JP2013169666A - Multilayer film for deep-drawing packaging - Google Patents
Multilayer film for deep-drawing packaging Download PDFInfo
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- JP2013169666A JP2013169666A JP2012033690A JP2012033690A JP2013169666A JP 2013169666 A JP2013169666 A JP 2013169666A JP 2012033690 A JP2012033690 A JP 2012033690A JP 2012033690 A JP2012033690 A JP 2012033690A JP 2013169666 A JP2013169666 A JP 2013169666A
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- 238000004806 packaging method and process Methods 0.000 title claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 46
- -1 polyethylene Polymers 0.000 claims abstract description 23
- 239000004698 Polyethylene Substances 0.000 claims abstract description 9
- 229920000573 polyethylene Polymers 0.000 claims abstract description 9
- 230000004888 barrier function Effects 0.000 claims abstract description 8
- 239000012790 adhesive layer Substances 0.000 claims abstract description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims description 23
- 239000000806 elastomer Substances 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 235000013305 food Nutrition 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 2
- 230000001954 sterilising effect Effects 0.000 abstract description 8
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 8
- 238000007710 freezing Methods 0.000 abstract description 2
- 230000008014 freezing Effects 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract description 2
- 230000003405 preventing effect Effects 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 16
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920000092 linear low density polyethylene Polymers 0.000 description 10
- 239000004707 linear low-density polyethylene Substances 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- 239000004677 Nylon Substances 0.000 description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000004840 adhesive resin Substances 0.000 description 4
- 229920006223 adhesive resin Polymers 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229940047670 sodium acrylate Drugs 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000007 Nylon MXD6 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 229920003233 aromatic nylon Polymers 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000015220 hamburgers Nutrition 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は深絞り包装用多層フィルムに関する。 The present invention relates to a multilayer film for deep drawing packaging.
深絞り包装は、例えば食品包装の分野で周知であり、プラスチックフィルム(底材)を加熱成形して1個又は複数個の容器(くぼみ)を形成し、その中に食品を入れ、開口部をプラスチックフィルム等(蓋材)で覆い、その周辺部を容器に接着又は溶着固定することによって包装する方法である。そして、成型された容器内を真空にする包装は「真空パック」、容器内にガスを充填する包装は「ガスパック」、成型容器そのままの包装は「ブリスターパック」と呼ばれる。 Deep drawn packaging is well known, for example, in the field of food packaging, and a plastic film (bottom material) is thermoformed to form one or more containers (recesses) into which food is placed, and an opening is formed. It is a method of packaging by covering with a plastic film or the like (cover material) and adhering or welding and fixing its peripheral part to a container. A package that evacuates the molded container is called a “vacuum pack”, a package that fills the container with gas is called a “gas pack”, and a package as it is is called a “blister pack”.
従来、ピンホールや高温殺菌後のカールの発生を抑制するため、ポリプロピレン樹脂から成る外層(A)、芳香族ナイロンと脂肪族ナイロンの混合物から成る中間層(B)、ガスバリヤ層(C)、及びシール層(D)が必要に応じて接着性樹脂を介し、(A)−(B)−(C)−(D)又は(A)−(C)−(B)−(D)の順で積層してなる多層フィルムが提案されている(特許文献1)。また、最外層を12ナイロン樹脂層、または12ナイロンと6ナイロンとの共重合ポリアミド樹脂層、中間層をポリオレフィン系接着樹脂層に挟まれたポリアミド樹脂層または、ポリオレフィン系接着樹脂層に挟まれたポリアミド樹脂層とエチレン−酢酸ビニル共重合体けん化物層、最内層にシール性樹脂層を配して成り、最外層の厚みが全体厚みの15%以下である深絞り成形用共押出複合フイルムが提案されている(特許文献2)。 Conventionally, in order to suppress the occurrence of curling after pinholes and high temperature sterilization, an outer layer (A) made of polypropylene resin, an intermediate layer (B) made of a mixture of aromatic nylon and aliphatic nylon, a gas barrier layer (C), and If necessary, the sealing layer (D) is passed through an adhesive resin in the order of (A)-(B)-(C)-(D) or (A)-(C)-(B)-(D). A multilayer film formed by laminating has been proposed (Patent Document 1). Further, the outermost layer is a 12 nylon resin layer, or a polyamide resin layer of 12 nylon and 6 nylon, and the intermediate layer is sandwiched between a polyamide resin layer or a polyolefin adhesive resin layer. A co-extruded composite film for deep drawing, comprising a polyamide resin layer, a saponified ethylene-vinyl acetate copolymer layer, and a sealing resin layer disposed on the innermost layer, wherein the outermost layer has a thickness of 15% or less of the total thickness. It has been proposed (Patent Document 2).
しかしながら、外層(最外層)にポリプロピレン又はナイロンを使用した従来の多層フィルムは次のような問題を有している。すなわち、上記の材料は低温衝撃に弱いため、冷凍流通される場合にはピンホールが発生し易い。更に、12ナイロンや6ナイロンとの共重合ナイロン等は、高価であり、しかも、ポリオレフィンに比べて吸水性が高いために湿度の影響でカールの具合が変化し易い。 However, the conventional multilayer film using polypropylene or nylon for the outer layer (outermost layer) has the following problems. That is, since the above materials are vulnerable to low temperature impact, pinholes are likely to occur when refrigerated. Furthermore, copolymer nylon such as 12 nylon and 6 nylon is expensive, and has higher water absorption than polyolefin, so the degree of curling tends to change due to the influence of humidity.
本発明は、上記実情に鑑みなされたものであって、その目的は、湿度の影響を受け難く、冷凍流通時の耐ピンホールに優れ、ボイル殺菌中のカールの発生を抑制でき、しかも、安価である深絞り包装用多層フィルムを提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is hardly affected by humidity, has excellent pinhole resistance during freezing distribution, can suppress the occurrence of curling during boil sterilization, and is inexpensive. It is providing the multilayer film for deep drawing packaging which is.
本発明者らは、上記実情に鑑み鋭意検討を重ねた結果、外層にポリエチレンを使用するならば、冷凍流通時の耐ピンホールを改善し得るとの知見を得た。しかしながら、外層にポリエチレンを使用した場合はボイル殺菌中にカールが発生する。 As a result of intensive studies in view of the above circumstances, the present inventors have found that if polyethylene is used for the outer layer, pinhole resistance during refrigeration can be improved. However, when polyethylene is used for the outer layer, curling occurs during boil sterilization.
本発明は、上記の知見を基に更に検討を重ねた結果完成されたものであり、その要旨は、少なくとも、外層、接着層、ガスバリヤ層、接着層、ヒートシール層の順に5層以上に積層された深絞り包装用多層フィルムであって、上記の外層は、熱可塑性エラストマーを5〜40重量%プレンドしたポリエチレンから成ることを特徴とする深絞り包装用多層フィルムに存する。 The present invention has been completed as a result of further studies based on the above findings, and the gist of the present invention is to laminate at least five layers in the order of an outer layer, an adhesive layer, a gas barrier layer, an adhesive layer, and a heat seal layer. A deep-drawn packaging multilayer film, wherein the outer layer is made of polyethylene which is made by blending 5 to 40% by weight of a thermoplastic elastomer.
本発明により前記の課題が解決される。 The above-described problems are solved by the present invention.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
(外層)
本発明の多層フィルムの外層は、熱可塑性エラストマーを5〜40重量%プレンドしたポリエチレンから成る。熱可塑性エラストマーは、特に限定されず、例えば、エチレン系エラストマー、スチレン系エラストマー等を使用することが出来る。
(Outer layer)
The outer layer of the multilayer film of the present invention is made of polyethylene with 5 to 40% by weight of a thermoplastic elastomer. A thermoplastic elastomer is not specifically limited, For example, an ethylene-type elastomer, a styrene-type elastomer, etc. can be used.
エチレン系エラストマーとしては、例えば、エチレン・プロピレン共重合エラストマー(EPR)、エチレン・ブテン共重合エラストマー(EBR)、エチレン・ヘキセン共重合エラストマー(EHR)、エチレン・オクテン共重合エラストマー(EOR)等のエチレン・α−オレフィン共重合体エラストマー;エチレン・プロピレン・エチリデンノルボルネン共重合体エラストマー、エチレン・プロピレン・ブタジエン共重合体エラストマー、エチレン・プロピレン・イソプレン共重合体エラストマー等のエチレン・α−オレフィン・ジエン三元共重合体エラストマー(EPDM)、エチレン−エチレン・ブチレン−エチレンブロック共重合体(CEBC)等を挙げることが出来る。 Examples of the ethylene elastomer include ethylene / propylene copolymer elastomer (EPR), ethylene / butene copolymer elastomer (EBR), ethylene / hexene copolymer elastomer (EHR), ethylene / octene copolymer elastomer (EOR) and the like.・ Α-olefin copolymer elastomer; ethylene / propylene / ethylidenenorbornene copolymer elastomer, ethylene / propylene / butadiene copolymer elastomer, ethylene / propylene / isoprene copolymer elastomer, etc. Examples thereof include copolymer elastomer (EPDM) and ethylene-ethylene / butylene-ethylene block copolymer (CEBC).
エチレン系エラストマーの市販品を例示すれば、ジェイエスアール(JSR)社製EDシリーズ、三井化学社製タフマーPシリーズ及びタフマーAシリーズ、デュポンダウ社製エンゲージEGシリーズ、旭化成社製タフテックHシリーズ等を挙げることが出来る。 Examples of commercially available ethylene elastomers include JSR (EDR) ED series, Mitsui Chemicals Tuffmer P series and Tuffmer A series, DuPont Dow Engage EG series, Asahi Kasei Toughtech H series, etc. I can do it.
スチレン系エラストマーとしては、スチレン・ブタジエン・スチレントリブロック体(SBS)、スチレン・イソプレン・スチレントリブロック体(SIS)、スチレン・ブタジエン・スチレントリブロック体の水素添加物(SEBS)、スチレン・イソプレン・スチレントリブロック体の水素添加物(SEPS)、スチレン−エチレン・ブチレン−エチレンブロック共重合体(SEBC)、スチレン−エチレン・ブチレン−スチレンブロック共重合体(SEBS)、水添スチレン・ブタジエンゴムスチレン系エラストマー(HSBR)等のスチレン系エラストマー等が挙げられる。なお、上記したスチレン・ブタジエン・スチレントリブロック体の水素添加物は、ポリマー主鎖をモノマー単位で見ると、スチレン−エチレン−ブテン−スチレンとなるので、通常、SEBSと略称されるものである。 Styrene elastomers include styrene / butadiene / styrene triblock (SBS), styrene / isoprene / styrene triblock (SIS), hydrogenated styrene / butadiene / styrene triblock (SEBS), styrene / isoprene / Hydrogenated styrene triblock (SEPS), styrene-ethylene / butylene-ethylene block copolymer (SEBC), styrene-ethylene / butylene-styrene block copolymer (SEBS), hydrogenated styrene / butadiene rubber styrene Examples thereof include styrenic elastomers such as elastomer (HSBR). The hydrogenated styrene / butadiene / styrene triblock is usually abbreviated as SEBS because the polymer main chain is styrene-ethylene-butene-styrene when viewed in monomer units.
スチレン系エラストマーの市販品を例示すれば、シェル社製クレイトンシリーズ、クラレ社製セプトンシリーズ、旭化成社製タフテックシリーズ、JSR社製ダイナロンシリーズ等を挙げることが出来る。 Examples of commercially available styrene elastomers include the Clayton series manufactured by Shell, the Septon series manufactured by Kuraray, the Tuftec series manufactured by Asahi Kasei, and the Dynalon series manufactured by JSR.
本発明においては、(a)スチレン−エチレン・ブチレン−エチレンブロック共重合体、(b)エチレン−エチレン・ブチレン−エチレンブロック共重合体、(c)スチレン−エチレン・ブチレン−スチレンブロック共重合体、(d)水添スチレン・ブタジエンゴムスチレン系エラストマー(HSBR)の群から選択された1種または2種以上のエラストマーが好適に使用される。 In the present invention, (a) styrene-ethylene-butylene-ethylene block copolymer, (b) ethylene-ethylene-butylene-ethylene block copolymer, (c) styrene-ethylene-butylene-styrene block copolymer, (D) One or more elastomers selected from the group of hydrogenated styrene / butadiene rubber styrene elastomers (HSBR) are preferably used.
ポリエチレンとしては、低密度ポリエチレン(LDPE)、直鎖低密度ポリエチレン(L−LDPE)、高密度ポリエチレン(HDPE)が知られているが、特に直鎖低密度ポリエチレン(L−LDPE)が好ましい。 As polyethylene, low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), and high density polyethylene (HDPE) are known, and linear low density polyethylene (L-LDPE) is particularly preferable.
ポリエチレンに対するエラストマー成分のプレンド量が5重量%未満の場合は、ボイル殺菌中のカールの抑制が不十分であり、40重量%を超える場合は、ボイル殺菌の際に外面同士(別の包装体同士)が融着する。エラストマー成分の好ましいブレンド量は10〜20重量%である。 When the blend amount of the elastomer component with respect to polyethylene is less than 5% by weight, curling suppression during boil sterilization is insufficient, and when it exceeds 40% by weight, the outer surfaces (between different packages) ) Are fused. A preferable blend amount of the elastomer component is 10 to 20% by weight.
(ガスバリヤ性樹脂層)
ガスバリヤ性樹脂層の構成樹脂としては、ポリアミド(PA)、エチレン−酢酸ビニル共重合体鹸化物(EVOH)、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリカーボネート(PC)等が挙げられる。これらの中では、ポリアミド(PA)又はエチレン−酢酸ビニル共重合体鹸化物(EVOH)が好ましく、特にポリアミド(PA)が好ましい。ポリアミドの具体例としては、ナイロン4、6、7、8、11、12、6・6、6・10、6・11、6・12、6T、6/6・6、6/12、6/6T、6I/6T、ナイロンMXD6等が挙げられる。また、PA/EVOH/PAのように異なるガスバリヤ性樹脂との積層体としてもよい。
(Gas barrier resin layer)
Examples of the constituent resin of the gas barrier resin layer include polyamide (PA), ethylene-vinyl acetate copolymer saponified product (EVOH), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like. Among these, polyamide (PA) or ethylene-vinyl acetate copolymer saponified product (EVOH) is preferable, and polyamide (PA) is particularly preferable. Specific examples of polyamides include nylon 4, 6, 7, 8, 11, 12, 6 · 6, 6 · 10, 6 · 11, 6 · 12, 6T, 6/6 · 6, 6/12, 6 / 6T, 6I / 6T, nylon MXD6 and the like. Moreover, it is good also as a laminated body with different gas barrier resin like PA / EVOH / PA.
(ヒートシール層)
ヒートシール層の構成樹脂としては、高密度ポリエチレン(HDPE)、中密度ポリエチレン(MDPE)、低密度ポリエチレン(LDPE)、ポリプロピレン(PP)、エチレン−酢酸ビニル共重合体(EVA)、エチレン−メタクリレート共重合体、エチレン−アクリル酸エチル共重合体、エチレン−メタクリル酸エチル共重合体、アイオノマー樹脂、EVA鹸化物、線状低密度ポリエチレン(L−LDPE)等が挙げられる。これらの中では線状低密度ポリエチレン(L−LDPE)が一般的である。
(Heat seal layer)
The constituent resin of the heat seal layer includes high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-methacrylate co-polymer. Examples include polymers, ethylene-ethyl acrylate copolymers, ethylene-ethyl methacrylate copolymers, ionomer resins, EVA saponified products, and linear low density polyethylene (L-LDPE). Among these, linear low density polyethylene (L-LDPE) is common.
(接着性樹脂層)
接着性樹脂層は、通常、変性ポリオレフィン樹脂(APO)にて構成される。斯かるAPOは、エチレン成分および/またはプロピレン成分を主たる構成成分としたポリオレフィン樹脂にα,β不飽和カルボン酸またはその誘導体を共重合および/またはグラフト重合させて製造される。
(Adhesive resin layer)
The adhesive resin layer is usually composed of a modified polyolefin resin (APO). Such APO is produced by copolymerizing and / or graft-polymerizing an α, β unsaturated carboxylic acid or a derivative thereof to a polyolefin resin mainly composed of an ethylene component and / or a propylene component.
上記のポリオレフィン樹脂としては、例えば、ポリエチレン、ポリプロピレン、エチレ
ン−プロピレン共重合体、エチレン−ブテン−1共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−エチルアクリル酸共重合体、エチレン−アクリル酸ナトリウム共重合体などが挙げられる。
Examples of the polyolefin resin include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-ethylacrylic acid. Examples thereof include a copolymer and an ethylene-sodium acrylate copolymer.
上記の共重合されるα,β−不飽和カルボン酸またはその誘導体としては、アクリル酸、メタクリル酸、メチルメタクリル酸、アクリル酸ナトリウム、アクリル酸亜鉛、酢酸ビニル、グリシジルメタクリレート等が挙げられ、分子鎖中に40モル%以内の範囲内で含まれる。共重合変性ポリオレフィン樹脂としては、例えばエチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−エチルアクリル酸共重合体、エチレン−アクリル酸ナトリウム共重合体などが挙げられる。 Examples of the α, β-unsaturated carboxylic acid or derivative thereof to be copolymerized include acrylic acid, methacrylic acid, methyl methacrylic acid, sodium acrylate, zinc acrylate, vinyl acetate, glycidyl methacrylate, and the like. It is contained in the range within 40 mol%. Examples of the copolymer-modified polyolefin resin include an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-ethylacrylic acid copolymer, and an ethylene-sodium acrylate copolymer.
上記のグラフトされるα,β−不飽和カルボン酸またはその誘導体としては、例えば、アクリル酸、メタクリル酸、エタクリル酸、マレイン酸、フマル酸あるいはこれらの酸無水物、または、これらの酸のエステル等が挙げられる。これらの変性用化合物の中では、特に無水マレイン酸が好適である。また、グラフト量は、ポリオレフィン樹脂に対し0.01〜25重量%、好ましくは0.05〜1.5重量%の範囲から選択される。 Examples of the grafted α, β-unsaturated carboxylic acid or derivative thereof include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, acid anhydrides thereof, and esters of these acids. Is mentioned. Of these modifying compounds, maleic anhydride is particularly preferred. The graft amount is selected from the range of 0.01 to 25% by weight, preferably 0.05 to 1.5% by weight, based on the polyolefin resin.
グラフト反応は、常法に従い、通常、ポリオレフィン樹脂とα,β−不飽和カルボン酸またはその誘導体とを樹脂温度150〜300℃で溶融混合することにより行われる。グラフト反応に際しては、反応を効率よく行なわせるために、α,α′−ビス−t−ブチルパーオキシ−p−ジイソプロピルベンゼン等の有機過酸化物を0.001〜0.05重量%配合するのがよい。 The grafting reaction is usually performed by melt-mixing a polyolefin resin and an α, β-unsaturated carboxylic acid or a derivative thereof at a resin temperature of 150 to 300 ° C. according to a conventional method. In the grafting reaction, 0.001 to 0.05% by weight of an organic peroxide such as α, α'-bis-t-butylperoxy-p-diisopropylbenzene is blended in order to carry out the reaction efficiently. Is good.
本発明の多層フィルムは、共押出しインフレーション法にて得られ、実質的には未延伸フィルムである。具体的には、例えば水冷急冷法を採用した共押出しインフレーション法によって製造することが出来る。ここに、水冷急冷法とは、一般的には、ダイから押し出されたフイルムをダイの下方に配置した水槽に導いて冷却した後に巻き取る方法を言う。通常、環状ダイの下方にサイズ用リングが内部に備えられた水槽を配置し、当該水槽の下方に安内板と巻取ロールとを順次に配置して成る設備を使用し、そして、環状ダイから複数種類の原料樹脂を実質的に延伸が起こらない様に共押し出しし、サイズ用リングの間を通過させて冷却した後、積層フイルムの円筒体を安内板を通して巻取ロールに供給して折り畳み、ダブルフイルムとして巻き取る。なお、共押出しインフレーション法に代えてTダイ法を採用してもよい。 The multilayer film of the present invention is obtained by a coextrusion inflation method and is substantially an unstretched film. Specifically, for example, it can be produced by a co-extrusion inflation method employing a water-cooled rapid cooling method. Here, the water-cooled rapid cooling method generally refers to a method in which a film extruded from a die is introduced into a water tank disposed below the die and cooled, and then wound up. Usually, a water tank provided with a size ring inside is arranged below the annular die, and an equipment comprising an an inner plate and a winding roll are sequentially arranged below the water tank, and the annular die is used. After co-extrusion of multiple types of raw resin so that stretching does not occur substantially, and after passing through the size ring and cooling, supply the cylindrical body of the laminated film to the take-up roll through the inner plate Fold it and wind it up as a double film. Note that the T-die method may be employed instead of the co-extrusion inflation method.
上記の様にして得られる本発明の多層フィルムは、通常、長さ方向(MD)及び幅方向(TD)の加熱収縮率(JIS K 6734)が何れも5%以下である。 The multilayer film of the present invention obtained as described above usually has a heat shrinkage ratio (JIS K 6734) in the length direction (MD) and the width direction (TD) of 5% or less.
本発明の多層フィルムにおいて、外層の厚さは、通常2〜50μm、好ましくは4〜30μm、ガスバリヤ層の厚さは、通常5〜70μm、好ましくは10〜50μm、ヒートシール層の厚さは、通常20〜100μm、好ましくは30〜70μm、各層間に配置される接着層の厚さは、通常2〜30μm、好ましくは5〜15μmとされる。 In the multilayer film of the present invention, the thickness of the outer layer is usually 2 to 50 μm, preferably 4 to 30 μm, the thickness of the gas barrier layer is usually 5 to 70 μm, preferably 10 to 50 μm, and the thickness of the heat seal layer is Usually, the thickness of the adhesive layer arranged between each layer is 20-30 μm, preferably 30-70 μm, and usually 2-30 μm, preferably 5-15 μm.
本発明の多層フィルムは、底材として各種の食品の深絞り包装に使用されるが、蓋材としては、本発明の多層フィルムの他、延伸ナイロン(ONy)/LLDPE、未延伸ポリプロピレン(CPP)/ONy/LLDPE等の蓋材として従来公知の多層フィルムが使用される。特に、本発明の多層フィルムは、その特徴を活かし、冷凍製品包装用として使用するのが好ましい。 The multilayer film of the present invention is used as a bottom material for deep-drawing packaging of various foods. As the cover material, in addition to the multilayer film of the present invention, stretched nylon (ONy) / LLDPE, unstretched polypropylene (CPP) A conventionally known multilayer film is used as a lid material such as / ONy / LLDPE. In particular, the multilayer film of the present invention is preferably used for packaging of frozen products taking advantage of its characteristics.
以下、本発明を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.
実施例1〜5及び比較例1、2:
先ず、表1に示す材料を使用し、水冷急冷法を採用した共押出インフレーション法によって、表2に示す総厚み200μの多層フィルムを製膜した。次いで、底材に表2に示す多層フィルムを使用し、蓋材に表3に示す多層フィルムを使用し、ムルチバック社製の深絞り成型機「R530」によって、ハンバーグを真空包装し、真空包装後、98℃で60分間ボイル殺菌した。そして、以下の各項目についての評価を行った。結果を表4及び表5に示す。
Examples 1 to 5 and Comparative Examples 1 and 2:
First, using the materials shown in Table 1, a multilayer film having a total thickness of 200 μ shown in Table 2 was formed by a coextrusion inflation method employing a water-cooled quenching method. Next, the multilayer film shown in Table 2 is used for the bottom material, the multilayer film shown in Table 3 is used for the lid, and the hamburger is vacuum-packed by a deep drawing machine “R530” manufactured by Mulchback Co., Ltd. Then, it boil-sterilized at 98 degreeC for 60 minutes. And the following items were evaluated. The results are shown in Tables 4 and 5.
(1)フランジのカール:
ボイル殺菌後にフランジのカール高さを測定した。蓋材とのシール部が10mm以上カールしているものは「×」、10mm未満のものは「○」とした。
(1) Flange curl:
The curl height of the flange was measured after boil sterilization. The case where the seal portion with the lid material is curled by 10 mm or more is indicated as “X”, and the case where the seal portion is less than 10 mm is indicated as “◯”.
(2)耐ピンホール性:
ボイル殺菌後に、−18℃で48時間以上冷凍保管し、振動試験機にて2000Km輸送に相当の試験を実施し、ピンホールの発生率を比較した。ピンホールの発生率が20%以上の場合には「×」、20%未満の場合に「○」した。
(2) Pinhole resistance:
After boil sterilization, the sample was stored frozen at −18 ° C. for 48 hours or more, a test equivalent to 2000 km transportation was carried out using a vibration tester, and the incidence of pinholes was compared. When the pinhole occurrence rate was 20% or more, “X” was indicated, and when it was less than 20%, “◯” was indicated.
(3)光沢:
ボイル殺菌後に目視にて比較した。光沢が失われていなかった場合は「○」、光沢が失われた場合は「×」とした。
(3) Gloss:
Visual comparison was made after boil sterilization. When the gloss was not lost, “◯” was indicated, and when the gloss was lost, “X” was indicated.
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