JP2005239230A - Laminated material for paper-made container and paper-made container for liquid using it - Google Patents
Laminated material for paper-made container and paper-made container for liquid using it Download PDFInfo
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- JP2005239230A JP2005239230A JP2004053199A JP2004053199A JP2005239230A JP 2005239230 A JP2005239230 A JP 2005239230A JP 2004053199 A JP2004053199 A JP 2004053199A JP 2004053199 A JP2004053199 A JP 2004053199A JP 2005239230 A JP2005239230 A JP 2005239230A
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- 239000002648 laminated material Substances 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 title claims abstract description 26
- 239000010410 layer Substances 0.000 claims abstract description 62
- 230000004888 barrier function Effects 0.000 claims abstract description 48
- 239000010408 film Substances 0.000 claims abstract description 26
- 229920006267 polyester film Polymers 0.000 claims abstract description 21
- 239000010409 thin film Substances 0.000 claims abstract description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 11
- 239000000565 sealant Substances 0.000 claims abstract description 11
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 10
- 239000011087 paperboard Substances 0.000 claims abstract description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000123 paper Substances 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract description 7
- 238000010030 laminating Methods 0.000 abstract description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 9
- 239000012790 adhesive layer Substances 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 235000020124 milk-based beverage Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
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Abstract
Description
本発明は、果汁飲料、ジュース、お茶類、コーヒー、乳飲料、スープ等の液体飲料等を充填包装する紙容器用積層材料及びそれを用いた液体用紙容器に関するものである。 The present invention relates to a laminated material for paper containers for filling and packaging liquid drinks such as fruit juice drinks, juices, teas, coffee, milk drinks, and soups, and a liquid paper container using the same.
従来、液体飲料等を充填包装する紙容器用積層材料としては、図３に示す如く、外側から順に熱可塑性樹脂層（２′）、接着剤層（１３′）、板紙からなる基材層（１′）、接着剤層（１４′）、ガスバリア層（３′）、接着剤層（１５′）、シーラント層（４′）を積層した多層構成のものが多く使用されており、前記構成中のガスバリア層（３′）としては、アルミニウム箔が多く使用されるが、リサイクル性が悪くなる等の問題があった。これらの問題を改善するべく、ガスバリア性、リサイクル性等の機能を兼ね備えるものとして、前記ガスバリア層（３′）として、二軸延伸ポリエステルフィルムの片面に無機酸化物の蒸着薄膜層、ガスバリア性被膜層を積層したガスバリアフィルムを使用した容器用積層材料が提案されている（例えば、特許文献１参照。）。
ところが、前記提案されている容器用積層材料は、液体用紙容器に使用され、製函された時に蒸着薄膜層に亀裂が発生し、極く小さいピンホールができて、ガスバリア性が低下してしまい、長期間、例えば、１８０日間の賞味期限の内容物を保存する容器への使用は難しかった。 However, the proposed laminate material for containers is used for liquid paper containers, and when deposited, cracks occur in the deposited thin film layer, creating extremely small pinholes, resulting in a decrease in gas barrier properties. It has been difficult to use the container for storing the contents of the expiration date of 180 days, for example, for a long time.
本発明の課題は、液体用紙容器に使用され、製函された場合でも、優れたガスバリア性を保持する紙容器用積層材料及びそれを用いた液体用紙容器を提供することにある。 An object of the present invention is to provide a laminated material for paper containers that retains excellent gas barrier properties even when used in a liquid paper container and boxed, and a liquid paper container using the same.
本発明の請求項１に係る発明は、板紙からなる基材層の一方の面に熱可塑性樹脂層が積層され、他方の面にガスバリア層、シーラント層が積層されてなる紙容器用積層材料において、該ガスバリア層が二軸延伸ポリエステルフィルムと、エチレン・ビニルアルコール共重合体フィルムと、二軸延伸ポリエステルフィルムの片面に無機酸化物の蒸着薄膜層、水溶性高分子と（ａ）一種以上の金属アルコキシド及びその加水分解物又は（ｂ）塩化錫の少なくとも一方を含むものからなるガスバリア性被膜層を積層したガスバリアフィルムとを積層した積層構成のものからなることを特徴とする紙容器用積層材料である。
The invention according to
本発明の請求項２に係る発明は、上記請求項１に係る発明において、前記無機酸化物が酸化アルミニウム、酸化珪素、酸化マグネシウム又はそれらの混合物であることを特徴とする紙容器用積層材料である。
The invention according to
本発明の請求項３に係る発明は、上記請求項１又は請求項２に係る発明において、前記水溶性高分子がポリビニルアルコールであることを特徴とする紙容器用積層材料である。
The invention according to
本発明の請求項４に係る発明は、上記請求項１乃至請求項３のいずれか１項に係る発明において、前記金属アルコキシドがテトラエトキシシラン、トリイソプロポキシアルミニウム又はそれらの混合物であることを特徴とする紙容器用積層材料である。
The invention according to
本発明の請求項５に係る発明は、上記請求項１乃至請求項４のいずれか１項記載の紙容器用積層材料を用いて、シーラント層面を紙容器の内容物に接する側にして製函されているものからなることを特徴とする液体用紙容器である。
The invention according to
本発明の紙容器用積層材料は、板紙からなる基材層の一方の面に熱可塑性樹脂層が積層され、他方の面にガスバリア層、シーラント層が積層されてなる紙容器用積層材料において、該ガスバリア層が二軸延伸ポリエステルフィルムと、エチレン・ビニルアルコール共重合体フィルムと、二軸延伸ポリエステルフィルムの片面に無機酸化物の蒸着薄膜層、水溶性高分子と（ａ）一種以上の金属アルコキシド及びその加水分解物又は（ｂ）塩化錫の少なくとも一方を含むものからなるガスバリア性被膜層を積層したガスバリアフィルムとを積層した積層構成のものからなり、前記無機酸化物が酸化アルミニウム、酸化珪素、酸化マグネシウム又はそれらの混合物であり、前記水溶性高分子がポリビニルアルコールであり、前記金属アルコキシドがテトラエトキシシラン、トリイソプロポキシアルミニウム又はそれらの混合物であるので、蒸着薄膜にピンホールが発生しても、優れたガスバリア性を保持し、この紙容器用積層材料を用いた液体用紙容器は長期に亘り優れた内容物保存性を有している。 The laminated material for paper containers of the present invention is a laminated material for paper containers in which a thermoplastic resin layer is laminated on one side of a base material layer made of paperboard, and a gas barrier layer and a sealant layer are laminated on the other side. The gas barrier layer comprises a biaxially stretched polyester film, an ethylene / vinyl alcohol copolymer film, a vapor-deposited thin film layer of an inorganic oxide on one side of the biaxially stretched polyester film, a water-soluble polymer, and (a) one or more metal alkoxides. And a hydrolyzate thereof or (b) a gas barrier film in which a gas barrier film layer comprising at least one of tin chloride is laminated, and the inorganic oxide is aluminum oxide, silicon oxide, Magnesium oxide or a mixture thereof, the water-soluble polymer is polyvinyl alcohol, and the metal alkoxide is Since it is traethoxysilane, triisopropoxyaluminum, or a mixture thereof, even if pinholes occur in the deposited thin film, it retains excellent gas barrier properties, and liquid paper containers using this paper container laminate material will be used for a long time. It has excellent content preservation.
本発明の紙容器用積層材料及びそれを用いた液体用紙容器を、実施の形態に沿って以下に詳細に説明する。 The laminated material for paper containers of the present invention and the liquid paper container using the same will be described in detail below along the embodiments.
図１は本発明の一実施形態の紙容器用積層材料の側断面図であり、外側から厚み方向に順に、熱可塑性樹脂層（２）、接着剤層（１３）、基材層（１）、接着剤層（１４）、ガスバリア層（３）、接着剤層（１５）、シーラント層（４）を積層した構成で、前記構成中のガスバリア層（３）は二軸延伸ポリエステルフィルム（５）と、エチレン・ビニルアルコール共重合体フィルム（６）と、二軸延伸ポリエステルフィルム（８）の片面に無機酸化物の蒸着薄膜層（９）、ガスバリア性被膜層（１０）を積層したガスバリアフィルム（７）とをそれぞれ接着剤層（１１）及び（１２）を介して積層した積層構成からなっている。 FIG. 1 is a side sectional view of a laminated material for paper containers according to an embodiment of the present invention. In order from the outside in the thickness direction, a thermoplastic resin layer (2), an adhesive layer (13), and a base material layer (1). , An adhesive layer (14), a gas barrier layer (3), an adhesive layer (15), and a sealant layer (4), wherein the gas barrier layer (3) is a biaxially stretched polyester film (5). And a gas barrier film (6) and a gas barrier film (6) and a biaxially stretched polyester film (8) on which an inorganic oxide vapor-deposited thin film layer (9) and a gas barrier coating layer (10) are laminated. 7) are laminated through adhesive layers (11) and (12), respectively.
前記基材層（１）は、坪量１００〜５００ｇ／ｍ2 の板紙からなっている。 The base layer (1) is made from paperboard having a basis weight of 100 to 500 g / m 2.
前記熱可塑性樹脂層（２）は、ポリオレフィン系樹脂が好ましく、特に価格、物性面から厚さ１０μｍ〜３０μｍの低密度ポリエチレン樹脂が好ましい。 The thermoplastic resin layer (2) is preferably a polyolefin-based resin, and particularly preferably a low-density polyethylene resin having a thickness of 10 μm to 30 μm in view of cost and physical properties.
前記ガスバリア層（３）で使用される二軸延伸ポリエステルフィルム（５）及び（８）の厚みは６μｍ〜２５μｍの範囲のものを使用し、エチレン・ビニルアルコール共重合体フィルム（６）の厚みは８μｍ〜１５μｍの範囲のものを使用する。 The thickness of the biaxially stretched polyester films (5) and (8) used in the gas barrier layer (3) is in the range of 6 μm to 25 μm, and the thickness of the ethylene / vinyl alcohol copolymer film (6) is The thing of the range of 8 micrometers-15 micrometers is used.
前記蒸着薄膜層（９）の無機酸化物としては、酸化アルミニウム、酸化珪素、酸化マグネシウム又はそれらの混合物が好ましく、その膜厚は５〜３００ｎｍの範囲内であることが望ましく、その値は適宜選択される。ただし、膜厚が５ｎｍ未満であると二軸延伸ポリエステルフイルムの全面に均一な薄膜が形成されないことがあり、ガスバリア性の機能を十分に果たすことができない場合がある。また、膜厚が３００ｎｍを超えた場合は蒸着薄膜にフレキシビリティを保持させることができず、成膜後に折り曲げ、引っ張りなどの外的要因により、蒸着薄膜に亀裂を生じる恐れがあるため良くない。 As an inorganic oxide of the said vapor deposition thin film layer (9), an aluminum oxide, a silicon oxide, magnesium oxide, or a mixture thereof is preferable, The film thickness is desirably in the range of 5 to 300 nm, and the value is appropriately selected. Is done. However, if the film thickness is less than 5 nm, a uniform thin film may not be formed on the entire surface of the biaxially stretched polyester film, and the gas barrier function may not be sufficiently achieved. On the other hand, when the film thickness exceeds 300 nm, the deposited thin film cannot be kept flexible, and the deposited thin film may be cracked due to external factors such as bending and pulling after the deposition.
前記蒸着薄膜層（９）の積層方法は、通常の真空蒸着法により形成することができ、真空蒸着法による真空蒸着装置の加熱手段としては電子線加熱方式や抵抗加熱方式、誘導加
熱方式等が好ましく、二軸延伸ポリエステルフィルムとの密着性を向上させるために、プラズマアシスト法やイオンビームアシスト法を用いることも可能である。また、蒸着薄膜層（９）の透明性を上げるために蒸着の際、酸素ガスなど吹き込んだりする反応蒸着を行っても一向に構わない。
The deposition method of the deposited thin film layer (9) can be formed by a normal vacuum deposition method, and as a heating means of the vacuum deposition apparatus by the vacuum deposition method, there are an electron beam heating method, a resistance heating method, an induction heating method, and the like. Preferably, a plasma assist method or an ion beam assist method can be used in order to improve the adhesion with the biaxially stretched polyester film. In addition, in order to increase the transparency of the vapor deposition thin film layer (9), it is possible to carry out reactive vapor deposition in which oxygen gas or the like is blown during vapor deposition.
前記ガスバリア性被膜層（１０）は、さらに高いガスバリア性を付与するためと無機酸化物の蒸着薄膜層（９）を保護する為に積層するものであり、その構成成分は水溶性高分子と、（ａ）１種以上の金属アルコキシド及び加水分解物または（ｂ）塩化錫の少なくとも一方を含む水溶液あるいは水／アルコール混合溶液を主剤とするコーティング剤を塗布して形成する。水溶性高分子と塩化錫を水系（水あるいは水／アルコール混合）溶媒で溶解させた溶液、あるいはこれに金属アルコキシドを直接または予め加水分解させるなど処理を行ったものを混合した溶液を蒸着薄膜層（９）上にコーティング、加熱乾燥し形成したものである。 The gas barrier coating layer (10) is laminated to give higher gas barrier properties and to protect the vapor-deposited thin film layer (9) of inorganic oxide, and its constituent components are a water-soluble polymer, It is formed by applying a coating agent mainly composed of an aqueous solution or water / alcohol mixed solution containing at least one of (a) one or more metal alkoxides and a hydrolyzate or (b) tin chloride. Evaporation thin film layer: A solution in which water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a solution in which metal alkoxide is directly or previously hydrolyzed is mixed. (9) It is formed by coating and heating and drying.
前記ガスバリア性被膜層（１０）に用いられる水溶性高分子は、ポリビニルアルコール、ポリビニルピロリドン、デンプン、メチルセルロース、カルボキシメチルセルロース、アルギン酸ナトリウム等が挙げられる。特にポリビニルアルコール（以下、ＰＶＡとする）を用いた場合にガスバリア性が最も優れる。ここでいうＰＶＡは、一般にポリ酢酸ビニルを鹸化して得られるもので、酢酸基が数十％残存している、いわゆる部分鹸化ＰＶＡから酢酸基が数％しか残存していない完全鹸化ＰＶＡまでを含み、特に限定されない。 Examples of the water-soluble polymer used in the gas barrier coating layer (10) include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used, gas barrier properties are most excellent. The PVA as used herein is generally obtained by saponifying polyvinyl acetate, ranging from a so-called partially saponified PVA in which several tens percent of acetic acid groups remain to completely saponified PVA in which only several percent of acetic acid groups remain. Including, but not limited to.
また、前記塩化錫は塩化第一錫（ＳｎＣｌ2）、塩化第二錫（ＳｎＣｌ4）あるいはこれらの混合物であっても良く、無水物でも水和物でも良い。 The tin chloride may be stannous chloride (SnCl 2 ), stannic chloride (SnCl 4 ), or a mixture thereof, and may be an anhydride or a hydrate.
さらに、前記金属アルコキシドはテトラエトキシシラン又はトリイソプロポキシアルミニウムあるいはそれらの混合物が好ましい。 Further, the metal alkoxide is preferably tetraethoxysilane, triisopropoxyaluminum or a mixture thereof.
前記ガスバリア性被膜層（１０）の積層方法は、通常用いられるディッピング法、ロールコーティング法、スクリーン印刷法、スプレー法などの公知の手段を用いることができる。乾燥後の被膜厚さが０．０１μｍ以上あればよいが、厚さが５０μｍを超えると膜にクラックが生じ易くなるため、０．０１〜５０μｍの範囲が好ましい。 As the method for laminating the gas barrier coating layer (10), known means such as a commonly used dipping method, roll coating method, screen printing method, spray method and the like can be used. The film thickness after drying may be 0.01 μm or more, but if the thickness exceeds 50 μm, cracks are likely to occur in the film, so the range of 0.01 to 50 μm is preferable.
前記シーラント層（４）としては、シール性があり、臭気等が少ない樹脂であれば特に限定されないが、低温シール性などの点から低密度ポリエチレン樹脂、直鎖状低密度ポリエチレン樹脂等が好ましい。厚みは３０μｍ〜１００μｍの範囲のものを使用する。 The sealant layer (4) is not particularly limited as long as it is a resin having a sealing property and a low odor, but a low density polyethylene resin, a linear low density polyethylene resin, or the like is preferable from the viewpoint of a low temperature sealing property. A thickness of 30 μm to 100 μm is used.
前記接着剤層（１１、１２、１３、１３′、１４、１４′、１５、１５′）は、一般的にポリウレタン系接着剤を使用する。塗布量は１ｇ／ｍ2 〜５ｇ／ｍ2（乾燥状態）が良く、積層方法は公知のグラビアコーティング法で積層する。 The adhesive layer (11, 12, 13, 13 ', 14, 14', 15, 15 ') generally uses a polyurethane adhesive. The coating amount 1g / m 2 ~5g / m 2 ( dry) good, lamination method to laminate in a known gravure coating method.
図２（ａ）は本発明の液体用紙容器の一実施形態を示す斜視図であり、（ｂ）は（ａ）の液体用紙容器の断面説明図である。液体用紙容器（２０）は胴部（２１）、トップ部（２２）、ボトム部（２３）から構成されており、かつ、トップ部（２２）には内容物充填用及び飲み口用の開口部（２４）が設けられている。内容物を充填した場合は前記開口部（２４）をプルタブ形状の蓋材で密封する。胴部（２１）、トップ部（２２）、ボトム部（２３）には通常は同一構成の本発明の紙容器用積層材料を用いるが、トップ部（２２）及びボトム部（２３）には異なる構成、例えばガスバリア層としてエチレン・ビニルアルコール共重合体フィルムを積層していない構成の紙容器用積層材料を用いても構わない。 2A is a perspective view showing an embodiment of the liquid paper container of the present invention, and FIG. 2B is a cross-sectional explanatory view of the liquid paper container of FIG. The liquid paper container (20) is composed of a body part (21), a top part (22), and a bottom part (23), and the top part (22) has openings for filling contents and drinking mouths. (24) is provided. When the contents are filled, the opening (24) is sealed with a pull tab-shaped lid. The body portion (21), the top portion (22), and the bottom portion (23) usually use the laminated material for paper containers of the present invention having the same configuration, but the top portion (22) and the bottom portion (23) are different. You may use the laminated material for paper containers of the structure which has not laminated | stacked the structure, for example, an ethylene-vinyl alcohol copolymer film, as a gas barrier layer.
本発明の液体用紙容器は上記に示した円筒形状の紙容器に限定されず、例えば四角形状
のものでも良い。
The liquid paper container of the present invention is not limited to the cylindrical paper container shown above, and may be, for example, a rectangular shape.
本発明の紙容器用積層材料及びそれを用いた液体用紙容器を具体的な実施例を挙げて以下に説明する。 The laminated material for paper containers and the liquid paper container using the same according to the present invention will be described below with specific examples.
基材層（１）として坪量３２０ｇ／ｍ2 の板紙を準備し、熱可塑性樹脂層（２）として密度０．９１５ｇ／ｃｍ3 の低密度ポリエチレン樹脂を準備し、ガスバリア層（３）に使用する材料として、厚さ１２μｍの二軸延伸ポリエステルフィルム、厚さ１５μｍのエチレン・ビニルアルコール共重合体フィルム（（株）クラレ、商品名：エバールフイルム）及び厚さ１２μｍの二軸延伸ポリエステルフィルムの片面に厚さ５０ｎｍの酸化珪素からなる蒸着薄膜層を積層し、その上にテトラエトキシシラン１０．４ｇに０．１Ｎ塩酸を８９．６ｇ加え、３０分攪拌し加水分解させた固形分３重量％（ＳｉＯ2換算）の溶液とポリビニルアルコール３重量％水／イソプロピルアルコール溶液（水／イソプロピルアルコ−ルは重量％比で９０／１０）を重量％比で６０／４０に混合した塗布液を用いて、厚さ０．０５μｍのガスバリア性被膜層を積層したガスバリアフィルム（７）を準備し、シーラント層（４）に使用する材料として密度０．９２０ｇ／ｃｍ3 の直鎖状低密度ポリエチレン樹脂を準備し、さらにポリウレタン系接着剤を準備した。これらの材料を用いてドライラミネート機及び溶融押出ラミネート機を用いて、低密度ポリエチレン樹脂（２０μｍ）／板紙／ポリウレタン系接着剤（５ｇ／ｍ2 ）／二軸延伸ポリエステルフィルム（１２μｍ）／ポリウレタン系接着剤（５ｇ／ｍ2 ）／エバールフィルム（１５μｍ）／ポリウレタン系接着剤（５ｇ／ｍ2 ）／ガスバリア性被膜層（０．０５μｍ）／酸化珪素薄膜（５０ｎｍ）／二軸延伸ポリエステルフィルム（１２μｍ）／ポリウレタン系接着剤（３ｇ／ｍ2 ）／直鎖状低密度ポリエチレン樹脂（６０μｍ）構成の本発明の紙容器用積層材料を作成した。
A paperboard with a basis weight of 320 g / m 2 is prepared as the base material layer (1), a low density polyethylene resin with a density of 0.915 g / cm 3 is prepared as the thermoplastic resin layer (2), and used for the gas barrier layer (3). As a material to be used, a biaxially stretched polyester film having a thickness of 12 μm, an ethylene / vinyl alcohol copolymer film having a thickness of 15 μm (Kuraray Co., Ltd., trade name: Eval Film), and a biaxially stretched polyester film having a thickness of 12 μm A vapor-deposited thin film layer made of silicon oxide having a thickness of 50 nm is laminated on the substrate, 89.6 g of 0.1N hydrochloric acid is added to 10.4 g of tetraethoxysilane, and the mixture is stirred for 30 minutes to hydrolyze to 3 wt% solid content ( the solution of
以下に本発明の比較用の実施例について説明する。 Examples for comparison of the present invention will be described below.
実施例１で使用した同一種類の材料及び方法で、積層構成が低密度ポリエチレン樹脂（２０μｍ）／板紙／ポリウレタン系接着剤（５ｇ／ｍ2 ）／二軸延伸ポリエステルフィルム（１２μｍ）／ポリウレタン系接着剤（５ｇ／ｍ2 ）／ガスバリア性被膜層（０．０５μｍ）／酸化珪素薄膜（５０ｎｍ）／二軸延伸ポリエステルフィルム（１２μｍ）／ポリウレタン系接着剤（３ｇ／ｍ2 ）／直鎖状低密度ポリエチレン樹脂（６０μｍ）である比較用の紙容器用積層材料を作成した。 The same type of material and method used in Example 1, with a laminated structure of low density polyethylene resin (20 μm) / paperboard / polyurethane adhesive (5 g / m 2 ) / biaxially stretched polyester film (12 μm) / polyurethane adhesive Agent (5 g / m 2 ) / gas barrier coating layer (0.05 μm) / silicon oxide thin film (50 nm) / biaxially stretched polyester film (12 μm) / polyurethane adhesive (3 g / m 2 ) / linear low density A comparative paper container laminate material made of polyethylene resin (60 μm) was prepared.
〈評価〉
実施例１の本発明の紙容器用積層材料及び実施例２の比較用の紙容器用積層材料を用いて、内容積２１４ｍｌの液体用紙容器を作成し、その紙容器の酸素透過度を以下の測定方法で測定し、評価した。その結果を表１に示す。
（１）酸素透過度測定方法
モダンコントロール社製（ＭＯＣＯＮ ＯＸＴＲＡＮ ２／２０）を用いて、３０℃、７０％ＲＨ雰囲気下で測定した。
<Evaluation>
Using the laminated material for paper containers of the present invention of Example 1 and the laminated material for paper containers for comparison of Example 2, a liquid paper container having an inner volume of 214 ml was prepared, and the oxygen permeability of the paper container was determined as follows. It measured and evaluated by the measuring method. The results are shown in Table 1.
(1) Oxygen permeability measuring method It measured in 30 degreeC and 70% RH atmosphere using the modern control company make (
１，１′…基材層
２，２′…熱可塑性樹脂層
３，３′…ガスバリア層
４，４′…シーラント層
５…二軸延伸ポリエステルフィルム
６…エチレン・ビニルアルコール共重合体フィルム
７…ガスバリアフィルム
８…二軸延伸ポリエステルフィルム
９…蒸着薄膜層
１０…ガスバリア性被膜層
１１，１２，１３，１３′，１４，１４′，１５，１５′…接着剤層
２０…液体用紙容器
２１…胴部
２２…トップ部
２３…ボトム部
２４…開口部
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| JP2004053199A JP4424005B2 (en) | 2004-02-27 | 2004-02-27 | Laminated material for paper container and liquid paper container using the same |
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| JP2004053199A JP4424005B2 (en) | 2004-02-27 | 2004-02-27 | Laminated material for paper container and liquid paper container using the same |
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| JP2005239230A true JP2005239230A (en) | 2005-09-08 |
| JP4424005B2 JP4424005B2 (en) | 2010-03-03 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007033974A1 (en) * | 2007-07-19 | 2009-01-22 | Keienburg Agentur für Verpackung GmbH | Liquid container whose jacket consists largely of pulp-containing material |
| JP2010089821A (en) * | 2008-10-08 | 2010-04-22 | Toppan Printing Co Ltd | Paper container for liquid |
| EP2384886A1 (en) | 2010-02-26 | 2011-11-09 | Günter Keienburg | Drinks can mainly comprised of material containing cellulose and a food-safe barrier coating for pressurised drinks |
| DE102010000562A1 (en) | 2010-02-26 | 2011-11-17 | Günter Keienburg | Beverage can for containing beverages with carbonic acid under high pressure, comprises a casing closed by bottom- and cover-elements, where the casing consists of a parallely wrapped laminate from cellulose containing material |
| DE102010037965A1 (en) | 2010-10-05 | 2012-04-05 | Günter Keienburg | Beverage can for containing beverages with carbonic acid under high pressure, comprises a casing closed by bottom- and cover-elements, where the casing consists of a parallely wrapped laminate from cellulose containing material |
| DE202011050151U1 (en) | 2011-05-17 | 2012-08-22 | Günter Keienburg | Beverage can, which largely consists of pulp-containing material and has a food-compatible barrier layer, for under pressure drinks |
-
2004
- 2004-02-27 JP JP2004053199A patent/JP4424005B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007033974A1 (en) * | 2007-07-19 | 2009-01-22 | Keienburg Agentur für Verpackung GmbH | Liquid container whose jacket consists largely of pulp-containing material |
| JP2010089821A (en) * | 2008-10-08 | 2010-04-22 | Toppan Printing Co Ltd | Paper container for liquid |
| EP2384886A1 (en) | 2010-02-26 | 2011-11-09 | Günter Keienburg | Drinks can mainly comprised of material containing cellulose and a food-safe barrier coating for pressurised drinks |
| DE102010000562A1 (en) | 2010-02-26 | 2011-11-17 | Günter Keienburg | Beverage can for containing beverages with carbonic acid under high pressure, comprises a casing closed by bottom- and cover-elements, where the casing consists of a parallely wrapped laminate from cellulose containing material |
| DE102010037965A1 (en) | 2010-10-05 | 2012-04-05 | Günter Keienburg | Beverage can for containing beverages with carbonic acid under high pressure, comprises a casing closed by bottom- and cover-elements, where the casing consists of a parallely wrapped laminate from cellulose containing material |
| DE202011050151U1 (en) | 2011-05-17 | 2012-08-22 | Günter Keienburg | Beverage can, which largely consists of pulp-containing material and has a food-compatible barrier layer, for under pressure drinks |
| WO2012155890A1 (en) | 2011-05-17 | 2012-11-22 | Keienburg Guenter | Drinks container which consists largely of cellulose-containing material, and has a food-compatible barrier layer, for pressurized drinks |
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