JP2000158588A - Manufacture of laminated metal plate - Google Patents

Manufacture of laminated metal plate

Info

Publication number
JP2000158588A
JP2000158588A JP10340364A JP34036498A JP2000158588A JP 2000158588 A JP2000158588 A JP 2000158588A JP 10340364 A JP10340364 A JP 10340364A JP 34036498 A JP34036498 A JP 34036498A JP 2000158588 A JP2000158588 A JP 2000158588A
Authority
JP
Japan
Prior art keywords
film
metal plate
temperature
polyester
laminating
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
Application number
JP10340364A
Other languages
Japanese (ja)
Other versions
JP3485003B2 (en
Inventor
Hiroki Iwasa
浩樹 岩佐
Yoichiro Yamanaka
洋一郎 山中
Takeshi Suzuki
威 鈴木
Masahiko Shigeno
雅彦 茂野
Shinsuke Watanabe
真介 渡辺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Priority to JP34036498A priority Critical patent/JP3485003B2/en
Publication of JP2000158588A publication Critical patent/JP2000158588A/en
Application granted granted Critical
Publication of JP3485003B2 publication Critical patent/JP3485003B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73115—Melting point
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91411—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature of the parts to be joined, e.g. the joining process taking the temperature of the parts to be joined into account
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91441—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time
    • B29C66/91443—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time following a temperature-time profile
    • B29C66/91445—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time following a temperature-time profile by steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91931—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
    • B29C66/91933—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined higher than said fusion temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91931—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
    • B29C66/91935—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined lower than said fusion temperature

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Laminated Bodies (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plasma & Fusion (AREA)

Abstract

PROBLEM TO BE SOLVED: To manufacture a laminated metal plate suitable as a material of a metal can excellent in moldability, impact resistance, taste characteristics and retort whitening resistance. SOLUTION: When a biaxially stretched polyester film comprising polyester wherein 93 mol% or more of a constitutional unit is an ethylene terephthalate unit and characterized by that a crystal size x of a (100) surface obtained by X-ray diffraction measurement is 6 nm or less is laminated to at least the single surface of a metal plate, the temp. T0 of the metal plate at the start time of lamination is set to the m.p. Tf of the film or higher and the temp. Tl of the metal plate on the outlet side of a laminating roll nip is set to the m.p. Tf of the film or lower and, further, a laminating index K defined by K=(T0-Tf) x×t/(T0-Tl) (wherein t is a nip time) is set to 1-20 msec.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は容器用フイルムラミ
ネート金属板に関するものである。更に詳しくは成形
性、耐衝撃性、味特性、耐レトルト白化性に優れる、絞
り加工やしごき成形等の成形加工によって製造される金
属缶の蓋や胴の素材に好適なラミネート金属板の製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-laminated metal plate for a container. More specifically, a method for producing a laminated metal sheet that is excellent in moldability, impact resistance, taste characteristics, and retort whitening resistance, and is suitable for a material of a lid or a body of a metal can produced by molding such as drawing or ironing. It is about.

【０００２】[0002]

【従来の技術】従来、金属缶の缶内面及び外面は腐食防
止を目的として、エポキシ系、フェノール系等の各種熱
硬化性樹脂を溶剤に溶解または分散させたものを塗布
し、金属表面を被覆することが広く行われてきた。しか
しながら、このような熱硬化性樹脂の被覆方法は塗料の
乾燥に長時間を要し、生産性が低下したり、多量の有機
溶剤による環境汚染など好ましくない問題がある。2. Description of the Related Art Conventionally, the inner and outer surfaces of a metal can are coated with various thermosetting resins, such as epoxy and phenol, dissolved or dispersed in a solvent to prevent corrosion. Has been widely practiced. However, such a method of coating the thermosetting resin requires a long time for drying the paint, and has unfavorable problems such as a decrease in productivity and environmental pollution due to a large amount of an organic solvent.

【０００３】これらの問題を解決する方法として、金属
缶の材料である鋼板、アルミニウム板等の金属板あるい
は該金属板にめっき等各種の表面処理を施した金属板に
フイルムをラミネートする方法がある。そして、フイル
ムのラミネート金属板を絞り成形やしごき成形加工して
金属缶を製造する場合、ラミネート金属板には次のよう
な特性が要求される。 （１）フィルムと金属板との接着性に優れていること。 （２）成形性に優れ、成形後にピンホールなどの欠陥を
生じないこと。 （３）金属缶に対する衝撃によって、フイルムが剥離し
たり、クラック、ピンホールが発生したりしないこと。 （４）缶の内容物の香り成分がフイルムに吸着したり、
フイルムの臭いによって内容物の風味がそこなわれない
こと（以下味特性と記載する）。 （５）絞り成形や蓋成形の後、印刷やシール剤硬化のた
め、あるいは内容物充填後の蒸気殺菌工程において、加
熱を受けた際に、フィルム外観が白く変色しないこと
（耐レトルト白化性）。As a method of solving these problems, there is a method of laminating a film on a metal plate, such as a steel plate or an aluminum plate, which is a material of a metal can, or a metal plate which has been subjected to various surface treatments such as plating. . When a metal can is manufactured by drawing or ironing a laminated metal plate of a film, the laminated metal plate is required to have the following characteristics. (1) The adhesiveness between the film and the metal plate is excellent. (2) It is excellent in moldability and does not generate defects such as pinholes after molding. (3) The film does not peel, crack, or pinhole due to impact on the metal can. (4) The scent component of the contents of the can adsorbs to the film,
The flavor of the contents is not degraded by the smell of the film (hereinafter referred to as taste characteristics). (5) The film appearance does not turn white and discolored when subjected to heating in the steam sterilization step after drawing or lid forming, for printing or sealing agent curing, or after filling the contents (retort whitening resistance) .

【０００４】これらの要求を解決するために多くの提案
がなされており、例えば特開平２−５７３３９号公報に
は特定の結晶性を有する金属板ラミネート用共重合ポリ
エステルフイルム等が開示されている。しかしながら、
これらの提案は上述のような多岐にわたる要求特性を総
合的に満足できるものではなく、特に優れたラミネート
性と優れた味特性が要求される用途では十分に満足でき
るレベルにあるとは言えなかった。Many proposals have been made to solve these requirements. For example, Japanese Patent Application Laid-Open No. 2-57339 discloses a copolymerized polyester film for metal plate lamination having specific crystallinity. However,
These proposals do not comprehensively satisfy the wide variety of required characteristics as described above, and cannot be said to be at a sufficiently satisfactory level particularly in applications where excellent laminating properties and excellent taste characteristics are required. .

【０００５】また、特開平１０−４４２３３号公報に
は、特定の構造を有する金属板ラミネート用ポリエステ
ルフイルム等が開示されている。この提案によって多岐
にわたる要求特性が解決されるが、缶に成形する際の成
形加工熱や成形後の加熱工程、内容物の充填後の高温殺
菌工程で、密着性の劣化やフィルム外観の白化、加工性
の劣化等が生じる難点があった。Japanese Patent Application Laid-Open No. 10-44233 discloses a polyester film for laminating a metal plate having a specific structure. This proposal solves a wide range of required properties.However, in the processing heat when forming into cans, the heating step after molding, and the high-temperature sterilization step after filling the contents, deterioration of adhesion and whitening of the film appearance, There was a problem that workability deteriorated.

【０００６】[0006]

【発明が解決しようとする課題】本発明の目的は上記し
た従来技術の問題点を解消することにあり、成形性、耐
熱性、耐衝撃性、味特性に優れるラミネート金属板の製
造方法、特に絞り成形やしごき成形等の成形加工によっ
て製造される成形性、耐衝撃性、味特性、耐レトルト白
化性に優れた金属缶の素材に好適なラミネート金属板の
製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a method for producing a laminated metal sheet having excellent moldability, heat resistance, impact resistance and taste characteristics, in particular, An object of the present invention is to provide a method for producing a laminated metal sheet suitable for a metal can material excellent in moldability, impact resistance, taste characteristics, and retort whitening resistance, which is produced by molding such as drawing or ironing.

【０００７】[0007]

【課題を解決するための手段】前記した本発明の目的
は、以下の手段によって達成できる。The above objects of the present invention can be achieved by the following means.

【０００８】（１）構成単位の９３モル％以上がエチレ
ンテレフタレート単位であるポリエステルからなり、Ｘ
線回折測定により得られる（１００）面の結晶サイズχ
が６ｎｍ以下である二軸延伸ポリエステルフィルムを金
属板の少なくとも片面にラミネートする際に、ラミネー
ト開始時の金属板の温度Ｔ0をフィルムの融点Ｔf以上、
ラミネートロールニップ出側の金属板の温度Ｔ1をフィ
ルムの融点Ｔf以下にするとともに、更に下式で定義さ
れるラミネートインデックスＫを１〜２０ｍｓｅｃの範
囲内にしてラミネートすることを特徴とするラミネート
金属板の製造方法。 Ｋ＝（Ｔ0−Ｔf）×ｔ／（Ｔ0−Ｔ1） 但し、ｔ：ニップ時間(1) 93% by mole or more of the structural unit is made of a polyester which is an ethylene terephthalate unit;
Crystal size of (100) plane obtained by X-ray diffraction measurementχ
When laminating a biaxially stretched polyester film having a thickness of 6 nm or less on at least one side of the metal plate, the temperature T 0 of the metal plate at the start of lamination is not less than the melting point Tf of the film,
Laminating characterized in that the temperature T 1 of the metal plate on the exit side of the laminating roll nip is not higher than the melting point Tf of the film, and the laminating index K defined by the following formula is further within the range of 1 to 20 msec. Manufacturing method of metal plate. K = (T 0 −T f ) × t / (T 0 −T 1 ) where t: nip time

【０００９】（２）前記（１）において、ニップ時間ｔ
が０．００５〜０．０５ｓｅｃの範囲内であることを特
徴とするラミネート金属板の製造方法。(2) In the above (1), the nip time t
Is in the range of 0.005 to 0.05 sec.

【００１０】（３）前記（１）または（２）において、
ポリエステルの構成単位の９６モル％以上がエチレンテ
レフタレート単位であることを特徴とするラミネート金
属板の製造方法。(3) In the above (1) or (2),
A method for producing a laminated metal sheet, wherein 96 mol% or more of the constituent units of the polyester are ethylene terephthalate units.

【００１１】（４）前記（１）〜（３）において、フィ
ルムの面配向係数が０．１５以下であることを特徴とす
るラミネート金属板の製造方法。(4) The method for producing a laminated metal sheet according to any one of (1) to (3), wherein the plane orientation coefficient of the film is 0.15 or less.

【００１２】（５）前記（１）〜（４）において、ポリ
エステルの融点が２４６℃以上、２８０℃以下であるこ
とを特徴とするラミネート金属板の製造方法。(5) The method for producing a laminated metal sheet according to (1) to (4), wherein the melting point of the polyester is 246 ° C. or more and 280 ° C. or less.

【００１３】[0013]

【発明の実施の形態】本発明は、鋭意検討の結果、構成
単位の９３モル％以上がエチレンテレフタレート単位で
あるポリエステルを二軸延伸し特定のＸ線回折測定によ
り得られる（１００）面の結晶サイズχを有するフィル
ムを用いて、ラミネートの際の熱履歴を制御することに
より、製缶工程での加熱履歴を経た後も、成形性、味特
性が良好で、特に耐衝撃性と耐白化性に優れるラミネー
ト鋼板が得られることを見出したことに基くものであ
る。BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies, the present invention has revealed that a (100) crystal obtained by biaxially stretching a polyester in which not less than 93 mol% of the constituent units are ethylene terephthalate units and performing a specific X-ray diffraction measurement. By controlling the heat history during lamination using a film with size χ, the moldability and taste characteristics are good even after passing through the heating history in the can making process, especially impact resistance and whitening resistance This is based on the finding that a laminated steel sheet having excellent resistance can be obtained.

【００１４】以下、本発明について詳細に説明する。本
発明で用いるエチレンテレフタレートを主たる構成成分
とするポリエステルとは、レトルト処理などの熱処理の
後で味特性を良好にする点で、エチレンテレフタレート
単位が９３モル％以上であることが必要であり、より好
ましくは９６モル％以上であると金属缶に飲料を長期充
填しても味特性が良好であるので望ましい。Hereinafter, the present invention will be described in detail. The polyester having ethylene terephthalate as a main component used in the present invention is required to have an ethylene terephthalate unit of 93 mol% or more from the viewpoint of improving taste characteristics after heat treatment such as retort treatment. Preferably, the content is 96 mol% or more, since the taste characteristics are good even if the beverage is filled into the metal can for a long period of time.

【００１５】一方、味特性を損ねない範囲で他のジカル
ボン酸成分、グリコール成分を共重合してもよく、ジカ
ルボン酸成分としては、例えばイシフタル酸、ナフタレ
ンジカルボン酸、ジフェニルジカルボン酸、ジフェニル
スルホンジカルボン酸、ジフェノキシエタンジカルボン
酸、５−ナトリウムスルホイソフタル酸、フタル酸等の
芳香族ジカルボン酸、シュウ酸、コハク酸、アジピン
酸、セバシン酸、ダイマー酸、マレイン酸、フマル酸等
の脂肪族ジカルボン酸、シクロヘキシンジカルボン酸等
の脂環族ジカルボン酸、ｐ−オキシ安息香酸等のオキシ
カルボン酸等を挙げることができる。On the other hand, other dicarboxylic acid components and glycol components may be copolymerized as long as taste characteristics are not impaired. Examples of the dicarboxylic acid component include isiftalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and diphenylsulfonedicarboxylic acid. , Diphenoxyethane dicarboxylic acid, 5-sodium sulfoisophthalic acid, aromatic dicarboxylic acids such as phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, Examples thereof include alicyclic dicarboxylic acids such as cyclohexyne dicarboxylic acid, and oxycarboxylic acids such as p-oxybenzoic acid.

【００１６】一方、グリコール成分としては例えばプロ
パンジオール、ブタンジオール、ペンタンジオール、ヘ
キサンジオール、ネオペンチルグリコール等の脂肪族グ
リコール、シクロヘキサンジメタノール等の脂環族グリ
コール、ビスフェノールＡ、ビスフェノールＳ等の芳香
族グリコール、ジエチレングリコール等が挙げられる。
なお、これらのジカルボン酸成分、グリコール成分は２
種以上を併用してもよい。On the other hand, examples of the glycol component include aliphatic glycols such as propanediol, butanediol, pentanediol, hexanediol and neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatics such as bisphenol A and bisphenol S. Glycol and diethylene glycol.
In addition, these dicarboxylic acid components and glycol components are 2
More than one species may be used in combination.

【００１７】また、本発明の効果を阻害しない限りにお
いて、共重合ポリエステルにトリメリット酸、トリメシ
ン酸、トリメチロールプロパン等の多官能化合物を共重
合してもよい。As long as the effects of the present invention are not impaired, a polyfunctional compound such as trimellitic acid, trimesic acid, and trimethylolpropane may be copolymerized with the copolymerized polyester.

【００１８】本発明で用いるポリエステルは、好ましく
少量共重合される成分としては、ブタンジオール、ジエ
チレングリコール、ポリエチレングリコール、シクロヘ
キサンジメタノール、セバシン酸、ダイマー酸、イソフ
タル酸などがあるが、味特性が厳しい用途ではエチレン
テレフタレートが９６モル％以上、特に好ましくは９８
モル％以上であることが好ましい。The polyester used in the present invention is preferably copolymerized in a small amount, such as butanediol, diethylene glycol, polyethylene glycol, cyclohexanedimethanol, sebacic acid, dimer acid, and isophthalic acid. In this case, the content of ethylene terephthalate is 96 mol% or more, particularly preferably 98 mol%.
It is preferably at least mol%.

【００１９】本発明で用いるポリエスエルの融点は好ま
しくは２４６℃以上、２８０℃以下、さらに好ましくは
２５０℃以上、２７５℃以下である。融点が２４６℃未
満であると耐熱性が低下し好ましくないことがある。ま
た融点が２８０℃を越えるとラミネート性、成形性が悪
化し好ましくないことがある。The melting point of the polyester used in the present invention is preferably from 246 ° C to 280 ° C, more preferably from 250 ° C to 275 ° C. If the melting point is lower than 246 ° C., the heat resistance may decrease, which is not preferable. On the other hand, when the melting point exceeds 280 ° C., the laminating property and the moldability deteriorate, which is not preferable.

【００２０】本発明で用いるフィルムは、上記ポリマを
２種以上ブレンドして使用してもかまわない。The film used in the present invention may be a mixture of two or more of the above polymers.

【００２１】本発明で用いるフィルムは、耐熱性、味特
性の点で、エチレンテレフタレートを主たる構成成分と
するポリエステルを二軸延伸化することが必要である。
二軸延伸の方法としては、同時二軸延伸、逐次二軸延伸
のいずれであってもよいが、二軸延伸フィルムはラミネ
ート性の点から、Ｘ線回折測定により得られる（１０
０）面の結晶サイズχが６ｎｍ以下であることが必要で
あり、好ましくは５．５ｎｍ以下、より好ましくは、５
ｎｍ以下、特に好ましくは４．５ｎｍ以下である。（１
００）面の結晶サイズχが６ｎｍを超えるとラミネート
性が不充分である。ここで（１００）面の結晶サイズχ
は、反射Ｘ線回折によりScherrerの式を用いて求められ
る。In the film used in the present invention, it is necessary to biaxially stretch a polyester containing ethylene terephthalate as a main component in view of heat resistance and taste characteristics.
The method of biaxial stretching may be either simultaneous biaxial stretching or sequential biaxial stretching, but a biaxially stretched film is obtained by X-ray diffraction measurement from the viewpoint of laminating properties (10
The crystal size の of the 0) plane needs to be 6 nm or less, preferably 5.5 nm or less, more preferably 5 nm or less.
nm or less, particularly preferably 4.5 nm or less. (1
When the crystal size of the (00) plane exceeds 6 nm, the laminating property is insufficient. Here, the crystal size of (100) planeχ
Is determined by reflection X-ray diffraction using Scherrer's equation.

【００２２】６ｎｍ以下の（１００）面の結晶サイズ
は、フィルムを構成するポリマーや、添加物、さらに延
伸条件、熱処理条件等により決定され、これらを任意に
設定することにより達成できる。例えば、熱処理温度を
低くしたり、熱処理時間を短くすると良いが、フィルム
に要求される特性を満たす範囲でなければならない。The crystal size of the (100) plane of 6 nm or less is determined by the polymer constituting the film, additives, stretching conditions, heat treatment conditions and the like, and can be achieved by arbitrarily setting these. For example, the heat treatment temperature may be lowered or the heat treatment time may be shortened, but the heat treatment temperature must be in a range satisfying the characteristics required for the film.

【００２３】本発明で用いるフィルムは、よりラミネー
ト性、味特性を向上させる点からポリエステルの固有粘
度が０．５ｄｌ／ｇ以上が好ましく、さらに好ましくは
０．６ｄｌ／ｇ以上、特に好ましくは０．６３ｄｌ／ｇ
以上である。固有粘度が０．５ｄｌ／ｇ未満ではオリゴ
マの溶出などにより味特性が悪化するため好ましくな
い。In the film used in the present invention, the intrinsic viscosity of the polyester is preferably at least 0.5 dl / g, more preferably at least 0.6 dl / g, particularly preferably at least 0.6 dl / g, from the viewpoint of further improving laminating properties and taste characteristics. 63 dl / g
That is all. When the intrinsic viscosity is less than 0.5 dl / g, taste characteristics are deteriorated due to elution of the oligomer and the like, which is not preferable.

【００２４】さらに本発明で用いるフィルムにおいて、
面配向係数が、０．１５以下であることが金属板のラミ
ネート性やその後の成形性、耐衝撃性を良好とする点で
好ましいが、特により一層ラミネート性を良好とする点
で、０．１４５以下であることが好ましく、さらに好ま
しくは０．１４以下である。面配向係数が高すぎるとラ
ミネート性のみならず成形性をも悪化させる。そのため
缶成形後の味特性も低下する。Further, in the film used in the present invention,
It is preferable that the plane orientation coefficient is 0.15 or less from the viewpoint of improving the laminating property of the metal plate, the subsequent formability, and the impact resistance. It is preferably 145 or less, more preferably 0.14 or less. If the plane orientation coefficient is too high, not only the laminability but also the moldability deteriorate. As a result, the taste characteristics after can molding are also reduced.

【００２５】本発明で用いるポリエステルは、好ましく
はジエチレングリコール成分量が０．０１〜３．５重量
％、さらに好ましくは０．０１〜２．５重量％、特に好
ましくは０．０１〜２．０重量％であることが製缶工程
での熱処理、製缶後のレトルト処理などの多くの熱履歴
を受けても優れた味特性を維持する上で望ましい。この
ことは、２００℃以上での耐酸化分解性が向上するもの
と考えられ、さらに公知の酸化防止剤を０．０００１〜
１重量％添加してもよい。また、特性を損ねない範囲で
ジエチレングリコールをポリマ製造時に添加しても良
い。The polyester used in the present invention preferably has a diethylene glycol content of 0.01 to 3.5% by weight, more preferably 0.01 to 2.5% by weight, particularly preferably 0.01 to 2.0% by weight. % Is desirable in order to maintain excellent taste characteristics even when subjected to many heat histories such as heat treatment in a can-making process and retort treatment after can-making. This is considered to improve oxidative decomposition resistance at 200 ° C. or higher.
You may add 1 weight%. Further, diethylene glycol may be added during the production of the polymer as long as the properties are not impaired.

【００２６】また、味特性を良好にする上で、フィルム
中のアセトアルデヒドの含有量を好ましくは２５ｐｐｍ
以下、さらに好ましくは２０ｐｐｍ以下が望ましい。ア
セトアルデヒドの含有量が２５ｐｐｍを越えると味特性
に劣る。フィルム中のアセトアルデヒドの含有量を２５
ｐｐｍ以下とする方法は特に限定されるものではない
が、例えばポリエステルを重縮反応等で製造する際の熱
分解によって生じるアセトアルデヒドを除去するため、
ポリエステルを減圧下あるいは不活性ガス雰囲気下にお
いて、ポリエステルの融点以下の温度で熱処理する方
法、好ましくはポリエステルを減圧下あるいは不活性ガ
ス雰囲気下において１５５℃以上、融点以下の温度で固
相重合する方法、ベント式押出機を使用して溶融押出す
る方法、ポリマを溶融押出する際に押出温度を高融点ポ
リマ側の融点＋３０℃以内、好ましくは融点＋２５℃以
内で、短時間、好ましくは平均滞留時間１時間以内で押
出す方法等を挙げることができる。In order to improve taste characteristics, the content of acetaldehyde in the film is preferably 25 ppm.
Below, more preferably 20 ppm or less is desirable. When the content of acetaldehyde exceeds 25 ppm, the taste characteristics are inferior. When the content of acetaldehyde in the film is 25
Although the method to be not more than ppm is not particularly limited, for example, in order to remove acetaldehyde generated by thermal decomposition when producing polyester by polycondensation reaction or the like,
A method in which the polyester is heat-treated at a temperature not higher than the melting point of the polyester under reduced pressure or an inert gas atmosphere, preferably a method in which the polyester is subjected to solid-state polymerization at a temperature of 155 ° C. or more and the melting point or lower under a reduced pressure or an inert gas atmosphere. Melt extrusion using a vent-type extruder, when the polymer is melt-extruded, the extrusion temperature is within the melting point of the high-melting polymer side + 30 ° C, preferably within the melting point + 25 ° C, in a short time, preferably an average residence time. A method of extruding within one hour can be used.

【００２７】本発明で用いるフィルムは単層、積層いず
れも使用できる。本発明の二軸延伸フイルムの厚さは、
金属にラミネートした後の成形性、金属に対する被覆
性、耐衝撃性、味特性の点で、３〜５０μｍであること
が好ましく、さらに好ましくは５〜３５μｍであり、特
に好ましくは８〜３０μｍである。積層にて使用される
場合、熱可塑性ポリマ、熱硬化性ポリマなどのポリマを
積層してもよく、ポリエステル、例えば高分子量ポリエ
チレンテレフタレート、イソフタル酸共重合ポリエチレ
ンテレフタレート、ブタンジオール、イソフタル酸残基
骨格を有する共重合ポリエチレンテレフタレート、さら
にジエチレングリコールを添加、共重合したポリエステ
ルなどが好ましく使用される。The film used in the present invention may be a single layer or a laminate. The thickness of the biaxially stretched film of the present invention,
It is preferably 3 to 50 μm, more preferably 5 to 35 μm, particularly preferably 8 to 30 μm in terms of moldability after lamination to metal, coatability to metal, impact resistance and taste characteristics. . When used in a laminate, a thermoplastic polymer, a polymer such as a thermosetting polymer may be laminated, polyester, for example, high molecular weight polyethylene terephthalate, isophthalic acid copolymerized polyethylene terephthalate, butanediol, isophthalic acid residue skeleton. A copolymerized polyethylene terephthalate, and a polyester obtained by further adding diethylene glycol and copolymerizing are preferably used.

【００２８】本発明で用いるフィルムの製造方法として
は、特に限定されないが例えば各ポリエステルを必要に
応じて乾燥した後、公知の溶融押出機に供給し、スリッ
ト状のダイからシート状に押出し、静電印加などの方式
によりキャスティングドラムに密着させ冷却固化し未延
伸シートを得る。延伸方式としては、同時二軸、逐次二
軸延伸いずれでもよいが、該未延伸シートをフイルムの
長手方向及び幅方向に延伸、熱処理し、目的とする面配
向度のフィルムを得る。好ましくはフィルムの品質の点
でテンター方式によるものが好ましく、長手方向に延伸
した後、幅方向に延伸する逐次二軸延伸方式、長手方
向、幅方向をほぼ同時に延伸していく同時二軸延伸方式
が望ましい。延伸倍率としてはそれぞれの方向に１．６
〜４．２倍、好ましくは１．７〜４．０倍である。長手
方向、幅方向の延伸倍率はどちらを大きくしてもよく、
同一としてもよい。また、延伸速度は１０００〜２００
０００％／分であることが望ましく、延伸温度はポリエ
ステルのガラス転移温度以上ガラス転移温度＋１００℃
以下であれば任意の温度とすることができるが、通常は
８０〜１７０℃が好ましい。更に二軸延伸の後にフイル
ムの熱処理を行うが、この熱処理はオーブン中、加熱さ
れたロール上等、従来公知の任意の方法で行なうことが
できる。熱処理温度は１２０℃以上２４５℃以下の任意
の温度とすることができるが、好ましくは１２０〜２４
０℃である。また熱処理時間は任意とすることができる
が、通常１〜６０ｓｅｃ間行うのが好ましい。熱処理は
フイルムをその長手方向および／または幅方向に弛緩さ
せつつ行ってもよい。さらに、再延伸を各方向に対して
１回以上行ってもよく、その後熱処理を行っても良い。The method for producing the film used in the present invention is not particularly limited. For example, after drying each polyester as required, the polyester is supplied to a known melt extruder, extruded into a sheet from a slit die, and then statically extruded. An unstretched sheet is obtained by bringing it into close contact with the casting drum by cooling and solidifying it by a method such as application of electricity. The stretching method may be either simultaneous biaxial stretching or sequential biaxial stretching, but the unstretched sheet is stretched in the longitudinal direction and width direction of the film and heat-treated to obtain a film having a desired degree of plane orientation. Preferably, a tenter method is preferable in terms of film quality.After stretching in the longitudinal direction, a sequential biaxial stretching method in which the film is stretched in the width direction, a simultaneous biaxial stretching method in which the film is stretched almost simultaneously in the longitudinal direction and the width direction. Is desirable. The draw ratio is 1.6 in each direction.
To 4.2 times, preferably 1.7 to 4.0 times. Either the stretching ratio in the longitudinal direction or the width direction may be increased,
They may be the same. The stretching speed is 1000 to 200
2,000% / min, and the stretching temperature is equal to or higher than the glass transition temperature of the polyester + glass transition temperature + 100 ° C.
Any temperature can be used as long as the temperature is as follows, but usually 80 to 170 ° C is preferable. After the biaxial stretching, the film is subjected to a heat treatment. This heat treatment can be carried out by any conventionally known method such as in an oven or on a heated roll. The heat treatment temperature can be any temperature from 120 ° C. to 245 ° C., but is preferably from 120 to 24 ° C.
0 ° C. Although the heat treatment time can be arbitrarily set, it is usually preferable to perform the heat treatment for 1 to 60 seconds. The heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. Further, re-stretching may be performed once or more in each direction, and then heat treatment may be performed.

【００２９】また、本発明で用いるフイルムの取扱い
性、加工性を向上させるために、平均粒子径０．０１〜
１０μｍの公知の内部粒子、無機粒子および／または有
機粒子などの外部粒子の中から任意に選定される粒子が
０．０１〜５０重量％含有されていることが好ましい。
特に平均粒子径０．１〜５μｍの内部粒子、無機粒子お
よび／または有機粒子が０．０１〜３重量％含有されて
いることが缶内面に使用されるフィルムとして好まし
い。Further, in order to improve the handleability and processability of the film used in the present invention, the average particle diameter is preferably 0.01 to 0.01.
It is preferable that 0.01 to 50% by weight of particles arbitrarily selected from known external particles such as 10 μm internal particles, inorganic particles and / or organic particles is contained.
In particular, it is preferable that the film used on the inner surface of the can contains 0.01 to 3% by weight of internal particles, inorganic particles and / or organic particles having an average particle diameter of 0.1 to 5 μm.

【００３０】内部粒子の析出方法としては公知の技術を
採用できるが、例えば特開昭４８−６１５５６号公報、
特開昭５１−１２８６０号公報、特開昭５３−４１３５
５号公報、特開昭５４−９０３９７号公報などに記載の
技術が挙げられる。さらに特開昭５９−２０４６１７号
公報などの他の粒子との併用も行うことができる。１０
μｍを越える平均粒子径を有する粒子を使用するとフィ
ルムの欠陥が生じ易くなるので好ましくない。As a method for depositing the internal particles, a known technique can be adopted, for example, Japanese Patent Application Laid-Open No. 48-61556,
JP-A-51-12860, JP-A-53-4135
No. 5, JP-A-54-90397 and the like. Further, it can be used in combination with other particles such as JP-A-59-204617. 10
It is not preferable to use particles having an average particle diameter exceeding μm, since defects in the film are likely to occur.

【００３１】無機粒子および／または有機粒子として
は、例えば湿式および乾式シリカ、コロイダルシリカ、
珪酸アルミ、酸化チタン、炭酸カルシウム、リン酸カル
シウム、硫酸バリウム、アルミナ、マイカ、カオリン、
クレー等の無機粒子およびスチレン、シリコーン、アク
リル酸類等を構成成分とする有機粒子等を挙げることが
できる。なかでも湿式および乾式コロイド状シリカ、ア
ルミナ等の無機粒子およびスチレン、シリコーン、アク
リル酸、メタクリル酸、ポリエステル、ジビニルベンゼ
ン等を構成成分とする有機粒子等を挙げることができ
る。これらの内部粒子、無機粒子および／または有機粒
子は二種以上を併用してもよい。Examples of the inorganic particles and / or organic particles include wet and dry silica, colloidal silica,
Aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin,
Examples include inorganic particles such as clay and organic particles containing styrene, silicone, acrylic acid, and the like as constituent components. Among them, inorganic particles such as wet and dry colloidal silica and alumina, and organic particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituents can be exemplified. Two or more of these internal particles, inorganic particles and / or organic particles may be used in combination.

【００３２】さらに、缶内面に使用される場合、中心線
平均粗さＲａは好ましくは０．００５〜０．０７μｍ、
さらに好ましくは０．００８〜０．０５μｍである。さ
らに、最大粗さＲｔとの比Ｒｔ／Ｒａが４〜５０、好ま
しくは６〜４０であると高速製缶性が向上する。Further, when used on the inner surface of a can, the center line average roughness Ra is preferably 0.005 to 0.07 μm,
More preferably, it is 0.008 to 0.05 μm. Further, when the ratio Rt / Ra to the maximum roughness Rt is 4 to 50, preferably 6 to 40, high-speed can-making properties are improved.

【００３３】また本発明で用いるフィルム上には各種コ
ーティングを施しても良く、その塗布化合物、方法、厚
みは、本発明の効果を損なわない範囲であれば、特に限
定されない。Various coatings may be applied to the film used in the present invention, and the coating compound, method and thickness are not particularly limited as long as the effects of the present invention are not impaired.

【００３４】次に、前記フィルムのラミネート方法につ
いて説明する。通常のラミネート金属板の製造を考える
と、熱せられた金属板にフィルムを接触させ、ロールで
圧着して、金属板界面のフィルム樹脂を溶融させて、金
属板に濡れさせることによって、金属板とフィルムの接
着を行っている。Next, a method of laminating the film will be described. Considering the production of a normal laminated metal plate, a film is brought into contact with a heated metal plate, pressed with a roll, melts the film resin at the metal plate interface, and wets the metal plate. The film is bonded.

【００３５】本発明が対象とする二軸延伸ポリエステル
フィルムを前記の方法で金属板にラミネートすると、加
熱された金属板によって、フィルム−金属板界面でフィ
ルム樹脂が融解する。緩和時間Ｔ１ρで表現される抑制
された分子運動性は、一旦フィルムが溶融してしまう
と、この抑制効果が解消されて、加熱によって容易に結
晶化を起こし、成形加工熱や成形後の加熱工程、内容物
の充填後の高温殺菌工程で、この接着界面に結晶成長
し、密着性の劣化やフィルム外観の白化、加工性の劣化
等が生じる。When the biaxially stretched polyester film of the present invention is laminated on a metal plate by the above-described method, the heated metal plate causes the film resin to melt at the film-metal plate interface. The suppressed molecular mobility represented by the relaxation time T1ρ is such that once the film is melted, this suppressing effect is eliminated, and crystallization is easily caused by heating. In the high-temperature sterilization step after the filling of the contents, crystals grow on this adhesive interface, and the adhesion is deteriorated, the appearance of the film is whitened, and the workability is deteriorated.

【００３６】本発明者等による詳細な検討の結果、ラミ
ネートに際して、このフィルムの分子運動性の抑制機能
を失わせないためには、高温の金属板に接している時間
を厳しく制限、特に、金属板がフィルムの融点以上の温
度でフィルムと接している時間を厳密に制約する必要が
あることが判明した。As a result of a detailed study by the present inventors, in order to prevent the function of suppressing the molecular mobility of the film from being lost during lamination, the time during which the film is in contact with a high-temperature metal plate is strictly limited. It has been found that the time that the plate is in contact with the film at a temperature above the melting point of the film must be strictly limited.

【００３７】また、ラミネート金属板を容器用途に用い
る場合、ラミネート後水冷されるまでのフィルム温度も
成形性や耐衝撃性に大きく影響することも判明した。す
なわち、ラミネート後水冷までのフィルム温度は、高い
ほどラミネート後の成形性能が優れるものの、フィルム
が融点を超えると耐衝撃性がなくなり、かつ結晶化抑制
効果も失われて、製缶工程中の加熱によって、この加熱
工程後、成形性もフィルムの密着性もなくなってしま
う。逆にラミネート後水冷までのフィルム温度が低い
と、耐衝撃性が優れるものの、ラミネート金属板のフィ
ルム加工性が不十分になり、高度の成形に耐えられな
い。When the laminated metal plate was used for a container, it was also found that the film temperature from lamination to water cooling greatly affected the moldability and impact resistance. In other words, the higher the film temperature from lamination to water cooling, the better the molding performance after lamination, but if the film exceeds the melting point, the film loses impact resistance and loses the crystallization suppression effect, and loses the crystallization suppressing effect. Therefore, after this heating step, neither the moldability nor the film adhesion is obtained. Conversely, when the film temperature from lamination to water cooling is low, the impact resistance is excellent, but the film processability of the laminated metal plate is insufficient, and the laminated metal plate cannot withstand advanced molding.

【００３８】フィルムの温度は、ラミネート時点で、金
属板に接する面が最も高い。ラミネート時の金属板の温
度とラミネート時間を制限することによって、フィルム
の持っている加工性や耐衝撃性、耐レトルト白化性を維
持できることが判明した。これは、樹脂の溶融には、温
度と時間が必要であるため、極めて短時間の高温状態で
あれば、融点以上の温度であっても、溶融せず、フィル
ムの本来持っている物性を実質的に残存させた状態で、
金属板と接する側のフィルムの極表層部が、金属板の表
面にそって変形するため、良好な接着が可能となってい
るものと考えられる。The temperature of the film is highest on the surface in contact with the metal plate at the time of lamination. It was found that by limiting the temperature of the metal plate during lamination and the lamination time, the workability, impact resistance and retort whitening resistance of the film can be maintained. This is because the melting of resin requires temperature and time, so if it is in a very high temperature state for a very short time, it does not melt even at a temperature higher than the melting point, and substantially possesses the inherent properties of the film. In a state where
It is considered that excellent adhesion is possible because the extreme surface layer portion of the film in contact with the metal plate is deformed along the surface of the metal plate.

【００３９】従来より行われているラミネート方法で
は、ラミネートに際して、短時間融着の達成が困難なた
め、より高速でのラミネートが必要である。In the conventional laminating method, it is difficult to achieve fusion in a short time during laminating, so that laminating at a higher speed is required.

【００４０】高度の成形が可能で、且つ製缶工程で加熱
後も密着性に優れるようにするには、金属板をフィルム
融点より高温にしてラミネートをはじめ、できるだけ短
時間でロールによるフィルム圧着を行いフィルム温度を
フィルムの融点以下の温度に下げることが不可欠であ
り、さらにニップをでたラミネートフィルムを、できる
だけ短時間でガラス転移点以下の温度まで冷却すること
も重要であることもわかった。In order to perform high-level molding and to provide excellent adhesion even after heating in the can-making process, the metal plate is heated to a temperature higher than the melting point of the film, and laminating is carried out in as short a time as possible. It was found that it was essential to lower the film temperature to a temperature lower than the melting point of the film, and it was also important to cool the niped laminated film to a temperature lower than the glass transition point in as short a time as possible.

【００４１】このような知見に更に検討を加えた結果、
フィルムのラミネート方法としては、以下に記載する方
法が好適であることが明らかになった。As a result of further study on such findings,
As a method for laminating a film, the following method was found to be suitable.

【００４２】本発明においては、前記の二軸延伸ポリエ
ステルフィルムを金属板にラミネートする際に、ラミネ
ート開始時の金属板の温度Ｔ0をフィルムの融点Ｔfの温
度以上、ラミネートロールのニップ出側の金属板の温度
Ｔ1をフィルムの融点Ｔf以下にするとともに、更に下式
で定義されるラミネートインデックスＫを１〜２０ｍｓ
ｅｃの範囲内にしてラミネートする必要がある。 Ｋ＝（Ｔ0−Ｔf）×ｔ／（Ｔ0−Ｔ1） 但し、ｔ ：ニップ時間In the present invention, when laminating the biaxially stretched polyester film on a metal plate, the temperature T 0 of the metal plate at the start of lamination should be equal to or higher than the melting point Tf of the film and the nip exit side of the laminating roll. 1~20ms with the laminate index K which is defined further by the following equation for the temperature T 1 of the metal plate below the melting point T f of the film
It is necessary to laminate within the range of ec. K = (T 0 −T f ) × t / (T 0 −T 1 ) where t: nip time

【００４３】ラミネートインデックスＫが１ｍｓｅｃ未
満では、フィルムが金属板に接着するのに充分でなく、
加工に耐えないで加工中に剥離する。また２０ｍｓｅｃ
を超えると、金属板との密着面の近傍の分子運動性の抑
制効果が失われてしまう。そのままでの成形性能は得ら
れるが、成形後フィルムの歪み取りなどの加熱を受ける
と、ラミネート金属板のフィルムと金属板界面近傍に、
球晶が成長し、密着性や加熱された後の成形性能、内容
物充填後の殺菌工程での白化等が生じてしまう。ラミネ
ートインデックスＫのより好ましい範囲は２〜１５ｍｓ
ｅｃ、特に好ましい範囲は５〜１０ｍｓｅｃである。When the lamination index K is less than 1 msec, the film is not enough to adhere to the metal plate.
Peel off during processing without enduring processing. Also 20msec
If it exceeds 300, the effect of suppressing the molecular mobility near the contact surface with the metal plate will be lost. Although the molding performance as it is can be obtained, when heated such as distortion removal of the film after molding, near the interface between the film of the laminated metal plate and the metal plate,
A spherulite grows, resulting in adhesion, molding performance after heating, whitening in a sterilization step after filling the contents, and the like. The more preferable range of the laminate index K is 2 to 15 ms.
ec, a particularly preferred range is 5 to 10 msec.

【００４４】良好な密着性、耐レトルト白化性、加工性
を得るために、ラミネート開始時の金属板温度Ｔ0をフ
ィルムの融点Ｔf以上、ラミネートロールのニップ出側
の金属板の温度Ｔ1をフィルムの融点Ｔf以下にする。In order to obtain good adhesion, retort whitening resistance, and workability, the temperature T 0 of the metal plate at the start of lamination should be equal to or higher than the melting point Tf of the film, and the temperature T 1 of the metal plate on the lamination roll nip exit side. Is not more than the melting point Tf of the film.

【００４５】ラミネート開始時の金属板温度Ｔ0がフィ
ルム融点＋４０℃を超えるとラミネート界面でフィルム
が溶融しやすくなり、またフィルム融点＋２℃を下回る
と、短時間のラミネートでは、金属板とフィルムを密着
させることが不十分となって、加工後の密着性確保が困
難となる場合が有る。従って、ラミネート開始時の金属
板温度Ｔ0は、フィルム融点＋２℃〜フィルム融点＋４
０℃の範囲であることが好ましく、より好ましい範囲は
フィルム融点＋１０℃〜フィルム融点＋４０℃の範囲、
特に好ましい範囲は、フィルム融点＋２０℃〜フィルム
融点＋３０℃の範囲である。When the temperature T 0 of the metal plate at the start of lamination exceeds the melting point of the film + 40 ° C., the film tends to melt at the lamination interface, and when the temperature T 0 falls below the melting point of the film + 2 ° C., the lamination of the metal plate and the film takes place in a short time. In some cases, the adhesion is insufficient, making it difficult to ensure the adhesion after processing. Therefore, the metal plate temperature T 0 at the start of lamination is from the film melting point + 2 ° C. to the film melting point + 4.
It is preferably in the range of 0 ° C, more preferably in the range of film melting point + 10 ° C to film melting point + 40 ° C,
A particularly preferred range is the range of the film melting point + 20 ° C to the film melting point + 30 ° C.

【００４６】ニップ時間（ニップ長さ／ラミネート速
度）が０．０５ｓｅｃを超えるとラミネート時間が長す
ぎて、加工性と耐衝撃性のどちらかがの特性が低下す
る。また、０．００５ｓｅｃを下回ると、金属板とフィ
ルムを密着させることが不十分となって、加工後の密着
性確保が困難となる場合が有る。従って、好ましいニッ
プ時間は０．００５〜０．０５ｓｅｃであり、より好ま
しくは、０．０１〜０．０４ｓｅｃ、特に好ましくは、
０．０１５〜０．０３ｓｅｃである。If the nip time (nip length / lamination speed) exceeds 0.05 sec, the lamination time is too long, and either the workability or the impact resistance is reduced. On the other hand, when the time is less than 0.005 sec, the metal plate and the film may not be sufficiently adhered to each other, and it may be difficult to secure the adhesion after processing. Therefore, a preferred nip time is 0.005 to 0.05 sec, more preferably 0.01 to 0.04 sec, and particularly preferably
It is 0.015 to 0.03 sec.

【００４７】ニップ加圧力とは、ロール加圧力をニップ
面積で割ったものであり、ニップ加圧力は１〜３０ｋｇ
／ｃｍ2が好ましい。低すぎると、融点以上であって
も、時間が短時間であるため、接着時の変形が充分でな
く十分な密着性を得にくい。さらに、接着中の冷却効果
も十分に得られない。加圧力が大きくても特に品質面の
不都合はないものの、ラミネートロールにかかる力が大
きく、設備的な強度が必要となり、設備が大きくなって
不経済となる。加圧力のより好ましい範囲は５〜２０ｋ
ｇ／ｃｍ2、特に好ましい範囲は５〜１５ｋｇ／ｃｍ2で
ある。The nip pressure is obtained by dividing the roll pressure by the nip area, and the nip pressure is 1 to 30 kg.
/ Cm 2 is preferred. If the temperature is too low, even if the temperature is equal to or higher than the melting point, the time is short. Further, the cooling effect during the bonding is not sufficiently obtained. Even if the pressing force is large, there is no particular problem in quality, but the force applied to the laminating roll is large, and equipment strength is required. The more preferable range of the pressing force is 5 to 20 k.
g / cm 2 , a particularly preferred range is 5 to 15 kg / cm 2 .

【００４８】また、ラミネートロール直径／ラミネート
速度の比率が０．３ｓｅｃを超えると短時間でラミネー
トしながら、ラミネートロール入側と出側の板温度を前
記所望の範囲にすることが困難になる。従って、ラミネ
ートロール直径／ラミネート速度の比率は０．３ｓｅｃ
以下にするのが好ましく、より好ましくは０．２５ｓｅ
ｃ以下、特に好ましくは０．２ｓｅｃ以下である。On the other hand, if the ratio of the diameter of the laminating roll / laminating speed exceeds 0.3 sec, it becomes difficult to keep the sheet temperature on the laminating roll entrance side and the lamination roll side in the above-mentioned desired range while laminating in a short time. Therefore, the ratio of laminating roll diameter / laminating speed is 0.3 sec.
Or less, more preferably 0.25 sec.
c or less, particularly preferably 0.2 sec or less.

【００４９】ラミネート後水冷まで時間が５ｓｅｃを超
えると結晶化が進行して、加工性、加工後密着性が劣化
するので、５ｓｅｃ未満が好ましい。より好ましくは２
ｓｅｃ未満、特に好ましくは１ｓｅｃ未満である。な
お、ラミネート時間は短くても特に不都合はない。水冷
に際しての水温は、特に規定はしないが、フィルムのガ
ラス転移点以下の温度が好ましい。２層以上のフィルム
にあっては、ガラス転移点が低い方の温度以下であるこ
とが好ましい。If the time from lamination to water cooling exceeds 5 seconds, crystallization proceeds and processability and adhesion after processing deteriorate, so that the time is preferably less than 5 seconds. More preferably 2
It is less than sec, particularly preferably less than 1 sec. There is no particular problem even if the lamination time is short. The water temperature during water cooling is not particularly limited, but is preferably a temperature equal to or lower than the glass transition point of the film. In the case of a film having two or more layers, the temperature is preferably lower than the temperature at which the glass transition point is lower.

【００５０】また、必要によっては、ラミネートした
後、表面にパラフィン系等のワックスを塗布して、製缶
の加工に際して潤滑性能を付与してもかまわない。If necessary, after lamination, a wax such as paraffin may be applied to the surface to impart lubricating performance when the can is processed.

【００５１】本発明の金属板とは特に限定されないが、
成形性の点で鉄やアルミニウムなどを素材とする金属板
が好ましい。さらに、鉄を素材とする金属板の場合、そ
の表面に接着性や耐腐食性を改良する無機酸化物被膜
層、例えばクロム酸処理、リン酸処理、クロム酸／リン
酸処理、電解クロム酸処理、クロメート処理、クロムク
ロメート処理などで代表される化成処理被覆層を設けて
もよい。特に金属クロム換算値でクロムとして６．５〜
１５０ｍｇ／ｍ2のクロム層と５〜３０ｍｇ／ｍ2の水和
酸化物を金属クロムの上層に有する金属板が好ましく、
さらに、展延性金属メッキ層、例えばニッケル、スズ、
亜鉛、アルミニウム、砲金、真ちゅうなどを設けてもよ
い。スズメッキの場合０．５〜１５ｍｇ／ｍ2、ニッケ
ルまたはアルミニウムの場合１．８〜２０ｇ／ｍ2のメ
ッキ量を有するものが好ましい。Although the metal plate of the present invention is not particularly limited,
From the viewpoint of formability, a metal plate made of iron, aluminum, or the like is preferable. Further, in the case of a metal plate made of iron, an inorganic oxide coating layer on the surface thereof for improving adhesion and corrosion resistance, for example, chromic acid treatment, phosphoric acid treatment, chromic acid / phosphoric acid treatment, electrolytic chromic acid treatment A chemical conversion treatment coating layer represented by, for example, a chromate treatment or a chromium chromate treatment may be provided. In particular, in terms of chromium metal, 6.5 to chrome
Preferably the metal plate having the upper layer of metallic chromium and 150 mg / m 2 of chromium layer and 5 to 30 mg / m 2 of hydrated oxide,
In addition, a spreadable metal plating layer, such as nickel, tin,
Zinc, aluminum, gunmetal, brass and the like may be provided. It is preferable that tin plating has a plating amount of 0.5 to 15 mg / m 2 , and nickel or aluminum has a plating amount of 1.8 to 20 g / m 2 .

【００５２】本発明のラミネート金属板は、絞り成形や
しごき成形によって製造されるツーピース金属缶の内面
被覆用に好適に使用することができる。また、ツーピー
ス缶の蓋部分、あるいはスリーピース缶の胴、蓋、底の
被覆用としても良好な金属接着性、成形性を有するため
好ましく使用することができる。The laminated metal sheet of the present invention can be suitably used for coating the inner surface of a two-piece metal can manufactured by drawing or ironing. Further, it can be preferably used for covering a lid portion of a two-piece can or a body, a lid, and a bottom of a three-piece can because it has good metal adhesion and moldability.

【００５３】[0053]

【実施例】以下、実施例によって本発明を詳細に説明す
る。The present invention will be described below in detail with reference to examples.

【００５４】金属板として、低炭素Ａｌ−キルド鋼の連
続鋳造スラブを、熱間圧延、脱スケール、冷間圧延、焼
鈍、調質圧延を施した、調質度Ｔ４ＣＡ、寸法０．１９
６ｍｍ×９２０ｍｍの冷延鋼帯を使用して、脱脂、酸洗
の後、電解クロメート処理によって、金属クロム１３０
ｍｇ／ｍ2、クロム酸化物１５ｍｇ／ｍ2のめっき施した
ＴＦＳを準備した。As a metal plate, a continuously cast slab of low carbon Al-killed steel was subjected to hot rolling, descaling, cold rolling, annealing, and temper rolling. Temper T4CA, size 0.19
After degreasing and pickling using a cold-rolled steel strip of 6 mm × 920 mm, metal chromium
mg / m 2, was prepared a plating applied was TFS of chromium oxide 15mg / m 2.

【００５５】また、二軸延伸ポリエステルフィルムとし
て、厚さ２５μｍの１層又は２層からなるＰＥＴフィル
ムを準備した。Further, as a biaxially stretched polyester film, a PET film having a thickness of 25 μm and consisting of one or two layers was prepared.

【００５６】準備した金属板に準備した二軸延伸ポリエ
ステルフィルムをラミネートした。ラミネートに際して
は、スチールロールによる加熱に続いて、誘導加熱ロー
ルを用いて、ラミネート時のＴＦＳの板温を２８２℃に
加熱し、幅１４００ｍｍのラミネートロールで加圧して
フィルムを両面にラミネートした。ラミネート後水温７
５℃の蒸留水中で冷却した後、両面にロールコーターを
用いてパラフィンワックスを片面あたり５０ｍｇ／ｍ2
塗布し、巻き取り、ラミネート金属板を製造した。２層
フィルムの場合は、Ｂ層がラミネート面になるようにラ
ミネートした。前記で得たラミネート金属板の性能を調
査した。The prepared biaxially stretched polyester film was laminated on the prepared metal plate. At the time of lamination, following the heating by the steel roll, the plate temperature of TFS at the time of lamination was heated to 282 ° C. using an induction heating roll, and the film was laminated on both sides by pressing with a lamination roll having a width of 1400 mm. Water temperature after lamination 7
After cooling in distilled water at 5 ° C., paraffin wax was applied to both sides using a roll coater at 50 mg / m 2 per side.
Coating and winding were performed to produce a laminated metal plate. In the case of a two-layer film, lamination was performed so that the layer B became a laminate surface. The performance of the laminated metal plate obtained above was investigated.

【００５７】準備した二軸延伸ポリエステルフィルムの
特性、ラミネート条件および性能の調査結果を表１に記
載した。なお表中の略号は以下の通りである。 ＰＥＴ：ポリエチレンテレフタレート ＰＥＴ／Ｉ：イソフタル酸共重合ポリエチレンテレフタ
レート（数字は共重合モル％）Table 1 shows the characteristics, lamination conditions and performance of the prepared biaxially stretched polyester films. The abbreviations in the table are as follows. PET: Polyethylene terephthalate PET / I: Polyethylene terephthalate copolymerized with isophthalic acid (numbers are mol% copolymerized)

【００５８】また、フィルムの特性は下記の（１）〜
（４）、ラミネート金属板の特性は下記の（５）〜
（９）の方法により測定、評価した。更に、（５）〜
（９）の評価結果について、総合評価を行い、（５）〜
（９）の評価が何れも良以上のものを総合評価：○、何
れかの評価で可以下の評価があった場合、総合評価：×
とした。The characteristics of the film are as follows:
(4) The characteristics of the laminated metal plate are as follows (5)-
It was measured and evaluated by the method of (9). Furthermore, (5)-
Comprehensive evaluation is performed on the evaluation result of (9), and (5) to
(9) All evaluations of good or better were evaluated as comprehensive: 総 合, and any of the evaluations that were acceptable or less were evaluated as overall: ×
And

【００５９】（１）結晶サイズχ （１００）面の結晶サイズχを反射Ｘ線回折によりSche
rrerの式を用いて求めた。ここで、測定Ｘ線波長は０．
１５４１８ｎｍ（ＣｕＫα）であり、（１００）面の回
折はブラッグ角度約１２．７゜に観測された。(1) Crystal size {The crystal size of the (100) plane} was determined by reflection X-ray diffraction.
It was determined using the rrer equation. Here, the measured X-ray wavelength is 0.1.
15418 nm (CuKα), and diffraction of the (100) plane was observed at a Bragg angle of about 12.7 °.

【００６０】（２）ポリエステルの融点 ポリエステルを結晶化させ、示差走査熱量計（パーキン
・エルマー社製ＤＳＣ−２型）により、１０℃／ｍｉｎ
の昇温速度で測定した。(2) Melting Point of Polyester The polyester was crystallized and subjected to 10 ° C./min by a differential scanning calorimeter (DSC-2, manufactured by Perkin Elmer).
The temperature was measured at a rate of temperature rise.

【００６１】（３）ポリエステルの固有粘度 ポリエステルをオルソクロロフェノールに溶解し、２５
℃において測定した。(3) Intrinsic viscosity of polyester Polyester is dissolved in orthochlorophenol,
Measured in ° C.

【００６２】（４）面配向係数 ナトリウムＤ線（波長５８９ｎｍ）を光源として、アッ
ベ屈折計を用いて測定した。長手方向、幅方向、厚み方
向の屈折率（Ｎｘ，Ｎｙ，Ｎｚ）から得られる面配向係
数ｆｎ＝（Ｎｘ＋Ｎｙ）／２−Ｎｚを計算して求めた。(4) Plane Orientation Coefficient Measured using an Abbe refractometer with sodium D line (wavelength 589 nm) as a light source. The plane orientation coefficient fn = (Nx + Ny) / 2-Nz obtained from the refractive indices (Nx, Ny, Nz) in the longitudinal direction, the width direction, and the thickness direction was calculated.

【００６３】（５）成形性 試料を絞り成形機を用いて、順次絞り比（成形前径／成
形後径）１．６、２．１および２．８の３段階、８０〜
１００℃において成形可能温度領域で成形した缶を得
た。第２段階及び第３段階の成形で得られた缶内に１％
の食塩水を入れて、食塩水中の電極と金属缶に６ｖの電
圧をかけて３ｓｅｃ後の電流値を読み取り、１０缶測定
後の平均値を求め、以下の評価をした。 優 ：０．００１ｍＡ未満 良 ：０．００１ｍＡ以上０．０１ｍＡ未満 可 ：０．０１ｍＡ以上０．１ｍＡ未満 不可：０．１ｍＡ以上(5) Formability The samples were drawn using a draw forming machine in three stages of drawing ratios (diameter before molding / diameter after molding) of 1.6, 2.1 and 2.8, from 80 to
A can molded at 100 ° C. in a moldable temperature range was obtained. 1% in the cans obtained in the second and third stages of molding
Was applied, a voltage of 6 V was applied to the electrode and the metal can in the saline solution, the current value was read after 3 sec, the average value after 10 can measurements was obtained, and the following evaluation was made. Excellent: less than 0.001 mA Good: 0.001 mA or more and less than 0.01 mA Acceptable: 0.01 mA or more and less than 0.1 mA Unacceptable: 0.1 mA or more

【００６４】（６）耐衝撃性 第３段階の絞り成形加工後、成形性の評価が良以上の缶
について、水を満注し、各試験について１０個ずつを高
さ１．２５ｍから塩ビタイル床面に落とした後、電極と
金属缶に６ｖの電圧をかけて３ｓｅｃ後の電流値を読み
取り、１０缶測定後の平均値を求め、以下の評価をし
た。 優 ：０．００１ｍＡ未満 良 ：０．００１ｍＡ以上０．０１ｍＡ未満 可 ：０．０１ｍＡ以上０．１ｍＡ未満 不可：０．１ｍＡ以上(6) Impact Resistance After the third stage of drawing, the cans having a good formability evaluation were filled with water, and 10 cans of each test were subjected to PVC tiles from a height of 1.25 m. After dropping on the floor, a voltage of 6 V was applied to the electrode and the metal can, the current value after 3 sec was read, the average value after 10 can measurements was obtained, and the following evaluation was made. Excellent: less than 0.001 mA Good: 0.001 mA or more and less than 0.01 mA Acceptable: 0.01 mA or more and less than 0.1 mA Unacceptable: 0.1 mA or more

【００６５】（７）耐レトルト白化性 第３段階の絞り成形加工後の缶について、水を満注した
のち蓋を巻き締め、各試験について１０個ずつを１２５
℃で３０分間の加圧水蒸気中に保持し、底面および胴部
分の白化程度を以下の基準で目視判定した。 優 ：変化なし。 良 ：ほとんど変化が認められない。 可 ：部分的にわずかに白化が認められる。 不可：全体に白化が認められる。(7) Retort Whitening Resistance The cans after the drawing in the third stage were filled with water and then tightly closed with a lid.
The sample was kept in pressurized steam at 30 ° C. for 30 minutes, and the degree of whitening of the bottom surface and the trunk was visually determined based on the following criteria. Excellent: No change. Good: Almost no change was observed. Acceptable: slight whitening is observed partially. Impossible: Whitening is observed throughout.

【００６６】（８）加熱加工後密着性 第３段階の絞り成形加工後の缶について、２００℃で２
分間加熱し、ワックス分を除去した後、缶上部をネック
イン絞り加工を加え、続いて、蓋巻き締め用にフランジ
成形を施した。このフランジ部分内外面のフィルムの密
着程度を以下の基準で判定した。 優 ：変化なし。 良 ：ほとんど変化が認められない。 可 ：端部にわずかにハガレが認められる。 不可：フランジ全体にハガレが認められる。(8) Adhesion after Heating The can after the drawing at the third stage was treated at 200 ° C. for 2 hours.
After heating for one minute to remove the wax, the upper part of the can was subjected to neck-in drawing, and subsequently, a flange was formed for tightening the lid. The degree of adhesion of the film on the inner and outer surfaces of the flange portion was determined based on the following criteria. Excellent: No change. Good: Almost no change was observed. Acceptable: slight peeling is observed at the end. Impossible: peeling was observed on the entire flange.

【００６７】（９）味特性 第３段階の絞り成形加工後の缶に１２０℃×３０分の加
圧蒸気処理を行った後、香料水溶液ｄ−リモネン２５ｐ
ｐｍ水溶液を３５０ｍｌ充填し、４０℃密封後４５日放
置し、その後開封して官能検査によって、臭気の変化を
以下の基準で評価した。 優：臭気に全く変化が見られない。 良：臭気にほとんど変化が見られない。 可：臭気にやや変化が見られる。 不可：臭気に変化が大きく見られる。(9) Taste Characteristics After the cans after the third-stage drawing process were subjected to a pressurized steam treatment at 120 ° C. for 30 minutes, a perfume aqueous solution d-limonene 25p
350 ml of a pm aqueous solution was filled, sealed at 40 ° C., left to stand for 45 days, and then opened, and a change in odor was evaluated by a sensory test according to the following criteria. Excellent: No change in odor was observed. Good: Almost no change in odor. Acceptable: slight change in odor is observed. Impossible: Changes in odor are large.

【００６８】[0068]

【表１】 [Table 1]

【００６９】本発明範囲を満足する発明例１〜８は、何
れも成形性が良好であり、さらに耐衝撃性〜加熱加工後
密着性の特性も良好で、総合評価が○である。Inventive Examples 1 to 8 satisfying the range of the present invention all have good moldability, and also have good properties from impact resistance to adhesion after heat processing, and the overall evaluation is ○.

【００７０】ポリエステルの構成単位が本発明に規定す
る範囲を外れる比較例１は、成形性が劣り、また耐衝撃
性、味特性、耐レトルト白化性が劣る。フィルムの結晶
サイズχが６ｎｍを超える比較例２は、成形性が劣り、
また耐衝撃性、味特性が劣る。In Comparative Example 1 in which the constitutional unit of the polyester is out of the range specified in the present invention, the moldability is poor, and the impact resistance, taste characteristics, and retort whitening resistance are poor. Comparative Example 2 in which the crystal size フ ィ ル ム of the film exceeds 6 nm is inferior in moldability,
In addition, impact resistance and taste characteristics are poor.

【００７１】ラミネートインデックスが本発明範囲を外
れる比較例３〜６は、本発明例に比べて成形性が劣り、
また耐レトルト白化性、加熱加工後密着性が本発明例に
比べて明らかに劣る。比較例１〜６はいずれも総合評価
が×である。Comparative Examples 3 to 6 in which the laminate index was out of the range of the present invention were inferior in moldability as compared with the examples of the present invention.
In addition, retort whitening resistance and adhesion after heating are clearly inferior to those of the examples of the present invention. All of Comparative Examples 1 to 6 are evaluated as x.

【００７２】[0072]

【発明の効果】本発明の二軸延伸ポリエステルフィルム
ラミネート金属板は缶などに成形する際の成形性に優れ
ているだけでなく、味特性、耐衝撃性、耐レトルト白化
性などに優れた特性を有し、成形加工によって製造され
る金属缶の蓋や胴等の素材として好適である。The biaxially stretched polyester film-laminated metal sheet of the present invention not only has excellent moldability when formed into a can or the like, but also has excellent properties such as taste characteristics, impact resistance, and retort whitening resistance. It is suitable as a material for a lid or a body of a metal can manufactured by molding.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 威 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 (72)発明者 茂野 雅彦 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 (72)発明者 渡辺 真介 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 Ｆターム(参考） 4F100 AB01A AB03 AB07 AK41B AK42B AL01B BA02 BA26 EA021 EH012 EH463 EJ192 EJ38B EJ462 EJ503 EJ691 EJ851 EJ943 EK06 GB16 JA04B JA20B JC00 JK09 JL00 JL01 YY00B 4J002 BC012 BC032 BG002 CF032 CF071 CP032 DE136 DE236 DG046 DH046 DJ016 DJ036 DJ056 FA082 FD016 GG01 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takeshi Suzuki 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Co., Ltd. (72) Masahiko Shigeno 1-2-1-2 Marunouchi, Chiyoda-ku, Tokyo Sun (72) Inventor Shinsuke Watanabe 1-2-2 Marunouchi, Chiyoda-ku, Tokyo F-term (reference) 4F100 AB01A AB03 AB07 AK41B AK42B AL01B BA02 BA26 EA021 EH012 EH463 EJ192 EJ38B EJ462 EJ503 EJ691 EJ851 EJ943 EK06 GB16 JA04B JA20B JC00 JK09 JL00 JL01 YY00B 4J002 BC012 BC032 BG002 CF032 CF071 CP032 DE136 DE236 DG046 DH046 DJ016 DJ036 DJ056 FA082 FD016 GG01

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 構成単位の９３モル％以上がエチレンテ
レフタレート単位であるポリエステルからなり、Ｘ線回
折測定により得られる（１００）面の結晶サイズχが６
ｎｍ以下である二軸延伸ポリエステルフィルムを金属板
の少なくとも片面にラミネートする際に、ラミネート開
始時の金属板の温度Ｔ0をフィルムの融点Ｔf以上、ラミ
ネートロールニップ出側の金属板の温度Ｔ1をフィルム
の融点Ｔf以下にするとともに、更に下式で定義される
ラミネートインデックスＫを１〜２０ｍｓｅｃの範囲内
にしてラミネートすることを特徴とするラミネート金属
板の製造方法。 Ｋ＝（Ｔ0−Ｔf）×ｔ／（Ｔ0−Ｔ1） 但し、ｔ：ニップ時間1. A polyester having an ethylene terephthalate unit in which 93 mol% or more of the structural unit has a crystal size ６ of (100) plane obtained by X-ray diffraction measurement of 6
When laminating a biaxially stretched polyester film having a thickness of at most 1 nm on at least one side of the metal plate, the temperature T 0 of the metal plate at the start of lamination is higher than the melting point Tf of the film and the temperature T of the metal plate at the laminating roll nip exit side. 1. A method for producing a laminated metal sheet, wherein 1 is set to be equal to or lower than the melting point Tf of the film, and laminating is further performed by setting a lamination index K defined by the following formula within a range of 1 to 20 msec. K = (T 0 −T f ) × t / (T 0 −T 1 ) where t: nip time 【請求項２】 ニップ時間ｔが０．００５〜０．０５ｓ
ｅｃの範囲内であることを特徴とする請求項１に記載の
ラミネート金属板の製造方法。2. The nip time t is 0.005 to 0.05 s.
The method for producing a laminated metal sheet according to claim 1, wherein the value is within the range of ec. 【請求項３】 ポリエステルの構成単位の９６モル％以
上がエチレンテレフタレート単位であることを特徴とす
る請求項１または請求項２に記載のラミネート金属板の
製造方法。3. The method for producing a laminated metal sheet according to claim 1, wherein 96 mol% or more of the constituent units of the polyester are ethylene terephthalate units. 【請求項４】 フィルムの面配向係数が０．１５以下で
あることを特徴とする請求項１〜請求項３のいずれかに
記載のラミネート金属板の製造方法。4. The method for producing a laminated metal sheet according to claim 1, wherein the plane orientation coefficient of the film is 0.15 or less. 【請求項５】 ポリエステルの融点が２４６℃以上、２
８０℃以下であることを特徴とする請求項１〜請求項４
のいずれかに記載のラミネート金属板の製造方法。5. A polyester having a melting point of 246 ° C. or higher,
The temperature is not higher than 80C.
The method for producing a laminated metal sheet according to any one of the above.
JP34036498A 1998-11-30 1998-11-30 Manufacturing method of laminated metal sheet Expired - Fee Related JP3485003B2 (en)

Priority Applications (1)

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JP34036498A JP3485003B2 (en) 1998-11-30 1998-11-30 Manufacturing method of laminated metal sheet

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Application Number Priority Date Filing Date Title
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JP2000158588A true JP2000158588A (en) 2000-06-13
JP3485003B2 JP3485003B2 (en) 2004-01-13

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Country Link
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002072346A1 (en) * 2001-03-14 2002-09-19 Jfe Steel Corporation Film-laminated metal sheet for container
US7666487B2 (en) * 2003-05-22 2010-02-23 Jfe Steel Corporation Easy-open end and laminated steel sheet

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002072346A1 (en) * 2001-03-14 2002-09-19 Jfe Steel Corporation Film-laminated metal sheet for container
US7198856B2 (en) 2001-03-14 2007-04-03 Jfe Steel Corporation Film-laminated metal sheet for container
US7435465B2 (en) 2001-03-14 2008-10-14 Jfe Steel Corporation Film-laminated metal sheet for container
US7666487B2 (en) * 2003-05-22 2010-02-23 Jfe Steel Corporation Easy-open end and laminated steel sheet

Also Published As

Publication number Publication date
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