable, and specifically, it is preferably a bicyclo 10 312 ΧΡ / invention specification (supplement) / 93-12/93124531 1298733 pentyl dimethoxy decane, di-tert-butyl Dimethoxydecane, bis(2-indenylcyclopentyl)dimethoxyoxydecane, bis(3-indolylcyclopentyl)dimethoxyoxydecane, di-third amyldecyloxydecane. The multistage polymerization means, for example, a polymerization method in which a relatively high molecular weight polypropylene is produced in the preceding stage polymerization, and a relatively low molecular weight polypropylene is produced in the latter stage polymerization to expand the molecular weight distribution. Specifically, when two-stage polymerization is employed, in the first stage, the ultimate viscosity [7?1] is 3.0 to 4.5 (11/port, preferably 3.5 to 4.5 (11/8 of polypropylene, in The content of the finally obtained polypropylene is 10 to 60% by weight, and then, in the second stage, the ultimate viscosity [?? 2nd] is 0.;!~5dl/g, preferably 0.3. The polypropylene of ~3 dl/g is produced in an amount of 90 to 40% by weight in the finally obtained polypropylene. In this case, copolymerization is carried out in the whole stage or in any of the stages. As described above, the current stage polymerization is carried out. When the ultimate viscosity [7?! st ] of the obtained polypropylene is within the above range, the amount of occurrence of white spots (acrylic bulk or the like) can be suppressed, and a sheet or a thermoformed body having a good appearance can be obtained. Further, the above propylene-based polymers (A) to (A may be combined with other polymers (Q) different from the polymer. That is, the above-mentioned propylene-based polymer (A) ～ (( A'') can also be used in the form of a resin composition in which a polymer (Q) is mixed [hereinafter, such a resin composition is a polypropylene resin) (B)] The polypropylene resin composition (B) of the present invention is a resin composition of the above propylene-based polymer (A) to (A'') and a polymer (Q), and the composition ratio thereof is the polymerization. The propylene-based polymer is 70 to 98% by weight, preferably 80 to 90% by weight, and the polymerization 11 312XP/invention specification (supplement)/93-12/93124531 1298733 (Q) is 2 to 3 0 The weight % is preferably from 10 to 20% by weight. The resin composition in the range of the mixing ratio can be further improved in the formability in the thermoformability, and as a result, the width of the sheet can be expanded, and the like. It is preferable to improve the productivity while improving the impact resistance. The polymer (Q) may be exemplified by polyethylene, poly-1 - butene, polyisobutylene, poly-1 -pentene, and polydecyl. a poly-α-olefin such as pentene; an ethylene·propylene copolymer having a propylene content of less than 7.5 wt%, an ethylene·1-butene copolymer, and a propylene·1-butene copolymer having a propylene content of less than 7.5 wt%; Ethylene or α-olefin·α-olefin copolymer; ethylene·propylene·5-ethylidene-2-norbornium having a propylene content of less than 7.5 wt% a copolymer of ethylene or an α-olefin·α-olefin·diene monomer such as a copolymer; a random copolymer of an ethylene monomer·diene monomer such as a styrene-butadiene random copolymer; styrene·butyl Hydrogenated (styrene-butadiene random copolymer) and other hydrogenated (ethylene monomer·two) copolymers such as diene styrene block copolymers, ethylene monomer, dilute monomer, and ethylene monomer Alkene monomer random copolymer); hydrogenation (styrene-butadiene-styrene block copolymer) and the like (ethylene monomer, diene monomer, ethylene monomer block copolymer) and the like. Among the polymers (Q), polyethylene is preferred. The polyethylene used is MFR (19 (TC, weight 2.16 kg) is 0. 1~10g/10 minutes, preferably 0. 1~5 g / 10 minutes of polyethylene. Specifically, suitable for use a low-density polyethylene having a long-chain branch, a low-density polyethylene having a linear molecular structure, a high-density polyethylene, or a mixture of two or more thereof produced by a high-pressure method. When the polymer (Q) is used for depolymerization When the resin or rubber other than ethylene is added, the amount of the resin varies depending on the type of the resin to be added and the type of the rubber, and is not impaired in 12 312 XP/invention specification (supplement)/93-] 2/93] 2453] 1298733 In the range of the object of the present invention, the content of the propylene polymer (A) to (A ' ') is usually about 10% by weight or less. Further, the polypropylene resin of the present invention is processed into a raw material. In the case of the sheet (C1) or (C2), a filler may be added within a range not exceeding the object of the present invention. The filler may be exemplified by talc, calcium carbonate, clay, mica, glass fiber, glass flakes, Glass beads, calcium citrate, cerium oxide, diatomaceous earth, alumina, oxidation , magnesium oxide, pumice powder, pumice ball, hydrazine, oxidized town, test carbonate, dolomite, sulfuric acid, potassium titanate, barium sulfate, calcium sulfite, montmorillonite, bentonite, graphite, aluminum powder , molybdenum sulfide, boron fiber, tantalum carbide fiber, polyester fiber, polyamide fiber, etc. The amount of the filler added varies depending on the type of the filler to be added, and is generally within the scope of the above-described object of the present invention. The content of the propylene-based polymer or the resin composition is about 30% by weight or less. Further, the propylene-based polymer of the present invention or a resin composition thereof is processed into a sheet (C 1 ) or (C). 2) In the range not exceeding the object of the present invention, stabilizers such as antioxidants, ultraviolet absorbers, metal soaps, hydrochloric acid absorbents, slip agents, flame retardants, antistatic agents, and foaming agents may be added. The additive is added in an amount depending on the kind of the additive, and is usually in the range of the above-mentioned object of the present invention, usually in the propylene-based polymer (A) to (A'') or the resin composition (B). content The sheet formed of the propylene-based polymer or the resin composition having the above physical properties and composition is rigid, and has improved heat resistance and thermoformability. Usually, it is supplied to an extruder. The propylene-based polymer and resin composition, 13 312XP / invention specification (supplement) / 93-12/93124531 1298733 adjust the resin temperature to 1 70 0 2 2 0 ° C (preferably 2 Ο 0~2) 50 ° C ), extruded by a T-die mounted on the front end of the extruder, while being cooled by cooling with a temperature adjusted to 3 Ο ° C or higher (preferably 60 0 to 90 ° C) The stretching speed is 0. 2~1 0 m / min, and the thickness of the sheet passing through the cooling roll is preferably 0.1 to 1 mm. Further, the present invention also includes a propylene sheet comprising a mixture of the above propylene-based polymer and the above-mentioned polypropylene-baked resin composition. The above polypropylene sheet comprises an unstretched sheet, a multilayer sheet, a uniaxial and biaxially stretched sheet. The stretching method may be a tenter type stepwise biaxial stretching method or a tubular simultaneous biaxial stretching method. When the polypropylene sheet is a multilayer sheet, the structure of each layer is indefinite, and even if only one layer of the acrylic polymer and the resin composition of the present invention is contained, the hot formability can be improved. The multilayer sheet may be exemplified by using the polypropylene resin and the resin composition of the present invention in a core layer and a random PP having a low melting point in a skin layer to obtain heat sealability. A high-performance sheet or the like which is a gas barrier resin such as an ethylene vinyl alcohol resin or the like is used for the improvement. In the thermoforming such as vacuum forming and pressure forming, the polypropylene sheet has a small undercut and a short heating time, so that the productivity is good. The obtained hot-formed body can be widely used for various packaging materials such as industrial materials and pharmaceuticals including food containers. Next, the present invention will be described in detail based on examples, but the present invention is not limited to the examples. The physical property measurement method in the examples is as follows. 1) Melt flow rate (MFR) according to ASTM-D 1 2 3 8 standard, at 2 30 ° C, weight 2.16 kg, 14 312XP / invention manual (supplement) / 93-12/93124531 1298733 Line measurement. 2) The melt tension was measured by using the CAPILOGRAPH 1C manufactured by Toyo Seiki Co., Ltd., and the tension of the strand extruded at 215 ° C and 15 mm / min was measured at a speed of 15 m / min. . Capillary shape: L = 8 mm, D = 2.095 mm 3 ) M w and Μ η Measurement was carried out by the GPC method under the following conditions. Device: 150Cvtype manufactured by Waters Co., Ltd.; sample concentration · 7.5 mg / 4 ml; column: Shodex AD - 806 ms manufactured by Showa Denko Co., Ltd.; measured temperature: 135 ° C; solvent: o-diphenylbenzene, polystyrene Conversion. 4) The ultimate viscosity [??] is measured in tetrahydronaphthalene solvent at 135 °C. 5) The intermediate pentavalent element fraction ([M5]) The absorption intensity of Pmmmm and Pw in the 13C-NMR spectrum is determined by the above formula (Eq-1). However, the peak assignment is carried out in accordance with Polymer, 1993, Vo 134, No 14, 3129-3131. 6) Melting point The peak of the heat of fusion using D S C at a heating rate of 10 ° C /min is a dazzling point. 7) Tensile modulus According to the standard of A S T Μ _ D - 8 8 2, it was measured under the following conditions. Test piece shape: No. 1 type (thickness 0.6 mm), chain length: 100 mm, and stretching speed: 10 mm/min. 15 312XP/Invention Manual (Repair)/93-12/93124531 1298733 8) DuPont Impact Strength
片材厚度：0 . 6 mm，落錘尖端徑：1 / 2英吋0，承擊口徑： 1 / 2英吋0 ，溫度：2 3 °C 9 )負重-變形溫度 按照A S T Μ - D - 6 4 8之標準測量。負重：0 . 4 5 M p a。 1 0 )熱成形性（回縮時間及3 0 in m拉伸時間） 由片材成形機成形之片材，在熱成形之預熱步驟中，如 圖1所示地發生變化。首先，將兩端固定之片材，因上下 加熱器之加熱發生熱膨脹，形成不定形之褶皺（步驟1 )。 進而因軟化及熱膨脹發生下垂（步驟2 )，當片材整體達到 熔點附近時，因殘餘應力而收縮，産生暫時回縮（步驟3 )。 再加熱後，片材完全熔融，因自身重量發生下引（步驟4 )。 通常在步驟3〜4之間，將片材送至模具上，利用真空吸收 等予以成形。在本發明中，步驟3之回縮時間越短、越難 以發生下引之片材之熱成形性越好。 使用淺野製作所製造之真空壓空成形機，在下述條件下 測量至該回縮發生之時間與回縮後下垂達30mm之時間。 上下加熱器溫度：3 5 0 °C ;上下加熱器間距：2 0 0 m in ;片 材尺寸：350x350mm;片材厚度·· 0.6mm。 (實施例1 ) 作為丙烯系聚合物，係利用以二環戊基二曱氧基矽烷爲 電子供應體之載體型鈦系觸媒（高立體規則性觸媒），將乙 稀構成單元之含量爲0 . 6 in ο 1 %之無規共聚合，藉由兩段聚 合調製成極限黏度[??]爲4 . 3 d 1 / g之高分子量體爲5 2重量 16 312XP/發明說明書(補件)/93-12/93124531 1298733 °/〇、極限黏度[77 ]爲2 · 1 d 1 / g之低分子量體爲4 8重量％之 量，使用將分子量分佈擴大之丙稀·乙烤共聚物，相對於該 共聚物1 0 0重量％，配合0 . 1重量份之為酚系抗氧化劑的四 [亞曱基-3 ( 3，5 -二第三丁基-4 -羥苯基）丙酸酯]曱烷（齊巴 思潘夏利提化學（股）製）、0 . 1重量份之為磷系抗氧化劑的 2, 2-亞曱基雙（4, 6 -二第三丁基笨基）辛基亞磷酸鹽（旭電 化工業（股）製）、0 . 0 2重量份之為内酯系抗氧化劑的3 -羥 基-5. 7 -第三丁基-呋喃-2 -酮與鄰二曱苯之反應生成物（齊 巴思潘夏利提化學（股）製）、以及0 · 1重量份之為中和劑的 硬脂酸鈣（日本油脂（股）製），再使用單軸擠出機，在樹脂 溫度2 3 0 °C下進行熔融混練並製造成顆粒。所得顆粒之所 測量之物性示於表1。 將上述所得顆粒供給於>1材成形機，將樹脂溫度調至 2 7 0 °C，由T形模具擠出，使用溫度保持爲8 0 °C之冷卻輥， 以1 . 2 m /分鐘之拉伸速度加工成形厚度0 . 6 m m之片材。對 所得片材之機械物性及熱成形性進行評估，結果示於表1。 (實施例2 ) 除使用以二環戊基二甲氧基矽烷爲電子供應體之載體 型鈦系觸媒，將乙烯構成單元之含量爲0 · 4 m ο 1 %之無規共 聚合，藉由兩段聚合調製成極限黏度[??]爲4. 3 d 1 / g之高 分子量體爲5 1重量％、極限黏度[]爲2 . 2 d 1 / g之低分子 量體爲4 9重量％之量，將分子量分佈擴大之丙烯*乙烯共聚 物取代實施例1所用之丙烯系聚合物之外，其他與實施例 1 一樣。結果一併示於表1。 17 312XP/發明說明書(補件)/93-12/93124531 1298733 (實施例3 ) 除使用以二環戊基二甲氧基矽烷爲電子供應體之載體 型鈦系觸媒，將乙稀構成單元之含量爲0 . 8 m ο 1 %之無規共 聚合，藉由兩段聚合調製成極限黏度[7?]爲4 · 2 d 1 / g之高 分子量體爲51重量％、極限黏度[7?]爲2.2dl/g之低分子 量體爲4 9重量％之量，將分子量分佈擴大之丙烯·乙烯共聚 物代替實施例1所用之丙烯系聚合物之外，其他與實施例 1 一樣。結果一併示於表1。 (實施例4 ) 除使用由與實施例1相同之丙烯系聚合物8 0重量％、在 1 9 0 °C、2 · 1 6 k g負重下測得之M F R爲0 · 3 5 g / 1 0分鐘之高壓 法低密.度聚乙烯（三井化學（股）製MIRASON 102)15重量％、 及在同樣條件下測得之M F R爲0. 3 2 g / 1 0分鐘之高密度聚乙 烯（三井化學（股）製HI-ZEX 5 2 0 2 B)5重量％所構成之樹脂組 合物代替實施例1所用之丙烯系聚合物之外，其他與實施 例1 一樣。結果一併示於表1。 (實施例5 ) 除使用由與實施例1相同之丙烯系聚合物85重量％、與 實施例4相同之高密度聚乙烯1 5重量％所構成之樹脂組合 物代替實施例1所用之丙烯系聚合物之外，其他與實施例 1 一樣。結果一併示於表1。 (比較例1 ) 除使用以環己基甲基二甲氧基矽烷爲電子供應體之載 體型鈦系觸媒（中立體規則性觸媒），藉由兩段聚合調製成 18 312XP/發明說明書(補件)/93-〗2/93124531 1298733 極限黏度[7?]爲3 · 7 d 1 / g之高分子量體爲5 0重量％ '極限 黏度[7?]爲2. 6dl/g之低分子量體爲50重量％之量，將分 子量分佈擴大之丙烯單獨聚合物代替實施例1所用之丙烯 系聚合物之外，其他與實施例1 一樣。該聚合物相當於習 知使用之材料。結果一併示於表1。 (比較例2 ) 除使用以二環戊基二甲氧基矽烷爲電子供應體之載體 型鈦系觸媒，藉由兩段聚合調製成極限黏度[]爲 4 . 3 d 1 / g之高分子量體爲5 2重量％、極限黏度[??]爲 1 . 9 d 1 / g之低分子量體爲4 8重量％之量，將分子量分佈擴 大之丙烯單聚物代替實施例1所用之丙烯系聚合物之外， 其他與實施例1 一樣。結果一併示於表1。 (比較例3 ) 除使用由與比較例1相同之丙烯單獨聚合物8 0重量％、 與實施例4相同之高壓法低密度聚乙烯1 5重量％、及與實 施例4相同之高密度聚乙烯5重量％所構成之樹脂組合物代 替比較例1所用之丙稀單獨聚合物之外，其他與實施例1 一樣。結果一併示於表1。 19 312XP/發明說明書(補件)/93-12/93124531 1298733 比較例3 1丨1 S 1〜 0.33 7.1 161· 0 120 ◦ cz> οα · τ"'·Η ι 1 ii 1 卜oo CO LO 比較例2 1 1 1 1 § 1 1 1—Η 0.40 9.3 0.98 163.6 92 1690 0.5 oo τ 1 r-H CD卜 寸οα 比較例1 1 1 1 § 1 1 1 r-H 1茭茗一 § ◦•卜— 1470 0.7 ο r-H τ^Η oo oo CO CNJ 習知材料 實施例5 S 1 1 1 1 1 s CD 丨其卜丨 * ^ | :·卜· | § 2 1560 0.7 1 CO卜 CO LO 實施例4 § 1 1 1 1 S ^ | 2 卜· | = 1420 0.8 1 LO CNI CO CO 實施例3 1 1 § 1 1 1 1 00 ^ ^ Ξ 2 CD ◦· OO d LO Η 1600 0.6 CNI τ—1 T—( LO CI5 OO CO i 實施例2 1 § 1 1 1 1 1 r-H Ο 〇· oo ◦· S — 1650 0.5 CO r 1 \ τ-Ή 卜CO CO CO 實施例1 g 1 1 1 1 1 1 ① g ^ S Ξ 〇◦·〇〇◦· = — 1630 0.6 LO r·1 < r H CO 03 CO CO ¢4 ¢4 g^- mm ^ 婆ΨΕ _ ψη /^-N /-N C /^N /~N s.s^^pi 。白择 1一·1 e cz> s ^ 裝戔 紱 ^ ο Si 片材物性（t=0· 6imn) 拉伸彈性率(MPa) 杜邦衝擊強度（J) /^N C〇 朗◦· 〒 ^loul ψ»η 熱成形性（t=0· 6mm) 回縮時間（s) 30mm拉伸時間（s) 備註 IG 寸<NIrn6/CNl-e6/ip}«)_s鑑&&餾/dxnro 1298733 (産業上可利用性） 由本發明丙烯樹脂或樹脂組合物得到之片材，具有優良 之剛性、耐熱性及熱成形性，可適合使用作為熱成形製品 之材料。 【圖式簡單說明】 圖1爲顯示真空成形時之加熱步驟中，成形片材之變化 步驟之圖。Sheet thickness: 0.6 mm, drop hammer tip diameter: 1 / 2 inch 0, bearing diameter: 1 / 2 inch 0, temperature: 2 3 °C 9) load-deformation temperature according to AST Μ - D - 6 4 8 standard measurement. Load: 0 . 4 5 M p a. 1 0) Thermoformability (retraction time and 30 in m stretching time) A sheet formed by a sheet forming machine was changed as shown in Fig. 1 in the preheating step of hot forming. First, the sheets fixed at both ends are thermally expanded by heating of the upper and lower heaters to form irregular wrinkles (step 1). Further, sagging occurs due to softening and thermal expansion (step 2), and when the entire sheet reaches the vicinity of the melting point, it shrinks due to residual stress, and temporary shrinkage occurs (step 3). After reheating, the sheet is completely melted and is indexed by its own weight (step 4). Usually, between the steps 3 and 4, the sheet is sent to a mold and formed by vacuum absorption or the like. In the present invention, the shorter the retracting time of the step 3, the more difficult it is to produce the hot formability of the sheet to be introduced. Using a vacuum air-molding machine manufactured by Asano, the time until the retraction occurred and the time after the retraction reached 30 mm were measured under the following conditions. Upper and lower heater temperature: 3 5 0 °C; upper and lower heater spacing: 200 mm in; sheet size: 350x350mm; sheet thickness · · 0.6mm. (Example 1) As a propylene-based polymer, a carrier-type titanium-based catalyst (high stereoregular catalyst) using dicyclopentyldimethoxy decane as an electron supply is used, and the content of ethylene constituent units is used. 0. 6 in ο 1 % of random copolymerization, prepared by two-stage polymerization to a limit viscosity [??] of 4. 3 d 1 / g of high molecular weight body is 5 2 weight 16 312XP / invention manual (complement ()) /93-12/93124531 1298733 ° / 极限, the ultimate viscosity [77] is 2 · 1 d 1 / g of the low molecular weight body is 48% by weight, using the propylene and bake copolymerization to expand the molecular weight distribution And [0,0% by weight of the copolymer, with 0.1 part by weight of a phenolic antioxidant of tetrakis[-indenyl-3(3,5-di-t-butyl-4-hydroxyphenyl) Propionate] decane (manufactured by Zibasi Panhari Chemical Co., Ltd.), 0.1 part by weight of a 2,2-indenylene bis (4,6-di-t-butyl group) which is a phosphorus-based antioxidant笨基) octyl phosphite (made by Asahi Kasei Co., Ltd.), 0. 02 parts by weight of lactone-based antioxidant 3-hydroxy-5. 7-tert-butyl-furan-2-one Reaction product with o-diphenylene齐巴思潘夏利提化学(股制)), and 0·1 parts by weight of a calcium stearate (made by Nippon Oil & Fats Co., Ltd.) as a neutralizing agent, and then using a uniaxial extruder at a resin temperature of 2 Melt kneading was carried out at 30 ° C and pelletized. The physical properties measured of the obtained pellets are shown in Table 1. The pellet obtained above was supplied to a > 1 material forming machine, and the temperature of the resin was adjusted to 270 ° C, and extruded by a T-die, using a cooling roll maintained at a temperature of 80 ° C, at 1.2 m / min. The drawing speed is processed to form a sheet having a thickness of 0.6 mm. The mechanical properties and thermoformability of the obtained sheet were evaluated, and the results are shown in Table 1. (Example 2) Except that a carrier-type titanium-based catalyst using dicyclopentyldimethoxydecane as an electron supply was used, a random copolymerization of a content of ethylene constituent units of 0 · 4 m ο 1 % was used. The low-molecular weight body having a limit viscosity [??] of 4. 3 d 1 / g is 51% by weight, and the ultimate viscosity [2] is 2. 2 d 1 / g. The amount of % is the same as that of Example 1 except that the propylene* ethylene copolymer having an expanded molecular weight distribution is substituted for the propylene-based polymer used in Example 1. The results are shown together in Table 1. 17 312XP/Invention Manual (Supplement)/93-12/93124531 1298733 (Example 3) In addition to using a carrier-type titanium catalyst using dicyclopentyldimethoxydecane as an electron donor, ethylene is a constituent unit. The content is 0. 8 m ο 1 % of random copolymerization, which is prepared by two-stage polymerization to a limit viscosity [7?] of 4 · 2 d 1 / g of high molecular weight body of 51% by weight, ultimate viscosity [7] The amount of the low molecular weight body of 2.2 dl/g was 49% by weight, and the propylene/ethylene copolymer having an expanded molecular weight distribution was substituted for the propylene-based polymer used in Example 1, and the same as in Example 1. The results are shown together in Table 1. (Example 4) The MFR measured by using 80 wt% of the same propylene-based polymer as in Example 1 at a weight of 19 ° C and 2 · 16 kg was 0 · 3 5 g / 1 0 The high-pressure method of low-density polyethylene (MIRASON 102 manufactured by Mitsui Chemicals Co., Ltd.) 15% by weight, and the MFR measured under the same conditions is 0.32 g / 10 minutes of high-density polyethylene (Mitsui Chemical composition: HI-ZEX 5 2 0 2 B) The resin composition composed of 5 wt% was replaced by the same procedure as in Example 1 except that the propylene polymer used in Example 1 was used. The results are shown together in Table 1. (Example 5) A resin composition composed of 85 wt% of the propylene-based polymer similar to that of Example 1 and 15 wt% of the high-density polyethylene similar to Example 4 was used instead of the propylene system used in Example 1. Other than the polymer, the same as in the first embodiment. The results are shown together in Table 1. (Comparative Example 1) A carrier-type titanium-based catalyst (medium-regular catalyst) using cyclohexylmethyldimethoxydecane as an electron supply was prepared by two-stage polymerization into 18 312 XP/invention specification ( ( ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) The amount of the compound was 50% by weight, and the propylene-based polymer having an expanded molecular weight distribution was substituted for the propylene-based polymer used in Example 1, and the same as in Example 1. The polymer is equivalent to the materials conventionally used. The results are shown together in Table 1. (Comparative Example 2) The carrier-type titanium-based catalyst using dicyclopentyldimethoxydecane as an electron supply was prepared by two-stage polymerization to form an ultimate viscosity [] of 4. 3 d 1 / g. The low molecular weight body having a molecular weight of 52% by weight and an ultimate viscosity [??] of 1.9 d 1 /g is 48% by weight, and the propylene monomer having an expanded molecular weight distribution is substituted for the propylene used in Example 1. Other than the polymer, the same as in the first embodiment. The results are shown together in Table 1. (Comparative Example 3) The same high-density polymerization as in Example 4 except that 80% by weight of the propylene individual polymer as in Comparative Example 1 was used, and 15% by weight of the high-pressure method low-density polyethylene similar to Example 4 was used. The resin composition composed of 5% by weight of ethylene was used in the same manner as in Example 1 except that the propylene monomer alone used in Comparative Example 1 was used. The results are shown together in Table 1. 19 312XP/Invention Manual (Supplement)/93-12/93124531 1298733 Comparative Example 3 1丨1 S 1~0.33 7.1 161· 0 120 ◦ cz> οα · τ"'·Η ι 1 ii 1 oo CO LO Comparison Example 2 1 1 1 1 § 1 1 1 - Η 0.40 9.3 0.98 163.6 92 1690 0.5 oo τ 1 rH CD οα οα Comparative Example 1 1 1 1 § 1 1 1 rH 1茭茗一§ ◦•卜——1470 0.7 ο rH τ^Η oo oo CO CNJ Conventional Material Example 5 S 1 1 1 1 1 s CD 丨 丨 丨 ^ ^ ^ 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 1 S ^ | 2 Bu· | = 1420 0.8 1 LO CNI CO CO Example 3 1 1 § 1 1 1 1 00 ^ ^ Ξ 2 CD ◦· OO d LO Η 1600 0.6 CNI τ—1 T—( LO CI5 OO CO i Example 2 1 § 1 1 1 1 1 rH Ο 〇 oo ◦ · S — 1650 0.5 CO r 1 \ τ-Ή Bu CO CO CO Example 1 g 1 1 1 1 1 1 1 g ^ S Ξ 〇 ◦·〇〇◦· = — 1630 0.6 LO r·1 < r H CO 03 CO CO ¢4 ¢4 g^- mm ^ ΨΕ ΨΕ _ ψη /^-N /-NC /^N /~N ss^ ^pi. 白选1·1 e cz> s ^ 戋绂^ ο Si Sheet physical properties (t=0· 6imn) Tensile modulus (MPa) DuPont impact strength (J) /^NC〇 ◦ ◦ lo ^loul ψ»η Thermoformability (t=0· 6mm) Retraction time (s) 30mm stretching time (s) Remarks IG inch <NIrn6/CNl-e6/ip}«)_s &amp & Distillation/dxnro 1298733 (Industrial Applicability) The sheet obtained from the acrylic resin or the resin composition of the present invention has excellent rigidity, heat resistance and thermoformability, and can be suitably used as a material for a thermoformed product. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a step of changing a formed sheet in a heating step during vacuum forming.
312XP/發明說明書(補件)/93-12/93124531 21312XP/Invention Manual (supplement)/93-12/93124531 21