TW200400212A - Polymer composition including a cyclic olefin copolymer - Google Patents
Polymer composition including a cyclic olefin copolymer Download PDFInfo
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- TW200400212A TW200400212A TW092113240A TW92113240A TW200400212A TW 200400212 A TW200400212 A TW 200400212A TW 092113240 A TW092113240 A TW 092113240A TW 92113240 A TW92113240 A TW 92113240A TW 200400212 A TW200400212 A TW 200400212A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/12—Syndiotactic polypropylene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
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Abstract
Description
200400212 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種包括環烯烴共聚物之聚合物組成物 ’關於一種含有一種由此組成物組成之層的膜及其特別應 用。 【先前技術】 企圖供醫藥應用的物件必須不僅符合一般要求，如良 好機械強度或低成本，也須符合此特別應用領域所極嚴格 而獨有的要求，例如，有關於該物件之生物相容性質，其 耐受消毒處理的能力，其可撓性，其透明性，其焊接性， 其衝擊強度（包括關於用液體塡充容器），可萃取之物質 (例如’用己烷可萃取者）之量及在某些情況下，其障壁 性等要求。 【發明內容】 迄今，供醫藥用途之商業上可得到之物件，例如，輸 液或血袋，及企圖用以保存與流體有關之藥物的袋已是基 於氯乙烯聚合物’例如基於p V C。雖然具有數項優點，但 此型聚合物具有某些缺點，如需要合倂高量的安定劑於其 中’以改良其熱安定性或合倂高量增塑劑於其中以得足夠 可撓性。因此，對於避免氯化聚合物之供醫藥應用的物件 有市場需求。 爲了得到此種物件，已知由以聚烯烴爲底之膜開始且 -4- (2) (2)200400212 將這些焊在一起（或在其自身之上）以製袋或囊。以 SLOLVAY爲名之 WO 〇〇/ 6 1 062專利申請案描述包含 COP (環烯烴聚合物）之此種膜。然而，申請人發現：當 單獨使用C 0 P時（亦即’作爲膜或由彼所出之層的純構 成成份），焊接極不容易且所得焊接物有差的品質，特別 是用工業方法中常用之短的焊接時間時。此外，當使用純 COP時，則即使在多層結構之僅一層中，熱消毒、透明性 和可撓性並非最恰當的。更特別地，包括純C Ο P層之多 層結構在熱消毒後易於剝離。 申請人發現：令人驚訝地，當添加間規聚丙烯（S 一 PP )至COP時，後者變得極易焊接且使醫藥袋或囊可被 熱消毒，是且保持（在熱消毒後）透明、可撓，具有高衝 擊強度且除此之外，顯出優越之障壁性（亦即，抗水蒸汽 、酸及醇）且在多層結構情況中在熱消毒後沒有剝離。此 外，s — PP經二茂金屬觸媒而得到，以致它顯出比其它非 二茂金屬P P樹脂還低量之可萃取化合物及較少之觸媒殘 留。 因此’本發明係關於一種包括C0p和s— PP之聚合 物組成物。 '' COP〃一詞被了解是意指C5至Cl2環性單體及/或 二-環性單體（二聚體）之均一或共聚物，其可以負載側 鏈以致達全部5至3 0碳。除了環性單體之外，共聚物通 常包括相對於環性單體，2至95重量％ (較佳地1 〇至80 重量％ )且相對於烯烴，5至9 8重量％ (較佳地2 0至9 0 -5- (3) 200400212 重量％ )之含量之C2至CiG嫌烴。基本的環性單體單元 可以是環戊烯、環己烯、原冰片烯、二環戊二條、四環十 二碳烯或甲基四環十二碳烯。它較佳是原冰片燦：200400212 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a polymer composition including a cyclic olefin copolymer 'and to a film containing a layer composed of the composition and a special application thereof. [Previous technology] Articles intended for medical applications must not only meet general requirements, such as good mechanical strength or low cost, but also meet the extremely strict and unique requirements of this particular application area, for example, regarding the biocompatibility of the article Properties, its ability to withstand sterilization, its flexibility, its transparency, its weldability, its impact strength (including the use of liquids to fill containers), extractable substances (eg 'extractable with hexane) The amount and, in some cases, its barrier properties. [Summary of the Invention] So far, commercially available articles for medical use, such as infusion or blood bags, and bags intended to hold fluid-related drugs have been based on vinyl chloride polymers', such as based on pVC. Although it has several advantages, this type of polymer has certain disadvantages, such as the need to incorporate a high amount of stabilizers therein to improve its thermal stability or to incorporate a high amount of plasticizers therein to obtain sufficient flexibility. . Therefore, there is a market demand for articles that avoid chlorinated polymers for medical applications. In order to obtain such articles, it is known to start with a polyolefin-based film and weld these (or on top of them) together to make bags or sacs. The WO 00/6 1 062 patent application under the name SLOLVAY describes such a film comprising a COP (cycloolefin polymer). However, the applicant found that when C 0 P is used alone (that is, 'as a pure constituent of the film or the layer from which it is made), welding is not easy and the quality of the resulting weld is poor, especially by industrial methods Commonly used in short welding time. In addition, when using pure COP, heat sterilization, transparency, and flexibility are not optimal even in only one layer of a multilayer structure. More specifically, a multi-layer structure including a pure CO layer is easily peeled off after heat sterilization. The applicant has found that, surprisingly, when syndiotactic polypropylene (S-PP) is added to the COP, the latter becomes extremely easy to weld and allows the medical bag or pouch to be heat sterilized, yes and maintained (after heat sterilization) Transparent, flexible, with high impact strength and in addition, it shows superior barrier properties (ie resistance to water vapor, acids and alcohols) and in the case of multilayer structures does not peel off after heat disinfection. In addition, s-PP is obtained via a dimetallocene catalyst, so that it shows a lower amount of extractable compounds and less catalyst residue than other non-metallocene PP resins. Therefore, the present invention relates to a polymer composition including COp and s-PP. '' The term COP〃 is understood to mean homogeneous or copolymers of C5 to Cl2 cyclic monomers and / or di-cyclic monomers (dimers), which can carry side chains to the full 5 to 30. carbon. In addition to the cyclic monomer, the copolymer usually includes 2 to 95% by weight (preferably 10 to 80% by weight) relative to the cyclic monomer and 5 to 98% by weight (preferably relative to the olefin) 20 to 9 0 -5- (3) 200400212 wt%) C2 to CiG suspected hydrocarbons. The basic cyclic monomer unit may be cyclopentene, cyclohexene, orbornene, dicyclopentadiene, tetracyclododecaene, or methyl tetracyclododecene. It is preferably raw borneol:
雙環[2.2.1]庚-2·烯 最終地，負有可爲線性之側鏈：Bicyclo [2.2.1] heptan-2 · ene Finally, there is a side chain that can be linear:
雙環[2·2·1]庚-2-烯Bicyclo [2 · 2 · 1] hept-2-ene
Rl，R2 ( =CxHY+ 1 而 X，y = 0，1，2， 或環性的，類似二環戊二烯者（其事實上是具有環戊 二烯側鏈之原冰片烯）：Rl, R2 (= CxHY + 1 and X, y = 0,1,2, or cyclic, similar to dicyclopentadiene (which is actually probenbornene with a cyclopentadiene side chain):
烯烴有利地是乙烯。COP有利地是具有或不具有側鏈 之原冰片烯的均一或共聚物；它更爲有利地是原冰片烯之 均聚物（有或沒有側鏈，但較佳有環戊二烯作爲側鏈，亦 即，它較佳是二環戊二烯之均聚物），或原冰片烯（有或 沒有側鏈）及乙烯之共聚物。在後項情況中，乙烯的含量 -6 - (4) (4)200400212 有利地介於3 0至9 5重量％ (較佳地4 0至8 0重量％間） 且原冰片烯含量介於5至70重量％ (較佳地20至60重 量％間）。 依本發明之s— PP可以是丙烯與最多30% C2— 〇8共 單體’較佳地乙烯之均聚物或共聚物。它較佳地是如W0 GG/ 6 1 0 62中所述之經控制結晶性的聚烯烴。它較佳地顯 出少於121°C (依ASTM標準D 1 5 25測得）之軟化點（或 ''維卡點〃），至少在已於合適條件下（其描述於W 0 0 0 / 0 6 1 0 62中，倂入本文作參考）加工後，即使樹脂之生 產者宣稱較高的値。依本發明之s 一 PP因此較佳地顯出有 區別的特徵以致它們的結晶性在加工期間可容易地減低。 在能將經減低之結晶性結合這些s - P P樹脂的範圍內，此 種結晶性簡便的控制在本發明之內容中是有利的，其條件 是使用合適的加工條件，因此增加整個結構的透明性和可 撓性。 依本發明之s — PP的多分散性有利地是少於8且較佳 地是少於4。此特徵反映分子質量之低分散，此增加熔融 溫度範圍和軟化溫度範圍之分離且對加工期間之結晶性可 能有更有效的作用。 再者，所用之s - P P的熔流指數有利地少於1 〇克/ 1 〇分鐘，較佳地少於6克/ 1 0分鐘（依 A S T Μ標準 D1238，在190 °C / 2.16公斤之乙烯聚合物及丁烯共聚物 之條件下且在2 3 0 °C / 2.1 6公斤之丙烯聚合物及丁烯均聚 物之條件下測得）。 -7- (5) (5)200400212 在依本發明之組成物中，S - P P通常以1 %或更多， 或甚至1 0 %或更多（按重量計，與摻合物之總重相比） 之量存在，同時摻合物之COP含量通常是70%或更多’ 或甚至 80%或更多。通常，s-PP以 30%或更少，或甚 至20%或更少之量存在，同時COP以99%或更少，或甚 至90%或更少之量存在。 除了 s — PP及COP樹脂之外，依本發明之組成物可 以包括其它熱塑性聚合物。這些其它的聚合物有利地選自 以下型式之非極結晶性或不定形聚烯烴或烴： 一由至少二種（：2至C1G烯組成之烯烴共聚物，其包 括至少60重量％乙烯及/或丙烯及/或丁烯但不包括多 於90重量％之相同共單體，或來自 -烯烴共聚物，其包括乙烯及/或丙烯及/或丁烯及 1〇至40重量％之一或多種不同共單體，此共單體有利地 選自。5至C1G烯烴〔例如乙烯和1 一辛烯之共聚物、^ 半烯之量使其能具有線性低密度聚乙烯（L L D P E )，極低 密度聚乙烯（VLDPE)或超低密度聚乙烯（ULDPE)〕及 羧酸或酯基，例如乙酸乙烯酯、丙烯酸甲基一、乙基一或 丁基酯及甲基丙酸甲酯或一氧化碳、或來自 -具有苯乙烯一及烯烴嵌段之彈性體共聚物（例如苯 乙烯一丁二烯一苯乙烯、苯乙烯一乙烯一丁烯一苯乙烯、 本乙烯一乙烯-丙烯一苯乙烯型之共聚物或類似者）或來 白The olefin is advantageously ethylene. COP is advantageously a homo- or copolymer of probenbornene with or without side chains; it is more advantageously a homopolymer of pro-norbornene (with or without side chains, but preferably with cyclopentadiene as a side Chain, that is, it is preferably a homopolymer of dicyclopentadiene), or a copolymer of orbornene (with or without side chains) and ethylene. In the latter case, the content of ethylene is -6-(4) (4) 200400212 is advantageously between 30 and 95% by weight (preferably between 40 and 80% by weight) and the original norbornene content is between 5 to 70% by weight (preferably between 20 and 60% by weight). The s-PP according to the present invention may be a homopolymer or copolymer of propylene and up to 30% C2-0 co-monomer ', preferably ethylene. It is preferably a polyolefin with controlled crystallinity as described in WO GG / 6 1 0 62. It preferably exhibits a softening point (or "vica point") of less than 121 ° C (measured in accordance with ASTM standard D 1 5 25), at least under suitable conditions (as described in W 0 0 0 / 0 6 1 0 62, 倂 is incorporated herein by reference) After processing, even the resin producer claims higher 値. The s-PP according to the present invention therefore preferably exhibits distinguishing characteristics so that their crystallinity can be easily reduced during processing. To the extent that reduced crystallinity can be combined with these s-PP resins, such simple control of crystallinity is advantageous in the context of the present invention, provided that appropriate processing conditions are used, thereby increasing the transparency of the entire structure Sex and flexibility. The polydispersity of s-PP according to the invention is advantageously less than 8 and preferably less than 4. This feature reflects the low dispersion of molecular mass, which increases the separation of the melting temperature range and the softening temperature range and may have a more effective effect on the crystallinity during processing. Furthermore, the melt flow index of the s-PP used is advantageously less than 10 g / 10 minutes, preferably less than 6 g / 10 minutes (according to AST M standard D1238, at 190 ° C / 2.16 kg) (Measured under the conditions of ethylene polymer and butene copolymer and at 230 ° C / 2.1 kg of propylene polymer and butene homopolymer). -7- (5) (5) 200400212 In the composition according to the present invention, S-PP is usually 1% or more, or even 10% or more (by weight, the total weight with the blend In comparison), while the COP content of the blend is usually 70% or more 'or even 80% or more. Generally, s-PP is present in an amount of 30% or less, or even 20% or less, while COP is present in an amount of 99% or less, or even 90% or less. In addition to s-PP and COP resins, the composition according to the present invention may include other thermoplastic polymers. These other polymers are advantageously selected from non-polar or amorphous polyolefins or hydrocarbons of the following type:-an olefin copolymer consisting of at least two (2 to C1G olefins) comprising at least 60% by weight ethylene and / Or propylene and / or butene but excluding more than 90% by weight of the same comonomer, or derived from an olefin copolymer, comprising ethylene and / or propylene and / or butene and one of 10 to 40% by weight or A variety of different comonomers, this comonomer is advantageously selected from 5 to C1G olefins [e.g. copolymers of ethylene and 1-octene, ^ halfene in an amount that enables them to have linear low density polyethylene (LLDPE), extremely Low-density polyethylene (VLDPE) or ultra-low-density polyethylene (ULDPE)] and carboxylic acids or ester groups, such as vinyl acetate, methyl mono, ethyl mono or butyl acrylate, and methyl methyl propionate or carbon monoxide Or from-an elastomeric copolymer having styrene- and olefin blocks (eg, styrene-butadiene-styrene, styrene-ethylene-butene-styrene, benzyl-ethylene-propylene-styrene type Copolymer or similar) or to white
一高度分枝之均聚物〔例如，低密度聚乙烯（L D P E (6) 200400212 )或中密度聚乙烯（mdpe)〕 -氫化烴，如石蠟或石蠟油。 有利地’依本發明之組成物另包括至少一種選 燃一乙燃一 丁烯一苯乙烯（SEBS )間之樹脂，最 含苯乙儲一乙烯一丁烯（SEB)、苯乙烯—乙烯一 苯乙嫌（SEPS)，最終地包括苯乙烯—乙烯—丙焊 )及乙烯- 1 一辛烯共聚物（較佳地藉二茂金屬技 。SEBS和/或SEPS是較佳的，因它們使利用膜 密度和可剝離之密封（在較低溫度下）皆可行且因 改良其衝擊強度。這些樹脂之總濃度通常等於或高 (按重量計，相關於總組成物），且較佳地等於 10%。它通常等於或低於29%，較佳地20%。 依本發明之組成物可以容易地加工成任何種類 ’從平坦者（如膜或片）至三維者（如容器），及 層結構或多層者。 在一較佳實體中，本發明係關於一種包括至少 層之膜，該層包含上述組成物。 ''膜〃一詞用來指一薄而平的結構或管狀者（ 膜之情況中），其通常具有1 000微米或更少， 500微米或更少，或甚至250微米或更少的厚度。 ，：100微米或更多之厚度是合適的，或甚至150微 多。 依本發明之膜除了包括基於s— PP和COP之 的基礎者之外尙有至少一其它的層。因C 0 P S對油 自苯乙 終地包 丙烯一 i ( SEP 術製） 之永久 爲它們 於1 % 或局於 之物體 成爲單 一基礎 在吹製 較佳地 實質上 米或更 組成物 脂敏感 (7) 200400212 ，甚至在低量時，如當碰觸或操作它時亦然，依本 膜較佳地包括至少一不包括COP之外層，且較佳 是二個此種外層。在那情況中，這些層安置在基礎 一側上。另外之層較佳地包括至少3 0 %之二茂金 之PP (間規或等規之均一或共聚物，例如與乙烯 經由二茂金屬觸媒技術所得之PP樹脂的選擇改良 構之純度（可卒取及觸媒殘餘之含量）。依本發明 實體，此膜包括至少在基礎層之一側上有一層，此 由二茂金屬技術製之S - PP及/或i一 PP及至少 SEBS、含 SEB 之 SEBS、SEPS、含 SEP 之 SEPS 及 金屬技術製之乙烯一 1-辛烯共聚物間所選之樹脂 上說明之相同理由。這些樹脂之總濃度通常等於 70%。 爲了進一步改良依本發明之膜的密封性，有利 包括至少一外層（密封層），其包括由二茂金屬技 s— PP及/或i— PP;至少一選自 SEBS、含SEB i 、含SEP之SEPS及由二茂金屬技術製之乙烯—1 共聚物間之樹脂；及至少一選自乙烯一乙酸乙烯酯 )、乙烯一丙烯酸甲酯（EMA )、乙烯一丙烯酸 EEA )或乙烯一丙烯酸丁酯（EBA )共聚物間之非 性或不定形聚烯烴。在最後所述之共聚物間，僅那 有至少10%共單體含量者自然地會被考慮作爲另 成成份。這些共聚物的濃度通常等於或高於0.1% 量計，相對於整個組成物），且較佳地高於1 %。 發明之 地甚至 層之每 屬技術 者）。 整個結 之較佳 層包括 一選自 由二茂 ，因如 或低於 地，它 術製之 ：SEBS -辛烯 (EVA 乙酯（ 極結晶 些顯現 外的構 (按重 它通常 •10- (8) (8)200400212 等於或低於1 5 %，較佳地低於1 0 %且最好較佳地低於7 %。EVA和EMA之混合物，較佳地以至少1 %之總量， 或甚至至少5 %，會給予好結果。亦即，這使得具有極再 現性之剝離強度之焊接物可能被製作，而此對於製作具有 可剝離之密封物的項目，如包括永久外部密封物和至少一 可剝離密封物之多室袋或囊是極有用的。 除了上述各層之外，由經濟觀點，令人感興趣地尙可 包括由（依本發明之膜之）碎屑製之層作爲在上述膜中之 內層。 依本發明之膜可藉任何已知之技術被壓紋（亦即可攜 帶浮凸圖形）以防止阻塞。 依本發明之膜可以另外包括一障壁層，此層包括一樹 脂如 E V Ο Η、P A....... 依本發明之膜的較佳結構包括以下各層： 1. 層A (外層）包括至少60%之由二茂金屬技術製之 s — PP及/或i— PP及0至40%之至少一選自SEBS、含 SEB之SEBS、SEPS、含SEP之SEPS及由二茂金屬技術 製之乙烯- 1 -辛烯共聚物所組成群之樹脂。 2. 包括s-PP/COP摻合物之層B (基礎層），該摻 合物包括至少70% COP，至少l%s — PP及〇— 29%之至 少一選白 SEBS、含 SEB 之 SEBS、SEPS、含 SEP 之 SEPS 及藉二茂金屬技術製之乙烯- 1 -辛烯共聚物所組成群之 樹脂。 3. 層C (密封層），其包括至少5 0 %之藉二茂金屬 -11 - (9) (9)200400212 技術製之s— PP及/或i— PP; 0至49%之至少一選自 SEBS、含 SEB 之 SEBS、SEPS、含 SEP 之 SEPS，及藉二 茂金屬技術製之乙烯- 1-辛烯共聚物所組成群之樹脂； 及至少1%之EVA和EMA之混合物， 及一碎屑層在層A及B 1間。 可選擇地，此較有利的膜包括一額外層（B /)於層 B和C之間，此層包括至少3 0重量％之藉二茂金屬技術 製之s— PP及/或i一 PP及0至70重量％之至少一選自 SEBS、含SEB之SEBS、含SEP之SEPS及藉二茂金屬技 術所製之乙烯- 1 -辛烯共聚物所組成群之樹脂。 依本發明之膜極易於焊接且因此極方便地被用來製袋 。因此，本發明也關於由上述之膜所製之袋。較佳地，此 袋是一包括至少一永久外部密封物和至少一可剝離之密封 物之多室袋。永久密封物意指一密封物，其不能用手容易 地剝離且其通常顯出至少200N/ m (依 ASTM/ISD F88)之剝離強度，而可剝離之密封物是一種 密封物’其易於用手剝離且其通常顯出少於2〇〇 ON/ m之 剝離強度。爲要分別得到有所給定之結構的永久及可剝離 之密封物所需之最適合的溫度，壓力及焊接時間可被一般 精於此技藝者使用一些實驗而很容易地決定。通常，永久 及可剝離之密封物使用熱氣或熱工具焊接來製作，而後者 是較佳的。 依本發明之膜及袋可用在任何應用中，其中其可撓性 ，密封性、透明性，對消毒的能力及障壁性是有價値的。 •12- (10) 200400212 醫藥領域是此種應用領域。醫藥領域是此一應用 本發明之袋確貫特別適合用來盛裝醫藥流體，如 液、營養......溶液。因其優越之障壁性質，亦 酸者’依本發明之膜可以焊接入一企圖儲存酸或 如用來淸洗或淸潔某些醫藥設備）之袋中。會給 好之結果的一應用是乙酸在雙室袋中之儲存，是 酸（高達5 0重量％ )和另一者（水）之濃縮溶 藉一可剝離之密封物來分隔，該密封物在用前必 侍到有正確濃度之乙酸ί谷液。依本發明之袋遠比 者能有更長的儲存期限，亦即較少之蒸發發生。 最終，依本發明之聚合物組成物也可利用地 成形之物件中。亦即，它是如此，以致在上述膜 部分應用領域中，後者必須連接至某些種類之設 灌流或滲析設備）且爲要實施此種連接，常使用 之連接部分，這些通常藉噴射成形所製。爲了要 聚合物構成成份之完整系統，且爲要得益於上列 ，這些噴射成形物件有利地包括與上述者相同之 成物。 【實施方式】 實例 在以下實例中： —i—PP 是來自 ATOFINA 之 EOD 9421 級（ D 1 2 3 8 是 5 之 MFI ) 領域。依 滲析、輸 即抗醇及 醇（其例 予相當良 一種含乙 液。雙室 須打破以 先前技藝 用在噴射 和袋之大 備（例如 管或類似 具有相同 之其優點 聚合物組A highly branched homopolymer [for example, low density polyethylene (LDPE (6) 200400212) or medium density polyethylene (mdpe)]-a hydrogenated hydrocarbon such as paraffin or paraffin oil. Advantageously, the composition according to the present invention further comprises at least one resin between selective combustion, ethylene combustion, butene and styrene (SEBS), most containing styrene ethylene storage, ethylene butene (SEB), and styrene-ethylene Styrene (SEPS), which ultimately includes styrene-ethylene-propylene welding, and ethylene-1 octene copolymers (preferably by metallocene technology. SEBS and / or SEPS are preferred because they make The use of film density and peelable seals (at lower temperatures) are both feasible and due to improved impact strength. The total concentration of these resins is usually equal to or higher (relative to the total composition by weight), and preferably equal to 10%. It is usually equal to or lower than 29%, preferably 20%. The composition according to the present invention can be easily processed into any kind of 'from flat (such as film or sheet) to three-dimensional (such as container), and Layer structure or multilayer. In a preferred entity, the present invention relates to a film comprising at least a layer comprising the above composition. The term "membrane" is used to refer to a thin and flat structure or a tube (a membrane Case), which typically has 1 000 microns or less, 500 microns Or less, or even 250 microns or less. Thickness: 100 microns or more is suitable, or even 150 microns or more. The film according to the present invention includes, in addition, foundations based on s-PP and COP. There is at least one other layer outside. Because C 0 PS to oil from styrene is finally covered with propylene-i (SEP technology), it is better for them to be a single base for 1% or local objects. It is better to blow. In fact, rice or the composition is sensitive to lipids (7) 200400212, even at low amounts, such as when touching or operating it. According to this film, it is preferable to include at least one layer that does not include COP, and more preferably Are two such outer layers. In that case, these layers are placed on one side of the foundation. The other layers preferably include at least 30% of the two metallocene PPs (isotactic or isotactic homogeneity or copolymers, such as The choice of PP resin obtained from the metallocene catalyst technology with ethylene improves the purity of the structure (removable and catalyst residue content). According to the entity of the present invention, this film includes at least one layer on one side of the base layer, This is made of S-PP and / or i-PP and up to The same reasons are explained on the selection of resins between SEBS, SEBS with SEB, SEPS, SEPS with SEP, and ethylene-1-octene copolymer made by metal technology. The total concentration of these resins is usually equal to 70%. To further To improve the sealability of the film according to the present invention, it is advantageous to include at least one outer layer (sealing layer), which includes a metallocene s-PP and / or i-PP; at least one selected from SEBS, SEB i, SEP-containing SEPS and resin between ethylene-1 copolymers made by metallocene technology; and at least one selected from ethylene-vinyl acetate), ethylene-methyl acrylate (EMA), ethylene-acrylate EEA), or ethylene-butyl acrylate (EBA) Amorphous or amorphous polyolefins among copolymers. Among the last-mentioned copolymers, only those with at least 10% comonomer content are naturally considered as additional ingredients. The concentration of these copolymers is usually equal to or higher than 0.1% by weight, relative to the entire composition), and preferably higher than 1%. The place of invention and even the layers are each a technologist). The preferred layer of the whole knot consists of one selected from the group consisting of dicene, for example, below or below ground, it is made of: SEBS-octene (EVA ethyl ester (some crystals show some external structure (by weight it is usually • 10- ( 8) (8) 200400212 is equal to or lower than 15%, preferably lower than 10% and most preferably lower than 7%. The mixture of EVA and EMA, preferably in a total amount of at least 1%, Or even at least 5%, it will give good results. That is, this makes it possible to produce welds with extremely reproducible peel strength, which is important for projects that have peelable seals, such as including permanent external seals and A multi-chamber bag or pouch with at least one peelable seal is extremely useful. In addition to the above layers, it may be interesting from an economic point of view to include a layer made of debris (in accordance with the film of the present invention) as a layer The inner layer in the above film. The film according to the present invention can be embossed (that is, it can carry an embossed pattern) to prevent blocking by any known technique. The film according to the present invention may further include a barrier layer, this layer includes A resin such as EV 〇 Η, P A ....... The preferred structure of the film according to the present invention It includes the following layers: 1. Layer A (outer layer) includes at least 60% of s-PP and / or i-PP made from metallocene technology and at least one of 0 to 40% selected from SEBS, SEBS with SEB, SEPS , SEP-containing SEPS and resins composed of ethylene-1-octene copolymer made of metallocene technology 2. Layer B (base layer) including s-PP / COP blend, the blend Including at least 70% COP, at least 1% s—PP and 0—29% of at least one white SEBS, SEBS with SEB, SEPS, SEPS with SEP, and ethylene- 1-octene copolymerization by metallocene technology Resin composed of materials. 3. Layer C (sealing layer), which includes at least 50% of s-PP and / or i-PP made by the technique of borrowing from a metallocene-11-(9) (9) 200400212; 0 to 49% of at least one resin selected from the group consisting of SEBS, SEBS with SEB, SEPS, SEPS with SEP, and ethylene- 1-octene copolymer made by metallocene technology; and at least 1% A mixture of EVA and EMA, and a chip layer between layers A and B 1. Optionally, this more advantageous film includes an additional layer (B /) between layers B and C, this layer comprising at least 30 Weight percent of two S—PP and / or i-PP made from metallocene technology and at least one of 0 to 70% by weight is selected from SEBS, SEBS containing SEB, SEPS containing SEP, and ethylene produced by metallocene technology-1-Sin Resin composed of olefin copolymers. The film according to the present invention is extremely easy to weld and is therefore very convenient for making bags. Therefore, the present invention also relates to a bag made of the above-mentioned film. Preferably, the bag is a multi-chamber bag comprising at least one permanent outer seal and at least one peelable seal. Permanent seal means a seal that cannot be easily peeled off by hand and usually exhibits a peel strength of at least 200 N / m (according to ASTM / ISD F88), while a peelable seal is a seal 'it is easy to use It is peeled by hand and it usually shows a peel strength of less than 2000 ON / m. In order to obtain the most suitable temperatures required for the permanent and peelable seals of a given structure, respectively, the pressure and welding time can be easily determined by a person skilled in the art using some experiments. Generally, permanent and peelable seals are made using hot air or hot tool welding, with the latter being preferred. The film and bag according to the present invention can be used in any application, among which flexibility, sealability, transparency, ability to sterilize and barrier properties are valuable. • 12- (10) 200400212 The medical field is one such application. This is the application in the medical field. The bag of the present invention is indeed particularly suitable for containing medicinal fluids, such as liquids, nutrients ... solutions. Because of its superior barrier properties, the film according to the present invention can be welded into a bag that attempts to store acid or, for example, to rinse or clean certain medical equipment. One application that will give good results is the storage of acetic acid in a dual-chamber bag, which is a concentrated solution of acid (up to 50% by weight) and the other (water) separated by a peelable seal, the seal Before use, you must wait for the correct concentration of acetic acid. The bag according to the present invention has a much longer shelf life, i.e. less evaporation occurs. Finally, the polymer composition according to the present invention can also be used in shaped articles. That is, it is such that, in the application area of the above-mentioned membrane part, the latter must be connected to some kind of perfusion or dialysis equipment) and in order to carry out such a connection, the commonly used connection part, these are usually by spray forming system. In order to have a complete system of polymer constituents, and to benefit from the above, these spray-formed articles advantageously include the same products as those described above. [Embodiment] Examples In the following examples: -i-PP is an EOD 9421 grade (D 1 2 3 8 is 5 MFI) from ATOFINA. It is resistant to alcohol and alcohol according to dialysis, infusion (for example, it is quite a kind of liquid containing B. The double chamber must be broken by the previous technique used in spraying and bag preparation (such as tubes or similar) which have the same advantages as the polymer group.
依 ASTM -13- (11) 200400212 -SEBS 是來自 SHELL 之 KRATON ® G 1657 級 一 EVA 和 EMA 是來自 ATOFINA 之 UL 002 1 8 及 16 MA03級（約3之MFI及約18% VA或ΜΑ ) —COP 是來自 TICONA 之 TOPAS ® 8007 級（30 之 MFI(ISO 1133，2 60〇C，2.16 公斤）） -濁度和透明度（=總發光透射比）已依 AS TM D 1003 — 00 來測量 -膜使用一平模及送料阻斷，藉共擠出而製作，每~ 層有其本身之獨立的單一螺旋擠出機（直徑60及45毫米 及25D之桶長度）。 在模送料阻斷及應接器上溫度設定約220 °C。筒上自 入口至出口約溫度設定是160至210/220 °C。 -袋藉著在以下條件下熱工具焊接這些膜而製成：溫 度=14 2 °C，壓力=6巴，時間=1.3秒。 比較實例1 : 包括以下各層之有可剝離密封物特性之多層膜被共擠 出： 層A (外層）=i— PP(90重量％)及SEBS(l〇重量 %之摻合物。 層 B1 : i— pp ( 1〇〇 重量 ％ ) 層B2:i—pp共聚物（75重量％) ，SEBS(22重量 % ) ，EVA ( 2重量％ )及EMA ( 1重量％ )之摻合物。 膜之總厚度是200微米，而層B1是40微米。其濁度 -14- (12) 200400212 是4%而其透明度是96%。 比較實例2 與比較實例1相同，除了層B1由COP ( 100重量％ )製之外。膜之總厚度是200微米，而層B1是40微米。 其濁度是5%而其透明度是95.5%。 實例3 :依本發明之膜 與比較實例1相同，除了層B1是由COP ( 85重量％ )和s - PP ( 1 5重量％ )之摻合物製之外。 膜總厚度共200微米，而層B1是40微米。其濁度是 6.2%且其透明度是95%。 蒸汽消毒和滴測試： 1 〇個袋分別由比較實例2和實例3之膜製得且塡充 以3升的水；每一系列之5個被蒸汽消毒（1 2 It / 2 5 0 °F ，3 0分鐘）。在蒸汽消毒後，由比較實例2所製之袋顯 出剝離。依本發明之袋（實例3 )不顯出剝離。經消毒和 未經消毒之二樣品的滴測試顯示依本發明之袋克服在平均 地板上2公尺高之滴測試，但比較實例2所製之袋不能克 服此測試。 含水乙酸儲存： 依比較實例1之膜所製之袋和依實例3之膜所製之袋 -15- (13) 200400212 塡充以50毫升之具有不同乙酸百分比（0、24、48、74、 96% )的水溶液。所有袋之總表面積是150公分2。袋在 2 3 °C及4 Ot：下儲存135天。結果（對2樣品之平均）在 表1中給予。 ' 表1 ··在1 3 5天儲存後來自水和乙酸之混合物在23 t及在 4 0°C下重量損失，單位爲公克 2 3°C_23 °C 4 0°C 4 0°C % HAc 比較實例1 實例3 比較實例1 實例3 0 -0,298 -0,244 -3,66 -2,851 0 -0,302 -0,3 17 -3,772 -3,333 24 -0,26 -0,208 -3,521 -2,49 -2,965 24 -0,281 -0,235 -3,521 48 -0,263 -0,168 -4,136 -2,296 48 -0,265 -0，198 -4,143 -2,54 74 -0,271 -0,098 -5,075 -1,614 74 -0,289 -0,116 -5,292 -1,91 96 -0,402 0,114 -9,862 -0,188 96 -0,46 0，146 -10,327 -0,171According to ASTM -13- (11) 200400212-SEBS is KRATON ® G 1657 grade from SHELL-EVA and EMA are UL 002 1 8 and 16 MA03 grade from ATOFINA (approximately 3 MFI and approximately 18% VA or MA) — COP is TOPAS ® 8007 grade (MFI 30 (ISO 1133, 2 60 ° C, 2.16 kg)) from TICONA-turbidity and transparency (= total luminous transmittance) have been measured in accordance with AS TM D 1003-00-film A flat die and feed block are used to make it by co-extrusion. Each layer has its own independent single screw extruder (60 and 45 mm diameter and barrel length of 25D). Set the temperature on the die feed block and the adaptor to about 220 ° C. The temperature setting from the inlet to the outlet of the cartridge is 160 to 210/220 ° C. -The bag is made by welding these films with hot tools under the following conditions: temperature = 14 2 ° C, pressure = 6 bar, time = 1.3 seconds. Comparative Example 1: A multilayer film having peelable sealant characteristics including the following layers was coextruded: Layer A (outer layer) = i-PP (90% by weight) and SEBS (10% by weight blend. Layer B1 : i-pp (100% by weight) layer B2: a blend of i-pp copolymer (75% by weight), SEBS (22% by weight), EVA (2% by weight), and EMA (1% by weight). The total thickness of the film is 200 micrometers and layer B1 is 40 micrometers. Its turbidity -14- (12) 200400212 is 4% and its transparency is 96%. Comparative Example 2 is the same as Comparative Example 1, except that layer B1 is composed of COP ( 100% by weight). The total thickness of the film is 200 microns and the layer B1 is 40 microns. Its turbidity is 5% and its transparency is 95.5%. Example 3: The film according to the present invention is the same as Comparative Example 1, Except that layer B1 is made of a blend of COP (85% by weight) and s-PP (15% by weight). The total thickness of the film is 200 microns, while layer B1 is 40 microns. Its turbidity is 6.2% and Its transparency is 95%. Steam sterilization and drip test: 10 bags were made from the films of Comparative Examples 2 and 3 and filled with 3 liters of water; 5 of each series were steam sterilized (1 2 It / 2 50 ° F, 30 minutes). After steam sterilization, the bag made from Comparative Example 2 showed peeling. The bag according to the present invention (Example 3) did not show peeling. Both sterilized and unsterilized samples The drop test showed that the bag according to the present invention overcomes the drop test of 2 meters high on the average floor, but the bag made in Comparative Example 2 cannot overcome this test. Aqueous acetic acid storage: The bag made according to the film of Comparative Example 1 and Bag made from the film of Example 15- (13) 200400212 Filled with 50 ml of an aqueous solution with different percentages of acetic acid (0, 24, 48, 74, 96%). The total surface area of all bags is 150 cm 2 .Bags are stored at 2 3 ° C and 4 Ot: 135 days. Results (average of 2 samples) are given in Table 1. 'Table 1 ····················································································· the mixture from water and acetic acid after storage at 135 days at 23 t and weight loss at 40 ° C in grams 2 3 ° C_23 ° C 4 0 ° C 4 0 ° C% HAc Comparative Example 1 Example 3 Comparative Example 1 Example 3 0 -0,298 -0,244 -3,66- 2,851 0 -0,302 -0,3 17 -3,772 -3,333 24 -0,26 -0,208 -3,521 -2,49 -2,965 24 -0,281 -0,235 -3,521 48 -0,263 -0,168 -4,136 -2,296 48 -0,265 -0,198 -4,143 -2,54 74 -0,271 -0,098 -5,075 -1,614 74 -0,289 -0,116 -5,292 -1,91 96 -0,402 0,114 -9,862 -0,188 96 -0,46 0,146- 10,327 -0,171
% HAc =在溶液中乙酸之重量百分比。 如表1中之結果可見的，依本發明所製之袋/膜/組 成物顯出明顯更低的重量損失。因此，有較少乙酸滲出且 因此較少氣味。 •16- (14) 200400212 機械性： 依比較實例2之膜顯出在破裂時50%之應變且依實例3 者顯出在破裂時1 50%之應變且當與依比較實例2之膜比較 時減低70 MPa之彈性模數（依ASTM D - 822/ISO 178/ DIN 5 3457 )。此指明依本發明所製之袋/膜/組成物比先 前技藝者更可撓。 -17-% HAc = weight percent of acetic acid in solution. As can be seen from the results in Table 1, the bags / films / compositions made according to the present invention show significantly lower weight loss. Therefore, there is less exudation of acetic acid and therefore less odor. • 16- (14) 200400212 Mechanical properties: The film according to Comparative Example 2 showed a strain of 50% upon rupture and according to Example 3 showed a strain of 150% upon rupture and when compared with the film according to Comparative Example 2 Reduce the elastic modulus of 70 MPa (according to ASTM D-822 / ISO 178 / DIN 5 3457). This indicates that bags / films / compositions made in accordance with the present invention are more flexible than those of prior art. -17-
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0204644A FR2839976B1 (en) | 2002-05-21 | 2002-05-21 | POLYMER COMPOSITION COMPRISING A OLEFINIC CYCLIC COPOLYMER |
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| TW200400212A true TW200400212A (en) | 2004-01-01 |
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| TW092113240A TW200400212A (en) | 2002-05-21 | 2003-05-15 | Polymer composition including a cyclic olefin copolymer |
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| US (1) | US20050238830A1 (en) |
| EP (1) | EP1509569A1 (en) |
| JP (1) | JP4209384B2 (en) |
| KR (1) | KR100933434B1 (en) |
| CN (1) | CN1303148C (en) |
| AU (1) | AU2003232758A1 (en) |
| FR (1) | FR2839976B1 (en) |
| TW (1) | TW200400212A (en) |
| WO (1) | WO2003097739A1 (en) |
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| DE602005007468D1 (en) * | 2004-01-30 | 2008-07-24 | Renolit Ag | SYNDICOTACTIC POLYPROPYLENE COMPOSITION COMPRISING A THERMOPLASTIC ELASTOMER |
| EP1758736A4 (en) * | 2004-06-24 | 2007-08-29 | Pliant Corp | Multi-layer polyolefin film |
| JP4803351B2 (en) * | 2004-09-21 | 2011-10-26 | 日本ゼオン株式会社 | Multilayer film and package comprising resin composition layer and polypropylene resin composition layer containing alicyclic structure-containing polymer |
| JP4692086B2 (en) * | 2004-10-29 | 2011-06-01 | 日本ゼオン株式会社 | Multilayer film and package comprising resin composition layer and polypropylene resin composition layer containing alicyclic structure-containing polymer |
| BRPI0606180A2 (en) * | 2005-02-23 | 2009-06-02 | Topas Advanced Polymers Inc | multilayer films including cycloolefin copolymer and styrene butadiene copolymer |
| US20070026173A1 (en) * | 2005-07-27 | 2007-02-01 | Owens-Illinois Healthcare Packaging Inc. | Multilayer containers and methods of manufacture |
| DE102006023301A1 (en) * | 2006-05-18 | 2008-02-28 | Raumedic Ag | Medical work equipment, medical assembly with such work equipment and use of such a medical work equipment |
| EP2223689B1 (en) | 2007-11-22 | 2014-04-02 | Mitsubishi Tanabe Pharma Corporation | Plastic container having cyclic polyolefin layer |
| US7736723B2 (en) * | 2007-12-03 | 2010-06-15 | Applied Extrusion Technologies, Inc. | Holographic films employing cycloolefin copolymers |
| JP5139140B2 (en) * | 2008-04-11 | 2013-02-06 | 積水化成品工業株式会社 | Polyolefin resin sheet |
| DE102008058272A1 (en) * | 2008-11-20 | 2010-05-27 | Fresenius Medical Care Deutschland Gmbh | Disposable bag comprising a multilayer film |
| US8863967B2 (en) * | 2009-01-06 | 2014-10-21 | Fujimori Kogyo Co., Ltd. | Pouring port, method for producing same and container for liquid provided with the pouring port |
| JP5411008B2 (en) * | 2010-01-22 | 2014-02-12 | シーアイ化成株式会社 | Laminated film and packaging container produced using the laminated film |
| CN102452205A (en) * | 2010-11-03 | 2012-05-16 | 上海富森实业有限公司 | Straight-line easily-torn thin film |
| CN102731954A (en) * | 2011-04-15 | 2012-10-17 | 烟台百特塑化制品有限公司 | Preparation method of SEBS nano saddle zipper preservative film bag |
| CN102602094B (en) * | 2012-02-24 | 2014-12-17 | 常州大学 | Novel multilayer co-extrusion medical transfusion film and preparation method thereof |
| JP5910196B2 (en) * | 2012-03-14 | 2016-04-27 | 東レ株式会社 | Film and laminated sheet using the same |
| EP2930211B1 (en) * | 2012-12-05 | 2020-10-07 | Zeon Corporation | Resin composition and medical drug container using same |
| WO2017223276A1 (en) * | 2016-06-24 | 2017-12-28 | Polyone Corporation | Coc polymer compounds for 3d printing |
| CN106433001A (en) * | 2016-09-27 | 2017-02-22 | 吕江鹏 | Cycloolefin copolymer and modified polyolefin composite watertight soft package material and preparation method and application thereof |
| CN110218361B (en) * | 2016-12-13 | 2021-02-23 | 福建鑫邦新材料科技有限公司 | Preparation method of modified starch antibacterial agent, antibacterial high-barrier polypropylene color master batch for hygienic product packaging material and preparation method thereof |
| JP7338953B2 (en) * | 2018-03-30 | 2023-09-05 | 大日本印刷株式会社 | Sealing material sheet for self-luminous display and self-luminous display using the same |
| CN109721828A (en) * | 2018-11-23 | 2019-05-07 | 金旸（厦门）新材料科技有限公司 | A kind of high heat resistance and cold-resistant high-gloss metal texture are exempted to spray PP material and preparation method thereof |
| CN112646258B (en) * | 2019-10-12 | 2023-01-03 | 中国石油化工股份有限公司 | High-barrier polyethylene composition, preparation method thereof, polyethylene film and application |
| CN111452471B (en) * | 2020-05-19 | 2022-04-29 | 崇州君健塑胶有限公司 | Membrane material for transfusion |
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| CN1022111C (en) * | 1988-04-06 | 1993-09-15 | 三井石油化学工业株式会社 | Cycloolefin type random copolymer compositions |
| JP2933497B2 (en) * | 1994-06-24 | 1999-08-16 | 株式会社トクヤマ | Polypropylene resin composition |
| US6042906A (en) * | 1996-08-12 | 2000-03-28 | Toyo Seikan Kaisha, Ltd. | Flavor-retaining plastic multi-layer container |
| US6051305A (en) * | 1997-01-22 | 2000-04-18 | Cryovac, Inc. | Printed polymeric film and process for making same |
| US6541123B1 (en) * | 1998-05-29 | 2003-04-01 | Mitsubishi Plastics, Inc. | Polyolefin film for stretch packaging |
| BE1012589A3 (en) * | 1999-04-08 | 2000-12-05 | Solvay | Thermoplastic multi-structure. |
| US7193013B2 (en) * | 2001-02-07 | 2007-03-20 | Idemitsu Kosan Co. Ltd. | Polyolefin resin composition |
-
2002
- 2002-05-21 FR FR0204644A patent/FR2839976B1/en not_active Expired - Fee Related
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2003
- 2003-05-12 AU AU2003232758A patent/AU2003232758A1/en not_active Abandoned
- 2003-05-12 JP JP2004506407A patent/JP4209384B2/en not_active Expired - Fee Related
- 2003-05-12 US US10/515,061 patent/US20050238830A1/en not_active Abandoned
- 2003-05-12 EP EP03752732A patent/EP1509569A1/en not_active Withdrawn
- 2003-05-12 KR KR1020047018695A patent/KR100933434B1/en not_active IP Right Cessation
- 2003-05-12 WO PCT/EP2003/004953 patent/WO2003097739A1/en active Application Filing
- 2003-05-12 CN CNB038113856A patent/CN1303148C/en not_active Expired - Fee Related
- 2003-05-15 TW TW092113240A patent/TW200400212A/en unknown
Also Published As
| Publication number | Publication date |
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| CN1653129A (en) | 2005-08-10 |
| WO2003097739A1 (en) | 2003-11-27 |
| EP1509569A1 (en) | 2005-03-02 |
| FR2839976B1 (en) | 2004-07-30 |
| JP4209384B2 (en) | 2009-01-14 |
| KR20040111654A (en) | 2004-12-31 |
| KR100933434B1 (en) | 2009-12-23 |
| US20050238830A1 (en) | 2005-10-27 |
| CN1303148C (en) | 2007-03-07 |
| JP2005526162A (en) | 2005-09-02 |
| FR2839976A1 (en) | 2003-11-28 |
| AU2003232758A1 (en) | 2003-12-02 |
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