JP2014095123A - Process liquid, steel sheet for container, and method of producing steel sheet for container - Google Patents
Process liquid, steel sheet for container, and method of producing steel sheet for container Download PDFInfo
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Abstract
Description
本発明は、容器用鋼板の製造に用いられる処理液、この処理液を用いて製造された容器用鋼板、および、この処理液を用いた容器用鋼板の製造方法に関する。 The present invention relates to a treatment liquid used for producing a steel plate for containers, a steel plate for containers produced using this treatment liquid, and a method for producing a steel plate for containers using this treatment liquid.
容器用鋼板(缶用表面処理鋼板)としては、従来から「ぶりき」と称される錫めっき鋼板が広く用いられている。このような錫めっき鋼板では、通常、重クロム酸などの6価のクロム化合物を含有する水溶液中に鋼板を浸漬する、または、この溶液中で電解処理を行うなどのクロメート処理によって、錫めっき表面にクロメート皮膜が形成される。
しかしながら、昨今の環境問題を踏まえて、Crの使用を規制する動きが各分野で進行しており、容器用鋼板においてもクロメート処理に替わる処理技術がいくつか提案されている。
例えば、特許文献1には、「Crを用いず、樹脂密着性に優れ」るものとして([0013])、「金属板の少なくとも片面に、ZrおよびOを含む皮膜を有し、該皮膜のF量が片面あたり0.1mg/m2未満であることを特徴とする表面処理金属板」が開示されており([請求項1])、ここでいう「金属板」は「電気Snめっき鋼板」である([請求項3])。
As a steel plate for containers (surface-treated steel plate for cans), a tin-plated steel plate conventionally referred to as “blink” has been widely used. In such a tin-plated steel plate, the surface of the tin-plated surface is usually obtained by immersing the steel plate in an aqueous solution containing a hexavalent chromium compound such as dichromic acid, or by performing a chromate treatment such as performing an electrolytic treatment in this solution. A chromate film is formed on the surface.
However, in light of recent environmental problems, movements for restricting the use of Cr have progressed in various fields, and several treatment techniques for replacing chromate treatment have been proposed for steel plates for containers.
For example,
近年、消費者の美観に関する要求の高まりによって、容器用鋼板に求められる種々の特性について、より一層の向上が求められている。
本発明者らは、特許文献1に開示された容器用鋼板(表面処理金属板)について、さらに検討を行なった。その結果、PETフィルム等の樹脂をラミネートした後にレトルト処理を行なった際に、樹脂であるフィルムに対する密着性(以下「樹脂密着性」ともいう)が不十分となる場合があることが分かった。
また、本発明者らは、ラミネート後の容器用鋼板を所定条件下でトマトジュースに浸漬すると、樹脂であるフィルムが変色する場合があり、変色に対する耐性(以下「耐変色性」ともいう)に劣ることが分かった。このとき、本発明者らは、この変色が、めっき層に含まれる錫(Sn)の酸化によるものであることを見出した。
In recent years, with the increasing demand for consumer aesthetics, further improvements have been required for various properties required for steel plates for containers.
The inventors further studied the steel plate for containers (surface-treated metal plate) disclosed in
In addition, when the present inventors immerse the laminated steel plate in tomato juice under a predetermined condition, the resin film may be discolored, which is resistant to discoloration (hereinafter also referred to as “discoloration resistance”). I found it inferior. At this time, the present inventors have found that this discoloration is due to oxidation of tin (Sn) contained in the plating layer.
本発明は、以上の点を鑑みてなされたものであり、樹脂密着性および耐変色性に優れる容器用鋼板を提供することを目的とする。 This invention is made | formed in view of the above point, and it aims at providing the steel plate for containers excellent in resin adhesiveness and discoloration resistance.
本発明者らは、上記目的を達成するために鋭意検討を行なった結果、容器用鋼板の皮膜を、特定の成分を含む処理液を用いて形成することで、樹脂密着性および耐変色性がいずれも良好となることを見出し、本発明を完成させた。 As a result of intensive studies to achieve the above object, the present inventors have formed a coating of a steel plate for containers using a treatment liquid containing a specific component, so that the resin adhesion and discoloration resistance are improved. They found that both were good and completed the present invention.
すなわち、本発明は、以下の(1)〜(8)を提供する。
(1)鋼板および上記鋼板の表面の少なくとも一部を覆う錫めっき層を有する錫めっき層付き鋼板と、上記錫めっき層付き鋼板の上記錫めっき層側の表面上に配置された皮膜とを有する容器用鋼板の製造に用いられて、上記皮膜を形成するための処理液であって、Zr化合物と、Ti化合物と、硝酸化合物と、乳酸化合物とを含有し、Zr量が、3〜40mmol/Lであり、Ti量が、1〜7mmol/Lであり、NO3 -量が、10〜100mmol/Lであり、乳酸量が、2〜14mmol/Lであり、F量が、0.1mmol/L未満であることを特徴とする処理液。
(2)上記Zr化合物、および、上記硝酸化合物の一部が、オキシ硝酸ジルコニウムであり、上記Ti化合物、および、上記乳酸化合物が、チタンラクテートである、上記(1)に記載の処理液。
(3)鋼板および上記鋼板の表面の少なくとも一部を覆う錫めっき層を有する錫めっき層付き鋼板と、上記錫めっき層付き鋼板の上記錫めっき層側の表面上に配置された皮膜とを有する容器用鋼板であって、上記皮膜は、上記(1)または(2)に記載の処理液を用いて形成され、上記錫めっき層付き鋼板の片面あたりのZr換算の付着量が1.0〜40.0mg/m2であって、上記錫めっき層付き鋼板の片面あたりのTi換算の付着量が0.3〜5.0mg/m2であることを特徴とする容器用鋼板。
(4)上記錫めっき層付き鋼板と上記皮膜との間に、上記錫めっき層付き鋼板の片面あたりのP換算の付着量が0.5〜30.0mg/m2であるリン含有層を有する、上記(3)に記載の容器用鋼板。
(5)上記錫めっき層付き鋼板が、表面にニッケル含有層を有する鋼板を用いて形成された、上記(3)または(4)に記載の容器用鋼板。
(6)上記(3)に記載の容器用鋼板を得る、容器用鋼板の製造方法であって、上記(1)または(2)に記載の処理液中に上記錫めっき層付き鋼板を浸漬する、または、浸漬した上記錫めっき層付き鋼板に陰極電解処理を施すことにより、上記皮膜を形成することを特徴とする容器用鋼板の製造方法。
(7)上記(4)に記載の容器用鋼板を得る、容器用鋼板の製造方法であって、PO4 3-量が70〜800mmol/Lである前処理液中に上記錫めっき層付き鋼板を浸漬する、または、浸漬した上記錫めっき層付き鋼板に陰極電解処理を施すことにより、上記リン含有層を形成した後に、上記(1)または(2)に記載の処理液中に、上記リン含有層が形成された上記錫めっき層付き鋼板を浸漬する、または、浸漬した上記リン含有層が形成された上記錫めっき層付き鋼板に陰極電解処理を施すことにより、上記皮膜を形成することを特徴とする容器用鋼板の製造方法。
(8)上記錫めっき層付き鋼板が、表面にニッケル含有層を有する鋼板を用いて形成された、上記(6)または(7)に記載の容器用鋼板の製造方法。
That is, the present invention provides the following (1) to (8).
(1) A steel plate with a tin plating layer having a tin plating layer covering at least a part of the surface of the steel plate and the steel plate, and a film disposed on the surface of the steel plate with the tin plating layer on the tin plating layer side. A treatment liquid for forming the coating film used in the production of a steel plate for containers, comprising a Zr compound, a Ti compound, a nitric acid compound, and a lactic acid compound, and the amount of Zr is 3 to 40 mmol / L, Ti amount is 1 to 7 mmol / L, NO 3 − amount is 10 to 100 mmol / L, lactic acid amount is 2 to 14 mmol / L, and F amount is 0.1 mmol / L. A treatment liquid characterized by being less than L.
(2) The treatment liquid according to (1), wherein the Zr compound and a part of the nitric acid compound are zirconium oxynitrate, and the Ti compound and the lactic acid compound are titanium lactate.
(3) A steel plate with a tin plating layer having a tin plating layer covering at least a part of the surface of the steel plate and the steel plate, and a film disposed on the surface of the steel plate with the tin plating layer on the tin plating layer side. It is a steel plate for containers, and the coating is formed using the treatment liquid described in (1) or (2) above, and the amount of adhesion in terms of Zr per side of the steel plate with the tin plating layer is 1.0 to a 40.0 mg / m 2, a container steel sheet for adhesion amount of Ti in terms of per side of the tin-plated layer with the steel sheet is characterized in that it is a 0.3~5.0mg / m 2.
(4) Between the said steel plate with a tin plating layer and the said film | membrane, it has the phosphorus containing layer whose adhesion amount of P conversion per single side of the said steel plate with a tin plating layer is 0.5-30.0 mg / m < 2 >. The steel plate for containers according to (3) above.
(5) The steel plate for containers according to (3) or (4), wherein the steel plate with a tin plating layer is formed using a steel plate having a nickel-containing layer on the surface.
(6) A method for producing a steel plate for a container according to (3) above, wherein the steel plate with a tin plating layer is immersed in the treatment liquid according to (1) or (2). Alternatively, a method for producing a steel plate for containers, wherein the film is formed by subjecting the immersed steel plate with a tin plating layer to cathodic electrolysis.
(7) A method for producing a container steel plate according to (4) above, wherein the steel plate with a tin plating layer is contained in a pretreatment liquid having a PO 4 3- content of 70 to 800 mmol / L. Or by subjecting the immersed steel sheet with a tin plating layer to cathodic electrolysis, the phosphorus-containing layer is formed, and then the phosphorus is added to the treatment liquid according to (1) or (2). Forming the film by immersing the steel sheet with the tin plating layer in which the content layer is formed, or by subjecting the steel sheet with the tin plating layer in which the immersed phosphorus content layer is formed to cathodic electrolysis. The manufacturing method of the steel plate for containers characterized.
(8) The manufacturing method of the steel plate for containers according to (6) or (7), wherein the steel plate with a tin plating layer is formed using a steel plate having a nickel-containing layer on the surface.
本発明によれば、樹脂密着性および耐変色性に優れる容器用鋼板を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the steel plate for containers excellent in resin adhesiveness and discoloration resistance can be provided.
〔容器用鋼板〕
本発明の容器用鋼板は、錫めっき層付き鋼板と、錫めっき層付き鋼板の錫めっき層側の表面上に配置された皮膜とを有し、この皮膜が、後述する本発明の処理液を用いて形成されることにより、樹脂密着性および耐変色性に優れる。
以下に、錫めっき層付き鋼板、および、皮膜の具体的な態様について詳述する。まず、錫めっき層付き鋼板の態様について詳述する。
[Steel plate for containers]
The steel plate for containers according to the present invention has a steel plate with a tin plating layer and a film disposed on the surface of the steel plate with a tin plating layer on the tin plating layer side. By using it, it is excellent in resin adhesiveness and discoloration resistance.
Below, the steel plate with a tin plating layer and the specific aspect of a membrane | film | coat are explained in full detail. First, the aspect of the steel plate with a tin plating layer is explained in full detail.
<錫めっき層付き鋼板>
錫めっき層付き鋼板は、鋼板および鋼板の表面の少なくとも一部を覆う錫めっき層を有する。以下に、鋼板および錫めっき層の態様について詳述する。
<Steel-coated steel sheet>
The steel sheet with a tin plating layer has a tin plating layer that covers at least a part of the surface of the steel sheet and the steel sheet. Below, the aspect of a steel plate and a tin plating layer is explained in full detail.
(鋼板)
錫めっき層付き鋼板中の鋼板の種類は特に制限されるものではなく、通常、容器材料として使用される鋼板(例えば、低炭素鋼板、極低炭素鋼板)を用いることができる。この鋼板の製造方法、材質なども特に規制されるものではなく、通常の鋼片製造工程から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造される。
(steel sheet)
The type of the steel plate in the steel plate with the tin plating layer is not particularly limited, and a steel plate (for example, a low carbon steel plate or an extremely low carbon steel plate) that is usually used as a container material can be used. The manufacturing method and material of the steel plate are not particularly restricted, and the steel plate is manufactured through processes such as hot rolling, pickling, cold rolling, annealing, and temper rolling from a normal steel slab manufacturing process.
鋼板は、必要に応じて、その表面にニッケル(Ni)含有層を形成したものを用い、該Ni含有層上に錫めっき層を形成してもよい。Ni含有層を有する鋼板を用いて錫めっきを施すことにより、島状Snを含む錫めっき層を形成することでき、溶接性が向上する。
Ni含有層としてはニッケルが含まれていればよく、例えば、Niめっき層、Ni−Fe合金層などが挙げられる。
鋼板にNi含有層を付与する方法は特に制限されず、例えば、公知の電気めっきなどの方法が挙げられる。また、Ni含有層としてNi−Fe合金層を付与する場合、電気めっきなどにより鋼板表面上にNi付与後、焼鈍することにより、Ni拡散層を配位させ、Ni−Fe合金層を形成することができる。
Ni含有層中のNi量は特に制限されず、片面当たりの金属Ni換算量として50〜2000mg/m2が好ましい。上記範囲内であれば、耐硫化黒変性により優れ、コスト面でも有利となる。
If necessary, a steel sheet having a nickel (Ni) -containing layer formed on the surface thereof may be used, and a tin plating layer may be formed on the Ni-containing layer. By performing tin plating using a steel sheet having a Ni-containing layer, a tin plating layer containing island-shaped Sn can be formed, and weldability is improved.
The Ni-containing layer only needs to contain nickel, and examples thereof include a Ni plating layer and a Ni—Fe alloy layer.
The method for applying the Ni-containing layer to the steel plate is not particularly limited, and examples thereof include known methods such as electroplating. Also, when a Ni-Fe alloy layer is applied as the Ni-containing layer, the Ni diffusion layer is coordinated to form a Ni-Fe alloy layer by annealing after applying Ni on the steel sheet surface by electroplating or the like. Can do.
The amount of Ni in the Ni-containing layer is not particularly limited, and is preferably 50 to 2000 mg / m 2 as metal Ni equivalent per one side. If it is in the above-mentioned range, it is more excellent in resistance to sulfur blackening and is advantageous in terms of cost.
(錫めっき層)
錫めっき層付き鋼板は、鋼板表面上に錫めっき層を有する。該錫めっき層は鋼板の少なくとも片面に設けられていればよく、両面に設けられていてもよい。
錫めっき層中における鋼板片面当たりのSn付着量は、0.1〜15.0g/m2が好ましい。Sn付着量が上記範囲内であれば、容器用鋼板の外観特性と耐食性に優れる。なかでも、これらの特性がより優れる点で、0.2〜15.0g/m2が好ましく、加工性がより優れる点で、1.0〜15.0g/m2がさらに好ましい。
(Tin plating layer)
The steel plate with a tin plating layer has a tin plating layer on the steel plate surface. The tin plating layer only needs to be provided on at least one side of the steel plate, and may be provided on both sides.
The Sn adhesion amount per one surface of the steel sheet in the tin plating layer is preferably 0.1 to 15.0 g / m 2 . When the Sn adhesion amount is within the above range, the outer appearance characteristics and corrosion resistance of the steel plate for containers are excellent. Especially, 0.2-15.0 g / m < 2 > is preferable at the point which these characteristics are more excellent, and 1.0-15.0 g / m < 2 > is further more preferable at the point which processability is more excellent.
なお、Sn付着量は、電量法または蛍光X線により表面分析して測定することができる。蛍光X線の場合、金属Sn量既知のSn付着量サンプルを用いて、金属Sn量に関する検量線をあらかじめ特定しておき、同検量線を用いて相対的に金属Sn量を特定する。 Note that the Sn adhesion amount can be measured by surface analysis using a coulometric method or fluorescent X-ray. In the case of fluorescent X-rays, a calibration curve relating to the amount of metallic Sn is specified in advance using an Sn adhesion amount sample with a known amount of metallic Sn, and the amount of metallic Sn is relatively identified using the calibration curve.
錫めっき層は、鋼板表面上の少なくとも一部を覆う層であり、連続層であってもよいし、不連続の島状であってもよい。 The tin plating layer is a layer covering at least a part on the surface of the steel plate, and may be a continuous layer or a discontinuous island shape.
錫めっき層としては、錫をめっきして得られる錫めっき層、または、錫めっき後通電加熱などにより錫を加熱溶融させ、錫めっき最下層(錫めっき/地鉄界面)にFe-Sn合金層が一部形成した錫めっき層も含む。
また、錫めっき層としては、Ni含有層を表面に有する鋼板に対して錫めっきを行い、さらに通電加熱などにより錫を加熱溶融させ、錫めっき最下層(錫めっき/地鉄界面)にFe−Sn−Ni合金、Fe−Sn合金層などが一部形成した錫めっき層も含む。
As the tin plating layer, a tin plating layer obtained by plating tin, or by heating and melting tin by energization heating after tin plating, the Fe-Sn alloy layer at the tin plating bottom layer (tin plating / base metal interface) Includes a tin plating layer partially formed.
In addition, as a tin plating layer, tin plating is performed on a steel sheet having a Ni-containing layer on the surface, and tin is further heated and melted by energization heating or the like, and Fe-- is added to the tin plating bottom layer (tin plating / base metal interface). It also includes a tin plating layer in which a part of Sn—Ni alloy, Fe—Sn alloy layer or the like is formed.
錫めっき層の製造方法としては、周知の方法(例えば、電気めっき法や溶融したSnに浸漬してめっきする方法)が挙げられる。
例えば、フェノールスルフォン酸錫めっき浴、メタンスルフォン酸錫めっき浴、またはハロゲン系錫めっき浴を用い、片面あたり付着量が所定量(例えば、2.8g/m2)となるように鋼板表面にSnを電気めっきした後、Snの融点(231.9℃)以上の温度でリフロー処理を行って、錫単体のめっき層の最下層にFe−Sn合金層を形成した錫めっき層を製造できる。リフロー処理は省略した場合、錫単体のめっき層を製造できる。
As a manufacturing method of a tin plating layer, a known method (for example, an electroplating method or a method of plating by immersing in molten Sn) may be mentioned.
For example, a phenol sulfonate tin plating bath, a methane sulfonate tin plating bath, or a halogen-based tin plating bath is used, and Sn is applied to the surface of the steel sheet so that the adhesion amount per side becomes a predetermined amount (for example, 2.8 g / m 2 ). After electroplating, a reflow process is performed at a temperature equal to or higher than the melting point of Sn (231.9 ° C.), and a tin plating layer in which an Fe—Sn alloy layer is formed in the lowermost layer of the tin plating layer can be manufactured. When the reflow process is omitted, a tin plating layer can be produced.
また、鋼板がその表面上にNi含有層を有する場合、Ni含有層上に錫めっき層を形成させ、リフロー処理を行うと、錫単体のめっき層の最下層(錫めっき/鋼板界面)にFe-Sn−Ni合金層、Fe−Sn合金層などが形成される。 Also, when the steel sheet has a Ni-containing layer on its surface, a tin plating layer is formed on the Ni-containing layer, and when reflow treatment is performed, the bottom layer of the tin simple plating layer (tin plating / steel sheet interface) is Fe. -Sn-Ni alloy layer, Fe-Sn alloy layer, etc. are formed.
<皮膜>
皮膜は、上述した錫めっき層付き鋼板の錫めっき層側の表面上に配置される。
皮膜は、その成分として、Zr(ジルコニウム元素)およびTi(チタニウム元素)を含有する。さらに、皮膜は、錫めっき層付き鋼板の片面あたりのZr換算の付着量(以下、「Zr付着量」ともいう)が1.0〜40.0mg/m2であり、錫めっき層付き鋼板の片面あたりのTi換算の付着量(以下、「Ti付着量」ともいう)が0.3〜5.0mg/m2である。
上記Zr付着量は、樹脂密着性および耐変色性がより優れるという理由から、5.0〜25.0mg/m2が好ましく、9.0〜22.0mg/m2がより好ましい。
上記Ti付着量は、樹脂密着性がより優れるという理由から、0.5〜3.0mg/m2が好ましく、1.0〜2.0mg/m2がより好ましい。
<Film>
A film | membrane is arrange | positioned on the surface by the side of the tin plating layer of the steel plate with a tin plating layer mentioned above.
The coating contains Zr (zirconium element) and Ti (titanium element) as its components. Further, the coating has a Zr equivalent adhesion amount (hereinafter also referred to as “Zr adhesion amount”) of 1.0 to 40.0 mg / m 2 per one side of the steel sheet with the tin plating layer, The adhesion amount in terms of Ti per side (hereinafter also referred to as “Ti adhesion amount”) is 0.3 to 5.0 mg / m 2 .
The Zr adhesion amount is preferably 5.0 to 25.0 mg / m 2 , and more preferably 9.0 to 22.0 mg / m 2 , because the resin adhesion and discoloration resistance are more excellent.
The Ti adhesion amount is preferably 0.5 to 3.0 mg / m 2 and more preferably 1.0 to 2.0 mg / m 2 because the resin adhesion is more excellent.
さらに、皮膜のTiとZrとの質量比(Ti/Zr)については、樹脂密着性および耐変色性がより優れるという理由から、0.01以上0.200未満が好ましく、0.04〜0.18がより好ましく、0.05〜0.11がさらに好ましい。 Furthermore, the mass ratio (Ti / Zr) between Ti and Zr of the film is preferably 0.01 or more and less than 0.200, because it is more excellent in resin adhesion and discoloration resistance. 18 is more preferable, and 0.05 to 0.11 is more preferable.
また、皮膜は、より優れた樹脂密着性および耐変色性が得られるという理由から、錫めっき層付き鋼板の片面あたりのF換算の付着量(以下、「F付着量」ともいう)が、0.2mg/m2未満であるのが好ましく、0.1mg/m2未満がより好ましく、0.07mg/m2未満がさらに好ましく、0.05mg/m2未満が特に好ましく、皮膜がF(フッ素元素)を実質的に含有しない態様が最も好ましい。 In addition, the coating film has an F-attached amount (hereinafter also referred to as “F-attached amount”) per one side of the steel plate with a tin plating layer, because of better resin adhesion and discoloration resistance. preferably less than .2mg / m 2, more preferably less than 0.1 mg / m 2, more preferably less than 0.07 mg / m 2, less than 0.05 mg / m 2 is particularly preferred, coating F (fluorine An embodiment which does not substantially contain (element) is most preferable.
上述したZr付着量およびTi付着量は、蛍光X線による表面分析により測定することができる。
F付着量は、XPS分析により皮膜の最表面におけるZrとFとの原子比を測定し、上記の蛍光X線による表面分析で測定したZr付着量を基に算出することができる。
The Zr adhesion amount and Ti adhesion amount described above can be measured by surface analysis using fluorescent X-rays.
The F adhesion amount can be calculated based on the Zr adhesion amount measured by the surface analysis using the fluorescent X-ray by measuring the atomic ratio of Zr and F on the outermost surface of the film by XPS analysis.
なお、皮膜中のZr、Ti等は、それぞれ、各種のジルコニウム化合物、チタン化合物として含まれ、これら化合物の種類や態様は特に限定されない。 In addition, Zr, Ti, etc. in a film | membrane are each contained as various zirconium compounds and titanium compounds, and the kind and aspect of these compounds are not specifically limited.
そして、本発明では、皮膜の赤外線吸収(IR)スペクトルにおいて、波数1050〜1150cm-1の範囲に、第二級ヒドロキシ基(CH−OH)に由来する吸収ピークを示す、すなわち、皮膜中に第二級ヒドロキシ基が含まれると考えられる。皮膜中に含まれる第二級ヒドロキシ基は、後述する本発明の処理液に含まれるチタンラクテート〔Ti(OH)2[OCH(CH3)COOH]2〕等の乳酸化合物に由来するものと考えられる。 And in this invention, in the infrared absorption (IR) spectrum of a film | membrane, the absorption peak which originates in a secondary hydroxy group (CH-OH) is shown in the range of wave number 1050-1150cm < -1 >, That is, it is 1st in a film | membrane. It is believed that secondary hydroxy groups are included. The secondary hydroxy group contained in the film is considered to be derived from a lactic acid compound such as titanium lactate [Ti (OH) 2 [OCH (CH 3 ) COOH] 2 ] contained in the treatment liquid of the present invention described later. It is done.
赤外線吸収(IR)スペクトルの測定条件は、例えば以下のものが挙げられる。
装置: Varian製 FTS−3100
測定方法: ATR/GEプリズム
分解能: 4cm-1
積算回数: 32回
Examples of the measurement conditions of the infrared absorption (IR) spectrum include the following.
Apparatus: FTS-3100 manufactured by Varian
Measuring method: ATR / GE prism Resolution: 4 cm -1
Integration count: 32 times
<リン含有層>
本発明の容器用鋼板は、上述した錫めっき層付き鋼板と、上述した皮膜との間に、P(リン元素)を含有するリン含有層を有するのが好ましい。具体的には、錫めっき層付き鋼板の片面あたりのP換算の付着量(以下、「P付着量」ともいう)が、0.5〜30.0mg/m2であるリン含有層を有するのが好ましい。
このようなリン含有層を有することで、本発明の容器用鋼板における錫めっき層の酸化が抑制されて、耐変色性がより優れる。また、リンを含有する層は、PETフィルム等の樹脂に対する密着性が劣る場合があるが、本発明において、リン含有層は上述した皮膜に覆われるため、樹脂密着性も良好である。
そして、本発明の容器用鋼板の耐変色性がさらに優れるという理由から、リン含有層のP付着量は、1.0〜10.0mg/m2が好ましく、2.0〜5.0mg/m2がより好ましい。なお、P付着量は、蛍光X線による表面分析により測定できる。
<Phosphorus-containing layer>
The container steel plate of the present invention preferably has a phosphorus-containing layer containing P (phosphorus element) between the above-described steel plate with a tin plating layer and the above-described coating. Specifically, it has a phosphorus-containing layer in which the adhesion amount in terms of P (hereinafter also referred to as “P adhesion amount”) per one side of the steel plate with a tin plating layer is 0.5 to 30.0 mg / m 2 . Is preferred.
By having such a phosphorus-containing layer, oxidation of the tin plating layer in the steel plate for containers of the present invention is suppressed, and discoloration resistance is further improved. Moreover, although the layer containing phosphorus may be inferior in the adhesiveness with respect to resin, such as PET film, in this invention, since the phosphorus containing layer is covered with the membrane | film | coat mentioned above, resin adhesiveness is also favorable.
And since the discoloration resistance of the steel plate for containers of the present invention is further excellent, the P adhesion amount of the phosphorus-containing layer is preferably 1.0 to 10.0 mg / m 2 , and 2.0 to 5.0 mg /
〔容器用鋼板の製造方法、処理液〕
上述した本発明の容器用鋼板を製造する方法としては、後述する本発明の処理液中に錫めっき層付き鋼板を浸漬する、または、本発明の処理液中に浸漬した錫めっき層付き鋼板に陰極電解処理を施すことにより、上述した皮膜を形成する皮膜形成工程を少なくとも備える方法(以下、「本発明の製造方法」ともいう)であるのが好ましい。
以下、本発明の製造方法について説明を行い、この説明の中で、併せて本発明の処理液についても説明する。
[Manufacturing method and processing solution for steel plate for containers]
As a method for producing the above-described steel plate for containers of the present invention, a steel plate with a tin plating layer is immersed in the processing solution of the present invention described later, or a steel plate with a tin plating layer immersed in the processing solution of the present invention. It is preferable that the method includes at least a film forming step for forming the above-described film by performing a cathodic electrolysis treatment (hereinafter also referred to as “production method of the present invention”).
Hereinafter, the production method of the present invention will be described, and in this description, the treatment liquid of the present invention will also be described.
<皮膜形成工程>
皮膜形成工程は、錫めっき層付き鋼板の錫めっき層側の表面上に、上述した皮膜を形成する工程であって、後述する本発明の処理液中に錫めっき層付き鋼板を浸漬する(浸漬処理)、または、浸漬した鋼板に陰極電解処理を施す工程である。陰極電解処理は、浸漬処理よりも、より高速に、均一な皮膜を得ることができるという理由から好ましい。なお、陰極電解処理と陽極電解処理とを交互に行う交番電解を実施してもよい。
以下に、使用される本発明の処理液、陰極電解処理の条件などについて詳述する。
<Film formation process>
The film forming step is a step of forming the above-described film on the surface on the tin plating layer side of the steel plate with the tin plating layer, and immersing the steel plate with the tin plating layer in the treatment liquid of the present invention described later (immersion) Treatment), or a step of subjecting the immersed steel plate to cathodic electrolysis. Cathodic electrolytic treatment is preferable because a uniform film can be obtained at a higher speed than immersion treatment. In addition, you may implement the alternating electrolysis which performs a cathode electrolytic treatment and an anodic electrolytic treatment alternately.
Hereinafter, the treatment liquid of the present invention used, conditions for the cathodic electrolysis, and the like will be described in detail.
(本発明の処理液)
本発明の処理液は、概略的には、上記皮膜にZrを供給するZr供給源としてZr化合物を含有し、上記皮膜にTiを供給するTi供給源としてTi化合物を含有する。本発明の容器用鋼板は、本発明の処理液を用いて皮膜が形成されることにより、樹脂密着性および耐変色性に優れる。
上記効果が得られるメカニズムは明らかではないが、皮膜中に析出するTi化合物が大きな比表面積かつ針状の形状を有しており、この化合物によるアンカー効果によって樹脂(フィルム)と皮膜との密着性が向上する、樹脂と皮膜との界面において高温下での水分の拡散が抑制されることで錫めっき層におけるSnの酸化が抑制される、皮膜中でZrとの複合化合物を形成することで上記効果が相乗的に向上する等の理由が考えられる。
なお、上記メカニズムは推測であり、上記メカニズム以外であっても本発明の範囲内であるとする。
(Processing liquid of the present invention)
The treatment liquid of the present invention generally contains a Zr compound as a Zr supply source for supplying Zr to the film, and contains a Ti compound as a Ti supply source for supplying Ti to the film. The steel plate for containers of the present invention is excellent in resin adhesion and discoloration resistance by forming a film using the treatment liquid of the present invention.
Although the mechanism by which the above effect is obtained is not clear, the Ti compound deposited in the film has a large specific surface area and a needle-like shape, and the adhesion between the resin (film) and the film due to the anchor effect of this compound The formation of a composite compound with Zr in the film suppresses the oxidation of Sn in the tin plating layer by suppressing the diffusion of moisture at a high temperature at the interface between the resin and the film. The reason is that the effect is synergistically improved.
Note that the above mechanism is speculative, and it is assumed that the mechanism other than the above mechanism is within the scope of the present invention.
本発明の処理液が含有するZr化合物について、Zrに換算した量(「Zr量」ともいう)は、3〜40mmol/Lである。Zr量が3mmol/L未満であると、形成される皮膜において、樹脂密着性を確保するためのZr付着量の確保が困難となる。一方、Zr量が40mmol/Lを超えると、効果が飽和し、コストの観点からも好ましくない。しかし、Zr量が3〜40mmol/Lであれば樹脂密着性が優れる。この効果がより優れるという理由から、Zr量は、5〜30mmol/Lが好ましく、10〜20mmol/Lがより好ましい。 For the Zr compound contained in the treatment liquid of the present invention, the amount converted to Zr (also referred to as “Zr amount”) is 3 to 40 mmol / L. When the amount of Zr is less than 3 mmol / L, it is difficult to ensure the amount of Zr adhesion for ensuring resin adhesion in the formed film. On the other hand, when the amount of Zr exceeds 40 mmol / L, the effect is saturated, which is not preferable from the viewpoint of cost. However, if the amount of Zr is 3 to 40 mmol / L, the resin adhesion is excellent. For the reason that this effect is more excellent, the amount of Zr is preferably 5 to 30 mmol / L, and more preferably 10 to 20 mmol / L.
本発明の処理液が含有するZr化合物としては、処理液のpH変動に対して沈殿が発生せず、安定的であるという理由から、オキシ硝酸ジルコニウムであるのが好ましい。オキシ硝酸ジルコニウム〔ZrO(NO3)2〕は、硝酸ジルコニルとも呼ばれる。本発明の処理液がオキシ硝酸ジルコニウムを含有することで、ジルコンフッ化カリウム等のフッ素系のジルコニウム供給源が不使用となり、皮膜のF付着量が低減される。 The Zr compound contained in the treatment liquid of the present invention is preferably zirconium oxynitrate because precipitation does not occur with respect to the pH fluctuation of the treatment liquid and it is stable. Zirconium oxynitrate [ZrO (NO 3 ) 2 ] is also called zirconyl nitrate. When the treatment liquid of the present invention contains zirconium oxynitrate, a fluorine-based zirconium supply source such as zircon potassium fluoride is not used, and the F adhesion amount of the film is reduced.
本発明の処理液が含有するTi化合物について、Tiに換算した量(「Ti量」ともいう)が、1〜7mmol/Lである。Ti量が1mmol/L未満であると、形成される皮膜において、樹脂密着性を確保するためのTi付着量の確保が困難となる。一方、Ti量が7mmol/Lを超えると、耐変色性が劣化する。しかし、Ti量が1〜7mmol/Lであると、樹脂密着性および耐変色性が優れる。これら効果がより優れるという理由から、Ti量は、2〜6mmol/Lが好ましく、3〜5mmol/Lがより好ましい。 For the Ti compound contained in the treatment liquid of the present invention, the amount converted to Ti (also referred to as “Ti amount”) is 1 to 7 mmol / L. When the amount of Ti is less than 1 mmol / L, it is difficult to ensure the amount of Ti adhesion for ensuring resin adhesion in the formed film. On the other hand, when the amount of Ti exceeds 7 mmol / L, discoloration resistance deteriorates. However, when the Ti amount is 1 to 7 mmol / L, the resin adhesion and the discoloration resistance are excellent. From the reason that these effects are more excellent, the amount of Ti is preferably 2 to 6 mmol / L, and more preferably 3 to 5 mmol / L.
本発明の処理液が含有するTi化合物としては、処理液の安定性が優れ、形成される皮膜において、樹脂密着性を確保するためのTi付着量を確保しやすいという理由から、チタンラクテートであるのが好ましい。チタンラクテート〔Ti(OH)2[OCH(CH3)COOH]2〕は、ジヒドロキシビス(ラクタト)チタンとも呼ばれ、本発明では、そのアンモニウム塩(モノアンモニウム塩、ジアンモニウム塩)をも含むものとする。
本発明の処理液がこのようなチタンラクテートを含有することで、形成される皮膜は第二級ヒドロキシ基(CH−OH)を有すると考えられる。また、チタンフッ化水素酸等のフッ素系のチタン供給源が不使用となるため、皮膜のF付着量が低減される。
The Ti compound contained in the treatment liquid of the present invention is titanium lactate because the stability of the treatment liquid is excellent and it is easy to ensure the amount of Ti adhesion for ensuring resin adhesion in the formed film. Is preferred. Titanium lactate [Ti (OH) 2 [OCH (CH 3 ) COOH] 2 ] is also called dihydroxybis (lactato) titanium, and in the present invention, it includes its ammonium salt (monoammonium salt, diammonium salt). .
When the treatment liquid of the present invention contains such titanium lactate, it is considered that the formed film has secondary hydroxy groups (CH—OH). Further, since a fluorine-based titanium supply source such as titanium hydrofluoric acid is not used, the F adhesion amount of the film is reduced.
さらに、本発明の処理液は、硝酸化合物を含有し、硝酸イオン(NO3 -)に換算した量(「NO3 -量」ともいう)は、10〜100mmol/Lである。NO3 -量が10mmol/L未満であると、処理液中の伝導度の確保が困難となり、高速操業性が低下する。一方、NO3 -量が100mmol/Lを超えると、形成される皮膜において、樹脂密着性を確保するためのZr付着量およびTi付着量の確保が困難となる。しかし、NO3 -量が10〜100mmol/Lであれば、高速操業性および樹脂密着性が優れる。この効果がより優れるという理由から、NO3 -量は、20〜80mmol/Lが好ましく、20〜50mmol/Lがより好ましい。 Furthermore, the treatment liquid of the present invention contains a nitric acid compound, and the amount converted to nitrate ion (NO 3 − ) (also referred to as “NO 3 − amount”) is 10 to 100 mmol / L. When the amount of NO 3 − is less than 10 mmol / L, it is difficult to ensure conductivity in the treatment liquid, and high-speed operability is deteriorated. On the other hand, NO 3 - the amount exceeds 100 mmol / L, in the film formed, ensuring Zr coating weight and Ti deposition amount for ensuring resin adhesion becomes difficult. However, when the amount of NO 3 − is 10 to 100 mmol / L, the high-speed operability and the resin adhesion are excellent. For the reason that this effect is more excellent, the NO 3 − amount is preferably 20 to 80 mmol / L, more preferably 20 to 50 mmol / L.
本発明の処理液が含有する硝酸化合物としては、硝酸イオン(NO3 -)を与えるものであれば、特に限定されず、例えば、硝酸カリウム、硝酸アンモニウム、硝酸ナトリウム等の硝酸塩が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。なかでも、処理液の安定性に優れるという理由から、硝酸カリウム、硝酸アンモニウムが好ましい。
また、本発明の処理液は、硝酸化合物として、これら硝酸塩のほかに、上記Zr化合物としてのオキシ硝酸ジルコニウムを含有していてもよい。すなわち、本発明の処理液においては、Zr化合物が硝酸化合物を兼ねていてもよい。
The nitrate compound contained in the treatment liquid of the present invention is not particularly limited as long as it provides nitrate ions (NO 3 − ), and examples thereof include nitrates such as potassium nitrate, ammonium nitrate, and sodium nitrate. One species may be used alone, or two or more species may be used in combination. Of these, potassium nitrate and ammonium nitrate are preferred because of the excellent stability of the treatment liquid.
Moreover, the treatment liquid of the present invention may contain zirconium oxynitrate as the Zr compound in addition to these nitrates as the nitrate compound. That is, in the treatment liquid of the present invention, the Zr compound may also serve as the nitric acid compound.
そして、本発明の処理液は、乳酸化合物を含有し、乳酸(CH3CH(OH)COOH)に換算した量(「乳酸量」ともいう)は、2〜14mmol/Lである。乳酸量が2mmol/L未満であると、形成される皮膜において、樹脂密着性が劣化する。一方、乳酸量が14mmol/Lを超えると、効果が飽和し、コストの観点からも好ましくない。しかし、乳酸量が2〜14mmol/Lであれば、樹脂密着性が優れる。この効果がより優れるという理由から、乳酸量は、4〜12mmol/Lが好ましく、6〜10mmol/Lがより好ましい。 The treatment solution of the present invention contains a lactic acid compound, (also referred to as "lactic acid amount") amount converted to lactic acid (CH 3 CH (OH) COOH) is 2~14mmol / L. When the amount of lactic acid is less than 2 mmol / L, the resin adhesion deteriorates in the formed film. On the other hand, when the amount of lactic acid exceeds 14 mmol / L, the effect is saturated, which is not preferable from the viewpoint of cost. However, if the amount of lactic acid is 2 to 14 mmol / L, the resin adhesion is excellent. From the reason that this effect is more excellent, the amount of lactic acid is preferably 4 to 12 mmol / L, and more preferably 6 to 10 mmol / L.
本発明の処理液が含有する乳酸化合物としては、特に限定されず、例えば、乳酸ならびに従来公知の乳酸塩、乳酸エステル、乳酸キレート等が挙げられるが、本発明の処理液は、このような乳酸化合物として、上記Ti化合物としてのチタンラクテートを含有することができる。すなわち、本発明の処理液においては、乳酸化合物がTi化合物を兼ねていてよい(または、Ti化合物が乳酸化合物を兼ねていてよい)。 The lactic acid compound contained in the treatment liquid of the present invention is not particularly limited, and examples thereof include lactic acid and conventionally known lactate salts, lactic acid esters, lactic acid chelates and the like. As the compound, titanium lactate as the Ti compound can be contained. That is, in the treatment liquid of the present invention, the lactic acid compound may also serve as the Ti compound (or the Ti compound may also serve as the lactic acid compound).
さらに、本発明の処理液は、形成される皮膜のF付着量を低減する観点から、F換算したF化合物の量(「F量」ともいう)が、0.1mmol/L未満であり、0.05mmol/L未満が好ましく、F化合物を実質的に含有しない態様が特に好ましい。 Further, in the treatment liquid of the present invention, the amount of F compound converted to F (also referred to as “F amount”) is less than 0.1 mmol / L from the viewpoint of reducing the F adhesion amount of the formed film. Less than .05 mmol / L is preferred, and an embodiment containing substantially no F compound is particularly preferred.
なお、本発明の処理液中の溶媒としては、通常水が使用されるが、有機溶媒を併用してもよい。 In addition, although water is normally used as a solvent in the processing liquid of this invention, you may use an organic solvent together.
本発明の処理液のpHは、特に限定されないが、pH1.5〜5.0が好ましい。この範囲内であれば、処理時間を短くすることができ、かつ、処理液の安定性に優れる。
pHの調整には公知の酸成分(例えば、リン酸、硫酸、硝酸)・アルカリ成分(例えば、水酸化ナトリウム、水酸化カリウム、アンモニア水)を使用することができる。
The pH of the treatment liquid of the present invention is not particularly limited, but is preferably pH 1.5 to 5.0. Within this range, the treatment time can be shortened and the stability of the treatment liquid is excellent.
For adjusting the pH, known acid components (for example, phosphoric acid, sulfuric acid, nitric acid) / alkali components (for example, sodium hydroxide, potassium hydroxide, aqueous ammonia) can be used.
本発明の処理液には、必要に応じて、ラウリル硫酸ナトリウム、アセチレングリコール、ポリエチレングリコールなどの界面活性剤が含まれていてもよい。また、付着挙動の経時的な安定性の観点から、処理液には、ピロリン酸塩などの縮合リン酸塩が含まれていてもよい。 The treatment liquid of the present invention may contain a surfactant such as sodium lauryl sulfate, acetylene glycol, and polyethylene glycol as necessary. Further, from the viewpoint of the stability of the adhesion behavior over time, the treatment liquid may contain a condensed phosphate such as pyrophosphate.
再び皮膜形成工程の説明に戻る。皮膜形成工程において、処理を実施する際の処理液の液温は、皮膜の形成効率、組織の均一性により優れ、かつ、低コストの点から、20〜80℃が好ましく、40〜60℃がより好ましい。 Returning to the description of the film forming process again. In the film forming step, the liquid temperature of the treatment liquid at the time of performing the treatment is preferably 20 to 80 ° C., and preferably 40 to 60 ° C. from the viewpoint of film formation efficiency and tissue uniformity and low cost. More preferred.
皮膜形成工程において、陰極電解処理を実施する際の電解電流密度は、形成される皮膜の樹脂密着性および耐変色性がより優れるという理由から、低電流密度であることが好ましく、より具体的には、0.05〜7.0A/dm2が好ましく、0.5〜5.0A/dm2がより好ましい。本発明の処理液を用いることにより、低電流密度での皮膜の形成が可能となる。 In the film formation step, the electrolysis current density at the time of carrying out the cathodic electrolysis treatment is preferably a low current density from the reason that the resin adhesion and discoloration resistance of the film to be formed are more excellent. is preferably 0.05~7.0A / dm 2, 0.5~5.0A / dm 2 is more preferable. By using the treatment liquid of the present invention, a film can be formed at a low current density.
このとき、陰極電解処理の通電時間は、付着量低下がより抑制されて安定的に皮膜の形成ができ、形成された皮膜の特性低下がより抑制される点から、0.1〜5秒が好ましく、0.3〜2秒がより好ましい。 At this time, the energization time of the cathodic electrolysis treatment is 0.1 to 5 seconds from the point that the decrease in the adhesion amount is further suppressed and the film can be stably formed, and the characteristic deterioration of the formed film is further suppressed. Preferably, 0.3 to 2 seconds is more preferable.
なお、陰極電解処理の後、必要に応じて、未反応物を除去するため、得られた鋼板の水洗処理および/または乾燥を行ってもよい。なお、乾燥の際の温度および方式については特に限定されず、例えば、通常のドライヤーや電気炉乾燥方式が適用できる。
なお、乾燥処理の際の温度としては、100℃以下が好ましい。上記範囲内であれば、皮膜の酸化を抑制することができ、皮膜組成の安定性が保たれる。なお、下限は特に限定されないが、通常室温程度である。
In addition, in order to remove an unreacted substance after a cathode electrolytic treatment, you may perform the water-washing process and / or drying of the obtained steel plate as needed. In addition, it does not specifically limit about the temperature and system in the case of drying, For example, a normal dryer and an electric furnace drying system are applicable.
In addition, as temperature in the case of a drying process, 100 degrees C or less is preferable. If it is in the said range, the oxidation of a film | membrane can be suppressed and stability of a film | membrane composition is maintained. The lower limit is not particularly limited, but is usually about room temperature.
<前処理工程>
本発明の製造方法は、上述した皮膜形成工程の前に、以下に説明する前処理工程を備えていてもよい。
前処理工程は、アルカリ性水溶液(特に、炭酸ナトリウム水溶液)中で錫めっき層付き鋼板に陰極電解処理を施す工程である。
通常、錫めっき層の作製時にその表面は酸化されて、錫酸化物が形成される。該鋼板に対して、陰極電解処理を施すことにより、不要な錫酸化物を除去して、錫酸化物量を調整できる。
前処理工程の陰極電解処理の際に使用される溶液としては、アルカリ性水溶液(例えば、炭酸ナトリウム水溶液)が挙げられる。アルカリ性水溶液中のアルカリ成分(例えば、炭酸ナトリウム)の濃度は特に制限されないが、錫酸化物の除去がより効率的に進行する点から、5〜15g/Lが好ましく、8〜12g/Lがより好ましい。
陰極電解処理の際のアルカリ性水溶液の液温は特に制限されないが、40〜60℃が好ましい。陰極電解処理の電解条件(電流密度、電解時間)は、適宜調整される。なお、陰極電解処理の後に、必要に応じて、水洗処理を施してもよい。
<Pretreatment process>
The manufacturing method of this invention may be equipped with the pre-processing process demonstrated below before the film formation process mentioned above.
The pretreatment step is a step of subjecting the steel plate with the tin plating layer to cathodic electrolysis in an alkaline aqueous solution (particularly, an aqueous sodium carbonate solution).
Usually, the surface of the tin-plated layer is oxidized to form tin oxide. By subjecting the steel plate to cathodic electrolysis, unnecessary tin oxide can be removed and the amount of tin oxide can be adjusted.
Examples of the solution used for the cathodic electrolysis in the pretreatment step include an alkaline aqueous solution (for example, an aqueous sodium carbonate solution). The concentration of the alkaline component (for example, sodium carbonate) in the alkaline aqueous solution is not particularly limited, but is preferably 5 to 15 g / L, more preferably 8 to 12 g / L from the viewpoint that removal of tin oxide proceeds more efficiently. preferable.
The temperature of the alkaline aqueous solution during the cathodic electrolysis is not particularly limited, but is preferably 40 to 60 ° C. The electrolysis conditions (current density, electrolysis time) of the cathodic electrolysis are appropriately adjusted. In addition, you may perform a water washing process after a cathode electrolytic process as needed.
また、本発明の製造方法が備える前処理工程は、上記工程に限定されず、例えば、リン供給源を含む溶液中に、錫めっき層付き鋼板を浸漬する、または、浸漬した錫めっき層付き鋼板に陰極電解処理を施す工程であってもよい。
このような前処理工程を経ることにより、錫めっき層付き鋼板の錫めっき層側の表面には、上述したリン含有層が形成される。その後、リン含有層が形成された錫めっき層付き鋼板は、上述した皮膜形成工程を経ることで、皮膜が形成される。
Moreover, the pretreatment process with which the manufacturing method of this invention is provided is not limited to the said process, For example, the steel plate with a tin plating layer is immersed in the solution containing a phosphorus supply source, or the steel plate with the tin plating layer which was immersed It may be a step of performing cathodic electrolysis treatment.
By passing through such a pretreatment process, the phosphorus-containing layer described above is formed on the surface on the tin plating layer side of the steel plate with the tin plating layer. Then, the steel plate with a tin plating layer in which the phosphorus-containing layer is formed undergoes the above-described film formation step, whereby a film is formed.
ここで、リン含有層を形成する前処理工程に使用される溶液(以下、「本発明の前処理液」ともいう)に含まれるP供給源としては、リン酸イオン(PO4 3-)を与えるP化合物であれば特に限定されず、例えば、リン酸(オルトリン酸)、リン酸アルミニウム、リン酸カルシウム、リン酸マグネシウム、リン酸マンガンなどのリン酸および/またはその塩が挙げられる。
本発明の前処理液中のP化合物について、リン酸イオン(PO4 3-)に換算した量(「PO4 3-量」ともいう)は、70〜800mmol/Lであるのが好ましい。PO4 3-量が70mmol/L未満であると、形成されるリン含有層において、耐変色性を確保するためのP付着量を確保するのが困難となる場合がある。一方、PO4 3-量が800mmol/Lを超えると、耐変色性の効果が飽和し、コストの観点からも好ましくない場合がある。しかし、PO4 3-量が70〜800mmol/Lであれば、耐変色性がより優れ、この効果がさらに優れるという理由から、100〜500mmol/Lがより好ましく、200〜400mmol/Lがさらに好ましい。
Here, as a P supply source contained in a solution used in the pretreatment step for forming the phosphorus-containing layer (hereinafter also referred to as “pretreatment liquid of the present invention”), phosphate ions (PO 4 3− ) are used. It will not specifically limit if it is a P compound to give, For example, phosphoric acid (orthophosphoric acid), aluminum phosphate, calcium phosphate, magnesium phosphate, phosphoric acid, such as manganese phosphate, and / or its salt are mentioned.
For the P compound in the pretreatment liquid of the present invention, the amount converted to phosphate ion (PO 4 3− ) (also referred to as “PO 4 3− amount”) is preferably 70 to 800 mmol / L. When the amount of PO 4 3− is less than 70 mmol / L, it may be difficult to ensure the P adhesion amount for ensuring discoloration resistance in the formed phosphorus-containing layer. On the other hand, when the amount of PO 4 3− exceeds 800 mmol / L, the effect of discoloration resistance is saturated, which may not be preferable from the viewpoint of cost. However, if the amount of PO 4 3- is 70 to 800 mmol / L, the discoloration resistance is more excellent, and this effect is further excellent, so that 100 to 500 mmol / L is more preferable, and 200 to 400 mmol / L is more preferable. .
本発明の前処理液を用いてリン含有層を形成する前処理工程において、浸漬または陰極電解処理の際の液温は特に制限されないが40〜60℃が好ましい。また、陰極電解処理の電解条件は適宜調整されるが、例えば、陰極電解処理を実施する際の電解電流密度は、所望のリン付着量を得るという理由から、0.05〜15.0A/dm2が好ましく、1.0〜12.0A/dm2がより好ましい。
このとき、陰極電解処理の通電時間は、特に制限されないが、0.1〜10.0秒が好ましく、0.3〜7.0秒がより好ましい。
短時間で所望のリン付着量を得るためには陰極電解処理を行うことが好ましい。
なお、浸漬または陰極電解処理の後に、必要に応じて、水洗処理を施してもよい。
In the pretreatment step of forming the phosphorus-containing layer using the pretreatment liquid of the present invention, the liquid temperature during immersion or cathodic electrolysis is not particularly limited, but is preferably 40 to 60 ° C. Moreover, although the electrolysis conditions for the cathodic electrolysis are appropriately adjusted, for example, the electrolysis current density during the cathodic electrolysis is 0.05 to 15.0 A / dm from the reason that a desired phosphorus adhesion amount is obtained. 2 is preferable, and 1.0 to 12.0 A / dm 2 is more preferable.
At this time, the energization time of the cathodic electrolysis treatment is not particularly limited, but is preferably 0.1 to 10.0 seconds, and more preferably 0.3 to 7.0 seconds.
In order to obtain a desired phosphorus adhesion amount in a short time, it is preferable to perform cathodic electrolysis.
In addition, you may perform a water washing process after immersion or a cathodic electrolysis process as needed.
本発明の製造方法によって得られた本発明の容器用鋼板は、DI缶、食缶、飲料缶など種々の容器の製造に使用される。 The steel plate for containers of the present invention obtained by the manufacturing method of the present invention is used for manufacturing various containers such as DI cans, food cans and beverage cans.
以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<錫めっき層付き鋼板の製造>
以下の2つの方法[(K−1)および(K−2)]によって、錫めっき層付き鋼板を製造した。
(K−1)
板厚0.22mmの鋼板(T4原板)について電解脱脂と酸洗を行い、その後錫めっきを施した。引き続き、錫の融点以上の温度で加熱溶融処理し、第4表に示す片面当たりのSn付着量の錫めっき層をT4原板の両面に形成した。
(K−2)
板厚0.22mmの鋼板(T4原板)を電解脱脂し、ワット浴を用いて第4表に示す片面当たりのNi付着量でニッケルめっき層を両面に形成後、10vol.%H2+90vol.%N2雰囲気中にて700℃で焼鈍してニッケルめっきを拡散浸透させることによりFe−Ni合金層(Ni含有層)(第4表にNi付着量を示す)を両面に形成した。
引き続き、上記表層にNi含有層を有する鋼板を、錫めっき浴を用い、第4表中に示す片面当たりのSn付着量でSn層を両面に形成後、Snの融点以上でリフロー処理を施し、錫めっき層をT4原板の両面に形成した。
<Manufacture of steel sheet with tin plating layer>
A steel plate with a tin plating layer was produced by the following two methods [(K-1) and (K-2)].
(K-1)
Electrolytic degreasing and pickling were performed on a steel plate (T4 original plate) having a thickness of 0.22 mm, and then tin plating was performed. Subsequently, it was heated and melted at a temperature equal to or higher than the melting point of tin, and a tin plating layer having an Sn adhesion amount per one side shown in Table 4 was formed on both sides of the T4 original plate.
(K-2)
A steel plate (T4 original plate) having a thickness of 0.22 mm was electrolytically degreased, and a nickel plating layer was formed on both sides with a Ni adhesion amount per one side shown in Table 4 using a Watt bath, and then 10 vol.% H 2 +90 vol. An Fe—Ni alloy layer (Ni-containing layer) (showing Ni adhesion amount in Table 4) was formed on both sides by annealing at 700 ° C. in an N 2 atmosphere to diffuse and infiltrate nickel plating.
Subsequently, a steel plate having a Ni-containing layer on the surface layer was formed using a tin plating bath, a Sn layer was formed on both sides with the Sn adhesion amount per one side shown in Table 4, and a reflow treatment was performed at a melting point of Sn or higher, Tin plating layers were formed on both sides of the T4 original plate.
<皮膜の形成>
第1表に示すに示す組成の前処理液(溶媒:水)に錫めっき層付き鋼板を浸漬し、第3表に示す条件にて、陰極電解処理を行い、リン含有層を形成した(前処理工程)。
その後、得られた鋼板を水洗し、pHを2.0に調整した第2表に示す組成の処理液(溶媒:水)を用い、第3表に示す浴温、電解条件(電流密度、通電時間)で陰極電解処理を施した。その後、得られた鋼板を水洗して、ブロアを用いて室温で乾燥を行い、皮膜を両面に形成した(皮膜形成工程)。
<Formation of film>
A steel sheet with a tin plating layer was immersed in a pretreatment liquid (solvent: water) having the composition shown in Table 1 and subjected to cathodic electrolysis under the conditions shown in Table 3 to form a phosphorus-containing layer (previous Processing step).
Thereafter, the obtained steel sheet was washed with water, and the treatment liquid (solvent: water) having the composition shown in Table 2 with the pH adjusted to 2.0 was used, and the bath temperature and electrolysis conditions (current density, energization) shown in Table 3 were used. Time). Then, the obtained steel plate was washed with water, dried at room temperature using a blower, and a film was formed on both sides (film formation process).
作製した鋼板に対して、以下の方法で、樹脂密着性および耐変色性を評価した。各成分量、および、評価結果を第4表にまとめて示す。
リン含有層のP付着量、ならびに、皮膜のZr付着量、Ti付着量およびF付着量は、上述の方法により測定した。
The produced steel sheet was evaluated for resin adhesion and discoloration resistance by the following methods. Table 4 summarizes the amount of each component and the evaluation results.
The P adhesion amount of the phosphorus-containing layer, the Zr adhesion amount, the Ti adhesion amount, and the F adhesion amount of the film were measured by the above-described methods.
<樹脂密着性>
作製した容器用鋼板の両面に、厚さ25μm、共重合比12mol%のイソフタル酸共重合ポリエチレンテレフタラートフィルムをラミネートして、ラミネート鋼板を作製した。ラミネートは、210℃に加熱した鋼板とフィルムを一対のゴムロールで挟んでフィルムを鋼板に融着させ、ゴムロール通過後1sec以内に水冷して行った。このとき、鋼板の送り速度は40m/min、ゴムロールのニップ長は17mmであった。ここで、ニップ長とは、ゴムロールと鋼板が接する部分の搬送方向の長さのことである。そして、作製したラミネート鋼板について、次の樹脂密着性の評価を行った。
樹脂密着性の評価は、温度150℃、相対湿度100%のレトルト雰囲気における180°ピール試験により行った。180°ピール試験とは、図1(a)に示すようなフィルム2を残して鋼板1の一部3を切り取った試験片(サイズ:30mm×100mm)を用い、図1(b)に示すように、試験片の一端に重り4(100g)を付けてフィルム2側に180°折り返して30min間放置して行うフィルム剥離試験のことである。そして、図1(c)に示す剥離長5を測定し、次のように樹脂密着性を評価し、◎または○であれば樹脂密着性が良好であるとした。
◎:剥離長が10mm未満
○:剥離長が10mm以上15mm未満
△:剥離長が15mm以上50mm未満
×:剥離長が50mm以上
<Resin adhesion>
A laminated steel plate was prepared by laminating an isophthalic acid copolymerized polyethylene terephthalate film having a thickness of 25 μm and a copolymerization ratio of 12 mol% on both surfaces of the produced steel plate for containers. Lamination was performed by sandwiching a steel plate and a film heated to 210 ° C. between a pair of rubber rolls, fusing the film to the steel plate, and cooling with water within 1 sec after passing through the rubber roll. At this time, the feeding speed of the steel plate was 40 m / min, and the nip length of the rubber roll was 17 mm. Here, the nip length is the length in the transport direction of the portion where the rubber roll and the steel plate are in contact. And about the produced laminated steel plate, the following resin adhesiveness evaluation was performed.
Evaluation of resin adhesion was performed by a 180 ° peel test in a retort atmosphere at a temperature of 150 ° C. and a relative humidity of 100%. The 180 ° peel test uses a test piece (size: 30 mm × 100 mm) obtained by cutting a
A: Peel length is less than 10 mm B: Peel length is 10 mm or more and less than 15 mm Δ: Peel length is 15 mm or more and less than 50 mm X: Peel length is 50 mm or more
<耐変色性>
作製した容器用鋼板の両面に、樹脂密着性を評価したときと同様にしてラミネートし、ラミネート鋼板を作製した。市販のトマトジュースを入れたビーカーに、ラミネート鋼板の試験片(サイズ:50mm×100mm)を入れ、55℃の恒温槽に20日間放置する試験を行った。気相部(トマトジュースに浸かっていない部分)の変色を評価した。
試験前後のラミネート鋼板のL値、a値、b値をスガ試験機製カラーメーターSM-Tで測定し、試験前後の色差を以下のように計算して求めた。
ΔE=((L試験前−L試験後)2+(a試験前−a試験後)2+(b試験前−b試験後)2)0.5
その結果、次のように耐変色性を評価し、◎または○であれば耐変色性が良好であるとした。
◎:色差が2未満
○:色差が2以上、7未満
△:色差が7以上、15未満
×:色差が15以上
<Discoloration resistance>
Lamination was performed on both surfaces of the produced steel plate for containers in the same manner as when the resin adhesion was evaluated to produce a laminated steel plate. A test piece (size: 50 mm × 100 mm) of a laminated steel plate was placed in a beaker containing a commercially available tomato juice, and a test was performed in a constant temperature bath at 55 ° C. for 20 days. Discoloration of the gas phase part (part not immersed in tomato juice) was evaluated.
The L value, a value, and b value of the laminated steel sheet before and after the test were measured with a color meter SM-T manufactured by Suga Test Instruments, and the color difference before and after the test was calculated as follows.
ΔE = ((before L test−after L test) 2 + (before a test−after a test) 2 + (before b test−after b test) 2 ) 0.5
As a result, the discoloration resistance was evaluated as follows, and if it was A or B, it was determined that the discoloration resistance was good.
◎: Color difference is less than 2 ○: Color difference is 2 or more, less than 7 Δ: Color difference is 7 or more, less than 15 ×: Color difference is 15 or more
上記第1〜4表に示す結果から明らかなように、本発明例はいずれも樹脂密着性および耐変色性に優れることが確認された。
これに対して、比較例1〜16は、樹脂密着性および耐変色性が劣っていた。
とりわけ、Ti量が1mmol/L未満、かつ乳酸量が2mmol/L未満である処理液B17〜20および23を用いた比較例1〜4,7〜10および13は、樹脂密着性が特に劣っていた。
また、Zr量が3mmol/L未満である処理液B21を用いた比較例5および11も、樹脂密着性が特に劣っており、耐変色性も良好な結果ではなかった。
また、NO3 -量が100mmol/Lを超える処理液B22を用いた比較例6および12も、樹脂密着性が特に劣っており、耐変色性も良好な結果ではなかった。
また、乳酸量が2mmol/L未満である処理液B24を用いた比較例14は、樹脂密着性および耐変色性ともに良好な結果が得られなかった。
また、乳酸量が2mmol/L未満、かつF量が0.1mmol/Lを超える処理液B25を用いた比較例15は、樹脂密着性および耐変色性がともに劣っていた。
さらに、Ti量が7mmol/Lを超える処理液B26を用いた比較例16は、耐変色性が特に劣っていた。
As is clear from the results shown in Tables 1 to 4 above, it was confirmed that all of the inventive examples were excellent in resin adhesion and discoloration resistance.
On the other hand, Comparative Examples 1-16 were inferior in resin adhesiveness and discoloration resistance.
In particular, Comparative Examples 1 to 4, 7 to 10 and 13 using the treatment liquids B17 to 20 and 23 having a Ti amount of less than 1 mmol / L and a lactic acid amount of less than 2 mmol / L are particularly inferior in resin adhesion. It was.
In addition, Comparative Examples 5 and 11 using the treatment liquid B21 having a Zr amount of less than 3 mmol / L were also particularly inferior in resin adhesion and did not have good discoloration resistance.
Further, Comparative Examples 6 and 12 using the treatment liquid B22 having an NO 3 - amount exceeding 100 mmol / L were also particularly inferior in resin adhesion and did not have good discoloration resistance.
Further, Comparative Example 14 using the treatment liquid B24 having a lactic acid content of less than 2 mmol / L did not give good results in both resin adhesion and discoloration resistance.
Further, Comparative Example 15 using the treatment liquid B25 in which the lactic acid amount was less than 2 mmol / L and the F amount was more than 0.1 mmol / L was inferior in both resin adhesion and discoloration resistance.
Further, Comparative Example 16 using the treatment liquid B26 having a Ti amount exceeding 7 mmol / L was particularly inferior in discoloration resistance.
1 容器用鋼板
2 フィルム
3 鋼板の切り取った部位
4 重り
5 剥離長
DESCRIPTION OF
Claims (8)
Zr化合物と、Ti化合物と、硝酸化合物と、乳酸化合物とを含有し、
Zr量が、3〜40mmol/Lであり、
Ti量が、1〜7mmol/Lであり、
NO3 -量が、10〜100mmol/Lであり、
乳酸量が、2〜14mmol/Lであり、
F量が、0.1mmol/L未満であることを特徴とする処理液。 A steel plate for a container comprising a steel plate and a steel plate with a tin plating layer having a tin plating layer covering at least a part of the surface of the steel plate, and a coating disposed on the surface of the steel plate with the tin plating layer on the tin plating layer side A treatment liquid for forming the film,
Containing a Zr compound, a Ti compound, a nitric acid compound, and a lactic acid compound,
The amount of Zr is 3 to 40 mmol / L,
Ti amount is 1-7 mmol / L,
NO 3 - amount is 10-100 mmol / L,
The amount of lactic acid is 2-14 mmol / L,
A treatment liquid, wherein the F amount is less than 0.1 mmol / L.
前記Ti化合物、および、前記乳酸化合物が、チタンラクテートである、請求項1に記載の処理液。 The Zr compound and a part of the nitric acid compound are zirconium oxynitrate,
The treatment liquid according to claim 1, wherein the Ti compound and the lactic acid compound are titanium lactate.
前記皮膜は、請求項1または2に記載の処理液を用いて形成され、前記錫めっき層付き鋼板の片面あたりのZr換算の付着量が1.0〜40.0mg/m2であって、前記錫めっき層付き鋼板の片面あたりのTi換算の付着量が0.3〜5.0mg/m2であることを特徴とする容器用鋼板。 A steel plate for a container comprising a steel plate and a steel plate with a tin plating layer having a tin plating layer covering at least a part of the surface of the steel plate, and a coating disposed on the surface of the steel plate with the tin plating layer on the tin plating layer side Because
The coating is formed using the treatment liquid according to claim 1 or 2, and a Zr conversion amount per one side of the steel plate with the tin plating layer is 1.0 to 40.0 mg / m 2 , A steel plate for containers, wherein the amount of adhesion in terms of Ti per side of the steel plate with a tin plating layer is 0.3 to 5.0 mg / m 2 .
請求項1または2に記載の処理液中に前記錫めっき層付き鋼板を浸漬する、または、浸漬した前記錫めっき層付き鋼板に陰極電解処理を施すことにより、前記皮膜を形成することを特徴とする容器用鋼板の製造方法。 It is a manufacturing method of the steel plate for containers which obtains the steel plate for containers according to claim 3,
The said coating film is formed by immersing the said steel plate with a tin plating layer in the processing liquid of Claim 1 or 2, or performing a cathodic electrolytic process to the immersed said steel plate with a tin plating layer, It is characterized by the above-mentioned. A method for manufacturing a steel sheet for containers.
PO4 3-量が70〜800mmol/Lである前処理液中に前記錫めっき層付き鋼板を浸漬する、または、浸漬した前記錫めっき層付き鋼板に陰極電解処理を施すことにより、前記リン含有層を形成した後に、請求項1または2に記載の処理液中に、前記リン含有層が形成された前記錫めっき層付き鋼板を浸漬する、または、浸漬した前記リン含有層が形成された前記錫めっき層付き鋼板に陰極電解処理を施すことにより、前記皮膜を形成することを特徴とする容器用鋼板の製造方法。 It is a manufacturing method of the steel plate for containers which obtains the steel plate for containers according to claim 4,
By immersing the steel sheet with a tin plating layer in a pretreatment solution having a PO 4 3- amount of 70 to 800 mmol / L, or by subjecting the immersed steel sheet with a tin plating layer to cathodic electrolytic treatment, After forming the layer, the steel sheet with the tin plating layer on which the phosphorus-containing layer is formed is immersed in the treatment liquid according to claim 1 or 2, or the phosphorus-containing layer on which the immersion is formed is formed. A method for producing a steel plate for containers, wherein the coating is formed by subjecting a steel plate with a tin plating layer to cathodic electrolysis.
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