JP3020731B2 - Metal can lid lamination coated transparent film - Google Patents
Metal can lid lamination coated transparent filmInfo
- Publication number
- JP3020731B2 JP3020731B2 JP4142703A JP14270392A JP3020731B2 JP 3020731 B2 JP3020731 B2 JP 3020731B2 JP 4142703 A JP4142703 A JP 4142703A JP 14270392 A JP14270392 A JP 14270392A JP 3020731 B2 JP3020731 B2 JP 3020731B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- film
- metal
- transparent film
- lid
- 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
- 229910052751 metal Inorganic materials 0.000 title claims description 23
- 239000002184 metal Substances 0.000 title claims description 23
- 238000003475 lamination Methods 0.000 title description 2
- 229920000728 polyester Polymers 0.000 claims description 41
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 11
- 230000007704 transition Effects 0.000 claims description 10
- 238000010030 laminating Methods 0.000 claims description 6
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000010408 film Substances 0.000 description 37
- -1 polyethylene terephthalate Polymers 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 12
- 230000001680 brushing effect Effects 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 241000519995 Stachys sylvatica Species 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002245 particle Substances 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
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 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
- 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal 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
- 241001391944 Commicarpus scandens Species 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
- 230000003796 beauty Effects 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 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
- 230000001771 impaired effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 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
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 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
- 238000005809 transesterification reaction Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 film for laminating a metal can lid, and more particularly to a transparent film for laminating a metal can lid which does not cause white spots during retorting of the 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 drinks such as coffee and tea and foods are usually subjected to a retort sterilization treatment, and a negative pressure is applied to the can during this treatment. Since this negative pressure can cause can deformation, the metal can is made of thicker tin-free steel or the like. Such a metal can is usually formed as a three-piece can composed of a can body and a canopy, or a two-piece can composed of a can body and a lid, in terms of ease of production.
【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 corrosion of metal cans, it has been attempted to bond and coat a thermoplastic resin film on the can surface instead of the conventional coating, and polyester films, especially polyethylene terephthalate films, have a good balance. Attention has been paid to its excellent properties, and several proposals based on this have been made. That is, (A) a biaxially oriented polyethylene terephthalate film is laminated on a metal plate via a low-melting polyester adhesive layer 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 material for can production (JP-A-1-92545, JP-A-2-573).
No. 39). (C) A biaxially oriented polyethylene terephthalate film having low orientation and heat set is laminated on a metal plate and used as a can-making material (JP-A-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 canopy of a three-piece can in which such a conventional polyester film is fusion-bonded and laminated, a retort sterilization treatment (usually 120 parts) is performed.
At the time of steam treatment at ~ 130 ° C), water droplets adhere to the bottom of the can, and the film or its surface layer which has melted and became amorphous during lamination is crystallized at the portion where the water droplets adhere, thereby producing white spots. . This phenomenon is called retort brushing, but is very disliked because it impairs the beauty of the product.
There is a strong demand for the development of a film that does not cause such a phenomenon, especially a film that covers the outside of the canopy.
【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 made intensive studies to develop a polyester film coated with a metal can lid that does not cause retort brushing, and as a result, have reached the present invention.
【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 comprising a polyester (I) having ethylene terephthalate as a main repeating unit and a polyester (II) having butylene terephthalate as a main repeating unit. The formation temperature is 65-120
C., a second transition point of 45 ° C. or higher and a melting point of 260 ° 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 having ethylene terephthalate as a main repeating unit, and may be a homopolymer or a copolymer.
In the case of a copolymer, the copolymer component may be an acid component or an alcohol component. As the copolymeric acid component, isophthalic acid, phthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as decanedicarboxylic acid,
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be exemplified. 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。In the present invention, the polyester (II)
Is a polyester having butylene terephthalate as a main repeating unit, and may be a homopolymer or a copolymer. The copolymer component in the copolymer may be an acid component or an alcohol component. As the copolymeric acid component, isophthalic acid, phthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as decanedicarboxylic acid,
Examples of alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and the like, and examples of the copolymerized alcohol component include aliphatic diols such as ethylene glycol and hexanediol, and alicyclic diols such as cyclohexanedimethanol. These can 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。The polyester (I) and the polyester (I
When the component (I) is a copolymer, the proportion of the copolymer component depends on the kind thereof, but as a result, it is preferable to satisfy the crystallization temperature, the secondary transition point, and the melting point described below. In addition, polyester (I) and polyester (II)
Is not particularly limited as long as it satisfies a crystallization temperature, a second transition point and a melting point, which will be described later. In terms of workability, heat resistance, impact resistance and the like, polyester (I) 8
0-30% by weight, polyester (II) 20-70% by weight
It is preferred to mix at the ratio of Particularly, 70 to 40% by weight of polyester (I) and 30 to 6% of polyester (II)
It is preferable to mix at 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 production methods. For example, a method of subjecting terephthalic acid, ethylene glycol and a copolymer component to an esterification reaction, and then subjecting the resulting reaction product to a polycondensation reaction to form a copolymerized polyester, or a transesterification reaction of dimethyl terephthalate, ethylene glycol and a copolymer component. And then subjecting the resulting reaction product to a polycondensation reaction to form a copolymerized polyester. In the production of polyester, if necessary, other additives such as lubricants, antioxidants, heat stabilizers, ultraviolet absorbers,
An antistatic agent 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。[0011] The polyester composition of the present invention includes:
Usually, a lubricant of 4 μm or less is added. The lubricant may be inorganic or organic, but inorganic is preferred. Examples of the inorganic lubricant include silica, alumina, titanium dioxide, calcium carbonate, and barium sulfate, and examples of the organic lubricant include silicone particles. If the average particle size of the lubricant is too large, coarse particles (eg, particles having a size of 10 μm or more) serve as starting points, and pinholes are formed, or in some cases, they are broken during film formation, which is not preferable. In particular, spherical silica having an average particle size of 1.5 μm or less is preferable.
【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。[0012] The metal can lid laminating coating film of the present invention comprises:
A polyester composition comprising the above polyester (I) and polyester (II), and the crystallization temperature of the polyester composition is 65 to 120 ° C., preferably 8 to 120 ° C.
0 ° C to 110 ° C, a secondary transition point of 45 ° C or higher, and a melting point of 26 ° C.
It is necessary that the temperature be 0 ° C. or less.
【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。When the crystallization temperature is lower than 65 ° C., film formation,
In particular, biaxial stretching is difficult, and it is easy to break. On the other hand, if the crystallization temperature exceeds 120 ° C., the crystallization speed of the polymer during the retort sterilization treatment is slow, and the crystals grow slowly and become large, so that white spots occur on the film and the retort brushing deteriorates. By using a film made of the polyester composition having a crystallization temperature in the range of 65 to 120 ° C., the crystallization rate of the polymer during the retort sterilization treatment is high, and a large number of fine crystals are generated in the film. (Retort brushing phenomenon) is greatly 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 secondary transition point is lower than 45 ° C.,
Moisture easily permeates the film, which may cause rust on the metal plate. Furthermore, stickiness occurs at the time of film formation, and handleability deteriorates. The appropriate second 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。With respect to the melting point, if it exceeds 260 ° C., it is unsuitable because the adhesiveness at the time of fusing and laminating the film on the metal plate is lowered. The melting point is preferably from 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。The melting point of the polyester composition is Du
The measurement is performed by raising the temperature at a rate of 20 ° C./min using a Pont Instruments 910 DSC and determining the melting peak. Further, the crystallization temperature, the secondary transition point, and the endothermic peak or inflection point were raised at a rate of 20 ° C./min,
After holding for 1 minute, the temperature is measured by quenching, raising the temperature again at a rate of 20 ° C./min, and determining the transition point, crystallization peak, endothermic peak or inflection point. The sample amount is about 15mg
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。The degree of polymerization of the polyester composition is preferably relatively low as long as it has a film-forming property, since the crystallization rate is high.
【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 in a conventional manner to form a film, and then biaxially stretched and heat-set to form a biaxially oriented film. The ratio of the biaxial orientation is preferably in a range where the plane orientation coefficient is 0.1 or more. The area stretch 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 equation. f = [(nx + ny) / 2] -nz In the above equation, f: plane orientation coefficient, nx, nY, nz:
These are the refractive index 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 each refractive index is measured with a monochromatic NaD line. The mounting liquid used was methylene iodide, and the measurement temperature was 2
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 transparent film covered with the metal can lid is formed by laminating the biaxially oriented film on a metal plate to form a lid. For example, it is possible to use a method in which a metal plate is heated, a film is pasted, rapidly cooled, and at least a surface layer (thin film portion) of the film in contact with the metal plate is melt-amorphized 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 covered on the top cover of a three-piece can or the lid of a two-piece can, and is particularly preferably laminated and covered on the outer surface of the lid.
【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 spherical silica having an average particle size 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 quenched and solidified to obtain an unstretched film. Next, the unstretched film was stretched longitudinally and transversely under the conditions shown in Table 2, and then heat-set to obtain a biaxially oriented film having a thickness of 12 μm.
Table 3 shows the properties of this film.
【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 bonded to tin-free steel (250 μm in thickness) heated at 200 ° C., cooled with water, and then a lid was formed. The retort brushing was evaluated. The results were as 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. 3 at 130 ° C for film laminated metal plate
Perform a 0 minute retort treatment and observe the change in appearance.
【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 ○ ・ ・ ・ ・ There is a slight haze in appearance × ・ ・ ・ ・ Generation of white spots (brushing) ×× ・ ・ ・ Generation of roughness in addition to white spots
【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 in Table 3, the film of the present invention contains:
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。According to the transparent film of the present invention, there is no occurrence of white spots (retort brushing) at the time of retort sterilization, no voids, and the appearance of the product is not impaired.
───────────────────────────────────────────────────── 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 (56)参考文献 特開 平1−121335(JP,A) 特開 平4−63836(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08J 5/00 - 5/24 B29B 11/16 B29B 15/08 - 15/14 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoji Murakami 3-37-19 Koyama, Sagamihara City, Kanagawa Prefecture Inside the Sagamihara Research Center, Teijin Limited (72) Inventor Masayoshi Ono 2-1-1 Uchisaiwaicho, Chiyoda-ku, Tokyo In Teijin Limited (56) References JP-A-1-121335 (JP, A) JP-A-4-63836 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08J 5 / 00-5/24 B29B 11/16 B29B 15/08-15/14
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) having ethylene terephthalate as a main repeating unit and a polyester (II) having butylene terephthalate as a main repeating unit, and having a crystallization temperature of 65. ~ 120 ° C, secondary transition point is 40
A transparent film laminated and covered with a metal can lid, which has a melting point of 260 ° C. or higher and a melting point of 260 ° C. or lower.
項1記載の金属缶蓋貼合せ被覆透明フィルム。2. The transparent film according to claim 1, wherein the outer surface of the metal can lid is laminated.
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) having ethylene terephthalate as a main repeating unit and a polyester (II) having butylene terephthalate as a main repeating unit, and having a crystallization temperature of 65. ~ 120 ° C, secondary transition point is 40
A transparent film for laminating and covering a metal can lid, wherein the transparent film has a melting point of not less than 260 ° C and a surface orientation coefficient of the film of not less than 0.1.
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 JPH05331302A (en) | 1993-12-14 |
JP3020731B2 true 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) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9307002D0 (en) * | 1993-04-02 | 1993-05-26 | Ici Plc | 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 |
DE60111318T2 (en) | 2000-09-05 | 2006-05-11 | Toyo Boseki K.K. | Polyester film, its use and laminated sheet metal made from this sheet, and metal can and metal lid made from this sheet |
KR100866471B1 (en) * | 2002-01-11 | 2008-10-31 | 토요 보세키 가부시기가이샤 | Polyester films |
CA2562146C (en) | 2004-04-01 | 2011-02-08 | Jfe Steel Corporation | Resin-coated metal sheet |
EP2799227B1 (en) | 2011-12-26 | 2019-03-06 | JFE Steel Corporation | Laminated metal sheet and food can container |
EP2839954B1 (en) | 2012-04-19 | 2020-04-29 | JFE Steel Corporation | Laminated metal sheet, and canning container for food |
JP5874659B2 (en) | 2013-02-28 | 2016-03-02 | Jfeスチール株式会社 | Laminated metal plate for 2-piece can and 2-piece laminated can body |
MY187478A (en) | 2014-12-12 | 2021-09-23 | Jfe Steel Corp | Resin-coated metal sheet for can lids |
NZ742868A (en) | 2015-12-09 | 2018-12-21 | Jfe Steel Corp | Laminated steel sheet for both-sided resin-coated container |
JP6683260B2 (en) * | 2017-05-31 | 2020-04-15 | Jfeスチール株式会社 | Resin-coated metal plate for containers |
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
Also Published As
Publication number | Publication date |
---|---|
JPH05331302A (en) | 1993-12-14 |
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