TWI485287B - 容器用鋼板及其製造方法 - Google Patents

容器用鋼板及其製造方法 Download PDF

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Publication number
TWI485287B
TWI485287B TW100133004A TW100133004A TWI485287B TW I485287 B TWI485287 B TW I485287B TW 100133004 A TW100133004 A TW 100133004A TW 100133004 A TW100133004 A TW 100133004A TW I485287 B TWI485287 B TW I485287B
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Taiwan
Prior art keywords
steel sheet
treatment
layer
amount
film
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TW100133004A
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English (en)
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TW201217577A (en
Inventor
Takeshi Suzuki
Norihiko Nakamura
Yuka Miyamoto
Yoichi Tobiyama
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Jfe Steel Corp
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Publication of TW201217577A publication Critical patent/TW201217577A/zh
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82After-treatment
    • C23C22/83Chemical after-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00Layered products having a non-planar shape
    • B32B1/08Tubular products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/18Layered products comprising a layer of metal comprising iron or steel
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
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    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236Cold rolling
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    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
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    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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    • C23C10/00Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
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    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
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    • C23C22/36Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
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    • C23C22/62Treatment of iron or alloys based thereon
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Description

容器用鋼板及其製造方法
本發明是關於容器用鋼板及其製造方法。
以往,在所有的罐種類中,皆對於罐所使用的鋼板(容器用鋼板)進行塗層,但是,近年來,從地球環保的觀點來看,著重於以層疊薄膜來取代塗層的技術而急速地擴展。
但是,以往,在層壓膜的基礎所使用的鋼板形成有鉻酸鹽轉化膜,但是,近年來開始呼籲鉛及鎘等有害物質的使用限制及對於製造工廠的勞動環境的關懷,而要求不使用鉻酸鹽處理膜。
並在飲料容器市場中,罐在於成本與品質的點上,暴露在與PET瓶、瓶、紙袋等容器的競爭,對於層疊容器用鋼板,也要求具有更優異的製罐加工性(尤其是薄膜密接性、加工薄膜密接性、抗蝕性等)。
為滿足以上要求有例如專利文獻1中,『在含Zr離子、F離子、銨離子、硝酸離子的溶液中,具有藉浸漬或電解處理的進行形成在鋼板上的Zr化合物處理膜,上述Zr化合物處理膜的附著量是金屬Zr量為1~100mg/m2 、F量為0.1mg/m2 以下為特徵的容器用鋼板。』所揭示([申請專利範圍第1項])。
[先前技術文獻] [專利文獻]
[專利文獻1] 日本特開2010-13728號公報
如上述,近年來,在飲料容器市場品質競爭的激烈化,對於層疊容器用鋼板,也尋求更為優異的薄膜密接性。尤其是將罐縮頸加工後的頸部份的薄膜,由於一般較為容易剝離,因此期待即使在嚴苛的條件下該等部份也不致發生剝離的容器用鋼板。
本發明人利用專利文獻1所揭示的容器用鋼板,針對縮頸部份相關的薄膜密接性(以下,又稱「高薄膜密接性」)進行了研討,得知並未到達現今所要求的水準而有改良的必要。
因此,本發明係以提供高薄膜密接性優異的容器用鋼板及其製造方法為目的。
本發明人,為解決上述課題努力加以研討的結果,發現在鋼板上形成預定的化學轉化處理膜上設置預定的酚醛樹脂層的容器用鋼板,具優異的高薄膜密接性而完成本發明。
亦即,本發明提供以下的(1)~(7)。
(1)一種容器用鋼板,係於鋼板上,具有金屬Zr量1~100mg/m2 、P量0.1~50mg/m2 、F量0.1mg/m2 以下的化學轉化處理膜,在該化學轉化處理膜上,具有C量0.1~50mg/m2 的酚醛樹脂層。
(2)如上述(1)項記載的容器用鋼板,藉著含Zr離子、磷酸離子、F離子之處理液中的浸漬處理或使用該處理液的電解處理,在上述鋼板上形成上述化學轉化處理膜,接著,將形成有上述化學轉化處理膜後的上述鋼板浸漬在含酚醛樹脂的水溶液中,或在上述化學轉化處理膜上塗抹該水溶液,藉隨後的乾燥所獲得。
(3)如上述(1)項或(2)項記載的容器用鋼板,上述鋼板,至少在其單面具有含金屬Ni量10~1000mg/m2 的Ni或含金屬Sn量100~15000mg/m2 的Sn的表面處理層。
(4)如上述(1)項或(2)項記載的容器用鋼板,上述鋼板是在其表面施以Ni電鍍或Fe-Ni合金電鍍而形成基底Ni層,並在上述基底Ni層上施以Sn電鍍,使該Sn電鍍的一部份與上述基底Ni層的一部份或全部藉著熔融熔錫處理予以合金化後形成含島狀Sn的Sn電鍍層,上述基底Ni層是含金屬Ni量5~150mg/m2 的Ni,上述Sn電鍍層是含金屬Sn量300~3000mg/m2 的Sn。
(5)如上述(1)項至(4)項中任一項記載的容器用鋼板,藉著含Zr離子、磷酸離子、F離子之處理液中的浸漬處理或使用該處理液的電解處理,在上述鋼板上形成上述化學轉化處理膜,接著,將形成有上述化學轉化處理膜後的上述鋼板浸漬在含酚醛樹脂的水溶液中,或在上述化學轉化處理膜上塗抹該水溶液,隨後使其乾燥。
(6)如上述(5)項記載的容器用鋼板,上述乾燥的溫度為70℃以上。
(7)如上述(6)項記載的容器用鋼板,在上述乾燥之後,進一步以溫度80℃以上的水清洗,再次進行乾燥。
根據本發明,可提供高薄膜密接性也優異的容器鋼板及其製造方法。
<容器用鋼板>
本發明的容器用鋼板是在鋼板上,具有金屬Zr量1~100mg/m2 、P量0.1~50mg/m2 、F量0.1mg/m2 以下的化學轉化處理膜,在該化學轉化處理膜上,具有C量0.1~50mg/m2 的酚醛樹脂層的容器用鋼板。
以下,針對本發明容器用鋼板的構成詳細說明。
<鋼板>
本發明所使用的鋼板尤其不加以限定,通常,可使用作為容器材料所使用的鋼板原板。並且,該鋼板原板的製造方法、材質等尤其不加以特別限制,可使用從通常的鋼片製造步驟經熱軋、酸洗、冷軋、退火、冷精軋等的各步驟製造之物。
本發明所使用的鋼板也可以在至少單面具有含鎳(Ni)及/或含錫(Sn)的表面處理層。
上述的表面處理層為Ni電鍍層、Sn電鍍層、Sn-Ni合金電鍍層等。
Ni對於塗料密接性、薄膜密接性、抗蝕性、熔接性等可發揮其效果。此時,表面處理層中,金屬Ni量從為了使該等的特性更為優異的理由及經濟性的觀點,以10~1000mg/m2 為佳。
Sn對於加工性、熔接性、抗蝕性等可發揮其效果。此時,表面處理層中,金屬Sn量從為了使該等的特性更為優異的理由及經濟性的觀點,以100~15000mg/m2 為佳,使熔接性更為優異的理由是以200~15000mg/m2 為佳,使加工性更為優異的理由則是以1000~15000mg/m2 更佳。
形成表面處理層(電鍍層)的方法尤其不加以限定,例如可使用電鍍法、浸漬電鍍法、真空蒸鍍法、濺鍍法等習知的方法,且為了形成擴散層也可以組合加熱處理。
Ni電鍍層除了施以金屬Ni電鍍所形成的層之外,也可施以鐵(Fe)-鎳(Ni)合金電鍍所形成的Fe-Ni合金電鍍層。
Sn電鍍層雖是藉金屬Sn施以電鍍(Sn電鍍)所形成,但是本發明的「Sn電鍍」是在金屬Sn內含混入有不可逆雜質的電鍍層及在金屬Sn添加微量元素的電鍍層。
又,本發明中,也可形成含島狀Sn的Sn電鍍層。此時,在鋼板的表面施以Ni電鍍或Fe-Ni合金電鍍以形成基底Ni層,在基底Ni層上施以Sn電鍍,藉熔融熔錫處理使得該Sn電鍍的一部份與基底Ni層的一部份或全部合金化形成含島狀Sn的Sn電鍍層。
藉熔融熔錫處理(逆流處理),使Sn熔解而與鋼板或基底Ni層合金化,形成Sn-Fe合金層或Sn-Fe-Ni合金層,提升合金層的抗蝕性,並形成島狀的Sn合金。島狀的Sn合金可以適當控制熔融熔錫處理形成。
Ni為高抗蝕金屬,可提升藉熔融熔錫處理所形成的含Fe及Sn金屬層的抗蝕性。
基底Ni層中的金屬Ni量從發現抗蝕性的觀點及經濟性的觀點,以5~150mg/m2 為佳。
作為基底Ni層在施以加熱處理形成擴散層的場合,也可在加熱處理的前後或與加熱處理同時,進行氮化處理。
Sn的優異抗蝕性是從金屬Sn量為300mg/m2 以上顯著地提升,Sn的含量越多,也可增加抗蝕性提升的程度。因此,含島狀Sn的Sn電鍍層的金屬Sn量是以300mg/m2 以上為佳。抗蝕性提升效果一旦金屬Sn量超過3000mg/m2 時即為飽和,從經濟性的觀點,Sn含量是以3000mg/m2 以下為佳。
又,電阻低的Sn柔軟,熔接時在電極間藉著使Sn加壓而擴展,可確保穩定的通電區域,尤其可發揮優異的熔接性。該優異的熔接性只要金屬量Sn在100mg/m2 以上即可發揮。又,顯示上述優異抗蝕性之金屬Sn量的範圍中,該熔接性的提升效果並不致於飽和。因此,為確保優異的抗蝕性及熔接性,以金屬Sn量為300mg/m2 以上3000mg/m2 以下為佳。
再者,表面處理層中的金屬Ni量或金屬Sn量,例如可藉螢光X射線法來測定。此時,使用金屬Ni量為已知的Ni附著量樣本,預先特定金屬Ni量的相關檢量線,利用該檢量線相對地特定金屬Sn量。金屬Sn量的場合也相同,使用金屬Sn量為已知的Sn附著量樣本,預先特定金屬Sn量的相關檢量線,利用該檢量線相對地特定金屬Sn量。
<化學轉化處理膜>
本發明的容器用鋼板具有形成在上述鋼板上之金屬Zr量1~100mg/m2 、P量0.1~50mg/m2 、F量0.1mg/m2 以下的化學轉化處理膜。
形成化學轉化處理膜的方法,可舉例如:藉著將鋼板浸漬在熔解Zr離子、磷酸離子、F離子後之處理液(酸性溶液)的浸漬處理進行的方法;藉著在含Zr離子、磷酸離子、F離子的處理液中之陰極電解處理進行的方法等,從可獲得均一處理膜的理由,以藉陰極電解處理進行的方法為佳。
尤其在陰極電解處理中,以硝酸離子與銨離子共存於處理液中為佳。藉此,可以數秒至數十秒程度的短時間處理,並可形成抗蝕性與密接性之提升效果優異的化學轉化處理膜。
再者,進行陰極電解處理的場合,陰極電解處理的浴溫從處理膜的形成效率、成本、所形成處理膜組織的均一性等的觀點,以10~40℃為佳(低溫陰極電解處理)。又,陰極電解處理的電解電流密度從處理膜附著量的降低抑制、穩定處理膜的形成、處理時間、處理膜特性的降低抑制等的觀點,以0.05~50A/dm2 為佳。另外,陰極電解處理的通電時間從處理膜附著量的降低抑制、穩定處理膜的形成、處理時間、處理膜特性的降低抑制等的觀點,則以0.01~5秒為佳。
化學轉化處理膜含有Zr化合物。在此,Zr化合物的功能為抗蝕性及密接性的確保。Zr化合物則可考慮Zr氫氧化物及Zr磷氧化物,該等Zr化合物具有優異的抗蝕性及密接性。此外,「Zr氫氧化物」是意味著Zr氧化物與Zr氫氧化物混合的狀態。
化學轉化處理膜中的金屬Zr量在1mg/m2 以上時,實用上,可確保無問題的抗蝕性與密接性。又,金屬Zr量一旦超過100mg/m2 時,隨著化學轉化處理膜密接性的劣化的同時使電阻上升而使得溶接性劣化。因此,化學轉化處理膜中的金屬Zr量為1~100mg/m2 ,並以1~20mg/m2 為佳,最好是1~10mg/m2
又,Zr磷氧化物增加時可發揮更具優異之抗蝕性與密接性,但可明確認知其效果是在P量為0.1mg/m2 以上的場合。又,P量超過50mg/m2 時隨著密接性劣化的同時使電阻上升而使得溶接性劣化。因此,化學轉化處理膜中的P量為0.1~50mg/m2 ,並以0.1~20mg/m2 為佳,最好是0.1~10mg/m2
F包含於處理液中,所以和Zr化合物一起進入處理膜中。處理膜中的F雖然對於塗料或薄膜通常的密接性不會有影響,但會造成蒸餾處理等高溫殺菌處理時的密接性與抗鏽性或者塗膜下腐蝕性劣化的原因。其理由可能是處理膜中的F溶出於水蒸氣或腐蝕液,使得與有機處理膜的結合分解,或造成基底鋼板腐蝕的原因。
化學轉化處理膜的F量一旦超過0.1mg/m2 時,由於開始使得該等的諸特性明顯劣化,所以在0.1mg/m2 以下。
為了設化學轉化處理膜的F量在0.1mg/m2 以下,在形成化學轉化處理膜之後,藉溫水中的浸漬處理或噴灑處理進行清洗處理即可。此時,可藉著高的處理溫度或長的處理時間可減少F量。
例如,為了設化學轉化處理膜中的F量為0.1mg/m2 以下,以40℃以上的溫水進行0.5秒以上的浸漬處理或噴灑處理即可。
化學轉化處理膜中的金屬Zr量、P量、F量,例如可藉螢光X射線分析等的定量分析來測定。
在處理液中的銨離子的濃度為100~10000ppm左右,硝酸離子的濃度為1000~20000ppm左右的範圍,對應生產設備與生產速度(能力)適當調整即可。
<酚醛樹脂層>
本發明的容器用鋼板具有形成在化學轉化處理膜的含酚醛樹脂的酚醛樹脂層。
酚醛樹脂成分可舉例如N,N-二乙醇胺變性後的水溶性酚醛樹脂。
由於酚醛樹脂本身為有機物,因此具有酚醛樹脂的本發明的容器用鋼板對於層疊膜可獲得非常優異的密接性。
此時,酚醛樹脂層中的C量小於0.1mg/m2 時,不能確保實用位準的密接性。另一方面,C量超過50mg/m2 時,電阻上升使得溶接性劣化,並會有因酚醛樹脂層中的凝聚破壞使得密接性降低的場合。
對此,C量只要是0.1~50mg/m2 ,即可確保實用上無問題位準的密接性,並可抑制電阻的上升。因此,酚醛樹脂層中的C量為0.1~50mg/m2 ,並以0.1~10mg/m2 為佳,並以0.1~8mg/m2 更佳。
再者,酚醛樹脂層中的C量可使用TOC(總有機碳分析儀),藉減去存在鋼板中的C量來測定。
形成酚醛樹脂層的方法尤其不加以限定,可舉例如將形成有化學轉化處理膜後的鋼板浸漬在含酚醛樹脂的水溶液之後乾燥的方法,及將含酚醛樹脂的水溶液塗抹在形成於鋼板上的化學轉化處理膜上之後,乾燥的方法等。
浸漬的場合在時間上尤其不加以限定,但以1秒以上為佳。
此外,其中任意的方法,乾燥的溫度皆以70℃以上為佳。
<清洗>
本發明中,為使得容器用鋼板的高薄膜密接性更為優異的理由,也可在形成酚醛樹脂層之後,將所獲得的容器用鋼板,進一步以水,並以溫度80℃以上為佳的水清洗之後,進行乾燥。
藉著此一清洗,使酚醛樹脂層的表面適度地粗面化,可使得高薄膜密接性更為良好。
另外,藉著如上述清洗,也可顯見除去存在於化學轉化處理膜中的F並使得F量減少點的效果。
此時,清洗的方法尤其不加以限於,如可舉例,將所獲得的容器用鋼板浸漬在水中的方法,或使用噴灑等將水塗佈於所獲得的容器用鋼板的方法等。
浸漬的場合,浸漬時間是以1秒以上為佳。
且,乾燥的溫度是以70℃以上為佳。
[實施例]
以下,雖舉實施例具體說明本發明,但本發明不僅限於此。
<表面處理層>
使用以下的處理法(1-0)~(1-7)的方法,在板厚0.17~0.23mm的鋼板上形成表面處理層。
(1-0)冷軋後,製作對退火、調壓後的原板施以脫脂、酸洗的鋼板。
(1-1)冷軋後,將退火、調壓後的原板脫脂、酸洗後,使用硫酸-鹽酸浴施以Sn-Ni合金電鍍,製作Ni、Sn電鍍鋼板。
(1-2)冷軋後,將退火、調壓後的原板脫脂、酸洗後,使用瓦特浴施以Ni電鍍,製作Ni電鍍鋼板。
(1-3)冷軋後,使用瓦特浴施以Ni電鍍,退火時形成Ni擴散層,製作Ni電鍍鋼板。
(1-4)冷軋後,將退火、調壓後的原板脫脂、酸洗後,使用電鍍浴施以Sn電鍍,製作Sn電鍍鋼板。
(1-5)冷軋後,將退火、調壓後的原板脫脂、酸洗後,使用電鍍浴施以Sn電鍍,隨後進行熔融熔錫處理(逆流處理),製作具有Sn合金層的Sn電鍍鋼板。
(1-6)冷軋後,在原板脫脂、酸洗後,使用瓦特浴施以Ni電鍍,在退火時形成Ni擴散層,並在脫脂、酸洗後,使用電鍍浴施以Sn電鍍,並隨後進行熔融熔錫處理,製作具有Sn合金層的Ni、Sn電鍍鋼板。
(1-7)冷軋後,將退火、調壓後的原板脫脂、酸洗後,使用硫酸-鹽酸浴施以Fe-Ni合金電鍍,接著,使用電鍍浴施以Sn電鍍,並隨後進行熔融熔錫處理(逆流處理),製作具有Sn合金層的Ni、Sn電鍍鋼板。
此外,進行(1-6)及(1-7)的處理的場合,以光學顯微鏡觀察表面,評估島狀Sn狀況時,可確認出整體形成有島狀。
<化學轉化處理膜>
藉上述的處理形成表面處理層之後,藉以下的處理法(2-1)~(2-3)形成化學轉化處理膜。
(2-1)使K2 ZrF6 (4.3g/L)與磷酸(1.2g/L)熔解添加硝酸銨,將上述鋼板浸漬在PH調整為2.65的處理液,在浴溫30℃,以第1表顯示的條件陰極電解形成化學轉化處理膜。
(2-2)使K2 ZrF6 (4.3g/L)與磷酸(1.2g/L)與酚醛樹脂(0.7g/L)熔解添加硝酸銨,將上述鋼板浸漬在PH調整為2.65的處理液,在浴溫30℃,以第1表顯示的條件陰極電解形成化學轉化處理膜。
(2-3)使K2 ZrF6 (4.3g/L)與磷酸鈉(1.4g/L)熔解添加磷酸,將上述鋼板浸漬在PH調整為2.65的處理液,在浴溫30℃,以第1表顯示的條件陰極電解形成化學轉化處理膜。
(水洗處理)
藉上述的處理形成化學轉化處理膜之後,以下述的處理法(3-1)進行水洗處理,控制化學轉化處理膜中的F量。
(3-1)在40℃的溫水浸漬1秒鐘。
<酚醛樹脂層>
藉上述的處理形成化學轉化處理膜,藉上述的處理進行水洗處理之後,以下述的處理(4-1)~(4-5)形成酚醛樹脂層。
(4-1)將溶解酚醛樹脂0.1g/L後的水溶液以輥塗機塗抹之後,以75℃乾燥形成酚醛樹脂層。
(4-2)在溶解酚醛樹脂0.5g/L後的水溶液,將上述鋼板浸漬1秒鐘之後,以75℃乾燥,形成酚醛樹脂層。
(4-3)將溶解酚醛樹脂3.0g/L後的水溶液以輥塗機塗抹之後,以75℃乾燥,形成酚醛樹脂層。
(4-4)在溶解酚醛樹脂0.01g/L後的水溶液,將上述鋼板浸漬1秒鐘之後,以輥滾壓,並以75℃乾燥,形成酚醛樹脂層。
(4-5)將溶解酚醛樹脂10.0g/L後的水溶液以輥塗機塗抹之後,以75℃乾燥,形成酚醛樹脂層。
此外,上述的任意場合,酚醛樹脂皆是使用上述之N,N-二乙醇胺變性後的水溶性酚醛樹脂(重量平均分子量:5000)。
<清洗>
藉上述的處理形成化學轉化處理膜之後,藉以下的處理法(5-1)進行清洗。
(5-1)在85℃的水中浸漬1秒鐘之後,以75℃乾燥。
再者,其中之一的實施例及比較例中,表面處理層中的金屬Ni量及金屬Sn量是藉螢光X射線法來測定,使用檢量線予以特定。
又,化學轉化處理膜中含有的金屬Zr量、P量、F量是以螢光X射線分析等的定量分析法來測定。且化學轉化處理膜及酚醛樹脂層中含有的C量是使用TOC(總有機碳分析儀),藉減去存在鋼板中的C量來測定。
<性能評估>
針對進行上述處理的試驗材,進行高薄膜密接性的評估。
首先,在實施例及比較例的各試驗材的兩面,將厚度20μm的PET薄膜以20℃層疊之後,進行拉深旋轉加工製作罐體,對製作的罐體施以縮頸加工形成縮頸部。並將該罐體以120℃進行30分鐘的蒸餾處理,評估縮頸部的薄膜的剝離狀況。
具體評估,完全無剝離的狀況為「◎」,產生實用上沒有問題程度的極些微剝離的狀況為「○」,部份產生剝離實用上有問題的狀況為「△」,而大部份產生剝離的狀況為「×」。將結果顯示於第1表。
從第1表顯示的結果,由比較例1~11可得知高薄膜密接性皆為不良。
尤其可得知化學轉化處理膜中含酚醛樹脂的比較例9中,不能獲得充分的高薄膜密接性。
且雖具有酚醛樹脂層,但其C量為本發明範圍外的比較例10、11也是仍就不能獲得充分的高薄膜密接性。
相對於此,可得知實施例1~9皆具有優異的高薄膜密接性。此時,在形成酚醛樹脂層之後進行清洗的實施例2與未進行清洗的實施例1比較,可得知具有更優異的高薄膜密接性。

Claims (7)

  1. 一種容器用鋼板,其特徵為:鋼板上,具有:金屬Zr量1~100mg/m2 、P量0.1~50mg/m2 、F量0.1mg/m2 以下的化學轉化處理膜,該化學轉化處理膜上具有C量0.1~50mg/m2 的酚醛樹脂層。
  2. 如申請專利範圍第1項記載的容器用鋼板,其中,藉著含Zr離子、磷酸離子、F離子之處理液中的浸漬處理或使用該處理液的電解處理,在上述鋼板上形成上述化學轉化處理膜,接著,將形成有上述化學轉化處理膜後的上述鋼板浸漬在含酚醛樹脂的水溶液中,或在上述化學轉化處理膜上塗抹該水溶液,藉隨後的乾燥所獲得。
  3. 如申請專利範圍第1項或第2項記載的容器用鋼板,其中,上述鋼板,至少在其單面具有含金屬Ni量10~1000mg/m2 的Ni或含金屬Sn量100~15000mg/m2 的Sn的表面處理層。
  4. 如申請專利範圍第1項或第2項記載的容器用鋼板,其中,上述鋼板是在其表面施以Ni電鍍或Fe-Ni合金電鍍而形成基底Ni層,並在上述基底Ni層上施以Sn電鍍,使該Sn電鍍的一部份與上述基底Ni層的一部份或全部藉著熔融熔錫處理予以合金化後形成含島狀Sn的Sn電鍍層,上述基底Ni層是含金屬Ni量5~150mg/m2 的Ni,上述Sn電鍍層是含金屬Sn量300~3000mg/m2 的Sn。
  5. 一種容器用鋼板之製造方法,係獲得申請專利範圍第1~4項任一項記載的容器用鋼板之製造方法,其特徵為:藉著含Zr離子、磷酸離子、F離子之處理液中的浸漬處理或使用該處理液的電解處理,在上述鋼板上形成上述化學轉化處理膜,接著,將形成有上述化學轉化處理膜後的上述鋼板浸漬在含酚醛樹脂的水溶液中,或在上述化學轉化處理膜上塗抹該水溶液,隨後使其乾燥。
  6. 如申請專利範圍第5項記載的容器用鋼板之製造方法,其中,上述乾燥的溫度為70℃以上。
  7. 如申請專利範圍第5項或第6項記載的容器用鋼板之製造方法,其中,在上述乾燥之後,進一步以溫度80℃以上的水清洗,再次進行乾燥。
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