JP4511839B2 - Resin composition for coating metal plate, resin-coated metal plate, can and can lid - Google Patents
Resin composition for coating metal plate, resin-coated metal plate, can and can lid Download PDFInfo
- Publication number
- JP4511839B2 JP4511839B2 JP2004004410A JP2004004410A JP4511839B2 JP 4511839 B2 JP4511839 B2 JP 4511839B2 JP 2004004410 A JP2004004410 A JP 2004004410A JP 2004004410 A JP2004004410 A JP 2004004410A JP 4511839 B2 JP4511839 B2 JP 4511839B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- metal plate
- resin composition
- coating
- olefin polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 title claims description 120
- 239000011347 resin Substances 0.000 title claims description 120
- 229910052751 metal Inorganic materials 0.000 title claims description 89
- 239000002184 metal Substances 0.000 title claims description 89
- 239000011342 resin composition Substances 0.000 title claims description 57
- 238000000576 coating method Methods 0.000 title claims description 33
- 239000011248 coating agent Substances 0.000 title claims description 32
- 229920000098 polyolefin Polymers 0.000 claims description 59
- 229920000554 ionomer Polymers 0.000 claims description 51
- 235000013824 polyphenols Nutrition 0.000 claims description 31
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000011247 coating layer Substances 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 235000018553 tannin Nutrition 0.000 claims description 3
- 229920001864 tannin Polymers 0.000 claims description 3
- 239000001648 tannin Substances 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 description 37
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- 230000007797 corrosion Effects 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 18
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- 238000011156 evaluation Methods 0.000 description 11
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- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
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- 238000003475 lamination Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- -1 aliphatic olefins Chemical class 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 3
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
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- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 2
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- 150000001336 alkenes Chemical class 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229960001285 quercetin Drugs 0.000 description 1
- 235000005875 quercetin Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
本発明は、金属板被覆用樹脂組成物、樹脂被覆金属板、缶及び缶蓋に関し、より詳細には、耐衝撃性（デント性）、耐食性、経時脆化性及び耐高温湿熱性に優れた樹脂被覆金属板を提供し得る金属板被覆用樹脂組成物、及びこの樹脂組成物から成る被覆を有する樹脂被覆金属板、並びにかかる樹脂被覆金属板から成る缶及び缶蓋に関する。 The present invention relates to a resin composition for coating a metal plate, a resin-coated metal plate, a can and a can lid, and more specifically, excellent in impact resistance (dent property), corrosion resistance, embrittlement with time, and resistance to high temperature and heat. The present invention relates to a resin composition for coating a metal plate capable of providing a resin-coated metal plate, a resin-coated metal plate having a coating made of this resin composition, and a can and a can lid made of such a resin-coated metal plate.
側面無継目缶（サイド・シームレス缶）は、アルミニウム板、ブリキ板或いはティン・フリー・スチール板等の金属素材を、絞りダイスと、ポンチとの間で少なくとも一段の絞り加工に付して、側面継目のない胴部と、該胴部に継目なしに一体に接続された底部とから成るカップに形成し、次いで所望により前記胴部に、しごき加工或いは曲げ伸ばしにより、側壁部を薄肉化したものが知られている。
このような側面無継目缶には、従来より、成形前の金属素材に予めポリエステルフィルムをラミネートして成る樹脂被覆金属板が使用されているが、ポリエステル樹脂被覆と金属素材との密着性、耐衝撃性等の点で未だ充分に満足するものが得られていない。
Side seamless cans (side seamless cans) are made by applying a metal material such as an aluminum plate, tin plate or tin-free steel plate to at least one stage of drawing between the drawing die and the punch. Formed in a cup consisting of a seamless body part and a bottom part integrally connected to the body part seamlessly, and then the body part is thinned by ironing or bending and stretching to the body part as desired. It has been known.
Conventionally, a resin-coated metal plate obtained by laminating a polyester film on a metal material before molding has been used for such side seamless cans. However, the adhesion between the polyester resin coating and the metal material, A product that is still satisfactory in terms of impact properties and the like has not yet been obtained.
また、実際の缶詰製品に要求される実用的な耐衝撃性として、耐デント性と呼ばれるものがある。これは、缶詰製品を落下して、或いは缶詰製品同士が相互に衝突して、缶詰製品に打痕と呼ばれる凹みが生じた場合にもなお、被覆の密着性やカバレージが完全に保たれることが要求されるという特性である。すなわち、デント試験で被覆が剥離し或いは被覆にピンホールやクラックが入る場合には、この部分から金属溶出や孔食による漏洩等を生じて、内容物の保存性を失うという問題を生じるのである。 Moreover, there is what is called dent resistance as practical impact resistance required for actual canned products. This means that even if the canned products fall or if the canned products collide with each other and the dents called dents are formed in the canned products, the adhesion and coverage of the coating can be maintained completely. Is required. In other words, if the coating peels off in the dent test or if pinholes or cracks enter the coating, this part causes metal elution or leakage due to pitting corrosion, resulting in the problem of losing the preservation of the contents. .
更に缶詰用缶においては、缶の外面に印刷等を施すのが普通であり、印刷インクを焼き付けるための加熱の影響がポリエステルフィルムに生じる。また、実際の製缶においては、樹脂被覆の歪み除去安定化等を目的として、缶の加熱が行われる場合があると共に、内容物充填後は、レトルト殺菌のような高温湿熱条件下に付される場合や、ホットベンダーに付される場合もあり、このような加熱を経ることによるポリエステルへの影響は無視できない。すなわち、ポリエステルは加熱により熱劣化して分子量が低下する傾向があり、これにより耐デント性が低下し、金属基体との密着性の低下或いは被覆性の低下やネックイン加工、巻締め加工等の際の加工性が低下する。 Furthermore, in a can for canning, it is normal to print on the outer surface of the can, and the influence of the heating for baking printing ink arises in a polyester film. In addition, in actual cans, the cans may be heated for the purpose of stabilizing the distortion removal of the resin coating and the like, and after filling the contents, they are subjected to high-temperature moist heat conditions such as retort sterilization. In some cases, it may be attached to a hot bender, and the influence on polyester due to such heating cannot be ignored. That is, the polyester tends to be thermally deteriorated by heating to decrease the molecular weight, thereby reducing the dent resistance, the adhesiveness with the metal substrate or the covering property, neck-in processing, winding processing, etc. The workability at the time decreases.
このような観点から、ポリエステル樹脂被覆金属板においては、種々の改良が提案されている。例えば、ポリエステル樹脂、ゴム状弾性体及びビニル重合体から成り、ポリエステル樹脂中にゴム状弾性体樹脂が微細分散し、且つ少なくともゴム状弾性体樹脂の一部がビニル重合体でカプセル化された構造を有する金属板被覆用樹脂組成物(特許文献１)が提案されている。 From such a viewpoint, various improvements have been proposed for the polyester resin-coated metal plate. For example, a structure comprising a polyester resin, a rubber-like elastic body, and a vinyl polymer, wherein the rubber-like elastic body resin is finely dispersed in the polyester resin, and at least a part of the rubber-like elastic body resin is encapsulated with the vinyl polymer. There has been proposed a resin composition for coating a metal plate (Patent Document 1).
またポリエステル樹脂から成る被覆を有する製缶用樹脂被覆金属板において、ポリエステル樹脂にアイオノマー樹脂等のエチレン系重合体及びトコフェロールを配合して成る樹脂被覆金属板が提案されている(特許文献２)。 In addition, a resin-coated metal plate for can making having a coating made of a polyester resin has been proposed (Patent Document 2), in which an ethylene polymer such as an ionomer resin and tocopherol are blended with a polyester resin.
上記特許文献１に記載された樹脂組成物を被覆して成る樹脂被覆金属板は、熱履歴を受けないときの耐衝撃性は向上されているが、レトルト殺菌のような高温湿熱条件下に付された場合や、またホットベンダーに付された場合にまで充分満足のいく耐食性や耐衝撃性が得られていない。またアイオノマー樹脂のようなビニル重合体を含有するポリエステル樹脂被覆においては、アイオノマー樹脂の凝集によるブツの発生や、またアイオノマー樹脂が加熱による焦げる傾向があることから、製膜性に劣るという問題もある。
また上記特許文献２に記載されたようにトコフェロールを配合した樹脂被覆においては、アイオノマー樹脂に起因する上記問題は解決されているとしても、樹脂組成物に配合するトコフェロールは液体であるため、ポリエステル樹脂に配合して熱成形で分解すると、液滴や蒸気が発生する場合があり、生産性が低下する場合がある。またポリエステル樹脂の経時脆化をより高いレベルで抑制し、耐衝撃性、密着性、耐熱脆化性、耐経時脆化性等がより改善された樹脂被覆金属板が望まれている。
The resin-coated metal plate formed by coating the resin composition described in Patent Document 1 has improved impact resistance when it is not subjected to thermal history, but is subjected to high-temperature and humid-heat conditions such as retort sterilization. However, even when applied to a hot bender, satisfactory corrosion resistance and impact resistance are not obtained. In addition, in polyester resin coatings containing vinyl polymers such as ionomer resins, there is a problem that film formation is inferior because ionomer resins tend to burn due to agglomeration of ionomer resins, or because the ionomer resins tend to burn by heating. .
Moreover, in the resin coating which mix | blended the tocopherol as described in the said patent document 2, even if the said problem resulting from an ionomer resin is solved, since the tocopherol mix | blended with a resin composition is a liquid, it is a polyester resin. If it is blended with and decomposed by thermoforming, droplets and steam may be generated, and productivity may be reduced. Further, there is a demand for a resin-coated metal plate that suppresses the embrittlement of the polyester resin over time at a higher level and has improved impact resistance, adhesion, heat embrittlement resistance, embrittlement resistance over time, and the like.
従って本発明の目的は、耐衝撃性、耐食性、耐経時脆化性、耐高温湿熱性等の諸特性に優れていると共に、ゲルの発生が抑制されていると共に、上記のような問題を生じない金属板被覆用樹脂組成物、及びこの被覆用樹脂組成物から成る被覆層を有する樹脂被覆金属板、並びにこの樹脂被覆金属板から成る缶体及び缶蓋を提供することである。 Therefore, the object of the present invention is excellent in various properties such as impact resistance, corrosion resistance, resistance to embrittlement with time, and resistance to high temperature and heat and heat, and the generation of gels is suppressed and the above-mentioned problems are caused. The present invention provides a resin composition for coating a metal plate, a resin-coated metal plate having a coating layer made of the resin composition for coating, and a can body and a can lid made of the resin-coated metal plate.
本発明によれば、熱可塑性ポリエステル樹脂、オレフィン系重合体、アイオノマー樹脂及びポリフェノールから成る樹脂組成物であって、該オレフィン系重合体は熱可塑性ポリエステル樹脂中に微細分散していると共に少なくとも一部がアイオノマー樹脂でカプセル化された構造を有しており、前記ポリフェノールが、タンニンより成るポリフェノールであり且つ０．０１乃至２重量％の量で含有されていることを特徴とする金属板被覆用樹脂組成物が提供される。
本発明の金属板被覆用樹脂組成物においては、
１．オレフィン系重合体が、エチレンと炭素数３以上のα−オレフィンとの共重合体であり、特にエチレンと炭素数３以上のα−オレフィンの共重合比が９５：５乃至７０：３０であること、
２．オレフィン系重合体が５乃至５０重量％の量で含有され、アイオノマー樹脂が１乃至２０重量％の量で含有されていること、
３．ポリフェノールが、２４０℃以上の熱分解温度を有すること、
が好適である。
According to the present invention, there is provided a resin composition comprising a thermoplastic polyester resin, an olefin polymer, an ionomer resin and a polyphenol, wherein the olefin polymer is finely dispersed in the thermoplastic polyester resin and at least a part thereof. Has a structure encapsulated with an ionomer resin, and the polyphenol is a polyphenol composed of tannin and is contained in an amount of 0.01 to 2% by weight. A composition is provided.
In the resin composition for coating a metal plate of the present invention,
1. The olefin polymer is a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, and particularly, the copolymerization ratio of ethylene and the α-olefin having 3 or more carbon atoms is 95: 5 to 70:30. ,
2. The olefin polymer is contained in an amount of 5 to 50% by weight, and the ionomer resin is contained in an amount of 1 to 20% by weight;
3. The polyphenol has a thermal decomposition temperature of 240 ° C. or higher,
Is preferred.
本発明によれば、上記樹脂組成物をキャスト成形法により成形して成ることを特徴とする未延伸フィルムが提供される。
本発明によればまた、上記樹脂組成物から成る被覆層が金属基体上に少なくとも一層形成されていることを特徴とする樹脂被覆金属板が提供される。
本発明によれば更にまた、上記樹脂被覆金属板から形成されることを特徴とする缶及び缶蓋が提供される。
According to the present invention, there is provided an unstretched film obtained by molding the resin composition by a cast molding method.
According to the present invention, there is also provided a resin-coated metal plate characterized in that at least one coating layer comprising the resin composition is formed on a metal substrate.
According to the present invention, there is further provided a can and a can lid formed from the resin-coated metal plate.
本発明の樹脂組成物によれば、ポリエステル樹脂中にアイオノマー樹脂でカプセル化されたオレフィン系重合体が微細分散されていることにより、耐衝撃性、耐食性、密着性等の諸特性に優れていると共に、ゲルの発生が抑制された樹脂被覆金属板を提供することが可能となる。特に０．０１乃至２重量％の量でポリフェノールが配合されているため、レトルト殺菌やホットベンダー等に付された後においても、優れた耐衝撃性(耐デント性)、耐食性、密着性を発現することができ、耐経時脆化性、耐高温湿熱性にも顕著に優れた樹脂被覆金属板を提供することが可能となる。
またオレフィン系重合体として、エチレンと炭素数３以上のα−オレフィンの共重合体を使用することにより、アイオノマー樹脂でカプセル化されたオレフィン系重合体のポリエステル樹脂への相溶性を向上させることが可能になると共に、オレフィン系重合体に適度な硬さを有する弾性を付与することが可能となり、ポリエステル樹脂中で微細分散させることが可能になると共に、強度も向上し、優れた加工性を付与することも可能となるのである。
According to the resin composition of the present invention, the olefin polymer encapsulated with an ionomer resin is finely dispersed in a polyester resin, and thus has excellent properties such as impact resistance, corrosion resistance, and adhesion. In addition, it is possible to provide a resin-coated metal plate in which the generation of gel is suppressed. In particular, since polyphenol is blended in an amount of 0.01 to 2% by weight, it exhibits excellent impact resistance (dent resistance), corrosion resistance, and adhesion even after being subjected to retort sterilization or hot bender. Accordingly, it is possible to provide a resin-coated metal plate that is remarkably excellent in resistance to embrittlement with time and resistance to high-temperature wet heat.
In addition, by using a copolymer of ethylene and an α-olefin having 3 or more carbon atoms as the olefin polymer, it is possible to improve the compatibility of the olefin polymer encapsulated with an ionomer resin into the polyester resin. It becomes possible to give elasticity having moderate hardness to the olefin polymer, and it can be finely dispersed in the polyester resin, and the strength is improved and excellent workability is imparted. It is also possible to do.
本発明の金属板被覆用樹脂組成物においては、熱可塑性ポリエステル樹脂、オレフィン系重合体、アイオノマー樹脂及びポリフェノールから成る樹脂組成物であって、該オレフィン系重合体は熱可塑性ポリエステル樹脂中に微細分散していると共に少なくとも一部がアイオノマー樹脂でカプセル化された構造を有しており、ポリフェノールが０．０１乃至２重量％の量で含有されていることが重要な特徴であり、これにより樹脂被覆金属板に優れた耐衝撃性、耐食性、経時脆化性、耐高温湿熱性等の諸特性を付与することができると共に、ゲルの発生も抑制され製膜性にも優れた樹脂組成物を提供することが可能となるのである。 The resin composition for coating a metal plate of the present invention is a resin composition comprising a thermoplastic polyester resin, an olefin polymer, an ionomer resin and a polyphenol, and the olefin polymer is finely dispersed in the thermoplastic polyester resin. And at least a part of the structure encapsulated with an ionomer resin, and an important feature is that the polyphenol is contained in an amount of 0.01 to 2% by weight. Providing a resin composition with excellent impact resistance, corrosion resistance, embrittlement with time, high temperature and heat and heat resistance, and excellent film-forming properties with reduced generation of gel. It becomes possible to do.
本発明においては、熱可塑性ポリエステル樹脂中に、ゴム状弾性を有するオレフィン系重合体が微細分散されていることにより、耐衝撃性を向上させることができる共に、かかるオレフィン系重合体がアイオノマー樹脂でカプセル化されているため、金属板との密着性に劣るオレフィン系重合体が直接金属板に接触することなく、金属板との接着性に優れているアイオノマー樹脂が金属板と接触することになり、耐衝撃性の向上と密着性の両方を満足し得ることが可能となるのである。 In the present invention, the olefin polymer having rubber-like elasticity is finely dispersed in the thermoplastic polyester resin, so that the impact resistance can be improved, and the olefin polymer is an ionomer resin. Because it is encapsulated, the ionomer resin with excellent adhesion to the metal plate will come into contact with the metal plate, without the olefin polymer inferior in adhesion to the metal plate coming into direct contact with the metal plate. Thus, it is possible to satisfy both the improvement in impact resistance and the adhesion.
ポリエステル樹脂中にアイオノマー樹脂でカプセル化したオレフィン系重合体を微細分散させるには、アイオノマー樹脂とポリエステル樹脂及びオレフィン系重合体との界面張力のバランスを適切にすることが重要であり、特にアイオノマー樹脂とオレフィン系重合体の間の界面張力をγoi、オレフィン系重合体とポリエステル樹脂の間の界面張力をγop、ポリエステル樹脂とアイオノマー樹脂の間の界面張力をγipとすると、Ｓｐｒｅａｄ Ｐａｒａｍｅｔｅｒλioは
λio＝γop−γip−γoi
で表され、オレフィン系重合体がアイオノマー樹脂でカプセル化されるには、λio＞０であることが必要である。
ポリエステル樹脂とオレフィン系重合体の相溶性は低いので、γop＞０であり、またアイオノマー樹脂とポリエステル樹脂は比較的強い化学的相互作用を示すため、オレフィン系重合体と安定したカプセル構造を形成することができる。
In order to finely disperse an olefin polymer encapsulated with an ionomer resin in a polyester resin, it is important to appropriately balance the interfacial tension between the ionomer resin, the polyester resin and the olefin polymer, and in particular, the ionomer resin. When the interfacial tension between the olefin polymer and the olefin polymer is γoi, the interfacial tension between the olefin polymer and the polyester resin is γop, and the interfacial tension between the polyester resin and the ionomer resin is γip, the spread parameter λio is λio = γop− γip−γoi
In order for the olefin polymer to be encapsulated with an ionomer resin, it is necessary that λio> 0.
Since the compatibility between the polyester resin and the olefin polymer is low, γop> 0, and since the ionomer resin and the polyester resin have a relatively strong chemical interaction, they form a stable capsule structure with the olefin polymer. be able to.
またかかる熱可塑性ポリエステル樹脂、オレフィン系重合体及びアイオノマー樹脂を含有する樹脂組成物に、ポリフェノールが０．０１乃至２重量％の量で配合されていることが、レトルト処理や、レトルト処理後の経時にも耐え得る耐高温湿熱性、耐経時脆化性を付与する上で重要である。すなわち、ポリフェノールがポリエステル樹脂の成形プロセスにおいて、さまざまな熱履歴による分子量低下を防止することは従来より知られていたが、熱可塑性ポリエステル樹脂とアイオノマー樹脂でカプセル化されたオレフィン系重合体から成る樹脂組成物にポリフェノールを配合すると、印刷や樹脂被膜のひずみ緩和のために加熱するような場合のみならず、レトルト殺菌やホットベンダー等のようなより過酷な条件で経時された場合にも耐デント性に優れ、しかも被膜にクラックが生じたような場合でもクラックから腐食が進むことが防止され、耐食性が著しく向上するという、予想外の新しい効果を得ることができたのである。 In addition, the resin composition containing the thermoplastic polyester resin, the olefin polymer and the ionomer resin contains polyphenol in an amount of 0.01 to 2% by weight. It is important for imparting high-temperature wet heat resistance and resistance to embrittlement over time. In other words, polyphenols have been conventionally known to prevent molecular weight reduction due to various thermal histories in the molding process of polyester resins, but resins made of olefin polymers encapsulated with thermoplastic polyester resins and ionomer resins. When polyphenol is added to the composition, it is resistant to dents not only when heating to relieve distortion in printing and resin coating, but also when subjected to harsh conditions such as retort sterilization and hot bender. In addition, even when cracks are generated in the coating, it is possible to obtain an unexpected new effect that corrosion is prevented from proceeding from the cracks and corrosion resistance is remarkably improved.
またポリフェノールは、一般に粉末状であるため、熱可塑性ポリエステル樹脂及びオレフィン系重合体等から成る樹脂組成物中に容易且つ均一に分散可能であり、トコフェロールを用いた場合のような加熱による液滴や蒸気の発生に伴う生産性の低下も有効に防止されている。更に、後述する実施例の結果からも明らかなように、ポリフェノールを配合した樹脂組成物においては、トコフェロールを配合した樹脂組成物よりも顕著に耐デント性、経時脆化抑制効果、耐食性が改善されているのである。 In addition, since polyphenol is generally in the form of a powder, it can be easily and uniformly dispersed in a resin composition comprising a thermoplastic polyester resin and an olefin polymer, and droplets produced by heating as in the case of using tocopherol. The reduction in productivity due to the generation of steam is also effectively prevented. Furthermore, as is clear from the results of the examples described later, in the resin composition containing polyphenol, the dent resistance, the effect of suppressing embrittlement with time, and the corrosion resistance are remarkably improved as compared with the resin composition containing tocopherol. -ing
更に前述した通り、アイオノマー樹脂は、密着性及び加工性を向上し、金属板上に均一な樹脂被覆を形成させるものであるが、その一方、加熱により焦げる傾向があり、またブツの発生等を招くおそれがあることから製膜性に劣っている。本発明においては上記樹脂組成物にポリフェノールを０．０１乃至２重量％の量で配合することにより、アイオノマー樹脂のこのような焦げを抑制し、製膜性を向上することが可能となる。
本発明においてポリフェノールは、上記範囲の量で配合されることが重要であり、上記範囲よりも少ないと、ポリフェノールを配合することにより得られる上述した優れた効果を樹脂組成物に充分に発現することができず、また上記範囲よりも多いとポリエステル樹脂のゲル化を生じて被膜の平滑性が失われてシームレス缶への成形が困難になる傾向がある。
Further, as described above, the ionomer resin improves adhesion and workability, and forms a uniform resin coating on the metal plate. The film-forming property is inferior because of the risk of incurring. In the present invention, by blending polyphenol in the above resin composition in an amount of 0.01 to 2% by weight, it is possible to suppress such scorching of the ionomer resin and improve the film forming property.
In the present invention, it is important that the polyphenol is blended in an amount within the above range. When the polyphenol is less than the above range, the above-described excellent effect obtained by blending the polyphenol is sufficiently expressed in the resin composition. However, if the amount is larger than the above range, the polyester resin is gelled, and the smoothness of the film is lost, so that there is a tendency that molding into a seamless can becomes difficult.
本発明においては、上記組成を有する金属板被覆用樹脂組成物において上記効果をより効率的に発現するためには、オレフィン系重合体として、エチレンと炭素数３以上のα−オレフィンとの共重合体、特にエチレンと炭素数３以上のα−オレフィンの共重合比が ９５：５乃至７０：３０であるオレフィン系共重合体であることが好ましい。
このようなオレフィン系共重合体は、側鎖を所定量有する重合体であり、オレフィン系重合体における側鎖を長くすることにより、樹脂に適度な硬さを与えて凝集破壊を防止し、強度を向上させることが可能になるのである。またポリエステル樹脂に対する相溶性を付与し、これによりオレフィン系重合体がポリエステル樹脂中でより微細に分散して、界面剥離を有効に防止することが可能となり、レトルト処理等の高温湿熱条件下で処理を受けた後においても優れた耐衝撃性、密着性を発現することが可能となるのである。
In this invention, in order to express the said effect more efficiently in the resin composition for metal plate coating | cover which has the said composition, as an olefin type polymer, it is a copolymer weight of ethylene and C3-C3 or more alpha olefins. It is preferable that the copolymer, particularly an olefin copolymer having a copolymerization ratio of ethylene and an α-olefin having 3 or more carbon atoms of 95: 5 to 70:30.
Such an olefin copolymer is a polymer having a predetermined amount of side chains, and by increasing the length of the side chains in the olefin polymer, it gives the resin an appropriate hardness to prevent cohesive failure and strength. It becomes possible to improve. Also, compatibility with the polyester resin is imparted, so that the olefin polymer is more finely dispersed in the polyester resin, and it is possible to effectively prevent the interfacial peeling, and the treatment is performed under high-temperature wet heat conditions such as retorting. It is possible to exhibit excellent impact resistance and adhesiveness even after receiving.
このことは後述する実施例の結果からも明らかである。すなわち、側鎖の炭素原子数が２個のエチレン−１−ブテン共重合体(共重合比８０：２０)を用いた樹脂組成物（実施例１２）や側鎖の炭素原子数が６個のエチレン−１−オクテン共重合体(共重合比８８：１２)を用いた樹脂組成物(実施例６)では、側鎖の少ないHDPEを用いた樹脂組成物（比較例６）、オレフィン系重合体を含有していない樹脂組成物(比較例７)に比して優れた耐食性、耐デント性等の性能を有していることが明らかである。 This is also clear from the results of Examples described later. That is, a resin composition (Example 12) using an ethylene-1-butene copolymer having 2 carbon atoms in the side chain (copolymerization ratio 80:20) or having 6 carbon atoms in the side chain. In a resin composition (Example 6) using an ethylene-1-octene copolymer (copolymerization ratio 88:12), a resin composition using HDPE with few side chains (Comparative Example 6), an olefin polymer It is apparent that the resin composition does not contain any of the resin compositions (Comparative Example 7) and has excellent performance such as corrosion resistance and dent resistance.
（熱可塑性ポリエステル樹脂）
本発明に用いるポリエステル樹脂としては、従来公知のポリエステルを使用することができる。具体的には、ジカルボン酸成分の５０％以上、特に８０％以上がテレフタル酸で、ジオール成分の５０％以上、特に８０％以上がエチレングリコールであるエチレンテレフタレート系ポリエステルであることが好ましい。
このポリエステルはホモポリエステルでも、共重合ポリエステルでも、或いはこれらの２種以上のブレンド物であってもよい。
(Thermoplastic polyester resin)
As the polyester resin used in the present invention, conventionally known polyesters can be used. Specifically, it is preferably an ethylene terephthalate-based polyester in which 50% or more, particularly 80% or more of the dicarboxylic acid component is terephthalic acid, and 50% or more, particularly 80% or more of the diol component is ethylene glycol.
This polyester may be a homopolyester, a copolyester, or a blend of two or more of these.
テレフタル酸以外のカルボン酸成分としては、イソフタル酸、ナフタレンジカルボン酸、ｐ−β−オキシエトキシ安息香酸、ビフェニル−４，４’−ジカルボン酸、ジフェノキシエタン−４，４’−ジカルボン酸、５−ナトリウムスルホイソフタル酸、ヘキサヒドロテレフタル酸、アジピン酸、セバシン酸、トリメリット酸、ピロメリット酸等を挙げることができる。 Examples of carboxylic acid components other than terephthalic acid include isophthalic acid, naphthalenedicarboxylic acid, p-β-oxyethoxybenzoic acid, biphenyl-4,4′-dicarboxylic acid, diphenoxyethane-4,4′-dicarboxylic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, adipic acid, sebacic acid, trimellitic acid, and pyromellitic acid.
エチレングリコール以外のジオール成分としては、１，４−ブタンジオール、プロピレングリコール、ネオペンチルグリコール、１，６−へキシレングリコール、ジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド付加物、グリセロール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、ソルビタン等を挙げることができる。 Diol components other than ethylene glycol include 1,4-butanediol, propylene glycol, neopentyl glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A ethylene oxide adduct, glycerol , Trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitan and the like.
この熱可塑性ポリエステル樹脂は、そのペレット状態において、フェノール／テトラクロロエタン混合溶媒を用いて測定した固有粘度が、０．７〜１．５の範囲、特に０．８〜１．２の範囲にあることが好ましい。更に、ガラス転移点は、５０℃以上、特に６０℃〜９０℃の範囲であることが内容物へのオリゴマー成分の溶出を防止する上で好ましい。 The thermoplastic polyester resin has an intrinsic viscosity measured in a pellet state using a phenol / tetrachloroethane mixed solvent in the range of 0.7 to 1.5, particularly in the range of 0.8 to 1.2. Is preferred. Furthermore, the glass transition point is preferably 50 ° C. or higher, particularly in the range of 60 ° C. to 90 ° C., in order to prevent the oligomer component from eluting into the contents.
(オレフィン系重合体)
本発明に用いるオレフィン系重合体は、耐衝撃性を向上させるべくゴム状弾性を有するものであり、ゴム弾性発現部のガラス転移点が５０℃以下、室温でのヤング率が１０００ＭＰａ以下、破断伸びが５０％以上のオレフィン系重合体であることが好ましい。
オレフィン系重合体としては、プロピレン、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン等のα−オレフィンを付加重合したときに現れる繰り返し単位や、イソブテンを付加した時の繰り返し単位等の脂肪族オレフィン、スチレンモノマーの他にｏ−，ｍ−，ｐ−メチルスチレン、ｏ−，ｍ−，ｐ−エチルスチレン、ｔ−ブチルスチレン等のアルキル化スチレン、モノクロロスチレン等のハロゲン化スチレン、α−メチルスチレン等のスチレン系モノマーの付加重合体単位等の芳香族オレフィン等が挙げられる。
使用し得るオレフィン系重合体を例示すると、エチレン・プロピレン共重合体、エチレン−ブテン−１共重合体、エチレン・ペンテン−１共重合体、エチレン−３−エチルペンテン共重合体、エチレン−オクタセン−１共重合体等のエチレンと炭素数３以上のαオレフィンの共重合体、前記２元共重合体にブタジエン、イソプレン、５−メチリデン−２−ノルボルネン、５−エチリデン−２−ノルボルネン、ジシクロペンタジエン、１，４−ヘキサジエン等を共重合したエチレン、炭素数３以上のα−オレフィン及び非共役ジエンから成る３元共重合体である。
(Olefin polymer)
The olefin polymer used in the present invention has rubber-like elasticity in order to improve impact resistance, the glass transition point of the rubber elasticity developing portion is 50 ° C. or less, the Young's modulus at room temperature is 1000 MPa or less, the elongation at break Is preferably 50% or more of an olefin polymer.
As an olefin polymer, when an α-olefin such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene is subjected to addition polymerization O-, m-, p-methylstyrene, o-, m-, p-ethylstyrene, t-butyl in addition to aliphatic olefins such as the repeating units appearing in the formula, repeating units when isobutene is added, and styrene monomers Examples include aromatic olefins such as alkylated styrene such as styrene, halogenated styrene such as monochlorostyrene, and addition polymer units of styrenic monomers such as α-methylstyrene.
Examples of olefin polymers that can be used include ethylene / propylene copolymer, ethylene-butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene-3-ethylpentene copolymer, ethylene-octacene- A copolymer of ethylene and an α-olefin having 3 or more carbon atoms, such as 1 copolymer; the binary copolymer is butadiene, isoprene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene; 1, a terpolymer composed of ethylene copolymerized with 1,4-hexadiene or the like, an α-olefin having 3 or more carbon atoms, and a non-conjugated diene.
本発明に用いるオレフィン系重合体としては、上述した通り、エチレンと炭素数３以上のα−オレフィン、特にプロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、４−メチル-１-ペンテン、２，４，４−トリメチル-１-ペンテン等との共重合体であり、また、炭素数３以上のα−オレフィンおよび非共役ジエンが２種以上の３元以上の共重合体であってもよい。特にエチレンと炭素数３以上のα−オレフィンの共重合比が９５：５乃至７０：３０であることが最も望ましい。
このようなオレフィン系重合体としては、例えば、エチレン・プロピレン共重合体、エチレン・ブテン共重合体、エチレン・ペンテン共重合体、エチレン・ヘキセン共重合体、エチレン・オクテン共重合体、エチレン・４メチルペンテン共重合体、エチレン・２，２，４トリメチルペンテン共重合体等を挙げることができる。
As described above, the olefin polymer used in the present invention is ethylene and an α-olefin having 3 or more carbon atoms, particularly propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1 -Copolymers with dodecene, 4-methyl-1-pentene, 2,4,4-trimethyl-1-pentene, etc., and more than 2 α-olefins and non-conjugated dienes having 3 or more carbon atoms A ternary or higher copolymer may be used. In particular, the copolymerization ratio of ethylene and α-olefin having 3 or more carbon atoms is most desirably 95: 5 to 70:30.
Examples of such olefin polymers include ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / pentene copolymers, ethylene / hexene copolymers, ethylene / octene copolymers, ethylene / 4 Examples thereof include a methylpentene copolymer and an ethylene / 2,4,4 trimethylpentene copolymer.
(アイオノマー樹脂)
本発明に用いるアイオノマー樹脂は、エチレンとα，β−不飽和カルボン酸との共重合体中のカルボキシル基の一部又は全部が金属陽イオンで中和されたイオン性塩であり、中和の程度、すなわちイオン濃度がその物理的性質に影響を及ぼしている。一般に、アイオノマー樹脂のメルトフローレート（以下、単にＭＦＲという）はイオン濃度に左右され、イオン濃度が大きいとＭＦＲが小さく、また融点はカルボキシル基濃度に左右され、カルボキシル基濃度が大きいほど融点も低くなる。
従って、本発明に用いるアイオノマー樹脂としては、勿論これに限定されるものではないが、ＭＦＲが１５ｇ／１０ｍｉｎ以下、特に５ｇ／１０ｍｉｎ乃至０．５ｇ／１０ｍｉｎの範囲にあり、且つ融点が１００℃以下、特に９７℃乃至８０℃の範囲にあるものであることが望ましい。
(Ionomer resin)
The ionomer resin used in the present invention is an ionic salt in which some or all of the carboxyl groups in the copolymer of ethylene and α, β-unsaturated carboxylic acid are neutralized with a metal cation. The degree, i.e. ion concentration, influences the physical properties. In general, the melt flow rate (hereinafter simply referred to as MFR) of an ionomer resin depends on the ion concentration. If the ion concentration is high, the MFR is small, and the melting point depends on the carboxyl group concentration. The higher the carboxyl group concentration, the lower the melting point. Become.
Accordingly, the ionomer resin used in the present invention is of course not limited thereto, but has an MFR of 15 g / 10 min or less, particularly 5 g / 10 min to 0.5 g / 10 min, and a melting point of 100 ° C. or less. Particularly, it is desirable that the temperature is in the range of 97 ° C to 80 ° C.
アイオノマー樹脂を構成するα，β−不飽和カルボン酸としては、炭素数３〜８の不飽和カルボン酸、具体的にはアクリル酸、メタクリル酸、マレイン酸、イタコン酸、無水マレイン酸、マレイン酸モノメチルエステル、マレイン酸モノメチルエステル等を挙げることができる。
特に、好適なベースポリマーとしては、エチレン−（メタ）アクリル酸共重合体やエチレン−（メタ）アクリル酸エステル−（メタ）アクリル酸共重合体を挙げることができる。
また、このようなエチレンとα，β−不飽和カルボン酸との共重合体中のカルボキシル基を中和する金属イオンとしては、Ｎａ＋，Ｋ＋，Ｌｉ＋，Ｚｎ＋，Ｚ２＋，Ｍｇ２＋，Ｃａ２＋，Ｃｏ２＋，Ｎｉ２＋，Ｍｎ２＋，Ｐｂ２＋，Ｃｕ２＋等を挙げることができるが、本発明においては、特に亜鉛により中和されているものが、架橋の程度が大きく、湿度敏感性が少ないことから、好適に用いることができる。また、金属イオンで中和されていない残余のカルボキシル基の一部は低級アルコールでエステル化されていてもよい。
またアイオノマー樹脂は、エチレンから誘導される構成単位を８０〜９９モル％、好ましくは８５〜９６モル％、不飽和カルボン酸から誘導される構成単位を１〜２０モル％、好ましくは４〜１５モル％の量で含有されていることが好ましい。
The α, β-unsaturated carboxylic acid constituting the ionomer resin is an unsaturated carboxylic acid having 3 to 8 carbon atoms, specifically acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, monomethyl maleate Examples thereof include esters and maleic acid monomethyl ester.
Particularly suitable base polymers include ethylene- (meth) acrylic acid copolymers and ethylene- (meth) acrylic acid ester- (meth) acrylic acid copolymers.
Moreover, as a metal ion which neutralizes the carboxyl group in such a copolymer of ethylene and an α, β-unsaturated carboxylic acid, Na + , K + , Li + , Zn + , Z 2+ , Mg 2+ , Ca 2+ , Co 2+ , Ni 2+ , Mn 2+ , Pb 2+ , Cu 2+, etc. In the present invention, those that are neutralized by zinc in particular have a high degree of crosslinking and are sensitive to humidity. Since there is little property, it can use suitably. Further, a part of the remaining carboxyl groups that are not neutralized with metal ions may be esterified with a lower alcohol.
The ionomer resin contains 80 to 99 mol% of structural units derived from ethylene, preferably 85 to 96 mol%, and 1 to 20 mol%, preferably 4 to 15 mol of structural units derived from an unsaturated carboxylic acid. % Is preferably contained.
（ポリフェノール）
本発明に用いるポリフェノールは、合成又は天然のポリフェノールを使用することができる。これに限定されないが、カテコール、レゾルシノール、ヒドロキノン、ピロガロール、フロログルシノール等の合成品や、オイゲノール、クエルセチン等の天然品を挙げることができる。またタンニンのようなポリフェノール化合物を用いてもよい。
尚、ポリエステル樹脂、オレフィン系重合体、アイオノマー樹脂などから成る樹脂組成物の形成には、溶融成形を用いることから、成形温度である２４０℃以上の温度で熱分解しない分解温度を有するポリフェノールを用いる必要がある。上記分解温度以下のポリフェノールを用いると、樹脂組成物の溶融成形時にポリフェノールが分解されてしまい、耐衝撃性、耐食性、密着性の充分な改善を図ることができなくなる。
(Polyphenol)
As the polyphenol used in the present invention, a synthetic or natural polyphenol can be used. Although not limited to this, synthetic products, such as catechol, resorcinol, hydroquinone, pyrogallol, and phloroglucinol, and natural products, such as eugenol and quercetin, can be mentioned. A polyphenol compound such as tannin may also be used.
In addition, since formation of a resin composition comprising a polyester resin, an olefin polymer, an ionomer resin or the like uses melt molding, polyphenol having a decomposition temperature that does not thermally decompose at a molding temperature of 240 ° C. or higher is used. There is a need. If a polyphenol having a decomposition temperature or lower is used, the polyphenol is decomposed during melt molding of the resin composition, and sufficient improvement in impact resistance, corrosion resistance, and adhesion cannot be achieved.
（樹脂組成物）
本発明の金属板被覆用樹脂組成物は、上記ポリエステル樹脂、オレフィン系重合体、アイオノマー樹脂、ポリフェノールから成り、アイオノマー樹脂でカプセル化されたオレフィン系重合体がポリエステル樹脂中に微細分散されて成るものである。
本発明において、アイオノマー樹脂でカプセル化されたオレフィン系重合体とは、オレフィン系重合体の界面の８０％以上、好ましくは９５％以上をアイオノマー樹脂が被覆し、ポリエステル樹脂とオレフィン系重合体との直接接触面積を２０％未満とした構造である。オレフィン系重合体の全てがアイオノマー樹脂でカプセル化されている必要はないが、少なくとも体積比で７０％以上のオレフィン系重合体がアイオノマー樹脂でカプセル化されていればよい。カプセル化されていないオレフィン系重合体が３０％よりも多く存在する場合は、樹脂組成物を金属板に被覆した際に、金属板に直接接触するオレフィン系重合体の比率が増加し、樹脂組成物と金属板との密着性を充分に確保できないおそれがある。
(Resin composition)
The resin composition for coating a metal plate of the present invention comprises the above polyester resin, olefin polymer, ionomer resin, and polyphenol, and the olefin polymer encapsulated with ionomer resin is finely dispersed in the polyester resin. It is.
In the present invention, an olefin polymer encapsulated with an ionomer resin means that 80% or more, preferably 95% or more of the interface of the olefin polymer is covered with an ionomer resin, and the polyester resin and the olefin polymer The direct contact area is less than 20%. It is not necessary that all of the olefin polymer is encapsulated with an ionomer resin, but it is sufficient that at least 70% or more of the olefin polymer is encapsulated with an ionomer resin. When the amount of unencapsulated olefin polymer is more than 30%, when the resin composition is coated on the metal plate, the ratio of the olefin polymer directly contacting the metal plate increases, and the resin composition There is a possibility that sufficient adhesion between the object and the metal plate cannot be secured.
本発明の樹脂組成物において、アイオノマー樹脂でカプセル化されたオレフィン系重合体の平均粒径は、５μｍ以下、特に０．１乃至３μｍの範囲にあることが優れた耐衝撃性を付与すると共に、金属板との密着性を向上させる上で望ましい。
また過剰量のアイオノマー樹脂がオレフィン系重合体をカプセル化しないで、単独でポリエステル樹脂中に分散していてもよいが、樹脂被覆金属板の加工性を向上させるためには、アイオノマー樹脂も平均粒径０．１乃至３μｍの範囲にあることが望ましい。
本発明において、ポリエステル樹脂中にアイオノマー樹脂でカプセル化されたオレフィン系重合体及び過剰のアイオノマー樹脂が、上記平均粒径を有するように微細分散するためには、樹脂組成物中、オレフィン系重合体は５乃至５０重量％、特に５乃至４０重量％の量で含有され、アイオノマー樹脂は１乃至２０重量％、特に５乃至２０重量％の量で含有されていることが好ましい。
また前述した通り、ポリフェノールは、樹脂組成物中０．０１乃至２重量％、特に０．０５乃至１．０重量％の量で含有されていることが、アイオノマー樹脂でカプセル化されたオレフィン系重合体による優れた耐衝撃性、耐食性、密着性を、レトルト殺菌やホットベンダー等の高温湿熱条件下に付された後においても発現させることが可能になると共に、ゲルの発生を抑制し優れた製膜性を付与する上で重要である。
In the resin composition of the present invention, the average particle diameter of the olefin polymer encapsulated with an ionomer resin is 5 μm or less, particularly in the range of 0.1 to 3 μm and imparts excellent impact resistance, It is desirable for improving the adhesion with the metal plate.
An excessive amount of ionomer resin may be dispersed alone in the polyester resin without encapsulating the olefin polymer. However, in order to improve the workability of the resin-coated metal plate, the ionomer resin is also an average particle. It is desirable that the diameter is in the range of 0.1 to 3 μm.
In the present invention, in order to finely disperse the olefin polymer encapsulated with the ionomer resin in the polyester resin and the excess ionomer resin so as to have the above average particle diameter, the olefin polymer is contained in the resin composition. Is preferably contained in an amount of 5 to 50% by weight, particularly 5 to 40% by weight, and the ionomer resin is preferably contained in an amount of 1 to 20% by weight, particularly 5 to 20% by weight.
As described above, the polyphenol is contained in the resin composition in an amount of 0.01 to 2% by weight, particularly 0.05 to 1.0% by weight. Excellent impact resistance, corrosion resistance, and adhesion due to coalescence can be expressed even after being subjected to high-temperature and humid heat conditions such as retort sterilization and hot bender. It is important for imparting film properties.
本発明においては、上記ポリエステル樹脂、オレフィン系重合体、アイオノマー樹脂及びポリフェノールから成る樹脂組成物に、それ自体公知の樹脂用配合剤、例えば、熱安定剤、非晶質シリカ等のアンチブロッキング剤、二酸化チタン等の顔料、各種帯電防止剤、滑剤等を公知の処方に従って配合することもできる。 In the present invention, the resin composition comprising the polyester resin, olefin polymer, ionomer resin, and polyphenol, a resin compounding agent known per se, for example, a heat stabilizer, an anti-blocking agent such as amorphous silica, Pigments such as titanium dioxide, various antistatic agents, lubricants, and the like can also be blended according to known formulations.
上記ポリエステル樹脂、オレフィン系重合体、アイオノマー樹脂及びポリフェノールとのブレンドは、所定温度で公知の各種混合機を用いてメルトブレンドすること、或いは予めオレフィン系重合体及びアイオノマー樹脂をメルトブレンドした後、ポリエステル樹脂中にドライブレンド或いはメルトブレンドすることによって上述したような相構造を形成することができる。前者の場合、一軸或いは二軸の押出機、ニーダー、バンバリーミキサーなどで混練すればよく、また後者のドライブレンドにおいては、ブレンダー、ヘンシェルミキサー、スーパーミキサーなどで混合し、直接押出し機のホッパーに供給すればよい。
これら何れの場合でもポリエステル樹脂とオレフィン系重合体等とは、最終的にはポリエステル樹脂の溶融温度以上の温度でブレンドが行われることになる。またアイオノマー樹脂及びオレフィン系重合体等を比較的高濃度で含有するマスターバッチを製造し、このマスターバッチをポリエステル樹脂にブレンドすることもできる。
The polyester resin, the olefin polymer, the ionomer resin and the polyphenol are blended with a known various mixer at a predetermined temperature, or after the olefin polymer and the ionomer resin are previously melt blended, The phase structure as described above can be formed by dry blending or melt blending in the resin. In the former case, it may be kneaded with a single or twin screw extruder, kneader, Banbury mixer, etc. In the latter dry blend, it is mixed with a blender, Henschel mixer, super mixer, etc., and supplied directly to the hopper of the extruder. do it.
In any of these cases, the polyester resin and the olefin polymer are finally blended at a temperature equal to or higher than the melting temperature of the polyester resin. It is also possible to produce a masterbatch containing a relatively high concentration of ionomer resin and olefin polymer, and blend this masterbatch with the polyester resin.
ポリエステル樹脂とオレフィン系重合体等は一般に、２６０℃及び剪断速度１２２ｓｅｃ−１における溶融粘度が２０００〜１００００ポイズの範囲となるように、上記範囲で混練されることが好ましい。熱可塑性ポリエステル樹脂においては、混練するほど、熱分解により粘度低下が著しくなるため、カプセル化されたオレフィン系重合体を微細な粒径でしかもマトリックスたる熱可塑性ポリエステル樹脂中に均一に分散させるためには、溶融粘度が上記範囲になるようにブレンドすることが好ましい。 In general, the polyester resin and the olefin polymer are preferably kneaded in the above range so that the melt viscosity at 260 ° C. and the shear rate of 122 sec −1 is in the range of 2000 to 10,000 poise. In thermoplastic polyester resins, the lower the viscosity due to thermal decomposition the more they are kneaded, so that the encapsulated olefin polymer has a fine particle size and is uniformly dispersed in the thermoplastic polyester resin as a matrix. Is preferably blended so that the melt viscosity is in the above range.
(フィルムの形成)
本発明のポリエステルフィルムは、Ｔ−ダイ法や、インフレーション製膜法等の押出し成形により成形されるキャストフィルムであることが好ましく、特に押出したフィルムを急冷したキャスト成形法による未延伸のフィルムであることが好ましい。
フィルムの厚みは、用いる用途によっても相違するが、一般に１乃至５００μｍ、特に３乃至１００μｍの範囲にあることが好ましい。尚、製缶用の樹脂被覆金属板の被覆には、後述するように３乃至４０μｍ、特に５乃至３５μｍの厚みとすることが好ましい。
(Film formation)
The polyester film of the present invention is preferably a cast film formed by extrusion molding such as a T-die method or an inflation film forming method, and is particularly an unstretched film by a cast molding method in which the extruded film is rapidly cooled. It is preferable.
The thickness of the film varies depending on the application to be used, but is generally in the range of 1 to 500 μm, particularly 3 to 100 μm. In addition, it is preferable that the coating of the resin-coated metal plate for can making has a thickness of 3 to 40 μm, particularly 5 to 35 μm, as will be described later.
（樹脂被覆金属板）
本発明の樹脂被覆金属板に用いる金属板としては、各種表面処理鋼板やアルミニウム等の軽金属板が使用される。表面処理鋼板としては、冷圧延鋼板を焼鈍した後二次冷間圧延し、亜鉛メッキ、錫メッキ、ニッケルメッキ、電解クロム酸処理、クロム酸処理等の表面処理の一種または二種以上行ったものを用いることができる。またアルミニウムメッキ、アルミニウム圧延等を施したアルミニウム被覆鋼板が用いられる。
また軽金属板としては、いわゆる純アルミニウム板の他にアルミニウム合金板が使用される。
金属板の元板厚は、金属の種類、容器の用途或いはサイズによっても相違するが、一般に０．１０乃至０．５０ｍｍの厚みを有するのがよく、この中でも表面処理鋼板の場合には０．１０乃至０．３０ｍｍの厚み、軽金属板の場合は０．１５乃至０．４０ｍｍの厚みを有するのがよい。
(Resin coated metal plate)
As the metal plate used for the resin-coated metal plate of the present invention, various surface-treated steel plates and light metal plates such as aluminum are used. As the surface-treated steel sheet, a cold-rolled steel sheet is annealed and then secondary cold-rolled and subjected to one or more surface treatments such as galvanizing, tin-plating, nickel-plating, electrolytic chromic acid treatment, and chromic acid treatment. Can be used. Further, an aluminum-coated steel sheet subjected to aluminum plating, aluminum rolling, or the like is used.
In addition to the so-called pure aluminum plate, an aluminum alloy plate is used as the light metal plate.
The original thickness of the metal plate varies depending on the type of metal and the use or size of the container, but generally it should have a thickness of 0.10 to 0.50 mm. The thickness is preferably 10 to 0.30 mm, and in the case of a light metal plate, the thickness is preferably 0.15 to 0.40 mm.
本発明の樹脂被覆金属板においては、上記樹脂組成物から成るポリエステルフィルムを金属板に熱接着することにより製造することができるが、押出しコート法により上記樹脂組成物を直接金属板上に押出しフィルムを形成することにより、本発明の樹脂組成物から成る被覆を形成することもできる。
押出コート法の場合、樹脂の層の種類に対応する押出機を使用し、ダイを通してポリエステルを押出すると共に、これを溶融状態で金属基体に押出コートして、熱接着させる。金属基体に対する樹脂組成物の熱接着は、溶融樹脂組成物層が有する熱量と、金属板が有する熱量とにより行われる。金属板の加熱温度は、一般に９０乃至２９０℃、特に１００乃至２８０℃の温度が適当である。
The resin-coated metal plate of the present invention can be produced by thermally bonding a polyester film comprising the above resin composition to the metal plate, but the resin composition is directly extruded onto the metal plate by an extrusion coating method. By forming the coating, it is also possible to form a coating made of the resin composition of the present invention.
In the case of the extrusion coating method, an extruder corresponding to the type of the resin layer is used to extrude the polyester through a die, and this is extrusion coated onto a metal substrate in a molten state and thermally bonded. The heat bonding of the resin composition to the metal substrate is performed by the heat amount of the molten resin composition layer and the heat amount of the metal plate. The heating temperature of the metal plate is generally 90 to 290 ° C, particularly 100 to 280 ° C.
本発明の樹脂被覆金属板においては、樹脂被覆層と金属素材との間にプライマー層を設けることなく、樹脂被覆層を金属素材に接着させることが可能であるが、勿論プライマー層を設けることを除外するものではなく、所望によりプライマー層を設けることも可能である。 In the resin-coated metal plate of the present invention, the resin coating layer can be adhered to the metal material without providing a primer layer between the resin coating layer and the metal material. It is not excluded and a primer layer can be provided as desired.
本発明の樹脂被覆金属板は、金属板表面、特に容器内面側となる金属表面に上述した樹脂組成物から成る被覆層が設けられていることが好ましく、この被覆層の厚みは、３乃至４０μｍ、特に５乃至３５μｍの厚みで金属表面上に形成されていることが好ましい。 The resin-coated metal plate of the present invention is preferably provided with a coating layer made of the above-described resin composition on the metal plate surface, particularly the metal surface on the inner surface side of the container, and the thickness of the coating layer is 3 to 40 μm. In particular, it is preferably formed on the metal surface with a thickness of 5 to 35 μm.
本発明の樹脂被覆金属板は、前述した通り、金属板の容器としたとき内面側となる側に本発明の樹脂組成物からなる被覆層が少なくとも１層設けられていればよいが、勿論必要に応じて他の被覆層を設けることができる。例えば、金属基体の容器外面側にも被覆層を形成でき、この被覆層は本発明の樹脂組成物から成っていてもよいし、それ以外のポリエステル樹脂から成っていてもよい。また、上記内面側の被覆層の上面に更にポリエステル表面層を設けてもよい。 As described above, the resin-coated metal plate of the present invention may be provided with at least one coating layer made of the resin composition of the present invention on the inner surface side when it is used as a metal plate container. Depending on the case, other coating layers can be provided. For example, a coating layer can be formed also on the outer surface side of the metal substrate, and this coating layer may be made of the resin composition of the present invention or may be made of other polyester resins. Further, a polyester surface layer may be further provided on the upper surface of the inner surface side coating layer.
（缶及び缶蓋）
本発明の缶は、上述した樹脂被覆金属板を本発明の樹脂組成物から成る被覆層が缶内面側となるように、従来公知の成形法により製缶することができるが、特に側面継ぎ目のないシームレス缶であることが好ましいことから、絞り加工、絞り・深絞り加工、絞り・しごき加工、絞り・曲げ伸ばし加工・しごき加工等の手段により製造される。その側壁部は、樹脂被覆金属板の絞り−再絞り加工による曲げ伸ばし或いは更にしごき加工により、樹脂被覆金属板の元厚の２０乃至９５％、特に３０乃至８５％の厚みとなるように薄肉化されていることが好ましい。
(Cans and can lids)
The can of the present invention can be produced by a conventionally known molding method so that the above-mentioned resin-coated metal plate is coated on the inner surface of the can with the resin composition of the present invention. Since it is preferably a seamless can, it is produced by means such as drawing, drawing / deep drawing, drawing / ironing, drawing / bending / drawing / ironing. The side wall of the resin-coated metal sheet is thinned so as to have a thickness of 20 to 95%, particularly 30 to 85% of the original thickness of the resin-coated metal sheet by bending and stretching by drawing-redrawing or further ironing. It is preferable that
また本発明の缶蓋も、上述した樹脂被覆金属板を本発明の樹脂組成物から成る被覆層が缶蓋内面側となるように成形する以外は従来公知の缶蓋の製法により成形することができる。
また缶蓋の形状も、内容物注出用開口を形成するためのスコア及び開封用のタブが設けられたイージーオープンエンド等の従来公知の形状を採用することができる。
The can lid of the present invention can also be formed by a conventionally known can lid manufacturing method, except that the above-described resin-coated metal plate is molded such that the coating layer made of the resin composition of the present invention is on the inner side of the can lid. it can.
Also, the shape of the can lid may be a conventionally known shape such as a score for forming the contents dispensing opening and an easy open end provided with a tab for opening.
本発明を以下の実施例で説明する。
各実施例及び比較例で用いたオレフィンの組成を表１、各実施例で作製したラミネート材の構成を表２に示した。表２で示したPET／IA５は、イソフタル酸５mol％共重合PET樹脂を、PET／IA １５は、イソフタル酸１５mol％共重合PET樹脂を示す。
また、今回用いた評価法を下記に示す。その評価結果は表３にまとめた。
The invention is illustrated in the following examples.
Table 1 shows the composition of the olefin used in each Example and Comparative Example, and Table 2 shows the configuration of the laminate material produced in each Example. The PET / IA5 shown in Table 2 indicates a 5 mol% copolymerized PET resin with isophthalic acid, and PET / IA15 indicates a 15 mol% copolymerized PET resin with isophthalic acid.
The evaluation method used this time is shown below. The evaluation results are summarized in Table 3.
［加工性評価］
表２の加工性評価欄の対象に示すものに加工し、そのときのクラック、フィルムの割れ等を評価した。
[Processability evaluation]
It processed into what is shown in the object of the workability evaluation column of Table 2, and the crack at that time, the crack of a film, etc. were evaluated.
［経時脆化評価］
樹脂被覆金属板を２２５℃３分、２０５℃２分間熱処理した後、その樹脂被覆金属板を３７℃に保持された水中に１ヶ月間経時させた。そして、樹脂被覆金属板から内面フィルムを塩酸にて単離させた。その内面フィルムの示差走査型熱量測定を行い、８０℃付近にあらわれる体積緩和ピークの吸熱量で経時脆化を評価した。
評価結果は、
○：レトルト処理フィルムの体積緩和ピークの吸熱量が０．７００Ｊ/ｇ未満
×；レトルト処理フィルムの体積緩和ピークの吸熱量が０．７００Ｊ/ｇ以上
で示した。
[Evaluation of embrittlement over time]
The resin-coated metal plate was heat-treated at 225 ° C. for 3 minutes and at 205 ° C. for 2 minutes, and then the resin-coated metal plate was aged in water maintained at 37 ° C. for 1 month. Then, the inner film was isolated from the resin-coated metal plate with hydrochloric acid. Differential scanning calorimetry of the inner surface film was performed, and the embrittlement with time was evaluated by the endothermic amount of the volume relaxation peak appearing near 80 ° C.
The evaluation result is
○: The endothermic amount of the volume relaxation peak of the retort-treated film was less than 0.700 J / g. X: The endothermic amount of the volume relaxation peak of the retort-treated film was 0.700 J / g or more.
［耐食性］
樹脂被覆金属板を２２５℃３分、２０５℃２分間熱処理した後、圧延機により相当ひずみ２０％になるよう圧延を行い、３０ｍｍ×３０ｍｍの十字状の切り込みをいれ、５０℃でクエン酸系腐食液に３日間経時した後のフィルムの剥離面積を計算し評価した。
評価結果は、
○：剥離率が５０％未満
×：剥離率が５０％以上
で示した。
[Corrosion resistance]
After heat-treating the resin-coated metal plate at 225 ° C for 3 minutes and at 205 ° C for 2 minutes, it was rolled to an equivalent strain of 20% with a rolling mill, and a 30 mm x 30 mm cross cut was made. The peeled area of the film after aging for 3 days was calculated and evaluated.
The evaluation result is
○: Peeling rate is less than 50% ×: Peeling rate is shown as 50% or more.
[耐デント性]
９５℃で蒸留水を充填後、１２５℃３０分のレトルト処理を行った後３７℃の保温庫内にて1ヶ月間経時した缶に対して、５℃雰囲気下において、１５°の斜面にむけて、缶を高さ５０ｃｍから垂直に落下させて、缶底に衝撃を与える。加工後蒸留水を抜き取り、缶底の衝撃加工部における樹脂被覆の割れ程度を加工部に６．３０Ｖの電圧をかけたときの電流値で評価した。
評価結果は、
○：平均電流値＜0.5ｍＡ
△：0.5ｍＡ≦平均電流値＜２ｍA
×：平均電流値≧２ｍＡ
で示した。
[Dent resistance]
After filling with distilled water at 95 ° C, after retorting at 125 ° C for 30 minutes, a can that has been aged for 1 month in a 37 ° C incubator is exposed to a 15 ° slope in a 5 ° C atmosphere. Then, the can is dropped vertically from a height of 50 cm to give an impact to the bottom of the can. Distilled water was extracted after processing, and the degree of cracking of the resin coating in the impact processing portion of the can bottom was evaluated by a current value when a voltage of 6.30 V was applied to the processing portion.
The evaluation result is
○: Average current value <0.5 mA
Δ: 0.5 mA ≦ average current value <2 mA
×: Average current value ≧ 2 mA
It showed in.
［耐レトルト性］
９５℃で蒸留水を充填後、１２５℃３０分のレトルト処理を行い、室温に戻し蒸留水を抜き取り、評価が金属缶である場合は缶内面、蓋である場合は蓋内面の腐食状態を観察した。
評価結果は、
○：腐食が全く認められない。
×：腐食等の異常が認められる。
で示した。
[Retort resistance]
After filling with distilled water at 95 ° C, perform retort treatment at 125 ° C for 30 minutes, return to room temperature, extract distilled water, and observe the corrosion state of the inner surface of the can when the evaluation is a metal can and the inner surface of the lid when the evaluation is a lid did.
The evaluation result is
○: No corrosion is observed.
X: Abnormalities such as corrosion are observed.
It showed in.
（実施例１〜１３）
樹脂被覆が２層フィルムの場合は、表層に表２に示したポリエステルと供給し、下層に表１および表２に示した樹脂成分を二軸押出機に投入して溶融混練し、２層Ｔダイによりフィルム厚さ２８μｍ（表層４μm、下層２４μm）となるように押し出し、冷却ロールにて冷却して得られたフィルムを巻取り、キャストフィルムを得た。また、単層フィルムの場合は、単層Tダイを用いて２８μｍのキャストフィルム得た。
次いで、このキャストフィルムを、ＴＦＳ鋼板（板厚０．１８ｍｍ、金属クロム量１２０ｍｇ／ｍ２、クロム水和酸化物量１５ｍｇ／ｍ２）の内面側に、一方、外面側に顔料として二酸化チタンを２０重量％配合したポリエステル樹脂から成るキャストフィルムを同時に熱ラミネートし、直ちに水冷を行って樹脂被覆金属板を得た。
この時のラミネート条件は、ラミネート時のＴＦＳ鋼板の温度を熱可塑性ポリエステル樹脂の融点よりも１５℃高く、また、ラミネートロールの温度は９０℃、通板速度は４０ｍ／ｍｉｎとした。
さらに、この樹脂被覆金属板にワックス系潤滑剤を塗布し、上記直径１６６ｍｍの円盤を打ち抜き、表２に示した樹脂被覆面が内面側となるように絞り加工を行って絞りカップとし、絞りカップを二度の薄肉化再絞り（ストレッチ）・しごき加工を行い、シームレスカップを得た。
このシームレスカップの諸特性は以下の通りであった。
シームレスカップ径：６６ｍｍ
シームレスカップ高さ：１２８ｍｍ
素板厚に対する側壁部の厚み：５０％
そして、このシームレスカップを常法に従って底成形を行い、２２０℃で熱処理（ヒートセット）を行った後、開口端縁部のトリミング、外面印刷、焼き付け乾燥、ネックイン加工、フランジ加工を順次行って缶胴径６６ｍｍ、缶高さ１２２ｍｍ、内容量３５０ｍｌのシームレス缶とした。
(Examples 1 to 13)
When the resin coating is a two-layer film, the polyester shown in Table 2 is supplied to the surface layer, and the resin components shown in Table 1 and Table 2 are introduced into the lower layer into a twin-screw extruder and melt-kneaded. The film obtained by extruding with a die to a film thickness of 28 μm (surface layer 4 μm, lower layer 24 μm) and cooling with a cooling roll was wound up to obtain a cast film. In the case of a single layer film, a 28 μm cast film was obtained using a single layer T die.
Next, the cast film was coated with 20% titanium dioxide as a pigment on the inner surface side of the TFS steel plate (plate thickness 0.18 mm, metal chromium amount 120 mg / m 2 , chromium hydrated oxide amount 15 mg / m 2 ). A cast film made of a polyester resin blended in weight% was laminated simultaneously with heat and immediately cooled with water to obtain a resin-coated metal plate.
The lamination conditions at this time were such that the temperature of the TFS steel plate during lamination was 15 ° C. higher than the melting point of the thermoplastic polyester resin, the temperature of the laminate roll was 90 ° C., and the sheet feeding speed was 40 m / min.
Further, a wax-based lubricant is applied to the resin-coated metal plate, the disk having a diameter of 166 mm is punched out, and a drawing cup is formed by drawing so that the resin-coated surface shown in Table 2 is the inner surface side. A thin cup was re-drawn (stretched) and ironed twice to obtain a seamless cup.
Various characteristics of this seamless cup were as follows.
Seamless cup diameter: 66mm
Seamless cup height: 128mm
Side wall thickness relative to base plate thickness: 50%
Then, this seamless cup is bottom-formed according to a conventional method, heat-treated at 220 ° C. (heat set), and then subjected to trimming of the opening edge, outer surface printing, baking drying, neck-in processing, and flange processing in order. A seamless can having a can body diameter of 66 mm, a can height of 122 mm, and an internal volume of 350 ml was obtained.
（実施例１４）
板厚０．２８ｍｍのアルミニウム合金板（Ａ３００４材）の外面側に、イソフタル酸15mol％共重合PET（IV0.9）を、一方、上記アルミニウム合金板の内面側に、表１および表２から成る組成の樹脂を用いた。
そして、板温を上記樹脂の融点よりも３０℃低い温度に加熱して、押出しコート設備を備えた押出機によって、内外面側の樹脂を同時に溶融混練して押出しを行ってラミネートし、それぞれの樹脂の厚さが２０μｍの樹脂被覆金属板を得た。
この時のラミネート条件は、ラミネート時のアルミニウム合金板の温度を熱可塑性ポリエステル樹脂の融点よりも３０℃低く、また、ラミネートロールの温度は９０℃、通板速度は４０ｍ／ｍｉｎとした。
この樹脂被覆金属板にワックス系潤滑剤を塗布し、直径１５４ｍｍの円盤を打ち抜き、上記成分１乃至成分３から成る樹脂被覆面が内面側となるように絞り加工を行い絞りカップを得た。次いでこの絞りカップに二度の薄肉化再絞り（ストレッチ）・しごき加工を行い、シームレスカップを得た。
このシームレスカップの諸特性は以下の通りであった。
シームレスカップ径：６６ｍｍ
シームレスカップ高さ：１２７ｍｍ
素板厚に対する側壁部の厚み４５％
このシームレスカップを、常法に従い底成形を行い、２２０℃にて熱処理（ヒートセット）を行った後、開口端縁部のトリミング加工、印刷及び焼き付け乾煥、ネックイン加工、フランジ加工を順次行って、缶胴径６６ｍｍ、缶高さ１２２ｍｍ、内容量３５０ｍｌ用のシームレス缶を得た。
(Example 14)
A 15 mol% copolymerized PET (IV 0.9) is formed on the outer surface side of an aluminum alloy plate (A3004 material) having a thickness of 0.28 mm, while Table 1 and Table 2 are formed on the inner surface side of the aluminum alloy plate. A resin having a composition was used.
Then, the plate temperature is heated to a temperature 30 ° C. lower than the melting point of the resin, and the extruder on the inner and outer surface sides is simultaneously melt-kneaded and extruded by an extruder equipped with an extrusion coating facility, and laminated. A resin-coated metal plate having a resin thickness of 20 μm was obtained.
The lamination conditions at this time were such that the temperature of the aluminum alloy plate during lamination was 30 ° C. lower than the melting point of the thermoplastic polyester resin, the temperature of the laminate roll was 90 ° C., and the sheet passing speed was 40 m / min.
A wax-based lubricant was applied to the resin-coated metal plate, a disk having a diameter of 154 mm was punched out, and a drawing cup was obtained by drawing so that the resin-coated surface composed of the above components 1 to 3 became the inner surface side. Next, the drawn cup was subjected to twice-thinning redrawing (stretching) and ironing to obtain a seamless cup.
Various characteristics of this seamless cup were as follows.
Seamless cup diameter: 66mm
Seamless cup height: 127mm
Side wall thickness 45% of base plate thickness
This seamless cup is bottom-formed according to a conventional method, heat-treated at 220 ° C (heat set), and then subjected to trimming of the edge of the opening, printing and baking drying, neck-in processing, and flange processing in order. Thus, a seamless can for a can body diameter of 66 mm, a can height of 122 mm, and an internal capacity of 350 ml was obtained.
（実施例１５）
板厚０．２３５ｍｍのアルミニウム合金（Ａ５１８２材）を用い、片面に表１および表２から成る組成の樹脂を用いた。
そして、板温を上記樹脂の融点よりも３０℃低い温度に加熱して、押出しコート設備を備えた押出機によって、上記樹脂を溶融混練して押出しを行ってラミネートし、樹脂被覆金属板を得た。
この時のラミネート条件は、ラミネート時のアルミニウム合金板の温度を熱可塑性ポリエステル樹脂の融点よりも３０℃低く、また、ラミネートロールの温度は９０℃、通板速度は４０ｍ／ｍｉｎとした。
次いで、この樹脂被覆金属板を、樹脂被覆面が蓋の内面側となるように直径６８．７ｍｍの蓋を打ち抜き、次いで蓋の外面側にパーシャル（部分）開口型のスコア加工（幅２２ｍｍ、スコア残厚１１０μｍ、スコア幅２０μｍ）、リベット加工ならびに開封用タブの取り付けを行い、ＳＯＴ蓋の作製を行った。
(Example 15)
An aluminum alloy (A5182 material) having a thickness of 0.235 mm was used, and a resin having the composition shown in Tables 1 and 2 was used on one side.
Then, the plate temperature is heated to a temperature 30 ° C. lower than the melting point of the resin, and the resin is melt-kneaded and extruded and laminated by an extruder equipped with an extrusion coating facility to obtain a resin-coated metal plate. It was.
The lamination conditions at this time were such that the temperature of the aluminum alloy plate during lamination was 30 ° C. lower than the melting point of the thermoplastic polyester resin, the temperature of the laminate roll was 90 ° C., and the sheet passing speed was 40 m / min.
Next, the resin-coated metal plate was punched with a 68.7 mm diameter lid so that the resin-coated surface was on the inner surface side of the lid, and then a partial (partial) opening type score processing (22 mm wide, score on the outer surface side of the lid) The remaining thickness was 110 μm, the score width was 20 μm), riveting and attachment of a tab for opening were performed to produce an SOT lid.
（比較例１）
実施例１〜１３と同様にキャストフィルムを作製しようとしたが、下層樹脂を均一に押し出すことが出来ず、また、膜揺れも激しかったことから、キャストフィルムを得ることが出来なかった。
(Comparative Example 1)
An attempt was made to produce a cast film in the same manner as in Examples 1 to 13, but the lower layer resin could not be extruded uniformly, and the film shake was severe, so a cast film could not be obtained.
（比較例２）
実施例１〜１３と同様にキャストフィルムを作製したが、この際、サブミクロン程度のブツの発生が見られた。その後、実施例１〜１３と同様にシームレス缶を得た。
(Comparative Example 2)
Cast films were produced in the same manner as in Examples 1 to 13, but at this time, generation of submicron irregularities was observed. Thereafter, seamless cans were obtained in the same manner as in Examples 1-13.
（比較例３）
実施例１〜１３と同様にキャストフィルムを作製したが、この際、膜揺れがあり、幅方向で膜厚が不均一になった。その後、実施例１〜１３と同様にシームレス缶を得た。
(Comparative Example 3)
A cast film was produced in the same manner as in Examples 1 to 13, but there was film shaking at this time, and the film thickness became non-uniform in the width direction. Thereafter, seamless cans were obtained in the same manner as in Examples 1-13.
（比較例４、５）
実施例１〜１３と同様にキャストフィルムを作製したが、この際、サブミクロン程度のブツの発生が見られた。その後、実施例１〜１３と同様にシームレス缶を得た。
(Comparative Examples 4 and 5)
Cast films were produced in the same manner as in Examples 1 to 13, but at this time, generation of submicron irregularities was observed. Thereafter, seamless cans were obtained in the same manner as in Examples 1-13.
（比較例６、７）
実施例１〜１３と同様にキャストフィルムを作製し、その後、実施例１〜１３と同様にシームレス缶を得た。
(Comparative Examples 6 and 7)
A cast film was produced in the same manner as in Examples 1 to 13, and then seamless cans were obtained in the same manner as in Examples 1 to 13.
表３に示す様に、実施例１〜１５におけるラミネート材は、加工性が良好で、この樹脂被覆金属板から製造したシームレス缶、缶蓋は耐デント性に優れていることが明らかであった。
一方、比較例１乃至７のキャストフィルムは、製膜性に劣るもの、加工性に劣るものがあり、また、シームレス缶が得られても、耐デント性、耐食性にそれぞれ劣ることが明らかであった。
As shown in Table 3, it was clear that the laminate materials in Examples 1 to 15 had good workability, and the seamless cans and can lids produced from this resin-coated metal plate were excellent in dent resistance. .
On the other hand, the cast films of Comparative Examples 1 to 7 are inferior in film formability and inferior in workability, and even when a seamless can is obtained, it is clear that the cast film is inferior in dent resistance and corrosion resistance. It was.
Claims (9)
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| WO1999027026A1 (en) * | 1997-11-26 | 1999-06-03 | Nippon Steel Corporation | Coating resin composition for metal sheets, and resin films, resin-coated metal sheets and resin-coated metal vessels each made by using the composition |
| JP2001328208A (en) * | 2000-05-19 | 2001-11-27 | Toyo Seikan Kaisha Ltd | Resin-coated metal panel, metal can, and can lid |
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| WO1999027026A1 (en) * | 1997-11-26 | 1999-06-03 | Nippon Steel Corporation | Coating resin composition for metal sheets, and resin films, resin-coated metal sheets and resin-coated metal vessels each made by using the composition |
| JP2001328208A (en) * | 2000-05-19 | 2001-11-27 | Toyo Seikan Kaisha Ltd | Resin-coated metal panel, metal can, and can lid |
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