TW561160B - Propylene polymer composition - Google Patents
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- TW561160B TW561160B TW87113500A TW87113500A TW561160B TW 561160 B TW561160 B TW 561160B TW 87113500 A TW87113500 A TW 87113500A TW 87113500 A TW87113500 A TW 87113500A TW 561160 B TW561160 B TW 561160B
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561160 A7 B7 i、發明説明(1 ) 本發明係有關丙烯系樹脂及丙烯系聚合物組成物,以 及由其所成之薄膜及層積物。 更詳細地說係有關一種具有優良之低溫熱封性及目前 所未有的剛性與熱封性之高度平衡性,且能改善防粘連性 、滑動性、成型性之丙烯系聚合物及丙烯系聚合物組成物 。以及由其所形成之薄膜或食品包裝用薄膜、纖維與成型 物。 聚丙烯因具有強韌、優良耐熱性等物性及低成本之優 點’因此以廣泛用樹脂方式被使用於多種各樣式的用途上 〇 · 例如,其具有極高透明性、強大彈性、耐熱性及吸濕 性極少等特徵’因此,被作爲雙軸延伸薄膜或層壓薄膜等 鑄造薄膜用。 又,結晶性丙烯系聚合物之薄膜因只有優良的剛性、 透明性及防濕性等,故廣泛地作爲包裝用薄膜。 一般,這些薄膜係以熱封方式製成袋狀,塡入商品後 再熱封袋口,以使商品密封。 近年來爲了提升一系列的製袋包裝過程之生產性而請 求高速化,相對地要求薄膜高性能化之情形下,因而廣泛 地使用層積性質不同之樹脂的多層薄膜。特別是此多層薄 膜之最外層所使用的樹脂薄膜需發揮出,於一系列製袋包 裝過程高速化時必要的低溫熱封性、捲取薄膜時無障礙之 必要的滑動性及防粘連性等優良性能。 另外,於片狀物、不織布等領域上亦需降低層壓溫度 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -4- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 —•44^~ 釋一^-----n — — ~、訂---------1--- 561160 經濟.部智慧財產局員工消費合作社印製 A7 ___ B7五、發明説明(2 ) 〇 拿丙烯系聚合物比較乙烯系聚合物時發現,其結晶化 開始時之必要過度冷卻度較大,且既使具相同之熔點( T m )下,其結晶化溫度(T c )亦較低。尤其是共聚合 物、立體規則性較低之聚合物等結晶性較低之物更明顯。 因此,其難於成型,且會降低樹脂特性,例如透明性、熱 封溫度(H S T )、彈性率、耐衝擊性等。特別是於薄膜 用途上,爲了追求能與直鏈狀低密度聚乙烯匹敵之低溫熱 封性下,會產生成型不良,特別是易造成不良之鑄造軋輥 釋放及,薄膜邊緣不安定‘,易有掃描滾軸之痕跡等問題。 因此,希望能有解決出問題之具有優良低溫熱封性的薄膜 、纖維、片狀物、成型物等出現。 目前,爲了改善丙烯均聚物之薄膜的低溫熱封性,而 有與少量之乙烯、1-丁烯等共聚合物的方法之提案。但 ,爲了得到充分的低溫熱封性之改良效果,則需出量的乙 烯或、1 -丁烯,結果會副產多量的粘性成分,而出現例 如大幅度地降低防粘連性及,滲色白化所造成的外觀不良 等不具實用性之問題。另外,會有降低結晶化率,因而降 低薄膜剛性及降低成型性、粘連性之傾向。 雖然亦曾出現於不活性溶劑中溶解粘性成分而去除之 方法,以解決此問題,但,此時亦會去除賦予低溫熱封性 之低溫熔解性結晶成分,結果現狀下低溫熱封性之改良效 果將不足。 又,曾嚐試與乙烯、1一丁烯以外之α-烯烴,例如 本紙張尺度適用中國國家標準(匚奶)八4規格(21〇父297公瘦)-5 - (請先閲讀背面之注意事項再填寫本頁) 裝 — I訂--- --1*—----- 經濟·部智慧財產局員工消费合作社印製 561160 A7 B7 五、發明説明(3 ) 1— 己烯、1 一辛烯、4 —甲基一 1—戊烯等共聚合物之 '方法。但,以目前之技術只能得到組成分布極廣之樹脂, 故難確保具有耐實用性之防粘連性或剛性及成型性等。 因目前使用齊格勒觸媒系而得到之丙烯系聚合物的分 子量分布,組成分布較廣且不均勻,故包含於其中之高結 晶成分可快速生成結晶核,其雖不會擴大結晶化開始時所 需之過度冷却度,而不會某程度地降低成型性。但,其組 成的不均勻會降低物性及含有粘性成分、高結晶性成分, 因此,無法發揮原有之樹脂物性。 近年來所開發的使用二茂金屬衍生物系觸媒而聚合之 聚丙烯的方法因係使用單面觸媒,故可使組成均勻及減少 粘性成分、高結晶性成分等降低物性之成分,因此,可發 揮出比以往觸媒更優良之物性。但,因其組成較均勻,故 過度冷却度較大,因此會使成型性明顯惡化。 另外,亦曾出現於利用以往之齊格勒觸媒聚合而成的 丙烯系聚合物中,以利用二茂金屬衍生物系觸媒聚合而成 之丙烯系聚合物作爲熱封改良劑的方法之提案(特開平 2— 173016號公報、特開平5—112682號公 報、特開平5 - 1 1 2 6 8 3號公報)。但,這些雖能改 善若干熱封性與薄膜剛性之平衡性,但聚合物却依然存在 成型性與物性之平衡性的問題。 因此,本發明之目的爲,提供一種除了不損及聚丙烯 薄膜原有之良好特性外,還能提升與直鏈狀低密度聚乙烯 匹敵之熱封性,且能維持高度之防粘連性、薄膜剛性及薄 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐·) - 6 - (請先閲讀背面之注意事項再填寫本頁)561160 A7 B7 i. Description of the invention (1) The present invention relates to a propylene resin and a propylene polymer composition, and a film and a laminate formed therefrom. More specifically, it relates to a propylene-based polymer and a propylene-based polymer which have excellent low-temperature heat-sealability and unprecedented balance between rigidity and heat-sealability, and can improve anti-blocking, sliding, and moldability.物 组合 物。 Composition. As well as the films, fibers, and moldings formed from it or food packaging. Polypropylene has the advantages of physical properties such as toughness, excellent heat resistance, and low cost. Therefore, it is widely used as a resin for various types of applications. For example, it has extremely high transparency, strong elasticity, heat resistance, and Features such as very little hygroscopicity, therefore, it is used as a cast film such as a biaxially stretched film or a laminated film. In addition, films of crystalline propylene-based polymers are widely used as packaging films because they have excellent rigidity, transparency, and moisture resistance. Generally, these films are formed into a bag shape by heat-sealing. After being inserted into a product, the bag opening is heat-sealed to seal the product. In recent years, in order to improve the productivity of a series of bag-making and packaging processes, high-speed is required, and when high-performance films are relatively required, multilayer films of resins having different lamination properties are widely used. In particular, the resin film used in the outermost layer of this multilayer film must exhibit the low-temperature heat-sealability necessary for a series of bag-making and packaging processes at high speeds, and the necessary sliding and anti-blocking properties without obstacles when winding the film. And other excellent performance. In addition, it is necessary to reduce the lamination temperature in areas such as sheets and non-woven fabrics. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm.) -4- (Please read the precautions on the back before filling this page ) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs— • 44 ^ ~ Shi Yi ^ ----- n — — ~, Order --------- 1 --- 561160 Ministry of Economic Affairs Intellectual Property Bureau Printed by employees' consumer cooperatives A7 ___ B7 V. Description of the invention (2) 〇 When comparing propylene polymers with ethylene polymers, it was found that the necessary degree of overcooling at the beginning of crystallization was large and even had the same melting point ( T m), the crystallization temperature (T c) is also lower. Copolymers and polymers with lower stereoregularity, such as those with lower crystallinity, are more pronounced. Therefore, it is difficult to mold, and resin characteristics such as transparency, heat-seal temperature (H S T), elastic modulus, impact resistance, and the like are reduced. Especially for film applications, in order to pursue low-temperature heat-sealability comparable to linear low-density polyethylene, molding defects will occur, especially the release of casting rolls that are likely to cause defects and the film edges are unstable. There are problems such as scanning the traces of the roller. Therefore, it is desired that films, fibers, sheets, moldings, and the like having excellent low-temperature heat-sealing properties to solve the problem appear. Currently, in order to improve the low-temperature heat-sealability of a film of a propylene homopolymer, a method has been proposed with a small amount of a copolymer such as ethylene and 1-butene. However, in order to obtain a sufficient improvement effect of low-temperature heat-sealability, an amount of ethylene or 1-butene is required to be produced. As a result, a large amount of viscous components are by-produced, and, for example, the anti-blocking property and the permeability are greatly reduced. Problems such as poor appearance due to color whitening are not practical. In addition, there is a tendency that the crystallization rate is lowered, thereby lowering the rigidity of the film and lowering the moldability and blocking properties. Although a method of dissolving a viscous component in an inert solvent and removing it has also appeared to solve this problem, at this time, the low-temperature melting crystalline component that imparts low-temperature heat-sealability is also removed. As a result, the low-temperature heat-sealability is present. The improvement effect will be insufficient. In addition, we have tried to use α-olefins other than ethylene and 1-butene. For example, this paper size applies the Chinese national standard (milk milk) 8-4 specifications (21〇 parent 297 thin) -5-(Please read the note on the back first Please fill in this page for matters) Packing — I order --- --1 * —----- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy · 561160 A7 B7 V. Description of the invention (3) 1- Hexene, 1 Copolymer of octene, 4-methyl-1, pentene and other methods. However, with the current technology, only resins with a very wide composition distribution can be obtained, so it is difficult to ensure practical anti-blocking properties, rigidity, and moldability. Due to the molecular weight distribution of propylene-based polymers currently obtained using Ziegler catalyst systems, the composition distribution is wide and uneven, so the high crystalline components contained therein can quickly generate crystal nuclei, which will not expand the crystallization start The degree of excessive cooling required at the same time without reducing the moldability to some extent. However, the non-uniformity of the composition lowers the physical properties, contains viscous components, and highly crystalline components, and therefore cannot exhibit the original resin physical properties. The method of polypropylene which is polymerized using a metallocene derivative catalyst developed in recent years uses a single-sided catalyst, so it can make the composition uniform and reduce the physical properties of components such as viscous components and highly crystalline components. , Can show better physical properties than conventional catalysts. However, since the composition is relatively uniform, the degree of overcooling is large, and the moldability is significantly deteriorated. In addition, it has also appeared in a method of using a conventional Ziegler catalyst to polymerize a propylene-based polymer, and using a propylene-based polymer polymerized by using a metallocene derivative-based catalyst as a heat seal improver. Proposal (Japanese Patent Application Laid-Open No. 2-173016, Japanese Patent Application Laid-Open No. 5-112682, Japanese Patent Application Laid-Open No. 5-1 1 2 6 8 3). However, although these can improve the balance between some heat-sealability and film rigidity, the polymer still has the problem of balance between moldability and physical properties. Therefore, the object of the present invention is to provide a heat-sealing performance comparable to that of a linear low-density polyethylene, while maintaining the high degree of anti-blocking properties, without compromising the original good properties of polypropylene films. The rigidity of the film and the size of the thin paper are applicable to the Chinese National Standard (CNS) A4 (210X297 mm ·)-6-(Please read the precautions on the back before filling this page)
561160 Α7 Β7 五、發明説明(4 ) 膜衝擊特性之’平衡性良好的丙烯系聚合物及丙烯系聚合 物組成物,以及由其所成之薄膜或食品包裝用薄膜、纖維 、片狀物、不織布等和種成型物。 另外’本發明之目的爲,提供一種適用於密封用途的 丙烯系樹脂及使用其之薄膜,以及至少層積一層由此樹脂 所成之層的層積物。 本發明者們針對上述問題提出專心檢討後發現,於利 用一茂金屬衍生物系觸媒而得到之組成均勻的丙燒系聚合 物中添加,不會降低丙烯系聚合物之物性及,於熔融丙燒 系聚合物內能誘發快速形成結晶核,而降低結晶化時所需 之過度冷却度的物質,例如造核劑、高分子核劑、高結晶 化度之丙烯系聚合物、低分子量之丙烯系聚合物等,結果 可提供一種具有優良之物性、成型性等平衡性的丙烯系聚 合物組成物,而完成了本發明。 即,本說明書之各項發明如下。 首先,第一項發明如下所示。 (1 ) 一種丙烯系聚合物組成物,其係於(]_ 一 A ) 丙烯均聚物,即,利用二茂金屬衍生物系觸媒而聚合之等 規五分率(mmmm分率)爲8 0〜9 9莫耳%、分子量 分布(Mw/Mn)爲3 · 5以下、極限粘度〔;/〕爲 0 · 5〜5 · 0分升/ g之丙烯系聚合物中,添加(]_ 一 B )造核劑1 〇 p p m以上而形成。 (2 ) —種丙烯系聚合物組成物,其係於(1 一 a) 的丙烯與乙烯及/或碳數4〜2 0之α -烯烴所形成的丙 本紙張尺度適用中.國國家標準(CNS ) Α4規格(210X297公釐.)-7 - (請先閲讀背面之注意事項再填寫本頁) •裝- 訂 經濟部智慧財產局員工消費合作社印製 561160 A7 B7 五、發明説明(5 ) (請先閲讀背面之注意事項再填寫本頁) 烯系無規共聚合物,即,利用二茂金屬衍生物系觸媒而聚 合之,得自丙烯之構造單位爲8 0〜1 0 0莫耳%、得自 乙烯及/或碳數4〜2 0之α -烯烴的構造單位爲〇〜 2〇莫耳%、分子量分布(Mw/Mn)爲3 · 5以下、 極限粘度〔/?〕爲〇 · 5〜5 · 0分升/g之丙烯系聚合 物中,添加(1 一 B)有機磷酸金屬鹽、滑石、二苄叉山 梨糖醇或其衍生物、醯胺化合物等造核劑1 0 p p m以上 而形成。 (3 ) —種丙烯系聚合物組成物,其特徵.爲,M D方 向之拉伸彈性率(TM (MP a ))與熱封溫度(HST (°C ))符合下列式(1 — I I )。 TM^22xHST-1850 ...... (1-1 I) . (4 ) 一種薄膜,其係,利用鑄造成型法對上述(1 )〜(3 )項中任何一項之丙烯系聚合物組成物進行製膜 而形成。 經濟部智慧財產局員工消费合作社印製 (5 ) —種食品包裝用薄膜,其係,利用鑄造成型法 對以有機磷酸金屬鹽、滑石作爲造核劑之上述(2 )的丙 烯系聚合物組成物進行製膜而形成。 又,第二項發明如下。 (6 ) —種聚丙烯系樹脂組成物及使用其之成型的薄 膜,其中前者爲,於(2 - A )丙烯均聚物,即,利用二 茂金屬衍生物系觸媒而聚合之等規五分率( mmmm分率)爲80〜9 9莫耳%、極限粘度〔;?〕爲 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐.).Q . 561160 Α? Β7 五、發明説明(e ) 1 · 0〜2 · 0分升/ g、分子量分布(Mw/Mn)爲 3 · 5以下之丙燒系聚合物.9 9〜5 0重量份中,添加( (請先閱讀背面之注意事項再填寫本頁) 2 - B )丙烯均聚物,即,利用二茂金屬衍生物而聚合之 極限粘度〔77〕0 · 0 1〜1 · 〇分升/ g、分子量分布 (Mw/Mn)爲3·5以下之丙烯系聚合物1〜5〇重 量份而形成的聚丙烯系樹脂組成物。 又,第三項發明如下。 (7) —種丙烯系樹脂,其係由,(3—A)之丙烯 與碳數5以上之α-烯烴的共聚合物及,(3—B)之差 不掃描型.熱量計所測定的結晶化溫度比(3 - A )高的丙 烯系聚合物所形成之,(3-A)爲55〜99重量份、 (3 — B)爲4 5〜1重量份的丙烯系樹脂。 Φ. 經濟部智慧財產局員工消費合作社印製 (8 )如(7 )所記載之丙烯系樹脂,其中.,利用差 不掃描型熱量計所測定之(3 - A )共聚合物的結晶化溫 度(T c a (°C))與丙烯系聚合物(3 — B)之結晶化 溫度(T c a ( °C ))與丙烯系聚合物(3 一 b )之結晶 化溫度(T c b ( °C ))符合下列式。、 Tcb-Tca^20 ...... ( 3 - I ) (9)如(7)或(8)所記載之丙烯系樹脂,其中 ,丙烯系樹脂之升溫分級色譜(T R E F )符合下列(i )、(i i )及(i i i )的關係。 (1)主要溶出峰値溫度爲丁?時,(丁?一5)。〇 〜(Tp + 5) °C之溫度範圍下的溶出量爲6 5重量%以 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -Θ 561160 Α7 Β7 五、發明説明(7 ) 上。 (請先閲讀背面之注意事項再填寫本頁) (i i ) 0 °C以下的溫莨範圍下的溶出量爲3重量% 以下。 (i i i ) Tp + l〇°C以上之溫度範圍下的溶出量 爲全體之1〜45重量%。 (1 0 )如(7 )〜(9 )中任何一項所記載之丙燃 系樹脂,其中,利用差示掃描型熱量計測定丙烯系樹脂時 ,熔解曲線中最高溫度側之峰頂溫度爲8 5 °C以上。 (1 1 )如(7 )〜(9 )中任何一項所.記載之丙嫌 系樹脂,其中,利用差示掃描型熱量計測定丙烯系樹脂時 ,熔解曲線中最低溫度側之峰頂溫度1 5 0 °C以下。 (1 2 )如(7 )〜(1 1 )中任何一次所記載之丙 烯系樹脂,其中,共聚合物(A)之升溫分級色譜符合下 列(A - i )及(A - i i )。 (A—i)以主要溶出峰値溫度爲Tp時,(Τρ— 5) °C〜(Τρ - + 5) °C之溫度範圍下的溶出量爲70 重量%以上。 經濟部智慧財產局員工消費合作社印製 (A - i i ) 0°C以下之溫度範圍下的溶出量爲3重 量%以下。 (1 3 )如(7 )〜(1 2 )中任何一項所記載之丙 烯系樹脂,其中,(3 - A)共聚合物至少符合下列(a 一 iii)、 (A — iv)及(A — v)中一項。 (A — iii) (3— A)共聚合物中的碳數爲5以 上之α -烯烴單位的含量(α -莫耳%)爲〇 · 1莫耳% 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公着·) - 1〇 - 561160 A7 B7 五、發明説明(8 ) 、1 2莫耳%以下。 (A - 1 v ) ( 3 - A 〇共聚合物之立體規則性指標 (請先閱讀背面之注意事項再填寫本頁) (P)爲85莫耳%以上。 (A — v) (3 - A)共聚合物於萘烷中,135 t: 下所測定之極限粘度(〔Ty〕)爲〇 · 5〜3 · 0分升/ g 0 (1 4 )如(7 )〜(1 2 )中任何一項所記載之丙 嫌系樹脂,其中,構成(3 —A)共聚合物之單位中的碳 數5以上之α—烯烴單位爲1—辛烯、1一十二碳烯、1 一癸儲中至少一種。 (1 5 )利用如(7 )〜(1 2 )中任何一項所記載 之丙嫌系樹脂所製得之薄膜或至少有一層成分爲此丙烯系 樹脂的層積物。 又,第四項發明如下。 經濟部智慧財產局員工消費合作社印製 (1 6 ) —種丙烯系無規共聚合物,其特徵爲,丙烯 與碳數5以上之α -烯烴的共聚合物之,利用差示掃描型 熱量計所測定的共聚合物之熔點(T m ( °C ))與共聚合 物中碳數5以上之α -烯烴單位的含量(莫耳%)) 符合下列式(4 一 I ),561160 Α7 Β7 V. Description of the invention (4) The propylene-based polymer and propylene-based polymer composition with good balance of film impact characteristics, and the film or film for food packaging made from it, fiber, sheet, Non-woven fabrics and other molded products. Another object of the present invention is to provide a laminate of an acrylic resin suitable for sealing applications, a film using the same, and at least one layer formed of the resin. The inventors of the present invention put forward an intensive review in view of the above problems and found that the addition to a propylene-based polymer having a uniform composition obtained by using a metallocene derivative-based catalyst does not reduce the physical properties of the propylene-based polymer and that Substances that can induce the rapid formation of crystalline nuclei in firing polymers and reduce the excessive cooling required during crystallization, such as nucleating agents, high molecular nucleating agents, propylene polymers with high crystallinity, and low molecular weight propylene As a result, a propylene-based polymer composition having an excellent balance of physical properties and moldability can be provided as a result, and the present invention has been completed. That is, each invention of this specification is as follows. First, the first invention is shown below. (1) A propylene-based polymer composition based on (] __ A) propylene homopolymer, that is, the isotactic quintile (mmmm fraction) polymerized by using a metallocene derivative-based catalyst is 80 to 99 mol%, a molecular weight distribution (Mw / Mn) of 3 · 5 or less, and an limiting viscosity [; /] of 0.5 to 5 · 0 dl / g of a propylene-based polymer is added with () _ A B) nucleating agent is formed above 10 ppm. (2) A propylene-based polymer composition, which is based on (1a) propylene and ethylene and / or α-olefins having a carbon number of 4 to 20, and the size of the propylene paper is applicable. National standards (CNS) Α4 Specification (210X297mm.)-7-(Please read the precautions on the back before filling out this page) • Binding-Order Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 561160 A7 B7 V. Invention Description (5 ) (Please read the notes on the back before filling out this page) Ethylene random copolymers, that is, polymerized by using a metallocene derivative catalyst, are derived from propylene with a structural unit of 8 0 ~ 1 0 0 Molar%, structural units derived from ethylene and / or α-olefins having 4 to 20 carbon atoms are 0 to 20 Molar%, molecular weight distribution (Mw / Mn) is 3.5 or less, limiting viscosity [/? ] Is 0.5 to 5.0 deciliters / g of a propylene-based polymer by adding (1 -B) an organic phosphate metal salt, talc, dibenzylidene sorbitol or a derivative thereof, a pyramine compound, and the like for nucleation The agent is formed above 10 ppm. (3) A propylene-based polymer composition, characterized in that the tensile elastic modulus (TM (MP a)) and heat-sealing temperature (HST (° C)) in the MD direction conform to the following formula (1-II) . TM ^ 22xHST-1850 ...... (1-1 I). (4) A thin film, which is a propylene-based polymer according to any one of the items (1) to (3) above by using a casting method. The composition is formed into a film. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (5)-a film for food packaging, which is composed of the propylene polymer of the above (2) using organic phosphate metal salt and talc as nucleating agent by casting The material is formed into a film. The second invention is as follows. (6) A polypropylene resin composition and a formed film using the same, in which the former is an isotactic (2-A) propylene homopolymer, that is, polymerized using a metallocene derivative catalyst The quintile (mmmm fraction) is 80 to 99 mol%, the limiting viscosity [;? 〕 Applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm.) For this paper size. Q. 561160 Α? Β7 5. Description of the invention (e) 1 · 0 ~ 2 · 0 dL / g, molecular weight distribution (Mw / Mn) is a propylene-based polymer of 3.5 or less. 9 9 to 50 parts by weight, add ((Please read the precautions on the back before filling out this page) 2-B) propylene homopolymer, That is, the limiting viscosity [77] of the polymerization using a metallocene derivative is 0. 0 1 to 1 · 0 deciliter / g, and the propylene-based polymer 1 to 5 has a molecular weight distribution (Mw / Mn) of 3.5 or less. A polypropylene resin composition formed in parts by weight. The third invention is as follows. (7) A kind of propylene resin, which is measured by (3-A) copolymer of propylene and α-olefin with 5 or more carbon atoms and (3-B) non-scanning type. Calorimeter measurement A propylene-based polymer having a crystallization temperature higher than (3-A), (3-A) is 55 to 99 parts by weight, and (3-B) is 4 to 5 to 1 parts by weight of a propylene-based resin. Φ. Printed (8) The propylene-based resin described in (7) by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Among them, the (3-A) crystallization of the copolymer measured by a differential scanning calorimeter Temperature (T ca (° C)) and the crystallization temperature (T ca (° C)) of the propylene polymer (3- B) and the crystallization temperature (T cb (° C)) Comply with the following formula. Tcb-Tca ^ 20 ...... (3-I) (9) The propylene-based resin as described in (7) or (8), wherein the temperature-grading chromatography (TREF) of the propylene-based resin conforms to the following ( i), (ii) and (iii). (1) What is the main dissolution peak temperature? (Ding? 1: 5). 〇 ~ (Tp + 5) ° C Dissolution amount is 65% by weight. Applicable to Chinese paper standard (CNS) A4 specification (210X297 mm) at this paper scale -Θ 561160 Α7 Β7 V. Description of the invention (7 ) On. (Please read the precautions on the reverse side before filling out this page) (i i) The dissolution amount in the temperature range below 0 ° C is 3% by weight or less. (i i i) The dissolution amount in a temperature range of Tp + 10 ° C or more is 1 to 45% by weight as a whole. (10) The propylene-based resin according to any one of (7) to (9), wherein when the propylene resin is measured by a differential scanning calorimeter, the peak temperature on the highest temperature side of the melting curve is 8 Above 5 ° C. (1 1) The acrylic resin according to any one of (7) to (9), wherein the peak temperature on the lowest temperature side of the melting curve when measuring the propylene resin with a differential scanning calorimeter 1 5 0 ° C or less. (1 2) The propylene-based resin as described in any one of (7) to (1 1), wherein the temperature-grading chromatography of the copolymer (A) complies with the following (A-i) and (A-i i). (A-i) When the main dissolution peak temperature is Tp, the dissolution amount in a temperature range of (Τρ-5) ° C to (Τρ-+ 5) ° C is 70% by weight or more. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (A-i i) The dissolution amount in the temperature range below 0 ° C is 3% by weight or less. (1 3) The propylene-based resin according to any one of (7) to (1 2), wherein the (3-A) copolymer has at least the following (a-iii), (A-iv), and ( A — v). (A — iii) (3 — A) The content of α-olefin units (α-mol%) with a carbon number of 5 or more in the copolymer is 0.1 mol% This paper size applies Chinese national standards (CNS ) Α4 specification (210X297) · 10- 561160 A7 B7 V. Description of the invention (8), 12 Molar% or less. (A-1 v) (3-A 〇 Copolymer's three-dimensional regularity index (please read the precautions on the back before filling this page) (P) is above 85 mole%. (A — v) (3- A) Copolymer in decalin, 135 t: The limiting viscosity ([Ty]) measured at 0.5: 3.0 ~ 3.0 dL / g 0 (1 4) such as (7) ~ (1 2) The acrylic resin according to any one of the above, wherein the α-olefin unit having 5 or more carbon atoms in the unit constituting the (3-A) copolymer is 1-octene, 1-12 dodecene, 1 (1 5) At least one of the deciduous deposits. (1 5) A film made of the acrylic resin as described in any one of (7) to (1 2) or at least one layer of this acrylic resin is laminated. The fourth invention is as follows. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (16)-a propylene-based random copolymer, which is characterized by the copolymerization of propylene with α-olefins having a carbon number of 5 or more. For polymers, the melting point (T m (° C)) of the copolymer measured by a differential scanning calorimeter corresponds to the content of the α-olefin unit (mole%) with 5 or more carbon atoms in the copolymer. under Determinant (4-I),
TmS140 且 TmS160 - 7α (4 - I) 又,利用差示掃描型熱量計所測定之共聚合物的結晶化溫 度(丁 c ( °c ))與熔點(丁 m (它))符合下列式(4 一 I I )。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-11 - 561160 Α7 Β7 五、發明説明(9 )TmS140 and TmS160-7α (4-I) The crystallization temperature (but c (° c)) and melting point (but m (it)) of the copolymer measured by a differential scanning calorimeter conform to the following formula ( 4 a II). This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -11-561160 Α7 Β7 V. Description of invention (9)
Tc^0.75Tm - 15 ...... (4-1 I ) -裝— (請先閱讀背面之注意事項再填寫本頁) (1 7 ) —種丙烯系無規共聚合物組成物,其特徵,爲, 於(4 - A)的丙烯與碳數5以上之α -烯烴所形成的丙 烯系無規共聚合物中,添加(4 - Β )之具有造核效果的 物質所形成之組成物的,利用差示掃描型熱量計所測定的 組成物之熔點(T m ( °C ))與組成物中碳數5以上之α 一烴烯含量(α -莫耳%))符合下列式(4 一 I ), TmS140 且 Tm$160 — 7α...... (4-1) 又,利用差示掃描型熱量計所測定之組成物的結晶化溫度 (T c ( °C ))與熔點(T m ( °C ))符合下列式(4 一 I I ) 〇Tc ^ 0.75Tm-15 ...... (4-1 I) -Pack — (Please read the precautions on the back before filling this page) (1 7) —A kind of propylene random copolymer composition, It is characterized by adding (4-B) a nucleating substance to a propylene-based random copolymer formed by (4-A) propylene and an α-olefin having 5 or more carbon atoms. For the composition, the melting point (T m (° C)) of the composition measured by a differential scanning calorimeter and the α-alkene content (α-mol%) of the carbon number 5 or more in the composition are as follows Formula (4--1), TmS140 and Tm $ 160 — 7α ... (4-1) Also, the crystallization temperature (T c (° C)) of the composition measured by a differential scanning calorimeter The melting point (T m (° C)) is in accordance with the following formula (4-II):
Tc^〇 . 75Tm-15 ...... (4-1 I ) (1 8)如(1 6)所記載之丙烯系無規共特徵,或 如(1 7 )所記載之丙烯系無規共聚合物組成物,其中, 經濟部智慧財產局員工消費合作社印製 碳數5以上之α-烯烴單位的含量爲〇.1〜12莫耳% 〇 (1 9 )如(1 6 )或(1 8 )所記載之丙烯系無規 共聚合物’或者(1 7 )或(1 8 )所記載之丙烯系無規 共聚合物組成物,其中,共聚合物之立體規則性指標(ρ )爲85莫耳%以上。 (20)如(16)、 (18)、 (19)中所記載 本紙張尺度適用中國國家標準(CNS ) Α4規格(210><297公釐) -12 - 561160 A7 ___— _B7 五、發明説明(彳〇 ) 之丙烯系無規共聚合物,或(1 7)〜(1 9 )中所記載 之丙烯系無規共聚合物組成物,其中,萘烷中溫度13 5 °C下所測定之極限粘度〔;;〕爲〇 · 5〜3分升/ g。 (請先閲讀背面之注意事項再填寫本頁} (21)如(16)或(18)〜(20)所記載之 丙燦系無規共聚合物,或者(1 7)〜(2 0)所記載之 丙烯系無規共聚合物組成物,其中,碳數5以上之α -燦 烴單位係含有1-辛烯、1一十二碳烯中至少一種。 (2 2)由上述(16)〜(2 1)中任何一項之共 聚合物或共聚合物組成物所製得之薄膜及,至少有一層成 分此共聚合物或共聚合物組成物的層積物及,含此共聚合 物或共聚合物組成物之纖維、片狀物或成型物。 又,第五項發明如下。 (2 3 ) —種丙烯系無規共聚合物,其特徵爲,丙嫌 與1-丁烯之共聚合物的利用差示掃描型熱量計所測定之 共聚π物的溶點(Tm ( C))與共聚合物中之1 一丁儲 單位的含量(α (莫耳%))符合下列式(5一1), Tm^l6〇-3a ...... (5—1) 經濟部智慧財產局員工消资合作社印製 又’利用差示掃描型熱量計所測定之共聚合物的結晶化溫 度(T c ( t ))與熔點(丁 m ( t ))符合下列式(5 - I I )Tc ^ 〇. 75Tm-15 ...... (4-1 I) (1 8) The propylene-based random features described in (1 6), or the propylene-based free features described in (1 7) Polymer composition, in which the content of α-olefin units with a carbon number of 5 or more printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 0.1-12 Molar% 〇 (19) such as (1 6) or The propylene-based random copolymer according to (18) or the propylene-based random copolymer according to (17) or (18), wherein the index of stereoregularity of the copolymer (ρ ) Is 85 mol% or more. (20) As stated in (16), (18), and (19), the paper size applies to the Chinese National Standard (CNS) A4 specification (210 > < 297 mm) -12-561160 A7 ___— _B7 V. Invention Describe the propylene-based random copolymers of (彳 〇), or the propylene-based random copolymers described in (17) to (19), in which the decalin temperature is 13 5 ° C. The measured limiting viscosity [;;] was 0.5 to 3 dL / g. (Please read the precautions on the back before filling out this page} (21) Crancan random copolymers as described in (16) or (18) to (20), or (1 7) to (2 0) The propylene-based random copolymer composition described in the above, wherein the α-branse unit having a carbon number of 5 or more contains at least one of 1-octene and 1-12 dodecene. (2 2) According to the above (16) ) ~ (2 1) The film and the film produced by the copolymer or copolymer composition of any one of at least one layer of the copolymer or copolymer composition containing the copolymer A fiber, a sheet, or a molded article of a polymer or copolymer composition. In addition, the fifth invention is as follows. (2 3) A propylene-based random copolymer, which is characterized in that The melting point (Tm (C)) of the copolymer π measured by a differential scanning calorimeter with an olefin copolymer is consistent with the content (α (mole%)) of 1 butyl storage unit in the copolymer. The following formula (5-1), Tm ^ 16-60-3a ... (5-1) Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and measured by' Differential Scanning Calorimeter Copolymerization Physical Crystallization temperature (T c (t)) and the melting point (d m (t)) satisfy the following formula (5 - I I)
Tc^〇 . 75Tm-l〇 · · · · .. r ^ - τ τ ^ 13 本紙張尺度適用中國國家標準(CNS ) M規格(210X297公釐) 561160 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(11 ) (2 4 ) —種丙烯系無規共聚合物組成物,其特徵爲 ’於(5 - A )丙烯與1 -丁烯所形成之丙烯系無規共聚 合物中添加(5 - B )具有造核效果之物質所形成的組成 物之’利用差示掃描型熱量計所測定的組成物之熔點( T m ( °C ))與組成物中1 一丁烯的含量(α (莫耳% ) 付合下列式(5 — I ), T m ^ 1 6 0 - 3 α ....... ( 5 - I ) 又,利用差示掃描型熱量計所測定之組成物时結晶化溫度 (丁 c ( °C )及熔點(丁 m ( °C ))符合下列式(5 — I I ) 〇Tc ^ 〇. 75Tm-l0 · · · · .. r ^-τ τ ^ 13 This paper size is applicable to China National Standard (CNS) M specification (210X297 mm) 561160 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (11) (2 4)-A propylene-based random copolymer composition characterized by 'Y- (5-A) propylene-based random copolymer formed by 1-butene The melting point (T m (° C)) of the composition measured by a differential scanning calorimeter and the composition of 1-butene in the composition formed by adding (5-B) a substance having a nucleation effect The content (α (mol%)) complies with the following formula (5 — I), T m ^ 1 6 0-3 α ....... (5-I) The crystallization temperature (butyl c (° C) and melting point (butyl m (° C))) of the measured composition conforms to the following formula (5 — II).
Tcg〇 · 75Τπι— 1〇 ...... (5 - I I) (2 5 )如(2 3 )所記載之丙烯系無規共聚合物或 (2 4 )所記載之丙烯系無規共聚合物組成物,其中,1 —丁烯含量爲0 · 1〜3莫耳%。 (2 6 )如(2 3 )、 ( 2 5 )所記載之丙烯系無規 共聚合物,或(2 4 )、 ( 2 5 )所記載之丙烯系無規共 聚合物組成物,其中,共聚合物之立體規則性指標(p ) 爲85莫耳%以上。 .(2 7 )如(2 3 )、 ( 2 5 )、 ( 2 6 )所記載之 丙烯系無規共聚合物,或(2 4 )〜(2 6 )所記載之丙 烯系無規共聚合物組成物,其中,萘烷中溫度1 3 5 t下 之極限粘度〔7?〕爲0 · 5〜3分升/ g。 ^紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -— (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 561160 A 7 B7 五、發明説明(12 ) (請先閲讀背面之注意事項再填寫本頁) (28)由上述(23)或(27)所記載之共聚合 物或共聚合物組成物所製得之薄膜及,至少有一層爲此共 聚合物或共聚合物組成物之層積物及,含此共聚合物或共 聚合物組成物之纖維、片狀物或成型物。 又,第六項發明如下。 (2 9 )—種丙烯系聚合物組成物,其係於(a )之 丙烯與碳數4以上的α -烯烴之共聚合物,即,利用二茂 金屬衍生物系觸媒而聚合之得自丙烯的構造單位爲8 〇〜 99 · 9吴耳% ’得自α -稀煙之構造單位爲q . 1〜 2 0莫耳%、極限粘度〔7/〕爲〇.5〜5.〇分升/运 之丙烯系無規共聚合物中,添加(Β)造核劑1 〇p pm 以上而形成。 (3 0 )如(2 9 )所記載之丙烯系聚合物組成物, 其中,α -烯烴之碳數爲5以上。 (3 1 )如(2 9 )所記載之丙綠系聚合物組成物, 經.¾部智慧財產局員工消费合作社印製 其中,α —烯烴爲1 一丁烯,且MD方向之拉伸彈性率( Τ Μ ( Μ P a ))與熱封溫度(H S 丁())符合下列 式(6 — I ) TM-22XHST-1850 ...... (6—" ‘ (3 2 )如(2 9 )所記載之丙烯系聚合物組成物, 其中,MD方向之拉伸彈性率(TM(MPa))與熱封 溫度(H S T ( °C ))符合下列式(6〜;[!)。 15 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐·) 561160 A7 B7 五、發明説明(13 ) TM222XHST- 170 0 ...... (6- I I) (請先閱讀背面之注意事項再填寫本頁} (3 3 )如(2 9 )所記載之丙烯系聚合物組成物, 其中,沸騰二乙基醚可溶成分量(E (重量%))與α〜 烯烴含量(α (莫耳%))符合下列式(6 - I I I) Ε^〇·2χα + 1·〇 (6 - III) (3 4 ) —種薄膜,其係利用鑄造成型法,由上述( 2 9 )〜(3 3 )之丙烯系聚合物組成物所製得。 <圖面之簡單說明> 圖1爲,本說明書中第一項發明之式(I I )的關係 圖。 圖中,黑顆粒爲實施粒,白顆粒爲比較例,數字則分 別爲實施例、比較例之號碼。 下面將詳細說明本說明書中的各項發明。 本說明書中的第一項發明係有關二種類之樹脂組成物 〇 經濟部智慧財產局員工消费合作社印製 第一種樹脂組成物爲,於(1 一 A)丙烯均聚物,即 ,利用二茂金屬衍生物系觸媒而聚合之等規分率( mmmm分率)爲8 0〜9 9莫耳%、分子量分布(Mw /Μη)爲3 · 5以下、極限粘度〔/?〕爲〇 · 5〜 5 · 0分升/g之丙烯系聚合物中,添加(1 一 Β)造核 劑1 0 ρ p m以上而形成的丙燦系聚合物組成物。 本紙張尺度適用中國國家橾準(CNS ) A4規格(210X 297公釐) -16 - 561160 A7 B7 五、發明説明(14 ) 首先,第一種樹脂組成物中的(1 - A)丙烯均聚物 之作爲立體規則性指標的等規五分率(m m m m分率)爲 (請先閲讀背面之注意事項再填寫本頁) 8 0〜9 9莫耳%,又以8 5〜9 7莫耳%爲佳。若等規 五分率不足8 0莫耳%時,薄膜剛性將不充足,又,超過 9 9莫耳%時,會使薄膜之耐衝擊性變差,故此兩數値均 不佳。而本發明之等規五分率(mmmm分率)係指,依 據 Cheng Η· N·,Ewen J. A·,Makcromol . chem·,( 1 989),190, 1350所記載之13 C - NMR光譜的峰値烯屬之丙烯構造單 位5個中具有內消旋構造(5個甲基之配列方.式爲同一方 向的mmmm構造)之含有比率0 又,丙嫌均聚物之分子量分布(Mw/Mn )爲 3 · 5以下,又以3 · 0以下較佳,更佳爲1 · 5〜 2 · 5。若分子量分布(Mw/Mn)超過3 . 5時,會 降低熱封性及耐粘連性。 另外,丙烯均聚物之極限粘度〔;?〕爲0 · 5〜 5 · 0分升/ g,又以0 · 5〜3分升/g較佳,更佳爲 1〜2 · 5分升/ g。 經濟·部智慧財產局員工消费合作社印製 本發明之丙儲均聚物可利用各種方法而製得,但,較 佳爲利用二茂金屬衍生物系觸媒使丙烯聚合物而製得。具 體地說即,於存在具有瓌戊二烯基環之周期表第4族的過 渡金屬化合物、甲基鋁氧烷或其與周期表第4族之過渡金 屬化合物起反應而形成的離子性配位化合物及有機鋁化合 物所形成的二茂金屬衍生物系觸媒之情形下進行聚合而製 得。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -17 - 561160 A7 B7 五、發明説明(15 ) (請先閱讀背面之注意事項再填寫本頁} 作爲主觸媒之具有環戊二烯基環的周期表第4族之過 渡金屬化合物係指,以介有.低級亞烷基或亞矽烷基而使選 自環脂肪族二烯基或其取代物,具體地說即,茚基、取代 茚基及其部分氫化物所形成之群中至少2個基鍵結而成的 多嚙配位化合物作爲配位體之,鉻、鈦及飴化合物。例如 言己載於 Η. H. Brintzinger et al, J. Organometal. Chem., 28 8, 63( 1 985)的乙撑—雙—(茚基)鉻二氯化物、或Am. Chem. Soc·,109,6544( 19 87)所記載之乙撑—雙一(茚基) 給二氯化物,或 H. Yamazaki et al,chimi.stry Letters, 1 85 3( 1 989)所記載之二甲基啞矽烷基雙(2,4 —二甲基環 戊二烯基)銷二氯化物、二甲基亞矽烷基雙(2,4,5 -三甲基環戊二烯基)鉻二氯化物或其配位化合物之給二 氯化物等銷及給化合物的立體硬質(stereorigid ) ‘對掌性 (chival)化合物。 經濟部智慧財產局員工消費合作社印製 具體例子如,乙撑雙(茚基)锆二氯化合物、乙撑雙 (4,5,6,7 -四羥基—1 一茚基)锆二氯化物、乙 撑雙(4 一甲基一 1 一茚基)鉻二氯化物、乙撑雙(5〜 甲基—1—茚基)锆二氯化物、乙撑雙(6 —甲基一 1〜 茚基)鉻二氯化物、乙撑雙(7 -甲基—1 一茚基)鉻二 氯化物、乙撑雙(2,3—二甲基一 1 一茚基)锆二氯化 物、乙撑雙(4,7 —二甲基一 1 一茚基)鉻二氯化物、 乙撑雙(茚基)給二氯化物、乙撑雙(4,5 ,6 ,7〜 四羥基一 1 一茚基)給二氯化物、乙撑雙(4 一甲基—1 一茚基)給二氯化物、乙撑雙(5 —甲基一 1 一茚基)耠 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公嫠) .18- 561160 A7 _B7_ 五、發明説明(16 ) (請先閲讀背面之注意事項再填寫本頁) 二氯化物、乙撑雙(6 —甲基一 1—茚基)給二氯化物、 乙撑雙(7 —甲基一 1 一茚基)給二氯化物、乙撑雙(2 ,3 —二甲基一 1 一茚基)給二氯化物、乙撑雙(4,7 一二甲基—1 一茚基)給二氯化物、二甲基亞矽烷基雙( 茚基)銷二氯化物、二甲基亞矽烷基雙(茚基)給二氯化 、二甲基亞矽烷基雙(4 一甲基茚基)锆二氯化物、二甲 基亞矽烷基雙(茚基)鈴二氯化物、二甲基亞矽烷基雙( 2,4,5 —二甲基環戊二烯基)鉻二氯化物、二甲基亞 矽烷基雙(2,4,5 —三甲基環戊二烯基).飴二氯化物 、二甲基亞矽烷基雙(2,4 一二甲基環戊二烯基)給二 氯化物、二甲基亞矽烷基雙(3 -甲基環戊二烯基)鍩二 氯化物、二甲基亞矽烷基雙(3 -甲基環戊二烯基)飴二 氯化物、二甲基亞矽烷基雙(2 —甲基一 4 一苯基茚基) 鉻二氯化物、二甲基亞矽烷基雙(苯并茚基)銷二氯化物 經濟·部智慧財產局員工消費合作社印製 或(二甲基甲矽烷基)(二甲基甲矽烷基)一雙(茚 基)鉻二氯化物、(乙撑)(乙撑)一雙(茚基)锆二氯 化物、(乙if)(乙撑)一雙(3 —甲基茚基)锆二氯化 物、(乙撑)(乙撑)一雙(4,7 —二甲基茚基)銷二 氯化物等,或這些化合物的鉻受給或鈦所取代之物。 又’作爲補助觸媒之與周期表第4族的過渡金屬化合 物起反應而形成離子性之配位化合物的化合物之較佳例子 如’三苯基甲胺四(五氟苯基)硼酸鹽、n,N —二甲基 苯胺四(五氟苯基)硼酸鹽、鋰四(五氟苯基)硼酸鹽般 本紙張尺度適用中周國家標準(CNS ) A4規格(210X297公釐)-19 - 561160 Α7 Β7 五、發明説明(17 ) 的含有(五氟苯基)硼酸鹽陰離子之化合物,或三苯基甲 胺四(五氟苯基)鋁酸鹽、·Ν,N -二甲基苯胺四(五氟 苯基)鋁酸鹽、鋰四(五氟苯基)鋁酸鹽般的含(五氟苯 基)鋁酸鹽陰離子之化合物。 另外,有機鋁化合物較佳爲,至少分子內具有1個 A 1 - c鍵結之化合物。其具體例子如,三乙基鋁、三異 丁基鋁、三己基鋁等三烷基鋁,或二乙基鋁鹵化物、二異 丁基鋁鹵化物等二烷基鋁鹵化物,或三烷基鋁與二烷基錦 鹵化物之混合物,或四乙基二鋁氧烷、四丁基,鋁氧烷等烷 基鋁氧烷。 ’ 這些有機鋁化合物中又以三烷基鋁、三烷基鋁與二烷 基鋁鹵化物之混合物、烷基鋁氧烷爲佳,特別佳爲三乙基 鋁、三異丁基鋁、三乙基鋁與二乙基鋁氯化物之混合物及 四乙基二鋁氧烷。有機鋁之較佳例子有二乙基鋁、三異丁 基鋁等。 這些二茂金屬衍生物系觸媒及/或補助觸媒亦可爲, 附載於載體之物,又,載體之例子如,聚苯乙烯等之有機 化合物’或二氧化矽、氧化鋁等無機氧化物。 聚合方法可爲,塊狀聚合法、溶液聚合法、氣相聚合 法、懸浮聚合法等,又,亦可爲分批式或連續式。 又’可預先與少量之α一烯烴,例如,乙烯、丙烯、 1 一 丁嫌、4 一甲基—1 一戊烯等進行預備聚合。即,所 丙嫌系聚合物亦包含使(1 — Α)成分之丙嫌均聚物與 少量(對最終樹脂爲〇 · 5莫耳%以下)之乙烯、丙烯等 (請先閲讀背面之注意事項再填寫本頁) •裝. 41k 經濟部智慧財產局員工消资合作社印製 本紙張尺度適用巾g®轉準(CNS) A4· (21GX297公兼.) -20- 561160 A7 B7 五、發明説明(18 ) α -烯烴進行預備聚合後,聚合丙烯而得到的丙烯系聚合 物。 (請先閲讀背面之注意事項再填寫本頁) 聚合溫度一般爲一 50〜25CTC,又,以〇〜 1 5 0 °C爲佳。又,聚合時間一般爲χ〜丄〇小時,壓力 一般爲常壓一 3〇〇k g/cm2G。 本發明組成物之(1 - B )成分的造核劑可爲,不會 降低丙烯系聚合物之物性,快速誘發結晶核、開始結晶化 之必要過度冷却度較小之物。 本發明所使用之造核劑的具體例子如,高熔點聚合物 、有機羧酸或其金屬鹽、芳香族磺酸鹽或其金屬鹽、有機 磷酸化合物或其金屬鹽、二苄叉山梨糖醇或其衍生物、玫 瑰酸部分金屬鹽、無機微粒子、亞胺類、酸胺類、喳吖酮 類、苯酮類或其混合物。 經濟部智慧財產局員工消費合作社印製 高熔點聚合物例子如,聚乙烯、聚丙烯等聚烯烴、或 聚乙烯基環己烷、聚乙烯基環戊烷等聚乙烯基環鏈烷,或 聚3 —甲基戊烯—1—、聚3 -甲基丁烯一 1、聚鏈烯基 矽烷等。金屬鹽之例子如,安息香酸鋁鹽、p - t 丁基安 息香酸鋁鹽、己二酸鈉、噻吩烷羧酸鈉、吡咯羧酸鈉等。 無機微粒子之例子如,滑石、雲母、石棉、玻璃纖維、玻 璃片、玻璃珠、矽酸鈣、蒙脫石、皂土、石墨、鋁粉末、 氧化錫、二氯化砂、砂藻土、氧化欽、氧化鎂、輕石粉末 、浮石、氫氧化鋁、氫氧化鎂、鹼性碳數鎂、白雲石、硫 酸鈣、鈦酸鉀、硫酸鋇、亞硫酸鈣、硫化鉬等。其中又以 下列式(1-I)所示有機磷酸金屬鹽、滑石等無機微粒 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐·) - 21 - 561160 Α7 Β7 五、發明説明(19 ) 子較少產生惡臭,故適用於當本發明之丙烯系聚合物組成 物作爲食品用途上。Tcg.75Tπ—10. (5-II) (2 5) The propylene-based random copolymer according to (2 3) or the propylene-based random copolymer according to (2 4) A polymer composition in which the 1-butene content is from 0.1 to 3 mole%. (2 6) The propylene-based random copolymer according to (2 3) or (2 5), or the propylene-based random copolymer according to (2 4) or (25), wherein: The stereoregularity index (p) of the copolymer is 85 mol% or more. (2 7) The propylene-based random copolymers according to (2 3), (2 5), (2 6), or the propylene-based random copolymers according to (2 4) to (2 6) The composition has a limiting viscosity [7?] At a temperature of 1 3 5 t in decalin of 0.5 to 3 dL / g. ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm.)--(Please read the notes on the back before filling this page) Binding and ordering 561160 A 7 B7 5. Description of the invention (12) (Please first (Please read the notes on the back and fill in this page) (28) At least one layer of the film made from the copolymer or copolymer composition described in (23) or (27) above Laminates of co-polymer composition and fibers, sheets or shaped articles containing the co-polymer or co-polymer composition. The sixth invention is as follows. (2 9) A propylene-based polymer composition based on a copolymer of propylene and an α-olefin having a carbon number of 4 or more in (a), that is, obtained by polymerization using a metallocene derivative catalyst The structural unit from propylene is 80 ~ 99 · 9 wu%. The structural unit derived from α-thin smoke is q. 1 ~ 20 mole%, and the limiting viscosity [7 /] is 0.5 ~ 5. It is formed by adding (B) a nucleating agent of 10 pp or more to the propylene-based random copolymer of deciliters / transport. (3 0) The propylene-based polymer composition according to (2 9), wherein the carbon number of the α-olefin is 5 or more. (3 1) The acrylic green polymer composition as described in (2 9), printed by the Consumer Cooperative of the Intellectual Property Bureau, where α-olefin is 1-butene, and the tensile elasticity in the MD direction is The rate (T Μ (Μ P a)) and heat-sealing temperature (HS 丁 ()) conform to the following formula (6 — I) TM-22XHST-1850 ...... (6— " '(3 2) such as The propylene-based polymer composition according to (2 9), wherein the tensile elastic modulus (TM (MPa)) and heat-sealing temperature (HST (° C)) in the MD direction conform to the following formula (6 ~; [!) . 15 This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm ·) 561160 A7 B7 V. Description of the invention (13) TM222XHST- 170 0 ...... (6- II) (Please read the back first For the matters needing attention, please refill this page} (3 3) The propylene polymer composition as described in (2 9), in which the amount of boiling diethyl ether soluble component (E (wt%)) and α ~ olefin content (Α (mole%)) conforms to the following formula (6-III) E ^ 〇 · 2χα + 1.0 (6-III) (3 4) A thin film which is formed by the above-mentioned (2 9 ) ~ (3 3) acrylic polymer group ≪ Simplified description of the drawing > Fig. 1 is a relationship diagram of the formula (II) of the first invention in the present specification. In the figure, black particles are implementation particles and white particles are comparative examples. The numbers of the examples and comparative examples are as follows. The inventions in this specification will be described in detail below. The first invention in this specification is related to two types of resin composition. 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The first resin composition is (1—A) propylene homopolymer, that is, the isotactic fraction (mmmm fraction) polymerized by using a metallocene derivative-based catalyst is 80 to 99 mol. %, A molecular weight distribution (Mw / Mη) of 3.5 or less, and a limiting viscosity [/?] Of 0.5 to 5.0 deciliters / g of a propylene-based polymer in which (1-B) a nucleating agent 1 is added The acrylic polymer composition formed above 0 ρ pm. The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -16-561160 A7 B7 V. Description of the invention (14) First, the Stereo regularity of (1-A) propylene homopolymer in a resin composition The target isotactic quintile (mmmm fraction) is (please read the notes on the back before filling in this page) 8 0 ~ 9 9 mole%, and preferably 8 5 ~ 97 mole%. If the isotactic When the quintile is less than 80 mol%, the rigidity of the film will be insufficient, and when it exceeds 99 mol%, the impact resistance of the film will be deteriorated, so both numbers are not good. The isotactic quintile (mmmm fraction) of the present invention refers to the 13 C-NMR according to Cheng Η · N ·, Ewen J. A ·, Makcromol. Chem ·, (1 989), 190, 1350 The 5 peaks of the olefinic propylene structural unit have a meso structure (the arrangement of 5 methyl groups. The formula is the mmmm structure in the same direction) with a content ratio of 0. Also, the molecular weight distribution of the propylene homopolymer ( Mw / Mn) is 3 · 5 or less, and preferably 3 · 0 or less, more preferably 1 · 5 ~ 2 · 5. When the molecular weight distribution (Mw / Mn) exceeds 3.5, heat sealability and blocking resistance are reduced. In addition, the limiting viscosity of propylene homopolymer [;? It is 0 · 5 ~ 5 · 0 deciliter / g, more preferably 0 · 5 ~ 3 deciliter / g, more preferably 1 ~ 2 · 5 deciliter / g. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The C-storage homopolymer of the present invention can be produced by various methods. However, it is more preferable to produce the propylene polymer by using a metallocene derivative catalyst. Specifically, in the presence of a transition metal compound of Group 4 of the periodic table having a pentadienyl ring, methylaluminoxane, or an ionic complex formed by reacting with a transition metal compound of Group 4 of the Periodic Table In the case of a metallocene derivative formed from a meta compound and an organoaluminum compound, the catalyst is polymerized and polymerized. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -17-561160 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before filling this page} As the main catalyst The transition metal compound of group 4 of the periodic table of the pentadienyl ring means a member selected from a cycloaliphatic dienyl group or a substitute thereof through a lower alkylene group or a silylene group, specifically, Indenyl, substituted indenyl and its partial hydride group formed by bonding at least two groups of multi-coordination complexes as ligands, chromium, titanium and rhenium compounds. For example, the words have been contained in rhenium. H. Brintzinger et al, J. Organometal. Chem., 28 8, 63 (1 985) ethylene-bis- (indenyl) chromium dichloride, or Am. Chem. Soc ·, 109, 6544 (19 87 Ethylene-bis (indenyl) to dichloride as described in), or dimethyl-silylsilyl bis (2, as described in H. Yamazaki et al, chimi.stry Letters, 1 85 3 (1 989)) 4-dimethylcyclopentadienyl) pin dichloride, dimethylsilyl bis (2,4,5-trimethylcyclopentadienyl) chromium dichloride Or its coordination compound to give dichloride and other stereorigid (chival) compounds. Specific examples printed by the consumer co-operatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as ethylene bis (indenyl) ) Zirconium dichloride compounds, ethylene bis (4,5,6,7-tetrahydroxy-1 mono-indenyl) zirconium dichloride, ethylene bis (4-methyl-1 1 indenyl) chromium dichloride, Ethylenebis (5 ~ methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1 ~ indenyl) chromium dichloride, ethylenebis (7-methyl-1-indenyl) Group) chromium dichloride, ethylene bis (2,3-dimethyl-1 1 indenyl) zirconium dichloride, ethylene bis (4,7-dimethyl-1 1 indenyl) chromium dichloride Ethylenebis (indenyl) to dichloride, ethylenebis (4,5,6,7 ~ tetrahydroxy-1 1-indenyl) to dichloride, ethylenebis (4-methyl-1-1indene) Base) for dichloride, ethylene bis (5-methyl-1, 1-indenyl) paper. The paper size is applicable to China National Standard (CNS) A4 (210X297 cm). 18- 561160 A7 _B7_ Instructions (16) (Please read the notes on the back before filling out this page) Dichloride, ethylenebis (6-methyl-1 1-indenyl) to dichloride, ethylenebis (7-methyl-1) Monoindenyl) gives dichloride, ethylenebis (2,3-dimethyl-1 1 indenyl) gives dichloride, ethylenebis (4,7 dimethyl-1 indenyl) gives two Chloride, dimethylsilylbis (indenyl) pin, dichloride, dimethylsilylbis (indenyl) pin, dichlorin, dimethylsilylbis (4-methylindenyl) Zirconium dichloride, dimethylsilylbis (indenyl) bell dichloride, dimethylsilylbis (2,4,5-dimethylcyclopentadienyl) chromium dichloride, Methylsilylbis (2,4,5-trimethylcyclopentadienyl). 饴 Dichloride, dimethylsilylbis (2,4-dimethylcyclopentadienyl) give Dichloride, dimethylsilylbis (3-methylcyclopentadienyl) 鍩 dichloride, dimethylsilylbis (3-methylcyclopentadienyl) 饴 dichloride, Dimethylsilylbis (2-methyl 4 Monophenylindenyl) Chromium dichloride, dimethylsilyl bis (benzoindenyl), dichloride, dichloride Economy, Ministry of Intellectual Property Bureau, employee consumer cooperative, or (dimethylsilyl) ( Dimethylsilyl) -bis (indenyl) chromium dichloride, (ethylene) (ethylene) -bis (indenyl) zirconium dichloride, (ethyl-if) (ethylene) -double (3- Methylindenyl) zirconium dichloride, (ethylene) (ethylene) bis (4,7-dimethylindenyl) pin dichloride, etc., or chromium substituted or titanium substituted for these compounds. Also, as a supplementary catalyst, preferred examples of compounds that react with a transition metal compound of Group 4 of the periodic table to form an ionic coordination compound are 'triphenylmethylamine tetrakis (pentafluorophenyl) borate, n, N —Dimethylaniline tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate. The paper size is applicable to the China National Standard (CNS) A4 specification (210X297 mm) -19- 561160 Α7 Β7 V. Compound of the invention (17) containing (pentafluorophenyl) borate anion, or triphenylmethylamine tetrakis (pentafluorophenyl) aluminate, · N, N-dimethylaniline Tetrakis (pentafluorophenyl) aluminate, lithium tetra (pentafluorophenyl) aluminate containing compounds containing (pentafluorophenyl) aluminate anions. The organoaluminum compound is preferably a compound having at least one A 1-c bond in the molecule. Specific examples thereof include trialkylaluminums such as triethylaluminum, triisobutylaluminum, and trihexylaluminum; or dialkylaluminum halides such as diethylaluminum halides and diisobutylaluminum halides; or Mixtures of alkyl aluminum and dialkyl carbohalides, or alkyl alumoxanes such as tetraethyldialuminoxane, tetrabutyl, and alumoxane. '' Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halides, and alkylalumoxane are preferred, and triethylaluminum, triisobutylaluminum, and Mixture of ethylaluminum and diethylaluminum chloride and tetraethyldialumoxane. Preferred examples of the organoaluminum include diethylaluminum, triisobutylaluminum, and the like. These metallocene-derived catalysts and / or auxiliary catalysts may be those attached to a carrier, and examples of the carrier include organic compounds such as polystyrene or inorganic oxides such as silica and alumina. Thing. The polymerization method may be a block polymerization method, a solution polymerization method, a gas phase polymerization method, a suspension polymerization method, or the like, or a batch method or a continuous method. Further, it is possible to perform preliminary polymerization with a small amount of α-olefin, for example, ethylene, propylene, 1-butane, 4-methyl-1pentene, and the like. In other words, the C-type polymer also includes a C-type homopolymer of (1-A) component and a small amount (0.5 mol% or less of the final resin) of ethylene, propylene, etc. (please read the note on the back first) (Please fill in this page again for details) (18) A propylene polymer obtained by polymerizing propylene after preliminary polymerization of an α-olefin. (Please read the precautions on the back before filling out this page) The polymerization temperature is generally 50 ~ 25CTC, and preferably 0 ~ 150 ° C. The polymerization time is generally from χ to 100 hours, and the pressure is usually from normal pressure to 300 k g / cm2G. The nucleating agent of the component (1-B) of the composition of the present invention may be one that does not reduce the physical properties of the propylene-based polymer, rapidly induces crystal nuclei, and starts to crystallize with a small degree of excessive cooling. Specific examples of the nucleating agent used in the present invention are, for example, a high melting point polymer, an organic carboxylic acid or a metal salt thereof, an aromatic sulfonate or a metal salt thereof, an organic phosphoric acid compound or a metal salt thereof, and dibenzylidene sorbitol. Or a derivative thereof, a partial metal salt of rose acid, an inorganic fine particle, an imine, an acid amine, a fluoracridone, a benzophenone, or a mixture thereof. Examples of high-melting polymers printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as polyolefins such as polyethylene and polypropylene, or polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane, or polymers 3-methylpentene-1, poly3-methylbutene-1, polyalkenylsilane and the like. Examples of the metal salt are aluminum benzoate, aluminum p-t butyl benzoate, sodium adipate, sodium thienylcarboxylate, sodium pyrrolecarboxylate, and the like. Examples of inorganic fine particles include talc, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, tin oxide, sand dichloride, diatomaceous earth, oxidation Chin, magnesia, pumice powder, pumice, aluminum hydroxide, magnesium hydroxide, basic carbon number magnesium, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, molybdenum sulfide, etc. Among them, the inorganic fine particles such as organic phosphate metal salt and talc shown by the following formula (1-I) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm ·)-21-561160 Α7 Β7 5. Description of the invention ( 19) Few odors are produced, so it is suitable for use as a food for the propylene polymer composition of the present invention.
•裝—— (請先閲讀背面之注意事項再填寫本頁) (式中,R1爲氫原子或碳數1〜4之烷基、R2及R3分 別爲氫原子、碳數1〜12之烷基、環烷基、芳基或芳烷 基。Μ爲鹼性金屬、鹼土類金屬、鋁及鋅,又Μ爲鹼性金 屬時m爲〇、η爲1 ,Μ爲二價金屬時η爲1或2,另外 當η爲1時m爲1 ,η爲2時m爲〇,Μ爲銘時爲m爲1 ,η 爲 2。) 另外,使含滑石等無機微粒子之丙烯系聚合物組成物 成型而得到的薄膜亦具有優良之滑動性,因此今提升製袋 、印刷等二次加工性,故適合作爲利用各種自動塡充包裝 層壓製品等之高速製造裝置用的廣泛使用之薄膜。 使含二苄叉山梨糖或衍生物之造核劑的丙烯系聚合物 組成物成型而形成的薄膜因具有特別優良之透明性,故可 增加顯示效果,因此適用於玩具、文具等包裝。 二苄叉山梨醇之衍生物的具體例子如,1 ,3 : 2, 本紙浪尺度適用中國國家標準(CNS ) Α4規格(210X297公釐.) -22 - 訂 經濟部智慧財產局員工消費合作社印製 561160 A7 B7 五、發明説明(2〇 ) (請先閲讀背面之注意事項再填寫本頁) 4 —雙(0 — 3 ,4 一二甲基苄叉)山梨糖醇,1 ,3 : 2,4 —雙(0 — 2,4—.二甲基苄叉)山梨糖醇、1 , 3 : 2,4 —雙(0 — 4 一乙基苄叉)山梨糖醇、1 ,3 ••2,4 —雙(0 — 4 —氯苄叉)山梨糖醇、1,3:2 ,4 一二苄山梨糖醇等。 使含醯胺化合物之造核劑的丙烯系聚合物組成物成型 而形成之薄膜因只有特別優良之剛性,故於高速製袋之情 形下不易產生卷取皺折等問題,因此適用爲利用高速製袋 機之廣泛使用的包裝薄膜。 醯胺化合物之具體例如,己二酸二醯替苯胺、辛二酸 二醯替苯胺等。 這些造核劑對一般丙燦系聚合物之添加量爲1〇 p pm以上,又以5 0〜3 0 0 0 p pm爲佳。若添加量 低於1 0 P p m時,將不具改善低溫熱封性之效果。又, 造核劑之添加量過多時,亦不具效果。 經濟部智慧財產局員工消費合作社印製 另外,添加量雖今因造核劑之種類而不同,但,對一 般丙嫌系樹脂組成物之透明性、耐衝擊性觀點,其添加量 較佳爲1 0 0 0 p P m以下,又以5 0 0 P p m以下特別 佳。更具體的添加量,例如其爲山梨糖醇予造核劑之二节 叉山梨糖醇時,添加量爲3 0 0 0 p p m以下*, 1 5 0 0 p pm以下更佳,特別佳爲5 0 〇 p pm以下。 又,雙(P —甲基苄叉)山梨糖醇、雙(二甲基卡叉)山 梨糖醇之添加量爲1 2 0 0 p pm以下,又以6 〇 〇 p pm以下更佳,特別佳爲3 0 0 p pm以下。有機磷酸 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐) :23-〜- 561160 Μ Β7_ 五、發明説明⑵) (請先閲讀背面之注意事項再填寫本頁) 金屬鹽之有機磷酸N a鹽的添加量爲5 0 0 p pm以下, 又以2 5 0 p p m以下更佳~,特別佳爲1 2 5 p P m以下 。有機磷酸A 1鹽之添加量爲1 9 0 0 P pm以下,又以 1500ppm以下更佳,特別佳爲5〇〇ppm以下。 淺因製粉社製滑石Μ M R之滑石則爲4 0 0 0 p P m以下 ,又以20〇〇ppm以下更佳,特別佳爲1Q00 p pm以下。新日本理化社製取尼傑斯特—NU — 1 〇〇 之醯胺系化合物爲3 0 0 0 p p m以下,又以1 5 0 0 p pm以下更佳,特別佳爲5 0 0 ρ pm以下。 經濟,部智慧財產局員工消費合作社印製 .其次,第一項發明之第二種樹脂組成物爲,於(1 一 A >)之由丙烯與乙烯及/或碳數4〜2 0的α —烯烴所 形成之丙烯系無規共聚合物,即,利用二茂金屬衍生物觸 媒而聚合之,得自丙烯之構造單位爲8 0〜1 0 0莫耳% ’得自乙烯及/或碳數4〜2 0之α烯烴的構造單位爲〇 〜2 0莫耳%,且分子量分布(Mw/Mn )爲 3 · 5以下、極限粘度〔7?〕爲〇 · 5〜5分升/ g之丙 燦系聚合物中’添加(1 一 B)造核劑1 〇 〇 p pm以上 之丙烯系聚合物組成物。 本樹脂組成物所使用的上述(1 - A >)成分爲丙燃 系無規共聚合物,其中得自乙燦及/或α -儲烴,特別是 碳數4〜2 0之α -烯烴的構造單位較佳爲4 〇重量%以 下,又以0〜2 0莫耳%更佳,特別佳爲〇〜1 〇莫耳% 。若此丙烯系無規共聚合物中得自乙烯及/或碳數4〜 2 0之α烯烴的構造單位超過2 0莫耳%時,會降低薄膜 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) 561160 五、發明説明(22 剛性。 (請先閱讀背面之注意事項再填寫本頁) 又丙烯系無規共聚合物之分子量分布(Mw/Mn )較佳爲3 · 5以下,又以3 · 〇以下更佳,特別佳爲 2 · 5以下。若分子量分布(Mw/Mri)超過3 · 5時 ’會降低熱封性及耐粘連性。 另外’丙嫌系無規共聚合物之極限粘度〔7?〕一般爲 ◦ · 5〜5 · 〇分升,又以〇 · 5〜3 · 〇分升/g 較佳,更佳爲l〜3d </g,特別佳爲丄· 〇〜2 · 5 分升/ g。 •沸騰二乙基醚萃取量較佳爲2 · 6重量%以下,又以 2.3重量%以下更佳。 經濟部智慧財產局員工消贫合作社印製 本樹脂組成物之丙烯系無規共聚合物係利用,使丙烯 與乙烯及/或碳數4〜2 0之α -烯烴混合接觸而製得。 反應系中的各單體之量比例無需具有經時一定性,即,既 使供給時各單體具有一定混合比,但經時之供給的單體混 合比可產生變化。又,可依共聚合物反應比來考量單體之 添加比率。另外,亦可利用將一定氣體連續導入反應系中 ,再以排壓閥連續將剩餘氣體排出之方式,使反應系中之 各單體於經時時仍能保有一定的單體量比。又,可以氫作 爲分子量調節劑。 本樹脂組成物所使用之(1 - A >)成分的丙烯系無 規共聚合物可利用同本發明之第一種樹脂組成物的丙烯均 聚物,一般於存在具有環戊二烯基環之周期表4族的過渡 金屬化合物,甲基鋁氧烷或其與周期表第4族之過渡金屬 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-25 561160 A7 _____B7___ 五、發明説明(23 ) (請先閱讀背面之注意事項再填寫本頁) 化合物起反應的形成離子性配位化合物之化合物及有機鋁 化合物所形成的芳環系觸媒之情形下,使丙烯與上述α -Μ烴聚合而製得。上述芳環烯系觸媒及補助觸媒之具體例 子可同上述本發明之第一種樹脂組成物的丙烯均聚物,以 此省略詳細說明。 述之丙烯系聚合物於符合後述式(I )之範圍下, 亦可摻合其他之聚合物。此其他聚合物例子如,高密度聚 乙烯、低密度聚乙烯、直鏈狀低密度聚乙烯,目前之丙烯 無規或嵌段共聚合物等。 . 至於聚合法、預備聚合、聚合條件可同上述本發明之 第一種樹脂組成物的丙烯均聚物。 本樹脂組成物所使用之(1 - B )造核劑同本發明的 第一種樹脂組成物之造核劑,在此省略說明。 本樹脂組成物中造核劑對丙烯系無規共聚合物之添加 量爲1 0 p pm以上。較佳之添加量範圍同本發明之第一 種樹脂組成物,在此省略說明。 經濟,部智慧財產局員工消費合作社印製 本發明之第一種及第二種樹脂組成物的M D方向之拉 伸彈性率(Τ Μ ( Μ P a ))與熱封溫度(H S T ( °C ) )較佳爲,符合下列式(1 一 I I ), TMS22XHST - 1850 ...... ( 1 - I I ) 又以符合下列式(1 一 I I )/更佳, TMS22XHST-1800...... (1 — I I) 一 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -26 - 561160 A7 B7 五、發明説明(24 ) 最佳爲符合下列式(1 一 I I ) 〃 TM^22xHST-1750 ...... (l-l I )" (請先聞讀背面之注意事項再填寫本頁) 上述之M D方向的拉伸彈性率(τ Μ )係依據J I S Κ - 7 1 2 7利用拉伸試驗而測得,即,於十字頭速度 爲5 0 0mm/分,測定方向爲MD方向(拉取方向)下 測得。又,薄膜厚度以2 5 // m爲代表値。 另外,上述之熱封溫度(H S T )係依據J I S Ζ - 1 7 0 7所測得之値。其詳細之測定條件等如實施例所 記載。 . 本發明之第一種及第二種樹脂組成物因係於,利用上 述之二茂金屬衍生物系觸媒所製得之丙烯系聚合物中,一 般添加1 0 p p m以上之造核劑,故利用此樹脂組成物製 膜時,可得到具有較高之剛性及熱封性的平衡性之薄膜。 下面將詳細說明本說明書之第二項發明。 經濟·部智慧財產局員工消費合作社印製 本發明之樹脂組成物爲,於(2 - A )丙烯均聚物, 即,利用二茂金屬衍生物系觸媒而聚合之等規五分率( mmmm分率)爲80〜99%、極限粘度〔77〕爲 1 · 0〜2 · 0分升/g、分子量分布(Mw/Mn比) 爲3 · 5以下之丙烯系聚合物9 9〜5 0重量份中,添加 (2 - B )丙烯均聚物,即,利用二茂金屬衍生物系觸媒 而聚合之極限粘度〔/?〕爲0 · 01〜1 . 〇、分子量分 布(Mw/Μη)爲3·5以下之丙烯系聚合物1〜50 重量份而形成之聚丙烯系樹脂組成物。 本紙張尺度適用中國國家揉準( CNS ) Α4規格(210X297公釐〇 :2Ί : 561160 A7 B7 五、發明説明(25 ) 本發明係依據(2 - B )成分之丙烯均聚物具有同第 一項發明中之造核劑機能,而完成的發明。 (請先閲讀背面之注意事項再填寫本頁) 本發明之(2 - A)成分爲,利用二茂金屬衍生物系 觸媒而聚合之丙烯均聚物,亦可爲預先與少量(〇 · 5莫 耳%以下)之乙烯或碳數4〜2 0之α烯烴進行預備聚合 的丙烯系聚合物,其中,聚丙烯之表示立體規則性的等規 極組物分率(mmmm分率)爲8 0〜9 9莫耳%,又以 85〜97莫耳%爲佳,又,極限粘度〔7?〕爲1 · 〇〜 2 · 0分升/ g,又以1 · 5〜1 · 8分升/.g爲佳、分 子量分布(Mw/Mn)爲3 · 5以下,又以3 · 0以下 爲佳。 若等規五分率(mmmm分率)低於8 0莫耳%時, 薄膜剛性將不足,又起過9 9莫耳%時,會使薄膜之耐衝 擊性變差。 又,極限粘度〔7?〕小於1 · 0分升/ g時,會使薄 膜成型性變差,又,超過2 · 0分升/ g時,會降氐流動 性而難於成型。 經濟·部智慧財產局員工消費合作社印製 另外,若分子量分布(Mw/Mn比)超過3 . 5時 ,會降低熱封性及耐粘連性。 因本發明中所使用的(2 - A)成分之丙嫌系聚合物 可利用向桌一項發明之弟一種樹脂組成物的丙嫌均聚物所 使用之觸媒而製得,在此省略說明。 聚合溫度一般爲一 5 0〜21 5 0°C,又以〇〜1 5 〇 t:爲佳,聚合時間一般爲1〜1 0小時,壓力一般爲常壓 本紙張尺度適用中國國家橾準( CNS ) A4規格(210X297公釐) 561160 A7 B7 五、發明説明(26 ) 一 300kg/Cm2G。 本發明所使用之(2 - )成分的丙烯系聚合物雖可 (請先閲讀背面之注意事項再填寫本頁) 利用同第一項發明之第一種樹脂組成物的丙烯均聚物之聚 合條件而製得,但,亦可利用反應時之聚合溫度、氫分壓 調整極限粘度。具體地地說即,(2-A)成分之丙烯系 聚合物可利用聚合溫度〇〜1Q0°C,又以30〜90°C 爲佳,氫分壓0〜5kg/cm2G,又以〇〜2 · 5kg / c m 2 G爲佳之條件而製得。 本發明之(2 - B)成分爲,利用二茂金.屬衍生物系 觸媒而聚合之丙烯均聚物·,亦可爲預先與少量(〇 · 5莫 耳%以下)之乙烯或碳數4〜2 0的α —烯烴進行預備聚 合的丙烯系聚合物,其極限粘度〔7?〕爲〇 · 〇 1〜 1 · 0分升/g,又以0 · 1〜〇 · 8分升/g爲佳,分 子量分布(Mw/Mn)爲3·5以下,又以3·0以下 爲佳。 經濟部智慧財產局員工消费合作社印製 若極限粘度〔7?〕小於〇 · 01分升/ g時,薄膜上 易產生黏性物,又,超過1 · 〇分升/ g時,會使熱封性 變差。 若分子量分布(Mw/Mn比)超過3 · 5時,會降 低熱封性及耐粘連性。 又’就薄膜剛性等觀點,(2 - B )成分之等規五分 率(mmmm分率)較佳爲8 〇〜9 9莫耳%。 基本上使(2 - B )成分聚合時所使用的二茂金屬衍 生物系觸媒及聚合方法可同上述(2 - A )成分之丙烯系 本紙張尺度適用中國國家揉率(CNS ) A4規格(210X297公釐.) 561160 Α7 Β7 五、發明説明(27 ) 聚合物。具體地說即,(2-B)成分之丙燦系聚合物可 利用’聚合溫度5 0〜1 5 .0 °C,又以5 〇〜1 〇 〇。(:爲 佳’氫分壓〇 · 1〜l〇kg/cm2G,又以〇 · 5〜5 kg/cm2G之條件而製得。 .本發明之丙烯系聚合物組成物中的(2 - A)成分及 (2 — B)成分之添加比率(重量份)爲99〜5〇 : 1 〜50,又以99〜75 : 1 : 25較佳,更佳爲99〜 90 : 1〜10。若(2 - B)成分之添加量小於iq% 時,會使熱封性變差,又,超過5 0 %時,會.降低拉伸彈 性率、耐衝擊性。 · 下面將詳細說明本說明書之第三項發明。 本發明之丙烯系聚合物係由,(3—A)的丙烯與碳 數5以上之α-烯烴的共聚合物55〜99重量份及、( 3 - Β )差示掃描型熱量計所測定之結晶化溫度比(3 一 Α)高的丙烯系聚合物4 5〜1重量份所形成。 本發明之(3 - Α)共聚合物爲,丙烯與碳數5以上 之α -烯烴的共聚合物。若使用丙烯均聚物時,其低溫熱 封性將不足。又,碳數5以上之α -烯烴的例子並無特別 限制’其具體例子如,1一戊烯、4一甲基一1一戊烯、 1—己烯、1 一庚烯、1 一辛烯、1 一壬烯、1—癸烯、 1 一十二碳烯、1 一十三碳烯、1 一十四碳烯、1 一十五 碳烯、1一十六碳烯、1一十七碳烯、1一十八碳烯等。 其中又以1 一辛烯、1 —h二碳烯、1 一癸烯爲佳。另外 ,α -烯烴若爲乙烯單位或1 一丁烯單位時,因其降低聚 本紙張尺度適用中,國國家標準(CNS ) A4規格(210X297公釐.) (請先閲讀背面之注意事項再填寫本頁) 裝. 訂 經濟部智慧財產局員工消費合作社印製 561160 A7 ___B7___ 五、發明説明(28 ) (請先閲讀背面之注意事項再填寫本頁) 丙烯之熔點的效率比碳數5以上之α -烯烴單位低,故改 良低溫熱封特性之效果將不足,因此此類α -烯烴不佳。 又,本發明之(3 - A )共聚合物較佳爲,符合下列(A —i)或(A - i i)之物。 (A - i ):以升溫分級色譜之主要溶出峰値溫度爲 Tp時,(Τρ — 5)°C〜(Tp + 5)°C之溫度範圍下 所溶出的量(W(A) p)爲70重量%以上。 (Λ - i i ):於於升溫分級色譜之0 °C以下的溫度 範圍下所溶出量(W(A) 〇)爲3重量%以下。 經濟部智慧財產局員工消費合作社印製 此W(A) p較佳爲75重量%以上,又以80重量 %以上更佳。若W (A) p低於7 0重量%時,會使組成 分布變廣,結果T R E F曲線中除了主要溶出峰値以外, 還會出現其他峰値,且主要溶出峰値之裙擺的高溫側或低 溫側會增加延伸帶。若主要溶出峰値之裙擺於高溫側延伸 或主要溶出峰値之高溫側出現副峰値時,易造成熱封特性 不足。又,主要溶出峰値之裙擺於低溫側延伸或主要溶出 峰値之低溫側出現副峰値時,薄膜、纖維、片狀物及成型 體爲成爲黏性物。另外,W ( A ) 〇較佳爲2重量%以下 ,又以1 · 5重量%以下爲佳。若W(A) 〇超過3重量 %時,薄膜、纖維、片狀物及成型物會成爲黏性物,故此 値不佳。 又,本發明之(3 - A)共聚合物更佳爲,符合下列 (A— iii)、 (A - iv)及(A — v)中至少 1 個 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐.)-31 - 561160 A7 B7 五、發明説明(29 ) (請先閱讀背面之注意事項再填寫本頁) (AA—i 1 i):(3—A)共聚合物中之碳數5 以上的焴烴單位含量莫耳%)爲〇·1莫耳%以 上,1 2莫耳%以下。 (Α — 1 v ) : ( 3 - A )共聚合物之立體規則性指 標(P)爲8 5莫耳%以上。 (A — v) : 3— Α)共聚合物之萘烷中,135 t: 下的極限粘度(々〕)爲0 · 5〜3 · 0分升/g。 又’ (3 —A)共聚合物中的碳數5以上之α -烯烴 單位含量(α莫耳%)較佳爲〇 · 2莫耳%以上且 1 1莫耳%以下,更佳爲〇 · 3莫耳%以上且1 〇莫耳% 以下。若低於〇 · i莫耳%時,改良熱封特性之效果不足 ’又’超過1 2莫耳%時,會降低共聚合物之結晶性及使 剛性變差。又’ (p )較佳爲9 〇莫耳%以上,又以9 5 莫耳%以上特別佳。若(P )低於8 5莫耳%時,會降低 共聚合物之結晶性及使剛性變差。至於(P )係指,利用 1 3 C — N M R所測得的三價基單位的等規分率,其求取方 法將於實施例中詳細說明。又〔7/〕較佳爲〇 . 5〜 經濟·部智慧財產局員工消资合作社印製 3 · 0分升/ g,若〔;/〕超出此範圍時,易造成成型不 良之現象。 另外’ (3-A)共聚合物中,以差示掃描型熱量計 測定之熔點(T m a ( t ))較佳爲符合下列式,• Equipment—— (Please read the notes on the back before filling this page) (where R1 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, R2 and R3 are a hydrogen atom and an alkyl group with 1 to 12 carbon atoms, respectively Base, cycloalkyl, aryl, or aralkyl. M is a basic metal, alkaline earth metal, aluminum, and zinc, and when M is a basic metal, m is 0, η is 1, and when M is a divalent metal, η is 1 or 2, and m is 1 when η is 1, m is 0 when η is 2, m is 1 when M is inscription, and η is 2.) In addition, a propylene polymer containing inorganic fine particles such as talc is composed. The film obtained from the product molding also has excellent sliding properties. Therefore, the secondary processability such as bag making and printing is improved. Therefore, it is suitable as a widely used film for high-speed manufacturing equipment using various automatic filling and packaging laminates. The film formed by molding a propylene-based polymer composition containing a nucleating agent of dibenzylidene sorbose or a derivative has particularly excellent transparency, so that it can increase the display effect, and is therefore suitable for packaging of toys and stationery. Specific examples of derivatives of dibenzylidene sorbitol are, for example, 1, 3: 2, the paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm.) -22-Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Consumption Cooperative Preparation 561160 A7 B7 V. Description of the invention (20) (Please read the notes on the back before filling out this page) 4 —Bis (0 — 3, 4 dimethylbenzyl fork) sorbitol, 1, 3: 2 , 4—bis (0—2,4—.dimethylbenzylidene) sorbitol, 1, 3: 2, 4—bis (0—4—ethylbenzylidene) sorbitol, 1, 3 •• 2,4-bis (0-4-chlorobenzyl fork) sorbitol, 1,3: 2, 4-dibenzyl sorbitol, etc. The film formed by molding a propylene-based polymer composition containing a nucleating agent containing an amidine compound has only particularly excellent rigidity, so it is difficult to cause problems such as wrinkling and wrinkling in the case of high-speed bag making, so it is suitable for using high-speed Widely used packaging film for bag making machines. Specific examples of the amidine compounds include diamidine adipate, diamidine suberate, and the like. The addition amount of these nucleating agents to general acrylic polymers is more than 10 p pm, and more preferably 50 to 3 00 p pm. If the added amount is less than 10 P p m, it will not have the effect of improving the low temperature heat sealability. In addition, when the amount of the nucleating agent is too much, it is not effective. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, although the amount added is different depending on the type of nucleating agent, from the viewpoint of transparency and impact resistance of general C-type resin compositions, the added amount is preferably Below 1 0 0 0 p P m, and below 5 0 P pm is particularly preferred. More specific addition amount, for example, when it is the bisegyl sorbitol of sorbitol pre-nucleating agent, the addition amount is 300 ppm or less *, more preferably 1 500 ppm or less, particularly preferably 5 0 〇p pm or less. The addition amount of bis (P-methylbenzyl fork) sorbitol and bis (dimethylcarpentyl) sorbitol is preferably 12 00 p pm or less, and more preferably 600 p pm or less, particularly It is preferably below 3 0 0 p pm. Organic phosphoric acid This paper is applicable in the national standard (CNS) A4 specification (210X297 mm): 23- ~-561160 Μ B7_ V. Description of the invention⑵) (Please read the precautions on the back before filling this page) Metal salt The organic phosphoric acid Na salt is added in an amount of 500 p pm or less, and more preferably 250 ppm or less, and particularly preferably 1 25 p P m or less. The addition amount of the organic phosphoric acid A 1 salt is 1900 P pm or less, more preferably 1500 ppm or less, and particularly preferably 500 ppm or less. The talc of the talc MM MR produced by Asahi Seisakusho is below 4 000 p P m, more preferably below 20,000 ppm, and particularly preferably below 1Q00 p pm. Nippon-Nu-1000's amidoamine compounds prepared by Shinnippon Chemical Co., Ltd. are below 300 ppm, more preferably below 15 000 p pm, particularly preferably below 50 0 ρ pm . Printed by the Consumer Cooperative of the Ministry of Economics and Intellectual Property of the Ministry. Secondly, the second resin composition of the first invention is (1-A >) made of propylene and ethylene and / or carbon number of 4 to 2 α-olefin formed propylene-based random copolymers, that is, polymerized by using a metallocene derivative catalyst, the structural unit derived from propylene is 80 ~ 100 mole% 'derived from ethylene and / Or the structural unit of α-olefins having 4 to 20 carbon atoms is 0 to 20 mole%, and the molecular weight distribution (Mw / Mn) is 3.5 or less, and the limiting viscosity [7?] Is 0.5 to 5 deciliters. / g of a propylene-based polymer is a propylene-based polymer composition containing (1-B) a nucleating agent at 1000 p pm or more. The above-mentioned (1-A >) component used in the present resin composition is a propylene-based random copolymer, which is obtained from Echan and / or α-hydrocarbon storage, especially α- 4-2 carbon number- The structural unit of the olefin is preferably 40% by weight or less, more preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%. If the structural unit of the propylene random copolymer obtained from ethylene and / or alpha olefins having 4 to 20 carbon atoms exceeds 20 mol%, the film will be reduced. The paper size is subject to the Chinese National Standard (CNS) Α4 Specifications (210 × 297 mm) 561160 V. Description of the invention (22 Rigidity. (Please read the notes on the back before filling out this page) The molecular weight distribution (Mw / Mn) of the propylene random copolymer is preferably 3 · 5 In the following, it is more preferably 3 · 〇 or less, and particularly preferably 2 · 5 or less. If the molecular weight distribution (Mw / Mri) exceeds 3 · 5 ', the heat-sealability and blocking resistance will be reduced. In addition, the C-base is random The limiting viscosity [7?] Of the copolymer is generally 5 to 5 deciliters, preferably 0.5 to 3 deciliters / g, more preferably 1 to 3d < / g, particularly丄 · 〇 ~ 2. 5 dl / g. • The amount of boiling diethyl ether extraction is preferably 2.6% by weight or less, and more preferably 2.3% by weight or less. Co-operative poverty alleviation agency of the Intellectual Property Bureau of the Ministry of Economic Affairs The propylene-based random copolymers for printing this resin composition are used to make propylene and ethylene and / or α-olefins having 4 to 20 carbon atoms. The ratio of the amount of each monomer in the reaction system does not need to be definite over time, that is, even if each monomer has a certain mixing ratio at the time of supply, the mixing ratio of the monomers supplied over time may change. In addition, the monomer addition ratio can be considered according to the reaction ratio of the copolymer. In addition, a certain gas can be continuously introduced into the reaction system, and the remaining gas can be continuously discharged by a pressure relief valve to make the reaction system Each monomer can maintain a certain monomer content ratio over time. In addition, hydrogen can be used as a molecular weight regulator. The propylene-based random copolymer of the (1-A >) component used in this resin composition can be used. The propylene homopolymer using the first resin composition of the present invention is generally used in the presence of a transition metal compound having a cyclopentadienyl ring in Group 4 of the periodic table, methylalumoxane or a group thereof with the Group 4 of the Periodic Table. The transition metal of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -25 561160 A7 _____B7___ V. Description of the invention (23) (Please read the precautions on the back before filling this page) The formation of the reaction of the compound In the case of an aromatic ring catalyst formed by a compound of an organic complex compound and an organoaluminum compound, propylene is polymerized with the above α-M hydrocarbon. Specific examples of the above aromatic cycloolefin catalyst and auxiliary catalyst It may be the same as the propylene homopolymer of the first resin composition of the present invention described above, and detailed description is omitted. The propylene-based polymer described above may be blended with other polymers within the range of formula (I) described later. Examples of this other polymer are, for example, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and current propylene random or block copolymers. As for the polymerization method, preliminary polymerization, and polymerization conditions, the same can be used. The above-mentioned propylene homopolymer of the first resin composition of the present invention. The (1-B) nucleating agent used in the resin composition is the same as the nucleating agent of the first resin composition of the present invention, and the description is omitted here. The addition amount of the nucleating agent to the propylene-based random copolymer in the resin composition is 10 p pm or more. The preferred range of the addition amount is the same as that of the first resin composition of the present invention, and the description is omitted here. Economy, Ministry of Intellectual Property Bureau Employees' Cooperatives printed the tensile elastic modulus (T Μ (Μ P a)) and heat sealing temperature (HST (° C) of the first and second resin compositions of the present invention in the MD direction )) Preferably, it is in accordance with the following formula (1-II), TMS22XHST-1850 ... (1-II) and in accordance with the following formula (1-II) / better, TMS22XHST-1800 ... .. (1 — II) A paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm.) -26-561160 A7 B7 V. Description of the invention (24) It is best to comply with the following formula (1—II) 〃 TM ^ 22xHST-1750 ...... (ll I) " (Please read the precautions on the back before filling out this page) The above-mentioned MD elastic modulus (τ Μ) is based on JIS Κ- 7 1 2 7 Measured by a tensile test, that is, measured at a crosshead speed of 500 mm / min and a measurement direction of the MD direction (pulling direction). The film thickness is represented by 2 5 // m as 値. In addition, the above-mentioned heat-sealing temperature (H S T) is a value measured in accordance with J I S Z-1 7 0 7. The detailed measurement conditions and the like are described in the examples. The first and second resin compositions of the present invention are generally based on the addition of a nucleating agent of 10 ppm or more to the propylene polymer obtained by using the above-mentioned metallocene derivative catalyst. Therefore, when a film is formed by using this resin composition, a thin film having high balance between rigidity and heat sealability can be obtained. The second invention of this specification will be described in detail below. The resin composition of the present invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is (2-A) a homopolymer of propylene, that is, an isotactic quintile of polymerization using a metallocene derivative catalyst ( mmmm fraction) is 80 to 99%, the limiting viscosity [77] is 1 · 0 to 2 · 0 deciliter / g, and the molecular weight distribution (Mw / Mn ratio) is 3 · 5 or less of a propylene polymer 9 9 to 5 In 0 parts by weight, a (2-B) propylene homopolymer is added, that is, the limiting viscosity [/?] Of polymerization using a metallocene derivative-based catalyst is 0. 01 to 1.0. The molecular weight distribution (Mw / Mn) is a polypropylene-based resin composition formed from 1 to 50 parts by weight of a propylene-based polymer of 3.5 or less. This paper size is applicable to China National Standard (CNS) A4 (210X297mm 0: 2Ί: 561160 A7 B7) V. Description of the invention (25) The invention is based on the (2-B) propylene homopolymer with the same first The invention is completed by the function of nucleating agent in this invention. (Please read the precautions on the back before filling this page.) The component (2-A) of the invention is polymerized by using a metallocene derivative catalyst. The propylene homopolymer may also be a propylene polymer that is preliminarily polymerized with a small amount (0.5 mol% or less) of ethylene or an alpha olefin having 4 to 20 carbon atoms. Among them, polypropylene indicates stereoregularity. The isotactic polar group fraction (mmmm fraction) is 80 to 99 mol%, preferably 85 to 97 mol%, and the limiting viscosity [7?] Is 1 · 〇 ~ 2 · 0 Deciliters / g, preferably 1 · 5 ~ 1 · 8 deciliters / .g, and molecular weight distribution (Mw / Mn) of 3 · 5 or less, and preferably 3 · 0 or less. If isotactic quintile (Mmmm fraction) When less than 80 mol%, the rigidity of the film will be insufficient, and when it is over 99 mol%, the impact resistance of the film will be deteriorated. When the degree [7?] Is less than 1.0 deciliters / g, the moldability of the film is deteriorated, and when it exceeds 2.0 deciliters / g, the fluidity is reduced and the molding is difficult. Printed by an employee consumer cooperative. In addition, if the molecular weight distribution (Mw / Mn ratio) exceeds 3.5, heat-sealability and blocking resistance will be reduced. Because of the (2-A) component used in the present invention, the polymer is a C-polymer. The material can be prepared by using the catalyst used in the acrylic homopolymer of a resin composition, a brother of one invention of the table, and the description is omitted here. The polymerization temperature is generally from 50 to 2150 ° C. 〇 ~ 1 5 〇t: better, the polymerization time is generally 1 ~ 10 hours, the pressure is generally normal pressure, the paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) 561160 A7 B7 V. Description of the invention (26) 300kg / Cm2G. Although the propylene-based polymer (2-) used in the present invention is acceptable (please read the precautions on the back before filling this page). Use the first resin composition of the first invention Propylene homopolymer based on the polymerization conditions, but the polymerization temperature during the reaction can also be used 2. Hydrogen partial pressure adjusts the limiting viscosity. Specifically, the (2-A) propylene polymer can be used at a polymerization temperature of 0 ~ 1Q0 ° C, preferably 30 ~ 90 ° C, and a hydrogen partial pressure of 0 ~ 5kg / cm2G, and it is prepared under the optimal condition of 0 ~ 2 · 5kg / cm2G. The (2-B) component of the present invention is a homopolymerization of propylene polymerized by using ferrocene, a derivative catalyst. It can also be a propylene polymer that has been preliminarily polymerized with a small amount (0.5 mole% or less) of ethylene or α-olefins having 4 to 20 carbon atoms. The limiting viscosity [7?] Is 0. 〇1 to 1.0 deciliter / g, and preferably 0.1 to 0.8 deciliter / g, and the molecular weight distribution (Mw / Mn) is preferably 3.5 or less, and more preferably 3.0 or less. If printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, if the limiting viscosity [7?] Is less than 0.01 deciliters / g, sticky substances are liable to occur on the film, and when it exceeds 1.0 deciliters / g, heat will be Sealability is poor. When the molecular weight distribution (Mw / Mn ratio) exceeds 3 · 5, heat sealability and blocking resistance are reduced. From the viewpoint of film rigidity and the like, the isotactic quintile (mmmm fraction) of the (2-B) component is preferably 80 to 99 mol%. Basically, the catalyst and polymerization method for the metallocene derivative used when polymerizing the (2-B) component can be the same as the propylene-based (2-A) component of this paper. This paper applies the Chinese national kneading rate (CNS) A4 specification. (210X297 mm.) 561160 Α7 Β7 V. Description of the invention (27) Polymer. Specifically, the acrylic polymer based on the (2-B) component can be used at a polymerization temperature of 50 to 15.0 ° C, and a temperature of 50 to 10.0. (: It is preferably a hydrogen partial pressure of 0.1 to 10 kg / cm2G, and is prepared under the conditions of 0.5 to 5 kg / cm2G. (2-A in the propylene polymer composition of the present invention ) And (2-B) ingredients are added at a ratio (parts by weight) of 99 to 50: 1 to 50, and more preferably 99 to 75: 1: 25, more preferably 99 to 90: 1 to 10. If (2-B) When the added amount of the component is less than iq%, the heat sealability will be deteriorated, and when it exceeds 50%, the tensile elastic modulus and impact resistance will be reduced. The third invention. The propylene-based polymer of the present invention comprises (3-A) 55 to 99 parts by weight of a copolymer of propylene and an α-olefin having 5 or more carbon atoms, and (3-Β) differential scanning. It is formed by 5 to 1 part by weight of a propylene polymer 4 having a higher crystallization temperature than that of (3-A) measured by a type calorimeter. The (3-A) copolymer of the present invention is one in which propylene has 5 or more carbon atoms. Copolymer of α-olefin. If a propylene homopolymer is used, its low-temperature heat-sealability will be insufficient. Examples of α-olefins having 5 or more carbon atoms are not particularly limited. A specific example thereof is 1-pentene Ene, 4-a 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1- 13-carbene, 1-14 Carbenes, 1-15 carbonenes, 1-16 carbonenes, 1-17 carbonenes, 1-18 carbonenes, etc. Among them, 1-octene, 1-h dicarbonene, 1-decane Alkenes are preferred. In addition, if α-olefins are ethylene units or 1-butene units, due to their reduced paper size, the national standard (CNS) A4 specification (210X297 mm.) (Please read the back first) Please pay attention to this page before filling in this page) Packing. Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives to print 561160 A7 ___B7___ V. Invention Description (28) (Please read the precautions on the back before filling this page) Efficiency ratio of the melting point of propylene The α-olefin unit having a carbon number of 5 or more is low, so the effect of improving the low-temperature heat-sealing characteristics will be insufficient, so this type of α-olefin is not good. In addition, the (3-A) copolymer of the present invention is preferably in accordance with The following (A — i) or (A-ii). (A-i): When the main dissolution peak temperature of the temperature-grading chromatography is Tp, (Τρ — 5) ° C ~ (T p + 5) The amount of dissolution (W (A) p) in the temperature range of 70 ° C is 70% by weight or more. (Λ-ii): The amount of dissolution in the temperature range of 0 ° C or less by temperature-grading chromatography (W (A) 〇) is 3% by weight or less. The W (A) p printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is preferably 75% by weight or more, and more preferably 80% by weight or more. If W (A When p is less than 70% by weight, the composition distribution will be broadened. As a result, in addition to the main dissolution peak peak, other peak peaks will appear in the TREF curve, and the high temperature side or low temperature side of the skirt of the main dissolution peak peak will appear. Add extension bands. If the skirt of the main dissolution peak is extended on the high-temperature side, or if the sub-peak is present on the high-temperature side of the main dissolution peak, the heat-sealing characteristics may be insufficient. In addition, when the skirt of the main elution peak extends on the low-temperature side or the sub-peak appears on the low-temperature side of the main elution peak, the film, fiber, sheet, and molded body become sticky. In addition, W (A) is preferably 2% by weight or less, and more preferably 1.5% by weight or less. If W (A) 〇 exceeds 3% by weight, the film, fiber, sheet, and molded article become sticky, so it is not good. In addition, the (3-A) copolymer of the present invention is more preferably in accordance with at least one of the following (A-iii), (A-iv), and (A-v). CNS) A4 specification (210X297 mm.)-31-561160 A7 B7 V. Description of invention (29) (Please read the notes on the back before filling this page) (AA—i 1 i): (3—A) Total The content of fluorene units in the polymer having a carbon number of 5 or more (mol%) is 0.1 mol% or more and 12 mol% or less. (A — 1 v): (3-A) The stereoregularity index (P) of the copolymer is 85 mol% or more. (A — v): 3 — A) In the decalin of the copolymer, the limiting viscosity (々) at 135 t: 0 · 5 ~ 3 · 0 dL / g. Also, the (3-A) copolymer having an α-olefin unit content (α mole%) having 5 or more carbon atoms is preferably 0.2 mole% or more and 11 mole% or less, and more preferably · 3 mol% or more and 10 mol% or less. If it is less than 0.1 mol%, the effect of improving the heat-seal characteristics is insufficient. When it exceeds 12 mol%, the crystallinity of the copolymer is reduced and the rigidity is deteriorated. Also, '(p) is preferably 90 mol% or more, and more preferably 95 mol% or more. If (P) is less than 85 mol%, the crystallinity of the copolymer is reduced and the rigidity is deteriorated. As for (P), the isotactic fraction of the trivalent base unit measured by 1 3 C — N M R is used, and the method for obtaining it will be described in detail in the examples. [7 /] is preferably 0.5 ~ 3 printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and Ministry of Economic Affairs. If [; /] is out of this range, it may easily cause defective molding. In the "(3-A) copolymer, the melting point (T m a (t)) measured by a differential scanning calorimeter is preferably in accordance with the following formula,
TmaS 140〇C 且 TmaS 160-7α ......(3-ii) 又以符合下列式者爲佳, 本紙張尺度適用中國國家揉準(〇奶)八4規格(210';<297公釐·) - 32 - 561160 Α7 Β7 五、發明説明(3〇 ) Tma‘ 130 〇C 且丁maS 155-7 α 更佳爲付合下列式者, Tma S 120 t 且 Tma S 150-7 α 特別佳爲符合下列式者, TmaS 115°C 且 TmaS 145-7α (3 -iv) (3-v) 經濟部智慧財產局員工消費合作社印製 若丁 m a超出這些範圍時,低溫熱封性將不足。 本發明之(3 — B )丙烯系聚合物爲,利用差示掃描 型熱量計所測定之結晶化溫度比(3 - A )共聚合物高之 物。若差示掃描型熱量計所測得之結晶化溫度比(3 一 A )共聚合物低時,將無法得到改良成型性之效果。· (3 - B )丙烯系聚合物之組成及構造並無特別限制 ,可使用由聚丙烯均聚物或丙烯與其他α -烯烴之共聚合 物等群中適合之結晶化溫度比(3 - A )共聚合物高者。 例如,聚丙烯均聚物中的立體規則性較高之等規聚丙烯, 具體地說即,立體規則性之指標的等規五分率爲8 5莫耳 %以上者,又以9 0莫耳%以上者較佳,更佳爲9 5莫耳 %以上者。 又,丙烯與其他α -烯烴之共聚合物的較佳例子如, 乙烯/丙烯共聚合物、乙烯/1-丁烯/丙烯共聚合物、 或1 一丁烯/丙烯共聚合物等。乙烯/丙烯共聚合物中又 以特願平8 — 288052號、特願平8 - 3132 0TmaS 140〇C and TmaS 160-7α ...... (3-ii) It is better to meet the following formula, this paper size is applicable to Chinese national standard (〇 奶) 8 4 size (210 '; < 297mm ·)-32-561160 Α7 Β7 V. Description of the invention (3〇) Tma '130 〇C and DmaS 155-7 α It is more preferable to meet the following formula, Tma S 120 t and Tma S 150-7 α is particularly suitable for those that meet the following formula: TmaS 115 ° C and TmaS 145-7α (3 -iv) (3-v) When printed by the consumer cooperative of the Intellectual Property Office of the Ministry of Economic Affairs, if the ma is outside these ranges, low temperature heat sealing Sex will be insufficient. The (3-B) propylene-based polymer of the present invention is one having a higher crystallization temperature than that of the (3-A) copolymer as measured by a differential scanning calorimeter. If the crystallization temperature measured by the differential scanning calorimeter is lower than that of the (3-A) copolymer, the effect of improving moldability cannot be obtained. · (3-B) The composition and structure of the propylene-based polymer is not particularly limited, and a suitable crystallization temperature ratio (3-from a homopolymer of polypropylene or a copolymer of propylene and other α-olefins) may be used. A) The higher the copolymer. For example, isotactic polypropylene with higher stereoregularity in polypropylene homopolymer, specifically, the isotactic quintile of the index of stereoregularity is 85 mol% or more, and 90 mol. Ears above 1% are better, more preferably above 95%. Preferable examples of copolymers of propylene and other α-olefins include ethylene / propylene copolymers, ethylene / 1-butene / propylene copolymers, and 1-butene / propylene copolymers. In the ethylene / propylene copolymers, Japanese Patent No. 8 — 288052 and Japanese Patent No. 8-3132 0
【 【 '· ϊ[['· Ϊ
Λ A 561160 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(31 ) 號所記載者爲佳。 另外,乙烯/1 -丁烯/丙烯共聚合物之較佳例子如 ,特願平9 — 209210號、特願平9 — 222356 號所記載者。 這些丙烯與其他α -烯烴之共聚合物具有,丙烯鏈之 立體規則性較高、熔點較低的結晶性較高之特徵。 又’ (3-Β)丙烯系聚合物的熔體指數較佳爲 0·1〜100g/min。 另外’本發明之丙烯系樹脂係由,(3 一 a )共聚合 物55〜9 9重量份及(·3 — B)丙烯系聚合物4 5〜1 重量份所形成,其中又以(3 一 Α)共聚合物6 5〜9 8 重量份及(3 — Β)丙烯系聚合物3 5〜2重量份所形成 者爲佳,更佳爲(3 - Α)共聚合物7 5〜9 5重量份與 (3 - Β)丙烯系聚合物2 5〜5重量份所形成者。若( 3 - A )共聚合物低於5 5重量份時,改良低溫熱封特性 之效果將不足。又,(3-A)丙烯系聚合物低於1重量 份時,將無法得到改良成型性之效果。 本發明之丙烯系樹脂中利用差示掃描型熱量計所測定 之(3 — A)共聚合物的結晶化溫度(丁 ^ a (°C))與 (3 — B )丙烯系聚合物之結晶化溫度(τ c b ( °C )) 較佳爲,符合下列式,Λ A 561160 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. It is better to record in the invention description (31). In addition, preferable examples of the ethylene / 1-butene / propylene copolymer are as described in Japanese Patent Application No. 9-209210 and Japanese Patent Application No. 9-222356. These copolymers of propylene and other? -Olefins have the characteristics of higher stereoregularity of propylene chains and higher crystallinity with lower melting points. The melt index of the (3-B) propylene polymer is preferably from 0.1 to 100 g / min. In addition, the propylene-based resin of the present invention is composed of (3—a) a copolymer of 55 to 9 9 parts by weight and (· 3 — B) a propylene-based polymer 4 of 5 to 1 part by weight, in which (3 A) Copolymer 6 5 to 9 8 parts by weight and (3-B) propylene polymer 3 5 to 2 parts by weight are preferred, and (3-Α) Copolymer 7 5 to 9 5 to 5 parts by weight of (3-B) propylene-based polymer 2. If the (3-A) copolymer is less than 55 parts by weight, the effect of improving low-temperature heat-sealing characteristics will be insufficient. When the (3-A) propylene-based polymer is less than 1 part by weight, the effect of improving moldability cannot be obtained. In the propylene resin of the present invention, the (3-A) crystallization temperature of the copolymer (D ^ a (° C)) and the (3-B) crystallization of the propylene polymer measured by a differential scanning calorimeter The temperature (τ cb (° C)) is preferably in accordance with the following formula,
Tcb-Tca^20 ...... (3 一" 又以符合下列式爲佳, 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) I ^ ^---------1T------0, (請先閲讀背面之注意事項再填寫本頁) 561160 A7 B7 五、發明説明(32 ) T c b ~ T c a ^ 3 0 ...... ( 3 - v i ) 特別佳爲符合下列式 (請先閲讀背面之注意事項再填寫本頁)Tcb-Tca ^ 20 ...... (3 一 " It is better to meet the following formula, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) I ^ ^ ------ --- 1T ------ 0, (Please read the notes on the back before filling this page) 561160 A7 B7 V. Description of the invention (32) T cb ~ T ca ^ 3 0 ...... ( 3-vi) It is best to meet the following formula (Please read the precautions on the back before filling this page)
Tcb- Tca-4〇 ...... ( 3 - v i i ) 右丁 c b - T c a太小時,會減少改良成型性之效果。 另外(3 - B )丙烯系聚合物中利用差示掃描型熱量 計所測定之熔點(T m b (艺))與結晶化溫度(τ c b (°C ))較佳爲,符合下列式,Tcb- Tca-4〇 ...... (3-v i i) Dc c-T c a is too small, reducing the effect of improving moldability. In addition, the melting point (T m b (art)) and crystallization temperature (τ c b (° C)) of the (3-B) propylene polymer measured by a differential scanning calorimeter are preferably in accordance with the following formula,
Tmb-Tcb^50 ...... ( 3 ~ v i i i ) 又以符合下列式爲佳,Tmb-Tcb ^ 50 ...... (3 ~ v i i i) It is better to meet the following formula,
Tmb — T cb^45 ...... (3 - i x) 特別佳爲符合下列式Tmb — T cb ^ 45 ...... (3-i x) is particularly preferred to conform to the following formula
Tmb~Tcb^40 ...... (3-x) 經濟部智慧財產局員工消費合作社印製 若T m b - T c b愈小,則可減少對低溫熱封性之不良影 響。 又,本發明之丙烯系樹脂的升溫分級色譜較佳爲,符合 下列(i )、 ( i i )、 ( i i i )之關係。 (i )以主要彳谷出峰値溫度爲T p時,(T p — 5 ) °C〜(Tp + 5) °C之溫度範圍下的溶出量(W (Η) p )爲6 5重量%以上。 (i i ) 0 °C以下之溫度範圍下的溶出量 本紙张尺度適用中.國國家揉準(CNS ) A4規格(210X297公嫠)-35 - 561160 A7 _ 五、發明説明(33 ) (W(Η) 0)爲3重量%以下。 (請先閲讀背面之注意事項再填寫本頁) (i i i ) T p + 1 0 X以上之溫度範圍下的溶出量 (W(H)10)爲全體之1〜45重量%。 此W(H) p又以70重量%以上爲佳,更佳爲75 蔞量%以上,特別佳爲80重量%以上。若W(H)p低 於6 5重量%時,低溫熱封性將不足。 又,W (H) 〇又以2重量%以下爲佳,更佳爲 1.5重量%以下,更佳爲1·5童量%以下。若 W ( Η ) 〇超過3重量%時,會降低防粘連性。 另外,W(H) 10又以2〜35重量%爲佳,更佳 _ 3〜2 5重量%,特別佳爲4〜2 0重量%。若 W(H) 10低於1重量%時,易造成成型不良,又,超 過4 5重量%時,低溫熱封性將不足。 經濟部智慧財產局員工消費合作社印製 本發明之丙烯系樹脂中利用差示掃描型熱量計所測定 @結晶化曲線中,最高溫度側的峰頂溫度較佳爲8 5 °C以 ^ ’又以9 0 °C以上爲佳,更佳爲9 5 °C以上,特別佳爲 1 〇 0 t以上。若最高溫度側之峰値溫度低於8 5 °C時, 會減少改良成型性之效果。 又,本發明之丙烯樹脂中利用差示掃描型熱量計所測 定的熔解曲線中,最低溫度側之峰頂溫度較佳爲1 5 0 °C &下,又以1 4 0 °C以下爲佳,更佳爲1 3 0 °C以下,特 SiH圭爲1 2 0 °C以下。若最低溫度側之峰頂溫度超過 1 5 〇 t時,低溫熱封性將不足。 本發明之丙烯系樹脂中(3 - A)共聚合物可利用實 本紙張用中國國家標準(CNS ) A4規格(210X297公嫠) -36 - 一 561160 A7 __ _B7 五、發明説明(34 ) 施例之製造方法聚合而製得,但非限此例,並無特別限制 〇 製造時所使用的觸媒較佳爲,於二茂金屬衍生物系過 渡金屬化合物中添加有機鋁化合物或硼化合物之二茂金屬 衍生物觸媒。又,此等二茂金屬衍生物與過渡金屬化合物 例子如,選自周期表第4族之過渡金屬化合物,即,鈦、 锆、鈴與1〜2個環戊二烯基、取代環戊二烯基、茚基、 取代茚基、四羥基茚基、取代四羥基茚基、氟烯基或取代 氟烯基等鍵結、或者與這些基中2個基共鍵結.後而交聯之 物鍵結等的化合物,或者具有含氫原子、氧原子、鹵原子 、烷基、烷氧基、芳基、乙醯丙酮基、羰基、氮、氧、硫 、磷、矽等配位體之化合物。 所使用之有機鋁化合物可爲各種鋁氧烷化合物。其中 又以甲基鋁氧烷特別適合。又,可使用其與三甲基鋁、三 乙基銘、二異丁基銘、一乙基銘一氯化物等有機銘化合物 之組合物。 另外,亦適用作爲離子化劑之硼化合物。其例子如, 三乙基銨四苯基硼化物般三烷基取代銨鹽,或N,N -二 甲基四苯基硼化物般N,N -二烷基苯胺鹽,或三五氟苯 基硼般苯基硼化合物。 又,可使用這些二茂金屬衍生物及/或有機鋁化合物 附載於其他載體之物。此時所使用之載體可爲,苯乙烯等 有機化合物或二氧化矽、氧化鋁等無機化合物。 另外,亦可使用預先與少量之α -烯烴,例如乙烯、 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐.)-37- (請先閱讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局員工消費合作社印製 561160 A7 B7 五、發明説明(35 ) 丙烯、1 - 丁烯或碳數5以上之α -烯烴等進行預備聚合 之物。 (請先閲讀背面之注意事項再填寫本頁) 丙烯與碳數5以上之α -烯烴的共聚合物並無特別限 制,可爲利用塊狀聚合、溶液聚合、氣相聚合、懸浮聚合 等任何一種方法,以分批式或連續式所製得之物。 將各單體供應給反應系之方法並無特別限制,可利用 各種方法。又,反應系中的各單體量比亦無需具有經時一 定性,例如可利用,以一定混合比供應各單體之方法,或 經時變化供應之各單體的混合比等方法。另外,於考量共 聚合反應性比時亦可採用分類添加任何單體之方法。又, 可利用將一定量之混合氣體連續導入反應系內,再將剩餘 之氣體連續由排出閥排出反應系之方法,以保持一定之反 應手中的各單體量比之方法。另外,亦可使用氫以作爲分 子量調節劑。 聚合條件並無特別限制,可採用已知方法之相同條件 。例如,聚合溫度一般爲一 5 0〜2 5 0 °C,又以〇〜 經濟,部智慧財產局員工消費合作社印製 1 50 C爲佳。聚合壓力爲常壓〜300kg/ cm2G。 又,聚合時間爲1分鐘〜1 〇小時。 本發明之丙嫌系樹脂中的(3 — B )丙嫌系聚合物可 利用實施例所示之製造方法聚合而製得,但非限制於此例 ’只要爲製得上述丙嫌系共聚合物之製造方法即可,並無 特別限制。 製造(3 - B)丙烯系聚合物時,例如可使用鎂、鈦 及鹵素爲必須成分的固體觸媒成分,有機鋁化合物等有機 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐.) 561160 Α7 Β7 五、發明説明(36 ) (請先閲讀背面之注意事項再填寫本頁) 金屬化合物觸媒成分及、矽烷化合物等供予電子化合物觸 媒成分所形成之觸媒。又,可使用上述二茂金屬衍生物系 過渡金屬化合物與有機鋁化合物或硼化合物等組合而成的 二茂金屬衍生物觸媒。 聚合條件並無特別限制,可採用同已知方法之條件。 例如,聚合溫度爲2 0〜1 5 0°C、聚合壓力爲大氣壓〜 4〇kg/cm2G。又,聚合時間爲分鐘〜丄〇小時。 另外’亦可使用氫以作爲分子量調節劑。必要時亦可與乙 嫌、1 - 丁烯、碳數5以上之α —烯烴等聚合.單體共聚合 〇 · 經濟/部智慧財產局員工消費合作社印製 本發明之丙烯系樹脂係由,(3—Α)共聚合物摻合 (3 - Β )丙烯系聚合物而形成,至於摻合之方式並無特 別限制’可爲任何方法。如後述之實施例,先各別製造( 3 - Α)共聚合物與(3 - Β )丙烯系聚合物後再摻合之 方法,至於製造方法並無限制。例如可利用,於第一階段 之反應槽中使丙烯系聚合體(3 - Β )聚合後,移送至第 二階段之反應槽,再與丙烯及碳數5以上之α -烯烴聚合 的方法而製得。此情形下,第一階段與第二階段所使用之 觸媒無需相同,可任意使用彼此互相適應之觸媒。 下面將說明本說明書之第四項發明。 本發明之第一種樣態爲,一種由丙烯及碳數5以上之 α -烯烴所形成的丙烯系無規共聚合物,其中,利用差示 掃描型熱量計所測得之共聚合物的熔點(T m ( °C ))與 共聚合物中碳數5以上之α -烯烴單位的含量(α (莫耳 本紙張尺度適用中國國家標準(CNS ) Α4規格(210 X 29*7公釐.)-39 - 56!16〇 A7 五、發明説明(37 % ))係符合下列式(4 一 I ),Tmb ~ Tcb ^ 40 ...... (3-x) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. If T m b-T c b is smaller, the adverse effects on low temperature heat sealability can be reduced. In addition, the temperature-rising fractionation chromatography of the propylene-based resin of the present invention preferably satisfies the following relationships (i), (i i), and (i i i). (i) When the main peak temperature is T p, the dissolution amount (W (Η) p) in the temperature range of (T p — 5) ° C to (Tp + 5) ° C is 6 5 weight %the above. (ii) Dissolution amount in the temperature range below 0 ° C This paper is applicable to the standard of this paper. National Standard (CNS) A4 (210X297 cm) -35-561160 A7 _ V. Description of the invention (33) (W ( Ii) 0) is 3% by weight or less. (Please read the precautions on the back before filling in this page.) (I i i) The dissolution amount (W (H) 10) in the temperature range above T p + 1 0 X is 1 to 45% by weight. The W (H) p is more preferably 70% by weight or more, more preferably 75% by weight or more, and particularly preferably 80% by weight or more. If W (H) p is less than 65% by weight, the low-temperature heat-sealability will be insufficient. W (H) is more preferably 2% by weight or less, more preferably 1.5% by weight or less, and even more preferably 1.5% by weight or less. When W (Η) 〇 exceeds 3% by weight, the blocking resistance is lowered. In addition, W (H) 10 is more preferably 2 to 35% by weight, more preferably 3 to 25% by weight, and particularly preferably 4 to 20% by weight. When W (H) 10 is less than 1% by weight, molding failure is liable to occur, and when it exceeds 45% by weight, low-temperature heat-sealability is insufficient. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed on the propylene resin of the present invention using a differential scanning calorimeter. The temperature is preferably 90 ° C or more, more preferably 95 ° C or more, and particularly preferably 1,000 t or more. If the peak temperature on the highest temperature side is lower than 85 ° C, the effect of improving moldability will be reduced. Moreover, in the melting curve measured by a differential scanning calorimeter in the propylene resin of the present invention, the peak top temperature on the lowest temperature side is preferably 150 ° C & and further below 140 ° C as It is better to be below 130 ° C, and SiH is below 120 ° C. If the peak temperature on the lowest temperature side exceeds 150 ° t, the low-temperature heat-sealability will be insufficient. The (3-A) co-polymer in the propylene resin of the present invention can be used in the paper of China National Standard (CNS) A4 (210X297 cm) -36-561160 A7 __ _B7 V. Description of the invention (34) It is prepared by the polymerization method of the example, but it is not limited to this example, and it is not particularly limited. The catalyst used in the production is preferably one in which an organoaluminum compound or a boron compound is added to a transition metal compound of a metallocene derivative Catalysts for metallocene derivatives. In addition, examples of these metallocene derivatives and transition metal compounds are, for example, transition metal compounds selected from Group 4 of the periodic table, that is, titanium, zirconium, boll, and 1 to 2 cyclopentadienyl, substituted cyclopentadienyl Alkenyl, indenyl, substituted indenyl, tetrahydroxyindenyl, substituted tetrahydroxyindenyl, fluoroalkenyl, or substituted fluoroalkenyl, etc., or co-bonded with two of these groups. Compounds such as organic bonds, or compounds having ligands such as hydrogen, oxygen, halogen, alkyl, alkoxy, aryl, acetone, carbonyl, nitrogen, oxygen, sulfur, phosphorus, and silicon Compound. The organoaluminum compound used may be various alumoxane compounds. Among them, methylalumoxane is particularly suitable. In addition, a combination with organic compounds such as trimethylaluminum, triethylammonium, diisobutylammonium, and monoethylammonium monochloride can be used. In addition, it is also suitable as a boron compound as an ionizing agent. Examples are trialkyl substituted ammonium salts like triethylammonium tetraphenylboride, or N, N -dialkylaniline salts like N, N-dimethyltetraphenylboride, or tripentafluorobenzene Boron-like phenylboron compounds. These metallocene derivatives and / or organoaluminum compounds can be used as a substance to be supported on another carrier. The carrier used at this time may be an organic compound such as styrene or an inorganic compound such as silica or alumina. In addition, you can also use a small amount of α-olefin in advance, such as ethylene. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm.)-37- (Please read the precautions on the back before filling this page) • Packing and printing printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 561160 A7 B7 V. Description of the invention (35) Propylene, 1-butene or α-olefins with a carbon number of 5 or more, etc. for preliminary polymerization. (Please read the notes on the back before filling this page) There are no particular restrictions on the copolymers of propylene and α-olefins with a carbon number of 5 or more. It can be any of block polymerization, solution polymerization, gas phase polymerization, and suspension polymerization. A process made in a batch or continuous process. The method for supplying each monomer to the reaction system is not particularly limited, and various methods can be used. In addition, the ratio of the amount of each monomer in the reaction system does not need to be constant over time. For example, a method of supplying each monomer at a certain mixing ratio or a method of varying the mixing ratio of each monomer supplied over time can be used. In addition, when considering the copolymerization reactivity ratio, a method of adding any monomer by classification may also be adopted. In addition, a method of continuously introducing a certain amount of mixed gas into the reaction system, and then continuously discharging the remaining gas from the reaction system through a discharge valve, can be used to maintain a certain ratio of the monomers in the reaction. Alternatively, hydrogen may be used as a molecular weight regulator. The polymerization conditions are not particularly limited, and the same conditions as known methods can be used. For example, the polymerization temperature is generally between 50 ° C and 250 ° C, and 0 ° C. Economy, the Ministry of Intellectual Property Bureau's employee cooperative prints it at 150 ° C. The polymerization pressure is from normal pressure to 300 kg / cm2G. The polymerization time is from 1 minute to 10 hours. The (3-B) acrylic polymer in the acrylic resin of the present invention can be produced by polymerization using the manufacturing method shown in the examples, but it is not limited to this example, as long as the acrylic copolymer is prepared as described above. The manufacturing method of the material is not particularly limited. When manufacturing (3-B) propylene-based polymers, for example, solid catalyst components such as magnesium, titanium, and halogen as essential components, organic aluminum compounds, and other organic paper sizes are applicable. National Standards (CNS) A4 specifications (210X297) Mm.) 561160 Α7 Β7 V. Description of the invention (36) (Please read the precautions on the back before filling out this page) Metal catalyst catalyst components and silane compounds such as catalysts formed by supplying electronic compound catalyst components. Further, a metallocene derivative catalyst in which the above-mentioned metallocene derivative-based transition metal compound is combined with an organoaluminum compound, a boron compound, or the like can be used. The polymerization conditions are not particularly limited, and conditions similar to known methods can be used. For example, the polymerization temperature is 20 to 150 ° C, and the polymerization pressure is atmospheric pressure to 40 kg / cm2G. The polymerization time is from minutes to 100 hours. Alternatively, hydrogen may be used as a molecular weight regulator. If necessary, it can also be polymerized with ethylene, 1-butene, and α-olefins with a carbon number of 5 or more. Copolymerization of monomers. • The propylene resin of the present invention is printed by the Ministry of Economy / Ministry of Intellectual Property Bureau, Consumer Cooperative, The (3-A) copolymer is formed by blending a (3-B) propylene-based polymer, and the method of blending is not particularly limited, and may be any method. As in the examples described later, the method of manufacturing the (3-A) copolymer and the (3-B) propylene polymer separately and then blending them is not limited as to the manufacturing method. For example, it is possible to use a method of polymerizing a propylene polymer (3-Β) in a reaction tank in the first stage, and then transferring it to a reaction tank in the second stage, and then polymerizing propylene and an α-olefin having a carbon number of 5 or more. be made of. In this case, the catalysts used in the first stage and the second stage need not be the same, and catalysts that are compatible with each other can be used arbitrarily. The fourth invention of this specification will be described below. The first aspect of the present invention is a propylene-based random interpolymer formed of propylene and an α-olefin having 5 or more carbons, wherein the copolymer is measured by a differential scanning calorimeter. Melting point (T m (° C)) and the content of α-olefin units with 5 or more carbon atoms in the copolymer .)-39-56! 16〇A7 V. Description of the invention (37%)) is in accordance with the following formula (4-I),
TmS140 且 Tm$l60 — 7α...... (4 - I (請先閱讀背面之注意事項再填寫本頁) 又’利用差示掃描型熱量計所測定之共聚合物的結晶化溫 度(T c ( °C ))與熔點(τ m ( °C ))係符合下列式( 4 — I I )TmS140 and Tm $ l60 — 7α ... (4-I (Please read the precautions on the back before filling out this page) and 'The crystallization temperature of the copolymer measured by a differential scanning calorimeter ( T c (° C)) and melting point (τ m (° C)) are in accordance with the following formula (4 — II)
Tc^O · 75Tm— 15 本樣態之丙烯系無規共聚合物所使用的碳數5以上之 烯烴例子如,1—戊烯、4 —甲基一 1 一戊烯、1 一 S烯、1 一辛烯、1 一癸烯、1—十二碳烯、1 一十四碳 燦、1 一十六碳嫌、1 —h八碳嫌、1 一二十碳燦等。又 ’可使用一種或二種以上,較佳爲至少含有1一辛烯、工 〜癸烯、1 一十二碳烯中一種。 本發明之丙烯系無規共聚合物的Tm (°C)及α (莫 耳% )需符合下列式(4 一 I )。Tc ^ O · 75Tm— 15 Examples of olefins having a carbon number of 5 or more used in the propylene random copolymers in this state, such as 1-pentene, 4-methyl-1, 1-pentene, 1-Sene, 1-octene, 1-decene, 1-dodecene, 1-14 carbon can, 1 16 carbon can, 1-h 8 carbon, 1 120 carbon, etc. Further, one or two or more kinds may be used, and preferably at least one of 1-octene, 1-decene, and 1-12 dodecene. The Tm (° C) and α (mole%) of the propylene-based random copolymer of the present invention need to conform to the following formula (4-I).
TmS140 且 TmS160 — 7α ...... (4—1) 經靖部智慧財產局員工消費合作社印製 若Tm超出1 40且1 6 Ο — 7α之範圍時,會降低 低溫熱封性與剛性之平衡性。又,就此物性之平衡性觀點 ,丁 m又以符合TmSl 30且TmSl 5 5 — 7α爲佳 ,更佳爲TmS120且TmS150 — 7α,特別佳爲 Tm$115 且 TmS145 - 7α。TmS140 and TmS160 — 7α ... (4-1) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Jing if the Tm exceeds the range of 1 40 and 1 6 0 — 7α, the low temperature heat sealability and Balance of rigidity. From the viewpoint of the balance of the physical properties, Tm is preferably in accordance with TmSl 30 and TmSl 5 5-7α, more preferably TmS120 and TmS150-7α, particularly preferably Tm $ 115 and TmS145-7a.
又此共聚合物之T c ( °C )與T m ( °C )需符合下歹IJ 本紙張尺度速用中國國家梂準(CNS ) Α4規格(210X297公釐) -40 - 561160 A7 B7 五、發明説明(38 ) — 式(4 一 I I )。The T c (° C) and T m (° C) of this copolymer must comply with the following IJ Standards for Quick Use of Chinese Paper (CNS) A4 Specification (210X297 mm) -40-561160 A7 B7 Five Explanation of the invention (38)-Formula (4-II).
Tc^〇 . 75Tm-15 (請先閲讀背面之注意事項再填寫本頁) 若Tc小於、、〇 · 75Tm — 1 5〃時,易產生成型 不良之現象。又,就不易產生成型不良之現象觀點,又以 Tc-〇·75Tm—10爲佳,更佳爲Teg 0 · 7 5 T m - 5。 本發明之丙烯系無規共聚合物中,碳數5以上之α 一 烯烴含量較佳爲〇 · 1〜1 2莫耳%,又以〇.· 2〜1 1 莫耳%更佳,特別佳爲〇·· 3〜1〇莫耳%。若其含量低 於0 · 1莫耳%時,改良低溫熱封性之效果將不足,又, 超過1 2莫耳%時,會降低共聚合物之結晶性而使剛性變 差。 經濟/部智慧財產局員工消费合作社印製 又’本發明之丙烯系無規共聚合物中作爲立體規則性 指標的利用1 3 C - N M R所測定之三價基單位的等規分率 (Ρ)爲8 5莫耳%以上,又以9 〇莫耳%以上更佳,特 別佳爲9 5莫耳%以上。若等規分率(ρ )低於 8 5莫耳%時,會降低共聚合物之結晶性而使剛性變差。 至於等規分率(Ρ )之求取方法如後述實施例所示。 另外’本發明之丙烯系無規共聚合物於萘烷中, 1 3 5 bC下所測得之極限粘度〔々〕爲〇 · 5〜3分升/ g ’又以0 · 6〜2 · 9分升/ g特別佳。若極限粘度〔 ;?〕超.出此範圍時,製膜等之情形下易產生成型不良之現 象0 -41 - 本紙张尺度適用中®國家標準(CNS ) A4規格(210Χ297公着) 561160 A7 B7 五、發明説明(39 ) (請先閲讀背面之注意事項再填寫本頁) 製造本發明之丙烯系無規共聚合物時所使用之二茂金 屬衍生物系觸媒可隨意使用,但,較佳爲二茂金屬衍生物 系過渡金屬化合物與有機鋁化合物或離子化劑(例如硼化 合物)等之組合物。又,此等二茂金屬衍生物系觸媒、聚 合條件等可同本說明書之第三項發明中所說明者,在此省 略說明。 本發明之第二種樣態爲,於(4 一 A )之丙烯與碳數 5以上的α -烯烴所形成之丙烯系無規共聚合物中,添加 (4 一 Β )具有造核效果的物質,所形成之丙.嫌無規共聚 合物組成物。 ‘ 此(4 一 Β )成分之具有造核效果的物質(以下稱爲 「造核劑」)係指,不會降低丙烯系聚合物之物性,且能 快速誘發結晶核之可減少結晶化開始時所需的過度冷却之 物。 經濟,部智慧財產局員工消费合作社印製 因本發明所使用之造核劑只需爲,不會降低丙烯系聚 合物性’且能快速誘發結晶核之可減少結晶化開始時所需 之過度冷却者,故其具體例、添加量可同上述,在此將省 略說明。 因本發明之第一種樣態的理由,本樣態之由(4 一 A )成分與(4 - B )成分所形成的丙烯系無規共聚合物組 成物中,同第一樣態之利用差示掃描型熱量計所測得的組 成物之熔點(T m ( °C ))與組成物中碳數5以上的α 一 烯烴單位之含量(α (莫耳%))需符合式(4 一 I)及 ’利用差示掃描型熱量計所測得之組成物的結晶化溫度( 本紙張瓦t適用中國國家梂準(CNS )八4胁(210X297公釐)7^2--- 561160 A7 B7 五、發明説明(40 ) τ c ( t ))與熔點(T m ( °C ))需符合式(4 — I工 )’又,此二式之較好樣態同第~種樣態,在此省略說明 〇 (請先閱讀背面之注意事項再填寫本頁) 同第一種樣態之丙烯系無規共聚合物所說明之理由, 本樣態之(4 一 A )成分的丙烯系無規共聚合物較佳爲, 具有相同範圍之碳數5以上的α -嫌烴含量,等規分率( Ρ )及極限粘度〔〕,在此省略說明。 下面將詳細說明本說明書之第五項發明。 本發明之第一種樣態的丙烯系無規共聚合.物爲,丙烯 與1 - 丁烯之共聚合物,又,此共聚合物之利用差示掃描 型熱量計所測定之共聚合物的熔點(T m ( °C ))與共聚 合物中1一丁烯單位的含量(α(莫耳%))符合下列式 (5 - I )。Tc ^ 〇. 75Tm-15 (Please read the precautions on the reverse side before filling out this page) If Tc is less than or equal to · 75Tm — 15〃, it is easy to produce molding defects. From the viewpoint that it is difficult to cause molding defects, Tc-75 · Tm-10 is more preferable, and Teg 0 · 7 5 T m -5 is more preferable. In the propylene-based random copolymer of the present invention, the α-olefin content of 5 or more carbon atoms is preferably 0.1 to 12 mol%, and more preferably 0.2 to 1 1 mol%, particularly It is preferably from 3 to 10 mole%. If the content is less than 0.1 mol%, the effect of improving the low-temperature heat-sealability will be insufficient, and when it exceeds 12 mol%, the crystallinity of the copolymer will be lowered and the rigidity will be deteriorated. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs / Ministry. The isotactic fraction (P) of the trivalent base unit measured by 1 3 C-NMR in the propylene random copolymer of the present invention as an index of stereoregularity. ) Is 85 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more. If the isotactic fraction (ρ) is less than 85 mol%, the crystallinity of the copolymer will be reduced and the rigidity will be deteriorated. The method for obtaining the isotactic fraction (P) is shown in the examples described later. In addition, the limiting viscosity [々] of the propylene random copolymer of the present invention in decalin measured at 1 3 5 bC is 0.5 to 3 dL / g, and 0 to 6 to 2 9 deciliters / g is particularly good. If the limiting viscosity [;?] Is out of this range, molding defects are likely to occur in the case of film making, etc. 0 -41-Applicable for this paper standard ® National Standard (CNS) A4 Specification (210 × 297) 561160 A7 B7 V. Description of the invention (39) (Please read the notes on the back before filling this page) The metallocene derivative catalyst used in the production of the propylene random copolymer of the present invention can be used at will, but, A combination of a metallocene derivative-based transition metal compound and an organoaluminum compound or an ionizing agent (for example, a boron compound) is preferred. It should be noted that these metallocene derivatives based catalysts, polymerization conditions, and the like may be the same as those described in the third invention of the present specification, and will not be described here. The second aspect of the present invention is that in the (4-A) propylene random copolymer formed by propylene and an α-olefin having 5 or more carbon atoms, the addition of (4-B) has a nucleation effect. Substance, formed by C. Suspected random copolymer composition. 'This (4-B) component has a nucleating effect (hereinafter referred to as "nucleating agent"), which means that it will not reduce the physical properties of a propylene-based polymer and can quickly induce crystallization nuclei to reduce the start of crystallization. Overcooled when needed. Economy, the Ministry of Intellectual Property Bureau employee consumer cooperative prints the nucleating agent used in the present invention as long as it does not reduce the properties of the propylene-based polymer, and can quickly induce crystalline nuclei, which can reduce the excessive cooling required at the beginning of crystallization Therefore, the specific examples and addition amounts can be the same as described above, and the description will be omitted here. For the reason of the first aspect of the present invention, the propylene-based random copolymer composition composed of the (4-A) component and the (4-B) component in this aspect is the same as that in the first aspect. The melting point (T m (° C)) of the composition measured with a differential scanning calorimeter and the content of α-olefin units (α (mole%)) with 5 or more carbon atoms in the composition must conform to the formula ( 4 Ⅰ) and 'The crystallization temperature of the composition measured by a differential scanning calorimeter (this paper tile is applicable to China National Standards (CNS) Yasaki (210X297 mm) 7 ^ 2 --- 561160 A7 B7 V. Description of the invention (40) τ c (t)) and melting point (T m (° C)) must conform to the formula (4-I engineering) '. The better form of this two formula is the same as the first ~ The state is omitted here. (Please read the precautions on the back before filling this page.) The reason explained in the first form of the propylene random copolymer is as follows: (4-A) The propylene-based random copolymer preferably has an α-hydrocarbon content having a carbon number of 5 or more in the same range, an isotactic fraction (P), and an intrinsic viscosity [], and descriptions thereof are omitted here. The fifth invention of this specification will be described in detail below. The first propylene-based random copolymerization of the present invention is a copolymer of propylene and 1-butene, and a copolymer of this copolymer measured by a differential scanning calorimeter The melting point (T m (° C)) and the content of 1-butene unit (α (mole%)) in the copolymer are in accordance with the following formula (5-I).
Tm^l60-3a ...... (51) 經濟·部智慧財產局員工消资合作社印製 若Tm超出'、1 6 0 - 3 α 〃之値時,會降低低溫熱 封性與剛性之平衡性。又,就此物性之平衡性觀點又以 TmS155-3a爲佳。 另外,此共聚合物之利用差示掃描型熱量計所測定的 共聚合物之結晶化溫度(T c ( °C ))與熔點(T m ( t ))符合下列式(5 - I I )。 TC^O . 75Tm-10 ...... (51 I) 若Tc小於、、〇 · 75Tm — 10〃時,易產生成型 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-43 - 561160 A7 B7 五、發明説明(41 ) 不良之現象。又,就不易產生成型不良之現象觀點,又以Tm ^ l60-3a ...... (51) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and Ministry of Economic Affairs. Balance of rigidity. From the viewpoint of the balance of the physical properties, TmS155-3a is preferred. In addition, the crystallization temperature (T c (° C)) and melting point (T m (t)) of the copolymer measured by a differential scanning calorimeter of this copolymer are in accordance with the following formula (5-I I). TC ^ O. 75Tm-10 ...... (51 I) If Tc is less than or equal to, ·········································································· -43-561160 A7 B7 V. Description of the invention (41) Defective phenomenon. In addition, from the viewpoint that it is difficult to cause molding defects,
Tc2〇 · 75Tm— 5 爲佳,更佳爲 Tc2〇 · 75 T m。 本發明之丙烯系無規共聚合物的1-丁烯含量較佳爲 0·1〜30莫耳%,又以〇·2〜29莫耳%更佳,特 別爲0·3〜28莫耳%。若此含量低於0·1莫耳%時 ’改良低溫熱封性之效果將不足,又,超過3 0莫耳%時 ’會降低共聚合物之結晶性而使剛性變差。 同上述本說明書之第四項發明的第一樣態.丙烯系無規 共聚合物之理由,本發明之丙烯系無規共聚合物較佳爲, 具有相同之等規分率(P )及極限粘度〔7?〕範圍,在此 省略詳細說明。 製造本發明之丙烯系無規共聚合物所使用的二茂金屬 衍生物系觸媒可爲各種觸媒,但,其中又以二茂金屬衍生 物系過渡金屬化合物與有機鋁化合物或離子化劑(例如硼 化合物)等之組合物爲佳。又,二茂金屬衍生物系觸媒, 聚合條件等可同本說明書中第三項發明所說明者,在此省 略詳細說明。 本發明第二種樣態的丙烯無規共聚合物組成物爲,於 (5 - A )之丙烯與1 -丁烯所形成的丙烯系無規共聚合 物中,添加(5 - B)之具有造核效果的物質,而形成之 組成物。 本樣態所使用的(5 - B )成分之造核劑可同第一發 明的第一樣態所使用之,不會降低丙烯系聚合物之物性, 本紙張尺度適用中國國家標準(CNS )八4規格(210 X 297公釐)-44 - (請先閱讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局員工消费合作社印製 561160 A7 _ B7_ 五、發明説明(42 ) 且可透發快速造核及能減少結晶化開始時所需之過度冷却 者,又,其具體例,添加量同上述,在此省略詳細說明。 (請先閲讀背面之注意事項再填寫本頁) 同本發明之第一種樣態的理由,本樣態中之(5 — A )成分與(5 - B )成分所形成的丙烯系無規共聚合物組 成物,利用差示掃描型熱量計所測定的組成物熔點(丁❿ (°C ))與組成物之1 一丁烯單位的含量(·α (莫耳% ) )需符合式(5 - I ),又,利用差示掃描型熱量計所測 定的組成物之結晶化溫度(丁 c ( °C ))與熔點( T m ( °C ))需符合(4 一 I I ),另外,此·式之較佳樣 態同第一種樣態,在此省略說明。 同第一種樣態所說明之理由,本樣態之丙烯系無規共 聚合物組成物的1 -丁烯含量、等規分率(P )、極限粘 .度〔々〕較佳爲同第一種樣態,在此省略詳細說明。 下面將詳細說明本說明書之第六項發明。 經濟部智慧財產局員工消費合作社印製 本發明係於一種(6 - A )之丙烯與碳數4以上的α -烯烴所形成的丙烯系無規共聚合物,即,利用二茂金屬 衍生物而聚合之得自丙烯的構造單位爲80〜99·9莫 耳%,得自α-烯烴之構造單位爲〇·1〜20莫耳%、 極限粘度〔7?〕爲0 · 5〜5 0分升/ g之丙烯系無規共 聚合中添加(B )之造核劑1 〇 p pm以上所形成的丙烯 系聚合物組成物。 又,本發明之(6 - A)成分的丙烯系無規共聚合物 之構造單位中需含有碳數4以上之α -嫌烴,但,就能得 到充分之改良熱封性的效果觀點,又以碳數5以上的α - 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐.)-45 - 561160 A7 ___ B7 五、發明説明(43 ) 烯烴爲佳,特別佳爲碳數6以上之α -烯烴。又,丙烯系 無規共聚合物中以丙稀爲起因的構造單位爲8 〇〜 (請先閲讀背面之注意事項再填寫本頁) 99 ·9莫耳%,以α—烯烴爲起因的構造單位爲〇·1 〜2 0莫耳%,但,又以起因於α -烯烴之構造單位爲 0·2〜15莫耳%爲佳,特別佳爲〇·3〜10莫耳% 〇 另外,若(6 - Α)成分之丙烯系無規共聚合物於萘 烷中,1 3 5 °C下所測定之極限粘度〔π〕爲〇 · 5〜 5 · 0分升/ g範圍以外時,製膜等的情形下易產生成型 不良之現象。又,此極限粘度〔77〕又以1 · 〇〜3 · 0 分升/ g特別佳。 (6 - A )成分之丙烯系無規共聚合物中所使用的碳 .數4以上之α-烯烴例子有,1一丁烯、1一戊烯、3— 甲基一1 一 丁烯、4 —甲基一 1 一戊烯、1 一己烯、1 一 辛烯、1一癸烯、1一十二碳烯、1一十四碳烯、1一 十六碳嫌、1 一十八碳燦、1 一二十碳儲等。 經濟部智慧財產局員工消費合作社印製 製造(6 - A )成分之丙烯系無規共聚合物時所使用 的二茂金屬衍生物系觸媒可爲各種觸媒,但,較佳爲二茂 金屬衍生物系過渡金屬化合物與有機鋁化合物或離子化劑 (例如硼化合物)等之衍生物。又,二茂金屬衍生物系觸 媒、聚合條件等可同第三項發明所說明者,在此省略詳細 說明。 本發明所使用的(B )成分之造核劑可同第1項發明 的第一種樣態所使用之不會降低丙烯系聚合物之物性,且 I紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐) -46 - ' 561160 Α7 Β7 五、發明説明(44 ) 可快速誘發結晶核及能減少結晶化開始時所需的過度冷却 者’其具體例、添加量亦同上述,在此省略詳細說明。 (請先閲讀背面之注意事項再填寫本頁) 當本發明之丙烯系聚合物組成物所使用的α 一烯烴爲 1 一丁儲時’其MD方向之拉伸彈性率(TM (MP a ) )與熱封溫度(H S 丁( °c ))較佳爲,符合下列式(6 一 I ), 丁 M$22xHS 丁一 1850...... (6 — I) 又以符合TM22 2 XHST - 1 8 0 0爲佳,.更佳爲 TMx22xHST - 1750。 又’ α —烯烴爲碳數5以上之α -烯烴時,TM ( MPa)與HST (°C)較佳爲,符合下列式(6 - I I ), TM^22xHST - 1700...... (6 - I I) 又以TM^2 2XHST — 1 6 5 0爲佳,更佳爲TMg 22XHST - 1600。 經濟部智慧財產局員工消費合作社印製 本發明之丙烯系聚合物組成物的沸騰醚可溶成分量( E (重量%))與1 一丁烯含量(α (莫耳%))較佳爲 ,符合下列式(6 - I I I ), E^O . 2xa + l〇 ...... (6—1 I I ) 又以ES〇 · 2Χα + 〇 · 5更佳。 若Ε大於〇 · 2xa + 10時,會使薄膜具有黏性及 本紙張尺度適用中國國家標準(CNS ) Μ規格(210Χ297公釐· > -47 - 561160 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(45 ) 降低拉伸彈性率。 以上本說明書之各項發·明的丙烯系無規共聚合物、丙 烯系無規共聚合物組成物、薄膜、層積物、纖維、片狀物 或成型物於必要時可添加各種添加劑,例如造核劑、熱安 定劑、防氧化劑、耐候劑、中和劑、增滑劑、防粘連劑、 滑劑、染料、顏料、塡充劑、防霧劑、防靜電劑等。 所使用之防氧化劑的例子如,季戊四醇一四〔3 —( 3,5 -二一 t e r t - 丁基一 4 —羥基苯基)丙酸鹽丁 (商品名:依魯卡隆克斯1010)、三(2.,4 一二一 t e r t -丁基苯基)亞磷酸鹽(商品名:依魯卡隆克斯 168)、十八烷基一 3 — (3,5 —二一 t e I* t - 丁 基- 4 -羥基苯基)丙酸鹽(商名品:依魯卡隆克斯 1076)、 1,3,5 —三甲基一 2,4,6 —三(3 ,5 -二一 t e I* t - 丁基一 4 一羥基苄基)苯(商品名 :依魯隆卡克斯1330)、三(3,5 -二—t e r t - 丁基- 4 一羥基苄基)三聚異氰酸鹽(商品名:依魯卡 隆克斯 31 14)、四(2,4 一二一 t e r t — 丁基苯 基)4,一聯苯撑一二亞磷酸鹽(商品名:P — E P Q )等磷系防氧化劑、苯酚系防氧化劑等。防氧化劑 對所使用之丙烯系樹脂或丙烯系樹脂組成物的添加量較佳 爲 1 〜lOOOOppm。 中和劑之例子如,硬脂酸鈣、硬脂酸鋅、硬脂酸鎂等 脂肪族余屬鹽、或組成式Tc20.75Tm-5 is more preferred, and Tc20.75Tm is more preferred. The 1-butene content of the propylene-based random copolymer of the present invention is preferably from 0.1 to 30 mol%, more preferably from 0.2 to 29 mol%, and particularly from 0.3 to 28 mol. %. If the content is less than 0.1 mol%, the effect of improving low-temperature heat-sealability will be insufficient, and when it exceeds 30 mol%, the crystallinity of the copolymer will be lowered and the rigidity will be deteriorated. As for the reason of the first state of the fourth invention of the present specification. The propylene-based random copolymer, the propylene-based random copolymer of the present invention preferably has the same isotactic fraction (P) and The range of the limiting viscosity [7?] Is omitted here. The metallocene derivative catalyst used in the production of the propylene-based random copolymer of the present invention can be various catalysts. Among them, the metallocene derivative transition metal compound and the organoaluminum compound or the ionizing agent are used. A composition such as a boron compound is preferred. The catalyst of the metallocene derivative, the polymerization conditions, etc. can be the same as those described in the third invention in this specification, and detailed descriptions are omitted here. The second aspect of the propylene random copolymer composition of the present invention is that (5-B) is added to a propylene-based random copolymer formed by (5-A) propylene and 1-butene. A substance that has a nucleating effect and is formed of a composition. The nucleating agent of the (5-B) component used in this state can be used in the same state as the first state of the first invention, and will not reduce the physical properties of the propylene-based polymer. This paper size applies the Chinese National Standard (CNS) 8 4 specifications (210 X 297 mm) -44-(Please read the notes on the back before filling out this page) • Binding and ordering printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 561160 A7 _ B7_ V. Description of the invention (42 ) Those who can transmit fast nucleation and reduce the excessive cooling required at the beginning of crystallization, and the specific examples, the added amount are the same as above, and detailed description is omitted here. (Please read the precautions on the back before filling out this page.) For the same reason as the first aspect of the present invention, the (5-A) component and (5-B) component in this aspect form a random acrylic system. For the copolymer composition, the melting point (butadiene (° C)) of the composition measured with a differential scanning calorimeter and the content of 1-butene unit (· α (mole%)) of the composition must conform to the formula (5-I), and the crystallization temperature (but c (° C)) and melting point (T m (° C)) of the composition measured by a differential scanning calorimeter must conform to (4-II), In addition, the preferred aspect of this formula is the same as the first aspect, and the description is omitted here. For the same reasons as described in the first aspect, the 1-butene content, isotactic fraction (P), and limiting viscosity [々] of the propylene random copolymer composition in this aspect are preferably the same. The first aspect is omitted here. The sixth invention of this specification will be described in detail below. The invention is printed by a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The present invention is a propylene-based random copolymer formed by a (6-A) propylene and an α-olefin having a carbon number of 4 or more, that is, using a metallocene derivative The structural unit derived from propylene is 80 ~ 99.9 mol%, the structural unit derived from α-olefin is 0.1 ~ 20 mol%, and the limiting viscosity [7?] Is 0 · 5 ~ 50. A propylene-based polymer composition in which a nucleating agent (B) is added at a rate of 10 ppm or more in a deciliter / g of propylene-based random copolymerization. In addition, the structural unit of the propylene-based random copolymer of the (6-A) component of the present invention needs to contain an α-phosphatic hydrocarbon having a carbon number of 4 or more. However, a sufficient viewpoint of improving the heat-sealing effect can be obtained. With α-carbon number 5 and above-this paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm.) -45-561160 A7 ___ B7 V. Description of the invention (43) The olefin is preferred, especially the carbon number Α-olefins of 6 or more. In addition, the propylene-based random copolymer has a structural unit caused by propylene as a factor of 80%. (Please read the precautions on the back before filling out this page.) 99 · 9 mol%, a structure caused by α-olefin The unit is from 0.1 to 20 mol%, but it is more preferable that the structural unit due to the α-olefin is from 0.2 to 15 mol%, particularly preferably from 0.3 to 10 mol%. If the propylene-based random copolymer of (6-Α) component is in decalin, the limiting viscosity [π] measured at 1 35 ° C is outside the range of 0.5 to 5.0 deciliters / g. In the case of film formation and the like, a molding defect is liable to occur. The limiting viscosity [77] is particularly preferably 1.0 to 3.0 deciliters / g. (6-A) Carbon used in propylene-based random copolymers of components. Examples of α-olefins having a number of 4 or more include 1-butene, 1-pentene, 3-methyl-1, 1-butene, 4-methyl-1, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-12 dodecene, 1-14 carbonene, 1-16 carbon, 1-18 carbon Can, 1-20 carbon storage, etc. The metallocene derivative catalyst used in the production of (6-A) propylene random copolymers by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be various catalysts, but it is preferred The metal derivative is a derivative of a transition metal compound, an organoaluminum compound, or an ionizing agent (for example, a boron compound). The catalyst and polymerization conditions of the metallocene derivative may be the same as those described in the third invention, and detailed descriptions thereof are omitted here. The nucleating agent of the component (B) used in the present invention can be the same as that used in the first aspect of the first invention, and does not reduce the physical properties of the propylene-based polymer, and the I paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -46-'561160 Α7 Β7 V. Description of the invention (44) Those who can quickly induce crystal nuclei and reduce the excessive cooling required at the beginning of crystallization' The specific examples and addition amounts are the same as above, Detailed description is omitted here. (Please read the notes on the back before filling this page.) When the α-olefin used in the propylene polymer composition of the present invention is 1-butane, its tensile modulus in the MD direction (TM (MP a) ) And heat-sealing temperature (HS D (° c)), preferably, conform to the following formula (6-I), D M $ 22xHS D1- 1850 ... (6 — I) and in accordance with TM22 2 XHST -1 8 0 0 is better, more preferably TMx22xHST-1750. When the α-olefin is an α-olefin having a carbon number of 5 or more, TM (MPa) and HST (° C) are preferably in accordance with the following formula (6-II), TM ^ 22xHST-1700 ... (6-II) TM ^ 2 2XHST-1650 is more preferable, and TMg 22XHST-1600 is more preferable. The amount of boiling ether solubles (E (wt%)) and 1-butene content (α (mole%)) of the propylene polymer composition printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is preferably , In accordance with the following formula (6-III), E ^ O. 2xa + l0 ... (6-1 II) is more preferably ES0.2 xα + 0.5. If Ε is greater than 0.2xa + 10, it will make the film sticky and the paper size will be applicable to the Chinese National Standard (CNS) M specification (210 × 297 mm A7 B7 5. Description of the invention (45) Decreasing the tensile elasticity. The propylene random copolymer, propylene random copolymer composition, film, laminate, fiber Various additives such as nucleating agents, heat stabilizers, antioxidants, weathering agents, neutralizers, slip agents, anti-blocking agents, lubricants, dyes, pigments, tinctures, flakes or shaped articles can be added when necessary. Fillers, anti-fogging agents, anti-static agents, etc. Examples of the antioxidants used are, for example, pentaerythritol tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate butyl ( Trade name: Ilukaronx 1010), tris (2, 4, 4 tter-butylphenyl) phosphite (trade name: Ilukaronx 168), octadecyl-1 — (3,5 —di-te I * t -butyl-4 -hydroxyphenyl) propionate (quote Famous products: Ilukaronx 1076), 1,3,5-trimethyl-2,4,6-tris (3,5-di-te I * t-butyl-4-hydroxybenzyl) benzene (Commercial name: Illuronkax 1330), tris (3,5-di-tert-butyl-4 monohydroxybenzyl) trimeric isocyanate (commercial name: Illuronkax 31 14 ), Tetra (2,4 tter — butylphenyl) 4, phosphorylated antioxidants such as biphenylene diphosphite (trade name: P — EPQ), phenolic antioxidants, etc. Antioxidants The addition amount of the propylene-based resin or the propylene-based resin composition used is preferably 1 to 1000 ppm. Examples of the neutralizing agent include aliphatic residual salts such as calcium stearate, zinc stearate, and magnesium stearate. Or composition
Mg4.5Al2 (〇H) 13C〇3· 3 · 5H2〇(商品名 I---^---^---------IT----- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 48 - 561160 A7 ____B7_ 五、發明説明(46 ) (請先閲讀背面之注意事項再填寫本頁) :D Η T - 4 A )所示之水滑石等水滑石類。又,中和劑 對所使用之丙烯系樹脂或丙烯系樹脂組成物的添加量較佳 爲 1 〜10000ppmo 另外,防粘連劑例子如,高士西里西亞公司製的合成 二氧化矽(商品名:賽西里亞)、水澤化學工業股份公司 製的合成二氧化矽(商品名:密滋卡西魯)等合成二氧化 矽。又,防粘連劑對所使用之丙烯系樹脂或丙烯系樹脂組 成物的添加量較佳爲1〜1 0 0 0 p pm.。 又,增滑劑例子如,芥酸酸胺、油酸醯胺、硬脂酸醯 胺、山窬酸醯胺、乙撑雙硬脂酸醯胺、乙撑雙油酸醯胺、 硬脂醯油醯胺、油烯基棕櫚醯胺等脂肪族醯胺等。又,增 滑劑對所使用之丙烯系樹脂或丙烯系樹脂組成物的添加量 較佳爲1〜lOOOppm。 本發明之丙烯系無規共聚合物或丙烯系無規共聚合物 組成物可利用熔融擠押成型法製膜。 經濟,部智慧財產局員工消費合作社印製 例如,利用漢式混煉機、V摻混機、螺帶式摻混機、 旋轉摻混機等乾式滲混機使構成本發明之樹脂、造核劑等 各種成分及必要時所使用的添加劑混合後,再利用單軸擠 押機、多軸擠押機、捏和機、班伯里混煉機混煉機混煉, 其後使其鑄造成型爲顆粒化,再利用吹塑成型等熔融擠押 成型法製膜。 或者利用漢氏混煉機對構成本發明之樹脂、造核劑等 各種成分及必要時所使用的各種添加劑進行乾混後,利用 鑄造成型法製膜。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -49 - 561160 A7 B7 五、發明説明(47 ) (請先閲讀背面之注意事項再填寫本頁) 至於製膜法,就能得到具有良好之剛性、熱封性及透 明性等薄膜觀點,較好係利用大型製膜機之能高速製膜的 T模鑄造製膜法,但,非限於此例,若係利用熔融擠押成 型法以製造薄膜時,可使用射出成型、吹煉成型、擠押成 型等,特別是鑄造成型、吹塑成型等任何製膜法。 例如,使用T模鑄造製膜法時,既使以拉取速度爲 5 〇m/分鐘或以上之高速製膜條件,亦適用於原1 〇〜 5 0 0#m的薄膜製膜用途上。又,本說明書中的各種樹 脂及樹脂組成物因只有上述之好特性,故適用.於利用共擠 押製膜法之層積膜的至少一層,且適用於經延伸之延伸薄 膜。另外亦適用於纖維、片狀物、成型物、不織布之層壓 用途上。 下面將以實施例具體說明本發明,但,非限於此例。 首先將說明丙烯系共聚合物之評估方法及薄膜的評估 方法。 1 .樹脂特性 經濟部智慧財產局員工消費合作社印製 (1 )極限粘度〔7/〕之測定方法 利用離合(股)公司之VMR — 〇 5 3型自動粘度計 ,於萘烷溶劑中,1 3 5 °C下測定。 (2 ) ( M w/Μ η )之測定方法 實施例1〜9及比較例1〜6係於此下列裝置及條件 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) :5〇 - 561160Mg4.5Al2 (〇H) 13C〇3 · 3 · 5H2〇 (brand name I --- ^ --- ^ --------- IT ----- (Please read the precautions on the back first (Fill in this page again) This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) _ 48-561160 A7 ____B7_ V. Invention Description (46) (Please read the precautions on the back before filling this page): D Η T-4 A) hydrotalcites and other hydrotalcites. The addition amount of the neutralizing agent to the propylene-based resin or propylene-based resin composition used is preferably 1 to 10,000 ppm. Examples of the anti-blocking agent include synthetic silicon dioxide (trade name: Sai, manufactured by Coats Silesia Company). Silia), synthetic silicon dioxide (trade name: Mizikasilu) manufactured by Mizusawa Chemical Industry Co., Ltd. and other synthetic silicon dioxide. The amount of the anti-blocking agent added to the propylene-based resin or propylene-based resin composition to be used is preferably from 1 to 100 p p. Examples of slip agents include erucamide, osmium oleate, osmium stearate, osmium behenate, osmethylene distearate, osmium bisoleate, and stearin Aliphatic amines such as oleylamine and oleyl palmitamide. The amount of the slip agent added to the propylene-based resin or propylene-based resin composition used is preferably 1 to 1,000 ppm. The propylene-based random copolymer or the propylene-based random copolymer composition of the present invention can be formed into a film by a melt extrusion molding method. Economic, Ministry of Intellectual Property Bureau employee consumer cooperatives print, for example, dry blenders such as Chinese mixers, V blenders, ribbon blenders, rotary blenders, etc. are used to make the resin and core of the present invention. After mixing various ingredients such as additives and additives used when necessary, they are mixed by a single-shaft extruder, multi-shaft extruder, kneader, Banbury mixer, and then casted into shape. For pelletization, the film is formed by a melt extrusion molding method such as blow molding. Alternatively, various components such as the resin and nucleating agent constituting the present invention and various additives used as necessary are dry-mixed with a Han's kneader and then formed into a film by a casting method. This paper size applies Chinese National Standard (CNS) A4 (210X297mm) -49-561160 A7 B7 V. Invention Description (47) (Please read the notes on the back before filling this page) As for the film making method, you can It has the viewpoint of obtaining thin films with good rigidity, heat-sealability and transparency. It is better to use the T-die casting film-forming method that can use high-speed film-forming of large film-making machines. When the molding method is used to manufacture a film, any film-forming method such as injection molding, blow molding, extrusion molding, etc., in particular, casting molding and blow molding can be used. For example, when using the T-die casting film-forming method, even at high-speed film-forming conditions with a pulling speed of 500 m / min or more, it is also applicable to the original film-forming applications of 100 to 500 #m. In addition, the various resins and resin compositions in this specification are suitable for at least one layer of a laminated film using a co-extrusion film method because they have only the above-mentioned good characteristics, and are suitable for an extended stretched film. It is also suitable for lamination of fibers, sheets, moldings, and non-woven fabrics. The present invention will be specifically described below by way of examples, but it is not limited to this example. First, a method for evaluating a propylene-based copolymer and a method for evaluating a film will be described. 1. Resin characteristics Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (1) The measuring method of the limiting viscosity [7 /] uses the VMR- 05 type 3 automatic viscometer from Clutch Corporation in a decalin solvent, 1 3 Measured at 5 ° C. (2) Measurement method of (M w / Μ η) Examples 1 to 9 and Comparative Examples 1 to 6 are based on the following devices and conditions. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm): 5 〇- 561160
G P C測定裝置之1 柱··昭和電工公司製Shodes ·υΤ806Ι^ 紅外檢測器:液體色譜用I R檢測器 紅外檢測流動元件:k B r元件(光路長1 m m ) 測定條件之1 溶劑:〇 —二氯苯 測定溫度:1 3 5 °C · 流速:1·0毫升/分 試料濃度:2毫克/毫升 注入量:2 0 0 # < 紅外吸收波長:3 . 4 2 # m 又,實施例2 6〜2 9及比較例2 0〜1 9係於下列 裝置及條件下測定(M w/Μ η )。 G P C測定裝置1 column of GPC measurement device · Shodes manufactured by Showa Denko Corporation · υΤ806Ι ^ Infrared detector: IR detector for liquid chromatography Infrared detection flow element: k B r element (optical path length 1 mm) Measurement condition 1 Solvent: 〇-2 Chlorobenzene measurement temperature: 1 3 5 ° C · Flow rate: 1.0 ml / min Sample concentration: 2 mg / ml Injection volume: 2 0 0 # < Infrared absorption wavelength: 3.4 2 # m Further, Example 2 6 to 29 and Comparative Examples 20 to 19 were measured under the following apparatus and conditions (M w / M η). G P C measuring device
柱:TOSO GMHHR-H(S)HHTColumn: TOSO GMHHR-H (S) HHT
檢測器:液體色譜用R I檢測器WATERS 150C 測定條件Detector: R I detector WATERS 150C for liquid chromatography Measurement conditions
溶劑:1,2,4 一三氯苯 測定溫度:1 4 5 °C 本紙浪尺度適用中國國家揉準(CNS ) Α4規格(210Χ297公釐.)-51 - (請先閲讀背面之注意事項再填寫本頁)Solvent: 1,2,4 Trichlorobenzene Measurement temperature: 1 4 5 ° C This paper is suitable for China National Standards (CNS) A4 (210 × 297 mm.) (Fill in this page)
經濟部智慧財產局員工消费合作社印製 561160 A7 B7 五、發明説明(49 ) (請先閲讀背面之注意事項再填寫本頁) 流速:1 · 〇毫升/分 試料濃度:2·2毫克/毫升 注入量·· 1 6 0微升 檢量線:Univers al Calibration .解析程序:Η T — G P C ( Ver. 1 · 0 ) (3 )測定熔點(丁 m )及結晶化溫度(T c ) 利用差示掃描型熱量計(巴金、耶魯曼公司製, DSC-7),預先將試料l〇mg放在氮氣下,以 2 3 0 °C進行3分鐘熔融步驟後,以1 0 °C /分鐘之方式 降溫至0 °C,並以此時所測得之結晶化發熱曲線的最大峰 値之峰頂溫度爲結晶化溫度。其後,於〇 °C下保持3分鐘 後,以1 0 °C /分鐘之方式升溫,並以此時所得熔解吸熱 曲線之最大峰値的峰頂溫度爲熔點。 (4)等規五分率 經濟部智慧財產局員工消費合作社印製 等規五分率係指,根據Cheng Η· N·,Ewen A·, Macromol. cem·,1989,90,1350 所記載之 1 3 C — NMR 光譜 的峰値烯屬之情下,丙烯構造單位5個中具有內消旋構造 (甲基5個之配列方式爲同一方向配列的mmmm構造) 者所佔之比率,又,係利用下列裝置及條件而求得。 裝置:曰本電子公司製的ΓΝΜ—Εχ400型 N M R裝置Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 561160 A7 B7 V. Invention Description (49) (Please read the notes on the back before filling this page) Flow rate: 1.0ml / min Sample concentration: 2.2mg / ml Injection volume: 160 microliter calibration curve: Univers al Calibration. Analysis program: Η T — GPC (Ver. 1 · 0) (3) Measurement of melting point (but m) and crystallization temperature (T c) A scanning calorimeter (Bakin, Yaleman, DSC-7), 10 mg of the sample was placed under nitrogen in advance, and the melting step was performed at 230 ° C for 3 minutes, and then at 10 ° C / minute. The temperature was reduced to 0 ° C, and the peak temperature of the maximum peak of the crystallization heating curve measured at this time was taken as the crystallization temperature. After that, it was held at 0 ° C for 3 minutes, and then heated at 10 ° C / min. The melting point was the peak top temperature of the maximum peak 値 of the melting endothermic curve obtained at this time. (4) Isotactic quintile The Isotactic quintile printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs refers to those recorded in Cheng Η · N ·, Ewen A ·, Macromol. In the case of 1 3 C — NMR spectrum peak oleene, the ratio of those with meso structure (the arrangement of 5 methyl groups is the mmmm structure aligned in the same direction) among the 5 propylene structural units. It was obtained using the following devices and conditions. Device: ΓΝΜ-Εχ400 N M R device manufactured by Yueben Electronics Co., Ltd.
試料濃度:2 2〇mg/NMR溶劑3mC 本纸張尺度逋用中.國國家標率(CNS ) ( 210X297公釐.)-52 - 561160 A7 B7 五、發明説明(5〇 ) NMR溶劑·· 1,2,4 —三氯苯/重苯(9〇/ 1 0 v 〇 ^ % ) (請先閲讀背面之注意事項再填寫本頁) 測定溫度:1 3 0 t 脈衝幅度:4 5 ° 脈衝重覆時間:1 0秒 積算回數:4〇00回 (5 )測定沸騰二乙基醚可溶出成分量(e) 利用圓筒爐紙揀取3 g通過1 m m 0網眼.之粉碎的丙 儲系無規共聚合物寺顆粒’並將1 6 0毫升的萃取溶劑之 二乙基醚放入平底燒瓶中,再以1回/5分鐘之回流頻率 於索克斯果特回流提取器進行1 〇小時萃取。萃取後以蒸 發器回收二乙基醚,再於真空乾燥器乾燥至恆量,接著由 此重量求取沸騰二乙基醚萃取量。 經濟部智慧財產局員工消費合作社印製 (6 )測定升溫分級色譜(T R E F )之主要溶出峰値溫 度(T p )、主要溶出峰値溫度之半値幅(T h )、〇 °c 下溶出量及(Tp — 5)°C〜(Tp + 5)°C之溫度範圍 下的溶出量(W P )。 利用下列裝置及操作手法、測定條件之情形下所得到 的升溫分級色譜(T R E F )求取。 T p :溶出曲線之主要溶出峰値的峰頂溫度 W〇:柱溫度爲0 °C下,未吸附塡充劑之情形下對全 體的溶出成分之重量分率(%) 本紙张尺度適用中國國家揉準(CNS ) A4規格(210X297公釐.)-53 - 561160 A7 B7 五、發明説明(51 ) w P : (Tp — 5)°C 〜(Tp + 5)°c 之溫度範圍 下對全體的溶出成分之重量分率(% ) (請先閲讀背面之注意事項再填寫本頁) w ( T p + 1 〇 ) : (Tp + 10)t:以上之溫度範 圍下對全體的溶出成分之重量分率(%) (6 — 1 )操作方法 將試料溶液導入溫度調至1 3 5 °C之T R E F柱中, 再以5 °C / h I*之速度緩緩降至〇 °C,使試料吸附塡充劑 。其後以4 0 °C / h r速度升至1 3 5 °C,得溶出曲線。 (6 - 2 )裝置 TREF柱·· GL賽耶斯公司製 矽膠柱(4 · 6 0 X 1 5 0 m m )流動單位:· GL賽耶斯公司製光程長1mm kB r單位 送液唧筒:先修科學公司製S S C - 3 1 0 0唧筒 氣門爐:GL賽耶斯公司製MODEL 554爐 TRET爐:GL賽耶斯公司製 經濟部智慧財產局員工消費合作社印製 二系列溫調器:理學工業公司製REX - C 1 〇 〇溫 調器Sample concentration: 2 20mg / NMR solvent 3mC This paper is in use. National standard rate (CNS) (210X297 mm.) -52-561160 A7 B7 V. Description of the invention (50) NMR solvent ·· 1,2,4-trichlorobenzene / heavy benzene (9〇 / 1 0 v 〇 ^%) (Please read the notes on the back before filling this page) Measurement temperature: 1 3 0 t Pulse amplitude: 4 5 ° Pulse Repeat time: 10 seconds Total number of times: 4,000 times (5) Determine the amount of boiling diethyl ether soluble components (e) Pick up 3 g through a cylinder furnace paper through a 1 mm 0 mesh. C-series random copolymer polymer granules' and put 160 ml of diethyl ether of the extraction solvent into a flat-bottom flask, and then reflux the extractor at Soxhout with a reflux frequency of 1 time / 5 minutes Extraction was performed for 10 hours. After the extraction, the diethyl ether was recovered by an evaporator, and then dried in a vacuum dryer to a constant amount, and then the boiling diethyl ether extraction amount was calculated from the weight. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (6) to determine the main dissolution peak temperature (T p) of the temperature-increased fractionation chromatography (TREF), the half dissolution range (T h) of the main dissolution peak temperature, and the dissolution amount at 0 ° c And the dissolution amount (WP) in the temperature range of (Tp — 5) ° C to (Tp + 5) ° C. It was determined by the temperature-raising fractional chromatography (TR E F) obtained under the conditions of the following apparatus and operation method and measurement conditions. T p: the peak temperature of the main dissolution peak of the dissolution curve W 0: the weight fraction (%) of the total dissolution component of the entire dissolution component at the column temperature of 0 ° C without adsorption of the filler, the paper size is applicable to China National Standard (CNS) A4 (210X297 mm.) -53-561160 A7 B7 V. Description of the invention (51) w P: (Tp — 5) ° C ~ (Tp + 5) ° c Weight fraction (%) of all dissolving components (Please read the precautions on the back before filling in this page) w (T p + 1 〇): (Tp + 10) t: Dissolving components for the entire temperature range above Weight fraction (%) (6 — 1) Operation method The sample solution is introduced into a TREF column whose temperature is adjusted to 13.5 ° C, and then slowly reduced to 0 ° C at a rate of 5 ° C / h I *, The sample was allowed to adsorb the pseudofiller. Thereafter, the temperature was raised to 40 ° C / h r to 135 ° C to obtain a dissolution curve. (6-2) Device TREF column · · GL Saiyes Silicone Column (4 · 6 0 X 1 50 mm) Flow Unit: · GL Saiyes Company's light path length 1mm kB r unit First repair SSC-3 1 0 0 cylinder valve furnace made by Scientific Corporation: GL Saiyes company MODEL 554 furnace TRET furnace: GL Saiyes company Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperative printed two series thermostat: Physics Industrial Corporation REX-C 1000 Thermostat
檢測器:液體色譜法用紅外檢測器,FOXBORO公司製 MIRAN 1A CVF 1 0方氣門:巴魯克公司製電動氣門 回路:巴魯克公司製5 00// <回路 本紙張尺度適用中周國家梂準(CNS ) A4規格(210X297公釐)-54 - 561160 A7 ---------- —____ B7 五、發明説明(52 ) (6〜3 )測定條件 溶劑:〇 -二氯苯 試料濃度:7 · 5 g / < (請先閲讀背面之注意事項再填寫本頁) 注入量:500// < _ 商流量:2 · 0 / m i η 檢測波數:3 · 4 1 // m 柱塡充劑:克勒蒙索魯伯p ( 3 0〜6 0網眼) 注溫度分布:± 0 · 2 t:以內 (7)共聚合物中的共聚用單體單位的含量(α (莫耳% ))及立體規則性指標(ρ (莫耳% )) 利用曰本電子公司製的J ΝΜ — Ε X 4 0 〇型NMR 裝置,以下列條件測定1 3 C - N M R光譜,再由此結果利 用後述各種方法算出各種共聚用單體單位的含量。Detector: Infrared detector for liquid chromatography, MIRAN 1A CVF 1 0 manufactured by FOXBORO. Square valve: Electric valve circuit made by Baruch: 5 00 // by Circuit of Baruch. Standard (CNS) A4 (210X297 mm) -54-561160 A7 ---------- —____ B7 V. Description of the invention (52) (6 ~ 3) Measurement conditions Solvent: 0-dichloro Benzene sample concentration: 7 · 5 g / < (Please read the precautions on the reverse side before filling out this page) Injection volume: 500 // < _ Flow rate: 2 · 0 / mi η Detection wave number: 3 · 4 1 // m column filler: Clemmon Solub p (3 0 ~ 6 0 mesh) Note temperature distribution: ± 0 · 2 t: within (7) content of comonomer units in the copolymer (Α (mol%)) and three-dimensional regularity index (ρ (mol%)) Using a J NM-E X 4 0 0 type NMR apparatus manufactured by Japan Electronics Co., Ltd., the 1 3 C-NMR spectrum was measured under the following conditions. From this result, the contents of various comonomer units were calculated by various methods described later.
試料濃度:2 2 0 m g / N M R溶劑3 J NMR溶劑:1 ,2,4 一三氯苯/苯—d6 (90 / 1 0 vol % ) 經濟·部智慧財產局員工消費合作社印製 測定溫度:1 3 0 °C 脈衝幅度:4 5 ° 脈衝重覆時間:4秒 積算回數:4000回 至於13 C — NMR之光譜解析則依據Kazuo Soga, Takeshi Shiono, Walter Kaminsky Makromol. Chem., Rapid 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐1 -55- 561160 A7 ___B7___ 五、發明説明(53 ) (請先閲讀背面之注意事項再填寫本頁)Sample concentration: 220 mg / NMR solvent 3 J NMR solvent: 1,2,4 trichlorobenzene / benzene — d6 (90/10 vol%) Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Consumer Consumption Cooperative Measure the temperature: 1 3 0 ° C Pulse amplitude: 4 5 ° Pulse repetition time: 4 seconds Total number of rounds: 4000 times Up to 13 C — The spectral analysis of NMR is based on Kazuo Soga, Takeshi Shiono, Walter Kaminsky Makromol. Chem., Rapid Paper Standards are applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm 1 -55- 561160 A7 ___B7___ V. Description of invention (53) (Please read the precautions on the back before filling this page)
Commun., 8, 305( 1 987), Alfonso Grassi, Adolfo Zambelli, Luigi Resconi, Enrico Alhizzati Romano Mazzocchi, Macromolecules,21,617(1988)們的報告而進行。 (7 — 1 )乙烯單位 丙烯與乙烯之無規共聚合物的利用1 3 C — N M R所測 得之光譜的各信號之化學位移與婦屬如表1所示。 共聚合物中乙烯單位的含量(α (莫耳%))係利用 1 3 C - N M R所測得之光譜,以下列式求取。. a = E/ Sxl00 其中S與E各爲, S=Iepe + Ippe + I + eee + Ippp + Ipee + Ipep E = Ieee + 2/3(Ipee + Iepe)+1/3(Ippe + Ipep) 又,I …=1 (12)Commun., 8, 305 (1 987), Alfonso Grassi, Adolfo Zambelli, Luigi Resconi, Enrico Alhizzati Romano Mazzocchi, Macromolecules, 21, 617 (1988). (7 — 1) Ethylene units The chemical shifts and genera of each signal of the spectrum measured by 1 3 C — N M R using the random copolymers of propylene and ethylene are shown in Table 1. The content of ethylene units (α (mole%)) in the copolymer is a spectrum measured using 1 3 C-N M R, and is determined by the following formula. a = E / Sxl00 where S and E are each, S = Iepe + Ippe + I + eee + Ippp + Ipee + Ipep E = Ieee + 2/3 (Ipee + Iepe) +1/3 (Ippe + Ipep) and , I… = 1 (12)
Ippe = I( 15) + 1(1 1) + (1(14)-1(1 1)/2 + 1(10) 經濟,部智慧財產局員工消费合作社印製Ippe = I (15) + 1 (1 1) + (1 (14) -1 (1 1) / 2 + 1 (10)
Ieee = I(18)/2 + I(17)/4Ieee = I (18) / 2 + I (17) / 4
Ippp = I( 19) + (1(6) + 1(7)/2 + 1(3) + 1( 13) + 1(11) + 1(14)-1(1 1)/2 Ipee=:I(20)Ippp = I (19) + (1 (6) + 1 (7) / 2 + 1 (3) + 1 (13) + 1 (11) + 1 (14) -1 (1 1) / 2 Ipee =: I (20)
Ipep = (I(8) + I(9)-2 X 1(11)/4 + 1(21) 另外,利用下列式求取作爲共聚合物之立體規則性指 標(P(莫耳%))的PPP鏈之等規三價基分率 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) - 56 - " 561160 A7 B7 五、發明説明(54 ) P=Im/Ixl〇〇 此I m及I分別爲 I m - I (22) 1 = (122) + 1(23) + 1(23)-( 1(8) + 1(9)/2 + 1(1 0) + 3/2 X 1( 1 1 )+ 1( 1 2) + 1(13)+1(15)} 又,此(1)、 (2)......等爲,丙烯與乙烯之無 規共聚合物利用1 3 C - N M R所測得的光譜信號。又, 1(1)、 1(2)......等爲各信號之強度。 (7 - 2) 1 - 丁烯單位 丙烯與1 一 丁烯之無規共聚合物的利用13C — NMR 所測得之光譜各信號的化學位移與埽屬如表2所示。 共聚合物中1 一丁烯單位之含量(α (莫耳%))係 ,利用1 3 C - N M R所測得之光譜,於注視主鏈甲撑碳下 以下列式求取。 1-丁烯單位之含量 (10/2+ 10X100 經濟,部智慧財產局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) (I ①+ 10+ I ③+ I ④+ 2Χ I ⑨) 至於Ζ_Ρ Ρ鏈S α /3碳之信號強度則以⑨之信號強度 C Ρ 連鎖S α /3之信號強度)作爲代用。 又,利用下列式求取共聚合物之立體規則性指標(Ρ (莫耳% ))。 本紙張尺度適用中國國家揉準(CNS ) Α4規格(210X297公釐) -57 - 561160 A7 B7 五、發明説明(55 ) π (I ⑫Χ100) (I⑫+ I⑬+ I⑭) (請先閲讀背面之注意事項再填寫本頁) 此①、②......等爲,丙烯與1一丁烯之無規共聚合 物利用1 3 C - N M R所測定的光譜信號。又,I①、I② 等爲信號之強度。 (7 - 3) 1 —辛烯單位 丙烯與1 -辛烯之無規共聚合物利用13 C - NM R.所 測得的光譜之各信號的化學位移與烯層如表3所示° 共聚合物中1 一辛烯單位之含量(α (莫耳%))係 ,利用1 3 C - N M R所測得之光譜,於注視主鏈甲撑碳下 ,以下列式求取。 (I ②/2+ I ④)xl〇〇 經濟,部智慧財產局員工消費合作社印製 至於P鏈s α /3碳之信號與P P 鏈τ α Θ碳之 信號重疊,故難於分離,因此,以Ρ tP鏈S α /3碳之信 號強度代替tΡ p鏈s α Θ碳之信號強度。 另外,利用下列式求取共聚合物之立體規則性指標( Ρ (莫耳% ))。 (I ⑯Χ100) (I⑯+ I⑰+ I⑱) 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公嫠)-58 - 561160 A7 B7 五、發明説明(56 ) 又,此①、②......等爲,丙烯與1 _辛烯之無規共 聚合物利用用1 3 C - N M R所測得之光譜信號。又,I① 、②......等爲,各信號之強度。 (7一4)1一十二碳烯單位 丙烯與1-十二碳烯之無規共聚合物的利用 1 3 C - N M R所測得之光譜各信號的化學位移與埽屬如袠 4所示。 共聚合物中十二碳烯單位之含量(α (莫.耳% ))係 ,利用1 3 C - N M R所測得之光譜,於注視主鏈甲撑碳下 ,以下列式求取。 1-十二碳烯單位之含量 (請先閲讀背面之注意事項再填寫本頁} (I ②/2+ I ④)Χ100 (I①+ I②+ I③+ I④) 至於_L__P Ρ鏈S α Θ碳之信號與Ρ Ρ 1鏈Τ α卢碳的 信號,及,Ρ 鏈S α Θ碳之信號與1 一辛烯單位的支 碳之信號重疊,故難於分離,因此,以Ρ 鏈S α /3碳 經濟部智慧財產局員工消资合作社印製 之信號強度代替IP Ρ鏈S α Θ碳之信號強度及P tP鏈 Sa/3碳之信號強度。 另外,利用下列式求取共聚合物之立體規則性指標( p (莫耳% ))。 (I ⑤X100) (I⑥+ I⑦+ I⑧) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.)-59 - 561160 A7 B7 五、發明説明(57 ) 此①、②......等爲,丙烯與1 一十二碳烯之無規共 聚合物利用1 3 C — N M R所測得之光譜信號。又’ I①、 I②......等爲各信號之強度。 (7 — 5) 1 -癸烯單位 求取共聚合物中1 -癸烯單位之含量(莫耳%)及立 體規則性指標(Ρ (莫耳% ))之方式中,除了利用表$ 取代表4以表示丙烯與1-癸烯之無規共聚合物的利用 1 3 C - N M R所測得之光譜的信號外,其他同上述。 至於JL_P Ρ鏈S α /3碳之信號與Ρ Ρ _£__鏈Τ α石碳的 信號,或Ρ £___Ρ鏈S α /3碳之信號與1〜癸烯單位的支鏈 甲撑碳之信號重疊,故難於分離,因此,以Ρ Ρ I鏈 Sa/3碳之信號代替。 -裝-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.)-60 - 561160 Α7 Β7 五、發明説明(58 ) $1 :乙烯/丙烯共聚合物的N M R光譜之埽屬 1 碼 化學位移 埽屬 號碼 化學位移 帰屬 1 45.1-47.3 PPP S a a 14 31.4 epp τ ^ r 2 42.3 PPP S a a 15 31.0 ??ΕΊ β δ 3 38.6 PPP Ί a γ 16 30.7 PPP S a /3 4 38.0 S a γ 17 30.5 PEEE S r δ 5 37.5 Sad 18 30.0 EEES δ δ 6 36.0 PPP S a /3 19 29.0 PPP Τ /3 /? 7 36.0 PPP T a ^ 20 27.3 PEE S β δ 8 34.9 EPP , PEP S a /3 21 24.6 PEP S a ^ 9 34.6 EPP , PEP S a /3 22 21.3-22.7 P /3 /3 10 34.1 EPP T r 7 23 20.6-21.3 ? β β 11 33.7 EEPP Ύ γ δ 24 19.8-20.6 ^ β β 12 33.3 Έ?ΕΊ δ δ 25 17.6 P a /3 13 31.6 PPP Τ a /3 26 17.2 P a 7 g主:Ε爲乙嫌單位’ Ρ爲丙燦單位,下線部分爲反轉單 位。化學位移之單位爲P P Μ。 (請先閲讀背面之注意事項再填寫本頁) 經濟·部智慧財產局員工消费合作社印製 本紙張尺度逋用中國國家標準(CNS ) Α4規格(210X297公釐)-61 - 561160 A7 B7 五、發明説明(59 ) 經濟,部智慧財產局員工消費合作社印製 表2:1—丁烯/丙烯共聚合物的NMR光譜之埽屬 號碼 化學位移 埽屬 1 45.7-47.4 P P S a a 2 43.0-44.9 P B S a a 3 42.3 P P S a a 4 40.3 B B S a a 5 38.6 P P P Tar 6 36.0 _P__P P TySr 及 PP_L_ τ a β 7 35.5 B單位 Ύ β β 8 31.6 p p ^ 'τ β r 9 30.6 P P_P S a β 10 28.6-29.8 p單位 τ β β 11 27.8-28.4 Β單位 Τ /3 /3 12 21.2-22.7 Β單位 支鏈甲撑碳 13 20.6-21.2 ? β β Ρ Ρ Ρ (mm) , Ρ Ρ Β (mm )、BPB(mm)、PPB(rr)、 Β Ρ Β ( r r ) 14 19.8-20.6 ? β β Ρ Ρ Ρ ( r r ) 15 17.6 Ρ α β 16 17.2 Ρ α β 17 11.1 Β單位 支鏈甲撑碳 註:B爲1 -丁烯單位,P爲丙烯單位,下線部分爲反 轉單位。化學位移之單位爲P P Μ。 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -62 - 561160 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(60 ) 表3 :1-辛烯/丙烯共聚合物的NMR光譜之帰屬 號碼 化學位移 婦屬 1 46.0-47.6 P P S a a 2 43.8-44.4 P 〇 S a a 3 42.3 P P JP_ S a a 4 41.5 〇〇 S a a 5 38.6 P JP_P T α T 6 36.2 C 6 7 36.0 P_P P Sa 冷及 PPf__ Ύ a β . 8 34.0 0單位 T /3 3 9 32.2 C 3 . 10 31.6 P P _P_ Ύ β γ 11 30.6 P S a β 12 30.2 C 4 13 28.2-29.8 P單位 Ύ β β 14 27.1 C 5 15 22.9 C 2 16 21.2-22.7 ? β β 17 20.6-21.2 ? β β 18 19.8-20.6 ? β β 19 17.6 Ρ α β 20 17.2 ? α β 21· 14.1 〇 β β 註: P爲丙烯單位 ,0爲1 一辛烯單位,下線部分爲反 轉單位。化學位移之單位爲P P Μ。 (請先閲讀背面之注意事項再填寫本頁) .裝- 訂 本紙浪尺度適用中國國家標準(CNS ) A4規格(210X297公嫠)-63 - 561160Ipep = (I (8) + I (9) -2 X 1 (11) / 4 + 1 (21) In addition, the stereoregularity index (P (mole%)) of the copolymer is calculated using the following formula Isotactic trivalent base fraction of the PPP chain This paper scale applies Chinese National Standard (CNS) A4 specifications (210X 297 mm)-56-" 561160 A7 B7 V. Description of the invention (54) P = Im / Ixl〇 〇 This I m and I are I m-I (22) 1 = (122) + 1 (23) + 1 (23)-(1 (8) + 1 (9) / 2 + 1 (1 0) + 3/2 X 1 (1 1) + 1 (1 2) + 1 (13) +1 (15)} In addition, these (1), (2), etc. are: Gauge copolymers use spectral signals measured by 1 3 C-NMR. In addition, 1 (1), 1 (2), etc. are the intensity of each signal. (7-2) 1-butene The random copolymer of propylene and 1-butene is shown in Table 2. The chemical shifts and genus of each signal of the spectrum measured by 13C-NMR are shown in Table 2. The content of 1-butene unit in the copolymer (α (Mole%)) is a spectrum measured by 1 3 C-NMR, and it is obtained by the following formula while looking at the main chain methylene carbon. Content of 1-butene unit (10/2 + 10X100 Economy, Ministry of Intellectual Property Bureau employee consumption cooperation Printed by the company (please read the precautions on the back before filling in this page) (I ① + 10+ I ③ + I ④ + 2X I ⑨) As for the signal strength of the Z_Ρ Ρ chain S α / 3 carbon, the signal strength of ⑨ The signal strength of C P chain S α / 3) is used as an alternative. The following formula is used to obtain the three-dimensional regularity index of the copolymer (P (mole%)). This paper standard applies to China National Standards (CNS) Α4 Specifications (210X297mm) -57-561160 A7 B7 V. Description of the invention (55) π (I ⑫Χ100) (I⑫ + I⑬ + I⑭) (Please read the precautions on the back before filling out this page) This ①, ② .. ... and so on. The random copolymers of propylene and 1-butene use 1 3 C-NMR to measure the spectral signals. In addition, I①, I②, etc. are the signal intensities. (7-3) 1—Sin The random copolymer of propylene and 1-octene uses 13 C-NM R. The measured chemical shifts and olefin layers of each signal of the spectrum are shown in Table 3. ° 1-octene unit in the copolymer The content (α (mole%)) is obtained by using a spectrum measured by 1 3 C-NMR, and looking at the main chain methylene carbon with the following formula. (I ② / 2 + I ④) x100 The economy, the Ministry of Intellectual Property Bureau employee consumer cooperative printed the signal for the P chain s α / 3 carbon and the signal for the PP chain τ α Θ carbon overlap, so it is difficult to separate, so, The signal strength of the tP p chain s α Θ carbon is replaced by the signal strength of the p tP chain S α / 3 carbon. In addition, the stereoregularity index (P (mole%)) of the copolymer was determined by the following formula. (I ⑯Χ100) (I⑯ + I⑰ + I⑱) The paper size applies to the Chinese National Standard (CNS) A4 specifications (210 × 297 males) -58-561160 A7 B7 V. Description of the invention (56) Also, this ①, ② ... ... and so on, the random copolymer of propylene and 1-octene uses a spectral signal measured by 1 3 C-NMR. In addition, I①, ②, etc. are the intensity of each signal. (7-4) Random copolymer of 1-12 dodecene units of propylene and 1-dodecene The chemical shifts of the signals in the spectrum measured by 1 3 C-NMR and the chemical properties are as shown in Figure 4 Show. The content of dodecene units (α (mole ear)) in the copolymer is based on the spectrum measured by 1 3 C-N M R, and it is determined by the following formula while looking at the main chain methylene carbon. Content of 1-dodecene units (please read the precautions on the back before filling in this page) (I ② / 2 + I ④) X100 (I① + I② + I③ + I④) As for _L__P Ρchain S α Θ carbon The signal of P and P 1 chain T α Lu carbon, and the signal of P chain S α Θ carbon and the signal of branched carbon of 1-octene unit overlap, so it is difficult to separate. Therefore, P chain S α / 3 The signal strength printed by the employee ’s cooperative of the Intellectual Property Bureau of the Ministry of Carbon Economy replaces the signal strength of the IP P chain S α Θ carbon and the signal strength of the P tP chain Sa / 3 carbon. In addition, the following formula is used to obtain the three-dimensionality of the copolymer Regularity index (p (mol%)). (I ⑤X100) (I⑥ + I⑦ + I⑧) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm.) -59-561160 A7 B7 V. Invention Explanation (57) These ①, ②, etc. are the spectral signals measured by 1 3 C-NMR for a random copolymer of propylene and dodecene. Also 'I①, I②. ..... etc. are the intensity of each signal. (7-5) 1-decene unit To find the content of 1-decene unit (mole%) and stereoregularity in the copolymer (P (mol%)), except for using Table $ instead of Table 4 to represent a random copolymer of propylene and 1-decene using a 1 C-NMR spectrum measured signal, Same as above. As for the signal of JL_P P chain S α / 3 carbon and the signal of P P _ £ __chain T α stone carbon, or the signal of P £ ___ P chain S α / 3 carbon and branched chain of 1 ~ decene unit The signal of formazan overlaps, so it is difficult to separate. Therefore, the signal of Sa / 3 carbon of PP chain is replaced.-Equipment-(Please read the precautions on the back before filling this page) Order the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs The paper size printed by the consumer cooperative is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm.)-60-561160 Α7 Β7 V. Description of the invention (58) $ 1: NMR spectrum of ethylene / propylene copolymers Code Chemical shift 埽 Number Chemical shift 帰 1 45.1-47.3 PPP S aa 14 31.4 epp τ ^ r 2 42.3 PPP S aa 15 31.0 ?? EΊ β δ 3 38.6 PPP Ί a γ 16 30.7 PPP S a / 3 4 38.0 S a γ 17 30.5 PEEE S r δ 5 37.5 Sad 18 30.0 EEES δ δ 6 36.0 PPP S a / 3 19 29.0 PPP Τ / 3 /? 7 36.0 PPP T a ^ 20 27.3 PEE S β δ 8 34.9 EPP, PEP S a / 3 21 24.6 PEP S a ^ 9 34.6 EPP, PEP S a / 3 22 21.3-22.7 P / 3/3 10 34.1 EPP T r 7 23 20.6 -21.3? Β β 11 33.7 EEPP Ύ γ δ 24 19.8-20.6 ^ β β 12 33.3 Έ? EΊ δ δ 25 17.6 P a / 3 13 31.6 PPP Τ a / 3 26 17.2 P a 7 g The unit 'P is a Bing Chan unit, and the lower line part is a reverse unit. The unit of chemical shift is P PM. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Ministry of Economic Affairs and Intellectual Property Bureau uses the Chinese National Standard (CNS) Α4 specification (210X297 mm) -61-561160 A7 B7 V. Description of the Invention (59) Economic, Ministry of Intellectual Property Bureau Employees' Cooperatives Printed Table 2: NMR Spectrum of Butene / Propylene Copolymer Copolymer Number Chemical Shift Coefficient 1 45.7-47.4 PPS aa 2 43.0-44.9 PBS aa 3 42.3 PPS aa 4 40.3 BBS aa 5 38.6 PPP Tar 6 36.0 _P__P P TySr and PP_L_ τ a β 7 35.5 B units Ύ β β 8 31.6 pp ^ 'τ β r 9 30.6 P P_P S a β 10 28.6-29.8 p Unit τ β β 11 27.8-28.4 Β Unit Τ / 3/3 12 21.2-22.7 Β Unit Branched Methyl Carbon 13 20.6-21.2? Β β Ρ Ρ Ρ (mm), PB Β (mm), BPB (mm ), PPB (rr), Β Ρ Β (rr) 14 19.8-20.6? Β β Ρ Ρ Ρ (rr) 15 17.6 ρ α β 16 17.2 ρ α β 17 11.1 Β unit branched chain carbon support Note: B is 1 -Butene units, P is a propylene unit, and the lower line is a reverse unit. The unit of chemical shift is P PM. (Please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -62-561160 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (60) Table 3: NMR spectrum of 1-octene / propylene copolymers. The genus number. Chemical shift. Women's genus. 1 46.0-47.6 PPS aa 2 43.8-44.4 P 〇s aa 3 42.3 PP JP_S aa 4 41.5 S aa 5 38.6 P JP_P T α T 6 36.2 C 6 7 36.0 P_P P Sa Cold and PPf__ Ύ a β. 8 34.0 0 Units T / 3 3 9 32.2 C 3. 10 31.6 PP _P_ Ύ β γ 11 30.6 PS a β 12 30.2 C 4 13 28.2-29.8 P units Ύ β β 14 27.1 C 5 15 22.9 C 2 16 21.2-22.7? Β β 17 20.6-21.2? Β β 18 19.8-20.6? Β β 19 17.6 ρ α β 20 17.2? α β 21 · 14.1 〇β β Note: P is a propylene unit, 0 is a 1-octene unit, and the lower part is a reverse unit. The unit of chemical shift is P PM. (Please read the precautions on the back before filling this page). Binding-Binding This paper applies the Chinese National Standard (CNS) A4 specification (210X297 cm) -63-561160
A 五、發明説明(61 ) 以p JL^P鏈(丙烯單位之2 - 1插入)爲例,其 13 C — NMR光譜與碳原子之關係如下圖所示。圖中的數 字爲’對應表3中各光譜之號碼的碳原子。又,〇爲甲基 υ (20) (19)A V. Description of the invention (61) Taking p JL ^ P chain (2-1 insertion of propylene unit) as an example, the relationship between its 13 C-NMR spectrum and carbon atoms is shown in the figure below. The numbers in the figure are the carbon atoms corresponding to the number of each spectrum in Table 3. 〇 is methyl υ (20) (19)
| I I (10) 一 ⑺ 一(11) — (5) -(7) -(3) ^ Ρ単位 上単位 ρ単位 另外’表3中c2至c6爲,各別之1 一辛.烯單位的支 鏈中的下列甲撑碳。 -裝-- (請先閲讀背面之注意事項再填寫本頁) 〇 一(15) —(9) 一(12) —(14) C2 C3 c4 c5| II (10) ⑺ ⑺ (11) — (5)-(7)-(3) ^ 単 単 単 単 単 另外 另外 另外 In addition, c2 to c6 in Table 3 are, one for each octene. The following methylene carbons in the branched chain. -Install-(Please read the notes on the back before filling this page) 〇 One (15) — (9) One (12) — (14) C2 C3 c4 c5
6 C ❿ 經濟部智慧財產局員工消費合作社印製 表4 : 1—十二·碳烯/丙烯共聚合物的N MR光譜之埽屬 號碼 化學位移 埽屬 號碼 化學位移 埽屬 1 46.0-47.6 Ρ P S a a 5 21.1-22.7 Ρ β β 2 43.8-44.4 P D S a a 6 20.6-21.2 Ρ β β 3 42.3 Ρ Ρ P S a a 7 19.8-20.6 Ρ β β 4 41.5 D D S a a 註:P爲丙烯單位,D爲1 一十二碳烯單位,下線部 分爲反轉單位。化學位移之單位爲Ρ PM ° .# 本紙張尺度適用中國國家梂準(CNS ) Α4規格(210Χ297公嫠)-64 - 561160 A7 B7 五、發明説明(62 ) 表5 : 1 號碼 化學位移 埽屬 號碼 化學位移 ^ m 埽屬 1 46.0-47.6 P P S a a 5 21.1-22.7 P /3 /3 2 43.8-44.4 P D S a a 6 20.6-21.2 ? β β 3 42.3 P PZ. S α a 7 19.8-20.6 ? β β 4 41.5 D D S a a 註:P爲丙烯單位,D爲1 一癸烯單位,下線部分爲 反轉單位。化學位移之單位爲p P Μ。 (請先閲讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製6 C 印 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4: 1—Dodecene / propylene copolymer N MR spectrum of the metal number chemical shift PS aa 5 21.1-22.7 P β β 2 43.8-44.4 PDS aa 6 20.6-21.2 P β β 3 42.3 P P PS aa 7 19.8-20.6 P β β 4 41.5 DDS aa Note: P is a unit of propylene, D is 1 1 Dodecene units, the lower part is the inverted unit. The unit of chemical shift is P PM °. # This paper size is applicable to China National Standard (CNS) Α4 size (210 × 297 mm) -64-561160 A7 B7 V. Description of the invention (62) Table 5: 1 Number of chemical shift Number chemical shift ^ m genus 1 46.0-47.6 PPS aa 5 21.1-22.7 P / 3/3 2 43.8-44.4 PDS aa 6 20.6-21.2? Β 3 42.3 P PZ. S α a 7 19.8-20.6? Β β 4 41.5 DDS aa Note: P is a propylene unit, D is a 1-decene unit, and the lower line is a reverse unit. The unit of chemical shift is p PM. (Please read the notes on the back before filling this page} Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
薄膜;1 9 1 °C 薄膜;1 9 2 °C 2 ·薄膜成型 利用塚田樹機製作所製的2 0 m m 0 T模鑄造成型 機’以下列條件,將丙烯系樹脂等製成膜厚2 5 // m或 3 0 // m的薄膜。又,使用氣動刮刀,並將空氣隙·設爲 5 · 5 c m 〇 〔成型條件〕 丁模出口樹脂溫度:2 5 // 3 0 β 冷硬軋輥溫度:3 0 °C 拉取速度:6·0m/分鐘 冷硬軋輥:鏡面 3 ·薄膜特性 利用上述方法製膜後,以4 0 °C對薄膜進行2 4小時 本紙張;^適用中國國家標準(CNS ) A4^ ( 21GX297公釐.)-65 - " -- 561160 經濟部智慧財產局員工消費合作社印製 A7 ___B7_五、發明説明(63 ) 的老化處理,其次將狀態調節爲溫度2 3 ± 2 t,溫度 5 〇 ± 1 〇 %下且1 6小時.以上,其後於同溫度、同濕度 下測定薄膜之特性。 (1 )測定拉伸彈性率(T Μ ) 依據J I S Κ 7 1 2 7之拉伸試驗以下列條件進行 測定。 十字頭速度:500mm/分 負荷單之:1 0 k g 測定方向:機械方向(M D ) (2 )薄膜衝擊性(F · I ) 薄膜衝擊性係指衝擊破壞強度,其爲,利用東洋精機 製薄膜衝擊試驗,以1英寸衝擊壓頭進行測定所得之値。 (3 )測定熱封溫度(H S 丁) 熱封溫度(HST)係依據J I S Ζ - 1707而 測得。其方式爲,利用下列熔著條件進行密封後,於室溫 下放置一夜,其次於室溫下以2 0 〇m/分鐘之剝離速度 ,利用T型剝離法測定剝離強度。又,熱封溫度爲,由熱 封溫度一剝離強度曲線所計算求得剝離強度爲3 0 0 g / 1 5 m m下之溫度。至於熱封桿之溫度則可利用表面溫度 計進行校正。 密封時間:1秒 本紙張尺度適用中國國家梂準(CNS ) A4規格(210X297公釐.) -66- (請先閲讀背面之注意事項再填寫本頁) .裝· 訂 .加 561160 A7 B7 五、發明説明(64 ) 密封面積siSmmxiOmn 密封壓力:2·〇kg/cm2 密封溫度:測定數個不同點之溫度,再以內插方式特 別指定熱封溫度。 (4 )評估防粘連性 將長方形(3 0 cmx 1 〇 cm)之薄膜分別固定於 1 0 c m X 1 〇 c m之固定器,再以下列密合條件密合後 ,評估其剝離強度。 . 密合條件1 一溫度:6 0 °C、時間:3小時、荷重: 36g/cm2、面積:lOcmxlOcm 密合條件2 -溫度:5 0 °C、時間:1周、荷重: 15g/cm2、面積:l〇cinxl〇cm 又,拉離試驗係以下列條件進行。 試驗速度:2Omm/分 負荷單之:2 k g (5)評估滑動性 將貼有薄膜之板物靜置於貼有薄膜之玻璃板後,將玻 璃板傾斜以評估板物滑出時之傾斜角Θ的t a η。又,其 係利用東洋精機製作所製的摩擦角測定機,以下列條件測 得。 測定面:金屬流軸面/金屬滾軸面 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ 297公釐·) ^67 - (請先閲讀背面之注意事項再填寫本頁) .裝· 訂 經濟部智慧財產局員工消资合作社印製 561160 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(65 ) 傾斜速度:2 · 7 ° /秒 板物重量:1 k g 板物剖面積:6 5 c m 2 面間壓力:1 5 g / c m 2 (6 )測定透明性(霧化率) 依據J I S K 7 1 0 5而測得 下面之實施例1〜9及比較例1〜6係有關本說明書 之第一項發明。 . 〔實施例1〕 (1 )丙烯聚合 將甲苯4 <、三異丁基銘8mmo <、四五憲|苯基硼 酸鹽二甲基苯胺鹽2 0 //mo <放入內容積1 〇 <的不透 鋼製局壓鍋中,升溫至4 0°C後加入氫1 〇mm 〇 < ,再 導入能使全壓成爲7 · Okg/cmG爲止的丙烯。其次 加入(1,2> —乙撑)(2,1,一乙撑)一雙(茚基 )給二氯化物5 // m 〇 <,以開始聚合反應。又,利用調 壓器供應能使壓力保持一定之丙烯。2小時後取出內容物 ,減壓下使其乾燥,得丙烯聚合物8 2 0 g。結果此丙嫌 聚合物之等規五分率(mmmm分率)8 8莫耳%、 ( V 〕=1 · 5 分升/g、Mw/Mn=l · 9。 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-68 - 561160 A7 ___B7 五、發明説明(66 ) (2)添加及混煉 將防氧化劑之依魯卡隆克斯1 0 1 0 (吉巴班謝提卡 (請先閲讀背面之注意事項再填寫本頁) 魯公司製)705ppm、依魯卡隆克斯168 (吉巴班 謝提卡魯公司製)75Oppm及、中和劑之硬脂酸鈣 5 0 0 P pm、造核劑之二甲基苄叉山梨糖醇(新日本理 化製:膠醇MD) lOOppm、增滑劑之芥酸醯胺 1 0 0 0 p p m、防粘連劑之二氧化矽系防粘連劑 1 8 0 Q p pm加入上述所得之丙烯聚合物中,並利用單 軸擠押機(塚田樹機製作所製:TL C 3 5 -.2 0型)進 行熔融混煉,得顆粒。 〔實施例2〕 除了將造核劑之膠醇MD (新日本理化(股)製)改 爲500ppm以外,其他同實施例1。 〔比較例1〕 除了未添加造核劑外,其他同實施例1。 經濟,部智慧財產局員工消費合作社印製 〔比較例2〕 除了使用非二茂金屬衍生物系觸媒而得到之丙烯聚合 物(出光石油化學製·· I D Ε Μ I T S U Ρ Ρ F 7 0 4 Ν Ρ )未添加造核劑外,其他同實施例1使薄膜 成型,以進行評估。結果此丙烯聚合物之等規五分率(m mmm分率)爲90莫耳%、 〔 7?〕=1.7分升/ g、 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐) 561160 A7 B7 五、發明説明(67 )Thin film; 19 1 ° C thin film; 19 2 ° C 2 · Thin film molding Using a 20 mm 0 T-die casting molding machine made by Tsutsuda Kiki Seisakusho 'to make a film thickness of 2 based on acrylic resin etc. under the following conditions // m or 3 0 // m film. Also, use an air scraper and set the air gap to 5 · 5 cm 〇 [forming conditions] Resin temperature at the die exit: 2 5 // 3 0 β Cold hard roll temperature: 3 0 ° C Pull speed: 6 · 0m / min cold hard roll: Mirror surface 3 · Film properties After film formation using the above method, the film is subjected to 40 ° C for 24 hours; ^ Applicable to China National Standard (CNS) A4 ^ (21GX297 mm.)- 65-"-561160 A7 ___B7_ printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. The aging treatment of invention description (63), followed by adjusting the state to a temperature of 2 3 ± 2 t and a temperature of 50% ± 1% After 16 hours and above, the characteristics of the film were measured at the same temperature and humidity. (1) Measurement of tensile elastic modulus (T M) The tensile test according to J I S K 7 1 2 7 was measured under the following conditions. Crosshead speed: 500mm / load-dividing sheet: 10 kg Measurement direction: Machine direction (MD) (2) Film impact resistance (F · I) Film impact resistance refers to the impact failure strength, which is the use of Toyo Seiki mechanism film For the impact test, the obtained 値 was measured with a 1-inch impact indenter. (3) Determination of heat-seal temperature (HS D) The heat-seal temperature (HST) is measured in accordance with J I S Z-1707. The method is as follows. After sealing under the following welding conditions, it is left at room temperature overnight, followed by a peeling speed of 200 m / min at room temperature, and the peeling strength is measured by a T-type peeling method. The heat-sealing temperature is a temperature at which the peel strength calculated from the heat-sealing temperature-peel strength curve is 300 g / 15 m m. As for the temperature of the heat-sealing rod, it can be corrected with a surface thermometer. Sealing time: 1 second This paper size applies to China National Standards (CNS) A4 specifications (210X297 mm.) -66- (Please read the precautions on the back before filling out this page). Binding, ordering, plus 561160 A7 B7 5 Description of the invention (64) Sealing area siSmmxiOmn Sealing pressure: 2.0 kg / cm2 Sealing temperature: Measure the temperature at several different points, and then specify the heat sealing temperature by interpolation. (4) Evaluation of anti-blocking property A rectangular (30 cm x 100 cm) film was fixed to a holder of 10 cm x 100 cm, and then adhered under the following adhesion conditions to evaluate the peel strength. Adhesion Conditions 1 Temperature: 60 ° C, Time: 3 hours, Load: 36g / cm2, Area: 10cmxlOcm Adhesion Conditions 2-Temperature: 50 ° C, Time: 1 week, Load: 15g / cm2, Area: 10cinx10cm The pull-off test was performed under the following conditions. Test speed: 2Omm / load sharing sheet: 2 kg (5) Evaluate the sliding property After placing the film-laminated plate on the glass-laminated plate, tilt the glass plate to evaluate the inclination angle when the plate slides out Ta η of Θ. In addition, it was measured using a friction angle measuring machine manufactured by Toyo Seiki Co., Ltd. under the following conditions. Measurement surface: metal flow axis surface / metal roller surface. The paper dimensions are applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm ·) ^ 67-(Please read the precautions on the back before filling this page). Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 561160 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by V. Invention Description (65) Tilt speed: 2 · 7 ° / sec. Weight of the board: 1 kg Area: 65 cm 2 Surface pressure: 15 g / cm 2 (6) Measurement of transparency (atomization rate) The following Examples 1 to 9 and Comparative Examples 1 to 6 were measured in accordance with JISK 7 1 0 5 Related to the first invention of this specification. [Example 1] (1) Polymerization of propylene: Toluene 4 <, triisobutylammon 8mmo <, tetrapenta | phenyl borate dimethylaniline salt 2 0 // mo < put in the inner volume 1 〇 < In an impervious steel local pressure cooker, after heating up to 40 ° C, hydrogen 10 mm was added, and propylene was introduced until the total pressure became 7 · Okg / cmG. Next, (1,2, gt; -Ethylene) (2,1,1-Ethylene) -bis (indenyl) was added to the dichloride 5 // m 0 < to start the polymerization reaction. In addition, a pressure regulator is used to supply propylene which can maintain a constant pressure. After 2 hours, the contents were taken out and dried under reduced pressure to obtain 820 g of a propylene polymer. Results The isotactic quintile (mmmm fraction) of this acrylic polymer was 88 mol%, (V) = 1.5 deciliters / g, Mw / Mn = l · 9. (Please read the note on the back first Please fill in this page again for this matter) This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) -68-561160 A7 ___B7 V. Description of the invention (66) (2) Adding and mixing the anti-oxidant eruka Ronks 1 0 1 0 (Jibba Banshe Tikka (please read the notes on the back before filling this page) Lu company) 705ppm, Iluka Lonk 168 (Jibba Ban Sheti Kalu company ) 75Oppm and neutralizer calcium stearate 5 0 0 P pm, nucleating agent dimethyl benzyl sorbitol (manufactured by New Japan Physicochemicals: Gum alcohol MD) 100 ppm, slipping agent erucamide 1 0 0 0 ppm, anti-blocking agent, silicon dioxide-based anti-blocking agent 1 8 0 Q p pm is added to the propylene polymer obtained above, and a uniaxial extruder (manufactured by Tsukuda Shuki Co., Ltd .: TL C 3 5 -.2 Type 0) Melt-kneading to obtain granules. [Example 2] Except that the nucleating agent's gum alcohol MD (Nippon Physico Chemical Co., Ltd.) was changed to 500 ppm, the others were the same. Example 1. [Comparative Example 1] The same as Example 1 except that no nucleating agent was added. Printed by the Consumer Cooperatives of the Ministry of Economy, Intellectual Property, and Property [Comparative Example 2] Except for the use of non-metallocene derivatives as catalysts The obtained propylene polymer (manufactured by Idemitsu Petrochemical Co., Ltd., ID E Μ ITSU PF PF 7 0 4 NP) was evaluated in the same manner as in Example 1 except that the nucleating agent was not added. As a result, the propylene polymer was evaluated. The isotactic quintile (m mmm fraction) is 90 mole%, [7?] = 1.7 deciliters / g, and this paper size is applicable to China National Standards (CNS) A4 (210X297 mm) 561160 A7 B7 V. Description of the invention (67)
Mw/Mn = 4 · 2。 (請先閲讀背面之注意事項再填寫本頁) 〔比較例3〕 除了將添加於得自非二茂金屬衍生物系觸媒而得到之 丙烯聚合物(出光石油化學製:IDEMITSU P P F 7 0 4NP )中的造核劑之膠醇MD (新日本理化 (股)製)改爲5 0 0 P P m外,其他同實施例1使薄膜 成型,以進行評估。結果此丙烯聚合物之等規五分率(m mmm分率)爲90莫耳%、 〔7?〕=1.7.分升/忌、Mw / Mn = 4 · 2. (Please read the precautions on the back before filling in this page) [Comparative Example 3] Except for a propylene polymer obtained by adding a catalyst derived from a non-ferrocene derivative (produced by Idemitsu Petrochemical: IDEMITSU PPF 7 0 4NP The nucleating agent (glycerol MD (manufactured by Nippon Physico Chemical Co., Ltd.)) in) was changed to 500 PP m, and the film was formed in the same manner as in Example 1 for evaluation. Results The isotactic quintile (m mmm fraction) of this propylene polymer was 90 mole%, [7?] = 1.7.
Mw/Mn=4.2o 此得自非二茂金屬衍生物之丙烯聚合物因添加造核劑 ,故會提高熱封溫度。 〔實施例3〕 (1 )丙烯聚合 經濟部智慧財產局員工消費合作社印製 將甲基4 <、三異丁基鋁8mmo <、四五氟苯基硼 酸鹽二甲基苯胺鹽2 0 #mmo <放入內容積1〇 <之不 銹鋼製高壓中,升溫至5 0°C後導入能使全壓成爲7 . 0 kg/cm2爲止。之乙基/丙基混合氣體(氣體組成比: 乙烯/丙烯=2/1〇〇)其次加入(1 ,2/ —乙撑) (2,1 > 一乙撑)一雙(茚基)給二氯化物5//mo < ,以開始聚合。其後,利用調壓器供應能保有一定壓力之 丙烯。2小時後取出內容物取出內容物,減壓下使其乾燥 本紙張尺度適用中國國家標準(CNS ) A4規格(210'乂297公釐)~-70- 561160 A7 ___ B7 五、發明説明(68 ) ,得丙烯聚合物700g。結果其乙烯含量=1 · 8重量 % > 〔^?〕— 1.8 分升/ g、Mw/Mn = 2.2。 (請先閲讀背面之注意事項再填寫本頁) (2 )添加及混煉 將防氧化劑之依魯卡隆克斯1 〇 1 〇 (吉巴班謝提卡 魯公司製)750ppm、依魯卡隆克斯168 (吉巴班 謝提卡魯公司製)7 5 0 p p m及、中和劑之硬脂酸鈣 500ppm、造核劑之膠醇(新日本理化製)5〇〇 p pm、增滑劑之芥酸醯胺5 0 0 p pm、防.粘連劑之二 氧化矽系防粘連劑2 3 0 0 p p m加入上述所得之丙烯聚 合物中,並利用單軸擠押機(塚田樹機製作所製:T L C 3 5 - 2 0型)進行熔融混煉,得顆粒。 〔實施例4〕 除了將乙烯/丙烯混合氣體組成物改爲1/1 〇 〇外 ,其他同實施例3 ,得丙烯系聚合物組成物。結果其乙烯 含里一 〇 · 48 重量 %、 〔^?〕=1 · 9 分升 / g、Mw / Μ η = 2 · 1。 經濟部智慧財產局員工消费合作社印製 〔實施例5〕 除了將乙烯/丙烯混合氣體組成物改爲3/1 〇 〇外 ,其他同實施例3,得丙烯系聚合物組成物。結果其乙嫌 含量= 2.5重量%、 〔^?〕=1.6分升/2、1^〜/ Μ η = 2 · 2 0 本紙張尺度適用中國國家橾準(CNS ) Α4規格(210X297公釐.)-- 561160 A7 ___B7_ 五、發明説明(69 ) 〔實施例6〕 除了將造核劑改爲滑石Μ M R (淺田製粉公司製) (請先閲讀背面之注意事項再填寫本頁) 2 0 0 0 P P m外,其他同實施例之添加及混煉過程使薄 膜成型,再評估薄膜。 〔實施例7〕 除了將造核劑改爲有機磷酸鈉鹽、NA-11(旭電 化公司製)25Oppm外,其他同實施例3之添加及混 煉過程使薄膜成型,再評估薄膜。 〔實施例8〕 除了將造核劑改爲有機磷酸鈉鹽、ΝΑ-21(旭電 工公司製)1 500ppm外,其他同實施例3之添加及 混煉過程使薄膜成型,再評估薄膜。 〔實施例9〕 經濟部智慧財產局員工消費合作社印製 除了將造核劑改爲醯胺系化合物、耶奴吉斯特- N U 一 100 (新日本理化製)1500ppm外,其他同實 施例3之添加及混煉過程使薄膜成型,再評估薄膜。 〔比較例4〕 除了未添加造核劑外,其他同實施例3。 本紙張尺度適用中國國家標準((:阳)八4規格(210父297公釐) -72 - 561160 A7 B7 五、發明説明(70 ) 〔比較例5〕 (請先閲讀背面之注意事項再填寫本頁) 除了使用得自非二茂金屬衍生物系觸媒之下列丙烯聚 合物及’將造核劑之添加量改爲1 〇 〇 〇 p p m外,其他 同實施例3。 (丙烯聚合) (1)調整固體觸媒成分 以氮氣充分取代附攪拌機之反應槽(內容.積5 0 0 < )後,投入乙醇9 · 7kg、碘640g及金屬鎂6 · 4 k g,於攪拌且回流條件下進行直到系內不再產生氫氣的 反應,得固體狀反應生成物。其後,減壓使含此固體狀反 應生成物之反應液乾燥,得目的之鎂化合物(固體生成物 )° 經濟部智慧財產局員工消費合作社印製 將上述鎂化合物(未粉碎之物)3 0kg、精製庚烷 1 50彡、四氯化矽4 · 5 <及鄰苯二酸二—η — 丁基 5 · 4 <加入經氮充分取代之附攪拌機的反應槽(內容積 500 <)中。於系內保時90 t下攪拌並投入四氯化鈦 144< ,於110°C下反應2小時後分離出固體成分, 其後以8 0 °C之精製庚烷洗淨。其次,加入四氯化鈦,於 1 1 0 °C下反應2小時後,以精製庚烷充分洗淨,得固體 觸媒成分。 本紙張尺度適用中國國家梂準(CNS ) A4規格(210><297公釐.) -73 - 561160 A7 B7 五、發明説明(71 ) (2 )聚合 未進行聚合前,先進行下列前處理。 (請先閲讀背面之注意事項再填寫本頁) 將精製庚烷2 3 0 <投入內容積5 0 0 <之附攪拌機 的反應槽中,再加入上述固體觸媒成分2 5 k g、對固體 觸媒成分中之T i爲1 · 〇莫耳/莫耳的三乙基鋁及 1·8莫耳/莫耳之二環戊基甲基二甲氧基矽烷。其後, 導入能使丙烯分壓成爲〇·3kg/cm2G之丙烯,於. 2 5 °C下反應4小時。結束反應後,以精製庚烷洗淨固體 觸媒成分數回後,加入二氧化碳,並攪拌4小時。 結束上述前處理後,進入真正的聚合反應。 經濟部智慧財產局員工消費合作社印製 將上述處理過之固體觸媒成分於成分中T i換算下爲 3mmo </h、三乙基鋁爲 4mmo </kg — PP、 環己基甲基二甲氧基矽烷爲lmmo </kg — ·ΡΡ分別 加入內容積2 〇 〇 <之附攪拌機的聚合裝置中,於聚合溫 度80°C、全壓28kg/cm2G下進行反應。又,此時 需將乙烯供應量調整爲具有一定乙烯含量及,將氫供應量 調整爲具有一定之分子量。結果此丙烯聚合物的乙烯構造 單位爲5 · 9莫耳%、分子量分布(Mw/Mn)= 4.0、 〔 7?〕= ι·7 分升/g。 〔比較例6〕 除了使用得自非二茂金屬衍生物系觸媒之如比較例5 所示的丙烯聚合物及未添加造核劑外,其他同實施例3。 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐.)-74- 561160 A7Mw / Mn = 4.2o The propylene polymer derived from non-dimetallocene derivatives will increase the heat sealing temperature due to the addition of a nucleating agent. [Example 3] (1) Printing of methyl 4 <, triisobutylaluminum 8mmo <, tetrapentafluorophenyl borate dimethylaniline salt 2 0 #mmo < Into a high pressure made of stainless steel with an internal volume of 10 <, the temperature was raised to 50 ° C, and the total pressure was brought to 7.0 kg / cm2. Ethyl / propyl mixed gas (gas composition ratio: ethylene / propylene = 2 / 1〇〇) followed by (1,2, ethylene) (2,1 > monoethylene) and double (indenyl) 5 / mo < is given to the dichloride to start polymerization. Thereafter, a pressure regulator was used to supply propylene which could maintain a certain pressure. Take out the contents after 2 hours, take out the contents, and dry them under reduced pressure. The size of the paper is applicable to China National Standard (CNS) A4 (210 '乂 297 mm) ~ -70- 561160 A7 ___ B7 V. Description of the invention (68 ) To obtain 700 g of a propylene polymer. As a result, its ethylene content = 1. 8% by weight > [^?]-1.8 dL / g, Mw / Mn = 2.2. (Please read the precautions on the back before filling this page) (2) Add and knead the anti-oxidant Elucaronx 1 〇〇〇 (made by Jiba Ban Sheticaru) 750ppm, Eluka Ronks 168 (manufactured by Giba Banshe Tikalu) 750 ppm and neutralizer 500 ppm calcium stearate, nucleating agent gum (manufactured by Nippon Physicochemical) 5000 ppm, Succinate erucamide 5 0 p pm, anti-blocking agent, silica-based anti-blocking agent 2 300 ppm is added to the propylene polymer obtained above, and a uniaxial extruder (Takada tree machine) is used. Manufacturing company: TLC 3 5-2 0) melt-kneaded to obtain pellets. [Example 4] A propylene-based polymer composition was obtained in the same manner as in Example 3 except that the ethylene / propylene mixed gas composition was changed to 1 / 1.00. As a result, the ethylene content was -0.48% by weight, [^?] = 1. 9 dL / g, and Mw / Mη = 2 · 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 5] A propylene polymer composition was obtained in the same manner as in Example 3 except that the ethylene / propylene mixed gas composition was changed to 3 / 1.00. As a result, the content of B = 2.5% by weight, [^?] = 1.6 dL / 2, 1 ^ ~ / Μ η = 2 · 2 0 This paper is in accordance with China National Standard (CNS) A4 (210X297 mm). )-561160 A7 ___B7_ V. Description of the invention (69) [Example 6] Except changing the nucleating agent to talc MR (made by Asada Milling Co., Ltd.) (Please read the precautions on the back before filling this page) 2 0 0 In addition to 0 PP m, the film was formed by the addition and kneading process of the same embodiment, and then the film was evaluated. [Example 7] Except that the nucleating agent was changed to an organic phosphate sodium salt and NA-11 (manufactured by Asahi Denka Co., Ltd.) at 25 ppm, the film was formed by the addition and kneading process of Example 3, and the film was evaluated. [Example 8] Except that the nucleating agent was changed to an organic phosphate sodium salt and NA-21 (manufactured by Asahi Denki Co., Ltd.) at 1,500 ppm, the film was formed by the addition and kneading process of Example 3, and the film was evaluated. [Example 9] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that the nucleating agent was changed to a fluorene-based compound, Yenugist-NU-100 (manufactured by New Japan Physicochemical Co., Ltd.) at 1500 ppm, and the same as Example 3 The addition and kneading process shapes the film and evaluates the film. [Comparative Example 4] The same procedure as in Example 3 was performed except that no nucleating agent was added. This paper scale applies Chinese national standard ((Yang) 8 4 specifications (210 father 297 mm) -72-561160 A7 B7 V. Description of invention (70) [Comparative example 5] (Please read the notes on the back before filling (This page) Except using the following propylene polymer obtained from a non-dimetallocene derivative-based catalyst and 'changing the amount of the nucleating agent to 1000 ppm, the same as in Example 3. (propylene polymerization) ( 1) After adjusting the solid catalyst component to fully replace the reaction tank (content: 50 0 <) with a stirrer with nitrogen, put in 9 · 7 kg of ethanol, 640 g of iodine and 6.4 kg of magnesium, under stirring and reflux conditions. The reaction proceeds until no more hydrogen is generated in the system to obtain a solid reaction product. Thereafter, the reaction solution containing the solid reaction product is dried under reduced pressure to obtain the desired magnesium compound (solid product). The Consumer Cooperative of the Property Bureau printed 30 kg of the above magnesium compound (unpulverized matter), refined heptane 150 mg, silicon tetrachloride 4 5 < and phthalic acid di-η-butyl 5. 4 < Add reaction with attached mixer fully replaced by nitrogen In the tank (with an internal volume of 500 <), stir and put titanium tetrachloride 144 < at 90 t in the system, and react at 110 ° C for 2 hours to separate the solid component, and then separate it at 80 ° C. Purified heptane was washed. Next, titanium tetrachloride was added, and after reacting at 110 ° C for 2 hours, it was thoroughly washed with refined heptane to obtain a solid catalyst component. This paper size is applicable to China National Standards (CNS) ) A4 specification (210 > < 297 mm.) -73-561160 A7 B7 V. Description of the invention (71) (2) Before polymerization, please perform the following pretreatment. (Please read the precautions on the back before (Fill in this page) Put the purified heptane 2 3 0 < into a reaction tank with a mixer with an internal volume of 50 0 < and add the above solid catalyst component 25 kg. The T i of the solid catalyst component is 1 mol / mol triethylaluminum and 1.8 mol / mol dicyclopentylmethyldimethoxysilane. Thereafter, a partial pressure of propylene was introduced to 0.3 kg / cm2G The propylene was reacted at 2.5 ° C for 4 hours. After the reaction was completed, the solid catalyst component was washed with purified heptane several times, then carbon dioxide was added and stirred. Mix for 4 hours. After the above pre-treatment is completed, it enters the real polymerization reaction. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the solid catalyst component processed above as 3 mm in terms of T i in the composition. Ethyl aluminum is 4mmo < / kg — PP, and cyclohexylmethyldimethoxysilane is lmmo < / kg — · PP is added to a polymerization device with a stirrer with an internal volume of 2000 < at the polymerization temperature. The reaction was performed at 80 ° C and a total pressure of 28 kg / cm2G. At this time, it is necessary to adjust the ethylene supply amount to have a certain ethylene content and the hydrogen supply amount to have a certain molecular weight. As a result, the ethylene structural unit of this propylene polymer was 5.9 mol%, molecular weight distribution (Mw / Mn) = 4.0, [7?] = Ι · 7 deciliter / g. [Comparative Example 6] The same procedure as in Example 3 was performed except that a propylene polymer as shown in Comparative Example 5 and a nucleating agent were used, which were obtained from a non-metallocene derivative catalyst. This paper size applies to China National Standard (CNS) A4 (210X297 mm.) -74- 561160 A7
7 B 五、發明説明(72 ) 經濟部智慧財產局員工消费合作社印製 表6 結晶核生成誘發 拉伸彈 薄膜彳 ®ϊ擊強度 熱封溫 物添加量ppm 性率 (1英寸)J/m 度。C 實施例 1 100 1.1 X 103 3.2 X 104 131 實施例2 500 1.1 X 103 3.2 X 104 131 實施例3 500 0.9 X 103 2.8 X 104 121 實施例4 500 1.2 X 103 2.8 X 104 127 實施例5 500 0.8 X 103 3.2 X 104 111 實施例6 2000 1.1 X 103 2.8 X 104 . 124 實施例7 250 1.0 X 103 2.8 X 104 124 實施例 8 1500 1.1 X 103 2.6 X 104 123 實施例9 1500 1.1 X 103 2.7 X 104 124 比較例 1 0 1.1 X 103 2.9 X 104 135 比較例2 0 1.2 X 103 2.9 X 104 146 比較例3 500 1.2 X 103 3.0 X 104 148 比較例 4 0 0.8 X 103 2.9 X 104 131 比較例5 1000 0.9 X 103 2.8 X 104 130 比較例6 0 0.9 X 103 2.8 X 104 126 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -75 - 561160 A7 _____ B7 五、發明説明(73 ) 下面之實施例1 0及比較例7係有關本說明書之第二 項發明。 (請先聞讀背面之注意事項再填寫本頁) 〔實施例1 0〕 (1 )製造A成分 將甲苯4 · 0 <、三異丁基8毫分子、四五氟苯基硼 酸鹽二甲基苯胺2 0微分子放入內容積1 〇 <之不銹製高 壓鍋中,升溫至4 0°C後加入氫1 0毫分子,.再導入能使 全壓成爲7 · Qkg/cm2G的丙烯。其次加入(1, —乙撑)(2,1> 一乙撑)一雙(茚基)給二氯5 微分子,以開始聚合反應。其後利用調壓器供應能保有一 定壓力之丙烯。2小時後取出內容物,減壓下使其乾燥, 得聚丙烯820g。 結果所得之聚丙燃的內消旋五組物分率(m m m m分 '率)爲9 1莫耳%、極限粘度〔;?〕爲1 · 5分升/ g、 分子量分布(Mw/Mn比)爲1 · 9。 經濟部智慧財產局員工消費合作社印製 (2 )製造B成分 將甲苯400毫升、三異丁基鋁1毫分子、四五氟苯 基硼酸鹽二甲基苯胺鹽4微小子放入內容積1<之不銹鋼 製高壓鍋中,升溫至5 5 °C後加入氫4毫分子,再導入能 使全壓成爲7 · 0kg/cm2G之丙烯。其後加入(1, 2 / -乙撑)(2,1 / 一乙撑)一雙(茚基)給二氯化 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)-76 - 561160 A7 B7 五、發明説明(74 ) (請先閲讀背面之注意事項再填寫本頁) 物1微分子,以開始聚合反應。其次利用調壓器供應能保 有一定壓力之丙烯。1小時後取出內容物,再投入大量甲 醇,過濾、乾燥後得聚丙烯7 5 g。 結果所得之聚丙烯的內消旋五組物分率(m m m m分 率)爲90莫耳%、極限粘度〔7?〕爲〇 . 5分升/ g、 分子量分布(Mw/Mn比)爲2 ·〇。 (3 )添加及混煉 將防氧化劑之「依魯卡隆克斯1 0 1 0」.(吉巴班謝 提卡魯公司製,商品名)750重量ppm、 「依魯卡隆 克斯168」(吉巴班謝提卡魯公司製,商品名)750 重量ppm及、中和劑之硬脂酸鈣5 0 0重量ppm、增 滑劑之芥酸醯胺1 0 0 0重量P p m、防粘連劑之二氧化 矽系防粘連劑1 8 0 0重量p pm加入上述A成分9 1重 量%、B成分9重量%中,並利用單軸擠押機(塚田樹機 製作所製T L C 3 5 - 2 0型)進行熔融混煉,得樹脂 組成物。 經濟/那智慧財產局員工消贫合作社印製 (4 )薄膜成型 以T模鑄造成型法,利用塚田樹機製作所製之2 〇 m m 0 T模鑄造成型機及上述2的條件進行膜厚2 5 的薄膜製膜,再依據上述3進行評估。結果如表7所 示。 本紙張尺度適用中國國家揉準(CNS ) Μ規格(2ΐ〇χ297公嫠)-77 - 561160 A7 B7 五、發明説明(75 ) 〔比較例7〕 (請先閲讀背面之注意事項再填寫本頁) 除了添加成分A而未添加成分B外’其他同實施例 1〇調整爲樹脂,並製成薄膜加以評估。結果如表7所示 。又,薄膜成型時會產生縮幅現象。 表7 拉伸彈性率 MPa 薄膜衝擊 (1英寸)J/m 熱封溫度°c 成型性 實施例10 1.1 X 103 2.9 X 104 130 解除縮幅 比較例7 1.1 X 103 2.9 X 104 135 解除縮幅 下面之實施例1 1〜1 6、比較例8〜1 2及參考例 係有關本說明書之第三項發明。 〔實施例1 1〕 <製造(3-A)共聚合物> 經濟部智慧財產局員工消費合作社印製 將甲苯5 · 〇 <、三異丁基鋁6mmo <、 1—辛烯 5 0 0毫升投入內容積1 〇 <的不銹鋼製高壓鍋中,再加 入四五氟苯基硼酸鹽二甲基苯胺鹽4 0 emo <及,2 — 乙基一 5 — 6二苯并茚基鉻二氯化物20//mo< ,升溫 至5〇°C,再導入能使全壓成爲8 · 0kg/cm2G的丙 烯氣體,以開始聚合反應。其次利用調壓器供應能使聚合 中維持一定壓力的丙烯。3小時後取出內容物,減壓下乾 準 橾 家 國 國 中 用 適 嫠 公 7 29 78 561160 A7 B7 五、發明説明(76 ) 燥後得共聚合物。 接著以混煉機對上述所得之共聚合物中添加下列添加 劑的處方進行擠押造粒。 (1) 防氧化劑 吉巴班謝提卡魯公司製的依魯卡隆克斯1010: 1,0 0 0 P P m 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 1,0 〇 0 P P m (2) 中和劑......硬脂酸鈣:1,OOOppm (3 )防粘連劑......二氧化矽系:1,8 0 0ppm (4)增滑劑......芥酸醯胺:500ppm 利用上述1之方法評估所得共聚合物顆粒的樹脂特性 (請先閲讀背面之注意事項再填寫本頁) -裝- 訂 .麯 經濟部智慧財產局員工消費合作社印製 <製造(3 - B)丙烯系聚合物〉 (1)調製鎂化合物 將乙醇97.22、碘640运及金屬鎂6.41^运 投入經氮氣充分取代之附攪拌機的反應槽(內容積5 0 0 中.,攪拌且回流條件下反應至系內不再產生氫氣爲止 ,得固體狀反應生成物。減壓乾燥含此固體反應生成物之 $紙張尺度適用中國國家揉準icNS ) A4規格(210X297公釐.) -79- — 561160 A7 B7 五、發明説明(77 ) 反應液,得目的之鎂化合物(固體生成物)。 (請先閲讀背面之注意事項再填寫本頁) (2)調製固體觸媒成分 將上述之鎂化合物(未粉碎之物)3 0kg、精製庚 烷(η —庚烷)150 <、四氯化矽4 · 5 <及鄰苯二酸 二一 η -丁基5 · 4 <加入經氮氣充分取代之附攪拌機的 反應槽(內容積5 0 0 < )中,於系內保持爲9 0°(:下攆 拌,並同時投入四氯化鈦1 4 4 <,再於1 1 0 °C下進行 2小時反應後分離出固體成分’其後以8 0 °C.之精製庚院 洗淨。接著加入四氯化鈦2 8 8 於1 1 0 °C下反應2 小時後,以8 0 °C之精製庚烷充分洗淨,得固體觸媒成分 (3 )前處理 將精製庚烷(η -庚烷)230 <投入內容積500 <之附攪拌機的反應槽中,再供應上述固體觸媒成分2 kg、對固體觸媒成分中之鈦原子爲1 . Omo mo彡的三乙基鋁及1 · 8mo </mo纟之二環戊基二 經濟部智慧財產局員工消費合作社印製 曱氧基矽烷。其後,導入能使丙烯分壓成爲0 · 3kg/ c m2G爲止之丙烯,於2 5 °C下反應4小時。結束反應後 ,以精製庚烷洗淨固體觸媒成分數回,再供應二氧化碳, 並攪拌2 4小時。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -80 - 561160 A7 B7 五、發明説明(78 ) (4 )正式聚合 (請先閲讀背面之注意事項再填寫本頁) 將丙烯導入內容積2 0 0 <之附攪拌機的聚合裝置裏 ,再分別供應經上述處理之固體觸媒成分於成分中鈦原子 換算下3mmo </kg — PP、三乙基鋁4mm〇 < / kg — PP、二環戊基二甲氧基矽烷lmm〇j/kg — PP,其後於聚合溫度80°C、聚合壓力(全壓)28 k g/cm2G下進行反應。又,本實施例中需將氫供應量 調節爲,能使其保有一定子量。結果所得(3 - B )聚合 物之等規五分率爲9 7 · 6莫耳%、溶體指敗爲5 . 9 g /1 0m i η。又,聚合中聚合裝置內氣體部分的組成分 析(氣相色譜)結果爲,氫濃度4 · 2莫耳%。 其次利用混煉機對上述所得之丙烯系聚合物粉末中添 加下列添加劑的處方進行擠押造粒。 (1 )防氧化劑 吉巴班謝提卡魯公司製的依魯卡隆克斯1 〇 1 〇 : 1,Ο Ο Ο ρ p m 經濟部智慧財產局員工消費合作社印製 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 1,Ο Ο Ο ρ p m (2 )中和劑......硬脂酸鈣:1,〇 〇 〇 ρ p m (3 )防粘連劑......二氧化矽系:i,〇 〇 〇 ppm (4 )增滑劑......芥酸醯胺·· 1 0 〇 〇 ρ p m 利用上述1之方法評估所得丙烯系聚合物顆粒的樹脂 81 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) 561160 A7 _____Β7 五、發明説明(79 ) 特性。 (請先閲讀背面之注意事項再填寫本頁) 利用乾燥混機使上述所得(3 - A )共聚合物8 0重 量份及(3 - B )丙烯系聚合物2 0重量份充分混合。 利用上述2之方法對所丙烯系聚合物進行製膜,再利 用3之方法評估此薄膜品質。結果如表8所示。 〔實施例1 2〕 除了將正式聚合中的乙嫌及氫供應量調節爲,能保有 一定乙烯含量及分子量外,其他同實施例1 ]_之方法,以 製造(3 - B)丙烯系聚合物。結果所得之(3 一 b )聚 合物的乙烯含量爲3·0莫耳%、等規五分率爲 99 · 2旲耳%、溶體指數爲8 · 5g/l〇mi η。又 ’本實施例於聚合中的聚合裝置內氣體部分之組成分析( 氣相色譜)結果爲、乙烯濃度1·2莫耳%、氫濃度 4· 3莫耳%。另外,除了將(3 —Α)共聚合物及(Β - 3 )丙烯系聚合物之添加比率改爲9 〇重量份及1 0重 量份外,其他同實施例1 1。結果如表8所示。 經濟,部智慧財產局員工消费合作社印製 〔實施例1 3〕 除了將薄膜成型時之冷硬軋輥溫度改爲6 0°C外,其 他同實施例1 2。結果如表8所示。 〔實施例1 4〕 除了將(3—A)共聚合物中,1一辛烯之添加量由 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公嫠)_ 82 - 561160 A7 五、發明説明(80 500毫升改爲3〇〇毫升、聚合溫度由50。。改爲40 C以η庚纟兀取代甲苯外.,其他同實施例1 1 ,以製造 (請先閲讀背面之注意事項再填寫本頁) (3 一 A )共聚合物,其後同實施例1 1 ,結果如表8所 示0 〔實施例1 5〕 除了將(3 —A)共聚合物中,以1 一十二碳烯 5 〇 〇毫升取代1 —辛I聚合溫度由5 0°C改爲4 〇。( ,以η -庚烷取代甲苯外,其他同實施例丨丨,以製造 3 - A )共聚合物,其後同實施例丄丄,結果如表8所^ 〔實施例1 6〕 除了將(3 —A)共聚合物中,以丄一癸烯5 〇〇毫 升取代1 一辛烯、聚合溫度由5〇。〇改爲4(}。〇,以η 一 庚烷取代甲苯外,其他同實施例1 1 ,以製造(3 一 A ) 共聚合物,其後同實施例1 1,結果如表8所示。 經濟,部智慧財產局員工消費合作社印製 〔比較例8〕 除了將實施例1 1所製造之(3 — A)共聚合物及( 3 - B )丙嫌系聚合物的添加比率改爲4 5重量份及5 5 重量份外,其他同實施例1 1,結果如表8所示。 〔比較例9 本紙張尺度適用中國國家橾準(CNS ) A4規格(210X297公釐)-83 - 561160 A7 _B7 五、發明説明⑷) (請先閱讀背面之注意事項再填寫本頁) 未添加(3 - B )丙烯系聚合物,而單獨使用實施例 11所製得之(3 — A)共.聚合物,並於薄膜成型時之冷 硬軋輥溫度爲6 0 °C下進行製膜。結果由冷硬軋輥取下之 情形變差,故無法得到完美的薄膜。 〔比較例1 0〕 除了將薄膜成型時之冷硬軋輥溫度改爲同實施例1 1 的3 0 °C外,其他同比較例9。 〔比較例1 1〕 · 除了(3— A)共聚合物中,以1 一丁烯500毫升 取代1 -辛烯,以η -庚烷取代甲苯外,其他同實施例 1 1以製造(3 - A )共聚合物,其後同實施例1 1 ,結 果如表8所示。 〔比較例1 2〕 經濟部智慧財產局員工消費合作社印製 除了( 3 — A)共聚合物之製造方法改爲下列方法外 ,其他同實施例1 1。 即,將甲苯6 · 0 <、三異丁基鋁6mmo <、四五 氟苯基硼酸鹽二甲基苯胺鹽2 0#mo <放入內容積1 0 <的不銹鋼製高壓鍋中,升溫至5 0°C,導入能使全壓成 爲7·0kg/cm2G爲止的容量比爲乙烯/丙烯=10 /100之混合氣體。 其次加入(1,2# —乙撑)(2,1>一乙撑)一 本紙張尺度適用中國國家揉準(CNS ) A4規格(210X297公釐)_ 84 - 561160 A7 ____ B7_ 五、發明説明(82 ) 雙(茚基)給二氯化物5 # m 〇 <,以開始聚合反應。其 後於聚合中利用調壓器供應_能保有一定壓力的丙烯。3小 時後取出內容物,減壓下乾燥得共聚合物。結果如表8戶彳7 B V. Description of the invention (72) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 6 Crystal nucleation-induced stretch elastic film 彳 ® impact strength Heat-sealed temperature-added substance ppm Sex ratio (1 inch) J / m degree. C Example 1 100 1.1 X 103 3.2 X 104 131 Example 2 500 1.1 X 103 3.2 X 104 131 Example 3 500 0.9 X 103 2.8 X 104 121 Example 4 500 1.2 X 103 2.8 X 104 127 Example 5 500 0.8 X 103 3.2 X 104 111 Example 6 2000 1.1 X 103 2.8 X 104. 124 Example 7 250 1.0 X 103 2.8 X 104 124 Example 8 1500 1.1 X 103 2.6 X 104 123 Example 9 1500 1.1 X 103 2.7 X 104 124 Comparative Example 1 0 1.1 X 103 2.9 X 104 135 Comparative Example 2 0 1.2 X 103 2.9 X 104 146 Comparative Example 3 500 1.2 X 103 3.0 X 104 148 Comparative Example 4 0 0.8 X 103 2.9 X 104 131 Comparative Example 5 1000 0.9 X 103 2.8 X 104 130 Comparative Example 6 0 0.9 X 103 2.8 X 104 126 (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm.) -75 -561160 A7 _____ B7 V. Description of Invention (73) The following Example 10 and Comparative Example 7 are the second invention related to this specification. (Please read the precautions on the reverse side before filling out this page) [Example 1 0] (1) To produce component A, toluene 4 · 0 <, triisobutyl 8 mmol, tetrapentafluorophenyl borate di Methylaniline 20 micromolecules were placed in a stainless steel autoclave with an internal volume of 10 ° C. After heating to 40 ° C, 10 mmoles of hydrogen were added, and then reintroduction was carried out so that the total pressure became 7 · Qkg / cm2G. Acrylic. Next, add (1, —Ethylene) (2,1 > 1 ethylene) and a double (indenyl) to the dichloro 5 micromolecules to start the polymerization reaction. Thereafter, a pressure regulator was used to supply propylene which could maintain a certain pressure. After 2 hours, the contents were taken out and dried under reduced pressure to obtain 820 g of polypropylene. As a result, the fractions (m m m m fractions) of the obtained meso-combustion meso groups were 91 mol% and the limiting viscosity [;? ] Was 1.5 deciliters / g, and the molecular weight distribution (Mw / Mn ratio) was 1 · 9. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (2) Manufacturing of component B. Put 400 ml of toluene, 1 mmol of triisobutylaluminum, 4 pentanofluorophenylborate dimethylaniline salt into the inner volume 1 In a stainless steel autoclave, add 4 mmol of hydrogen after heating up to 5 5 ° C, and then introduce propylene which can make the total pressure to 7.0 kg / cm2G. After that, (1, 2 /-ethylene) (2, 1/1 ethylene) and a pair (indenyl) are added to the dichloride. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -76. -561160 A7 B7 V. Description of the invention (74) (Please read the precautions on the back before filling out this page) 1 micromolecule of object to start the polymerization reaction. Secondly, a pressure regulator is used to supply propylene which can maintain a certain pressure. After 1 hour, the contents were taken out, and then a large amount of methanol was added. After filtering and drying, 75 g of polypropylene was obtained. As a result, the meso fraction of the obtained polypropylene (mmmm fraction) was 90 mole%, the limiting viscosity [7?] Was 0.5 dl / g, and the molecular weight distribution (Mw / Mn ratio) was 2 〇. (3) Add and knead "Ilucaronx 1 0 1 0" which is an antioxidant. (Made by Jiba Ban Sheticaru Company, trade name) 750 ppm by weight, "Ilucaronx 168 (Produced by Jiba Banshe Tikalu Company, trade name) 750 ppm by weight and neutralizer calcium stearate 5 0 0 ppm by weight, slip agent erucamide erucamide 1 0 0 0 0 weight P pm, Anti-blocking agent silica-based anti-blocking agent 1 8 0 0 weight p pm is added to the above-mentioned A component 91 1% by weight, B component 9% by weight, and a uniaxial extruder (TLC 3 by TSUDA Kiki Machine Manufacturing Co., Ltd.) is used. -20 type) melt-kneaded to obtain a resin composition. Printed by the Economic / Nasal Property Bureau employee anti-poverty cooperative (4) Thin film molding is made by T-die casting molding method, using the 200mm 0 T-die casting molding machine manufactured by Tsukata Kiki Seisakusho and the above 2 conditions for film thickness 2 5 The film was formed into a thin film, and then evaluated in accordance with 3 above. The results are shown in Table 7. This paper size is applicable to China National Standards (CNS) M specifications (2ΐ〇χ297 公 嫠) -77-561160 A7 B7 V. Description of the invention (75) [Comparative Example 7] (Please read the precautions on the back before filling in this page ) Except that component A was added but component B was not added, the resin was adjusted in the same manner as in Example 10, and a film was prepared and evaluated. The results are shown in Table 7. In addition, a shrinkage phenomenon occurs during film formation. Table 7 Tensile modulus of elasticity MPa Film impact (1 inch) J / m Heat sealing temperature ° c Formability Example 10 1.1 X 103 2.9 X 104 130 Comparative example 7 1.1 X 103 2.9 X 104 135 Examples 1 to 1 to 6, comparative examples 8 to 12 and reference examples relate to the third invention of this specification. [Example 1 1] < Production of (3-A) copolymer > Printed by toluene 5. · <, triisobutylaluminum 6mmo <, 1-octene 5,000 ml was put into a stainless steel autoclave with an internal volume of 10, and then tetrapentafluorophenyl borate dimethylaniline salt 4 0 emo < and 2 ethyl ethyl 5-6 dibenzoindene The base chromium dichloride 20 / mo < was heated to 50 ° C, and then a propylene gas capable of bringing the total pressure to 8.0 kg / cm2G was introduced to start the polymerization reaction. Secondly, a pressure regulator is used to supply propylene which can maintain a certain pressure during the polymerization. After 3 hours, take out the contents and dry under reduced pressure. Appropriately used in public countries 7 29 78 561160 A7 B7 V. Description of the invention (76) Copolymer was obtained after drying. Next, the formulation obtained by adding the following additives to the copolymer obtained above was extruded and granulated with a kneader. (1) Antioxidant Ilucaronx 1010 by Jiba Ban Shetikaru Company: 1,0 0 0 PP m Ilucaronx 1 6 8 by Jiba Ban Shetikaru Company: 1, 0 0 0 PP m (2) Neutralizer ... Calcium stearate: 1,000 ppm (3) Anti-blocking agent ... Silicon dioxide-based: 1, 8 0 0 ppm ( 4) Slip agent ... Erucamide: 500ppm Use the method of 1 above to evaluate the resin characteristics of the copolymer particles obtained (please read the precautions on the back before filling this page)-Pack-Book. Qu Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs < Manufacture of (3-B) Propylene-based Polymers> (1) Modulation of magnesium compounds Put ethanol 97.22, iodine 640 and metal magnesium 6.41 ^ into a mixer with nitrogen fully replaced The reaction tank (with an internal volume of 500). The reaction product was stirred and refluxed until no more hydrogen gas was generated in the system to obtain a solid reaction product. The $ paper scale containing this solid reaction product was dried under reduced pressure. Applicable to China Knead the icNS) A4 specification (210X297 mm.) -79- — 561160 A7 B7 V. Description of the invention (77) The reaction solution to obtain the target magnesium compound (solid product). (Please read the precautions on the back before filling this page) (2) Preparation of solid catalyst components: 30 kg of the above magnesium compound (unpulverized matter), refined heptane (η-heptane) 150 <, tetrachloro Silicone 4 · 5 < and phthalic acid di-n-butyl 5 · 4 < were added to a reaction tank (with an internal volume of 50 0 <) with a stirrer which was fully replaced by nitrogen, and kept in the system as 90 ° (: mix under the simmer, and simultaneously put titanium tetrachloride 1 4 4 <, and then react at 1 10 ° C for 2 hours to separate the solid component ', and then refine at 80 ° C. Wash in Gengyuan. Then add titanium tetrachloride 2 8 8 and react at 110 ° C for 2 hours, then wash thoroughly with 80 ° C refined heptane to obtain solid catalyst component (3). Refined heptane (η-heptane) 230 < Into a reaction tank with an internal volume of 500 < with a stirrer, and then supplied 2 kg of the above solid catalyst component, the titanium atom in the solid catalyst component was 1. Omo mo Triethyl aluminum and 1,8 mo < / mo bicyclopentyl di bicarbonate were printed by ethoxysilanes at the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Later, the introduction of propylene silane was introduced. Propylene up to 0.3 kg / cm2G was reacted at 25 ° C for 4 hours. After the reaction was completed, the solid catalyst component was washed back with purified heptane for several times, and then carbon dioxide was supplied, followed by stirring for 24 hours. This paper Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm.) -80-561160 A7 B7 V. Description of invention (78) (4) Formal polymerization (please read the precautions on the back before filling this page) Import propylene Inner volume 2 0 0 < In the polymerization device with a mixer, the solid catalyst components treated as described above are separately supplied in terms of titanium atoms in the composition, 3mmo < / kg — PP, triethylaluminum 4mm. ≪ / kg — PP, dicyclopentyldimethoxysilane 1 mmOj / kg — PP, and then reacted at a polymerization temperature of 80 ° C and a polymerization pressure (full pressure) of 28 kg / cm2G. Also, in this example, The hydrogen supply needs to be adjusted so that it can maintain a stator quantity. As a result, the isotactic quintile of the obtained (3-B) polymer is 97.6 mole%, and the melt index is 5.9 g / 10 m i η. The composition analysis (gas chromatography) of the gas portion in the polymerization device during the polymerization showed that hydrogen The degree is 4 · 2 mol%. Secondly, the compound obtained by adding the following additives to the propylene polymer powder obtained above is extruded and granulated by a kneader. (1) Antioxidant Jibaban Shetikaru Company Lukaronx 1 〇1 〇: 1, 〇 〇 Ο ρ pm Printed by Jiubaban Shetikalu Company, Iluka lonx 1 6 8: 1, 〇 〇 Ο ρ pm (2) Neutralizer ... Calcium stearate: 1, 000 ρ pm (3) Anti-blocking agent ... Silicon dioxide: i, 〇〇〇〇 ppm (4) Slip agent ... erucamide erucic acid · 10 〇〇〇ρ pm The resin of the propylene polymer particles obtained by the method of 1 above was evaluated 81 The paper size is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm.) 561160 A7 _____ Β7 V. Description of the invention (79) Characteristics. (Please read the precautions on the back before filling in this page.) Using a dry mixer, mix 80 parts by weight of the (3-A) copolymer and 20 parts by weight of the (3-B) propylene polymer. Film formation was performed on the propylene-based polymer by the method of the above 2 and then the quality of the film was evaluated by the method of 3. The results are shown in Table 8. [Example 1 2] Except that the supply of ethylene and hydrogen in the formal polymerization was adjusted so as to maintain a certain ethylene content and molecular weight, the same method as in Example 1 was used to produce (3-B) propylene-based polymerization. Thing. As a result, the (3-b) polymer obtained had an ethylene content of 3.0 mole%, an isotactic quintile of 99.2 mole%, and a solution index of 8.5 g / l0 mi η. Further, the composition analysis (gas chromatography) of the gas portion in the polymerization device in the polymerization in this example showed that the ethylene concentration was 1.2 mole% and the hydrogen concentration was 4.3 mole%. In addition, except that the addition ratio of the (3-A) copolymer and the (B-3) propylene-based polymer was changed to 90 parts by weight and 10 parts by weight, the procedure was the same as in Example 11. The results are shown in Table 8. Printed by the Consumers' Cooperative of the Ministry of Economics and Intellectual Property of the Ministry [Example 1 3] Except that the temperature of the cold hard roll during film forming was changed to 60 ° C, the others were the same as in Example 12. The results are shown in Table 8. [Example 1 4] In addition to the (3-A) copolymer, the amount of 1-octene added by this paper standard applies the Chinese National Standard (CNS) A4 specification (210X297 cm) _ 82-561160 A7 V. Invention Description (80 500 ml was changed to 300 ml, and the polymerization temperature was changed from 50 ° C to 40 ° C instead of toluene except η-heptane. The others were the same as in Example 1 1 for manufacturing (please read the precautions on the back first) (Fill in this page) (3-A) copolymer, followed by the same as in Example 1 1, the results are shown in Table 8 0 [Example 1 5] Except the (3-A) copolymer, 1 to 10 Dicarbene 5000 ml substituted 1-octane I Polymerization temperature was changed from 50 ° C to 4 0. (except that toluene was replaced by η-heptane, the others were the same as in Example 丨 丨 to make 3-A) copolymerization The results are the same as in Example VIII. The results are shown in Table 8. [Example 16] Except that (3-A) copolymer was replaced with 5,000 ml of decane-decene, and 1-octene was polymerized. The temperature was changed from 50% to 4 ° C. Except that toluene was replaced by η-heptane, and the others were the same as in Example 11 to produce a (3-A) copolymer. The results are shown in Table 8. Printed by the Consumer Cooperatives of the Ministry of Economics and Intellectual Property Bureau [Comparative Example 8] In addition to the (3-A) copolymer and (3-B) C which were produced in Example 11 The addition ratio of the polymer was changed to 4 5 parts by weight and 5 5 parts by weight, the rest were the same as in Example 11 and the results are shown in Table 8. [Comparative Example 9 This paper size applies to China National Standard (CNS) A4 specifications ( 210X297mm) -83-561160 A7 _B7 V. Description of the invention ⑷) (Please read the notes on the back before filling this page) No (3-B) propylene polymer was added, and it was prepared by using Example 11 alone (3-A) co-polymer, and the film was formed at a cold hard roll temperature of 60 ° C during film forming. As a result, the situation of taking off from the cold hard roll became worse, so a perfect film could not be obtained. [Comparative Example 1] Except that the temperature of the chill roll during film forming was changed to 30 ° C as in Example 1 1 and the others, it was the same as Comparative Example 9. [Comparative Example 1 1] In the polymer, 500 ml of 1-butene was used to replace 1-octene and η-heptane was used to replace toluene. 11 was used to manufacture (3-A) co-polymer, which was the same as in Example 11 1 and the results are shown in Table 8. [Comparative Example 1 2] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs except (3-A) The manufacturing method of the copolymer was changed to the following method, and the others were the same as those in Example 11. That is, toluene 6. 0 <, triisobutylaluminum 6mmo <, tetrapentafluorophenyl borate dimethylaniline salt 2 0 # mo < Into a stainless steel autoclave with an internal volume of 10 <, heat up to 50 ° C, and introduce a capacity ratio up to a total pressure of 7.0 kg / cm2G. Ethylene / propylene = 10/100 Of mixed gas. Secondly, add (1, 2 # — ethylene) (2, 1 > one ethylene). One paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) _ 84-561160 A7 ____ B7_ V. Description of the invention (82) Bis (indenyl) gives dichloride 5 # m 0 < to start polymerization. Later in the polymerization, a pressure regulator was used to supply propylene which could maintain a certain pressure. After 3 hours, the contents were taken out and dried under reduced pressure to obtain a copolymer. The results are shown in Table 8.
TpC ° 〔參考例〕 於市售之直鏈狀低密度聚乙烯(出光莫阿提克 V 0 3 9 8 CN)中添加同實施例1 1之添加劑處方,再 同實施例1 1進行評估。結果如表8所示。 (請先閲讀背面之注意事項再填寫本頁) -訂 經濟部智慧財產局員工消費合作社印製 準 標 家 -釐 公 97 2 85 561160 Β7 五、發明説明(83 ) 表8 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 共 重 共聚用單體的 觀 1-辛烯 <— <— 1·辛嫌 1-辛烯 1-辛烯 合 a mol% 4.0 <— <— 3.2 3.8 4.4 物 [V] g/dl 1.5 <— 1.7 1.9 1.9 3-Α Tm °C 108.0 <— <— 114.0 108.7 103.9 的 Tc °C 67.8 <— <— 74.6 67.0 63.2 樹 P mol% 96.4 <— <— 97.5 97.0 97.4 脂 Tp °C 64.7 <r— <— 70.6 64.3 61.4 特 WO wt% 0.69 <— <— 0.59 1.08 1.06 性 Wp wt% 90.8 <"― <— 91.7 88.2 89.1 Β Tm °C 165.9 150.6 165.9 <— <— Tc °C 117.0 106.9 <— 117.0 <— <— 配合率Α/Β 80/20 90/10 90/10 80/20 80/20 80/20 冷硬軋輥。C 30 30 60 30 30 30 薄 C 102 100 103 108 101 100 膜 防粘連 條件1 45 46 41 38 39 43 品 性 N/m2 條件2 24 26 21 19 20 24 質 滑動性 tan Θ 0.26 0.21 0.19 0.38 0.29 0.31 霧化率 % 1.0 1.1 1.6 1.5 1.2 1.0 拉伸彈性率Mpa 540 510 560 670 530 480 防粘連性 I——^----0f, (請先閲讀背面之注意事項再填寫本頁) Μ 經濟部智慧財產局員工消費合作社印製 ‘條件1 :密合條件;溫度6 0 °C、3小時、荷重3 6 k g / c m 2 條件2 :密合條件;溫度5 0 °C、1小時:荷重1 5 k g / c m 2 本紙張尺度適用中國國家揉準(CNS ) Α4規格(210X297公釐·) - 86 - 561160 7 Β 五、發明説明(84 ) 表8 (^續) 比較例8 比較例9 比較例10 比較例11 比較例12 參考例 共 重 共聚用單體的 觀 1-辛烯 <— <— 1-丁烯 乙烯 市販LL 合 a mol% 4.0 <— <— 9.0 8.7 4.1 物 [V] g/dl 1.5 <— 2.2 1.7 1.9 3-Α· Tm °C 108.0 <— <— 121.9 110.9 102.7 的 Tc °C 67.8 <— <— 84.3 75.8 88.5 樹 P mol% 96.4 <— 97.6 97.8 — 脂 Tp °C 64.7 <— <— 79.1 71.6 69.3 特 WO wt% 0.69 <— <— 0.34 0.64 2.64 性 Wp wt% 90.8 <— 86.8 68.7 57.4 Β Tm t 165.9 一 — 165.9 <— — Tc °C 117.0 — — 117.0 <— — 配合率Α/Β 45/55 100/- 100/- 80/20 80/20 100/- 冷硬軋輥。C 30 60 30 30 30 30 薄 熱酣SJTC 135 — 100 118 108 99 膜 防粘連 條件1 25 一 42 40 87 129 品 性 N/m2 條件2 5 — 20 19 49 53 質 滑動性 tan Θ 0.29 — 0.29 0.24 0.41 0.87 霧化率 % 3.8 — 1.0 3.6 1.3 1.4 拉伸彈性率Mpa 900 — 490 600 310 110 防粘連性 I--------^裝-- (請先閲讀背面之注意事項再填寫本頁)TpC ° [Reference Example] A commercially available linear low-density polyethylene (Idemitsu Moatik V 0 3 9 8 CN) was added with the same additive formulation as in Example 11 and evaluated again in Example 11. The results are shown in Table 8. (Please read the precautions on the back before filling out this page)-Order printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-Centrum 97 2 85 561160 B7 V. Description of the invention (83) Table 8 12 Example 13 Example 14 Example 15 Example 16 Example 1-octene <-<-1 octane 1-octene 1-octene a mol% 4.0 < — ≪ — 3.2 3.8 4.4 substance [V] g / dl 1.5 < — 1.7 1.9 1.9 3-Α Tm ° C 108.0 < — < — 114.0 108.7 103.9 Tc ° C 67.8 < — < — 74.6 67.0 63.2 Tree P mol% 96.4 <-<-97.5 97.0 97.4 Fat Tp ° C 64.7 < r- <-70.6 64.3 61.4 Special WO wt% 0.69 <-<-0.59 1.08 1.06 Wp wt% 90.8 < " ― < — 91.7 88.2 89.1 Β Tm ° C 165.9 150.6 165.9 < — < — Tc ° C 117.0 106.9 < — 117.0 < — < — compounding ratio Α / Β 80/20 90/10 90 / 10 80/20 80/20 80/20 Cold hardened roll. C 30 30 60 30 30 30 thin Atomization rate% 1.0 1.1 1.6 1.5 1.2 1.0 Tensile elasticity rate Mpa 540 510 560 670 530 480 Anti-blocking I —— ^ ---- 0f, (Please read the precautions on the back before filling this page) Μ Ministry of Economy Printed on 'Consumer Cooperative of Intellectual Property Bureau' 'Condition 1: Closed condition; temperature 60 ° C, 3 hours, load 36 kg / cm 2 Condition 2: Closed condition; temperature 50 ° C, 1 hour: load 1 5 kg / cm 2 This paper size is applicable to the Chinese National Standard (CNS) Α4 size (210X297 mm ·)-86-561160 7 Β 5. Description of the invention (84) Table 8 (^ continued) Comparative Example 8 Comparative Example 9 Comparison Example 10 Comparative Example 11 Comparative Example 12 Reference Example 1-octene < — < — 1-butene ethylene market LL a amol% 4.0 < — < — 9.0 8.7 4.1 Product [V] g / dl 1.5 < — 2.2 1.7 1.9 3-Α · Tm ° C 108.0 < — < — 121.9 110.9 102.7 Tc ° C 67.8 < — ≪ — 84.3 75.8 88.5 tree P mol% 96.4 < — 97.6 97.8 — fat Tp ° C 64.7 < — — <79.1 71.6 69.3 special WO wt% 0.69 < — < — 0.34 0.64 2.64 Wp wt% 90.8 < — 86.8 68.7 57.4 Β Tm t 165.9 One — 165.9 < — — Tc ° C 117.0 — — 117.0 < — — Mixing ratio Α / Β 45/55 100 /-100 /-80/20 80/20 100 /-Cold hard roll. C 30 60 30 30 30 30 SJTC 135 — 100 118 108 99 Film anti-blocking conditions 1 25-42 40 87 129 Characteristic N / m2 condition 2 5 — 20 19 49 53 Mass sliding property tan Θ 0.29 — 0.29 0.24 0.41 0.87 Atomization rate% 3.8 — 1.0 3.6 1.3 1.4 Tensile elasticity Mpa 900 — 490 600 310 110 Anti-blocking property I -------- ^ install-(Please read the precautions on the back before filling in this page)
、1T 經濟部智慧財產局員工消費合作社印製 條件1 :密合條件;溫度6 0 t、3小時、荷重3 6 k g / c m 2 條件2 :密合條件;溫度5 0 °C、1小時、荷重1 5 k g / c m 2 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐.) -87 - 561160 A7 B7 五、發明説明(85 ) 下面之實施例1 7〜2 1及比較例1 3〜1 6係有關 本說明書的第四項發明。 (請先閲讀背面之注意事項再填寫本頁) 〔實施例1 7〕 (1 )調製二氧化矽附載甲基鋁氧烷之η -庚烷懸浮液 以2 0 0°C對S i〇2 (富士西里西亞公司製,商品名 :P - 1 0 ) 2 7 · 1 g進行2小時的減壓、乾燥處理, 得乾燥二氧化矽2 5 · 9 g。 . 利用乾冰/甲醇浴使此乾燥二氧化矽冷却至一 7 8 °C ,再投入甲苯4 0 0毫/中,攪拌下以1 0小時利用滴入 漏斗滴入1.5莫耳的甲基鋁氧烷甲苯溶液 1 4 5 . 5毫升。以此狀態放置4小時後,以6小時時間 將溫度由一 7 8 °C升2 0 °C,再以此狀態放置4小時,其 後以1小時時間將溫度由2 0 t升至8 0 °C,於8 0 °C下 放置4小時後結束二氧化矽與甲基鋁氧烷之反應。 經濟部智慧財產局員工消費合作社印製 於6 0 t下過濾此懸浮液後,於6 0 °C下依序以 4 0 0毫升之甲苯及4 0 0毫升的η —己烷洗淨所得固體 物二次。 於6 0 °C下對洗淨後的固體物進行4小時減壓乾燥處 理' 得二氧化矽附載甲基鋁氧烷3 3 · 69g。又,甲基 銘氧院之附載量爲2 3 · 1 2重量%。 將η -庚烷加入上述所得全量之二氧化矽附載甲基鋁 氧烷中,使令容量成爲5 0 0毫升,以調製甲基鋁氧烷濃 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公嫠)-88 - 561160 A7 _B7五、發明説明(86 ) 度0 2 7莫耳/ <之懸浮液。 (2)調製二氧化矽附載二茂金屬衍生物系觸媒 於氮氣下,將上述所得之二氧化矽附載甲基鋁氧烷懸 浮溶液7 4毫升(2 0毫分子)、消旋一二甲基亞矽烷基 雙一 2 -乙基—4,5 -苯并茚基鉻二氯化物之庚烷溶液 4 0微分子加入於3 0 0毫升的施嫩克容液中,室溫下攪 拌1 0分鐘,以調製二氧化矽附載二茂金屬衍生物系觸媒 (請先閲讀背面之注意事' ΙΦ ,項再填· 裝—— 寫本頁) 經濟部智慧財產局員工消費合作社印製 (3 )聚合 將η -庚烷5 · 0 <、三異丁基鋁5毫分子、1 一辛 烯4 0 0毫/及上述所得的二氧化矽附載二茂金屬衍生物 觸媒4 0微分子加入內容積1 〇 <之不銹鋼製高壓鍋中, 升溫至5 0°C後,導入能使全壓成爲8 · 0kg/cm2G 爲止的丙烯氣體,以開始聚合。其次,利用調壓器供應能 使聚合中壓力保持一定的丙烯,4小時後取出內容物,減 壓下乾燥,得丙烯-辛烯無規共聚合物粉末。 (4 )添加劑處方 利用混煉機對於上述所得之共聚合物粉末中添加下列 添加劑之處方進行擠押造粒,得顆粒。再以上述1之方法 評估此顆粒之樹脂特性。結果如表9所示。 本紙張尺度適用中國國家標準(CNS ) A嫩( 210X297公釐)89 -~" ~ 訂 •Φ 561160 A7、 1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Conditions 1: Closed conditions; Temperature 60 t, 3 hours, Load 36 kg / cm 2 Condition 2: Closed conditions; Temperature 50 ° C, 1 hour Load 15 kg / cm 2 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm.) -87-561160 A7 B7 5. Description of the invention (85) The following Examples 1 7 ~ 21 1 and Comparative Examples 1 3 to 16 are the fourth invention related to this specification. (Please read the precautions on the back before filling in this page) [Example 17] (1) Preparation of η-heptane suspension of silicon dioxide and methylaluminoxane at 200 ° C to Si02 (Manufactured by Fuji Silesia, trade name: P-1 0) 2 7 · 1 g was subjected to reduced pressure and drying treatment for 2 hours to obtain dry silica 2 5 · 9 g. Use a dry ice / methanol bath to cool this dry silica to 78 ° C, and then add toluene 400 m / m, and add 1.5 mol of methylaluminum oxide to the dropping funnel over 10 hours with stirring. Alkyl toluene solution 145. 5 ml. After being left in this state for 4 hours, the temperature was raised from 7 8 ° C to 20 ° C in 6 hours, then left in this state for 4 hours, and then the temperature was raised from 20 t to 80 in 1 hour. ° C, after 4 hours at 80 ° C, the reaction between silicon dioxide and methylalumoxane is completed. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs after filtering this suspension at 60 t, and then washing the resulting solid with 400 ml of toluene and 400 ml of η-hexane at 60 ° C in order.物 Secondary. The washed solid was dried under reduced pressure for 4 hours at 60 ° C to obtain 3 3 · 69 g of methyl aluminoxane with silica on it. In addition, the attached amount of methyl ming oxygen hospital was 2 3 · 12 2% by weight. Add η-heptane to the above-obtained total amount of silica-supported methylaluminoxane, so that the volume becomes 500 ml, to adjust the concentration of methylaluminoxane. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 gong) -88-561160 A7 _B7 V. Description of the invention (86) Degree 0 2 7 mol / < suspension. (2) The silicon dioxide-supported metallocene derivative catalyst was prepared under nitrogen, and the obtained silicon dioxide-supported methylaluminoxane suspension solution was 74 ml (20 mmol), and racemic dimethylformamide was prepared. 40 micromolecules of a hexane solution of bissilylbis-ethyl-4,5-benzoindenylchromium dichloride in 300 ml of Schlenk solution were stirred at room temperature for 1 0 minutes to modulate the silica-supported metallocene-derived catalyst (please read the note on the back 'ΙΦ first, and then fill in and install-write this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ( 3) Polymerization: η-heptane 5.0 ·, triisobutylaluminum 5 mmol, 1 octene 400 mmol / and the above-obtained silica-supported metallocene derivative catalyst 40 µ Molecules were added to a stainless steel autoclave with an internal volume of 10, and after raising the temperature to 50 ° C, a propylene gas was introduced so that the total pressure could reach 8.0 kg / cm2G to start polymerization. Next, a pressure regulator was used to supply propylene which kept the pressure constant during the polymerization. After 4 hours, the contents were taken out and dried under reduced pressure to obtain a propylene-octene random copolymer powder. (4) Formulation of additives Extrusion granulation was performed by using a kneader to add the following additives to the copolymer powder obtained above to obtain granules. The resin characteristics of this pellet were evaluated by the method of 1 above. The results are shown in Table 9. This paper size applies to Chinese National Standard (CNS) A tender (210X297 mm) 89-~ " ~ Order • Φ 561160 A7
經濟部智慧財產局員工消費合作社印製 五、發明説明(87 ) 防氧化劑 吉巴班謝提卡魯公司製的依魯卡隆克斯1〇10: 1,0 0 0 p p m 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 1,0 0 0 p p m 中和劑......硬脂酸鈣:1,OOOppm 防粘連劑......二氧化矽系:1,8 0 0 ppni 增滑劑......芥酸醯胺:500ppm (5)薄膜成型及評估薄膜 利用上述2之方法對上述顆粒進行製膜,再以上述3 之方法評估此薄膜品質。結果如表9所示。 〔實施例1 8〕 除了將聚合時放入之1 一辛烯量由3 0 0毫升改爲 5 0 0毫升及,聚合溫度由5 0°C改爲4 0°C外,其他同 實施例1 7。所得共聚合物之樹脂特性及薄膜品質的評估 結果如表9所不。 〔實施例1 9〕 (1)調製觸媒及製造共聚合物 將η —庚烷5· 0<、三異丁基鋁6毫分子、1 一辛 烯3 0 0毫升投入內容積1 0 <的不銹鋼製高壓鍋中,再 一请先聞讀背面之注意事項存填寫本 •裝· 1Τ 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -90 · 561160 A7 ____B7 五、發明説明(88 ) (請先閲讀背面之注意事項再填寫本頁) 加入四五氟苯基硼酸鹽二甲基苯胺鹽4 〇微分子、消旋— 二甲基亞矽烷基雙-2 -乙基一 4,5 -苯并茚基鍩二氯 化物2 0微莫耳,升溫至5 0 °C後導入能使全壓成爲 8·0kg/cm2G爲止之丙烯氣體,以開始聚合反應。 又’利用調整供應能使聚合中保有一定壓力之丙烯。3小 時後取出內容物,減壓下乾燥,得丙烯一丁烯無規共聚合 物粉末。 (2 )添加劑處方 利用混煉機對於上述所得之共聚合物粉末中添加下列 添加劑的處方進行擠押造粒,得顆粒。再以上述1之方法 評估此顆粒之樹脂特性。結果如表9所示。 防氧化劑 吉巴班謝提卡魯公司製的依魯卡隆克斯1〇1〇: 1,0 0 0 ρ p m 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 經濟部智慧財產局員工消費合作社印製 1,0 0 0 ρ p m 中和劑......硬脂酸鈣:1,0 0 0 ρ p m 防粘連劑·· ··二氧化矽系:1,800ppm 增滑劑......芥酸醯胺:5 0 〇 Ρ P m 造核劑··…··淺田製粉公司製的滑石MMR = 1 ,0 0 0 ρ P m 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公嫠)· 91 - 561160 A7 B7_ 五、發明説明(8g ) '~" (3)薄膜成型及評估薄膜 同實施例1 7。 (請先閲讀背面之注意事項再填寫本頁) 〔實施例2〇〕 除了將聚合時放入之1 一辛烯量由3 〇 〇毫升改爲 5 0 0毫升及,聚合溫度由5 〇艺改爲4 0°C及,造核劑 由滑石NMR1 ,〇〇〇pPm改爲新日本理化公司製的 膠醇MD (二甲基苄叉山梨糖醇)1 ,〇〇〇ppm外, 其他同實施例1 9。所得之共聚合物的樹脂特性及薄膜品 質之評估結果如表9所示。‘ 〔實施例2 1〕 除了以1 一十二碳烯7 0 〇毫升取代1 一辛烯及,聚 合溫度由5 0 °C改爲4 0 °C外,其他同實施例1 7。所得 之共聚合物的樹脂特性及薄膜品質如表9所示。 經濟/部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家揉準(CNS ) A4規格(21〇Χ297公釐)-92 - 561160Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (87) Antioxidant Jiuba Banxie Kalu company 1010: 1, 0 0 ppm Guiba Banxie Ilucaronx 1 6 8: 1, 0 0 0 0 ppm neutralizing agent made by the Caro Company ... calcium stearate: 1, 000 ppm anti-blocking agent ... silicon dioxide Department: 1, 8 0 0 ppni slip agent ... Erucamide erucic acid: 500 ppm (5) Film formation and evaluation film The above-mentioned particles were formed into a film by the method of 2 above, and then evaluated by the method of 3 above The quality of this film. The results are shown in Table 9. [Example 1 8] Except that the amount of 1-octene put during polymerization was changed from 300 ml to 500 ml and the polymerization temperature was changed from 50 ° C to 40 ° C, the other examples were the same 1 7. The evaluation results of the resin properties and film quality of the obtained copolymer are shown in Table 9. [Example 1 9] (1) Preparation of catalysts and production of copolymers η-heptane 5.0 · 0, triisobutylaluminum 6 mmol, 1 octene 300 ml was put into the inner volume 1 0 & lt In a stainless steel pressure cooker, please read and read the notes on the back again and fill in this book. 1T This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) -90 · 561160 A7 ____B7 V. Invention Note (88) (Please read the notes on the back before filling this page) Add tetrapentafluorophenyl borate dimethylaniline salt 4 〇Micromolecule, racemic — dimethylsilyl bis-2 -ethyl A 4,5 -benzoindenylfluorene dichloride 20 micromolar was heated to 50 ° C and then a propylene gas was introduced so that the total pressure could reach 8.0 kg / cm2G to start the polymerization reaction. Also, propylene can be kept under pressure during the polymerization by adjusting the supply. After 3 hours, the contents were taken out and dried under reduced pressure to obtain a propylene-butene random copolymer powder. (2) Prescription of additives Extrusion granulation was performed by using a kneader to formulate the following additives in the copolymer powder obtained above to obtain granules. The resin characteristics of this pellet were evaluated by the method of 1 above. The results are shown in Table 9. Antioxidant Ilucaronx made by Jiba Ban Shetikaru Company 1010: 1, 0 0 0 ρ pm Ilucaronx made by Jiba Ban Shetikaru Company 1 6 8: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1. 0 0 0 ρ pm Neutralizer ... Calcium stearate: 1, 0 0 0 ρ pm Anti-blocking agent ···· Silica dioxide series: 1,800 ppm slip agent ... Erucamide erucic acid: 5 0 〇Ρ P m nucleating agent ... talc MMR = 1, 0 0 0 ρ P m by Asada Milling Co., Ltd. Paper size Applicable to China National Standard (CNS) A4 specification (210X297 cm) · 91-561160 A7 B7_ 5. Description of the invention (8g) '~ " (3) Film forming and evaluation film The same as in Example 17. (Please read the precautions on the back before filling this page) [Example 2〇] Except for changing the amount of 1-octene put during polymerization from 300 ml to 5000 ml, and the polymerization temperature changed from 500 ml It was changed to 40 ° C, and the nucleating agent was changed from talc NMR1, 000pPm to Gum Alcohol MD (dimethylbenzyl sorbitol) manufactured by Shin Nippon Physico Chemical Co., Ltd., except for 0.001 ppm. Example 19. The evaluation results of the resin properties and film quality of the obtained copolymer are shown in Table 9. ‘[Example 2 1] Example 1 was the same as Example 1 except that 1-octene was replaced by 700 ml of dodecene and the polymerization temperature was changed from 50 ° C to 40 ° C. The resin characteristics and film quality of the obtained copolymer are shown in Table 9. Printed by the Consumers' Cooperative of the Ministry of Economy / Ministry of Intellectual Property Bureau This paper size is applicable to China National Standard (CNS) A4 (21〇 × 297mm) -92-561160
7 7 A B 五、發明説明(9〇 ) 表9_ 實施例 17 18 19 20 21 共聚合用單體的種類 1-辛烯 1-辛烯 1-辛烯 1-辛烯 1-十二碳烯 樹 共聚合用單體含量mol% 3.3 3.8 4.1 4.9 3.8 脂 熔點(Tm) °C 112.0 107.5 108.0 99.9 108.7 特 結晶化溫度(Tc) °C 76.3 73.0 80.2 71.0 73.6 性 立體規則性指標(P) mol% 96.2 96.3 96.7 97.7 97.0 極限粘度 dl/g 1.2 1.5 1.8 2.0 * 1.2 薄 熱封溫度 °C 106 99 95 92 100 膜 防粘連 密合條件1 38 39 41 41 38 品 性 N/m2 密合條件2 19 20 25 18 17 質 滑動性tan 0 0.38 0.29 0.32 0.28 0.31 霧化率 % 1.5 1.4 1.8 2.0 1.5 拉伸彈性率 Mpa 670 560 560 500 580 防粘連性 (請先閲讀背面之注意事項再填寫本頁) 條件1 :密合條件;溫度6 0 °C、3小時、荷重3 6 經濟部智慧財產局員工消費合作社印製 k g / c m 2 條件2 :密合條件;溫度5 0 °C、1小時、荷重1 5 k g / c m 2 本紙張尺度適用中國國家梂準(CNS ) A4規格(210父297公釐.) -93 - 561160 A7 一 —____B7 _ _ 五、發明説明(91 ) 〔比較例1 3〕 (請先閲讀背面之注意事項再填寫本頁) 除了將添加劑處方改爲下列之物外’其他同實施例 2 〇。結果薄膜成型時會產生成型不良之現象,而無法得 到完美的薄膜。又,所得共聚合物之樹脂特性如表1 0所 示。 防氧化劑 吉巴班謝提卡魯公司製的依魯卡隆克斯1 0 1 0 : 1,0 0 〇 ρ p m 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 1,0 〇 0 p p m 中和劑......硬脂酸鈣:1,0 0 0 P p m 防粘連劑......二氧化矽系:1,8 0 0 p p m 增滑劑......芥酸醯胺:5 0 0 p p m 〔比較例1 4〕 經濟部智慧財產局員工消費合作社印製 除了將丙烯系無規共聚合物之製造方法改爲下列方式 外,其他同實施例1 7。結果薄膜成型時會產生成型不良 之現象,而無法得到完美的薄膜。又,樹脂特性如表1〇 所示。 即’將甲苯6 z、甲基鋸氧院6毫分子放入內容積 1 0 <之不銹鋼製高壓鍋中,升溫至3 0°C後導入能使會 壓爲7 · 0kg/cm2G爲止的乙烯與丙烯之混合氣體( 氣體組成比(體積比):乙烯/丙烯=30/70)。其 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) ~QA . ' ---- 561160 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明(92 ) 次加入消旋一二甲基亞矽烷基雙一 2 —乙基一 4,5 -苯 并茚基锆二氯化物〇 · 6微_分子,以開始聚合反應。又, 利用調壓器供應能使聚合中保有一定壓力的丙烯。1小時 後取出內容物,減壓乾燥,得丙烯- 丁烯無規共聚合物粉 末。 〔比較例1 5〕 除了將丙烯系無規共聚合物之製造方法改爲下列方式 外,其他同實施例1 7。又,樹脂特性及薄膜品質如表 1 0所示。 即’將甲苯6 <、三異丁基鋁6毫分子、四五氟苯基 硼酸鹽二甲基苯胺鹽2 0微分子放入內容積1 〇 <之不銹 鋼製高壓鍋中,升溫至5 0°C後導入能使全壓成爲7 . 〇 kg/cm2G爲止的乙烯及丙烯之混合氣體(氣體組成比 (體積比):乙烯/丙烯=10/1 〇〇)。其次加入( 1’2/—乙撑)(2,1/ —乙撑)一雙(茚基)給二 氯化物5微分子,以開始聚合反應。又,利用調壓器供應 能使聚合中保有一定壓力的丙烯。3小時後取出內容物, 減壓下乾燥,得丙烯-乙烯無規共聚合物粉末。 〔比較例1 6〕 除了以1 一丁烯5 0 0毫分子取代1 一辛烯及,聚合 溫度由4 0 °C改爲5 0 t外,其他同比較例1 3。所得共 聚合物之樹脂特,性及薄膜品質如表1 〇所示。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐.) _ 95 _ (請先閱讀背面之注意事 ♦ 項再填- :寫本頁) 裝·7 7 AB V. Description of the invention (90) Table 9_ Example 17 18 19 20 21 Types of copolymerization monomers 1-octene 1-octene 1-octene 1-octene 1-dodecene tree Copolymerization monomer content mol% 3.3 3.8 4.1 4.9 3.8 Lipid melting point (Tm) ° C 112.0 107.5 108.0 99.9 108.7 Special crystallization temperature (Tc) ° C 76.3 73.0 80.2 71.0 73.6 Stereo regularity index (P) mol% 96.2 96.3 96.7 97.7 97.0 Intrinsic viscosity dl / g 1.2 1.5 1.8 2.0 * 1.2 Thin heat seal temperature ° C 106 99 95 92 100 Film anti-adhesion and adhesion conditions 1 38 39 41 41 38 Characteristic N / m2 Adhesion conditions 2 19 20 25 18 17 Mass sliding property tan 0 0.38 0.29 0.32 0.28 0.31 Atomization rate% 1.5 1.4 1.8 2.0 1.5 Tensile modulus Mpa 670 560 560 500 580 Anti-blocking (please read the precautions on the back before filling this page) Condition 1: Adhering conditions; temperature 60 ° C, 3 hours, load 3 6 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, kg / cm 2 Condition 2: Adhering conditions; temperature 50 ° C, 1 hour, load 15 kg / cm 2 This paper size applies to China National Standard (CNS) A4 (210 mm 297 mm.) -9 3-561160 A7 I — ____B7 _ _ V. Description of the invention (91) [Comparative Example 1 3] (Please read the precautions on the back before filling this page) Except changing the additive prescription to the following, the other examples 2 〇. As a result, a molding failure occurs during film molding, and a perfect film cannot be obtained. The resin characteristics of the obtained copolymer are shown in Table 10. Antioxidant Ilucaronx made by Jiba Ban Shetikaru Company 1 0 1 0: 1, 0 0 〇ρ pm Ilucaronx made by Jiba Ban Shetikaru Company 1 6 8: 1, 0 0 0 ppm Neutralizer ... Calcium stearate: 1, 0 0 0 P pm Anti-blocking agent ... Silicon dioxide-based: 1, 8 0 0 0 ppm Slip agent ...... Erucamide: 500 ppm [Comparative Example 1 4] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that the production method of the propylene-based random copolymer is changed to the following method. Same as in Example 17. As a result, poor molding occurs during film molding, and a perfect film cannot be obtained. The resin characteristics are shown in Table 10. That is, 'toluene 6 z and methyl ammonium oxygen 6 millimoles were placed in a stainless steel autoclave with an internal volume of 10 < and the temperature was raised to 30 ° C, and then ethylene was introduced so that the pressure could reach 7.0 kg / cm2G. Gas mixture with propylene (Gas composition ratio (volume ratio): ethylene / propylene = 30/70). The size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm.) ~ QA. Spin the dimethylsilylene bis-2-ethyl-4,5-benzoindenyl zirconium dichloride 0.6 molecules to start the polymerization reaction. In addition, the pressure regulator is used to supply propylene which can keep a certain pressure during polymerization. After 1 hour, the contents were taken out and dried under reduced pressure to obtain a propylene-butene random copolymer powder. [Comparative Example 15] Except that the method for producing a propylene-based random copolymer was changed to the following method, the procedure was the same as in Example 17. The resin characteristics and film quality are shown in Table 10. That is, 'toluene 6 <, 6 isomoles of triisobutylaluminum, 20 micromolecules of tetrapentafluorophenyl borate dimethylaniline salt were placed in a stainless steel autoclave with an internal volume of 1 0 < After 0 ° C, a mixed gas of ethylene and propylene (gas composition ratio (volume ratio): ethylene / propylene = 10/1 00) was introduced so that the total pressure could reach 7.0 kg / cm2G. Next, (1'2 / -Ethylene) (2,1 / -Ethylene) -bis (indenyl) was added to 5 micromolecules of dichloride to start the polymerization reaction. In addition, a pressure regulator is used to supply propylene which can maintain a certain pressure during polymerization. After 3 hours, the contents were taken out and dried under reduced pressure to obtain a propylene-ethylene random copolymer powder. [Comparative Example 16] The same procedure as in Comparative Example 13 was performed except that 1-octene was replaced with 500-mole of 1-octene and the polymerization temperature was changed from 40 ° C to 50 t. The resin characteristics, film properties, and film quality of the obtained copolymer are shown in Table 10. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm.) _ 95 _ (Please read the notes on the back first ♦ Items and fill in-: Write this page)
-、tT 561160 B7 五、發明説明(93 ) 表1〇 比較例 13 14 15 16 共聚合用單體的種類 1-辛烯 乙烯 乙烯 1-辛烯 樹 共聚合用單體含量mol% 4.9 24.4 8.7 9.0 脂 熔點(Tm) °C 99.9 88.2 110.9 121.9 特 結晶化溫度(Tc) °C 56.1 48.5 75.8 84.3 性 立體規則性指標(P) mol% 97.7 97.6 97.8 97.6 極限粘度 dl/g 2.0 1.7 1.7 2.2 薄 熱封溫度 °C — 一 109 116 膜 防粘連 密合條件1 — — 85 41 品 性 N/m2 密合條件2 — — 51 21 質 滑動性tan 0 — 一 0.44 0.25 霧化率 % — — 1.4 3.5 拉伸彈性率 Mpa 一 一 320 540 防粘連性 (請先閲讀背面之注意事項再填寫本頁) 條件1 :密合條件;溫度6 0 °C、3小時、荷重3 6 經濟部智慧財產局員工消費合作社印製 k g / c m 2 條件2 :密合條件;溫度5 0 °C、 1小時、荷重1 5 k . g / c m 2 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公羡·) - 96 - 561160 A7 __ B7_ 五、發明説明(94 ) 下面之實施例2 2〜2 5及比較例1 7〜1 9係有關 本說明書之第五項發明。 (請先閲讀背面之注意事項再填寫本頁) 〔實施形態2 2〕 (1 )調製觸媒及製造共聚合物 將η -庚烷5 · 0 <、三異丁基鋁6毫分子、1 一丁 烯5 0 0毫升投入內容積1 0 <之不銹鋼製高壓鍋中,再 加入四五氟苯基硼酸鹽二甲基苯胺鹽40微分子、消旋-二甲基亞矽烷基雙一 2 —'乙基一 4,5 -苯并茚基鉻二氯 化物2 0微分子,升溫至5 0°C後導入能使全壓成爲 8·〇kg/cm2G爲止的丙烯氣體,以開始聚合。又, 利用調壓器供應能使聚合中保有一定壓力之丙烯。3小時 後取出內容物,減壓下乾燥,得丙烯-丁烯無規共聚合物 粉末。 (2 )添加劑處方 經濟部智慧財產局員工消费合作社印製 利用混煉機對於上述所得共聚合物粉末中添加下列添 加劑之處方進行擠押造粒,得顆粒。再利用上述1之方法 評估此顆粒之樹脂特性。結果如表1 1所示。 防氧化劑 吉巴班謝提卡魯公司製的依魯卡隆克斯1 0 1 0 : 1,0 0 0 p P m 本紙張尺度適用中.國國家標準(CNS ) A4規格(210 X 297公釐.) .Q7- 56Π6〇 A7 B7 五、發明説明(95 ) 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 1,〇 Ο Ο ρ p m (請先閲讀背面之注意事項再填寫本頁) 中和劑......硬脂酸鈣:1 ,〇〇〇ρ ρ m 防粘連劑......二氧化矽系:1,8 Ο Ο Ρ P m 增滑劑......芥酸醯胺:500ppm (3)薄膜成型及評估薄膜 利用2 0 m m 0 T模鑄造機(塚田樹機製作所製) ’以下列成型條件對上述顆粒進行製膜,再以上述3之方 法評估薄膜品質。結果如表1 1所示。 〔實施例2 3〕 除了將添加劑處方改爲下列之物外,其他同實施例 2 2,得共聚合物組成物,其後同上述評估樹脂特性及薄 膜品質。結果如表1 1所示。 防氧化劑 經濟部智慧財產局員工消費合作社印製 吉巴班謝提卡魯公司製的依魯卡隆克斯1〇1〇: 1,Ο Ο Ο ρ p m 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 1,Ο Ο Ο ρ p m 中和劑......硬脂酸鈣:1,〇 〇 〇 ρ p m 防粘連劑......二氧化矽系:1,8 Ο Ο ρ p m 增滑劑......芥酸醯胺:500ppm 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) _ 98 - 561160 A7 B7 五、發明説明(96 ) 造核劑......淺田製粉公司製之滑石MMR : 1 ’〇〇〇p p m (請先閲讀背面之注意事項再填寫本頁) 〔實施例2 4〕 除了將1 一丁烯之使用量改爲1 〇 〇毫升,聚合溫度 改爲6 0 °C外,其他同實施例2 3。又,樹脂特性及薄膜 品質如表1 1所示。 〔實施例2 5〕 除了將添加劑處方改爲下列之物外,其他同實施例 2 4 ’得共聚合物組成物,再同上述評估樹脂特性及薄膜 品質。 防氧化劑 吉巴班謝提卡魯公司製的依魯卡隆克斯1 0 1 0 : 1,0 0 0 p p m 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 經濟,部智慧財產局員工消资合作社印製 1,0 0 0 ρ p m 中和劑......硬脂酸鈣:1 ,0〇0 p p m 防粘連劑......二氧化矽系:1,8 0 0 p p m 增滑劑......芥酸醯胺:5 OOp pm 造核劑......新日本理化公司製的膠醇MD (二甲基 苯叉山梨糖醇):1,OOOppm 本紙張尺度適用中國國家標準(CNS ) A4規格(210\297公釐.) -99 - 561160 B7 五、發明説明(97 ) 表1 1 實施例13 實施例14 實施例15 實施例16 樹 脂 特 性 1-丁嫌含量 mol% 9.0 9.0 3.8 3.8 熔點(Tm) °C 121.9 112.4 141.7 142.2 結晶化溫度(Tc) °C 84.3 95.0 99.8 109.5 立體規則性指標(P) mol% 97.6 97.6 98.3 98.3 極限粘度 dl/g 2.0 2.0 2.2 2.2 造核劑的種類 — 塔魯支MMR _ 膠醇MD 薄 膜 品 質 熱封溫度 °C 116 111 136 129 防粘連 性 N/m2 密合條件1 42 39 26 26 密合條件2 22 23 15 18 滑動性tan 0 0.26 0.28 0.19 0.22 霧化率 % 3.2 2.1 15 1.8 拉伸彈性率 Mpa 490 660 1100 1200 防粘連性 I-------^^裝-- (請先閲讀背面之注意事項再填寫本頁) 訂 條件1 :密合條件;溫度6 0 °C、3小時、荷重3 6 k g X c τη 2 經濟部智慧財產局員工消費合作社印製 條件2 :密合條件;溫度5 0 °C、 1小時、荷重1 5 k g / c m 2 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -1〇〇 - 561160 A7 _ _B7 五、發明説明(98 ) 〔比較例1 7〕 (請先閲讀背面之注意事項再填寫本頁) 除了將丙烯系無規共聚_合物之製造方法改爲下列方式 外’其他同實施例2 2。結果樹脂特性及薄膜品質如表 1 2所示。 (1) 調製鎂化合物 將乙醇97 · 2kg、碘640g及金屬鎂6 · 4 、 k g投入空氣經氮氣充分取代之附攪拌機的反應槽(內容 積5 0 0 <)中,攪拌、回流條件下進行反應直到系內不 再產生氫氣爲止,得固體狀反應生成物。減壓下使含此固 體反應生成物之反應液乾燥、得鎂化合物(固體生成物) 〇 (2) 調製固體觸媒成分 經濟,部智慧財產局員工消費合作社印製 將上述鎂化合物(未粉碎之物)3 0 k g、精製庚烷 (η —庚烷)1 50 <、四氯化矽4 · 5 <及鄰苯二酸二 一 η -丁基5 · 4 <加入經氮氣充分取代之附攪拌機的反 應槽(內容積5 0 0 <)中,其後於系內保持爲9 0°C下 ,攪拌的同時加入四氯化鈦1 44 < ,再於1 1 〇°C下進 行2小時反應,其次由反應液分離出固體成分,再以8 0 °C之精製庚烷洗淨。接著將四氯化鈦2 2 8 <加入此固體 成分中,於1 1 0 °C下進行2小時反應後,利用精製庚烷 充分洗淨固體成分,得固體觸媒成分。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公鏖) -1〇1 - 561160 A7 B7 五、發明説明(") (3 )前處理 (請先閲讀背面之注意事項再填寫本頁) 將精製庚烷2 3 0 <投.入內容積5 0 0 <的附攪拌機 之反應槽中,再供應上述固體觸媒成分25kg,對固體 觸媒成分中之鈦原子爲1·0莫耳/莫耳的三乙基鋁,對 固體觸媒成分中之鈦原子爲1·8莫耳/莫耳的二環戊基 二甲氧基矽烷。其後導入能使丙烯分壓成爲 0 · 3kg/cm2G爲止的丙烯,25°C下進行4小時反 應。結束反應後利用精製庚烷洗淨固體觸媒數回,再供應 二氧化碳,進行2 4小時攪拌。 (4 )聚合 將η -庚烷1 · 2 <、1 一丁烯90g投入受氮氣取 代之內容積2 <的不銹鋼製高壓鍋中,升溫至7 O°C後導 入能使全壓保有4 · 0kg/cm2G之丙烯與氫的混合氣 體(體積比16/1)。其次投入經上述處理之固體觸媒 成分於此成分中鈦原子換算下2·5微分子、三乙基鋁 經濟部智慧財產局員工消黄合作社印製 1 ,0 0 0微分子、二環戊基二甲氧基砍院2 5微分子, 以進行1小時聚合反應。又,利用調壓器供應能使聚合中 之壓力及氣體組成維持一定的丙烯與氫之混合氣體(體積 比1 6 / 1 )。結束聚合後過濾所生成之聚合物,減壓下 乾燥,得丙烯-丁烯無規共聚合物粉末。 〔比較例1 8〕 除了將1 - 丁烯之添加量改爲6 0 g外,其他同實施 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -102 - 561160 Β 五、發明説明(100) 例1 7。結果樹脂特性及薄膜品質如表1 2所示。 〔比較例1 9〕 除了將1 一丁烯之添加量改爲3 0 g外,其他同實施 例1 7。結果樹脂特性及薄膜品質如表1 2所示。 經濟部智慧財產局員工消费合作社印製 表1 2 比較例17 比較例18 比較例19 樹 脂 特 性 1-丁烯含量 mol% 8.2 5.9 3.7 熔點(Tm) °C 145.2. 148.2 155.0 結晶化溫度(Tc) °C 100.0 102.8 109.5 立體規則性指標(P) mol% 99.0 99.0 98.7 極限粘度 dl/g 1.7 1.8 1.7 造核劑的種類 — — — 薄 膜 品 質 熱封溫度 °C 138 141 149 防粘連 性 N/m2 密合條件1 24 24 21 密合條件2 14 12 15 滑動性tan 0 0.39 0.46 0.48 霧化率 % 3.6 3.7 3.9 拉伸彈性率 Mpa 720 830 930 防粘連性 條件1 ·挖合條件,溫度6 0 C、3小時、何重3 6 k g / c m 2 條件2 :密合條件;溫度5 0 °C、1小時、荷重1 5 k g / c m 2 (請先閱讀背面之注意事項再填寫本頁) ,0 項再填· 裝·-, TT 561160 B7 V. Description of the invention (93) Table 10 Comparative Example 13 14 15 16 Types of copolymerization monomers 1-octeneethylene ethylene 1-octene tree copolymerization monomer content mol% 4.9 24.4 8.7 9.0 Lipid melting point (Tm) ° C 99.9 88.2 110.9 121.9 Special crystallization temperature (Tc) ° C 56.1 48.5 75.8 84.3 Stereo regularity index (P) mol% 97.7 97.6 97.8 97.6 Limit viscosity dl / g 2.0 1.7 1.7 2.2 Thin heat Sealing temperature ° C — a 109 116 film anti-adhesion close condition 1 — — 85 41 character N / m2 close condition 2 — — 51 21 mass sliding tan 0 — a 0.44 0.25 atomization rate% — — 1.4 3.5 pull Tensile modulus Mpa-320 540 Anti-blocking (please read the precautions on the back before filling out this page) Condition 1: Adhering conditions; temperature 60 ° C, 3 hours, load 3 6 Intellectual Property Bureau, Ministry of Economic Affairs, employee consumption Cooperative printed kg / cm 2 Condition 2: close condition; temperature 50 ° C, 1 hour, load 15 k.g / cm2 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 public envy ·) -96-561160 A7 __ B7_ V. Description of the invention (94) Below Example 2 and Comparative Example 1 2~2 7~1 5 9 based fifth invention related to this description. (Please read the precautions on the back before filling this page) [Embodiment 2 2] (1) Preparation of catalysts and production of copolymers η-heptane 5.0 · <, triisobutylaluminum 6 mmol, 1 500 ml of 1-butene was poured into a stainless steel autoclave with an internal volume of 10 < and 40 micromolecules of tetrapentafluorophenylborate dimethylaniline and racemic-dimethylsilyl bisone were added. 20 micromolecules of 2-'ethyl-4,5-benzoindenyl chromium dichloride. After heating to 50 ° C, a propylene gas is introduced so that the total pressure becomes 8.0 kg / cm2G to start polymerization. . In addition, the pressure regulator is used to supply propylene which can keep a certain pressure during polymerization. After 3 hours, the contents were taken out and dried under reduced pressure to obtain a propylene-butene random copolymer powder. (2) Additive prescription Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Using a kneader, the following additives were added to the copolymer powder obtained above to extrude and granulate to obtain granules. Then, the method of 1 above was used to evaluate the resin characteristics of the particles. The results are shown in Table 11. Antioxidant Ilucaronx 1 0 1 0: 1, 0 0 0 p P m, manufactured by Jiba Ban Sheticarlu Company. The paper size is applicable. National Standard (CNS) A4 (210 X 297) %.) .Q7- 56Π6〇A7 B7 V. Description of the Invention (95) Ilucaronx 1 6 8: 1, 〇〇 〇 ρ pm (by the back of the book) Note: Please fill in this page again.) Neutralizer ... Calcium stearate: 1, 〇〇〇ρ ρ m Anti-blocking agent ... Silicon dioxide: 1, 8 〇 〇 P P m Slip agent ... Erbium erucate: 500ppm (3) Film molding and evaluation film Using a 20 mm 0 T-die casting machine (made by Tsukuda Shuki Co., Ltd.) 'The above pellets were prepared under the following molding conditions. Film, and then evaluate the film quality by the above 3 methods. The results are shown in Table 11. [Example 2 3] A copolymer composition was obtained in the same manner as in Example 22 except that the additive formulation was changed to the following, and the resin characteristics and film quality were evaluated in the same manner as described above. The results are shown in Table 11. Antioxidant Bureau of Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Jiluban Xantikaru Company of Jibaban Shetikaru Company 1010: 1, 〇 〇 Ο ρ pm Ilukaronx 1 6 8: 1, 〇 〇 Ο ρ pm Neutralizer ... Calcium stearate: 1, 00〇ρ pm Anti-blocking agent ... Silicon dioxide Series: 1, 8 Ο Ο ρ pm slip agent ... Erucamide erucic acid: 500ppm This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm.) _ 98-561160 A7 B7 V. Description of the invention (96) Nucleating agent ... Talc MMR made by Asada Milling Co., Ltd .: 1 '0000 ppm (please read the precautions on the back before filling this page) [Example 2 4] Except for 1 The amount of monobutene was changed to 100 ml, the polymerization temperature was changed to 60 ° C, and the others were the same as in Example 23. The resin characteristics and film quality are shown in Table 11. [Example 2 5] A copolymer composition was obtained in the same manner as in Example 24 except that the additive formulation was changed to the following, and the resin characteristics and film quality were evaluated in the same manner as described above. Antioxidant Ilucaronx manufactured by Jiba Ban Shetikaru Company 1 0 1 0: 1, 0 0 ppm ppm Ilucaronx manufactured by Giba Ban Shetikaru Company 1 6 8: Economy Printed by the Intellectual Property Cooperative of the Ministry of Intellectual Property Bureau, 1. 0 0 0 0 ρ pm Neutralizer ... Calcium stearate: 1, 000 ppm Anti-blocking agent ... Silicon dioxide Series: 1, 8 0 ppm Slip agent ... Erucamide: 5 OOp pm Nucleating agent ... Gum alcohol MD (Dimethylbenzene Fork Pear) manufactured by Shin Nihon Chemical Co., Ltd. Sugar alcohol): 1,000 ppm This paper is sized to the Chinese National Standard (CNS) A4 (210 \ 297 mm.) -99-561160 B7 V. Description of the invention (97) Table 1 1 Example 13 Example 14 Example 15 Example 16 Resin properties 1-Butan content mol% 9.0 9.0 3.8 3.8 Melting point (Tm) ° C 121.9 112.4 141.7 142.2 Crystallization temperature (Tc) ° C 84.3 95.0 99.8 109.5 Stereotacticity index (P) mol% 97.6 97.6 98.3 98.3 Intrinsic viscosity dl / g 2.0 2.0 2.2 2.2 Type of nucleating agent—Taruchi MMR _ Gum MD Film quality heat-seal temperature ° C 116 111 136 129 Anti-blocking N / m2 Adhesive conditions 1 42 39 26 26 Adhesive conditions 2 22 23 15 18 Sliding tan 0 0.26 0.28 0.19 0.22 Atomization rate% 3.2 2.1 15 1.8 Tensile elastic modulus Mpa 490 660 1100 1200 Anti-blocking property I ------- ^^- (Please read the precautions on the back before filling this page) Condition 1: Closed conditions; temperature 60 ° C, 3 hours, load 36 kg X c τη 2 Printed conditions for employee cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 : Adhering conditions; temperature 50 ° C, 1 hour, load 15 kg / cm 2 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm.) -1〇- 561160 A7 _ _B7 V. Description of the Invention (98) [Comparative Example 17] (Please read the precautions on the reverse side before filling out this page) The same method as in Example 22 was used except that the method for producing a propylene-based random copolymer was changed to the following method. Results The resin characteristics and film quality are shown in Table 12 below. (1) Prepare a magnesium compound. Put 97 · 2kg of ethanol, 640g of iodine, and 6.4 · kg of magnesium metal into a reaction tank (with an internal volume of 50 0 <) with a stirrer which is fully replaced by nitrogen with nitrogen. The reaction was performed until hydrogen was no longer generated in the system to obtain a solid reaction product. The reaction solution containing this solid reaction product is dried under reduced pressure to obtain a magnesium compound (solid product). 〇 (2) The solid catalyst component is prepared economically. (Substance) 30 kg, refined heptane (η-heptane) 1 50 <, silicon tetrachloride 4, 5 < and phthalic acid di-η-butyl 5, 4 < In the reaction tank (with an internal volume of 50 0 <) with a stirrer being replaced, and then maintained at 90 ° C in the system, titanium tetrachloride 1 44 < was added while stirring, and then at 1 1 0 ° The reaction was carried out at C for 2 hours, and then the solid component was separated from the reaction solution, and then washed with purified heptane at 80 ° C. Next, titanium tetrachloride 2 2 8 was added to the solid component, and the reaction was performed at 110 ° C for 2 hours, and then the solid component was sufficiently washed with purified heptane to obtain a solid catalyst component. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 cm) -101-561160 A7 B7 V. Description of the invention (") (3) Pre-processing (Please read the precautions on the back before filling this page ) Put the purified heptane 2 3 0 < into the reaction tank with a mixer with an internal volume of 50 0 < and supply 25 kg of the above solid catalyst component. The titanium atom in the solid catalyst component is 1.0 Moore / Moore's triethylaluminum has a dicyclopentyldimethoxysilane of 1.8 mole / mol for the titanium atom in the solid catalyst component. Thereafter, propylene was introduced so that the propylene partial pressure became 0.3 kg / cm2G, and the reaction was carried out at 25 ° C for 4 hours. After the reaction was completed, the solid catalyst was washed several times with purified heptane, and then carbon dioxide was supplied, followed by stirring for 24 hours. (4) Polymerization Put 90 g of η-heptane 1.2 and 1-butene into a stainless steel autoclave with internal volume 2 < replaced by nitrogen, heat up to 7 ° C and introduce it to maintain full pressure of 4 0kg / cm2G mixed gas of propylene and hydrogen (volume ratio 16/1). Secondly, put the solid catalyst component processed as above into 2.5 micromolecules in terms of titanium atom in this component, printed by the Xiaohuang Cooperative of the staff of the Intellectual Property Bureau of the Ministry of Economics, Ministry of Economic Affairs, and printed with 1,000,000 micromolecules, dicyclopentane Dimethoxy group cuts 25 micromolecules for 1 hour polymerization. In addition, a pressure regulator is used to supply a mixed gas of propylene and hydrogen (volume ratio of 16/1) that can maintain a constant pressure and gas composition during polymerization. After the polymerization was completed, the polymer produced was filtered and dried under reduced pressure to obtain a propylene-butene random copolymer powder. [Comparative Example 1] Except changing the addition amount of 1-butene to 60 g, other papers in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm.) Are applied to this paper size -102-561160 Β V. DESCRIPTION OF THE INVENTION (100) Example 17 Results The resin characteristics and film quality are shown in Table 12. [Comparative Example 19] The same procedure as in Example 17 was performed except that the amount of 1-butene was changed to 30 g. Results The resin characteristics and film quality are shown in Table 12. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 2 Comparative Example 17 Comparative Example 18 Comparative Example 19 Resin properties 1-butene content mol% 8.2 5.9 3.7 Melting point (Tm) ° C 145.2. 148.2 155.0 Crystallization temperature (Tc) ° C 100.0 102.8 109.5 Stereo regularity index (P) mol% 99.0 99.0 98.7 Limit viscosity dl / g 1.7 1.8 1.7 Type of nucleating agent — — — Film quality heat-seal temperature ° C 138 141 149 Anti-blocking N / m2 density Combining conditions 1 24 24 21 Adhering conditions 2 14 12 15 Sliding tan 0 0.39 0.46 0.48 Atomization rate% 3.6 3.7 3.9 Tensile elastic modulus Mpa 720 830 930 Anti-blocking condition 1 · Closing conditions, temperature 6 0 C, 3 hours, weight 3 6 kg / cm 2 Condition 2: close condition; temperature 50 ° C, 1 hour, load 15 kg / cm 2 (Please read the precautions on the back before filling this page), item 0 Refill
、1T # 本紙張尺度適用中國國家榇準(CNS ) Α4規格(210X297公釐) -103 - 561160 A7 B7 五、發明説明(101 ) 又下面實施例2 6〜2 9及比較例2 0〜2 3係有關 本說明書的第6項發明。 (請先閲讀背面之注意事項再填寫本頁) 〔實施例2 6〕 (1 )聚合 將η -庚烷5 · 0 <、三異丁基鋁6毫分子、1 一丁 烯5 0毫升投入內容積1 〇 <的不銹鋼製高壓鍋中,再力口 入四五氟苯基硼酸鹽二甲基苯胺鹽4〇微分子、消旋一二 甲基亞矽烷基雙一 2 —乙基一 5 — 6 -苯并茚基錆二氯化 物2 0微分子,升溫至4 0 °C後導入使全壓成爲8 · 0 k g/c m2G爲止的丙烯氣體以開始聚合反應。又,聚合 中利用調壓器供應能使壓力保持一定的丙烯。1小時後取 出內容物,減壓下乾燥,得丙烯-辛烯規共聚合物。 (2)添加及混煉 經濟部智慧財產局員工消资合作社印製 利用單軸擠押機(塚田樹機製作所製:TL C 3 5 -2 0型)對於上述所得之共聚合物中添加下列添加劑之處 方進行擠押造粒。 防氧化劑 吉巴班謝提卡魯公司製的依魯卡隆克斯1 0 1 0 : 1 , 0 0 0 p p m 吉巴班謝提卡魯公司製的依魯卡隆克斯1 6 8 : 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X297公釐) -104 - 561160 A7 ___B7 _ 五、發明説明(1〇2) 1,0 0 0 p p m 中和劑......硬脂酸鈣:1 ,0〇0 p p m 防粘連劑......二氧化矽系:1,800pPlT 增滑劑......芥酸醯胺:5 0 0 p p m 造核劑......新日本理化公司製的膠醇Md ( 苯叉山梨糖醇):1,0 0 0 p p m 〔實施例2 7〕 除了將實施例2 6中的1 —辛烯添加量改.爲3 〇 Q _ 升、聚合溫度改爲5 0 CT、造核劑改爲滑石(淺田製粉^公 司製)1 ,OOOppm外,其他同實施例26之添加及 混煉 ' - v ^ w ^ ··· ,· 〆、n ^ 〇 ,其後使薄膜成型,再評估薄膜,結果如袠 〔比較例2 0〕 除了未添加造核劑外,其他同實施例2 (請先閲讀背面之注意事項再填寫本頁} 裝· 、-!! 經濟部智慧財產局員工消費合作社印製 〔比較例2 1〕 除了未添加造核劑外,其他同實施例2 7 561160 A7 B7 五、發明説明(彳〇3) 表1 3 實施例26 比較例20 實施例27 比較例21 樹 1-辛烯含量 mol% 4.9 4.9 4.1 4.1 脂 極限粘度m dl/g 2.0 2.0 1.8 1.8 特· 熔點(Tm) °C 99.9 99.9 108 108 性 立體規則性指標(P) mol% 97.7 97.7 96.7 96.7 薄 熱封溫度 °C 90 95 93 100 膜 防粘連性 N/m2 28 23 26 20 品 滑動性 tan Θ 0.31 0.25 0.35 - 0.29 質 霧化率 % 1.8 1·1 1.5 1.0 拉伸彈性率 Mpa 457 360 510 490 22 X HTS-1700 280 390 346 500 11 — l· — — I-^裝! (請先閲讀背面之注意事項再填寫本頁) 〔實施例2 8〕 (1 )聚合 經濟部智慧財產局員工消費合作社印製 將η -庚垸5 · 0 <、三異丁基銘6毫分子、1 一丁 烯5 0 0毫升投入內容積1 0 ζ的不銹鋼製高壓鍋中,再 加入四五氟苯基硼酸鹽二甲基苯胺鹽2 0微分子、消旋-二甲基亞矽烷基雙一 2 —乙基一 5 - 6 -苯并茚基鉻二氯 化物1 0微分子,升溫至5 後導入使全壓成爲8 · 0 k g/c m2G爲止的丙烯氣體以開始聚合。又,聚合中利 用調壓器供應能使壓力保持一定的丙烯。4小時後取出內 容物,減壓下乾燥,得丙烯-辛烯無規共聚合物。 本紙張尺度適用中國國家標準(CNS ) A4規格(210父297公釐.) -1〇6 - 561160 A7 B7 五、發明説明(綱) (2)添加及混煉 (請先閱讀背面之注意事項再填寫本頁) 利用單軸擠押機(塚田樹機製作所製:TL C 3 5 -2 0型)對於上述所得之共聚合物中添加同實施例2 6之 添加劑之處方進行擠押造粒。 (3 )薄膜成型 利用2 Omm0 T模鑄造成型機(塚田樹機製作所 製)以同實施例2 6之成型條件將所得顆粒製成膜厚3 0 // m的薄膜。 (4 )評估薄膜 製膜後於4 0°C下進行老化步驟,再以上述3之方法 評估薄膜品質。結果如表1 4所示。 〔實施例2 9〕 經濟部智慧財產局員工消費合作社印製 除了將1 一丁烯之使用量改爲1 〇 〇毫升、聚合溫度 改爲6 0 °C,其他同實施例2 8進行聚合、添加及混煉、 薄膜成型及評估薄膜。結果如表1 4所示。 〔比較例2 2〕 除了未添加造核劑外,其他同實施例2 8。 〔比較例2 3〕 除了未添加造核劑外,其他同實施例2 9。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -1〇7 - 561160 A7 B7 五、發明説明(1〇5) 表1 4 實施例28 比較例22 實施例29 比較例23 樹 1-辛烯含量 mol% 9.0 9.0 3.8 3.8 脂 極限粘度[7?] dl/g 2.0 2.0 2.2 2.2 特 熔點(Tm) °C 122 122 142 142 性 立體規則性指標(P) mol% 97.6 97.6 97.9 97.9 沸騰醚抽出量 wt% 1.2 1.2 0.5 0.5 薄 熱封溫度 °C 111 116 129 136 膜 防粘連性 N/m2 23 22 18 15 品 滑動性’ tan Θ 0.28 0.26 0.22 0.19 質 霧化率 % 2.1 3.2 1.8 1.5 拉伸彈性率 Mpa 661 490 1200 1100 22 X HTS-1700 592 702 988 1142 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 由上述內容得知,本發明可得到剛性、熱封性及由其 形成薄膜。 本發明之丙烯系聚合物及丙烯系聚合物組成物因不損 及聚丙烯樹脂之原有特性及,能具有可與直鏈狀低密度聚 乙烯匹敵之優良低溫熱封性,故可得到優良之剛性與熱封 性的平衡性。另外,由其製成的薄膜除了可保有丙烯系樹 脂原有的剛性、透明性及防濕性等優良特性外,不會產生 黏性物,故具有優良之防粘連性、滑動性,因此可大幅改 善成型性。 又,本發明之丙烯系樹脂適合作爲層壓或共擠押層積 本紙張尺度適用中國國家標準(CNS ) A4規格(210父297公釐) -108- 561160 A7 B7 五、發明説明(106 ) 之密封層。另外,因只有優良之低溫熱封性、防粘連性、 滑動性、剛性,故適合使甩於一般纖維、片狀物及成型物 或至少含一層由此樹脂形成之層的層積物。 (請先閲讀背面之注意事項再填寫本頁) ,裝. 訂 参 經濟,部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐.) -109 -、 1T # This paper size applies to China National Standards (CNS) A4 specifications (210X297 mm) -103-561160 A7 B7 V. Description of the invention (101) The following examples 2 6 to 2 9 and comparative example 2 0 to 2 3 is the sixth invention related to this specification. (Please read the precautions on the back before filling this page) [Example 2 6] (1) Polymerization of η-heptane 5.0 · <, triisobutylaluminum 6 mmol, 1 monobutene 50 ml Into a stainless steel pressure cooker with an inner volume of 10, and then add the tetrapentafluorophenyl borate dimethylaniline salt 40 micromolecules, racemic dimethylsilyl bis 2-ethyl one 20 micromolecules of 5-6-benzoindenylfluorene dichloride were heated to 40 ° C, and then a propylene gas was introduced so that the total pressure became 8.0 kg / c m2G to start the polymerization reaction. In addition, during the polymerization, a pressure regulator was used to supply propylene capable of maintaining a constant pressure. After 1 hour, the contents were taken out and dried under reduced pressure to obtain a propylene-octene gauge copolymer. (2) Adding and mixing the printing and use of a single-shaft extruder (manufactured by Tsukata Tree Machine Co., Ltd .: TL C 3 5-2 0) from the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The additives are extruded and granulated. Antioxidant Ilucaronx manufactured by Jiba Ban Shetikaru Company 1 0 1 0: 1, 0 0 ppm Paper size applies to Chinese National Standard (CNS) A4 specification (210 X297 mm) -104-561160 A7 ___B7 _ 5. Description of the invention (102) 1, 0 0 0 ppm neutralizer ... stearin Calcium acid: 1,000 ppm Anti-blocking agent ... Silicon dioxide-based: 1,800 pPlT slip agent ... Erucamide: 50 0 ppm Nucleating agent ... ... Gum alcohol Md (phenylene sorbitol) manufactured by Shinnippon Chemical Co., Ltd .: 1, 0 0 0 ppm [Example 2 7] In addition to changing the 1-octene addition amount in Example 2 6 to 3 〇 _ liter, polymerization temperature was changed to 50 CT, nucleating agent was changed to talc (manufactured by Asada Milling Co., Ltd.) 1, except that it was added and kneaded in the same manner as in Example 26 except for the value of 0.00ppm.--V ^ w ^ ·, 〆, n ^ 〇, then formed the film, and then evaluate the film, the results are as follows [Comparative Example 20] Except that no nucleating agent was added, the same as Example 2 (Please read the precautions on the back before filling This page} 装 · 、-!! Intellectual property of the Ministry of Economic Affairs Printed by an employee consumer cooperative [Comparative Example 2 1] Except that no nucleating agent is added, the same as in Example 2 7 561160 A7 B7 V. Description of the invention (彳 03) Table 1 3 Example 26 Comparative Example 20 Example 27 Comparison Example 21 Tree 1-octene content mol% 4.9 4.9 4.1 4.1 Lipid limiting viscosity m dl / g 2.0 2.0 1.8 1.8 T Melting point (Tm) ° C 99.9 99.9 108 108 Stereo regularity index (P) mol% 97.7 97.7 96.7 96.7 Thin heat-seal temperature ° C 90 95 93 100 Film anti-blocking property N / m2 28 23 26 20 Product slip tan Θ 0.31 0.25 0.35-0.29 Mass atomization rate% 1.8 1 · 1 1.5 1.0 Tensile elastic modulus Mpa 457 360 510 490 22 X HTS-1700 280 390 346 500 11 — l · — — I- ^ installed! (Please read the precautions on the back before filling out this page) [Example 2 8] (1) Intellectual Property Bureau, Ministry of Polymerization and Economy Printed by the Consumer Consumption Cooperative, put η-heptane 5.0 · <, triisobutylamine 6 mmol, 1 butene 500 ml into a stainless steel autoclave with an internal volume of 10 ζ, and add tetrapentafluorophenyl Borate dimethylaniline salt 20 micromolecules, racemic-dimethylsilyl bisone 2-ethyl A 5--6-- benzoindenyl chromium dichloride was 10 micro molecule, introduced so that the total pressure was raised to be 5 after 8 · 0 k g / c propylene gas until the m2G to start polymerization. In addition, during the polymerization, a pressure regulator was used to supply propylene capable of maintaining a constant pressure. After 4 hours, the contents were taken out and dried under reduced pressure to obtain a propylene-octene random copolymer. This paper size applies to Chinese National Standard (CNS) A4 specifications (210 father 297 mm.) -106-561160 A7 B7 V. Description of the invention (Outline) (2) Addition and mixing (Please read the precautions on the back first) Fill out this page again) Extrusion granulation was performed using a single-shaft extruder (manufactured by Tsukuda Tree Co., Ltd .: TL C 3 5-2 0) to add the same additives as in Example 26 to the copolymer obtained above. . (3) Film formation The obtained pellets were formed into a film with a film thickness of 3 0 // m by using a 20 mm T-die casting molding machine (made by Tsukata Machine Co., Ltd.) under the same molding conditions as in Example 26. (4) Evaluation film After the film is formed, the aging step is performed at 40 ° C, and then the quality of the film is evaluated by the above 3 methods. The results are shown in Table 14. [Example 2 9] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs except that the amount of 1-butene was changed to 100 ml and the polymerization temperature was changed to 60 ° C. Adding and kneading, film forming and evaluating films. The results are shown in Table 14. [Comparative Example 2 2] Except that no nucleating agent was added, it was the same as in Example 28. [Comparative Example 2 3] Except that no nucleating agent was added, it was the same as in Example 29. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm.) -107-561160 A7 B7 V. Description of the invention (105) Table 1 4 Example 28 Comparative Example 22 Example 29 Comparative Example 23 Tree 1-octene content mol% 9.0 9.0 3.8 3.8 Lipid limiting viscosity [7?] Dl / g 2.0 2.0 2.2 2.2 Special melting point (Tm) ° C 122 122 142 142 Stereo regularity index (P) mol% 97.6 97.6 97.9 97.9 Boiling ether extraction weight% 1.2 1.2 0.5 0.5 Thin heat-seal temperature ° C 111 116 129 136 Film anti-blocking property N / m2 23 22 18 15 Product sliding property 'tan Θ 0.28 0.26 0.22 0.19 Mass atomization rate% 2.1 3.2 1.8 1.5 Tensile Elasticity Mpa 661 490 1200 1100 22 X HTS-1700 592 702 988 1142 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. It is known from the above that the present invention Rigidity, heat-sealability, and film formation can be obtained. The propylene-based polymer and the propylene-based polymer composition of the present invention can obtain excellent low-temperature heat-sealability comparable to linear low-density polyethylene because it does not impair the original characteristics and properties of the polypropylene resin. Excellent balance between rigidity and heat sealability. In addition, the film made of it has excellent rigidity, transparency, and moisture resistance properties of acrylic resins, and does not produce sticky materials, so it has excellent anti-blocking properties and sliding properties. Significantly improve moldability. In addition, the acrylic resin of the present invention is suitable for lamination or co-extrusion. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 father 297 mm) -108- 561160 A7 B7 V. Description of the invention (106) Of the sealing layer. In addition, since it has only excellent low-temperature heat-sealing properties, anti-blocking properties, sliding properties, and rigidity, it is suitable for being thrown on general fibers, sheets, and molded products or laminates containing at least one layer formed of this resin. (Please read the precautions on the back before filling out this page), binding. Ordering Printed by the Consumer Cooperatives of the Ministry of Economy and Intellectual Property Bureau This paper size applies to China National Standard (CNS) A4 (210X297 mm.) -109-
Claims (1)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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JP22263497A JP4033947B2 (en) | 1997-04-16 | 1997-08-19 | Propylene polymer composition and film comprising the same |
JP23061197 | 1997-08-27 | ||
JP3996098 | 1998-02-23 | ||
JP05495798A JP4065048B2 (en) | 1998-03-06 | 1998-03-06 | PROPYLENE RANDOM COPOLYMER, COMPOSITION THEREOF, FILM AND LAMINATE COMPRISING THEM |
JP05495898A JP4047962B2 (en) | 1998-03-06 | 1998-03-06 | PROPYLENE RANDOM COPOLYMER, COMPOSITION THEREOF, FILM AND LAMINATE COMPRISING THEM |
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TW561160B true TW561160B (en) | 2003-11-11 |
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TW87113500A TW561160B (en) | 1997-08-19 | 1998-08-17 | Propylene polymer composition |
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1998
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