JP2009114362A - Aqueous sealing compound and can for chlorine-based solvent using the same - Google Patents
Aqueous sealing compound and can for chlorine-based solvent using the same Download PDFInfo
- Publication number
- JP2009114362A JP2009114362A JP2007290297A JP2007290297A JP2009114362A JP 2009114362 A JP2009114362 A JP 2009114362A JP 2007290297 A JP2007290297 A JP 2007290297A JP 2007290297 A JP2007290297 A JP 2007290297A JP 2009114362 A JP2009114362 A JP 2009114362A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- sealing compound
- resin
- modified polyolefin
- aqueous
- 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
- 238000007789 sealing Methods 0.000 title claims abstract description 69
- 150000001875 compounds Chemical class 0.000 title claims abstract description 61
- 239000002904 solvent Substances 0.000 title claims description 27
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- 229910052801 chlorine Inorganic materials 0.000 title 1
- 239000000460 chlorine Substances 0.000 title 1
- 229920000098 polyolefin Polymers 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims description 38
- 229920000554 ionomer Polymers 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 14
- 239000000806 elastomer Substances 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
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- 239000005029 tin-free steel Substances 0.000 description 7
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- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
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- 238000005336 cracking Methods 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
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- 239000000758 substrate Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 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 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
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- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 239000005011 phenolic resin Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229920003298 Nucrel® Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
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- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920001289 polyvinyl ether Polymers 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
本発明は、水性シーリングコンパウンドに関するものであり、より詳細には、耐溶剤性、金属密着性、巻締性に優れると共に、落下変形に耐え得る接着性及び密封性を有するシール材を形成可能な水性シーリングコンパウンドに関する。 The present invention relates to an aqueous sealing compound. More specifically, the present invention is excellent in solvent resistance, metal adhesion, and winding properties, and can form a sealing material having adhesiveness and sealability that can withstand drop deformation. It relates to an aqueous sealing compound.
金属製容器の開口端への蓋の巻締めに使用されるシーリングコンパウンドとして、ジエン系ゴム等の熱可塑性エラストマーを主体とするものが提案されている(例えば、特許文献１)。しかしながら、従来の熱可塑性エラストマーを主体としたシーリングコンパウンドは、溶剤に溶解或いは膨潤してしまうことがあり、溶剤等を内容物とする大型缶への適用には十分満足するものではなかった。また一般に溶剤等を内容物とする大型缶においては、容器を構成する金属表面には被覆が施されていないため、上記ジエン系ゴム等の熱可塑性エラストマーを主体とするシーリングコンパウンドでは、金属基体と十分な密着性を得ることができず、落下により変形を生じた場合等には満足する密封性を得ることができなかった。 As a sealing compound used for winding a lid around an opening end of a metal container, a material mainly composed of a thermoplastic elastomer such as a diene rubber has been proposed (for example, Patent Document 1). However, a conventional sealing compound mainly composed of a thermoplastic elastomer may be dissolved or swelled in a solvent, and is not sufficiently satisfactory for application to a large can containing a solvent or the like. In general, in a large can containing a solvent or the like, the metal surface constituting the container is not coated. Therefore, in a sealing compound mainly composed of a thermoplastic elastomer such as diene rubber, the metal base and Sufficient adhesion could not be obtained, and satisfactory sealability could not be obtained when deformation occurred due to dropping.
また耐溶剤性に優れたシーリングコンパウンドとして、ウレタン系シーリングコンパウンドも提案されているが(特許文献２等)、やはり大型缶における落下変形時の密封性の点で十分満足するものではなく、また所望の性質を発現させるためには２００℃以上の高温加熱の必要があり、設備負担の問題等、未だ十分満足するものではなかった。
更にポリオレフィンを用いたシール材も提案されており、例えばエチレン・α−オレフィン共重合体から押出成形によりシール状成形物を作成し、これをキャップ内面側等に装着した後、樹脂の軟化温度以上に加熱して密着密封させるものである（特許文献３等）。しかしながら、エチレン・α−オレフィン共重合体はある程度の溶剤耐性は有するものの、塩素系の溶剤に対しては膨潤が大きく、シール材がはみ出すという問題があると共に、金属に対する密着性が悪いため、樹脂被覆が施されていない金属基体と十分な密着性を得ることができず、上述した落下変形にも耐えることができない。また予めシール状成形物を成形或いは蓋で直接溶融成形するものは、既存のライニング装置を利用することができず、別途成形加工装置が必要になるため、経済性の点で未だ十分満足するものではない。
In addition, a urethane-based sealing compound has been proposed as a sealing compound having excellent solvent resistance (Patent Document 2, etc.), but it is still not satisfactory in terms of hermeticity at the time of drop deformation in a large can, and is desired. In order to develop the above properties, it is necessary to heat at a high temperature of 200 ° C. or higher, and the problem of equipment burden has not yet been fully satisfied.
Furthermore, a sealing material using polyolefin has also been proposed. For example, a seal-like molded product is produced by extrusion molding from an ethylene / α-olefin copolymer, and after this is mounted on the inner surface of the cap, the temperature is higher than the softening temperature of the resin. And tightly sealed by heating (Patent Document 3, etc.). However, although the ethylene / α-olefin copolymer has a certain solvent resistance, it has a problem of large swelling with respect to a chlorinated solvent and a seal material sticking out, and also has poor adhesion to a metal. It is not possible to obtain sufficient adhesion with a metal substrate that is not coated, and it cannot withstand the drop deformation described above. In addition, the ones that are molded in advance or directly melt-molded with a lid cannot be used with existing lining equipment, and a separate molding equipment is required. is not.
更に、ポリエチレン又はポリプロピレンとＥＰＤＭ等の熱可塑性エラストマーの混合物から成り、押出成形によりシール状成形物を作成するか、或いは蓋に直接シール状に成形するシール材も提案されているが(特許文献４及び５等)、上記ポリオレフィンを用いた樹脂シール材と同様に、金属に対する密着性に劣っているため、大型缶における落下変形に耐えるものではなかった。
またエチレンとα−オレフィン又はジエンとの共重合エラストマー、及び芳香族ビニルとジエンとの共重合水素添加樹脂に、酸変性ポリオレフィン又は高級脂肪酸塩を配合して成る水性分散型の接着剤組成物が提案されている(特許文献６及び７)。かかる接着剤組成物においては、酸変性ポリオレフィンとしてワックスタイプのものが用いられていると共に、上記共重合エラストマー自体も金属に対する密着力に乏しく、密着性の点で十分満足するものではなかった。
Furthermore, a sealing material that is made of a mixture of polyethylene or polypropylene and a thermoplastic elastomer such as EPDM and that forms a seal-like molding by extrusion molding or is directly molded into a seal on a lid has been proposed (Patent Document 4). And 5 etc.), as in the case of the resin sealing material using the polyolefin, the adhesiveness to the metal is inferior.
In addition, an aqueous dispersion type adhesive composition comprising a copolymerized elastomer of ethylene and α-olefin or diene, and a copolymerized hydrogenated resin of aromatic vinyl and diene with an acid-modified polyolefin or a higher fatty acid salt. It has been proposed (Patent Documents 6 and 7). In such an adhesive composition, a wax type is used as the acid-modified polyolefin, and the copolymer elastomer itself has poor adhesion to metal, and is not sufficiently satisfactory in terms of adhesion.
酸変性ポリオレフィンを含む水分散型接着剤組成物も知られており、例えば酸変性ポリオレフィンに、ポリウレタンとの組成物、及びフェノール樹脂とα，βエチレン性不飽和カルボン酸共重合樹脂を併用する組成物が提案されているが（特許文献８及び９)、これらは何れも接着性を引き出すために高温での加熱硬化が必要であり、設備負担が大きいと共に、接着性や塩素系溶剤に対する耐性の点で充分満足するものではなかった。
またエチレン性不飽和カルボン酸とブタジエン共重合ゴムと酸変性ポリオレフィンから成る金属缶用水性接着剤も提案されているが（特許文献１０）、エチレン性不飽和カルボン酸とブタジエン共重合ゴムは芳香族系や塩素系溶剤には膨潤崩壊してしまう欠点があり、接着性の点でも満足するものではなかった。
すなわち上記刊行物で実際に用いられている酸変性ポリオレフィンはアンモニア中和型の分散体で、かつメルトフローレートが３００ｇ／１０分である。かかる樹脂自体の凝集力はそれほど強くなく、消防法で規定される１８Ｌ缶の最低板厚である０．３２ｍｍでは落下変形のみならず１００ｋＰａの規格に耐えるものではないため、板厚を厚くする必要があり、コスト負担が大となる。
A water-dispersed adhesive composition containing an acid-modified polyolefin is also known. For example, a composition comprising a polyurethane and a phenol resin and an α, β-ethylenically unsaturated carboxylic acid copolymer resin in combination with an acid-modified polyolefin. Although these have been proposed (Patent Documents 8 and 9), both of these require heat curing at high temperatures in order to bring out adhesiveness, have a large equipment burden and are resistant to adhesiveness and chlorinated solvents. We were not satisfied with point enough.
An aqueous adhesive for metal cans composed of an ethylenically unsaturated carboxylic acid, a butadiene copolymer rubber, and an acid-modified polyolefin has also been proposed (Patent Document 10), but an ethylenically unsaturated carboxylic acid and a butadiene copolymer rubber are aromatic. However, these solvents and chlorinated solvents have the disadvantage of swelling and disintegrating and are not satisfactory in terms of adhesion.
That is, the acid-modified polyolefin actually used in the above publication is an ammonia-neutralized dispersion and has a melt flow rate of 300 g / 10 min. The cohesive strength of the resin itself is not so strong, and the minimum plate thickness of 18 L cans specified by the Fire Service Act of 0.32 mm does not withstand not only drop deformation but also 100 kPa standard, so it is necessary to increase the plate thickness. There is a large cost burden.
従って本発明の目的は、上述した問題を生じることがなく、既存のライニング装置による塗工が可能であると共に、金属に対する濡れ性が良好であり、且つ低温短時間での接着が可能な水性シーリングコンパウンドを提供することである。
本発明の他の目的は、塩素系溶剤にも耐性を有する耐溶剤性、金属密着性、巻締性に優れると共に、１８リットル缶等の大型缶に適用した場合、板厚０．３２ｍｍにおいても落下変形にも耐え得る密封性を有するシール材を形成可能な水性シーリングコンパウンドを提供することである。
Accordingly, an object of the present invention is to provide an aqueous sealing that does not cause the above-described problems, can be applied with an existing lining apparatus, has good wettability to metal, and can be bonded in a low temperature and in a short time. To provide a compound.
Another object of the present invention is that it has excellent solvent resistance, metal adhesion, and winding properties that are resistant to chlorinated solvents, and has a plate thickness of 0.32 mm when applied to large cans such as 18 liter cans. An object of the present invention is to provide an aqueous sealing compound capable of forming a sealing material having a sealing property that can withstand dropping deformation.
本発明によれば、１価金属イオンで中和して成る酸変性ポリオレフィンを主成分とし且つ全固形分の３０重量％以上の量で含有して成る水性シーリングコンパウンドであって、前記酸変性ポリオレフィンが、３０ｇ／１０分以下のメルトフローレート（以下、「ＭＦＲ」ということがある）及び０．９乃至１．０ｇ／ｃｍ３の密度を有することを特徴とする水性シーリングコンパウンドが提供される。
本発明の水性シーリングコンパウンドにおいては、
１．酸変性ポリオレフィンが、エチレン・不飽和カルボン酸共重合体のアイオノマーであって、金属種がナトリウムであること、
２．酸変性ポリオレフィンがエマルジョンの形態であること、
３．酸変性ポリオレフィンが、引っ張り破壊強度が１５ＭＰａ／ｃｍ２以上であること、
４．酸変性ポリオレフィン１００重量部に対して、１０乃至１２０重量部のエチレン系エラストマー及び／又は二トリル系エラストマーを配合して成ること、
５．酸変性ポリオレフィンの水性分散体１００重量部に対して、０．５乃至１０重量部の界面活性剤を配合して成ること、
が好適である。
According to the present invention, there is provided an aqueous sealing compound comprising an acid-modified polyolefin neutralized with monovalent metal ions as a main component and an amount of 30% by weight or more of the total solid content, the acid-modified polyolefin Provides an aqueous sealing compound characterized by having a melt flow rate of 30 g / 10 min or less (hereinafter sometimes referred to as “MFR”) and a density of 0.9 to 1.0 g / cm 3 .
In the aqueous sealing compound of the present invention,
1. The acid-modified polyolefin is an ionomer of an ethylene / unsaturated carboxylic acid copolymer and the metal species is sodium;
2. The acid-modified polyolefin is in the form of an emulsion;
3. The acid-modified polyolefin has a tensile breaking strength of 15 MPa / cm 2 or more,
4). 10 to 120 parts by weight of ethylene elastomer and / or nitrile elastomer is blended with 100 parts by weight of the acid-modified polyolefin,
5). 0.5 to 10 parts by weight of a surfactant is blended with 100 parts by weight of an aqueous dispersion of acid-modified polyolefin,
Is preferred.
本発明によればまた、上記水性シーリングコンパウンドを塗布乾燥して成る塗膜が形成された金属缶用蓋を缶胴に巻き締めた後に、前記ポリオレフィンの溶融温度以上に加熱することにより密封されて成ることを特徴とする塩素系溶剤用缶が提供される。 According to the present invention, the lid for a metal can on which a coating film formed by applying and drying the aqueous sealing compound is wound around a can body, and then sealed by heating to a temperature higher than the melting temperature of the polyolefin. A can for chlorinated solvents is provided.
本発明の水性シーリングコンパウンドは、既存のライニング装置及び乾燥設備によりシール材を形成可能な低温製膜性、乾燥性、濡れ性等が確保されており、しかも塩素系溶剤にも対応可能な耐溶剤性を有している。
また一般に溶剤等の危険物に用いる缶、缶蓋は内面無塗装のものが用いられているが、本発明の水性シーリングコンパウンドにおいては、金属基体への接着性にも優れている。
しかも本発明のシーリングコンパウンドにおいては、金属缶の巻き締め部に用いた場合に、加熱溶融時の樹脂のはみ出しや、冷却後の巻き締め部の空隙の発生が有効に防止されており、従来のシーリングコンパウンドでは実現できなかった板厚０．３２ｍｍでの１８リットル缶等の大型缶における１．２ｍの落下耐性を有する接着性及び密封性を有していると共に、内圧１００ｋＰａでの充分な持続密封性を有する金属缶の製造が可能となった。
The water-based sealing compound of the present invention has a low-temperature film-forming property, a drying property, a wettability, etc. that can form a sealing material with an existing lining apparatus and drying equipment, and is also a solvent-resistant solvent that can handle chlorinated solvents It has sex.
In general, the cans and can lids used for dangerous substances such as solvents are not coated on the inner surface, but the aqueous sealing compound of the present invention is excellent in adhesion to a metal substrate.
In addition, in the sealing compound of the present invention, when used in a metal can winding portion, the occurrence of resin protrusion during heating and melting and voids in the winding portion after cooling is effectively prevented. Adhesiveness and sealability with a drop resistance of 1.2m in large cans such as 18 liter cans with a plate thickness of 0.32mm, which could not be realized with sealing compounds, and sufficient continuous sealing at an internal pressure of 100kPa It became possible to manufacture metal cans that have properties.
本発明の水性シーリングコンパウンドにおいては、１価金属イオンで中和して成る酸変性ポリオレフィンを主成分とし且つ全固形分の３５重量％以上の量で含有して成り、酸変性ポリオレフィンが、３０ｇ／１０分以下のメルトフローレート（ＭＦＲ：ＪＩＳ Ｋ７２１０準拠）及び０．９乃至１．０ｇ／ｃｍ３の密度を有することが重要な特徴である。
酸変性ポリオレフィンは、一般にオレフィンやアルミ基材への密着が良いことから、塗工材として種々の水分散方法が開示されているが、本発明においては、１価金属イオンで中和されて成る酸変性ポリオレフィンで、しかもメルトフローレート及び密度が上記範囲にあることものを使用することにより、樹脂の凝集力が向上されて、ティンフリースチール(ＴＦＳ)やブリキに対する接着性を顕著に向上でき、これをシーリング剤として用いることにより、板厚の薄い１８Ｌ缶等大型金属缶においても巻き締め部の落下衝撃に耐えることを見出した。
The aqueous sealing compound of the present invention comprises an acid-modified polyolefin neutralized with monovalent metal ions as a main component and is contained in an amount of 35% by weight or more of the total solid content. It is an important feature that it has a melt flow rate of 10 minutes or less (MFR: JIS K7210 compliant) and a density of 0.9 to 1.0 g / cm 3 .
Since acid-modified polyolefins generally have good adhesion to olefins and aluminum substrates, various water dispersion methods have been disclosed as coating materials, but in the present invention, they are neutralized with monovalent metal ions. By using an acid-modified polyolefin having a melt flow rate and density in the above ranges, the cohesive strength of the resin is improved, and adhesion to tin-free steel (TFS) and tinplate can be significantly improved. It has been found that by using this as a sealing agent, even a large metal can such as a thin 18L can withstands the drop impact of the tightening portion.
本発明においては、１価金属イオンで中和された酸変性ポリオレフィンの１９０℃の温度におけるメルトフローレート（ＭＦＲ）が３０ｇ／１０分以下、特に０．１乃至２０ｇ／１０分の範囲にあること、及び密度が０．９乃至１．０ｇ／ｃｍ３、特に０．９２乃至０．９８ｇ／ｃｍ３の範囲にあることが重要であり、これにより１８リットル以上の大型缶とした場合にも接着性及び密封性を保持できる皮膜凝集力を確保することが可能となる。
すなわち後述する実施例の結果から明らかなように、１価金属で中和されていない酸変性ポリオレフィンを用いて成るシーリングコンパウンドは、水性分散液にすることができず（比較例４）、またＭＦＲが上記範囲よりも大きい酸変性ポリオレフィンを用いて成るシーリングコンパウンド（比較例２及び３）や密度が上記範囲にないシーリングコンパウンド（比較例６）では、満足する接着性及び密封性を得ることができず、塩素系溶剤に対する耐性試験、落下変形試験、耐内圧試験のいずれにおいても満足する結果が得られていない。特にＭＦＲが上記範囲よりも大きいほど、樹脂の溶融粘度が小さく流れやすくなることに加えて、樹脂の熱膨張による膨張圧のため巻き締め後の加熱溶融時に樹脂が巻き締め部の外に押し出される一方、加熱処理後冷却されると樹脂が収縮し巻き締め内部に空隙が生じ、密封性を損なうなどの弊害が出る。
これに対して、本発明の水性シーリングコンパウンドは、塩素系溶剤に対する耐性試験、落下変形試験、耐内圧試験のいずれにおいても優れた結果が得られており、優れた耐溶剤性、接着性及び密封性が得られていることが明らかである。
In the present invention, the acid-modified polyolefin neutralized with monovalent metal ions has a melt flow rate (MFR) at a temperature of 190 ° C. of 30 g / 10 min or less, particularly 0.1 to 20 g / 10 min. , And a density of 0.9 to 1.0 g / cm 3 , particularly 0.92 to 0.98 g / cm 3 , and it is important to adhere to a large can of 18 liters or more. It is possible to secure a film cohesive force capable of maintaining the properties and sealing properties.
That is, as is apparent from the results of Examples described later, a sealing compound using an acid-modified polyolefin not neutralized with a monovalent metal cannot be made into an aqueous dispersion (Comparative Example 4), and MFR Satisfactory adhesion and sealability can be obtained with a sealing compound (Comparative Examples 2 and 3) using an acid-modified polyolefin with a greater than the above range or a sealing compound (Comparative Example 6) with a density not within the above range. In addition, satisfactory results were not obtained in any of a resistance test against a chlorinated solvent, a drop deformation test, and an internal pressure resistance test. In particular, as the MFR is larger than the above range, the melt viscosity of the resin becomes smaller and more easily flows. In addition, the resin is pushed out of the tightened portion during the heat melting after the tightening due to the expansion pressure due to the thermal expansion of the resin. On the other hand, when cooled after the heat treatment, the resin shrinks and voids are formed inside the winding, resulting in problems such as impaired sealing performance.
On the other hand, the aqueous sealing compound of the present invention has obtained excellent results in any of a resistance test against a chlorinated solvent, a drop deformation test, and an internal pressure test, and has excellent solvent resistance, adhesion and sealing. It is clear that sex is obtained.
（酸変性ポリオレフィン）
本発明の水性シーリングコンパウンドの主成分と成る酸変性オレフィンにおけるオレフィン単位としてはエチレン、プロピレンを挙げることができ、特にエチレンを好適に用いることができる。
また他のオレフィンとして、ブテン−１、ペンテン−１、へキセン−１、ネオヘキセン−１、オクテン−１等を２５モル％以下の量で共重合成分とすることができる。共重合成分が２５モル％を超えると、皮膜凝集力が弱くなるので好ましくない。
(Acid-modified polyolefin)
Examples of the olefin unit in the acid-modified olefin that is the main component of the aqueous sealing compound of the present invention include ethylene and propylene, and ethylene can be particularly preferably used.
As other olefins, butene-1, pentene-1, hexene-1, neohexene-1, octene-1 and the like can be used as a copolymerization component in an amount of 25 mol% or less. When the copolymerization component exceeds 25 mol%, the film cohesive force becomes weak, which is not preferable.
上記オレフィン単位から成るポリオレフィンを変性する酸成分としては、α，β−エチレン性不飽和カルボン酸を挙げることができる。
α，β−エチレン性不飽和カルボン酸としては、これに限定されないが、アクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸等を挙げることができ、特にアクリル酸を好適に用いることができる。
酸成分の変性は、グラフト共重合、ブロック共重合、ランダム共重合のいずれの形態でもよいが、水分散性の点からランダム共重合が特に好ましい。
酸成分は、２〜２５モル％の範囲でポリオレフィンに共重合されていることが好適である。２モル％以下では水分散性が困難となると共に、金属に対する接着性が劣るようになる。その一方２５モル％以上では溶剤耐性、特に塩素系の溶剤に対する耐性が弱くなるので、好ましくない。
Examples of the acid component that modifies the polyolefin composed of the olefin unit include α, β-ethylenically unsaturated carboxylic acid.
Examples of the α, β-ethylenically unsaturated carboxylic acid include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like, and acrylic acid can be particularly preferably used. .
The modification of the acid component may be in any form of graft copolymerization, block copolymerization, and random copolymerization, but random copolymerization is particularly preferred from the viewpoint of water dispersibility.
The acid component is preferably copolymerized with polyolefin in the range of 2 to 25 mol%. If it is 2 mol% or less, water dispersibility becomes difficult and adhesion to metal becomes inferior. On the other hand, if it is 25 mol% or more, the solvent resistance, particularly the resistance to a chlorinated solvent, is weak, which is not preferable.
本発明においては、酸変性ポリオレフィンにおける酸成分のカルボキシル基は、全カルボキシル基量の３０モル％以上が金属塩になっていることが重要である。これにより酸変性ポリオレフィンの水分散性を改良することが可能となるからである。
本発明において、酸変性ポリオレフィンのカルボキシル基を中和して成る金属としてはナトリウム、カリウム、リチウム等の１価アルカリ金属であることが水分散性の点で重要であるが、金属塩の一部をアミン塩又は／及びアルカリ土類金属塩とすることもできる。この場合、全カルボキシル基量の３０モル％以下にとどめることが重要であり、これより多いとアミン塩の場合凝集力が低下し、接着力が低下し、またアルカリ土類金属の場合水分散安定性が劣るようになる。
アミンとしてはアンモニア、アルキルアミン、モルホリン、イミダゾール、アルカノールアミン等を挙げることができ、アルカリ土類金属としてはカルシウム、バリウム、ストロンチウム、亜鉛等を挙げることができる。
また本発明においては、樹脂に適度な柔軟性を付与する目的で、アクリル酸エステル、酢酸ビニル等を酸変性ポリオレフィンの共重合成分として使用することもできる。
In the present invention, it is important that the carboxyl group of the acid component in the acid-modified polyolefin is a metal salt at 30 mol% or more of the total carboxyl group amount. This is because the water dispersibility of the acid-modified polyolefin can be improved.
In the present invention, it is important in terms of water dispersibility that the metal formed by neutralizing the carboxyl group of the acid-modified polyolefin is a monovalent alkali metal such as sodium, potassium or lithium. Can be amine salts and / or alkaline earth metal salts. In this case, it is important to keep it below 30 mol% of the total amount of carboxyl groups. If it is more than this, the cohesive strength is lowered in the case of an amine salt, and the adhesive strength is lowered. Inferiority.
Examples of the amine include ammonia, alkylamine, morpholine, imidazole, alkanolamine, and examples of the alkaline earth metal include calcium, barium, strontium, and zinc.
In the present invention, acrylic acid ester, vinyl acetate or the like can also be used as a copolymerization component of acid-modified polyolefin for the purpose of imparting appropriate flexibility to the resin.
本発明に好適に使用できる、１価金属イオンで中和された酸変性ポリオレフィンの水分散体としては、これに限定されないが、市販のアイオノマー樹脂の水分散体をそのまま用いることもできるし、或いはアイオノマー樹脂や、エチレン−アクリル酸又はエチレン−アクリル酸エステルを事前に金属塩にしたものを水分散させるか、非エステルではそのままアルカリ金属水溶液に分散させる方法により、水分散体を調製することができるが、これに限定されるものではなく、従来公知の方法により行うことができる。
尚、アイオノマー樹脂の水分散体としては、例えば三井化学（株）製 ケミパール（登録商標）等、アイオノマー樹脂としては、例えば三井・デュポンポリケミカル（株）製 ハイミラン（登録商標）、デュポン（株）製 サーリンＡ（登録商標）等、エチレン−アクリル酸、エチレン−アクリル酸エステルとしては三井・デュポンポリケミカル（株）製 ニュクレル（登録商標）やエルバロイ（登録商標）等を入手することができるが、これに限定されず、他社の同様な樹脂ならいずれも使用できる。
The aqueous dispersion of acid-modified polyolefin neutralized with a monovalent metal ion that can be suitably used in the present invention is not limited to this, but an aqueous dispersion of a commercially available ionomer resin can be used as it is, or An aqueous dispersion can be prepared by dispersing in water an ionomer resin or an ethylene-acrylic acid or ethylene-acrylic acid ester previously converted into a metal salt, or in a non-ester as it is in an aqueous alkali metal solution. However, it is not limited to this, and can be performed by a conventionally known method.
As an ionomer resin aqueous dispersion, for example, Chemipearl (registered trademark) manufactured by Mitsui Chemical Co., Ltd., and as an ionomer resin, for example, High Milan (registered trademark), DuPont manufactured by Mitsui DuPont Polychemical Co., Ltd. Manufactured Surlyn A (registered trademark), such as ethylene-acrylic acid, ethylene-acrylic ester, Mitsui-DuPont Polychemical Co., Ltd. Nukurel (registered trademark), Elvalloy (registered trademark), etc. However, the present invention is not limited to this, and any similar resin from other companies can be used.
本発明においては、１価イオンで中和された酸変性ポリオレフィンは、水分散体の総固形分の主成分、すなわち最も含有量が多く且つ総固形分に対して３５重量％以上、特に５０重量％以上の量で含有していることが重要である。酸変性ポリオレフィンの含有量が３５重量％より少ないとシーリングコンパウンド皮膜の接着力が弱くなったり、溶剤耐性が劣るようになる。
本発明に用いる１価イオンで中和された酸変性ポリオレフィンは、所望の凝集力を得るために、引っ張り破壊強度が１５ＭＰａ／ｃｍ２以上であることが好ましい。
また本発明に用いる１価イオンで中和された酸変性ポリオレフィンは、低温製膜性の観点から、軟化温度が１００℃以下 好ましくは８０℃以下であることが好適である。
In the present invention, the acid-modified polyolefin neutralized with monovalent ions is the main component of the total solid content of the aqueous dispersion, that is, the most content and 35% by weight or more, particularly 50% with respect to the total solid content. It is important that it is contained in an amount of at least%. When the content of the acid-modified polyolefin is less than 35% by weight, the adhesive strength of the sealing compound film becomes weak or the solvent resistance becomes poor.
In order to obtain a desired cohesive force, the acid-modified polyolefin neutralized with monovalent ions used in the present invention preferably has a tensile breaking strength of 15 MPa / cm 2 or more.
The acid-modified polyolefin neutralized with monovalent ions used in the present invention preferably has a softening temperature of 100 ° C. or lower, preferably 80 ° C. or lower, from the viewpoint of low-temperature film-forming properties.
（配合可能なその他成分）
本発明の水性シーリングコンパウンドにおいては、上述した１価金属イオンで中和された酸変性ポリオレフィンを主成分として、全固形分の３５重量％以上の量で含有する限り、他の樹脂成分を含有させることもできる。
他の樹脂成分としては、ポリオレフィン系エラストマーを挙げることができ、例えば、エチレンと、プロピレン、ブテン−１、ペンテン−１、へキセン−１、ネオヘキセン−１等のα−オレフィン及び／又はイソプレン、ブタジエン、ジシクロペンタジエン、ペンタジエン−１，４、ジビニルベンゼン、メチリデンノルボネン、エチリデンノルボネン等の共役ジエン、とからなる共重合体を挙げることができる。これらは単独でも、複数組み合わせで使用してもよい。
また他の樹脂成分としては、オレフィンとα，βエチレン性不飽和酸の水分散体を挙げることができ、例えば、エチレン−酢酸ビニル、エチレン−（メタ）アクリル酸、エチレン−（メタ）アクリル酸エステル等の、オレフィンとα，βエチレン性不飽和酸等のエマルジョン重合により得られる水分散体を挙げることができる。またエチレン−（メタ）アクリル酸ではアミン中和の水分散体も使用できる
(Other ingredients that can be blended)
In the aqueous sealing compound of the present invention, as long as the acid-modified polyolefin neutralized with the above-mentioned monovalent metal ions is contained as a main component in an amount of 35% by weight or more of the total solid content, other resin components are included. You can also
Examples of other resin components include polyolefin-based elastomers, such as ethylene and α-olefins such as propylene, butene-1, pentene-1, hexene-1, and neohexene-1, and / or isoprene and butadiene. , Dicyclopentadiene, pentadiene-1,4, conjugated dienes such as divinylbenzene, methylidene norbornene, and ethylidene norbornene. These may be used alone or in combination.
Examples of other resin components include an aqueous dispersion of an olefin and an α, β-ethylenically unsaturated acid, such as ethylene-vinyl acetate, ethylene- (meth) acrylic acid, ethylene- (meth) acrylic acid. An aqueous dispersion obtained by emulsion polymerization of an olefin such as an ester and an α, β-ethylenically unsaturated acid may be mentioned. For ethylene- (meth) acrylic acid, an amine-neutralized aqueous dispersion can also be used.
更に他の樹脂成分としては、ブタジエン−マレイン酸等のジエン系モノマーと不飽和酸の共重合エラストマー類、ＳＢＲ等の芳香族ビニルと共役ジエンの共重合エラストマー類、ＮＢＲ等のニトリルを含むエラストマー類、及びこれらのエラストマー類の酸変性体、或いはネオプレン、ブチルラバー、天然ゴム等を挙げることができる。
これら樹脂成分の中で、特に好ましい成分としてエチレン−プロピレン−ブタジエン三元共重合エラストマー（ＥＰＤＭ）、およびニトリル−ブタジエン共重合エラストマー（ＮＢＲ）が挙げられる。ＮＢＲは酸変性であっても非変性であってもよい。
これらは、膨潤はするものの種々エラストマー類の中では比較的耐溶剤性のよいものであり、本発明の酸変性ポリエチレンエマルジョンに配合することにより、乾燥皮膜のヒビワレを抑制し均一な皮膜を作成できる。酸変性ポリオレフィン１００重量部に対して１０乃至１２０重量部の量で配合することが好ましい。これより少ないとヒビワレを抑制できず、またこれより多いと金属基体に対する接着性が弱くなる。
更にまた、従来水性塗料に一般的に使用される樹脂成分、例えばエポキシアクリル、アルキッド、ポリエステル、ナイロン、ウレタン等の水分散体も配合することができる。これらはラテックス、エマルジョン、ソープフリーエマルジョン、或いは水溶液の形態で入手でき、酸変性オレフィン分散体の製膜性、被塗面への濡れ性向上、皮膜柔軟性付与、増粘等の粘度調整の目的で使用することもできる。
Still other resin components include copolymer elastomers of diene monomers such as butadiene-maleic acid and unsaturated acids, copolymer elastomers of aromatic vinyl and conjugated diene such as SBR, and elastomers containing nitrile such as NBR. And acid-modified products of these elastomers, neoprene, butyl rubber, natural rubber and the like.
Among these resin components, particularly preferred components include ethylene-propylene-butadiene terpolymer elastomer (EPDM) and nitrile-butadiene copolymer elastomer (NBR). NBR may be acid-modified or non-modified.
Although they swell, they have relatively good solvent resistance among various elastomers, and by blending with the acid-modified polyethylene emulsion of the present invention, it is possible to create a uniform film by suppressing cracking of the dry film. . It is preferably blended in an amount of 10 to 120 parts by weight with respect to 100 parts by weight of the acid-modified polyolefin. If it is less than this, cracking cannot be suppressed, and if it is more than this, the adhesion to the metal substrate is weakened.
Furthermore, resin components generally used in conventional water-based paints, for example, water dispersions such as epoxy acryl, alkyd, polyester, nylon, and urethane can also be blended. These can be obtained in the form of latex, emulsion, soap-free emulsion, or aqueous solution. The purpose of adjusting the viscosity of the acid-modified olefin dispersion is to improve the film-forming property, improve the wettability of the coated surface, give the film flexibility, and increase the viscosity. Can also be used.
（その他添加剤）
本発明の水性シーリングコンパウンドにおいては、従来よりシーリングコンパウンドに用いられていた従来公知の種々の添加剤、例えば界面活性剤、粘度調整剤、粘着付与剤、充填剤等を従来公知の処方に従って配合することができる。
界面活性剤は、水分散安定、濡れ性を向上するために使用することが望ましい。市販の界面活性剤を使用することができるが、特にノニオン系或いはアニオン系の界面活性剤を用いることが好適であり、酸変性ポリオレフィン樹脂の水性分散体１００重量部に対して０．５乃至１０重量部の量で配合することが好ましい。
粘度調製剤としては、メチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース等のセルロース類、アルギン酸ナトリウム、ポリビニルアルコール、ポリアクリル酸又はナトリウム塩、ポリビニルエーテル、ポリエチレンオキサイド、ポリビニルピロリドン、ポリアクリルアミド、カラヤガム、活性白土、ベントナイト等、ポリエチレングリコール、ポリプロピレングリコール、及びこれらグリコールの共重合樹脂、ポリビニルアルコール、ポリビニルブチラール等を挙げることができ、酸変性ポリオレフィン樹脂の水性分散体１００重量部に対して０．１乃至８重量部の量で配合することが好ましい。
(Other additives)
In the aqueous sealing compound of the present invention, various conventionally known additives conventionally used in sealing compounds, such as surfactants, viscosity modifiers, tackifiers, fillers, etc., are blended according to conventionally known formulations. be able to.
It is desirable to use a surfactant to improve water dispersion stability and wettability. Commercially available surfactants can be used, but it is particularly preferable to use nonionic or anionic surfactants, and 0.5 to 10 per 100 parts by weight of the aqueous dispersion of acid-modified polyolefin resin. It is preferable to mix | blend in the quantity of a weight part.
As viscosity modifiers, celluloses such as methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium alginate, polyvinyl alcohol, polyacrylic acid or sodium salt, polyvinyl ether, polyethylene oxide, polyvinyl pyrrolidone, polyacrylamide, karaya gum, active Examples include clay, bentonite, polyethylene glycol, polypropylene glycol, copolymer resins of these glycols, polyvinyl alcohol, polyvinyl butyral, and the like, and 0.1 to 8 with respect to 100 parts by weight of the aqueous dispersion of acid-modified polyolefin resin. It is preferable to mix | blend in the quantity of a weight part.
粘着付与剤としては、ロジン、水添ロジン、ロジンエステル等のロジン系樹脂、テルペン樹脂、フェノール樹脂、天然樹脂変性、フェノール樹脂、キシレン樹脂、石油樹脂等を挙げることができる。
充填剤としては、従来からシーリングコンパウンドに使用されている充填剤はいずれも使用できるが、全固形分中４０重量％以下の量で配合することが必要である。上記範囲よりも多いと皮膜が硬くなりすぎ皮膜凝集力及び密着力が低下するので好ましくない。
充填剤としては、コロイダルシリカ、無水珪酸、含水珪酸、合成珪酸等のシリカ充填剤、軟質乃至重質炭酸カルシウム、活性化炭酸カルシウム、カオリン、焼成クレー、珪酸アルミ、タルク、ドロマイト、硫酸アルミナ、硫酸バリウム、炭酸マグネシウム、珪酸マグネシウム、珪酸カルシウム、珪酸アルミニウム、酸化マグネシウム、硫酸カルシウム、酸化亜鉛、合成亜鉛、二酸化チタン、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、マイカ、カーボンブラック ポリマー架橋微粒子等を挙げることができる。
これらの中で水酸化アルミニウムや珪酸アルミニウム等のアルミニウム化合物が分散性等の観点から特に好ましい充填剤である。
Examples of the tackifier include rosin resins such as rosin, hydrogenated rosin, and rosin ester, terpene resins, phenol resins, natural resin modifications, phenol resins, xylene resins, petroleum resins, and the like.
As the filler, any of the fillers conventionally used in sealing compounds can be used, but it is necessary to blend in an amount of 40% by weight or less based on the total solid content. If it exceeds the above range, the film becomes too hard and the film cohesive force and adhesive force are lowered, which is not preferable.
As fillers, silica fillers such as colloidal silica, anhydrous silicic acid, hydrous silicic acid, synthetic silicic acid, soft to heavy calcium carbonate, activated calcium carbonate, kaolin, calcined clay, aluminum silicate, talc, dolomite, alumina sulfate, sulfuric acid Barium, magnesium carbonate, magnesium silicate, calcium silicate, aluminum silicate, magnesium oxide, calcium sulfate, zinc oxide, synthetic zinc, titanium dioxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, mica, carbon black polymer crosslinked fine particles, etc. Can be mentioned.
Among these, aluminum compounds such as aluminum hydroxide and aluminum silicate are particularly preferable fillers from the viewpoint of dispersibility.
本発明の水性シーリングコンパウンドは、１価金属により中和された酸変性ポリオレフィンの水性分散体に、上述した他の成分を配合することにより調製することができる。
また本発明の水性シーリングコンパウンドはライニング装置により缶端（缶蓋）に塗布乾燥させて、塗膜を形成した後、缶端（缶蓋）を缶胴に巻き締め、シーリングコンパウンドに用いられたポリオレフィンの溶融温度以上（ポリエチレンの場合では１３０℃以上）に、巻締め部を加熱することにより接着性及び密封性に優れた巻締め部を形成することができる。
尚、本発明のシーリングコンパウンドは、低温製膜性に優れていることから、５０乃至１００℃で１乃至１０分の範囲で乾燥することにより塗膜形成を行うことができる。また巻締め後の加熱方法は、高周波加熱、オーブン等従来公知の方法により行うことができる。
The aqueous sealing compound of the present invention can be prepared by blending the above-mentioned other components with an aqueous dispersion of acid-modified polyolefin neutralized with a monovalent metal.
The aqueous sealing compound of the present invention is applied to the can end (can lid) by a lining device and dried to form a coating film, and then the can end (can lid) is wound around the can body, and the polyolefin used for the sealing compound By heating the tightening portion to a melting temperature of 130 ° C. or more (in the case of polyethylene, 130 ° C. or more), it is possible to form a tightening portion having excellent adhesion and sealing properties.
In addition, since the sealing compound of this invention is excellent in low-temperature film forming property, it can form a coating film by drying in 50 to 100 degreeC for 1 to 10 minutes. Moreover, the heating method after winding can be performed by a conventionally known method such as high-frequency heating or an oven.
（評価方法）
１．メルトフローレート（ＭＦＲ）測定
ポリテトラフルオロエチレン加工された板上に塗布乾燥し水分を除去した後、ＪＩＳ−Ｋ７２１０の公知の方法に従って、１９０℃、試験荷重２．１６ｋｇｆの条件で測定した。
２．酸含有量測定
赤外線吸収スペクトルから求めた。
(Evaluation methods)
1. Melt Flow Rate (MFR) Measurement After coating and drying on a polytetrafluoroethylene-processed plate to remove moisture, measurement was performed under the conditions of 190 ° C. and a test load of 2.16 kgf according to a known method of JIS-K7210.
2. Acid content measurement The acid content was determined from an infrared absorption spectrum.
３．樹脂の引っ張り強度
ホットプレスにて１８０℃に加熱溶融し厚み１ｍｍのフィルムを作成し、テンシロンを用いて、２０℃の雰囲気温度にて３００ｍｍ／分の速度で行った。
４．接着力
ティンフリースチール（ＴＦＳ）（東洋鋼鈑（株）製板厚０．３２mm）に塗布、８０℃で１０分乾燥し塗布厚み約７０μｍの酸変性ポリエチレンの塗装板を作成した。
この塗装板から長さ５０ｍｍ、巾１０ｍｍの試片を切り出し、同一寸法の無塗装ＴＦＳ板と重ね合わせ、ホットプレスにて１７０℃−２秒加熱し接着させた。この接着試片の接着力をＴピール法により測定する。
3. Tensile strength of resin A film having a thickness of 1 mm was prepared by heating and melting at 180 ° C. with a hot press, and using Tensilon at an ambient temperature of 20 ° C. at a speed of 300 mm / min.
4). Adhesive strength Coated to tin-free steel (TFS) (plate thickness 0.32 mm manufactured by Toyo Kohan Co., Ltd.) and dried at 80 ° C. for 10 minutes to prepare a coated plate of acid-modified polyethylene having a coating thickness of about 70 μm.
A specimen having a length of 50 mm and a width of 10 mm was cut out from this coated plate, overlapped with a non-coated TFS plate having the same dimensions, and heated and bonded at 170 ° C. for 2 seconds. The adhesive strength of this adhesive specimen is measured by the T peel method.
５．落下試験
実施例で作成された天地巻き締め１８Ｌ缶に天面口部より水を満中となるように充填し、キャップを装着固定した。この充填缶について下記の条件で落下試験を行った。
［水平落下］
缶胴の一平面を落下面に対して水平にし、１．２ｍの高さから落下させ、５分放置後缶に穴をあけ大気圧に戻して、漏洩の有無を調べた。
［対角落下］
缶胴の対角面を落下面に対して水平にし、１．２ｍの高さから落下させ、５分放置後缶に穴をあけ大気圧に戻して、漏洩の有無を調べた。
［評価］ ○：漏洩見られず良好
△：僅か滲みが見られる程度
×：水の滲み出しが、または漏出が明瞭に見られる
5). Drop test
The top and bottom 18L can created in the example was filled with water from the top surface so that it was full, and a cap was attached and fixed. A drop test was performed on the filled can under the following conditions.
[Horizontal drop]
One plane of the can body was made level with respect to the dropping surface, dropped from a height of 1.2 m, left for 5 minutes, then a hole was made in the can and returned to atmospheric pressure, and the presence of leakage was examined.
[Diagonal drop]
The diagonal surface of the can body was made horizontal with respect to the falling surface, dropped from a height of 1.2 m, left for 5 minutes, then a hole was made in the can and returned to atmospheric pressure, and the presence of leakage was examined.
[Evaluation] ○: No leakage was observed
Δ: Slight bleeding
X: Exudation of water or leakage is clearly seen
６．耐内圧試験
実施例で作成された天地巻き締め１８Ｌ缶に水圧試験機により、１００ｋＰａの水圧をかけ、５分間放置後内圧減少の有無（リーク）を調べた。
［評価］ ○：リークは見られない
△：内圧減少みられるも僅かな程度
×：明瞭にリーク
７．クロロホルム浸漬試験
ＴＦＳ板に作成した皮膜を所定温度にて乾燥後、クロロホルムに２時間浸漬し、膨潤状態（膨れ）及びスパチュラのヘリで密着程度を観察した。
［評価］ ○：変化なし。密着良好
△：わずかに膨れ傾向見られるも、密着は維持している
×：かなり膨れ、密着も弱いかまたは自然に剥離する。
6). Internal pressure resistance test The water pressure of 100 kPa was applied to the top and bottom 18L can made in the Example by a water pressure tester, and the presence or absence (leakage) of the internal pressure was examined after being left for 5 minutes.
[Evaluation] ○: Leak is not seen
Δ: Slight but slight decrease in internal pressure
X: Leak clearly Chloroform immersion test The film prepared on the TFS plate was dried at a predetermined temperature, then immersed in chloroform for 2 hours, and the degree of adhesion was observed with a swollen state (swelling) and a spatula helicopter.
[Evaluation] ○: No change. Good adhesion
Δ: Slight swelling tendency is observed, but adhesion is maintained
X: Swells considerably, adhesion is weak, or peels off spontaneously.
８．樹脂はみ出し試験
実施例で作成された天地巻き締め缶の高周波加熱時における巻き締め部よりのシーリング剤のはみ出し状態を観察した
［評価］ ○：はみ出しは見られない
△：缶外面部に数箇所僅かにはみ出しの見られる程度
×：缶内外面全周にはみ出しが見られる
９．製膜性
ＴＦＳ板に作成した皮膜を所定温度にて乾燥後、皮膜のヒビワレ状態を観察した。
［評価］ ○：ヒビワレなく良好
△：数箇所にヒビワレが見られる。
×：全面にヒビワレが見られる
8). Resin protrusion test The protruding state of the sealing agent from the winding part during high-frequency heating of the top and bottom winding cans prepared in the examples was observed [Evaluation] ○: No protrusion
Δ: Excessive appearance of several protrusions on the outer surface of the can
X: Projection is seen all around inner and outer surfaces of can. Film-forming property After the film formed on the TFS plate was dried at a predetermined temperature, the cracked state of the film was observed.
[Evaluation] ○: Good without cracks
Δ: Cracking is observed in several places.
×: Cracks are seen on the entire surface
（使用樹脂）
［樹脂例１］
エチレン−アクリル酸のナトリウム型アイオノマーの水分散体（三井化学（株）製ケミパールＳ３００）を用いた。ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表１に示す。
(Used resin)
[Resin Example 1]
An aqueous dispersion of sodium-ionomer of ethylene-acrylic acid (Chemical S300 manufactured by Mitsui Chemicals, Inc.) was used. Table 1 shows the MFR, density, acid content, softening temperature, and tensile strength.
［樹脂例２〜６］
エチレン−アクリル酸のナトリウム型アイオノマーの水分散体として、三井化学（株）製ケミパールＳ１００、Ｓ６５０、Ｓ２００、Ｓ１２０、ＳＡ１００を用いた。ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表１に示す。
尚、ＳＡ１００はエチルアクリレートを一部共重合させたアイオノマー樹脂である。
[Resin Examples 2 to 6]
As an aqueous dispersion of sodium-type ionomer of ethylene-acrylic acid, Chemipearl S100, S650, S200, S120, and SA100 manufactured by Mitsui Chemicals, Inc. were used. Table 1 shows the MFR, density, acid content, softening temperature, and tensile strength.
SA100 is an ionomer resin obtained by partially copolymerizing ethyl acrylate.
［樹脂例７〜１０］
ナトリウム型アイオノマー樹脂（三井・デュポンポリケミカル（株）製 ハイミラン１５５５，１７０７，１６０５，１８５６）を用いた。ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表２に示す。
[Resin Examples 7 to 10]
Sodium type ionomer resin (High Milan 1555, 1707, 1605, 1856 manufactured by Mitsui DuPont Polychemical Co., Ltd.) was used. Table 2 shows the MFR, density, acid content, softening temperature, and tensile strength.
［樹脂例１１］
酸含量５重量％、ＭＦＲが３３ｇ／１０分、密度０．９３のエチレン−アクリル酸共重合樹脂（三井・デュポンポリケミカル（株）製ニュクレルＡＮ４２１１５Ｃ）を、アクリル酸と等モル量の水酸化ナトリウム水溶液の入った耐圧容器に入れ、１６０℃で６０分加熱撹拌し、固形分３２％の乳白色のカルボン酸ナトリウム型アイオノマー樹脂とした水分散体を調製した。ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表３に示す
[Resin Example 11]
An ethylene-acrylic acid copolymer resin (Mitsui / Dupont Polychemical Co., Ltd. Nuclerel AN42115C) having an acid content of 5% by weight, MFR of 33 g / 10 min, and a density of 0.93 is mixed with acrylic acid in an equimolar amount of sodium hydroxide. The mixture was placed in a pressure vessel containing an aqueous solution and heated and stirred at 160 ° C. for 60 minutes to prepare an aqueous dispersion as a milky white sodium carboxylate ionomer resin having a solid content of 32%. Table 3 shows the MFR, density, acid content, softening temperature, and tensile strength.
［樹脂例１２］
酸含量１０重量％、ＭＦＲが３５ｇ／１０分、密度０．９３のエチレン−アクリル酸共重合樹脂（三井・デュポンポリケミカル（株）製ニュクレルＮ１０３５）を用いて、水酸化ナトリウムに変えて水酸化カリウムを用いる以外は樹脂例１１の場合と同様にして水分散体を調製した。ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表３に示す
[Resin Example 12]
Using an ethylene-acrylic acid copolymer resin having an acid content of 10% by weight, an MFR of 35 g / 10 min, and a density of 0.93 (Nucleel N1035 manufactured by Mitsui DuPont Polychemical Co., Ltd.), it was changed to sodium hydroxide for hydroxylation. An aqueous dispersion was prepared in the same manner as in Resin Example 11 except that potassium was used. Table 3 shows the MFR, density, acid content, softening temperature, and tensile strength.
［樹脂例１３〜１５］
樹脂例１１と同様にして、ナトリウム型アイオノマー（三井化学（株）製ニュクレルＮ０９３３ＨＣ，ＡＮ４２２１Ｃ，Ｎ０３５Ｃ）から成る水分散体を作成した。ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表３に示す
[Resin Examples 13 to 15]
In the same manner as in Resin Example 11, an aqueous dispersion composed of a sodium ionomer (Nucleel N0933HC, AN4221C, N035C manufactured by Mitsui Chemicals, Inc.) was prepared. Table 3 shows the MFR, density, acid content, softening temperature, and tensile strength.
［樹脂例１６］
酸含有量２０重量％、ＭＦＲが８ｇ／１０分、密度０．９４のエチレン−アクリル酸メチル共重合樹脂（三井・デュポンポリケミカル（株）製 エルバロイ１８２０ａｃ）を耐圧容器に入れ、ベンゼン、アクリル酸エステルの１．２倍モル量の水酸化ナトリウムのメタノール溶液を入れ１３０℃の温度で溶解し、同温度に保ち撹拌しながら約２時間反応させた後、酢酸にて所定量の中和を行い沈殿した樹脂を取出した。この樹脂のＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表３に示す
[Resin Example 16]
An ethylene-methyl acrylate copolymer resin (Mitsui / DuPont Polychemical Co., Ltd. Elvalloy 1820ac) having an acid content of 20% by weight, MFR of 8 g / 10 min, and a density of 0.94 is placed in a pressure vessel, benzene, acrylic acid Add a 1.2-fold molar amount of sodium hydroxide methanol solution to the ester, dissolve at 130 ° C, react at the same temperature for about 2 hours with stirring, then neutralize with acetic acid for a specified amount. The precipitated resin was removed. Table 3 shows the MFR, density, acid content, softening temperature, and tensile strength of this resin.
［樹脂例１７］
アンモニア中和によるエチレン−アクリル酸共重合樹脂（三井化学（株）製 ケミパールＳ７５Ｎ）を用いた。ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表４に示す。
[Resin Example 17]
Ethylene-acrylic acid copolymer resin by neutralization with ammonia (Chemical S75N manufactured by Mitsui Chemicals, Inc.) was used. Table 4 shows the MFR, density, acid content, softening temperature, and tensile strength.
［樹脂例１８］
アクリル酸含量１０重量％、ＭＦＲ５００ｇ／１０分、密度０．９３のエチレン−アクリル酸共重合樹脂（三井・デュポンポリケミカル（株）製 ニュクレルＮ１０５０）を出発原料として樹脂例１１と同様にナトリウム型アイオノマー樹脂の水分散体を作成し、ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を測定した。結果を表４に示す。
[Resin Example 18]
Sodium-type ionomer in the same manner as in Resin Example 11 starting from an ethylene-acrylic acid copolymer resin (Mitsui / DuPont Polychemical Nucrel N1050) having an acrylic acid content of 10% by weight, MFR of 500 g / 10 min, and a density of 0.93 An aqueous dispersion of the resin was prepared, and MFR, density, acid content, softening temperature, and tensile strength were measured. The results are shown in Table 4.
［樹脂例１９、２０］
樹脂例１８と同様にして、ナトリウム型アイオノマー樹脂（三井・デュポンポリケミカル（株）製 ニュクレルＮ１１０Ｈ）、及びマレイン酸変性（グラフト）オレフィン系樹脂（三井化学（株）製 アドマーＮＳ１０１）についての水性分散体を作製し、ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を測定した。結果を表４に併せて示す。
[Resin Examples 19 and 20]
In the same manner as in Resin Example 18, aqueous dispersion of sodium ionomer resin (Mitsui / DuPont Polychemical Co., Ltd. Nucrel N110H) and maleic acid-modified (graft) olefin resin (Mitsui Chemicals Co., Ltd. Admer NS101) A body was prepared, and MFR, density, acid content, softening temperature, and tensile strength were measured. The results are also shown in Table 4.
［樹脂例２１、２２］
エチレン−酢酸ビニル共重合樹脂（三井化学（株）製 ケミパールＶ１００;酢ビ含量２５重量％）、及びエチレン−αオレフィン系熱可塑性エラストマー（三井化学（株）製 ケミパールＡ１００）の水分散体について、ＭＦＲ、密度、酸含量、軟化温度、引っ張り強度を表４に示す。
[Resin Examples 21 and 22]
About the water dispersion of ethylene-vinyl acetate copolymer resin (Mitsui Chemicals Co., Ltd. Chemipearl V100; vinyl acetate content 25% by weight) and ethylene-α-olefin thermoplastic elastomer (Mitsui Chemicals Co., Ltd. Chemipearl A100) Table 4 shows the MFR, density, acid content, softening temperature, and tensile strength.
（実施例１）
樹脂例１の水分散体（固形分３５％）１００部に対してアニオン界面活性剤（花王（株）製ニューレックスＲ）を２部、メチルセルロース(信越（株)製ＳＨ１５００)を０．３部添加したシーリングコンパウンドを調製し、前記方法により接着力測定及びクロロホルム浸漬試験を行った。塗布乾燥皮膜には散発的なヒビワレが見られるものの、以下の実用特性には特に影響を及ぼすほどではなかった。
このシーリングコンパウンドを、ＴＦＳ製（板厚０．３２ｍｍ）の１８Ｌ缶の口部を設けた天板、及び地板の溝部にライニングマシンにて乾燥重量が７００ｍｇとなるように塗布し、８０℃−１０分乾燥した。次いで所定の方法で１８Ｌ缶の缶胴に巻き締めた後、高周波加熱により天地巻き締め部をピーク温度が１７０℃となるように加熱処理を行い天地巻き締め１８Ｌ缶を作成し、落下試験及び耐内圧試験を行った。落下試験の結果は、缶は著しく変形したが漏洩は見られなかった。また耐内圧試験の結果は、水圧１００ｋＰａの内圧を５分間かけリークの状態を調べたが、リークはなく気密性を維持していた。
結果を表５に示す。
Example 1
2 parts of an anionic surfactant (Newex R manufactured by Kao Corporation) and 0.3 parts of methylcellulose (SH1500 manufactured by Shin-Etsu Co., Ltd.) per 100 parts of the aqueous dispersion (solid content 35%) of Resin Example 1 The added sealing compound was prepared, and the adhesion strength measurement and the chloroform immersion test were performed by the above-described methods. Although sporadic cracking was observed in the coated and dried film, the following practical properties were not particularly affected.
This sealing compound was applied to the top plate provided with the mouth of an 18 L can made of TFS (plate thickness: 0.32 mm) and the groove portion of the base plate so that the dry weight would be 700 mg with a lining machine, and 80 ° C.-10 Dried for minutes. Next, after being wound around the can body of the 18L can by a predetermined method, the top and bottom winding part is heat-treated by high frequency heating so that the peak temperature becomes 170 ° C., and a top and bottom winding 18L can is prepared. An internal pressure test was performed. As a result of the drop test, the can was remarkably deformed but no leakage was observed. As a result of the internal pressure resistance test, the internal pressure of 100 kPa of water pressure was applied for 5 minutes to check the state of leakage, but there was no leakage and the airtightness was maintained.
The results are shown in Table 5.
（実施例２〜３）
樹脂例２〜３の水分散体を使用して、実施例１と同様にシーリングコンパウンド、及び１８Ｌ缶を作成し、同様の方法で評価を行った。結果を表５に示す。
(Examples 2-3)
Using the aqueous dispersions of Resin Examples 2 to 3, a sealing compound and an 18L can were prepared in the same manner as in Example 1, and evaluated in the same manner. The results are shown in Table 5.
（実施例４〜６）
樹脂例４〜６の水分散体を使用して、各々１００重量部に対してアニオン界面活性剤（花王（株）製ニューレックスＲ）を２部、エチレン−プロピレン−ブタジエン共重合エマルジョン（固形分５０％；住友精化ＥＰ１２０）２５重量部を加えシーリングコンパウンドを作成した。このシーリングコンパウンドを用いて実施例１と同様にして溶剤耐性、接着力を評価、及び１８Ｌ缶を作成し、落下耐性、耐内圧などの評価を行った。結果を表５に示す。
これらシーリングコンパウンドの乾燥皮膜には特にヒビワレ等は見られず良好な製膜性を示し、実用特性等も満足するものであった。
(Examples 4 to 6)
Using the aqueous dispersions of Resin Examples 4 to 6, 2 parts of an anionic surfactant (Nurex R manufactured by Kao Corporation) for each 100 parts by weight, ethylene-propylene-butadiene copolymer emulsion (solid content) 50%; Sumitomo Seika EP120) 25 parts by weight was added to prepare a sealing compound. Using this sealing compound, the solvent resistance and the adhesive strength were evaluated in the same manner as in Example 1, and an 18L can was prepared to evaluate the drop resistance and the internal pressure resistance. The results are shown in Table 5.
The dry film of these sealing compounds did not show any cracks or the like, showed good film forming properties, and satisfied practical properties.
（実施例７）
樹脂例７を出発原料として、所定量の水とともに耐圧容器に入れ、１４５℃に加熱しながら約１００分攪拌し固形分２７％の水分散体を作成した。この水分散体を用いて実施例１と同様にしてシーリングコンパウンド、及び１８Ｌ缶を作成し、同様の方法で評価を行った。結果を表５に示す
(Example 7)
Using Resin Example 7 as a starting material, it was placed in a pressure vessel together with a predetermined amount of water and stirred for about 100 minutes while being heated to 145 ° C. to prepare an aqueous dispersion having a solid content of 27%. Using this aqueous dispersion, a sealing compound and an 18L can were prepared in the same manner as in Example 1, and evaluated in the same manner. The results are shown in Table 5.
（実施例８〜１０）
樹脂例８〜１０の水分散体を使用して、実施例７と同様にして水分散体を作成し、次いで実施例４におけるＥＰＤＭの代わりにＮＢＲ（ＬＸ５３１Ｂ；ゼオン固形分５８％）を用いる以外は実施例４と同様にしてシーリングコンパウンド、及び１８Ｌ缶を作成し、実施例１と同様の方法で評価を行った。結果を表５に示す。
(Examples 8 to 10)
An aqueous dispersion was prepared in the same manner as in Example 7 using the aqueous dispersions of Resin Examples 8 to 10, and then NBR (LX531B; ZEON solid content: 58%) was used instead of EPDM in Example 4. Prepared a sealing compound and 18L can in the same manner as in Example 4, and evaluated in the same manner as in Example 1. The results are shown in Table 5.
（実施例１１〜１５）
樹脂例１１〜１５の水分散体を用いて、実施例４におけるＥＰＤＭの代わりにＮＢＲ（ＪＳＲ：０９１０）を用いる以外は実施例４と同様にしてシーリングコンパウンド、及び１８Ｌ缶を作成し、実施例１と同様の方法で評価を行った。結果を表５に示す。
(Examples 11 to 15)
A sealing compound and an 18 L can were prepared in the same manner as in Example 4 except that NBR (JSR: 0910) was used instead of EPDM in Example 4 using the aqueous dispersions of Resin Examples 11-15. Evaluation was performed in the same manner as in 1. The results are shown in Table 5.
（実施例１６）
樹脂例１６で作成したアイオノマー樹脂を用いて、実施例７と同様にシーリングコンパウンド及び１８Ｌ缶を作成し、評価を行った。結果を表５に示す。
(Example 16)
Using the ionomer resin prepared in Resin Example 16, a sealing compound and an 18L can were prepared and evaluated in the same manner as in Example 7. The results are shown in Table 5.
（比較例１）
樹脂例１７の水分散体を用いて、実施例１と同様にシーリングコンパウンドを作成し、評価を行った。
接着強度、クロロホルム耐性を調べたところ、接着力は２２ｋｇ／ｃｍと比較的良好な強度を示した。またクロロホルム耐性もやや膨潤傾向を示すが剥離しづらく、特に問題は見られない状態であった。
一方、１８Ｌ缶の作成に際し、実施例１と同様にして作成したところ（乾燥塗布量７００ｍｇ）、天地巻き締を作成した後、高周波加熱により加熱処理を行ったところ溶融樹脂のはみ出しが生じてしまった。
乾燥塗布重量を４００ｍｇに下げて作成したところ、溶融樹脂のはみ出しは見られなかったが、耐内圧試験でスローリークが生じ、気密性を維持することはできなかった。
結果を表６に示す。
(Comparative Example 1)
Using the aqueous dispersion of Resin Example 17, a sealing compound was prepared and evaluated in the same manner as in Example 1.
When the adhesive strength and chloroform resistance were examined, the adhesive strength showed a relatively good strength of 22 kg / cm. The chloroform resistance also showed a tendency to swell, but it was difficult to peel off, and no particular problem was observed.
On the other hand, when the 18L can was made in the same manner as in Example 1 (dry coating amount 700 mg), the top and bottom windings were made, and then the heat treatment was performed by high-frequency heating, and the molten resin protruded. It was.
When the dry coating weight was reduced to 400 mg, the molten resin did not protrude, but a slow leak occurred in the internal pressure resistance test, and the airtightness could not be maintained.
The results are shown in Table 6.
（比較例２、３）
比較例１と同様にして樹脂例１８、１９を用いてシーリングコンパウンド及び１８Ｌ缶を作成し、評価したところ、接着力は弱く、またクロロホルム浸漬でも膨潤とともに、樹脂例１８においては剥離しやすく密着力がとぼしくなる傾向を示し、耐性に乏しい結果となった。
また巻き締め後の高周波加熱においても比較例１と同様の結果であり商品価値は認められなかった。
結果を表６に示す。
(Comparative Examples 2 and 3)
In the same manner as in Comparative Example 1, sealing compounds and 18L cans were prepared and evaluated using Resin Examples 18 and 19, and the adhesion was weak. However, the results showed poor resistance.
Moreover, also in the high frequency heating after winding, it was the same result as the comparative example 1, and the commercial value was not recognized.
The results are shown in Table 6.
（比較例４）
樹脂例２０のマレイン酸変性オレフィン系樹脂（アドマーＮＳ１０１）の粉体を、ホットプレスにて１７０℃の温度でＴＦＳ上に厚みおよそ７０μｍの皮膜を作成して接着試片を作成し、接着力を測定したところ約１１ｋｇ／ｃｍと接着力はそれほど強いものではなかった。クロロホルム耐性は良好であった。
この粉状樹脂を１８Ｌ缶の天地蓋に７００ｍｇ量均一に入れ、１５０℃で加熱溶融させた。この蓋を缶に巻き締め、加熱処理後、落下耐性、耐内圧性を調べた。
対角落下において変形部からの漏洩がみられ、商品とするにはやや問題があった。
結果を表６に示す。
(Comparative Example 4)
Using a maleic acid-modified olefin resin (Admer NS101) of Resin Example 20, a film having a thickness of about 70 μm was formed on TFS at a temperature of 170 ° C. with a hot press, and an adhesive specimen was prepared. When measured, the adhesive strength was not so strong as about 11 kg / cm. Chloroform resistance was good.
An amount of 700 mg of this powdery resin was put uniformly into an 18 L can top cover and melted by heating at 150 ° C. The lid was wrapped around a can, and after heat treatment, the drop resistance and the internal pressure resistance were examined.
Leakage from the deformed part was observed in the diagonal fall, and there was a slight problem to make the product.
The results are shown in Table 6.
（比較例５，６）
樹脂例２１、２２の樹脂の水分散体を用いて、実施例１と同様にしてシーリングコンパウンド及び１８Ｌ缶を作成し、評価した。いずれも耐性に乏しく缶体での評価も悪かった。
結果を表６に示す。
(Comparative Examples 5 and 6)
Sealing compounds and 18L cans were prepared and evaluated in the same manner as in Example 1 using the aqueous dispersions of the resins of Resin Examples 21 and 22. In either case, the resistance was poor and the evaluation of the can was poor.
The results are shown in Table 6.
（実施例１７）
実施例１のシーリングコンパウンド１００重量部にＳＹＮＴＨＯＭＥＲ６６１７（三洋貿易；ＮＢＲ 固形分４８％）を４０重量部混合してシーリングコンパウンドを調製した。このシーリングコンパウンドを用いて、実施例１と同様にして１８Ｌ缶を作成し、同様の方法で評価した。結果を表７に示す。
(Example 17)
A sealing compound was prepared by mixing 100 parts by weight of the sealing compound of Example 1 with 40 parts by weight of SYNTHOMER 6617 (Sanyo Trading; NBR solid content 48%). Using this sealing compound, an 18L can was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 7.
（実施例１８〜２２）
表７に記載した組成のシーリングコンパウンドを作成し、実施例１と同様にして１８Ｌ缶を作成し、同様の方法で評価した。結果を表７に示す。
(Examples 18 to 22)
A sealing compound having the composition shown in Table 7 was prepared, and an 18L can was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 7.
（比較例７〜１０）
表８に記載した組成のシーリングコンパウンドについて、実施例１７と同様にして評価を行った。結果を表９に併せて示す。本発明の酸変性ポリオレフィンの量が３５重量％より少ない場合にはいずれも接着力が乏しかったり、巻き締め後の加熱時に樹脂が巻き締め部から流れ出てきたりするため、１８Ｌ缶としての商品価値のないものであった。
(Comparative Examples 7 to 10)
The sealing compound having the composition described in Table 8 was evaluated in the same manner as in Example 17. The results are also shown in Table 9. When the amount of the acid-modified polyolefin of the present invention is less than 35% by weight, the adhesive strength is poor, or the resin flows out from the tightening portion during heating after the tightening. It was not.
（比較例１１）
アクリル酸変性ＮＢＲ（酸；１０重量％）のラテックス１００部と、ＭＦＲが３００ｇ／１０分のアンモニア中和型アクリル酸変性ポリエチレンエマルジョン(酸；２０重量％)１００部の混合物を用いて、実施例１と同様にして評価を行った。この皮膜は引っ張り強度が弱く、クロロホルム耐性もそれほどよくはなかった。１８Ｌ缶を作成したが巻き締め内部より樹脂のはみ出しが見られた。水平落下では漏洩は見られなかったものの対角落下では漏洩が見られ、また耐内圧も０．３２ｍｍ板厚の蓋で１００ｋＰａでリークが生じた。缶蓋への塗布量を乾燥重量で４００ｍｇに減らして缶体を作成したところ、巻き締め内部よりの樹脂ハミだしは見られなかったが、落下耐性、耐内圧性とも不良であった。
(Comparative Example 11)
Example: Using a mixture of 100 parts of latex of acrylic acid-modified NBR (acid; 10% by weight) and 100 parts of ammonia-neutralized acrylic acid-modified polyethylene emulsion (acid; 20% by weight) with an MFR of 300 g / 10 min. Evaluation was performed in the same manner as in Example 1. This film had low tensile strength and chloroform resistance was not so good. Although an 18L can was produced, the resin protruded from the inside of the clamp. Leakage was not observed in the horizontal fall, but was found in the diagonal fall, and leak occurred at 100 kPa with a 0.32 mm thick lid. When the can body was prepared by reducing the amount of application to the can lid to 400 mg by dry weight, no resin scooping from the inside of the tightening was seen, but both the drop resistance and the internal pressure resistance were poor.
（比較例１２）
金属缶用ウレタン系接着剤である市販のキャニーボンド（東亜合成）を用いて、１８Ｌ缶に使用する板厚３２ｍｍの天地蓋に所定量塗布し８０℃−１０分予備乾燥した後巻き締めた。この缶の巻き締め部を高周波加熱によりピーク温度が２００℃となるように加熱処理しウレタンの硬化と接着を行った。
この缶の落下試験では漏洩が生じ、また耐内圧も１００ｋＰａでもリークが生じた。またウレタン皮膜はこの条件では硬化が不十分であり低温短時間接着が困難であり、商品価値は見られなかった。
(Comparative Example 12)
Using a commercially available canny bond (Toagosei Co., Ltd.), which is a urethane adhesive for metal cans, a predetermined amount was applied to a 32 mm thick top cover used for 18 L cans, pre-dried at 80 ° C. for 10 minutes, and then tightened. The winding portion of the can was heat-treated by high frequency heating so that the peak temperature became 200 ° C., and urethane was cured and bonded.
In the can drop test, leakage occurred, and leakage occurred even at an internal pressure resistance of 100 kPa. Further, the urethane film was insufficiently cured under these conditions, and it was difficult to bond at a low temperature for a short time, and no commercial value was observed.
Claims (7)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2819177A4 (en) * | 2012-02-23 | 2015-11-18 | Kolon Inc | Back sheet for solar module and method for manufacturing same |
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| EP2819177A4 (en) * | 2012-02-23 | 2015-11-18 | Kolon Inc | Back sheet for solar module and method for manufacturing same |
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