JP3145206B2 - Inner container for bag-in-box - Google Patents
Inner container for bag-in-boxInfo
- Publication number
- JP3145206B2 JP3145206B2 JP26958892A JP26958892A JP3145206B2 JP 3145206 B2 JP3145206 B2 JP 3145206B2 JP 26958892 A JP26958892 A JP 26958892A JP 26958892 A JP26958892 A JP 26958892A JP 3145206 B2 JP3145206 B2 JP 3145206B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- mol
- inner container
- bag
- ethylene
- 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
- 239000010410 layer Substances 0.000 claims description 57
- 239000012790 adhesive layer Substances 0.000 claims description 33
- 239000002344 surface layer Substances 0.000 claims description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- 229920001169 thermoplastic Polymers 0.000 claims description 16
- 239000004416 thermosoftening plastic Substances 0.000 claims description 16
- 238000007127 saponification reaction Methods 0.000 claims description 12
- 239000004711 α-olefin Substances 0.000 claims description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000011342 resin composition Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 26
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 25
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 25
- 229920000728 polyester Polymers 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- 101100160821 Bacillus subtilis (strain 168) yxdJ gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001155 polypropylene 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
- 239000002994 raw material Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、バッグインボックス用
内容器に関するもので、詳しくは、液体注入口の打ち抜
き加工性に優れ、ガスバリヤー性が長期間にわたり維持
されるバッグインボックス用内容器を提供するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inner container for a bag-in-box, and more particularly, to an inner container for a bag-in-box which is excellent in punching property of a liquid inlet and maintains gas barrier properties for a long period of time. Is provided.
【０００２】[0002]
【従来の技術】一般に、エチレン−酢酸ビニル共重合体
ケン化物（以下、ＥＶＯＨと略記する）は、透明性、帯
電防止性、耐油性、耐溶剤性、ガスバリヤー性、保香性
などにすぐれているが、耐衝撃性、耐屈曲疲労性、延伸
性、熱成形性、吸湿又は吸水時のガスバリヤー性は低い
という欠点も有する材料である。このため、包装材料を
目的とする用途においては、ＥＶＯＨのフィルムの表裏
両面に低密度ポリエチレン、ポリプロピレン、ナイロ
ン、ポリエステルなどのフィルムを積層することによっ
てガスバリヤー性、香気保持性、食品の変色防止性など
のＥＶＯＨの特性を維持しながら、落下強度、熱成形
性、防湿性などのＥＶＯＨの欠点を補って各種包装用途
に利用されているのが実情である。2. Description of the Related Art In general, saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) is excellent in transparency, antistatic property, oil resistance, solvent resistance, gas barrier property, fragrance retention property and the like. However, it is a material having disadvantages such as low impact resistance, bending fatigue resistance, stretchability, thermoformability, and low gas barrier properties when absorbing moisture or water. Therefore, in applications intended for packaging materials, gas barrier properties, aroma retention properties, and food discoloration prevention properties can be achieved by laminating films of low-density polyethylene, polypropylene, nylon, polyester, etc. on both sides of the EVOH film. It is used in various packaging applications while compensating for the drawbacks of EVOH, such as drop strength, thermoformability, and moisture resistance, while maintaining the characteristics of EVOH such as.
【０００３】近年、ワインやジュース等の飲料用液体や
写真の現像液などの液体を輸送・保存するための包装用
容器としてバッグインボックスなるものが利用されるよ
うになってきた。このバッグインボックスなるものは、
ダンボール箱の内部に液体注入口を設けたフレキシブル
なプラスチックの包装容器を収納させたもので各種液体
の輸送手段として多用されており、そのバッグインボッ
クスの内容器として上記のＥＶＯＨ積層体も用いられる
に至っている。[0003] In recent years, bag-in-box containers have been used as packaging containers for transporting and storing liquids for beverages such as wine and juice, and liquids for photographic developers. This bag-in-box is
A flexible plastic packaging container provided with a liquid injection port is housed inside a cardboard box, and is frequently used as a means for transporting various liquids. The above-described EVOH laminate is also used as an inner container of the bag-in-box. Has been reached.
【０００４】このときの該内容器の要求性能としては、
輸送時等における極めて激しい屈曲疲労に対しても優れ
たガスバリヤー性を保持することが重要であるので種々
の工夫が試みられており、直鎖状低密度ポリエチレン層
／接着剤層／ＥＶＯＨ層／接着剤／直鎖状低密度ポリエ
チレン（以下、ＬＬＤＰＥと略記する）層の積層体（特
開昭６０−１６１１４６号公報）、ＬＬＤＰＥ層／接着
剤層／ＥＶＯＨ層／接着剤層／エチレン−酢酸ビニル共
重合体樹脂層又は，二軸延伸ナイロン層又は，二軸延伸
ポリプロピレンの積層体（特開昭６０−１６８６４９号
公報）、表面層／カルボン酸変性ＬＬＤＰＥ／ＥＶＯＨ
層／カルボン酸変性ＬＬＤＰＥ／表面層の積層体（特開
昭６０−２４２０５４号公報）等が提案されている。The required performance of the inner container at this time is as follows:
Since it is important to maintain excellent gas barrier properties against extremely severe bending fatigue at the time of transportation and the like, various attempts have been made, and linear low-density polyethylene layers / adhesive layers / EVOH layers / Laminate of adhesive / linear low-density polyethylene (hereinafter abbreviated as LLDPE) layer (JP-A-60-161146), LLDPE layer / adhesive layer / EVOH layer / adhesive layer / ethylene-vinyl acetate Laminated body of copolymer resin layer, biaxially oriented nylon layer, or biaxially oriented polypropylene (Japanese Patent Laid-Open No. 60-168649), surface layer / carboxylic acid-modified LLDPE / EVOH
A laminate of a layer / a carboxylic acid-modified LLDPE / surface layer (JP-A-60-24205) has been proposed.
【０００５】[0005]
【発明が解決しようとする問題点】しかしながら、上記
の如きＥＶＯＨを中間層とする積層フイルムは、耐屈曲
疲労性は向上しているものの、長期間の保存や輸送に耐
えるだけの高度なガスバリヤー性は、未だ不充分であ
る。この原因は、該積層フィルムより該内容器を製造す
るに当たっては、該内容器に液体注入口を作る必要があ
り、該積層フィルムに打ち抜き穴をあけるのであるが、
このときＥＶＯＨ層に柔軟性が少ないのでＥＶＯＨ層に
クラックが発生して、このクラックが輸送時等のストレ
スなどにより成長することになり、最終的にガスバリヤ
ー性を損なう結果となるのである。However, the laminated film using EVOH as an intermediate layer as described above has a high gas barrier which can withstand long-term storage and transportation, although its bending fatigue resistance is improved. Sex is still inadequate. The cause is that when manufacturing the inner container from the laminated film, it is necessary to make a liquid injection port in the inner container, and a punch hole is made in the laminated film.
At this time, cracks occur in the EVOH layer because flexibility is small in the EVOH layer, Ri Do that the crack grows due stress such as during transport, ultimately it to result in impairing the gas barrier property.
【０００６】[0006]
【問題点を解決するための手段】そこで、本発明者ら
は、上記の問題点を解決するために鋭意研究を重ねた結
果、エチレン含有量２０〜５５モル％、ケン化度９０モ
ル％以上のＥＶＯＨ１００重量部に対し、ガラス転移温
度（Ｔｇ）が−１５０℃〜２５℃、結晶融解熱（△Ｈ
ｕ）が３０Ｊ／ｇ以下の熱可塑性ポリエステル１〜１０
０重量部を配合してなる樹脂組成物の層（Ａ）を中間層
とし、該中間層の両側に接着剤層を設け、更に該接着剤
層の外側に表面層を設けたバッグインボックス用内容器
は、液体注入口の製造時にクラックが発生することな
く、長期間にわたる輸送時等においても良好なガスバリ
ヤー性を維持できることを見いだし本発明を完成した。
以下に、本発明を詳細に説明する。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the ethylene content is 20 to 55 mol% and the saponification degree is 90 mol% or more. With respect to 100 parts by weight of EVOH, a glass transition temperature (Tg) of -150 ° C to 25 ° C, and a heat of crystal fusion (ΔH
u) is a thermoplastic polyester having a content of 30 J / g or less.
A bag-in-box in which a layer (A) of the resin composition containing 0 parts by weight is used as an intermediate layer, an adhesive layer is provided on both sides of the intermediate layer, and a surface layer is provided outside the adhesive layer. The present inventors have found that the inner container can maintain good gas barrier properties even during transportation for a long period of time without cracking during the production of the liquid inlet, and completed the present invention.
Hereinafter, the present invention will be described in detail.
【０００７】本発明で用いるＥＶＯＨは、エチレン含有
量２０〜５５モル％、ケン化度９０モル％以上、好まし
くは９５モル％以上でなければならない。エチレン含有
量が２０モル％未満では、高湿時のガスバリヤー性が低
下し、一方５５モル％を越えると充分なガスバリヤー性
が得られない。又、ケン化度が９０モル％未満では、ガ
スバリヤー性や耐湿性が低下する。かかるＥＶＯＨの中
でも極限粘度 (１５％のフェノールを含有する水溶液
中、３０℃で測定) が０.７〜１.５ｄｌ／ｇ、好ましく
は、０．８〜１．３ｄｌ／ｇのものが機械的強度、加工
性の点で好適である。The EVOH used in the present invention must have an ethylene content of 20 to 55 mol% and a saponification degree of 90 mol% or more, preferably 95 mol% or more. If the ethylene content is less than 20 mol%, the gas barrier property at high humidity decreases, while if it exceeds 55 mol%, sufficient gas barrier property cannot be obtained. On the other hand, when the saponification degree is less than 90 mol%, the gas barrier property and the moisture resistance are reduced. Among such EVOHs, those having an intrinsic viscosity (measured at 30 ° C. in an aqueous solution containing 15% of phenol) of 0.7 to 1.5 dl / g, preferably 0.8 to 1.3 dl / g are used. It is suitable in terms of strength and workability.
【０００８】又、該ＥＶＯＨは、透明性、ガスバリヤー
性などの特性を損なわない範囲で少量のプロピレン、イ
ソブテン、α−オクテン、α−ドデセン、α−オクタデ
セン等のα−オレフィン、不飽和カルボン酸又はその
塩、部分アルキルエステル、完全アルキルエステル、ニ
トリル、アミド、無水物、不飽和スルホン酸又はその塩
などのコモノマーを含んでいても差支えない。本発明に
おいて、前記ＥＶＯＨに配合される熱可塑性ポリエステ
ルは、示差走査型熱量計（昇温速度１０℃／分）により
測定されたガラス転移温度（Ｔｇ）が−１５０℃〜２５
℃、示差走査型熱量計（昇温速度２０℃／分）により測
定された結晶融解熱（△Ｈｕ）が３０Ｊ／ｇ以下である
ことが必要であり、Ｔｇが−１５０℃未満のものは、混
合物がブロッキングし、作業性が劣り、Ｔｇが、２５℃
を越えるものは、耐屈曲疲労性、延伸性が問題となる。
又、結晶融解熱（△Ｈｕ）が３０Ｊ／ｇを越えるもの
は、耐屈曲疲労性、延伸性が低下するので好ましくな
い。The EVOH is a small amount of α-olefins such as propylene, isobutene, α-octene, α-dodecene and α-octadecene, and unsaturated carboxylic acids as long as the properties such as transparency and gas barrier properties are not impaired. Alternatively, a comonomer such as a salt thereof, a partial alkyl ester, a complete alkyl ester, a nitrile, an amide, an anhydride, an unsaturated sulfonic acid or a salt thereof may be contained. In the present invention, the thermoplastic polyester blended in the EVOH has a glass transition temperature (Tg) of from −150 ° C. to 25 measured by a differential scanning calorimeter (heating rate: 10 ° C./min).
° C, the heat of crystal fusion (ΔHu) measured by a differential scanning calorimeter (heating rate: 20 ° C / min) is required to be 30 J / g or less. The mixture blocks, the workability is poor, and the Tg is 25 ° C.
If the ratio exceeds the above, bending fatigue resistance and stretchability become problems.
Further, those having a heat of crystal fusion (△ Hu) of more than 30 J / g are not preferred because the bending fatigue resistance and the stretchability are reduced.
【０００９】かかる熱可塑性ポリエステルは、２０〜７
０重量％のテレフタル酸やイソフタル酸等の芳香族ジカ
ルボン酸と８０〜３０重量％のアジピン酸やセバシン酸
等の脂肪族ジカルボン酸を酸成分と、１，６−ヘキサン
ジオール、１，４−ブタンジオール、エチレングリコー
ル、プロピレングリコール等の炭素数が２〜６のアルキ
レングリコールの重縮合により製造されるもので、ガラ
ス転移温度（Ｔｇ）及び結晶融解熱（△Ｈｕ）は、上記
の配合組成によりコントロールすることができる。即
ち、ガラス転移温度（Ｔｇ）は、芳香族酸と脂肪族酸の
配合比によりコントロールでき、脂肪族酸の比率を上げ
るとガラス転移温度は低下する。また、結晶融解熱（△
Ｈｕ）は、フタル酸等の結晶性を崩す原料を増量するこ
とにより低下する。[0009] Such thermoplastic polyesters are preferably 20 to 7
0% by weight of an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid; and 80 to 30% by weight of an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, as an acid component, 1,6-hexanediol, 1,4-butane It is produced by polycondensation of alkylene glycols having 2 to 6 carbon atoms such as diol, ethylene glycol and propylene glycol. The glass transition temperature (Tg) and heat of crystal fusion (△ Hu) are controlled by the above composition. can do. That is, the glass transition temperature (Tg) can be controlled by the mixing ratio of the aromatic acid and the aliphatic acid, and the glass transition temperature decreases as the ratio of the aliphatic acid increases. The heat of crystal fusion (△
Hu) is reduced by increasing the amount of a raw material that breaks the crystallinity such as phthalic acid.
【００１０】本発明のバッグインボックス用内容器は、
少なくとも表面層／接着剤層／中間層（Ａ）／接着剤層
／表面層の５層積層体からなるもので、該表面層は、密
度０．８６〜０．９５ｇ／ｃｍ３（２０℃）のエチレン
−α−オレフィン共重合体が好ましい。ここで言う密度
とは、２０℃においてＪＩＳ Ｋ ６７６０によって測
定される値であり、密度が上記範囲より小さいときは、
積層体の機械的諸物性が不足したり、ブロッキングが発
生したりする。逆に、大きいときは、耐屈曲疲労性が不
十分となり好ましくない。また、エチレン−α−オレフ
ィンとは、エチレンとブテン−１，ペンテン−１，４−
メチルペンテン−１，ヘキセン−１，オクテン−１等の
炭素数１８以下の共重合物である。これらの中でも炭素
数が４〜８オレフィンを用いたエチレン−α−オレフィ
ン共重合体が好適に用いられる。[0010] The inner container for a bag-in-box of the present invention comprises:
It comprises at least a five-layer laminate of a surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer, and the surface layer has a density of 0.86 to 0.95 g / cm 3 (20 ° C.) The ethylene-α-olefin copolymer is preferred. The density here is a value measured according to JIS K 6760 at 20 ° C. When the density is smaller than the above range,
The mechanical properties of the laminate are insufficient, or blocking occurs. Conversely, when it is large, the bending fatigue resistance becomes insufficient, which is not preferable. Further, ethylene-α-olefin refers to ethylene and butene-1, pentene-1,4-
It is a copolymer having 18 or less carbon atoms, such as methylpentene-1, hexene-1, and octene-1. Among these, an ethylene-α-olefin copolymer using a C 4-8 olefin is preferably used.
【００１１】更に、接着剤層に用いられる接着性樹脂と
しては、不飽和カルボン酸又はその無水物で変性された
密度０．８６〜０．９５ｇ／ｃｍ３（測定条件は、上記
の表面層の場合と同じ）のエチレン−α−オレフィン共
重合体が好ましく、上記の表面層で述べたのと同じ樹脂
を不飽和カルボン酸又はその無水物で共重合又はグラフ
ト変性することにより得ることができる。勿論、ここで
言う変性には、未変性のエチレン−α−オレフィン共重
合体に不飽和カルボン酸又はその無水物のブレンドも含
まれる。不飽和カルボン酸又はその無水物としては、マ
レイン酸、無水マレイン酸、フマル酸、アクリル酸、メ
タクリル酸、クロトン酸、イタコン酸、シトラコン酸、
ヘキサヒドロ無水フタル酸等が挙げられ、中でも、無水
マレイン酸が好適に用いられる。Further, as the adhesive resin used for the adhesive layer, a density modified with an unsaturated carboxylic acid or an anhydride thereof is 0.86 to 0.95 g / cm 3 (measurement conditions are as follows. Ethylene-α-olefin copolymer) is preferable, and can be obtained by copolymerizing or graft-modifying the same resin as described in the above surface layer with an unsaturated carboxylic acid or an anhydride thereof. Of course, the modification referred to here includes a blend of an unmodified ethylene-α-olefin copolymer and an unsaturated carboxylic acid or an anhydride thereof. As unsaturated carboxylic acids or anhydrides thereof, maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid,
Hexahydrophthalic anhydride and the like can be mentioned, and among them, maleic anhydride is preferably used.
【００１２】このときの、エチレン−α−オレフィン共
重合体に含有される不飽和カルボン酸又はその無水物量
は、０．０１〜１０重量％が好ましく、更に好ましく
は、０．１〜３重量％である。該変性物中の含有量が少
ないと中間層及び表面層との接着力が低下し、逆に多い
と架橋反応を起こし、成形性が悪くなり好ましくない。
また、本発明の表面層／接着剤層／中間層（Ａ）／接着
剤層／表面層の積層体の各層の厚みは、それぞれ１０〜
６００μ／２〜５０μ／１〜１００μ／２〜５０μ／１
０〜６００μの範囲から選択され、好ましくは、３０〜
２００μ／５〜１０μ／５〜３０μ／５〜１０μ／３０
〜２００μである。The amount of the unsaturated carboxylic acid or anhydride contained in the ethylene-α-olefin copolymer at this time is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 3% by weight. It is. If the content in the modified product is small, the adhesive strength between the intermediate layer and the surface layer is reduced. If the content is large, a crosslinking reaction is caused, and the moldability is deteriorated.
The thickness of each layer of the laminate of the surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer of the present invention is 10 to 10 respectively.
600μ / 2-50μ / 1-100μ / 2-50μ / 1
0 to 600 μm, preferably 30 to
200 μ / 5 to 10 μ / 5 to 30 μ / 5 to 10 μ / 30
~ 200μ.
【００１３】本発明の最大の特徴は、中間層に特定のポ
リエステル樹脂を含有するＥＶＯＨを採用したことにあ
り、中間層にかかるＥＶＯＨを用いる本発明の積層体
は、表面層／接着剤層／中間層（Ａ）／接着剤層／表面
層の構成に限らず、該表面層の外側に更に層を設けた表
面層／接着剤層／中間層（Ａ）／接着剤層／表面層／接
着剤層／表面層、表面層／接着剤層／表面層／接着剤層
／中間層（Ａ）／接着剤層／表面層／接着剤層／表面層
等の６層以上の積層体とすることも可能である。更に、
ナイロン層を用いた、表面層／接着剤層／ナイロン層／
中間層（Ａ）／接着剤層／表面層、表面層／接着剤層／
ナイロン層／中間層（Ａ）／ナイロン層／接着剤層／表
面層、表面層／接着剤層／ナイロン層／接着剤層／中間
層（Ａ）／接着剤層／表面層等の積層体とすることも可
能であり、このときに、用いられるナイロン層の樹脂と
しては、ナイロン６、ナイロン６−６６、ナイロン１
２、アモルファスナイロン、又はこれらのブレンド物が
挙げられる。The greatest feature of the present invention is that EVOH containing a specific polyester resin is used for the intermediate layer. The laminate of the present invention using the EVOH for the intermediate layer has a surface layer / adhesive layer / Not limited to the configuration of the intermediate layer (A) / adhesive layer / surface layer, but also a surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer / adhesive layer further provided outside the surface layer A laminate of six or more layers such as an agent layer / surface layer, a surface layer / adhesive layer / surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer / adhesive layer / surface layer. Is also possible. Furthermore,
Surface layer / adhesive layer / nylon layer /
Intermediate layer (A) / adhesive layer / surface layer, surface layer / adhesive layer /
Nylon layer / intermediate layer (A) / nylon layer / adhesive layer / surface layer, surface layer / adhesive layer / nylon layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer It is also possible to use nylon 6, nylon 6-66, nylon 1
2, amorphous nylon, or blends thereof.
【００１４】また、本発明の積層体の各層には、成形加
工性、物性等の向上のために酸化防止剤、スリップ剤、
ハイドロタルサイト類、帯電防止剤、可塑剤、着色剤等
を本発明の効果を阻害しない範囲で添加することもでき
る。本発明のバッグインボックス用内容器は、主に、ヒ
ートシール法及びブロー成形法により製造することがで
きる。ヒートシール法では、インフレーション法又はエ
クストルード法により製膜された中間層用及び表面層用
のフイルムを、接着剤層を介してドライラミした積層体
又は各層を共押出法等により積層した積層体をそのま
ま、あるいは必要に応じて２重又は３重に重ね合わせ
て、液体注入口の密封取り付け用の穴を打ち抜き、その
穴に、予め射出成形で成形した液体注入口の密封栓をヒ
ートシール法で融着させる。そのときに、該積層体と打
ち抜き処理のしていない別の積層体とを合わせて四方ヒ
ートシールしてバッグインボックス等内容器とする。ブ
ロー成形法では、押出機から押し出された円筒状の上記
の積層体を金型で型締めして成形する。液体注入口の密
封栓は、予め射出成形で成形したものを金型内にセット
しておき、ブロー成形時に成形容器と融着させる。その
後、液体注入口をあける。Further, each layer of the laminate of the present invention is provided with an antioxidant, a slip agent,
Hydrotalcites, antistatic agents, plasticizers, coloring agents, and the like can be added as long as the effects of the present invention are not impaired. The inner container for a bag-in-box of the present invention can be manufactured mainly by a heat sealing method and a blow molding method. In the heat sealing method, a laminate obtained by dry laminating a film for an intermediate layer and a film for a surface layer formed by an inflation method or an extruding method via an adhesive layer or a laminate obtained by laminating each layer by a co-extrusion method or the like. As it is, or double or triple as necessary, a hole for sealing and mounting the liquid inlet is punched out, and a sealing plug of the liquid inlet previously formed by injection molding is inserted into the hole by a heat sealing method. Let it fuse. At this time, the laminated body and another laminated body which has not been subjected to the punching process are combined and heat-sealed in four directions to obtain a bag-in-box or other inner container. In the blow molding method, the cylindrical laminated body extruded from an extruder is molded by clamping with a die. The sealing stopper of the liquid inlet is previously molded by injection molding and set in a mold, and is fused to a molding container during blow molding. Thereafter, the liquid inlet is opened.
【００１５】[0015]
【作用】本発明のバッグインボックス用内容器は、中間
層に特定のポリエステル樹脂を含有するＥＶＯＨ層を用
いているので、該内容器の製造時の打ち抜き工程におい
て、クラックが発生することなく長期間のガスバリヤー
性に優れたバッグインボックス用内容器が得られる。Since the inner container for a bag-in-box of the present invention uses an EVOH layer containing a specific polyester resin in the intermediate layer, the inner container has a long length without cracks in the punching step at the time of manufacturing the inner container. An inner container for a bag-in-box having excellent gas barrier properties during a period can be obtained.
【００１６】[0016]
【実施例】以下に、実施例を挙げて本発明を具体的に説
明する。尚、実施例中「部」、「％」とあるのは、特に
断わりのない限り、重量基準を意味する。熱可塑性ポリエステル（Ｐ−１〜４）の製造 以下の方法にて４種類の熱可塑性ポリエステルを製造し
た。撹拌機、精留塔、窒素導入管及び真空装置の付いた
４つ口の２リットルのフラスコに酸成分（テレフタル酸
５５モル％、アジピン酸２５モル％、セバシン酸２５モ
ル％）４５部と１，４−ブタンジオール５５部及び触媒
としてテトライソプロピルチタネート０．０１５部を仕
込み、１４０〜２２０℃で４〜５時間反応させた後、更
に、２２０℃で２時間反応を行い、最終的に、固有粘度
が１．５ｄｌ／ｇになるまで２５０℃以下，０．２ｍｍ
Ｈｇの条件で反応させて、ガラス転移温度（Ｔｇ）；−
２５℃，結晶融解熱（△Ｈｕ）；１３Ｊ／ｇの熱可塑性
ポリエステル（Ｐ−１）を得た。同様に以下に示す配合
組成の熱可塑性ポリエステル（Ｐ−２〜４）を得た。The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” mean on a weight basis unless otherwise specified. Production of thermoplastic polyesters (P-1 to 4) Four kinds of thermoplastic polyesters were produced by the following methods. 45 parts of an acid component (55 mol% of terephthalic acid, 25 mol% of adipic acid, 25 mol% of sebacic acid) and 45 parts of 1 were placed in a four-necked 2-liter flask equipped with a stirrer, a rectification column, a nitrogen inlet tube and a vacuum device. 55 parts of 1,4-butanediol and 0.015 part of tetraisopropyl titanate as a catalyst were reacted at 140 to 220 ° C. for 4 to 5 hours, and further reacted at 220 ° C. for 2 hours. 250 ° C or less, 0.2mm until the viscosity becomes 1.5dl / g
The reaction is carried out under the condition of Hg to obtain a glass transition temperature (Tg);
A thermoplastic polyester (P-1) having a heat of crystal fusion (， Hu) of 13 J / g at 25 ° C. was obtained. Similarly, thermoplastic polyesters (P-2 to 4) having the following composition were obtained.
【００１７】Ｐ−２；酸成分（テレフタル酸４０モル
％、アジピン酸６０モル％）４０部と１，４ブタンジオ
ール６０部を配合した、Ｔｇ；−３０℃，△Ｈｕ；１７
Ｊ／ｇ，固有粘度；１．０ｄｌ／ｇの熱可塑性ポリエス
テル Ｐ−３；酸成分（テレフタル酸６０モル％、アジピン酸
３０モル％、セバシン酸１０モル％）４５部と１，４ブ
タンジオール５５部を配合した、Ｔｇ；−２５℃，△Ｈ
ｕ；２０Ｊ／ｇ，固有粘度；０．７ｄｌ／ｇの熱可塑性
ポリエステル Ｐ−４；酸成分（テレフタル酸６０モル％、セバシン酸
４０モル％）４５部とグリコール成分（１，４ブタンジ
オール４０モル％、分子量１０００００のポリテトラメ
チレングリコール６０モル％）５５部を配合した、Ｔ
ｇ；−６０℃，△Ｈｕ；２０Ｊ／ｇ，固有粘度；１．６
ｄｌ／ｇｇの熱可塑性ポリエステルP-2: 40 g of an acid component (40 mol% of terephthalic acid, 60 mol% of adipic acid) and 60 parts of 1,4-butanediol were blended. Tg: -30 ° C., ΔHu: 17
J / g, intrinsic viscosity; 1.0 dl / g thermoplastic polyester P-3; 45 parts of an acid component (terephthalic acid 60 mol%, adipic acid 30 mol%, sebacic acid 10 mol%) and 1,4 butanediol 55 -25 ° C, ΔH
u; 20 J / g, intrinsic viscosity; 0.7 dl / g thermoplastic polyester P-4; 45 parts of an acid component (60 mol% of terephthalic acid, 40 mol% of sebacic acid) and a glycol component (40 mol of 1,4 butanediol) %, Polytetramethylene glycol having a molecular weight of 100,000 and 60 mol%),
g; -60 ° C, ΔHu; 20 J / g, intrinsic viscosity; 1.6
dl / gg thermoplastic polyester
【００１８】実施例１ ３種５層の共押出装置を用いて、中間層が、エチレン含
有量３５モル％、ケン化度９９．２モル％のＥＶＯＨ９
０部に対して、熱可塑性ポリエステル（Ｐ−１）１０部
を配合した樹脂組成物の層（Ａ−１），両外層が、ＭＩ
（メルトインデックス）２．５ｇ／１０分（１９０℃、
荷重２１６０ｇ），密度０．８９０ｇ／ｃｍ３、エチレ
ン含有量９０モル％のエチレン−１−ブテンランダム共
重合体ＬＬＤＰＥ（Ｂ−１），中間層と両外層との間に
ＭＩが３．０の無水マレイン酸含有量０．５％のＬＬＤ
ＰＥ（Ｂ−１）からなる接着樹脂層（Ｃ−１）とからな
り、（Ｂ−１）／（Ｃ−１）／（Ａ−１）／（Ｃ−１）
／（Ｂ−１）が３５μ／１０μ／１０μ／１０μ／３５
μの構成を有する５層共押出積層フィルムを下記の如き
共押出成形条件で得た。Example 1 Using a three-type five-layer coextrusion apparatus, an intermediate layer was formed of EVOH9 having an ethylene content of 35 mol% and a saponification degree of 99.2 mol%.
Layer (A-1) of the resin composition in which 10 parts of thermoplastic polyester (P-1) was blended with 0 parts, and both outer layers
(Melt index) 2.5 g / 10 minutes (190 ° C,
Load: 2160 g), density: 0.890 g / cm 3 , ethylene-butene random copolymer LLDPE (B-1) having an ethylene content of 90 mol%, and an MI of 3.0 between the intermediate layer and both outer layers. LLD with maleic anhydride content of 0.5%
(B-1) / (C-1) / (A-1) / (C-1)
/ (B-1) is 35 μ / 10 μ / 10 μ / 10 μ / 35
A five-layer coextrusion laminated film having a structure of μ was obtained under the following coextrusion molding conditions.
【００１９】共押出成形条件 押出機（Ａ）：３０ｍｍф，スクリュー；フルフライト
型，Ｌ／Ｄ；２８ 温度条件（℃）：供給部；１８０，圧縮部；２００，計
量部；２２０ 吐 出 量 ：１．５ｋｇ／ｈｒ 押出機（Ｂ）：３０ｍｍф，スクリュー；フルフライト
型，Ｌ／Ｄ；２６ 温度条件（℃）：供給部；１６０，圧縮部；２００，計
量部；２２０ 吐 出 量 ：３．０ｋｇ／ｈｒ 押出機（Ｃ）：４０ｍｍф，スクリュー；フルフライト
型，Ｌ／Ｄ；２４ 温度条件（℃）：供給部；２００，圧縮部；２１０，計
量部；２１０ 吐 出 量 ：１０．０ｋｇ／ｈｒ フィードブロック温度：２２０℃ ダイ温度：２２０℃ Co-extrusion molding conditions Extruder (A): 30 mmф, screw; full flight type, L / D; 28 Temperature condition (° C.): supply section: 180, compression section; 200, measuring section; 220 discharge amount: 1.5 kg / hr Extruder (B): 30 mmф, screw; full flight type, L / D; 26 Temperature condition (° C.): supply section; 160, compression section; 200, measuring section; 220 discharge amount: 3. 0 kg / hr Extruder (C): 40 mmф, screw; full flight type, L / D; 24 Temperature condition (° C.): supply section; 200, compression section; 210, measuring section; 210 discharge amount: 10.0 kg / hr Feed block temperature: 220 ° C Die temperature: 220 ° C
【００２０】得られた積層フィルム（５００ｍｍ×７０
０ｍｍ）を２枚重ねにして、打ち抜き機により、液体注
入用の穴（直径４３ｍｍ）をあけた。次に、穴のあけて
いない積層フィルム（５００ｍｍ×７００ｍｍの２枚重
ね）を上記の積層フィルムと重ね合わせて四方ヒートシ
ールしてバッグインボックス用内容器を製造した。その
際に、液体注入用の穴に高密度ポリエチレン製の密封栓
を取り付け回りを熱シールして密着固定した。次に、か
かる内容器をダンボール箱に入れ、その中に水を約１８
リットル入れて約２０００ｋｍの走行輸送テストを行っ
た。上記テスト後、内容器の密封栓回りの積層フィルム
の状況をＳＥＭ（電子顕微鏡，５００倍）で目視観察し
た。なお、テスト前後の該内容器の酸素透過量（ｃｃ／
ａｉｒ・ｂａｇ・ｄａｙ）を２０℃，６５％ＲＨの条件
下でＭｏｄｅｒｎ Ｃｏｎｔｏｒｏｌ社製の酸素透過量
測定器（ＯＸ−ＴＲＡＮ１０／５０）を用いて調べた。The obtained laminated film (500 mm × 70
0 mm) were stacked, and a hole (diameter: 43 mm) for liquid injection was made by a punching machine. Next, a laminated film without holes (500 mm × 700 mm laminated) was superposed on the laminated film and heat-sealed on all sides to produce a bag-in-box inner container. At that time, a high-density polyethylene sealing stopper was attached to the hole for liquid injection and heat-sealed around and tightly fixed. Next, place the inner container in a cardboard box, and put water therein for about 18 hours.
A running transport test of about 2000 km in liters was conducted. After the test, the state of the laminated film around the sealing stopper of the inner container was visually observed with an SEM (electron microscope, 500 times). The oxygen permeation amount (cc / cc) of the inner container before and after the test
The air / bag / day) was examined under the conditions of 20 ° C. and 65% RH using an oxygen permeation meter (OX-TRAN 10/50) manufactured by Modern Control.
【００２１】実施例２〜４ 表１に示す中間層、接着剤層、表面層を用いて、実施例
１と同様に内容器を作製して評価を行った。 比較例１ 実施例１において中間層をエチレン含有量３５モル％、
ケン化度９９．２モル％のＥＶＯＨに替えた他は、実施
例１と同様にして５層の積層フィルムを得て、内容器を
作製して評価を行った。 比較例２ 表１に示す中間層、接着剤層、表面層を用いて、実施例
１と同様に内容器を作製して評価を行った。実施例及び
比較例の評価結果を表１に示す。Examples 2 to 4 Using the intermediate layer, the adhesive layer and the surface layer shown in Table 1, an inner container was prepared and evaluated in the same manner as in Example 1. Comparative Example 1 In Example 1, the intermediate layer was formed such that the ethylene content was 35 mol%,
Except for changing to EVOH having a saponification degree of 99.2 mol%, a laminated film of five layers was obtained in the same manner as in Example 1, and an inner container was produced and evaluated. Comparative Example 2 An inner container was prepared and evaluated in the same manner as in Example 1 using the intermediate layer, the adhesive layer, and the surface layer shown in Table 1. Table 1 shows the evaluation results of the examples and the comparative examples.
【００２２】[0022]
【表１】 積 層 構 成1) 評 価 項 目 中間層 表面層 接着剤層 ＳＥＭ観察 酸素透過率2) 実施例１ Ａ−１ Ｂ−１ Ｃ−１ 異状無し ０.０５／０.０８ 実施例２ Ａ−２ Ｂ−２ Ｃ−２ 異状無し ０.１０／０.１２ 実施例３ Ａ−３ Ｂ−３ Ｃ−３ 異状無し ０.１２／０.１５実施例４ Ａ−４ Ｂ−４ Ｃ−３ 異状無し ０.２０／０.２０ 比較例１ Ａ−５ Ｂ−１ Ｃ−１ クラック発生 ０.１５／２５.０比較例２ Ａ−６ Ｂ−２ Ｃ−２ クラック発生 ０.３０／１０.０ [Table 1] Laminated layer structure 1) Evaluation items Intermediate layer Surface layer Adhesive layer SEM observation Oxygen permeability 2) Example 1 A-1 B-1 C-1 No abnormality 0.05 / 0.08 Example 2 A-2 B-2 C-2 No abnormality 0.10 / 0.12 Example 3 A-3 B-3 C-3 No abnormality 0.12 / 0.15 Example 4 A-4 B-4 C-3 No abnormality 0.20 / 0.20 Comparative example 1 A-5 B-1 C-1 Crack generation 0.15 / 25.0 Comparative example 2 A-6 B-2 C-2 Crack generation 0.30 /10.0
【００２３】１）各構成樹脂は、以下のとおり。 Ａ−１；エチレン含有量３５モル％、ケン化度９９．２
モル％のＥＶＯＨ９０部に対して、熱可塑性ポリエステ
ル（Ｐ−１）１０部を配合した樹脂組成物 Ａ−２；エチレン含有量４４モル％、ケン化度９９．８
モル％のＥＶＯＨ９５部に対して、熱可塑性ポリエステ
ル（Ｐ−２) ５部を配合した樹脂組成物 Ａ−３；エチレン含有量３０モル％、ケン化度９９．０
モル％のＥＶＯＨ８５部に対して、熱可塑性ポリエステ
ル（Ｐ−３）１５部を配合した樹脂組成物 Ａ−４；エチレン含有量３５モル％、ケン化度９５．０
モル％のＥＶＯＨ９５部に対して、熱可塑性ポリエステ
ル（Ｐ−４）５部を配合した樹脂組成物 Ａ−５；エチレン含有量３５モル％、ケン化度９９．２
モル％のＥＶＯＨのみ Ａ−６；エチレン含有量４４モル％、ケン化度９９．８
モル％のＥＶＯＨのみ1) Each constituent resin is as follows. A-1; ethylene content 35 mol%, degree of saponification 99.2
Resin composition A-2 in which 10 parts of a thermoplastic polyester (P-1) is blended with 90 parts by mol of EVOH, and an ethylene content of 44 mol% and a saponification degree of 99.8.
Resin composition A-3 in which 5 parts of a thermoplastic polyester (P-2) is blended with 95 parts by mol of EVOH of mol%, ethylene content is 30 mol%, and saponification degree is 99.0.
Resin composition A-4 in which 15 parts of thermoplastic polyester (P-3) is blended with 85 parts by mol of EVOH of mol%; ethylene content 35 mol%, saponification degree 95.0.
Resin composition A-5 in which 5 parts of a thermoplastic polyester (P-4) is blended with 95 parts of EVOH of 95% by mole; ethylene content: 35% by mole; saponification degree: 99.2.
Mol-6 EVOH only A-6; ethylene content 44 mol%, degree of saponification 99.8
Mol% EVOH only
【００２４】Ｂ−１；ＭＩ２．５ｇ／１０分、密度０．
８９０ｇ／ｃｍ3、エチレン含有量９０モル％のエチレ
ン−１−ブテンランダム共重合体 Ｂ−２；ＭＩ４．０ｇ／１０分、密度０．８７２ｇ／ｃ
ｍ3、エチレン含有量８２モル％のエチレン−１−ブテ
ンランダム共重合体 Ｂ−３；ＭＩ０．８ｇ／１０分、密度０．８６４ｇ／ｃ
ｍ3、エチレン含有量８０モル％のエチレン−プロピレ
ン共重合体 Ｂ−４；ＭＩ２．０ｇ／１０分、密度０．９２０ｇ／ｃ
ｍ3、エチレン含有量９７モル％のエチレン−４−メチ
ルペンテン−１共重合体 Ｃ−１；上記Ｂ−１に無水マレイン酸を０．５％グラフ
トしたもの。 Ｃ−２；上記Ｂ−２に無水マレイン酸を２．５％グラフ
トしたもの１０部にＢ−１を９０部ブレンドしたもの。 Ｃ−３；上記Ｂ−３に無水マレイン酸を３％グラフトし
たもの。 ２）酸素透過率は、テスト前／テスト後の値でそれぞれ
表している。B-1: MI 2.5 g / 10 min, density 0.
890 g / cm 3 , ethylene-1-butene random copolymer having an ethylene content of 90 mol% B-2; MI 4.0 g / 10 min, density 0.872 g / c
m 3 , ethylene-1-butene random copolymer having an ethylene content of 82 mol% B-3; MI 0.8 g / 10 min, density 0.864 g / c
m 3 , ethylene-propylene copolymer B-4 having an ethylene content of 80 mol%; MI 2.0 g / 10 min, density 0.920 g / c
m 3 , ethylene-4-methylpentene-1 copolymer having an ethylene content of 97 mol% C-1; a product obtained by grafting 0.5% of maleic anhydride onto the above B-1. C-2: 90 parts of B-1 blended with 10 parts of the above B-2 grafted with 2.5% maleic anhydride. C-3: Maleic anhydride grafted to B-3 above at 3%. 2) Oxygen permeability is represented by values before and after the test.
【００２５】[0025]
【発明の効果】本発明のバッグインボックス用内容器
は、中間層に特定のポリエステル樹脂を含有したＥＶＯ
Ｈ層を用いているので、該内容器の製造時の打ち抜き工
程において、クラックが発生することなくガスバリヤー
性に優れたバッグインボックス用内容器が得られ、長時
間の輸送等の衝撃にも耐え得ることができ極めて有用性
が高いものである。The inner container for a bag-in-box according to the present invention is an EVO having a specific polyester resin in the intermediate layer.
Since the H layer is used, a bag-in-box inner container having excellent gas barrier properties can be obtained without cracks in the punching process during the production of the inner container, and can be subjected to impacts such as long-time transportation. It can withstand and is extremely useful.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−168649（ＪＰ，Ａ) 特開 昭60−161146（ＪＰ，Ａ) 特開 昭60−242054（ＪＰ，Ａ) 特開 昭62−130847（ＪＰ，Ａ) 特開 平４−45930（ＪＰ，Ａ) 特開 昭63−218352（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 1/00 - 35/00 B65D 77/00 - 77/40 ────────────────────────────────────────────────── (5) References JP-A-60-168649 (JP, A) JP-A-60-161146 (JP, A) JP-A-60-242054 (JP, A) JP-A-62 130847 (JP, A) JP-A-4-45930 (JP, A) JP-A-63-218352 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B32B 1/00-35 / 00 B65D 77/00-77/40
Claims (3)
化度９０モル％以上のエチレン−酢酸ビニル共重合体ケ
ン化物１００重量部に対し、ガラス転移温度(Ｔｇ) が
−１５０℃〜２５℃、結晶融解熱（△Ｈｕ）が３０Ｊ／
ｇ以下の熱可塑性ポリエステル１〜１００重量部を配合
してなる樹脂組成物の層（Ａ）を中間層とし、該中間層
の両側に接着剤層を設け、更に該接着剤層の外側に表面
層を設けたことを特徴とするバッグインボックス用内容
器。1. A glass transition temperature (Tg) of -150 ° C. to 25 ° C. with respect to 100 parts by weight of a saponified ethylene-vinyl acetate copolymer having an ethylene content of 20 to 55 mol% and a saponification degree of 90 mol% or more. , Heat of crystal fusion (△ Hu) is 30 J /
g of a thermoplastic composition of 1 to 100 parts by weight as a resin composition layer (A) as an intermediate layer, an adhesive layer provided on both sides of the intermediate layer, and a surface outside the adhesive layer. An inner container for a bag-in-box, comprising a layer.
ｃｍ3（２０℃）のエチレン−α−オレフィン共重合体
からなる請求項１記載のバッグインボックス用内容器。2. The surface layer has a density of 0.86 to 0.95 g /
The bag-in-box inner container according to claim 1, comprising an ethylene-α-olefin copolymer of cm 3 (20 ° C).
無水物で変性された密度０．８６〜０．９５ｇ／ｃｍ3
（２０℃）のエチレン−α−オレフィン共重合体からな
る請求項１記載のバッグインボックス用内容器。3. An adhesive layer having a density of 0.86 to 0.95 g / cm 3 modified with an unsaturated carboxylic acid or an anhydride thereof.
The inner container for a bag-in-box according to claim 1, comprising an ethylene-α-olefin copolymer (20 ° C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26958892A JP3145206B2 (en) | 1992-09-11 | 1992-09-11 | Inner container for bag-in-box |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26958892A JP3145206B2 (en) | 1992-09-11 | 1992-09-11 | Inner container for bag-in-box |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0691823A JPH0691823A (en) | 1994-04-05 |
| JP3145206B2 true JP3145206B2 (en) | 2001-03-12 |
Family
ID=17474454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26958892A Expired - Fee Related JP3145206B2 (en) | 1992-09-11 | 1992-09-11 | Inner container for bag-in-box |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3145206B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4954103B2 (en) * | 2008-01-21 | 2012-06-13 | 日本合成化学工業株式会社 | Packaging film |
| WO2012124129A1 (en) * | 2011-03-15 | 2012-09-20 | The Nippon Synthetic Chemical Industry Co., Ltd. | Resin composition and molded product thereof |
| KR101404772B1 (en) * | 2013-11-19 | 2014-06-12 | (주)성림산업 | Endothelium and enveloped unified method for manufacturing container bag |
| TW201925321A (en) * | 2017-11-22 | 2019-07-01 | 日商三菱化學股份有限公司 | Resin composition, melt-molding material, multilayer structure, and liquid-packaging material |
-
1992
- 1992-09-11 JP JP26958892A patent/JP3145206B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0691823A (en) | 1994-04-05 |
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