TW201338980A - Easy-to-tear laminated film and easy-to-tear packaging bag - Google Patents

Easy-to-tear laminated film and easy-to-tear packaging bag Download PDF

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TW201338980A
TW201338980A TW101149913A TW101149913A TW201338980A TW 201338980 A TW201338980 A TW 201338980A TW 101149913 A TW101149913 A TW 101149913A TW 101149913 A TW101149913 A TW 101149913A TW 201338980 A TW201338980 A TW 201338980A
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film
mxd6
mass
biaxially stretched
stretched film
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TW101149913A
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Masao Takashige
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Idemitsu Unitech Co Ltd
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    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/08—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 of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • 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
    • 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
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Abstract

An easy-to-tear laminated film comprising: a biaxially stretched film which is produced using a raw material comprising a virgin raw material and a heat history product, wherein the virgin raw material comprises 40 to 85 parts by mass inclusive of Ny6 and 15 to 60 parts by mass inclusive of MXD6, the heat history product is produced by melt-kneading Ny6 with MXD6 at the same ratio as that employed in the virgin raw material until the melting point of MXD6 becomes 233 to 238 DEG C inclusive, and the content ratio of the heat history product is 5 to 40 mass% inclusive in terms of raw material content; an adhesive layer of which the dynamic elastic modulus (E') at 25 DEG C fulfills formula [A] shown below; and a seal layer. LogE' ≥ 7.7 [A].

Description

易裂性積層膜及易裂性包裝袋 Fragmentable laminated film and fragile packaging bag

本發明係關於一種易裂性積層膜、及使用該膜而成之易裂性包裝袋。 The present invention relates to a cleavable laminated film and a cleavable packaging bag using the same.

雙軸延伸尼龍膜(以下亦稱作ONy膜)之強度或耐衝擊性、耐針孔性等優異，故而用於高溫蒸煮食品等各種食品用之包裝材料、藥品用包裝材料、及電子零件用包裝材料等非常廣泛之領域。 Biaxially stretched nylon film (hereinafter also referred to as ONy film) is excellent in strength, impact resistance, pinhole resistance, etc., and is therefore used for various food packaging materials, pharmaceutical packaging materials, and electronic parts for high-temperature cooking foods. A wide range of fields such as packaging materials.

另一方面，對上述各領域中使用之包裝用ONy膜，除搬送時或熱處理時等必需之強度外，亦要求可於開封時容易開封之撕裂性。迄今為止，已知一種以包含尼龍6(Ny6)及己二醯間苯二甲胺(MXD6)之混合樹脂作為原料之易裂性ONy膜(參照文獻1：日本專利特開平5-220837號公報、文獻2：日本專利特開平5-200958號公報)。 On the other hand, in the ONy film for packaging used in the above various fields, in addition to the strength necessary for transportation or heat treatment, tearing property which can be easily opened at the time of opening is also required. Heretofore, a crackable ONy film containing a mixed resin of nylon 6 (Ny6) and m-xylylenediamine (MXD6) as a raw material has been known (refer to Japanese Laid-Open Patent Publication No. Hei 5-220837) Document 2: Japanese Patent Laid-Open No. Hei 5-200958).

文獻1或文獻2所記載之易裂性ONy膜帶來直線撕裂性優異之表基材，即便於製作積層膜時亦可維持其優異之直線撕裂性，故而製成易裂性袋實用價值較高。然而，若包含Ny6與MXD6之混合樹脂之雙軸延伸膜於構成積層膜後置於過於嚴酷之條件下，則有於雙軸延伸膜之層內發生所謂之層內剝離之虞。若發生如上所述之層內剝離，則積層膜之強度不穩定，於構成袋之情形時產生實用上之問題。因此，提出有一種易裂性ONy膜，其係對包含Ny6與MXD6樹脂之混合樹脂(初始樹脂)添加將Ny6與MXD6熔融混練使 MXD6之熔點為233~238℃而成之熱歷程品，藉此改善層內剝離性(參照文獻3：日本專利特開2007-39664號公報)。 The crackable ONy film described in Document 1 or Document 2 provides a surface substrate excellent in linear tearing property, and maintains excellent linear tear property even when a laminated film is produced, so that it is made into a crackable bag. The value is higher. However, if the biaxially stretched film containing the mixed resin of Ny6 and MXD6 is placed under too severe conditions after constituting the laminated film, so-called in-layer peeling occurs in the layer of the biaxially stretched film. If the in-layer peeling as described above occurs, the strength of the laminated film is unstable, which causes a practical problem in the case of constituting the bag. Therefore, there is proposed a crackable ONy film which is obtained by melt-kneading Ny6 and MXD6 by adding a mixed resin (initial resin) containing Ny6 and MXD6 resin. MXD6 has a melting point of 233 to 238 ° C, thereby improving the in-layer peelability (refer to Japanese Laid-Open Patent Publication No. 2007-39664).

若如文獻3所示，使用添加有將Ny6及MXD6熔融混練而成之熱歷程品的原料進行管式法之雙軸延伸，則存在氣泡不穩定而左右搖晃、或氣泡時而破裂之製造上之問題。又，若成形穩定性如此降低，則結果亦產生膜之厚度精度(膜厚偏差精度)亦降低之問題。 As shown in the literature 3, biaxial stretching by a tubular method using a raw material to which a thermal process product in which Ny6 and MXD6 are melt-kneaded is used, and there is a case where the bubble is unstable and shakes left and right, or the bubble is broken. The problem. Further, if the molding stability is lowered as a result, the thickness accuracy (film thickness deviation accuracy) of the film is also lowered.

另一方面，如易裂性ONy膜之表基材係於與內基材(密封劑膜)積層後製成包裝袋使用。此時，易裂性ONy膜單體之易裂性良好，進而積層強度較高，但亦有無法發揮積層後之易裂性(尤其是直線撕裂性)之情況。進而，於製成包裝袋後，亦存在產生開封端(開口)發生捲曲之所謂開口捲曲現象之情形。 On the other hand, a surface substrate such as a crackable ONy film is used in a packaging bag after being laminated with an inner substrate (sealant film). At this time, the crackable ONy film monomer has good crackability, and the laminate strength is high. However, the cracking property (especially the linear tear property) after lamination may not be exhibited. Further, after the packaging bag is formed, there is a case where a so-called opening curl phenomenon in which the opening end (opening) is curled is generated.

本發明之目的在於提供一種易裂性積層膜、及使用該膜而成之易裂性包裝袋，該易裂性積層膜係使用對包含Ny6及MXD6之混合樹脂進而添加該樹脂之熱歷程品而成之原料，提高所獲得之延伸膜之厚度精度(厚度偏差精度)，並且與密封劑膜之積層強度優異，亦不易發生延伸膜之層內剝離，積層膜之易裂性(直線撕裂性)優異，進而於製袋後不易產生開口捲曲。 An object of the present invention is to provide a cleavable laminated film and a cleavable packaging bag using the same, which is a thermal process product comprising a mixed resin containing Ny6 and MXD6 and further adding the resin. The raw material is formed to improve the thickness precision (thickness deviation accuracy) of the obtained stretch film, and the laminate strength with the sealant film is excellent, and the layer peeling of the stretched film is less likely to occur, and the laminate film is easily cracked (linear tear) Excellent), and it is less likely to cause opening curl after bag making.

為解決上述課題，本發明提供如下所述之易裂性積層膜及易裂性包裝袋。 In order to solve the above problems, the present invention provides a cleavable laminated film and a cleavable packaging bag as described below.

(1)一種易裂性積層膜，其特徵在於具備：雙軸延伸膜，其 係含有：初始原料，其包含40質量份以上85質量份以下之尼龍6(Ny6)、及15質量份以上60質量份以下之己二醯間苯二甲胺(MXD6)(其中，Ny6+MXD6=100重量份)；及熱歷程品，其係將Ny6及MXD6以與上述初始原料相同之比率進行熔融混練使MXD6之熔點為233℃以上238℃以下而成，且該雙軸延伸膜使用上述熱歷程品之調配比率以原料總量基準計為5質量%以上40質量%以下之原料而成；接著層，其於25℃下之動彈性係數E'滿足下述式[A]：LogE'≧7.7 [A]；及密封層。 (1) A crackable laminated film characterized by comprising: a biaxially stretched film, The invention comprises: a starting material comprising 40 parts by mass or more and 85 parts by mass or less of nylon 6 (Ny6), and 15 parts by mass or more and 60 parts by mass or less of dioxan m-xylylenediamine (MXD6) (wherein Ny6+MXD6) And a heat course product obtained by melt-kneading Ny6 and MXD6 at the same ratio as the above-mentioned starting materials to form a melting point of MXD6 of 233 ° C or more and 238 ° C or less, and the biaxially stretched film is used as described above. The blending ratio of the heat history product is 5% by mass or more and 40% by mass or less based on the total amount of the raw materials; and the subsequent layer, the dynamic elastic coefficient E' at 25 ° C satisfies the following formula [A]: LogE' ≧7.7 [A]; and sealing layer.

(2)如上述之本發明之易裂性積層膜，其係進而積層雙軸延伸膜或無延伸膜而成。 (2) The crackable laminated film of the present invention as described above, which is obtained by laminating a biaxially stretched film or without a stretched film.

(3)如上述之本發明之易裂性積層膜，其中上述進而積層之雙軸延伸膜係上述(1)之雙軸延伸膜，或以Ny6、MXD6、乙烯-乙烯醇共聚物、聚酯(PET、PBT等)、聚烯烴、聚苯乙烯及聚碳酸酯中之任一者為原料之雙軸延伸膜。 (3) The cleavable laminated film of the present invention as described above, wherein the above-mentioned laminated biaxially stretched film is the biaxially stretched film of the above (1), or Ny6, MXD6, ethylene-vinyl alcohol copolymer, polyester (PET, PBT, etc.), polyolefin, polystyrene, and polycarbonate are biaxially stretched films of raw materials.

(4)如上述之本發明之易裂性積層膜，其中上述進而積層之雙軸延伸膜、及如上述(1)之雙軸延伸膜為共擠壓多層延伸而成者。 (4) The cleavable laminated film of the present invention, wherein the biaxially stretched film further laminated and the biaxially stretched film of the above (1) are formed by coextruding a plurality of layers.

(5)一種易裂性包裝袋，其特徵在於：其係使用上述之本發明之易裂性積層膜進行製袋而成。 (5) A fragile packaging bag characterized in that it is formed into a bag by using the above-mentioned crackable laminated film of the present invention.

根據本發明，可提供一種易裂性積層膜、及使用該膜而成之易裂性包裝袋，該易裂性積層膜係使用對包含Ny6及MXD6之混合樹脂進而添加該樹脂之熱歷程品而成的原 料，提高所獲得之延伸膜之厚度精度(厚度偏差精度)，並且與密封劑膜之積層強度優異，亦不易發生延伸膜之層內剝離，積層膜之易裂性(直線撕裂性)優異，進而於製袋後不易產生開口捲曲。 According to the present invention, it is possible to provide a cleavable laminated film and a cleavable packaging bag using the same, and the cleavable laminated film is a thermal process product comprising a mixed resin containing Ny6 and MXD6 and further adding the resin. Original In order to improve the thickness accuracy (thickness deviation accuracy) of the obtained stretched film, and to have excellent laminated strength with the sealant film, it is also less likely to cause interlayer peeling of the stretched film, and the laminate film is excellent in cracking property (linear tear property). Further, it is less likely to cause opening curl after the bag is formed.

以下，對用於實施本發明之一形態進行詳述。具體而言，對本發明之易裂性積層膜之構成要素即雙軸延伸尼龍膜(以下僅稱作「ONy膜」)進行說明，此後對易裂性積層膜及易裂性包裝袋進行說明。 Hereinafter, one embodiment for carrying out the invention will be described in detail. Specifically, a biaxially stretched nylon film (hereinafter simply referred to as "ONy film") which is a constituent element of the cleavable laminated film of the present invention will be described, and thereafter, the cleavable laminated film and the cleavable packaging bag will be described.

[ONy膜之構成] [The composition of ONy film]

本實施形態之ONy膜含有：初始原料，其包含40質量份以上85質量份以下之尼龍6(Ny6)、及15質量份以上60質量份以下之己二醯間苯二甲胺(MXD6)(其中，Ny6+MXD6=100重量份)；及熱歷程品，其係將Ny6及MXD6以與上述初始原料相同之比率進行熔融混練使MXD6之熔點為233℃以上238℃以下而成。又，上述熱歷程品之調配比率以原料總量基準計為5質量%以上40質量%以下。 The ONY film of the present embodiment contains a starting material containing 40 parts by mass or more and 85 parts by mass or less of nylon 6 (Ny6), and 15 parts by mass or more and 60 parts by mass or less of hexamethylene m-xylylenediamine (MXD6) ( Here, Ny6+MXD6=100 parts by weight); and a thermal process product obtained by melt-kneading Ny6 and MXD6 at the same ratio as the above-mentioned starting materials, and the melting point of MXD6 is 233° C. or higher and 238° C. or lower. Moreover, the blending ratio of the above-mentioned heat history product is 5% by mass or more and 40% by mass or less based on the total amount of the raw materials.

此處，將Ny6之化學式示於下述式(1)，將MXD6之化學式示於下述式(2)。 Here, the chemical formula of Ny6 is shown in the following formula (1), and the chemical formula of MXD6 is shown in the following formula (2).

H-[NH-(CH2)5-CO]n-OH‧‧‧(1) H-[NH-(CH 2 ) 5 -CO]n-OH‧‧‧(1)

上述之所謂初始原料係通常意指並非具有Ny6與MXD6 相互混合並經熔融混練之歷程的混合原料之狀態之原料。例如，即便Ny6或MXD6具有各自單獨地經熔融混練之歷程(例如回收再利用品)但該等並未混合而經熔融混練之情形，亦為初始原料。惟就成為ONy膜時之物性方面而言，較佳為使用回收再利用次數儘可能少之初始原料。再者，即便Ny6及MXD6具有相互混合而經熔融混練之歷程，但若該混練較弱因而MXD6之熔點不太降低而超過238℃，則該等Ny6與MXD6仍為構成初始原料者，而非構成熱歷程品者。 The above-mentioned so-called initial raw material system generally means that it does not have Ny6 and MXD6. A raw material in a state of a mixed raw material which is mixed with each other and melt-kneaded. For example, even if Ny6 or MXD6 has a process in which each of them is separately melt-kneaded (for example, a recycled product), the materials are melted and kneaded without being mixed, and are also starting materials. However, in terms of physical properties when the ONY film is used, it is preferred to use an initial raw material having as few recycling times as possible. Furthermore, even if Ny6 and MXD6 have a process of melt-kneading with each other, if the kneading is weak and the melting point of MXD6 is not lowered to exceed 238 ° C, then these Ny6 and MXD6 are still the initial raw materials, and not The person who constitutes the hot course.

即，於本實施形態中，於構成初始原料之Ny6及MXD6中添加有熱歷程品之三者(或二者)於所謂之乾式混合後進行熔融混練，構成ONy膜。 In other words, in the present embodiment, three or more of the thermal process products added to Ny6 and MXD6 constituting the starting material are melt-kneaded after so-called dry mixing to form an ONy film.

上述所謂熱歷程品係指Ny6與MXD6之調配品通過擠壓機一次者，就本發明而言，係使用根據示差掃描熱量計(DSC)MXD6樹脂之熔點保持於233℃以上、238℃以下之範圍內者。 The above-mentioned "heat history" means that the blend of Ny6 and MXD6 is passed through an extruder. For the purposes of the present invention, the melting point of the MXD6 resin according to the differential scanning calorimeter (DSC) is maintained at 233 ° C or higher and 238 ° C or lower. Within the scope.

本實施形態之ONy膜中，作為原料，Ny6為40質量份以上85質量份以下，MXD6為15質量份以上60質量份以下，較佳為，Ny6為60質量份以上85質量份以下，MXD6為15質量份以上40質量份以下。該Ny6與MXD6之比率係關於包含初始原料與熱歷程品二者之原料的比率。 In the ONY film of the present embodiment, Ny6 is 40 parts by mass or more and 85 parts by mass or less, and MXD6 is 15 parts by mass or more and 60 parts by mass or less, preferably Ny6 is 60 parts by mass or more and 85 parts by mass or less, and MXD6 is MXD6. 15 parts by mass or more and 40 parts by mass or less. The ratio of Ny6 to MXD6 is the ratio of the raw materials containing both the starting material and the thermal process.

若原料中之Ny6與MXD6之比率為該範圍，則不僅易裂性(尤其是直線撕裂性)優異，雙軸延伸後之膜之厚度精度亦極其優異。 When the ratio of Ny6 to MXD6 in the raw material is in this range, not only is the cracking property (especially linear tearing property) excellent, but the thickness precision of the film after biaxial stretching is also extremely excellent.

又，熱歷程品中之MXD6之熔點為233℃以上、238℃以下，較佳為235℃以上、237℃以下。若熱歷程品中之MXD6之熔點未達233℃，則ONy膜之直線撕裂性及衝擊強度降低。另一方面，若熱歷程品中之MXD6之熔點超過238℃，則厚度精度惡化。 Further, the melting point of MXD6 in the thermal process product is 233 ° C or more and 238 ° C or less, preferably 235 ° C or more and 237 ° C or less. If the melting point of MXD6 in the thermal process product is less than 233 ° C, the linear tearing property and impact strength of the ONy film are lowered. On the other hand, if the melting point of MXD6 in the thermal process product exceeds 238 ° C, the thickness accuracy deteriorates.

再者，於製造熱歷程品之過程中，若混練時之溫度或壓力較高，則熱歷程品中之MXD6之熔點更大地降低。 Further, in the process of manufacturing the thermal process product, if the temperature or pressure during the kneading is high, the melting point of the MXD6 in the thermal process product is further lowered.

此處，所謂熱歷程品中之MXD6之熔點，係指於與初始原料熔融混練前之狀態下測得之熔點。 Here, the melting point of MXD6 in the thermal process product means the melting point measured in a state before being melt-kneaded with the initial raw material.

本實施形態之ONy膜係如下所述用作易裂性積層膜(以及易裂性包裝袋)之表基材，故而就易裂性之觀點而言，較佳為MD(Machine Direction，縱向)方向及TD(Transverse Direction，橫向)方向中之任一方向撕裂強度均為70 N/cm以下。 The ONy film of the present embodiment is used as a surface substrate of a cleavable laminated film (and a cleavable packaging bag) as described below. Therefore, from the viewpoint of cracking property, MD (Machine Direction) is preferable. The tear strength in any of the direction and the TD (Transverse Direction) direction is 70 N/cm or less.

於本實施形態之ONy膜中，熱歷程品之調配比率以原料總量基準計為5質量%以上40質量%以下，較佳為15質量%以上30質量%以下。 In the ONY film of the present embodiment, the blending ratio of the thermal process product is 5% by mass or more and 40% by mass or less based on the total amount of the raw materials, and preferably 15% by mass or more and 30% by mass or less.

若熱歷程品之調配比率為5質量%以上，則即便於過於嚴酷之條件下使用ONy膜，亦不易發生層內剝離。 When the blending ratio of the thermal course product is 5% by mass or more, even if the ONY film is used under too severe conditions, the in-layer peeling is unlikely to occur.

此處，所謂層內剝離，係指於將ONy膜與適當之密封劑膜積層後，於過於嚴酷之條件下使用時，ONy膜(尼龍層)內發生剝離之現象。層內剝離之機制並不明確，但可認為係ONy膜內Ny6及MXD6層狀地配向而其界面上發生剝離。 Here, the term "interlayer peeling" refers to a phenomenon in which an ONy film (nylon layer) is peeled off when an ONy film is laminated with an appropriate sealant film and used under an excessively severe condition. The mechanism of the in-layer peeling is not clear, but it is considered that Ny6 and MXD6 in the ONy film are layered and the interface is peeled off.

若發生如上所述之層內剝離，則積層膜之強度不穩定， 於構成袋之情形時有於過於嚴酷之使用條件下產生破袋等問題之虞。如上所述之過於嚴酷之使用條件，例如可藉由測定積層膜之積層強度(剝離強度)之試驗而再現。 If the in-layer peeling as described above occurs, the strength of the laminated film is unstable. In the case of constituting a bag, there is a problem that the bag is broken under too severe conditions of use. The use conditions which are too severe as described above can be reproduced, for example, by a test for measuring the laminate strength (peel strength) of the laminated film.

又，若熱歷程品之調配比率未達5質量%，則雙軸延伸後之膜之厚度精度惡化。另一方面，若熱歷程品之調配比率超過40質量%，則易裂性降低。 Further, if the blending ratio of the thermal history product is less than 5% by mass, the thickness accuracy of the film after biaxial stretching is deteriorated. On the other hand, if the blending ratio of the thermal course product exceeds 40% by mass, the cracking property is lowered.

[ONy膜之製造方法] [Method of manufacturing ONy film]

本實施形態之ONy膜可藉由管式法之同時雙軸延伸法較佳地製造。具體而言，可按以下方式製造。 The ONy film of the present embodiment can be preferably produced by a simultaneous biaxial stretching method by a tubular method. Specifically, it can be manufactured in the following manner.

首先，於擠壓步驟中，將包含初始原料及熱歷程品之原料以270℃進行熔融混練，此後將熔融物自模嘴以圓筒狀膜(熔融原片)之形式擠出。繼而，於冷卻步驟中，將熔融原片以水進行急冷而製成原片膜。 First, in the extrusion step, the raw material containing the initial raw material and the thermal process product was melt-kneaded at 270 ° C, and thereafter the melt was extruded from the die nozzle in the form of a cylindrical film (melted original sheet). Then, in the cooling step, the molten raw sheet is quenched with water to prepare an original sheet film.

繼而，於延伸步驟中，如圖1所示，將上述原片膜11***至一對夾輥12間後，一面向其中壓入氣體一面以加熱器13進行加熱，並且於延伸起始點利用空氣冷卻環14噴附空氣15使之膨脹為氣泡16，並利用下游側之一對夾輥17拉取，藉此進行管式法之MD方向及TD方向之同時雙軸延伸。此時，較佳為MD方向及TD方向各自之延伸倍率為2.8倍以上。於延伸倍率未達2.8倍之情形時，有衝擊強度降低而實用性上產生問題之虞。 Then, in the extending step, as shown in FIG. 1, after the original film 11 is inserted between the pair of nip rolls 12, a gas is pressed into the surface to be heated by the heater 13, and is used at the extension starting point. The air cooling ring 14 sprays the air 15 to expand it into the air bubbles 16, and pulls the nip roller 17 by one of the downstream sides, thereby performing simultaneous biaxial stretching in the MD direction and the TD direction of the tubular method. In this case, it is preferable that the stretching ratio of each of the MD direction and the TD direction is 2.8 times or more. When the stretching ratio is less than 2.8 times, there is a problem that the impact strength is lowered and the practicality is problematic.

上述延伸步驟後，藉由將經延伸之膜置於拉幅式熱處理爐(未圖示)中，以160~210℃實施熱固定，可獲得本實施形態之ONy膜18。 After the above stretching step, the stretched film is placed in a tenter type heat treatment furnace (not shown) and heat-set at 160 to 210 ° C to obtain the ONy film 18 of the present embodiment.

再者，可對ONy膜適當添加必需之添加劑。作為上述添加劑，例如可列舉抗黏連劑(無機填料等)、撥水劑(伸乙基雙硬脂醯胺等)、潤滑劑(硬脂酸鎂等)。 Further, an essential additive may be appropriately added to the ONy film. Examples of the above additives include an anti-blocking agent (such as an inorganic filler), a water repellent (such as ethyl bis-stearylamine), and a lubricant (such as magnesium stearate).

[易裂性積層膜之構成] [Composition of a crackable laminated film]

本實施形態之易裂性積層膜具備按以下方式於ONy膜上經由接著層(AD)積層有密封層(密封劑膜(SL))的構成。 The cleavable laminated film of the present embodiment has a structure in which a sealing layer (sealant film (SL)) is laminated on the ONy film via the adhesive layer (AD) as follows.

ONy(Ny6+MXD6)/AD/SL ONy (Ny6+MXD6)/AD/SL

作為密封劑膜，可根據用途使用各種樹脂膜。例如，若為高溫蒸煮用，則較佳為使用市售之高溫蒸煮用CPP(Cast Polypropylene，流延聚丙烯)膜。又，若為重貨包裝用，則較佳為使用直鏈狀低密度聚乙烯(LLDPE)。 As the sealant film, various resin films can be used depending on the application. For example, in the case of high-temperature cooking, a commercially available CPP (Cast Polypropylene) film for high-temperature cooking is preferably used. Further, in the case of heavy packaging, it is preferred to use a linear low density polyethylene (LLDPE).

此處，較佳為於上述接著層中使用所謂之乾式積層用之接著劑。其中，該接著層於25℃下之動彈性係數E'必需滿足下述式[A]：LogE'≧7.7 [A](Log為常用對數)。 Here, it is preferable to use a so-called adhesive for dry laminate in the above-mentioned adhesive layer. Wherein, the dynamic elastic coefficient E' of the adhesive layer at 25 ° C must satisfy the following formula [A]: LogE' ≧ 7.7 [A] (Log is a common logarithm).

若LogE'未達7.7，則例如積層強度較高，但於將積層膜(包裝袋)撕裂(開封)時無法獲得易裂性。具體而言，撕裂時，ONy膜及密封層產生所謂之拉伸(ONy膜及密封劑膜延伸而無法澈底切斷之現象)，無法獲得良好之開封性(直線撕裂性)。 If the LogE' is less than 7.7, for example, the buildup strength is high, but the cracking property cannot be obtained when the laminated film (package) is torn (opened). Specifically, in the case of tearing, the ONy film and the sealing layer cause so-called stretching (the phenomenon in which the ONy film and the sealant film are stretched and cannot be cut off at the same time), and good opening property (linear tear property) cannot be obtained.

上述E'例如可利用如下所述之方法進行測定。將接著劑之主劑與硬化劑調合後，於平坦之玻璃板之表面流動而形成薄膜，自該薄膜切取試驗片，利用試驗機(維布隆振動 電容器)對該試驗片反覆製造振動而求得動彈性係數E'。測定溫度為25℃。 The above E' can be measured, for example, by the method described below. After the main agent of the adhesive is blended with the hardener, it flows on the surface of the flat glass plate to form a film, and the test piece is cut out from the film, and the test machine (Vibron vibration) is used. Capacitor) The test piece was repeatedly subjected to vibration to obtain a dynamic elastic coefficient E'. The measurement temperature was 25 °C.

根據上述實施形態，由於使用具有特定原料構成之雙軸延伸尼龍膜，故而該膜之厚度精度優異。該厚度精度對印刷適合性或製造積層膜時之積層適合性造成影響，故而較為重要。 According to the above embodiment, since the biaxially stretched nylon film having a specific material composition is used, the film has excellent thickness precision. This thickness accuracy is important for the printing suitability or the suitability of the laminate when the laminated film is produced.

又，由於將上述雙軸延伸尼龍膜作為表基材，並利用特定之接著劑積層密封劑膜，故而與密封劑膜之積層強度優異，亦不易發生延伸膜之層內剝離，積層膜之直線撕裂性優異，進而於製袋後不易產生開口捲曲。 Further, since the biaxially stretched nylon film is used as the surface substrate and the sealant film is laminated with a specific adhesive, the laminate layer is excellent in the strength of the laminate, and the in-layer peeling of the stretched film is less likely to occur, and the film is straight. It has excellent tearing property and is less likely to cause opening curl after bag making.

[本發明之其他構成] [Other constitution of the present invention]

上述實施形態中，以單層之形式使用作為表基材之ONy膜，本發明中，亦可進而積層雙軸延伸膜或無延伸膜。作為上述雙軸延伸膜，例如可為與上述ONy膜相同之膜，亦可為以Ny6、MXD6、乙烯乙烯醇共聚物(EVOH)、聚酯(PET(Polyethylene Terephthalate，聚對苯二甲酸乙二酯)、PBT(Polybutylene Terephthalate，聚對苯二甲酸丁二酯)等)、聚烯烴、聚苯乙烯及聚碳酸酯等作為原料者。 In the above embodiment, an ONy film as a surface substrate is used in the form of a single layer, and in the present invention, a biaxially stretched film or a non-stretched film may be further laminated. The biaxially stretched film may be, for example, the same film as the above-mentioned ONy film, or may be Ny6, MXD6, ethylene vinyl alcohol copolymer (EVOH), or polyester (PET (Polyethylene Terephthalate). As a raw material, ester, PBT (Polybutylene Terephthalate, etc.), polyolefin, polystyrene, and polycarbonate.

例如，亦可製成如下所述之構成。再者，將上述實施形態中之雙軸延伸膜僅表記為「Ny6+MXD6」：(Ny6+MXD6)/MXD6/(Ny6+MXD6)/AD/SL For example, the configuration described below can also be made. Further, the biaxially stretched film in the above embodiment is simply referred to as "Ny6+MXD6": (Ny6+MXD6)/MXD6/(Ny6+MXD6)/AD/SL

(Ny6+MXD6)/EVOH/(Ny6+MXD6)/AD/SL (Ny6+MXD6)/EVOH/(Ny6+MXD6)/AD/SL

PET/AD/(Ny6+MXD6)/AD/SL PET/AD/(Ny6+MXD6)/AD/SL

該等之中，就(Ny6+MXD6)/MXD6/(Ny6+MXD6)或 (Ny6+MXD6)/EVOH/(Ny6+MXD6)而言，使用對應之原料進行共擠壓，並對所獲得之原片進行共延伸，藉此製作雙軸延伸膜即可。 Among these, (Ny6+MXD6)/MXD6/(Ny6+MXD6) or (Ny6+MXD6)/EVOH/(Ny6+MXD6), the co-extrusion is carried out using the corresponding raw materials, and the obtained original sheet is co-stretched, thereby producing a biaxially stretched film.

再者，該等積層品可為利用接著劑等之乾式積層品，亦可為多層延伸品。 Further, the laminate may be a dry laminate using an adhesive or the like, or may be a multilayer laminate.

實施例 Example

繼而，利用實施例及比較例進而詳細地說明本發明。惟本發明不受該等例任何限制。 Next, the present invention will be described in detail by way of examples and comparative examples. However, the invention is not limited by these examples.

[評價方法] [Evaluation method]

使用各種原料，利用圖1之裝置進行管式雙軸延伸，進而，以所獲得之ONy膜製造積層膜並進行如下所示之評價。雙軸延伸方法等之詳情如下所述。將原料構成及結果示於表1。 Tube-type biaxial stretching was carried out using the apparatus of Fig. 1 using various materials, and a laminated film was produced from the obtained ONy film, and evaluation was performed as follows. Details of the biaxial stretching method and the like are as follows. The raw material composition and results are shown in Table 1.

(厚度精度) (thickness accuracy)

於延伸膜18之寬度方向上每隔1 cm測定厚度，以下述式求得厚度精度(%)。 The thickness was measured every 1 cm in the width direction of the stretched film 18, and the thickness precision (%) was obtained by the following formula.

((膜最大厚度-膜最小厚度)/2/膜平均厚度)×100% ((maximum film thickness - minimum film thickness) / 2 / film average thickness) × 100%

繼而，基於以該式求得之厚度精度(%)，按以下基準進行評價： Then, based on the thickness accuracy (%) obtained by the formula, the evaluation was performed on the following basis:

A：4%以下 A: 4% or less

B：超過4%且為6%以下 B: more than 4% and less than 6%

C：超過6% C: more than 6%

(積層強度及層內剝離) (layering strength and layer peeling)

將延伸膜18(表基材膜)、及密封劑膜(高溫蒸煮用CPP膜 [Idemitsu Unitec製造之Unilax RT680，厚度60 μm]進行乾式積層而製作積層膜。關於使用之表基材膜及接著劑之詳情，示於下述實施例、比較例及表1。再者，乾式積層後之積層膜以40℃進行3天熟化。 Stretch film 18 (surface film) and sealant film (CPP film for high temperature cooking) [Unilax RT680 manufactured by Idemitsu Unitec, thickness: 60 μm] was subjected to dry lamination to produce a laminated film. The details of the substrate film and the adhesive used in the table are shown in the following examples, comparative examples and Table 1. Further, the laminated film after the dry lamination was aged at 40 ° C for 3 days.

自上述積層膜切割15 mm寬之短條狀試驗片，徒手對其端部進行約數cm之界面剝離，將表基材膜(延伸膜18)及密封劑膜分離。其後，將各膜片設置於拉伸試驗機(Instron萬能試驗機1123型)中，以300 mm/min之速度進行積層部分之剝離試驗，測定積層強度(90度剝離)。 A strip test piece of 15 mm width was cut from the laminated film, and the end portion was peeled off by an interface of about several cm by hand, and the surface substrate film (stretch film 18) and the sealant film were separated. Thereafter, each of the films was placed in a tensile tester (Instron Universal Testing Machine Model 1123), and a peeling test of the laminated portion was performed at a speed of 300 mm/min, and the laminated strength (90-degree peeling) was measured.

將其積層強度(剝離強度)為5 N/m以上者記作A，未達5 N/m且為3 N/m以上者記作B，未達3 N/m者記作C，進行評價。 When the laminate strength (peeling strength) is 5 N/m or more, it is referred to as A, and if it is less than 5 N/m and 3 N/m or more, it is referred to as B, and if it is less than 3 N/m, it is recorded as C, and evaluation is performed. .

若剝離試驗中途於表基材膜內部發生層內剝離，則剝離強度急劇減少，故而可以是否表現上述舉動而判斷是否發生層內剝離。例如，剝離試驗開始時剝離強度為7 N/m左右，若於剝離試驗中途急劇減少至1~2 N/m左右，則可判斷發生層內剝離。 When the in-layer peeling occurs in the inside of the surface substrate film in the peeling test, the peeling strength is drastically reduced, and whether or not the peeling is formed can be judged whether or not the in-layer peeling occurs. For example, the peel strength at the start of the peeling test is about 7 N/m, and if it is drastically reduced to about 1 to 2 N/m in the middle of the peeling test, it can be judged that the in-layer peeling occurs.

繼而，將表基材膜內部未顯示層內剝離之舉動者記作A，將顯示層內剝離之舉動者記作B，進行評價。 Then, the person who did not show the inside of the surface of the surface of the base film was referred to as A, and the person who peeled off the inside of the display layer was referred to as B, and was evaluated.

(易裂性) (fragile)

根據直線撕裂性進行評價。具體而言如下所述。 Evaluation was based on the linear tear property. Specifically, it is as follows.

如圖2所示，於20 cm寬之積層膜18'上以2 cm之間隔劃出縫隙21，沿該等縫隙21撕裂積層膜18'後，測定膜片18A之另一端之寬度We，如下所述求得與原間隔Ws之偏差α。 As shown in FIG. 2, the slit 21 is drawn at intervals of 2 cm on the 20 cm wide laminated film 18', and after the laminated film 18' is torn along the slits 21, the width We of the other end of the film 18A is measured, The deviation α from the original interval Ws is obtained as follows.

α=|[(Ws-We)/Ws]|×100 α=|[(Ws-We)/Ws]|×100

對10片膜片18A進行該測定，將其平均值α(%)為30%以下者記作A(直線撕裂性良好)，α(%)超過30%者記作B(直線撕裂性不良)，進行評價。若α(%)超過30%，則難以筆直地將膜撕裂。 This measurement was performed on ten sheets 18A, and the average value α (%) was 30% or less, and A (linear tear property was good), and α (%) exceeding 30% was recorded as B (straight tear property). Bad), evaluation. If α (%) exceeds 30%, it is difficult to tear the film straight.

(開口捲曲) (opening curl)

如圖3所示，製袋時，對積層膜18'以袋之開口部之朝向成為該積層膜18'之TD方向(橫取)的方式取兩塊。圖4中表示開口部41朝向積層膜18'之TD方向之包裝袋42。再者，該包裝袋42之尺寸為150 mm(長度)×130 mm(寬度)，密封寬度為10 mm。繼而，以下述方式測定該包裝袋42之開口捲曲並進行評價。 As shown in Fig. 3, when the bag is formed, the laminated film 18' is taken in two in such a manner that the direction of the opening of the bag becomes the TD direction (horizontal direction) of the laminated film 18'. In Fig. 4, a package 42 in which the opening portion 41 faces the TD direction of the laminated film 18' is shown. Further, the package 42 has a size of 150 mm (length) × 130 mm (width) and a sealing width of 10 mm. Then, the opening curl of the packaging bag 42 was measured and evaluated in the following manner.

即，如圖5所示，將上述包裝袋42於溫度23℃、相對濕度50%之環境中放置3小時，測定因開口捲曲之開口部41之厚度L。此後，將10個包裝袋42之開口部41之厚度L的平均值未達2 mm之情形記作A，將2 mm以上且未達4 mm之情形記作B，將4 mm以上之情形記作C，進行評價。 That is, as shown in Fig. 5, the packaging bag 42 was allowed to stand in an environment of a temperature of 23 ° C and a relative humidity of 50% for 3 hours, and the thickness L of the opening 41 which was curled by the opening was measured. Thereafter, the case where the average value of the thickness L of the opening portions 41 of the ten packaging bags 42 is less than 2 mm is denoted by A, and the case where 2 mm or more and less than 4 mm is referred to as B, and the case where 4 mm or more is recorded Let C be evaluated.

[實施例1] [Example 1] (延伸膜之製造) (Manufacture of stretch film)

對將Ny6顆粒70質量份與MXD6顆粒30質量份混合而成之初始原料，調配以原料總量基準(初始原料與熱歷程品之合計量基準)計為20質量%之已按該調配比進行一次熔融混合並經顆粒化之熱歷程品(MXD6之熔點為236℃者)。 The initial raw material obtained by mixing 70 parts by mass of the Ny6 particles with 30 parts by mass of the MXD6 particles is adjusted to 20% by mass based on the total amount of the raw materials (the total basis of the initial raw material and the thermal process product). A thermal process product which melts and granulates once (the melting point of MXD6 is 236 ° C).

將該乾式混合品於擠壓機中以270℃進行熔融混練後， 將熔融物自模嘴以圓筒狀膜之形式擠出，繼而以水(15℃)進行急冷而製作原片膜。再者，MXD6之熔點係使用PerkinElmer公司製造之示差掃描熱量測定裝置(DSC)以升溫速度10℃/min自50℃升溫至280℃進行測定。均以首輪之峰值作為熔點。再者，熱歷程品係以270℃進行10分鐘熱處理而成。 After the dry mixture was melt-kneaded at 270 ° C in an extruder, The melt was extruded from a die in the form of a cylindrical film, and then quenched with water (15 ° C) to prepare an original film. Further, the melting point of MXD6 was measured by heating from 50 ° C to 280 ° C at a temperature increase rate of 10 ° C/min using a differential scanning calorimeter (DSC) manufactured by PerkinElmer Co., Ltd. The peak of the first round is used as the melting point. Further, the thermal history product was heat-treated at 270 ° C for 10 minutes.

用作Ny6者係宇部興產(股)製造之尼龍6[UBE Nylon 1022FD(商品名)，相對黏度ηr=3.6]，用作MXD6者係三菱瓦斯化學(股)製造之己二醯間苯二甲胺[MX Nylon 6007(商品名)，相對黏度ηr=2.7]。 Nylon 6 [UBE Nylon 1022FD (trade name), relative viscosity ηr = 3.6] manufactured by Ny6, Ltd., used as a MXD6, is a bismuth benzene produced by Mitsubishi Gas Chemical Co., Ltd. Methylamine [MX Nylon 6007 (trade name), relative viscosity ηr = 2.7].

繼而，如圖1所示，將該原片膜11***至一對夾輥12間後，一面向其中壓入氣體一面以加熱器13(設定溫度310℃)進行加熱，並且於延伸起始點利用空氣冷卻環14以15 m3/min之風量噴附空氣15使之膨脹成氣泡16，以下游側之一對夾輥17拉取，藉此進行管式法之MD方向及TD方向之同時雙軸延伸。該延伸時之倍率於MD方向設為3.0倍，於TD方向設為3.2倍。延伸成形性良好。 Then, as shown in FIG. 1, the original film 11 is inserted between a pair of nip rolls 12, and a gas is pressed into the surface while being heated by a heater 13 (set temperature: 310 ° C), and at the starting point of elongation. The air cooling ring 14 is used to spray the air 15 at a flow rate of 15 m 3 /min to expand into the air bubbles 16, and the nip roller 17 is pulled by one of the downstream sides, thereby performing the MD direction and the TD direction of the tubular method. Biaxial extension. The magnification at the time of this extension was 3.0 times in the MD direction and 3.2 times in the TD direction. The elongation formability is good.

對所獲得之ONy膜利用上述方法測定厚度精度。又，將ONy膜作為表基材進行乾式積層，製造積層膜。作為積層用之接著劑，使用Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比16：1)。 The thickness precision of the obtained ONy film was measured by the above method. Further, an ONy film was dry-laid as a surface substrate to produce a laminated film. As an adhesive for lamination, TAKELAC A-615/A-65 (combination ratio 16:1) manufactured by Mitsui Chemicals was used.

[實施例2~8、比較例1~11] [Examples 2 to 8 and Comparative Examples 1 to 11]

將表基材之樹脂、層構成、熱歷程品之調配量、熱歷程品之熔點、及與密封劑之積層中使用之接著劑之種類 (logE')如表1所示進行變更，此外以與實施例1相同之方式製造ONy膜。再者，熱歷程品均使用初始品，為以與初始品相同之Ny6/MXD調配比進行熔融混練而製造者。 The resin of the surface substrate, the layer constitution, the amount of the thermal process product, the melting point of the thermal process product, and the type of the adhesive used in the laminate with the sealant (logE') was changed as shown in Table 1, and an ONy film was produced in the same manner as in Example 1. Further, the thermal process product was produced by using the initial product and melting and kneading at the same Ny6/MXD blending ratio as the initial product.

再者，實施例5、7、比較例5、7係對表基材進行共擠壓成形(膜總厚度為25 μm，各層之厚度為8 μm/9 μm/8 μm)而成者，實施例6、比較例6係於ONy面乾式積層聚酯膜(PET膜，厚度12 μm)而成者。各層之厚度為12 μm/3 μm/15 μm。 Further, in Examples 5 and 7, and Comparative Examples 5 and 7, the surface substrate was co-extruded (the total thickness of the film was 25 μm, and the thickness of each layer was 8 μm / 9 μm / 8 μm). Example 6 and Comparative Example 6 were obtained by using an ONy-surface dry laminated polyester film (PET film, thickness: 12 μm). The thickness of each layer is 12 μm / 3 μm / 15 μm.

OPET與ONy之積層係於與ONy與密封劑之積層相同之條件下使用與ONy與密封劑之積層中使用之接著劑相同者。 The laminate of OPET and ONy is the same as the adhesive used in the laminate of ONy and the sealant under the same conditions as the laminate of ONy and the sealant.

實施例8及比較例8係利用PET/AD/(Ny6+MXD6)之共擠壓多層延伸製造表基材並進行評價。 In Example 8 and Comparative Example 8, a watch substrate was produced by coextrusion multilayer extension of PET/AD/(Ny6+MXD6) and evaluated.

1) Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比為16：1) 1) TAKELAC A-615/A-65 manufactured by Mitsui Chemicals (16:1 blending ratio)

2) Toyo-Morton製造之AD590/CAT56(調合比為100：16) 2) AD590/CAT56 manufactured by Toyo-Morton (adjustment ratio 100:16)

3) Mitsui Chemicals製造之TAKELAC AD590+CAT56(調合比為100：16) 3) TAKELAC AD590+CAT56 manufactured by Mitsui Chemicals (adjustment ratio 100:16)

4) Mitsui Chemicals製造之TAKELAC A-520/A-40(調合比為6：1) 4) TAKELAC A-520/A-40 manufactured by Mitsui Chemicals (combination ratio is 6:1)

5) Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比為5：1) 5) TAKELAC A-615/A-65 manufactured by Mitsui Chemicals (5:1 blending ratio)

6) Toyo-Morton製造之AD590+CAT56(調合比為16：1) 6) AD590+CAT56 manufactured by Toyo-Morton (with a blend ratio of 16:1)

7) Mitsui Chemicals製造之TAKELAC A-520/A-40(調合比為6：1) 7) TAKELAC A-520/A-40 manufactured by Mitsui Chemicals (combination ratio is 6:1)

8) Toyo-Morton製造之AD590+CAT56(調合比為100：16) 8) AD590+CAT56 manufactured by Toyo-Morton (mixing ratio is 100:16)

9) Mitsui Chemicals製造之TAKELAC A975/A-3(調合比為7：1) 9) TAKELAC A975/A-3 manufactured by Mitsui Chemicals (adjustment ratio 7:1)

10) Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比為16：1) 10) TAKELAC A-615/A-65 manufactured by Mitsui Chemicals (16:1 blending ratio)

11) Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比為16：1) 11) TAKELAC A-615/A-65 manufactured by Mitsui Chemicals (16:1 blending ratio)

12) Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比為16：1) 12) TAKELAC A-615/A-65 manufactured by Mitsui Chemicals (16:1 blending ratio)

13) Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比為16：1) 13) TAKELAC A-615/A-65 manufactured by Mitsui Chemicals (16:1 blending ratio)

14) Dainippon Ink and Chemicals製造之LX-75/KW-40(調合 比為5：1) 14) LX-75/KW-40 manufactured by Dainippon Ink and Chemicals The ratio is 5:1)

15) Dainippon Ink and Chemicals製造之LX-75/KW-40(調合比為5：1) 15) LX-75/KW-40 manufactured by Dainippon Ink and Chemicals (5:1 blending ratio)

16) Dainippon Ink and Chemicals製造之LX-75/KW-40(調合比為5：1) 16) LX-75/KW-40 manufactured by Dainippon Ink and Chemicals (5:1 blending ratio)

17) Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比為16：1) 17) TAKELAC A-615/A-65 manufactured by Mitsui Chemicals (16:1 blending ratio)

18) Mitsui Chemicals製造之TAKELAC A-615/A-65(調合比為16：1) 18) TAKELAC A-615/A-65 manufactured by Mitsui Chemicals (16:1 blending ratio)

19) Dainippon Ink and Chemicals製造之LX-75/KW-40(調合比為5：1) 19) LX-75/KW-40 manufactured by Dainippon Ink and Chemicals (combination ratio is 5:1)

[評價結果] [Evaluation results]

根據表1之各實施例可知，由特定原料所獲得之膜18厚度精度優異，又，積層膜18'積層強度及易裂性(直線撕裂性)亦優異。進而，積層膜18'不發生層內剝離，亦幾乎無開口捲曲。又，延伸成形性均良好。 According to each of the examples of Table 1, it is understood that the film 18 obtained from a specific raw material is excellent in thickness precision, and the laminated film 18' is also excellent in laminate strength and cracking property (linear tear property). Further, the laminated film 18' does not undergo in-layer peeling, and there is almost no open curl. Moreover, the stretch formability was good.

另一方面，比較例1中，由於接著劑之logE'較小為7.4，故而易裂性(直線撕裂性)較差。比較例2中，由於未調配熱歷程品，故而發生層內剝離現象，又，膜之厚度精度亦較差，不適於二次加工。比較例3中，由於熱歷程品之調配量過多，故而易裂性較差。比較例4中，由於熱歷程品之熔點過低，故而易裂性較差，包裝袋之開口捲曲亦較大。 On the other hand, in Comparative Example 1, since the log E' of the adhesive was as small as 7.4, the cracking property (linear tearing property) was inferior. In Comparative Example 2, since the thermal history product was not blended, the in-layer peeling phenomenon occurred, and the thickness accuracy of the film was also poor, which was not suitable for secondary processing. In Comparative Example 3, since the amount of the thermal history product was too large, the cracking property was poor. In Comparative Example 4, since the melting point of the thermal history product was too low, the cracking property was poor, and the opening curl of the packaging bag was also large.

比較例5中，由於未調配熱歷程品，故而發生層內剝離現象，膜之厚度精度亦較差，不適於二次加工。比較例6 中，由於接著劑之logE'較小為7.4，故而易裂性(直線撕裂性)較差。 In Comparative Example 5, since the thermal process product was not prepared, the in-layer peeling phenomenon occurred, and the thickness accuracy of the film was also poor, which was not suitable for secondary processing. Comparative Example 6 In the case, since the logE' of the adhesive is as small as 7.4, the cracking property (linear tearing property) is inferior.

比較例7中，由於未調配熱歷程品，且接著劑之logE'亦較小為7.4，故而發生層內剝離現象，厚度精度亦較差，且易裂性亦較差。比較例8中，由於接著劑之logE'較小為7.4，故而易裂性較差。又，比較例9中，由於僅使用Ny6作為原料，未調配MXD6，故而未表現易裂性。又，包裝袋之開口捲曲較大，推測填充時出現故障。比較例10中，由於MXD6之調配量較少，進而亦未調配熱歷程品，故而容易發生層內剝離，易裂性亦較差。又，膜之厚度精度亦較差。進而，包裝袋之開口捲曲亦較大。比較例11中，MXD6之調配量過多，另一方面，未調配熱歷程品。因此，容易發生層內剝離，易裂性亦較差。進而，膜之厚度精度亦非常差。 In Comparative Example 7, since the thermal history product was not blended, and the logE' of the adhesive was also small to 7.4, the in-layer peeling phenomenon occurred, the thickness precision was poor, and the cracking property was also inferior. In Comparative Example 8, since the log E' of the adhesive was as small as 7.4, the cracking property was inferior. Further, in Comparative Example 9, since only Ny6 was used as a raw material, MXD6 was not formulated, and thus cracking property was not exhibited. Moreover, the opening of the packaging bag has a large curl, and it is presumed that there is a failure in filling. In Comparative Example 10, since the amount of the MXD6 was small, and the thermal history product was not blended, the in-layer peeling was likely to occur, and the cracking property was also inferior. Moreover, the thickness accuracy of the film is also poor. Further, the opening of the package is also curled. In Comparative Example 11, the amount of MXD6 was too large, and on the other hand, the thermal process product was not prepared. Therefore, it is easy to cause peeling in the layer and the cracking property is also poor. Furthermore, the thickness accuracy of the film is also very poor.

11‧‧‧原片膜 11‧‧‧ original film

12‧‧‧夾輥 12‧‧‧Pinch roller

13‧‧‧加熱器 13‧‧‧heater

14‧‧‧空氣冷卻環 14‧‧‧Air cooling ring

15‧‧‧空氣 15‧‧‧ Air

16‧‧‧氣泡 16‧‧‧ bubbles

17‧‧‧夾輥 17‧‧‧Pinch roller

18‧‧‧ONy膜(延伸膜) 18‧‧‧ONy film (stretch film)

18'‧‧‧積層膜 18'‧‧‧ laminated film

18A‧‧‧膜片 18A‧‧‧ diaphragm

21‧‧‧縫隙 21‧‧‧ gap

41‧‧‧開口部 41‧‧‧ openings

42‧‧‧包裝袋 42‧‧‧Packing bags

L‧‧‧厚度 L‧‧‧ thickness

MD‧‧‧縱向 MD‧‧‧ portrait

TD‧‧‧橫向 TD‧‧ transverse

We‧‧‧寬度 We‧‧‧Width

Ws‧‧‧原間隔 Ws‧‧ Original interval

圖1係製造實施形態之ONy膜之雙軸延伸裝置之概略圖。 Fig. 1 is a schematic view showing a biaxial stretching device for manufacturing an ONy film of an embodiment.

圖2係表示實施例中直線撕裂性之評價方法之圖。 Fig. 2 is a view showing a method of evaluating the linear tearing property in the embodiment.

圖3係表示實施例中包裝袋之製造方法之圖。 Fig. 3 is a view showing a method of manufacturing a packaging bag in the embodiment.

圖4係實施例之包裝袋之正面圖。 Figure 4 is a front elevational view of the package of the embodiment.

圖5係表示實施例中開口捲曲之測定方法之圖。 Fig. 5 is a view showing a method of measuring the opening curl in the embodiment.

Claims (5)

一種易裂性積層膜，其特徵在於具備：第一雙軸延伸膜，其係含有：初始原料，其包含40質量份以上85質量份以下之尼龍6、及15質量份以上60質量份以下之己二醯間苯二甲胺，且Ny6+MXD6=100重量份，其中，Ny6為尼龍6，MXD為己二醯間苯二甲胺；及熱歷程品，其係將尼龍6及己二醯間苯二甲胺以與上述初始原料相同之比率進行熔融混練使己二醯間苯二甲胺之熔點為233℃以上238℃以下而成，且該第一雙軸延伸膜使用上述熱歷程品之調配比率以原料總量基準計為5質量%以上40質量%以下的原料而成；接著層，其於25℃下之動彈性係數E'滿足下述式[A]：LogE'≧7.7 [A]；及密封層。 A cleavable laminated film comprising: a first biaxially stretched film comprising: 40 parts by mass or more and 85 parts by mass or less of nylon 6 and 15 parts by mass or more and 60 parts by mass or less or less Dixylylenediamine, and Ny6+MXD6=100 parts by weight, wherein Ny6 is nylon 6, MXD is m-xylylenediamine; and thermal process product, which is nylon 6 and hexamethylene The m-xylylenediamine is melt-kneaded in the same ratio as the above-mentioned starting materials, and the melting point of the m-xylylenediamine is 233° C. or more and 238° C. or less, and the first biaxially stretched film is made of the above thermal process product. The blending ratio is 5% by mass or more and 40% by mass or less based on the total amount of the raw materials; and the subsequent layer, the dynamic elastic modulus E' at 25 ° C satisfies the following formula [A]: LogE' ≧ 7.7 [ A]; and the sealing layer. 如請求項1之易裂性積層膜，其係進而積層第二雙軸延伸膜或無延伸膜而成。 The crackable laminated film of claim 1, which is formed by laminating a second biaxially stretched film or without a stretched film. 如請求項2之易裂性積層膜，其中上述第二雙軸延伸膜為上述之第一雙軸延伸膜，或以尼龍6、己二醯間苯二甲胺、乙烯乙烯醇共聚物、聚酯、聚烯烴、聚苯乙烯及聚碳酸酯中之任一者為原料之雙軸延伸膜。 The cleavable laminated film of claim 2, wherein the second biaxially stretched film is the first biaxially stretched film described above, or is nylon 6, hexamethylenediamine, ethylene vinyl alcohol copolymer, poly A biaxially stretched film of a raw material of any one of an ester, a polyolefin, a polystyrene, and a polycarbonate. 如請求項3之易裂性積層膜，其中上述第二雙軸延伸膜、及上述第一雙軸延伸膜為共擠壓多層延伸而成者。 The cleavable laminated film according to claim 3, wherein the second biaxially stretched film and the first biaxially stretched film are formed by coextruding a plurality of layers. 一種易裂性包裝袋，其特徵在於：其係使用如請求項1至4中任一項之易裂性積層膜進行製袋而成。 A cleavable packaging bag characterized in that it is formed into a bag by using a cleavable laminated film according to any one of claims 1 to 4.
TW101149913A 2011-12-28 2012-12-25 Easy-to-tear laminated film and easy-to-tear packaging bag TW201338980A (en)

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TWI826667B (en) * 2019-03-28 2023-12-21 日商東洋紡股份有限公司 Gas barrier polyamide film

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JP7018705B2 (en) * 2016-12-21 2022-02-14 共同印刷株式会社 Laminated film
TWI667289B (en) 2018-04-18 2019-08-01 財團法人工業技術研究院 Polyamide composition and film and method for manufacturing the same

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TWI826667B (en) * 2019-03-28 2023-12-21 日商東洋紡股份有限公司 Gas barrier polyamide film
US11878494B2 (en) 2019-03-28 2024-01-23 Toyobo Co., Ltd. Gas barrier polyamide film

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