JPH05331302A - Transparent film for laminating to metal can lid - Google Patents
Transparent film for laminating to metal can lidInfo
- Publication number
- JPH05331302A JPH05331302A JP4142703A JP14270392A JPH05331302A JP H05331302 A JPH05331302 A JP H05331302A JP 4142703 A JP4142703 A JP 4142703A JP 14270392 A JP14270392 A JP 14270392A JP H05331302 A JPH05331302 A JP H05331302A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- film
- lid
- metal
- transparent 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 238000010030 laminating Methods 0.000 title description 4
- 229920000728 polyester Polymers 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 230000007704 transition Effects 0.000 claims abstract description 11
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims abstract description 5
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- -1 polyethylene terephthalate Polymers 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000001680 brushing effect Effects 0.000 description 8
- 241000519995 Stachys sylvatica Species 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000005029 tin-free steel Substances 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- 235000013361 beverage Nutrition 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属缶蓋貼合せ被覆透
明フィルムに関し、更に詳しくは金属缶レトルト時に白
斑の発生しない金属缶蓋貼合せ被覆透明フィルムに関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent cover film for sticking on a metal can lid, and more particularly to a transparent film for sticking on a metal can lid without causing white spots during retorting of a metal can.
【０００２】[0002]
【従来の技術】コーヒー、紅茶などの各種飲料及び食品
用の金属缶は、通常、レトルト殺菌処理を行うが、この
処理時に缶に陰圧がかかる。この陰圧は缶変形をもたら
すことがあるため、金属缶は厚さの厚いティンフリース
チールなどで作られる。かかる金属缶は、通常、製造の
容易さの点から、缶胴及び天地蓋からなるスリーピース
缶、又は缶胴と蓋よりなるツーピース缶として形成され
る。2. Description of the Related Art Metal cans for various beverages such as coffee and tea and foods are usually subjected to retort sterilization treatment, but a negative pressure is applied to the cans during this treatment. This negative pressure can cause deformation of the can, so metal cans are made of thick, tin-free steel or the like. Such a metal can is usually formed as a three-piece can consisting of a can body and a top lid or a two-piece can consisting of a body and a lid in view of ease of manufacturing.
【０００３】一方、金属缶の腐食を防止するために、従
来の塗装に代えて熱可塑性樹脂フィルムを缶表面に貼合
せ被覆することが試みられており、ポリエステルフィル
ム、特にポリエチレンテレフタレートフィルムがバラン
スのとれた特性を有するとして注目され、これをベース
としたいくつかの提案がされている。すなわち、 （Ａ） 二軸配向ポリエチレンテレフタレートフィルム
を低融点ポリエステルの接着層を介して金属板にラミネ
ートし、製缶材料として用いる（特開昭５６−１０４５
１号、特開平１−１９２５４６号）。 （Ｂ） 非晶性もしくは極めて低結晶性の芳香族ポリエ
ステルフィルムを金属板にラミネートし、製缶材料とし
て用いる（特開平１−９２５４５号、特開平２−５７３
３９号）。 （Ｃ） 低配向で、熱固定された二軸配向ポリエチレン
テレフタレートフィルムを金属板にラミネートし、製缶
材料として用いる（特開昭６４−２２５３０号）。On the other hand, in order to prevent the corrosion of metal cans, it has been attempted to apply a thermoplastic resin film to the surface of the can by laminating instead of conventional coating, and a polyester film, particularly a polyethylene terephthalate film, is balanced. It has attracted attention as having excellent properties, and several proposals based on it have been made. That is, (A) a biaxially oriented polyethylene terephthalate film is laminated on a metal plate via an adhesive layer of low melting point polyester and used as a can-making material (JP-A-56-1045).
No. 1, JP-A-1-192546). (B) An amorphous or extremely low crystalline aromatic polyester film is laminated on a metal plate and used as a can-making material (JP-A-1-92545, JP-A-2-573).
39). (C) A low orientation, heat-set, biaxially oriented polyethylene terephthalate film is laminated on a metal plate and used as a can-making material (Japanese Patent Laid-Open No. 64-22530).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、かかる
従来のポリエステルフィルムを融着積層させた、スリー
ピース缶の天地蓋では、レトルト殺菌処理（通常１２０
〜１３０℃のスチーム処理）時に、該缶の地蓋に水滴が
付着し、積層時に溶融して非晶状態となったフィルムま
たはその表面層が該水滴付着部分で結晶化して、白斑が
発生する。この現象は、レトルトブラッシングと呼ばれ
るが、商品の美観を害するため、非常に嫌われており、
このような現象の起こらないフィルム、中でも天地蓋外
面被覆のフィルムの開発が強く望まれている。However, in the top and bottom lid of a three-piece can in which such a conventional polyester film is fusion-bonded and laminated, a retort sterilization treatment (usually 120
At the time of steam treatment at 130 ° C.), water droplets adhere to the can lid of the can, and the film or its surface layer that is melted into an amorphous state at the time of lamination is crystallized at the water droplet adhered portion, and white spots occur. . This phenomenon is called retort brushing, but it is very disliked because it spoils the aesthetics of the product.
It is strongly desired to develop a film that does not cause such a phenomenon, especially a film that covers the outer surface of the top and bottom of the roof.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、このよう
なレトルトブラッシングが起こらない金属缶蓋貼合せ被
覆ポリエステルフィルムを開発すべく鋭意検討を重ねた
結果、本発明に到達した。[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive studies to develop a polyester film for metal can lid laminating and coating which does not cause such retort brushing.
【０００６】すなわち、本発明は、エチレンテレフタレ
ートを主たる繰返し単位とするポリエステル（Ｉ）とブ
チレンテレフタレートを主たる繰返し単位とするポリエ
ステル（II）とを配合したポリエステル組成物からな
り、該ポリエステル組成物の結晶化温度が６５〜１２０
℃、二次転移点が４５℃以上、融点が２６０℃以下であ
ることを特徴とする金属缶蓋貼合せ被覆透明フィルムで
ある。That is, the present invention comprises a polyester composition in which a polyester (I) containing ethylene terephthalate as the main repeating unit and a polyester (II) containing butylene terephthalate as the main repeating unit are blended, and a crystal of the polyester composition. Temperature of 65-120
C., a second-order transition point is 45.degree. C. or higher, and a melting point is 260.degree. C. or lower.
【０００７】本発明においてポリエステル（Ｉ）は、エ
チレンテレフタレートを主たる繰返し単位とするポリエ
ステルであり、ホモポリマーでもコポリマーでもよい。
コポリマーの場合の共重合成分は、酸成分でもアルコー
ル成分でもよい。この共重合酸成分としてはイソフタル
酸、フタル酸、ナフタレンジカルボン酸等の如き芳香族
ジカルボン酸、アジピン酸、アゼライン酸、セバシン
酸、デカンジカルボン酸等の如き脂肪族ジカルボン酸、
シクロヘキサンジカルボン酸の如き脂環族ジカルボン酸
等が例示できる。これらの中、脂肪族ジカルボン酸が好
ましい。また共重合アルコール成分としてはブタンジオ
ール、ヘキサンジオール等の如き脂肪族ジオール、シク
ロヘキサンジメタノールの如き脂環族ジオール等が例示
できる。これらは単独または二種以上を使用することが
できるが、結晶性ポリエステルであることが好ましい。In the present invention, the polyester (I) is a polyester containing ethylene terephthalate as a main repeating unit and may be a homopolymer or a copolymer.
In the case of a copolymer, the copolymerization component may be an acid component or an alcohol component. Examples of the copolymerized acid component include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid,
Examples thereof include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Of these, aliphatic dicarboxylic acids are preferred. Examples of the copolymerized alcohol component include aliphatic diols such as butanediol and hexanediol, and alicyclic diols such as cyclohexanedimethanol. These may be used alone or in combination of two or more, but are preferably crystalline polyesters.
【０００８】また、本発明においてポリエステル（II）
は、ブチレンテレフタレートを主たる繰返し単位とする
ポリエステルであり、ホモポリマーでもコポリマーでも
よい。コポリマーでの共重合成分は、酸成分でもアルコ
ール成分でもよい。この共重合酸成分としてはイソフタ
ル酸、フタル酸、ナフタレンジカルボン酸等の如き芳香
族ジカルボン酸、アジピン酸、アゼライン酸、セバシン
酸、デカンジカルボン酸等の如き脂肪族ジカルボン酸、
シクロヘキサンジカルボン酸の如き脂環族ジカルボン酸
等が例示でき、また共重合アルコール成分としてはエチ
レングリコール、ヘキサンジオール等の如き脂肪族ジオ
ール、シクロヘキサンジメタノールの如き脂環族ジオー
ル等が例示できる。これらは単独または二種以上を使用
することができる。Further, in the present invention, polyester (II)
Is a polyester containing butylene terephthalate as a main repeating unit, and may be a homopolymer or a copolymer. The copolymerization component in the copolymer may be an acid component or an alcohol component. Examples of the copolymerized acid component include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid,
Examples thereof include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and examples of the copolymerized alcohol component include aliphatic diols such as ethylene glycol and hexanediol, and alicyclic diols such as cyclohexanedimethanol. These may be used alone or in combination of two or more.
【０００９】ポリエステル（Ｉ）及びポリエステル（I
I）がコポリマーである場合の共重合成分の割合は、そ
れらの種類にもよるが、結果として、後述する結晶化温
度、二次転移点及び融点を満足するようにするのが好ま
しい。また、ポリエステル（Ｉ）とポリエステル（II）
の配合割合も後述する結晶化温度、二次転移点及び融点
を満足すれば、特に限定されるものではないが、加工
性、耐熱性、耐衝撃性等の点で、ポリエステル（Ｉ）８
０〜３０重量％、ポリエステル（II）２０〜７０重量％
の割合で配合するのが好ましい。特にポリエステル
（Ｉ）７０〜４０重量％、ポリエステル（II）３０〜６
０重量％の割合で配合するのが好ましい。Polyester (I) and polyester (I
When I) is a copolymer, the proportion of the copolymerization component depends on the kind thereof, but as a result, it is preferable that the crystallization temperature, the second-order transition point and the melting point are satisfied. Also, polyester (I) and polyester (II)
The compounding ratio is not particularly limited as long as it satisfies the crystallization temperature, the second-order transition point and the melting point described later, but in terms of processability, heat resistance, impact resistance, etc., polyester (I) 8
0-30% by weight, polyester (II) 20-70% by weight
It is preferable to mix them in a ratio of. Particularly, polyester (I) 70 to 40% by weight, polyester (II) 30 to 6
It is preferably blended in a proportion of 0% by weight.
【００１０】本発明におけるポリエステル（Ｉ）及びポ
リエステル（II）は、それぞれその製法によって限定さ
れることはない。たとえば、テレフタル酸、エチレング
リコール及び共重合成分をエステル化反応させ、次いで
得られる反応生成物を重縮合反応させて共重合ポリエス
テルとする方法、或いはジメチルテレフタレート、エチ
レングリコール及び共重合成分をエステル交換反応さ
せ、次いで得られる反応生成物を重縮合反応させて共重
合ポリエステルとする方法、が好ましく用いられる。ポ
リエステルの製造においては、必要に応じ、他の添加剤
例えば、滑剤、酸化防止剤、熱安定剤、紫外線吸収剤、
帯電防止剤等も添加することができる。The polyester (I) and the polyester (II) in the present invention are not limited by their respective production methods. For example, a method in which terephthalic acid, ethylene glycol, and a copolymerization component are subjected to an esterification reaction, and then the resulting reaction product is subjected to a polycondensation reaction to obtain a copolymerized polyester, or dimethyl terephthalate, ethylene glycol, and a copolymerization component are transesterified. Then, the resulting reaction product is subjected to a polycondensation reaction to obtain a copolyester, which is preferably used. In the production of polyester, if necessary, other additives such as lubricants, antioxidants, heat stabilizers, ultraviolet absorbers,
Antistatic agents and the like can also be added.
【００１１】本発明におけるポリエステル組成物には、
通常４μｍ以下の滑剤を添加する。この滑剤は無機、有
機系の如何を問わないが、無機系が好ましい。無機系滑
剤としては、シリカ、アルミナ、二酸化チタン、炭酸カ
ルシウム、硫酸バリウム等が例示でき、有機系滑剤とし
てはシリコーン粒子等が例示できる。滑剤の平均粒径が
大きすぎる場合は、粗大粒子（例えば１０μｍ以上の粒
子）が起点となり、ピンホールを生じたり、場合によっ
ては製膜時に破断するので、好ましくない。特に、平均
粒径１．５μｍ以下の真球状シリカが好適である。The polyester composition of the present invention includes
Usually, a lubricant of 4 μm or less is added. This lubricant may be inorganic or organic, but is preferably inorganic. Examples of the inorganic lubricant include silica, alumina, titanium dioxide, calcium carbonate, barium sulfate and the like, and examples of the organic lubricant include silicone particles and the like. If the average particle size of the lubricant is too large, coarse particles (for example, particles having a particle size of 10 μm or more) are used as a starting point to generate pinholes or, in some cases, break during film formation, which is not preferable. In particular, spherical silica having an average particle size of 1.5 μm or less is suitable.
【００１２】本発明の金属缶蓋貼合せ被覆フィルムは、
上記ポリエステル（Ｉ）とポリエステル（II）とを配合
したポリエステル組成物からなると共に、該ポリエステ
ル組成物の結晶化温度が６５〜１２０℃、好ましくは８
０〜１１０℃で、二次転移点が４５℃以上、融点が２６
０℃以下であることが必要である。The metal can lid laminating coated film of the present invention comprises:
The polyester composition comprises a polyester composition in which the polyester (I) and the polyester (II) are blended, and the crystallization temperature of the polyester composition is 65 to 120 ° C., preferably 8
0 to 110 ° C, second-order transition point of 45 ° C or higher, melting point of 26
It is necessary to be 0 ° C or lower.
【００１３】この結晶化温度が６５℃未満では、製膜、
特に二軸延伸が困難で破断し易くなる。一方、結晶化温
度が１２０℃を越えると、レトルト殺菌処理時のポリマ
ーの結晶化速度が遅く、結晶がゆっくり成長して大きく
なるため、フィルムに白斑が生じ、レトルトブラッシン
グが悪化する。結晶化温度が６５〜１２０℃の範囲内の
ポリエステル組成物からなるフィルムを用いることによ
り、レトルト殺菌処理時のポリマーの結晶化速度が速
く、フィルム中に微小結晶が多数生成し、その結果、白
斑（レトルトブラッシング現象）が大幅に改善されると
共に、製膜も容易である。If the crystallization temperature is less than 65 ° C., film formation,
In particular, biaxial stretching is difficult and it tends to break. On the other hand, when the crystallization temperature exceeds 120 ° C., the crystallization rate of the polymer during the retort sterilization treatment is slow, the crystals grow slowly and become large, and white spots appear on the film, and retort brushing deteriorates. By using a film made of a polyester composition having a crystallization temperature in the range of 65 to 120 ° C., the crystallization rate of the polymer during retort sterilization is high, and a large number of fine crystals are generated in the film, resulting in white spots. (Retort brushing phenomenon) is significantly improved, and film formation is easy.
【００１４】また、二次転移点が４５℃未満の場合は、
水分がフィルムを透過し易くなり、金属板に錆が発生す
るおそれが生ずる。更に、製膜時に粘着が発生し、取扱
い性が悪化する。二次転移点は、通常４５〜７０℃が適
当である。When the second-order transition point is lower than 45 ° C.,
Moisture easily permeates the film, which may cause rust on the metal plate. Furthermore, tackiness is generated during film formation, which deteriorates handleability. The appropriate second-order transition point is usually 45 to 70 ° C.
【００１５】融点については、２６０℃を越えると、フ
ィルムを金属板に融着積層させるときの接着性が低下す
るので不適当である。金属板への接着処理の容易さの点
から、融点は２４０〜２６０℃であることが好ましい。
また、ポリエステル組成物は、ポリエステル（II）成分
により、２０５〜２２０℃の範囲に吸熱ピーク又は変曲
点を有する。Regarding the melting point, if it exceeds 260 ° C., the adhesiveness when the film is fused and laminated on a metal plate is lowered, so that it is not suitable. The melting point is preferably 240 to 260 ° C. from the viewpoint of easy adhesion treatment to the metal plate.
Further, the polyester composition has an endothermic peak or an inflection point in the range of 205 to 220 ° C. depending on the polyester (II) component.
【００１６】ここで、ポリエステル組成物の融点は、Du
Pont Instruments 910 ＤＳＣを用い、２０℃／分の速
度で昇温して、融解ピークを求めることにより測定す
る。また、結晶化温度、二次転移点及び吸熱ピーク又は
変曲点は、２０℃／分の速度で昇温して、２９０℃で３
分間保持した後、急冷し再度２０℃／分の速度で昇温し
て転移点、結晶化ピーク及び吸熱ピーク又は変曲点を求
めることにより測定する。尚、サンプル量は約１５ｍｇ
とする。Here, the melting point of the polyester composition is Du
It is measured by using a Pont Instruments 910 DSC, heating at a rate of 20 ° C./min, and determining a melting peak. In addition, the crystallization temperature, the second-order transition point and the endothermic peak or inflection point are increased at a rate of 20 ° C./minute to reach 3 at 290 ° C.
After holding for a minute, the temperature is rapidly cooled, the temperature is raised again at a rate of 20 ° C./minute, and the transition point, the crystallization peak, the endothermic peak or the inflection point is determined, and the measurement is performed. The sample amount is about 15 mg
And
【００１７】ポリエステル組成物の重合度としては、製
膜性を有する範囲内で、比較的低いものが結晶化速度が
速く好ましい。Regarding the degree of polymerization of the polyester composition, a relatively low degree of crystallization is preferable because it has a film-forming property.
【００１８】かかるポリエステル組成物を常法により溶
融押出しダイから吐出してフィルム状に成形し、次いで
二軸延伸熱固定して二軸配向フィルムとする。二軸配向
の割合は、面配向係数が０．１以上となる範囲が好まし
い。面積延伸倍率では９倍以上が好ましい。二軸配向フ
ィルムはバランスタイプが好ましい。The polyester composition is discharged from a melt extrusion die by a conventional method to form a film, and then biaxially stretched and heat-set to obtain a biaxially oriented film. The biaxial orientation ratio is preferably in the range where the plane orientation coefficient is 0.1 or more. The area draw ratio is preferably 9 times or more. The biaxially oriented film is preferably a balanced type.
【００１９】ここで、面配向係数とは、以下の式により
定義されるものである。 ｆ＝［（ｎX ＋ｎY ）／２］−ｎZ 上記式において、ｆ：面配向係数、ｎX ，ｎY ，ｎZ ：
それぞれ、フィルムの横，縦，厚さ方向の屈折率であ
る。Here, the plane orientation coefficient is defined by the following formula. f = [(nX + nY) / 2] -nZ In the above formula, f: plane orientation coefficient, nX, nY, nZ:
These are the refractive indices in the horizontal, vertical and thickness directions of the film, respectively.
【００２０】なお、屈折率は以下のようにして測定す
る。アッベの屈折計の接眼側に偏光板アナライザーを取
り付け、単色光ＮａＤ線で、それぞれの屈折率を測定す
る。マウント液はヨウ化メチレンを用い、測定温度は２
５℃である。The refractive index is measured as follows. A polarizing plate analyzer is attached to the eyepiece side of the Abbe refractometer, and the refractive index of each is measured with a monochromatic NaD ray. Methylene iodide was used as the mount solution, and the measurement temperature was 2
It is 5 ° C.
【００２１】本発明の透明フィルムは、厚みが１２〜３
０μｍであることが好ましい。The transparent film of the present invention has a thickness of 12 to 3
It is preferably 0 μm.
【００２２】本発明の金属缶蓋貼合せ被覆透明フィルム
は前記二軸配向フィルムを金属板に貼合せて蓋を作るこ
とで形成されるが、該二軸配向フィルムを金属板に貼合
せるには、例えば、金属板を加熱しておき、フィルムを
貼合わせた後、急冷し、金属板に接するフィルムの少な
くとも表層部（薄膜部）を溶融非晶化して融着される方
法などを用いることが好ましい。The metal can lid sticking coated transparent film of the present invention is formed by sticking the biaxially oriented film to a metal plate to form a lid. To bond the biaxially oriented film to the metal plate, For example, it is possible to use a method in which a metal plate is heated, the films are pasted together, then rapidly cooled, and at least the surface layer part (thin film part) of the film in contact with the metal plate is melted to be amorphous and fused. preferable.
【００２３】本発明の透明フィルムは、スリーピース缶
の天地蓋やツーピース缶の蓋に貼合せ被覆されている
が、特に好ましくは該蓋の缶外面に貼合せ被覆されてい
る。The transparent film of the present invention is laminated and coated on the top / bottom lid of a three-piece can or the lid of a two-piece can, and particularly preferably, it is laminated and coated on the outer surface of the can.
【００２４】[0024]
【実施例】以下、実施例により本発明を更に詳細に説明
する。The present invention will be described in more detail with reference to the following examples.
【００２５】[0025]
【実施例１〜８、比較例１〜４】平均粒径１．５μｍの
真球状シリカを含有するポリエチレンテレフタレート
（ＰＥＴ）とポリブチレンテレフタレート（ＰＢＴ）と
を、表１に示す割合で配合してポリエステル組成物を調
整し、該ポリエステル組成物を２８０℃で溶融押出し、
急冷固化して未延伸フィルムを得た。次いで、この未延
伸フィルムを表２に示す条件で縦延伸、横延伸し、続い
て熱固定して厚み１２μｍの二軸配向フィルムを得た。
このフィルムの特性を表３に示す。Examples 1 to 8 and Comparative Examples 1 to 4 Polyethylene terephthalate (PET) containing true spherical silica having an average particle diameter of 1.5 μm and polybutylene terephthalate (PBT) were blended in the proportions shown in Table 1. Preparing a polyester composition, melt extruding the polyester composition at 280 ° C.,
It was rapidly cooled and solidified to obtain an unstretched film. Next, this unstretched film was longitudinally stretched and laterally stretched under the conditions shown in Table 2, and subsequently heat-set to obtain a biaxially oriented film having a thickness of 12 μm.
The characteristics of this film are shown in Table 3.
【００２６】得られた二軸配向フィルムを、２００℃に
加熱したティンフリースチール（厚み２５０μｍ）に貼
合せ、水冷した後、蓋を成形した。レトルトブラッシン
グの評価を行った。その結果は、表３に示す通りであっ
た。The obtained biaxially oriented film was attached to tin-free steel (thickness 250 μm) heated to 200 ° C., cooled with water, and then a lid was formed. The retort brushing was evaluated. The results are shown in Table 3.
【００２７】なお、レトルトブラッシングは下記の方法
で評価した。フィルム積層金属板いついて１３０℃で３
０分間のレトルト処理を行い、外観の変化を観察する。The retort brushing was evaluated by the following method. Film laminated metal plate at 3 ℃ at 130 ℃
A retort treatment is performed for 0 minutes, and a change in appearance is observed.
【００２８】◎・・・・外観変化なし ○・・・・外観にかすかにくもりあり ×・・・・白斑（ブラッシング）発生 ××・・・白斑に加え表面にざらつき発生◎ ・ ・ ・ No change in appearance ○ ・ ・ ・ ・ Slightly cloudy appearance × ・ ・ ・ ・ White spots (blushing) XX ・ ・ ・ White spots and rough surface
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【表３】 [Table 3]
【００３２】なお、表中の固有粘度ＩＶは溶媒にＯ−ク
ロロフェノールを用い、３５℃で測定を行った。The intrinsic viscosity IV in the table was measured at 35 ° C. using O-chlorophenol as a solvent.
【００３３】表３の結果から、本発明のフィルムには、
レトルトブラッシングが発生しないことがわかる。From the results shown in Table 3, the film of the present invention is
It can be seen that retort brushing does not occur.
【００３４】[0034]
【発明の効果】本発明の金属缶蓋貼合せ被覆透明フィル
ムは、レトルト殺菌処理時に白斑（レトルトブラッシン
グ）が発生せず、ボイドがなく、製品の美観を害するこ
とがない。EFFECTS OF THE INVENTION The transparent film covered with a metal can lid of the present invention does not cause white spots (retort brushing) during retort sterilization treatment, has no voids, and does not impair the aesthetic appearance of the product.
フロントページの続き (72)発明者 村上 洋二 神奈川県相模原市小山３丁目37番19号 帝 人株式会社相模原研究センター内 (72)発明者 小野 正義 東京都千代田区内幸町２丁目１番１号 帝 人株式会社内Front Page Continuation (72) Inventor Yoji Murakami 3-37-19 Oyama, Sagamihara City, Kanagawa Teijin Limited Sagamihara Research Center (72) Inventor Masayoshi Ono 2-1-1 Uchisaiwaicho, Chiyoda-ku, Tokyo Teijin Within the corporation
Claims (3)
単位とするポリエステル（Ｉ）とブチレンテレフタレー
トを主たる繰返し単位とするポリエステル（II）とを配
合したポリエステル組成物からなり、該ポリエステル組
成物の結晶化温度が６５〜１２０℃、二次転移点が４０
℃以上、融点が２６０℃以下であることを特徴とする金
属缶蓋貼合せ被覆透明フィルム。1. A polyester composition comprising a polyester (I) containing ethylene terephthalate as the main repeating unit and a polyester (II) containing butylene terephthalate as the main repeating unit, and the crystallization temperature of the polyester composition is 65. ~ 120 ℃, the second transition point is 40
A transparent film laminated with a metal can lid, which has a melting point of 260 ° C. or higher and a melting point of 260 ° C. or higher.
項１記載の金属缶蓋貼合せ被覆透明フィルム。2. The transparent film laminated with a metal can lid according to claim 1, wherein the outer surface of the metal can lid is bonded and coated.
単位とするポリエステル（Ｉ）とブチレンテレフタレー
トを主たる繰返し単位とするポリエステル（II）とを配
合したポリエステル組成物からなり、該ポリエステル組
成物の結晶化温度が６５〜１２０℃、二次転移点が４０
℃以上、融点が２６０℃以下であり、フィルムの面配向
係数が０．１以上であることを特徴とする金属缶蓋貼合
せ被覆用透明フィルム。3. A polyester composition comprising a polyester (I) containing ethylene terephthalate as a main repeating unit and a polyester (II) containing butylene terephthalate as a main repeating unit, and the crystallization temperature of the polyester composition is 65. ~ 120 ℃, the second transition point is 40
A transparent film for metal can lid sticking coating, which has a surface orientation coefficient of 0.1 or more and a melting point of 260 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4142703A JP3020731B2 (en) | 1992-06-03 | 1992-06-03 | Metal can lid lamination coated transparent film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4142703A JP3020731B2 (en) | 1992-06-03 | 1992-06-03 | Metal can lid lamination coated transparent film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05331302A true JPH05331302A (en) | 1993-12-14 |
| JP3020731B2 JP3020731B2 (en) | 2000-03-15 |
Family
ID=15321603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4142703A Expired - Fee Related JP3020731B2 (en) | 1992-06-03 | 1992-06-03 | Metal can lid lamination coated transparent film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3020731B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH073050A (en) * | 1993-04-02 | 1995-01-06 | Imperial Chem Ind Plc <Ici> | Polyester film |
| EP0664209A1 (en) * | 1994-01-24 | 1995-07-26 | TOYO KOHAN Co., Ltd | Metal sheet laminated with resin films |
| JPH09194604A (en) * | 1996-01-24 | 1997-07-29 | Unitika Ltd | Film for metal laminate |
| WO2000009593A1 (en) * | 1998-08-11 | 2000-02-24 | Toyo Kohan Co., Ltd. | Resin film having excellent processability in embossing and decorative metal sheet covered therewith |
| EP1473319A4 (en) * | 2002-01-11 | 2005-03-23 | Toyo Boseki | Polyester films |
| US7691483B2 (en) | 2004-04-01 | 2010-04-06 | Jfe Steel Corporation | Resin-coated metal sheet |
| WO2013099563A1 (en) | 2011-12-26 | 2013-07-04 | Ｊｆｅスチール株式会社 | Laminated metal plate and can container for food |
| WO2013157379A1 (en) | 2012-04-19 | 2013-10-24 | Ｊｆｅスチール株式会社 | Laminated metal sheet, and canning container for food |
| WO2014132541A1 (en) | 2013-02-28 | 2014-09-04 | Ｊｆｅスチール株式会社 | Laminated metal plate for two-piece cans and two-piece laminated can body |
| WO2017098818A1 (en) | 2015-12-09 | 2017-06-15 | Ｊｆｅスチール株式会社 | Laminated steel sheet for double face resin-coated container |
| KR20170084165A (en) | 2014-12-12 | 2017-07-19 | 제이에프이 스틸 가부시키가이샤 | Resin-coated metal sheet for can lid |
| US9931822B2 (en) | 2000-09-05 | 2018-04-03 | Toyo Boseki Kabushiki Kaisha | Polyester film, use thereof and metal laminated sheet made of said film, and metal can and metal lid made of the sheet |
| WO2018221385A1 (en) * | 2017-05-31 | 2018-12-06 | Ｊｆｅスチール株式会社 | Resin-coated metal plate for container |
| CN110920167A (en) * | 2018-09-19 | 2020-03-27 | 宝山钢铁股份有限公司 | Boiling-resistant discoloring iron-clad film and metal plate clad with same |
-
1992
- 1992-06-03 JP JP4142703A patent/JP3020731B2/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH073050A (en) * | 1993-04-02 | 1995-01-06 | Imperial Chem Ind Plc <Ici> | Polyester film |
| EP0664209A1 (en) * | 1994-01-24 | 1995-07-26 | TOYO KOHAN Co., Ltd | Metal sheet laminated with resin films |
| JPH09194604A (en) * | 1996-01-24 | 1997-07-29 | Unitika Ltd | Film for metal laminate |
| WO2000009593A1 (en) * | 1998-08-11 | 2000-02-24 | Toyo Kohan Co., Ltd. | Resin film having excellent processability in embossing and decorative metal sheet covered therewith |
| US9931822B2 (en) | 2000-09-05 | 2018-04-03 | Toyo Boseki Kabushiki Kaisha | Polyester film, use thereof and metal laminated sheet made of said film, and metal can and metal lid made of the sheet |
| EP1473319A4 (en) * | 2002-01-11 | 2005-03-23 | Toyo Boseki | Polyester films |
| US7572865B2 (en) | 2002-01-11 | 2009-08-11 | Toyo Boseki Kabushiki Kaisha | Polyester films |
| US7691483B2 (en) | 2004-04-01 | 2010-04-06 | Jfe Steel Corporation | Resin-coated metal sheet |
| WO2013099563A1 (en) | 2011-12-26 | 2013-07-04 | Ｊｆｅスチール株式会社 | Laminated metal plate and can container for food |
| KR20140135221A (en) | 2012-04-19 | 2014-11-25 | 제이에프이 스틸 가부시키가이샤 | Laminated metal sheet, and canning container for food |
| WO2013157379A1 (en) | 2012-04-19 | 2013-10-24 | Ｊｆｅスチール株式会社 | Laminated metal sheet, and canning container for food |
| WO2014132541A1 (en) | 2013-02-28 | 2014-09-04 | Ｊｆｅスチール株式会社 | Laminated metal plate for two-piece cans and two-piece laminated can body |
| CN105008232A (en) * | 2013-02-28 | 2015-10-28 | 杰富意钢铁株式会社 | Laminated metal plate for two-piece cans and two-piece laminated can body |
| US10227156B2 (en) | 2013-02-28 | 2019-03-12 | Jfe Steel Corporation | Laminated metal sheet for two-piece can and two-piece laminated can body |
| KR20170084165A (en) | 2014-12-12 | 2017-07-19 | 제이에프이 스틸 가부시키가이샤 | Resin-coated metal sheet for can lid |
| US10399303B2 (en) | 2014-12-12 | 2019-09-03 | Jfe Steel Corporation | Resin-coated metal sheet for can lids |
| WO2017098818A1 (en) | 2015-12-09 | 2017-06-15 | Ｊｆｅスチール株式会社 | Laminated steel sheet for double face resin-coated container |
| KR20180072813A (en) | 2015-12-09 | 2018-06-29 | 제이에프이 스틸 가부시키가이샤 | Laminated steel plates for double-sided resin coated containers |
| WO2018221385A1 (en) * | 2017-05-31 | 2018-12-06 | Ｊｆｅスチール株式会社 | Resin-coated metal plate for container |
| US11401092B2 (en) | 2017-05-31 | 2022-08-02 | Jfe Steel Corporation | Resin-coated metal sheet for container |
| CN110920167A (en) * | 2018-09-19 | 2020-03-27 | 宝山钢铁股份有限公司 | Boiling-resistant discoloring iron-clad film and metal plate clad with same |
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| Publication number | Publication date |
|---|---|
| JP3020731B2 (en) | 2000-03-15 |
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