JP2021020392A - ガスバリア積層体及びこれを用いた包装材 - Google Patents
ガスバリア積層体及びこれを用いた包装材 Download PDFInfo
- Publication number
- JP2021020392A JP2021020392A JP2019138978A JP2019138978A JP2021020392A JP 2021020392 A JP2021020392 A JP 2021020392A JP 2019138978 A JP2019138978 A JP 2019138978A JP 2019138978 A JP2019138978 A JP 2019138978A JP 2021020392 A JP2021020392 A JP 2021020392A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- gas barrier
- barrier laminate
- polyvinyl alcohol
- based resin
- 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.)
- Granted
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 92
- 239000005022 packaging material Substances 0.000 title claims abstract description 43
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 87
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 72
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 33
- -1 Polypropylene Polymers 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 43
- 239000004743 Polypropylene Substances 0.000 claims description 41
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- 230000003746 surface roughness Effects 0.000 claims description 12
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
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- 239000012462 polypropylene substrate Substances 0.000 abstract 1
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- 239000007788 liquid Substances 0.000 description 20
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- 238000010438 heat treatment Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
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- 229920001567 vinyl ester resin Polymers 0.000 description 9
- 238000007127 saponification reaction Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
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- 238000010894 electron beam technology Methods 0.000 description 6
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- 239000000243 solution Substances 0.000 description 4
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 2
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- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 2
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- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
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- 239000005020 polyethylene terephthalate Substances 0.000 description 2
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- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
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- 239000012748 slip agent Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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Abstract
Description
図1は、本実施形態に係るガスバリア積層体を示す模式断面図である。図1に示すガスバリア積層体10は、基材層1と、第1のポリビニルアルコール系樹脂層3aと、金属酸化物層5と、第2のポリビニルアルコール系樹脂層3bとをこの順序で備える積層構造を有する。
基材層1は、ポリプロピレン系樹脂からなる。ポリプロピレン系樹脂としては、例えば、プロピレンのホモポリマー、ランダムコポリマー及びブロックコポリマーが挙げられる。基材層1に耐熱性が求められる場合、ポリプロピレン系樹脂はプロピレンのホモポリマーであることが好ましい。ただし、プロピレンのホモポリマーフィルムは、上述のとおり、その表面が葉脈状となりやすいという欠点を有している。葉脈状のフィルム表面の面粗さSaは、例えば、0.2μm超であり、0.21〜0.5μmであってもよい。
・測定モード:Phase
・スキャンスピード:4μm/sec
・スキャンレンジ:10/−20μm
・スキャン回数:1回
・補間:完全補間
・面補正:4次
・鏡筒レンズ:1倍
・対物レンズ:5倍
第1のポリビニルアルコール系樹脂層3aを構成する樹脂としては、ビニルエステル単位がケン化されてなるビニルアルコール単位を有するものであればよく、例えば、ポリビニルアルコール(PVA)、エチレン−ビニルアルコール共重合体(EVOH)が挙げられる。耐熱性やガスバリア性の観点から、EVOHを好適に用いることができる。
金属酸化物層5はガスバリア性を有する。金属酸化物として、酸化ケイ素(SiOx)及び酸化アルミニウム(AlOx)等が挙げられる。これらの金属酸化物を採用することで、厚さを抑えつつ高いガスバリア性を得ることができる。加工時に引っ張り延伸性に優れる観点から、金属酸化物層5は酸化ケイ素で構成されていてよい。
第2のポリビニルアルコール系樹脂層3bを構成するポリビニルアルコール系樹脂に関しては、第1のポリビニルアルコール系樹脂層3aについて説明した内容を参照することができる。
ガスバリア積層体10は、例えば、基材層1上に第1のポリビニルアルコール系樹脂層3aを形成する工程と、第1のポリビニルアルコール系樹脂層3a上に金属酸化物層5を形成する工程と、金属酸化物層5上に第2のポリビニルアルコール系樹脂層3bを形成する工程とを経て製造される。
本工程においては、ポリビニルアルコール系樹脂及び液状媒体を含む塗布液を用いることができる。当該塗布液は、例えば合成により得られたポリビニルアルコール系樹脂の粉末を、液状媒体に溶解させて得ることができる。液状媒体としては、水、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミドN−メチルピロリドン、各種グリコール類、トリメチロールプロパン等の多価アルコール類、エチレンジアミン、ジエチレントリアミン等のアミン類などが挙げられる。これらは単独で又は二種以上組み合わせて用いてよい。環境負荷低減等の観点から、液状媒体として水を用いることができる。この場合、ポリビニルアルコール系樹脂の粉末を、高温(例えば80℃)の水に溶解させることで塗布液を得ることができる。
金属酸化物層5は、例えば真空成膜で形成することができる。真空成膜では、物理気相成長法又は化学気相成長法を用いることができる。物理気相成長法としては、真空蒸着法、スパッタリング法、イオンプレーティング法等を挙げることができるが、これらに限定されるものではない。化学気相成長法としては、熱CVD法、プラズマCVD法、光CVD法等を挙げることができるが、これらに限定されるものではない。
本工程は、第1のポリビニルアルコール系樹脂層3aを形成する工程と同様に、塗布液を用いることができる。塗布液に関しては、第1のポリビニルアルコール系樹脂層3aを形成する工程の項にて説明した内容を参照することができる。
図3に示す包装材50は、ガスバリア積層体10と、ガスバリア積層体10の内面10F上に設けられたポリプロピレン系シーラント層20とを備える。包装材50の全質量を基準として、基材層1及びポリプロピレン系シーラント層20の合計の質量比率が85質量%以上(好ましくは90質量%以上又は95質量%以上)であり、包装材50はモノマテリアルを実現している。
(基材層)
・ポリプロピレン系樹脂:プロピレンのモノポリマー(モノPP)
(ポリビニルアルコール系樹脂層)
・EVOH:エバールL171B(株式会社クラレ製)
・PVA:ポバール60−98(株式会社クラレ製)
・TEOS:KBE04(信越化学工業株式会社製)
(シーラント層)
・ポリプロピレン系シーラントフィルム:トレファンZK207#60(CPP、厚さ60μm、東レ株式会社)
上記モノPPを使用してOPPフィルム(基材層)を製膜すると同時に、OPPフィルムの表面にEVOHの層(第1のポリビニルアルコール系樹脂層)を押出法によって形成した。EVOHの層の単位面積あたりの質量は0.97g/m2であった。EVOHの層の厚さは0.8μmであり、面粗さSaは0.08μmであった。EVOHの層を剥がしてOPPフィルムの面粗さSaを測定したところ、その値は0.23μmであった。面粗さSaは、三次元非接触表面形状計測システム(Vertscan R3300h Lite、株式会社菱化システム製)を使用し、上述の条件で測定した。
金属酸化物層として、SiOx膜(50nm)の代わりに、AlOx膜(50nm)を形成したことの他は、実施例1と同様にしてガスバリア積層体及び包装材を作製し、各評価を行った。AlOx膜は、電子ビーム加熱によってアルミニウムインゴットを蒸発させ、酸素を導入して形成した。表1に結果を示す。
PVAとTEOSの質量比が50/50の層を形成する代わりに、PVAとTEOSの質量比が97/3の層を形成したことの他は、実施例1と同様にしてガスバリア積層体及び包装材を作製し、各評価を行った。表1に結果を示す。
PVAとTEOSの質量比が50/50の層を形成せず、OPPフィルムの表面にSiOx膜(50nm)を直接形成したことの他は、実施例1と同様にしてガスバリア積層体及び包装材を作製し、各評価を行った。表2に結果を示す。
第1のポリビニルアルコール系樹脂層として、EVOHの層(単位面積あたりの質量0.97g/m2、厚さ0.8μm)を形成する代わりに、PVAの層(単位面積あたりの質量2.8g/m2、厚さ2.3μm)を形成したことの他は、実施例1と同様にしてガスバリア積層体及び包装材を作製し、各評価を行った。表2に結果を示す。
第1のポリビニルアルコール系樹脂層として、EVOHの層(単位面積あたりの質量0.97g/m2、厚さ0.8μm)を形成する代わりに、EVOHの層(単位面積あたりの質量0.40g/m2、厚さ0.33μm)を形成したことの他は、実施例1と同様にしてガスバリア積層体及び包装材を作製し、各評価を行った。表2に結果を示す。
Claims (13)
- ポリプロピレン系基材層と、
第1のポリビニルアルコール系樹脂層と、
金属酸化物層と、
をこの順序で備える積層構造を有し、
前記第1のポリビニルアルコール系樹脂層の単位面積あたりの質量が0.5〜2.5g/m2である、ガスバリア積層体。 - 前記第1のポリビニルアルコール系樹脂層の前記金属酸化物層と接する側の面粗さSaが0.2μm以下である、請求項1に記載のガスバリア積層体。
- 前記第1のポリビニルアルコール系樹脂層の前記金属酸化物層と接する側の面粗さSaが0.1μm以下である、請求項1に記載のガスバリア積層体。
- 前記ポリプロピレン系基材層がプロピレンのモノポリマー層である、請求項1〜3のいずれか一項に記載のガスバリア積層体。
- 前記第1のポリビニルアルコール系樹脂層とともに前記金属酸化物層を挟む第2のポリビニルアルコール系樹脂層を更に備える、請求項1〜4のいずれか一項に記載のガスバリア積層体。
- 前記第2のポリビニルアルコール系樹脂層がシラン化合物を含む、請求項5に記載のガスバリア積層体。
- 前記第2のポリビニルアルコール系樹脂層の質量に対する、前記シラン化合物の質量比が0.05〜0.95である、請求項6に記載のガスバリア積層体。
- 前記第2のポリビニルアルコール系樹脂層の厚さが0.1〜1.0μmである、請求項5〜7のいずれか一項に記載のガスバリア積層体。
- 前記第1のポリビニルアルコール系樹脂層の厚さが0.4〜2.0μmである、請求項1〜8のいずれか一項に記載のガスバリア積層体。
- 前記金属酸化物層が厚さ5〜100nmの蒸着層である、請求項1〜9のいずれか一項に記載のガスバリア積層体。
- 前記ポリプロピレン系基材層の前記第1のポリビニルアルコール系樹脂層が設けられている側の反対側の表面上に、プロピレンと他のモノマーとの共重合体層を更に備え、
前記他のモノマーがエチレン及びブテンの少なくとも一方である、請求項1〜10のいずれか一項に記載のガスバリア積層体。 - ポリプロピレン系基材層と第1のポリビニルアルコール系樹脂層との間に、密着層を更に備える、請求項1〜11のいずれか一項に記載のガスバリア積層体。
- 請求項1〜12のいずれか一項に記載のガスバリア積層体と、
前記ガスバリア積層体の表面上に設けられたポリプロピレン系シーラント層と、
を備え、
包装材の全質量を基準として、前記ポリプロピレン系基材層及び前記ポリプロピレン系シーラント層の合計の質量比率が85質量%以上である、包装材。
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