JP2794609B2 - Resin-coated steel sheet for drawn and ironed cans and drawn and ironed cans - Google Patents
Resin-coated steel sheet for drawn and ironed cans and drawn and ironed cansInfo
- Publication number
- JP2794609B2 JP2794609B2 JP2120408A JP12040890A JP2794609B2 JP 2794609 B2 JP2794609 B2 JP 2794609B2 JP 2120408 A JP2120408 A JP 2120408A JP 12040890 A JP12040890 A JP 12040890A JP 2794609 B2 JP2794609 B2 JP 2794609B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- drawn
- ironed
- steel sheet
- ironing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Shaping Metal By Deep-Drawing, Or The Like (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、絞りしごき缶用樹脂被覆鋼板および絞りし
ごき缶に関するものである。Description: TECHNICAL FIELD The present invention relates to a resin-coated steel sheet for drawn and ironed cans and a drawn and ironed can.
（従来の技術） 従来、絞りしごきに対する加工性に顕著に優れてお
り、内面に樹脂被覆を備えた状態で、しごき率が60％以
上の高度のしごき率でのしごき加工が可能となると共
に、絞りしごき加工により、樹脂被膜の密着性、耐食性
及び外観特性に優れた絞りしごき缶を得ることが出来る
絞りしごき缶用樹脂被覆鋼板が特開昭60−168643号公報
に提案されている。(Prior art) Conventionally, it is remarkably excellent in workability against drawing and ironing, and it is possible to perform ironing at a high ironing rate of 60% or more with a resin coating on the inner surface, Japanese Patent Application Laid-Open No. 60-168643 proposes a resin-coated steel sheet for a drawn and ironed can which can obtain a drawn and ironed can excellent in adhesion, corrosion resistance and appearance characteristics of a resin film by drawing and ironing.
その提案内容は、絞りしごき缶としたとき内側となる
べき最表面に配向可能で且つ腐食成分に対してバリヤー
性を有するポリエチレンテレフタレート樹脂等の熱可塑
性樹脂の被覆層とこの被覆層の下に密着下地となるクロ
ム水和酸化物等の無機酸化物皮膜層を有し且つ絞りしご
き缶としたとき外側となるべき面にSn等の展延性金属の
メッキ層を有することを特徴とする絞りしごき缶用樹脂
被覆鋼板である。The proposal consists of a coating layer of a thermoplastic resin such as polyethylene terephthalate resin, which can be oriented on the outermost surface that should be inside when drawn and ironed and has a barrier property against corrosive components, and adheres under this coating layer. A drawn ironing can having an inorganic oxide film layer such as hydrated chromium oxide as a base and having a plated layer of a spreadable metal such as Sn on a surface to be an outer side when the drawn iron is made into a drawn iron. Resin-coated steel sheet.
（発明が解決しようとする課題） このような絞りしごき缶用樹脂被覆鋼板を絞りしごき
加工して、樹脂被膜の密着性、耐腐食性及び外面特性に
優れた絞りしごき缶を得るためには、前記公報に明記さ
れるように、絞りしごき加工に際して、絞りしごき缶用
樹脂被覆鋼板の被覆樹脂を適性延伸温度（樹脂の結晶化
温度よりも低く、且つガラス転移温度（Tg）±30℃以内
の温度、例えば樹脂がPET樹脂の場合40〜100℃）にする
必要があり、一方、公知のエキストルージョンラミネー
ト法等で製造され、絞りしごき工程に供せられる絞りし
ごき缶用樹脂被覆鋼板は通常、常温であるため、従来の
製缶工程に樹脂被覆鋼板の予熱工程を付加しなければな
らないと言う問題点がある。(Problems to be Solved by the Invention) In order to obtain a drawn and ironed can excellent in adhesion, corrosion resistance and outer surface properties of the resin film by drawing and ironing such a resin-coated steel sheet for a drawn and ironed can, As specified in the above-mentioned publication, at the time of drawing and ironing, the coating resin of the resin-coated steel sheet for drawing and ironing can is subjected to an appropriate stretching temperature (lower than the crystallization temperature of the resin, and a glass transition temperature (Tg) within ± 30 ° C.). Temperature, for example, 40 to 100 ° C. when the resin is PET resin) .On the other hand, a resin-coated steel sheet for a drawn ironing can which is manufactured by a known extrusion lamination method or the like and subjected to a drawing ironing step is usually used. Since it is at room temperature, there is a problem that a preheating step of a resin-coated steel sheet must be added to the conventional can-making process.
本発明は、樹脂被覆鋼板を予熱することなく常温のま
ま絞りしごき加工に供しても、絞りしごきに対する加工
性に顕著に優れており、内面に樹脂被覆を備えた状態
で、しごみ率が60％以上でのしごき加工が可能となると
共に、樹脂被膜の密着性、耐食性に優れた絞りしごき缶
を得ることができる絞りしごき缶用樹脂被覆鋼板及び上
記特性を有する絞りしごき缶を提供することを目的とす
る。The present invention, even when subjected to drawing and ironing at room temperature without preheating the resin-coated steel sheet, is remarkably excellent in workability against drawing and ironing, and with a resin coating on the inner surface, the shrinkage rate is 60%. % Or more, and at the same time, to provide a resin-coated steel sheet for drawn and ironed cans and a drawn and ironed can having the above-mentioned characteristics, which can obtain a drawn and ironed can having excellent adhesion and corrosion resistance of the resin film while being capable of being ironed at not less than 10%. Aim.
（課題を解決するための手段） 本発明の要旨は次の通りである。(Means for Solving the Problems) The gist of the present invention is as follows.
（１） 両面にSnめっきを施した鋼板片面の上に結晶性
ポリエステル95〜5wt％と非晶性ポリエステル５〜95wt
％とを下記式で定義されるアロイ化率が20〜80％となる
ように熱反応させた熱可塑性ポリエステル樹脂組成物が
被覆されてなることを特徴とする絞りしごき缶用樹脂被
覆鋼板。(1) 95 to 5 wt% of crystalline polyester and 5 to 95 wt% of amorphous polyester on one side of a steel plate with Sn plating on both sides
And a thermoplastic polyester resin composition thermally reacted so that an alloying ratio defined by the following formula is 20 to 80%.
Tm1又はTg1;原料の結晶性ポリエステル樹脂の融点又
はガラス転移温度 Tm2又はTg2;原料の結晶性ポリエステル樹脂と非晶性
ポリエステル樹脂を完全熱溶融反応させた時の融点又
は、ガラス転移温度、即ち同じモノマー組成をもつラン
ダム共重合体ポリエステル樹脂の融点又はガラス転移温
度 Tm3又はTg3;熱反応で得られた熱可塑性ポリエステル
樹脂組成物の融点又はガラス転移温度 （２） 前項１の絞りしごき缶用樹脂被覆鋼板の樹脂組
成物被覆面が缶内面になるように絞りしごき缶加工した
ことを特徴とする絞りしごき缶。 T m1 or T g1 ; melting point or glass transition temperature of the raw material crystalline polyester resin T m2 or T g2 ; melting point or glass transition when the raw material crystalline polyester resin and the amorphous polyester resin are completely hot-melted Temperature, that is, melting point or glass transition temperature Tm3 or Tg3 of random copolymer polyester resin having the same monomer composition; melting point or glass transition temperature of thermoplastic polyester resin composition obtained by thermal reaction (2) A drawn and ironed can, characterized in that the drawn and ironed can is processed so that the resin composition coated surface of the resin-coated steel sheet for the drawn and ironed can is the inner surface of the can.
上記Tm1,Tm2,Tm3或はTg1,Tg2,Tg3は示差熱分析計（Pe
rkin Elmer−７型）を用いて10℃／分で昇温して得られ
る融点或はガラス転移温度である。また結晶性、非晶性
の区別は、示差熱分析計を用いて同様の方法で融点のピ
ークを発現するものを結晶性ポリエステル、又ガラス転
移温度のみを発現するもの、あるいはガラス転移温度及
び融点のピークが現れないものを非晶性ポリエステルと
いう。The above T m1 , T m2 , T m3 or T g1 , T g2 , T g3 is a differential thermal analyzer (Pe
rkin Elmer-7 type) at a temperature of 10 ° C./min. In addition, the distinction between crystalline and non-crystalline is achieved by using a differential thermal analyzer in the same manner as that of a crystalline polyester, a polyester that develops only the glass transition temperature, or a glass polyester that develops only the glass transition temperature. Are not amorphous polyesters.
上記結晶性ポリエステルとはポリエチレンテレフタレ
ート（以下、PETと略す）、ポリブチレンテレフタレー
ト（以下、PBTと略す）、ポリエチレンナフタレート
（以下、PENと略す）、及びその共重合体が例として挙
げられるが、これらに限定するものではなく、少なくと
も融点が200℃以上の熱可塑性ポリエステルを言う。Examples of the crystalline polyester include polyethylene terephthalate (hereinafter abbreviated as PET), polybutylene terephthalate (hereinafter abbreviated as PBT), polyethylene naphthalate (hereinafter abbreviated as PEN), and copolymers thereof. It is not limited to these, but refers to a thermoplastic polyester having a melting point of at least 200 ° C.
上記非晶性ポリエステルとはポリエチレンイソフタレ
ート（以下、PEIと略す）、シクロヘキサン・ジメタノ
ール30mol％のポリエチレンテレフタレートコポリエス
テル、イソフタール酸20mol％以上のポリエチレンテレ
フタレート、ポリアリレート、ポリエステルポリカーボ
ネート等が例として挙げられるが、これらに限定するも
のでなく、ガラス転移温度が20℃以上、好ましくは40℃
以上の非晶性の熱可塑性ポリエステルを言う。Examples of the amorphous polyester include polyethylene isophthalate (hereinafter abbreviated as PEI), polyethylene terephthalate copolyester of 30 mol% of cyclohexane / dimethanol, polyethylene terephthalate of 20 mol% or more of isophthalic acid, polyarylate, polyester polycarbonate and the like. However, the glass transition temperature is not limited to these, and is preferably 20 ° C. or higher, preferably 40 ° C.
The above amorphous thermoplastic polyester is referred to.
以下、本発明の内容を更に詳しく説明する。 Hereinafter, the contents of the present invention will be described in more detail.
本発明者らは、両面Snめっきした鋼板の片面側に公知
の方法で熱可塑性樹脂を被覆し、缶内面が樹脂被膜とな
るよう絞りしごき加工を行って缶を製造した。The present inventors produced a can by coating a thermoplastic resin on one side of a steel plate plated with Sn on both sides by a known method, and drawing and ironing the inner surface of the can to form a resin film to produce a can.
先ず本発明者らは、熱可塑性樹脂として、公知のPET
を選択し、更にこれも公知の非晶質の状態の樹脂を使用
した。しかし、公知の方法に従って製造した常温の樹脂
被覆鋼板は、軽度な絞りしごき加工には耐えても、本発
明者らが目標とする60％以上の絞りしごきには耐えられ
ないものであった。この理由について検討した結果、通
常の非晶性PETを用いただけでは、絞りしごき加工の途
中で樹脂が加工される過程で当初非晶質であったPETが
加工により一部晶質化し、引続き行われる加工には晶質
化しているために耐えられないと考えた。そこで、本発
明者らは、晶質化しないポリエステル樹脂として、PEI
を用いて同じ加工を行った。このPEIは、予想した通り
非晶質で、絞り加工には優れた特性を示したが、引続き
行われるしごき加工は、樹脂が加工用のポンチ（しごき
加工は、通常３個のダイス間に金属板をポンチで押し込
み、ポンチ／ダイス間でしごき加工される）に付着し、
缶内面から樹脂が剥離するとともに、缶体をポンチから
取り外す（ストリップアウトと言われる）ことが出来な
かった。First, the present inventors, as a thermoplastic resin, known PET
And a resin in a known amorphous state was also used. However, a normal temperature resin-coated steel sheet manufactured according to a known method was not able to withstand the 60% or more draw ironing targeted by the present inventors, even though it could endure mild drawing and ironing. As a result of studying the reason for this, only ordinary amorphous PET was used, and PET was initially amorphous in the process of processing the resin during drawing and ironing. It was thought that it was unbearable due to the crystallinity of the process. Therefore, the present inventors, as a polyester resin that does not crystallize, PEI
The same processing was performed using. As expected, this PEI was amorphous and showed excellent properties in drawing. However, in the subsequent ironing, the resin is a punch for processing (ironing is usually performed by placing metal between three dies). The plate is pressed with a punch and ironed between the punch and the die).
The resin was peeled from the inner surface of the can, and the can body could not be removed from the punch (called strip-out).
その他PEIを単に混合したPETやPET、PEI、更にPBTの
混合物を使用して同じ絞りしごき加工を行ったが、満足
出来る結果を得られなかった。即ち、結晶性樹脂の成分
が多い時は、加工性に劣り、非晶性樹脂の成分が多い時
は、ストリップアウト性が悪く、これら二成分或は三成
分を適宜混合した範囲では、加工性、ストリップアウト
性の両方を満足するものは得られなかった。In addition, the same drawing and ironing process was carried out using PET or a mixture of PET, PEI, and PBT in which PEI was simply mixed, but satisfactory results were not obtained. That is, when the content of the crystalline resin is large, the workability is poor, and when the content of the amorphous resin is large, the strip-out property is poor. However, none satisfying both of the strip-out properties was obtained.
次に、本発明者らは、PET、PEIの単独組成では勿論の
こと、単に混合したのみでは樹脂溶融時に一部エステル
交換反応が起こるとしても、それぞれ単味の特性が現れ
ていると考え、本発明者らは、テレフタレートとイソフ
タレートとの共重合体樹脂を作成し、同様の試験に供し
たが満足のいく結果は得られなかった。しかし、このテ
レフタレートとイソフタレートとの共重合体樹脂を使用
した試験で極めて限られた樹脂組成の範囲で、略目標に
近い特性が得られた。そおで、本発明者らは、得られた
結果を鋭意解析した結果、良好な金属との密着性を得る
ためには、従来知見の如く樹脂の結晶性を制御するだけ
では過酷な絞りしごき加工に耐えることは出来ず、樹脂
の融点、並びに結晶性について制御することが肝要であ
るとの結論に至った。即ち、非晶質な状態で絞りしごき
加工される際に加工によって極力結晶化せず、且つ適当
な温度範囲に融点が存在する樹脂組成物が本発明の目的
に適うことを見出した。この樹脂組成物を得る方法とし
て、PET及びPEI、即ち、結晶性ポリエステルと非晶性ポ
リエステルの好ましくは少なくとも一方が触媒活性を有
している状態で結晶性ポリエステル95〜5wt％と非晶性
ポリエステル５〜95wt％とを熱溶融させ、アロイ化率を
20〜80％にコントロールした樹脂組成物が絞りしごき缶
用の樹脂被覆鋼板用の樹脂として優れたものであること
を見出した。ここで触媒活性を有している状態とは、原
料ポリエステルを加熱した場合に、分子量（又は極限粘
度）の上昇をもたらすものを指す。このような触媒活性
を有する原料を用いることによりアロイ化に要する時間
を短くすることが出来る。Next, the present inventors consider that, even if only a single composition of PET and PEI is used, even if a simple transesterification reaction occurs when the resin is melted only by mixing, it is believed that each has a simple characteristic, The present inventors have prepared a copolymer resin of terephthalate and isophthalate and have conducted similar tests, but no satisfactory results have been obtained. However, in a test using the copolymer resin of terephthalate and isophthalate, characteristics close to the target were obtained in a very limited range of the resin composition. Therefore, the present inventors have conducted intensive analysis of the obtained results, and found that, in order to obtain good adhesion to a metal, severe drawing and ironing processing was required only by controlling the crystallinity of the resin as in the conventional knowledge. And it was concluded that it was important to control the melting point and crystallinity of the resin. That is, it has been found that a resin composition which does not crystallize as much as possible when drawing and ironing in an amorphous state and has a melting point in an appropriate temperature range is suitable for the purpose of the present invention. As a method for obtaining this resin composition, PET and PEI, that is, 95 to 5% by weight of the crystalline polyester and the amorphous polyester in a state where at least one of the crystalline polyester and the amorphous polyester has a catalytic activity. 5 to 95 wt% is melted by heat to reduce the alloying rate.
It has been found that the resin composition controlled at 20 to 80% is excellent as a resin for a resin-coated steel sheet for a drawn and ironed can. Here, the state having catalytic activity refers to a state in which when the raw material polyester is heated, the molecular weight (or the intrinsic viscosity) increases. By using a raw material having such a catalytic activity, the time required for alloying can be shortened.
以下本発明の構成要件の限定理由について説明する。 Hereinafter, the reasons for limiting the constituent elements of the present invention will be described.
なお、本発明におけるアロイ化率は、次の式で定義さ
れる。The alloying ratio in the present invention is defined by the following equation.
Tm1又はTg1;原料の結晶性ポリエステル樹脂の融点又
はガラス転移温度 Tm2又はTg2;原料の結晶性ポリエステル樹脂と非晶性
ポリエステル樹脂を完全熱溶融反応させた時の融点又
は、ガラス転移温度、即ち同じモノマー組成をもつラン
ダム共重合体ポリエステル樹脂の融点又はガラス転移温
度 Tm3又はTg3;熱反応で得られた熱可塑性ポリエステル
樹脂組成物の融点又はガラス転移温度 この式の意味するところを説明すると、次のとおりと
なる。結晶性のポリエステル樹脂（Ａ）と非晶性のポリ
エステル樹脂（Ｂ）を熱溶融反応させた場合、エステル
交換反応が起こって、時間の経過とともに反応が進み、
最後には結晶性ポリエステル（Ａ）を形成するジカルボ
ン酸／ジオール単位と非晶性ポリエステル樹脂（Ｂ）を
形成するジカルボン酸／ジオール単位とが組成比に応じ
てランダムに結合したポリエステル樹脂（Ｃ）が形成さ
れる。この現象を結晶性ポリエステル樹脂（Ａ）側につ
いてのみ着目すると、熱溶融反応により結晶性ポリエス
テル（Ａ）に時間の経過とともに非晶性ポリエステル樹
脂（Ｂ）を形成するジカルボン酸／ジオール単位が導入
されていくことになる。このことは、結晶性ポリエステ
ル樹脂の融点および／またはTgの低下をもたらす。この
ため、どの程度結晶性ポリエステル樹脂に非晶性ポリエ
ステル樹脂の構成単位が導入されたかは、上記式により
定量的に把握することができる。 T m1 or T g1 ; melting point or glass transition temperature of the raw material crystalline polyester resin T m2 or T g2 ; melting point or glass transition when the raw material crystalline polyester resin and the amorphous polyester resin are completely hot-melted Temperature, that is, melting point or glass transition temperature Tm3 or Tg3 of random copolymer polyester resin having the same monomer composition; melting point or glass transition temperature of thermoplastic polyester resin composition obtained by thermal reaction Is described as follows. When the crystalline polyester resin (A) and the amorphous polyester resin (B) are subjected to a hot-melt reaction, a transesterification reaction occurs, and the reaction proceeds over time,
Finally, a polyester resin (C) in which dicarboxylic acid / diol units forming the crystalline polyester (A) and dicarboxylic acid / diol units forming the amorphous polyester resin (B) are randomly bonded in accordance with the composition ratio. Is formed. Focusing on this phenomenon only on the crystalline polyester resin (A) side, a dicarboxylic acid / diol unit that forms the amorphous polyester resin (B) is introduced into the crystalline polyester (A) with the lapse of time due to a thermal melting reaction. Will go on. This results in a decrease in the melting point and / or Tg of the crystalline polyester resin. Therefore, it can be quantitatively grasped by the above formula how much the structural unit of the amorphous polyester resin has been introduced into the crystalline polyester resin.
アロイ化率の限定理由はアロイ化率が20％未満では、
しごき加工等に発生する熱で晶質部分が増加し、被覆樹
脂が高しごき率に追随出来ない。又、アロイ化率が80％
を超えるものでは、被覆樹脂非晶質部分が増え、見掛け
の溶融温度が低下し、ストリップアウト性を大きく悪化
させるからである。The reason for limiting the alloying rate is that if the alloying rate is less than 20%,
The crystalline portion increases due to heat generated during ironing or the like, and the coating resin cannot follow a high ironing rate. The alloying rate is 80%
If the ratio exceeds 1, the coating resin amorphous portion increases, the apparent melting temperature decreases, and the strip-out property is greatly deteriorated.
結晶性ポリエステルと非晶性ポリエステルをアロイ化
するに当たり、その混合比率（非晶性ポリエステル÷ポ
リエステル樹脂全量×100）を５〜95％にした理由につ
いて以下説明する。The reason why the mixing ratio (amorphous polyester ÷ total amount of polyester resin × 100) in alloying the crystalline polyester and the amorphous polyester is 5 to 95% will be described below.
先ず、混合比率を５％以上としたのは、５％未満で
は、結晶性樹脂の影響が強く、厳しいしごき加工時、延
伸により樹脂が加工出来ない程晶質化するからである。
又、上限を95％としたのは95％を超えると、見掛けの融
点が235℃以下となり、しごき加工時にポンチに融着
し、ストリップアウト性が著しく悪くなるからである。
実用上、しごき加工時の延伸性及びポンチ打抜き時のス
トリップアウト性のバランスの観点から、上記混合比率
を５〜95％にしてアロイ化率を20〜80％になるようにし
た樹脂組成物が、絞りしごき缶用の樹脂被覆鋼板用樹脂
として優れているのである。First, the reason for setting the mixing ratio to 5% or more is that if the mixing ratio is less than 5%, the influence of the crystalline resin is strong, and during severe ironing, the resin becomes too crystalline to be processed by stretching.
Also, the upper limit is set to 95%, because if it exceeds 95%, the apparent melting point becomes 235 ° C. or less, and it is fused to the punch at the time of ironing, and the strip-out property is significantly deteriorated.
Practically, from the viewpoint of the balance between the stretchability at the time of ironing and the strip-out property at the time of punching, a resin composition in which the above mixing ratio is 5 to 95% and the alloying ratio is 20 to 80% is used. It is excellent as a resin for a resin-coated steel plate for drawing and ironing cans.
（実施例） 以下、実施例に基づき本発明の内容を具体的に説明す
る。(Examples) Hereinafter, the contents of the present invention will be specifically described based on examples.
両面に片面当りSn2.8g/m2のめっきを施した鋼板（板
厚み0.30mm、硬度Ｔ−１相当）の片面に、Ｔダイを用い
て、第１表に示した樹脂組成物を50μｍ被覆した。この
時Ｔダイでの樹脂融解温度は、265〜300℃であり、被覆
時の鋼板温度は、150〜200℃であった。又、Ｔダイで樹
脂が被覆された鋼板は10秒以内に、100℃以下迄急冷し
た。尚、急冷した理由は、高温での樹脂の結晶化を防止
するためである。こうして得られた常温の樹脂被覆鋼板
を、缶内面が樹脂被覆面になるようにして下記の成形条
件にて絞りしごき加工を行って缶を製造し、缶内面（樹
脂被覆面）の健全性を評価するために、缶の中に1.0％
食塩水を入れ、缶体を陽極とし、缶中央部に設置した白
金を陰極として＋6Vの電圧をかけたときに流れる電流値
を測定した（以下QTV試験と略す。）又同じく、缶内面
の健全性を評価する目的で、缶の中に硫酸20g/、硫酸
銅（CuSO4 7H2O）50g/を含む溶液を入れ10分間放置
し、液を除去、水洗後に内面に析出したCu（溶液はCuの
化学めっき液で欠陥があれば、欠陥部から鉄が溶出し
て、Cuが置換めっきされる）を観察した（以下、硫酸銅
試験と略す。） これらの結果をストリップアウト性評価結果、および
絞りしごき加工後の缶内面観察結果とともに第２表に示
した。50 μm of the resin composition shown in Table 1 was coated on one surface of a steel plate (plate thickness 0.30 mm, hardness T-1 equivalent) having both surfaces plated with Sn 2.8 g / m 2 per side using a T die. did. At this time, the resin melting temperature at the T-die was 265 to 300 ° C, and the steel sheet temperature at the time of coating was 150 to 200 ° C. The steel sheet coated with the resin by the T-die was rapidly cooled to 100 ° C. or less within 10 seconds. The reason for the rapid cooling is to prevent crystallization of the resin at a high temperature. The room temperature resin-coated steel sheet thus obtained is drawn and ironed under the following molding conditions so that the inner surface of the can becomes the resin-coated surface to produce a can, and the soundness of the inner surface of the can (the resin-coated surface) is checked. 1.0% in the can to evaluate
A saline solution was charged, and the current flowing when a voltage of +6 V was applied to the can body as an anode and platinum placed in the center of the can as a cathode was measured (hereinafter abbreviated as QTV test). For the purpose of evaluating the properties, a solution containing 20 g of sulfuric acid and 50 g of copper sulfate (CuSO 4 7H 2 O) was placed in a can and left for 10 minutes. The liquid was removed, and after washing with water, If there was a defect in the chemical plating solution of Cu, iron was eluted from the defective portion and Cu was subjected to displacement plating. (Hereinafter, abbreviated as copper sulfate test.) Table 2 shows the results of observation of the inner surface of the can after drawing and ironing.
（成形条件） 1.絞りしごき直前の樹脂温度：常温 2.ブランク径 :137mmφ 3.絞り条件 :1st絞り比 H/D＝38/86mmφ 2nd絞り比 H/D＝50/65mmφ 4.しごきポンチ径 :3段アイアニング 65.5mmφ 5.総しごき率 :70.5％ （発明の効果） 以上説明したように本発明の熱可塑性ポリエステル樹
脂組成物を使用して得た絞りしごき缶用樹脂被覆鋼板
は、常温のまま絞りしごき加工に供しても、非常に優れ
た内面特性を持った絞りしごき缶が得られるので、従来
の熱可塑性樹脂を使用して得た絞りしごき缶用樹脂被覆
鋼板では必須とされる製缶メーカーでの絞りしごき缶用
樹脂被覆鋼板の予熱工程を省略することができ、缶製造
コストダウンが図れる。(Molding conditions) 1. Resin temperature just before drawing and ironing: normal temperature 2. Blank diameter: 137mmφ 3. Drawing condition: 1st drawing ratio H / D = 38 / 86mmφ 2nd drawing ratio H / D = 50 / 65mmφ 4. Ironing punch diameter : 3-stage ironing 65.5mmφ 5. Total ironing rate: 70.5% (Effect of the Invention) As described above, the resin-coated steel sheet for drawn and ironed cans obtained by using the thermoplastic polyester resin composition of the present invention has an extremely excellent inner surface even when subjected to drawing and ironing at room temperature. Pre-heating process of resin-coated steel sheets for drawn ironing cans, which is indispensable for can-manufacturers, required for conventional drawn-ironing cans that can be obtained using conventional thermoplastic resin because they can produce drawn ironed cans with characteristics Can be omitted, and can manufacturing cost can be reduced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平岡 孝之 山口県玖珂郡和木町和木６丁目１番２号 三井石油化学工業株式会社内 (58)調査した分野(Int.Cl.6，ＤＢ名) B32B 15/08 B21D 22/28──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Takayuki Hiraoka 61-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Pref. Mitsui Petrochemical Industry Co., Ltd. (58) Field surveyed (Int. Cl. 6 , DB name) ) B32B 15/08 B21D 22/28
Claims (2)
晶性ポリエステル95〜5wt％と非晶性ポリエステル５〜9
5wt％とを下記式で定義されるアロイ化率が20〜80％と
なるように熱反応させた熱可塑性ポリエステル樹脂組成
物が被覆されてなることを特徴とする絞りしごき缶用樹
脂被覆鋼板。 Tm1又はTg1;原料の結晶性ポリエステル樹脂の融点又は
ガラス転移温度 Tm2又はTg2;原料の結晶性ポリエステル樹脂と非晶性ポ
リエステル樹脂を完全熱溶融反応させた時の融点又は、
ガラス転移温度、即ち同じモノマー組成をもつランダム
共重合体ポリエステル樹脂の融点又はガラス転移温度 Tm3又はTg2;熱反応で得られた熱可塑性ポリエステル樹
脂組成物の融点又はガラス転移温度1. A steel sheet having both sides Sn-plated, on one side of which 95 to 5% by weight of crystalline polyester and 5 to 9% of amorphous polyester
A resin-coated steel sheet for drawn and ironed cans, which is coated with a thermoplastic polyester resin composition obtained by thermally reacting 5 wt% with an alloying ratio defined by the following formula of 20 to 80%. T m1 or T g1 ; melting point or glass transition temperature of the crystalline polyester resin of the raw material T m2 or T g2 ; melting point when the crystalline polyester resin of the raw material and the amorphous polyester resin are completely heat-melted, or
Glass transition temperature, that is, melting point or glass transition temperature of random copolymer polyester resin having the same monomer composition Tm3 or Tg2 ; melting point or glass transition temperature of thermoplastic polyester resin composition obtained by thermal reaction
樹脂組成物被覆面が缶内面になるように絞りしごき缶加
工したことを特徴とする絞りしごき缶。2. A drawn and ironed can, characterized in that the drawn and ironed can is drawn and ironed so that the resin-coated surface of the resin-coated steel sheet for drawn and ironed cans according to claim 1 is the inner surface of the can.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2120408A JP2794609B2 (en) | 1990-05-10 | 1990-05-10 | Resin-coated steel sheet for drawn and ironed cans and drawn and ironed cans |
| EP19900121797 EP0432497B1 (en) | 1989-11-15 | 1990-11-14 | Resin-coated steel sheet for drawn-and-ironed cans and drawn-and-ironed cans manufactured therefrom |
| KR1019900018396A KR930011749B1 (en) | 1989-11-15 | 1990-11-14 | Resin coated steel for draw wiping can and draw wiping can |
| CA 2029943 CA2029943C (en) | 1989-11-15 | 1990-11-14 | Resin-coated steel sheet for drawn-and-ironed cans and drawn-and-ironed cans manufactured therefrom |
| DE1990621701 DE69021701T2 (en) | 1989-11-15 | 1990-11-14 | Resin-coated steel sheet for ironed cans and ironed cans made from them. |
| CN90109273A CN1040960C (en) | 1989-11-15 | 1990-11-15 | Resin coated steel sheets for drawn and ironed cans and drawn and ironed cans |
| US08/210,747 US5714273A (en) | 1989-11-15 | 1994-03-18 | Resin-coated steel sheet for drawn-and-ironed cans and drawn-and-ironed cans manufactured therefrom |
| US08/962,779 US5964113A (en) | 1989-11-15 | 1997-11-03 | Method for manufacturing a resin-coated steel sheet for drawn-and-ironed cans |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2120408A JP2794609B2 (en) | 1990-05-10 | 1990-05-10 | Resin-coated steel sheet for drawn and ironed cans and drawn and ironed cans |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0416340A JPH0416340A (en) | 1992-01-21 |
| JP2794609B2 true JP2794609B2 (en) | 1998-09-10 |
Family
ID=14785482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2120408A Expired - Lifetime JP2794609B2 (en) | 1989-11-15 | 1990-05-10 | Resin-coated steel sheet for drawn and ironed cans and drawn and ironed cans |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2794609B2 (en) |
-
1990
- 1990-05-10 JP JP2120408A patent/JP2794609B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0416340A (en) | 1992-01-21 |
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