JPH0747649A - Polyester composite film for lamination of metal - Google Patents
Polyester composite film for lamination of metalInfo
- Publication number
- JPH0747649A JPH0747649A JP19474993A JP19474993A JPH0747649A JP H0747649 A JPH0747649 A JP H0747649A JP 19474993 A JP19474993 A JP 19474993A JP 19474993 A JP19474993 A JP 19474993A JP H0747649 A JPH0747649 A JP H0747649A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- film
- polyester
- metal
- composite film
- 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
- 229920000728 polyester Polymers 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000003475 lamination Methods 0.000 title abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 polyethylene terephthalate isophthalate Polymers 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 238000010030 laminating Methods 0.000 claims description 22
- 229920001225 polyester resin Polymers 0.000 claims description 17
- 239000004645 polyester resin Substances 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000000796 flavoring agent Substances 0.000 abstract description 12
- 235000019634 flavors Nutrition 0.000 abstract description 12
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 71
- 238000000034 method Methods 0.000 description 33
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 239000005028 tinplate Substances 0.000 description 20
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000539 dimer Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940087305 limonene Drugs 0.000 description 3
- 235000001510 limonene Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属貼合せ用ポリエステ
ル複合フイルムに関し、更に詳細には缶壁部が長い金属
缶（例えば、ビール缶、炭酸飲料缶、ジュース缶、エア
ゾール缶等）を得るためのラミネート鋼板の構成材料と
して好適なポリエステル複合フイルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composite film for laminating metal, and more particularly, for obtaining a metal can having a long can wall (for example, beer can, carbonated beverage can, juice can, aerosol can, etc.). The present invention relates to a polyester composite film suitable as a constituent material for a laminated steel sheet.
【０００２】[0002]
【従来の技術】従来、金属缶において金属臭が内容物へ
移行することおよび内容物により金属缶内面が腐食され
ることを防止するために塗装が施されているが、最近、
工程簡素化、衛生性向上、公害防止等の目的で、有機溶
剤を使用せずにブリキ、ティンフリースチール、アルミ
ニウム等の金属板にポリエステルフイルムを加熱、加圧
接着して得たラミネートした後、絞り加工等により製缶
する方法の検討が進められている。2. Description of the Related Art Conventionally, coating is applied to a metal can to prevent a metallic odor from migrating to the contents and the inner surface of the metal can from being corroded by the contents.
For the purpose of process simplification, improvement of hygiene, pollution prevention, etc., without using an organic solvent, tin, tin-free steel, after laminating the polyester film on a metal plate such as aluminum by heating and pressure bonding, The method of making cans by drawing is being studied.
【０００３】たとえば、特公昭５７−２３５８４号公
報、特公昭５９−３４５８０号公報、特公昭６２−６１
４２７号公報等にその技術内容が開示されている。しか
しながら、当該技術ではフイルムの構成ポリマーの融点
以上の温度で鋼板とラミネートして十分に密着させた場
合、製缶加工時の衝撃、すなわち、ストッパーに高速で
当った衝撃で缶底部に局所的なフイルム破れ（クラッ
ク）が発生する。係る欠点を回避するため、フイルムの
柔軟性を向上させて耐変形性と耐衝撃性を確保しようと
した場合は、製缶工程でダイスとポンチによる加工発熱
によりフイルムがポンチに粘着し、その結果缶壁部のフ
イルムが引き裂かれて破れることが多発する。さらに、
製缶加工工程後の熱処理工程等での搬送時に搬送ピンの
跡がつき易い。すなわち、耐熱性不足に起因した種々の
問題が発生する。また、柔軟性を向上させたポリエステ
ルは、缶充填物中の香気成分を吸着する特性が悪化、す
なわち、耐フレーバー性が劣るという欠点を有してい
る。以上より金属缶内層保護層として満足されるもので
はない。For example, JP-B-57-23584, JP-B-59-34580 and JP-B-62-61.
The technical contents are disclosed in Japanese Patent No. 427 and the like. However, in the art, when the film is laminated and sufficiently adhered to the steel plate at a temperature equal to or higher than the melting point of the polymer constituting the film, the shock is generated during the can manufacturing process, that is, the shock that hits the stopper at a high speed causes local damage to the bottom of the can. Film tears (cracks) occur. In order to avoid such drawbacks, when the flexibility of the film is improved and deformation resistance and impact resistance are to be secured, the film adheres to the punch due to the processing heat generated by the die and punch in the can making process, and as a result, The film on the can wall often tears and tears. further,
Traces of transport pins are likely to be left during transport in the heat treatment process after the can manufacturing process. That is, various problems occur due to insufficient heat resistance. Further, the polyester having improved flexibility has a drawback that the property of adsorbing the aroma component in the can filling is deteriorated, that is, the flavor resistance is poor. From the above, it is not satisfactory as the protective layer for the inner layer of the metal can.
【０００４】係る欠点を回避するために、特開平２−８
１６３０号公報において、２種２層の複合ポリエステル
フイルムを用いる方法が開示されている。しかしなが
ら、成形加工性と耐熱性とのバランスにおいて、市場要
求を満足させるレベルまで達成することは困難であっ
た。In order to avoid such a drawback, Japanese Patent Laid-Open No. 2-8
Japanese Patent No. 1630 discloses a method of using a two-kind two-layer composite polyester film. However, in terms of the balance between moldability and heat resistance, it has been difficult to achieve a level that satisfies market requirements.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記事情に鑑
みてなされたものであって、製缶加工時での変形性、耐
衝撃性及び密着性が確保され、かつ耐熱性に優れ製缶加
工時のポンチ粘着や搬送ピンの跡型が発生せず、更に、
耐フレーバー性の良好な金属貼合せ用ポリエステル複合
フイルムを提供する。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is possible to secure the deformability, the impact resistance and the adhesion at the time of the can manufacturing process, and it is also excellent in heat resistance. Punch adhesion during processing and traces of transport pins do not occur, and moreover,
Provided is a polyester composite film for metal laminating, which has good flavor resistance.
【０００６】[0006]
【課題を解決するための手段】本発明は、Ａ層、Ｂ層、
Ａ層より構成されるポリエステル複合フイルムであっ
て、Ａ層は融点が２１０〜２３０℃のポリエチレンテレ
フタレートとイソフタレートとの共重合体よりなり、Ｂ
層は全酸成分の５０モル％以上がテレフタル酸残基、５
〜５０モル％が炭素数１０以上の脂肪族ジカルボン酸残
基を含有し、全アルコール成分の３５〜６０モル％がエ
チレングリコール残基、４０〜６５モル％が１，４ブタ
ンジオール残基よりなるガラス転移点が４０℃以下のポ
リエステル樹脂よりなることを特徴とする金属貼合せ用
ポリエステル複合フイルムである。The present invention is directed to an A layer, a B layer,
A polyester composite film composed of an A layer, wherein the A layer is made of a copolymer of polyethylene terephthalate and isophthalate having a melting point of 210 to 230 ° C.
In the layer, 50 mol% or more of all acid components are terephthalic acid residues, and 5
To 50 mol% contains an aliphatic dicarboxylic acid residue having 10 or more carbon atoms, 35 to 60 mol% of all alcohol components are ethylene glycol residues, and 40 to 65 mol% are 1,4 butanediol residues. A polyester composite film for metal laminating, comprising a polyester resin having a glass transition point of 40 ° C. or lower.
【０００７】本発明におけるＡ層を構成するポリエステ
ル樹脂は、融点が２１０〜２３０℃のポリエチレンテレ
フタレートとイソフタレートとの共重合体である必要が
ある。かかるポリエステル樹脂は、その製造工程で副生
するジエチレングリコール残基を含むことは許される。
また、上記の融点範囲であればその他の共重合成分を含
まない方が良い。耐フレーバー性の点よりジエチレング
リコール残基の含有量も出来るだけ少ない方が良い。イ
ソフタレートの共重合割合はポリエステルの製造工程で
副生するジエチレングリコール残基の量により異なるが
一般には８〜１２モル％の範囲である。融点が２１０℃
未満では耐熱性が低く製缶加工時にポンチ粘着が発生し
製缶工程の操業性が低くなり、かつ、缶壁部のフイルム
が引き裂かれて破れが発生する等の問題が起るので好ま
しくない。逆に、２３０℃を越えると、金属板との加熱
ラミネート時の密着性が低下し製缶加工時に缶壁部にお
いて局所的なフイルム剥離を起点としたフイルム破れ
（クラック）が発生しやすくなるので好ましくない。The polyester resin constituting the layer A in the present invention must be a copolymer of polyethylene terephthalate and isophthalate having a melting point of 210 to 230 ° C. Such polyester resin is allowed to contain a diethylene glycol residue produced as a by-product in the manufacturing process.
Further, it is better not to include other copolymerization components within the above melting point range. From the viewpoint of flavor resistance, it is better that the content of diethylene glycol residue is as low as possible. The copolymerization ratio of isophthalate varies depending on the amount of diethylene glycol residue by-produced in the polyester production process, but is generally in the range of 8 to 12 mol%. Melting point 210 ° C
If it is less than the above range, heat resistance is low and sticking of the punch occurs during the can manufacturing process, which lowers the operability of the can manufacturing process, and causes problems such as tearing of the film on the can wall and tearing. On the other hand, if the temperature exceeds 230 ° C., the adhesion during heat lamination with a metal plate decreases, and film breakage (cracks) starting from local film peeling on the can wall portion during the can manufacturing process easily occurs. Not preferable.
【０００８】Ａ層は、上層と下層の２層が存在するがそ
れぞれの層の厚みは同じであってもかまわないが、金属
板とラミネートされる側とその反対層とではその機能が
異なるのでそれぞれ厚みを変えて対応するのがより好ま
しい実施対応である。金属板とラミネートされる側のＡ
層Ａ2 層は金属板との接着性付与が、一方、反対層Ａ 1
層は、耐熱性や耐フレーバー性を付与するがその主機能
である。The layer A has two layers, an upper layer and a lower layer.
The layers may have the same thickness, but the metal
Its function is on the side laminated with the board and the opposite layer.
Since it is different, it is more preferable to respond by changing the thickness of each.
It is a new implementation response. A on the side laminated with a metal plate
Layer A2The layer provides adhesion to the metal plate, while the opposite layer A 1
The layer imparts heat resistance and flavor resistance, but its main function
Is.
【０００９】それぞれを接着層および保護層とし称し区
分すると、接着層の層厚みは１〜１０μｍが好ましい。
２〜５μｍがより好ましい。１μｍ未満では、金属板と
の密着性が不充分となるので好ましくない。逆に、１０
μｍを越えた場合は金属板との密着性が飽和し、かつ、
変形性や耐衝撃性が低下するので好ましくない。一方、
保護層の層厚みは１〜２０μｍが好ましく２〜１５μｍ
がより好ましい。１μｍ未満では、耐熱性や耐フレーバ
ー性の向上効果が充分でなくなるので好ましくない。逆
に、２０μｍを越えると耐熱性や耐フレーバー性の向上
効果が飽和するとともに変形性や耐衝撃性が低下するの
で好ましくない。When each of them is referred to as an adhesive layer and a protective layer and classified, the layer thickness of the adhesive layer is preferably 1 to 10 μm.
2-5 micrometers is more preferable. If it is less than 1 μm, the adhesion to the metal plate becomes insufficient, which is not preferable. Conversely, 10
If it exceeds μm, the adhesion with the metal plate will be saturated, and
Deformability and impact resistance are reduced, which is not preferable. on the other hand,
The layer thickness of the protective layer is preferably 1 to 20 μm, and preferably 2 to 15 μm.
Is more preferable. When it is less than 1 μm, the effect of improving heat resistance and flavor resistance becomes insufficient, which is not preferable. On the contrary, if it exceeds 20 μm, the effect of improving the heat resistance and the flavor resistance is saturated, and the deformability and the impact resistance are deteriorated, which is not preferable.
【００１０】本発明におけるＢ層を構成するポリエステ
ル樹脂は、全酸成分の５０モル％以上がテレフタル酸残
基、５〜５０モル％が炭素数１０以上の脂肪族ジカルボ
ン酸残基を含有し、全アルコール成分の３５〜６０モル
％がエチレングリコール残基、４０〜６５モル％が１，
４ブタンジオール残基よりなるガラス転移点が４０℃以
下よりなる必要がある。テレフタル酸が５０モル％未満
では、耐熱性が不足するので好ましくない。炭素数１０
以上の脂肪族ジカルボン酸としては、セバシン酸、エイ
コ酸、ドデカンジカルボン酸、ダイマー酸等が挙げられ
る。ダイマー酸とはオレイン酸等の高級不飽和脂肪酸の
二量化反応によって得られ、通常不飽和結合を分子中に
有するが、水素添加をして不飽和度を下げたものも使用
できる。水素添加をした方が耐熱性や柔軟性が向上する
のでより好ましい。また、二量化反応の過程で、直鎖分
岐状構造、脂環構造、芳香核構造が生成されるがこれら
の構造や量も特に限定されない。炭素数が１０未満の脂
肪族ジカルボン酸残基では、変形性や耐衝撃性の付与が
充分でないので好ましくない。該脂肪族ジカルボン酸残
基の含有量は全酸成分中５〜５０モル％である必要があ
る。５モル％未満では、変形性や耐衝撃性の付与が不充
分となるので好ましくない。逆に、５０モル％を越える
と変形性や耐衝撃性が飽和し、かつ、耐熱性が低下する
ので好ましくない。In the polyester resin constituting the layer B in the present invention, 50 mol% or more of all the acid components contain terephthalic acid residues, and 5 to 50 mol% contain aliphatic dicarboxylic acid residues having 10 or more carbon atoms, 35 to 60 mol% of all alcohol components are ethylene glycol residues, 40 to 65 mol% are 1,
The glass transition point of the 4-butanediol residue must be 40 ° C. or lower. When the content of terephthalic acid is less than 50 mol%, heat resistance becomes insufficient, which is not preferable. Carbon number 10
Examples of the above aliphatic dicarboxylic acids include sebacic acid, eicosic acid, dodecanedicarboxylic acid, dimer acid and the like. The dimer acid is obtained by a dimerization reaction of a higher unsaturated fatty acid such as oleic acid, and usually has an unsaturated bond in the molecule, but those having hydrogenation to reduce the degree of unsaturation can also be used. Hydrogenation is more preferable because heat resistance and flexibility are improved. Further, in the course of the dimerization reaction, a linear branched structure, an alicyclic structure, and an aromatic nucleus structure are produced, but the structure and amount thereof are not particularly limited. An aliphatic dicarboxylic acid residue having a carbon number of less than 10 is not preferable because it does not provide sufficient deformability and impact resistance. The content of the aliphatic dicarboxylic acid residue needs to be 5 to 50 mol% in all the acid components. When it is less than 5 mol%, the impartation of deformability and impact resistance becomes insufficient, which is not preferable. On the contrary, if it exceeds 50 mol%, the deformability and the impact resistance are saturated, and the heat resistance is lowered, which is not preferable.
【００１１】該ポリエステル樹脂は、全アルコール成分
の３５〜６０モル％がエチレングリコール残基、４０〜
６５モル％が１，４ブタンジオール残基である必要があ
る。本範囲内であることが該ポリエステル樹脂のレジン
の取扱い性とコストとのバランスが良好である。上記範
囲よりエチレングリコール残基が多くなると樹脂の結晶
性が低くなり取扱い性が悪くなる。逆に、１，４ブタン
ジオール残基の量が上記範囲を越えるとコストが高くな
るので好ましくない。なお、ジエチレングリコール等の
エーテル基を含有するアルコール成分とポリエステルの
製造工程で副生する量を含有することが許される。ま
た、１０モル％以下であればプロピレングリコール、ネ
オペンチルグリコール、シクロヘキサンジメタノール等
の他のグリコール残基を含有してもよい。In the polyester resin, 35 to 60 mol% of all alcohol components are ethylene glycol residues and 40 to 40 mol%.
It is necessary that 65 mol% be 1,4 butanediol residues. Within this range, the balance between the handleability of the resin of the polyester resin and the cost is good. If the ethylene glycol residue is more than the above range, the crystallinity of the resin will be low and the handling will be poor. On the contrary, if the amount of the 1,4 butanediol residue exceeds the above range, the cost becomes high, which is not preferable. It should be noted that it is allowed to contain an alcohol component containing an ether group such as diethylene glycol and an amount by-produced in the polyester production process. Further, other glycol residues such as propylene glycol, neopentyl glycol and cyclohexanedimethanol may be contained as long as they are 10 mol% or less.
【００１２】Ｂ層を構成するポリエステル樹脂は、ガラ
ス転移点が４０℃以下である必要がある。３０℃以下が
より好ましい。ガラス転移点が４０℃を越えた場合は、
変形性や耐衝撃性の付与が充分でなくなるので好ましく
ない。Ｂ層を構成するポリエステル樹脂は、上記範囲内
であればその構成は任意に設定することができる。該Ｂ
層厚みは１０〜６０μｍが好ましい。１５〜４０μｍが
より好ましい。１０μｍ未満では変形性や耐衝撃性の付
与が充分でなくなるので好ましくない。逆に６０μｍを
越えると変形性や耐衝撃性の付与が飽和し、かつ、耐熱
性が低下するので好ましくない。また、コスト的にも不
利になる。The polyester resin forming the layer B must have a glass transition point of 40 ° C. or lower. 30 ° C or lower is more preferable. If the glass transition temperature exceeds 40 ° C,
Deformability and impact resistance are not sufficiently imparted, which is not preferable. The polyester resin forming the layer B can be arbitrarily set within the above range. The B
The layer thickness is preferably 10 to 60 μm. 15-40 micrometers is more preferable. If it is less than 10 μm, the deformability and impact resistance are not sufficiently imparted, which is not preferable. On the other hand, if it exceeds 60 μm, the impartation of deformability and impact resistance is saturated, and the heat resistance is lowered, which is not preferable. Also, it is disadvantageous in terms of cost.
【００１３】Ａ層、Ｂ層を構成するポリエステル樹脂
は、いずれもが極限粘度で０．５以上のものであること
が好ましい。０．７以上のものがより好ましい。また、
各層を構成するポリエステル樹脂は１種類でもかまわな
いし、２種以上をブレンドして用いてもかまわない。更
に、これらのポリエステル樹脂には、必要に応じて酸化
防止剤、熱安定剤、紫外線吸収剤、可塑剤、顔料、帯電
防止剤、潤滑剤、結晶核剤、無機あるいは有機粒子より
なる潤滑剤等を配合させることは何ら制限を受けない。
前記したポリエステル樹脂の製造方法も何ら制限はな
く、エステル交換法あるいは直接重合法のどちらの製造
法で製造されたものであっても使用できる。また、分子
量を高めるために固相重合法で製造したものであっても
かまわない。缶に内容物を充填後のレトルト処理等での
ポリエステル樹脂からのオリゴマーの析出を少くする点
より、Ａ層を構成するポリエステル樹脂は減圧法固相重
合法で製造したオリゴマー含有量の低いポリエステル樹
脂を用いるのが特に好ましい実施態様である。It is preferable that each of the polyester resins constituting the layers A and B has an intrinsic viscosity of 0.5 or more. It is more preferably 0.7 or more. Also,
The polyester resin constituting each layer may be of one type, or may be a blend of two or more types. Further, these polyester resins may include antioxidants, heat stabilizers, ultraviolet absorbers, plasticizers, pigments, antistatic agents, lubricants, crystal nucleating agents, lubricants composed of inorganic or organic particles, etc., if necessary. There is no limitation in blending.
The method for producing the polyester resin described above is not particularly limited, and any one produced by a transesterification method or a direct polymerization method can be used. Further, it may be produced by a solid phase polymerization method in order to increase the molecular weight. The polyester resin constituting the layer A is a polyester resin having a low oligomer content produced by a reduced pressure solid phase polymerization method from the viewpoint of reducing the precipitation of oligomers from the polyester resin in the retort treatment after filling the can with contents. Is a particularly preferred embodiment.
【００１４】本発明の複合フイルムは、以上のごとくＡ
層、Ｂ層、Ａ層の順に構成されておれば、未延伸のフイ
ルムであっても、延伸フイルムであってもどちらでもか
まわない。該層構成のフイルムは多層押出法で製造する
のが好ましい。延伸フイルムの場合は１軸延伸および２
軸延伸のいずれでもかまわないが等方性より２軸延伸フ
イルムが好ましい。該複合フイルムの製造方法も何ら制
限を受けない。たとえば、延伸フイルムの場合は、Ｔダ
イ法、チェーブラー法のいずれの方法も適用できる。本
発明の複合ポリエステルフイルムを金属貼合せ用として
使用する時は、Ａ2表面を金属板側として用いる必要が
ある。該貼合せ方法は特に限定されないが通電法で加熱
した金属板に複合ポリエステルフイルムを圧着し熱接着
させる方法が最も好ましい実施態様である。As described above, the composite film of the present invention is
It does not matter whether it is an unstretched film or a stretched film as long as it is composed of a layer, a B layer and an A layer in this order. The film having the layer structure is preferably produced by a multi-layer extrusion method. Uniaxial stretching and 2 in case of stretched film
Any of axial stretching may be used, but a biaxially stretched film is preferable because of its isotropic property. The manufacturing method of the composite film is not limited at all. For example, in the case of a stretched film, either the T-die method or the chabler method can be applied. When the composite polyester film of the present invention is used for metal laminating, it is necessary to use the A 2 surface as the metal plate side. The laminating method is not particularly limited, but a method in which a composite polyester film is pressure-bonded to a metal plate heated by an electric current method and heat-bonded is the most preferable embodiment.
【００１５】以下に本発明を実施例に基づき説明する。
実施例で用いた測定方法は次の通りである。 （１） 融点（Ｔｍ）、ガラス転移点（Ｔｇ） 示差走査型熱量計を用いて求める。サンプルを３００℃
で５分間加熱溶融した後液体窒素で急冷しその１０ｍｇ
を１０℃／分の昇温速度で昇温していった際に、ガラス
状態からゴム状態への転移に基づく比熱変化を読みとり
この温度をガラス転移点（Ｔｇ）とした。また、結晶融
解に基づく吸熱ピーク温度を融点（Ｔｍ）とした。The present invention will be described below based on examples.
The measuring method used in the examples is as follows. (1) Melting point (Tm), glass transition point (Tg) Obtained using a differential scanning calorimeter. Sample at 300 ° C
After heating and melting for 5 minutes at 10mg
When the temperature was raised at a heating rate of 10 ° C./min, the specific heat change due to the transition from the glass state to the rubber state was read and this temperature was taken as the glass transition point (Tg). In addition, the endothermic peak temperature based on crystal melting was defined as the melting point (Tm).
【００１６】（２） 接着性 ２３０℃に加熱した金属ロールとゴムロールとの間を複
合ポリエステルフイルムと厚さ０．２９ｍｍのブリキと
を重ね合せ（複合ポリエステルのＡ2 層表面をブリキと
接触）、圧力２０ｋｇ／ｃｍで通過させた。通過後のフ
イルムとブリキのラミネート品の接着力（ラミネート強
さ）をテンシロンで測定した。 ○：ラミネート強さが２００ｇ／ｃｍ以上 ×：ラミネート強さが２００ｇ／ｃｍ未満(2) Adhesiveness A composite polyester film and a tin plate having a thickness of 0.29 mm are superposed between a metal roll heated to 230 ° C. and a rubber roll (the surface of the A 2 layer of the composite polyester is brought into contact with the tin plate), The pressure was 20 kg / cm. The adhesive strength (laminate strength) of the laminated film and tin product after passing was measured by Tensilon. ◯: Laminate strength is 200 g / cm or more ×: Laminate strength is less than 200 g / cm
【００１７】（３） ステック温度 所定の温度に加温した金属ロールに（２）の方法でブリ
キ板にラミネートしたラミネートフイルムのフイルム面
を接触させ、手で押え粘着により抵抗が急激に増大する
温度を測定。５℃ピッチで評価し、最後は１℃ピッチで
評価しステック温度を求めた。ステック温度が８０℃未
満では、製缶工程でポンチの粘着が起り製缶の操業性が
低下するので好ましくない。(3) Stick temperature The temperature at which the resistance rapidly increases by contacting the film surface of the laminated film laminated on the tin plate by the method (2) with a metal roll heated to a predetermined temperature and pressing it by hand to adhere. Measure. The stick temperature was evaluated at 5 ° C pitch and finally at 1 ° C pitch. If the stick temperature is less than 80 ° C, sticking of the punch will occur during the can making process and the operability of the can will be reduced, which is not preferable.
【００１８】（４） 耐熱性 （２）の方法でブリキ板にラミネートしたラミネートフ
イルムを５ｃｍ×５ｃｍに切断したものフイルム面に、
１００ｇの分銅を置き２００℃で５分間加熱した後の分
鋼の跡型の発生状況を目視で評価した。(4) Heat resistance A laminate film laminated on a tin plate by the method of (2) is cut into 5 cm × 5 cm, and the film surface is
After the weight of 100 g was placed and heated at 200 ° C. for 5 minutes, the generation state of traces of the weight steel was visually evaluated.
【００１９】（５） 耐衝撃性 （２）の方法でブリキ板にラミネートしたラミネートフ
イルムのフイルム面に、先端径４ｍｍ、重量０．４ｋｇ
の錘を高さ３０ｃｍより垂直に落下し変形させ製缶のモ
デルとした。該製缶モデルラミネートフイルムを２２０
℃で１０分間熱処理した後、水をはったオートクレーブ
に入れて１２０℃で３０分間加熱しレトルトのモデル処
理を行なった。該レトルトモデル処理ラミネートフイル
ムの製缶モデルで変形した部分にブリキ板側より、底面
が平坦で重量が０．４ｋｇの錘を高さ２４ｃｍより垂直
に落下させ衝撃を与えた。該衝撃を与えたラミネートフ
イルムのフイルム側に塩ビ製のパイプを接着剤で接合
し、この中に１％食塩水を入れ電極を挿入し、ブリキ板
を陽極として６Ｖの電圧をかけ３０秒後の電流値（ｍ
Ａ）を測定した。１０回の測定値の平均値で表示した。
０．２ｍＡ以下であることが好ましい。(5) Impact resistance On the film surface of the laminated film laminated on the tin plate by the method of (2), the tip diameter is 4 mm and the weight is 0.4 kg.
The weight was dropped vertically from a height of 30 cm and deformed to make a model of a can. The can model laminating film is 220
After heat treatment at 10 ° C. for 10 minutes, the retort was modeled by placing it in a water-filled autoclave and heating at 120 ° C. for 30 minutes. On the deformed portion of the canned model of the retort model-treated laminated film, a weight having a flat bottom and a weight of 0.4 kg was vertically dropped from a tin plate side from a height of 24 cm to give an impact. A vinyl chloride pipe was bonded to the film side of the laminated film which was shocked with an adhesive, 1% saline was put into this, and an electrode was inserted. A voltage of 6 V was applied for 30 seconds after the tin plate was used as an anode. Current value (m
A) was measured. The average value of 10 measurements was displayed.
It is preferably 0.2 mA or less.
【００２０】（６） 熱処理後のしわ （２）の方法でブリキ板にラミネートしたラミネートフ
イルムをプレス機で１００ｋｇ／ｃｍ2 の圧力でプレス
成形しカップを得た。該カップを２００℃で５分間加熱
した後のフイルムの皺の発生状態を目視評価した。(6) Wrinkles after heat treatment The laminated film laminated on the tin plate by the method of (2) was press-molded with a press at a pressure of 100 kg / cm 2 to obtain a cup. After the cup was heated at 200 ° C. for 5 minutes, the state of wrinkling of the film was visually evaluated.
【００２１】（７） 耐フレーバー性 Ａ1 層側を内面として１０ｃｍ角のフイルムをインパル
スシーラーで三方シールをする。該三方シール袋にｄ−
リモネン３０ｃｍを充填し、開封口をインパルスシーラ
ーで密封をする。該密封袋を４０℃の恒温室で１０日間
静置し、ｄ−リモネンの吸着を行なう。該吸着袋を開封
しｄ−リモネンを排出させた後、未シール部分のフイル
ムを４ｃｍ角の大きさに切出し、表面に付着しているｄ
−リモネンをキムワイプできれいにふきとりフイルムの
重量Ｗ1 を測定する。該フイルムを６０℃で２４時間真
空乾燥した後、再度フイルムの重量Ｗ2 を測定する。ｄ
−リモネンの吸着量を次式により求め重量％で表示し
た。 ｄ−リモネン吸着量（％）＝Ｗ1 −Ｗ2 ／Ｗ2 ｄ−リモネン吸着量が２％以下のものが実用的である。(7) Flavor resistance A 10 cm square film with the A1 layer side as the inner surface is three-way sealed with an impulse sealer. D- in the three-sided seal bag
30 cm of limonene is filled and the opening is sealed with an impulse sealer. The sealed bag is allowed to stand in a thermostatic chamber at 40 ° C. for 10 days to adsorb d-limonene. After the suction bag was opened and d-limonene was discharged, the unsealed film was cut into a size of 4 cm square and adhered to the surface d
- to measure the weight W 1 of the film wipe clean the limonene in the Kimwipe. After vacuum drying the film at 60 ° C. for 24 hours, the weight W 2 of the film is measured again. d
-The amount of limonene adsorbed was calculated by the following formula and expressed in% by weight. Adsorption amount of d-limonene (%) = W 1 -W 2 / W 2 It is practical that the adsorption amount of d-limonene is 2% or less.
【００２２】実施例１ Ａ層レジンとして平均粒径が３μｍの球状ゼオライト２
０００ｐｐｍを含むテレフタル酸／イソフタル酸（モル
比８８／１２）とエチレングリコールからの共重合ポリ
エステル（Ｔｍ２２５℃）〔ポリエステルＡ〕を、Ｂ層
レジンとしてイルガノックス１３３０を０．２重量％を
含むテレフタル酸／炭素数３６ケのダイマー酸（モル比
９５／５）とエチレングリコール／１，４ブタンジオー
ル（モル比３０／７０）からの共重合ポリエステル（Ｔ
ｍ１８６℃、Ｔｇ２２℃）〔ポリエステルＢ〕をそれぞ
れ別々の押出し機で溶融させ、この溶融体をダイ内で合
流および分流をさせた後、冷却ドラム上に押出して冷却
させＡ／Ｂ／Ａ層からなる三層構成の層厚み３２μｍ
（Ａ1 層厚み８μｍ、Ｂ層厚み２０μｍ、Ａ2 層厚み４
μｍ）の未延伸フイルムを得た。得られたフイルムおよ
びブリキ板とのラミネートフイルム（Ａ2 層面側をラミ
ネート、以下の実施例および比較例は全てＡ2層面側を
ラミネート）の特性を表１に示す。本実施例で得られた
複合フイルムは、接着性、製缶操業性、耐熱性、耐衝撃
性、耐フレーバー性の全ての特性に優れており、金属貼
合せ用フイルムとして実用性が高いものであった。Example 1 Spherical zeolite 2 having an average particle size of 3 μm as a layer A resin
A terephthalic acid containing 0.2% by weight of Irganox 1330 as a layer B resin is a copolymerized polyester (Tm225 ° C.) [polyester A] made of terephthalic acid / isophthalic acid (molar ratio 88/12) containing 000 ppm and ethylene glycol. / Copolymerized polyester of dimer acid having 36 carbon atoms (molar ratio 95/5) and ethylene glycol / 1,4 butanediol (molar ratio 30/70) (T
[polyester B] is melted by separate extruders, and the melts are combined and split in a die, and then extruded on a cooling drum to be cooled, and from the A / B / A layer. Layer thickness of 32μm
(A 1 layer thickness 8 μm, B layer thickness 20 μm, A 2 layer thickness 4
to obtain an unstretched film (μm). Table 1 shows the properties of the obtained film and the laminated film with the tin plate (A 2 layer side is laminated, and A 2 layer side is laminated in all of the following Examples and Comparative Examples). The composite film obtained in this example is excellent in all the properties of adhesiveness, canning operability, heat resistance, impact resistance, and flavor resistance, and is highly practical as a metal laminating film. there were.
【００２３】比較例１ Ａ層レジンとしてポリエステルＡに替えて、平均粒径が
３μｍの球状シリカ２０００ｐｐｍを含むテレフタル酸
／イソフタル酸（モル比９５／５）とエチレングリコー
ルとからの共重合ポリエステル（Ｔｍ＝２４５℃）〔ポ
リエステルＣ〕を用いる以外実施例１と同じ方法で得た
未延伸フイルムおよびブリキ板とのラミネートフイルム
の特性を表１に示す。本比較例で得られた複合フイルム
は、接着性に劣り、金属貼合せ用フイルムとしては実用
性の低いものであった。Comparative Example 1 Instead of polyester A as the A-layer resin, a copolymerized polyester (Tm) of terephthalic acid / isophthalic acid (molar ratio 95/5) containing 2000 ppm of spherical silica having an average particle size of 3 μm and ethylene glycol was used. = 245 ° C) [Polyester C] The characteristics of the unstretched film and the laminated film with a tin plate obtained by the same method as in Example 1 are shown in Table 1. The composite film obtained in this comparative example was inferior in adhesiveness and was not practical as a metal laminating film.
【００２４】比較例２ Ａ層レジンとしてポリエステルＡに替えて、平均粒径３
μｍの球状シリカ２０００ｐｐｍを含むテレフタル酸／
イソフタル酸（モル比６７／３３）とエチレングリコー
ルとからの共重合ポリエステル（Ｔｍ＝１７０℃、メト
ラー社の融点測定装置にて測定）を用いる以外、実施例
１と同じ方法で得た未延伸フイルムおよびラミネートフ
イルムの特性を表１に示す。本比較例で得られた複合フ
イルムは、ステック温度が低く、かつ耐熱性が悪く製缶
操業特性が劣り金属貼合せ用フイルムとしては実用性の
低いものであった。Comparative Example 2 Instead of polyester A as the A layer resin, an average particle size of 3 was used.
terephthalic acid containing 2000 ppm of spherical silica of μm /
An unstretched film obtained by the same method as in Example 1 except that a copolyester (Tm = 170 ° C., measured with a melting point measuring device of METTLER CORPORATION) of isophthalic acid (molar ratio 67/33) and ethylene glycol is used The characteristics of the laminated film are shown in Table 1. The composite film obtained in this comparative example had a low stick temperature, poor heat resistance and poor can-making operation characteristics, and was not practical as a metal laminating film.
【００２５】比較例３ Ｂ層レジンのポリエステルＢのテレフタル酸／ダイマー
酸のモル比を８５／１５から１００／０に変更（Ｔｍ＝
１９５℃、Ｔｇ５０℃）〔ポリエステルＥ〕する以外、
実施例１と同じ方法で得た未延伸フイルムおよびブリキ
板とのラミネートフイルムの特性を表１に示す。本比較
例で得られたフイルムは耐衝撃性に劣り、金属貼合せ用
フイルムとしては実用性の低いものであった。Comparative Example 3 The molar ratio of terephthalic acid / dimer acid of polyester B of the layer B resin was changed from 85/15 to 100/0 (Tm =
195 ° C., Tg 50 ° C.) [Polyester E],
Table 1 shows the properties of the unstretched film obtained by the same method as in Example 1 and the laminated film with a tin plate. The film obtained in this Comparative Example was inferior in impact resistance and was not practical as a metal laminating film.
【００２６】比較例４ Ａ層レジン、Ｂ層レジン共にポリエステルＡを用いる以
外、実施例１と同じ方法で得た未延伸フイルムおよびブ
リキ板とのラミネートフイルムの特性を表１に示す。本
比較例で得られた複合フイルムは耐衝撃性に劣り、金属
貼合せ用フイルムとしては実用性の低いものであった。Comparative Example 4 Table 1 shows the properties of the unstretched film and the laminated film with the tin plate obtained by the same method as in Example 1 except that the polyester A was used for both the A layer resin and the B layer resin. The composite film obtained in this comparative example was inferior in impact resistance and was not practical as a metal laminating film.
【００２７】比較例５ Ａ層レジン、Ｂ層レジン共にポリエステルＢを用いる以
外、実施例１と同じ方法で得た未延伸フイルムおよびブ
リキ板とのラミネートフイルムの特性を表１に示す。本
比較例で得られた複合フイルムは耐フレーバー性に劣り
金属貼合せ用フイルムとしては実用性の低いものであっ
た。Comparative Example 5 Table 1 shows the characteristics of an unstretched film and a laminated film with a tin plate obtained by the same method as in Example 1 except that polyester B was used for both the A layer resin and the B layer resin. The composite film obtained in this comparative example was inferior in flavor resistance and was not practical as a metal laminating film.
【００２８】実施例２ Ａ層レジンとして、平均粒径２．５μｍの不定形シリカ
７００ｐｐｍを含むテレフタル酸／イソフタル酸（モル
比８３／１７）とエチレングリコールとからの共重合ポ
リエステル（Ｔｍ２１５℃）〔ポリエステルＦ〕を、Ｂ
層レジンとしてポリエステルＢをそれぞれ別の押出し機
で溶融させ、この溶融体をダイ内で合流および分流させ
た後、冷却ドラム上に押出して冷却させＡ／Ｂ／Ａ層か
らなる三層構成の未延伸フイルムを得た。該未延伸フイ
ルムまず縦方向に８５℃で３．３倍、次いで横方向に１
００℃で３．４倍に延伸した後、１７０℃で熱セットを
行ない総厚み３２μｍ（Ａ1 層７μｍ、Ｂ層２０μｍ、
Ａ 層５μｍ）の２軸延伸フイルムを得た。得られたフ
イルムおよびブリキ板とのラミネートフイルムの特性を
表１に示す。本実施例で得られた複合フイルムは全ての
特性に優れており、金属貼合せ用フイルムとして実用性
の高いものであった。Example 2 As the A layer resin, a copolymerized polyester (Tm 215 ° C.) of terephthalic acid / isophthalic acid (molar ratio 83/17) containing 700 ppm of amorphous silica having an average particle size of 2.5 μm and ethylene glycol [Tm 215 ° C.] Polyester F], B
Polyester B as a layer resin is melted by separate extruders, and the melts are combined and split in a die, and then extruded onto a cooling drum and cooled to form a three-layer structure of A / B / A layer. A stretched film was obtained. The unstretched film is first stretched 3.3 times at 85 ° C. in the machine direction and then 1 in the transverse direction.
After stretching 3.4 times at 00 ° C., heat setting was performed at 170 ° C. to obtain a total thickness of 32 μm (A 1 layer 7 μm, B layer 20 μm,
A biaxially stretched film of A layer 5 μm) was obtained. The properties of the obtained film and the laminated film with the tin plate are shown in Table 1. The composite film obtained in this example was excellent in all properties and was highly practical as a metal laminating film.
【００２９】比較例６ Ａ層レジンとしてポリエステルＦに替えてポリエステル
Ｃを用いる以外、実施例２と同じ方法で得た２軸延伸フ
イルムおよびブリキ板とのラミネートフイルムの特性を
表１に示す。本比較例で得られた複合フイルムは接着性
に劣り金属貼合せ用フイルムとしては実用性の低いもの
であった。Comparative Example 6 Table 1 shows the characteristics of the biaxially stretched film obtained by the same method as in Example 2 and the laminated film with the tin plate, except that polyester C was used instead of polyester F as the A layer resin. The composite film obtained in this comparative example was inferior in adhesiveness and was not practical as a metal laminating film.
【００３０】比較例７ Ａ層レジンとしてポリエステルＦに替えて平均粒径が
２．５μｍの不定形シリカ７００ｐｐｍを含むテレフタ
ル酸／イソフタル酸（モル比８０／２０）とエチレング
リコールとからの共重合ポリエステル（Ｔｍ２００℃）
〔ポリエステルＧを用いる以外、実施例２と同じ方法で
得た２軸延伸フイルムおよび金属板とのラミネートフイ
ルムの特性を表１に示す。本比較例で得られた複合フイ
ルムは、ステック温度が低く、かつ耐熱性が悪く製缶操
業性が劣り金属貼合せ用フイルムとしては実用性の低い
ものであった。Comparative Example 7 Copolymerized polyester of terephthalic acid / isophthalic acid (molar ratio 80/20) containing 700 ppm of amorphous silica having an average particle size of 2.5 μm in place of polyester F as the A layer resin, and ethylene glycol (Tm200 ° C)
[Characteristics of a biaxially stretched film obtained by the same method as in Example 2 except for using polyester G and a laminated film with a metal plate are shown in Table 1. The composite film obtained in this comparative example had a low stick temperature, poor heat resistance and poor can-making operability, and was not practical as a metal laminating film.
【００３１】比較例８ Ｂ層レジンとしてポリエステルＢに替えてポリエステル
Ｅを用いる以外、実施例２と同じ方法で得た２軸延伸フ
イルムおよびブリキ板とのラミネートフイルムの特性を
表１に示す。本比較例で得られた複合フイルムは耐衝撃
性に劣り金属貼合せ用フイルムとしては実用性の低いも
のであった。Comparative Example 8 Table 1 shows the characteristics of the biaxially stretched film obtained by the same method as in Example 2 and the laminated film with the tin plate, except that polyester E was used instead of polyester B as the B layer resin. The composite film obtained in this comparative example was inferior in impact resistance and was not practical as a metal laminating film.
【００３２】比較例９ Ａ層レジン、Ｂ層レジン共にポリエステルＦを用いる以
外、実施例２と同じ方法で得た２軸延伸フイルムおよび
ブリキ板とのラミネートフイルムの特性を表１に示す。
本比較例で得られた複合フイルムは接着性に劣り金属貼
合せ用フイルムとして実用性の低いものであった。Comparative Example 9 Table 1 shows the characteristics of the biaxially stretched film obtained by the same method as in Example 2 and the laminated film with the tin plate, except that the polyester F was used for both the A layer resin and the B layer resin.
The composite film obtained in this comparative example was inferior in adhesiveness and was not practical as a metal laminating film.
【００３３】比較例１０ Ａ層レジン、Ｂ層レジン共にポリエステルＢを用いる以
外、実施例２と同じ方法で得た２軸延伸フイルムおよび
ブリキ板とのラミネートフイルムの特性を表１に示す。
本比較例で得られた複合ポリエステルフイルムは耐フレ
ーバー性が劣り金属貼合せ用フイルムとして実用性の低
いものであった。Comparative Example 10 Table 1 shows the characteristics of the biaxially stretched film obtained by the same method as in Example 2 except that polyester B was used for both the A layer resin and the B layer resin, and the laminated film with the tin plate.
The composite polyester film obtained in this comparative example was inferior in flavor resistance and was not practical as a metal laminating film.
【００３４】実施例３ Ａ層レジンとして、平均粒径が３μの架橋ポリメチルメ
タアクリレート系のビーズ２０００ｐｐｍを含むテレフ
タル酸／イソフタル酸（モル比８５／１５）とエチレン
グリコールとからの共重合ポリエステル（Ｔｍ２２０
℃）〔ポリエステルＨ〕を、Ｂ層レジンとしてテレフタ
ル酸／セバシン酸（モル比８５／１５）とエチレングリ
コール／１．４ブタンジオール（モル比７０／３０）か
らの共重合ポリエステル（Ｔｍ２００℃、Ｔｇ２２℃）
〔ポリエステルＩ〕を用い実施例１と同じ方法方法で総
厚み３２μｍ（Ａ1 層７μｍ、Ｂ層２０μｍ、Ｃ層５μ
ｍ）の未延伸フイルムを得た。該未延伸フイルムおよび
ブリキ板とのラミネートフイルムの特性を表１に示す。
本実施例で得られた複合フイルムは全ての特性が優れて
おり金属貼合せ用フイルムとして実用性が高いものであ
った。Example 3 As the layer A resin, a copolymerized polyester (ethylene glycol) of terephthalic acid / isophthalic acid (molar ratio 85/15) containing 2000 ppm of crosslinked polymethylmethacrylate beads having an average particle size of 3 μm ( Tm220
C) [Polyester H] as a B layer resin, a copolymerized polyester (Tm 200 ° C., Tg 22) of terephthalic acid / sebacic acid (molar ratio 85/15) and ethylene glycol / 1.4 butanediol (molar ratio 70/30). ℃)
A total thickness of 32 μm (A 1 layer 7 μm, B layer 20 μm, C layer 5 μm was obtained by the same method as in Example 1 using [Polyester I].
An unstretched film of m) was obtained. The properties of the unstretched film and the laminated film with a tin plate are shown in Table 1.
The composite film obtained in this example was excellent in all properties and was highly practical as a metal laminating film.
【００３５】実施例４ Ｂ層レジンとしてポリエステルＢに替え、テレフタル酸
／ドデカンジカルボン酸（モル比９０／１０）とエチレ
ングリコール／１，４ブタンジオール（モル比２０／８
０）からの共重合ポリエステル（Ｔｍ１９５℃、Ｔｇ２
０℃）〔ポリエステルＪ〕を用いる以外、実施例２と同
じ方法で得た２軸延伸フイルムおよびブリキ板とのラミ
ネートフイルムの特性を表１に示す。本実施例で得た複
合フイルムは全ての特性に優れており実用性の高いもの
であった。Example 4 Polyester B was used as the B layer resin, and terephthalic acid / dodecanedicarboxylic acid (molar ratio 90/10) and ethylene glycol / 1,4 butanediol (molar ratio 20/8) were used.
0) copolymerized polyester (Tm 195 ° C., Tg 2
The characteristics of the biaxially stretched film obtained by the same method as in Example 2 and the laminated film with a tin plate are shown in Table 1 except that (Polyester J) is used. The composite film obtained in this example was excellent in all properties and highly practical.
【００３６】[0036]
【発明の効果】本発明の金属貼合せ用ポリエステル複合
フイルムは、三層構成よりなり、かつ、各層を構成する
ポリエステル樹脂の特性が適正な範囲に制御されている
ため、たとえば、金属板と貼合せた後に製缶加工し缶壁
部が長い金属缶を製造する用途に適用した場合に、金属
板との熱接着性や製缶加工性に優れ、かつ、耐熱性に優
れており製缶加工工程での操業性が良好で、更に、製缶
後の耐衝撃性や耐フレーバー性に優れており極めて有用
である。EFFECTS OF THE INVENTION The polyester composite film for metal laminating of the present invention has a three-layer structure and the properties of the polyester resin constituting each layer are controlled within an appropriate range. When applied to the production of metal cans with long can walls after they have been combined, they have excellent heat adhesion to metal plates and can processability, as well as excellent heat resistance, and can process It is very useful because it has good operability in the process and has excellent impact resistance and flavor resistance after can making.
【００３７】[0037]
【表１】 [Table 1]
フロントページの続き (72)発明者 太田 三郎 愛知県犬山市大字木津字前畑344番地 東 洋紡績株式会社犬山工場 (72)発明者 森 邦治 愛知県犬山市大字木津字前畑344番地 東 洋紡績株式会社犬山工場 (72)発明者 井坂 勤 大阪市北区堂島浜二丁目２番８号 東洋紡 績株式会社本社内Front page continued (72) Inventor Saburo Ota 344 Maebata, Kizu, Inuyama City, Aichi Prefecture Toyobo Co., Ltd.Inuyama Plant (72) Inventor Kuniharu Mori 344 Maebata, Kizu character, Inuyama City, Aichi Prefecture Toyobo Co., Ltd. Inuyama Factory (72) Inventor Tsutomu Isaka 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd.
Claims (1)
ステル複合フイルムであって、Ａ層は融点が２１０〜２
３０℃のポリエチレンテレフタレートとイソフタレート
との共重合体よりなり、Ｂ層は全酸成分の５０モル％以
上がテレフタル酸残基、５〜５０モル％が炭素数１０以
上の脂肪族ジカルボン酸残基を含有し、全アルコール成
分の３５〜６０モル％がエチレングリコール残基、４０
〜６５モル％が１，４ブタンジオール残基よりなるガラ
ス転移点が４０℃以下のポリエステル樹脂よりなること
を特徴とする金属貼合せ用ポリエステル複合フイルム。1. A polyester composite film comprising an A layer, a B layer and an A layer, wherein the A layer has a melting point of 210-2.
It is composed of a copolymer of polyethylene terephthalate and isophthalate at 30 ° C., and in the layer B, 50 mol% or more of all acid components are terephthalic acid residues, and 5 to 50 mol% are aliphatic dicarboxylic acid residues having 10 or more carbon atoms. Containing 35 to 60 mol% of the total alcohol component is an ethylene glycol residue, 40
A polyester composite film for metal laminating, which comprises a polyester resin having a glass transition point of 40 ° C. or lower, in which ˜65 mol% is 1,4 butanediol residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19474993A JP3304002B2 (en) | 1993-08-05 | 1993-08-05 | Polyester composite film for metal lamination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19474993A JP3304002B2 (en) | 1993-08-05 | 1993-08-05 | Polyester composite film for metal lamination |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0747649A true JPH0747649A (en) | 1995-02-21 |
| JP3304002B2 JP3304002B2 (en) | 2002-07-22 |
Family
ID=16329597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19474993A Expired - Lifetime JP3304002B2 (en) | 1993-08-05 | 1993-08-05 | Polyester composite film for metal lamination |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3304002B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002355926A (en) * | 2001-05-30 | 2002-12-10 | Mitsubishi Polyester Film Copp | Laminated polyester film for heat lamination of metal plate |
| WO2004085144A3 (en) * | 2003-03-28 | 2005-03-31 | Corus Staal Bv | A sheet material for forming applications, metal container made from such a sheet material and process for producing said sheet material |
| WO2019059322A1 (en) * | 2017-09-22 | 2019-03-28 | 三菱ケミカル株式会社 | Copolyester film |
-
1993
- 1993-08-05 JP JP19474993A patent/JP3304002B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002355926A (en) * | 2001-05-30 | 2002-12-10 | Mitsubishi Polyester Film Copp | Laminated polyester film for heat lamination of metal plate |
| WO2004085144A3 (en) * | 2003-03-28 | 2005-03-31 | Corus Staal Bv | A sheet material for forming applications, metal container made from such a sheet material and process for producing said sheet material |
| WO2019059322A1 (en) * | 2017-09-22 | 2019-03-28 | 三菱ケミカル株式会社 | Copolyester film |
| CN111108146A (en) * | 2017-09-22 | 2020-05-05 | 三菱化学株式会社 | Copolyester film |
| KR20200055071A (en) * | 2017-09-22 | 2020-05-20 | 미쯔비시 케미컬 주식회사 | Copolymer polyester film |
| JPWO2019059322A1 (en) * | 2017-09-22 | 2020-11-05 | 三菱ケミカル株式会社 | Copolymerized polyester film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3304002B2 (en) | 2002-07-22 |
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