CN103108990B - 容器用钢板 - Google Patents
容器用钢板 Download PDFInfo
- Publication number
- CN103108990B CN103108990B CN201180044320.1A CN201180044320A CN103108990B CN 103108990 B CN103108990 B CN 103108990B CN 201180044320 A CN201180044320 A CN 201180044320A CN 103108990 B CN103108990 B CN 103108990B
- Authority
- CN
- China
- Prior art keywords
- steel plate
- tunicle
- tin
- nickel
- chemical treatment
- 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.)
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
- B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying 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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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical 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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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical 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
- C23C22/05—Chemical 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical 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
- C23C22/05—Chemical 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
- C23C22/06—Chemical 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
- C23C22/34—Chemical 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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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical 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
- C23C22/05—Chemical 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
- C23C22/06—Chemical 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
- C23C22/34—Chemical 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
- C23C22/36—Chemical 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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- C—CHEMISTRY; METALLURGY
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- C23C—COATING 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明的目的在于提供即便在进行代替铬酸盐处理的表面处理的情况下,也保持优异的耐腐蚀性,并且显示优异的膜密合性和外观特性的容器用钢板。本发明的容器用钢板在钢板的至少一面具有化学处理被膜层,该化学处理被膜层包含选自以金属锆量计含有0.1~9mg/m2的锆的锆被膜、以磷量计含有0.1~8mg/m2的磷酸的磷酸被膜、以及以碳量计含有0.05~8mg/m2的酚醛树脂的酚醛树脂被膜中的至少2种以上的被膜,规定大小的粒子在化学处理被膜层表面所占的面积比率为0.1~50%。
Description
技术领域
本发明涉及容器用钢板。
背景技术
作为饮料用、食品用的容器,大多使用将镀镍钢板,镀锡钢板或锡系合金镀覆钢板等钢板进行制罐而成的金属容器。这样的金属容器中,需要在制罐前或者制罐后进行涂装,近年来,从地球环境保护的观点考虑,为了减少废溶剂等由涂料引起的废弃物、二氧化碳等废气,大多对膜进行层压来代替涂装。
另外,作为涂装、层压膜的基底所使用的容器用钢板,多数情况下,为了确保钢板与涂装或膜的密合性以及耐腐蚀性,使用利用6价铬酸盐等铬酸盐实施了防锈处理的钢板(例如,参照专利文献1)。并且,这些铬酸盐处理钢板根据需要,在铬酸盐处理被膜上形成由有机树脂构成的被覆层。
然而,最近,因为铬酸盐处理所使用的6价铬在环境上是有害的,所以有代替一直以来对容器用钢板实施的铬酸盐处理的动向。另一方面,因为利用铬酸盐处理在钢板表面形成的铬酸盐被膜具有高度的耐腐蚀性以及涂装(或者膜)密合性,所以可预测在不进行这样的铬酸盐处理的情况下,这些特性明显降低。因此,一直要求对容器用钢板的表面实施代替铬酸盐处理的防锈处理,形成具有良好的耐腐蚀性以及涂装(或者膜)密合性的防锈层,作为代替上述铬酸盐处理的防锈处理,提出了以下的表面处理方法。
例如,专利文献2以及3中提出了一种容器用钢板,在钢板的至少一面具有化学处理被膜层,该被膜化学处理被膜层包含选自含有规定量的锆的锆被膜、含有规定量的磷酸的磷酸被膜、以及含有规定量的酚醛树脂的酚醛树脂被膜中的至少2种以上的被膜,化学处理被膜层中的任意粒子为一定值以下的大小。
专利文献1:日本特开2000-239855号公报
专利文献2:日本特开2009-1851号公报
专利文献3:日本特开2009-1853号公报
发明内容
另一方面,近年来,饮料容器市场中,PET瓶、瓶、纸等材料的品质竞争日益激化,对上述的容器用钢板也要求显示更优异的有机树脂密合性(其中,膜密合性)。特别是,将罐缩颈加工后的颈部分的膜,由于一般容易剥离,所以期待即便在严苛的条件下在该部分也不发生剥离的容器用钢板。
本发明的本发明人等使用专利文献2以及3中记载的容器用钢板,对颈部分相关的膜密合性进行了研究,结果发现没有达到近来一直追求的水平,需要进一步的改进。
并且,由于消费者对商品的美观的意识在提高,所以对罐的外观特性的要求变得更加严苛。特别是,从罐外面的印刷面的印象来看,对于钢板表面的颜色,相比于一般暗的色调更优选明亮色调。
因此,本发明鉴于上述实际情况,其目的在于提供即便在进行代替铬酸盐处理的表面处理的情况下,也保持优异的耐腐蚀性,并且显示优异的膜密合性以及外观特性的容器用钢板。
本发明的发明人等为解决上述课题进行了深入研究,结果发现通过使用含有规定大小的粒子的化学处理被膜层能够解决上述课题。
即,本发明的发明人等发现通过下述构成能够解决上述课题。
(1)一种容器用钢板,其特征在于,在钢板的至少一面具有化学处理被膜层,该化学处理被膜层包含选自以金属锆量计含有0.1~9mg/m2的锆的锆被膜、以磷量计含有0.1~8mg/m2的磷酸的磷酸被膜、以及以碳量计含有0.05~8mg/m2的酚醛树脂的酚醛树脂被膜中的至少2种以上的被膜,
将长径的长度设为a(nm)、短径的长度设为b(nm)时,(a+b)/2>200(nm)的粒子在化学处理被膜层表面所占的面积比率为0.1~50%,所述长径是在连结化学处理被膜层中的任意粒子的一端和另一端的线段中具有最大长度的线段,所述短径是在连结粒子的一端和另一端的线段且与长径正交的线段中具有最大长度的线段。
(2)根据(1)中记载的容器用钢板,其中,钢板是在钢板表面形成有实施了镀镍或铁-镍合金镀覆的基底镍层,并形成有施加于基底镍层上的镀锡的一部分与基底镍层的一部分或全部合金化而形成的包含岛状锡的镀锡层的镀覆钢板。
(3)根据(2)中记载的容器用钢板,其中,基底镍层以金属镍量计含有5mg/m2~150mg/m2的镍,镀锡层以金属锡量计含有300mg/m2~3000mg/m2的锡,镀锡的一部分与基底镍层的一部分或全部的合金化通过熔融熔锡处理来进行。
(4)根据(1)中记载的容器用钢板,其中,钢板在至少一面具有镀锡层,镀锡层上设有化学处理被膜层。
(5)根据(4)中记载的容器用钢板,其中,镀锡层以金属锡量计含有100mg/m2~5600mg/m2的锡。
(6)根据(1)中记载的容器用钢板,其中,钢板在至少一面具有以金属镍量计含有10mg/m2~1000mg/m2的镍的镀镍层,镀镍层上设有化学处理被膜层。
(7)根据(1)~(6)中任一项记载的容器用钢板,其中,化学处理被膜层至少包含锆被膜。
(8)根据(1)~(7)中任一项记载的容器用钢板,其中,化学处理被膜层包含锆被膜、磷酸被膜和酚醛树脂被膜。
根据本发明,能够提供即便在进行代替铬酸盐处理的表面处理的情况下,也保持优异的耐腐蚀性保持,并且显示优异的膜密合性以及外观特性的容器用钢板。
具体实施方式
以下,对本发明的容器用钢板进行详述。
更具体而言,本发明的容器用钢板在钢板的至少一面具有化学处理被膜层,该化学处理被膜层包含选自以金属锆量计含有0.1~9mg/m2的锆的锆被膜,以磷量计含有0.1~8mg/m2的磷酸的磷酸被膜,以及以碳量计含有0.05~8mg/m2的酚醛树脂的酚醛树脂被膜中的至少2种以上的被膜。
首先,对构成容器用钢板的钢板以及化学处理被膜层进行详述。
<钢板>
作为成为本发明的容器用钢板的原板的钢板,没有特别限制,通常,可以使用作为容器材料使用的钢板。另外,该原板的制造方法、材质等没有特别限制,从通常的钢片制造工序经由热轧、酸洗、冷轧、退火、调质轧制等各工序来制造,可以在钢板表面设有化学处理层、镀层等金属表面处理层。对赋予表面处理层的方法,没有特别限制,例如,可以使用电镀法、真空蒸镀法、溅射法等公知的方法,也可以组合用于赋予扩散层的加热处理。
在钢板的表面可以设有金属表面处理层,从确保作为容器所要求的耐腐蚀性的方面考虑,优选设置后述的基底镀层。
以下,对本发明中可优选地使用的基底镀层进行详述。
(基底镍层和镀锡层的复合镀层)
第1,作为上述基底镀层的例子,对由施加在钢板表面的基底镍层和形成于该基底镍层上的岛状锡镀层构成的复合镀层进行说明。
这里所说的基底镍层是指在钢板的至少一面形成的含有镍的镀层,有由金属镍形成的金属镍镀层的情况,或者,实施了铁-镍合金镀覆的铁-镍合金镀层的情况。另外,岛状锡镀层优选通过在该基底镍层上实施镀锡,利用熔融熔锡处理,将基底镍层的一部分或全部与镀锡层的一部分合金化而形成的合金镀层。但是,即便在镍单独的镀层上实施镀锡并进行熔融熔锡处理也难以形成上述那样的岛状锡,因此,作为基底镍层优选使用铁-镍合金镀层。
以下,对这样的镀镍层以及岛状锡镀层进行详细说明。
由上述的镍或铁-镍合金构成的基底镍层是为提高耐腐蚀性而形成。由于镍是高耐腐蚀金属,所以像本发明的容器用钢板那样,通过在钢板的表面镀覆镍,能够提高熔融熔锡处理时形成的含有铁和锡的合金层的耐腐蚀性。
镀镍的合金层的耐腐蚀性提高的效果由镀覆的镍的量决定,如果基底镍层中的金属镍量为5mg/m2以上,则耐腐蚀性提高的效果显著增大。另一方面,基底镍层中的镍量越多耐腐蚀性提高的效果越增加,如果基底镍层中的金属镍量大于150mg/m2,则不但耐腐蚀性提高的效果饱和,而且由于镍是昂贵的金属,所以镀覆大于150mg/m2的量的镍在经济上变得不利。因此,优选基底镍层中的镍量为5mg/m2~150mg/m2。
另外,利用扩散镀覆法形成基底镍层时,对钢板表面实施镀镍后,在退火炉中进行用于形成扩散层的扩散处理,但也可以在该扩散处理的前后或扩散处理的同时进行氮化处理。进行氮化处理时,作为本发明的基底镍层的镍的效果和氮化处理层的效果不会互相干扰,共同发挥这些效果。
作为镀镍以及铁-镍合金镀覆的方法,例如,可以利用通常电镀法中进行的公知的方法(例如,阴极电解法)。
上述的镀镍或铁-镍镀覆后进行镀锡。应予说明,本说明书中的“镀锡”不只是利用金属锡的镀覆,还包括金属锡中不可逆地混入杂质的情形,金属锡中添加有微量元素的情形。镀锡的方法,没有特别限定,例如,使用公知的电镀法、将钢板浸渍于熔融的锡而镀覆的方法即可。
通过上述的镀锡得到的镀锡层是为了提高耐腐蚀性和可焊性而形成的。锡因为其本身具有高耐腐蚀性,所以作为金属锡或者作为通过以下说明的熔融熔锡处理(回流处理)形成的锡合金也能够发挥优异的耐腐蚀性以及可焊性。
但是,这时,镀锡层以包含岛状锡的方式形成。这是因为钢板的整面用锡镀覆的情况下,膜层压、涂料涂布后的热处理时,钢板有时被暴露在熔点(232℃)以上时,由于锡的熔融或锡的氧化不能确保膜密合性。因此,将锡进行岛状化,露出对应海部的铁-镍基底(该部不熔融),确保膜密合性。
锡的优异的耐腐蚀性,金属锡量从300mg/m2以上显著提高,锡的含量越多,耐腐蚀性的提高的程度越增加。因此,优选包含岛状锡的镀锡层中的金属锡量为300mg/m2以上。另外,如果金属锡量大于3000mg/m2,则耐腐蚀性提高效果饱和,因此从经济性的观点考虑,优选锡含量为3000mg/m2以下。
另外,电阻低的锡柔软,焊接时在电极间锡被加压而扩展,能够确保稳定的通电域,因此发挥特别优异的可焊性。该优异的可焊性只要金属锡量为100mg/m2以上就可发挥。另外,显示上述的优异的耐腐蚀性的金属锡量的范围中,该可焊性的提高效果不饱和。因此,为了确保优异的耐腐蚀性以及可焊性,优选使金属锡量为300mg/m2~3000mg/m2。
在如上所述的镀锡后进行熔融熔锡处理(回流处理)。进行熔融熔锡处理的目的在于,将锡熔融并与基底的钢板、基底金属(例如,基底镍层)合金化,形成锡-铁合金层或锡-铁-镍合金层,提高合金层的耐腐蚀性,并且形成岛状的锡合金。该岛状的锡合金可通过适当地控制熔融熔锡处理来形成。
(镀锡层)
第2,作为上述基底镀层的例子,对在钢板的至少一面形成的镀锡层(不含岛状锡的镀锡层)进行说明。
锡具有优异的加工性、可焊性以及耐腐蚀性,但为了只通过镀锡得到足够的耐腐蚀性,优选金属锡量为例如100mg/m2以上。另外,金属锡量越增加耐腐蚀性提高,单独镀锡时,如果金属锡量大于5600mg/m2,则耐腐蚀性提高效果饱和。因此,从经济性的观点考虑,单独使用镀锡的情况下,优选金属锡量为5600mg/m2以下。另外,与上述情况同样,可以通过在镀锡后进行熔融熔锡处理,能够与钢板中的铁形成铁-锡合金层,另外,能够赋予光泽,并能够实现耐腐蚀性的更进一步提高。
另外,从耐腐蚀性提高等观点考虑,优选上述复合镀层或镀锡层在钢板的两面形成。从减少制造成本等观点考虑,在钢板的一侧的面形成提高耐腐蚀性等的复合镀层或镀锡层以外的表面处理层等时,复合镀层或镀锡层至少在钢板的另一侧的面形成即可。这样,对只在钢板的一面形成有复合镀层或镀锡层的容器用钢板进行制罐加工时,例如,以复合镀层或镀锡层形成的面成为容器内面侧的方式进行加工。
(镀镍层)
第3,作为上述基底镀层的例子,对在钢板的至少一面形成的镀镍层进行说明。
因为镍是高耐腐蚀金属,所以像本发明的容器用钢板那样,通过在钢板的表面镀镍,能够进一步提高耐腐蚀性。另外,可以设置使镍和铁合金化而成的Fe-Ni合金镀层。
由镀镍引起的耐腐蚀性提高的效果由镀覆的镍的量决定,如果镀镍层中的镍量为10mg/m2以上,耐腐蚀性提高的效果显著增大。但是,为了确保足够的耐腐蚀性,优选镀镍层中的镍量为150mg/m2以上。
另一方面,镀镍层中的镍量越增多,耐腐蚀性提高的效果越增加,但如果镍量大于1000mg/m2,不仅耐腐蚀性提高的效果饱和,而且因为镍是昂贵的金属,所以大于1000mg/m2的量的镍在经济上也不利。
应予说明,本发明的镀镍层不只是利用纯的镍金属形成,只要镍量为10mg/m2~1000mg/m2的范围内也可以利用镍合金形成。另外,出于提高机械强度的目的,也可以对钢板实施氮化处理,即便在实施了氮化处理的钢板上形成镀镍层,即便钢板的厚度变薄也不会降低不易产生压坏和变形等氮化处理所得到的效果。
另外,形成上述镀镍层后,可以进行用于赋予扩散层的加热处理,并且,例如,利用扩散镀覆法形成镀镍层时,在钢板表面实施镀镍后,在退火炉中进行用于形成扩散层的扩散处理,也可以在该扩散处理的前后或扩散处理的同时进行氮化处理。
另外,从耐腐蚀性提高的观点考虑,优选上述镀镍层形成在钢板的两面,从制造成本减少等观点考虑,在钢板的一侧的面实施提高耐腐蚀性的镀镍以外的表面处理等时,镀镍层可以至少在钢板的另一侧的面形成。这样,对只在钢板的一面形成镀镍层的容器用钢板进行制罐加工时,例如,以形成有镀镍层的面成为容器内面侧的方式进行加工。
(关于各成分的测定方法)
上述Ni镀层中的金属Ni量以及Sn镀层中的金属Sn量例如可以通过荧光X射线法进行测定。这时,使用已知金属Ni量的Ni附着量样品,预先确定金属Ni量相关的校正曲线,使用该校正曲线相对地确定金属Ni量。对于金属Sn量也同样,使用已知金属Sn量的Sn附着量样品,预先确定金属Sn量相关的校正曲线,使用该校正曲线相对地确定金属Sn量。
<化学处理被膜层>
在上述钢板上形成化学处理被膜层。化学处理被膜层包含锆被膜、磷酸被膜和酚醛树脂被膜中的至少任2种的被膜。以下,对本发明的化学处理被膜层进行详细说明。
化学处理被膜层以具有Zr成分、磷酸成分、以及酚醛树脂成分中的至少2种以上的成分的被膜的形式形成时,能够发挥优异的实用性能。另外,通过成为具有磷酸成分和酚醛树脂成分中的至少一种和Zr成分的被膜,能够进一步提高实用性能中的特别是耐腐蚀性和密合性。并且,通过使化学处理被膜层为Zr成分、磷酸成分和酚醛树脂成分复合而成的复合被膜,能够发挥更优异的密合性。特别是在被膜量少的范围,互相补充各特性,复合Zr被膜、磷酸被膜、酚醛树脂被膜这3种而成的被膜使性能更稳定地发挥。
(化学处理被膜层中的粒子的大小)
本发明的容器用钢板,如上所述,在钢板的至少一面具有化学处理被膜层。
对于该化学处理被膜层中含有的粒子(例如,化学处理被膜层是包含Zr成分的被膜时,氧化锆、磷酸锆等锆化合物的粒子),就任意选择的粒子的大小而言,将连结该粒子的一端a1和另一端a2的线段中具有最大长度的线段(以下,称为“长径”)的长度设为a(nm),连结粒子的一端b1和另一端b2的线段且与长径正交的线段中具有最大长度的线段(以下,称为“短径”)的长度设为b(nm)时,[(a+b)/2]>200(nm)的粒子(以后,也适当称为粒子A)在化学处理被膜层表面所占的面积比率必须为0.1~50%。
如果粒子A在化学处理被膜层表面所占的面积比率为0.1~50%,则得到的容器用钢板显示更优异的膜密合性,并显示优异的外观特性。如果粒子A的面积比率小于0.1%,容器用钢板的有机树脂密合性差。如果粒子A的面积比率大于50%,因粒子产生的可见光的散射或吸收的效果导致钢板表面的色调变暗,所以容器用钢板的外观特性恶化。
其中,从得到的钢板的膜密合性和色调的平衡的观点考虑,粒子A的面积比率更优选为1~20%,进一步优选为1~10%。
从得到的钢板的外观特性、有机树脂密合性的方面考虑,作为粒子A的[(a+b)/2]的上限值,优选为1000nm以下,更优选为450nm以下。如果超过上述范围的粒子A的面积率大于50%,则色调变暗而不优选。
另外,由于粒子尺寸越大粒子自身的强度降低,所以容易发生被膜内的凝聚破坏。因此,从得到的容器用钢板的有机树脂密合性更优异的方面考虑,优选粒子A的[(a+b)/2]为200~300nm。
另外,具有[(a+b)/2]大于200(nm)的粒子结构的锆被膜,详细内容如后所述,可以通过在20℃~50℃的温度条件下进行阴极电解处理而得到,本申请发明中的长径a的值、短径b的值可以通过对这样电解处理而得到的容器用钢板的表面用扫描型电子显微镜(SEM)进行观察来测定。应予说明,优选SEM的倍率为30000倍左右。具体而言,例如,对在容器用钢板表面的SEM照片上选择的任意粒子(通过目视使其包含大小最大的粒子)的长径a以及短径b进行测定,根据SEM照片的倍率换算,由此能够得到长径a以及短径b的实际的值。
(锆被膜)
本发明的化学处理被膜层中包含的锆被膜是为确保耐腐蚀性和有机树脂的密合性(以下,称为“有机树脂密合性”)而形成。
锆被膜例如以由氧化锆、氢氧化锆、氟化锆、磷酸锆等1种锆化合物构成的被膜,或者,以由它们中的2种以上的锆化合物构成的复合被膜的形式形成。
这样的锆被膜具有优异的耐腐蚀性和有机树脂密合性,本发明的发明人等认为其理由如下。即,认为对于耐腐蚀性,锆被膜由聚合物状的锆配合物形成三维交联体,利用该交联体具有的阻隔性发挥耐腐蚀性。另外,对于密合性,存在于锆被膜的内部的羟基或磷酸基的羟基和存在于钢板等金属表面的羟基进行脱水缩合,金属表面和锆被膜介由氧原子形成共价键,发挥密合性。
具体而言,如果锆被膜的附着量换算成金属锆量为0.1mg/m2以上,则可确保实用上没有问题的等级的耐腐蚀性和有机树脂密合性。另一方面,随着锆被膜的附着量的增加,耐腐蚀性和有机树脂密合性的提高效果也增加,但如果锆被膜的附着量换算成金属锆量大于9mg/m2,则锆被膜变得过厚,所以在加工时等成为凝聚破坏的原因,锆被膜本身的密合性以及与膜的密合性降低,并且电阻上升而可焊性降低。另外,如果锆被膜的附着量以金属锆量计大于9mg/m2,则有时发现被膜的附着不均导致外观不均,另外,电解处理后的清洗工序中,有时析出物的附着不充分的被膜被冲洗(剥离)。
因此,本发明的容器用钢板中,锆被膜的附着量以金属锆量计必须为0.1mg/m2~9mg/m2。优选锆被膜的附着量以金属锆量计为1mg/m2~8mg/m2。通过使锆被膜的附着量为1mg/m2~8mg/m2的范围,能够确保蒸馏后的耐腐蚀性,并且能够减少微小的附着不均。
(磷酸被膜)
另外,上述化学处理被膜层中包含的磷酸被膜是为了确保耐腐蚀性和有机树脂密合性而形成的。磷酸被膜,例如以由与基底(钢板、镀镍层、镀锡层、锆被膜、酚醛树脂被膜)反应而形成的磷酸铁、磷酸镍、磷酸锡、磷酸锆、磷酸苯酚酯等1种磷酸化合物构成的被膜,或者,以由它们中的2种以上的磷酸化合物构成的复合被膜的形式形成。这样的磷酸被膜具有优异的耐腐蚀性和有机树脂密合性,本发明的本发明人等认为其理由是磷酸离子与各种金属离子配位,如上所述形成三维交联体被膜,另外,即便铁、镍等金属离子溶出(腐蚀的第一阶段),由于形成磷酸盐化合物而金属离子不熔化,具有减少进一步的腐蚀的效果。
具体而言,如果磷酸被膜的附着量换算成磷量为0.1mg/m2以上,则可确保实用上没有问题的等级的耐腐蚀性和有机树脂密合性。另一方面,随着磷酸被膜的附着量的增加,耐腐蚀性和有机树脂密合性的提高效果也增加,如果磷酸被膜的附着量换算成磷量大于8mg/m2,则磷酸被膜变得过厚,所以在加工时等成为凝聚破坏的原因,磷酸被膜本身的密合性以及与膜的密合性降低,并且电阻上升而可焊性降低。另外,如果磷酸被膜的附着量以磷量计大于8mg/m2,则有时发现被膜的附着不均成为外观不均,并且,电解处理后的清洗工序中,有时析出物的附着不充分的被膜被冲洗(剥离)。
因此,本发明的容器用钢板中,磷酸被膜的附着量以磷量计必须为0.1mg/m2~8mg/m2。优选磷酸被膜的附着量以磷量计为1mg/m2~6mg/m2。通过使磷酸被膜的附着量为1mg/m2~6mg/m2的范围,能够确保蒸馏后的耐腐蚀性,并且能够减少微小的附着不均。
(酚醛树脂被膜)
另外,上述化学处理被膜层,如上所述,还可以包含含有酚醛树脂成分的酚醛树脂被膜。
酚醛树脂被膜是为了确保有机树脂密合性而形成。因为酚醛树脂本身是有机物,所以与以有机物为原料的层压膜具有非常优异的密合性。
经受表面处理层较大变形的加工时,表面处理层本身因其加工而凝聚破坏,有时密合性恶化,锆被膜、磷酸被膜含有酚醛树脂时,具有显著提高这些被膜的加工密合性的效果。
具体而言,如果酚醛树脂被膜的附着量换算成碳量为0.05mg/m2以上,则确保实用上没有问题的等级的有机树脂密合性。另一方面,伴随酚醛树脂被膜的附着量的增加,有机树脂密合性的提高效果也增加,但如果酚醛树脂被膜的附着量换算成碳量大于8mg/m2,则酚醛树脂被膜变得过厚,所以酚醛树脂被膜本身的密合性降低,并且电阻上升而可焊性降低。另外,如果酚醛树脂被膜的附着量以碳量计大于8mg/m2,则有时发现被膜的附着不均成为外观不均,并且,电解处理后的清洗工序中,有时析出物的的附着不充分的被膜被冲洗(剥离)。
因此,本发明的容器用钢板中,酚醛树脂被膜的附着量以碳量计必须为0.05mg/m2~8mg/m2。酚醛树脂被膜的附着量以碳量计优选为0.1mg/m2~6mg/m2。通过使酚醛树脂被膜的附着量为0.1mg/m2~6mg/m2的范围,能够减少微小的附着不均(附着引起的黄变),并且,能够充分发挥上述酚醛树脂的添加效果。
(化学处理被膜层中的各成分的含量的测定方法)
本发明的化学处理被膜层中含有的金属锆量、磷量可以通过例如荧光X射线分析等定量分析法进行测定。另外,化学处理被膜层中的碳量,例如,从通过基于气相色谱法的总碳量测定法测定的值中将钢板中含有的碳量作为背景扣除而求得。
如上所述,本发明的容器用钢板,通过在上述镀覆钢板的至少一面形成包含锆被膜、磷酸被膜和酚醛树脂被膜中的至少2种以上的化学处理被膜层,从而能够具有优异的膜密合性。另外,上述化学处理被膜层,通过至少含有锆被膜,从而能够进一步提高耐腐蚀性以及膜密合性。并且,上述化学处理被膜层通过含有锆被膜、磷酸被膜和酚醛树脂被膜的全部,从而能够显著提高膜密合性。
[本发明的容器用钢板的制造方法]
以上,对本发明的容器用钢板的构成进行了说明,接下来,对用于得到上述容器用钢板的制造方法进行详细说明。
首先,在对本发明的化学处理被膜层的形成方法进行说明之前,对上述的熔融熔锡处理的方法进行简单说明,该熔融熔锡处理在对钢板或者实施了镍系镀覆的镀覆钢板实施镀锡后进行。
熔融熔锡处理也叫回流处理,是为了通过镀Sn后,升高温度至作为Sn的熔点的232℃以上,从而将表面的Sn熔融,发出表面光泽而进行的。另外,通过进行熔融熔锡处理,将表面的Sn熔融并与基底钢板、基底金属合金化而形成Sn-Fe合金层或Sn-Fe-Ni合金层,从而提高合金层的耐腐蚀性。另外,通过适当地控制该熔融熔锡处理,从而能够形成岛状Sn。由此,能够制造具有不存在金属Sn的有机树脂密合性优异的Fe-Ni合金镀层或Fe-Ni-Sn合金镀层露出的镀覆构造的钢板。
熔融熔锡处理通过在数秒钟(例如,10秒以内)尽可能均匀地升温加热至作为Sn的熔点的232℃以上、优选240℃左右,一得到金属光泽就用冷水等迅速冷却至室温附近(例如,50℃左右)来进行。
<容器用钢板的制造方法>
本发明的容器用钢板的制造方法是如下方法:对在钢板的至少一面形成上述那样的基底镀层的镀覆钢板进行低温阴极电解处理,在上述基底镀层上形成上述那样的化学处理被膜层。作为形成这样的化学处理被膜的方法,例如,有将钢板浸渍在溶解有锆离子、磷酸离子、低分子的酚醛树脂等的酸性溶液中的方法,使用这样的酸性溶液进行阴极电解处理的方法等。
这里,在利用上述浸渍的处理方法中,因为对成为化学处理被膜层的基底的钢板、在钢板表面形成的镀层进行蚀刻,形成各种被膜,所以化学处理被膜层的附着量变得不均匀,另外,化学处理被膜层的形成所需的处理时间变长,工业上不利。
另一方面,在利用阴极电解处理的方法中,由强制的电荷移动和钢板界面的氢产生引起的表面清洁化与由氢离子浓度(pH)的上升引起的附着促进效果互相结合,均匀的被膜可通过数秒钟左右(实际上有0.01秒左右的情况)的短时间处理而形成,工业上极其有利。因此,本发明的容器用钢板的制造方法中,优选通过阴极电解处理形成化学处理被膜层。
(阴极电解处理所使用的化学处理液的成分)
为了通过阴极电解处理形成上述化学处理被膜层,需要根据上述的化学处理被膜层中包含的锆被膜、磷酸被膜、酚醛树脂被膜中要形成的被膜的种类,决定电解处理中使用的化学处理液中的成分。具体而言,要形成只包含锆被膜的化学处理被膜层时,作为化学处理液,使用酸性溶液中含有100质量ppm~7500质量ppm锆离子的溶液即可,要形成包含锆被膜和磷酸被膜的化学处理被膜层时,作为化学处理液,使用使酸性溶液中含有100质量ppm~7500质量ppm的锆离子和50质量ppm~5000质量ppm的磷酸离子而成的溶液即可,要形成包含锆被膜、磷酸被膜和酚醛树脂被膜的化学处理被膜层时,作为化学处理液,使用酸性溶液中含有100质量ppm~7500质量ppm的锆离子、50质量ppm~5000质量ppm的磷酸离子和10质量ppm~1500质量ppm的质均分子量为5000左右的低分子量的酚醛树脂的溶液即可。
应予说明,也可以在作为上述阴极电解处理的化学处理液使用的酸性溶液中添加单宁酸。这样,通过在处理液中添加单宁酸,单宁酸与钢板表面的铁原子结合而在钢板表面形成单宁酸铁的被膜,能够提高防锈性、密合性。因此,将本发明的容器用钢板使用于重视防锈性、密合性的用途时,也可以根据需要在添加了单宁酸的酸性溶液中进行化学处理被膜层的形成。
另外,作为本发明的化学处理被膜层的形成中使用的酸性溶液的溶剂,例如,可以使用蒸馏水等。上述酸性溶液的溶剂并不限定于此,可以根据溶解的材料、形成方法以及化学处理被膜层的形成条件等适当地选择。其中,从基于稳定的各成分的附着量稳定性的工业生产率、成本、环境方面考虑,优选使用蒸馏水。
另外,本发明的化学处理层的形成中使用的化学处理液中,例如,可以将像H2ZrF6这样的Zr配合物作为Zr的供给源使用。上述的Zr配合物中的Zr通过阴极电极界面中的pH的上升而发生水解反应,成为Zr4+而存在于化学溶液中。这样的Zr离子在化学处理液中更迅速地反应,成为ZrO2、Zr3(PO4)4、Zr(HPO3)2等化合物,与存在于金属表面的羟基(-OH)通过脱水缩合反应等形成Zr被膜。另外,在化学处理液中添加酚醛树脂时,例如,可以通过使酚醛树脂发生氨基醇改性而使其具有水溶性。并且,为了调节化学处理液的pH,可以添加例如硝酸、氨等。
(阴极电解处理的处理条件)
用于形成本发明的化学处理被膜层的阴极电解处理,优选在化学处理液的温度(浴温)为20℃~50℃的条件下,反复通电、无通电来间断地进行。其中,优选40~50℃的条件。
另外,上述阴极电解处理优选以0.01A/dm2~20A/dm2的电解电流密度进行。其中,从得到的钢板的膜密合性更优异的方面考虑,优选0.5~10A/dm2。电解电流密度小于0.01A/dm2时,导致被膜附着量的降低,并且稳定的被膜的形成变得困难,另外有时需要长电解处理时间,使生产率降低,耐腐蚀性、涂装密合性等降低。另一方面,电解电流密度大于20A/dm2时,被膜附着量超过所需要量且饱和,根据情况,利用电解化学处理后的水洗等清洗工序中附着不充分的被膜被冲洗(剥离)等,不经济。另外,导致电解处理时化学处理液的温度上升,为了维持上述的低温阴极电解处理的温度条件,有时需要冷却化学处理液。
另外,上述阴极电解处理优选按2次~优选4次以上的间断的通电、0.5秒~10秒的总计通电时间来进行。所希望的粒径的粒状析出物以1次的连续通电难以形成,在电解时插入无通电时间进行间断电解是有效的,能够通过最低2次、优选4次以上的间断的通电而稳定地形成。这是因为考虑粒状析出物的析出点(site)在无通电时间段形成。作为无通电时间,优选0.1~2秒。
通电的时间总计小于0.5秒时,难以引起粒状析出物的生长,目标粒径分布的被膜的形成变得困难。另一方面,通电时间大于10秒时,被膜附着量超过需要量,且附着量饱和,根据情况,利用电解化学处理后的水洗等清洗工序中附着不充分的被膜被冲洗(剥离)等,不经济,另外,导致化学处理液的温度的上升,为了维持上述的低温阴极电解处理的温度条件,有时需要化学处理液的冷却这样多余的处理。
通过按上述的电解电流密度、通电次数、以及通电时间进行阴极电解处理,能够在钢板表面形成适当附着量的被膜。
实施例
接下来,利用实施例以及比较例对本发明进行更具体的说明,本发明不只限定于下述的实施例。
<钢板的制成>
首先,按以下所示的方法制成形成有化学处理被膜层的钢板。
(A1:具有Ni镀层以及Sn镀层的钢板的制造方法)
冷轧后,将经退火以及调压的厚度为0.17~0.23mm的钢基材(钢板)进行脱脂以及酸洗后,使用瓦特浴(Wattsbath)实施镀Ni,然后使用费罗斯坦浴(ferrostanbath)实施镀Sn,然后进行熔融熔锡处理,制成具有Sn合金层的Ni、Sn镀覆钢板。
(A2:具有Sn镀层的钢板的制造方法)
冷轧后,将经退火以及调压的厚度为0.17~0.23mm的钢基材(钢板)进行脱脂以及酸洗后,使用费罗斯坦浴实施镀Sn,然后进行熔融熔锡处理,制成具有Sn合金层的复合镀覆钢板。
(A3:将A1的Sn镀层进一步合金化的钢板的制造方法)
冷轧后,将厚度为0.17~0.23mm的钢基材(钢板)进行脱脂以及酸洗后,使用瓦特浴实施镀Ni,退火时形成Ni扩散层,脱脂、酸洗后,使用费罗斯坦浴实施镀Sn,然后,进行熔融熔锡处理,制成具有Sn合金层的Ni、Sn镀覆钢板。
(A4:存在Ni镀层的钢板的制造方法)
冷轧后,将经退火以及调压的厚度为0.17~0.23mm的钢基材(钢板)进行脱脂以及酸洗后,在其两面使用瓦特浴实施镀Ni,制成Ni镀覆钢板(A4)。
应予说明,对于上述的(A1)~(A4),金属镍以及金属锡的附着量的最低值、最适值以及最高值,分别如以下的表1。
[表1]
表1
接下来,在按上述的(A1)~(A4)的方法制成的钢板的表面(两面),按以下所示的方法形成(B1)Zr被膜、磷酸被膜和酚醛树脂被膜,(B2)Zr被膜和磷酸被膜,(B3)磷酸被膜和酚醛树脂被膜,(B4)Zr被膜和酚醛树脂被膜。并且,在电解处理液中添加单宁酸,形成由Zr被膜和磷酸被膜构成的化学处理被膜层(B5)。
(B1)在使氟化Zr、磷酸和酚醛树脂溶解在蒸馏水中而成的处理液中浸渍将按上述(A1)~(A4)的方法制成的钢板,进行阴极电解处理后,水洗、干燥。
(B2)在使氟化Zr和磷酸溶解在蒸馏水而成的处理液中浸渍按上述(A1)~(A4)的方法制成的钢板,进行阴极电解处理后,水洗、干燥。
(B3)在使磷酸和酚醛树脂溶解于蒸馏水中而成的处理液中浸渍按上述(A1)~(A4)的方法制成的钢板,进行阴极电解处理后,水洗、干燥。
(B4)在使氟化Zr和酚醛树脂溶解在蒸馏水中而成的处理液中浸渍按上述(A1)~(A4)的方法制成的钢板,进行阴极电解处理后,水洗、干燥。
(B5)在使氟化Zr、磷酸和单宁酸溶解在蒸馏水中而成的处理液中浸渍按上述(A1)~(A4)的方法制成的钢板,进行阴极电解处理后,水洗、干燥。
应予说明,上述的(B1)~(B5)中使用的化学处理液的成分分别如以下的表2。
[表2]
表2
对于按上述的方法制成的各容器用钢板,通过使用荧光X射线的定量分析法对化学处理被膜层中的金属Zr量、P量进行测定。另外,化学处理被膜层中的碳量通过从利用基于气相色谱法的总碳量测定法测定的值中将钢板中含有的碳量作为背景扣除而求得。
<性能评价方法>
接下来,将按上述的方法制成的各容器用钢板作为试验材,对这些实施例以及比较例的试验材,评价膜密合性、外观、耐腐蚀性各性能。以下,对其具体的评价方法以及评价基准进行说明。
(1)膜密合性
将厚度为20μm的PET膜在200℃层压在实施例和比较例的各试验材的两面后,进行减薄拉深加工制成罐体,对该罐体实施缩颈加工,再将该罐体没入水中,在130℃进行60分钟的蒸馏处理,评价罐的颈部分的膜的剥离状况。
其结果,完全没有剥离的状况为◎,产生实用上没有问题的程度的极小的剥离的状况为○,部分产生剥离且实用上有问题的状况为△,大部分产生剥离的状况为×。将结果汇总示于表3。
实用上必须是“○”“◎”。
(2)外观
目视观察实施例和比较例的各试验材,实用上足够明亮的色调,且化学处理被膜层上完全没有黑色的不均的状况为◎;实用上没有问题的程度的亮度,且仅有些许黑色的不均的状况为○;产生些许黑色不均,且呈现实用上有问题的暗度的状况为△;明显暗,且产生黑色的不均的状况为×。将结果汇总示于表3。
实用上,必须为“○”“◎”。
将以上的结果示于下述表3。应予说明,下述表3中一并示出实施例和比较例的各试验材中的镀层量和各被膜的附着量。另外,下述表3所示的Ni量、Sn量是通过荧光X射线测定法求得的值,就各被膜的附着量而言,对Zr被膜量(Zr量)和磷酸被膜量(P量)是用荧光X射线进行定量分析而求得的值,对酚醛树脂被膜量(C量)是利用基于气相色谱法的总碳量测定法(将钢中含有的C量作为背景而扣除)而求得的值。
应予说明,多次进行通电时的无通电时间是0.5秒。
另外,对处理表面进行SEM观察,将作为连结任意粒子的一端和另一端的线段中具有最大长度的线段的长径的长度设为a(nm)、作为连结粒子的一端和另一端的线段且与长径正交的线段中具有最大长度的线段的短径的长度设为b(nm),求出{(a+b)/2}(nm)的值作为本实施例所含被膜中的粒子的粒径(nm)。
另外,通过SEM观察照片(10μm×10μm)求出化学处理被膜层表面的{(a+b)/2}>200nm的粒子所占的面积比率。
应予说明,后述的各实施例的{(a+b)/2}的最大值为1000nm以下,特别在粒子A的面积率为20%以下的实施例中{(a+b)/2}的最大值为450nm。
(3)耐腐蚀性
在实施例的各试验材的一侧的面涂布环氧-酚醛树脂后,在200℃的温度条件下保持30分钟来进行烧结。然后,在涂布有该树脂的部分实施达到钢基材的深度的十字划格(crosscut),在由柠檬酸(1.5质量%)-食盐(1.5质量%)的混合液构成的试验液中在45℃的温度条件下浸渍72小时,清洗以及干燥后,进行胶带剥离试验,评价十字划格部的涂膜(环氧-酚醛树脂膜)下的腐蚀状况和平板部的腐蚀状况。
其结果,各实施例中,在涂膜下未看到腐蚀,可确认具有优异的耐腐蚀性。
[表3]
[表4]
[表5]
[表6]
[表7]
应予说明,比较例6中,通过浸渍处理而不是电解处理进行化学处理被膜层的形成。
上述表3所示,对于Zr附着量、P附着量、C附着量以及具有规定大小的粒子的面积率在本发明的范围内的实施例1~41,显示优异的膜密合性以及外观特性。应予说明,上述耐腐蚀性也优异。
特别是钢板的处理法为A1,A3以及A4时,面积率为1~20%,显示更优异的膜密合性。另外,面积率为10%以下时,显示更优异的外观特性。
另一方面,在分别与专利文献1的实施例1、8、34、50以及52相当的比较例1~5中,膜密合性差。
另外,如比较例6~13所示,Zr附着量、P附着量、C附着量、以及、具有规定大小的粒子的面积率在本发明的范围外时,膜密合性或外观特性差。
以上,对本发明的优选的实施方式进行了说明,当然本发明不限于上述例。显而易见,只要是本领域技术人员,在专利权利要求所记载的范畴内能想到各种变更例或修正例,可知对于这些当然也属于本发明的技术的范围。
Claims (9)
1.一种容器用钢板,其特征在于,在钢板的至少一面具有化学处理被膜层,所述化学处理被膜层包含选自以金属锆量计含有0.1~9mg/m2的锆的锆被膜、以磷量计含有0.1~8mg/m2的磷酸的磷酸被膜、以及以碳量计含有0.05~8mg/m2的酚醛树脂的酚醛树脂被膜中的至少2种以上的被膜,
将长径的长度设为a、短径的长度设为b时,{(a+b)/2}>200的粒子在化学处理被膜层表面所占的面积比率为1~20%,a、b、{(a+b)/2}>200的单位为nm,所述长径是在连结所述化学处理被膜层中的任意粒子的一端和另一端的线段中具有最大长度的线段,所述短径是在连结所述粒子的一端和另一端的线段且与所述长径正交的线段中具有最大长度的线段。
2.根据权利要求1所述的容器用钢板,其中,所述钢板是在钢板表面形成有实施了镀镍或铁-镍合金镀覆的基底镍层,并形成有施加于所述基底镍层上的镀锡的一部分与所述基底镍层的一部分或全部合金化而形成的包含岛状锡的镀锡层的镀覆钢板。
3.根据权利要求2所述的容器用钢板,其中,所述基底镍层以金属镍量计含有5mg/m2~150mg/m2的镍,所述镀锡层以金属锡量计含有300mg/m2~3000mg/m2的锡,所述镀锡的一部分与所述基底镍层的一部分或全部的合金化通过熔融熔锡处理来进行。
4.根据权利要求1所述的容器用钢板,其中,所述钢板在至少一面具有镀锡层,所述镀锡层上设有所述化学处理被膜层。
5.根据权利要求4所述的容器用钢板,其中,所述镀锡层以金属锡量计含有100mg/m2~5600mg/m2的锡。
6.根据权利要求1所述的容器用钢板,其中,所述钢板在至少一面具有以金属镍量计含有10mg/m2~1000mg/m2的镍的镀镍层,所述镀镍层上设有所述化学处理被膜层。
7.根据权利要求1~6中任一项所述的容器用钢板,其中,所述化学处理被膜层至少包含所述锆被膜。
8.根据权利要求1~6的中任一项所述的容器用钢板,其中,所述化学处理被膜层包含所述锆被膜、所述磷酸被膜和所述酚醛树脂被膜。
9.根据权利要求7所述的容器用钢板,其中,所述化学处理被膜层包含所述锆被膜、所述磷酸被膜和所述酚醛树脂被膜。
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PCT/JP2011/070985 WO2012036204A1 (ja) | 2010-09-15 | 2011-09-14 | 容器用鋼板 |
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CN104718312B (zh) | 2012-08-29 | 2017-03-15 | Ppg工业俄亥俄公司 | 含有钼的锆预处理组合物,用于处理金属基材的相关方法和相关的涂覆的金属基材 |
KR20150046303A (ko) | 2012-08-29 | 2015-04-29 | 피피지 인더스트리즈 오하이오 인코포레이티드 | 리튬을 함유하는 지르코늄 전처리 조성물, 관련된 금속 기판 처리 방법 및 관련된 코팅된 금속 기판 |
EP3000917B1 (en) * | 2013-05-21 | 2020-03-11 | Nippon Steel Corporation | Steel sheet for containers, and method for producing steel sheet for container |
CN106661737B (zh) | 2014-10-09 | 2019-05-17 | 新日铁住金株式会社 | 化学转化处理钢板和化学转化处理钢板的制造方法 |
JP6467195B2 (ja) | 2014-11-10 | 2019-02-06 | 三桜工業株式会社 | 車輌配管用被覆金属管 |
WO2016076073A1 (ja) * | 2014-11-10 | 2016-05-19 | 新日鐵住金株式会社 | めっき鋼板およびその製造方法 |
JP6008068B1 (ja) * | 2014-12-01 | 2016-10-19 | 新日鐵住金株式会社 | 表面処理鋼板および表面処理鋼板の製造方法 |
CN107208301B (zh) | 2015-01-26 | 2018-11-16 | 东洋钢钣株式会社 | 表面处理钢板、金属容器及表面处理钢板的制造方法 |
WO2016121276A1 (ja) | 2015-01-26 | 2016-08-04 | 東洋鋼鈑株式会社 | 表面処理鋼板、金属容器及び表面処理鋼板の製造方法 |
CN107208828B (zh) * | 2015-02-13 | 2020-01-14 | 三樱工业株式会社 | 车辆配管用被覆金属管及其制造方法 |
TWI565810B (zh) * | 2015-06-23 | 2017-01-11 | 新日鐵住金股份有限公司 | 容器用鋼板及容器用鋼板之製造方法 |
KR102087669B1 (ko) * | 2015-06-23 | 2020-03-11 | 닛폰세이테츠 가부시키가이샤 | 용기용 강판 및 용기용 강판의 제조 방법 |
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EP3504356A1 (en) | 2016-08-24 | 2019-07-03 | PPG Industries Ohio, Inc. | Alkaline composition for treating metal substrates |
DE102017117080A1 (de) * | 2017-07-28 | 2019-01-31 | Thyssenkrupp Ag | Stahlblech mit einer Konversionsschicht, Verfahren zur Herstellung eines konversionsbeschichteten Stahlblechs und Behandlungsmittel zur Applizierung einer Konversionsschicht auf einem Stahlblech |
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