TWI586535B - Multi-layer film for lamination with low adsorptive properties, composite film using the same and packaging material - Google Patents
Multi-layer film for lamination with low adsorptive properties, composite film using the same and packaging material Download PDFInfo
- Publication number
- TWI586535B TWI586535B TW102135773A TW102135773A TWI586535B TW I586535 B TWI586535 B TW I586535B TW 102135773 A TW102135773 A TW 102135773A TW 102135773 A TW102135773 A TW 102135773A TW I586535 B TWI586535 B TW I586535B
- Authority
- TW
- Taiwan
- Prior art keywords
- resin
- layer
- film
- multilayer film
- low
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
Description
本發明是有關於一種可較佳地用作對食品、藥品、工業零件等進行包裝的包裝材的膜，且本發明是有關於一種積層用多層膜及使用該膜的包裝材，上述積層用多層膜的外觀、易撕裂性、熱封性、耐捲曲性優異，並且來自內容物的揮發成分的非吸附性等亦良好。 The present invention relates to a film which can be preferably used as a packaging material for packaging foods, pharmaceuticals, industrial parts, and the like, and the present invention relates to a multilayer film for laminated layers and a packaging material using the same, the multilayer for the above laminated layer The film is excellent in appearance, tearability, heat sealability, and curl resistance, and the non-adsorptivity of the volatile component derived from the content is also good.
於近年來的通用設計(universal design)化傾向中，作為對社會弱者(高齡者、幼兒、殘障者等)的關照，消費者容易開封的方式、例如易開封性、易撕裂性逐漸受到重視。然而，若欲提高易開封性、易撕裂性，則有以下問題：作為包裝材原本的功能的熱封強度降低，由此導致搬送時或店頭陳列時的袋破損、內容物的散落等。 In recent years, in the general design trend, as a concern for the weak (aged, young, disabled, etc.), consumers are more likely to open the seal, such as easy opening and tearing. . However, if it is desired to improve the easy-opening property and the tearability, there is a problem that the heat-sealing strength which is the original function of the packaging material is lowered, thereby causing damage to the bag at the time of conveyance or storefront display, scattering of the contents, and the like.
作為賦予有易撕裂性的膜，已提出了一種於包含含有脂環式結構的聚合物的層上積層包含其他熱塑性樹脂的層而成的包裝膜(例如參照專利文獻1)。該包裝膜由於薄至50μm，故撕裂性良好，另外防濕性亦優異，但主要被用作纏繞膜(wrapping film) 或伸縮膜(stretch film)，且並未保證成形為容器或袋時的強度等。另外，該膜是以單體形式的使用為目的，並未設想積層用膜形式的使用。 A film having a layer containing another thermoplastic resin laminated on a layer containing a polymer having an alicyclic structure has been proposed as a film having a tear-off property (see, for example, Patent Document 1). Since the packaging film is as thin as 50 μm, it has good tearability and is excellent in moisture resistance, but is mainly used as a wrapping film. Or a stretch film, and the strength and the like when formed into a container or a bag are not guaranteed. Further, the film is intended for use in a monomer form, and the use of a film form for lamination is not contemplated.
同樣地，亦提供了一種於環狀聚烯烴系樹脂組成物層的兩鄰接層上積層聚烯烴系樹脂層而成的積層用膜(例如參照專利文獻2)。專利文獻2中提供的膜是與其他基材貼合而使用，且為了維持密封強度，將兩面設定為烯烴系樹脂，為了抑制來自內容物的揮發成分的吸附，將環狀聚烯烴系樹脂組成物層設定為中間層。藉由具有此種多層構成，可藉由中間層在某種程度上控制內容物的吸附，但無法完全防止揮發成分透過密封層部分，於長期保存的情形時，有時揮發成分到達中間層(環狀烯烴系樹脂組成物層)而產生密封層與中間層的脫層(delamination)。另外，該文獻2的實施例中使用的環狀聚烯烴系樹脂為玻璃轉移溫度低的等級(grade)，非吸附性的水準(level)未達到實用水準，進而，密封層的厚度比率高，由此實質上無法防止揮發成分對積層用膜的吸附的可能性(possibility)高。 In the same manner, a film for a laminate in which a polyolefin resin layer is laminated on two adjacent layers of a cyclic polyolefin-based resin composition layer (see, for example, Patent Document 2). The film provided in Patent Document 2 is used in combination with another substrate, and in order to maintain the sealing strength, both surfaces are set to an olefin resin, and in order to suppress adsorption of volatile components from the content, a cyclic polyolefin resin is formed. The object layer is set to the middle layer. By having such a multilayer structure, the adsorption of the contents can be controlled to some extent by the intermediate layer, but the volatile component cannot be completely prevented from passing through the sealing layer portion, and in the case of long-term storage, the volatile component sometimes reaches the intermediate layer ( The cyclic olefin resin composition layer) causes delamination of the sealing layer and the intermediate layer. Further, the cyclic polyolefin-based resin used in the examples of the document 2 has a low glass transition temperature, the level of non-adsorptivity does not reach a practical level, and further, the thickness ratio of the sealing layer is high. Therefore, it is substantially impossible to prevent the possibility that the volatile component adsorbs to the film for lamination is high.
就食品安全性等觀點而言，近年來，內容物視認性亦不斷受到重視。即，於貼合的基材具有透明性的情形時，積層用膜亦必須為透明，另外，具有表面光澤性的情況下，亦可期待與透明基材貼合時的美觀性亦變良好的效果。 In terms of food safety and the like, in recent years, the visibility of content has also received increasing attention. In other words, when the bonded substrate has transparency, the film for lamination must be transparent, and when it has surface gloss, it is expected that the appearance when it is bonded to the transparent substrate is also excellent. effect.
另外，積層用膜是於製造後靜置保管直至實質上與基材貼合為止。通常，為了獲得與黏接劑等的濡濕性，通常對積層用 膜表面實施電暈處理等表面處理，但已知於將通常的烯烴系樹脂設定為表面層的情形時，存在多層膜製造後進行的表面處理度的經時劣化。即，於將經保管的積層用膜與基材貼合時，有時由保管期間導致產生黏接強度(積層強度)的不均勻，故引起產品性能的偏差。黏接強度的降低會產生積層用膜與基材間的脫層，故導致無法充分發揮積層用膜的易撕裂性的效果。 Further, the film for lamination is left to stand after production until it is substantially bonded to the substrate. Usually, in order to obtain the wettability with an adhesive or the like, it is usually used for lamination. Although the surface of the film is subjected to a surface treatment such as a corona treatment, it is known that when a normal olefin-based resin is used as a surface layer, the degree of surface treatment after the production of the multilayer film deteriorates with time. In other words, when the deposited film for lamination is bonded to the substrate, unevenness in the adhesive strength (layering strength) may occur during the storage period, which may cause variations in product properties. The decrease in the adhesive strength causes delamination between the film for lamination and the substrate, so that the effect of the tearability of the film for lamination cannot be sufficiently exhibited.
[專利文獻1]日本專利特開2000-334890號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-334890
[專利文獻2]日本專利特開2012-111182號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-111182
本發明的課題是鑒於如上所述的問題而成，其是有關於一種對食品、藥品、化粧品、衛生用品、工業零件等進行包裝的包裝材，且其提供一種積層用多層膜及使用該膜的包裝材，所述積層用多層膜的易撕裂性、高熱封強度、耐捲曲性、表面層外觀、揮發成分的吸附抑制性或積層適性良好。 An object of the present invention is to provide a packaging material for packaging food, medicine, cosmetics, sanitary products, industrial parts, and the like in view of the above problems, and to provide a multilayer film for lamination and use of the same The packaging material has good tearability, high heat-sealing strength, curl resistance, surface layer appearance, adsorption inhibition property of volatile components, or laminate property.
本發明者等人為了解決上述課題而進行了努力研究，結果發現，藉由使用具有至少4層的多層構成的多層膜，並且尤其選擇密封層及與其鄰接的層的厚度或所使用的樹脂種類並加以組合，且於表面層(積層的層)中使用環狀聚烯烴系樹脂，可將該些課題全部解決，從而完成了本發明。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that a multilayer film having a multilayer structure of at least four layers is used, and in particular, the thickness of the sealing layer and the layer adjacent thereto or the type of resin to be used are selected. Further, the above-mentioned problems can be solved by using a cyclic polyolefin-based resin in a surface layer (layer of layers), and the present invention has been completed.
即，本發明提供一種低吸附性積層用多層膜及使用該膜 的複合膜、包含該複合膜的包裝材，上述低吸附性積層用多層膜是將表面層(A)、中間層(B)、中間層(C)及密封層(D)以(A)/(B)/(C)/(D)的順序積層而成的多層膜，上述表面層(A)以環狀聚烯烴系樹脂(a)作為主成分，上述中間層(B)以不具有環狀結構的烯烴系樹脂(b)作為主成分，上述中間層(C)以環狀聚烯烴系樹脂(c)作為主成分，上述密封層(D)以不具有環狀結構的烯烴系樹脂(d)作為主成分，並且上述低吸附性積層用多層膜的特徵在於：上述中間層(C)的環狀聚烯烴系樹脂(c)的40質量%以上包含玻璃轉移點為100℃以上的環狀聚烯烴系樹脂，且相對於中間層(C)的總厚度之厚度比率為15%~30%，上述密封層(D)的烯烴系樹脂(d)的80質量%以上包含密度為0.90g/cm3以上的烯烴系樹脂，且相對於密封層(D)的總厚度之厚度比率為10%~25%。 In other words, the present invention provides a multilayer film for low-adsorption laminate, a composite film using the film, and a packaging material comprising the composite film, wherein the low-adhesion laminate film has a surface layer (A) and an intermediate layer (B). a multilayer film in which the intermediate layer (C) and the sealing layer (D) are laminated in the order of (A)/(B)/(C)/(D), and the surface layer (A) is a cyclic polyolefin resin. (a) as the main component, the intermediate layer (B) has a olefin-based resin (b) having no cyclic structure as a main component, and the intermediate layer (C) has a cyclic polyolefin-based resin (c) as a main component. The sealing layer (D) has a olefin-based resin (d) having no cyclic structure as a main component, and the multilayer film for low-adsorption laminate is characterized by a cyclic polyolefin-based resin of the intermediate layer (C) ( 40% by mass or more of c) includes a cyclic polyolefin resin having a glass transition point of 100 ° C or more, and a thickness ratio of 15% to 30% with respect to the total thickness of the intermediate layer (C), the above sealing layer (D) 80% by mass or more of the olefin-based resin (d) contains an olefin-based resin having a density of 0.90 g/cm 3 or more, and a thickness ratio of 10% to 25% with respect to the total thickness of the sealing layer (D).
本發明的低吸附性積層用多層膜的易撕裂性、高熱封強度、積層特性等的性能平衡優異，且可有效地抑制來自內容物的揮發成分的吸附。尤其藉由使與密封層鄰接的中間層中含有具有高玻璃轉移點的環狀聚烯烴系樹脂，可有效地抑制透過密封層的來自內容物的揮發成分對膜的吸附。另外，藉由將表面層(積層的層)設定為環狀聚烯烴系樹脂，表面光澤性優異並且電暈處理等的表面處理度不會經時劣化，另外藉由將多層構成設定為非對稱，捲曲性亦得到抑制，可提供一種積層特性優異且外觀亦良好 的包裝材。另外，藉由選擇使用具有易撕裂性者作為基材，即便不設置撕口(notch)等撕裂開始部，亦可製成於縱向及橫向上均具有易撕裂性的包裝材，故具有社會弱者亦可簡單地撕開而不費餘力的易開封性。進而，藉由在密封層中使用烯烴系樹脂，可確保密封部難以收縮或皺褶等的優異密封性、對通用的容器等的易密封性。進而，由於在中間層中亦使用烯烴系樹脂，故亦具有亦可承受重物的包裝的強度、由膜的彎曲疲勞等所得的耐針孔性等。根據該些情況，使用本發明中所提供的積層用多層膜的複合膜可較佳地用作食品、糖果、化粧品、衛生用品、醫藥品、香煙、工業藥品、雜貨用等的包裝材。 The multilayer film for low-adhesive laminated layers of the present invention is excellent in balance of properties such as tearability, high heat-sealing strength, and lamination property, and can effectively suppress adsorption of volatile components from the content. In particular, by including the cyclic polyolefin-based resin having a high glass transition point in the intermediate layer adjacent to the sealing layer, adsorption of the volatile component from the content through the sealing layer to the film can be effectively suppressed. In addition, by setting the surface layer (layered layer) to a cyclic polyolefin-based resin, the surface glossiness is excellent, and the surface treatment degree such as corona treatment is not deteriorated with time, and the multilayer structure is set to be asymmetric. , curling property is also suppressed, and it is excellent in laminated property and good in appearance. Packaging material. Further, by selecting a user having a tearing property as a base material, a tearing start portion such as a notch can be provided, and a packaging material having tearability in both the longitudinal direction and the lateral direction can be obtained. Those with social weakness can also simply tear open the easy-opening without any effort. Further, by using an olefin-based resin in the sealing layer, it is possible to ensure excellent sealing properties such as shrinkage and wrinkles of the sealing portion, and easy sealing property to a general-purpose container or the like. Further, since an olefin-based resin is also used in the intermediate layer, it also has the strength of a package that can withstand heavy objects, pinhole resistance obtained by bending fatigue of the film, and the like. According to such a case, the composite film using the multilayer film for lamination provided by the present invention can be preferably used as a packaging material for foods, confectionery, cosmetics, sanitary products, pharmaceuticals, cigarettes, industrial chemicals, and miscellaneous goods.
本發明的多層膜具有至少4層樹脂層，且是於其表面層(A)側經由黏接層等與基材膜貼合而使用。 The multilayer film of the present invention has at least four resin layers and is bonded to the base film via an adhesive layer or the like on the surface layer (A) side thereof.
表面層(A)以環狀聚烯烴系樹脂(a)作為主成分。本發明中所謂主成分，是指相對於形成該樹脂層的樹脂成分的總質量，含有65質量%以上的規定為該主成分的特定樹脂，較佳是指含有90質量%以上。 The surface layer (A) has a cyclic polyolefin resin (a) as a main component. In the present invention, the main component is a specific resin containing 65 mass% or more of the main component, and preferably contains 90% by mass or more, based on the total mass of the resin component forming the resin layer.
上述環狀聚烯烴系樹脂(a)例如可列舉：降冰片烯系聚合物、乙烯脂環式烴聚合物、環狀共軛二烯聚合物等。該些聚合物中，較佳為降冰片烯系聚合物。另外，降冰片烯系聚合物可 列舉：降冰片烯系單體的開環聚合物(以下稱為「COP」)、將降冰片烯系單體與乙烯等烯烴共聚合而成的降冰片烯系共聚物(以下稱為「COC」)等。進而，尤佳為COP及COC的氫化物。另外，環狀烯烴系樹脂的重量平均分子量較佳為5,000~500,000，更佳為7,000~300,000。 Examples of the cyclic polyolefin-based resin (a) include a norbornene-based polymer, a vinyl alicyclic hydrocarbon polymer, and a cyclic conjugated diene polymer. Among these polymers, a norbornene-based polymer is preferred. In addition, norbornene-based polymers can A ring-opening polymer of a norbornene-based monomer (hereinafter referred to as "COP"), a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer with an olefin such as ethylene (hereinafter referred to as "COC" ")Wait. Further, it is particularly preferred to be a hydride of COP and COC. Further, the cyclic olefin resin preferably has a weight average molecular weight of 5,000 to 500,000, more preferably 7,000 to 300,000.
成為上述降冰片烯系聚合物的原料的降冰片烯系單體為具有降冰片烯環的脂環族系單體。此種降冰片烯系單體例如可列舉：降冰片烯、四環十二烯、亞乙基降冰片烯、乙烯基降冰片烯、亞乙基四環十二烯、二環戊二烯、二甲橋四氫茀、苯基降冰片烯、甲氧基羰基降冰片烯、甲氧基羰基四環十二烯等。該些降冰片烯系單體可單獨使用，亦可併用兩種以上。 The norbornene-based monomer which is a raw material of the norbornene-based polymer is an alicyclic monomer having a norbornene ring. Examples of such a norbornene-based monomer include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylene tetracyclododecene, and dicyclopentadiene. Dimethyl hydrazine, phenyl norbornene, methoxycarbonyl norbornene, methoxycarbonyl tetracyclododecene, and the like. These norbornene-based monomers may be used singly or in combination of two or more.
上述降冰片烯系共聚物為將上述降冰片烯系單體與可共聚的烯烴共聚合而成者，此種烯烴例如可列舉：乙烯、丙烯、1-丁烯等具有2個~20個碳原子數的烯烴；環丁烯、環戊烯、環己烯等環烯烴；1,4-己二烯等非共軛二烯等。該些烯烴可分別單獨使用，亦可併用兩種以上。 The norbornene-based copolymer is obtained by copolymerizing the norbornene-based monomer and a copolymerizable olefin. Examples of the olefin include 2 to 20 carbons such as ethylene, propylene, and 1-butene. An olefin having an atomic number; a cyclic olefin such as cyclobutene, cyclopentene or cyclohexene; a non-conjugated diene such as 1,4-hexadiene; and the like. These olefins may be used alone or in combination of two or more.
於本發明中，藉由將此種環狀聚烯烴系樹脂(a)設定為表面層(A)的主成分，多層膜的表面光澤性良好，並且藉由電暈處理等對該表面進行處理時的其處理度的經時降低的程度低，即便於長期保管多層膜的情形時，亦可使產品性狀一定。 In the present invention, by setting such a cyclic polyolefin-based resin (a) as a main component of the surface layer (A), the surface glossiness of the multilayer film is good, and the surface is treated by corona treatment or the like. The degree of reduction in the degree of treatment over time is low, and even when the multilayer film is stored for a long period of time, the product properties can be made constant.
用作表面層(A)的主成分的環狀聚烯烴系樹脂(a)的玻璃轉移點(Tg)並無特別限定，就如上所述的表面光澤性、表 面處理度的維持，以及抑制來自內容物的揮發成分暫且到達表面層為止時的進一步的吸附，或抑制來自黏接層的低分子量化合物、揮發成分等向內容物的移動的觀點等而言，較佳為含有40質量%以上的玻璃轉移點(Tg)為100℃以上的環狀聚烯烴系樹脂作為樹脂成分。另外，本發明的玻璃轉移點、熔點等是藉由示差掃描熱量測定(Differential Scanning Calorimetry，DSC)來測定。 The glass transition point (Tg) of the cyclic polyolefin-based resin (a) used as the main component of the surface layer (A) is not particularly limited, and the surface glossiness as described above, The maintenance of the surface treatment degree, and the prevention of further adsorption when the volatile component from the content temporarily reaches the surface layer, or the viewpoint of suppressing the movement of the low molecular weight compound or the volatile component from the adhesive layer to the content, It is preferable to contain 40% by mass or more of a cyclic polyolefin resin having a glass transition point (Tg) of 100 ° C or more as a resin component. Further, the glass transition point, melting point and the like of the present invention are measured by differential scanning calorimetry (DSC).
如上所述，Tg為100℃以上的環狀聚烯烴系樹脂的相對於形成表面層(A)的樹脂成分之含有率較佳為40質量%以上，進而，於上述含有率為50質量%以上的情況下，所得的多層膜成為易撕裂性、膜剛性、吸附抑制性更優異的多層膜，因而較佳。 As described above, the content of the cyclic polyolefin-based resin having a Tg of 100 ° C or higher is preferably 40% by mass or more based on the resin component forming the surface layer (A), and further, the content is 50% by mass or more. In the case of the multilayer film obtained, the multilayer film which is more excellent in tearability, film rigidity, and adsorption inhibition property is preferable.
另外，就可藉由與其他樹脂層的共擠出積層法來製造的方面、及工業上的原料獲取容易性的觀點而言，上述環狀聚烯烴系樹脂(a)的Tg較佳為200℃以下。具有此種Tg的環狀聚烯烴系樹脂(a)較佳為降冰片烯系單體的含有比率為40質量%~90質量%的範圍，更佳為50質量%~90質量%，進而佳為60質量%~85質量%。若含有比率為該範圍，則膜的剛性、易撕裂性、積層特性提高。 In addition, the cyclic polyolefin resin (a) preferably has a Tg of 200 in terms of the production by a co-extrusion lamination method with another resin layer and the ease of obtaining industrial materials. Below °C. The cyclic polyolefin-based resin (a) having such a Tg preferably has a content ratio of the norbornene-based monomer of 40% by mass to 90% by mass, more preferably 50% by mass to 90% by mass, and further preferably It is 60% by mass to 85% by mass. When the content ratio is in this range, the rigidity, the tearability, and the lamination property of the film are improved.
另一方面，高玻璃轉移點(Tg)的降冰片烯系共聚物的拉伸強度低，有時亦極易斷裂、易破裂，故考慮到與成膜時、切割(slit)時的抽取或捲取適性或者積層強度的平衡，亦較佳為將高Tg品與具有低於100℃的玻璃轉移點的低Tg品摻合。 On the other hand, a high glass transition point (Tg) norbornene-based copolymer has a low tensile strength and is sometimes easily broken and easily broken, so that it is considered to be extracted at the time of film formation, slitting, or It is also preferred to blend the high Tg product with a low Tg product having a glass transition point of less than 100 ° C for the balance of roll take-up or laminate strength.
尤其於剛性過高而存在因搬送時的掉落導致輕易地破 裂、袋破損等問題的情形時，藉由調配Tg低於100℃的COC，可提高強度。另外，調配與COC的相容性良好的不含環狀結構的聚丙烯系樹脂或聚乙烯系樹脂等的聚烯烴系樹脂亦有效。 Especially when the rigidity is too high, it is easily broken due to the drop during transportation. In the case of problems such as cracking or bag breakage, the strength can be improved by blending COC having a Tg lower than 100 °C. In addition, a polyolefin-based resin such as a polypropylene-based resin or a polyethylene-based resin which does not contain a cyclic structure and which has good compatibility with COC is also effective.
關於可用作上述環狀聚烯烴系樹脂(a)的市售品，降冰片烯系單體的開環聚合物(COP)例如可列舉日本瑞翁(Zeon)股份有限公司製造的「瑞諾(ZEONOR)」等，降冰片烯系共聚物(COC)例如可列舉：三井化學股份有限公司製造的「阿佩爾(Apel)」、寶理塑膠(Polyplastics)公司製造的「托帕斯(TOPAS)」等。 For a commercially available product which can be used as the above-mentioned cyclic polyolefin-based resin (a), a ring-opening polymer (COP) of a norbornene-based monomer is exemplified by Reno, manufactured by Zeon Co., Ltd., Japan. (ZEONOR), etc. Examples of the norbornene-based copolymer (COC) include "Apel" manufactured by Mitsui Chemicals Co., Ltd., and "Topas" (TOPAS) manufactured by Polyplastics Co., Ltd. )"Wait.
上述表面層(A)的厚度以及於總厚度中所佔的厚度比率並無特別限定。兼顧後述其他樹脂層來選擇，就容易利用共擠出積層法來製造的觀點而言，厚度較佳為3μm以上，厚度比率較佳為5%~25%的範圍。 The thickness of the surface layer (A) and the thickness ratio in the total thickness are not particularly limited. From the viewpoint of easy selection by the co-extrusion lamination method, the thickness is preferably 3 μm or more, and the thickness ratio is preferably in the range of 5% to 25%.
與上述表面層(A)鄰接的中間層(B)是以不具有環狀結構的烯烴系樹脂(b)作為主成分。藉由設置該中間層(B)，可表現出多層膜的剛性、耐寒性、耐衝擊性、耐針孔性以及耐捲曲性。即，該中間層(B)中所用的烯烴系樹脂(b)較佳為根據用途來選擇。 The intermediate layer (B) adjacent to the surface layer (A) is a main component of the olefin-based resin (b) having no cyclic structure. By providing the intermediate layer (B), the rigidity, cold resistance, impact resistance, pinhole resistance, and curl resistance of the multilayer film can be exhibited. That is, the olefin-based resin (b) used in the intermediate layer (B) is preferably selected depending on the use.
就與上述表面層(A)及後述中間層(C)積層時的層間黏接性優異的方面、及工業上的獲取容易性的觀點而言，上述烯烴系樹脂(b)較佳為使用聚乙烯系樹脂或聚丙烯系樹脂。 The olefin-based resin (b) is preferably used in the viewpoint of excellent interlayer adhesion when the surface layer (A) and the intermediate layer (C) described later are laminated, and industrial ease of availability. A vinyl resin or a polypropylene resin.
為了維持易撕裂性、耐針孔性、表面層(A)與中間層 (C)的層間強度，上述聚乙烯系樹脂較佳為密度為0.900g/cm3~0.950g/cm3，更佳為密度為0.905g/cm3~0.945g/cm3。 In order to maintain the tearability, the pinhole resistance, and the interlayer strength of the surface layer (A) and the intermediate layer (C), the polyethylene resin preferably has a density of 0.900 g/cm 3 to 0.950 g/cm 3 , more The density is preferably 0.905 g/cm 3 to 0.945 g/cm 3 .
上述聚乙烯系樹脂可列舉：超低密度聚乙烯(VLDPE)、線性低密度聚乙烯(LLDPE)、線性中密度聚乙烯(LMDPE)、低密度聚乙烯(LDPE)等、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)的聚乙烯樹脂，或乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-甲基丙烯酸甲酯共聚物(EMMA)、乙烯-丙烯酸乙酯共聚物(EEA)、乙烯-丙烯酸甲酯(EMA)共聚物、乙烯-丙烯酸乙酯-馬來酸酐共聚物(E-EA-MAH)、乙烯-丙烯酸共聚物(EAA)、乙烯-甲基丙烯酸共聚物(EMAA)等乙烯系共聚物；進而可列舉乙烯-丙烯酸共聚物的離子聚合物(ionomer)、乙烯-甲基丙烯酸共聚物的離子聚合物等，可單獨使用亦可混合使用兩種以上。該些樹脂中，就不損及環狀聚烯烴系樹脂所具有的易撕裂性效果而具有撕裂性的觀點、及作為多層膜的耐針孔性等觀點而言，較佳為使用LLDPE、LMDPE。 Examples of the polyethylene-based resin include ultra low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE), low density polyethylene (LDPE), and medium density polyethylene (MDPE). ), polyethylene resin of high density polyethylene (HDPE), or ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), Ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), etc. The ethylene-based copolymer may, for example, be an ionomer of an ethylene-acrylic acid copolymer or an ionic polymer of an ethylene-methacrylic acid copolymer, and may be used singly or in combination of two or more. Among these resins, LLDPE is preferably used from the viewpoint of having tear properties which do not impair the tearing effect of the cyclic polyolefin resin, and the pinhole resistance of the multilayer film. , LMDPE.
LDPE只要為由高壓自由基聚合法所得的分支狀低密度聚乙烯即可，較佳為藉由高壓自由基聚合法使乙烯進行均聚合所得的分支狀低密度聚乙烯。 The LDPE may be a branched low-density polyethylene obtained by a high-pressure radical polymerization method, and is preferably a branched low-density polyethylene obtained by homopolymerization of ethylene by a high-pressure radical polymerization method.
LLDPE、LMDPE為藉由使用單點觸媒(single-site catalyst)的低壓自由基聚合法，將乙烯單體作為主成分，使丁烯-1、己烯-1、辛烯-1、4-甲基戊烯等α-烯烴作為共單體與其進行共聚合而成者。共單體含有率較佳為0.5莫耳%~20莫耳%的範圍， 更佳為1莫耳%~18莫耳%的範圍。 LLDPE and LMDPE are low-pressure radical polymerization methods using a single-site catalyst, and ethylene monomer is used as a main component to make butene-1, hexene-1, octene-1, 4- An α-olefin such as methylpentene is copolymerized with a comonomer. The comonomer content is preferably in the range of 0.5 mol% to 20 mol%. More preferably, it ranges from 1 mol% to 18 mol%.
上述單點觸媒可列舉：元素週期表第IV族或第V族過渡金屬的茂金屬化合物、與有機鋁化合物及/或離子性化合物的組合等茂金屬觸媒系等的各種單點觸媒。另外，單點觸媒由於活性點均勻，故與活性點不均勻的多點觸媒相比較，所得的樹脂的分子量分佈變狹窄(sharp)，故形成為膜時低分子量成分的析出少，可獲得樹脂層間的黏接強度的穩定性優異的物性的樹脂，故較佳。 Examples of the single-point catalyst include various single-catalysts such as a metallocene compound of a Group IV or Group V transition metal of the periodic table, and a metallocene catalyst system such as a combination with an organoaluminum compound and/or an ionic compound. . Further, since the single site catalyst has a uniform activity point, the molecular weight distribution of the obtained resin becomes sharper than that of the multi-point catalyst having a non-uniform active point, so that precipitation of a low molecular weight component is small when formed into a film. A resin having excellent physical properties such as excellent adhesion between the resin layers is obtained, which is preferable.
如上所述，聚乙烯系樹脂的密度較佳為0.900g/cm3~0.950g/cm3，更佳為0.905g/cm3~0.940g/cm3的範圍。若密度為該範圍，則具有適度的剛性，耐針孔性等機械強度亦優異，膜成膜性、擠出適性提高。另外，熔點通常較佳為60℃~130℃的範圍，更佳為70℃~125℃。若熔點為該範圍，則加工穩定性或與上述環狀聚烯烴系樹脂(a)的共擠出加工性提高。另外，上述聚乙烯系樹脂的熔融流率(Melt Flow Rate，MFR)(190℃、21.18N)較佳為2g/10min~20g/10min，更佳為3g/10min~10g/10min。若MFR為該範圍，則膜的擠出成形性提高。 As described above, the density of the polyethylene resin is preferably 0.900g / cm 3 ~ 0.950g / cm 3, more preferably in the range of 0.905g / cm 3 ~ 0.940g / cm 3 of. When the density is in this range, it has moderate rigidity, and is excellent in mechanical strength such as pinhole resistance, and film formability and extrusion suitability are improved. Further, the melting point is usually preferably in the range of 60 ° C to 130 ° C, more preferably 70 ° C to 125 ° C. When the melting point is in this range, the processing stability or the co-extrusion processability with the cyclic polyolefin-based resin (a) is improved. Further, the melt flow rate (MFR) (190 ° C, 21.18 N) of the polyethylene resin is preferably 2 g/10 min to 20 g/10 min, more preferably 3 g/10 min to 10 g/10 min. When the MFR is in this range, the extrusion formability of the film is improved.
此種聚乙烯系樹脂與環狀烯烴系樹脂的相容性亦良好，故亦可維持積層時的透明性。另外，不使用黏接性樹脂等的情況下亦可保持表面層(A)與中間層(C)的層間黏接強度，由於亦具有柔軟性，故耐針孔性亦變良好。 Since the compatibility between the polyethylene resin and the cyclic olefin resin is also good, the transparency at the time of lamination can be maintained. Further, when the adhesive resin or the like is not used, the interlayer adhesion strength between the surface layer (A) and the intermediate layer (C) can be maintained, and since the flexibility is also obtained, the pinhole resistance is also improved.
上述聚丙烯系樹脂例如可列舉：丙烯均聚物、丙烯-α-烯烴無規共聚物、例如丙烯-乙烯共聚物、丙烯-丁烯-1共聚物、丙 烯-乙烯-丁烯-1共聚物、茂金屬觸媒系聚丙烯等。該些聚合物可分別單獨使用，亦可併用。理想的是丙烯-α-烯烴無規共聚物，尤佳為使用茂金屬觸媒進行聚合而成的丙烯-α-烯烴無規聚合物。於使用該些聚丙烯系樹脂作為中間層(B)的情形時，膜的耐熱性提高，可提高軟化溫度，故可較佳地用作100℃以下的煮沸(boil)或熱填充、或者100℃以上的殺菌釜殺菌(retort sterilization)等蒸汽、高壓加熱殺菌特性優異的包裝材用的積層用膜。 Examples of the polypropylene-based resin include a propylene homopolymer, a propylene-α-olefin random copolymer, for example, a propylene-ethylene copolymer, a propylene-butene-1 copolymer, and a propylene. An ene-ethylene-butene-1 copolymer, a metallocene catalyst-based polypropylene, or the like. These polymers may be used singly or in combination. A propylene-α-olefin random copolymer is desirable, and a propylene-α-olefin random polymer obtained by polymerizing using a metallocene catalyst is particularly preferred. When the polypropylene resin is used as the intermediate layer (B), the heat resistance of the film is improved and the softening temperature can be increased, so that it can be preferably used as a boil or hot fill of 100 ° C or less, or 100. A film for lamination for packaging materials having excellent steam and high-pressure heat sterilization characteristics such as retort sterilization at a temperature of °C or higher.
另外，該些聚丙烯系樹脂較佳為MFR(230℃)為0.5g/10min~30.0g/10min，且熔點為110℃~165℃，更佳為MFR(230℃)為2.0g/10min~15.0g/10min，且熔點為115℃~162℃。若MFR及熔點為該範圍，則膜的成膜性提高。 Further, the polypropylene resin preferably has an MFR (230 ° C) of 0.5 g/10 min to 30.0 g/10 min, and a melting point of 110 ° C to 165 ° C, more preferably MFR (230 ° C) of 2.0 g/10 min. 15.0 g/10 min and a melting point of 115 ° C to 162 ° C. When the MFR and the melting point are in this range, the film formability of the film is improved.
於本發明的多層膜中，中間層(B)以烯烴系樹脂作為主成分，亦可於不損及本發明的效果的範圍內混合其他樹脂，另外，亦可具有將含有其他樹脂的樹脂層積層而成的2層以上的構成。此時可混合使用的其他樹脂較佳為上述表面層(A)中所用的環狀聚烯烴系樹脂等可應用共擠出積層法的樹脂。另外，於積層其他樹脂層的情形時，亦較佳為選擇可應用共擠出積層法的樹脂。 In the multilayer film of the present invention, the intermediate layer (B) may contain an olefin resin as a main component, or may blend other resins in a range that does not impair the effects of the present invention, or may have a resin layer containing other resins. A structure in which two or more layers are laminated. The other resin which can be used in this case is preferably a resin which can be applied by a co-extrusion lamination method, such as a cyclic polyolefin-based resin used in the surface layer (A). Further, in the case of laminating other resin layers, it is also preferred to select a resin to which a co-extrusion lamination method can be applied.
於本發明的多層膜中，中間層(C)中使用的樹脂與上述表面層(A)中所用的環狀聚烯烴系樹脂相同，為了將來自內容物的揮發成分對膜的吸附設定為實用水準，中間層(C)的環狀聚烯烴系樹脂(c)的40質量%以上包含玻璃轉移點為100℃以上的環狀聚烯烴系樹脂，且就低吸附性及易撕裂性的觀點而言，必須 將該中間層(C)的相對於總厚度之厚度比率設定為15%~30%。 In the multilayer film of the present invention, the resin used in the intermediate layer (C) is the same as the cyclic polyolefin-based resin used in the surface layer (A), and the adsorption of the volatile component from the content is practical. 40% by mass or more of the cyclic polyolefin resin (c) of the intermediate layer (C) contains a cyclic polyolefin resin having a glass transition point of 100 ° C or more, and has a low adsorption property and a tearing property. In terms of The thickness ratio of the intermediate layer (C) to the total thickness is set to 15% to 30%.
Tg低於100℃的環狀聚烯烴系樹脂與Tg為100℃以上的環狀聚烯烴系樹脂相比較，就吸附性的觀點而言較差，由此於本發明中，必須於中間層(C)中以充分的比例含有高Tg的環狀聚烯烴系樹脂，另外，為了兼具低吸附性與易撕裂性，限定厚度比率。即，於不滿足該些規定的情形時，無法表現出本發明中的一部分目標性能。Tg為100℃以上的環狀聚烯烴系樹脂亦以如上所述的商品名而市售，故確認Tg而選擇。 The cyclic polyolefin-based resin having a Tg of less than 100 ° C is inferior in terms of adsorptivity as compared with a cyclic polyolefin-based resin having a Tg of 100 ° C or more, and thus, in the present invention, it is necessary to be in the intermediate layer (C). The cyclic polyolefin resin having a high Tg is contained in a sufficient ratio, and the thickness ratio is limited in order to have both low adsorptivity and tearability. That is, when the above-mentioned regulations are not satisfied, some of the target performances in the present invention cannot be expressed. A cyclic polyolefin-based resin having a Tg of 100 ° C or more is also commercially available as described above, and thus Tg is selected and selected.
尤其就獲得性能平衡優異的多層膜的方面而言，最佳為將中間層(C)中所用的樹脂的90質量%以上設定為包含環狀聚烯烴系樹脂者，且將其設定為Tg為100℃以上的環狀聚烯烴系樹脂、與Tg低於100℃的環狀聚烯烴系樹脂的混合物。 In particular, in order to obtain a multilayer film having excellent performance balance, it is preferable to set 90% by mass or more of the resin used in the intermediate layer (C) to include a cyclic polyolefin resin, and set it to Tg. A mixture of a cyclic polyolefin resin having a temperature of 100 ° C or higher and a cyclic polyolefin resin having a Tg of less than 100 ° C.
本發明的多層膜的密封層(D)是以不具有環狀結構的烯烴系樹脂(d)作為主成分，並且必須使其80質量%以上包含密度為0.90g/cm3以上的烯烴系樹脂，且密封層(D)相對於總厚度之厚度比率為10%~25%。尤佳的厚度比率為10%~20%。藉由設定為此種相對較薄的密封層且使用高密度的樹脂，即便將通常被視為容易吸附的烯烴系樹脂設定為密封層，亦抑制其吸附。 The sealing layer (D) of the multilayer film of the present invention contains an olefin-based resin (d) having no cyclic structure as a main component, and 80% by mass or more of the olefin-based resin having a density of 0.90 g/cm 3 or more. And the thickness ratio of the sealing layer (D) to the total thickness is 10% to 25%. A particularly good thickness ratio is 10% to 20%. By setting such a relatively thin sealing layer and using a high-density resin, even if an olefin-based resin which is generally considered to be easily adsorbed is set as a sealing layer, adsorption is suppressed.
就防止來自內容物的揮發成分的吸附的觀點而言，提出了於密封層中亦使用環狀聚烯烴系樹脂，但該情形時，必須提高密封時的溫度，或密封側(例如容器)的表面樹脂種類的選擇範圍變窄。即，於用作對通用容器的蓋材時，有時無法獲得充分的 密封強度，缺乏作為積層用膜的通用性。 From the viewpoint of preventing adsorption of volatile components from the contents, it has been proposed to use a cyclic polyolefin-based resin in the sealing layer. However, in this case, it is necessary to increase the temperature at the time of sealing or the sealing side (for example, a container). The selection range of the surface resin type is narrowed. That is, when used as a cover material for a general-purpose container, sometimes sufficient is not obtained. The sealing strength lacks versatility as a film for lamination.
上述烯烴系樹脂(d)可為聚乙烯系樹脂，亦可為聚丙烯系樹脂，另外亦可為該等的共聚物，只要滿足本發明中規定的密度範圍，則可較佳地使用，就低吸附性與密封強度的平衡優異的觀點而言，尤佳為LLDPE。 The olefin-based resin (d) may be a polyethylene-based resin or a polypropylene-based resin, or may be a copolymer of the above-mentioned olefin-based resin, and may be preferably used as long as it satisfies the density range specified in the present invention. From the viewpoint of excellent balance between low adsorptivity and seal strength, LLDPE is particularly preferred.
於提高密封強度的情形時，有效的是提高密封層(D)的厚度比率。另一方面，若厚度比率變高，則低吸附性能變低，故較佳為根據用途、使用方法來設計。尤佳的密封層(D)的厚度為3μm~15μm的範圍，更佳為5μm~10μm的範圍。 In the case of improving the sealing strength, it is effective to increase the thickness ratio of the sealing layer (D). On the other hand, when the thickness ratio is high, the low adsorption performance is low, and therefore it is preferably designed according to the use and the method of use. The thickness of the sealing layer (D) which is particularly preferable is in the range of 3 μm to 15 μm, more preferably in the range of 5 μm to 10 μm.
對於本發明的多層膜而言，就以與其他基材貼合而使用為目的之觀點、容易使用(容易積層)的觀點、耐針孔性及剛性的觀點而言，膜的總厚度通常為10μm~100μm的範圍，較佳為20μm~60μm的範圍。 In the multilayer film of the present invention, the total thickness of the film is usually from the viewpoint of being used in combination with other substrates, the viewpoint of ease of use (easy stacking), pinhole resistance, and rigidity. The range of 10 μm to 100 μm is preferably in the range of 20 μm to 60 μm.
另外，於將本發明的多層膜積層於基材上而成的複合膜中，就表現出易撕裂性的觀點而言，較佳為作為含有環狀聚烯烴系樹脂的樹脂層的表面層(A)與中間層(C)的合計厚度相對於總厚度之比率為40%以上。 In addition, in the composite film obtained by laminating the multilayer film of the present invention on a substrate, it is preferably a surface layer of a resin layer containing a cyclic polyolefin resin from the viewpoint of exhibiting tearability. The ratio of the total thickness of (A) to the intermediate layer (C) to the total thickness is 40% or more.
本發明的多層膜是與其他基材貼合而使用，此時可使用的其他基材並無特別限定，就容易表現出本發明的效果的觀點而言，較佳為使用具有高剛性、高光澤的塑膠基材，特別是經雙軸延伸的樹脂膜。另外，於無需透明性的用途的情形時，亦可單獨或組合使用鋁箔。 The multilayer film of the present invention is used in combination with another substrate, and the other substrate which can be used in this case is not particularly limited, and from the viewpoint of easily exhibiting the effects of the present invention, it is preferred to use high rigidity and high hardness. A glossy plastic substrate, especially a biaxially stretched resin film. Further, in the case where the use of transparency is not required, the aluminum foil may be used singly or in combination.
就易撕裂性等觀點而言，經延伸的樹脂膜例如可列舉：雙軸延伸聚酯(PET)、易裂性雙軸延伸聚酯(PET)、雙軸延伸聚丙烯(OPP)、雙軸延伸聚醯胺(PA)、以乙烯乙烯醇共聚物(EVOH)作為中心層的共擠出雙軸延伸聚丙烯、雙軸延伸乙烯乙烯醇共聚物(EVOH)、塗佈有聚偏二氯乙烯(PVDC)的共擠出雙軸延伸聚丙烯等。該等可單獨或複合而使用。 The stretched resin film may, for example, be a biaxially stretched polyester (PET), a crackable biaxially stretched polyester (PET), a biaxially oriented polypropylene (OPP), or a double, in terms of tearability and the like. Axillary extended polyamine (PA), coextruded biaxially oriented polypropylene with ethylene vinyl alcohol copolymer (EVOH) as the center layer, biaxially stretched ethylene vinyl alcohol copolymer (EVOH), coated with polyvinylidene chloride Co-extrusion biaxially oriented polypropylene of ethylene (PVDC). These can be used individually or in combination.
上述各樹脂層中，視需要可於不損及本發明的目的之範圍內添加防霧劑、抗靜電劑、熱穩定劑、成核劑、抗氧化劑、潤滑劑、抗結塊劑(antiblocking agent)、脫模劑、紫外線吸收劑、著色劑等成分。尤其為了賦予膜成形時的加工適性、填充機的包裝適性，層(A)及層(D)的膜表面的摩擦係數為1.5以下，其中較佳為1.0以下，故較佳為於樹脂層(A)中適當添加潤滑劑或抗結塊劑。 In each of the above resin layers, an antifogging agent, an antistatic agent, a heat stabilizer, a nucleating agent, an antioxidant, a lubricant, and an antiblocking agent may be added as needed within a range not impairing the object of the present invention. ), release agent, UV absorber, colorant and other ingredients. In particular, in order to impart workability at the time of film formation and package suitability of the filling machine, the film surface of the layer (A) and the layer (D) has a coefficient of friction of 1.5 or less, preferably 1.0 or less, and is preferably a resin layer ( Add a lubricant or an anti-caking agent as appropriate in A).
本發明的多層膜的製造方法並無特別限定，例如可列舉以下方法：分別利用各擠出機使表面層(A)、中間層(B)、中間層(C)及密封層(D)中所用的各樹脂或樹脂混合物加熱熔融，藉由共擠出多層模具法或進料塊(feed block)法等方法於熔融狀態下積層(A)/(B)/(C)/(D)後，藉由膨脹(inflation)或T字模-冷卻輥法等成形為膜狀，於上述共擠出法後，於表面層(A)上積層基材。共擠出法可相對較自由地調整各層的厚度的比率，可獲得衛生性優異、成本績效(cost performance)亦優異的多層膜，故較佳。進而，於使用本發明中所用的環狀聚烯烴系樹脂(a)、 與作為中間層(B)的低密度聚乙烯系樹脂的情形時，由於兩者間熔點與Tg之差大，故有時於共擠出加工時膜外觀劣化，難以形成均勻的層構成。為了抑制此種劣化，較佳為可於相對較高的溫度下進行熔融擠出的T字模-冷卻輥法。 The method for producing the multilayer film of the present invention is not particularly limited, and examples thereof include a surface layer (A), an intermediate layer (B), an intermediate layer (C), and a sealing layer (D) by using respective extruders. Each resin or resin mixture used is heated and melted, and laminated (A)/(B)/(C)/(D) in a molten state by a co-extrusion multilayer mold method or a feed block method. The film is formed into a film shape by an expansion or a T-die-cooling roll method, and the substrate is laminated on the surface layer (A) after the co-extrusion method. The coextrusion method is relatively free to adjust the ratio of the thickness of each layer, and a multilayer film excellent in hygienic properties and excellent in cost performance can be obtained, which is preferable. Further, the cyclic polyolefin resin (a) used in the present invention is used, In the case of the low-density polyethylene-based resin as the intermediate layer (B), since the difference between the melting point and the Tg is large, the film appearance may deteriorate during the co-extrusion processing, and it may be difficult to form a uniform layer structure. In order to suppress such deterioration, a T-die-cooling roll method which can perform melt extrusion at a relatively high temperature is preferred.
本發明的複合膜為於藉由上述製造方法所得的多層膜積層上述基材而成的膜，積層方法例如可列舉：乾式積層、濕式積層、無溶劑積層、擠出積層等方法。 The composite film of the present invention is a film obtained by laminating the above-mentioned base material in a multilayer film obtained by the above-described production method, and examples of the lamination method include a dry laminate, a wet laminate, a solventless laminate, and an extrusion laminate.
上述乾式積層中所用的黏接劑例如可列舉：聚醚-聚胺基甲酸酯系黏接劑、聚酯-聚胺基甲酸酯系黏接劑等。另外，亦可使用各種黏著劑，較佳為使用感壓性黏著劑。感壓性黏著劑例如可列舉：使聚異丁烯橡膠、丁基橡膠、該等的混合物溶解於苯、甲苯、二甲苯、己烷般的有機溶劑中而成的橡膠系黏著劑；或於該些橡膠系黏著劑中調配松脂酸松香酯、萜烯-酚共聚物、萜烯-茚共聚物等增黏劑(tackifier)而成者；或者以有機溶劑將丙烯酸-2-乙基己酯-丙烯酸正丁酯共聚物、丙烯酸-2-乙基己酯-丙烯酸乙酯-甲基丙烯酸甲酯共聚物等玻璃轉移點為-20℃以下的丙烯酸系共聚物溶解而成的丙烯酸系黏著劑等。 Examples of the adhesive used in the dry laminate include a polyether-polyurethane-based adhesive, a polyester-polyurethane-based adhesive, and the like. Further, various adhesives can be used, and a pressure-sensitive adhesive is preferably used. The pressure-sensitive adhesive may, for example, be a rubber-based adhesive obtained by dissolving a polyisobutylene rubber, a butyl rubber, or the like in an organic solvent such as benzene, toluene, xylene or hexane; or a rubber-based adhesive in which a tackifier such as rosin rosin ester, a terpene-phenol copolymer or a terpene-ruthenium copolymer is blended; or 2-ethylhexyl acrylate-acrylic acid is used as an organic solvent. An acrylic adhesive obtained by dissolving an acrylic copolymer having a glass transition point of -20 ° C or lower, such as a n-butyl ester copolymer or a 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer.
對於表面層(A)的最表面，為了提高上述黏接劑或黏著劑的塗佈性，或者於對最表面實施印刷等後與基材積層的情形等時，為了提高與黏接劑、黏著劑、印刷油墨的密接性等，較佳為對上述層(A)實施表面處理。此種表面處理例如可列舉：電暈處理、電漿處理、鉻酸處理、火焰處理、熱風處理、臭氧-紫外線 處理等表面氧化處理或噴砂等表面凹凸處理，較佳為電暈處理。本發明的表面層(A)藉由以環狀聚烯烴系樹脂作為主成分，即便於進行此種處理後長期保存，其處理度亦不會經時劣化，故可穩定地提供最終產品。 In order to improve the applicability of the above-mentioned adhesive or adhesive, or to laminate the surface with the substrate after printing on the outermost surface, etc., in order to improve the adhesion to the adhesive, adhesion to the surface of the surface layer (A) The adhesion between the agent and the printing ink is preferably such that the layer (A) is subjected to surface treatment. Such surface treatments include, for example, corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment. The surface unevenness treatment such as surface oxidation treatment or sand blasting is preferably corona treatment. In the surface layer (A) of the present invention, the cyclic polyolefin resin is used as a main component, and even if it is stored for a long period of time after such treatment, the degree of treatment does not deteriorate over time, so that the final product can be stably supplied.
包含本發明的複合膜的包裝材可列舉：食品、藥品、化粧品、衛生用品、工業零件、雜貨、雜誌等用途中所用的包裝袋、容器、容器的蓋材等。尤其由於內容物所含的揮發成分對膜的收附、吸附少，且密封強度的經時降低亦少，故可較佳地用於含有揮發性成分的醫藥品或工業藥品用等。 Examples of the packaging material containing the composite film of the present invention include packaging bags, containers, and lid materials for containers used in foods, pharmaceuticals, cosmetics, sanitary products, industrial parts, miscellaneous goods, magazines, and the like. In particular, since the volatile component contained in the content has less adhesion to the film and less adsorption, and the sealing strength is less reduced over time, it can be preferably used for a pharmaceutical product or an industrial drug containing a volatile component.
上述包裝袋較佳為藉由將本發明的複合膜的密封層(D)彼此重疊並進行熱封、或將密封層(D)與基材重合並進行熱封，而使密封層(D)形成為內側而成的包裝袋。例如可將該複合膜2片以所需的包裝袋的大小切出，將該等重疊並將三邊熱封而製成袋狀後，自未熱封的一邊填充內容物並進行熱封而密封，藉此用作包裝袋。進而，亦可藉由自動包裝機對卷狀的膜以圓筒(枕套(pillow))形密封端部後，將上下密封，藉此形成包裝袋。 Preferably, the packaging bag is formed by overlapping the sealing layer (D) of the composite film of the present invention and heat-sealing, or by heat-sealing the sealing layer (D) and the substrate to form a sealing layer (D). A bag formed into the inside. For example, two sheets of the composite film can be cut out in the size of a desired packaging bag, and the three layers are stacked and heat-sealed to form a bag shape, and then the contents are filled from the unsealed side and heat-sealed. Sealed and used as a packaging bag. Further, the roll film may be sealed in a cylinder (pillow) shape by an automatic packaging machine, and then the upper and lower sides may be sealed to form a packaging bag.
另外，亦可將密封層(D)與可熱封的其他膜、片材、容器熱封，藉此形成包裝袋、容器、容器的蓋。此時，可使用的其他膜可使用機械強度相對較弱的LDPE、EVA、聚丙烯等的膜或片材。 Alternatively, the sealing layer (D) may be heat-sealed with other heat sealable films, sheets, and containers to form a lid for the packaging bag, container, or container. At this time, other films which can be used may be films or sheets of LDPE, EVA, polypropylene, or the like which are relatively weak in mechanical strength.
使用本發明的複合膜的包裝材中，由於膜自身具有易撕裂性，故無需設置撕裂開始部，但為了進一步減弱初期的撕裂強 度而提高開封性，亦可於密封部中形成V撕口、I撕口、穿孔(perforation)、微多孔等任意的撕裂開始部。 In the packaging material using the composite film of the present invention, since the film itself has tearability, it is not necessary to provide a tear start portion, but in order to further weaken the initial tear strength The degree of opening is improved, and an arbitrary tear start portion such as a V tear, a tear, a perforation, or a microporous may be formed in the sealing portion.
繼而，列舉實施例及比較例對本發明加以更詳細說明。 Next, the present invention will be described in more detail by way of examples and comparative examples.
實施例1 Example 1
使用降冰片烯系單體的開環聚合物[三井化學股份有限公司製造的「阿佩爾(Apel)APL8008T」，MFR：15g/10min(260℃、21.18N)，玻璃轉移點：70℃；以下稱為「COC(3)」]作為表面層(A)用樹脂。使用直鏈狀中密度聚乙烯[密度：0.930g/cm3，熔點：125℃，MFR：5g/10min(190℃、21.18N)；以下稱為「LMDPE」]作為中間層(B)用樹脂。使用降冰片烯系單體的開環聚合物[三井化學股份有限公司製造的「阿佩爾(Apel)APL6015T」，MFR：10g/10min(260℃、21.18N)，玻璃轉移點：145℃；以下稱為「COC(1)」]60質量份與COC(3)40質量份的樹脂混合物作為中間層(C)用樹脂。進而，使用直鏈狀低密度聚乙烯[密度：0.920g/cm3，熔點：110℃，MFR：5g/10min(190℃、21.18N)；以下稱為「LLDPE」]作為密封層(D)用樹脂。將該些樹脂分別供給於表面層(A)用擠出機(口徑為50mm)、中間層(B)用擠出機(口徑為50mm)、中間層(C)用擠出機(口徑為50mm)及密封層(D)用擠出機(口徑為40mm)，於200℃~250℃下熔融，將該經熔融的樹脂分別供給於具有進料塊的T字模-冷卻輥法的共擠出多層膜製造裝置(進料塊及T字模溫度：250℃)， 進行共熔融擠出，獲得膜的層構成為(A)/(B)/(C)/(D)的四層構成、且各層的厚度為6μm/15μm/6μm/3μm(合計為30μm)的共擠出多層膜(1)後，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側以成為3.5g/m2的方式塗佈胺基甲酸酯系黏接劑後，乾式積層雙軸延伸聚酯(厚度為12μm)(熔點為260℃，東洋紡製造)，獲得複合膜(1)。 a ring-opening polymer of norbornene-based monomer [Apel APL8008T manufactured by Mitsui Chemicals, Inc., MFR: 15 g/10 min (260 ° C, 21.18 N), glass transition point: 70 ° C; Hereinafter, it is referred to as "COC (3)" as a resin for the surface layer (A). Linear medium-density polyethylene [density: 0.930 g/cm 3 , melting point: 125 ° C, MFR: 5 g/10 min (190 ° C, 21.18 N); hereinafter referred to as "LMDPE") as the resin for the intermediate layer (B) . a ring-opening polymer of norbornene-based monomer [Apel APL6015T manufactured by Mitsui Chemicals, Inc., MFR: 10 g/10 min (260 ° C, 21.18 N), glass transition point: 145 ° C; Hereinafter, 60 parts by mass of "COC (1)"] and a resin mixture of 40 parts by mass of COC (3) are used as the resin for the intermediate layer (C). Further, a linear low-density polyethylene [density: 0.920 g/cm 3 , melting point: 110 ° C, MFR: 5 g/10 min (190 ° C, 21.18 N); hereinafter referred to as "LLDPE") was used as the sealing layer (D). Use resin. The resin was supplied to an extruder (surface diameter: 50 mm) for the surface layer (A), an extruder (caliber of 50 mm) for the intermediate layer (B), and an extruder (caliber of 50 mm for the intermediate layer (C)). And the sealing layer (D) is melted at 200 ° C to 250 ° C using an extruder (caliber of 40 mm), and the molten resin is separately supplied to a co-extrusion of a T-die-cooling roll method having a feed block. The multilayer film manufacturing apparatus (feed block and T-die temperature: 250 ° C) was subjected to co-melting extrusion, and the layer structure of the film was obtained as a four-layer structure of (A)/(B)/(C)/(D), and After the thickness of each layer was 6 μm / 15 μm / 6 μm / 3 μm (total 30 μm) of the coextruded multilayer film (1), the surface of the surface layer (A) was subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. After the processing side to be 3.5g / m 2 and was a urethane-based bonding agent, dry laminated biaxially-oriented polyester (thickness of 12 m) (mp 260 ℃, manufactured by Toyobo) to give compound Membrane (1).
實施例2 Example 2
除了使用COC(1)作為表面層(A)用樹脂及中間層(C)用樹脂以外，與實施例1同樣地以膜的各層的厚度成為(A)/(B)/(C)/(D)=12μm/30μm/12μm/6μm(合計為60μm)的方式與實施例1同樣地製作共擠出多層膜(2)，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜(2)。 In the same manner as in Example 1, except that the COC (1) was used as the resin for the surface layer (A) and the resin for the intermediate layer (C), the thickness of each layer of the film was (A)/(B)/(C)/( A coextruded multilayer film (2) was produced in the same manner as in Example 1 except that D) = 12 μm / 30 μm / 12 μm / 6 μm (total 60 μm), and the surface of the surface layer (A) was subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. The biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film (2).
實施例3 Example 3
使用COC(1)60質量份與COC(3)40質量份的樹脂混合物作為表面層(A)用樹脂。使用LLDPE作為中間層(B)用樹脂，使用降冰片烯系單體的開環聚合物[三井化學股份有限公司製造的「阿佩爾(Apel)AP6013T」，MFR：15g/10min(260℃、21.18N)，玻璃轉移點：125℃；以下稱為「COC(2)」]60質量份與COC(3)40質量份的樹脂混合物作為中間層(C)用樹脂。使用利用茂金屬觸媒進行聚合而成的丙烯-α-烯烴無規共聚物[密度：0.900g/cm3，熔點：135℃，MFR：4g/10min(230℃、21.18N)；以下 稱為「MRCP」)作為密封層(D)用樹脂。以膜的各層的厚度成為(A)/(B)/(C)/(D)=6μm/12μm/6μm/6μm(合計為30μm)的方式與實施例1同樣地製作共擠出多層膜(3)，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜(3)。 A resin mixture of 60 parts by mass of COC (1) and 40 parts by mass of COC (3) was used as the resin for the surface layer (A). Using LLDPE as the resin for the intermediate layer (B), a ring-opening polymer of norbornene-based monomer [Apel AP6013T manufactured by Mitsui Chemicals, Inc., MFR: 15 g/10 min (260 ° C, 21.18N), glass transition point: 125 ° C; hereinafter referred to as "COC (2)"] 60 parts by mass and COC (3) 40 parts by mass of a resin mixture as a resin for the intermediate layer (C). A propylene-α-olefin random copolymer obtained by polymerization using a metallocene catalyst [density: 0.900 g/cm 3 , melting point: 135 ° C, MFR: 4 g/10 min (230 ° C, 21.18 N); hereinafter referred to as "MRCP") is a resin for the sealing layer (D). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was (A) / (B) / (C) / (D) = 6 μm / 12 μm / 6 μm / 6 μm (total 30 μm). 3) Corona treatment is applied to the surface layer (A) surface. The surface tension of the moisturizing agent was 40 dyne/cm. The biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film (3).
實施例4 Example 4
使用COC(1)50質量份及COC(3)50質量份的樹脂混合物作為表面層(A)用樹脂及中間層(C)用樹脂，另外，使用LMDPE作為中間層(B)用樹脂。使用低密度聚乙烯[密度：0.920g/cm3，熔點：115℃，MFR：8g/10min(190℃、21.18N)；以下稱為「LDPE」]作為密封層(D)用樹脂，以膜的各層的厚度成為(A)/(B)/(C)/(D)=6μm/12μm/6μm/6μm(合計為30μm)的方式與實施例1同樣地製作共擠出多層膜(4)，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜(4)。 A resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (3) was used as the resin for the surface layer (A) and the resin for the intermediate layer (C), and LMDPE was used as the resin for the intermediate layer (B). Low density polyethylene [density: 0.920 g/cm 3 , melting point: 115 ° C, MFR: 8 g/10 min (190 ° C, 21.18 N); hereinafter referred to as "LDPE") as a resin for the sealing layer (D), with a film A coextruded multilayer film (4) was produced in the same manner as in Example 1 except that the thickness of each layer was (A) / (B) / (C) / (D) = 6 μm / 12 μm / 6 μm / 6 μm (total 30 μm). The surface layer (A) surface is subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. The biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film (4).
實施例5 Example 5
使用COC(1)70質量份、COC(3)30質量份的樹脂混合物作為表面層(A)用樹脂。另外，使用MRCP作為中間層(B)用樹脂。使用COC(1)60質量份、COC(3)40質量份的樹脂混合物作為中間層(C)用樹脂。使用高密度聚乙烯[密度：0.966g/cm3，熔點：128℃，MFR：10g/10min(190℃、21.18N)；以下稱為「HDPE」]85質量份與乙烯丁烯橡膠[密度：0.890g/cm3，熔點： 66℃，MFR：3g/10min(190℃、21.18N)；以下稱為「EBR」]15質量份的樹脂混合物作為密封層(D)用樹脂。以膜的各層的厚度成為(A)/(B)/(C)/(D)=15μm/15μm/15μm/5μm(合計為50μm)的方式與實施例1同樣地製作共擠出多層膜(5)，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜(5)。 A resin mixture of 70 parts by mass of COC (1) and 30 parts by mass of COC (3) was used as the resin for the surface layer (A). Further, MRCP is used as the resin for the intermediate layer (B). A resin mixture of 60 parts by mass of COC (1) and 40 parts by mass of COC (3) was used as the resin for the intermediate layer (C). High-density polyethylene [density: 0.966 g/cm 3 , melting point: 128 ° C, MFR: 10 g/10 min (190 ° C, 21.18 N); hereinafter referred to as "HDPE"] 85 parts by mass with ethylene butylene rubber [density: 0.890 g/cm 3 , melting point: 66 ° C, MFR: 3 g/10 min (190 ° C, 21.18 N); hereinafter referred to as "EBR"] 15 parts by mass of a resin mixture as a resin for the sealing layer (D). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was (A)/(B)/(C)/(D)=15 μm/15 μm/15 μm/5 μm (total 50 μm). 5), the surface layer (A) surface is subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film (5).
實施例6 Example 6
使用COC(1)50質量份及降冰片烯系單體的開環聚合物[三井化學股份有限公司製造的「阿佩爾(Apel)AP6013T」，MFR：15g/10min(260℃、21.18N)，玻璃轉移點：125℃；以下稱為「COC(2)」]50質量份的樹脂混合物作為表面層(A)用樹脂及中間層(C)用樹脂。使用LLDPE 90質量份與COC(2)10質量份的樹脂混合物作為中間層(B)用樹脂。使用LLDPE 80質量份與EBR 20質量份的樹脂混合物作為密封層(D)用樹脂。以膜的層的厚度成為(A)/(B)/(C)/(D)=6μm/12μm/6μm/6μm(合計為30μm)的方式與實施例1同樣地獲得共擠出多層膜(6)後，對表面層(A)的表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜(6)。 50 parts by mass of COC (1) and a ring-opening polymer of norbornene-based monomer [Apel AP6013T manufactured by Mitsui Chemicals, Inc., MFR: 15 g/10 min (260 ° C, 21.18 N) Glass transition point: 125 ° C; hereinafter referred to as "COC (2)"] 50 parts by mass of a resin mixture as a resin for the surface layer (A) and a resin for the intermediate layer (C). 90 parts by mass of LLDPE and 10 parts by mass of COC (2) resin mixture were used as the resin for the intermediate layer (B). A resin mixture of 80 parts by mass of LLDPE and 20 parts by mass of EBR was used as the resin for the sealing layer (D). A coextruded multilayer film was obtained in the same manner as in Example 1 in such a manner that the thickness of the layer of the film was (A)/(B)/(C)/(D)=6 μm/12 μm/6 μm/6 μm (total 30 μm). After 6), the surface of the surface layer (A) is subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. The biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film (6).
實施例7 Example 7
使用COC(1)50質量份與COC(3)50質量份的樹脂混合 物作為表面層(A)用樹脂。另外，使用MRCP90質量份與COC(2)10質量份的樹脂混合物作為作為中間層(B)用樹脂。使用COC(1)60質量份與COC(3)40質量份的樹脂混合物作為中間層(C)用樹脂。使用LLDPE作為密封層(D)用樹脂，以膜的各層的厚度成為(A)/(B)/(C)/(D)=6μm/12μm/6μm/6μm(合計為30μm)的方式與實施例1同樣地製作共擠出多層膜(7)，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側以成為密度2g/m2的方式塗佈胺基甲酸酯系黏接劑後，乾式積層雙軸延伸聚丙烯(厚度20μm)(熔點為162℃，東洋紡製造)，獲得複合膜(7)。 A resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (3) was used as the resin for the surface layer (A). Further, a resin mixture of 90 parts by mass of MRCP and 10 parts by mass of COC (2) was used as the resin for the intermediate layer (B). A resin mixture of 60 parts by mass of COC (1) and 40 parts by mass of COC (3) was used as the resin for the intermediate layer (C). LLDPE is used as the resin for the sealing layer (D), and the thickness of each layer of the film is (A)/(B)/(C)/(D)=6 μm/12 μm/6 μm/6 μm (total 30 μm). In the same manner as in Example 1, a coextruded multilayer film (7) was produced, and the surface of the surface layer (A) was subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. After the urethane-based adhesive was applied to the treated surface side at a density of 2 g/m 2 , a dry laminated biaxially oriented polypropylene (thickness: 20 μm) (melting point: 162 ° C, manufactured by Toyobo Co., Ltd.) was obtained to obtain a composite film. (7).
比較例1 Comparative example 1
不設置表面層(A)，使用LMDPE作為中間層(B)用樹脂。使用COC(3)50質量份與超低密度聚乙烯[密度：0.880g/cm3，熔點：85℃，MFR：5g/10min(190℃、21.18N)；以下稱為「VLLDPE」]50質量份的樹脂混合物作為中間層(C)用樹脂。使用VLLDPE作為密封層(D)用樹脂。以膜的各層的厚度成為(B)/(C)/(D)=21μm/3μm/6μm(合計為30μm)的方式與實施例1同樣地製作共擠出多層膜，對表面層(B)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜。 The surface layer (A) is not provided, and LMDPE is used as the resin for the intermediate layer (B). 50 parts by mass of COC (3) and ultra low density polyethylene [density: 0.880 g/cm 3 , melting point: 85 ° C, MFR: 5 g/10 min (190 ° C, 21.18 N); hereinafter referred to as "VLLDPE") 50 mass The resin mixture as a resin for the intermediate layer (C). VLLDPE was used as the resin for the sealing layer (D). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was (B) / (C) / (D) = 21 μm / 3 μm / 6 μm (total 30 μm), and the surface layer (B) was formed. The surface is subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film.
比較例2 Comparative example 2
使用COC(1)作為表面層(A)用樹脂。使用LMDPE作為 中間層(B)用樹脂。使用COC(1)70質量份與COC(2)30質量份的樹脂混合物作為中間層(C)用樹脂。使用LLDPE作為密封層(D)用樹脂。以膜的各層的厚度成為(A)/(B)/(C)/(D)=10μm/10μm/10μm/30μm(合計為60μm)的方式與實施例1同樣地製作共擠出多層膜，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜。 COC (1) was used as the resin for the surface layer (A). Use LMDPE as The intermediate layer (B) is made of a resin. A resin mixture of 70 parts by mass of COC (1) and 30 parts by mass of COC (2) was used as the resin for the intermediate layer (C). LLDPE was used as the resin for the sealing layer (D). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was (A)/(B)/(C)/(D)=10 μm/10 μm/10 μm/30 μm (total 60 μm). The surface layer (A) surface is subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film.
比較例3 Comparative example 3
使用COC(3)作為表面層(A)用樹脂及中間層(C)用樹脂。使用LMDPE作為中間層(B)用樹脂。使用MRCP作為密封層(D)用樹脂。以膜的各層的厚度成為(A)/(B)/(C)/(D)=6μm/16μm/6μm/2μm(合計為30μm)的方式與實施例1同樣地製作共擠出多層膜，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜。 COC (3) is used as the resin for the surface layer (A) and the resin for the intermediate layer (C). LMDPE was used as the resin for the intermediate layer (B). MRCP was used as the resin for the sealing layer (D). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was (A)/(B)/(C)/(D)=6 μm/16 μm/6 μm/2 μm (total 30 μm). The surface layer (A) surface is subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film.
比較例4 Comparative example 4
使用COC(1)70質量份與COC(3)30質量份的樹脂混合物作為表面層(A)用樹脂。使用MRCP作為中間層(B)用樹脂。使用COC(1)60質量份與COC(3)40質量份的樹脂混合物作為中間層(C)用樹脂。使用VLLDPE 80質量份與EBR 20質量份的樹脂混合物作為作為密封層(D)用樹脂。以膜的各層的厚度成為(A)/(B)/(C)/(D)=30μm/30μm/10μm/30μm(合計為 100μm)的方式與實施例1同樣地製作共擠出多層膜，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜。 A resin mixture of 70 parts by mass of COC (1) and 30 parts by mass of COC (3) was used as the resin for the surface layer (A). MRCP was used as the resin for the intermediate layer (B). A resin mixture of 60 parts by mass of COC (1) and 40 parts by mass of COC (3) was used as the resin for the intermediate layer (C). 80 parts by mass of VLLDPE and 20 parts by mass of EBR resin mixture were used as the resin for the sealing layer (D). The thickness of each layer of the film is (A) / (B) / (C) / (D) = 30 μm / 30 μm / 10 μm / 30 μm (total A coextruded multilayer film was produced in the same manner as in Example 1 in a manner of 100 μm, and the surface of the surface layer (A) was subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film.
比較例5 Comparative Example 5
使用COC(1)50質量份與COC(2)50質量份的樹脂混合物作為表面層(A)用樹脂。使用LLDPE作為中間層(B)用樹脂。使用COC(1)20質量份與COC(3)80質量份的樹脂混合物作為中間層(C)用樹脂。使用LLDPE 80質量份與EBR 20質量份的樹脂混合物作為密封層(D)用樹脂。以膜的各層的厚度成為(A)/(B)/(C)/(D)=6μm/15μm/3μm/6μm(合計為30μm)的方式與實施例1同樣地製作共擠出多層膜，對表面層(A)表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜。 A resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (2) was used as the resin for the surface layer (A). LLDPE was used as the resin for the intermediate layer (B). A resin mixture of 20 parts by mass of COC (1) and 80 parts by mass of COC (3) was used as the resin for the intermediate layer (C). A resin mixture of 80 parts by mass of LLDPE and 20 parts by mass of EBR was used as the resin for the sealing layer (D). A coextruded multilayer film was produced in the same manner as in Example 1 so that the thickness of each layer of the film was (A)/(B)/(C)/(D)=6 μm/15 μm/3 μm/6 μm (total 30 μm). The surface layer (A) surface is subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film.
比較例6 Comparative Example 6
利用與實施例1相同的方法來製作將使用COC(1)50質量份與COC(2)50質量份的樹脂混合物的表面層、與使用MRCP的密封層積層而成的二層膜。使膜的各層的厚度成為表面層/密封層=20μm/20μm(合計為40μm)，對表面層的表面實施電暈處理。濡濕試劑的表面張力為40dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜。 A two-layer film obtained by laminating a surface layer of a resin mixture of 50 parts by mass of COC (1) and 50 parts by mass of COC (2) and a sealing layer using MRCP was produced in the same manner as in Example 1. The thickness of each layer of the film was changed to a surface layer/sealing layer = 20 μm / 20 μm (total 40 μm), and the surface of the surface layer was subjected to corona treatment. The surface tension of the moisturizing agent was 40 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film.
比較例7 Comparative Example 7
利用與實施例1相同的方法來製作將使用VLLDPE的表面層 與使用LLDPE的密封層積層而成的二層膜。使膜的各層的厚度成為表面層/密封層=15μm/15μm(合計為30μm)，對表面層的表面實施電暈處理。濡濕試劑的表面張力為38dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜。 A surface layer to be used using VLLDPE was produced in the same manner as in Example 1. A two-layer film laminated with a sealing layer using LLDPE. The thickness of each layer of the film was changed to a surface layer/sealing layer = 15 μm / 15 μm (total 30 μm), and the surface of the surface layer was subjected to corona treatment. The surface tension of the moisturizing agent was 38 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film.
比較例8 Comparative Example 8
不積層相當於表面層(A)的樹脂層，使用LLDPE作為中間層(B)用樹脂，使用COC(3)作為中間層(C)用樹脂，使用LLDPE作為密封層(D)用樹脂，製作三層的多層膜。使膜的各層的厚度成為(B)/(C)/(D)=9μm/12μm/9μm(合計為30μm)，對中間層(B)的表面實施電暈處理。濡濕試劑的表面張力為38dyne/cm。於處理面側與實施例1同樣地乾式積層雙軸延伸聚酯，獲得複合膜。 A resin layer corresponding to the surface layer (A) is not laminated, LLDPE is used as the resin for the intermediate layer (B), COC (3) is used as the resin for the intermediate layer (C), and LLDPE is used as the resin for the sealing layer (D). Three-layer multilayer film. The thickness of each layer of the film was (B) / (C) / (D) = 9 μm / 12 μm / 9 μm (total 30 μm), and the surface of the intermediate layer (B) was subjected to corona treatment. The surface tension of the moisturizing agent was 38 dyne/cm. A biaxially stretched polyester was dry-laid on the treated surface side in the same manner as in Example 1 to obtain a composite film.
撕開性試驗 Tear test
依據日本工業標準(Japanese Industrial Standards，JIS)K7128將所得的複合膜分別切出成63mm×76mm的大小的試片，使用埃爾門多夫(Elmendorf)撕裂試驗機(測試機(Tester)產業股份有限公司製造)測定撕裂強度。根據所得的撕裂強度按照下述基準來評價撕開性。 The obtained composite film was cut out into a test piece of 63 mm × 76 mm according to Japanese Industrial Standards (JIS) K7128, and an Elmendorf tear tester (Tester industry) was used. The tear strength was measured by the company. According to the obtained tear strength, the tearability was evaluated in accordance with the following criteria.
○：撕裂強度小於110。 ○: The tear strength is less than 110.
×：撕裂強度為110以上。 ×: The tear strength was 110 or more.
吸附性試驗 Adsorption test
將各複合膜製成縱100mm×橫100mm的三方密封袋後，測定 質量後，加入水楊酸甲酯(吸附試驗1)及二氧化氯[克萊貝林凝膠(Cleverin Gel)：大幸藥品](吸附試驗2)2g，藉由熱封將開口部密封。於密封容器中於25℃恆溫條件下放置2週後，開封並去除內容物，測定袋的質量，根據變化率求出吸附率。 The composite film was made into a three-way sealed bag of 100 mm in length × 100 mm in width, and then measured. After the mass, 2 g of methyl salicylate (adsorption test 1) and chlorine dioxide [Cleverin Gel: Daxun Pharmaceutical] (adsorption test 2) were added, and the opening was sealed by heat sealing. After standing at a constant temperature of 25 ° C for 2 weeks in a sealed container, the contents were opened and removed, the mass of the bag was measured, and the adsorption rate was determined from the rate of change.
○：數值小於1% ○: The value is less than 1%
△：數值為1%以上、小於2% △: The value is 1% or more and less than 2%.
×：數值為2%以上 ×: The value is 2% or more
積層強度 Laminated strength
對上述吸附試驗中使用的複合膜的前後的積層強度進行測定，求出強度的降低率。 The laminate strength before and after the composite film used in the above adsorption test was measured, and the rate of decrease in strength was determined.
○：小於10% ○: less than 10%
×：10%以上 ×: 10% or more
外觀 Exterior
將各複合膜製成縱100mm×橫100mm的三方密封袋後，加入水傷酸甲酯、二氧化氯2g，藉由熱封將開口部密封。於密封容器中於25℃恆溫條件下放置2週後，觀察由黏接劑部的積層的浮起或脫層所致的外觀變化。 Each composite film was formed into a three-way sealed bag of 100 mm in length × 100 mm in width, and then methyl sulphate and 2 g of chlorine dioxide were added, and the opening was sealed by heat sealing. After standing at a constant temperature of 25 ° C for 2 weeks in a sealed container, the change in appearance due to the floating or delamination of the laminate of the adhesive portion was observed.
○：並無外觀變化 ○: No appearance change
×：有積層的浮起等外觀變化 ×: There is a change in appearance such as floating of the laminate
密封強度試驗 Seal strength test
將各複合膜製成縱100mm×橫100mm的三方密封袋後，測定質量後，加入水楊酸甲酯2g，藉由熱封將開口部密封。於密封容 器中於45℃恆溫條件下放置2週後，測定密封強度而求出強度降低率。 Each composite film was formed into a three-dimensional sealed bag of 100 mm in length × 100 mm in width, and after measuring the mass, 2 g of methyl salicylate was added, and the opening was sealed by heat sealing. Sealing capacity After standing at a constant temperature of 45 ° C for 2 weeks, the sealing strength was measured to determine the strength reduction rate.
○：小於5% ○: less than 5%
×：5%以上 ×: 5% or more
捲曲性 Curl
將各多層膜切出成縱橫10cm四方，於40℃、濕度90%下保存24小時。於平面上將膜攤開，測定兩端面上卷的高度，按照下述基準進行評價。 Each of the multilayer films was cut into a square of 10 cm in length and width, and stored at 40 ° C and a humidity of 90% for 24 hours. The film was spread on a flat surface, and the height of the roll on both end faces was measured, and it evaluated based on the following criteria.
○：高度小於3cm ○: height less than 3cm
△：高度為3cm以上 △: the height is 3cm or more
×：膜兩端重疊而完全變圓 ×: Both ends of the film overlap and completely rounded
將上述所得的結果示於表1~表2中。 The results obtained above are shown in Tables 1 to 2.
本發明的低吸附性積層用多層膜具有易撕裂性、高熱封強度、揮發性成分的吸附抑制性等。另外，亦具有優異的積層強度、由彎曲所得的耐針孔性、耐捲曲性、外觀。因此，本發明的 多層膜適於對食品、糖果、醫藥品、香煙、工業藥品、工業零件、雜貨等進行包裝的包裝材。 The multilayer film for low-adsorption laminate of the present invention has tearability, high heat-sealing strength, adsorption inhibition property of a volatile component, and the like. In addition, it also has excellent lamination strength, pinhole resistance, curl resistance, and appearance obtained by bending. Therefore, the present invention The multilayer film is suitable for packaging materials for packaging food, candy, pharmaceuticals, cigarettes, industrial medicines, industrial parts, groceries, and the like.
Claims (9)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012256247 | 2012-11-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201420345A TW201420345A (en) | 2014-06-01 |
| TWI586535B true TWI586535B (en) | 2017-06-11 |
Family
ID=50775870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102135773A TWI586535B (en) | 2012-11-22 | 2013-10-03 | Multi-layer film for lamination with low adsorptive properties, composite film using the same and packaging material |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5822956B2 (en) |
| KR (1) | KR102131124B1 (en) |
| TW (1) | TWI586535B (en) |
| WO (1) | WO2014080679A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6562245B2 (en) * | 2015-02-24 | 2019-08-21 | 住友ベークライト株式会社 | Multilayer film and package |
| JP6620438B2 (en) * | 2015-06-30 | 2019-12-18 | 大日本印刷株式会社 | Low adsorptive coextrusion multilayer sealant film |
| JP6702068B2 (en) * | 2015-09-08 | 2020-05-27 | 王子ホールディングス株式会社 | Semi-transparent stretched film |
| WO2017094491A1 (en) * | 2015-11-30 | 2017-06-08 | Dic株式会社 | Package structure for patch |
| JP6839924B2 (en) * | 2016-03-15 | 2021-03-10 | Dic株式会社 | Lid material |
| JP7395922B2 (en) * | 2019-10-03 | 2023-12-12 | Ｔｏｐｐａｎホールディングス株式会社 | Low adsorption laminate |
| JP6773995B2 (en) * | 2020-02-17 | 2020-10-21 | キョーラク株式会社 | Multiple bags |
| CN114889280B (en) * | 2022-06-17 | 2024-01-02 | 应城市恒天药业包装有限公司 | Disposable high-barrier membrane for intravenous nutrition infusion bag and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012153420A (en) * | 2011-01-28 | 2012-08-16 | Dic Corp | Easily penetrable lid material |
| JP2012224071A (en) * | 2011-04-06 | 2012-11-15 | Dic Corp | Multilayer film and packaging material comprising the film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000334890A (en) | 1999-03-24 | 2000-12-05 | Nippon Zeon Co Ltd | Packaging film |
| JP5720202B2 (en) | 2010-11-26 | 2015-05-20 | 大日本印刷株式会社 | Low adsorptive sealant film and laminate and packaging bag using the same |
| JP5825809B2 (en) * | 2011-03-18 | 2015-12-02 | 藤森工業株式会社 | Laminated structure for packaging and packaging container |
-
2013
- 2013-09-10 WO PCT/JP2013/074361 patent/WO2014080679A1/en active Application Filing
- 2013-09-10 KR KR1020157014103A patent/KR102131124B1/en active IP Right Grant
- 2013-09-10 JP JP2013555690A patent/JP5822956B2/en active Active
- 2013-10-03 TW TW102135773A patent/TWI586535B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012153420A (en) * | 2011-01-28 | 2012-08-16 | Dic Corp | Easily penetrable lid material |
| JP2012224071A (en) * | 2011-04-06 | 2012-11-15 | Dic Corp | Multilayer film and packaging material comprising the film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2014080679A1 (en) | 2017-01-05 |
| JP5822956B2 (en) | 2015-11-25 |
| TW201420345A (en) | 2014-06-01 |
| KR20150088807A (en) | 2015-08-03 |
| WO2014080679A1 (en) | 2014-05-30 |
| KR102131124B1 (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI586535B (en) | Multi-layer film for lamination with low adsorptive properties, composite film using the same and packaging material | |
| JP7140105B2 (en) | Laminated film and food packaging bag | |
| JP5713190B2 (en) | Easy-open multilayer film and packaging material using the film | |
| JP5459535B2 (en) | Coextruded multilayer film and packaging material comprising the film | |
| JP5413647B2 (en) | Coextruded multilayer film and packaging material comprising the film | |
| TWI755577B (en) | Laminated films and food packaging bags | |
| JP5779866B2 (en) | Multilayer film and packaging material using the film | |
| JP6172398B2 (en) | Multilayer film, laminated film for packaging material, packaging bag and standing pouch | |
| JP5787157B2 (en) | Easy tearable multilayer film, method for producing the same, and packaging material using the film | |
| JP5741935B2 (en) | Multilayer film and packaging material comprising the film | |
| KR20160147721A (en) | Multilayer sealant film | |
| JP6375974B2 (en) | Easy tear multilayer sealant film and packaging material | |
| JP7140104B2 (en) | Laminated film and food packaging bag | |
| JP5716286B2 (en) | Coextruded multilayer film and packaging material comprising the film | |
| JP5991504B2 (en) | Easy-penetrating lid | |
| TWI583549B (en) | Laminate and package material using the same | |
| JP2005199514A (en) | Multilayered laminated resin film and laminated material using it | |
| JPWO2019220912A1 (en) | Multi-layer film and packaging | |
| JP5935372B2 (en) | Twist packaging film and twist package | |
| JP7207604B2 (en) | Alcohol permeation suppressing film, and packaging material and package using alcohol permeation suppressing film | |
| JP5569659B1 (en) | Laminated body and packaging material using the same | |
| JP6839924B2 (en) | Lid material | |
| JP7257777B2 (en) | Laminated films and packaging materials |