JPH09239938A - Metal laminating film, laminate metal plate and metal vessel using the film - Google Patents
Metal laminating film, laminate metal plate and metal vessel using the filmInfo
- Publication number
- JPH09239938A JPH09239938A JP5356196A JP5356196A JPH09239938A JP H09239938 A JPH09239938 A JP H09239938A JP 5356196 A JP5356196 A JP 5356196A JP 5356196 A JP5356196 A JP 5356196A JP H09239938 A JPH09239938 A JP H09239938A
- Authority
- JP
- Japan
- Prior art keywords
- film
- metal
- resistant layer
- metal plate
- laminated
- 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 102
- 239000002184 metal Substances 0.000 title claims abstract description 102
- 238000010030 laminating Methods 0.000 title claims abstract description 39
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 24
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- -1 melamine compound Chemical class 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 238000004458 analytical method Methods 0.000 claims abstract description 5
- 238000001028 reflection method Methods 0.000 claims abstract description 5
- 238000005299 abrasion Methods 0.000 claims description 29
- 230000003068 static effect Effects 0.000 claims description 15
- 229920006267 polyester film Polymers 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000088 plastic resin Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 64
- 238000000034 method Methods 0.000 description 38
- 238000007639 printing Methods 0.000 description 32
- 238000001723 curing Methods 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 229910000576 Laminated steel Inorganic materials 0.000 description 14
- 238000000576 coating method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 235000014214 soft drink Nutrition 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 235000013405 beer Nutrition 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005429 filling process Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000007646 gravure printing Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 235000013324 preserved food Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920000180 alkyd Polymers 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
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 108010067216 glycyl-glycyl-glycine Proteins 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000010354 integration 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
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004826 seaming Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GZXOHHPYODFEGO-UHFFFAOYSA-N triglycine sulfate Chemical compound NCC(O)=O.NCC(O)=O.NCC(O)=O.OS(O)(=O)=O GZXOHHPYODFEGO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、清涼飲料、ビー
ル、缶詰等の金属容器の耐熱、美粧、防錆用として使用
される金属ラミネート用フィルム、当該フィルムを金属
にラミネートしたラミネート金属板、並びに当該ラミネ
ート金属板を製缶してなる金属容器に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal laminating film used for heat resistance, cosmetics and rust prevention of metal containers for soft drinks, beer, canned foods, etc., a laminated metal plate obtained by laminating the film on a metal, and The present invention relates to a metal container formed by making the laminated metal plate.
【０００２】[0002]
【従来の技術】各種清涼飲料、ビール、缶詰等の金属容
器の材料としては、主として鋼やアルミニウム等の金属
板が使用されており、その表面には内容物の表示もしく
はブランド表示等を目的として様々の印刷・着色が施さ
れる。これらの金属容器への印刷・着色法として現在実
用化されているのは、金属板を所定の寸法にスリット加
工した後、オフセット印刷等により印刷してから焼付処
理を行う方法、あるいはスリット加工後円筒状に曲げ加
工し、シーム溶接した後オフセット印刷等により印刷・
焼付けを行う方法である。そしてその後フランジ加工、
インサイドコーティングと焼付け、シーミング加工等を
行うことにより金属容器を作成している。2. Description of the Related Art Metal plates such as steel and aluminum are mainly used as materials for metal containers for various soft drinks, beer, canned foods, etc., with the purpose of displaying contents or branding on the surface thereof. Various printing and coloring are applied. Currently used as a printing / coloring method for these metal containers is a method of slitting a metal plate to a predetermined size, printing by offset printing, etc., and then baking, or after slitting. After bending into a cylindrical shape and seam welding, printing by offset printing etc.
This is a method of baking. And then flanging,
A metal container is created by performing inside coating, baking, and seaming.
【０００３】ところが金属材に直接印刷する方法では、
平板状で印刷するにしても又円筒状に成形した後印刷す
る方法を採用するにしても、グラビア印刷の如き金属製
凹版を用いた印刷法を採用することはできない。なぜな
らば、金属材は硬質であるため、その印刷面全域に金属
製凹版を均一に接触させることが極めて困難であるから
である。そのため従来はゴム版や可撓性樹脂版のような
弾力性を持った版が使用されているが、このような弾力
性凹版を用いた場合の印刷精度は悪く、鮮明な印刷が得
られ難いばかりでなく、ハーフトーン印刷や写真印刷の
ように広範囲の階調設定を必要とする複雑な印刷は困難
であり、極く単調な印刷・着色しか行われていないのが
実情である。However, in the method of printing directly on a metal material,
Neither printing on a flat plate, or printing after forming into a cylindrical shape, a printing method using a metal intaglio, such as gravure printing, cannot be used. This is because the metal material is hard and it is extremely difficult to make the metal intaglio uniformly contact the entire printing surface. Therefore, conventionally, a plate having elasticity such as a rubber plate or a flexible resin plate has been used, but when such an elastic intaglio plate is used, the printing accuracy is poor and it is difficult to obtain clear printing. Not only that, complex printing that requires a wide range of gradation settings such as halftone printing and photo printing is difficult, and in reality, only extremely monotonous printing / coloring is performed.
【０００４】更に美麗で立体感のある印刷を可能にする
には多数の塗料を用いた多重印刷が必要となるが、それ
に伴って印刷インキの乾燥・焼付けに長時間かかるた
め、この様な多重印刷を製缶工程に組込むと、印刷イン
キの乾燥・焼付けが律速となって製缶速度が極端に遅く
なるという問題も生じてくる。そのため工業規模での実
用可能な重ね印刷数にも自ずと制限があり、満足のいく
鮮明度及び美的意匠感を持った印刷は得られない。In order to achieve more beautiful and three-dimensional printing, multiple printing using a large number of paints is required. However, it takes a long time to dry and print the printing ink, and such multiple printing is required. Incorporating printing into the can manufacturing process also causes a problem in that the drying and baking of the printing ink is the rate-determining factor and the can manufacturing speed becomes extremely slow. Therefore, the number of overprints that can be practically used on an industrial scale is naturally limited, and printing with satisfactory sharpness and aesthetic design cannot be obtained.
【０００５】またスリット加工された金属板にオフセッ
ト印刷する方法も知られているが、やはりハーフトーン
印刷等が困難であり、満足のいく鮮明度と美的意匠感を
持った印刷が得られない点では、前記グラビア印刷の場
合と同様である。A method of offset printing on a slit-processed metal plate is also known, but it is still difficult to perform halftone printing and the like, and printing with satisfactory sharpness and aesthetic design cannot be obtained. Then, it is the same as the case of the gravure printing.
【０００６】上記のような問題点を解決する方法として
商標デザインを印刷したフィルムを金属板に積層する方
法が提案されている（例えば、特開平４−２９２９４２
号公報）。この方法において、該金属板用積層フィルム
としては、一般には熱可塑性樹脂フィルムが用いられて
おり、製缶時のシーム溶接や内容物封入後の熱処理やレ
トルト処理等による熱可塑性樹脂フィルムの軟化や白化
現象を抑止する目的で硬化耐熱層が設けられる。また、
該硬化耐熱層は製缶工程を始め各工程での傷付き防止や
通板性を付与する性質も有している。例えば、特開平５
−１１９７９号公報において、該硬化耐熱層は静摩擦係
数が０．２以下の特性を有することが好ましいことが提
案されている。As a method for solving the above problems, a method of laminating a film on which a trademark design is printed on a metal plate has been proposed (for example, Japanese Patent Laid-Open No. 4-292942).
Issue). In this method, as the laminated film for a metal plate, a thermoplastic resin film is generally used, and the thermoplastic resin film is softened by seam welding at the time of can making, heat treatment after enclosing the contents, retort treatment, or the like. A hardening heat-resistant layer is provided for the purpose of suppressing the whitening phenomenon. Also,
The cured heat-resistant layer also has a property of preventing scratches in each process including the can-making process and imparting plate passing property. For example, Japanese Unexamined Patent Publication
-11979 proposes that the cured heat-resistant layer preferably has a coefficient of static friction of 0.2 or less.
【０００７】確かに、硬化耐熱層の滑り性を良くするこ
とで通板性や傷付き防止性は改良されるが、傷付き防止
性においては未だ不充分であり、製缶工程や食品の充填
工程等で発生した硬化耐熱層表面の傷により、印刷フィ
ルムを用いる大きな特徴の一つである商標印刷の鮮明度
が部分的に阻害され高度の市場要求を満足させることが
できなかった。It is true that the slipperiness of the cured heat-resistant layer improves the stripability and scratch resistance, but the scratch resistance is still insufficient, and the can-making process and the filling of foods are not complete. Due to scratches on the surface of the cured heat-resistant layer generated during the process, the sharpness of trademark printing, which is one of the major features of using a printing film, is partially hindered, and it has not been possible to satisfy high-level market demands.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、上記の欠点
を解決しようとするものであり、その目的は、金属板に
ラミネートすることによって鮮明かつ美麗で高紙感を持
った美粧金属板を得ることのできる金属ラミネート用フ
ィルム、及び当該フィルムを用いたラミネート金属板、
並びに該金属板を製缶してなる金属容器を提供すること
にある。SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks, and an object thereof is to provide a decorative metal plate having a clear, beautiful and high paper feeling by laminating it on a metal plate. A metal laminating film that can be obtained, and a laminated metal plate using the film,
Another object of the present invention is to provide a metal container formed by canning the metal plate.
【０００９】[0009]
【課題を解決するための手段】本発明は、基材としての
熱可塑性樹脂フィルムと、このフィルムの少なくとも片
面上に積層された硬化耐熱層とを含有する金属ラミネー
ト用フィルムであり、硬化耐熱層が、ビスフェノールＡ
骨格を有するエポキシ樹脂とメラミン化合物との硬化反
応物からなり、かつ当該硬化耐熱層の内部全反射法によ
る表面赤外線吸収分析において、下記式（Ｉ）および
（ＩＩ）を同時に満足することを特徴とする金属ラミネ
ート用フィルムである。The present invention is a film for metal laminating containing a thermoplastic resin film as a base material and a cured heat resistant layer laminated on at least one side of the film. But bisphenol A
A cured product of an epoxy resin having a skeleton and a melamine compound, and simultaneously satisfies the following formulas (I) and (II) in a surface infrared absorption analysis of the cured heat-resistant layer by a total internal reflection method. It is a film for metal laminating.
【００１０】[0010]
【数２】 [Equation 2]
【００１１】好適な実施態様は、上記硬化耐熱層表面の
耐摩耗性指数が１．２％以下であり、硬化耐熱層の厚さ
が、０．３〜１０ｇ／ｍ2 であり、硬化耐熱層表面の静
摩擦係数が０．０５〜０．２０であり、上記熱可塑性樹
脂フィルムがポリエステル系フィルムである。また本発
明のフィルムの透明度がヘイズ値で５％以下である。In a preferred embodiment, the wear resistance index of the surface of the cured heat resistant layer is 1.2% or less, the thickness of the cured heat resistant layer is 0.3 to 10 g / m 2 , and the cured heat resistant layer is The coefficient of static friction of the surface is 0.05 to 0.20, and the thermoplastic resin film is a polyester film. The transparency of the film of the present invention is 5% or less in haze value.
【００１２】また、本発明は、金属板と、この金属板の
片面上に積層された上記の金属ラミネート用フィルムと
を含有することを特徴とするラミネート金属板であり、
上記金属ラミネート用フィルムが、熱可塑性樹脂フィル
ムの片面上に硬化耐熱層が積層された金属ラミネート用
フィルムである場合には、当該フィルムが、熱可塑性樹
脂フィルムを金属板側として金属板に積層されている。
さらに、本発明は、上記ラミネート金属板を用いて、硬
化耐熱層が外側となるように製缶してなることを特徴と
する金属容器である。Further, the present invention is a laminated metal plate comprising a metal plate and the above-mentioned metal laminating film laminated on one side of the metal plate,
When the film for metal laminating is a film for metal laminating in which a cured heat-resistant layer is laminated on one surface of a thermoplastic resin film, the film is laminated on a metal plate with the thermoplastic resin film being the metal plate side. ing.
Furthermore, the present invention is a metal container characterized in that the laminated metal plate is used to make a can so that the cured heat-resistant layer is on the outside.
【００１３】次に本発明を詳細に説明する。本発明の金
属ラミネート用フィルムは、基材としての熱可塑性樹脂
フィルムと、このフィルムの少なくとも片面に積層され
る硬化耐熱層とを有する。Next, the present invention will be described in detail. The film for metal laminating of the present invention has a thermoplastic resin film as a base material, and a cured heat resistant layer laminated on at least one surface of the film.
【００１４】熱可塑性樹脂フィルムに用いられる樹脂
は、鮮明で美麗な多重印刷を可能とし、かつラミネート
金属体の製缶加工時における湾曲加工等が容易に行える
よう、適度の可撓性を有する性質を有することが好まし
い。さらに、製缶加工時のシーム溶接や製缶後のインサ
イドコーティング処理、内容物を封入したあとで行われ
る煮沸処理、あるいはその後のレトルト処理等で受ける
熱に耐えるように、融点が１６０℃程度以上、特に１７
５℃程度以上であることが好ましい。融点が１６０℃程
度未満の場合、インサイドコーティング処理時の加熱等
によってピンホール欠陥が生じたり、フィルムが溶融も
しくは軟化収縮して平滑性を喪失したり光沢を失い、更
には該フィルムにプリスター状の凹凸やストレスクラッ
ク、デラミネーション等の欠陥を生じ易くなる。The resin used for the thermoplastic resin film has a property of moderate flexibility so that clear and beautiful multiple printing can be carried out and bending processing etc. at the time of can manufacturing processing of the laminated metal body can be easily carried out. It is preferable to have Furthermore, in order to withstand the heat received during seam welding during can making, inside coating after can making, boiling after enclosing the contents, or subsequent retort treatment, the melting point is 160 ° C or higher. , Especially 17
It is preferably about 5 ° C. or higher. If the melting point is less than about 160 ° C., pinhole defects may occur due to heating during the inside coating treatment, the film may melt or soften and shrink to lose smoothness or lose gloss, and the film may have a plister shape. Defects such as unevenness, stress cracks, and delamination are likely to occur.
【００１５】上記の条件を満足するような熱可塑性樹脂
フィルムとしては、好ましくはポリエステル樹脂、ポリ
プロピレン樹脂、ポリメチルペンテン−１、ポリカーボ
ネート、ポリイミド、ポリフェニレンスルフィド（ＰＰ
Ｓ）、ポリエーテルケトン（ＰＥＫ）、ポリエーテルエ
ーテルケトン（ＰＥＥＫ）等、あるいはこれらの各種変
性樹脂よりなるフィルムが例示される。中でも、耐熱性
と経済性とのバランスよりポリエステル系樹脂フィルム
が特に好ましい。The thermoplastic resin film satisfying the above conditions is preferably polyester resin, polypropylene resin, polymethylpentene-1, polycarbonate, polyimide, polyphenylene sulfide (PP).
Examples of the film include S), polyetherketone (PEK), polyetheretherketone (PEEK) and the like, or various modified resins thereof. Above all, a polyester resin film is particularly preferable from the viewpoint of balance between heat resistance and economy.
【００１６】熱可塑性樹脂フィルムの厚さは、好ましく
は３〜５０μｍ、より好ましくは５〜３０μｍの範囲で
ある。フィルム厚が３μｍ未満の場合、加工適性が劣
り、逆に５０μｍを超える場合、目的とした効果が飽和
し、かつ経済的に不利となり好ましくない。The thickness of the thermoplastic resin film is preferably in the range of 3 to 50 μm, more preferably 5 to 30 μm. When the film thickness is less than 3 μm, the processability is poor, and when it exceeds 50 μm, the intended effect is saturated and it is economically disadvantageous, which is not preferable.
【００１７】硬化耐熱層は、製缶工程を始め各工程での
熱可塑性樹脂フィルムの傷付き防止や通板性を付与する
役割を果たすものであり、また製缶時のシーム溶接や内
容物封入後の熱処理やレトルト処理等による熱可塑性樹
脂フィルムの軟化や白化現象を抑制する役割も果たすも
のである。The hardened heat-resistant layer plays a role of preventing scratches of the thermoplastic resin film in each process including the can-making process and imparting plateability, and also seam welding and encapsulation of contents during can-making. It also plays a role of suppressing softening and whitening of the thermoplastic resin film due to subsequent heat treatment or retort treatment.
【００１８】硬化耐熱層に用いられる材料としては、ビ
スフェノールＡ骨格を有するエポキシ樹脂とメラミン化
合物が使用される。これらの化合物を使用することによ
り、耐摩耗性に優れた硬化耐熱層を形成することができ
る。As a material used for the cured heat resistant layer, an epoxy resin having a bisphenol A skeleton and a melamine compound are used. By using these compounds, it is possible to form a cured heat resistant layer having excellent wear resistance.
【００１９】ビスフェノールＡ骨格を有するエポキシ樹
脂としては、分子量が１０００〜２００００、エポキシ
当量が５００〜１００００のいわゆる固形タイプ物が好
ましい。このエポキシ樹脂は、硬化耐熱層を塗布法によ
り形成する場合、塗布液の粘度と硬化耐熱層の特性をバ
ランスさせる点で、分子量の異なるものを２種以上併用
するのが好ましい。メラミン化合物としては、メチロー
ル化メラミンおよびアルコキシメチロールメラミンの使
用が好ましい。特に、ヘキサアルコキシメチロールメラ
ミンの使用が好ましい。上記の各化合物は単一組成であ
っても２種以上の配合品であってもかまわない。The epoxy resin having a bisphenol A skeleton is preferably a so-called solid type product having a molecular weight of 1,000 to 20,000 and an epoxy equivalent of 500 to 10,000. When the cured heat resistant layer is formed by the coating method, it is preferable to use two or more kinds of the epoxy resins having different molecular weights in order to balance the viscosity of the coating solution and the characteristics of the cured heat resistant layer. As the melamine compound, it is preferable to use methylolated melamine and alkoxymethylol melamine. Particularly, it is preferable to use hexaalkoxymethylol melamine. Each of the above compounds may have a single composition or a mixture of two or more kinds.
【００２０】上記エポキシ樹脂とメラミン化合物の配合
比は、重量比で好ましくは９１：９〜５０：５０であ
る。メラミン化合物の配合比が９未満の場合、硬化耐熱
層の硬度や耐熱性が低くなり、逆にメラミン化合物の配
合比が５０を超える場合、硬度が高くなりすぎると共に
耐摩耗性が低くなる場合があるので好ましくない。The weight ratio of the epoxy resin to the melamine compound is preferably 91: 9 to 50:50. When the blending ratio of the melamine compound is less than 9, the hardness and heat resistance of the cured heat-resistant layer may be low, and conversely, when the blending ratio of the melamine compound is more than 50, the hardness may be too high and the abrasion resistance may be low. It is not preferable because it exists.
【００２１】上記エポキシ樹脂とメラミン化合物の反応
には、従来公知の触媒を用いてもよく、例えば、ベンゼ
ンスルホン酸、ｐ−トルエンスルホン酸等のスルホン酸
化合物およびそれらの塩等が挙げられる。A conventionally known catalyst may be used in the reaction between the epoxy resin and the melamine compound, and examples thereof include sulfonic acid compounds such as benzenesulfonic acid and p-toluenesulfonic acid, and salts thereof.
【００２２】上記エポキシ樹脂とメラミン化合物以外
に、他の材料を用いてもよく、例えば、シリコン系樹
脂、メラミン系樹脂、尿素系樹脂、アクリル系樹脂、ウ
レタン系樹脂、飽和ポリエステル系樹脂、アルキッド系
樹脂、オキサゾリン系樹脂、及びそれらの各種変性樹脂
等の種々の硬化反応性樹脂が使用される。これらの硬化
反応性樹脂は単独でもよいが、２種以上併用することが
好ましい。また、耐熱性に優れていることが要求される
ので、融点もしくは分解温度が２５０℃以上、より好ま
しくは３００℃以上のものが好ましい。In addition to the above epoxy resin and melamine compound, other materials may be used. For example, silicone resin, melamine resin, urea resin, acrylic resin, urethane resin, saturated polyester resin, alkyd resin. Various curing reactive resins such as resins, oxazoline resins, and various modified resins thereof are used. These curing reactive resins may be used alone, but it is preferable to use two or more kinds in combination. Further, since it is required to have excellent heat resistance, it is preferable that the melting point or the decomposition temperature is 250 ° C. or higher, more preferably 300 ° C. or higher.
【００２３】硬化耐熱層には、その表面の滑り性を向上
させる目的で添加剤を配合することが好ましい。このよ
うな添加剤としては、例えば、シリコーン化合物、フッ
素化合物、高級炭化水素鎖を含む各種ワックス類等や、
架橋高分子からなるポリマー微粒子等の有機微粒子、シ
リカ、炭酸カルシウム等の無機微粒子が挙げられる。It is preferable to add an additive to the cured heat resistant layer for the purpose of improving the slipperiness of the surface. Examples of such additives include silicone compounds, fluorine compounds, various waxes containing higher hydrocarbon chains, and the like.
Examples thereof include organic fine particles such as polymer fine particles made of a crosslinked polymer, and inorganic fine particles such as silica and calcium carbonate.
【００２４】これらの添加剤は、硬化耐熱層の透明性が
低下しないような成分であることが好ましく、またその
配合量も透明性が低下しないような範囲であることが好
ましく、例えば硬化耐熱層組成物中、好ましくは０．０
５〜１重量％、より好ましくは０．１〜０．５重量％で
ある。この配合量が０．０５重量％未満の場合、フィル
ムの滑り性が不充分となり、逆に１重量％を超える場
合、フィルムの透明性が低下するので好ましくない。These additives are preferably components that do not reduce the transparency of the cured heat-resistant layer, and the amount of the additives added is preferably in a range that does not reduce the transparency. For example, the cured heat-resistant layer. In the composition, preferably 0.0
It is 5 to 1% by weight, and more preferably 0.1 to 0.5% by weight. If the content is less than 0.05% by weight, the slipperiness of the film will be insufficient, and conversely if it exceeds 1% by weight, the transparency of the film will decrease, which is not preferable.
【００２５】硬化耐熱層に上記の添加剤を配合すること
により、その表面の静摩擦係数が、好ましくは０．０５
〜０．２０、より好ましくは０．０６〜０．１７となっ
て滑り性が良好となる。By incorporating the above-mentioned additives into the cured heat-resistant layer, the coefficient of static friction of the surface thereof is preferably 0.05.
To 0.20, more preferably 0.06 to 0.17, and the slipperiness becomes good.
【００２６】該硬化耐熱層の厚さは、好ましくは０．３
〜１０ｇ／ｍ2 、より好ましくは０．３〜５ｇ／ｍ2 の
範囲である。厚さが０．３ｇ／ｍ2 未満の場合、熱可塑
性樹脂フィルム表面の保護効果が不充分であり、逆に、
１０ｇ／ｍ2 を超える場合、ラミネート金属板の曲げ加
工時に硬化耐熱層にクラックが生じ易くなる。The thickness of the cured heat resistant layer is preferably 0.3.
The range is from 10 to 10 g / m 2 , more preferably from 0.3 to 5 g / m 2 . If the thickness is less than 0.3 g / m 2, the effect of protecting the surface of the thermoplastic resin film is insufficient, and conversely,
If it exceeds 10 g / m 2 , cracks are likely to occur in the cured heat-resistant layer during bending of the laminated metal plate.
【００２７】硬化耐熱層表面は、耐摩耗性が良好である
ことが必要であり、本発明では、硬化耐熱層の内部全反
射法による表面赤外線吸収分析において下記式（Ｉ）お
よび（ＩＩ）を満足する。The surface of the cured heat-resistant layer must have good wear resistance. In the present invention, the following formulas (I) and (II) are used in the surface infrared absorption analysis of the cured heat-resistant layer by the total internal reflection method. Be satisfied.
【００２８】[0028]
【数３】 (Equation 3)
【００２９】ここで、（Ｉ）式は、前記した必須の構成
成分であるエポキシ樹脂とメラミン化合物との組成比の
尺度である。式（Ｉ）の値が０．３未満である場合、メ
ラミン化合物の配合量が少なすぎて、硬化耐熱層の硬度
や耐熱性が低くなり、逆に３．０を超える場合、メラミ
ン樹脂の配合量が多すぎて、硬度が高くなりすぎると共
に耐摩耗性が低くなる。式（Ｉ）の値は、好ましくは
０．４〜２．５、より好ましくは０．５〜２．５、特に
好ましくは０．６〜２．４である。Here, the formula (I) is a measure of the composition ratio between the epoxy resin and the melamine compound, which are the above-mentioned essential constituents. When the value of the formula (I) is less than 0.3, the amount of the melamine compound compounded is too small and the hardness and heat resistance of the cured heat-resistant layer become low. If the amount is too large, the hardness becomes too high and the abrasion resistance becomes low. The value of formula (I) is preferably 0.4 to 2.5, more preferably 0.5 to 2.5, and particularly preferably 0.6 to 2.4.
【００３０】式（ＩＩ）は、得られる硬化耐熱層の硬化
度の尺度である。この硬化度は、エポキシ樹脂とメラミ
ン化合物の組成比と、エポキシ樹脂中のエポキシ環の硬
化反応後残存量の支配を受けることを見い出して求めた
ものである。即ち、下記式により求めたものである。Formula (II) is a measure of the degree of cure of the resulting cured heat resistant layer. This degree of curing is determined by finding that it is governed by the composition ratio of the epoxy resin and the melamine compound and the residual amount of the epoxy ring in the epoxy resin after the curing reaction. That is, it is obtained by the following formula.
【００３１】[0031]
【数４】 (Equation 4)
【００３２】式（ＩＩ）の値が０．２５を超える場合、
エポキシ樹脂中のエポキシ環の硬化反応後残存量が多く
硬化度が低いので、得られる硬化耐熱層の耐摩耗性が劣
る。式（ＩＩ）の値は、好ましくは０．２３以下、より
好ましくは０．２０以下である。When the value of the formula (II) exceeds 0.25,
Since the amount of the epoxy ring remaining in the epoxy resin after the curing reaction is large and the degree of curing is low, the resulting cured heat-resistant layer has poor wear resistance. The value of the formula (II) is preferably 0.23 or less, more preferably 0.20 or less.
【００３３】上記式（Ｉ）および（ＩＩ）を同時に満足
するような硬化耐熱層を得るためには、エポキシ樹脂と
メラミン化合物の組成比と後述する形成方法の最適化に
より達成できる。In order to obtain a cured heat resistant layer which simultaneously satisfies the above formulas (I) and (II), the composition ratio of the epoxy resin and the melamine compound and the formation method described later can be optimized.
【００３４】硬化耐熱層表面の耐摩耗性がさらに良好と
なるためには、後述する耐摩耗性指数が、好ましくは
１．２％以下、より好ましくは１．０％以下、特に好ま
しくは０．８％以下である。耐摩耗性指数が１．２％を
超える場合、硬化耐熱層表面の耐摩耗性が悪く、ラミネ
ート金属板の製缶工程や製缶後の食品の充填工程で硬化
耐熱層表面が傷付き、商標印刷の鮮明性が悪化して商品
価値が低下する。In order to further improve the wear resistance of the surface of the cured heat-resistant layer, the wear resistance index described below is preferably 1.2% or less, more preferably 1.0% or less, and particularly preferably 0. It is 8% or less. If the abrasion resistance index exceeds 1.2%, the abrasion resistance of the surface of the cured heat-resistant layer is poor, and the surface of the cured heat-resistant layer is scratched during the can manufacturing process for laminated metal plates and the food filling process after can manufacturing. The clarity of printing deteriorates and the commercial value decreases.
【００３５】本発明においては、耐摩耗性指数は次のよ
うにして測定される。ダンボール（ＪＩＳ Ｚ １５１
６規定「両面段ボール３種」）の板目表紙の上に硬化耐
熱層側を表面として本発明のフィルムをセロテープで接
着し固定化する。一方、２ポンドハンマーの球状頭部側
にガーゼを１６枚重ねて固定し、このガーゼ部をメチル
エチルケトンに１０秒間浸漬後、過剰のメチルエチルケ
トンを除去する。次いで、ダンボールに固定したフィル
ム表面に、上記２ポンドハンマーを定規で位置固定し、
柄の端を握って１６０ｍｍの巾を２秒／１往復の速度で
１００回往復させる。フィルムのハンマーを往復させた
部分とそうでない部分のヘイズを測定し、その差を耐摩
耗性の尺度とする。測定場所を変えて２０回測定した平
均値を耐摩耗性指数とする。In the present invention, the abrasion resistance index is measured as follows. Cardboard (JIS Z 151
The film of the present invention is adhered and fixed with cellophane tape on the surface of the cured heat-resistant layer as a surface on a 6-sheet "3 types of double-faced corrugated board"). On the other hand, 16 pieces of gauze are superposed and fixed on the spherical head side of a 2-pound hammer, and the gauze portion is immersed in methyl ethyl ketone for 10 seconds, and then excess methyl ethyl ketone is removed. Then, position the 2 pound hammer with a ruler on the film surface fixed to the cardboard,
Grasp the end of the handle and reciprocate the width of 160 mm 100 times at a speed of 2 seconds / 1 reciprocation. The haze of the part where the hammer was reciprocated and the part where it was not moved was measured, and the difference was used as a measure of abrasion resistance. The abrasion resistance index is an average value measured 20 times at different measurement locations.
【００３６】本発明において、耐摩耗性指数を１．２％
以下とする手段は特に限定されないが、硬化耐熱層に用
いられる硬化反応性樹脂の種類およびその配合量、硬化
耐熱層の厚さおよび後述する硬化耐熱層の形成方法によ
り調整する方法が好ましい。In the present invention, the abrasion resistance index is 1.2%.
The following means is not particularly limited, but a method of adjusting by the type and amount of the curing reactive resin used in the cured heat resistant layer, the thickness of the cured heat resistant layer and the method for forming the cured heat resistant layer described later is preferable.
【００３７】硬化耐熱層の形成方法も特に限定されない
が、硬化性樹脂を溶剤に溶解し、熱可塑性樹脂フィルム
に塗布して乾燥・硬化を行う、いわゆる塗布法が好まし
い実施態様である。また、硬化方法は熱で行うことが好
ましい。電子線、紫外線、Ｘ線等の他のエネルギーで硬
化反応する成分を配合した場合には、配合成分に応じた
硬化方法が採用される。The method for forming the cured heat-resistant layer is not particularly limited, but a so-called coating method, in which a curable resin is dissolved in a solvent, and the thermoplastic resin film is dried and cured, is a preferred embodiment. Further, the curing method is preferably performed by heat. When a component that undergoes a curing reaction with other energy such as electron beams, ultraviolet rays, and X-rays is blended, a curing method according to the blending component is adopted.
【００３８】塗布法でかつ熱硬化法で実施する場合は、
乾燥条件や硬化条件により、耐摩耗性が大きく影響を受
ける。このような方法の場合は、乾燥工程と硬化工程よ
りなる２段加熱方式が好ましい。硬化工程は、高温かつ
効率的な加熱が必要であり、赤外線加熱が好ましい。２
段加熱方式の場合の各工程の温度は、硬化性樹脂の組
成、乾燥工程や硬化工程の炉長等により適宜選択すべき
ものであるが、乾燥工程は、好ましくは１４０℃以下、
より好ましくは１３５℃以下で行い、かつ硬化工程は好
ましくは１４０℃以上、より好ましくは１４５℃以上で
行う。乾燥温度が１４０℃を超える場合、塗膜が不均一
となり硬化度がむしろ低くなり、また硬化温度が１４０
℃未満である場合、得られる硬化耐熱層の硬化度が不充
分となり、硬化耐熱層表面の耐摩耗性が劣る場合があ
る。When carrying out by a coating method and a thermosetting method,
Abrasion resistance is greatly affected by drying conditions and curing conditions. In the case of such a method, a two-step heating method including a drying step and a curing step is preferable. The curing step requires high temperature and efficient heating, and infrared heating is preferable. Two
The temperature of each step in the case of the step heating method should be appropriately selected depending on the composition of the curable resin, the drying step and the furnace length of the curing step, etc., but the drying step is preferably 140 ° C. or lower,
More preferably, it is performed at 135 ° C. or lower, and the curing step is preferably performed at 140 ° C. or higher, more preferably 145 ° C. or higher. If the drying temperature is higher than 140 ° C, the coating film will be non-uniform and the degree of cure will be rather low.
If the temperature is lower than 0 ° C, the resulting cured heat-resistant layer may have an insufficient degree of curing, resulting in poor wear resistance of the surface of the cured heat-resistant layer.
【００３９】商標印刷の鮮明度及び美的意匠感を高める
ために、本発明の金属ラミネート用フィルムの透明度
は、ヘイズ値で好ましくは５％以下、より好ましくは
４．５％以下である。In order to improve the sharpness and aesthetic design of trademark printing, the transparency of the metal laminating film of the present invention is preferably 5% or less, more preferably 4.5% or less in terms of haze value.
【００４０】このようにして得られた金属ラミネート用
フィルムに、印刷が行われる。印刷方法としては、特に
限定されないが、例えばグラビア印刷等が採用される。
本発明の金属ラミネート用フィルムが、熱可塑性樹脂フ
ィルムの片面のみに硬化耐熱層が形成されている場合に
は、熱可塑性樹脂フィルム側に印刷を行うのが好まし
い。Printing is performed on the metal laminating film thus obtained. The printing method is not particularly limited, but, for example, gravure printing or the like is adopted.
When the film for metal lamination of the present invention has a cured heat-resistant layer formed on only one surface of the thermoplastic resin film, it is preferable to print on the thermoplastic resin film side.
【００４１】印刷された金属ラミネート用フィルムは、
熱可塑性樹脂フィルムの片面のみに硬化耐熱層が形成さ
れている場合には、印刷された熱可塑性樹脂フィルムを
金属板側として金属板へラミネートされる。熱可塑性樹
脂フィルムの両面に硬化耐熱層が形成されている場合に
は、印刷された耐熱硬化層を金属板側として金属板へラ
ミネートされる。The printed metal laminating film is
When the cured heat-resistant layer is formed only on one side of the thermoplastic resin film, the printed thermoplastic resin film is laminated on the metal plate with the metal plate side. When the cured heat resistant layer is formed on both sides of the thermoplastic resin film, the printed heat resistant cured layer is laminated on the metal plate with the metal plate side.
【００４２】そのラミネート方法は、特に限定されるも
のではなく、ドライラミネート法やサーマルラミネート
法が好適に使用できる。金属板と強固に接合し、かつ製
缶時のシーム溶接やその後の煮沸あるいはレトルト処理
等によって接合力を失うことがないように、硬化性樹脂
を介してラミネートすることが好ましい。このような硬
化性樹脂としては、例えば、エポキシ樹脂、ポリウレタ
ン樹脂、ポリエステル樹脂、ポリエステルポリウレタン
樹脂等、あるいはこれらの各種変性樹脂を挙げることが
でき、これらは通常ラミネート用フィルムに塗布し、部
分硬化状態として金属板と合体し、ラミネート時に完全
硬化させるようにするのが良い。The laminating method is not particularly limited, and a dry laminating method or a thermal laminating method can be preferably used. It is preferable to laminate with a curable resin so that it is firmly bonded to a metal plate and that the bonding strength is not lost by seam welding during can making and subsequent boiling or retort treatment. Examples of such a curable resin include epoxy resin, polyurethane resin, polyester resin, polyester polyurethane resin, and various modified resins thereof, which are usually applied to a laminating film and partially cured. It is advisable to combine it with a metal plate so that it is completely cured during lamination.
【００４３】このようにして得られたラミネート金属板
は、美粧されかつ表面の耐摩耗性に優れており、このラ
ミネート金属板をそのままの状態で様々のパネル材や美
粧外板材等として使用できるばかりでなく、これを硬化
耐熱層を外側として常法に従って所望の形状に製缶する
と、極めて美麗で意匠性の高い金属容器を得ることがで
きるので、例えば清涼飲料、ビール、缶詰の如き金属缶
材として好適に用いることができる。The laminated metal plate thus obtained is beautiful and has excellent surface abrasion resistance, and the laminated metal plate can be used as it is as various panel materials, cosmetic outer plate materials and the like. However, when a can is formed into a desired shape according to a conventional method with the cured heat-resistant layer as the outer side, a very beautiful and highly designed metal container can be obtained, and therefore, a metal can material such as a soft drink, beer, and a canned product can be obtained. Can be suitably used as.
【００４４】[0044]
【実施例】次に実施例を挙げて本発明をより具体的に説
明するが、本発明はもとより下記実施によって制限を受
けるものではなく、前述の趣旨を逸脱しない限度におい
て変更して実施することはいずれも本発明の技術的範囲
に含まれる。実施例中、単に部とあるのは重量部を表
し、％とあるのは重量％を示す。各測定項目は以下の方
法に従った。EXAMPLES Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following embodiments, and the present invention may be modified within the scope of the above-mentioned gist. Both are included in the technical scope of the present invention. In the examples, “parts” means “parts by weight”, and “%” means “% by weight”. Each measurement item followed the following method.
【００４５】１．硬化耐熱層の内部全反射法による表面
赤外吸収分析 ＦＴ−ＩＲ ＡＴＲ法により硬化耐熱層のＩＲスペクト
ルを下記条件で測定し、１５５０cm-1付近に現れるトリ
アジン環の吸収の吸光度、９１０cm-1付近に現れるエポ
キシ環の吸収の吸光度および８３０cm-1付近に現れるビ
スフェノールＡ骨格の吸収の吸光度を測り、式（Ｉ）お
よび式（ＩＩ）の値を求めた。 測定条件 装置 ：ＦＴＳ−１５／８０（ＢＩＯ−ＲＡＤ製ＦＴ
−ＩＲ） 光源 ：グローバー 検出器 ：ＤＴＧＳ（Deutrium Triglycine Sulfate) ビームスプリッター：Ｇｅコート／ＫＢｒ 分解能 ：８cm-1 積算回数：３００回 アポダイゼーション：三角形 位相補正：Mertz 法 ゼロフィリング因子：２ 付属装置：ＡＴＲ測定用付属装置（Harrick 製） ＩＲＥ ：Ｇｅ（５０×５×２mm )、カット角４５°1. The surface infrared absorption analysis FT-IR ATR method by total internal reflection method of the cured heat-resistant layer and IR spectrum of the cured heat-resistant layer under the following conditions, the absorbance of the absorption of a triazine ring appearing near 1550 cm -1, 910 cm around -1 The absorbance of the epoxy ring appearing in Fig. 3 and the absorbance of the bisphenol A skeleton appearing near 830 cm -1 were measured to obtain the values of formula (I) and formula (II). Measurement condition Device: FTS-15 / 80 (FT manufactured by BIO-RAD
-IR) Light source: Grover Detector: DTGS (Deutrium Triglycine Sulfate) Beam splitter: Ge coat / KBr Resolution: 8 cm -1 Integration number: 300 times Apodization: Triangle Phase correction: Mertz method Zero filling factor: 2 Auxiliary device: ATR measurement Accessory device (made by Harrick) IRE: Ge (50 × 5 × 2mm), cutting angle 45 °
【００４６】２．耐摩耗性評価法 ダンボール（ＪＩＳ Ｚ １５１６規定「両面段ボール
３種」）の板目表紙の上に硬化耐熱層側を表面とし、サ
ンプルフィルムをセロテープで接着し固定化する。一
方、２ポンドハンマーの球状頭部側にガーゼを１６枚重
ねて固定をする。該ガーゼを固定したハンマーのガーゼ
取付部をメチルエチルケトンに１０秒間浸漬する。浸漬
を止めメチルエチルケトンを自然流下させた後、ハンマ
ーを２回垂直方向に大きく振り過剰のメチルエチルケト
ンを振り切る。ダンボールに固定したサンプルの表面
に、上記２ポンドハンマーを定規で位置固定し、柄の端
を握って１６０ｍｍの巾を２秒／１往復の速度で１００
回往復させる。加重はハンマーの自重のみとして力はハ
ンマーの往復のみにかける。ガーゼは毎回交換をする。
試料のハンマーを往復させた部分の傷付き度をフィルム
のヘイズを測定して判定をする。すなわち、往復させた
部分とそうでない部分とのヘイズ値（％）の差を耐摩耗
性指数とした。耐摩耗性指数が小さい程、耐摩耗性は良
好である。ヘイズ値は、６ｍｍφの面積で東洋精器製の
ヘイズメーターで測定をした。測定場所をずらして２０
回測定した測定値の平均値で表示した。数値が小さい
程、耐摩耗性は良好である。2. Abrasion resistance evaluation method A sample heat-resistant layer side is used as a surface on a corrugated cardboard (JIS Z 1516 standard “double-sided corrugated cardboard type 3”) sheet surface, and a sample film is adhered and fixed with cellophane tape. On the other hand, 16 pieces of gauze are piled up and fixed on the spherical head side of the 2 pound hammer. The gauze mounting part of the hammer to which the gauze is fixed is immersed in methyl ethyl ketone for 10 seconds. After stopping the immersion and allowing the methyl ethyl ketone to flow down naturally, shake the hammer twice in the vertical direction and shake off the excess methyl ethyl ketone. On the surface of the sample fixed on the corrugated cardboard, position the 2 pound hammer with a ruler, hold the end of the handle, and hold a width of 160 mm for 100 seconds at a speed of 2 seconds / reciprocation.
Make a round trip twice. The weight is applied only to the weight of the hammer, and the force is applied only to the reciprocation of the hammer. Replace the gauze every time.
The haze of the film is measured to determine the degree of scratches on the part of the sample where the hammer is reciprocated. That is, the difference in haze value (%) between the reciprocated portion and the other portion was defined as the abrasion resistance index. The smaller the abrasion resistance index, the better the abrasion resistance. The haze value was measured with a haze meter manufactured by Toyo Seiki in an area of 6 mmφ. Shift the measurement location to 20
The average value of the measured values measured twice was displayed. The smaller the value, the better the abrasion resistance.
【００４７】３．フィルムの静摩擦係数 硬化耐熱層表面同士の静摩擦係数をＡＳＴＭ−Ｄ−１８
９４に準じて測定した。 ４．フィルムの透明度 ６ｍｍφの面積で東洋精器製のヘイズメーターでヘイズ
値を測定し、これを透明性の尺度とした。数値が小さい
程、透明性が良好である。3. Static friction coefficient of film The static friction coefficient between the surfaces of the cured heat-resistant layers is determined by ASTM-D-18.
It measured according to 94. 4. Haze value was measured with a haze meter manufactured by Toyo Seiki in an area of 6 mmφ of transparency of the film, and this was used as a measure of transparency. The smaller the value, the better the transparency.
【００４８】実施例１ 極限粘度が０．８０であるポリエチレンテレフタレート
（ガラス転移温度：６５℃）とポリエチレンテレフタレ
ート−ポリテトラメチレングリコールエーテルブロック
共重合体とを、ポリテトラメチレングリコールエーテル
成分としての含有量が４重量％となるように配合し、成
膜次いで２軸延伸して厚さ１２μｍのフィルム（２００
℃における収縮応力：０．５ｋｇ／ｍｍ2 ）を得た。こ
れとは別に、ビスフェノールＡ型エポキシ樹脂５０部、
ポリエステル樹脂３０部、ヘキサメトキシメチロール化
メラミン２０部、ｐ−トルエンスルホン酸０．５部、シ
リコーン樹脂１部、ポリエチレンワックス０．２部およ
びフッ素樹脂０．２部よりなる硬化耐熱樹脂組成物をメ
チルエチルケトン／エチルアセテート／トルエンを主成
分とした溶剤に溶解し塗布液を調製した。この塗布液を
上記フィルムの片面上にグラビアロール法で乾燥後の厚
みで１ｇ／ｍ2 となるように塗布し、乾燥温度１００
℃、硬化温度１７５℃で処理し、硬化耐熱層を形成して
金属ラミネート用フィルムを得た。乾燥工程後の残留溶
剤は９５ｐｐｍであった。乾燥工程は熱風で硬化工程は
赤外線で加熱を行った。得られたフィルムの式（Ｉ）お
よび式（ＩＩ）の値はそれぞれ１．２および０．１４で
あり、耐摩耗性指数は０．１％、静摩擦係数は０．１１
であり、滑り性および耐摩耗性は共に優れたものであっ
た。また透明度はヘイズ値で３．６％であった。Example 1 Content of polyethylene terephthalate (glass transition temperature: 65 ° C.) having an intrinsic viscosity of 0.80 and polyethylene terephthalate-polytetramethylene glycol ether block copolymer as a polytetramethylene glycol ether component Of 4% by weight, a film formed and biaxially stretched to form a film having a thickness of 12 μm (200
Shrinkage stress at 0 ° C .: 0.5 kg / mm 2 ) was obtained. Separately, 50 parts of bisphenol A type epoxy resin,
A cured heat-resistant resin composition comprising 30 parts of a polyester resin, 20 parts of hexamethoxymethylolated melamine, 0.5 part of p-toluenesulfonic acid, 1 part of a silicone resin, 0.2 parts of a polyethylene wax and 0.2 part of a fluororesin was added to methyl ethyl ketone. / Ethyl acetate / toluene was dissolved in a solvent as a main component to prepare a coating liquid. This coating solution was applied onto one side of the above film by a gravure roll method so that the thickness after drying was 1 g / m 2, and the drying temperature was 100.
C., and a curing temperature of 175.degree. C. to form a cured heat resistant layer to obtain a metal laminating film. The residual solvent after the drying step was 95 ppm. The drying process was heated with hot air, and the curing process was heated with infrared light. The values of the formula (I) and the formula (II) of the obtained film are 1.2 and 0.14, respectively, the abrasion resistance index is 0.1%, and the static friction coefficient is 0.11.
And both the slip property and the wear resistance were excellent. Further, the haze value of the transparency was 3.6%.
【００４９】このフィルムの熱可塑性樹脂フィルム側に
コロナ処理を施し、印刷を行った後、この印刷面上に接
着剤（東洋インキ社製のポリウレタン系接着剤「アドコ
ート」及び硬化剤の混合物）を固形分換算で４ｇ／ｍ2
コーティングし、乾燥し４０℃で２４時間エージング
し、次いで接着剤層を介して、フィルムを脱脂処理した
冷延鋼板上にサーマルラミネート法によってラミネート
して、ラミネート鋼板を得た。Corona treatment was applied to the thermoplastic resin film side of this film, printing was performed, and then an adhesive (a mixture of a polyurethane adhesive "Adcoat" and a curing agent manufactured by Toyo Ink Co., Ltd.) was applied on the printed surface. 4 g / m 2 in terms of solid content
After coating, drying and aging at 40 ° C. for 24 hours, the film was laminated on the degreased cold rolled steel sheet through the adhesive layer by the thermal lamination method to obtain a laminated steel sheet.
【００５０】このラミネート鋼板を用いて常法により清
涼飲料用の金属容器を作成したところ、得られた容器ボ
デー部のラミネート面は鮮明で光沢に富んだ美しい外観
を有しており、優れた光沢を有するものであった。When a metal container for soft drinks was prepared by using this laminated steel sheet by a conventional method, the laminated surface of the body part of the container thus obtained had a clear and glossy beautiful appearance and had an excellent gloss. It was something that had.
【００５１】尚上記製缶工程では、ラミネート用フィル
ムに２７０℃以上の熱が加わり、それによって該フィル
ムのポリエチレンテレフタレート層は若干軟化している
ものと思われるが、エポキシ変性ウレア樹脂よりなる硬
化耐熱層によって保護されているため収縮変形や光沢の
低下、及び印刷インキ層の変質は殆ど認められなかっ
た。またこの容器を１００℃の熱水及び１２５℃の水蒸
気で処理したが、ラミネート用フィルム層の白濁や熱劣
化は全く認められず、美しい外観が損なわれることはな
かった。In the above can making process, it is considered that the polyethylene terephthalate layer of the film is slightly softened by the heat of 270 ° C. or more applied to the laminating film. Since it was protected by the layer, shrinkage deformation, deterioration of gloss, and deterioration of the printing ink layer were hardly observed. The container was treated with hot water at 100 ° C. and steam at 125 ° C., but no turbidity or thermal deterioration of the laminating film layer was observed, and the beautiful appearance was not impaired.
【００５２】また、製缶工程でのラミネート鋼板の枚様
片の移送時のこすれや、製缶工程あるいは食品充填工程
での缶同志の接触によるこすれ等によるラミネートフィ
ルム表面の傷発生はなく鮮明で光沢に富んだ美しい外観
を有しており、実用性の高いものであった。In addition, there is no scratch on the surface of the laminated film due to rubbing during transfer of the laminated steel sheet pieces in the can making process, or rubbing due to contact between cans in the can making process or food filling process, and there is no visible damage. It had a beautiful glossy appearance and was highly practical.
【００５３】比較例１ 実施例１において、乾燥温度を８０℃、硬化温度を１３
５℃としたこと以外は実施例１と同じ方法で金属ラミネ
ート用フィルムを得た。乾燥後の残留溶剤量は６００ｐ
ｐｍであった。得られたフィルムの式（Ｉ）および式
（ＩＩ）の値はそれぞれ１．２および０．２７であり、
耐摩耗性指数は１．５％、静摩擦係数は０．１１であ
り、滑り性は良好であるが耐摩耗性の劣るものであっ
た。また透明度はヘイズ値で３．５％であった。このフ
ィルムを用い、実施例１と同じ方法でラミネート鋼板及
び金属容器を得た。得られたラミネート鋼板及び金属容
器は、ラミネートされたフィルムの硬化耐熱層表面の耐
摩耗性が劣り、製缶工程あるいは食品充填工程でラミネ
ートフィルム表面が部分的に傷付いて美粧性が低下し、
商品価値の低いものであった。Comparative Example 1 In Example 1, the drying temperature was 80 ° C. and the curing temperature was 13
A metal laminating film was obtained in the same manner as in Example 1 except that the temperature was 5 ° C. The amount of residual solvent after drying is 600p
pm. The values of the formula (I) and the formula (II) of the obtained film are 1.2 and 0.27, respectively,
The abrasion resistance index was 1.5% and the static friction coefficient was 0.11, and the sliding property was good, but the abrasion resistance was poor. The transparency was 3.5% in haze value. Using this film, a laminated steel plate and a metal container were obtained in the same manner as in Example 1. The resulting laminated steel sheet and metal container have poor wear resistance of the cured heat-resistant layer surface of the laminated film, and the laminated film surface is partially scratched in the can making process or the food filling process to reduce the cosmetic appearance,
It was of low commercial value.
【００５４】比較例２ 実施例１において、ビスフェノールＡ型エポキシ樹脂の
配合量を６５部、ヘキサメトキシメチロール化メラミン
の配合量を５部に変更したこと以外は実施例１と同じ方
法で金属ラミネート用フィルムを得た。得られたフィル
ムの式（Ｉ）および式（ＩＩ）の値はそれぞれ０．２５
および０．０５であり、耐摩耗性指数は１．８％、静摩
擦係数は０．１１であり、滑り性は良好であるが耐摩耗
性の劣るものであった。また透明度はヘイズ値で３．６
％であった。このフィルムを用い、実施例１と同じ方法
でラミネート鋼板及び金属容器を得た。得られたラミネ
ート鋼板及び金属容器は、ラミネートフィルムの硬化耐
熱層表面の耐摩耗性が劣り、比較例１と同様に実用性の
劣るものであった。Comparative Example 2 A metal laminate was prepared in the same manner as in Example 1 except that the amount of bisphenol A type epoxy resin was changed to 65 parts and the amount of hexamethoxymethylolated melamine was changed to 5 parts. I got a film. The value of the formula (I) and the formula (II) of the obtained film are respectively 0.25.
And 0.05, the abrasion resistance index was 1.8%, the static friction coefficient was 0.11, and the sliding property was good, but the abrasion resistance was poor. The haze value of the transparency is 3.6.
%Met. Using this film, a laminated steel plate and a metal container were obtained in the same manner as in Example 1. The obtained laminated steel sheet and metal container had poor wear resistance on the surface of the cured heat-resistant layer of the laminated film, and were inferior in practicality as in Comparative Example 1.
【００５５】比較例３ 実施例１において、ビスフェノールＡ型エポキシ樹脂の
配合量を３０部、ヘキサメトキシメチロール化メラミン
の配合量を３５部に変更したこと以外は実施例１と同じ
方法で金属ラミネート用フィルムを得た。得られたフィ
ルムの式（Ｉ）および式（ＩＩ）の値はそれぞれ３．４
５および０．１０であり、耐摩耗性指数は２．２％、静
摩擦係数は０．１０であり、滑り性は良好であるが耐摩
耗性の劣るものであった。また透明度はヘイズ値で３．
６％であった。このフィルムを用い、実施例１と同じ方
法でラミネート鋼板及び金属容器を得た。得られたラミ
ネート鋼板及び金属容器は、ラミネートフィルムの硬化
耐熱層表面の耐摩耗性が劣り、比較例１と同様に実用性
の劣るものであった。Comparative Example 3 For metal laminating in the same manner as in Example 1 except that the amount of bisphenol A type epoxy resin was changed to 30 parts and the amount of hexamethoxymethylolated melamine was changed to 35 parts. I got a film. The values of the formula (I) and the formula (II) of the obtained film are 3.4, respectively.
5 and 0.10, the abrasion resistance index was 2.2%, and the static friction coefficient was 0.10. The slip property was good, but the wear resistance was poor. The transparency is haze value of 3.
It was 6%. Using this film, a laminated steel plate and a metal container were obtained in the same manner as in Example 1. The obtained laminated steel sheet and metal container had poor wear resistance on the surface of the cured heat-resistant layer of the laminated film, and were inferior in practicality as in Comparative Example 1.
【００５６】実施例２ 実施例１において、ｐ−トルエンスルホン酸の配合量を
０．７部に変更し、かつ乾燥温度を８０℃、硬化温度を
１６０℃としたこと以外は実施例１と同じ方法で金属ラ
ミネート用フィルムを得た。得られたフィルムの式
（Ｉ）および式（ＩＩ）の値はそれぞれ１．２０および
０．１６であり、耐摩耗性指数は０．２％、静摩擦係数
は０．１０であった。また透明度はヘイズ値で３．５％
であった。このフィルムを用い実施例１と同じ方法で得
たラミネート鋼板及び金属容器は、ラミネートフィルム
の硬化耐熱層表面の耐摩耗性および滑り性が優れてお
り、実施例１と同様に実用性の高いものであった。Example 2 The same as Example 1 except that the compounding amount of p-toluenesulfonic acid was changed to 0.7 part, and the drying temperature was 80 ° C. and the curing temperature was 160 ° C. A metal laminating film was obtained by the method. The values of the formula (I) and the formula (II) of the obtained film were 1.20 and 0.16, respectively, the abrasion resistance index was 0.2%, and the static friction coefficient was 0.10. The transparency is 3.5% in haze value.
Met. A laminated steel sheet and a metal container obtained by using this film in the same manner as in Example 1 have excellent wear resistance and slipperiness on the surface of the cured heat-resistant layer of the laminated film, and are as highly practical as Example 1. Met.
【００５７】実施例３ 実施例１において、硬化耐熱樹脂組成物をビスフェノー
ルＡ型エポキシ樹脂８０部、ヘキサメトキシメチロール
化メラミン２０部、高級脂肪酸ワックス０．１部、フッ
素樹脂０．４部、シリコーン樹脂１．２部およびｐ−ト
ルエンスルホン酸０．０７部よりなる配合物に変更し、
かつ乾燥温度を８０℃および硬化温度を１６５℃とした
こと以外は、実施例１と同じ方法で金属ラミネート用フ
ィルムを得た。乾燥後の残留溶剤は１５５ｐｐｍであっ
た。得られたフィルムの式（Ｉ）および式（ＩＩ）の値
はそれぞれ０．７６および０．１１であり、耐摩耗性指
数は０．２％、静摩擦係数は０．０９であった。また透
明度はヘイズ値で３．７％であった。このフィルムを用
い実施例１と同じ方法で得たラミネート鋼板及び金属容
器は、ラミネートフィルムの硬化耐熱層表面の耐摩耗性
および滑り性が優れており、実施例１と同様に実用性の
高いものであった。Example 3 In Example 1, 80 parts of a bisphenol A type epoxy resin, 20 parts of hexamethoxymethylolated melamine, 0.1 part of a higher fatty acid wax, 0.4 part of a fluororesin and a silicone resin were used. Changed to a formulation consisting of 1.2 parts and 0.07 part p-toluenesulfonic acid,
A film for metal laminating was obtained in the same manner as in Example 1, except that the drying temperature was 80 ° C and the curing temperature was 165 ° C. The residual solvent after drying was 155 ppm. The values of the formula (I) and the formula (II) of the obtained film were 0.76 and 0.11, respectively, the abrasion resistance index was 0.2%, and the static friction coefficient was 0.09. The transparency was 3.7% in haze value. A laminated steel sheet and a metal container obtained by using this film in the same manner as in Example 1 have excellent wear resistance and slipperiness on the surface of the cured heat-resistant layer of the laminated film, and are as highly practical as Example 1. Met.
【００５８】比較例４ 実施例３において、ビスフェノールＡ型エポキシ樹脂の
配合量を９６部、ヘキサメトキシメチロール化メラミン
の配合量を４部に変更したこと以外は、実施例３と同じ
方法で金属ラミネート用フィルムを得た。得られたフィ
ルムの式（Ｉ）および式（ＩＩ）の値はそれぞれ０．１
１および０．０４であり、耐摩耗性指数は２．２％、静
摩擦係数は０．０９であり、滑り性は良好であるが耐摩
耗性に劣るものであった。また透明度はヘイズ値で３．
７％であった。このフィルムを用い、実施例１と同じ方
法で得たラミネート鋼板および金属容器は、ラミネート
フィルムの硬化耐熱層表面の耐摩耗性が劣り、比較例１
と同様に実用性の劣るものであった。Comparative Example 4 A metal laminate was prepared in the same manner as in Example 3 except that the content of the bisphenol A type epoxy resin was changed to 96 parts and the content of hexamethoxymethylolated melamine was changed to 4 parts. A film for use was obtained. The values of the formula (I) and the formula (II) of the obtained film are each 0.1.
1 and 0.04, the abrasion resistance index was 2.2%, the static friction coefficient was 0.09, and the sliding property was good, but the abrasion resistance was poor. The transparency is haze value of 3.
7%. A laminated steel sheet and a metal container obtained by using this film in the same manner as in Example 1 were inferior in abrasion resistance on the surface of the cured heat-resistant layer of the laminated film, and Comparative Example 1
It was inferior in practicality as well.
【００５９】比較例５ 実施例３において、ビスフェノールＡ型エポキシ樹脂の
配合量を４５部、ヘキサメトキシメチロール化メラミン
の配合量を５５部に変更したこと以外は、実施例３と同
じ方法で金属ラミネート用フィルムを得た。得られたフ
ィルムの式（Ｉ）および式（ＩＩ）の値はそれぞれ３．
６０および０．１２であり、耐摩耗性指数は１．９％、
静摩擦係数は０．０８であり、滑り性は良好であるが耐
摩耗性に劣るものであった。また透明度はヘイズ値で
３．６％であった。このフィルムを用い、実施例１と同
じ方法で得たラミネート鋼板および金属容器は、ラミネ
ートフィルムの硬化耐熱層表面の耐摩耗性が劣り、比較
例１と同様に実用性の劣るものであった。Comparative Example 5 A metal laminate was prepared in the same manner as in Example 3 except that the amount of bisphenol A type epoxy resin was changed to 45 parts and the amount of hexamethoxymethylolated melamine was changed to 55 parts. A film for use was obtained. The values of the formula (I) and the formula (II) of the obtained film are 3.
60 and 0.12, the abrasion resistance index is 1.9%,
The coefficient of static friction was 0.08, and the sliding property was good, but the wear resistance was poor. Further, the haze value of the transparency was 3.6%. The laminated steel sheet and the metal container obtained by using this film in the same manner as in Example 1 were inferior in wear resistance on the surface of the cured heat-resistant layer of the laminated film, and were inferior in practicality as in Comparative Example 1.
【００６０】比較例６ 実施例３において、乾燥温度を８０℃、硬化温度を１３
５℃（熱風加熱）としたこと以外は、実施例１と同じ方
法で金属ラミネート用フィルムを得た。得られたフィル
ムの式（Ｉ）および式（ＩＩ）の値はそれぞれ０．７６
および０．２８であり、耐摩耗性指数は１．５％、静摩
擦係数は０．１０であり、滑り性は良好であるが耐摩耗
性に劣るものであった。また透明度はヘイズ値で３．７
％であった。このフィルムを用い、実施例１と同じ方法
で得たラミネート鋼板および金属容器は、ラミネートフ
ィルムの硬化耐熱層表面の耐摩耗性が劣り、比較例１と
同様に実用性の劣るものであった。Comparative Example 6 In Example 3, the drying temperature was 80 ° C. and the curing temperature was 13.
A film for metal laminating was obtained by the same method as in Example 1 except that the temperature was 5 ° C. (heating with hot air). The values of the formula (I) and the formula (II) of the obtained film are 0.76, respectively.
And 0.28, the wear resistance index was 1.5%, and the static friction coefficient was 0.10. The slip properties were good, but the wear resistance was poor. Also, the transparency is 3.7 as a haze value.
%Met. The laminated steel sheet and the metal container obtained by using this film in the same manner as in Example 1 were inferior in wear resistance on the surface of the cured heat-resistant layer of the laminated film, and were inferior in practicality as in Comparative Example 1.
【００６１】[0061]
【発明の効果】以上の説明で明らかなように、本発明の
金属ラミネート用フィルムは硬化耐熱層表面の耐摩耗性
に優れているので、このフィルムを用いると、高光沢で
美しい外観を有するラミネート金属板及び金属容器を提
供することができる。As is apparent from the above description, the metal laminating film of the present invention has excellent abrasion resistance on the surface of the cured heat-resistant layer. Therefore, when this film is used, a laminate having a high gloss and a beautiful appearance is obtained. A metal plate and a metal container can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｇ 59/00 Ｃ０８Ｇ 59/00 (72)発明者 永野 煕 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内 (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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08G 59/00 C08G 59/00 (72) Inventor Nagano Hei Ai prefecture Inuyama city Kizuji Maebata 344 Toyobo Co., Ltd. Inuyama Factory (72) Inventor Tsutomu Isaka 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd.
Claims (9)
このフィルムの少なくとも片面上に積層された硬化耐熱
層とを含有する金属ラミネート用フィルムであって、 硬化耐熱層が、ビスフェノールＡ骨格を有するエポキシ
樹脂とメラミン化合物との硬化反応物を含有し、かつ当
該硬化耐熱層の内部全反射法による表面赤外線吸収分析
において、下記式（Ｉ）および（ＩＩ）を同時に満足す
ることを特徴とする金属ラミネート用フィルム。 【数１】 1. A thermoplastic resin film as a substrate,
A film for metal laminating comprising a cured heat resistant layer laminated on at least one side of the film, wherein the cured heat resistant layer contains a curing reaction product of an epoxy resin having a bisphenol A skeleton and a melamine compound, and A film for metal laminating, which simultaneously satisfies the following formulas (I) and (II) in a surface infrared absorption analysis by a total internal reflection method of the cured heat-resistant layer. [Equation 1]
％以下であることを特徴とする請求項１に記載の金属ラ
ミネート用フィルム。2. The abrasion resistance index of the surface of the cured heat resistant layer is 1.2.
% Or less, The film for metal laminating according to claim 1, wherein
ｍ2 であることを特徴とする請求項１に記載の金属ラミ
ネート用フィルム。3. The cured heat-resistant layer has a thickness of 0.3 to 10 g /
The film for metal laminating according to claim 1, wherein the film is m 2 .
〜０．２０であることを特徴とする請求項１に記載の金
属ラミネート用フィルム。4. The coefficient of static friction of the surface of the cured heat-resistant layer is 0.05.
It is -0.20, The film for metal laminating of Claim 1 characterized by the above-mentioned.
フィルムであることを特徴とする請求項１に記載の金属
ラミネート用フィルム。5. The film for metal laminating according to claim 1, wherein the thermoplastic resin film is a polyester film.
を特徴とする請求項１に記載の金属ラミネート用フィル
ム。6. The film for metal laminating according to claim 1, which has a haze value of 5% or less.
れた請求項１〜６のいずれかに記載の金属ラミネート用
フィルムとを含有することを特徴とするラミネート金属
板。7. A laminated metal plate comprising a metal plate and the metal laminating film according to claim 1, which is laminated on one side of the metal plate.
ミネート用フィルムが、熱可塑性樹脂フィルムの片面上
に硬化耐熱層が積層された金属ラミネート用フィルムで
あって、当該フィルムが、熱可塑性樹脂フィルムを金属
板側として金属板に積層されていることを特徴とする請
求項７に記載のラミネート金属板。8. The metal laminating film according to any one of claims 1 to 6, wherein the cured heat resistant layer is laminated on one surface of a thermoplastic resin film, and the film is a thermosetting film. The laminated metal plate according to claim 7, wherein the plastic resin film is laminated on the metal plate with the metal plate side being the metal plate side.
属板を用いて、硬化耐熱層が外側となるように製缶して
なることを特徴とする金属容器。9. A metal container, characterized in that the laminated metal plate according to claim 7 or 8 is used to make a can so that the cured heat-resistant layer is on the outside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5356196A JP3845892B2 (en) | 1996-03-11 | 1996-03-11 | Film for metal lamination, laminated metal plate and metal container using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5356196A JP3845892B2 (en) | 1996-03-11 | 1996-03-11 | Film for metal lamination, laminated metal plate and metal container using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09239938A true JPH09239938A (en) | 1997-09-16 |
| JP3845892B2 JP3845892B2 (en) | 2006-11-15 |
Family
ID=12946237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5356196A Expired - Fee Related JP3845892B2 (en) | 1996-03-11 | 1996-03-11 | Film for metal lamination, laminated metal plate and metal container using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3845892B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1009405C2 (en) * | 1998-06-15 | 1999-12-16 | Dsm Nv | Object comprising a support and a layer located on the support. |
| JP2005247389A (en) * | 2004-03-05 | 2005-09-15 | Toyo Aluminium Kk | Package |
| WO2008083934A1 (en) * | 2007-01-11 | 2008-07-17 | Dsm Ip Assets B.V. | Substrates with barrier properties at high humidity |
| EP1995059A1 (en) * | 2007-05-24 | 2008-11-26 | DSM IP Assets B.V. | Substrates with barrier properties at high humidity |
-
1996
- 1996-03-11 JP JP5356196A patent/JP3845892B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1009405C2 (en) * | 1998-06-15 | 1999-12-16 | Dsm Nv | Object comprising a support and a layer located on the support. |
| WO1999066097A1 (en) * | 1998-06-15 | 1999-12-23 | Dsm N.V. | A composite material comprising a substrate with a barrier layer |
| US6632519B1 (en) | 1998-06-15 | 2003-10-14 | Dsm N.V. | Composite material comprising a substrate and a barrier layer applied to the substrate |
| US6893679B2 (en) | 1998-06-15 | 2005-05-17 | Dsm N.V. | Process for preparing a composite material by vapor depositing a barrier layer on a substrate |
| KR100602337B1 (en) * | 1998-06-15 | 2006-07-14 | 디에스엠 아이피 어셋츠 비.브이. | Composite Materials Including Barrier Layers and Substrates |
| JP2005247389A (en) * | 2004-03-05 | 2005-09-15 | Toyo Aluminium Kk | Package |
| WO2008083934A1 (en) * | 2007-01-11 | 2008-07-17 | Dsm Ip Assets B.V. | Substrates with barrier properties at high humidity |
| EP1995059A1 (en) * | 2007-05-24 | 2008-11-26 | DSM IP Assets B.V. | Substrates with barrier properties at high humidity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3845892B2 (en) | 2006-11-15 |
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