JP5499128B2 - Packaging material manufacturing method - Google Patents
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- JP5499128B2 JP5499128B2 JP2012209005A JP2012209005A JP5499128B2 JP 5499128 B2 JP5499128 B2 JP 5499128B2 JP 2012209005 A JP2012209005 A JP 2012209005A JP 2012209005 A JP2012209005 A JP 2012209005A JP 5499128 B2 JP5499128 B2 JP 5499128B2
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- 239000005022 packaging material Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000010410 layer Substances 0.000 claims description 76
- 239000010419 fine particle Substances 0.000 claims description 67
- 230000002209 hydrophobic effect Effects 0.000 claims description 67
- 239000012790 adhesive layer Substances 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011164 primary particle Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000007756 gravure coating Methods 0.000 claims description 4
- 238000007606 doctor blade method Methods 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- -1 carrero Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 14
- 229910002012 Aerosil® Inorganic materials 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 9
- 235000013618 yogurt Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 239000004922 lacquer Substances 0.000 description 6
- 239000000565 sealant Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000004831 Hot glue Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 239000002648 laminated material Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009816 wet lamination Methods 0.000 description 1
Landscapes
- Packages (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、包装材料に関する。より具体的には、食品、飲料品、医薬品、化粧品、化学品等を包装するために用いる包装材料に関する。特に、内容物の非付着性に優れた包装材料に関する。 The present invention relates to a packaging material. More specifically, the present invention relates to a packaging material used for packaging foods, beverages, pharmaceuticals, cosmetics, chemicals, and the like. In particular, the present invention relates to a packaging material excellent in non-adhesiveness of contents.
従来より多種多様の包装材料が知られているが、その内容物も多岐にわたる。例えば、ゼリー菓子、プリン、ヨーグルト、液体洗剤、練り歯磨き、カレールー、シロップ、ワセリン、洗顔クリーム、洗顔ムース等のように、食品、飲料品、医薬品、化粧品、化学品等がある。また、内容物の性状も固体、半固体、液体、粘性体、ゲル状物等のように様々なものがある。 A wide variety of packaging materials are known in the past, but their contents are also diverse. For example, there are foods, beverages, pharmaceuticals, cosmetics, chemicals and the like such as jelly confectionery, pudding, yogurt, liquid detergent, toothpaste, carrero, syrup, petrolatum, face wash cream, face wash mousse and the like. In addition, the contents have various properties such as solid, semi-solid, liquid, viscous material, and gel-like material.
これらの内容物を包装するための包装材料においては、密封性が要求されるほかに、内容物、包装形態、用途等に応じて熱接着性、遮光性、耐熱性、耐久性等が要求される。
ところが、これらの特性を満たしている包装材料であっても、次のような問題がある。すなわち、内容物が包装材料に付着するという問題である。内容物が包装材料に付着すれば、内容物をすべて使い切ることが困難になり、それだけ無駄が生じることになる。また、内容物をすべて使い切るためには包装材料に付着した内容物を別途に回収しなければならず、手間がかかる。このため、包装材料では、上記のような密封性等のほか、内容物が包装材料に付着しにくい性質（非付着性）を備えていることが必要である。
The packaging materials for packaging these contents are required to have hermeticity as well as thermal adhesiveness, light shielding, heat resistance, durability, etc. depending on the contents, packaging form, application, etc. The
However, even packaging materials that satisfy these characteristics have the following problems. That is, there is a problem that the contents adhere to the packaging material. If the contents adhere to the packaging material, it becomes difficult to use up all the contents, resulting in waste. In addition, in order to use up all the contents, the contents attached to the packaging material must be collected separately, which is troublesome. For this reason, the packaging material needs to have a property (non-adhesiveness) that the contents are difficult to adhere to the packaging material in addition to the above-described sealing property and the like.
これに対し、接着層を介して一体化された基材層とヒートシール層とを備えた蓋材において、ヒートシール層が、付着防止効果を有するグリセリン酸エステル、ポリグリセリン脂肪酸エステル、ペンタエリスリトール脂肪酸エステル、ポリオキシプロピレン・ポリオキシエチレンブロックポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、脂肪酸アミド等を含むポリオレフィンからなり、その厚さが１０μｍよりも厚く、接着層と該ヒートシール層との間にポリオレフィンからなる中間層が設けられていることを特徴とする充填物付着防止蓋材が提案されている（特許文献１）。 On the other hand, in a lid provided with a base material layer and a heat seal layer integrated through an adhesive layer, the heat seal layer has an anti-adhesion effect, glyceric acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid. It consists of polyolefin containing ester, polyoxypropylene / polyoxyethylene block polymer, sorbitan fatty acid ester, polyoxyethylene alkyl ether, fatty acid amide, etc., and its thickness is thicker than 10 μm, between the adhesive layer and the heat seal layer There has been proposed a filler adhesion prevention lid material characterized in that an intermediate layer made of polyolefin is provided (Patent Document 1).
しかしながら、上記のような蓋材では、使用できるヒートシール層の種類又は厚みが制限される上、グリセリン酸エステル等の添加剤の使用量を厳格に制御しなければならない。添加剤の使用量が多すぎるとヒートシール性能を低下させる一方、添加剤の使用量を少なくすればそれだけ付着防止効果が低下する。この点において実用化を進める上ではさらなる改善の余地がある。 However, in the lid material as described above, the type or thickness of the heat seal layer that can be used is limited, and the amount of additive such as glycerate must be strictly controlled. When the amount of the additive used is too large, the heat sealing performance is lowered. On the other hand, when the amount of the additive used is reduced, the adhesion preventing effect is lowered accordingly. In this respect, there is room for further improvement in promoting practical use.
従って、本発明の主な目的は、良好な熱接着性を維持しつつ、優れた非付着性を持続的に発揮できる包装材料を提供することにある。 Accordingly, a main object of the present invention is to provide a packaging material capable of continuously exhibiting excellent non-adhesiveness while maintaining good thermal adhesiveness.
本発明者は、従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定の構造を有する積層体を包装材料として採用することにより上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by adopting a laminate having a specific structure as a packaging material, and has completed the present invention. It was.
すなわち、本発明は、下記の包装材料の製造方法に係る。
１． 少なくとも基材層及び熱接着層を有する積層体からなる包装材料を製造する方法であって、
前記包装材料は、熱接着層が包装材料の一方の面の最外層として積層されており、前記熱接着層が他の層と隣接していない最外面に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子が付着し、疎水性酸化物微粒子が三次元網目状構造からなる多孔質層を形成しており、疎水性酸化物微粒子が内容物と接触可能な状態で使用されるものであり、
当該熱接着層の表面に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子を付着させる工程を含み、疎水性酸化物微粒子を溶媒に分散させてなる分散体を用いて熱接着層上に塗膜を形成した後に乾燥する方法により前記工程を実施する、包装材料の製造方法。
２． 前記工程が、ロールコーティング、グラビアコーティング、バーコート、ドクターブレードコーティング又は刷毛塗りである、前記項１に記載の製造方法。
３． 前記溶媒がアルコールである、前記項１又は２に記載の製造方法。
４． 疎水性酸化物微粒子の付着量が０．０１〜１０ｇ／ｍ２である、前記項１〜３のいずれかに記載の製造方法。
５． 分散体がワックスを含まない、前記項１〜４のいずれかに記載の製造方法。
６． 多孔質層の厚みが０．１〜５μｍである、前記項１〜５に記載の製造方法。
７． 疎水性酸化物微粒子は熱接着層の全面に付着している、前記項１〜６のいずれかに記載の製造方法。
８． 前記包装材料が蓋材である、前記項１〜７のいずれかに記載の製造方法。
９． 前記項１〜８のいずれかに記載の製造方法により得られる包装材料。
１０． 前記項８に記載の製造方法により得られる蓋材。
１１． 容器に内容物が充填され、その開口部と蓋材の熱接着層とが接するような状態で密封される蓋材である、前記項１０に記載の蓋材。
That is, this invention concerns on the manufacturing method of the following packaging material.
1. A method for producing a packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer,
The packaging material has a thermal adhesive layer laminated as an outermost layer on one side of the packaging material, and the thermal adhesive layer is hydrophobic with an average primary particle diameter of 3 to 100 nm on the outermost surface not adjacent to the other layer. The oxide fine particles are adhered, the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure, and the hydrophobic oxide fine particles are used in a state where they can come into contact with the contents.
Including a step of adhering hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm to the surface of the thermal adhesive layer, and applying the dispersion onto the thermal adhesive layer using a dispersion obtained by dispersing the hydrophobic oxide fine particles in a solvent. The manufacturing method of the packaging material which implements the said process by the method of drying after forming a film | membrane.
2. Item 2. The manufacturing method according to Item 1, wherein the step is roll coating, gravure coating, bar coating, doctor blade coating, or brush coating.
3. Item 3. The method according to Item 1 or 2, wherein the solvent is alcohol.
4). Item 4. The production method according to any one of Items 1 to 3, wherein the adhesion amount of the hydrophobic oxide fine particles is 0.01 to 10 g / m 2 .
5. Item 5. The method according to any one of Items 1 to 4 , wherein the dispersion does not contain a wax .
6). Item 6. The method according to Items 1 to 5 , wherein the porous layer has a thickness of 0.1 to 5 µm.
7). Item 7. The manufacturing method according to any one of Items 1 to 6, wherein the hydrophobic oxide fine particles are attached to the entire surface of the thermal adhesive layer.
8). Item 8. The manufacturing method according to any one of Items 1 to 7, wherein the packaging material is a lid.
9. The packaging material obtained by the manufacturing method in any one of said claim | item 1 -8.
10. The lid | cover material obtained by the manufacturing method of said claim | item 8.
11. Item 11. The cover material according to Item 10, which is a cover material that is sealed in a state in which the container is filled with the contents and the opening and the thermal adhesive layer of the cover material are in contact with each other.
本発明の包装材料は、良好な熱接着性を維持しながらも、優れた非付着性を発揮することができる。すなわち、熱接着層の種類、厚み等の制限を受けることなく、熱接着性を実用上阻害せずに、高い非付着性を得ることができる。より具体的には、熱接着時において、熱接着される領域上に存在する疎水性酸化物微粒子は当該熱接着層中に埋め込まれるので熱接着を阻害しない一方、熱接着される領域外に存在する疎水性酸化物微粒子はそのまま熱接着層上に保持されているのでその高い非付着性を発揮することができる。 The packaging material of the present invention can exhibit excellent non-adhesiveness while maintaining good thermal adhesiveness. That is, high non-adhesiveness can be obtained without impeding the thermal adhesiveness practically without being restricted by the type and thickness of the thermal adhesive layer. More specifically, at the time of thermal bonding, the hydrophobic oxide fine particles existing on the heat-bonded region are embedded in the heat-bonding layer and thus do not inhibit the heat-bonding, but exist outside the heat-bonded region. Since the hydrophobic oxide fine particles are held on the thermal adhesive layer as they are, their high non-adhesiveness can be exhibited.
また、本発明の製造方法によれば、熱接着層に疎水性酸化物微粒子を付与するだけで良いので、熱接着層を構成する原材料への添加剤の配合の制御をする必要がなく、よってその配合率の制御等が不要となる分、生産効率、コスト等の面で有利である。しかも、前記のように、熱接着層に接着しろを考慮せずに全面に疎水性酸化物微粒子を付着させるだけで熱接着を行うことができるという点でも有利である。 Further, according to the production method of the present invention, it is only necessary to impart hydrophobic oxide fine particles to the thermal adhesive layer, so there is no need to control the blending of additives into the raw materials constituting the thermal adhesive layer. This is advantageous in terms of production efficiency, cost, etc., because it is not necessary to control the mixing ratio. Moreover, as described above, it is advantageous in that the thermal bonding can be performed only by attaching the hydrophobic oxide fine particles to the entire surface without considering the bonding margin to the thermal bonding layer.
このような包装材料は、蓋材として使用できるほか、ピロー袋、ガセット袋、自立袋、三方シール袋、四方シール袋等の袋体、成形容器、包装シート、チューブ等の様々な用途に効果的に利用することができる。 Such packaging materials can be used as lidding materials, and are effective for various uses such as pillow bags, gusset bags, self-supporting bags, three-side seal bags, four-side seal bags, etc., molded containers, packaging sheets, tubes, etc. Can be used.
１ 基材層
２ 熱接着層
３ 疎水性酸化物微粒子
４ 容器
５ 内容物
1 Base Material Layer 2 Thermal Adhesive Layer 3 Hydrophobic Oxide Fine Particles 4 Container 5 Contents
１．包装材料
本発明の包装材料は、少なくとも基材層及び熱接着層を有する積層体からなる包装材料であって、前記熱接着層が包装材料の一方の面の最外層として積層されており、前記熱接着層が他の層と隣接していない最外面に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子が付着していることを特徴とする。
1. Packaging material The packaging material of the present invention is a packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer, wherein the thermal adhesive layer is laminated as an outermost layer on one surface of the packaging material, Hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm are attached to the outermost surface where the thermal adhesive layer is not adjacent to other layers.
図１に本発明の包装材料の断面構造の模式図を示す。図１の包装材料では、基材層１に熱接着層２が積層された積層体からなる。熱接着層２は包装材料（積層体）の一方の最外層に積層されている。最外層である熱接着層２において、他の層（図１では基材層）と隣接していない側の面（最外面）に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子３が付着している。疎水性酸化物微粒子３は熱接着層２に付着して固定されている。すなわち、疎水性酸化物微粒子と内容物とが接触しても疎水性酸化物微粒子が脱落しない程度に付着している。図１において、疎水性酸化物微粒子３は、一次粒子が含まれていても良いが、その凝集体（二次粒子）が多く含まれていることが望ましい。特に、疎水性酸化物微粒子が三次元網目状構造からなる多孔質層をなしていることがより好ましい。すなわち、熱接着層２の上には疎水性酸化物微粒子により形成された三次元網目状構造からなる多孔質層が積層されていることが好ましい。 FIG. 1 shows a schematic diagram of a cross-sectional structure of the packaging material of the present invention. The packaging material of FIG. 1 is composed of a laminate in which a thermal adhesive layer 2 is laminated on a base material layer 1. The thermal adhesive layer 2 is laminated on one outermost layer of the packaging material (laminate). In the thermal bonding layer 2 that is the outermost layer, hydrophobic oxide fine particles 3 having an average primary particle diameter of 3 to 100 nm are attached to the surface (outermost surface) on the side that is not adjacent to another layer (base material layer in FIG. 1). doing. The hydrophobic oxide fine particles 3 are adhered and fixed to the heat bonding layer 2. That is, even if the hydrophobic oxide fine particles and the content come into contact with each other, the hydrophobic oxide fine particles are adhered to such an extent that they do not fall off. In FIG. 1, the hydrophobic oxide fine particles 3 may contain primary particles, but it is desirable that the hydrophobic oxide fine particles 3 contain many aggregates (secondary particles). In particular, it is more preferable that the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure. That is, it is preferable that a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles is laminated on the thermal bonding layer 2.
図２には、本発明の包装材料を容器の蓋材として用いて作製された包装体の断面構造の模式図を示す。なお、図２では、疎水性酸化物微粒子３の表記は省略されている。容器４に内容物５が充填され、その開口部と包装材料の熱接着層２とが接するような状態で密封される。つまり、熱接着層２に付着している疎水性酸化物微粒子が内容物５と接触可能な状態で本発明の包装材料が使用されることになる。このような場合であっても、熱接着層２は疎水性酸化物微粒子によって保護され、優れた非付着性を有するので、たとえ内容物が熱接着層２近傍に接触しても（接近しても）、内容物の熱接着層への付着が疎水性酸化物微粒子（又は疎水性酸化物微粒子からなる多孔質層）によって遮られ、なおかつ、はじかれる。このため、内容物が熱接着層近傍に付着したままの状態とならずに、疎水性酸化物微粒子（又は疎水性酸化物微粒子からなる多孔質層）にはじかれて内容物が容器に戻る。なお、容器４の材質としては、金属、合成樹脂、ガラス、紙、それらの複合材等から適宜選択でき、その材質に応じて熱接着層の種類や成分を適宜調整することができる。このように、本発明の包装材料は、熱接着層側の最外面（特に疎水性酸化物微粒子（又は疎水性酸化物微粒子からなる多孔質層））に内容物が接触可能な状態で当該内容物が包装材料に包装されてなる製品のために好適に用いることができる。 In FIG. 2, the schematic diagram of the cross-sectional structure of the package body produced using the packaging material of this invention as a cover material of a container is shown. In FIG. 2, the description of the hydrophobic oxide fine particles 3 is omitted. The container 4 is filled with the contents 5 and sealed in such a state that the opening and the thermal adhesive layer 2 of the packaging material are in contact with each other. That is, the packaging material of the present invention is used in a state where the hydrophobic oxide fine particles adhering to the heat bonding layer 2 can come into contact with the contents 5. Even in such a case, the thermal adhesive layer 2 is protected by the hydrophobic oxide fine particles and has excellent non-adhesiveness. The adhesion of the contents to the thermal adhesive layer is blocked and repelled by the hydrophobic oxide fine particles (or the porous layer made of hydrophobic oxide fine particles). For this reason, the content does not remain in the vicinity of the thermal adhesive layer, but is repelled by the hydrophobic oxide fine particles (or the porous layer made of the hydrophobic oxide fine particles) and returns to the container. In addition, as a material of the container 4, it can select suitably from a metal, a synthetic resin, glass, paper, those composite materials, etc., The kind and component of a heat bonding layer can be adjusted suitably according to the material. Thus, the packaging material of the present invention has the contents in a state in which the contents can contact the outermost surface (particularly hydrophobic oxide fine particles (or a porous layer made of hydrophobic oxide fine particles)) on the thermal adhesive layer side. It can be suitably used for products in which an object is packaged in a packaging material.
基材層としては、公知の材料又は積層材料を採用することができる。例えば、紙、合成紙、樹脂フィルム、蒸着層付き樹脂フィルム、アルミニウム箔等の単体又はこれらの複合材料・積層材料を好適に用いることができる。 A known material or a laminated material can be adopted as the base material layer. For example, a simple substance such as paper, synthetic paper, a resin film, a resin film with a vapor deposition layer, an aluminum foil, or a composite material / laminated material thereof can be suitably used.
これらの材料には、公知の包装材料で採用されている各層が任意の位置に積層されていても良い。例えば、印刷層、印刷保護層（いわゆるＯＰ層）、着色層、接着剤層、接着強化層、プライマーコート層、アンカーコート層、防滑剤層、滑剤層、防曇剤層等が挙げられる。 In these materials, each layer employed in a known packaging material may be laminated at an arbitrary position. For example, a printing layer, a printing protective layer (so-called OP layer), a colored layer, an adhesive layer, an adhesion reinforcing layer, a primer coat layer, an anchor coat layer, an anti-slip agent layer, a lubricant layer, an anti-fogging agent layer, etc.
積層材料を用いる場合の積層方法も限定的でなく、例えばドライラミネート法、押し出しラミネート法、ウエットラミネート法、ヒートラミネート法等の公知の方法を採用することができる。 The lamination method in the case of using a laminated material is not limited, and known methods such as a dry lamination method, an extrusion lamination method, a wet lamination method, and a heat lamination method can be employed.
基材層の厚みは限定されないが、包装材料としての強度、柔軟性、コスト等の観点より通常１５〜５００μｍの範囲内で適宜設定すれば良い。 Although the thickness of a base material layer is not limited, What is necessary is just to set suitably in 15-500 micrometers normally from viewpoints, such as the intensity | strength as a packaging material, a softness | flexibility, and cost.
熱接着層としては、公知の材料を採用することができる。例えば、公知のシーラントフィルムのほか、ラッカータイプ接着剤、イージーピール接着剤、ホットメルト接着剤等の接着剤により形成される層を採用することができる。本発明では、この中でも、ラッカータイプ接着剤又はホットメルト接着剤を採用するのが好ましく、特にホットメルト接着剤により形成される熱接着層（ホットメルト層）を好適に採用することができる。ホットメルト層を形成する場合には、ホットメルト接着剤を溶融状態で塗布した後、冷却固化するまでに疎水性酸化物微粒子を付与すれば熱接着層に疎水性酸化物微粒子をそのまま付着させることができるため、本発明包装材料の連続的な生産が容易となる。 A well-known material can be employ | adopted as a heat contact bonding layer. For example, in addition to a known sealant film, a layer formed of an adhesive such as a lacquer type adhesive, an easy peel adhesive, or a hot melt adhesive can be employed. Among these, in the present invention, it is preferable to employ a lacquer type adhesive or a hot melt adhesive, and particularly a thermal adhesive layer (hot melt layer) formed by the hot melt adhesive can be suitably employed. When forming a hot melt layer, after applying the hot melt adhesive in a molten state, if the hydrophobic oxide fine particles are applied before cooling and solidifying, the hydrophobic oxide fine particles are allowed to adhere to the thermal adhesive layer as they are. Therefore, continuous production of the packaging material of the present invention is facilitated.
熱接着層の厚みは特に限定されないが、密封性、生産性、コスト等の観点より通常２〜１５０μｍ程度とすることが好ましい。特に、本発明の包装材料では、熱接着するに際して、熱接着される領域上に存在する疎水性酸化物微粒子が熱接着層中に埋め込まれ、熱接着層が最表面となることにより熱接着を行うことができる。このため、上記厚みの範囲内において、疎水性酸化物微粒子を熱接着層にできるだけ多く埋め込むことができる厚みに設定することが望ましい。 The thickness of the thermal adhesive layer is not particularly limited, but it is usually preferably about 2 to 150 μm from the viewpoint of sealing performance, productivity, cost, and the like. In particular, in the packaging material of the present invention, when thermally bonding, the hydrophobic oxide fine particles existing on the heat bonded region are embedded in the heat bonding layer, and the heat bonding layer becomes the outermost surface so that the heat bonding is performed. It can be carried out. Therefore, it is desirable to set the thickness within the above thickness range so that as many hydrophobic oxide fine particles as possible can be embedded in the thermal adhesive layer.
熱接着層に付着する疎水性酸化物微粒子は、一次粒子平均径が通常３〜１００ｎｍであり、好ましくは５〜５０ｎｍであり、より好ましくは５〜２０ｎｍである。一次粒子平均径を上記範囲とすることにより、疎水性酸化物微粒子が適度な凝集状態となり、その凝集体中にある空隙に空気等の気体を保持することができる結果、優れた非付着性を得ることができる。すなわち、この凝集状態は、熱接着層に付着した後も維持されるので、優れた非付着性を発揮することができる。 Hydrophobic oxide fine particles adhering to the thermal adhesive layer usually have an average primary particle diameter of 3 to 100 nm, preferably 5 to 50 nm, and more preferably 5 to 20 nm. By setting the average primary particle diameter in the above range, the hydrophobic oxide fine particles are in an appropriate aggregated state, and can hold a gas such as air in the voids in the aggregate, resulting in excellent non-adhesiveness. Can be obtained. That is, this agglomerated state is maintained even after adhering to the thermal adhesive layer, so that excellent non-adhesiveness can be exhibited.
なお、本発明において、一次粒子平均径の測定は、走査型電子顕微鏡（ＦＥ−ＳＥＭ）で実施することができ、走査型電子顕微鏡の分解能が低い場合には透過型電子顕微鏡等の他の電子顕微鏡を併用して実施しても良い。具体的には、粒子形状が球状の場合はその直径、非球状の場合はその最長径と最短径との平均値を直径とみなし、走査型電子顕微鏡等による観察により任意に選んだ２０個分の粒子の直径の平均を一次粒子平均径とする。 In the present invention, the average primary particle diameter can be measured with a scanning electron microscope (FE-SEM). When the resolution of the scanning electron microscope is low, other electrons such as a transmission electron microscope are used. You may carry out together with a microscope. Specifically, when the particle shape is spherical, the diameter is considered as the diameter, and when the particle shape is non-spherical, the average value of the longest diameter and the shortest diameter is regarded as the diameter, and 20 arbitrarily selected by observation with a scanning electron microscope or the like. The average diameter of the particles is defined as the average primary particle diameter.
疎水性酸化物微粒子の比表面積（ＢＥＴ法）は特に制限されないが、通常５０〜３００ｍ２／ｇとし、特に１００〜３００ｍ２／ｇとすることが好ましい。 The specific surface area of the hydrophobic oxide fine particles (BET method) is not particularly limited, and usually 50 to 300 m 2 / g, it is preferable that the particular 100 to 300 m 2 / g.
疎水性酸化物微粒子としては、疎水性を有するものであれば特に限定されず、表面処理により疎水化されたものであっても良い。例えば、親水性酸化物微粒子をシランカップリング剤等で表面処理を施し、表面状態を疎水性とした微粒子を用いることもできる。酸化物の種類も、疎水性を有するものであれば限定されない。例えばシリカ（二酸化ケイ素）、アルミナ、チタニア等の少なくとも１種を用いることができる。これらは公知又は市販のものを採用することができる。例えば、シリカとしては、製品名「ＡＥＲＯＳＩＬ Ｒ９７２」、「ＡＥＲＯＳＩＬ Ｒ９７２Ｖ」、「ＡＥＲＯＳＩＬ Ｒ９７２ＣＦ」、「ＡＥＲＯＳＩＬ Ｒ９７４」、「ＡＥＲＯＳＩＬ ＲＸ２００」、「ＡＥＲＯＳＩＬ ＲＹ２００」（以上、日本アエロジル株式会社製）、「ＡＥＲＯＳＩＬ Ｒ２０２」、「ＡＥＲＯＳＩＬ Ｒ８０５」、「ＡＥＲＯＳＩＬ Ｒ８１２」、「ＡＥＲＯＳＩＬ Ｒ８１２Ｓ」、（以上、エボニック デグサ社製）等が挙げられる。チタニアとしては、製品名「ＡＥＲＯＸＩＤＥ ＴｉＯ２ Ｔ８０５」（エボニック デグサ社製）等が例示できる。アルミナとしては、製品名「ＡＥＲＯＸＩＤＥ Ａｌｕ Ｃ」（エボニック デグサ社製）等をシランカップリング剤で処理して粒子表面を疎水性とした微粒子が例示できる。 The hydrophobic oxide fine particles are not particularly limited as long as they have hydrophobicity, and may be those hydrophobized by surface treatment. For example, fine particles in which hydrophilic oxide fine particles are subjected to a surface treatment with a silane coupling agent or the like to make the surface state hydrophobic can also be used. The type of oxide is not limited as long as it has hydrophobicity. For example, at least one of silica (silicon dioxide), alumina, titania and the like can be used. These may be known or commercially available. For example, as silica, product names “AEROSIL R972”, “AEROSIL R972V”, “AEROSIL R972CF”, “AEROSIL R974”, “AEROSIL RX200”, “AEROSIL RY200” (above, manufactured by Nippon Aerosil Co., Ltd.), “AEROSIL R202” "AEROSIL R805", "AEROSIL R812", "AEROSIL R812S" (above, manufactured by Evonik Degussa). Examples of titania include “AEROXIDE TiO 2 T805” (manufactured by Evonik Degussa). Examples of alumina include fine particles in which the product name “AEROXIDE Alu C” (manufactured by Evonik Degussa) is treated with a silane coupling agent to make the particle surface hydrophobic.
この中でも、疎水性シリカ微粒子を好適に用いることができる。とりわけ、より優れた非付着性が得られるという点において、表面にトリメチルシリル基を有する疎水性シリカ微粒子が好ましい。これに対応する市販品としては、例えば前記「ＡＥＲＯＳＩＬ Ｒ８１２」、「ＡＥＲＯＳＩＬ Ｒ８１２Ｓ」（いずれもエボニック デグサ社製）等が挙げられる。 Among these, hydrophobic silica fine particles can be preferably used. In particular, hydrophobic silica fine particles having a trimethylsilyl group on the surface are preferable in that better non-adhesiveness can be obtained. Examples of commercially available products corresponding to this include “AEROSIL R812” and “AEROSIL R812S” (both manufactured by Evonik Degussa).
熱接着層に付着させる疎水性酸化物微粒子の付着量（乾燥後重量）は限定的ではないが、通常０．０１〜１０ｇ／ｍ２とするのが好ましく、０．２〜１．５ｇ／ｍ２とするのがより好ましく、０．３〜１ｇ／ｍ２とするのが最も好ましい。上記範囲内に設定することによって、より優れた非付着性が長期にわたって得ることができる上、疎水性酸化物微粒子の脱落抑制、コスト等の点でもいっそう有利となる。熱接着層に付着した疎水性酸化物微粒子は、三次元網目構造を有する多孔質層を形成していることが好ましく、その厚みは０．１〜５μｍ程度が好ましく、０．２〜２．５μｍ程度がさらに好ましい。このようなポーラスな層状態で付着することにより、当該層に空気を多く含むことができ、より優れた非付着性を発揮することができる。 The amount (weight after drying) of the hydrophobic oxide fine particles to be adhered to the thermal adhesive layer is not limited, but is usually preferably 0.01 to 10 g / m 2, and preferably 0.2 to 1.5 g / m 2. 2 is more preferable, and 0.3 to 1 g / m 2 is most preferable. By setting within the above range, more excellent non-adhesiveness can be obtained over a long period of time, and it is further advantageous in terms of suppression of falling off of hydrophobic oxide fine particles, cost, and the like. The hydrophobic oxide fine particles attached to the heat bonding layer preferably form a porous layer having a three-dimensional network structure, and the thickness is preferably about 0.1 to 5 μm, and preferably 0.2 to 2.5 μm. The degree is further preferred. By adhering in such a porous layer state, the layer can contain a lot of air, and more excellent non-adhesiveness can be exhibited.
また、疎水性酸化物微粒子は、熱接着層の全面（基材層側と反対側の面の全面）に付着していても良いし、熱接着層が熱接着される領域（いわゆる接着しろ）を除いた領域に付着していても良い。本発明では、熱接着層の全面に付着している場合でも、熱接着される領域上に存在する疎水性酸化物微粒子のほとんど又は全部が当該熱接着層中に埋没するので熱接着が阻害されることはなく、工業的生産上でも熱接着層の全面に付着している方が望ましい。 Further, the hydrophobic oxide fine particles may be attached to the entire surface of the thermal adhesive layer (the entire surface opposite to the base material layer side), or a region where the thermal adhesive layer is thermally bonded (so-called adhesive margin). It may be attached to the area excluding. In the present invention, even when adhering to the entire surface of the heat bonding layer, most or all of the hydrophobic oxide fine particles present on the heat bonded region are buried in the heat bonding layer, so that the heat bonding is hindered. In view of industrial production, it is desirable to adhere to the entire surface of the thermal adhesive layer.
２．包装材料の製造方法
本発明の包装材料は、例えば、少なくとも基材層及び熱接着層を有する積層体からなる包装材料を製造する方法であって、当該熱接着層の表面に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子を付着させる工程（以下「付着工程」ともいう。）を含む包装材料の製造方法によって好適に得ることができる。
2. Packaging Material Production Method The packaging material of the present invention is, for example, a method for producing a packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer, and has an average primary particle diameter of 3 on the surface of the thermal adhesive layer. It can be suitably obtained by a method for producing a packaging material including a step of attaching hydrophobic oxide fine particles of ˜100 nm (hereinafter also referred to as “attachment step”).
積層体の製造自体は公知の方法に従って実施することができる。例えば、単層基材又はドライラミネート法、押し出しラミネート法、ウエットラミネート法、ヒートラミネート法等により作製された積層材料に対して、前記１．で説明した方法により熱接着層を形成すれば良い。 The laminate itself can be produced according to a known method. For example, with respect to a laminated material produced by a single layer base material or a dry laminating method, an extrusion laminating method, a wet laminating method, a heat laminating method, etc. A thermal adhesive layer may be formed by the method described in (1).
付着工程を実施する方法は特に限定されない。例えば、ロールコーティング、グラビアコーティング、バーコート、ドクターブレードコーティング、刷毛塗り、粉体静電法等の公知の方法を採用することができる。ロールコーティング等を採用する場合は、疎水性酸化物微粒子を溶媒に分散させてなる分散体を用いて熱接着層上に塗膜を形成した後に乾燥する方法により付着工程を実施することができる。この場合の溶媒は限定されず、水のほか、例えばアルコール（エタノール）、シクロヘキサン、トルエン、アセトンＩＰＡ、プロピレングリコール、ヘキシレングリコール、ブチルジグリコール、ペンタメチレングリコール、ノルマルペンタン、ノルマルヘキサン、ヘキシルアルコール等の有機溶剤を適宜選択することができる。この際、微量の分散剤、着色剤、沈降防止剤、粘度調整剤等を併用することもできる。溶媒に対する疎水性酸化物微粒子の分散量は通常１０〜１００ｇ／Ｌ程度とすれば良い。乾燥する場合は、自然乾燥又は強制乾燥（加熱乾燥）のいずれであっても良いが、工業的には強制乾燥することがこのましい。乾燥温度は、熱接着層に影響を与えない範囲であれば制限されないが、通常は１５０℃以下、特に８０〜１２０℃とすることが好ましい。 The method for performing the attaching step is not particularly limited. For example, known methods such as roll coating, gravure coating, bar coating, doctor blade coating, brush coating, and electrostatic powder method can be employed. When roll coating or the like is employed, the adhesion step can be carried out by a method of forming a coating film on the thermal adhesive layer using a dispersion obtained by dispersing hydrophobic oxide fine particles in a solvent and then drying. The solvent in this case is not limited, and in addition to water, for example, alcohol (ethanol), cyclohexane, toluene, acetone IPA, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, normal pentane, normal hexane, hexyl alcohol, etc. The organic solvent can be appropriately selected. At this time, a very small amount of a dispersant, a colorant, an anti-settling agent, a viscosity modifier and the like can be used in combination. The dispersion amount of the hydrophobic oxide fine particles with respect to the solvent is usually about 10 to 100 g / L. When drying, either natural drying or forced drying (heat drying) may be used, but industrially forced drying is preferable. The drying temperature is not limited as long as it does not affect the thermal adhesive layer, but is usually 150 ° C. or less, and preferably 80 to 120 ° C.
本発明の製造方法では、前記の付着工程中及び／又は付着工程後に積層体を加熱することもできる。積層体を加熱することにより熱接着層に対する疎水性酸化物微粒子の付着力（固定力）をより高めることができる。この場合の加熱温度Ｔは、熱接着層の種類等に応じて適宜設定することができ、通常は用いる熱接着層の融点Ｔｍ（溶融開始温度）℃に対してＴｍ−５０≦Ｔ≦Ｔｍ＋５０の範囲とすることが好ましい。また、本発明の包装材料には、公知の包装材料と同様に必要に応じて、エンボス加工、ハーフカット加工、ノッチ加工等を施しても差し支えない。 In the manufacturing method of this invention, a laminated body can also be heated during the said adhesion process and / or after an adhesion process. By heating the laminate, the adhesion (fixing force) of the hydrophobic oxide fine particles to the thermal adhesive layer can be further increased. The heating temperature T in this case can be set as appropriate according to the type of the thermal adhesive layer and the like, and usually Tm−50 ≦ T ≦ Tm + 50 with respect to the melting point Tm (melting start temperature) ° C. of the thermal adhesive layer used. It is preferable to be in the range. Further, the packaging material of the present invention may be subjected to embossing, half-cutting, notching, etc., as necessary, similarly to known packaging materials.
以下に実施例及び比較例を示し、本発明の特徴をより具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。 The features of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the scope of the present invention is not limited to the examples.
実施例１〜９及び比較例１〜３
表１に示すような各タイプの熱接着層を有する積層体に対して疎水性酸化物微粒子を付着させたサンプルを作製した。具体的には下記のようにして各サンプルを作製した。
Examples 1-9 and Comparative Examples 1-3
Samples were prepared in which hydrophobic oxide fine particles were adhered to a laminate having each type of thermal bonding layer as shown in Table 1. Specifically, each sample was produced as follows.
（１）積層体の作製 (1) Production of laminate
＜ホットメルトタイプ＞
厚み１５μｍのアルミニウム箔（１Ｎ３０、軟質箔；ＡＬと略称）の片面にポリウレタン系ドライラミネート接着剤（乾燥後重量３．５ｇ／ｍ２；Ｄと略称）を用いて、裏印刷（印刷と略称）を施した厚み１２μｍのポリエチレンテレフタレートフィルム（ＰＥＴと略称）の印刷面と貼り合わせ、基材層を作製した。この基材層のアルミニウム面にアンカーコート（主成分：ポリエステル系樹脂；ＡＣと略称）処理を施した上、低密度ポリエチレン樹脂（ＬＤＰＥと略称）を乾燥後膜厚２０μｍとなるように押出し積層した。さらに、低密度ポリエチレン上にホットメルト剤（ワックス３５重量部、ロジン３５重量部及びエチレン−酢酸ビニル共重合体３０重量部；ＨＭと略称）を乾燥後重量２０ｇ／ｍ２となるようにグラビアホットメルトコートした。これによって、「ＰＥＴ／印刷／Ｄ／ＡＬ／ＡＣ／ＬＤＰＥ／ＨＭ」なる構成の積層体を得た。
<Hot melt type>
Using a polyurethane dry laminate adhesive (weight after drying: 3.5 g / m 2 ; abbreviated as D) on one side of a 15 μm thick aluminum foil (1N30, soft foil; abbreviated as AL), back printing (abbreviated as printing) The substrate was bonded to the printed surface of a 12 μm thick polyethylene terephthalate film (abbreviated as PET). The aluminum surface of this base material layer was subjected to an anchor coat (main component: polyester resin; abbreviated as AC) treatment, and a low density polyethylene resin (abbreviated as LDPE) was extruded and laminated to a film thickness of 20 μm after drying. . Further, a gravure hot so that a hot melt agent (35 parts by weight of wax, 35 parts by weight of rosin and 30 parts by weight of ethylene-vinyl acetate copolymer; abbreviated as HM) is dried on low density polyethylene to a weight of 20 g / m 2. Melt coated. As a result, a laminate having a configuration of “PET / printing / D / AL / AC / LDPE / HM” was obtained.
＜シーラントタイプ＞
厚み１５μｍのアルミニウム箔（１Ｎ３０、軟質箔；ＡＬと略称）の片面にポリウレタン系ドライラミネート接着剤（乾燥後重量３．５ｇ／ｍ２；Ｄと略称）を用いて、裏印刷（印刷と略称）を施した厚み１２μｍのポリエチレンテレフタレートフィルム（ＰＥＴと略称）の印刷面と貼り合わせ、基材層を作製した。この基材層のアルミニウム面にアンカーコート（主成分：ポリエステル系樹脂；ＡＣと略称）処理を施した上、低密度ポリエチレン樹脂（乾燥後膜厚２０μｍ；ＬＤＰＥと略称）を用いて厚み３０μｍのシーラントフィルム（主成分：メタロセン触媒ポリエチレン；シーラントと略称）を押出しラミネートした。これによって、「ＰＥＴ／印刷／Ｄ／ＡＬ／ＡＣ／ＬＤＰＥ／シーラント」なる構成の積層体を得た。
<Sealant type>
Using a polyurethane dry laminate adhesive (weight after drying: 3.5 g / m 2 ; abbreviated as D) on one side of a 15 μm thick aluminum foil (1N30, soft foil; abbreviated as AL), back printing (abbreviated as printing) The substrate was bonded to the printed surface of a 12 μm thick polyethylene terephthalate film (abbreviated as PET). The aluminum surface of this base material layer is subjected to anchor coating (main component: polyester resin; abbreviated as AC), and then a sealant having a thickness of 30 μm using a low density polyethylene resin (film thickness after drying: 20 μm; abbreviated as LDPE). A film (main component: metallocene-catalyzed polyethylene; abbreviated as sealant) was extruded and laminated. As a result, a laminate having a configuration of “PET / printing / D / AL / AC / LDPE / sealant” was obtained.
＜ラッカータイプ＞
厚み１５μｍのアルミニウム箔（１Ｎ３０、軟質箔；ＡＬと略称）の片面にポリウレタン系ドライラミネート接着剤（乾燥後重量３．５ｇ／ｍ２；Ｄと略称）を用いて、裏印刷（印刷と略称）を施した厚み１２μｍのポリエチレンテレフタレートフィルム（ＰＥＴと略称）の印刷面と貼り合わせ、基材層を作製した。この基材層のアルミニウム面にポリウレタン系ドライラミネート接着剤（乾燥後重量３．５ｇ／ｍ２；Ｄと略称）を用いて、別途用意した厚み１２μｍのポリエチレンテレフタレートフィルム（ＰＥＴと略称）を貼り合わせた上、ヒートシールラッカー（主成分：アクリル樹脂＋ポリエステル樹脂：ラッカーと略称）を乾燥後重量５ｇ／ｍ２となるように塗布した。これによって、「ＰＥＴ／印刷／Ｄ／ＡＬ／Ｄ／ＰＥＴ／ラッカー」なる構成の積層体を得た。
<Lacquer type>
Using a polyurethane dry laminate adhesive (weight after drying: 3.5 g / m 2 ; abbreviated as D) on one side of a 15 μm thick aluminum foil (1N30, soft foil; abbreviated as AL), back printing (abbreviated as printing) The substrate was bonded to the printed surface of a 12 μm thick polyethylene terephthalate film (abbreviated as PET). A separately prepared polyethylene terephthalate film (abbreviated as PET) having a thickness of 12 μm was bonded to the aluminum surface of the base material layer using a polyurethane dry laminate adhesive (weight after drying: 3.5 g / m 2 ; abbreviated as D). Furthermore, a heat seal lacquer (main component: acrylic resin + polyester resin: abbreviated as lacquer) was applied after drying to a weight of 5 g / m 2 . In this way, a laminate having a configuration of “PET / printing / D / AL / D / PET / lacquer” was obtained.
（２）疎水性酸化物微粒子の付着
疎水性酸化物微粒子（製品名「ＡＥＲＯＳＩＬ Ｒ８１２Ｓ」エボニック デグサ社製、ＢＥＴ比表面積：２２０ｍ２／ｇ、一次粒子平均径：７ｎｍ）５ｇをエタノール１００ｍＬに分散させてコート液を調製した。このコート液を前記（１）で作製された積層体の熱接着層の面に乾燥後重量で０．３〜１．０ｇ／ｍ２となるようにグラビアコート方式又はバーコート方式で付与した後、１００℃で１０秒程度をかけて乾燥させてエタノールを蒸発させることにより、サンプル（包装材料）を得た。
(2) Adhesion of hydrophobic oxide fine particles 5 g of hydrophobic oxide fine particles (product name “AEROSIL R812S” manufactured by Evonik Degussa, BET specific surface area: 220 m 2 / g, primary particle average diameter: 7 nm) are dispersed in 100 mL of ethanol. A coating solution was prepared. After applying this coating liquid to the surface of the thermal adhesive layer of the laminate prepared in (1) above by a gravure coating method or a bar coating method so that the weight after drying is 0.3 to 1.0 g / m 2. The sample (packaging material) was obtained by drying at 100 ° C. for about 10 seconds to evaporate ethanol.
（３）疎水性酸化物微粒子からなる多孔質層の観察（確認）
実施例の包装材料において、疎水性酸化物微粒子からなる層の構造をＦＥ−ＳＥＭにより観察した。その結果、いずれの包装材料についても、疎水性酸化物微粒子により形成された三次元網目構造を有する多孔質層が観察された。その一例として、実施例４（Ａ）の観察結果を図３に示す。図３に示すように、熱接着層（シーラント）の上に黒色と白色が混ざった層が認められる。この白色の部分は疎水性酸化物からなる多孔質層である。このように、前記コート液を塗布及び乾燥することにより、疎水性酸化物微粒子からなる多孔質層が形成されることがわかる。
(3) Observation (confirmation) of porous layer made of hydrophobic oxide fine particles
In the packaging material of the example, the structure of the layer made of hydrophobic oxide fine particles was observed by FE-SEM. As a result, a porous layer having a three-dimensional network structure formed of hydrophobic oxide fine particles was observed for any packaging material. As an example, the observation result of Example 4 (A) is shown in FIG. As shown in FIG. 3, a layer in which black and white are mixed is recognized on the heat bonding layer (sealant). This white portion is a porous layer made of a hydrophobic oxide. Thus, it turns out that the porous layer which consists of hydrophobic oxide microparticles | fine-particles is formed by apply | coating and drying the said coating liquid.
試験例１（シール強度）
各実施例及び比較例で得られたサンプルについてシール強度を調べた。
Test example 1 (seal strength)
The seal strength of the samples obtained in each example and comparative example was examined.
実施例１〜６及び比較例１〜２について
各包装材料から蓋材の形状（タブ付きの直径７５ｍｍの円形）に切り抜いた蓋材を用いて包装体を作製した。具体的には、フランジ付き紙／ポリエチレン製容器（フランジ幅３ｍｍ、フランジ外径７０ｍｍ、高さ約５５ｍｍ、内容積約１３０ｃｍ３、厚み約３００μｍの紙にポリエチレン１００μｍをコーティングしたものをポリエチレンが容器内側になるように成形したもの）のフランジ上に前記蓋材をヒートシールすることによって包装体をそれぞれ作製した。前記ヒートシール条件は、温度１６０℃及び圧力１ｋｇ／ｃｍ２で１秒間とした。各包装体上の蓋材のタブを開封始点からみて仰角４５度の方向に１００ｍｍ／分の速度で引っ張り、開封時の最大荷重をシール強度（Ｎ）とし、各包装体についてｎ＝６点測定し、その平均値を求めた。その結果を表１に示す。
About Examples 1-6 and Comparative Examples 1-2 A package was produced using a lid material cut out from each packaging material into a lid material shape (circular shape with a tab of 75 mm in diameter). Specifically, a flanged paper / polyethylene container (with a flange width of 3 mm, a flange outer diameter of 70 mm, a height of about 55 mm, an internal volume of about 130 cm 3 and a thickness of about 300 μm coated with 100 μm of polyethylene on the inside of the container. Each of the packaging bodies was produced by heat-sealing the lid material on the flanges of the molded product. The heat sealing conditions were a temperature of 160 ° C. and a pressure of 1 kg / cm 2 for 1 second. Pull the tab of the lid on each package from the opening start point at an angle of elevation of 45 degrees at a speed of 100 mm / min. The maximum load at the time of opening is the seal strength (N), and n = 6 points for each package The average value was obtained. The results are shown in Table 1.
実施例７〜９及び比較例３について
各包装材料から蓋材の形状（タブ付きの縦６２ｍｍ×横６７ｍｍの矩形）に切り抜いた蓋材を用いて包装体を作製した。具体的には、フランジ付きポリスチレン製容器（フランジ幅４ｍｍ、フランジ外径６０ｍｍ×６５ｍｍ□、高さ約４８ｍｍ、内容積約１００ｃｍ３になるように成形したもの）のフランジ上に前記蓋材をヒートシールすることによって包装体をそれぞれ作製した。前記ヒートシール条件は、温度２１０℃及び圧力２ｋｇ／ｃｍ２にて１秒間で２ｍｍ幅のリング（凹状）シール）とした。各包装体上の蓋材のタブを開封始点からみて仰角４５度の方向に１００ｍｍ／分の速度で引っ張り、開封時の最大荷重をシール強度（Ｎ）とし、各包装体についてｎ＝６点測定し、その平均値を求めた。その結果を表１に示す。
About Examples 7-9 and Comparative Example 3 A package was produced using a lid material cut out from each packaging material into a lid material shape (rectangular length 62 mm × width 67 mm). Specifically, the lid material is heated on the flange of a flanged polystyrene container (formed with a flange width of 4 mm, a flange outer diameter of 60 mm × 65 mm □, a height of about 48 mm, and an internal volume of about 100 cm 3 ). Each package was produced by sealing. The heat seal conditions were a ring (concave) seal with a width of 2 mm in 1 second at a temperature of 210 ° C. and a pressure of 2 kg / cm 2 . Pull the tab of the lid on each package from the opening start point at an angle of elevation of 45 degrees at a speed of 100 mm / min. The maximum load at the time of opening is the seal strength (N), and n = 6 points for each package The average value was obtained. The results are shown in Table 1.
試験例２（密封性（パンク強度））
試験例１で作製した包装体を試験サンプルとし、｛乳及び乳製品の成分規格等に関する省令（昭和５４年４月１６日厚生省令第１７号）｝の封緘強度試験法に準じて封緘強度試験を行った。但し、容器内に空気を流入し続け、空気漏れする時点の内圧（ｍｍＨｇ）を測定した。各包装体についてｎ＝３点測定し、その平均値を求めた。その結果を表１に示す。
Test Example 2 (Sealing property (puncture strength))
Using the package produced in Test Example 1 as a test sample, sealing strength test according to the sealing strength test method of {Ministerial Ordinance on Milk and Dairy Product Component Standards (April 16, 1979 Ministry of Health and Welfare Ordinance No. 17)} Went. However, the internal pressure (mmHg) at the time when air continued to flow into the container and air leaked was measured. N = 3 points were measured for each package, and the average value was determined. The results are shown in Table 1.
試験例３（接触角）
各包装材料の熱接着層側を試験面とし、接触角測定装置（固液界面解析装置「Ｄｒｏｐ Ｍａｓｔｅｒ３００」協和界面科学株式会社製）を用いて純水の接触角を測定した。その結果を表１に示す。
Test Example 3 (Contact angle)
The contact angle measuring device (solid-liquid interface analyzer “Drop Master 300” manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle of pure water using the thermal adhesive layer side of each packaging material as a test surface. The results are shown in Table 1.
試験例４（落下角）
各包装材料の熱接着層側を試験面とし、この面を上面として水平な平台にクリップで固定し、市販のヨーグルト（製品名「おいしいカスピ海」ソフトヨーグルト、グリコ乳業株式会社製１滴：約０．４ｇ）を至近距離から垂らし、水平な平台を傾け、ヨーグルト液滴が転げ落ちたときの角度を求めた。その結果を表１に示す。なお、比較例１〜３は、９０度でも転げ落ちずに垂れ流れた。
Test example 4 (drop angle)
Use the heat adhesive layer side of each packaging material as the test surface and fix it with a clip on a horizontal flat table with this surface as the top surface. Commercial yogurt (product name “Delicious Caspian Sea” soft yogurt, 1 drop manufactured by Glico Dairies Co., Ltd .: approx. 0.4 g) was hung from the closest distance, the horizontal flat was tilted, and the angle at which the yogurt droplet fell was determined. The results are shown in Table 1. In addition, Comparative Examples 1-3 flowed down without falling even at 90 degrees.
試験例５（輸送テスト）
試験例１で用いた包装体中に市販のヨーグルト（製品名「おいしいカスピ海」ソフトヨーグルト、グリコ乳業株式会社製）を１００ｇ（フランジ付き紙／ポリエチレン製容器）及び８５ｇ（フランジ付きポリスチレン製容器）それぞれ充填し、試験例１と同様にして蓋材をヒートシールをした。ヨーグルトを充填した包装体を１５００ｋｍの距離を長距離トラックで輸送した後、手指で蓋材を開封し、各蓋材の熱接着層側の面の状態を目視で観察した。その結果を表１に示す。なお、評価は、ヨーグルトの付着なしの場合は「◎」とし、周辺部に若干リング状の付着がある場合（付着面積割合２０％以下）は「○」とし、付着がやや目立つ場合（付着面積割合２０％超え９０％未満）は「△」とし、ほぼ全面に付着が認められる場合（付着面積割合９０％以上）は「×」とした。この場合、「◎」「○」が良好と評価される。
Test example 5 (transport test)
100 g (flanged paper / polyethylene container) and 85 g (flanged polystyrene container) of commercially available yogurt (product name “Delicious Caspian Sea” soft yogurt, manufactured by Glico Dairies Co., Ltd.) in the package used in Test Example 1 Each was filled, and the lid was heat sealed in the same manner as in Test Example 1. After the package filled with yogurt was transported by a long distance truck at a distance of 1500 km, the lid was opened with fingers, and the state of the surface of each lid on the side of the thermal adhesive layer was visually observed. The results are shown in Table 1. The evaluation is “◎” when there is no yogurt adhering, and “○” when there is some ring-like adhering in the periphery (adhesive area ratio 20% or less), and the adhering is slightly noticeable (adhesive area) The ratio was more than 20% and less than 90%), and the case where adhesion was found on almost the entire surface (adhesion area ratio of 90% or more) was marked with “X”. In this case, “◎” and “◯” are evaluated as good.
表１の結果からも明らかなように、従来品（比較例）では非付着性は全く発揮されていないのに対し、本発明（実施例）では高い非付着性を発揮していることがわかる。また、シール強度、密封性（パンク値）の点においても実用上差し支えのない良好な性能を示していることがわかる。また、接触角及び落下角の結果からも、本発明の包装材料が高い非付着性を示すことがわかる。特に、本発明の包装材料の熱接着層側の最外面（疎水性酸化物微粒子が付着した面）は純水の接触角が１５０度以上を示し、従来の包装材料には見られない優れた内容物非付着性を有する。 As is clear from the results in Table 1, the non-adhesive property is not exhibited at all in the conventional product (comparative example), whereas the high non-adhesive property is exhibited in the present invention (example). . In addition, it can be seen that the present invention shows good performance that is practically satisfactory in terms of seal strength and sealability (puncture value). Moreover, it turns out that the packaging material of this invention shows high non-adhesiveness also from the result of a contact angle and a fall angle. In particular, the outermost surface on the thermal adhesive layer side of the packaging material of the present invention (the surface on which hydrophobic oxide fine particles are adhered) has a contact angle of pure water of 150 degrees or more, which is superior to conventional packaging materials. It has non-adhesive contents.
Claims (11)
前記包装材料は、熱接着層が包装材料の一方の面の最外層として積層されており、前記熱接着層が他の層と隣接していない最外面に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子が付着し、疎水性酸化物微粒子が三次元網目状構造からなる多孔質層を形成しており、疎水性酸化物微粒子が内容物と接触可能な状態で使用されるものであり、
当該熱接着層の表面に一次粒子平均径３〜１００ｎｍの疎水性酸化物微粒子を付着させる工程を含み、疎水性酸化物微粒子を溶媒に分散させてなる分散体を用いて熱接着層上に塗膜を形成した後に乾燥する方法により前記工程を実施する、包装材料の製造方法。 A method for producing a packaging material comprising a laminate having at least a base material layer and a thermal adhesive layer,
The packaging material has a thermal adhesive layer laminated as an outermost layer on one side of the packaging material, and the thermal adhesive layer is hydrophobic with an average primary particle diameter of 3 to 100 nm on the outermost surface not adjacent to the other layer. The oxide fine particles are adhered, the hydrophobic oxide fine particles form a porous layer having a three-dimensional network structure, and the hydrophobic oxide fine particles are used in a state where they can come into contact with the contents.
Including a step of adhering hydrophobic oxide fine particles having an average primary particle diameter of 3 to 100 nm to the surface of the thermal adhesive layer, and applying the dispersion onto the thermal adhesive layer using a dispersion obtained by dispersing the hydrophobic oxide fine particles in a solvent. The manufacturing method of the packaging material which implements the said process by the method of drying after forming a film | membrane.
The lid | cover material of Claim 10 which is a lid | cover material filled with the contents in a container and sealed in the state which the opening part and the heat bonding layer of a lid | cover material contact | connect.
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