JP3248650B2 - Multilayer film, multilayer sheet and container laminated with the same - Google Patents
Multilayer film, multilayer sheet and container laminated with the sameInfo
- Publication number
- JP3248650B2 JP3248650B2 JP14811494A JP14811494A JP3248650B2 JP 3248650 B2 JP3248650 B2 JP 3248650B2 JP 14811494 A JP14811494 A JP 14811494A JP 14811494 A JP14811494 A JP 14811494A JP 3248650 B2 JP3248650 B2 JP 3248650B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- sheet
- resin layer
- multilayer film
- multilayer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 claims description 124
- 239000011347 resin Substances 0.000 claims description 124
- 239000010410 layer Substances 0.000 claims description 82
- 239000004743 Polypropylene Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 13
- -1 polypropylene Polymers 0.000 claims description 13
- 239000004840 adhesive resin Substances 0.000 claims description 12
- 229920006223 adhesive resin Polymers 0.000 claims description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 12
- 229920001225 polyester resin Polymers 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 229920005668 polycarbonate resin Polymers 0.000 claims description 7
- 239000004431 polycarbonate resin Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 14
- 239000003205 fragrance Substances 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 14
- 239000005020 polyethylene terephthalate Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 11
- 235000013305 food Nutrition 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 7
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 7
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 235000015205 orange juice Nutrition 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920005673 polypropylene based resin Polymers 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 230000001953 sensory effect Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 2
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101000986765 Homo sapiens Oxytocin receptor Proteins 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 102100028139 Oxytocin receptor Human genes 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 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
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリプロピレン系樹脂、
ポリスチレン系樹脂等からなる賦形性樹脂シートに対し
熱接着性を有し、低臭性、保香性及び酸素バリアー性に
優れた熱接着用多層フィルム、その多層フィルムと賦形
性樹脂シートとを熱接着した多層シート及びそれを成形
した容器に関するものである。主な利用分野は、食品包
装材分野であり、これを用いることによってプラスチッ
ク臭気の食品への吸着防止、食品の香気成分の保持、食
品の酸素による劣化の防止が可能になる。より具体的に
は、常温流通可能な無菌加工米飯や、レトルト食品向け
の包装材料として使用できる。The present invention relates to a polypropylene resin,
It has a thermal adhesive property to a shape-forming resin sheet made of a polystyrene-based resin and the like, and has a low-odor property, a fragrance-retaining property and an excellent oxygen-barrier property. And a container formed from the same. The main application field is the food packaging material field, and by using this, it is possible to prevent the adsorption of plastic odor to foods, to retain food flavor components, and to prevent foods from deteriorating due to oxygen. More specifically, it can be used as a packaging material for aseptically processed cooked rice that can be distributed at room temperature or for retort foods.
【０００２】[0002]
【従来の技術】従来、レトルト食品等酸素バリアー性の
必要な素材の包装材料としては、ポリプロピレン系樹脂
（以下ＰＰと略記する）とエチレン−酢酸ビニル共重合
体鹸化物（以下ＥＶＯＨと略記する）との複合シートが
主にＰＰ／接着材層（以下ＡＤと略記する）／ＥＶＯＨ
／ＡＤ／ＰＰといった構成のシートとして、幅広く使用
されている。しかし、この食品包装材の欠点は、食品と
接触する面がＰＰであることから、ＰＰ中に存在する臭
気成分（製造時の分解生成物、ＰＰ中に含まれる炭化水
素類、添加剤等）が包装後に食品に移行したり、食品の
持つ香気成分がＰＰに吸着されるといった問題があっ
た。2. Description of the Related Art Conventionally, packaging materials for materials requiring oxygen barrier properties, such as retort foods, are polypropylene resin (hereinafter abbreviated as PP) and saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH). Is mainly composed of PP / adhesive layer (hereinafter abbreviated as AD) / EVOH
It is widely used as a sheet having a configuration such as / AD / PP. However, the disadvantage of this food packaging material is that since the surface that comes into contact with food is PP, odor components present in PP (decomposition products during production, hydrocarbons contained in PP, additives, etc.) However, there has been a problem that after packaging, the food is transferred to the food, or a flavor component of the food is adsorbed to the PP.
【０００３】[0003]
【発明が解決しようとする課題】このように従来より低
臭性、保香性及び酸素バリアー性に優れ、且つ、簡便に
作製することのできる多層シートがなく、これら特性を
有する包装材料が強く望まれていた。本発明者らは、低
臭性、保香性、酸素バリアー性、熱接着性及び成形性等
の特性を向上すべく鋭意検討した結果、ＰＥＴ等のポリ
エステル系樹脂ないしはポリカーボネート系樹脂層、酸
素バリアー性の高いＥＶＯＨ樹脂層、任意の賦形性樹脂
シートと熱接着可能な接着材層を有する熱接着用多層フ
ィルムを作成し、このフィルムを賦形性樹脂シートに簡
便な方法で熱接着することにより、かかる問題点を解決
できることを見いだし、本発明に至った。よって、本発
明の目的は、低臭性、保香性、酸素バリアー性、熱接着
性及び成形性等の特性に優れた包装材を提供することに
ある。As described above, there is no multi-layer sheet which is superior in low odor, fragrance retention and oxygen barrier properties and can be easily manufactured, and a packaging material having these characteristics is strongly used. Was desired. The present inventors have conducted intensive studies to improve properties such as low odor, fragrance retention, oxygen barrier properties, heat adhesion and moldability. As a result, polyester-based resins such as PET or polycarbonate-based resin layers, oxygen barrier A multi-layer film for heat bonding having a highly adhesive EVOH resin layer and an adhesive layer that can be thermally bonded to any shape-forming resin sheet, and heat-bonding this film to the shape-forming resin sheet by a simple method. As a result, it has been found that such a problem can be solved, and the present invention has been accomplished. Accordingly, an object of the present invention is to provide a packaging material having excellent properties such as low odor, fragrance retention, oxygen barrier properties, thermal adhesion, and moldability.
【０００４】[0004]
【課題を解決するための手段】すなわち、本発明は、ポ
リエステル系樹脂及びポリカーボネート系樹脂から選択
される１種以上の樹脂からなる樹脂層（Ａ）、接着性樹
脂層（Ｂ）、エチレン−酢酸ビニル共重合体鹸化物樹脂
層（Ｃ）及び接着性樹脂層（Ｄ）を有し、（Ａ）、
（Ｂ）、（Ｃ）及び（Ｄ）の順に構成されていて、
（Ｄ）が任意の賦形性樹脂シートと熱接着可能な接着材
層であることを特徴とする賦形性樹脂シートとの熱接着
用多層フィルムであり、該フィルムの片面もしくは両面
の表面層が、無機フィラーを含有しているか、又は、該
熱接着用多層フィルムを共押出法で作成する際に、ダイ
より押出された多層フィルムの片面もしくは両面が接す
るキャストロールもしくはタッチロールとして、表面を
粗面化したものを用いることにより、該熱接着用多層フ
ィルムの片面もしくは両面が、粗面化されていることが
好ましい。又、本発明は、前記の多層フィルムの接着性
樹脂層（Ｄ）面を、賦形性樹脂シート（Ｅ）の片面ない
しは両面に、熱接着する多層シートの製造方法であり、
該多層シートにおいて、賦形性シート（Ｅ）が、ポリプ
ロピレン系樹脂５０〜８０重量％、無機フィラー２０〜
５０重量％を含む樹脂組成物からなることが好ましい。
更に、本発明は、該多層シートを熱加工により成形した
容器である。That is, the present invention relates to a resin layer (A) comprising at least one resin selected from a polyester resin and a polycarbonate resin, an adhesive resin layer (B), and ethylene-acetic acid. (A) having a saponified vinyl copolymer resin layer (C) and an adhesive resin layer (D);
(B), (C) and (D) in order,
(D) is a multilayer film for heat bonding with a shape- forming resin sheet , characterized in that it is an adhesive layer capable of being thermally bonded to an arbitrary shape- forming resin sheet, and a surface layer on one side or both sides of the film. However, contains an inorganic filler, or, when preparing the multilayer film for thermal bonding by co-extrusion method, as a cast roll or touch roll contacting one or both sides of the multilayer film extruded from the die, the surface It is preferable that one or both surfaces of the multilayer film for thermal bonding is roughened by using a roughened one. Further, the present invention is a method for producing a multilayer sheet in which the surface of the adhesive resin layer (D) of the multilayer film is thermally bonded to one or both surfaces of the shape-forming resin sheet (E),
In the multilayer sheet, the shape-forming sheet (E) comprises 50 to 80% by weight of a polypropylene-based resin and 20 to 80% by weight of an inorganic filler.
It is preferable that the resin composition contains 50% by weight.
Further, the present invention is a container obtained by molding the multilayer sheet by thermal processing.
【０００５】以下、本発明を詳細に説明する。本発明の
樹脂層（Ａ）を構成する樹脂としては、ポリエステル系
樹脂、ポリカーボネート系樹脂といった低臭性、保香性
に優れた樹脂が用いられる。ポリエステル系樹脂として
は、高分子鎖にエステル結合を有する、テレフタル酸と
エチレングリコールを重縮合して得られるポリエチレン
テレフタレート（以下ＰＥＴと略記する）やテレフタル
酸とブチレングリコールを重縮合して得られるポリブチ
レンテレフタレート（以下ＰＢＴと略記する）が具体的
に挙げられる。また、加工特性を向上させる目的等で上
記ポリエステル中のジカルボン酸成分のコモノマーとし
てイソフタル酸、セバシン酸、アジピン酸、アゼライン
酸等を用いることができ、グリコール成分のコモノマー
として、ジエチレングリコール、ネオペンチルグリコー
ル、１，４−シクロヘキサンジメタノール等を共重合成
分として導入したＰＥＴ、ＰＢＴも用いることができ
る。また、前記に挙げたポリエステル系樹脂を１種また
は、２種以上混合した樹脂組成物や結晶化促進材、熱安
定剤、各種フィラーを添加した樹脂組成物も好適に用い
られる。Hereinafter, the present invention will be described in detail. As the resin constituting the resin layer (A) of the present invention, a resin having low odor and excellent in fragrance retention, such as a polyester resin and a polycarbonate resin, is used. Examples of the polyester-based resin include polyethylene terephthalate (hereinafter abbreviated as PET) obtained by polycondensation of terephthalic acid and ethylene glycol having an ester bond in a polymer chain, and polystyrene obtained by polycondensation of terephthalic acid and butylene glycol. Butylene terephthalate (hereinafter abbreviated as PBT) is specifically exemplified. Further, isophthalic acid, sebacic acid, adipic acid, azelaic acid, and the like can be used as a comonomer of the dicarboxylic acid component in the polyester for the purpose of improving processing characteristics, and diethylene glycol, neopentyl glycol, and the like. PET and PBT in which 1,4-cyclohexanedimethanol or the like is introduced as a copolymer component can also be used. Further, a resin composition in which one or more of the above-mentioned polyester resins are mixed, and a resin composition in which a crystallization accelerator, a heat stabilizer, and various fillers are added are also suitably used.
【０００６】ポリカーボネート系樹脂としては、高分子
鎖中にカーボネート結合を有するものが使用でき、ビス
フェノールＡとホスゲンとの反応で得られるもの等が挙
げられる。また、加工特性を向上させる目的等でビスフ
ェノールＡ以外の他の２価フェノールとしてハイドロキ
ノン、４，４−ジヒドロキシジフェニル、ビス（４−ヒ
ドロキシフェニル）アルカン、ビス（４−ヒドロキシフ
ェニル）シクロアルカン、ビス（４−ヒドロキシフェニ
ル）スルフィド、ビス（４−ヒドロキシフェニル）エー
テル等の化合物をコポリマーとして共重合させたものも
好適に用いられる。また、前記に挙げたポリカーボネー
ト系樹脂を１種または、２種以上混合した樹脂組成物や
熱安定剤、各種フィラーを添加した樹脂組成物も好適に
用いられる。さらに、加工性能向上の為に前記ポリエス
テル系樹脂及びポリカーボネート樹脂から選ばれた１種
または２種以上を混合したものも好適に用いれられる。As the polycarbonate resin, those having a carbonate bond in a polymer chain can be used, and examples thereof include those obtained by reacting bisphenol A with phosgene. Further, for the purpose of improving the processing characteristics, other dihydric phenols other than bisphenol A include hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis ( Those obtained by copolymerizing a compound such as 4-hydroxyphenyl) sulfide or bis (4-hydroxyphenyl) ether as a copolymer are also preferably used. Further, a resin composition in which one or more of the above-mentioned polycarbonate resins are mixed, a heat stabilizer, and a resin composition in which various fillers are added are also preferably used. Further, for improving the processing performance, a mixture of one or more selected from the polyester-based resins and the polycarbonate resins is also preferably used.
【０００７】本発明の樹脂層（Ａ）において、性能やコ
スト面からポリエステル系樹脂のなかではＰＥＴが、ポ
リカーボネート系樹脂の中では、ビスフェノールＡ以外
の２価フェノ−ルをコモノマーとして反応し加工適性を
向上させたものが特に好適に用いられる。In the resin layer (A) of the present invention, PET among polyester-based resins and divalent phenol other than bisphenol A as a comonomer among polycarbonate-based resins react as a comonomer from the viewpoint of performance and cost, and are suitable for processing. Particularly, those having improved properties are preferably used.
【０００８】次に接着性樹脂層（Ｂ）及び接着性樹脂層
（Ｄ）は、樹脂層（Ａ）、樹脂層（Ｃ）及び賦形性樹脂
シートとの接着性を有する物であれば特に限定するもの
では無く、無水マレイン酸、アクリル酸等の重合反応性
を有する酸含有ビニルモノマー、ビニルアクリレート、
メタメチルアクリレート等の重合反応性を有するエステ
ル含有ビニルモノマー、分子内にエポキシ基を含有する
ビニルモノマーとオレフィンとの共重合体等が用いられ
る。[0008] Next, the adhesive resin layer (B) and the adhesive resin layer (D) are not particularly limited as long as they have adhesiveness to the resin layer (A), the resin layer (C) and the shape-forming resin sheet. Without limitation, maleic anhydride, acid-containing vinyl monomer having polymerization reactivity such as acrylic acid, vinyl acrylate,
An ester-containing vinyl monomer having polymerization reactivity such as metamethyl acrylate, a copolymer of an olefin with a vinyl monomer having an epoxy group in the molecule, and the like are used.
【０００９】具体的には、無水マレイン酸と共重合した
直鎖状低密度ポリエチレン、エチレン−アクリル酸共重
合体（ＥＡＡ）、エチレン−メタアクリル酸共重合体
（ＥＭＡＡ）、エチレン−メチルメタアクリレート共重
合体（ＥＭＭＡ）、エチレン−酢酸ビニル共重合体（Ｅ
ＶＡ）等が挙げられる。またこれらの共重合体の混合物
及び、グラフト共重合体も好適に用いる事が出来る。特
に熱接着、即ち、熱ラミネート、押出しラミネート等で
の賦形性樹脂シートとの接着性から、接着性樹脂として
は、ビカット軟化点が８０℃未満のＥＶＡ系樹脂及び無
水マレイン酸変性ＰＥ樹脂を主成分として含有するもの
が好適に用いられる。樹脂層（Ｂ）及び樹脂層（Ｄ）
は、それぞれ異なった樹脂種を用いても良いが、後述す
る多層フィルムの製造工程を簡便にする為に、同一の樹
脂を用いたものが好ましい。Specifically, linear low density polyethylene copolymerized with maleic anhydride, ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate Copolymer (EMMA), ethylene-vinyl acetate copolymer (E
VA) and the like. Also, a mixture of these copolymers and a graft copolymer can be suitably used. In particular, due to thermal adhesion, that is, adhesiveness with a shape-forming resin sheet in heat lamination, extrusion lamination, etc., as the adhesive resin, an EVA-based resin having a Vicat softening point of less than 80 ° C. and a maleic anhydride-modified PE resin are used. Those containing as a main component are preferably used. Resin layer (B) and resin layer (D)
Although different resin types may be used, it is preferable to use the same resin in order to simplify the manufacturing process of a multilayer film described later.
【００１０】次に樹脂層（Ｃ）としては、酸素バリアー
性の高いエチレン−酢酸ビニル共重合体鹸化物が用いら
れる。具体的には、エチレン比が２０〜６０ｍｏｌ％で
酢酸ビニルの鹸化率が９０％以上のものが好適に用いら
れる。またその中でもエチレン比が３０〜５０ｍｏｌ％
で酢酸ビニルの鹸化率が９５％以上の物が、フィルム製
膜時の熱安定性に優れることから特に好ましい。Next, as the resin layer (C), a saponified ethylene-vinyl acetate copolymer having a high oxygen barrier property is used. Specifically, those having an ethylene ratio of 20 to 60 mol% and a saponification rate of vinyl acetate of 90% or more are suitably used. Among them, the ethylene ratio is 30 to 50 mol%
In particular, those having a saponification ratio of vinyl acetate of 95% or more are particularly preferred because of their excellent thermal stability during film formation.
【００１１】多層フィルムの厚み比は、特に限定するも
のでは無く、任意の厚み比をとることが出来る。多層フ
ィルムの厚み比は、樹脂層（Ａ）／樹脂層（Ｂ）／樹脂
層（Ｃ）／樹脂層（Ｄ）＝（２〜１０）／（１）／（２
〜１０）／（１〜３）が好ましく、低臭性、保香性、酸
素バリアー性、接着性及び成形性の面で良好な結果が得
られる。 さらに酸素バリアー性を考慮すると樹脂層
（Ｃ）の厚みが５μ以上であることが好ましい。多層フ
ィルムの総厚みは、特に限定するものでは無いが、前述
の樹脂層の最小厚みと賦形性樹脂シートとの接着性を考
慮すると２０〜５００μの範囲が好ましく、特に好まし
くは２０〜２５０μの範囲である。総厚みが５００μを
越えた場合は、熱圧着時の熱伝導が不良になり接着性が
低下する為に好ましくない。[0011] The thickness ratio of the multilayer film is not particularly limited, and may be any thickness ratio. The thickness ratio of the multilayer film is as follows: resin layer (A) / resin layer (B) / resin layer (C) / resin layer (D) = (2 to 10) / (1) / (2
-10) / (1-3) are preferable, and good results are obtained in terms of low odor, fragrance retention, oxygen barrier properties, adhesiveness and moldability. Further, in consideration of the oxygen barrier property, the thickness of the resin layer (C) is preferably 5 μm or more. The total thickness of the multilayer film is not particularly limited, but is preferably in the range of 20 to 500 μ, particularly preferably in the range of 20 to 250 μ in consideration of the minimum thickness of the resin layer and the adhesiveness with the shapeable resin sheet. Range. If the total thickness exceeds 500 μm, heat conduction during thermocompression bonding becomes poor and adhesiveness is reduced, which is not preferable.
【００１２】多層フィルムは、公知の手法により作成す
る事が出来るが、共押し出し法が好ましい。具体的に
は、３台以上の押出し機に各層を構成する樹脂を供給
し、ダイ内で積層するマルチマニホールドダイや、フィ
ードブロックを設置したコートハンガーダイでのキャス
ト法が挙げられる。また他の方法としては、各樹脂層を
単独でキャスト製膜やインフレーション製膜により作成
後、各樹脂層を規定の順番で熱圧着することによって作
成する事も出来る。The multilayer film can be prepared by a known method, but a co-extrusion method is preferred. Specifically, there is a casting method using a multi-manifold die in which a resin constituting each layer is supplied to three or more extruders and laminating in a die, or a coat hanger die provided with a feed block. As another method, it is also possible to form each resin layer independently by casting or inflation film forming and then thermocompression-bond each resin layer in a prescribed order.
【００１３】尚、多層フィルムの表面は、フィルム巻き
取り後に生じる、接着性樹脂層の粘着により、ポリエス
テル系樹脂ないしはポリカーボネート系樹脂層とのブロ
ッキング防止の為に、荒れていた方が好ましい。表面を
荒らす手法としては、樹脂層に無機フィラーを添加する
方法、及びフィルムを冷却固化させるキャストロール、
タッチロールの表面を粗面化したものを使用する方法等
が挙げられる。It is preferable that the surface of the multilayer film is rough due to the adhesion of the adhesive resin layer generated after winding the film to prevent blocking with the polyester resin or polycarbonate resin layer. As a method of roughening the surface, a method of adding an inorganic filler to the resin layer, and a cast roll for cooling and solidifying the film,
A method in which the surface of the touch roll is roughened is used.
【００１４】本発明の賦形性樹脂シート（Ｅ）を構成す
る樹脂は、多層フィルムと熱接着で接着後、真空成形や
圧空成形出来るものであれば、各種のものが使用出来
る。成形性の観点及び燃焼しても有害ガスを発生しない
点からポリプロピレン系樹脂、ポリスチレン系樹脂及び
ポリエチレンテレフタレート系樹脂が好適に使用され
る。Various resins can be used as the resin constituting the shape-forming resin sheet (E) of the present invention, as long as they can be vacuum-formed or pressure-formed after being bonded to the multilayer film by thermal bonding. A polypropylene-based resin, a polystyrene-based resin, and a polyethylene terephthalate-based resin are preferably used from the viewpoint of moldability and that no harmful gas is generated even when burned.
【００１５】シート（Ｅ）を構成するポリプロピレン系
樹脂としては、モノマーがプロピレン単独のプロピレン
ホモポリマー、エチレン等の他のオレフィンとのブロッ
クあるいはランダム共重合体や、ポリエチレン等他のポ
リオレフィン樹脂との混合物等が挙げられる。また、前
記ポリプロピレン系樹脂５０〜８０重量％とタルク、炭
酸カルシウム等の無機フィラーを２０〜５０重量％から
なる組成物が耐熱性良好であることから特に好適に使用
される。As the polypropylene resin constituting the sheet (E), the monomer is a propylene homopolymer of propylene alone, a block or random copolymer with other olefins such as ethylene, or a mixture with another polyolefin resin such as polyethylene. And the like. A composition comprising 50 to 80% by weight of the polypropylene resin and 20 to 50% by weight of an inorganic filler such as talc or calcium carbonate is particularly preferably used because of its good heat resistance.
【００１６】シート（Ｅ）を構成するポリスチレン系樹
脂としては、スチレン単独ポリマー、ゴム補強されたハ
イインパクトポリスチレン（以下ＨＩ−ＰＳと略記す
る）、スチレン−ブタジエン−スチレンブロック共重合
体等が挙げられる。また、スチレンと共重合性のあるメ
タクリル酸メチルやアクリロニトリル、ｎ−ブチルアク
リレート等の共重合体も好適に使用される。これらポリ
スチレン系樹脂は、１種あるいは２種以上混合した形で
使用することも出来る。また、ポリスチレン系樹脂５０
〜８０重量％と無機フィラーを２０〜５０重量％からな
る組成物も使用する事が出来る。Examples of the polystyrene resin constituting the sheet (E) include a styrene homopolymer, a rubber-reinforced high impact polystyrene (hereinafter abbreviated as HI-PS), a styrene-butadiene-styrene block copolymer and the like. . Further, copolymers such as methyl methacrylate, acrylonitrile, and n-butyl acrylate, which are copolymerizable with styrene, are also preferably used. These polystyrene resins can be used alone or in a mixture of two or more. In addition, polystyrene resin 50
A composition comprising about 80% by weight and 20 to 50% by weight of an inorganic filler can also be used.
【００１７】シート（Ｅ）を構成するポリエチレンテレ
フタレート系樹脂としては、具体的にはエチレングリコ
ールとテレフタル酸を重縮合して得られる一般的なポリ
エチレンテレフタレートや、成形時の結晶化抑制、加工
性改良等の為に、他のコモノマー成分を共重合させたコ
ポリマー型の物が挙げられる。コモノマー成分の具体例
としては、ジカルボン酸成分としてイソフタル酸、セバ
シン酸、アジピン酸、アゼライン酸等のもの、グリコー
ル成分として、ジエチレングリコール、ネオペンチルグ
リコール、１，４−シクロヘキサンジメタノール、ブタ
ンジオール等のものが挙げられる。Examples of the polyethylene terephthalate resin constituting the sheet (E) include a general polyethylene terephthalate obtained by polycondensation of ethylene glycol and terephthalic acid, crystallization suppression during molding, and improvement in processability. For example, a copolymer type product obtained by copolymerizing another comonomer component may be used. Specific examples of the comonomer component include dicarboxylic acid components such as isophthalic acid, sebacic acid, adipic acid, and azelaic acid, and glycol components include diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, and butanediol. Is mentioned.
【００１８】本発明における、賦形性樹脂シート（Ｅ）
の厚さは５０〜１５００μｍが好ましい。多層フィルム
と賦形性樹脂シート（Ｅ）との接着は、多層フィルムの
接着性樹脂層（Ｄ）面を賦形性樹脂シートの片面ないし
は両面に熱接着すれば特に限定されるものでは無い。具
体的には、多層フィルムとシート状の賦形性樹脂を同時
に給紙して加熱・圧着する熱ラミネート法や、賦形性樹
脂をシート状に製膜する段階で多層フィルムを供給−熱
接着する押出しラミネート法が好適に使用される。さら
に多層シートを容器に成形する直前に、容器寸法幅まで
にスリットした多層フィルムと賦形性樹脂シートを熱ラ
ミネート機に供給して熱接着し容器成形する方法が、再
使用困難な耳屑の発生量が少なくすみ、製造コストも低
く抑えられて特に好ましい。In the present invention, the shape-forming resin sheet (E)
Is preferably 50 to 1500 μm. The adhesion between the multilayer film and the shapeable resin sheet (E) is not particularly limited as long as the surface of the adhesive resin layer (D) of the multilayer film is thermally bonded to one or both surfaces of the shapeable resin sheet. Specifically, a multi-layer film and a sheet-like forming resin are simultaneously fed and heated / pressed, or a heat lamination method, or a multilayer film is supplied at the stage of forming the forming resin into a sheet-heat bonding. The extrusion lamination method is preferably used. Immediately before forming the multilayer sheet into a container, a method of supplying a multilayer film slit to the width of the container and a shapeable resin sheet to a heat laminating machine and thermally bonding the container to form a container is difficult to reuse. It is particularly preferable because the generation amount is small and the production cost is also low.
【００１９】尚、本発明においては、該多層フィルムが
賦形性樹脂シートの少なくとも片面に接着していれば良
く、酸素バリアー性の向上や包装体の外面に対する低臭
性、保香性を期待して同一面に同一多層フィルムを２層
以上接着することや、賦形性樹脂層の両面に多層フィル
ムを接着することを制限するものでは無い。多層シート
中の多層フィルムと賦形性樹脂シートの厚み比及び総厚
みは、特に限定されるものでは無いが、多層シートを真
空成形や圧空成形で賦形する際の成形性を考慮すると、
多層フィルム／賦形性樹脂シートの比＝（１）／（１以
上）、特に好ましくは（１）／（１．５以上）である。
又、総厚みは、１００〜２０００μが好ましい。総厚み
が１００μ未満及び２０００μを越えると、容器を成形
する成形条件幅が非常に狭くなり、良好な容器を得るこ
とが困難になる。In the present invention, it is sufficient that the multilayer film is adhered to at least one surface of the shape-forming resin sheet, and an improvement in oxygen barrier properties, a low odor property on the outer surface of the package, and a fragrance retention property are expected. There is no limitation on bonding two or more layers of the same multilayer film to the same surface and bonding the multilayer film to both surfaces of the shape-forming resin layer. The thickness ratio and the total thickness of the multilayer film and the shapeable resin sheet in the multilayer sheet are not particularly limited, but when considering the moldability when shaping the multilayer sheet by vacuum forming or pressure forming,
The ratio of the multilayer film / the shapeable resin sheet = (1) / (1 or more), particularly preferably (1) / (1.5 or more).
Further, the total thickness is preferably from 100 to 2000 μ. When the total thickness is less than 100 μm or more than 2000 μm, the width of molding conditions for molding the container becomes very narrow, and it becomes difficult to obtain a good container.
【００２０】本発明における容器とは、該多層シートを
熱加工して成形出来る各種のものが挙げられる。成形方
法は特に限定するものでは無く、具体的には熱、圧、負
圧を利用した真空成形や圧空成形等のものが挙げられ
る。またこれら成形によって作製される容器としては、
カップ、トレイ等のものが挙げられる。尚、最終的な容
器形態としては、樹脂層（Ａ）が容器内面（被包装物と
接触する面）に配置された形態が望ましい。しかし、賦
形性樹脂層にＰＥＴ等の保香性樹脂を用いれば、樹脂層
（Ａ）を容器の内・外面どちらに用いても同等の効果が
得られることから、樹脂層（Ａ）の位置を特に限定する
ものでは無い。The container in the present invention includes various containers which can be formed by subjecting the multilayer sheet to heat processing. The molding method is not particularly limited, and specific examples include vacuum molding using heat, pressure, and negative pressure, and pressure molding. In addition, as containers produced by these moldings,
Examples include cups and trays. In addition, as a final container form, a form in which the resin layer (A) is disposed on the inner surface of the container (the surface that comes into contact with the item to be packaged) is desirable. However, if a fragrance retaining resin such as PET is used for the shape-forming resin layer, the same effect can be obtained regardless of whether the resin layer (A) is used for the inner or outer surface of the container. The position is not particularly limited.
【００２１】[0021]
【実施例】以下実施例により本発明を詳述する。尚、各
実施例及び比較例に記載の樹脂特性評価方法及び多層フ
ィルム、積層体シート及び容器の各種測定方法について
は後述する。The present invention will be described in detail with reference to the following examples. In addition, the resin property evaluation methods and the various measurement methods of the multilayer film, the laminate sheet, and the container described in each of Examples and Comparative Examples will be described later.
【００２２】実施例１ 樹脂層（Ａ）としてＩＶ＝０．７５のポリエチレンテレ
フタレート（ＰＥＴと略記する）、樹脂層（Ｂ）及び樹
脂層（Ｄ）としてＥＶＡ樹脂（三菱化成（株）社製、商
品名「ＡＸ１４３Ｅ」）、樹脂層（Ｃ）としてエチレン
−酢酸ビニル共重合体鹸化物（ＥＶＯＨと略記する、ク
ラレ（株）社製、商品名「Ｅ−１５１Ｂ」、ＭＩ＝１．
６、エチレン含量４４ｍｏｌ％）を用いた。Example 1 Polyethylene terephthalate (abbreviated as PET) with IV = 0.75 as the resin layer (A), and EVA resin (manufactured by Mitsubishi Kasei Co., Ltd.) as the resin layer (B) and the resin layer (D). Trade name "AX143E"), saponified ethylene-vinyl acetate copolymer (EVOH, Kuraray Co., Ltd., trade name "E-151B", MI = 1.
6, ethylene content 44 mol%).
【００２３】（製膜）３台の４０ｍｍφ押出し機と３種
４層積層用のフィードブロック及びコートハンガーダイ
を備えた共押出設備を用い、前記の樹脂を供給し、キャ
スト法により樹脂層（Ａ）／樹脂層（Ｂ）／樹脂層
（Ｃ）／樹脂層（Ｄ）の順に構成され、構成比が２０μ
／１０μ／３０μ／１０μである３種４層の多層フィル
ムを作成した。尚、製膜の際表面になる樹脂層（Ａ）を
荒らす為に、キャストのタッチロールは粗面化したもの
を用いた。(Coating) Using a co-extrusion facility equipped with three 40 mmφ extruders, a feed block for laminating three types and four layers, and a coat hanger die, the resin is supplied, and the resin layer (A) is cast by a casting method. ) / Resin layer (B) / resin layer (C) / resin layer (D) in the order of 20 μm.
A multilayer film of three types and four layers of / 10 μ / 30 μ / 10 μ was prepared. In addition, in order to roughen the resin layer (A) which becomes a surface at the time of film formation, the cast touch roll used what was roughened.
【００２４】（各種評価）表１に得られた多層フィルム
の各種評価結果をしめす。本発明品が十分な酸素バリア
ー性、層間接着強度、賦形性樹脂接着強度、低臭性、保
香性を示していることがわかる。(Various evaluations) Table 1 shows the results of various evaluations of the multilayer film obtained. It can be seen that the product of the present invention shows sufficient oxygen barrier properties, interlayer adhesive strength, shapeable resin adhesive strength, low odor, and fragrance retention.
【００２５】実施例２ 樹脂層（Ｂ）として酸変性ＰＥ（ポリエチレン）（三井
石油化学（株）社製、商品名「ＳＦ６００」）を使用し
た以外は、実施例１と同様の樹脂及び構成比となる様に
製膜し、多層フィルムを作成した。実施例１と同様の評
価を行い、結果を表１に記載した。各種特性で良好な結
果が得られた。Example 2 The same resin and composition ratio as in Example 1 except that an acid-modified PE (polyethylene) (trade name “SF600” manufactured by Mitsui Petrochemical Co., Ltd.) was used as the resin layer (B). To form a multilayer film. The same evaluation as in Example 1 was performed, and the results are shown in Table 1. Good results were obtained with various characteristics.
【００２６】実施例３ 樹脂層（Ａ）として変性ＰＣ（ポリカーボネート）（日
本ＧＥプラスチック（株）社製、商品名「のＳＰ１０１
０」）を使用した以外は実施例１と同様の樹脂及び構成
比となる様に製膜し、多層フィルムを作成した。実施例
１と同様の評価を行い、結果を表１に記載した。各種特
性で良好な結果が得られた。Example 3 Modified PC (polycarbonate) (manufactured by Nippon GE Plastics Co., Ltd., trade name "SP101") as the resin layer (A)
0)), except that resin was used and the composition ratio was the same as in Example 1 to prepare a multilayer film. The same evaluation as in Example 1 was performed, and the results are shown in Table 1. Good results were obtained with various characteristics.
【００２７】実施例４ 樹脂層（Ａ）としてＩＶ＝０．７５のＰＥＴが８０重量
％及びＩＶ＝０．７のＰＢＴが２０重量％のブレンド物
を用いた以外は、実施例１と同様の樹脂及び構成比とな
る様に製膜し、多層フィルムを作成した。実施例１と同
様の評価を行い結果を表１に記載した。各種特性で良好
な結果が得られた。Example 4 A resin layer (A) was prepared in the same manner as in Example 1 except that a blend of 80% by weight of PET with IV = 0.75 and 20% by weight of PBT with IV = 0.7 was used. A film was formed so as to have a resin and a composition ratio to prepare a multilayer film. The same evaluation as in Example 1 was performed, and the results are shown in Table 1. Good results were obtained with various characteristics.
【００２８】実施例５ 樹脂層（Ａ）としてＩＶ＝０．７５のＰＥＴが８０重量
％及び変性ＰＣ（ＳＰ１０１０）２０重量％のブレンド
物を用いた以外は、実施例１と同様の樹脂及び構成比と
なる様に製膜し、多層フィルムを作成した。実施例１と
同様の評価を行い結果を表１に記載した。各種特性で良
好な結果が得られた。Example 5 The same resin and composition as in Example 1 except that a blend of 80% by weight of PET with IV = 0.75 and 20% by weight of modified PC (SP1010) was used as the resin layer (A). The film was formed so as to have a ratio, and a multilayer film was prepared. The same evaluation as in Example 1 was performed, and the results are shown in Table 1. Good results were obtained with various characteristics.
【００２９】実施例６ 樹脂層（Ｂ）及び樹脂層（Ｄ）として、ＥＶＡ樹脂（三
菱化成（株）社製、商品名「ＡＸ１４３Ｅ」）が８０重
量％と酸変性ＰＥ（ＳＦ６００）が２０重量％のブレン
ド物を用いた以外は、実施例１と同様の樹脂及び構成比
となる様に製膜し、多層フィルムを作成した。実施例１
と同様の評価を行い結果を表１に記載した。各種特性で
良好な結果が得られた。Example 6 As the resin layer (B) and the resin layer (D), 80% by weight of an EVA resin (trade name “AX143E” manufactured by Mitsubishi Kasei Co., Ltd.) and 20% by weight of acid-modified PE (SF600) were used. %, Except that a blend was used to form a multilayer film. Example 1
The same evaluation was performed and the results are shown in Table 1. Good results were obtained with various characteristics.
【００３０】比較例１ 樹脂層（Ａ）としてＰＰ（ＭＩ＝１、ホモポリマー型）
を使用した以外は実施例１と同様の樹脂及び構成比とな
る様に製膜し、多層フィルムを作成した。実施例１と同
様の評価を行い結果を表１に記載した。本フィルムは、
保香性、低臭性の面で実施例に比較し劣っていた。Comparative Example 1 PP (MI = 1, homopolymer type) as the resin layer (A)
A film was formed so as to have the same resin and composition ratio as in Example 1 except for using, to prepare a multilayer film. The same evaluation as in Example 1 was performed, and the results are shown in Table 1. This film is
It was inferior to Examples in terms of fragrance retention and low odor.
【００３１】比較例２ 樹脂層（Ｂ）及び樹脂層（Ｄ）としてＰＰ（ＭＩ＝１、
ホモポリマ−型）を使用した以外は実施例１と同様の樹
脂及び構成比となる様に製膜し、多層フィルムを作成し
た。実施例１と同様の評価を行い結果を表１に記載し
た。本フィルムは層間接着性及びＰＰ以外の賦形性樹脂
層（Ｅ）との接着性が劣っていた。Comparative Example 2 As the resin layer (B) and the resin layer (D), PP (MI = 1,
Except for using a homopolymer type), a film was formed to have the same resin and composition ratio as in Example 1 to prepare a multilayer film. The same evaluation as in Example 1 was performed, and the results are shown in Table 1. This film was inferior in interlayer adhesiveness and adhesiveness with the shape-forming resin layer (E) other than PP.
【００３２】実施例７ 実施例１で得られた多層フィルムの樹脂層（Ｄ）面をタ
ルク３０％充填ＰＰからなる形性樹脂シート（Ｅ）と熱
ラミネートし多層シートを得た。これを用いた成型容器
は外観上問題無かった。また、該多層シートを熱加工し
て得られた容器は、十分な酸素バリアー性を有し、低臭
性、保香性に優れていた。Example 7 The resin layer (D) of the multilayer film obtained in Example 1 was thermally laminated with a formable resin sheet (E) made of PP filled with talc 30% to obtain a multilayer sheet. The molded container using this had no problem in appearance. Further, the container obtained by subjecting the multilayer sheet to thermal processing had sufficient oxygen barrier properties, and was excellent in low odor and fragrance retention.
【００３３】実施例８ 実施例３に記載の多層フィルムを用いた事以外は、実施
例７と同様に行い、表２に記載した評価結果を得た。本
実施例で得られた容器も成形性、低臭性、保香性が優れ
ていた。Example 8 The same procedures as in Example 7 were carried out except that the multilayer film described in Example 3 was used, and the evaluation results shown in Table 2 were obtained. The container obtained in this example was also excellent in moldability, low odor, and fragrance retention.
【００３４】実施例９ 実施例５に記載の多層フィルムを用いた事以外は、実施
例７と同様に行い、表２に記載した評価結果を得た。本
実施例で得られた容器も成形性、低臭性、保香性が優れ
ていた。Example 9 The same procedure as in Example 7 was carried out except that the multilayer film described in Example 5 was used, and the evaluation results shown in Table 2 were obtained. The container obtained in this example was also excellent in moldability, low odor, and fragrance retention.
【００３５】比較例３ タルク３０％添加ＰＰ（以下ＰＰ−Ｆと略記する）、Ｅ
ＶＡ樹脂及びＥＶＯＨ樹脂を使用し、層構成ＰＰ−Ｆ／
ＥＶＡ／ＥＶＯＨ／ＥＶＡ／ＰＰ−Ｆ（構成比２５０／
２０／３０／２０／２５０μ）からなるシートを３種５
層のキャスト法共押出し設備にて作成し、実施例７に記
載の方法にて同形状の容器の成形及び評価を実施し、評
価結果を表２に記載した。本比較例は実施例 ７，８，
９に比較し保香性、低臭性が極めて劣っていた。Comparative Example 3 PP containing 30% talc (hereinafter abbreviated as PP-F), E
Using VA resin and EVOH resin, layer structure PP-F /
EVA / EVOH / EVA / PP-F (composition ratio 250 /
20/30/20 / 250μ) 3 sheets 5
The layers were formed by a co-extrusion method using a cast method, and a container having the same shape was molded and evaluated by the method described in Example 7, and the evaluation results are shown in Table 2. This comparative example is described in Examples 7, 8,
Compared with No. 9, the fragrance retention and the low odor were extremely poor.
【００３６】比較例４ ２０μ厚の無延伸ＰＥＴフィルムを比較例３に記載の総
厚さ０．５７ｍｍで、ＰＰ−Ｆ／ＥＶＡ／ＥＶＯＨ／Ｅ
ＶＡ／ＰＰ−Ｆの構成からなる多層シートにポリウレタ
ン系の接着剤でドライラミネートした。無延伸ＰＥＴフ
ィルムが容器の内側になるように実施例７に記載の方法
にて同形状の容器の成形を行い、評価した。評価結果を
表２に記載した。本比較例は実施例 ７，８，９に比較
し低臭性が劣っている。Comparative Example 4 A non-stretched PET film having a thickness of 20 μm was prepared by using PP-F / EVA / EVOH / E with a total thickness of 0.57 mm described in Comparative Example 3.
A multilayer sheet having a VA / PP-F configuration was dry-laminated with a polyurethane adhesive. A container having the same shape was formed by the method described in Example 7 so that the unstretched PET film was inside the container, and the container was evaluated. The evaluation results are shown in Table 2. This comparative example is inferior to Examples 7, 8, and 9 in low odor.
【００３７】（樹脂特性評価方法） （１）固有粘度（ＩＶ） 固有粘度（ＩＶ）とは、溶媒としてフェノール／テトラ
クロロエタン（重量比：５０／５０）を用い、その溶液
濃度が０．５ｇ／１０ミリリットルにて、３０℃の恒温
槽でウベローデ粘度計を用いて測定した粘度を示す。 （２）ＭＩ ＭＩは、ＪＩＳ Ｋ ７２１０に準じて、１９０℃ 荷
重２．１６ｋｇの条件で、１０分間当りに流動した樹脂
の重量を示す。 （多層フィルム、多層シート及び容器の各種測定方法） （３）酸素バリアー性 酸素透過率測定機（モコン社 ＯＸＴＲＡＮ−１０／５
０Ａ）にて、２３℃５０％ＲＨ下で酸素透過率を測定す
る。 （４）層間接着性 ３種４層フィルムの樹脂層（Ａ）／樹脂層（Ｂ）／樹脂
層（Ｃ）／樹脂層（Ｄ）の樹脂層（Ｂ）と樹脂層（Ｃ）
の間を引き剥し、２種２層フィルムを得た。この２層フ
ィルムの接着界面を引き剥し、剥離強度を測定した。剥
離角１８０゜、１５ｍｍ幅、引張り速度 ２００ｍｍ／
ｍｉｎの条件で剥離試験を実施し、その時の値を層間接
着強度とした。層間接着強度の単位は、ｇ／１５ｍｍで
ある。(Resin Characteristic Evaluation Method) (1) Intrinsic Viscosity (IV) Intrinsic viscosity (IV) means phenol / tetrachloroethane (weight ratio: 50/50) as a solvent and a solution concentration of 0.5 g / It shows the viscosity measured using a Ubbelohde viscometer in a thermostat at 30 ° C. at 10 ml. (2) MI MI indicates the weight of the resin flowing per 10 minutes under the conditions of 190 ° C. and a load of 2.16 kg according to JIS K7210. (Various measuring methods for multilayer films, multilayer sheets, and containers) (3) Oxygen barrier property Oxygen permeability measuring instrument (OXTRAN-10 / 5, Mocon Corporation)
At 0A), the oxygen permeability is measured at 23 ° C. and 50% RH. (4) Interlayer adhesion Resin layer (A) / resin layer (B) / resin layer (C) / resin layer (D) resin layer (B) and resin layer (C) of three-layer four-layer film
Was peeled off to obtain a two-layer, two-layer film. The adhesive interface of the two-layer film was peeled off, and the peel strength was measured. 180 ° peel angle, 15mm width, pulling speed 200mm /
The peel test was performed under the condition of min, and the value at that time was defined as the interlayer adhesive strength. The unit of the interlayer adhesive strength is g / 15 mm.
【００３８】（５）賦形性樹脂シートの接着性 ロール表面温度８０℃の熱ラミネート機にて、多層フィ
ルム（接着性樹脂層が接着面とする）と、賦形性樹脂シ
ート（Ｅ）として０．５ｍｍ厚で、タルク３０％添加Ｐ
Ｐ（ホモポリマー型ＰＰにタルク３０％添加）、０．５
ｍｍ厚のＨＩ−ＰＳ、０．５ｍｍ厚のＰＥＴシートを用
い、それぞれ２ｍ／分のライン速度で供給し熱ラミネー
トを行った。熱ラミネートを実施したシートを１５ｍｍ
幅で取り出し、多層フィルムと賦形性樹脂シートとの接
着界面を剥離界面として、剥離角１８０゜、引張り速度
２００ｍｍ／ｍｉｎで剥離試験を実施し、その時の剥
離強度を多層フィルムと賦形性樹脂シート（Ｅ）との接
着強度とした。対賦形性樹脂シートとの接着強度は、ｇ
／１５ｍｍである。 （６）低臭性 多層フィルムを用い、内面に樹脂層（Ａ）が来るように
し、内容積２００ｃｃの袋を作成し、中に空気を詰めた
まま袋を封じて、８０℃のオーブンに１時間入れる。１
時間経過後に、袋内部の臭気を官能評価する。 （７）保香性 多層フィルムを用い、内面に樹脂層（Ａ）が来るように
し、内容積２００ｃｃの袋を作成し、中にオレンジジュ
ースをヘッドスペースを生じないように入れて密封す
る。このオレンジシュースを１０℃で１ケ月保存。この
オレンジジュ−スの風味を官能評価を行う。(5) Adhesiveness of Shapeable Resin Sheet A multi-layer film (adhesive resin layer is an adhesive surface) and a shapeable resin sheet (E) by a heat laminating machine at a roll surface temperature of 80 ° C. 0.5mm thick, 30% talc added P
P (30% talc added to homopolymer type PP), 0.5
A HI-PS having a thickness of mm and a PET sheet having a thickness of 0.5 mm were supplied at a line speed of 2 m / min to perform thermal lamination. 15mm heat-laminated sheet
The film was taken out in width, and a peeling test was performed at a peel angle of 180 ° and a pulling speed of 200 mm / min using the adhesive interface between the multilayer film and the shapeable resin sheet as the peeling interface. The adhesive strength with the sheet (E) was used. The adhesive strength with the shape-forming resin sheet is g
/ 15 mm. (6) Low odor property Using a multilayer film, make the resin layer (A) come on the inner surface, make a bag with an inner volume of 200 cc, seal the bag with the air filled therein, and place it in an 80 ° C. oven. Insert time. 1
After a lapse of time, the odor inside the bag is sensory evaluated. (7) Perfume retention Using a multilayer film, a resin layer (A) is provided on the inner surface, a bag with an inner volume of 200 cc is prepared, and orange juice is put into the bag so as not to generate a head space and sealed. Store this orange sauce at 10 ° C for one month. The taste of the orange juice is subjected to a sensory evaluation.
【００３９】（成形性及び容器評価方法） （８）成形性 多層フィルムと賦形性樹脂シート（Ｅ）を熱ラミネート
して得られる多層シートを用い、それぞれ開口部９５ｍ
ｍφ、高さ４５ｍｍの丸型カップを真空成形機で成形
し、カップの外観を観察し成形性を評価した。 （９）酸素バリアー性 前記成形容器の内、賦形性樹脂層（Ｅ）としてＰＰ−Ｆ
シートを用いた成形品の開口部をステンレス箔にエポキ
シ樹脂で貼り付ける。容器外部環境を２３℃ ５０％Ｒ
Ｈの空気とし、酸素透過率測定機［モコン社 ＯＸＴＲ
ＡＮ−１０／５０Ａ］にてこの容器の酸素透過率を測定
した。 （１０）低臭性 前記成形容器の内、賦形性樹脂シート（Ｅ）としてＰＰ
−Ｆシートを用いて得た成形品に０．０３ｍｍのアルミ
ホイルで蓋をして８０℃のオーブンにいれて、３０分間
加熱した。加熱後に取り出し、容器内部の臭気を官能評
価した。 （１１）保香性 前記成形容器の内、賦形性樹脂シート（Ｅ）としてＰＰ
−Ｆシートを用いて得た成形品にオレンジジュースをヘ
ッドスペースが無いように充填して、０．０３ｍｍのア
ルミホイルを蓋材として、ＥＶＡ系ホットメルト接着剤
で密封し、１０℃で１ケ月間保存する。１ケ月後に開
封、オレンジジュースの風味を官能評価した。(Formability and Container Evaluation Method) (8) Formability A multilayer film obtained by heat laminating a multilayer film and a shapeable resin sheet (E) was used, and each opening was 95 m long.
A round cup having a diameter of mφ and a height of 45 mm was molded by a vacuum molding machine, and the appearance of the cup was observed to evaluate the moldability. (9) Oxygen barrier property PP-F is used as the shape-forming resin layer (E) in the molding container.
The opening of the molded product using the sheet is attached to stainless steel foil with epoxy resin. The environment outside the container is 23 ℃ 50% R
H air and oxygen permeability meter [MOCON OXTR
AN-10 / 50A], the oxygen permeability of this container was measured. (10) Low-odor property Of the above-mentioned molding container, PP is used as the shape-forming resin sheet (E).
The molded product obtained using the -F sheet was covered with a 0.03 mm aluminum foil, placed in an oven at 80 ° C, and heated for 30 minutes. After heating, the container was taken out, and the odor inside the container was organoleptically evaluated. (11) Perfume-retaining property Of the above-mentioned molded container, PP is used as the shape-forming resin sheet (E)
-Fill the molded product obtained using the F sheet with orange juice so that there is no head space, seal with an EVA hot melt adhesive using aluminum foil of 0.03 mm as a lid, and store at 10 ° C for one month. Save for a while. One month later, the package was opened and the flavor of the orange juice was sensory evaluated.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【表２】 [Table 2]
【００４２】[0042]
【発明の効果】以上のとおり、本発明はポリプロピレン
系樹脂、ポリスチレン系樹脂等からなる賦形性樹脂シー
トに対し熱接着性を有し、低臭性、保香性及び酸素バリ
アー性に優れた熱接着用多層フィルム、その多層フィル
ムと賦形性樹脂シートとを熱接着した多層シート及びそ
れを成形した容器を提供するものであり、常温流通可能
な無菌加工米飯や、レトルト食品向けの包装材料として
使用できる。As described above, the present invention has a thermal adhesive property to a shape-forming resin sheet made of a polypropylene-based resin, a polystyrene-based resin, or the like, and has excellent low odor, fragrance retention, and oxygen barrier properties. The present invention provides a multilayer film for thermal bonding, a multilayer sheet obtained by thermally bonding the multilayer film and a shape-forming resin sheet, and a container formed by molding the same. Can be used as
Claims (6)
ト系樹脂から選択される１種以上の樹脂からなる樹脂層
（Ａ）、接着性樹脂層（Ｂ）、エチレン−酢酸ビニル共
重合体鹸化物樹脂層（Ｃ）及び接着性樹脂層（Ｄ）を有
し、（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）の順に構成され
ていて、（Ｄ）が任意の賦形性樹脂シートと熱接着可能
な接着材層であることを特徴とする賦形性樹脂シートと
の熱接着用多層フィルム。1. A resin layer (A), an adhesive resin layer (B), and a saponified ethylene-vinyl acetate copolymer resin layer (C) comprising at least one resin selected from a polyester resin and a polycarbonate resin. ) And an adhesive resin layer (D), and are constituted in the order of (A), (B), (C) and (D), wherein (D) can be thermally bonded to an arbitrary shapeable resin sheet. A shapeable resin sheet characterized by a
Multi-layer film for adhesion of heat.
無機フィラーを含有し表面が粗面化している、請求項１
に記載の熱接着用多層フィルム。2. The film according to claim 1, wherein one or both surface layers of the film contain an inorganic filler and have a roughened surface.
2. The multilayer film for thermal bonding according to item 1.
を共押出法で作成する際に、ダイより押出された多層フ
ィルムの片面もしくは両面が接するキャストロールもし
くはタッチロールとして、表面を粗面化したものを用い
ることで、表面を粗面化することを特徴とする多層フィ
ルムの製造方法。3. When the multilayer film for thermal bonding according to claim 1 is produced by a co-extrusion method, the surface of the multilayer film extruded from a die is roughened as a cast roll or a touch roll in contact with one or both surfaces thereof. A method for producing a multilayer film, characterized in that the surface is roughened by using a roughened one.
層フィルムの接着性樹脂層（Ｄ）面を、賦形性樹脂シー
ト（Ｅ）の片面ないしは両面に、熱接着する多層シート
の製造方法。4. A multilayer sheet wherein the surface of the adhesive resin layer (D) of the multilayer film according to any one of claims 1 to 3 is thermally bonded to one or both surfaces of the shape-forming resin sheet (E). Manufacturing method.
系樹脂５０〜８０重量％、無機フィラー２０〜５０重量
％を含む樹脂組成物からなる、請求項４の方法で製造し
た多層シート。5. The multilayer sheet produced by the method according to claim 4, wherein the shape-forming sheet (E) comprises a resin composition containing 50 to 80% by weight of a polypropylene resin and 20 to 50% by weight of an inorganic filler.
トを熱加工により成形した容器。6. A container obtained by molding the multilayer sheet according to claim 4 by thermal processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14811494A JP3248650B2 (en) | 1994-06-29 | 1994-06-29 | Multilayer film, multilayer sheet and container laminated with the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14811494A JP3248650B2 (en) | 1994-06-29 | 1994-06-29 | Multilayer film, multilayer sheet and container laminated with the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0811267A JPH0811267A (en) | 1996-01-16 |
| JP3248650B2 true JP3248650B2 (en) | 2002-01-21 |
Family
ID=15445572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14811494A Expired - Fee Related JP3248650B2 (en) | 1994-06-29 | 1994-06-29 | Multilayer film, multilayer sheet and container laminated with the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3248650B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10265756A (en) * | 1997-03-26 | 1998-10-06 | Mitsubishi Chem Corp | Resin composition for bonding and laminate |
| JP2008155385A (en) * | 2006-12-21 | 2008-07-10 | Yamato Esuron Kk | Food storage container and laminated film |
-
1994
- 1994-06-29 JP JP14811494A patent/JP3248650B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0811267A (en) | 1996-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1574328B1 (en) | Packaging films containing coextruded polyester and nylon layers | |
| US4647509A (en) | Thermoformable multilayer barrier structures | |
| EP3152128B1 (en) | Blister packaging components | |
| US20070259142A1 (en) | Rigid and semirigid packaging articles | |
| US9248947B2 (en) | Film for thermal adhesion to a rigid biopolymer structure | |
| JPS58212944A (en) | Laminate | |
| US8574694B2 (en) | Packaging sheet with improved cutting properties | |
| EP0096581B1 (en) | Laminated materials | |
| WO2020206301A1 (en) | Recyclable film for thermoforming | |
| WO2015187174A1 (en) | Blister packaging components | |
| JP4923688B2 (en) | Easy-open multilayer film | |
| JPS63288748A (en) | Polymer multilayer sheet proper to manufacture of microwave processable vessel and vessel manufactured from said sheet | |
| EP0972634A2 (en) | Laminate, multi-layer container and sealed container | |
| JP3248650B2 (en) | Multilayer film, multilayer sheet and container laminated with the same | |
| JPH0532800A (en) | Polyester-based resin composition and film having heat sealing property | |
| JP4240252B2 (en) | Laminate, multilayer container and sealed container | |
| JPS6140517Y2 (en) | ||
| JP2000263703A (en) | Multilayer sheet and container | |
| JP4240251B2 (en) | Laminate, multilayer container and sealed container | |
| JP2000264331A (en) | Composite tray container | |
| JP4209515B2 (en) | Gas pack lid | |
| JP2000296587A (en) | Laminate and sealed vessel | |
| JPH02204035A (en) | Multi-layered sheet | |
| EP2599822A2 (en) | Packaging sheet with improved cutting properties | |
| JP2000301675A (en) | Laminate and sealed container |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071109 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081109 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081109 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091109 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101109 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |