TW200416134A

TW200416134A - Multilayered structure and packing body

Info

Publication number: TW200416134A
Application number: TW092136264A
Authority: TW
Inventors: Toyokazu Yamada; Hitoshi Itaya; Yosuke Arai
Original assignee: Idemitsu Unitech Co Ltd
Priority date: 2002-12-20
Filing date: 2003-12-19
Publication date: 2004-09-01
Also published as: CN1509867A; KR20040055651A

Abstract

Disclosed is a multilayered structure, having a backing material layer consisting of polystyrene resin of 25-75% by weight, polyolefine resin of 75-25 % by weigh, connection aromatic vinyl content of 30-80% by weight, saturated with double bond conjugate diene by the hydrogen of 35% or more, wherein the polystyrene resin and the polyolefine resin together constitute 1-20 weight portion of 100 weight, an intermediate layer consisting of a polymer solution of aromatic vinyl and conjugate diene, and a surface layer consisting of polyolefine resin. The multilayered structure is oil-resistant, has a packing body and is superior in recycling characteristics.

Description

200416134 Π) 玫、發明說明【發明所屬之技術領域】本發明係有關主要由聚苯乙烯系樹脂所成之多層構造物及其用途。特別適用於食品或醫療品之容器、蓋、包裝材料等之包裝體之聚苯乙燦系樹脂多層構造物及使用其之包裝體。【先前技術】200416134 Π) Description of the invention [Technical field to which the invention belongs] The present invention relates to a multilayer structure mainly made of polystyrene resin and its use. It is especially suitable for the polystyrene-based resin multilayer structure of packaging bodies such as containers for food or medical products, lids, packaging materials and the like, and packaging bodies using the same. [Prior art]

聚苯乙稀系樹脂薄片因其熱成形性及剛性，使用於多數之食品容器等之包裝材料。又，相對於由樹脂薄片所成形之容器之蓋材’爲減少容器中殘留之氧氣，而使用成形之鎖蓋。食品或醫藥品大部份爲加熱殺菌、消毒後包裝者，聚苯乙烯系統之包裝材料亦無問題。Polystyrene resin sheets are used for packaging materials such as most food containers because of their thermoformability and rigidity. In addition, a lid material for a container formed of a resin sheet is used to reduce the amount of oxygen remaining in the container, and a formed lock cap is used. Most food or pharmaceutical products are packaged after heat sterilization and disinfection, and there is no problem with the packaging material of the polystyrene system.

但是，近年，爲防止由異物混入食品、〇 -1 5 7等食物中毒、院內感染等，高度要求食品或醫藥品之安全性。聚本乙嫌系樹脂之包裝材料於包裝後加熱殺菌、消毒、高溫下包裝時，耐油性、耐藥品性、耐熱性差，被要求改善。又，近年，由於微波爐普及化，.提出食品於包裝之情形下直接加熱之形態’極需提昇包裝材料之耐熱性、耐油性。又，鎖蓋由外部熱封時，加熱側與融合側之樹脂融點相同時，於可融合之溫度時，加熱側之溶融成爲外觀不良。又，檢討使用較加熱側樹脂低融點之樹脂爲融合側樹脂，以謀求封口性及外觀兩全，一般低融點之樹脂剛性低， -5- (2) (2)200416134 作爲成形蓋剛性不足，爲不易作業者。一般，聚苯乙烯系樹脂薄片剛性、熱成形性優，耐藥品性、耐熱性差。與聚烯烴系容器有不能熱封之問題’要求開發可與聚烯烴系可熱封者，無外觀不良，剛性、熱成形優之熱成形鎖蓋用薄片。一方面，聚烯烴系樹脂薄片爲耐油性、耐藥品性、耐熱性優，熱成形性、剛性則不及聚苯乙烯系樹脂薄片。活用聚苯乙烯系樹脂薄片之剛性、熱成形性，提高耐油性、耐熱性、熱封性之手法，已檢討於聚苯乙烯混合聚烯烴或相溶化。但是，與內容物之接觸面存在聚苯乙烯時，由於油的滲透產生強度之下降，有殘留單體類轉移至內容物之問題（如日本特開平1 0 -1 1 9 1 9 9號公報，日本特開平1-235793號公報、日本特開2000-52505號公報、日本特開2000-26679號公報），又，單單混合或相溶化，由於加熱側與融合側之樹脂融點無差異，以可融合之溫度熱封時，不能解決加熱部份溶融之外觀不良問題。爲持有耐油性、耐熱性之其他的方法，或加熱側樹脂與融合側樹脂之融點差，亦檢討以聚烯烴共聚壓法之層合方法。接合聚苯乙烯與聚烯烴之技術，有使用乙烯-醋酸乙烯共聚物（EVA)系接合劑，苯乙烯-丁二烯系共聚物，苯乙烯-異戊二烯系共聚物等之接合層的方法。但是，一般進行薄片製造時之回收因混入異種材料，性能下降，因回收之熱履歷等接合層之成分劣化，因膠凝化之外觀不良等於實用上有困難（參閱日本特開昭58-197049號公報 (3) 200416134However, in recent years, in order to prevent food from being mixed with foreign substances, food poisoning such as 0-57, hospital infections, etc., the safety of food or pharmaceuticals is highly required. The packaging materials of polyethylene resins are poor in oil resistance, chemical resistance, and heat resistance when they are heat-sterilized, sterilized, and packaged at high temperatures after packaging, and they are required to be improved. Also, in recent years, as microwave ovens become popular, it has been proposed that the form of direct heating of food in the case of packaging 'is highly required to improve the heat resistance and oil resistance of packaging materials. In addition, when the lock cover is heat-sealed from the outside, when the melting point of the resin on the heating side and the fusion side is the same, the melting on the heating side becomes a poor appearance at the fusionable temperature. In addition, it is reviewed to use a resin with a lower melting point than the resin on the heating side as the fusion side resin in order to achieve both sealing and appearance. Generally, the resin with a low melting point has low rigidity. -5- (2) (2) 200416134 as the rigidity of the forming cap Insufficient, difficult to operate. Generally, polystyrene-based resin sheets have excellent rigidity, thermoformability, and poor chemical resistance and heat resistance. There is a problem that it cannot be heat-sealed with a polyolefin-based container ', and it is required to develop a sheet that can be heat-sealable with a polyolefin-based heat-resistant, non-defective appearance, and excellent in rigidity and thermoformability. On the one hand, polyolefin resin sheets are excellent in oil resistance, chemical resistance, and heat resistance, but are not as good in thermoformability and rigidity as polystyrene resin sheets. Using the rigidity and thermoformability of polystyrene resin sheets to improve oil resistance, heat resistance, and heat-sealability, we have reviewed the use of polystyrene blended with polyolefins or dissolved. However, when polystyrene is present on the contact surface with the content, there is a problem that the residual monomers are transferred to the content due to the decrease in strength due to the penetration of the oil (for example, Japanese Patent Laid-Open No. 1 0 -1 1 9 1 9 9 (Japanese Patent Application Laid-Open No. 1-235793, Japanese Patent Application Laid-Open No. 2000-52505, Japanese Patent Application Laid-Open No. 2000-26679), and simply mixing or dissolving, because there is no difference in the melting point of the resin on the heating side and the fusion side, When heat-sealed at a fusion temperature, the problem of poor appearance due to the melting of the heated part cannot be solved. In order to hold other methods of oil resistance and heat resistance, or the difference in melting point between the heating-side resin and the fusion-side resin, the lamination method by the polyolefin copolymerization method was also reviewed. Techniques for joining polystyrene and polyolefin include bonding layers using ethylene-vinyl acetate copolymer (EVA) -based adhesives, styrene-butadiene-based copolymers, and styrene-isoprene-based copolymers. method. However, in general, during the manufacture of flakes, the performance is reduced due to the mixing of different materials, the components of the bonding layer such as the recovered thermal history are deteriorated, and the appearance of gelation is not equal to practical difficulties (see Japanese Patent Application Laid-Open No. 58-197049 Bulletin (3) 200416134

一方面’亦有接合聚丙烯薄膜之方法，由於聚丙烯不能與聚苯乙烯直接熱接合，須介以接合性樹脂、故須接合劑。但是’作爲接合性樹脂或接合劑之乙烯-醋酸乙烯共聚物組成物爲得到充分之層間強度醋酸乙烯含量以較高者爲理想’但回收時有膠凝化等之問題，爲控制膠凝化降低醋酸乙烯之含量時有層間強度不充足之問題。亦有以乙烯多元共聚物或接枝變性聚烯烴聚合物爲接合樹脂之方法，因價位高不泛用（參閱日本特開平09-290492號公報）。本發明有鑑於上述課題，以提供耐油性、熱封性、回收性優之聚苯乙烯系多層構造物及包裝體爲目的。本發明者等深入硏究結果，介以由聚苯乙烯系樹脂、聚烯烴系樹脂及相溶化劑所成之中間層或接合層，取代接合樹脂或接合劑，於聚苯乙烯系樹脂樹形成聚烯烴系樹脂層，發現得到優特性之多層構造物，完成本發明。On the one hand, there is also a method for bonding polypropylene films. Since polypropylene cannot be directly thermally bonded to polystyrene, a bonding resin must be used, so a bonding agent is required. However, "the ethylene-vinyl acetate copolymer composition as a bonding resin or a bonding agent is preferably one having a high vinyl acetate content with sufficient interlaminar strength." However, there are problems such as gelation during recovery. There is a problem of insufficient interlayer strength when reducing the content of vinyl acetate. There is also a method using an ethylene multipolymer or a graft-denatured polyolefin polymer as a bonding resin, which is not widely used due to its high price (see Japanese Patent Application Laid-Open No. 09-290492). The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a polystyrene-based multilayer structure and a package having excellent oil resistance, heat-sealing properties, and recyclability. The inventors have intensively researched the results, and replaced the bonding resin or the bonding agent with an intermediate layer or a bonding layer made of a polystyrene-based resin, a polyolefin-based resin, and a compatibilizing agent to form a polystyrene-based resin tree. A polyolefin-based resin layer was found to have a multilayer structure with excellent characteristics, and completed the present invention.

【發明內容】〔發明之揭示〕依本發明可提供以下之多層構造物及由多層構成物所形成之容器、蓋、包裝體。〔1〕基材層由聚苯乙烯系樹脂所成，介著中間層形成有聚烯烴系樹脂所成表面層，該中間層係由聚苯乙烯系樹脂25〜75重量份與聚烯烴 75〜25重量份，及結合芳香族乙烯含有量爲30〜80重量份 -7- (4) 200416134 所成，該中間層係上述聚苯乙烯系樹脂與聚烯烴系樹脂合倂 1 0 0重量份而言，配合1〜2 〇重量份相溶化劑，該相溶化劑，係根據共軛二烯之雙鍵3 5 %以上由氫飽和’芳香族乙烯與共軛二烯之嵌段共聚物所成者。〔2〕基材層由聚苯乙烯系樹脂與聚烯烴系樹脂所成[Summary of the Invention] [Disclosure of the Invention] According to the present invention, the following multilayer structures and containers, lids, and packages formed from the multilayer structures can be provided. [1] The base material layer is made of polystyrene resin, and a surface layer made of polyolefin resin is formed through an intermediate layer. The intermediate layer is made of 25 to 75 parts by weight of polystyrene resin and 75 to 55 parts by weight of polyolefin. 25 parts by weight and a combined aromatic ethylene content of 30 to 80 parts by weight-7- (4) 200416134, the intermediate layer is a combination of 100 parts by weight of the polystyrene resin and a polyolefin resin In other words, 1 to 20 parts by weight of a compatibilizing agent is blended, and the compatibilizing agent is formed by a hydrogen-saturated 'aromatic ethylene and conjugated diene block copolymer based on more than 35% of the double bonds of the conjugated diene. By. [2] The base material layer is made of polystyrene resin and polyolefin resin

介著中間層形成有聚烯烴系樹脂所成表面層，該中間層係由聚苯乙烯系樹脂2 5〜7 5重量份與聚烯烴 75〜25重量份，及結合芳香族乙烯含有量爲30〜8〇重量份所成相溶化劑，該相溶化劑，係根據共軛二烯之雙鍵3 5 %以上由氫飽和，芳香族乙烯與共軛二烯之嵌段共聚物所成者。〔3〕基材層由聚苯乙烯系樹脂所成，A surface layer made of a polyolefin-based resin is formed through the intermediate layer. The intermediate layer is composed of polystyrene-based resin 2 5 to 75 parts by weight and polyolefin 25 to 25 parts by weight, and the combined aromatic ethylene content is 30. ~ 80 parts by weight of the compatibilizer formed by the block copolymer of aromatic vinyl and conjugated diene based on the conjugated diene's double bond by more than 35% by hydrogen saturation. [3] The base material layer is made of polystyrene resin,

介著接合層形成有聚乙烯系樹脂所成之第一表面層，及由聚丙烯系樹脂所成之第二表面層，該接合層係由聚苯乙烯系樹脂、聚丙烯系樹脂及相溶化劑所成之多層構造物。〔4〕基材層由聚苯乙烯系樹脂所成，介著接合層形成有聚乙烯系樹脂所成之第一表面層，及由聚苯乙烯系樹脂、聚丙烯系樹脂及相溶化劑所成之第二表面層，接合層係由聚苯乙烯系樹脂、聚丙烯系樹脂及相溶化劑所成之多層構造物。 -8- (5) (5)200416134 〔5〕基材層由聚苯乙烯系樹脂所成、介著中間層形成有聚乙烯系樹脂所成之第一表面層’ 及聚丙烯系樹脂所成之第二表面層， s亥中間層，係由聚苯乙嫌系樹脂2 5〜7 5重量份及聚丙烯75〜25重量份，及結合芳香族乙烯基含量爲30〜80重量份所成，該中間層，係上述聚苯乙烯系樹脂及聚丙烯系樹脂合倂1 0 0重量份而言，配合有i〜2 0重量份相溶化劑，該相溶化劑，係根據共軛二烯之雙鍵35%以上由氫元素飽和’由芳香族乙烯及共軛二烯之嵌段共聚物所成之多餍構造物。〔6〕基材層由聚苯乙烯系樹脂所成、藉由接合層形成有第一表面層及第二表面層，該接合層，係由聚苯乙烯系樹脂25〜75重量份及聚丙烯75〜2 5重量份，及結合芳香族乙烯基含量爲3〇〜80重量份所成，該接合層係，上述聚苯乙烯系樹脂及上述聚丙烯系樹脂合倂1 〇〇重量份而言，配合1〜2 0重量份相溶化劑，該相溶化劑，係根據共軛二烯之雙鍵3 5 %以上由氫元素飽和’由芳香族乙烯及共軛二烯之嵌段共聚物所成者，該第一表面層，係由聚乙烯系樹脂所成，該第二表面層，係聚苯乙烯系樹脂25〜75重量份及聚丙烯75〜25重量份，及結合芳香族乙烯基含量爲3〇〜8〇重量份所成’ -9- (6) (6)200416134 該第二表面層係，上述聚苯乙烯系樹脂及上述聚丙烯系樹脂合倂100重量份而言，配合1〜20重量份相溶化劑該相溶化劑，係根據共軛二烯之雙鍵35%以上由氫元素飽和’由芳香族乙烯及共軛二烯之嵌段共聚物所成之多層構造物。〔7〕如第3或4項之多層構造物，其中上述接合層及/或第二表面層之相溶化劑爲，芳香族乙烯基與共軛二烯之嵌段共聚物之氫添加物者。〔8〕如第1或2項之多層構造物，其中上述表面層之聚烯烴系樹脂爲聚丙烯樹脂者。〔9〕上述相溶化劑之玻璃轉移溫度爲-60 °C以下之如〔1〕〜〔8〕中之任一項之多層構造物。〔1 〇〕上述表面層之內容物側係由如〔1〕、〔 2〕、〔8〕或〔9〕中之任一項所記載之多層構造物所成之容器、蓋、包裝體。〔1 1〕上述表面層之內容物側係由如〔3〕〜〔7〕、〔9〕中之任一項所記載之多層構造物所成之容器、蓋、包裝體。〔用以實施發明之最佳型態〕以下詳細說明本發明。〔第一多層構造物〕 -10- (7) (7)200416134 本發明之第一多層構造物係由基材層、中間層及表面層所形成者。基材層所使用之聚苯乙烯系樹脂可列舉如苯乙烯、甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、二甲基苯乙烯、對甲基苯乙烯、氯苯乙烯、溴苯乙烯、乙烯基二甲苯等之單獨聚合物或共聚物，苯乙烯-馬來酸酐共聚物、苯乙烯-丙烯酸共聚物、苯乙烯-丙烯酸酯共聚物、苯乙烯（甲基 )丙酸共聚物苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物等。又，可使用上述之苯乙烯系樹脂以丁二烯橡膠、苯乙烯丁二烯橡膠、乙烯-丙烯橡膠等混合或接枝聚合之耐衝擊性聚苯乙烯。以聚苯乙烯、橡膠變性之耐衝擊性聚苯乙烯爲理想，使用橡膠變性之耐衝擊性聚苯乙烯更爲理想。又，苯乙烯系樹脂之溶融指數（MFR :日本 JIS K 7210)以0.5〜20g/10分鐘爲理想，更理想爲1〜l〇g/l〇分鐘。又，基材層使用聚苯乙烯系樹脂及聚烯烴系樹脂之組成物時可輕量化又提高耐熱性爲理想。此時，爲改善2種樹脂之相容性可使用相溶化劑。理想組成物以3 0〜1 0 0重量份聚苯乙烯系樹脂，7 0〜0 重量份聚烯烴系樹脂所成。更理想爲50〜90重量份聚苯乙烯系樹脂、50〜10重量份聚烯烴系樹脂所成，聚苯乙燦系樹脂低於3 0重量份時容器之剛性降低不能表現聚苯乙烯系樹脂之特徵。 -11 - (8) 200416134 基材層所使用之聚乙烯系樹脂可列舉如α 如乙烯、丙烯、1-丁烯、異丁烯、4_甲基-1-戊合或共聚合所得之樹脂者無特別限制。共聚物物、嵌段共聚物之任一者均可。2種或3種t 之共聚物橡膠，或含有α-烯烴與其他之單體. 烯烴系熱可膠性彈性物亦可。此等共聚物橡膠烯-丙烯共聚物橡膠（EPR )、乙烯-丁烯共| EBR)、乙烯-丙烯·二烯共聚物橡膠（EPDM ) 系樹脂以高密度聚乙烯之耐油性、耐藥品性高，聚丙烯系樹脂之耐熱性高，耐油性、耐藥品可合倂提高更爲理想。溶融指數（MFR :日本JIS Κ 7210)以〇分鐘爲理想，更理想爲0.3〜2 0g/ 10分鐘。介於基材層及表面層之中間層係由聚苯乙烯烴系樹脂及相溶化劑所成。中間層使用之聚苯乙烯系樹脂或聚烯烴系基材層及/表面層所使用之聚苯乙烯系樹脂或脂相同。中間層所使用之聚苯乙烯系樹脂或聚，係與基材層及/表面層所使用之聚苯乙烯系烴系樹脂相同亦可相異亦可。中間層之配合量爲2 5〜7 5重量％聚苯乙烯想爲50〜70重量％，聚烯烴系樹脂爲75〜25重爲5 0〜3 0重量％。相溶化劑以聚本乙細系樹脂樹脂合計1〇〇重量份爲1〜20重量份。理想爲7 ;-烯烴，例烯等單獨聚爲隨機共聚乂上α -烯烴共聚物等之可列舉如乙轻物橡膠（等。聚烯烴爲理想。又性及耐熱性 .1 〜60g/ 1 〇烯系樹脂聚樹脂，係與聚烯烴系樹烯烴系樹脂樹脂或聚烯系樹脂，理量％，理想與聚烯烴系 i〜1 〇重量份 -12- (9) (9)200416134 。苯乙烯系樹脂低於2 5重量％時與基材層之層間強度不足，又，聚苯乙烯系樹脂超過75重量％時與表面層之層間強度不足。爲改善之聚苯乙烯系樹脂與聚烯烴系樹脂之相溶性，於中間層添加相溶化劑。相溶化劑可列舉如芳香族乙烯與共軛二烯，即與丁二烯、異丙烯之嵌段共聚物。嵌段共聚物爲結合芳香族含量30〜80重量％，顯示橡膠彈性者。例如苯乙烯-丁二烯-苯乙烯共聚物（SBS)、苯乙烯-異丙烯-苯乙烯共聚物（SIS)等。其中，亦以SBS之加氫物之苯乙烯-乙烯-丁烯-苯乙烯共聚物（SEBS)或SBS之部份加物之苯乙烯-丁二烯-丁烯-苯乙烯共聚物（SBBS)，構造上於側鏈無雙鍵，受到熱履曆時不易交聯者爲理想。相溶化劑，回收時重複受到熱履歷，添加氫者由於可防止凝膠化爲理想。相關之相溶化劑之例，如部份加氫之嵌段共聚物。部份加氫嵌段共聚物，係具有至少1個芳香族乙烯爲主體之聚合物嵌段X與至少1個共軛二烯爲主的聚合物嵌段Y。芳香族乙烯爲主體之聚合物嵌段X以芳香族乙烯與共軛二烯之重量比爲 100/0〜60/40。理想爲 100/0〜80/20 之組成範圍而成之聚合物嵌段。芳香族乙烯與共軛二烯共聚合時，，此嵌段相關之共軛二烯之分佈’可爲隨機、傾斜（沿分子鏈單體成分增加或減少）’一部份嵌段狀或此等之任意組合之任一者。此處提供之芳香族乙烯例如由苯乙烯、^ -甲基苯乙 -13- (10) (10)200416134 嫌、P -甲基苯乙烯、P -三級丁基苯乙烯等α烷基苯乙烯，對甲氧基苯乙烯、乙烯基萘、1,1-二苯基乙烯、二乙烯基苯等之中選擇1種或2種以上，其中亦以苯乙烯爲理想。又，共軛二烯爲主體之聚合物 Υ係由共軛二烯與芳香族乙烯之重量比爲100/0〜60/40，理想爲100/0〜8 0/20 之組成範圍所成之聚合物嵌段。共軛二烯與芳香族乙烯共聚合時，此嵌段相關之芳香族乙烯之分佈，可爲隨機、傾斜（沿分子鏈單體成分增加或減少），一部份嵌段狀或此等之任意組合之任一者均可。此處提供之共軛二烯，例如丁二烯、異丙烯、間戊二烯、甲基戊二烯、苯基丁二烯、3，4 -二甲基-1，3 -己二烯、 4,5-二乙基-1，3-辛二烯等之中所選1種或2種以上，其中，亦以丁二烯及/或異戊二烯爲理想。上述嵌段共聚物之分子構造爲直鏈狀、分枝狀、放射狀或此等之組合等之任一者均可。其中亦以X爲2個以上之構造爲理想，例如Χ-Υ-Χ、Χ-Υ-Χ-Υ、Υ-Χ-Υ-Χ-Υ構造爲理想，Χ-Υ-Χ構造特別理想。嵌段X或嵌段Υ各自爲同一之構造亦可，單體成分之含量、此等分子鏈相關之分佈、嵌段之分子量，微構造等之各構造相異者亦可。例如兩末端之分子量爲相異之 X · Υ - X，亦可。部份加氫嵌段共聚物之芳香族乙烯含量爲30〜80重量 %，理想爲40〜80重量％，更理想爲45〜75重量％。芳香族乙烯含量低於3 0重量％時，嵌段共聚物與苯乙烯系樹 -14- (11) 200416134 脂之親和性不足，存在於苯乙之界面之嵌段共聚物不充分，超過 8 0重量％時，與苯乙烯嵌段共聚物納入苯乙烯系樹脂〇部份加氫嵌段共聚物加氫鍵含量爲20〜90重量％，理想 40〜75重量％。此處，添加氫基含量爲嵌段共聚合物中以1 合之結合樣式組合之共範~~‘讎合之組合者之比例。氫添加前含量低於20重量％時，嵌段性不足，相溶化效果不充分。，與烯烴系樹脂之親和性過剩系樹脂相，相溶化劑效果也不本發明所使用之部份加氫聚物加氫，該嵌段共聚物中之以上爲飽和狀者。加氫率低於烯烴系樹脂之親和性降低，嵌相，相溶化效果成爲不充分。段共聚物中殘存之乙烯鍵含量爲爲5%以下，再理想爲3%以係相對於最初之共軛二烯1 〇〇之量。段共聚物中殘存之乙烯 %系樹脂相與烯烴系樹脂相缺乏相溶化效果。一方面，系樹脂之親和性過剩，由於相’相溶化劑效果也不充分前之共軛二烯嵌段中之乙烯爲3 0〜80重量％，更理想爲前之共軛二烯嵌段中之乙烯，2-結合，3,4-結合及1，4-結之中，爲1，2 -結合，3，4 -結之共軛二烯嵌段中之乙烯基共聚物與烯烴系樹脂之親和一方面，超過 90重量％時，由於嵌段共聚物納入烯烴充分。嵌段共聚物係由上述嵌段共共軛二烯爲準之雙鍵之3 5 % 35%時，由於嵌段共聚物與段共聚物納入苯乙烯系樹脂又，本發明所使用之部份嵌，理想爲低於10%，更理想下，此處，殘存乙烯鍵含量未加氫而殘留之乙烯基構造鍵含量爲10%以上時，相溶 -15- (12) (12)200416134 化效果不充分。部份加氫嵌段共聚物之芳香族乙烯爲主體之聚合物嵌段X之重量平均分子量爲5 000〜5 000 0，共軛二烯爲主餅之聚合物嵌段Y以5 000〜70 000爲理想。聚合物嵌段X之分子量低於5 0 00時，與苯乙烯之親和性降低，聚合物嵌段Y之分子量低於5 000時，與烯烴系樹脂之親和性降低相溶化效果差。又，聚合物嵌段X之分子量超過50000，聚合物嵌段Y之分子量超過7 0000時，由於作爲嵌段共聚物之分子量過大溶融粘度上昇，由苯乙烯系樹脂與烯烴系樹脂所成之樹脂組成物中分散不充分，相溶效果差。部份加氫嵌段共聚物之溶融指數（MFR :日本JIS K 7210)以0·1〜50g/10分鐘爲理想，更理想爲〇·5〜30g/ 1 〇分鐘，再理想爲1〜2 0 g / 1 0分鐘。溶融指數低於〇 . 1 g / 1 0分鐘時，溶融粘度過高不能得到充分之相溶化效果 ’又，超過5 0 g / 1 0分鐘時，苯乙烯系樹脂與烯烴系樹脂之界面強度下降。又，使用部份加氫苯乙烯-丁二烯-丁烯-苯乙烯嵌段共聚物時可廉價製造且效果良好。相溶化劑之玻璃轉移溫度以較低者低溫衝擊性良好爲理想。玻璃轉移溫度以-6 0 °C以下爲理想，· 7 〇它以下者更理想。多層構造物厚度無特別限定爲0.1〜2mm，理想爲 0.2〜1.5111111。表面層爲〇.〇〇5〜0.1111111，理想爲0.01〜0.1111111 ，介入之中間層爲0.005mm以上，理想爲〇.〇lnim以上， -16- (13) (13)200416134 其餘爲基材層。全體之厚度爲0.1mm以下時，容器成形有裂膜的實用上之問題。又超過2mm以上時，薄片之捲裝有困難，捲裝物不能使用於對應之容器成形機。表面層之厚度低於〇.〇〇5mm時容器成形時裂膜有實用上的問題。又，超過〇 . 1 mm時熱成形循環顯著下降或招致剛性降低。中間層之厚度低於〇.〇〇5mm時成形之容器會裂膜，表面層與基材層之接合強度降低不能保護內容物。以熱成形形成蓋時亦同樣，全體厚度低於0.1mm時蓋之成形有裂膜的實用上之問題。又超過2mm時薄片之捲裝有困難，捲裝物不能使用於對應之容器成形機。表面層之厚度低於〇.〇〇5mm時蓋之成形時會裂膜有實用上的問題。又，超過0.1mm時熱成形循環顯著下降或招致剛性降低。中間層之厚度低於〇.〇〇5mm時成形之蓋會裂膜，表面層與基材層之接合強度降低不能保護內容物。又基材層、中間層及表面層在不損及其特性範圍，可含有滑劑、軟化劑、可塑劑、抗氧化劑、防帶電劑、碳酸鈣、滑石、磷酸鎂、氫氧化鋁、硫酸鋇、矽酸鈣、氧化鈦脫模劑等之其他成分，又，亦可著色。又，本發明之第一多層構造物，可於上述基材層之中間層之反側，層合其他層。例如提高氧氣隔離性、減少成爲容器後之變形之目的，可層合乙烯-乙烯醇共聚物、聚 -17- (14) (14)200416134 偏氯乙烯、尼龍、聚乙烯對苯二甲酸酯等之樹脂層或鋁蒸鍍層，銘范、銘、鐵、銅等之優隔氣性之材料所成之層。此等層亦可爲含無機塡充料之樹脂層，或與金屬、紙等之複合材料。本發明之第一多層構造物可由共擠壓或貼合加工等而製造。共擠壓成形法，例如聚苯乙烯基材層、表面層及其間介入之中間層各自使用不同之擠壓機溶融擠壓，可列舉如於注料區層合之平板製膜之方法，或使用多層模於模內層合之製膜方法等。貼合加工可使用擠壓貼合。通常，以使用由聚烯烴系樹脂薄膜與溶融狀態之聚苯乙烯系樹脂之中間層及基材層共擠壓之二層構造物以貼合之共擠壓貼合法爲合適。成形中發生之廢料在不損及特性之範圍可以使用於基材層回收，或作爲基材層一部份之新設層回收亦可。本發明之第一層構造物不使用接合性樹脂或接合劑，介以中間層，由聚苯乙烯系樹脂所成基材層層合表面層，亦可具有充分之層間強度，活化聚苯乙烯系樹脂之熱成形性、剛性，賦予聚烯烴系樹脂具有之耐油性、耐藥品性、耐熱性。又，本發明之多層構造物，由於不使用接合性樹脂或接合劑，可防止回收時之凝膠化。〔由第一多層構造物所之容器，蓋、包裝體〕本發明之包裝體係由上述之片狀多層構造物所形成。 -18- (15) (15)200416134 包裝物之例，可列舉如容器及/或蓋。本發明之包裝體係將上述之片狀多層構造物加熱溶融賦予所望之型狀者，通常以適合之真空成形、壓空成形等得到。又，使用上述樹脂由射出成型、射出吹模成型、吹模成型等成形而得。圖1(a) 、（b)所示爲本發明之第一層構造物之斷面圖。圖1(a)所示之多層構造物10由表面層1、中間層 2、基材層3所成，圖1所示多層構造物1 1係由表面層1 、中間層2、基材層3、回收基材層4成回收基材層4係片狀多層構成物粉碎所成者，配合與基材層相同者所成之層’本發明之基材層爲基材層3與回收基材層4所成。圖2所示爲由本發明之第一多層構造物所成容器及蓋之斷面圖。圖2(a) 、（b)所示容器20及蓋30係由圖1(a) 之多層構造物所製造，多層構造物10之表面層i爲內容物之側。多層構造物1 〇形成延伸之翼緣5。又’容器20之翼緣部5之形狀無特別的限定，通常 ’爲圓、四角等形狀。又，容器之型狀爲杯型或盤狀均可〇由於本發明之容器及/或蓋爲優耐油性、耐藥品性、耐熱性’可作爲食品或醫藥品優良之包裝體。具體的如便當、豆腐、菜餚等之包裝體。又’回收時不易凝膠化，具優回收性。 -19- (16) (16)200416134 〔第二多層構造物〕本發明之弟—^多層構物係由基材層、接合層及與第一表面層及第二表面層所形成者。基材層可使用與上述之第一多層構造物相同之者。第一表面層所使用之聚乙烯系樹脂爲乙烯之單獨聚合物，或乙烯與α -烯烴，例如丙烯、1 - 丁烯、異丁烯、4 _ 甲基-1 -戊烯等單獨聚合或共聚合所得之樹脂者無特別限制。共聚物爲隨機共聚物、嵌段共聚物之任一者均可。第一表面層之聚乙烯系樹脂以密度爲900 kg/ cm3以上者爲理想，更理想爲920 kg/ cm3以上者，耐藥品性高，依保護內容物之觀點爲優秀者。溶融指數（MFR:日本JIS K 7210)以0.1〜60g/l〇分鐘爲理想，更理想爲〇·3〜20g/ 1 〇分鐘。第二表面層之聚丙烯系樹脂爲丙烯之單獨聚合物，或丙烯與α-烯烴，例如乙烯、1-丁烯、異丁烯、4 -甲基-1-戊烯等單獨聚合或共聚合所得之樹脂者無特別限制。共聚物爲隨機共聚物、嵌段共聚物之任一者均可。又，第二表面層可使用聚苯乙烯系樹脂、聚丙烯系樹脂及相溶化劑所成之組成物。但是，必要使用融點較第一表面層使用之聚乙烯系樹脂爲高之成分。融點差異理想爲1 0 °C以上，更理想爲2(TC以上。第二表面層亦以聚丙烯單獨聚合物（均質P P )爲聚丙烯系樹脂中融點高耐熱性優爲佳。溶融指數（MFR:日本JIS K 7210)以0.1〜60g/10 -20- (17) (17)200416134 分鐘爲理想，更理想爲0.3〜2 0 g / 1 〇分鐘。本發明第一表面層與第二表面層由於使用融點不同之樹脂，可防止熱封時之外觀不良。介於基材層與表面層之接合層，由聚苯乙烯系樹脂、聚丙烯系樹脂及相溶化劑所成。即，上述第一多層構造物相關之中間層之聚烯烴系樹脂係使用聚丙烯系樹脂。接合劑所使用之聚苯乙烯系樹脂與基材層及/或二表面層所使用之聚苯乙烯系樹脂相同。接合劑所使用之聚苯乙烯系樹脂與基材層及/或二表面層所使用之聚苯乙烯系樹脂相同亦可相異亦可。聚丙烯系樹脂以與第二表面層同種者爲理想，更理想爲相同者。本發明由於接合層使用聚丙烯系樹脂第一與第二兩方之表面層層合時可具優界面強度。相溶化劑及接合劑相關之聚苯乙烯系樹脂、聚丙烯系樹脂及相溶化劑之配合量，可與上述之第一多層構造物之中間層相同。又，第二多層構造物接合層使用之相溶化劑，使用廉價SBS之部份加氫物之SBBS，可抑制向來EVA系接合劑回收時發生之凝膠化，比向來使用S I S、S B S系相溶化劑時得到更優異之界面強度。第二多層構造物體之厚度及各層之厚度相同於第一多層構造物之各層所述範圍，又，相關於第一表面層與第二表面層，其厚度與第一多層構造物表面層相同，接合層與 -21 - (18) (18)200416134 中間層之厚度相同。基材層、接合層及各表面層，在不損及其特性範圍，可含有滑劑 '軟化劑、可塑劑、抗氧化劑、防帶電劑、碳酸鈣、滑石、磷酸鎂 '氫氧化鋁、硫酸鋇、矽酸鈣、氧化鈦脫模劑等之其他成分，又，亦可著色。又，第二多層構造物，層合其他層作爲上述基材層之一部份，例如提高氧氣隔離性、減少成爲容器後之變形之目的，可層合乙烯-乙烯醇共聚物、聚偏氯乙烯、聚醯胺、聚乙烯對苯二甲酸酯等之樹脂層。此等層亦可爲含無機塡充料之樹脂層。第二多層構造物與第一多層構造物同樣，可由共擠壓或貼合加工等而製造。通常，以使用由聚丙烯系樹脂薄膜與溶融狀態之聚苯乙烯系樹脂之接合層、基材層、接合層及表面層共擠壓之四層構造物以貼合之共擠壓貼合法爲合適。第一多層構造物係具第一多層構造物之特徵以外，具有第一表面層及融點較高的第二表面層，熱封時外觀優爲其特徵。所以本發明之多層構造物，可與聚烯烴系之容器或包裝體熱封，同時倂持聚苯乙烯系樹脂之熱成形性及剛性。〔由第二多層構造物所之容器，棻、包裝體〕本發明之容器、蓋、包裝體係由上述之片狀多層構造物所形成。 -22. (19) 200416134 本發明之容器、蓋、包裝體係由上述之片狀多層構造物加熱溶融，賦予所望之型狀者，通常以適合之真空成形、壓空成形等得到。又，可使用上述樹脂由射出成型、射出吹模成型、吹模成型等成形而得。圖3所示爲本發明之第二多層構造物之斷面圖。圖3所示之多層構造物12由第一表面層7、接合層 8a、基材層3、接合層8b、第二表面層9所成。A first surface layer made of a polyethylene-based resin and a second surface layer made of a polypropylene-based resin are formed through the bonding layer. The bonding layer is made of polystyrene-based resin, polypropylene-based resin, and miscible. Multi-layer structure formed by the agent. [4] The base material layer is made of polystyrene resin, a first surface layer made of polyethylene resin is formed through the bonding layer, and is made of polystyrene resin, polypropylene resin, and a compatibilizing agent. The second surface layer and the bonding layer are multilayer structures made of polystyrene resin, polypropylene resin, and a compatibilizing agent. -8- (5) (5) 200416134 [5] The base layer is made of a polystyrene resin, a first surface layer made of a polyethylene resin through an intermediate layer, and a polypropylene resin The second surface layer, the intermediate layer, is made of polystyrene resin 2 to 5 5 parts by weight and 75 to 25 parts by weight of polypropylene, and the combined aromatic vinyl content is 30 to 80 parts by weight The intermediate layer is composed of 100 parts by weight of the above polystyrene resin and polypropylene resin, and is blended with i ~ 20 parts by weight of a compatibilizer. The compatibilizer is based on a conjugated diene. More than 35% of the double bonds are saturated with hydrogen element. It is a polyfluorene structure made of block copolymers of aromatic ethylene and conjugated diene. [6] The base layer is made of polystyrene resin, and a first surface layer and a second surface layer are formed by a bonding layer. The bonding layer is made of 25 to 75 parts by weight of polystyrene resin and polypropylene. 75 to 25 parts by weight, and a combined aromatic vinyl content of 30 to 80 parts by weight. The bonding layer is composed of 1,000 parts by weight of the polystyrene resin and polypropylene resin. 1 to 20 parts by weight of a compatibilizer, the compatibilizer is saturated with hydrogen based on 35% or more of the double bonds of the conjugated diene, and is a block copolymer of aromatic ethylene and conjugated diene. The first surface layer is made of polyethylene resin, and the second surface layer is 25 to 75 parts by weight of polystyrene resin and 75 to 25 parts by weight of polypropylene, and combines aromatic vinyl The content is from 30 to 80 parts by weight. '-9- (6) (6) 200416134 The second surface layer system is composed of 100 parts by weight of the polystyrene resin and polypropylene resin, and 1 to 20 parts by weight of the compatibilizing agent, which is based on the hydrogenation of more than 35% of the double bonds of the conjugated diene. Saturated 'much layer structure and an aromatic vinyl-conjugated diene block copolymer formed by the. [7] The multilayer structure according to item 3 or 4, wherein the compatibility agent of the bonding layer and / or the second surface layer is a hydrogen additive of a block copolymer of an aromatic vinyl and a conjugated diene. . [8] The multilayer structure according to item 1 or 2, wherein the polyolefin resin of the surface layer is a polypropylene resin. [9] A multilayer structure having a glass transition temperature of the above-mentioned miscible agent of -60 ° C or lower as described in any one of [1] to [8]. [10] The content side of the surface layer is a container, a lid, or a package formed of a multilayer structure as described in any one of [1], [2], [8], or [9]. [1 1] The content side of the surface layer is a container, a lid, or a package formed of the multilayer structure according to any one of [3] to [7] and [9]. [Best Mode for Carrying Out the Invention] The present invention will be described in detail below. [First multi-layer structure] -10- (7) (7) 200416134 The first multi-layer structure of the present invention is formed by a base material layer, an intermediate layer, and a surface layer. Examples of the polystyrene resin used in the substrate layer include styrene, methylstyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, p-methylstyrene, chlorostyrene, and bromine. Individual polymers or copolymers of styrene, vinyl xylene, etc., styrene-maleic anhydride copolymer, styrene-acrylic copolymer, styrene-acrylate copolymer, styrene (meth) propionic acid copolymer Styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, and the like. Further, the above-mentioned styrene-based resin may be an impact-resistant polystyrene mixed or graft-polymerized with butadiene rubber, styrene butadiene rubber, ethylene-propylene rubber, or the like. Polystyrene and rubber-modified impact-resistant polystyrene are ideal, and rubber-modified impact-resistant polystyrene is more ideal. The melting index (MFR: JIS K 7210) of the styrene resin is preferably 0.5 to 20 g / 10 minutes, and more preferably 1 to 10 g / 10 minutes. When a composition of a polystyrene-based resin and a polyolefin-based resin is used as the base material layer, it is preferable to reduce weight and improve heat resistance. In this case, a miscible agent may be used to improve the compatibility of the two resins. The ideal composition is made of 30 to 100 parts by weight of a polystyrene resin and 70 to 0 parts by weight of a polyolefin resin. More preferably, it is made of 50 to 90 parts by weight of a polystyrene resin and 50 to 10 parts by weight of a polyolefin resin. When the polystyrene resin is less than 30 parts by weight, the rigidity of the container decreases, and the polystyrene resin cannot be expressed. Characteristics. -11-(8) 200416134 The polyethylene resin used in the substrate layer can be exemplified by α such as ethylene, propylene, 1-butene, isobutylene, 4-methyl-1-pentane, or copolymerized resin Special restrictions. Either a copolymer or a block copolymer may be used. 2 or 3 t copolymer rubbers, or containing α-olefins and other monomers. Olefin-based heat-curable elastomers are also possible. These copolymer rubber ene-propylene copolymer rubbers (EPR), ethylene-butene copolymers | EBR), ethylene-propylene-diene copolymer rubber (EPDM) series resins have high-density polyethylene oil resistance and chemical resistance High, polypropylene resin has high heat resistance, oil resistance and chemical resistance can be improved. The melting index (MFR: Japanese JIS K 7210) is preferably 0 minutes, and more preferably 0.3 to 20 g / 10 minutes. The intermediate layer between the substrate layer and the surface layer is made of a polystyrene resin and a compatibilizing agent. The polystyrene resin or polyolefin-based base material layer and / or surface layer used for the intermediate layer are the same polystyrene resin or grease. The polystyrene resin or polystyrene used in the intermediate layer may be the same as or different from the polystyrene hydrocarbon resin used in the base layer and / or the surface layer. The blending amount of the intermediate layer is 25 to 75% by weight of polystyrene, and 50 to 70% by weight is desired. The polyolefin resin is 75 to 25% by weight and 50 to 30% by weight. The compatibilizing agent is 1 to 20 parts by weight based on 100 parts by weight of the polyethylene resin. Ideally, 7-olefins, such as olefins, etc., are individually copolymerized into random copolymers, and α-olefin copolymers can be listed such as ethylene light rubber (etc.). Polyolefins are ideal. Reactivity and heat resistance. 1 ~ 60g / 1 〇ene-based resin polyresin, based on polyolefin resin and olefin-based resin or polyolefin-based resin, the amount of%, ideally with polyolefin-based i ~ 10 -10 parts by weight-(9) (9) 200416134. benzene When the ethylene-based resin is less than 25% by weight, the interlayer strength with the base layer is insufficient, and when the polystyrene-based resin is more than 75% by weight, the interlayer strength with the surface layer is insufficient. Polystyrene-based resins and polyolefins for improvement For the compatibility of resins, a compatibilizer is added to the intermediate layer. Examples of the compatibilizer include aromatic ethylene and conjugated diene, ie, block copolymers with butadiene and isopropylene. Block copolymers are combined with aromatics. Group content of 30 to 80% by weight, showing rubber elasticity. For example, styrene-butadiene-styrene copolymer (SBS), styrene-isopropylene-styrene copolymer (SIS), etc. Among them, SBS is also used. Hydrogenated styrene-ethylene-butene-styrene copolymer (S EBS) or styrene-butadiene-butene-styrene copolymer (SBBS), which is part of the addition of SBS, has no double bonds on the side chain and is not easily cross-linked when subjected to thermal history. The thermal history is repeated during recovery. Those who add hydrogen are ideal because they can prevent gelation. Examples of related compatibilizers, such as partially hydrogenated block copolymers. Partially hydrogenated block copolymers have At least one aromatic ethylene-based polymer block X and at least one conjugated diene-based polymer block Y. The aromatic ethylene-based polymer block X is composed of an aromatic ethylene and a conjugated diene. The weight ratio of olefin is 100/0 ~ 60/40. Ideally, it is a polymer block composed of a composition range of 100/0 ~ 80/20. When aromatic ethylene is copolymerized with conjugated diene, this block is related The distribution of the conjugated diene can be random, oblique (increasing or decreasing the monomer component along the molecular chain), part of a block, or any combination of these. The aromatic vinyls provided herein are Made of styrene, ^ -methylphenethyl-13- (10) (10) 200416134, P-methylstyrene, P-tertiary Α alkylstyrene such as styrene, p-methoxystyrene, vinylnaphthalene, 1,1-diphenylethylene, divinylbenzene, etc. are selected from one or two or more, among which styrene is also used Further, the polymer fluorene containing conjugated diene as the main component is composed of a weight ratio of conjugated diene to aromatic ethylene of 100/0 to 60/40, and ideally a composition range of 100/0 to 8 0/20. The polymer block formed. When the conjugated diene is copolymerized with aromatic ethylene, the distribution of aromatic ethylene related to this block can be random and inclined (increasing or decreasing the monomer component along the molecular chain), a part Either a block shape or any combination of these may be used. Conjugated dienes provided herein, such as butadiene, isopropylene, isoprene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, One or two or more of 4,5-diethyl-1,3-octadiene and the like are selected. Among them, butadiene and / or isoprene are preferred. The molecular structure of the block copolymer may be any of linear, branched, radial, or a combination thereof. Among them, it is also ideal that X is two or more structures, for example, X-Y-X, X-Y-X-Y, Y-X-Y-X-Y structure is ideal, and X-Y-X structure is particularly ideal. Block X or block Υ may have the same structure, and the content of the monomer component, the distribution of these molecular chains, the molecular weight of the block, and the microstructure may also be different. For example, the molecular weights at the two ends are different X · Υ-X, it is also acceptable. The aromatic ethylene content of the partially hydrogenated block copolymer is 30 to 80% by weight, preferably 40 to 80% by weight, and more preferably 45 to 75% by weight. When the content of aromatic ethylene is less than 30% by weight, the affinity of the block copolymer with the styrene-based tree-14- (11) 200416134 is insufficient, and the block copolymer existing at the interface of styrene is insufficient, exceeding 8 At 0% by weight, the styrene resin is incorporated into the styrene block copolymer. The hydrogenated bond content of the partially hydrogenated block copolymer is 20 to 90% by weight, preferably 40 to 75% by weight. Here, the content of the added hydrogen group is the proportion of the combination of the 1-in-one combination pattern in the block copolymer to the ′ -incorporated combination. When the content before hydrogen addition is less than 20% by weight, the blockability is insufficient, and the compatibility effect is insufficient. The compatibility with the olefin-based resin is excessive, and the compatibilizing agent is not effective. Part of the hydrogenated polymer used in the present invention is hydrogenated, and the above block copolymer is saturated. The hydrogenation rate is lower than that of the olefin-based resin, the affinity is reduced, and the intercalation effect is insufficient. The residual ethylene bond content in the segmented copolymer is 5% or less, and desirably 3% to 100% of the original conjugated diene. The residual ethylene-based resin phase in the segment copolymer and the olefin-based resin phase lack a compatibility effect. On the one hand, because the resin has excessive affinity, the ethylene in the conjugated diene block before the effect of the phase-miscibility agent is not sufficient is 30 to 80% by weight, and more preferably the former conjugated diene block. Among ethylene, 2-bond, 3,4-bond, and 1,4-bond, it is a 1,2-bond, 3,4-bond conjugated diene block vinyl copolymer and olefin On the other hand, when the affinity of the resin exceeds 90% by weight, the block copolymer is sufficiently incorporated into the olefin. When the block copolymer is 35% 35% of the double bond based on the above-mentioned block conjugated diene, the block copolymer and the segment copolymer are incorporated into the styrene resin, and the part used in the present invention It is ideally less than 10%, and more preferably, when the content of the remaining vinyl bonds is not hydrogenated and the content of the remaining vinyl structural bonds is 10% or more, it is compatible with -15- (12) (12) 200416134 The effect is insufficient. Partially hydrogenated block copolymer of aromatic ethylene as the main polymer block X has a weight average molecular weight of 5 000 to 50000, and the polymer block Y of the conjugated diene-based cake is 5 000 to 70 000 is ideal. When the molecular weight of the polymer block X is less than 5,000, the affinity with the styrene is decreased, and when the molecular weight of the polymer block Y is less than 5,000, the affinity with the olefin resin is reduced and the compatibility effect is poor. In addition, when the molecular weight of the polymer block X exceeds 50,000 and the molecular weight of the polymer block Y exceeds 70,000, the molecular weight of the block copolymer becomes too large, and the melt viscosity increases, and the resin made of a styrene resin and an olefin resin Insufficient dispersion in the composition and poor compatibility. The melt index (MFR: Japan JIS K 7210) of the partially hydrogenated block copolymer is preferably from 0.1 to 50 g / 10 minutes, more preferably from 0.5 to 30 g / 10 minutes, and even more preferably from 1 to 2 0 g / 10 minutes. When the melt index is less than 0.1 g / 10 minutes, the melt viscosity is too high to obtain a sufficient compatibility effect. Also, when it exceeds 50 g / 10 minutes, the interface strength of the styrene resin and the olefin resin decreases. . In addition, when a partially hydrogenated styrene-butadiene-butene-styrene block copolymer is used, it can be produced inexpensively and has good effects. The lower the glass transition temperature of the compatibilizing agent, the better the low-temperature impact resistance is desirable. The glass transition temperature is preferably -60 ° C or lower, and more preferably 70 ° C or lower. The thickness of the multilayer structure is not particularly limited to 0.1 to 2 mm, and is preferably 0.2 to 1.5111111. The surface layer is 0.05 to 0.1111111, ideally 0.01 to 0.1111111, and the intervening intermediate layer is 0.005 mm or more, ideally 0.001 inim or more, -16- (13) (13) 200416134, and the rest are substrate layers. When the overall thickness is 0.1 mm or less, there is a practical problem in forming a container with a cracked film. If it exceeds 2 mm, it is difficult to roll the sheet, and the roll cannot be used in a corresponding container forming machine. When the thickness of the surface layer is less than 0.05 mm, there is a practical problem in the cracked film when the container is formed. When the thickness exceeds 0.1 mm, the thermoforming cycle is significantly reduced or rigidity is reduced. When the thickness of the intermediate layer is less than 0.05 mm, the formed container will crack, and the bonding strength between the surface layer and the substrate layer will not be able to protect the contents. The same applies to the case where the lid is formed by thermoforming. When the overall thickness is less than 0.1 mm, there is a practical problem in forming the lid with a cracked film. When it exceeds 2mm, it is difficult to roll the sheet, and the package cannot be used in the corresponding container forming machine. When the thickness of the surface layer is less than 0.05 mm, there is a practical problem that the film is cracked when the cover is formed. When the thickness exceeds 0.1 mm, the thermoforming cycle is significantly reduced or rigidity is reduced. When the thickness of the intermediate layer is less than 0.05 mm, the formed lid will crack, and the joint strength between the surface layer and the substrate layer will not be able to protect the contents. In addition, the base material layer, the intermediate layer, and the surface layer can contain slippers, softeners, plasticizers, antioxidants, anti-charge agents, calcium carbonate, talc, magnesium phosphate, aluminum hydroxide, and barium sulfate within the scope of their characteristics , Calcium Silicate, Titanium Mould Release Agent, etc. Further, the first multilayer structure of the present invention may be laminated on the opposite side of the intermediate layer of the base layer described above with other layers. For example, the purpose of improving the oxygen barrier property and reducing the deformation after becoming a container can be laminated ethylene-vinyl alcohol copolymer, poly-17- (14) (14) 200416134 vinylidene chloride, nylon, polyethylene terephthalate Such as the resin layer or aluminum vapor deposition layer, Ming Fan, Ming, iron, copper and other materials made of superior gas barrier layer. These layers may also be resin layers containing inorganic rhenium fillers, or composite materials with metals, paper, and the like. The first multilayer structure of the present invention can be produced by co-extrusion or lamination processing. Co-extrusion molding methods, such as polystyrene substrate layer, surface layer, and intervening intermediate layers, are melt-extruded using different extruders. Examples include the method of flat film lamination in the injection area, or A method for forming a film by laminating a multilayer mold in a mold. For lamination, extrusion lamination can be used. In general, a co-extrusion lamination method using a two-layer structure in which a polyolefin-based resin film and a polystyrene resin in a molten state are co-extruded with a base layer is suitable. The waste generated during molding can be used for recovery of the base material layer as long as it does not damage the characteristics, or it can be recovered as a new layer as part of the base material layer. The first-layer structure of the present invention does not use a bonding resin or a bonding agent, and the surface layer is laminated with a base material made of polystyrene resin through an intermediate layer, and it may also have sufficient interlayer strength to activate polystyrene Based on the thermoformability and rigidity of the resin, it gives the polyolefin resin the oil resistance, chemical resistance, and heat resistance. In addition, the multilayer structure of the present invention can prevent gelation at the time of recovery because no bonding resin or bonding agent is used. [Container, lid, and packaging body made of the first multilayer structure] The packaging system of the present invention is formed of the above-mentioned sheet-like multilayer structure. -18- (15) (15) 200416134 Examples of packaging materials include containers and / or lids. The packaging system of the present invention which heat-melts the above-mentioned sheet-like multilayer structure to give a desired shape is usually obtained by suitable vacuum forming, pressure forming, and the like. The resin is obtained by injection molding, injection blow molding, and blow molding. Figures 1 (a) and (b) are sectional views of the first-layer structure of the present invention. The multilayer structure 10 shown in FIG. 1 (a) is composed of a surface layer 1, an intermediate layer 2, and a substrate layer 3. The multilayer structure 11 shown in FIG. 1 is composed of a surface layer 1, an intermediate layer 2, and a substrate layer. 3. Recycling the base material layer 4% of the recovered base material layer 4 is a sheet-like multilayer structure obtained by pulverizing, and a layer formed by combining the same with the base material layer. Material layer 4. Fig. 2 is a sectional view showing a container and a lid formed of a first multilayer structure of the present invention. The container 20 and the lid 30 shown in Figs. 2 (a) and 2 (b) are manufactured from the multilayer structure of Fig. 1 (a), and the surface layer i of the multilayer structure 10 is the side of the contents. The multilayer structure 10 forms an extended flange 5. The shape of the flange portion 5 of the container 20 is not particularly limited, and generally, the shape is a circle, a four-corner shape, or the like. In addition, the shape of the container may be cup-shaped or tray-shaped. Since the container and / or the lid of the present invention are excellent in oil resistance, chemical resistance, and heat resistance, they can be used as excellent packaging bodies for food or pharmaceuticals. Specific packaging such as bento, tofu, dishes, etc. In addition, it is difficult to gelate during recovery, and has excellent recoverability. -19- (16) (16) 200416134 [Second multi-layer structure] ^ The multi-layer structure of the present invention is formed by a base material layer, a bonding layer, and a first surface layer and a second surface layer. As the base layer, the same one as the first multilayer structure described above can be used. The polyethylene resin used in the first surface layer is a separate polymer of ethylene, or ethylene is separately polymerized or copolymerized with α-olefins such as propylene, 1-butene, isobutylene, and 4-methyl-1-pentene. The obtained resin is not particularly limited. The copolymer may be any of a random copolymer and a block copolymer. The polyethylene resin of the first surface layer preferably has a density of 900 kg / cm3 or more, more preferably 920 kg / cm3 or more, has high chemical resistance, and is excellent in terms of protecting the content. The melting index (MFR: JIS K 7210 in Japan) is preferably from 0.1 to 60 g / 10 minutes, and more preferably from 0.3 to 20 g / 10 minutes. The polypropylene resin of the second surface layer is a separate polymer of propylene, or a polymer obtained by separate polymerization or copolymerization of propylene and α-olefins, such as ethylene, 1-butene, isobutylene, and 4-methyl-1-pentene. The resin is not particularly limited. The copolymer may be any of a random copolymer and a block copolymer. As the second surface layer, a composition made of a polystyrene resin, a polypropylene resin, and a compatibilizing agent can be used. However, it is necessary to use a component having a higher melting point than the polyethylene resin used in the first surface layer. The difference in melting point is preferably 10 ° C or more, more preferably 2 (TC or more. The second surface layer also uses polypropylene alone polymer (homogeneous PP) as the polypropylene resin. The melting point is high and the heat resistance is better. Melting The index (MFR: Japanese JIS K 7210) is preferably 0.1 to 60 g / 10 -20- (17) (17) 200416134 minutes, more preferably 0.3 to 20 g / 10 minutes. The first surface layer and the first surface layer of the invention Because the two surface layers use resins with different melting points, they can prevent appearance defects during heat sealing. The bonding layer between the base material layer and the surface layer is made of polystyrene resin, polypropylene resin, and compatibilizer. That is, the polyolefin-based resin of the intermediate layer related to the first multilayer structure is a polypropylene-based resin. The polystyrene-based resin used in the adhesive and the polystyrene used in the base material layer and / or the two surface layers. The vinyl resin is the same. The polystyrene resin used in the bonding agent may be the same as or different from the polystyrene resin used in the base layer and / or the second surface layer. The polypropylene resin may be the same as the second surface. The same layer is ideal, and the same is more ideal. Polypropylene resin is used as the lamination layer, and the first and second surface layers can be laminated with excellent interfacial strength. Mixing of polystyrene resin, polypropylene resin and compatibilizer related to the dissolving agent and bonding agent The amount can be the same as the intermediate layer of the first multilayer structure described above. Also, the compatibilizing agent used in the bonding layer of the second multilayer structure uses SBBS, which is a partially hydrogenated product of inexpensive SBS, which can suppress the traditional EVA system. The gelation that occurs during the recovery of the bonding agent has better interfacial strength than the conventional SIS and SBS-based compatibilizers. The thickness of the second multilayer structure and the thickness of each layer are the same as those of the first multilayer structure. The range is related to the first surface layer and the second surface layer, the thickness of which is the same as the surface layer of the first multilayer structure, and the bonding layer has the same thickness as the intermediate layer of -21-(18) (18) 200416134. The base material layer, the bonding layer, and each surface layer may contain lubricants 'softeners, plasticizers, antioxidants, antistatic agents, calcium carbonate, talc, magnesium phosphate' aluminum hydroxide, sulfuric acid, without impairing their characteristics. Barium, calcium silicate, Other components such as titanium release agents can also be colored. Also, in the second multilayer structure, other layers are laminated as a part of the above-mentioned base material layer, for example, to improve oxygen barrier properties and reduce For the purpose of deformation, resin layers such as ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyamide, polyethylene terephthalate, etc. can be laminated. These layers can also be resin layers containing inorganic rhenium filler. Like the first multilayer structure, the second multilayer structure can be manufactured by co-extrusion or lamination. Generally, a bonding layer composed of a polypropylene resin film and a molten polystyrene resin is used. The four-layer structure of the base material layer, the bonding layer and the surface layer co-extruded is suitable for co-extrusion. The first multi-layer structure has the features of the first multi-layer structure, a first surface layer and a second surface layer with a higher melting point. Therefore, the multilayer structure of the present invention can be heat-sealed with a polyolefin-based container or package while retaining the thermoformability and rigidity of a polystyrene resin. [Container, container, and packaging body of the second multilayer structure] The container, lid, and packaging system of the present invention are formed of the above-mentioned sheet-like multilayer structure. -22. (19) 200416134 The container, lid, and packaging system of the present invention are obtained by heating and melting the sheet-like multilayer structure described above to give the desired shape, and are usually obtained by suitable vacuum forming and pressure forming. The resin can be obtained by injection molding, injection blow molding, blow molding, or the like. FIG. 3 is a cross-sectional view of a second multilayer structure of the present invention. The multilayer structure 12 shown in FIG. 3 is composed of a first surface layer 7, a bonding layer 8a, a base material layer 3, a bonding layer 8b, and a second surface layer 9.

圖4所示爲由本發明之第二層構造物所成容器及蓋之斷面圖。圖4所示容器21及蓋31係由圖3之多層構造物所製造，多層構造物12之第一表面層7爲內容物之側。多層構造物1 2形成延伸之翼緣6。又，容器2 1及蓋3 1之翼緣部6之形狀無特別的限定，通常，爲圓、四角等形狀。又，容器之型狀爲杯型或盤狀均可。Fig. 4 is a sectional view showing a container and a lid formed of a second-layer structure of the present invention. The container 21 and the lid 31 shown in Fig. 4 are made of the multilayer structure of Fig. 3, and the first surface layer 7 of the multilayer structure 12 is the side of the contents. The multilayer structure 12 forms an extended flange 6. In addition, the shape of the flange portion 6 of the container 21 and the lid 31 is not particularly limited, and is generally a shape such as a circle or a corner. The shape of the container may be a cup shape or a plate shape.

由於本發明之容器及/或蓋爲優耐油性、耐藥品性、耐熱性，可作爲食品或醫藥品優良之包裝體。具體的如便當、豆腐、菜餚等之包裝體。又，回收時不易凝膠化，具優回收性。【實施方式】以下說明本發明之實施例，本發明不限定於此等之實施例。 -23- (20) (20)200416134 C _〜多層構造物〕第一多層構造物相關之實施例及比較例所示之物性之測定方法及評價方如以下所述。 (1 )層間強度 1 5 // m雙軸延伸尼龍薄膜（日本出光UNITEC (股）製：UNlLONglOO)及30//m未延伸聚丙烯薄膜以乾式貼合’得到厚度4 5 // m之尼龍/聚丙烯2層薄膜。以此薄膜爲蓋材，以聚丙烯層爲熱封側，熱封於評價用容器。以 1 9 0 °C，3秒鐘，壓力0 · 2 5 Μ P a之條件進行。熱封部份切成1 5mm幅度，作爲測定用樣本。以200mm/分引伸速度作1 8 0度剝離（蓋與容器之角度）測定強度。 (2 )耐油性評價用容器裝入容積5 0 mL日本日淸沙拉油，以微波爐（輸出6 0 0 W )加熱所定之時間，進行確認容器的變形狀況。 3分鐘之加熱時間容器無變形：◎ 2分鐘之加熱時間容器無變形：〇Since the container and / or lid of the present invention is excellent in oil resistance, chemical resistance, and heat resistance, it can be used as an excellent package for food or medicine. Specific packaging such as bento, tofu, dishes, etc. In addition, it is difficult to gelate during recovery, and has excellent recoverability. [Embodiment] Examples of the present invention will be described below, and the present invention is not limited to these embodiments. -23- (20) (20) 200416134 C _ ~ Multilayer structure] The measurement methods and evaluation methods for the physical properties shown in the examples and comparative examples related to the first multilayer structure are as follows. (1) Interlayer strength of 1 5 // m biaxially stretched nylon film (Japan Idemitsu Unitec Co., Ltd .: UNlLONglOO) and 30 // m unstretched polypropylene film are dry-laminated to obtain nylon with a thickness of 4 5 // m / Polypropylene 2-layer film. This film was used as a cover material, and a polypropylene layer was used as a heat-sealing side, and then heat-sealed to a container for evaluation. It was carried out under the conditions of 190 ° C, 3 seconds, and a pressure of 0.25 MPa. The heat-sealed portion was cut into a 15 mm width as a measurement sample. The strength was measured at 180 ° peeling (angle between lid and container) at an extension speed of 200 mm / min. (2) Oil resistance evaluation container was filled with 50 mL of Japanese sundial salad oil and heated in a microwave oven (output 600 W) for a predetermined time to confirm the deformation of the container. No deformation of the container during the heating time of 3 minutes: ◎ No deformation of the container during the heating time of 2 minutes: 〇

2分鐘之加熱時間容器變形：X2 minutes heating time container deformation: X

1分鐘以下之加熱時間容器變形：XX (3 )回收性（凝膠化）評價用薄片以日本朋來製粉碎機粉碎，設置單層衣架式模頭之日本製鋼所（股）製LOBOTEX溶融擠壓，以模頭出口溫度2 3 0 °C得〇.5mm厚度之單層薄片。 -24- (21) 200416134 單層薄片以日本森田精機工業（股）製JC-2型粉碎機粉碎，再以LABOTEX製作薄片。以上述方法於LAB OTEX重複成形5次後之〇.5mm厚度薄片，以目視檢查其外觀。外觀無問題：〇Deformation of the container during heating time of less than 1 minute: XX (3) Recyclability (gelation) The flakes for evaluation were pulverized with a Japanese-made pulverizer, and a single-layer hanger-type die made by Japan Steel Works Co., Ltd. was melt-melted. Press to obtain a single-layer sheet with a thickness of 0.5 mm at a die exit temperature of 230 ° C. -24- (21) 200416134 The single-layer sheet was pulverized by JC-2 type pulverizer manufactured by Morita Seiki Industries, Ltd., and the sheet was made by LABOTEX. A 0.5 mm-thick sheet was repeatedly formed five times in LAB OTEX in the manner described above, and its appearance was visually inspected. No problem in appearance: 〇

凝膠化及/或燒焦：XGelation and / or Scorching: X

凝膠化及/或燒焦於重複5次前發生：X XGelation and / or scorch occurred before repeating 5 times: X X

實施例1 以100重量％聚丙烯（日本出光石油化學（股）製出光PP:F-704 NT) (PP1)爲表面層，60重量％耐衝擊性聚苯乙烯（日本出光石油化學（股）製出光PS : ET-63 ) (PS1 ) 、3 5重量％ ( P P 1 ) 、5重量％相溶化劑（日本旭Example 1 100% by weight of polypropylene (Nippon Idemitsu Petrochemical Co., Ltd. Idemitsu PP: F-704 NT) (PP1) was used as a surface layer, and 60% by weight of impact-resistant polystyrene (Nippon Idemitsu Petrochemical Co., Ltd.) Light-producing PS: ET-63) (PS1), 35 wt% (PP1), 5 wt% miscibility agent (Japan Asahi

化（股）製TOFFTEC P2000:苯乙烯-丁二烯-丁烯-苯乙烯共聚物：玻璃轉移溫度（Tg ) -77t：)(相溶化劑1 ) 之組成物爲介入之中間層，使用8 0重量％耐衝擊性聚苯乙烯（日本出光石油化學（股）製出光PS: HT-52 )( PS2 )及20重量％—般聚苯乙烯（日本出光石油化學（股 )製出光PS : HH-30 ) ( PS3 )所之組成物爲基材層，以多層共擠壓法（模頭溫度23 0 °C )成形3層之薄片。薄片幅爲800mm，表面層厚度爲25//m，中間層厚度爲25// m，基材層厚度爲45 0 // m之評價用薄片。所得之薄片以曰本淺野硏究所（股）製真空壓空成形機（FK_ 043 1 - 1 〇 )以表面層爲內容物側熱成形，得到評價用容器 -25- (22) (22)200416134 (縱140mmx橫140mmx高60mm 之角容器）。評價層間強度、耐油性、回收性。評價結果如表1所示0 實施例2 以 6 1重量％耐衝擊性聚苯乙烯（日本出光石油化學 (股）製出光PS : HT-52 ) ( PS2 ) 、35重量％聚丙烯（日本出光石油化學（股）製出光 E_203 gV) (PP2) 、4 重量％相溶化劑（TOFFTEC P2000 )(相溶化劑1)之組成物爲基材層以外，以實施例1之方法得到薄片及容器。評價結果如表1所示。實施例3 以日本旭化（股）製TOFFTEC H-1043:苯乙烯-乙烯-丁烯-苯乙烯共聚物：玻璃轉移溫度（Tg ) -64°C )( 相溶化劑2 )爲中間層之相溶化層以外，以實施例1之方法得到薄片及容器。評價結果如表1所示。實施例4 以25//m厚度之無延伸聚丙烯薄膜（CPP薄膜）（日本出光 UNITEC (股）製：UNILUX RS510C ) (PP3) 之貼合面爲中間層側以實施例1之方法以多層擠壓法僅擠壓中間層及基材層之2層構造物以擠壓貼合法層合得到3 層之多層構造物。薄片幅800爲mm，表面層厚度爲25// -26- (23) (23)200416134 m，中間層厚度爲25/zm，基材層之厚度爲450//m之評價用薄片。有關評價用容器依實施例1之方法評價。評價結果如表1所示。比較例1 8 0重量％耐衝擊性聚苯乙烯（日本出光石油化學（股 )製出光PS: HT-52) (PS2)及20重量％—般聚苯乙烯 (曰本出光石油化學（股）製出光 PS: HH-30) (PS3) 所之組成物爲基材層，以多層共擠壓法（模頭溫度23 0 °C )成形單層之薄片。以25 //m厚度之無延伸聚丙烯薄膜 (CPP薄膜）（曰本出光UNITEC (股）製：UNILUX RS510C) (PP3)之貼合面以醋酸乙酯稀釋之聚酯系聚氨基甲酸乙酯接合劑塗覆乾燥後壓合之乾式貼合法得到層合之多層構造物。薄片幅爲表面層厚度爲25//m，基材層之厚度爲4 7 5 // m之評價用薄片。有關評價用容器依實施例 1之方法評價。評價結果如表1所示。比較例2 以25 // m厚度之EVA系特殊無延伸聚丙烯薄膜（ CPP 薄膜）（日本大日本 INK化學工業（製）： DIFAREN 2 8 0 K) ( PP4 )之接合層配置於基材層側，依實施例1之方法僅擠壓基材層之擠壓貼合法得到層合2層之多層構造物。薄片幅800爲mm，表面層厚度爲25//m ，基材層之厚度爲4 75 // m之評價用薄片。有關評價用容 -27- (24) 200416134 器依實施例1之方法評價結果如表1所示。比較例3 以乙烯-醋乙烯共聚物（E V A )系接合劑（接合劑1 ) (日本東曹（股）製：MELSEN M MX13:醋酸乙烯含量 1 8重量％ )作爲中間層使用外，依實施例1之方法。評價結果如表1所示。TOFFTEC P2000: styrene-butadiene-butene-styrene copolymer: glass transition temperature (Tg) -77t :) (compatibility agent 1) is an intervening intermediate layer. Use 8 0% by weight impact-resistant polystyrene (Japan Idemitsu Petrochemical Co., Ltd., Idemitsu PS: HT-52) (PS2) and 20% by weight of ordinary polystyrene (Japan Idemitsu Petrochemical Co., Ltd., Idemitsu PS: HH -30) (PS3) is composed of a base material layer, and a three-layer sheet is formed by a multi-layer co-extrusion method (die temperature of 23 0 ° C). An evaluation sheet having a sheet width of 800 mm, a surface layer thickness of 25 // m, an intermediate layer thickness of 25 // m, and a substrate layer thickness of 45 0 // m. The obtained sheet was thermoformed with a vacuum pressure forming machine (FK_043 1-1 〇) made by Asano Laboratories Co., Ltd. with the surface layer as the content side to obtain a container for evaluation -25- (22) (22) 200416134 (140mm x 140mm x 60mm high angle container). The interlayer strength, oil resistance, and recyclability were evaluated. The evaluation results are shown in Table 1. 0 Example 2 61% by weight of impact-resistant polystyrene (Nippon Idemitsu Petrochemical Co., Ltd. produced PS: HT-52) (PS2), 35% by weight polypropylene (Nippon Idemitsu The composition of the photochemical E-203 gV) (PP2) and 4% by weight of a miscibility agent (TOFFTEC P2000) (compatibility agent 1) manufactured by Petrochemical Co., Ltd. was used as the base material layer, and a sheet and a container were obtained by the method of Example 1. The evaluation results are shown in Table 1. Example 3 TOFFTEC H-1043 manufactured by Asahi Kasei Co., Ltd .: styrene-ethylene-butene-styrene copolymer: glass transition temperature (Tg) -64 ° C) (miscibility agent 2) was used as an intermediate layer. Except for the miscible layer, a sheet and a container were obtained by the method of Example 1. The evaluation results are shown in Table 1. Example 4 A 25 // m-thick non-stretched polypropylene film (CPP film) (manufactured by Idemitsu Unitec Co., Ltd .: UNILUX RS510C) (PP3) was used as the intermediate layer side, and the method of Example 1 was used to form a multilayer The extrusion method only squeezes the two-layer structure of the intermediate layer and the base material layer to extrude and laminate to obtain a three-layer multilayer structure. An evaluation sheet having a sheet width of 800 mm, a surface layer thickness of 25 //-26- (23) (23) 200416134 m, an intermediate layer thickness of 25 / zm, and a substrate layer thickness of 450 // m. The evaluation container was evaluated according to the method of Example 1. The evaluation results are shown in Table 1. Comparative Example 180 0% by weight of impact-resistant polystyrene (Idemitsu PS: HT-52) (PS2) manufactured by Idemitsu Petrochemical Co., Ltd. and 20% by weight polystyrene (Itomitsu Idemitsu Petrochemical Co., Ltd.) The composition of PS: HH-30) (PS3) was used as the substrate layer, and a single-layer sheet was formed by a multi-layer coextrusion method (die temperature of 23 0 ° C). Polyester-based polyurethane diluted with ethyl acetate with a bonding surface of 25 // m thick non-stretched polypropylene film (CPP film) (made by Idemitsu Unitec Co., Ltd .: UNILUX RS510C) (PP3) The adhesive is applied and dried, followed by a dry sticking method to obtain a laminated multilayer structure. The sheet web is an evaluation sheet having a surface layer thickness of 25 // m and a substrate layer thickness of 4 7 5 // m. The evaluation container was evaluated according to the method of Example 1. The evaluation results are shown in Table 1. Comparative Example 2 A bonding layer with a thickness of 25 // m of an EVA-based special non-stretch polypropylene film (CPP film) (Japan Dainippon INK Chemical Industry (manufactured by): DIFAREN 2 8 0 K) (PP4) was disposed on the substrate layer On the other hand, according to the method of Example 1, only the base material layer was extruded to obtain a multilayer structure with two layers laminated. An evaluation sheet having a sheet width of 800 mm, a surface layer thickness of 25 // m, and a substrate layer thickness of 4 75 // m. About evaluation capacity -27- (24) 200416134 The evaluation results of the device according to the method of Example 1 are shown in Table 1. Comparative Example 3 An ethylene-vinyl acetate copolymer (EVA) -based adhesive (Adhesive 1) (manufactured by Tosoh Corporation, Japan: MELSEN M MX13: vinyl acetate content 18% by weight) was used as an intermediate layer. The method of Example 1. The evaluation results are shown in Table 1.

比較例4 以乙烯-醋乙烯共聚物（E V A )系接合劑（接合劑1 ) (曰本東曹（股）製：MELS ΕΝ Μ MX11:醋酸乙烯含量 1 3重量％ )作爲中間層使用外，依實施例1之方法。評價結果如表1所示。比較例5 使用60重量％耐衝擊性聚苯乙烯（日本出光石油化學（股）製出光PS:ET-63) (PS1) 、35重量％(?卩1) 、5重量％相溶化劑（日本旭化（股）製TOFFTEC P2000 (相溶化劑1 )之組成物爲表面之表面層及以使用80重量％耐衝擊性聚苯乙烯（日本出光石油化學（股）製出光 PS: HT-52) (PS2)及20重量％—般聚苯乙烯（日本出光石油化學（股）製出光PS : HH-30 ) ( PS3 )所之組成物爲基材層，以多層共擠壓法（模頭溫度23 0 °C )成形2 層之薄片。 -28- (25) (25)200416134 得到薄片幅爲800mm’表面層厚度爲25/^m，基材層爲4 7 5 μ m之評價用薄片。依實施例1之方法評價。評價結果如表1所示。比較例6 使用6 1重量％耐衝擊性聚苯乙烯（日本出光石油化學（股）製出光PS : HT-52 ) ( PS2 ) 、35重量％聚丙烯 (日本出光石油化學（股）製出光E-203gV) (PP2) 、4 重量％相溶化劑（TOFFTEC P2000 )(相溶化劑1)之組成物以23 0 °C模頭溫度成形爲單層。得到薄片幅800mm，厚度爲5 00 // m之評價用薄片以外，依實施例1之方法。評價結果如表1所示。又，由於爲單層薄片，無法測定層間強度。比較例7 以1 〇〇重量％耐衝擊性聚苯乙烯（日本出光石油化學 (股）製出光PS : HT-52) ( PS2)以23CTC模頭溫度成形爲單層。得到薄片幅800mm，厚度爲500//m之評價用薄片以外’依實施例1之方法。評價結果如表1所示。又，由於爲單層薄片，無法測定層間強度。 -29- (26)200416134 比較例7 1 1 PS2 無法測定〇比較例6 1 PS1(61)+ PP1(35)+ 相溶化劑 1(4) 無法測定 X 〇比較例5 PS1(60)+ PP 1(35)+ 相溶化劑 1(5) 1 PS2(80)+ PS3(20) 3.〇g /15mm 幅 X 〇比較例4 PP1 接合劑2 PS2(80)+ PS3(20) l.Og /15mm 幅〇〇比較例3 PP1 接合劑1 PS2(80)+ PS3(20) 2.0kg /15mm 幅〇 X 比較例2 PP4 擠壓貼合 1 PS2(80)+ PS3(20) j 2.〇kg /15mm 幅〇 X 比較例1 PP3 乾式貼合 1 PS2(80)+ PS3(20) 2.5kg /15 mm 幅〇實施例4 PP3 擠壓貼合 PS1(60)+ PP1(35)+ 相溶化劑 1(5) PS2(80)+ PS3(20) 2.0kg /15mm 幅〇〇實施例3 PP1 PS1(60)+ PP1(35)+ 相溶化劑 2(5) PS2(80)+ PS3(20) 2.5kg /15mm 幅 ◎ 〇實施例2 PP1 PS1(60)+ PP 1(35)+ 相溶化劑 1(5) PS1(61)+ PP1(35)+ 相溶化劑 1(4) 2.2kg /15mm 幅 ◎ 〇實施例1 PP1 _1 PS1(60)+ PP1(35)+ 相溶化劑 1(5) PS2(80)+ PS3(20) 1 2.1kg /15mm 幅〇〇表面層中間層基材層層間強度耐油性回收性Comparative Example 4 An ethylene-vinyl acetate copolymer (EVA) -based adhesive (adhesive 1) (made by Tosoh Corporation: MELS ΕΜ MX11: vinyl acetate content 13% by weight) was used as an intermediate layer, Follow the method of Example 1. The evaluation results are shown in Table 1. Comparative Example 5 60% by weight of impact-resistant polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd., PS: ET-63) (PS1), 35% by weight (? 卩 1), and 5% by weight miscibility agent (Japan The composition of TOFFTEC P2000 (compatibility agent 1) manufactured by Asahi Kasei Co., Ltd. is a surface layer and 80% by weight of impact-resistant polystyrene is used (Idemitsu PS: HT-52) (PS2) and 20% by weight—general polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd., Idemitsu PS: HH-30) (PS3) as a substrate layer, and a multilayer coextrusion method (die temperature) 23 0 ° C) forming a two-layer sheet. -28- (25) (25) 200416134 A sheet having a width of 800 mm was obtained, and the thickness of the surface layer was 25 / ^ m, and the base sheet was 4 7 5 μm for evaluation. The evaluation was performed according to the method of Example 1. The evaluation results are shown in Table 1. Comparative Example 6 61% by weight of impact-resistant polystyrene (Nippon Idemitsu Petrochemical Co., Ltd. produced light PS: HT-52) (PS2), 35% by weight polypropylene (Idemitsu E-203gV manufactured by Idemitsu Petrochemical Co., Ltd.) (PP2), 4% by weight miscibility agent (TOFFTEC P2000) (compatibility agent 1) The composition was formed into a single layer at a die temperature of 230 ° C. A sheet with a width of 800 mm and a thickness of 5 00 // m was obtained. The method of Example 1 was followed. The evaluation results are shown in Table 1. In addition, the interlaminar strength cannot be measured because it is a single-layer sheet. Comparative Example 7 100% by weight of impact-resistant polystyrene (manufactured by Japan Idemitsu Petrochemical Co., Ltd., PS: HT-52) (PS2) at 23CTC The die was temperature-molded into a single layer. A sheet having a width of 800 mm and a thickness of 500 // m other than the sheet for evaluation was obtained according to the method of Example 1. The evaluation results are shown in Table 1. In addition, it was impossible to measure because it was a single-layer sheet. Interlaminar strength. -29- (26) 200416134 Comparative Example 7 1 1 PS2 cannot be measured 〇 Comparative Example 6 1 PS1 (61) + PP1 (35) + Compatibilizer 1 (4) X cannot be measured 〇 Comparative Example 5 PS1 (60 ) + PP 1 (35) + Compatibilizer 1 (5) 1 PS2 (80) + PS3 (20) 3.〇g / 15mm width X 〇 Comparative Example 4 PP1 adhesive 2 PS2 (80) + PS3 (20) l.Og / 15mm width 〇〇Comparative example 3 PP1 adhesive 1 PS2 (80) + PS3 (20) 2.0kg / 15mm width 〇X Comparative example 2 PP4 Extrusion lamination 1 PS2 (80) + PS3 (20) j 〇kg / 15mm width 〇X Comparative example 1 PP3 dry lamination 1 PS2 (80) + PS3 (20) 2.5kg / 15 mm width. Example 4 PP3 extrusion lamination PS1 (60) + PP1 (35) + compatibilizer 1 (5) PS2 (80) + PS3 (20) 2.0kg / 15mm width 0.00 Example 3 PP1 PS1 (60) + PP1 (35) + miscibility agent 2 (5) PS2 (80) + PS3 (20) 2.5kg / 15mm width ◎ Example 2 PP1 PS1 (60) + PP 1 (35) + Compatibilizer 1 (5) PS1 (61) + PP1 (35) + Compatibilizer 1 (4) 2.2kg / 15mm width ◎ Example 1 PP1 _1 PS1 (60) + PP1 (35) + compatibilizer 1 (5) PS2 (80) + PS3 (20) 1 2.1kg / 15mm width 〇〇 surface layer intermediate layer substrate layer interlayer strength oil resistance recoverability

-30- (27) 200416134-30- (27) 200416134

PP1:日本出光石油化學（股）製出光PP: F-704 NT PP2:日本出光石油化學（股）製出光E-203 gV PP3 :日本出光 UNITEC (股）製：UNILUXPP1: Idemitsu Petrochemical Co., Ltd. Idemitsu PP: F-704 NT PP2: Idemitsu Petrochemical Co., Ltd. Idemitsu E-203 gV PP3: Japan Idemitsu UNITEC (Unit): UNILUX

RS510CRS510C

PP4 :日本大日本 INK化學工業（製）：DIFAREN 280 KPP4: Japan Dainippon INK Chemical Industry (manufacturing): DIFAREN 280 K

PS1:日本出光石油化學（股）製出光PS: ET-63 PS2:日本出光石油化學（股）製出光PS: HT-52 PS3:日本出光石油化學（股）製出光PS: HH-30 相溶化劑1 :曰本旭化（股）製TOFFTEC P2000 相溶化劑2 :日本旭化（股）製TOFF TEC H-1043 EVA接合劑 1 :日本東曹（股）製：MELSEN Μ ΜΧ1 3 EVA接合劑 2 :日本東曹（股）製：MELSEN Μ ΜΧ1 1PS1: Idemitsu Petrochemical Co., Ltd. Idemitsu PS: ET-63 PS2: Idemitsu Petrochemical Co., Ltd. Idemitsu PS: HT-52 PS3: Idemitsu Petrochemical Co., Ltd. Idemitsu PS: HH-30 Compatibility Agent 1: Tofftec P2000 compatible by Asahi Kasei Co., Ltd. 2: TOFF TEC H-1043 EVA cement manufactured by Asahi Kasei Co., Ltd. 1: MELSEN ΜΜχ1 3 EVA cement manufactured by Tosoh Co., Ltd. 2: Japan Tosoh (stock) system: MELSEN Μ MX1 1

由表1可知實施例之薄片層間強度極高，耐油性優，且，回收時不會有凝膠化情形。〔第二多層構造物〕第二多層構造物相關之實施例及比較例所示之物性之測定方法及評價方如以下所述。 (1 )熱封外觀以多層構造物之第一表面層相向對折，由第二表面層側熱封。以160°c，5秒鐘’ 0·25 Mpa壓力進行。 -31 - (28) (28)200416134 以目視觀察熱封後之第二表面層，無溶融或拉絲，表面無粗糙等的不良外觀者爲〇，有者爲X。 (2 )層間強度以多層構造物之第一表面層相向對折，由第二表面層側熱封。以1 6 0 °C，5秒鐘，0 · 2 5 Μ P a壓力進行。熱封部份切成1 5 mm幅度，作爲測定用樣本。以2 00mm/分引伸速度作90度剝離測定強度。其結果’得到充分層間強度者爲〇，其他不能得到熱封界面之接合強度，或多層構造物之層間發生脫落者爲X。 (3 )回收性與上述第一多層構造物「（ 3 )回收性」同法方法進行。實施例5 以100重量％高密度聚乙烯（HDPE)(日本出光石油化學（股）製出光HD : 1 10Y :密度966kg/ m3 : MFR ·· 1 3 g / 1 0 分鐘：融點（Tm ) = 1 3 1 · 7。(：）（ PE 1 )爲第一表面層，以55重量％耐衝擊性聚苯乙烯（HIPS )(日本出光石油化學（股）製出光PS: ET-63: MFR = 2.5g / 1〇分鐘）（PS1) 、35重量％聚丙儲（日本出光石油化學（股）製出光 PP:F-704 NT:Tm=164t：) (PP1) 、5 重量 %相溶化劑（日本旭化（股）製 TOFFTEC P2000 ：苯乙烯-丁二烯-丁烯-苯乙烯共聚物（S B B S ):玻璃轉移溫度 (Tg ) _77°C )(相溶化劑1 )之組成物爲介入之中間層 -32- (29) (29)200416134 ，使用80重量％耐衝擊性聚苯乙烯（日本出光石油化學 (股）製出光PS: HT-52) (PS2)及20重量％一般&本乙烯（日本出光石油化學（股）製出光PS : HH_30 )( PS3 )所之組成物爲基材層，55重量％耐衝擊性聚苯乙嫌 (曰本出光石油化學（股）製出光PS: ET_63) (PS1) 、35重量％聚丙烯（日本出光石油化學（股）製出光PP :F-704 NT) ( p P 1 ) 、1〇重量％相溶化劑（日本旭化（股）製Τ Ο F F T E C P 2 0 0 0 )(相溶化劑1 )之組成物爲第二表面層，以多層共擠壓法（模頭溫度2 3 0 °C )成形5層之薄片。薄片幅爲8 0 0 m m ’第一*表面層厚度爲2 5 // m ’接合層厚度爲25//m，第二表面層厚度爲25//m，基材層厚度爲 4〇〇//111全體厚度爲50〇111111之評價用薄片。所得之薄片以日本淺野硏究所（股）製真空壓空成形機（FK-043 1 - 1 0 )以表面層爲內容物側熱成形，得到評價用容器（縱140mmx橫140mmx高60mm之角容器）。評價層間強度、耐油性、回收性。評價結果如表2所示。實施例6 使用1 0 0重量％聚丙烯（日本出光石油化學（股）製出光PP : F-704 NT) ( PP1 )爲第二表面層以外，以實施例5之方法得到薄片及容器。評價結果如表2所示。 -33- (30) (30)200416134 實施例7 使用日本旭化（股）製TOFFTEC H-1043 (苯乙燃·乙烯-丁烯·苯乙烯共聚物）（SBBS) : (Tg)_64°C)(相溶化劑2 )作爲接合劑及第二表面層之相溶化劑以外，依實施例5之方法。評價結果如表2所示。實施例8 以25//m厚度之無延伸聚丙烯薄膜（cpp薄膜）（日本出光 UNITEC (股）製：UNILUX RS510C) (PP3) 之貼合面爲中間層側以實施例5之方法以多層擠壓法濟壓僅第一表面層、接合層、基材層、接合層之4層，以擠壓貼合層合得到5層之多層構造物。薄片幅爲8 00mm，第 —表面層厚度爲25/zm，接合層厚度爲25//m，第二表面層厚度爲25//m’基材層厚度爲 400//m全體厚度爲 5 0 0mm之評價用薄片。依實施例5之方法，評價結果如表2所示。比較例8 以100重量％高密度聚乙烯（出光HD : 1 10Y ) ( PE1From Table 1, it can be seen that the interlaminar strength of the sheet is extremely high, the oil resistance is excellent, and there is no gelation during recovery. [Second multilayer structure] The measurement methods and evaluation methods for the physical properties shown in the examples and comparative examples related to the second multilayer structure are as follows. (1) Appearance of heat-sealing The first surface layer of the multilayer structure is folded in opposite directions, and the second surface layer is heat-sealed. It was carried out at 160 ° c, 5 seconds' pressure of 0.25 Mpa. -31-(28) (28) 200416134 Visually observe the second surface layer after heat-sealing. If there is no melting or drawing, and the surface does not have a rough appearance such as rough, it is 0, some are X. (2) Interlayer strength The first surface layer of the multilayer structure is folded opposite to each other and heat-sealed by the second surface layer side. It was performed at 160 ° C, 5 seconds, and a pressure of 0.25 MPa. The heat-sealed portion was cut into a 15 mm width as a measurement sample. The strength was measured at 90 ° peeling at an extension speed of 200 mm / min. As a result, it is 0 if sufficient interlayer strength is obtained, and the joint strength of other heat-sealable interfaces cannot be obtained, or X is obtained when interlayer delamination occurs in the multilayer structure. (3) Recyclability Performed in the same manner as the above-mentioned "(3) Recyclability" of the first multilayer structure. Example 5 100% by weight of high-density polyethylene (HDPE) (manufactured by Idemitsu Petrochemical Co., Ltd.) HD: 1 10Y: density 966kg / m3: MFR ·· 1 3 g / 10 minutes: melting point (Tm) = 1 3 1 · 7. (:) (PE 1) is the first surface layer, and 55% by weight of impact-resistant polystyrene (HIPS) (produced by Idemitsu Petrochemical Co., Ltd.) PS: ET-63: MFR = 2.5g / 10 minutes) (PS1), 35% by weight polypropylene storage (Japan Idemitsu Petrochemical Co., Ltd. Idemitsu PP: F-704 NT: Tm = 164t :) (PP1), 5% by weight miscibility agent ( TOFFTEC P2000 made by Asahi Kasei Co., Ltd .: styrene-butadiene-butene-styrene copolymer (SBBS): glass transition temperature (Tg) _77 ° C) (compatibility agent 1) is involved Interlayer -32- (29) (29) 200416134, using 80% by weight impact-resistant polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd., PS: HT-52) (PS2) and 20% by weight The composition of ethylene (Idemitsu Petrochemical Co., Ltd., Idemitsu PS: HH_30) (PS3) is a base material layer, and 55% by weight of impact-resistant polystyrene is called Idemitsu PS: ET_63) (PS1), 35% by weight polypropylene (Nippon Idemitsu Petrochemical Co., Ltd. Idemitsu PP: F-704 NT) (p P 1), 10% by weight miscible agent (Japan Asahi Chemical ( The composition of T 0 FFTECP 2 0 0 0) (compatibility agent 1) is the second surface layer, and a five-layer sheet is formed by a multilayer coextrusion method (die temperature 2 30 ° C). 8 0 0 mm 'the first * surface layer thickness is 2 5 // m' the bonding layer thickness is 25 // m, the second surface layer thickness is 25 // m, and the substrate layer thickness is 400 // 111 The overall thickness of the evaluation sheet was 50 011 111. The obtained sheet was thermoformed by using a vacuum pressure forming machine (FK-043 1-10) made by Asano Laboratories, Ltd., with the surface layer as the content side, and evaluated. A container (vertical container of 140 mm x 140 mm x 60 mm in height) was evaluated. The interlayer strength, oil resistance, and recyclability were evaluated. The evaluation results are shown in Table 2. Example 6 100% by weight polypropylene (Japan Idemitsu Petrochemical Co., Ltd. ) Production of light PP: F-704 NT) (PP1) except for the second surface layer, a sheet and a container were obtained by the method of Example 5. The evaluation results are shown in Table 2 -33- (30) (30) 200416134 Example 7 Tofftec H-1043 (styrene-ethylene-butene-styrene copolymer) manufactured by Asahi Kasei Co., Ltd. (SBBS): (Tg) _64 ° C) (compatibility agent 2) The method of Example 5 was used except for the bonding agent and the compatibility agent of the second surface layer. The evaluation results are shown in Table 2. Example 8 A 25 // m-thick non-stretched polypropylene film (cpp film) (manufactured by Idemitsu Unitec Co., Ltd .: UNILUX RS510C) (PP3) was used as the intermediate layer side. The extrusion method compresses only four layers of the first surface layer, the bonding layer, the substrate layer, and the bonding layer, and laminates them by extrusion bonding to obtain a five-layer multilayer structure. The sheet width is 800 mm, the thickness of the first surface layer is 25 / zm, the thickness of the bonding layer is 25 // m, the thickness of the second surface layer is 25 // m ', the thickness of the substrate layer is 400 // m, and the overall thickness is 50. 0mm sheet for evaluation. According to the method of Example 5, the evaluation results are shown in Table 2. Comparative Example 8 100% by weight high-density polyethylene (HD: 1 10Y) (PE1

)爲第一表面層，以78重量°/。耐衝擊性聚苯乙烯（出光 PS: ET-63) (PS1) 、12重量％高密度聚乙烯（出光HD :1 10Y ) ( PEI ) 、1 0重量％相溶化劑（日本旭化（股）製TOFFPLENTP126:苯乙烯-丁二烯-苯乙烯共聚物（SBS )Tg = -7 0°C )(相溶化劑3 )之組成物爲介入之接合層’ -34- (31) 200416134 使用80重量％耐衝擊性聚苯乙烯（日本出光石油化學（股）製出光PS:HT-52) (PS2)及20重量％—般聚苯乙烯（日本出光石油化學（股）製出光PS: HH-30) ( PS3 )所之組成物爲基材層，7 8重量％耐衝擊性聚苯乙丨希（出光PS: ET-63) (PS1) 、12重量％高密度聚乙儲（出光 H D : 1 1 0 Y ) ( ΡΕ1 ) 、10 重量％相溶化劑（T 〇 F F p L Ε Ν) Is the first surface layer, with a weight of 78 / °. Impact-resistant polystyrene (Idemitsu PS: ET-63) (PS1), 12% by weight high-density polyethylene (Idemitsu HD: 1 10Y) (PEI), 10% by weight miscible agent (Japan Asahi Chemical Co., Ltd.) Production of TOFFPLENTP126: styrene-butadiene-styrene copolymer (SBS) Tg = -7 0 ° C) (compatibility agent 3) The composition is intervening bonding layer '-34- (31) 200416134 Use 80 weight % Impact resistance polystyrene (Japan Idemitsu Petrochemical Co., Ltd. Idemitsu PS: HT-52) (PS2) and 20% by weight-general polystyrene (Japan Idemitsu Petrochemical Co., Ltd. Idemitsu PS: HH-30 ) (PS3) The composition is a base material layer, 78% by weight of impact-resistant polystyrene 丨 Greek (Idemitsu PS: ET-63) (PS1), 12% by weight high density polyethylene storage (Idemitsu HD: 1 1 0 Y) (ΡΕ1), 10% by weight compatibilizer (T 〇FF p L Ε Ν

ΤΡ126)爲第二表面層，以多層共擠壓法（検頭溫度230 °C )成形5層之薄片。薄片幅爲800mm，第一表面層厚度爲25// m’接合層厚度爲25//m，第二表面層厚度爲25//m，基材層厚度爲 400 // m全體厚度爲5 00mm之評價用薄片。相關之評價用容器，依實施例5之方法。評價結果如表2所示。比較例9TP126) is a second surface layer, and a 5-layer sheet is formed by a multi-layer co-extrusion method (head temperature 230 ° C). The sheet width is 800mm, the thickness of the first surface layer is 25 // m ', the thickness of the bonding layer is 25 // m, the thickness of the second surface layer is 25 // m, the thickness of the substrate layer is 400 // m, and the overall thickness is 5000mm Evaluation sheet. The related evaluation container was the same as that of Example 5. The evaluation results are shown in Table 2. Comparative Example 9

使用聚丙烯（出光PP: F-704 NT) (PP1)爲第二表面層以外，以實施例5之方法得到薄片及容器。評價結果如表2所示。比較例1 0 以25//m厚度之無延伸聚丙烯薄膜（1^11^乂113-5 1 0 C )( P P 2 )之貼合面配置於接合層側，依比較例8之方法，以多層擠壓法僅擠壓第一表面層、接合層、基材層、接合層之4層，以擠壓貼合層合得到5層之多層構造物。薄片幅爲8 00mm，第一表面層厚度爲25 ，接合層厚 -35- (32) (32)200416134 度爲25//m，第二表面層厚度爲25//m，基材層厚度爲 40 0 // m全體厚度爲5 00mm之評價用薄片。依實施例5之方法，評價結果如表2所示。比較例1 1 以25//m厚度之無延伸聚丙烯薄膜（uNILUX RS-5 1 0C ) ( PP2 )之貼合面配置於接合層側，依比較例8之方法，以多層擠壓法僅擠壓第一表面層、接合層、基材層、接合層之4層，以乾式貼合層合得到5層之多層構造物。薄片幅爲800mm，第一表面層厚度爲25//m，接合層厚度爲25//m，第二表面層厚度爲25//m，基材層厚度爲 4〇〇 // m全體厚度爲5 00mm之評價用薄片。相關之評價用容器’依實施例5之方法，評價結果如表2所示。 -36- 200416134 比較例11 PEl(lOO) (Ν PS1(78)+ ΡΕ1(12)+ 相溶化劑 3(10) (Ν PS2(80)+ PS3(20) ο 寸 PS1(78)+ ΡΕ1(12)+ 相溶化劑 3(10) (Ν PP2(100) 乾式貼合 (Ν ο (Ν 〇〇 X 比較例10 PEl(lOO) (Ν PS1(78)+ ΡΕ1 (12)+ 相溶化劑 3(10) (Ν PS2(80)+ PS3(20) Ο 寸 PS1(78)+ ΡΕ1(12)+ 相溶化劑 3(1〇) <N PP2(100) 熱貼合 m (Ν ο (Ν m 〇 X 〇比較例9 PEl(lOO) (Ν 太太歡〇二二垵g un (Ν PS2(80)+ PS3(20) ο ο 太太S A 二二娣c S S UTi <N PP1(100) tn (Ν m (Ν ΠΊ 〇 X 〇比較例8 PEl(lOO) (η (Ν 太太δ ^ εί ^2 〇二二節^ <N PS2(80)+ PS3(20) ο ο PS1(78)+ PE1(12)+ 相溶化劑 3(10) kn (N ^ ^ ίφ w s s ^ (Ν ο X 〇〇實施例8 PEl(lOO) WO (Ν tn CN PS2(80)+ PS3(20) ο 寸太夂S υο tn \ Ί ^ m ^ S ^ g：孽— <N PP2(100) 熱貼合 tn (Ν ο (Ν m 〇〇〇實施例7 ί PEl(lOO) (D (Ν 太太g ^ ϊίί ^ 〇以藝〜 ^T) <N PS2(80)+ PS3(20) ο 寸太太S a g & I" <N §ll〇 i!r κη (Ν m (Ν m 〇〇〇實施例6 PEl(lOO) j <Ν 太；ts 二=娣c <N PS2(80)+ PS3(20) ο 寸太太s =二锑c g &璧— (N PP1(100) <Ν m r4 m 〇〇〇實施例5 PEl(lOO) (η (Ν 太太S ^ ^ {Φ — κη (N PS2(80)+ PS3(20) ο ο 太太g s g: ^ ^ κη (N ^ ^ ίφ w p十® — CLh pH -Kr- tn (Ν m (N m 〇〇〇成分 (重量％) 厚度(V ηι) 成分 (重量％) 厚度("m)J 成分 (重量％) 厚度(//ηι) 成分 (重量％) 厚度("m) 成分 (重量％) 厚度(Vm) 第一表面層接合層基材層接合層第二表面層表面層之融點，差(°c) 1熱封外觀| 層間強度 |回收性|Using polypropylene (Idemitsu PP: F-704 NT) (PP1) as the second surface layer, a sheet and a container were obtained in the same manner as in Example 5. The evaluation results are shown in Table 2. Comparative Example 10 A 25 // m-thick non-stretched polypropylene film (1 ^ 11 ^ 乂 113-5 1 0 C) (PP 2) was disposed on the bonding layer side, and according to the method of Comparative Example 8, In the multilayer extrusion method, only four layers of the first surface layer, the bonding layer, the substrate layer, and the bonding layer are extruded, and the five-layer multilayer structure is obtained by lamination and lamination. The sheet width is 800 mm, the thickness of the first surface layer is 25, the thickness of the bonding layer -35- (32) (32) 200416134 degrees is 25 // m, the thickness of the second surface layer is 25 // m, and the thickness of the substrate layer is 40 0 // m Evaluation sheet with an overall thickness of 5000 mm. According to the method of Example 5, the evaluation results are shown in Table 2. Comparative Example 1 1 A 25 // m-thick non-stretched polypropylene film (uNILUX RS-5 1 0C) (PP2) was placed on the bonding layer side. According to the method of Comparative Example 8, the multilayer extrusion method was used only. Four layers of the first surface layer, the bonding layer, the base material layer, and the bonding layer were extruded and laminated in a dry manner to obtain a five-layer multilayer structure. The sheet width is 800mm, the thickness of the first surface layer is 25 // m, the thickness of the bonding layer is 25 // m, the thickness of the second surface layer is 25 // m, and the thickness of the substrate layer is 400 // m. The overall thickness is An evaluation sheet of 5,000 mm. The related evaluation container 'was subjected to the method of Example 5 and the evaluation results are shown in Table 2. -36- 200416134 Comparative Example 11 PEl (100) (N PS1 (78) + PE1 (12) + Compatibilizer 3 (10) (Ν PS2 (80) + PS3 (20) ο inch PS1 (78) + PE1 ( 12) + compatibilizer 3 (10) (N PP2 (100) dry lamination (N ο (Ν〇〇X Comparative Example 10 PEl (lOO) (NPS1 (78) + PE1 (12) + compatibilizer 3 (10) (N PS2 (80) + PS3 (20) 〇 inch PS1 (78) + PE1 (12) + compatibilizing agent 3 (1〇) < N PP2 (100) Hot lamination m (Ν ο (Ν m 〇X 〇 Comparative Example 9 PEl (100) (N Mrs. Huan 02 二 g un (N PS2 (80) + PS3 (20) ο ο Mrs. SA 娣 c 娣 SS UTi < N PP1 (100) tn (N m (N ΠΊ 〇X 〇 Comparative Example 8 PEl (lOO) (η (wife Mrs. δ ^ εί ^ 2 〇 Section 22) ^ < N PS2 (80) + PS3 (20) ο ο PS1 (78) + PE1 (12) + compatibilizer 3 (10) kn (N ^ ^ ίφ wss ^ (N ο X 〇〇 Example 8 PEl (100) WO (N tn CN PS2 (80) + PS3 (20) ο inch too夂 S υο tn \ Ί ^ m ^ S ^ g: 孽 — < N PP2 (100) thermal lamination tn (N ο (Ν m 〇〇〇 Example 7) PEl (lOO) (D (Ν wife g ^ ϊίί ^ 〇以艺〜 ^ T) < N PS2 (80) + PS3 (20) ο Mrs. Inch S ag & I " < N §ll〇i! r κη (N m (Ν m 〇〇〇 Example 6 PEl (100) j < N too; ts; = 娣 c < N PS2 (80) + PS3 (20) 太 inch wife s = diantimony cg & 璧— (N PP1 (100) < N m r4 m 〇〇〇 Example 5 PEl (lOO) (η (N Mrs. S ^ ^ {Φ — κη (N PS2 (80) + PS3 (20) ο οr wife gsg : ^ ^ κη (N ^ ^ ίφ wp 十 ® — CLh pH -Kr- tn (N m (N m 〇〇〇〇 Composition (wt.%) Thickness (V ηι) Ingredient (wt.%) Thickness (" m) J Ingredient (wt.%) Thickness (// ηι) Ingredient (wt.%) Thickness (" m) Ingredient (wt.%) Thickness (Vm) First surface layer bonding layer Substrate layer bonding layer Second surface layer Surface layer fusion Point, difference (° c) 1 Heat seal appearance | Interlayer strength | Recyclability |

-37- (34) (34)200416134 PE1:日本出光石油化學（股）製出光HD· 11〇Y ΡΡ1 :日本出光石油化學（股）製出光PP: F-7〇4NT PP2 :日本出光 UNITEC (股）製：UNILUX RS510C psi:日本出光石油化學（股）製出光ps: ET-63 PS2 :日本出光石油化學（股）製出光PS : HT·52 PS3 :日本出光石油化學（股）製出光PS : HH-30 相溶化劑1 :曰本旭化（股）製T0FFTEC P2000 相溶化劑2 ··曰本旭化（股）製T0FFTEC H_1043 相溶化劑3 :日本旭化（股）製TOFFPLEN TP126 由表2可知實施例之薄片層間強度極高，耐油性優，無不良外觀，且，回收時不會有凝膠化情形。〔產業上之利用領域〕依本發明可得到耐油性、熱封性、回收性優之聚苯乙烯系多層構造物及包裝體。-37- (34) (34) 200416134 PE1: Idemitsu HD · 11〇Y PP1, manufactured by Idemitsu Petrochemical Co., Ltd. PP: F-7〇4NT PP2: Idemitsu UNITEC ( Stock: System: UNILUX RS510C psi: Japan Idemitsu Petrochemical Co., Ltd. Idemitsu ps: ET-63 PS2: Japan Idemitsu Petrochemical Co., Ltd. Idemitsu PS: HT · 52 PS3: Japan Idemitsu Petrochemical Co., Ltd. Idemitsu PS : HH-30 Compatibilizer 1: Toffftec P2000 manufactured by Asahi Kabushiki Co., Ltd. 2 · T0FFTEC H_1043 manufactured by Asahi Chemical Co., Ltd. 3: TOFFPLEN TP126 manufactured by Asahi Kasei Co., Ltd. by Table 2 shows that the interlaminar strength of the sheet in the examples is extremely high, the oil resistance is excellent, there is no bad appearance, and no gelation occurs during recovery. [Application field in industry] According to the present invention, a polystyrene-based multilayer structure and a packaging body having excellent oil resistance, heat sealability, and recyclability can be obtained.

【圖式簡單說明】圖1所不爲本發明之第一多層構造物之斷面圖。圖2所示爲由發明之第一多層構造物所成之容器及蓋 ’ （a)爲蓋之斷面圖，（b)爲容器之斷面圖。圖3所示爲本發明之第二一多層構造物之斷面圖。圖4所示爲由發明之第二多層構造物所成之容器及蓋 ’ （a)爲蓋之斷面圖，（b)爲容器之斷面圖。 -38- (35) 200416134 主要元件對照表 1 :表面層 2 :中間層 3 :基材層 4 :回收基材層 5 :基材層 6 :翼緣部[Brief Description of the Drawings] FIG. 1 is not a sectional view of the first multilayer structure of the present invention. Fig. 2 shows a container and a lid formed by the first multilayer structure of the invention (a) is a sectional view of the lid, and (b) is a sectional view of the container. FIG. 3 is a cross-sectional view of a second multi-layer structure of the present invention. Fig. 4 shows a container and a lid formed of the second multilayer structure of the invention (a) is a sectional view of the lid, and (b) is a sectional view of the container. -38- (35) 200416134 Main component comparison table 1: Surface layer 2: Intermediate layer 3: Substrate layer 4: Recycled substrate layer 5: Substrate layer 6: Flange portion

7 :第一表面層 8 a :接著層 8 b :接著層 9 :第二表面層 1 〇 :多層構造物 1 1 :多層構造物 1 2 :多層構造物 20 :容器7: First surface layer 8a: Adhesive layer 8b: Adhesive layer 9: Second surface layer 10: Multi-layer structure 11: Multi-layer structure 12: Multi-layer structure 20: Container

21 :容器 30 :蓋 31 :蓋 -39-21: Container 30: Lid 31: Lid -39-

Claims

200416134 Π) Patent application scope 1. A multilayer structure characterized in that the substrate layer is made of polystyrene resin, and a surface layer made of polyolefin resin is formed through an intermediate layer, and the intermediate layer is The polystyrene resin is composed of 5 to 75 parts by weight, 75 to 25 parts by weight of polyolefin, and 30 to 80 parts by weight of aromatic vinyl. The intermediate layer is the polystyrene resin. Combined with 100 parts by weight of a polyolefin-based resin, 1 to 20 parts by weight of a compatibilizing agent is blended. The compatibilizing agent is saturated with hydrogen based on 35% or more of the double bonds of the conjugated diene, and is aromatic. A block copolymer of ethylene and a conjugated diene. 2. A multilayer structure characterized in that the base layer is made of polystyrene resin and polyolefin resin, and a surface layer made of polyolefin resin is formed through an intermediate layer, and the intermediate layer is made of poly 25 ~ 75 parts by weight of styrenic resin and 75 ~ 25 parts by weight of polyolefin, and a combination of 30 to 80 parts by weight of aromatic vinyl, which is based on conjugated diene Over 35% of the double bonds are formed by hydrogen-saturated, block copolymers of aromatic ethylene and conjugated diene. 3. A multilayer structure characterized in that the base layer is made of polystyrene resin, a first surface layer made of polyethylene resin is formed through a bonding layer, and a polypropylene resin is formed The second surface layer, the bonding layer is made of a polystyrene resin, a polypropylene resin, and a compatible -40- (2) 200416134 chemical agent. 4. A multilayer structure characterized in that the base layer is made of polystyrene resin, a first surface layer made of polyethylene resin is formed through a bonding layer, and a polystyrene resin, The first surface layer made of a polypropylene-based resin and a compatibilizer, and the bonding layer is made of a polystyrene-based resin, a polypropylene-based resin, and a compatibilizer. 5. The multilayer structure according to item 3 of the scope of the patent application, characterized in that the base layer is made of polystyrene storage resin, and the first surface layer is made of polyethylene resin through the intermediate layer, And a second surface layer made of polypropylene resin, and the intermediate layer is made of 25 to 75 parts by weight of polystyrene resin and 75 to 25 parts by weight of polypropylene, and the combined aromatic vinyl content is 30 to 80 weight The intermediate layer is composed of 100 parts by weight of the polystyrene resin and polypropylene resin described above, and 1 to 20 parts by weight of a compatibilizing agent is blended. More than 35% of the double bonds of conjugated diene are saturated with hydrogen and formed by block copolymers of aromatic ethylene and conjugated diene. 6. A multilayer structure according to item 4 of the scope of patent application, characterized in that the surface layer «I The base layer is made of polystyrene resin and the first surface layer is formed by a bonding layer -41-(3) 200416134 The bonding layer is made of 25 to 75 parts by weight of polystyrene resin and 75 to 25 parts by weight of polypropylene and 30 to 80 parts by weight of aromatic vinyl. For 100 parts by weight of the styrene resin and the above-mentioned polypropylene-based resin, 丨 ~ 20 parts by weight of a compatibilizing agent is blended.

The compatibilizing agent is based on the fact that more than 35% of the double bonds of the conjugated diene are saturated with hydrogen and are formed by block copolymers of aromatic ethylene and conjugated diene. The first surface layer is made of poly The second surface layer is made of 25 to 75 parts by weight of polystyrene resin and 75 to 25 parts by weight of polypropylene, and the combined aromatic vinyl content is 30 to 80 parts by weight. For the two surface layer system, 100 parts by weight of the polystyrene resin and the polypropylene resin are combined, and i to 20 parts by weight of the compatibilizing agent is added. The compatibilizing agent is based on the double bond of the conjugated diene. More than 35% are saturated with hydrogen element. 'Aromatic ethylene and conjugated diene block copolymer. 7 · If the multi-layer structure according to item 3 or 4 of the scope of patent application, wherein the compatibilizing agent of the bonding layer and / or the second surface layer is the hydrogen addition of the block copolymer of aromatic vinyl and conjugated diene The person. 8) If the multilayer structure of item 1 or 2 of the patent application scope, wherein the polyolefin resin of the surface layer is a polypropylene resin. 9 · The multilayer structure according to any one of claims 1-4, wherein the glass transition temperature of the above-mentioned miscibility agent is -60 t: the following. 1 〇-A container, lid, and packaging body formed of a multilayer structure such as the item 1 or 2 of the scope of application for a patent (42) 200416134, characterized in that the surface layer is on the content side. 1 1. A container, a lid, and a packaging body formed of a multilayer structure according to any one of claims 3 to 6 of the scope of patent application, characterized in that the above-mentioned first surface layer is on the content side.

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