TWI686302B - Laminated film and packaging materials - Google Patents

Laminated film and packaging materials Download PDF

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TWI686302B
TWI686302B TW105123144A TW105123144A TWI686302B TW I686302 B TWI686302 B TW I686302B TW 105123144 A TW105123144 A TW 105123144A TW 105123144 A TW105123144 A TW 105123144A TW I686302 B TWI686302 B TW I686302B
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layer
mass
copolymer
ethylene
propylene
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TW105123144A
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TW201710092A (en
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小橋一範
松原弘明
渡邊康史
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日商迪愛生股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/40Applications of laminates for particular packaging purposes

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

本發明藉由苯乙烯系彈性體將苯乙烯導入具有含有丙烯系樹脂之印刷層的積層薄膜的該印刷層中,藉此保持較佳的熔切強度,而且即使在與聚氯乙烯等樹脂片材接觸時,亦不易發生印刷脫落,可實現優異的印刷密合性。又,藉由使用苯乙烯系彈性體,其與丙烯系樹脂的相容性變得良好,可實現較佳的透明性,又可實現優異的耐衝擊性。 The present invention uses styrene-based elastomer to introduce styrene into the printed layer having a laminated film containing a printed layer of acryl-based resin, thereby maintaining a better fusion-cutting strength, and even with resin sheets such as polyvinyl chloride When the material is in contact, it is not easy to cause printing to fall off, which can achieve excellent printing adhesion. In addition, by using a styrene-based elastomer, its compatibility with the propylene-based resin becomes good, and it is possible to achieve good transparency and excellent impact resistance.

Description

積層薄膜及包裝材料 Laminated film and packaging materials

本發明係關於一種用於包裝食品、雜貨、雜誌等之包裝材料的積層薄膜及包含該薄膜的包裝材料。 The present invention relates to a laminated film used for packaging packaging materials for food, groceries, magazines, etc., and packaging materials containing the film.

以往係使用積層有複數樹脂的積層薄膜來作為用於包裝麵包或其他食品等的包裝用薄膜。從容易得到熱封性等的觀點來看,可廣泛應用使用烯烴系樹脂的積層薄膜來作為這種包裝用薄膜(例如參照專利文獻1~2)。 Conventionally, a laminated film in which plural resins are laminated is used as a packaging film for packaging bread or other foods. From the viewpoint of easily obtaining heat sealability and the like, a laminated film using an olefin-based resin can be widely used as such a packaging film (for example, refer to Patent Documents 1 to 2).

用於各種包裝的積層薄膜,為了標示出處或內容、賦予設計性等,大多於表層設置印刷,但若該印刷的密合性低,則發生印刷的脫落,故藉由電暈處理等的表面處理來實現印刷密合性的提高。 Laminated films used in various packages are often provided with a print on the surface layer to indicate the location, content, design, etc. However, if the adhesion of the print is low, the print will fall off, so the surface is treated by corona treatment, etc. Processing to achieve improved print adhesion.

先前技術文獻Prior technical literature 專利文獻Patent Literature

專利文獻1 日本特開2002-210897號公報 Patent Document 1 Japanese Patent Application Publication No. 2002-210897

專利文獻2 日本特開2007-152730號公報 Patent Literature 2 Japanese Patent Application Publication No. 2007-152730

然而,以往的積層薄膜中,由於在印刷層與聚氯乙烯等樹脂片材表面接觸時,會有將印刷轉印至該樹脂片材,而印刷脫落的情況,故而要求進一步提高印刷密合性。另一方面,若為了提高積層薄膜表層的印刷密合性而進行電暈處理等的表面處理,雖然印刷密合性提高,但會熔切薄膜而使其密合時的熔切強度容易降低,故難以藉由表面處理進一步提高印刷密合性。 However, in the conventional laminated film, when the printing layer is in contact with the surface of a resin sheet such as polyvinyl chloride, the printing may be transferred to the resin sheet and the printing may fall off, so it is required to further improve the printing adhesion . On the other hand, if surface treatment such as corona treatment is performed in order to improve the printing adhesion of the surface layer of the laminated film, although the printing adhesion is improved, the film will be fused and the fused strength at the time of adhesion is likely to decrease, Therefore, it is difficult to further improve the printing adhesion by surface treatment.

本發明所欲解決之課題在於提供一種具有較佳熔切強度、並可實現優異之印刷密合性的積層薄膜。 The problem to be solved by the present invention is to provide a laminated film which has better fused cutting strength and can achieve excellent printing adhesion.

再者,除了上述課題以外,本發明之課題還有提供一種具有較佳透明性與優異耐衝擊性的積層薄膜。 Furthermore, in addition to the above-mentioned problems, the object of the present invention is to provide a laminated film having better transparency and excellent impact resistance.

本發明藉由一種積層薄膜解決上述課題:其係一側的表層包含印刷層、另一側的表層包含密封層的積層薄膜,其中,該印刷層含有丙烯系樹脂及苯乙烯系彈性體,印刷層中的苯乙烯含量為2~15質量%。 The present invention solves the above-mentioned problem by means of a laminated film: a laminated film whose surface layer on one side includes a printed layer and the surface layer on the other side includes a sealing layer, wherein the printed layer contains an acrylic resin and a styrene-based elastomer, and is printed The styrene content in the layer is 2 to 15% by mass.

在本發明中,藉由苯乙烯系彈性體將苯乙烯導入具有含有丙烯系樹脂之印刷層的積層薄膜的該印刷層中,藉此保持較佳的熔切強度,而且即使在與聚氯乙烯等的樹脂片材接觸時,亦可實現印刷不易脫落的優異印刷密合性。又,藉由使用苯乙烯系彈性體,可使其與丙烯系樹脂的相容性變得良好,實現較佳的透明性,又可實現優異的耐衝擊性。 In the present invention, styrene is introduced into the printed layer having a laminated film containing a printed layer of acryl-based resin through a styrene-based elastomer, thereby maintaining a better melt-cutting strength, and even with PVC When a resin sheet such as is in contact, excellent print adhesion that is difficult for printing to come off can be achieved. In addition, by using a styrene-based elastomer, the compatibility with the propylene-based resin can be improved to achieve better transparency and excellent impact resistance.

用以實施發明之形態Forms for carrying out the invention

本發明之積層薄膜,其一側的表層包含實施各種印刷的印刷層,另一側的表層包含密封層,該印刷層含有丙烯系樹脂及苯乙烯系彈性體,印刷層中的苯乙烯含量為2~15質量%。 In the laminated film of the present invention, the surface layer on one side includes a printing layer for performing various printings, and the surface layer on the other side includes a sealing layer, the printing layer contains an acrylic resin and a styrene elastomer, and the styrene content in the printing layer is 2~15% by mass.

[印刷層] [Printed layer]

用於本發明之積層薄膜的印刷層含有丙烯系樹脂及苯乙烯系彈性體。作為丙烯系樹脂,較佳可應用用於包裝用薄膜的丙烯系樹脂,可舉例如:丙烯均聚物、丙烯-α-烯烴共聚物,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。該等共聚物可分別單獨使用,亦可合併使用。 The printed layer used in the laminated film of the present invention contains an acrylic resin and a styrene elastomer. As the propylene-based resin, a propylene-based resin used for packaging films is preferably applied, and examples thereof include propylene homopolymers and propylene-α-olefin copolymers, such as propylene-ethylene copolymers and propylene-butene-1 copolymerization. Products, propylene-ethylene-butene-1 copolymer, metallocene catalyst polypropylene, etc. These copolymers can be used individually or in combination.

特別是在將積層薄膜作為透明積層薄膜的情況下,從容易得到較佳透明性及與中間層之密合性的觀點來看,較佳為使用丙烯-乙烯無規共聚物作為樹脂成分。在使用丙烯-乙烯無規共聚物的情況下,印刷層所包含之丙烯系樹脂中丙烯-乙烯無規共聚物的比例較佳為60質量%以上,更佳為70質量%以上。又,作為丙烯系樹脂,實質上僅使用丙烯-乙烯無規共聚物亦為較佳。 In particular, when the laminated film is used as a transparent laminated film, it is preferable to use a propylene-ethylene random copolymer as the resin component from the viewpoint of easily obtaining better transparency and adhesion to the intermediate layer. When a propylene-ethylene random copolymer is used, the proportion of the propylene-ethylene random copolymer in the propylene-based resin included in the printed layer is preferably 60% by mass or more, and more preferably 70% by mass or more. In addition, as the propylene-based resin, it is substantially preferable to use only a propylene-ethylene random copolymer.

作為丙烯-乙烯無規共聚物,從容易得到較佳耐結塊性的觀點來看,乙烯含量較佳為10質量%以下,更佳為8質量%以下,再佳為6質量%。又,從容易得到較佳耐衝擊性的觀點來看,乙烯含量較佳為2質量%以上,更佳為3質量%以上,再佳為4質量%以上。 As the propylene-ethylene random copolymer, from the viewpoint of easily obtaining better blocking resistance, the ethylene content is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass. In addition, from the viewpoint of easily obtaining better impact resistance, the ethylene content is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 4% by mass or more.

又,丙烯-乙烯無規共聚物的熔流速率(MFR),只要在可形成積層薄膜的範圍內,則並無特別是限制,但從容易得到良好成形性的觀點來看,較佳為0.5g/10分鐘以上,更佳為3g/10分鐘以上,再佳為5g/10分鐘以上。又,從容易得到較佳耐衝擊性的觀點來看,MFR較佳為20g/10分鐘以下,更佳為15g/10分鐘以下,再佳為12g/10分鐘以下。 In addition, the melt flow rate (MFR) of the propylene-ethylene random copolymer is not particularly limited as long as it can form a laminated film, but from the viewpoint of easily obtaining good formability, it is preferably 0.5 g/10 minutes or more, more preferably 3 g/10 minutes or more, and still more preferably 5 g/10 minutes or more. In addition, from the viewpoint of easily obtaining better impact resistance, the MFR is preferably 20 g/10 minutes or less, more preferably 15 g/10 minutes or less, and still more preferably 12 g/10 minutes or less.

丙烯-乙烯無規共聚物的密度較佳為0.88g/cm3以上,更佳為0.89g/cm3以上。 The density of the propylene-ethylene random copolymer is preferably 0.88 g/cm 3 or more, and more preferably 0.89 g/cm 3 or more.

從剛性降低導致製袋適用性降低或滑動性的方面來看,丙烯-乙烯無規共聚物的熔點較佳為110℃以上,更佳為115℃以上。又,從低溫時的裂開性或破袋的方面來看,較佳為150℃以下,更佳為145℃以下。 The melting point of the propylene-ethylene random copolymer is preferably 110° C. or higher, and more preferably 115° C. or higher, from the viewpoint of a decrease in rigidity leading to a decrease in the suitability for bag making or sliding properties. Moreover, from the viewpoint of cracking properties or bag breakage at low temperatures, it is preferably 150°C or lower, and more preferably 145°C or lower.

印刷層中丙烯系樹脂的含量,較佳為印刷層所包含之樹脂成分中的60質量%以上,更佳為65質量%以上。又,該含量較佳為95質量%以下,更佳為90質量%以下。 The content of the propylene-based resin in the printing layer is preferably 60% by mass or more, and more preferably 65% by mass or more of the resin component contained in the printing layer. In addition, the content is preferably 95% by mass or less, and more preferably 90% by mass or less.

在本發明中,從容易實現積層薄膜之較佳透明性的觀點來看,樹脂成分中嵌段共聚物的含量較佳為10質量%以下,更佳為5質量%以下,特佳為實質上不包含。本發明之積層薄膜,在使用嵌段共聚物含量較少之印刷層的情況下,可實現特佳的效果。 In the present invention, from the viewpoint of easily achieving better transparency of the laminated film, the content of the block copolymer in the resin component is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably substantially Not included. The laminated film of the present invention can achieve particularly good effects when a printed layer with a low content of block copolymer is used.

作為用於印刷層的苯乙烯系彈性體,可舉例如:具有苯乙烯系聚合物嵌段、及苯乙烯與共軛二烯化合物之無規共聚物的雙鍵部分被氫化的苯乙烯系無規共聚物嵌段的共聚物(A-1);通式a-b-a或a-b(a係苯乙烯系聚合物嵌段,b係使共軛二烯聚合物嵌段或共軛二烯聚合物中之雙鍵部分氫化所得到的烯烴聚合物嵌段)所表示的苯乙烯系嵌段共聚物(A-2)等。包含「該等共軛二烯部分之雙鍵部分被氫化之嵌段部分」的苯乙烯系彈性體,該部分與丙烯系樹脂的相容性優異,故容易得到特佳的透明性。 Examples of the styrene-based elastomer used in the printing layer include styrene-based elastomers having a styrene-based polymer block and a random copolymer of styrene and a conjugated diene compound whose hydrogenated double bonds are partially hydrogenated. Copolymer (A-1) with regular copolymer blocks; general formula aba or ab (a is a styrene polymer block, b is a conjugated diene polymer block or a conjugated diene polymer The styrene-based block copolymer (A-2) represented by the olefin polymer block obtained by partial hydrogenation of the double bond and the like. The styrene-based elastomer containing the "blocked portion where the double bond portion of the conjugated diene portion is hydrogenated" has excellent compatibility with the propylene-based resin, so it is easy to obtain excellent transparency.

作為用作該共聚物(A-1)或(A-2)之原料的共軛二烯化合物,可舉例如:1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-戊二烯、2-甲基-1,3-戊二烯、1,3-己二烯、4,5-二乙基-1,3-辛二烯、3-丁基-1,3-辛二烯、氯丁二烯等,從工業上之取得容易度的觀點來看,較佳為使用1,3-丁二烯、異戊二烯。又,作為形成苯乙烯系聚合物嵌段的苯乙烯系化合物,可舉例如:苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、第三丁基苯乙烯、二乙烯苯、1,1-二苯基苯乙烯、N,N-二甲基-對胺基甲基苯乙烯、N,N-二乙基-對胺基乙基苯乙烯等,但較佳為使用苯乙烯。 As the conjugated diene compound used as a raw material of the copolymer (A-1) or (A-2), for example, 1,3-butadiene, isoprene, 2,3-dimethyl -1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl -1,3-octadiene, chloroprene and the like are preferably 1,3-butadiene and isoprene from the viewpoint of industrial availability. In addition, examples of the styrene-based compound forming the styrene-based polymer block include styrene, α-methylstyrene, p-methylstyrene, tert-butylstyrene, divinylbenzene, and 1, 1-Diphenylstyrene, N,N-dimethyl-p-aminomethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc., but styrene is preferably used.

作為市售品,例如,作為共聚物(A-1),可舉例如:苯乙烯-丁二烯無規共聚物氫化物(以下簡稱為HSBR)的JSR股份有限公司製「DYNARON 1320P、DYNARON 2320P」,又,作為苯乙烯系嵌段共聚物(A-2),可舉例如:苯乙烯-異戊二烯-苯乙烯嵌段共聚物(以下簡稱為SIS)的JSR股份有限公司製「SIS5200」、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(以下簡稱為SEBS)的「JSR股份有限公司製DYNARON 8600P、DYNARON 8903P」、苯乙烯-乙烯.丙烯-苯乙烯嵌段共聚物(以下簡稱為SEPS)的KURARAY股份有限公司製「SEPTON 2063、SEPTON 2004」等。 As a commercially available product, for example, as the copolymer (A-1), for example, styrene-butadiene random copolymer hydride (hereinafter abbreviated as HSBR) manufactured by JSR Corporation "DYNARON 1320P, DYNARON 2320P" Also, examples of the styrene-based block copolymer (A-2) include: "SIS5200" manufactured by JSR Co., Ltd. of styrene-isoprene-styrene block copolymer (hereinafter abbreviated as SIS). ", styrene-ethylene-butene-styrene block copolymer (hereinafter referred to as SEBS) "DYNARON 8600P, DYNARON 8903P made by JSR Co., Ltd.", styrene-ethylene. "SEPTON 2063, SEPTON 2004" manufactured by KURARAY Co., Ltd. of propylene-styrene block copolymer (hereinafter abbreviated as SEPS), etc.

在本發明中,為了提高印刷的密合性,相對於印刷層中之樹脂成分的苯乙烯含量較佳為2質量%以上,更佳為2.5質量%以上,再佳為3質量%以上。又,為了抑制透明性的降低,印刷層中的苯乙烯含量較佳為15質量%以下,更佳為13質量%以下。 In the present invention, in order to improve the adhesion of printing, the styrene content relative to the resin component in the printing layer is preferably 2% by mass or more, more preferably 2.5% by mass or more, and still more preferably 3% by mass or more. In order to suppress the decrease in transparency, the styrene content in the printed layer is preferably 15% by mass or less, and more preferably 13% by mass or less.

印刷層中苯乙烯系彈性體的含量,只要適當調整以使苯乙烯含量在上述範圍內即可,但為了抑制剛性的降低,較佳為印刷層所包含之樹脂成分中的40質量%以下,更佳為30質量%以下。又,下限並無特別限制,但較佳為5質量%以上,更佳為10質量%以上。 The content of the styrene-based elastomer in the printed layer may be appropriately adjusted so that the styrene content is within the above range, but in order to suppress the reduction in rigidity, it is preferably 40% by mass or less of the resin component contained in the printed layer. It is more preferably 30% by mass or less. In addition, the lower limit is not particularly limited, but it is preferably 5% by mass or more, and more preferably 10% by mass or more.

亦可於印刷層中適當合併使用上述丙烯系樹脂及苯乙烯彈性體以外的其他樹脂。作為該其他樹脂,除了上述以外的烯烴系樹脂,例如,可使用超低密度聚乙烯(VLDPE)、線性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)等的聚乙烯樹脂;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)等的乙烯系共聚物;再者,乙烯-丙烯酸共聚物的離子聚合物、乙烯-甲基丙烯酸共聚物的離子聚合物等。 Other resins other than the above-mentioned acrylic resin and styrene elastomer may be appropriately used in combination in the printed layer. As this other resin, olefin resins other than the above, for example, polyethylene resins such as ultra-low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), etc.; ethylene- Vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate- Ethylene copolymers such as maleic anhydride copolymers (E-EA-MAH), ethylene-acrylic acid copolymers (EAA), ethylene-methacrylic acid copolymers (EMAA), etc. Furthermore, ionic polymerization of ethylene-acrylic acid copolymers Ionic polymer of ethylene-methacrylic acid copolymer, etc.

於印刷層中使用該其他樹脂的情況下,其含量較佳為樹脂成分中的30質量%以下,更佳為20質量%以下。 When the other resin is used in the printing layer, the content is preferably 30% by mass or less in the resin component, and more preferably 20% by mass or less.

在不損及本發明之目的的範圍內,可於印刷層中適當添加防霧劑、抗靜電劑、熱穩定劑、造核劑、抗氧化劑、增滑劑、抗結塊劑、脫模劑、紫外線吸收劑等成分來作為上述樹脂成分以外的其他成分。 Anti-fogging agents, antistatic agents, heat stabilizers, nucleating agents, antioxidants, slip agents, anti-caking agents, mold release agents can be added to the printed layer as long as the purpose of the present invention is not compromised , Ultraviolet absorbers and other components as other components than the above resin components.

較佳為對印刷層表面進行處理,使表面的濕潤張力在38mN/m以下的範圍,更佳在35mN/m以下。若濕潤張力在該範圍內,則不會大幅降低熔切強度,而可提高印刷密合性。作為該表面處理方法,可舉例如:電暈放電處理、電漿處理、鉻酸處理、火焰處理、熱風處理、臭氧.紫外線處理等的表面氧化處理、或噴沙法(sandblast)等的表面凹凸處理等,其中,較佳為電暈放電處理。又,濕潤張力的下限並無特別限制,但較佳為30mN/m以上。 Preferably, the surface of the printed layer is treated so that the wetting tension of the surface is in the range of 38 mN/m or less, more preferably 35 mN/m or less. If the wetting tension is within this range, the fused cutting strength will not be greatly reduced, and the printing adhesion can be improved. As the surface treatment method, for example: corona discharge treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone. Among them, surface oxidation treatment such as ultraviolet treatment, surface roughness treatment such as sandblasting, etc., among which corona discharge treatment is preferred. In addition, the lower limit of the wetting tension is not particularly limited, but it is preferably 30 mN/m or more.

[密封層] [Sealing layer]

用於本發明的密封層,係用於將積層薄膜的密封層彼此接著、或將積層薄膜與其他容器或薄膜等接著的層體。該密封層,只要因應使用態樣或被密封對象,適當選擇可得到較佳密封強度的樹脂種類即可。例如,在將密封層彼此密封以用作包裝袋的情況下,從可得到適度之密封強度的觀點來看,較佳可使用含有丙烯-乙烯(無 規)共聚物、丙烯-1-丁烯共聚物等丙烯-α-烯烴共聚物的密封層等,其中,特佳為含有1-丁烯-丙烯共聚物的密封層。 The sealing layer used in the present invention is a layered body for adhering the sealing layers of the laminated film to each other or the laminated film and other containers or films. As for the sealing layer, it is only necessary to appropriately select the type of resin that can obtain a better sealing strength in accordance with the aspect of use or the object to be sealed. For example, in the case where the sealing layers are sealed to each other to be used as a packaging bag, from the viewpoint of obtaining a moderate seal strength, it is preferable to use propylene-ethylene-containing (no (Regulation) Sealing layers of propylene-α-olefin copolymers such as copolymers and propylene-1-butene copolymers, among them, particularly preferred is a sealing layer containing a 1-butene-propylene copolymer.

在使用1-丁烯-丙烯共聚物的情況下,密封層可為包含1-丁烯-丙烯共聚物的密封層,但從容易抑制裂開的觀點來看,密封層中所包含之樹脂成分中1-丁烯-丙烯共聚物的含量較佳為55質量%以下,更佳為50質量%以下,再佳為45質量%以下。又,從容易得到較佳低溫密封性的觀點來看,丙烯含量較佳為2莫耳%以上,更佳為3莫耳%以上,再佳為5莫耳%以上。 In the case of using a 1-butene-propylene copolymer, the sealing layer may be a sealing layer containing a 1-butene-propylene copolymer, but from the viewpoint of easily suppressing cracking, the resin component contained in the sealing layer The content of the 1-butene-propylene copolymer in the medium is preferably 55% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less. In addition, from the viewpoint of easily obtaining better low-temperature sealing properties, the propylene content is preferably 2 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more.

又,在使用1-丁烯-丙烯共聚物的情況下,其含量較佳為10質量%以上,更佳為15質量%以上。若1-丁烯-丙烯共聚物的含量在該範圍內,則容易得到較佳低溫密封性及耐裂性,又,亦有利於低成本化。 In addition, when a 1-butene-propylene copolymer is used, its content is preferably 10% by mass or more, and more preferably 15% by mass or more. If the content of the 1-butene-propylene copolymer is within this range, it is easy to obtain good low-temperature sealing properties and crack resistance, and it is also advantageous for cost reduction.

作為與上述1-丁烯-丙烯共聚物合併使用的樹脂,可適當使用其他聚烯烴系樹脂,但從容易適當調整密封強度的觀點來看,較佳可使用1-丁烯-丙烯共聚物以外的丙烯-α-烯烴共聚物、及乙烯-α-烯烴共聚物。 As the resin used in combination with the above 1-butene-propylene copolymer, other polyolefin-based resins can be suitably used, but from the viewpoint of easy adjustment of the seal strength, preferably other than 1-butene-propylene copolymer Propylene-α-olefin copolymer and ethylene-α-olefin copolymer.

1-丁烯-丙烯共聚物或乙烯-α-烯烴共聚物中之α-烯烴的含量並無特別限制,但較佳為1~20質量%,更佳為1.5~15質量%。作為α-烯烴,可例舉:乙烯、丙烯、1- 丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯等。其中,較佳可使用於上述中間層處所列舉的丙烯-乙烯無規共聚物。從容易得到良好成形性的觀點來看,MFR較佳為0.5~20g/10分鐘,更佳為2~10g/10分鐘。 The content of α-olefin in the 1-butene-propylene copolymer or ethylene-α-olefin copolymer is not particularly limited, but it is preferably 1 to 20% by mass, and more preferably 1.5 to 15% by mass. As the α-olefin, ethylene, propylene, 1- Butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc. Among them, the propylene-ethylene random copolymer listed above in the intermediate layer is preferably used. From the viewpoint of easily obtaining good formability, the MFR is preferably 0.5 to 20 g/10 minutes, and more preferably 2 to 10 g/10 minutes.

在含有1-丁烯-丙烯共聚物的情況下,容易調整低溫下易開封密封時的熱封溫度或強度,且熱封溫度範圍大,容易得到易開封密封的適度熱封強度。為了得到易開封強度2~6N/15mm,較佳為以其重量比為20/80~50/50的比例而合併使用1-丁烯-丙烯共聚物與丙烯共聚物所形成的樹脂層,而且,作為此處所使用的1-丁烯-丙烯共聚物,特佳為源自1-丁烯之成分的含量為60~95莫耳%者。 In the case of containing a 1-butene-propylene copolymer, it is easy to adjust the heat sealing temperature or strength at the time of easy opening and sealing at a low temperature, and the heat sealing temperature range is large, and it is easy to obtain a moderate heat sealing strength for easy opening and sealing. In order to obtain an easy-opening strength of 2 to 6 N/15 mm, it is preferable to use a resin layer formed by using a 1-butene-propylene copolymer and a propylene copolymer in combination at a weight ratio of 20/80 to 50/50, and As the 1-butene-propylene copolymer used here, it is particularly preferable that the content of the component derived from 1-butene is 60 to 95 mol%.

在不損及本發明之目的的範圍內,亦可於密封層中適當添加防霧劑、抗靜電劑、熱穩定劑、造核劑、抗氧化劑、增滑劑、抗結塊劑、脫模劑、紫外線吸收劑等成分來作為上述樹脂成分以外的其他成分。 Anti-fogging agents, antistatic agents, heat stabilizers, nucleating agents, antioxidants, slip agents, anti-caking agents, mold release can also be added to the sealing layer as long as the object of the present invention is not compromised Agents, ultraviolet absorbers and other components are used as components other than the above resin components.

[中間層] [middle layer]

在本發明之積層薄膜中,於上述印刷層與密封層之間適當設計中間層亦為較佳。作為該中間層,較佳可使用烯烴系樹脂。 In the laminated film of the present invention, it is also preferable to appropriately design an intermediate layer between the printing layer and the sealing layer. As the intermediate layer, an olefin-based resin is preferably used.

作為用於中間層的烯烴系樹脂,例如,可使用丙烯-α-烯烴共聚物(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)、丙烯均聚物、超低密度聚乙烯(VLDPE)、線性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)等的聚乙烯樹脂;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)等的乙烯系共聚物;再者,乙烯-丙烯酸共聚物的離子聚合物、乙烯-甲基丙烯酸共聚物的離子聚合物等。該等成分可分別單獨使用,亦可合併使用。 As the olefin-based resin used for the intermediate layer, for example, propylene-α-olefin copolymer (propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer, metallocene catalyst-based polypropylene, etc. can be used ), propylene homopolymer, ultra low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE) and other polyethylene resins; 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) and other ethylene-based copolymers; furthermore, ethylene-acrylic acid copolymer ionic polymer, ethylene-methacrylic acid copolymer Ionic polymers, etc. These ingredients can be used individually or in combination.

其中,從與印刷層、密封層之接著性的觀點來看,較佳可使用可用於印刷層的丙烯系樹脂,例如,較佳可使用丙烯均聚物、丙烯-α-烯烴共聚物,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。該等成分可分別單獨使用,亦可合併使用。 Among them, from the viewpoint of adhesion to the printing layer and the sealing layer, it is preferable to use a propylene-based resin that can be used in the printing layer, for example, it is preferable to use a propylene homopolymer and a propylene-α-olefin copolymer, for example Propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer, metallocene catalyst-based polypropylene, etc. These ingredients can be used individually or in combination.

又,可因應需求,以1種以上的丙烯系樹脂為主要成分,且其含量較佳為75質量%以上,並混合超低密度聚乙烯(VLDPE)、線性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)等的聚乙烯樹脂;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)等的乙烯系共聚物;再者,乙烯-丙烯酸共聚物的離子聚合物、乙烯-甲基丙烯酸共聚物的離子聚合物等。 In addition, according to demand, more than one type of propylene resin can be used as the main component, and its content is preferably 75% by mass or more, and mixed with ultra-low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low Polyethylene resins such as density polyethylene (LDPE); ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-propylene Ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene -Ethylene copolymers such as methacrylic acid copolymers (EMAA); ionic polymers of ethylene-acrylic acid copolymers, ionic polymers of ethylene-methacrylic acid copolymers, etc.

在不損及本發明之目的的範圍內,亦可於中間層中適當添加防霧劑、抗靜電劑、熱穩定劑、造核劑、抗氧化劑、增滑劑、抗結塊劑、脫模劑、紫外線吸收劑等成分來作為上述樹脂成分以外的其他成分。 Anti-fogging agents, antistatic agents, heat stabilizers, nucleating agents, antioxidants, slip agents, anti-caking agents, mold release can also be added to the intermediate layer as long as the purpose of the present invention is not compromised Agents, ultraviolet absorbers and other components are used as components other than the above resin components.

[積層薄膜] [Laminated Film]

本發明之積層薄膜,係至少具有上述印刷層、中間層及密封層的積層薄膜,且其係積層薄膜之一側的表層包含印刷層、另一側的表層包含密封層的積層薄膜。該構成的積層薄膜,具有良好的包裝適用性,且在裝入內容物時不易裂開,可實現較佳的耐裂性。又,容易實現良好的熔切密封強度、耐衝擊性、耐破袋性,適合用作各種包裝用的薄膜。 The laminated film of the present invention is a laminated film having at least the above-mentioned printed layer, intermediate layer, and sealing layer, and the surface layer on one side of the laminated film includes a printed layer, and the surface layer on the other side includes a sealing layer. The laminated film of this structure has good packaging applicability, and is not easily cracked when the contents are loaded, and can achieve better crack resistance. In addition, it is easy to achieve good fusion seal strength, impact resistance, and bag-break resistance, and is suitable for use as a film for various packaging.

本發明之積層薄膜的厚度,只要因應使用的用途或態樣而適當調整即可,但從容易兼具包裝用途中之減容化(volume reduction)及配送時之耐破袋性的觀點來看,其總厚度較佳為20~60μm,更佳為25~50μm。 The thickness of the laminated film of the present invention may be appropriately adjusted according to the application or form to be used, but from the viewpoint of easy combination of volume reduction in packaging applications and resistance to bag breakage during delivery The total thickness is preferably 20-60 μm, more preferably 25-50 μm.

各層的厚度比例並無特別限制,但印刷層的厚度較佳為總厚度的10~35%,中間層較佳為45~85%,密封層較佳為5~20%。各層的厚度只要在上述範圍內適當調整即可,例如印刷層的厚度較佳為2~20μm,更佳為3~15μm。中間層的厚度較佳為3~30μm,更佳為5~20μm。密封層的厚度較佳為1~10μm,更佳為2~8μm。 The thickness ratio of each layer is not particularly limited, but the thickness of the printed layer is preferably 10 to 35% of the total thickness, the intermediate layer is preferably 45 to 85%, and the sealing layer is preferably 5 to 20%. The thickness of each layer may be appropriately adjusted within the above range. For example, the thickness of the printed layer is preferably 2 to 20 μm, and more preferably 3 to 15 μm. The thickness of the intermediate layer is preferably 3 to 30 μm, and more preferably 5 to 20 μm. The thickness of the sealing layer is preferably 1-10 μm, more preferably 2-8 μm.

本發明之積層薄膜,可積層上述印刷層、中間層及密封層以外的任意其他樹脂層,但其他樹脂層的厚度較佳為總厚度中的20%以下,特佳為包含上述印刷層、中間層及密封層的構成。 The laminated film of the present invention may be laminated with any other resin layer other than the above-mentioned printed layer, intermediate layer, and sealing layer, but the thickness of the other resin layer is preferably 20% or less of the total thickness, particularly preferably including the above-mentioned printed layer, intermediate The composition of the layer and the sealing layer.

本發明之積層薄膜的製造方法並無特別限定,可舉例如下述共擠製法:分別以各擠製機將用於各層的樹脂或樹脂混合物進行加熱熔融,再藉由共擠製多層模具法或進料器具法等方法在熔融狀態下進行積層後,藉由吹氣法或T字模.冷卻輥法等將其成形為薄膜狀。該共擠製法,可比較自由地調整各層的厚度比例,並可得到衛生性優異、性價比亦為優異的多層薄膜,因而較佳。由該製造方法所得到的積層薄膜,實質上可得到無延伸的多層薄膜,故亦可以真空成形進行深抽拉成形等的二次成形。 The manufacturing method of the laminated film of the present invention is not particularly limited, and for example, the following co-extrusion method: each resin or resin mixture used for each layer is heated and melted by each extruder, and then the multi-layer die method by co-extrusion or After the feeding equipment method and other methods are laminated in the molten state, by the blowing method or T-shaped mold. It is formed into a film shape by a cooling roll method or the like. This co-extrusion method can adjust the thickness ratio of each layer relatively freely, and can obtain a multilayer film with excellent hygiene and excellent cost performance, which is preferable. The laminated film obtained by this manufacturing method can substantially obtain a non-stretched multi-layer film, and therefore secondary forming such as deep drawing forming can also be performed by vacuum forming.

為了提高與印刷油墨的接著性等,於印刷層實施表面處理亦為較佳。作為這種表面處理,可舉例如:電暈處理、電漿處理、鉻酸處理、火焰處理、熱風處理、臭氧.紫外線處理等的表面氧化處理、或噴沙法等的表面凹凸處理,但較佳為電暈處理。 In order to improve adhesion to printing ink, etc., it is also preferable to perform surface treatment on the printing layer. As such surface treatment, for example: corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone. Surface oxidation treatment such as ultraviolet treatment or surface roughness treatment such as sandblasting is preferred, but corona treatment is preferred.

作為包含本發明之積層薄膜的包裝材料,可舉例如用於食品、藥品、工業零件、雜貨、雜誌等用途的包裝袋、容器、容器的覆蓋材料等。 Examples of the packaging material including the laminated film of the present invention include packaging bags, containers, and covering materials for containers used in applications such as food, medicine, industrial parts, groceries, and magazines.

該包裝袋,較佳為以下述方式所形成的包裝袋:將本發明之積層薄膜的密封層作為熱封層,並將密封層彼此重疊而進行熱封、或將印刷層與密封層重疊而進行熱封,藉此將密封層作為內側。例如,將2片該積層薄膜裁切成所期望的包裝袋大小,將其重疊並將3邊進行熱封以形成袋狀後,從未熱封的1邊填充內容物,再進行熱封密封,藉此可將其用作包裝袋。再者,亦可藉由自動包裝機將滾筒狀的薄膜的端部密封成圓筒形後,藉由將上下密封來形成包裝袋。 The packaging bag is preferably a packaging bag formed by using the sealing layer of the laminated film of the present invention as a heat sealing layer, overlapping the sealing layers with each other to perform heat sealing, or overlapping the printed layer and the sealing layer Heat sealing is performed, whereby the sealing layer is used as the inner side. For example, after cutting two pieces of the laminated film into a desired bag size, overlapping them, and heat-sealing the three sides to form a bag shape, filling the contents from the unheated one side, and then heat-sealing , Which can be used as a packaging bag. Furthermore, the end of the drum-shaped film can be sealed into a cylindrical shape by an automatic packaging machine, and the packaging bag can be formed by sealing the top and bottom.

又,在形成長形麵包用包裝袋的情況下,藉由將印刷面向內折並密封,可形成具有折邊部的包裝袋。本發明之積層薄膜,即使在形成具有這種折邊部之包裝袋的情況下,亦可確保優異的印刷密合性及較佳的熔切密封強度,故特別適合應用於該形態的包裝袋用途。 In addition, in the case of forming a bag for long bread, by folding and sealing the printing surface inward, a bag with a folded portion can be formed. The laminated film of the present invention, even in the case of forming a packaging bag having such a hemming portion, can ensure excellent printing adhesion and better fusion seal strength, so it is particularly suitable for packaging bags of this form use.

又,亦可藉由將密封層與可熱封的其他薄膜重疊並進行熱封,來形成包裝袋、容器、容器的外蓋。此時,作為使用之其他薄膜,可使用機械強度較弱的LDPE、EVA、聚丙烯等薄膜。又,亦可使用將LDPE、EVA、聚丙烯等薄膜與易撕性較為良好的延伸薄膜,例如雙軸延伸聚對苯二甲酸乙二酯薄膜(OPET)、雙軸延伸聚丙烯薄膜(OPP)等進行貼合的積層薄膜。 In addition, the outer cover of the packaging bag, the container, and the container may also be formed by overlapping the sealing layer with other heat-sealable films and heat-sealing. At this time, as other films used, films with low mechanical strength such as LDPE, EVA, and polypropylene can be used. In addition, LDPE, EVA, polypropylene and other films and stretch films with good tearability, such as biaxially stretched polyethylene terephthalate film (OPET) and biaxially stretched polypropylene film (OPP), can also be used The laminated film to be laminated.

[實施例] [Example]

接著,列舉實施例及比較例更詳細地說明本發明。此外,樹脂組成等的摻合中的「份」及「%」係質量基準。 Next, the present invention will be described in more detail with examples and comparative examples. In addition, "parts" and "%" in the blending of resin composition and the like are quality standards.

(實施例1) (Example 1)

使用下述各種樹脂,作為形成印刷層(A)、中間層及密封層之各層的樹脂成分,調整形成各層的樹脂混合物。將該等樹脂混合物分別供給至印刷層(A)用擠製機(口徑50mm)、中間層(B)用擠製機(口徑50mm)及密封層(C)用擠製機(口徑50mm),於200~230℃下進行熔融,將該經熔融的樹脂供給至具有進料器具的T字模.冷卻輥法的共擠製多層薄膜製造裝置(進料器具及T字模溫度:250℃)並進行熔融擠製,得到薄膜的層體構成為(A)/(B)/(C)的3層構成、且各層的厚度為7μm/20μm/3μm(合計30μm)的共擠製多層薄膜(X1)。以使 濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 The following various resins are used as the resin component of each layer forming the printing layer (A), the intermediate layer, and the sealing layer, and the resin mixture forming each layer is adjusted. These resin mixtures were supplied to an extruder (caliber 50 mm) for the printing layer (A), an extruder (caliber 50 mm) for the intermediate layer (B) and an extruder (caliber 50 mm) for the sealing layer (C), Melt at 200 ~ 230 ℃, the molten resin is supplied to the T-shaped mold with feeding equipment. The co-extrusion multilayer film manufacturing apparatus (feeding equipment and T-die temperature: 250°C) of the cooling roll method was melt-extruded to obtain a film layer structure consisting of three layers (A)/(B)/(C) A co-extruded multilayer film (X1) composed of 7 μm/20 μm/3 μm (total 30 μm) in each layer. so that The surface tension measured by the wet reagent is 34mN/m, and the corona treatment is performed on the printed layer (A).

印刷層(A):丙烯-乙烯共聚物(1)〔乙烯含量:4.2%、密度:0.90g/cm3、MFR:6g/10分鐘(190℃、21.18N)〕85質量份、苯乙烯-乙烯丁烯-苯乙烯嵌段聚合物〔苯乙烯含量35%、密度:0.92g/cm3、MFR:10g/10分鐘(230℃、21.2N)(以下稱為SEBS(1)〕15質量份 Printed layer (A): propylene-ethylene copolymer (1) [ethylene content: 4.2%, density: 0.90 g/cm 3 , MFR: 6 g/10 minutes (190°C, 21.18N)] 85 parts by mass, styrene- Ethylene butene-styrene block polymer [styrene content 35%, density: 0.92g/cm 3 , MFR: 10g/10 minutes (230°C, 21.2N) (hereinafter referred to as SEBS(1)] 15 parts by mass

中間層(B):丙烯均聚物(1)〔密度:0.90g/cm3、MFR:7.5g/10分鐘〕75質量份、丙烯-乙烯共聚物(2)〔乙烯含量:5.2%、密度:0.90g/cm3、MFR:5.4g/10分鐘〕15質量份、直鏈狀低密度聚乙烯〔密度:0.905g/cm3、MFRI:4.0g/10分鐘〕10質量份 Intermediate layer (B): propylene homopolymer (1) [density: 0.90 g/cm 3 , MFR: 7.5 g/10 minutes] 75 parts by mass, propylene-ethylene copolymer (2) [ethylene content: 5.2%, density : 0.90g/cm 3 , MFR: 5.4g/10 minutes] 15 parts by mass, linear low-density polyethylene [density: 0.905g/cm 3 , MFRI: 4.0g/10 minutes] 10 parts by mass

密封層(C):丙烯-乙烯共聚物(2)〔乙烯含量:5.2%、密度:0.90g/cm3、MFR:5.4g/10分鐘〕50質量份、1-丁烯-丙烯共聚物(密度:0.90g/cm3、MFR:4g/10分鐘)45質量份、高密度聚乙烯(密度:0.955g/cm3)5質量份 Sealing layer (C): propylene-ethylene copolymer (2) [ethylene content: 5.2%, density: 0.90 g/cm 3 , MFR: 5.4 g/10 minutes] 50 parts by mass, 1-butene-propylene copolymer ( Density: 0.90g/cm 3 , MFR: 4g/10min) 45 parts by mass, high density polyethylene (density: 0.955g/cm 3 ) 5 parts by mass

(實施例2) (Example 2)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X2)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X2) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

印刷層(A):丙烯-乙烯共聚物(1)80質量份、SEBS(1)20質量份 Printed layer (A): 80 parts by mass of propylene-ethylene copolymer (1), 20 parts by mass of SEBS (1)

(實施例3) (Example 3)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X3)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X3) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

印刷層(A):丙烯-乙烯共聚物(1)85質量份、氫化苯乙烯丁二烯橡膠〔苯乙烯含量16%、密度:0.90g/cm3、MFR:10g/10分鐘(230℃、21.2N)(以下稱為HSBR(1)〕15質量份 Printed layer (A): 85 parts by mass of propylene-ethylene copolymer (1), hydrogenated styrene butadiene rubber [styrene content 16%, density: 0.90 g/cm 3 , MFR: 10 g/10 minutes (230°C, 21.2N) (hereinafter referred to as HSBR (1)) 15 parts by mass

(實施例4) (Example 4)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X4)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X4) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

印刷層(A):丙烯-乙烯共聚物(1)80質量份、HSBR(1)20質量份 Printed layer (A): 80 parts by mass of propylene-ethylene copolymer (1), 20 parts by mass of HSBR (1)

(實施例5) (Example 5)

除了以使印刷層(A)/中間層(B)/密封層(C)所形成之積層薄膜的各層厚度為5μm/22μm/3μm(合計30μm)的方式進行共擠製以外,以與實施例1相同的方式得到共擠製多層薄膜(X5)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 Except for co-extrusion in such a way that the thickness of each layer of the laminated film formed by the printed layer (A)/intermediate layer (B)/sealing layer (C) was 5 μm/22 μm/3 μm (total 30 μm) 1 A co-extruded multilayer film (X5) was obtained in the same way. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

(實施例6) (Example 6)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X6)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X6) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

印刷層(A):丙烯-乙烯共聚物(1)75質量份、SEBS(1)15質量份、結晶性乙烯-1-丁烯共聚物(1)〔密度:0.88g/cm3、MFR:4g/10分鐘(190℃、21.18N)〕10質量份 Printed layer (A): 75 parts by mass of propylene-ethylene copolymer (1), 15 parts by mass of SEBS (1), crystalline ethylene-1-butene copolymer (1) [Density: 0.88 g/cm 3 , MFR: 4g/10min (190℃, 21.18N)] 10 parts by mass

(實施例7) (Example 7)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X7)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X7) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

印刷層(A):丙烯-乙烯共聚物(1)75質量份、HSBR(1)15質量份、結晶性乙烯-1-丁烯共聚物(1)10質量份 Printing layer (A): 75 parts by mass of propylene-ethylene copolymer (1), 15 parts by mass of HSBR (1), and 10 parts by mass of crystalline ethylene-1-butene copolymer (1)

(實施例8) (Example 8)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X8)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X8) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

印刷層(A):丙烯-乙烯共聚物(1)70質量份、苯乙烯-乙烯丁烯-苯乙烯嵌段聚合物〔苯乙烯含量15%、密度:0.90g/cm3、MFR:30g/10分鐘(230℃、21.2N)、(以下稱為SEBS(2))〕20質量份、結晶性乙烯-1-丁烯共聚物(1)10質量份 Print layer (A): 70 parts by mass of propylene-ethylene copolymer (1), styrene-ethylene butene-styrene block polymer [styrene content 15%, density: 0.90 g/cm 3 , MFR: 30 g/ 10 minutes (230°C, 21.2N), (hereinafter referred to as SEBS(2))] 20 parts by mass, 10 parts by mass of crystalline ethylene-1-butene copolymer (1)

(實施例9) (Example 9)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X9)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X9) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

印刷層(A):丙烯-乙烯共聚物(1)70質量份、氫化苯乙烯丁二烯橡膠〔苯乙烯含量10%、密度:0.89g/cm3、MFR:10g/10分鐘(230℃、21.2N)(以下稱為HSBR(2)〕20質量份、結晶性乙烯-1-丁烯共聚物(1)10質量份 Printed layer (A): 70 parts by mass of propylene-ethylene copolymer (1), hydrogenated styrene butadiene rubber [styrene content 10%, density: 0.89 g/cm 3 , MFR: 10 g/10 minutes (230°C, 21.2N) (hereinafter referred to as HSBR (2)) 20 parts by mass, 10 parts by mass of crystalline ethylene-1-butene copolymer (1)

(實施例10) (Example 10)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X10)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X10) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

作為印刷層(A)用樹脂,丙烯-乙烯共聚物(1)70質量份、極性基改性苯乙烯-乙烯丁烯-苯乙烯嵌段聚合物〔苯乙烯含量25%、密度:0.91g/cm3、MFR:10g/10分鐘(230℃、21.2N)、(以下稱為f-SEBS)〕20質量份、結晶性乙烯-1-丁烯共聚物(1)10質量份 As a resin for the printing layer (A), 70 parts by mass of a propylene-ethylene copolymer (1), a polar group-modified styrene-ethylene butene-styrene block polymer [styrene content 25%, density: 0.91 g/ cm 3 , MFR: 10 g/10 minutes (230° C., 21.2 N), (hereinafter referred to as f-SEBS)] 20 parts by mass, crystalline ethylene-1-butene copolymer (1) 10 parts by mass

(比較例1) (Comparative example 1)

除了將用於印刷層(A)之樹脂混合物的樹脂成分變更為下列組成以外,以與實施例1相同的方式得到共擠製多層薄膜(X11)。以使濕試劑所測量之表面張力為34mN/m的方式,於印刷層(A)實施電暈處理。 A co-extruded multilayer film (X11) was obtained in the same manner as in Example 1, except that the resin composition of the resin mixture used for the printing layer (A) was changed to the following composition. The printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 34 mN/m.

印刷層(A):丙烯-乙烯共聚物(1)55質量份、丙烯-乙烯-1-丁烯三元共聚物〔密度:0.90g/cm3、MFR:5.4g/10分鐘(190℃、21.18N)〕35質量份、結晶性乙烯-1-丁烯共聚物(1)10質量份 Printed layer (A): 55 parts by mass of propylene-ethylene copolymer (1), propylene-ethylene-1-butene terpolymer [density: 0.90 g/cm 3 , MFR: 5.4 g/10 minutes (190°C, 21.18N)] 35 parts by mass, 10 parts by mass of crystalline ethylene-1-butene copolymer (1)

(比較例2) (Comparative example 2)

與比較例1相同的方式得到共擠製多層薄膜(X11)後,以使濕試劑所測量之表面張力為40mN/m的方式,於印刷層(A)實施電暈處理,得到共擠製多層薄膜(X12)。 After the co-extruded multilayer film (X11) was obtained in the same manner as in Comparative Example 1, the printed layer (A) was subjected to corona treatment so that the surface tension measured by the wet reagent was 40 mN/m to obtain a co-extruded multilayer Thin film (X12).

使用上述實施例及比較例所得到的積層薄膜,進行下述試驗及評價。所得到的結果如下表所示。此外,表中之樹脂組成的數值,係用於各層中之樹脂成分中的各成分的含量(質量份)。 Using the laminated films obtained in the above examples and comparative examples, the following tests and evaluations were performed. The results obtained are shown in the table below. In addition, the numerical value of the resin composition in the table is the content (parts by mass) of each component in the resin components in each layer.

[印刷適用性(油墨吸附性)] [Printing applicability (ink adsorption)]

以塗布量12g/m2將油墨(胺基甲酸酯型油墨Grossa709白;DIC公司製)塗布於實施例及比較例所得到之薄膜的印刷層(A)表面。將聚氯乙烯片材重疊於塗布 面,施加500g/cm2的載重,並於50℃下靜置24小時後,剝離聚氯乙烯片材,目視確認評價薄膜表面的油墨脫落情況。 An ink (urethane type ink Grossa709 white; manufactured by DIC) was applied at a coating amount of 12 g/m 2 on the surface of the printed layer (A) of the film obtained in Examples and Comparative Examples. The polyvinyl chloride sheet was overlaid on the coated surface, a load of 500 g/cm 2 was applied, and after standing at 50° C. for 24 hours, the polyvinyl chloride sheet was peeled off, and the ink peeling off on the surface of the evaluation film was visually confirmed.

○:無油墨脫落 ○: No ink drop

○-:油墨脫落的區域為聚氯乙烯片材接觸面的10%以下 ○-: The area where the ink falls off is less than 10% of the contact surface of the PVC sheet

△:油墨脫落的區域超過聚氯乙烯片材接觸面的10%,且為25%以下 △: The area where the ink drops off exceeds 10% of the contact surface of the PVC sheet, and is less than 25%

×:油墨脫落的區域超過聚氯乙烯片材接觸面的25% ×: The area where the ink falls off exceeds 25% of the contact surface of the PVC sheet

[熔切強度] [Fuse Cutting Strength]

使用脈衝機,將實施例及比較例所得到之薄膜的印刷層(A)彼此重疊,以溫度300℃實施熔切密封。於23℃下使密封之薄膜自然冷卻後,以使熔切密封部為寬度方向之中央部的方式,將樣本裁切成高度70mm、寬度15mm的細長片材狀。在23℃、50%Rh的恆溫室中,使用拉伸試驗機(A&D股份有限公司製),以300mm/分鐘的速度,將該經裁切出的樣本進行剝離,測量熔切強度。以下列基準從所得到之熔切強度的值評價熱封強度。 Using a pulse machine, the printed layers (A) of the films obtained in Examples and Comparative Examples were overlapped with each other, and the fusion cut sealing was performed at a temperature of 300°C. After the sealed film was naturally cooled at 23° C., the sample was cut into an elongated sheet shape with a height of 70 mm and a width of 15 mm so that the fusion cut seal portion was the central portion in the width direction. In a thermostatic chamber at 23° C. and 50% Rh, using a tensile tester (manufactured by A&D Co., Ltd.), the cut sample was peeled off at a speed of 300 mm/minute, and the fused shear strength was measured. The heat seal strength was evaluated from the obtained value of the fused shear strength on the following criteria.

○:熔切強度為13N/15mm範圍以上 ○: The fusing strength is above 13N/15mm

×:熔切強度小於13N/15mm範圍 ×: The fusion cutting strength is less than 13N/15mm

[透明性] [Transparency]

在23℃、50%Rh的恆溫室中,以依據JIS K7105的方法,使用霧度計(日本電飾工業股份有限公司製)測量實施例及比較例所得到之薄膜的霧度。 In a constant temperature room at 23° C. and 50% Rh, the haze of the films obtained in Examples and Comparative Examples was measured using a haze meter (manufactured by Nippon Electric Industry Co., Ltd.) in accordance with JIS K7105.

[衝擊強度] [Impact strength]

於0℃環境下,藉由TESTER SANGYO製薄膜衝擊試驗機,使用1英吋撞芯(impact shaft)直徑,以薄膜衝擊法測量實施例及比較例所得到之薄膜的衝擊強度。 The impact strength of the films obtained in Examples and Comparative Examples was measured by a film impact method using a film impact tester made by TESTER SANGYO under a 0°C environment using a 1 inch impact shaft diameter.

Figure 105123144-A0305-02-0024-1
Figure 105123144-A0305-02-0024-1

Figure 105123144-A0305-02-0025-2
Figure 105123144-A0305-02-0025-2

Figure 105123144-A0305-02-0025-3
Figure 105123144-A0305-02-0025-3

由上述表明確可知,實施例1~10的本發明之積層薄膜,具有較佳的熔切強度及優異的印刷密合性。又,本發明之積層薄膜,其透明性高,耐衝擊性亦為優異。另一方面,比較例1~2之積層薄膜,無法兼具較佳熔切強度與印刷密合性。 As is clear from the above table, the laminated films of the present invention of Examples 1 to 10 have better fused cutting strength and excellent print adhesion. In addition, the laminated film of the present invention has high transparency and excellent impact resistance. On the other hand, the laminated films of Comparative Examples 1 to 2 cannot have both better squeeze strength and print adhesion.

Claims (9)

一種積層薄膜,其係一側的表層包含印刷層、另一側的表層包含密封層的積層薄膜,其特徵為:該印刷層包含丙烯系樹脂及苯乙烯系彈性體,印刷層中的苯乙烯含量為2~15質量%。 A laminated film having a printed layer on one side and a sealing layer on the other side, characterized in that the printed layer includes an acrylic resin and a styrene elastomer, and the styrene in the printed layer The content is 2~15% by mass. 如請求項1之積層薄膜,其中,該印刷層表面的濕潤張力為38mN/m以下。 The laminated film according to claim 1, wherein the wet tension of the surface of the printed layer is 38 mN/m or less. 如請求項1或2之積層薄膜,其中,該密封層含有共聚物,該共聚物具有包含1-丁烯的結構單元。 The laminated film according to claim 1 or 2, wherein the sealing layer contains a copolymer having a structural unit containing 1-butene. 如請求項1或2之積層薄膜,其中,於該印刷層及密封層之間具有含有丙烯系樹脂的中間層。 The laminated film according to claim 1 or 2, wherein an intermediate layer containing an acrylic resin is provided between the printed layer and the sealing layer. 如請求項1或2之積層薄膜,其中,該印刷層所包含之樹脂成分中之丙烯系樹脂的含量為60~95質量%,苯乙烯系彈性體的含量為5~40質量%。 The laminated film according to claim 1 or 2, wherein the content of the acrylic resin in the resin component contained in the printed layer is 60 to 95% by mass, and the content of the styrene elastomer is 5 to 40% by mass. 如請求項1或2之積層薄膜,其中,霧度值為10%以下。 The laminated film according to claim 1 or 2, wherein the haze value is 10% or less. 如請求項1或2之積層薄膜,其用於包裝材料。 The laminated film of claim 1 or 2 is used for packaging materials. 一種包裝材料,其特徵為:包含如請求項1至7中任一項之積層薄膜。 A packaging material characterized by comprising the laminated film according to any one of claims 1 to 7. 如請求項8之包裝材料,其係食品用的包裝袋。 If the packaging material of claim 8 is a food packaging bag.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007045051A (en) * 2005-08-11 2007-02-22 Toyobo Co Ltd Polyolefinic resin laminated film
JP2007152730A (en) * 2005-12-05 2007-06-21 Toyobo Co Ltd Polyolefinic resin laminated film
US20150183253A1 (en) * 2013-12-30 2015-07-02 Avery Dennison Corporation Films for Printing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007045051A (en) * 2005-08-11 2007-02-22 Toyobo Co Ltd Polyolefinic resin laminated film
JP2007152730A (en) * 2005-12-05 2007-06-21 Toyobo Co Ltd Polyolefinic resin laminated film
US20150183253A1 (en) * 2013-12-30 2015-07-02 Avery Dennison Corporation Films for Printing

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