JP2001047554A - Laminated steel plate for can in general - Google Patents
Laminated steel plate for can in generalInfo
- Publication number
- JP2001047554A JP2001047554A JP2000093272A JP2000093272A JP2001047554A JP 2001047554 A JP2001047554 A JP 2001047554A JP 2000093272 A JP2000093272 A JP 2000093272A JP 2000093272 A JP2000093272 A JP 2000093272A JP 2001047554 A JP2001047554 A JP 2001047554A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- laminated
- steel sheet
- resin layer
- general
- 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
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ラミネート後に缶
外面を塗装したり、製缶時に雰囲気温度が250℃を超え
るような強加熱が部分的に施されたりする一般缶の胴部
材や蓋部材、特に例えば18L缶、ペール缶などのような
大型一般缶の胴部材や蓋部材として好適な一般缶用ラミ
ネート鋼板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a body member and a cover member of a general can, in which the outer surface of the can is painted after lamination, or a strong heating such that the ambient temperature exceeds 250.degree. More particularly, the present invention relates to a laminated steel sheet for a general can suitable as a body member or a lid member of a large general can such as an 18L can or a pail.
【０００２】[0002]
【従来の技術】一般缶用途の大型缶の分野において、生
産性や省エネルギーの観点から、各種ラミネート鋼板を
使用した高耐食缶を製造する試みがなされている。例え
ば、特公平1-55104号公報、特公昭64-139号公報に、オ
レフィン樹脂やポリエチレンテレフタレート（PET）樹
脂を缶内面にラミネートした大型缶に関する技術が開示
されている。2. Description of the Related Art In the field of large cans for general cans, attempts have been made to produce highly corrosion-resistant cans using various laminated steel sheets from the viewpoint of productivity and energy saving. For example, Japanese Patent Publication No. 1-55104 and Japanese Patent Publication No. 64-139 disclose a technique relating to a large can in which an olefin resin or a polyethylene terephthalate (PET) resin is laminated on the inner surface of the can.
【０００３】また、飲料缶用途においても、レトルト後
耐食性や缶加工性の向上を目的として、結晶化度、配向
度、延伸倍率を詳細に規定した各種PET樹脂をラミネー
トしたラミネート缶やラミネート鋼板に関する技術が開
示されている。[0003] Also, in the case of beverage cans, the present invention relates to a laminated can or a laminated steel sheet laminated with various PET resins whose degree of crystallinity, degree of orientation and stretch ratio are specified in detail for the purpose of improving corrosion resistance after retort and can processability. Techniques are disclosed.
【０００４】[0004]
【発明が解決しようとする課題】外面塗装する一般缶
（以下、外面塗装一般缶）は、160℃以上の加熱を受け
るため、ラミネート樹脂に、融点の高いPET樹脂を適用
する必要がある。しかし、PET樹脂ラミネート缶は、加
水分解の点でアルカリ性の内容物に適用できないことか
ら、PET樹脂ラミネート缶へ適用する内容物は、中性、
酸性の内容物に限られる。PET樹脂は、特に香気成分の
保持などで食品用途に適した樹脂であることが知られて
おり、外面塗装一般缶は、食品内容物へ適用できるこ
と、すなわち食品用途適性を兼ね備えることが好まし
い。A general can to be coated on the outside (hereinafter referred to as a general can for external coating) is heated to 160 ° C. or higher, so that a PET resin having a high melting point must be applied to the laminate resin. However, since PET resin laminated cans cannot be applied to alkaline contents in terms of hydrolysis, the contents applied to PET resin laminated cans are neutral,
Limited to acidic contents. It is known that PET resin is a resin suitable for food use, particularly for retaining an aroma component, and it is preferable that an externally coated general can be applicable to food contents, that is, to have food application suitability.
【０００５】本発明者らは、PET樹脂ラミネート鋼板を
用いた外面塗装一般缶について検討し、以下の問題点の
あることを見い出した。 （１）外面塗装一般缶は、150〜200℃の温度で10〜20分
間、塗装仕様に応じて繰り返し加熱され、製缶加工され
る。前述の飲料缶用途の素材では、ラミネート後にこの
ような長時間の加熱が行なわれることがなく、一般缶特
有の製缶工程である。このような製缶工程を経ると、PE
T樹脂の中でも融点の低い90mol％以下のエチレンテレフ
タレート単位を有するPET樹脂は加熱後加工耐食性の劣
化を生じる傾向が顕著であった。[0005] The present inventors have studied an externally coated general can using a PET resin-laminated steel sheet, and have found the following problems. (1) General cans for exterior coating are repeatedly heated at a temperature of 150 to 200 ° C. for 10 to 20 minutes according to the coating specifications, and are canned. In the above-mentioned material for beverage cans, such long-time heating is not performed after lamination, and this is a can-making process unique to general cans. After going through such a can making process, PE
Among the T resins, the PET resin having a low melting point and having an ethylene terephthalate unit of 90 mol% or less had a remarkable tendency to deteriorate the corrosion resistance after heating.
【０００６】（２）大型一般缶は、製缶時巻締め部のシ
ールなどを行なう際、しばしば高周波加熱されるが、そ
の際の温度制御は難しく、250℃以上の温度で短時間加
熱される場合が多い。また、大型一般缶の内、胴部を接
着して製缶する接着缶（以下、大型接着缶）などでは、
バーナーなどで加熱されて胴かしめ部がシールされる場
合があり、この際も250℃以上の温度で短時間加熱され
る。(2) Large-sized cans are often heated by high frequency when sealing the sealing portion at the time of can-making, but the temperature control at that time is difficult, and the cans are heated at a temperature of 250 ° C. or more for a short time. Often. In addition, among the large general cans, the adhesive cans (hereinafter referred to as large adhesive cans), which are made by bonding the body, can be used.
In some cases, the caulked portion is sealed by being heated by a burner or the like, and in this case, the body is heated at a temperature of 250 ° C. or more for a short time.
【０００７】一度溶融したPET樹脂は、空冷され再凝固
するが、その際、93mol％以上のエチレンテレフタレー
ト単位を有するPET樹脂は、球晶が成長し、通常白化す
る。90mol％以下のエチレンテレフタレート単位を有す
るPET樹脂であればこの白化は抑制される。[0007] Once melted, the PET resin is air-cooled and re-solidified. At that time, the PET resin having an ethylene terephthalate unit of 93 mol% or more grows spherulites and usually whitens. If the PET resin has an ethylene terephthalate unit of 90 mol% or less, the whitening is suppressed.
【０００８】（３）大型一般缶（大型接着缶を含む）
は、前記したように製缶加工時の加熱を受ける。この
時、既存の93mol％以上のエチレンテレフタレート単位
を有するPET樹脂を母層とするPET樹脂フィルムをラミネ
ートした鋼板は、加工部でフィルム剥がれが生じた。(3) Large general cans (including large adhesive cans)
Is heated during can-making as described above. At this time, the existing steel sheet laminated with a PET resin film having a PET resin having an ethylene terephthalate unit of 93 mol% or more as a mother layer suffered film peeling at the processed part.
【０００９】したがって、本発明の目的は、前記問題点
を解決し、缶外面を塗装したり、製缶時に雰囲気温度が
250℃を超えるような強加熱が部分的に施されたりする
一般缶の胴部材や蓋部材、特に例えば18L缶、ペール缶
などのような大型一般缶の胴部材や蓋部材として好適な
一般缶用ラミネート鋼板を提供することにある。Accordingly, an object of the present invention is to solve the above-mentioned problems and to paint the outer surface of a can or to reduce the ambient temperature during can-making.
General cans or lids of general cans that are partially subjected to intense heating such as exceeding 250 ° C., in particular, for example, 18L cans, general cans suitable as body members and lids of large general cans such as pail cans It is to provide a laminated steel sheet for use.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく、素材鋼板の表面処理皮膜の構成および
樹脂層の構成が異なる種々のラミネート鋼板について、
加熱後加工耐食性、加工後加熱密着性、耐白化性などの
観点から詳細な調査検討を行ない、その結果以下の知見
を得た。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have developed various laminated steel sheets having different configurations of a surface treatment film and a resin layer of a base steel sheet.
Detailed investigations were conducted from the viewpoints of post-heating corrosion resistance, post-processing heat adhesion, and whitening resistance. As a result, the following findings were obtained.
【００１１】（１）外面塗装一般缶の特徴である、150
〜200℃の高温度での繰り返し加熱による樹脂層の劣化
や加熱後加工耐食性の劣化について検討した結果、融点
の低い90mol％以下のエチレンテレフタレート単位を有
するPET樹脂は200℃程度の高温加熱で脆化する傾向のあ
ることが判明した。この原因はラミネート時の加熱など
で生じた非晶部分で球晶を発生することによる。これら
の樹脂ラミネート鋼板では、加熱後に加工を受けると、
フィルムが脆化しているため、クラックなどを生じ耐食
性が劣化することが判明した。[0011] (1) The characteristic of a general can coated on the outer surface is 150
As a result of examining the deterioration of the resin layer due to repeated heating at high temperatures of up to 200 ° C and the deterioration of post-heating corrosion resistance, PET resins having a low melting point of 90 mol% or less ethylene terephthalate units are brittle at high temperatures of about 200 ° C. It was found that there was a tendency to change. This is due to the generation of spherulites in the amorphous portions generated by heating during lamination. In these resin-laminated steel sheets, when processed after heating,
It was found that since the film was brittle, cracks occurred and the corrosion resistance was deteriorated.
【００１２】一方、93mol％以上のエチレンテレフタレ
ート単位を有するPET樹脂を母層とするラミネート鋼板
では、ラミネート時の加熱により母層の配向が崩れにく
く、従って非晶部も生じにくいため、球晶の生成も少な
く、200℃程度の高温加熱でも脆化は穏やかであった。On the other hand, in a laminated steel sheet using a PET resin having 93 mol% or more of ethylene terephthalate units as a base layer, the orientation of the base layer hardly collapses due to heating during lamination, and an amorphous portion is hardly generated. Generation was small, and embrittlement was mild even at a high temperature of about 200 ° C.
【００１３】93mol％以上のエチレンテレフタレート単
位を有するPET樹脂であっても、製膜時の配向度が小さ
かったり、ラミネート時に母層の融点を上回る温度でラ
ミネートされ、製膜時の配向が損なわれているフィルム
では、加熱後加工耐食性が劣るので、ラミネート時のフ
ィルムの面配向係数を0.05以上にすることが望ましいこ
とが判明した。また、200℃程度の高温加熱する場合、
エチレンテレフタレート単位の割合を増加して、母層を
97mol％以上のエチレンテレフタレート単位を有するPET
樹脂とすると加熱後加工耐食性が優れることが判明し
た。Even a PET resin having an ethylene terephthalate unit of 93 mol% or more has a small degree of orientation at the time of film formation or is laminated at a temperature higher than the melting point of the base layer at the time of lamination, and the orientation at the time of film formation is impaired. It has been found that it is desirable to set the plane orientation coefficient of the film at the time of lamination to 0.05 or more, since the film has poor corrosion resistance after processing after heating. When heating at a high temperature of about 200 ° C,
Increase the proportion of ethylene terephthalate units to increase the
PET with 97 mol% or more ethylene terephthalate units
It was found that when the resin was used, post-heating corrosion resistance was excellent.
【００１４】（２）製缶加工時の加熱による加工部での
樹脂層の剥離は、樹脂層の成分に起因した以下の２点が
主な原因であることが判明した。(2) It has been found that peeling of the resin layer at the processed portion due to heating during can manufacturing is mainly caused by the following two points caused by the components of the resin layer.
【００１５】第１は、母層の熱収縮である。すなわち、
93mol％以上のエチレンテレフタレート単位を有する高
融点のPET単層フィルム、またはこの樹脂を母層とする2
層フィルムは、製膜方向にかかわらず、フィルムが200
℃において5％以上の熱収縮を生じる場合に、軽加工部
でも剥がれを生じることが判明した。熱収縮を抑制する
ためには、フィルム製膜時に熱固定を210℃以上の条件
で施したフィルムを使用することが必要である。The first is heat shrinkage of the base layer. That is,
High melting point PET monolayer film having 93 mol% or more ethylene terephthalate units, or this resin as a base layer 2
Regarding the layer film, regardless of the
It was found that when heat shrinkage of 5% or more was caused at ℃, peeling occurred even in a lightly processed portion. In order to suppress heat shrinkage, it is necessary to use a film that has been heat-set at 210 ° C. or higher during film formation.
【００１６】第２は、樹脂層が接着層を備える場合に、
高温加熱による接着層の特性の変化に起因したものであ
る。すなわち、接着層が85mol％未満のエチレンテレフ
タレート単位を有するPET樹脂の場合は、150℃程度の加
熱により接着層が軟化するため、加工部の樹脂層の内部
応力により接着層が破壊され、母層の剥離を生じる。Second, when the resin layer has an adhesive layer,
This is due to a change in the properties of the adhesive layer due to high-temperature heating. That is, in the case of a PET resin in which the adhesive layer has an ethylene terephthalate unit of less than 85 mol%, the adhesive layer is softened by heating at about 150 ° C. Is caused.
【００１７】接着層が90mol％超えのエチレンテレフタ
レート単位を有するPET樹脂の場合は、ラミネート時に
接着層樹脂内に生じた非晶部分で、塗装時の繰り返し加
熱により球晶が発生し、接着層と鋼板界面に歪みが発生
することにより密着力が低下し剥離を生じる。In the case of a PET resin in which the adhesive layer has an ethylene terephthalate unit of more than 90 mol%, spherulites are generated in the amorphous portion generated in the adhesive layer resin at the time of lamination by repeated heating during coating, and the adhesive layer is formed. Due to the occurrence of distortion at the steel plate interface, the adhesion decreases and peeling occurs.
【００１８】接着層が85mol％以上90mol％以下のエチレ
ンテレフタレート単位を有するPET樹脂の場合は、熱軟
化の程度が改善され、かつ球晶の発生も抑制されるため
200℃程度の高温加熱でも剥離を生じない。When the adhesive layer is a PET resin having an ethylene terephthalate unit of 85 mol% or more and 90 mol% or less, the degree of thermal softening is improved and the generation of spherulites is suppressed.
No exfoliation occurs even at a high temperature of about 200 ° C.
【００１９】なお、本明細書において、母層とは、樹脂
層が単層で構成される場合は、この層そのもの、複層で
構成される場合は、その内で最も厚い樹脂層を指してい
る。In the present specification, when the resin layer is composed of a single layer, the mother layer refers to this layer itself, and when composed of a plurality of layers, refers to the thickest resin layer. I have.
【００２０】また、各種缶用鋼板について検討した結
果、より優れた加熱後加工密着性を得るには、素材鋼板
としてめっき層の最外層に金属クロム換算で3mg／m2以
上のクロム水和酸化物層を有する表面処理鋼板が必要で
あることが判明した。In addition, as a result of studying various steel sheets for cans, it was found that, in order to obtain better work adhesion after heating, the outermost layer of the plating layer as a material steel sheet had a chromium hydrate oxidation of 3 mg / m 2 or more in terms of metal chromium. It has been found that a surface-treated steel sheet having a material layer is necessary.
【００２１】（３）大型一般缶（大型接着缶を含む）の
製缶工程で特有のPET樹脂の融点を超える加熱部での白
化現象は、球晶の生成によることが確認された。通常の
ホモ-PET樹脂は溶融などにより配向結晶を失い非晶化す
ると、結晶化速度が早く球晶を生成しやすい。球晶の成
長抑制には、90mol％以下のエチレンテレフタレート単
位を有するPET樹脂が効果的であるが、加熱脆化の観点
からこのような樹脂の適用は難しい。(3) It has been confirmed that the whitening phenomenon in the heating section exceeding the melting point of the PET resin, which is peculiar to the PET resin in the manufacturing process of large general cans (including large adhesive cans), is caused by the formation of spherulites. When a normal homo-PET resin loses its oriented crystal due to melting or the like and becomes amorphous, the crystallization speed is high and spherulites are easily generated. To suppress the growth of spherulites, a PET resin having an ethylene terephthalate unit of 90 mol% or less is effective, but it is difficult to apply such a resin from the viewpoint of heat embrittlement.
【００２２】そこで、93mol％以上のエチレンテレフタ
レート単位を有する高融点のPET樹脂について、球晶の
成長抑制を検討した。その結果、PET樹脂合成の際に巻
込まれる不純物が核になって球晶が成長すること、ま
た、前記不純物を10ppm未満にすることにより、球晶生
成による白化を抑制できることを見い出した。また、不
純物の多くは、樹脂合成時の触媒成分であるので、触媒
成分を10ppm以下にすれば、前記球晶生成を抑制する効
果が十分あることが分かった。Therefore, suppression of spherulite growth was examined for a high melting point PET resin having an ethylene terephthalate unit of 93 mol% or more. As a result, it has been found that spherulites grow by impurities incorporated in the synthesis of the PET resin as nuclei, and that the whitening due to spherulite formation can be suppressed by reducing the impurities to less than 10 ppm. In addition, since most of the impurities are catalyst components at the time of resin synthesis, it was found that the effect of suppressing the formation of spherulites was sufficient if the catalyst components were set to 10 ppm or less.
【００２３】本発明は、このような知見に基づくもので
あり、前記課題を解決する本発明の手段は、以下の通り
である。 （１）缶内面となる側の鋼板面にラミネート樹脂層を有
する一般缶用ラミネート鋼板であって、前記ラミネート
樹脂層の母層が、93mol％以上のエチレンテレフタレー
ト単位を含み、かつ、樹脂合成時に混入する触媒成分な
どの不純物が10ppm未満であり、また前記ラミネート樹
脂層の面配向係数が0.05以上であり、かつラミネート樹
脂層を200℃で15分保持した際の収縮率が5％未満である
ことを特徴とする一般缶用ラミネート鋼板（第1発
明）。The present invention is based on such findings, and the means of the present invention for solving the above problems are as follows. (1) A laminated steel sheet for a general can having a laminated resin layer on the steel sheet surface on the inner side of the can, wherein the base layer of the laminated resin layer contains 93 mol% or more of ethylene terephthalate units, and Impurities such as catalyst components to be mixed are less than 10 ppm, the plane orientation coefficient of the laminate resin layer is 0.05 or more, and the shrinkage ratio when the laminate resin layer is kept at 200 ° C. for 15 minutes is less than 5%. A laminated steel sheet for general cans (first invention).
【００２４】（２）前記（１）において、鋼板が、その
最外層に金属クロム換算で3mg／m2以上のクロム水和酸
化物層を有する表面処理鋼板であり、またラミネート樹
脂層の厚さが10μm以上であることを特徴とする一般缶
用ラミネート鋼板（第2発明）。(2) In the above (1), the steel sheet is a surface-treated steel sheet having a chromium hydrated oxide layer of 3 mg / m 2 or more in terms of metal chromium in its outermost layer, and the thickness of the laminated resin layer Is not less than 10 μm. (2nd invention).
【００２５】（３）缶内面となる側の鋼板面にラミネー
ト樹脂層を有する一般缶用ラミネート鋼板であって、前
記ラミネート樹脂層は、接着層とその上層としての母層
からなり、前記接着層は、85mol％以上90mol％以下のエ
チレンテレフタレート単位を含み、厚さ1μm以上5μm以
下の樹脂層であり、前記母層は、97mol％以上のエチレ
ンテレフタレート単位を含む樹脂層であり、かつ、前記
ラミネート樹脂層を200℃で15分保持した際の熱収縮率
が5％未満であることを特徴とする一般缶用ラミネート
鋼板（第3発明）。(3) A laminated steel sheet for a general can having a laminated resin layer on the steel sheet surface on the inner side of the can, wherein the laminated resin layer comprises an adhesive layer and a base layer as an upper layer thereof. Is a resin layer containing 85 mol% or more and 90 mol% or less ethylene terephthalate units and having a thickness of 1 μm or more and 5 μm or less, wherein the base layer is a resin layer containing 97 mol% or more ethylene terephthalate units and the laminate A laminated steel sheet for general cans, wherein the resin layer has a heat shrinkage of less than 5% when held at 200 ° C. for 15 minutes (third invention).
【００２６】[0026]
【発明の実施の形態】以下、本発明の詳細をその限定理
由とともに説明する。本発明においては、缶内面となる
側の鋼板面に用いるラミネート樹脂層の母層のエチレン
テレフタレート単位を93mol％以上含むことが必要であ
る。93mol％未満では、共重合時に生成する低分子量の
不純物成分が内容物中へ溶出するようになり、更には、
高温加熱時の樹脂層の脆化が著しく、加熱後加工耐食性
が劣化するためである。母層のエチレンテレフタレート
単位を97mol％以上含有させることによって、前記効果
がより優れる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below together with the reasons for limiting the same. In the present invention, it is necessary to contain 93 mol% or more of ethylene terephthalate units of the base layer of the laminated resin layer used on the steel sheet surface on the inner side of the can. If it is less than 93 mol%, low molecular weight impurity components generated during copolymerization will elute into the contents, and furthermore,
This is because the resin layer is remarkably embrittled at the time of high-temperature heating, and the post-heating processing corrosion resistance deteriorates. The above effect is more excellent when the ethylene terephthalate unit of the base layer is contained at 97 mol% or more.
【００２７】缶内面側に用いるラミネート樹脂層の母層
の樹脂合成時に混入する触媒成分に起因した不純物濃度
は低いことが望ましい。不純物を核とした結晶化（球晶
の成長）が促進され、加熱時の樹脂の機械特性の劣化
や、白化を生じやすいためである。このような観点か
ら、不純物濃度は100ppm以下が望ましい。It is desirable that the concentration of impurities caused by the catalyst component mixed during the resin synthesis of the mother layer of the laminated resin layer used on the inner side of the can be low. This is because crystallization (growth of spherulites) with impurities as nuclei is promoted, and the mechanical properties of the resin during heating are likely to be degraded and whitened. From such a viewpoint, the impurity concentration is desirably 100 ppm or less.
【００２８】特にラミネート樹脂層の母層のエチレンテ
レフタレート単位が93mol％以上では、触媒成分に起因
した不純物濃度が高い場合に特に球晶生成が著しいた
め、触媒成分に起因した不純物による結晶化促進の傾向
が顕著になる。不純物を核とした結晶化（球晶の生成）
を抑制し、加熱時の樹脂の機械特性の劣化や、バーナー
加熱部などでおこる樹脂の白化を防止するには、ラミネ
ート樹脂層の母層の樹脂合成時に混入する触媒成分に起
因した不純物を10ppm未満にすることが有効である。ま
た、母層の樹脂は、アンチモン系の触媒で合成された樹
脂より、ゲルマニウム系の触媒で合成された樹脂の方
が、不純物濃度が低いのでより好ましい。In particular, when the ethylene terephthalate unit in the mother layer of the laminated resin layer is 93 mol% or more, spherulite formation is remarkable particularly when the impurity concentration due to the catalyst component is high, and therefore, the crystallization promotion by the impurity due to the catalyst component is promoted. The tendency becomes remarkable. Crystallization using impurities as nuclei (spherulite formation)
In order to prevent the deterioration of the mechanical properties of the resin during heating and to prevent the whitening of the resin from occurring in the burner heating section, etc., 10 ppm of impurities caused by the catalyst component mixed during the resin synthesis of the mother layer of the laminated resin layer are used. It is effective to make it less than. As for the resin of the mother layer, a resin synthesized with a germanium-based catalyst is more preferable than a resin synthesized with an antimony-based catalyst because the impurity concentration is lower.
【００２９】ラミネートされた樹脂層を200℃で15分保
持した際の収縮率を5％未満としたのは、5％以上ある場
合、加工後加熱を受ける部分で樹脂層剥離を生じるため
である。収縮率を5％未満にするには、例えば、フィル
ム製膜時の熱固定温度を210℃以上で製膜したフィルム
を用いることが必要である。The reason why the shrinkage ratio when the laminated resin layer is held at 200 ° C. for 15 minutes is less than 5% is that if it is 5% or more, the resin layer peels off in the portion that is heated after processing. . In order to reduce the shrinkage to less than 5%, for example, it is necessary to use a film formed at a heat setting temperature of 210 ° C. or higher during film formation.
【００３０】また、ラミネート樹脂層が接着層を備える
場合、接着層が85mol％未満のエチレンテレフタレート
単位を有するPET樹脂の場合は、150℃程度の加熱により
接着層が軟化するため、加工部の樹脂層の内部応力によ
り接着層が破壊され、母層の剥離が生じる。接着層が90
mol％超えのエチレンテレフタレート単位を有するPET樹
脂の場合は、ラミネート時に接着層樹脂内に生じた非晶
部分で、塗装時の繰り返し加熱により球晶が発生し、接
着層と鋼板界面に歪みが発生することにより、密着力が
低下し剥離を生じる。したがって、200℃程度の高温加
熱する場合、接着層は、85mol％以上90mol％以下のエチ
レンテレフタレート単位を含む樹脂層であることが必要
である。When the laminated resin layer has an adhesive layer, and when the adhesive layer is a PET resin having an ethylene terephthalate unit of less than 85 mol%, the adhesive layer is softened by heating at about 150 ° C. The adhesive layer is destroyed by the internal stress of the layer, and peeling of the mother layer occurs. 90 adhesive layers
In the case of PET resin with more than mol% ethylene terephthalate units, spherulites are generated in the amorphous part generated in the adhesive layer resin during lamination due to repeated heating during coating, and distortion occurs at the interface between the adhesive layer and the steel sheet By doing so, the adhesion decreases and peeling occurs. Therefore, when heating at a high temperature of about 200 ° C., the adhesive layer needs to be a resin layer containing 85 mol% or more and 90 mol% or less of ethylene terephthalate units.
【００３１】ラミネート鋼板の樹脂層全体の総厚みとし
ては10〜55μmが望ましい。10μm未満では、樹脂層のピ
ンホールなどにより現行の塗装鋼板並みの耐食性の保持
が難しい。55μmを超えると缶成型時の巻締めの際、シ
ール不良の原因となる。樹脂層の母層（複層の層構成の
場合は最も厚い樹脂層）は、接着層（例えばエチレンテ
レフタレート単位が85mol％以上90mol％以下の共重合PE
T樹脂層）を介してラミネートされているか、母層融点
以上の鋼板温度で母層の一部を溶融させる形でラミネー
トされているものが好ましい。The total thickness of the entire resin layer of the laminated steel sheet is preferably from 10 to 55 μm. If the thickness is less than 10 μm, it is difficult to maintain corrosion resistance equivalent to that of the current coated steel sheet due to pinholes in the resin layer. If it exceeds 55 μm, it may cause poor sealing when tightening during can molding. The mother layer of the resin layer (the thickest resin layer in the case of a multilayer structure) is formed of an adhesive layer (for example, copolymerized PE having an ethylene terephthalate unit of 85 mol% to 90 mol%).
(T resin layer) or those in which a part of the base layer is melted at a steel sheet temperature not lower than the melting point of the base layer.
【００３２】母層を接着層を介してラミネートする場
合、接着層の厚さは1〜5μmであることが望ましい。接
着層の厚さが1μm未満では、良好な密着性が得られず、
5μmを超えても、密着性が飽和し、却って加熱時の脆化
の影響を受けるためである。When the mother layer is laminated via an adhesive layer, the thickness of the adhesive layer is desirably 1 to 5 μm. If the thickness of the adhesive layer is less than 1 μm, good adhesion cannot be obtained,
If the thickness exceeds 5 μm, the adhesiveness is saturated, and on the contrary, it is affected by embrittlement during heating.
【００３３】ラミネート用の素材鋼板としては、めっき
層の最外層に、金属クロム換算で3mg／m2以上のクロム
水和酸化物層を有する表面処理鋼板であることが好まし
い。前記クロム水和酸化物層が金属クロム換算で3mg／m
2以上になると、樹脂層との密着性が更に優れる。上限
については特に定めはないが、30mg/m2以上ではラミネ
ート後の色調が暗くなる傾向があるため好ましくない。As a material steel sheet for lamination, a surface-treated steel sheet having a chromium hydrated oxide layer of 3 mg / m 2 or more in terms of metal chromium in the outermost layer of the plating layer is preferable. The chromium hydrated oxide layer is 3 mg / m in terms of metal chromium.
When it is 2 or more, the adhesion to the resin layer is further excellent. There is no particular upper limit, but if it is 30 mg / m 2 or more, the color tone after lamination tends to be dark, which is not preferable.
【００３４】また、鋼板の表面粗さは、ラミネート時の
気泡の巻き込みなどに影響するので、中心線平均粗さ
で、0.003〜0.2μmの範囲が好ましい。Since the surface roughness of the steel sheet affects the entrapment of air bubbles during lamination, the center line average roughness is preferably in the range of 0.003 to 0.2 μm.
【００３５】ラミネートされたフィルムの面配向係数を
0.05以上としたのは、一般缶は、飲料缶と比較して、製
缶加工度が小さく、かつ、塗装製缶時の加熱が厳しいこ
とを考慮したためでる。ラミネート樹脂層の母層のエチ
レンテレフタレート単位を93mol％以上含む場合に、飲
料缶などとは異なり、面配向係数を0.05以上の高い領域
に規定することにより、一般缶での要求性能に適した加
工後加熱耐食性が得られる。The plane orientation coefficient of the laminated film is
The reason for setting the ratio to 0.05 or more is that the general can takes into account that the degree of can-making process is smaller than that of a beverage can and that heating during coating can is severe. When the ethylene terephthalate unit of the mother layer of the laminate resin layer contains 93 mol% or more, unlike the beverage cans, etc., by setting the plane orientation coefficient to a high area of 0.05 or more, processing suitable for the required performance of general cans Post-heat corrosion resistance is obtained.
【００３６】フィルムの製膜時の延伸倍率は、製膜方向
と幅方向にそれぞれ1.5〜4.5倍の範囲としたものが望ま
しい。The stretching ratio at the time of film formation is desirably 1.5 to 4.5 times each in the film forming direction and the width direction.
【００３７】フィルムを鋼板にラミネートする際の鋼板
の温度は、フィルムの配向を保持し球晶の生成を抑制す
るために、上限を母層の融点を大きく超えない範囲、望
ましくは母層の融点+10℃以下の範囲に制御することが
望ましい。The temperature of the steel sheet at the time of laminating the film to the steel sheet is not more than the upper limit, preferably not higher than the melting point of the base layer, in order to maintain the orientation of the film and suppress the formation of spherulites. It is desirable to control the temperature within a range of + 10 ° C or lower.
【００３８】また、ラミネート樹脂層が接着層を備える
場合、ラミネート直前の鋼板温度を接着層の融点以上か
つ母層の融点未満に保持してラミネートすることが好ま
しい。母層の融点以上にすると、ラミネート時に母層の
配向層が溶融して非晶部分を多く生成するようになり、
製缶時の加熱で球晶などを生じやすくなるため、好まし
くない。When the laminating resin layer has an adhesive layer, it is preferable that the lamination is performed while maintaining the temperature of the steel sheet immediately before lamination at a temperature equal to or higher than the melting point of the adhesive layer and lower than the melting point of the base layer. If it is higher than the melting point of the base layer, the orientation layer of the base layer will melt during lamination and generate a lot of amorphous parts,
It is not preferable because spherulites and the like are easily generated by heating during can-making.
【００３９】[0039]
【実施例】次に具体的な実施例について説明する。 ＜実施例1＞ （鋼板）板厚0.32mmの冷延鋼板に、又はこの鋼板に化成
処理の下地処理を施した後、化成処理を施して金属クロ
ム層とその上にクロム水和酸化物層を有する表面処理鋼
板を調製した。前記で調製した表面処理鋼板の下地処理
の内容、及びめっき層の付着量（金属クロム層のクロム
量、クロム水和酸化物層のクロム付着量）を表1〜表2に
示す。EXAMPLES Next, specific examples will be described. <Example 1> (Steel sheet) A cold rolled steel sheet having a thickness of 0.32 mm, or after a base treatment of a chemical conversion treatment is applied to this steel sheet, a chemical conversion treatment is applied to the metal chromium layer and a chromium hydrated oxide layer thereon. Was prepared. Tables 1 and 2 show the contents of the base treatment of the surface-treated steel sheet prepared as described above and the amount of the plating layer (the amount of chromium in the metal chromium layer and the amount of chromium in the chromium hydrated oxide layer).
【００４０】（樹脂のラミネート）前記で調製した表面
処理鋼板の一方の面に、フィルムラミネートによって、
PET樹脂を被覆した。すなわち、フィルムとの接着部を
接着面樹脂の融点-50℃〜母層樹脂の融点+10℃の範囲に
加熱した鋼板に、1層構造（母層のみ）又は2層構造（母
層+接着層）のフィルムをラミネートロールで加圧しな
がらラミネートし、ラミネート後水冷した。フィルムの
母層樹脂は、いずれも三菱化学ポリエステルフィルム製
のものを用いた。ラミネートに供したPET樹脂の内容及
び膜厚を、表1〜表2に示す。(Lamination of Resin) On one surface of the surface-treated steel sheet prepared as described above,
PET resin was coated. That is, a single-layer structure (base layer only) or a two-layer structure (base layer + bonding) is applied to a steel sheet whose adhesive portion with the film is heated to a temperature in the range of the melting point of the bonding surface resin -50 ° C to the melting point of the base layer resin + 10 ° C. The film of (layer) was laminated while being pressed with a laminating roll, and the laminate was cooled with water. As the base resin of the film, those made of Mitsubishi Chemical polyester film were used. Tables 1 and 2 show the content and film thickness of the PET resin used for lamination.
【００４１】前記で得たラミネート鋼板について、次の
ようにして、加熱後加工耐食性、加工後加熱密着性、耐
抽出性、加熱耐白化性を評価し、またフィルムの熱収縮
率、面配向係数を調査した。The laminated steel sheet obtained above was evaluated for the corrosion resistance after heating, the heat adhesion after heating, the extraction resistance, and the whitening resistance after heating as described below. investigated.
【００４２】（１）加熱後加工耐食性 缶外面クリヤ塗装を想定して、ラミネート鋼板を180℃
で20分加熱した後、下記の条件でラミネート面が凸にな
るようにデュポン衝撃加工を行なった。その後、下記の
浸漬試験を行ない、溶出鉄量または溶出錫量を求め、TF
S（金属クロム層：100mg/m2、クロム水和酸化物層：10m
g/m2、何れも金属クロム換算の付着量）に2回塗装し、
同様の試験をした場合の鉄溶出量と比較し、溶出量が1/
2未満の少ないものを◎、1/2以上同等以下の少ないもの
を、多いものを×と評価した。(1) Corrosion resistance after heating The laminated steel sheet was heated to 180 ° C., assuming clear coating on the outer surface of the can.
After heating for 20 minutes, DuPont impact processing was performed under the following conditions so that the laminate surface became convex. Then, perform the following immersion test to determine the amount of dissolved iron or dissolved tin, and TF
S (metal chromium layer: 100 mg / m 2 , chromium hydrated oxide layer: 10 m
g / m 2 , both of which are coated on metal chrome)
Compared to the iron elution amount in the same test, the elution amount was 1 /
A sample with less than 2 was evaluated as ◎, and a sample with less than or equal to 1/2 or less was evaluated as x.
【００４３】デュポン衝撃加工条件：1/2インチ径の圧
子を300gの荷重で50cmの高さから落下させ加工。 浸漬条件：1.5％クエン酸+1.5％NaCl、38℃、7日。DuPont impact processing conditions: A 1/2 inch diameter indenter was dropped from a height of 50 cm with a load of 300 g to perform processing. Immersion conditions: 1.5% citric acid + 1.5% NaCl, 38 ° C., 7 days.
【００４４】（２）加工後加熱密着性 ラミネート鋼板のラミネート面に凹次いで凸のデュポン
衝撃加工を施した後、180℃で20分の加熱を行なった。
その際、加工部で樹脂層の剥離の有無を評価し、凹部加
工で剥離無しを◎、凸部加工で剥離無しを、凹凸両方の
加工で剥離有りを×と評価した。(2) Heat Adhesion After Processing The laminated surface of the laminated steel sheet was subjected to concave and convex DuPont impact processing, and then heated at 180 ° C. for 20 minutes.
At that time, the presence / absence of peeling of the resin layer was evaluated at the processed portion, and the absence of peeling at the concave portion processing was evaluated as ◎;
【００４５】（３）耐抽出性 ラミネート鋼板を95℃で1時間、純水中に浸漬し、抽出
された有機成分をガスクロマトグラフを用いて分析し、
抽出物無しを、抽出物有りを×と評価した。食品用途に
適用する場合は、本評価が○であることが好ましい。(3) Extraction resistance The laminated steel sheet was immersed in pure water at 95 ° C. for 1 hour, and the extracted organic components were analyzed using a gas chromatograph.
The absence of extract was evaluated as x when the extract was present. When applied to food applications, it is preferable that this evaluation be ○.
【００４６】（４）加熱耐白化性 ラミネート鋼板を180℃で20分加熱後、製缶ラインのバ
ーナー加熱部に通板し、白化の有無を評価し、白化無し
を、白化有りを×とした。(4) Heat Whitening Resistance After heating the laminated steel sheet at 180 ° C. for 20 minutes, the sheet was passed through a burner heating section of a can-making line to evaluate the presence or absence of whitening. .
【００４７】（５）フィルムの熱収縮率 ラミネート後の鋼板から樹脂層を剥離し、樹脂層を200
℃で15分加熱し、加熱処理前後でのフィルムの収縮率
（2層の場合はフィルム全体の収縮率）を求めた。(5) Thermal Shrinkage of Film The resin layer was peeled off from the laminated steel sheet,
The film was heated at 15 ° C. for 15 minutes, and the shrinkage ratio of the film before and after the heat treatment (shrinkage ratio of the whole film in the case of two layers) was determined.
【００４８】（６）フィルムの面配向係数 前記（５）と同様、ラミネート後の鋼板から樹脂層を剥
離し、アッベ方式の屈折計を用いて面配向係数を測定し
た。光源にはナトリウムＤ線を使用し、長手、幅、厚み
の３方向の屈折率、Ｎｘ，Ｎｙ，Ｎｚから下式より計算
した。 面配向係数 Ｎｓ＝（Ｎｘ＋Ｎｙ）／２−Ｎｚ 評価結果、熱収縮率及び面配向係数の調査結果を表1、
表２に併せて記載した。(6) Surface Orientation Coefficient of Film As in the case of (5), the resin layer was peeled off from the laminated steel sheet, and the surface orientation coefficient was measured using an Abbe refractometer. A sodium D line was used as a light source, and the refractive index in three directions of longitudinal, width and thickness, Nx, Ny and Nz, was calculated by the following equation. Plane Orientation Coefficient Ns = (Nx + Ny) / 2-Nz Evaluation results, heat shrinkage ratio and investigation results of plane orientation coefficient are shown in Table 1,
It is also described in Table 2.
【００４９】[0049]
【表1】 【table 1】
【００５０】[0050]
【表2】 [Table 2]
【００５１】表1、表2において、第1発明範囲を外れる
比較例は、以下に説明するように、加工後加熱密着性、
加熱耐白化性、加熱後加工耐食性、耐抽出性の内の少な
くとも一つの特性が劣る。In Tables 1 and 2, the comparative examples outside the scope of the first invention are as follows, as will be described below.
At least one of heat whitening resistance, post-heat processing corrosion resistance, and extraction resistance is inferior.
【００５２】表1の比較例1に示すように、面配向係数が
0．05未満では良好な加熱耐白化性が得られない。ま
た、球晶を非晶部で生成するため加熱密着性も劣る。更
に膜厚が10μｍ未満と薄いため加工耐食性も悪い。As shown in Comparative Example 1 in Table 1, the plane orientation coefficient was
If it is less than 0.05, good heat whitening resistance cannot be obtained. Further, since spherulites are generated in the amorphous part, the adhesiveness under heating is poor. Further, since the film thickness is as thin as less than 10 μm, the processing corrosion resistance is poor.
【００５３】表1の比較例1と発明例3の比較に示すよう
に、母層が93mol％未満のエチレンテレフタレート単位
である場合、耐抽出性が劣る。As shown in the comparison between Comparative Example 1 and Inventive Example 3 in Table 1, when the mother layer is less than 93 mol% of ethylene terephthalate units, the extraction resistance is poor.
【００５４】表2の比較例1、4に示すように、フィルム
の熱固定温度が低く、200℃での熱収縮率が5％以上であ
るものは、加工後加熱密着性が劣る。As shown in Comparative Examples 1 and 4 in Table 2, films having a low heat setting temperature and a heat shrinkage at 200 ° C. of 5% or more have poor heat adhesion after processing.
【００５５】表2の比較例2〜4に示すように、フィルム
母層樹脂中の、主として触媒起因の不純物の濃度が10pp
mを超える場合は、加熱耐白化性が劣る。As shown in Comparative Examples 2 to 4 in Table 2, the concentration of impurities mainly caused by the catalyst in the resin of the film base layer was 10 pp.
If it exceeds m, the heat whitening resistance is poor.
【００５６】これに対して、第１発明範囲を満足する表
1、表2の発明例はいずれも、加工後加熱密着性、加熱耐
白化性、加熱後加工耐食性、耐抽出性に優れる。また、
発明例9と発明例10の比較から分かるように、表面処理
鋼板のめっき層の最外層が金属クロム換算で3mg／m2以
上のクロム水和酸化物層の場合、加工後加熱密着性が更
に優れる。On the other hand, a table satisfying the first invention range.
1. All of the invention examples shown in Table 2 are excellent in post-processing heat adhesion, heat whitening resistance, post-processing corrosion resistance, and extraction resistance. Also,
As can be seen from the comparison between Invention Example 9 and Invention Example 10, when the outermost layer of the plating layer of the surface-treated steel sheet is a chromium hydrated oxide layer of 3 mg / m 2 or more in terms of metal chromium, the heat adhesion after processing is further improved. Excellent.
【００５７】＜実施例2＞ （鋼板）板厚0.32mmの冷延鋼板に、又はこの鋼板に化成
処理の下地処理を施した後、化成処理を施して金属クロ
ム層とその上にクロム水和酸化物層を有する表面処理鋼
板を調製した。前記で調製した表面処理鋼板の下地処理
の内容、及びめっき層の付着量（金属クロム層のクロム
量、クロム水和酸化物層のクロム付着量）を表3〜表4に
示す。<Example 2> (Steel sheet) A cold rolled steel sheet having a thickness of 0.32 mm, or after a base treatment of a chemical conversion treatment is applied to this steel sheet, a chemical conversion treatment is applied to the metal chromium layer and chromium hydration on the metal chromium layer A surface-treated steel sheet having an oxide layer was prepared. Tables 3 and 4 show the content of the base treatment of the surface-treated steel sheet prepared as described above and the amount of the plating layer (the amount of chromium in the metal chromium layer and the amount of chromium in the chromium hydrated oxide layer).
【００５８】（樹脂のラミネート）前記で調製した表面
処理鋼板の一方の面に、フィルムラミネートによって、
PET樹脂を被覆した。すなわち、フィルムとの接着部を
接着層樹脂の融点〜母層樹脂の融点の範囲に加熱した鋼
板に、2層構造（母層+接着層）のフィルムをラミネート
ロールで加圧しながらラミネートし、ラミネート後水冷
した。フィルムの母層樹脂は、いずれも三菱化学ポリエ
ステルフィルム製のものを用いた。ラミネートに供した
PET樹脂の内容及び膜厚を、表3〜表4に示す。(Lamination of Resin) On one surface of the surface-treated steel sheet prepared as described above,
PET resin was coated. That is, a film having a two-layer structure (base layer + adhesive layer) is laminated on a steel sheet in which a portion to be bonded to the film is heated to a range from the melting point of the adhesive layer resin to the melting point of the base layer resin while pressing with a laminating roll. After that, it was water-cooled. As the base resin of the film, those made of Mitsubishi Chemical polyester film were used. Laminated
Tables 3 and 4 show the content and film thickness of the PET resin.
【００５９】前記で得たラミネート鋼板について、次の
ようにして、200℃で高温加熱した場合の加熱後加工耐
食性、加工後加熱密着性を評価し、またフィルムの熱収
縮率を調査した。The laminated steel sheet obtained above was evaluated for corrosion resistance after heating when heated at a high temperature of 200 ° C. and adhesion to heat after processing, and the heat shrinkage of the film was investigated as follows.
【００６０】（１）加熱後加工耐食性 ラミネート鋼板を200℃で15分加熱した後、実施例1と同
様、デュポン衝撃加工後、浸漬試験を行ない、溶出鉄量
または溶出錫量を求め、2回塗装のTFSの鉄溶出量と比較
し、溶出量が同等以下のものを、多いものを×と評価し
た。(1) Corrosion resistance after heating After heating the laminated steel sheet at 200 ° C. for 15 minutes, as in Example 1, after the DuPont impact processing, an immersion test was carried out to determine the amount of dissolved iron or dissolved tin, and twice. Compared to the iron elution amount of the TFS of the coating, those with the same or lower elution amount were evaluated as x and those with the higher elution amount were evaluated as x.
【００６１】（２）加工後加熱密着性 ラミネート面に、実施例1と同様デュポン衝撃加工を施
した後、200℃で15分の加熱を行ない、加工部で樹脂層
の剥離の有無を評価し、剥離無しを、剥離有りを×と評
価した。評価結果及び熱収縮率の調査結果を表3〜表4に
併せて記載した。(2) Heat Adhesion After Processing The laminated surface was subjected to DuPont impact processing in the same manner as in Example 1, and then heated at 200 ° C. for 15 minutes to evaluate whether the resin layer had peeled off at the processed portion. , No peeling was evaluated, and peeling was evaluated as x. The evaluation results and the results of the investigation of the heat shrinkage are also shown in Tables 3 and 4.
【００６２】[0062]
【表3】 [Table 3]
【００６３】[0063]
【表4】 [Table 4]
【００６４】表3、表4において、第3発明範囲を外れる
比較例は、以下に説明するように、加工後加熱密着性、
加熱後加工耐食性の少なくとも一方が劣る。In Tables 3 and 4, the comparative examples outside the scope of the third invention are as follows.
At least one of the corrosion resistance after heating is inferior.
【００６５】表3の比較例1に示すように、樹脂層の接着
層が90mol％超えのエチレンテレフタレート単位を含む
場合、接着層の非晶の樹脂層で加熱時に球晶が生成し、
加工後加熱密着性が劣化する。As shown in Comparative Example 1 in Table 3, when the adhesive layer of the resin layer contains more than 90 mol% of ethylene terephthalate units, spherulites are generated in the amorphous resin layer of the adhesive layer when heated,
After processing, heat adhesion deteriorates.
【００６６】表3の比較例2に示すように、樹脂層の接着
層が85mol％未満のエチレンテレフタレート単位を含む
場合、接着層の樹脂層が低温で軟化するため、加工後加
熱密着性が劣化する。As shown in Comparative Example 2 in Table 3, when the adhesive layer of the resin layer contains less than 85 mol% of ethylene terephthalate units, the resin layer of the adhesive layer softens at a low temperature, so that the heat adhesion after processing deteriorates. I do.
【００６７】表3の比較例3に示すように、樹脂層の最外
層が97mol％未満のエチレンテレフタレート単位である
場合、加熱時の樹脂層の脆化が著しく、加熱後加工部で
クラックが生じ良好な耐食性が得られない。As shown in Comparative Example 3 in Table 3, when the outermost layer of the resin layer was less than 97 mol% of ethylene terephthalate units, the resin layer was remarkably embrittled during heating, and cracks occurred in the processed portion after heating. Good corrosion resistance cannot be obtained.
【００６８】表3の比較例4に示すように、樹脂層が第3
発明範囲内であっても、接着層の膜厚が5μm超えの場
合、良好な加熱後加工耐食性が得られない。As shown in Comparative Example 4 in Table 3, the resin layer
Even within the range of the invention, if the thickness of the adhesive layer exceeds 5 μm, good post-heating work corrosion resistance cannot be obtained.
【００６９】表4の比較例1,2に示すように、フィルムの
熱固定温度が低く、200℃での熱収縮率が5％以上である
ものは、加工加熱後密着性が劣る。特に母層中の不純物
濃度が高い比較例2は、熱収縮が著しい。As shown in Comparative Examples 1 and 2 in Table 4, films having a low heat setting temperature and a heat shrinkage at 200 ° C. of 5% or more have poor adhesion after processing and heating. In particular, in Comparative Example 2 in which the impurity concentration in the mother layer is high, the heat shrinkage is remarkable.
【００７０】これに対して、第3発明範囲を満足する表
3、表4の発明例は、200℃の高温加熱した場合でも、い
ずれも加工後加熱密着性、加熱後加工耐食性に優れる。On the other hand, a table satisfying the third invention range.
3. The invention examples shown in Table 4 are excellent in heat adhesion after processing and corrosion resistance after processing even when heated at a high temperature of 200 ° C.
【００７１】[0071]
【発明の効果】第1発明、第2発明によれば、加熱耐白化
性及び加工後加熱密着性、または更に加熱後加工耐食
性、耐抽出性に優れたラミネート鋼板が得られる。第3
発明によれば、高温加熱した場合に加工後加熱密着性及
び加熱後加工耐食性に優れたラミネート鋼板が得られ
る。According to the first and second aspects of the present invention, a laminated steel sheet having excellent heat whitening resistance and post-processing heat adhesion, or further excellent post-processing corrosion resistance and extraction resistance can be obtained. number 3
ADVANTAGE OF THE INVENTION According to this invention, when heated at high temperature, the laminated steel sheet excellent in the heat adhesion after processing and the corrosion resistance after processing can be obtained.
【００７２】本発明のラミネート鋼板は、缶外面を塗装
したり、製缶時に雰囲気温度が250℃を超えるような強
加熱が部分的に施されたりする一般缶の胴部材や蓋部
材、特に18L缶、ペール缶のような大型一般缶の胴部材
や蓋部材への使用に好適である。また、本発明のラミネ
ート鋼板は、食品用途適性を兼ね備えているので、前記
缶を中性、酸性の食品内容物に適用することができる。The laminated steel sheet of the present invention can be used for coating the outer surface of a can or for subjecting the body member and cover member of a general can, which is subjected to partial heating to a high ambient temperature of more than 250 ° C. during can making, particularly 18L. It is suitable for use as a body member and a lid member of large general cans such as cans and pail cans. Further, since the laminated steel sheet of the present invention also has suitability for food use, the can can be applied to neutral and acidic food contents.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大庭 直幸 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 森 慎一郎 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 豊文 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 AA22B AB03B AK42 AK42A AK42C AK42J AL01 BA02 BA03 BA07 BA10A BA10C BA13 DA01 EJ37A EJ38 EJ69B GB16 GB18 GB23 JA03 JA03A JA03C JA20A JB02 JJ03 JK06 JL01 JL08A YY00A YY00C ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naoyuki Oba 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Co., Ltd. (72) Inventor Shinichiro Mori 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Sun (72) Inventor Toyofumi Watanabe 1-2-2 Marunouchi, Chiyoda-ku, Tokyo F-term (reference) 4F100 AA22B AB03B AK42 AK42A AK42C AK42J AL01 BA02 BA03 BA07 BA10A BA10C BA13 DA01 EJ37A EJ38 EJ69B GB16 GB18 GB23 JA03 JA03A JA03C JA20A JB02 JJ03 JK06 JL01 JL08A YY00A YY00C
Claims (3)
脂層を有する一般缶用ラミネート鋼板であって、前記ラ
ミネート樹脂層の母層が、93mol％以上のエチレンテレ
フタレート単位を含み、かつ、樹脂合成時に混入する触
媒成分などの不純物が10ppm未満であり、また前記ラミ
ネート樹脂層の面配向係数が0.05以上であり、かつラミ
ネート樹脂層を200℃で15分保持した際の収縮率が5％未
満であることを特徴とする一般缶用ラミネート鋼板。1. A laminated steel sheet for a general can having a laminated resin layer on the steel sheet surface on the side serving as the inner surface of the can, wherein the base layer of the laminated resin layer contains 93 mol% or more of ethylene terephthalate units, and The impurities such as catalyst components mixed during the synthesis are less than 10 ppm, the plane orientation coefficient of the laminate resin layer is 0.05 or more, and the shrinkage ratio when the laminate resin layer is held at 200 ° C. for 15 minutes is less than 5%. A laminated steel sheet for general cans, characterized in that:
に金属クロム換算で3mg／m2以上のクロム水和酸化物層
を有する表面処理鋼板であり、またラミネート樹脂層の
厚さが10μm以上であることを特徴とする一般缶用ラミ
ネート鋼板。2. The steel sheet according to claim 1, wherein the outermost layer is a surface-treated steel sheet having a chromium hydrated oxide layer of 3 mg / m 2 or more in terms of chromium metal, and the thickness of the laminated resin layer is 10 μm. A laminated steel sheet for general cans characterized by the above.
脂層を有する一般缶用ラミネート鋼板であって、前記ラ
ミネート樹脂層は、接着層とその上層としての母層から
なり、前記接着層は、85mol％以上90mol％以下のエチレ
ンテレフタレート単位を含み、厚さ1μm以上5μm以下の
樹脂層であり、前記母層は、97mol％以上のエチレンテ
レフタレート単位を含む樹脂層であり、かつ、前記ラミ
ネート樹脂層を200℃で15分保持した際の熱収縮率が5％
未満であることを特徴とする一般缶用ラミネート鋼板。3. A laminated steel sheet for a general can having a laminated resin layer on the steel sheet surface on the side to be the inner surface of the can, wherein the laminated resin layer comprises an adhesive layer and a base layer as an upper layer thereof, and the adhesive layer is A resin layer having a thickness of 1 μm or more and 5 μm or less, containing 85 mol% or more and 90 mol% or less of ethylene terephthalate units, wherein the mother layer is a resin layer containing 97 mol% or more of ethylene terephthalate units and the laminate resin 5% thermal shrinkage when the layer is kept at 200 ° C for 15 minutes
A laminated steel sheet for general cans, wherein
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|---|---|---|---|
| JP2000093272A JP4345189B2 (en) | 1999-05-31 | 2000-03-30 | Laminated steel sheet for general cans |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-151213 | 1999-05-31 | ||
| JP15121399 | 1999-05-31 | ||
| JP2000093272A JP4345189B2 (en) | 1999-05-31 | 2000-03-30 | Laminated steel sheet for general cans |
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|---|---|
| JP2001047554A true JP2001047554A (en) | 2001-02-20 |
| JP4345189B2 JP4345189B2 (en) | 2009-10-14 |
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ID=26480528
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005161784A (en) * | 2003-12-05 | 2005-06-23 | Nippon Steel Corp | Laminated steel sheet for coating/printing |
| JP2006007517A (en) * | 2004-06-24 | 2006-01-12 | Toyo Seikan Kaisha Ltd | Resin coated metal sheet, metal can and lid for metal can |
| JP2006168122A (en) * | 2004-12-15 | 2006-06-29 | Jfe Steel Kk | Laminated steel sheet excellent in scratch resistance and slip properties, and can body using it |
| JP2011255624A (en) * | 2010-06-10 | 2011-12-22 | Fujifilm Corp | Polyester film laminate, and its manufacturing method |
-
2000
- 2000-03-30 JP JP2000093272A patent/JP4345189B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005161784A (en) * | 2003-12-05 | 2005-06-23 | Nippon Steel Corp | Laminated steel sheet for coating/printing |
| JP4571795B2 (en) * | 2003-12-05 | 2010-10-27 | 新日本製鐵株式会社 | Laminated steel sheet for paint printing |
| JP2006007517A (en) * | 2004-06-24 | 2006-01-12 | Toyo Seikan Kaisha Ltd | Resin coated metal sheet, metal can and lid for metal can |
| JP4654617B2 (en) * | 2004-06-24 | 2011-03-23 | 東洋製罐株式会社 | Reseal can |
| JP2006168122A (en) * | 2004-12-15 | 2006-06-29 | Jfe Steel Kk | Laminated steel sheet excellent in scratch resistance and slip properties, and can body using it |
| JP4635593B2 (en) * | 2004-12-15 | 2011-02-23 | Ｊｆｅスチール株式会社 | Laminated steel sheet for large cans with excellent scratch resistance and sliding properties, and large can bodies using the same |
| JP2011255624A (en) * | 2010-06-10 | 2011-12-22 | Fujifilm Corp | Polyester film laminate, and its manufacturing method |
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| Publication number | Publication date |
|---|---|
| JP4345189B2 (en) | 2009-10-14 |
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