TWI788511B - Antirust treatment solution for end surface of plated steel sheet, chemical conversion treatment method for end surface of plated steel sheet, chemical conversion treated steel sheet and formed product - Google Patents

Antirust treatment solution for end surface of plated steel sheet, chemical conversion treatment method for end surface of plated steel sheet, chemical conversion treated steel sheet and formed product Download PDF

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TWI788511B
TWI788511B TW108102631A TW108102631A TWI788511B TW I788511 B TWI788511 B TW I788511B TW 108102631 A TW108102631 A TW 108102631A TW 108102631 A TW108102631 A TW 108102631A TW I788511 B TWI788511 B TW I788511B
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chemical conversion
steel sheet
plated steel
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end surface
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TW201936990A (en
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松野雅典
上野晋
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日商日新製鋼股份有限公司
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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
    • C23C22/68—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 solutions with pH between 6 and 8
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • 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
    • B32B15/04—Layered 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
    • B32B15/08—Layered 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
    • B32B15/082—Layered 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 vinyl resins; comprising acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • 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
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers

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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

本發明的目的在於提供一種可形成耐腐蝕性進一步得到提高的化學轉化處理皮膜的端面防鏽處理液。所述目的藉由如下鍍覆鋼板的端面防鏽處理液而達成，所述鍍覆鋼板的端面防鏽處理液包含：含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子、蝕刻劑、選自由己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮所組成的群組中的一種以上的黏結促進劑、以及矽烷偶合劑。 An object of the present invention is to provide an end surface antirust treatment solution capable of forming a chemical conversion treatment film with further improved corrosion resistance. The object is achieved by an end surface antirust treatment solution of a plated steel sheet comprising: an organic resin containing a fluororesin, a compound containing a group 4 element, or a group 4 element ions, etchant, one or more substances selected from the group consisting of ester compounds of adipic acid or phthalic acid and an alcohol having 1 to 3 carbon atoms, and n-methyl-2-pyrrolidone Adhesion promoters, and silane coupling agents.

Description

鍍覆鋼板的端面防鏽處理液、鍍覆鋼板的端面 的化學轉化處理方法、化學轉化處理鋼板及成形加工品 Anti-rust treatment solution for the end face of plated steel plate, end face of plated steel plate Chemical conversion treatment method, chemical conversion treatment steel plate and formed products

本發明是有關於一種鍍覆鋼板的端面防鏽處理液、鍍覆鋼板的化學轉化處理方法、化學轉化處理鋼板及成形加工品。 The invention relates to an anti-rust treatment solution for the end surface of a plated steel plate, a chemical conversion treatment method for the plated steel plate, a chemical conversion treated steel plate and a formed product.

先前，於外裝建材等各種用途中，使用鋼板或於鋼板的表面實施了Zn系鍍敷處理等的鍍敷鋼板。該些鍍敷鋼板於該狀態下有耐腐蝕性或耐變色性等不充分的情況，因此有時於其表面形成包含有機樹脂的化學轉化處理皮膜。 Conventionally, in various applications such as exterior building materials, steel sheets or plated steel sheets that have been subjected to Zn-based plating treatment or the like on the surface of the steel sheets have been used. In this state, these plated steel sheets may have insufficient corrosion resistance, discoloration resistance, etc., and therefore a chemical conversion treatment film containing an organic resin may be formed on the surface.

另外，所述鍍敷鋼板亦大多用作成形加工品。於對鍍敷鋼板進行成形加工時，為了提高利用成形而生成的端面或利用成形加工而生成的基材鋼板的露出部位等的耐腐蝕性，有時於成形加工等後在端面或露出部位形成化學轉化處理皮膜。 In addition, the above-mentioned plated steel sheet is also often used as a formed product. When forming a plated steel sheet, in order to improve the corrosion resistance of the end surface formed by forming or the exposed portion of the base steel sheet produced by forming, it may be formed on the end surface or exposed portion after forming, etc. Chemical conversion treatment film.

作為用於在端面上形成化學轉化處理皮膜的處理液，於專利文獻1中記載了一種處理液，其包含：對皮膜賦予耐腐蝕性的選自Ca、Mg、Mn及Zn中的金屬成分、以及形成皮膜的磷酸根離子及具有環氧乙烷基的有機化合物。根據專利文獻1，所述處理液中，有機化合物的環氧乙烷基與磷酸根離子鍵結而生成由磷酸酯形成的皮膜，於所述皮膜中所述金屬成分變成氧化物或氫氧 化物而分散。 As a treatment solution for forming a chemical conversion treatment film on the end surface, a treatment solution is described in Patent Document 1, which includes: a metal component selected from Ca, Mg, Mn, and Zn that imparts corrosion resistance to the film, As well as phosphate ions and organic compounds with oxirane groups that form the film. According to Patent Document 1, in the treatment liquid, the oxirane group of the organic compound is bonded to the phosphate ion to form a film composed of a phosphate ester, and the metal component in the film becomes an oxide or a hydroxide. compound and dispersed.

作為用於在端面上形成化學轉化處理皮膜的另一處理液，於專利文獻2中記載了一種處理液，其包含：作為防鏽劑的磷酸二氫鎂、磷酸氫鎂或L-抗壞血酸、以及作為用以自端面阻斷水的黏合劑成分的二氧化矽微粒子。 As another treatment solution for forming a chemical conversion treatment film on the end surface, a treatment solution is described in Patent Document 2, which contains: magnesium dihydrogen phosphate, magnesium hydrogen phosphate or L-ascorbic acid as a rust preventive agent, and Silica microparticles as a binder component to block water from the end face.

作為用於在端面上形成化學轉化處理皮膜的又一處理液，於專利文獻3中記載了一種使選自作為腐蝕抑制材的不飽和醇類、飽和直鏈一級胺類、飽和直鏈二級胺類、飽和直鏈三級胺類、硫脲類、膦酸類、嗎啉類及咪唑啉類中的有機系腐蝕抑制劑溶解而成的水溶液。 As yet another treatment solution for forming a chemical conversion treatment film on the end surface, Patent Document 3 describes a treatment liquid that is selected from unsaturated alcohols, saturated linear primary amines, saturated linear secondary Aqueous solution in which organic corrosion inhibitors in amines, saturated linear tertiary amines, thioureas, phosphonic acids, morpholines and imidazolines are dissolved.

作為用於在端面上形成化學轉化處理皮膜的又一處理液，於專利文獻4中記載了一種丙烯酸漆，其是以丙烯酸或甲基丙烯酸的酯類為主體，並於其中調配了使苯乙烯及乙酸乙烯酯等乙烯系單體反應而獲得的共聚物樹脂等。根據專利文獻4，以乾燥時的膜厚成為5μm~30μm的方式塗佈所述丙烯酸漆而形成皮膜，藉此端面被均勻地被覆而充分發揮防鏽作用。 As yet another treatment solution for forming a chemical conversion treatment film on the end surface, an acrylic paint is described in Patent Document 4, which is mainly composed of acrylic acid or methacrylic acid esters, and styrene is blended therein. Copolymer resins obtained by reacting with vinyl monomers such as vinyl acetate, etc. According to Patent Document 4, the acrylic varnish is applied to form a film so that the film thickness when dried is 5 μm to 30 μm, whereby the end surface is uniformly covered and the antirust function is sufficiently exhibited.

作為用於在端面上形成化學轉化處理皮膜的又一處理液，於專利文獻5中記載了一種包含水性胺基甲酸酯塗料及用以提高塗佈性的鋅粉末的水性塗料。 As yet another treatment liquid for forming a chemical conversion treatment film on an end surface, Patent Document 5 describes an aqueous paint comprising a water-based urethane paint and zinc powder for improving coatability.

作為用於在端面上形成化學轉化處理皮膜的又一處理液，於專利文獻6~專利文獻10中記載了一種化學轉化處理液，其可藉由含有第4族金屬的化合物而使氟樹脂交聯，從而提高含 有氟樹脂的有機樹脂皮膜的耐水性。 As yet another treatment solution for forming a chemical conversion treatment film on the end surface, a chemical conversion treatment solution is described in Patent Documents 6 to 10, which can convert fluororesins by compounds containing Group 4 metals. associated, thereby increasing the There is water resistance of organic resin film of fluororesin.

[現有技術文獻] [Prior art literature]

[專利文獻] [Patent Document]

[專利文獻1]日本專利特開2005-248310號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2005-248310

[專利文獻2]日本專利特開2010-053404號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2010-053404

[專利文獻3]日本專利特開2003-3280號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2003-3280

[專利文獻4]日本專利特開平7-224391號公報 [Patent Document 4] Japanese Patent Laid-Open No. 7-224391

[專利文獻5]日本專利特開2013-010845號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2013-010845

[專利文獻6]國際公開第2011/158513號 [Patent Document 6] International Publication No. 2011/158513

[專利文獻7]國際公開第2011/158516號 [Patent Document 7] International Publication No. 2011/158516

[專利文獻8]日本專利特開2012-21207號公報 [Patent Document 8] Japanese Patent Laid-Open No. 2012-21207

[專利文獻9]日本專利特開2012-177146號公報 [Patent Document 9] Japanese Patent Laid-Open No. 2012-177146

[專利文獻10]日本專利特開2012-177147號公報 [Patent Document 10] Japanese Patent Laid-Open No. 2012-177147

專利文獻1~專利文獻3中記載的處理液存在如下問題：抑制紅鏽的產生的作用(防鏽作用)並不那麼高，無法長期維持防鏽效果。 The treatment liquids described in Patent Document 1 to Patent Document 3 have a problem that the effect of suppressing the generation of red rust (rust prevention effect) is not so high, and the rust prevention effect cannot be maintained for a long period of time.

另外，於如專利文獻4中記載般使用丙烯酸漆的情況下，必須形成膜厚5μm以上的厚皮膜。進而，所述丙烯酸漆包含有機溶劑，因此需要揮發溶劑的回收步驟。由於該些因素，使用了專利文獻4中記載的丙烯酸漆的防鏽處理的成本容易變高。另 外，由丙烯酸漆形成的丙烯酸皮膜的耐候性並不那麼高。 Moreover, when using an acrylic varnish as described in patent document 4, it is necessary to form a thick film with a film thickness of 5 micrometers or more. Furthermore, the acrylic lacquer contains an organic solvent, so a recovery step of a volatile solvent is required. Due to these factors, the cost of antirust treatment using the acrylic varnish described in Patent Document 4 tends to increase. Other In addition, the weather resistance of the acrylic film formed by acrylic paint is not so high.

另外，於使用專利文獻5中記載的水性胺基甲酸酯樹脂的情況下，為了提高塗佈性而使用含有鋅粉末的處理液，因此於處理液附著於端部以外時附著部位因鋅粉末而著色，外觀可能受損。 In addition, in the case of using the water-based urethane resin described in Patent Document 5, a treatment liquid containing zinc powder is used in order to improve coatability, so when the treatment liquid adheres to other than the end portion, the attached part is affected by the zinc powder. While coloring, the appearance may be damaged.

相對於此，若如專利文獻6~專利文獻10中記載般使用含有氟樹脂及第4族金屬的化學轉化處理液來形成化學轉化處理皮膜，則可形成透明且耐候性優異的皮膜，而且亦可藉由氟樹脂的交聯來提高化學轉化處理皮膜的耐水性，因此非常有用。 On the other hand, if a chemical conversion treatment film is formed using a chemical conversion treatment solution containing a fluororesin and a Group 4 metal as described in Patent Documents 6 to 10, a transparent film with excellent weather resistance can be formed, and also It is very useful because the water resistance of the chemical conversion treatment film can be improved by crosslinking the fluororesin.

但是，所述鍍敷鋼板的成形加工品由於在屋外的各種環境下使用，因此不僅對提高化學轉化處理皮膜的耐候性，而且對進一步抑制紅鏽的產生(進一步提高耐腐蝕性)的要求依然存在。 However, since the formed products of the above-mentioned plated steel sheets are used in various outdoor environments, there is still a demand for not only improving the weather resistance of the chemical conversion treatment film, but also further suppressing the generation of red rust (further improving the corrosion resistance). exist.

鑒於所述課題，本發明的目的在於提供一種可形成耐腐蝕性進一步得到提高的化學轉化處理皮膜的端面防鏽處理液、使用所述端面防鏽處理液的化學轉化處理方法、以及具有利用所述化學轉化處理方法而形成的化學轉化處理皮膜的化學轉化處理鋼板及成形加工品。 In view of the above problems, the object of the present invention is to provide an end surface antirust treatment liquid capable of forming a chemical conversion treatment film with further improved corrosion resistance, a chemical conversion treatment method using the end surface antirust treatment liquid, and a Chemical conversion-treated steel sheets and shaped processed products having a chemical conversion treatment film formed by the above-mentioned chemical conversion treatment method.

鑒於所述課題，本發明的一態樣是有關於一種鍍覆鋼板的化學轉化處理用的端面防鏽處理液。所述端面防鏽處理液包含：含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子、蝕刻劑、選自由己二酸或鄰苯二甲酸與碳數1以上 且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮所組成的群組中的一種以上的黏結促進劑、以及矽烷偶合劑。 In view of the above problems, one aspect of the present invention relates to an end surface antirust treatment liquid for chemical conversion treatment of a plated steel sheet. The end surface antirust treatment solution includes: organic resin containing fluororesin, compound containing group 4 elements or ions of group 4 elements, etchant, selected from adipic acid or phthalic acid and carbon number 1 or more And one or more adhesion promoters and silane coupling agents in the group consisting of ester compounds of alcohols with 3 or less and n-methyl-2-pyrrolidone.

另外，本發明的另一態樣是有關於一種鍍敷鋼板的化學轉化處理方法。所述化學轉化處理方法包括在鍍覆鋼板的端面賦予鍍覆鋼板的化學轉化處理用的端面防鏽處理液的步驟。所述端面防鏽處理液包含：含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子、蝕刻劑、以及選自由己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮所組成的群組中的一種以上的黏結促進劑。 In addition, another aspect of the present invention relates to a chemical conversion treatment method for a plated steel sheet. The chemical conversion treatment method includes the step of applying an end surface antirust treatment liquid for chemical conversion treatment of the plated steel sheet to the end surface of the plated steel sheet. The end surface antirust treatment solution includes: organic resin containing fluororesin, compound containing group 4 elements or ions of group 4 elements, etchant, and a mixture of adipic acid or phthalic acid and carbon number 1 or more And one or more adhesion promoters in the group consisting of ester compounds of alcohols with 3 or less and n-methyl-2-pyrrolidone.

另外，本發明的又一態樣是有關於一種具有鍍敷鋼板、以及形成於所述鍍敷鋼板的端面的化學轉化處理皮膜的化學轉化處理鋼板。所述化學轉化處理皮膜包含：含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子、選自由己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮所組成的群組中的一種以上的黏結促進劑、以及矽烷偶合劑。 In addition, another aspect of the present invention relates to a chemical conversion-treated steel sheet having a plated steel sheet and a chemical conversion-treated film formed on an end surface of the plated steel sheet. The chemical conversion treatment film includes: an organic resin containing a fluororesin, a compound containing a group 4 element or an ion of a group 4 element, an alcohol selected from adipic acid or phthalic acid and a carbon number of 1 to 3 One or more adhesion promoters and silane coupling agents in the group consisting of ester compounds and n-methyl-2-pyrrolidone.

另外，本發明的又一態樣是有關於一種藉由鍍敷鋼板的成形加工製作而成的成形加工品。所述成形加工品包含形成於所述鍍敷鋼板的端面的化學轉化處理皮膜，所述化學轉化處理皮膜包含：含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子、選自由己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮所組成的群組中的一種以 上的黏結促進劑、以及矽烷偶合劑。 In addition, another aspect of the present invention relates to a formed product produced by forming a plated steel sheet. The formed product includes a chemical conversion treatment film formed on the end surface of the plated steel sheet, and the chemical conversion treatment film contains: an organic resin containing a fluororesin, a compound containing a group 4 element, or an ion of a group 4 element , one selected from the group consisting of an ester compound of adipic acid or phthalic acid and an alcohol having 1 to 3 carbon atoms, and n-methyl-2-pyrrolidone Adhesion promoters on the surface, and silane coupling agents.

根據本發明，可提供一種可形成耐腐蝕性進一步得到提高的化學轉化處理皮膜的端面防鏽處理液、使用所述端面防鏽處理液的化學轉化處理方法、以及具有利用所述化學轉化處理方法而形成的化學轉化處理皮膜的化學轉化處理鋼板及成形加工品。 According to the present invention, it is possible to provide an end surface antirust treatment solution capable of forming a chemical conversion treatment film with improved corrosion resistance, a chemical conversion treatment method using the end surface antirust treatment solution, and a method with Chemical conversion treated steel sheets and formed products with a chemical conversion treatment film formed.

本發明者等人進行了努力研究，結果發現藉由使包含含有氟樹脂的有機樹脂及含有第4族元素的化合物或第4族元素的離子的水系處理液中進而含有特定的化合物(以下，亦簡稱為「黏結促進劑」)與矽烷偶合劑，並製成端面防鏽處理液，可進一步提高形成於鍍敷鋼板的端面的化學轉化處理皮膜的耐腐蝕性。本發明者等人對帶來所述耐腐蝕性提高的作用效果進行了進一步研究，結果發現作為所述黏結促進劑，可使用己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮，藉此完成了本發明。 The inventors of the present invention have conducted diligent research and found that by making an aqueous treatment solution containing an organic resin containing a fluororesin and a compound containing a group 4 element or an ion of a group 4 element further contain a specific compound (hereinafter, Also referred to as "adhesion promoter") and silane coupling agent, and made into an end surface antirust treatment solution, it can further improve the corrosion resistance of the chemical conversion treatment film formed on the end surface of the plated steel plate. The inventors of the present invention conducted further research on the effect of improving the corrosion resistance, and found that as the adhesion promoter, adipic acid or phthalic acid and a carbon number of 1 to 3 can be used. Alcohol ester compound and n-methyl-2-pyrrolidone, thereby completing the present invention.

即，所述黏結促進劑通常可作為乳液而對水系處理液中存在的氟樹脂進行軟質化。藉由所述黏結促進劑而軟質化的氟樹脂變得更容易熔合，形成耐水性更高的化學轉化處理皮膜，因此認為化學轉化處理皮膜的耐候性進一步提高。 That is, the adhesion promoter is usually used as an emulsion to soften the fluororesin present in the aqueous treatment liquid. The fluororesin softened by the adhesion promoter becomes easier to fuse and forms a chemical conversion treatment film with higher water resistance, so the weather resistance of the chemical conversion treatment film is considered to be further improved.

1.水系處理液 1. Water treatment fluid

所述水系處理液包含含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子及所述黏結促進劑。所述水系處理液亦可進而包含蝕刻劑等其他成分。 The aqueous treatment liquid includes an organic resin containing a fluororesin, a compound containing a group 4 element or an ion of a group 4 element, and the adhesion promoter. The aqueous treatment solution may further include other components such as etchant.

1-1.有機樹脂 1-1. Organic resin

有機樹脂為包含氟樹脂的有機樹脂。氟樹脂可提高化學轉化處理皮膜的耐候性(耐紫外線性及耐光性等)以及耐腐蝕性(防止紅鏽等)。再者，有機樹脂只要不使化學轉化處理皮膜的耐候性及耐腐蝕性明顯下降，則亦可包含氟樹脂以外的樹脂。 The organic resin is an organic resin containing a fluororesin. Fluorine resin can improve the weather resistance (ultraviolet resistance, light resistance, etc.) and corrosion resistance (prevention of red rust, etc.) of the chemical conversion treatment film. In addition, the organic resin may contain resins other than fluororesins as long as the weather resistance and corrosion resistance of the chemical conversion treatment film are not remarkably reduced.

氟樹脂大致分為溶劑系氟樹脂與水系氟樹脂。該些中，較佳為使用容易用於不存在揮發溶劑的回收問題的水系處理液中的水系氟樹脂。 Fluororesins are broadly classified into solvent-based fluororesins and water-based fluororesins. Among these, it is preferable to use a water-based fluororesin that can be easily used in a water-based treatment liquid without the problem of recovery of a volatile solvent.

所謂水系氟樹脂，是指具有親水性官能基的氟樹脂。親水性官能基的較佳的例子中包含羧基及磺酸基、以及該些的鹽等。羧基或磺酸基的鹽的例子中包含銨鹽、胺鹽及鹼金屬鹽等。 The so-called water-based fluororesin refers to a fluororesin having a hydrophilic functional group. Preferable examples of the hydrophilic functional group include a carboxyl group, a sulfonic acid group, and their salts. Examples of salts of carboxyl or sulfonic acid groups include ammonium salts, amine salts, and alkali metal salts.

水系氟樹脂較佳為親水性官能基的量為0.05質量%以上且5質量%以下的量。親水性官能基的量為0.05質量%以上且5質量%以下的量的氟樹脂即便幾乎不使用乳化劑，亦可作為水系乳液。幾乎不含乳化劑的化學轉化處理皮膜可作為耐水性優異的化學轉化處理皮膜。 In the water-based fluororesin, the amount of the hydrophilic functional group is preferably not less than 0.05% by mass and not more than 5% by mass. A fluororesin having a hydrophilic functional group of 0.05% by mass to 5% by mass can be used as an aqueous emulsion even without using an emulsifier. A chemical conversion treatment coating that contains almost no emulsifier can be used as a chemical conversion treatment coating with excellent water resistance.

水系氟樹脂中的親水性官能基的含量只要將水系氟樹脂中所含的親水性官能基的總莫耳質量除以水系氟樹脂的數量平 均分子量而求出即可。羧基的莫耳質量為45，磺酸基的莫耳質量為81，因此藉由求出水系氟樹脂中所含的羧基及磺酸基各自的數量並分別乘以莫耳質量，而求出水系氟樹脂中所含的親水性官能基的總莫耳質量。水系氟樹脂的數量平均分子量可利用凝膠滲透層析法(Gel Permeation Chromatography，GPC)測定而得。 The content of the hydrophilic functional group in the water-based fluororesin is equal to the total molar mass of the hydrophilic functional groups contained in the water-based fluororesin divided by the amount of the water-based fluororesin. It is sufficient to obtain the average molecular weight. The molar mass of the carboxyl group is 45, and the molar mass of the sulfonic acid group is 81. Therefore, by obtaining the respective numbers of carboxyl groups and sulfonic acid groups contained in the water-based fluororesin and multiplying them by the molar masses, the water-based The total molar mass of the hydrophilic functional groups contained in the fluororesin. The number average molecular weight of the water-based fluororesin can be determined by gel permeation chromatography (Gel Permeation Chromatography, GPC).

水系氟樹脂中的羧基於鋼板或鍍敷層(或基底化學轉化處理皮膜)的表面形成氫鍵等，有助於提高化學轉化處理皮膜與鋼板或鍍敷層(或基底化學轉化處理皮膜)表面的密接性，但H+難以解離，因此難以產生與含有第4族元素的化合物或第4族元素的離子的交聯反應。另一方面，關於水系氟樹脂中的磺酸基，H+容易解離，因此雖容易產生與含有第4族元素的化合物或第4族元素的離子的交聯反應，但另一方面，若不與含有第4族元素的化合物或第4族元素的離子交聯反應而於未反應的狀態下殘存於皮膜中，則水分子的吸附作用強，因此有使化學轉化處理皮膜的耐水性明顯下降之虞。因此，為了發揮各自的特徵，較佳為於水系氟樹脂中包含羧基及磺酸基此兩者。該情況下，羧基與磺酸基的比率較佳為以羧基/磺酸基的莫耳比計為5以上且60以下的範圍內。 The carboxyl group in the water-based fluororesin forms hydrogen bonds on the surface of the steel plate or the plating layer (or the base chemical conversion treatment film), which helps to improve the surface of the chemical conversion treatment film and the steel plate or plating layer (or the base chemical conversion treatment film). Adhesiveness, but H + is difficult to dissociate, so it is difficult to produce a cross-linking reaction with a compound containing a group 4 element or an ion of a group 4 element. On the other hand, with regard to the sulfonic acid group in the water-based fluororesin, H + is easily dissociated, so although it is easy to produce a cross-linking reaction with a compound containing a group 4 element or an ion of a group 4 element, on the other hand, if there is no Reacting with compounds containing group 4 elements or ionic cross-linking of group 4 elements and remaining in the film in an unreacted state, the adsorption of water molecules is strong, so the water resistance of the chemical conversion treatment film will be significantly reduced risk. Therefore, it is preferable to include both carboxyl groups and sulfonic acid groups in the water-based fluororesin in order to exhibit respective characteristics. In this case, the ratio of the carboxyl group to the sulfonic acid group is preferably within a range of 5 or more and 60 or less in terms of the carboxyl group/sulfonic acid group molar ratio.

水系氟樹脂的數量平均分子量較佳為1000以上，更佳為1萬以上，尤佳為20萬以上。 The number average molecular weight of the water-based fluororesin is preferably at least 1,000, more preferably at least 10,000, and most preferably at least 200,000.

若水系氟樹脂的數量平均分子量的下限為所述值，則可充分提高化學轉化處理皮膜的透水性及耐水性，可抑制濕氣或腐 蝕性氣體等貫穿化學轉化處理皮膜所導致的鍍敷鋼板的腐蝕。另外，若水系氟樹脂的數量平均分子量的下限為所述值，則因光能等的作用而產生的自由基難以作用於聚合物鏈的末端，因此亦可抑制因水等的相乘作用而水系氟樹脂水解所導致的化學轉化處理皮膜的劣化。藉由增大水系氟樹脂的分子量，分子間力變強，化學轉化處理皮膜的凝聚力提高，因此可進一步提高化學轉化處理皮膜的耐水性。另外，藉由增大水系氟樹脂的分子量，可將水系氟樹脂的主鏈的原子間的鍵結穩定化，亦不易產生水系氟樹脂的水解所導致的化學轉化處理皮膜的劣化。 If the lower limit of the number average molecular weight of the water-based fluororesin is the above value, the water permeability and water resistance of the chemical conversion treatment film can be sufficiently improved, and moisture or corrosion can be suppressed. Corrosion of galvanized steel sheets caused by corrosive gases and the like penetrating through the chemical conversion treatment film. In addition, if the lower limit of the number average molecular weight of the water-based fluororesin is the above value, it is difficult for radicals generated by the action of light energy to act on the ends of the polymer chain, so that the synergistic effect of water and the like can also be suppressed. Deterioration of chemical conversion treatment film due to hydrolysis of water-based fluororesin. By increasing the molecular weight of the water-based fluororesin, the intermolecular force becomes stronger, and the cohesion of the chemical conversion treatment film increases, so the water resistance of the chemical conversion treatment film can be further improved. In addition, by increasing the molecular weight of the water-based fluororesin, the bonds between the atoms in the main chain of the water-based fluororesin can be stabilized, and the deterioration of the chemical conversion treatment film caused by the hydrolysis of the water-based fluororesin is less likely to occur.

另一方面，水系氟樹脂的數量平均分子量較佳為200萬以下。若水系氟樹脂的數量平均分子量的上限為200萬以下，則不易產生水系處理液的凝膠化等，進一步提高水系處理液的保存穩定性。 On the other hand, the number average molecular weight of the water-based fluororesin is preferably 2 million or less. When the upper limit of the number average molecular weight of the water-based fluororesin is 2 million or less, gelation of the water-based treatment liquid is less likely to occur, and the storage stability of the water-based treatment liquid is further improved.

就進一步提高化學轉化處理皮膜的耐候性及耐腐蝕性的觀點而言，相對於所述氟樹脂的總質量，水系氟樹脂較佳為包含6質量%以上的氟(F)原子，更佳為包含8質量%以上的氟(F)原子，進而佳為包含13質量%以上的氟(F)原子。另外，就容易進行塗料化且進一步提高化學轉化處理皮膜的密接性及乾燥性的觀點而言，相對於所述氟樹脂的總質量，水系氟樹脂較佳為包含20質量%以下的氟(F)原子。水系氟樹脂中的氟(F)原子的含量可藉由螢光X射線分析裝置進行測定。 From the viewpoint of further improving the weather resistance and corrosion resistance of the chemical conversion treatment film, the water-based fluororesin preferably contains 6% by mass or more of fluorine (F) atoms relative to the total mass of the fluororesin, more preferably It contains 8 mass % or more of fluorine (F) atoms, and more preferably contains 13 mass % or more of fluorine (F) atoms. In addition, from the viewpoint of being easy to paint and further improving the adhesion and drying properties of the chemical conversion treatment film, it is preferable that the water-based fluororesin contains 20% by mass or less of fluorine (F )atom. The content of fluorine (F) atoms in the water-based fluororesin can be measured by a fluorescent X-ray analyzer.

作為水系氟樹脂，較佳為含氟烯烴樹脂。含氟烯烴樹脂 的例子中包含氟烯烴與含親水性官能基的單體的共聚物。 The water-based fluororesin is preferably a fluoroolefin resin. Fluorinated Olefin Resin Examples include copolymers of fluoroolefins and monomers containing hydrophilic functional groups.

所述氟烯烴的例子中包含四氟乙烯、三氟乙烯、氯三氟乙烯、六氟丙烯、氟乙烯、偏二氟乙烯、五氟丙烯、2,2,3,3-四氟丙烯、3,3,3-三氟丙烯、溴三氟乙烯、1-氯-1,2-二氟乙烯及1,1-二氯-2,2-二氟乙烯等。該些氟烯烴可單獨使用，亦可組合使用兩種以上。就進一步提高耐紫外線性的觀點而言，該些氟烯烴中，較佳為包含四氟乙烯及六氟丙烯等的全氟烯烴、以及偏二氟乙烯等。再者，就抑制氯離子所導致的腐蝕的觀點而言，較佳為氯三氟乙烯等包含氯的氟烯烴的含量少(例如為0.1莫耳%以下)。 Examples of the fluoroolefin include tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, pentafluoropropylene, 2,2,3,3-tetrafluoropropylene, 3 , 3,3-trifluoropropene, bromotrifluoroethylene, 1-chloro-1,2-difluoroethylene and 1,1-dichloro-2,2-difluoroethylene, etc. These fluoroolefins may be used alone or in combination of two or more. Among these fluoroolefins, perfluoroolefins including tetrafluoroethylene, hexafluoropropylene, and the like, vinylidene fluoride, and the like are preferable from the viewpoint of further improving ultraviolet resistance. Furthermore, from the viewpoint of suppressing corrosion by chlorine ions, the content of fluoroolefins containing chlorine such as chlorotrifluoroethylene is preferably small (for example, 0.1 mol % or less).

所述含親水性官能基的單體的例子中包含公知的含羧基的單體及含磺酸基的單體。該些含親水性官能基的單體可單獨使用，亦可組合使用兩種以上。 Examples of the hydrophilic functional group-containing monomer include known carboxyl group-containing monomers and sulfonic acid group-containing monomers. These hydrophilic functional group-containing monomers may be used alone or in combination of two or more.

作為所述含羧基的單體的一例，可列舉以下的式(1)所示的不飽和羧酸、及包含該些的酯或酸酐等的不飽和羧酸類。 Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids represented by the following formula (1) and unsaturated carboxylic acids including esters and acid anhydrides thereof.

Figure 108102631-A0305-02-0011-1
Figure 108102631-A0305-02-0011-1

(式中，R1、R2及R3獨立地表示氫原子、烷基、羧基或酯基。n為0~20的整數) (In the formula, R 1 , R 2 and R 3 independently represent a hydrogen atom, an alkyl group, a carboxyl group or an ester group. n is an integer from 0 to 20)

所述式(1)所示的不飽和羧酸的具體例中包含丙烯酸、甲基丙烯酸、乙酸乙烯酯、丁烯酸、肉桂酸、衣康酸、衣康酸單酯、馬來酸、馬來酸單酯、反丁烯二酸、反丁烯二酸單酯、5-己烯酸、5-庚烯酸、6-庚烯酸、7-辛烯酸、8-壬烯酸、9-癸烯酸、10-十一烯酸、11-十二烯酸、17-十八烯酸及油酸等。 Specific examples of the unsaturated carboxylic acid represented by the formula (1) include acrylic acid, methacrylic acid, vinyl acetate, crotonic acid, cinnamic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid, Toric acid monoester, fumaric acid, fumaric acid monoester, 5-hexenoic acid, 5-heptenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9 -decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 17-octadecenoic acid, oleic acid, etc.

作為所述含羧基的單體的其他例子，可列舉以下的式(2)所示的含羧基的乙烯醚單體。 As another example of the said carboxyl group-containing monomer, the carboxyl group-containing vinyl ether monomer represented by following formula (2) is mentioned.

Figure 108102631-A0305-02-0012-2
Figure 108102631-A0305-02-0012-2

(式中，R4及R5獨立地表示飽和或不飽和的直鏈或環狀烷基。n為0或1。m為0或1) (In the formula, R 4 and R 5 independently represent a saturated or unsaturated linear or cyclic alkyl group. n is 0 or 1. m is 0 or 1)

所述式(2)中所示的含羧基的乙烯醚單體的具體例中包含丙酸3-(2-烯丙氧基乙氧基羰酯)、丙酸3-(2-烯丙氧基丁氧基羰酯)、丙酸3-(2-乙烯氧基乙氧基羰酯)及丙酸3-(2-乙烯氧基丁氧基羰酯)等。 Specific examples of the carboxyl-containing vinyl ether monomer shown in the formula (2) include 3-(2-allyloxyethoxycarbonyl propionate), 3-(2-allyloxypropionate) Butoxycarbonyl propionate), 3-(2-vinyloxyethoxycarbonyl propionate) and 3-(2-vinyloxybutoxycarbonyl propionate) etc.

作為所述含磺酸基的單體的具體例，可列舉：磺酸乙烯酯、磺酸烯丙酯、磺酸甲基烯丙酯、苯乙烯磺酸、2-丙烯醯胺-2-甲基丙烷磺酸、2-甲基丙烯醯氧基乙烷磺酸、3-甲基丙烯醯氧基丙烷磺酸、4-甲基丙烯醯氧基丁烷磺酸、3-甲基丙烯醯氧基-2-羥基 丙烷磺酸、3-丙烯醯氧基丙烷磺酸、烯丙氧基苯磺酸、甲基烯丙氧基苯磺酸、異戊二烯磺酸及3-烯丙氧基-2-羥基丙烷磺酸等。 Specific examples of the sulfonic acid group-containing monomer include: vinyl sulfonate, allyl sulfonate, methyl allyl sulfonate, styrenesulfonic acid, 2-acrylamide-2-methyl 2-methacryloxyethanesulfonic acid, 2-methacryloxyethanesulfonic acid, 3-methacryloxypropanesulfonic acid, 4-methacryloxybutanesulfonic acid, 3-methacryloxybutanesulfonic acid 2-hydroxyl Propanesulfonic acid, 3-acryloxypropanesulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, isoprenesulfonic acid and 3-allyloxy-2-hydroxypropane Sulfonic acid etc.

所述氟烯烴與含親水性官能基的單體的共聚物亦可視需要進而與可共聚的其他單體進行共聚。作為所述可共聚的其他單體，可列舉：羧酸乙烯酯類、烷基乙烯醚類及非氟系烯烴類等。 The copolymer of fluoroolefins and monomers containing hydrophilic functional groups can also be further copolymerized with other copolymerizable monomers as needed. Examples of the other copolymerizable monomers include vinyl carboxylates, alkyl vinyl ethers, and fluorine-free olefins.

所述羧酸乙烯酯類可提高所述水系氟樹脂的相容性及化學轉化處理皮膜的光澤，或者可提升玻璃轉移溫度。所述羧酸乙烯酯類的例子中包含乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、己酸乙烯酯、新癸酸(versatic acid)乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、環己基羧酸乙烯酯、苯甲酸乙烯酯及對-第三丁基苯甲酸乙烯酯等。 The vinyl carboxylate can improve the compatibility of the water-based fluororesin and the gloss of the chemical conversion treatment film, or can increase the glass transition temperature. Examples of vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, vinyl caproate, and versatic acid. Vinyl ester, vinyl laurate, vinyl stearate, vinyl cyclohexyl carboxylate, vinyl benzoate, p-tert-butyl vinyl benzoate, etc.

所述烷基乙烯醚類可提高化學轉化處理皮膜的光澤及柔軟性。所述烷基乙烯醚類的例子中包含甲基乙烯醚、乙基乙烯醚及丁基乙烯醚等。 The alkyl vinyl ethers can improve the gloss and softness of the chemical conversion treatment film. Examples of the alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and the like.

所述非氟系烯烴類可提高化學轉化處理皮膜的可撓性。所述非氟系烯烴類的例子中包含乙烯、丙烯、正丁烯及異丁烯等。 The non-fluorine-based olefins can improve the flexibility of the chemical conversion treatment film. Examples of the non-fluorine-based olefins include ethylene, propylene, n-butene, isobutene, and the like.

例如，藉由利用乳化聚合法使所述單體共聚，可獲得具有親水性官能基的氟烯烴共聚物的乳液。此時，以氟烯烴共聚物具有0.05質量%以上且5質量%以下的量的親水性官能基的方式調整原料單體組成物中的氟烯烴的量，藉此可幾乎不使用乳化劑而製造氟烯烴共聚物的水系乳液。使用幾乎不含(1質量%以下) 乳化劑的氟烯烴共聚物的乳液所形成的化學轉化處理皮膜由於幾乎不含乳化劑，因此幾乎未觀察到乳化劑的殘留所導致的耐水性的劣化，而發揮優異的耐水性。 For example, by copolymerizing the monomers by emulsion polymerization, an emulsion of a fluoroolefin copolymer having a hydrophilic functional group can be obtained. At this time, by adjusting the amount of fluoroolefin in the raw material monomer composition so that the fluoroolefin copolymer has a hydrophilic functional group in an amount of 0.05% by mass to 5% by mass, it can be produced without using an emulsifier. Aqueous emulsion of fluoroolefin copolymer. Almost no use (less than 1% by mass) Since the chemical conversion treatment film formed by the emulsifier fluoroolefin copolymer emulsion contains almost no emulsifier, deterioration of water resistance due to emulsifier residue is hardly observed, and excellent water resistance is exhibited.

認為利用所述方法製作的氟樹脂於水系處理液中亦以粒子狀存在。氟樹脂的乳液的平均粒徑較佳為50nm以上且300nm以下。藉由將乳液的平均粒徑設為50nm以上，可提高水系處理液的保存穩定性。另外，藉由將乳液的平均粒徑設為300nm以下，增加乳液的表面積而使彼此容易熔合，可使低溫(例如55℃)下燒結時的造膜更容易。例如，於利用乳化聚合法製備乳液時，藉由使剪切速度或攪拌時間最佳化，可將乳液的平均粒徑設為所述範圍內。 It is considered that the fluororesin produced by the method described above exists in the form of particles in the aqueous treatment liquid. The average particle diameter of the emulsion of the fluororesin is preferably not less than 50 nm and not more than 300 nm. By setting the average particle diameter of the emulsion to 50 nm or more, the storage stability of the aqueous treatment liquid can be improved. In addition, by setting the average particle size of the emulsion to 300nm or less, the surface area of the emulsion is increased to facilitate fusion with each other, making it easier to form a film during sintering at a low temperature (eg, 55°C). For example, when preparing an emulsion by the emulsion polymerization method, the average particle diameter of an emulsion can be made into the said range by optimizing a shear rate or stirring time.

相對於水100質量份，水系處理液中的氟樹脂的含量較佳為10質量份以上且70質量份以下。若氟樹脂的含量為10質量份以上，則更不易產生乾燥過程中大量的水蒸發所導致的化學轉化處理皮膜的成膜性及緻密性的下降。另一方面，若氟樹脂的含量為70質量份以下，則水系處理液的保存穩定性進一步提高。 The content of the fluororesin in the aqueous treatment liquid is preferably not less than 10 parts by mass and not more than 70 parts by mass relative to 100 parts by mass of water. When the content of the fluororesin is more than 10 parts by mass, it is less likely to cause a decrease in the film-forming property and compactness of the chemical conversion treatment film caused by evaporation of a large amount of water during the drying process. On the other hand, when the content of the fluororesin is 70 parts by mass or less, the storage stability of the aqueous treatment liquid is further improved.

另外，相對於固體成分(除去水、其他溶媒的成分)的合計量，水系處理液中的氟樹脂的含量較佳為70質量%以上且99質量%以下。 In addition, the content of the fluororesin in the aqueous treatment liquid is preferably not less than 70% by mass and not more than 99% by mass relative to the total amount of solid content (components excluding water and other solvents).

1-2.含有第4族元素的化合物或第4族元素的離子 1-2. Compounds containing Group 4 elements or ions of Group 4 elements

含有第4族元素的化合物或第4族元素的離子容易與氟樹脂、尤其是水系氟樹脂中的羧基或磺酸基等官能基反應，促進水 系氟樹脂的硬化或交聯反應。因此，含有第4族元素的化合物或第4族元素的離子會提高氟樹脂的密接性且即便於低溫乾燥下亦可提高化學轉化處理皮膜的耐水性。 Compounds containing group 4 elements or ions of group 4 elements are easy to react with functional groups such as carboxyl or sulfonic acid groups in fluororesins, especially water-based fluororesins, and promote water It is the hardening or crosslinking reaction of fluororesin. Therefore, a compound containing a group 4 element or an ion of a group 4 element improves the adhesion of the fluororesin and improves the water resistance of the chemical conversion treatment film even under low-temperature drying.

含有第4族元素的化合物可設為4A族金屬的含氧酸鹽、氟化物、氫氧化物、有機酸鹽、碳酸鹽、過氧化鹽、銨鹽、鹼金屬鹽及鹼土類金屬鹽等。再者，含氧酸鹽是指具有氧與其他元素的酸(碳酸或硫酸等)的鹽。含氧酸鹽的例子中包含氫酸鹽、碳酸鹽、硫酸鹽等。第4族元素的離子的例子包含源自所述化合物的第4族元素的離子。 Compounds containing Group 4 elements include oxo acid salts, fluorides, hydroxides, organic acid salts, carbonates, peroxides, ammonium salts, alkali metal salts, and alkaline earth metal salts of Group 4A metals. Furthermore, the oxo acid salt refers to a salt of an acid (carbonic acid, sulfuric acid, etc.) containing oxygen and other elements. Examples of oxo acid salts include hydrogenates, carbonates, sulfates, and the like. Examples of the ions of the Group 4 element include ions of the Group 4 element derived from the compound.

所述含有第4族元素的化合物或第4族元素的離子的例子中包含鈦(Ti)化合物、鋯(Zr)化合物及鉿(Hf)化合物。該些中，就抑制後述的光觸媒所導致的耐候性的下降的觀點而言，較佳為鋯化合物。 Examples of the compound containing the Group 4 element or the ion of the Group 4 element include titanium (Ti) compound, zirconium (Zr) compound, and hafnium (Hf) compound. Among these, zirconium compounds are preferable from the viewpoint of suppressing a decrease in weather resistance by a photocatalyst described later.

含有第4族元素的化合物或第4族元素的離子與三聚氰胺樹脂不同，不易產生醚鍵或甲醯醚鍵等氧化及水解等所導致的化學轉化處理皮膜的耐候劣化。另外，含有第4族元素的化合物或第4族元素的離子與三聚氰胺樹脂不同，亦不易產生因酸性雨中所含的硫酸根離子或硝酸根離子等酸性物質而交聯結構斷裂所導致的化學轉化處理皮膜的耐候劣化。 Compounds containing group 4 elements or ions of group 4 elements are different from melamine resins, and are less likely to cause weather resistance deterioration of the chemical conversion treatment film caused by oxidation and hydrolysis of ether bonds or formyl ether bonds. In addition, compounds containing group 4 elements or ions of group 4 elements are different from melamine resins, and are not easy to produce chemical transformations caused by broken cross-linked structures due to acidic substances such as sulfate ions or nitrate ions contained in acid rain Handle the weather resistance deterioration of the film.

另外，含有第4族元素的化合物或第4族元素的離子以比使用了異氰酸酯樹脂的交聯部分所形成的胺基甲酸酯鍵更強的鍵結力使氟樹脂交聯，因此亦不易產生交聯結構的斷裂所導致的 耐候劣化的推進。 In addition, compounds containing Group 4 elements or ions of Group 4 elements cross-link the fluororesin with a stronger bonding force than the urethane bond formed by the cross-linked part using the isocyanate resin, so it is not easy to cross-link the fluororesin. caused by the breakage of the cross-linked structure Advancement of weathering degradation.

另外，含有第4族元素的化合物或第4族元素的離子亦使化學轉化處理皮膜的皮膜密接性、耐水性及耐變色性提高。例如，若利用包含含有第4族元素的化合物或第4族元素的離子的水系處理液而於含Al的Zn系合金鍍敷鋼板的表面形成化學轉化處理皮膜，則可抑制存在於鍍敷鋼板的表面的牢固的Al氧化物所導致的皮膜密接性的下降。另外，若利用包含含有第4族元素的化合物或第4族元素的離子的水系處理液而於含Al的Zn系合金鍍敷鋼板的表面形成化學轉化處理皮膜，則藉由蝕刻反應等而溶出的Al離子與含有第4族元素的化合物或第4族元素的離子反應而生成的反應產物於鍍敷層與化學轉化處理皮膜的界面濃縮，而使鍍敷鋼板的初期的耐腐蝕性及耐變色性提高。 In addition, compounds containing Group 4 elements or ions of Group 4 elements also improve the film adhesion, water resistance, and discoloration resistance of the chemical conversion treatment film. For example, if a chemical conversion treatment film is formed on the surface of a Zn-based alloy plated steel sheet containing Al using an aqueous treatment solution containing a compound containing a group 4 element or an ion of a group 4 element, the presence of a chemical conversion film on the plated steel sheet can be suppressed. Decrease in film adhesion due to strong Al oxide on the surface. In addition, when a chemical conversion treatment film is formed on the surface of an Al-containing Zn-based alloy plated steel sheet using an aqueous treatment solution containing a compound containing a group 4 element or an ion of a group 4 element, it will be eluted by an etching reaction or the like. The reaction product formed by the reaction of the Al ion with the compound containing the group 4 element or the ion of the group 4 element is concentrated at the interface between the plating layer and the chemical conversion treatment film, so that the initial corrosion resistance and corrosion resistance of the plated steel sheet are improved. Improved discoloration.

水系處理液中的含有第4族元素的化合物或第4族元素的離子的以金屬原子換算計的含量例如可設為0.5g/L，就使水系氟樹脂充分交聯而進一步提高化學轉化處理皮膜的密接性的觀點而言，較佳為2g/L以上。就所述觀點而言，含有第4族元素的化合物或第4族元素的離子的含量更佳為1g/L以上，進而佳為2g/L以上。再者，就抑制化學轉化處理皮膜為多孔質狀所導致的化學轉化處理皮膜的加工性及耐候性的下降的觀點而言，水系處理液中的含有第4族元素的化合物或第4族元素的離子的含量較佳為30g/L以下。水系處理液中的含有第4族元素的化合物或第4族元素的離子的以金屬原子換算計的含量可使用螢光X射線分析裝 置而測定。 The content of the compound containing the group 4 element or the ion of the group 4 element in the water-based treatment liquid can be set to 0.5 g/L, for example, so that the water-based fluororesin can be fully cross-linked and the chemical conversion treatment can be further improved. From the viewpoint of the adhesiveness of the film, it is preferably 2 g/L or more. From this point of view, the content of the compound containing the Group 4 element or the ion of the Group 4 element is more preferably 1 g/L or more, and more preferably 2 g/L or more. Furthermore, from the viewpoint of suppressing the decrease in processability and weather resistance of the chemical conversion treatment film caused by the porous state of the chemical conversion treatment film, the compound containing the fourth group element or the fourth group element in the aqueous treatment liquid The content of ions is preferably below 30g/L. The content in terms of metal atoms of compounds containing Group 4 elements or ions of Group 4 elements in the water-based treatment liquid can be determined using a fluorescent X-ray analyzer. Set and measure.

1-3.黏結促進劑 1-3. Adhesion promoter

黏結促進劑可將水系處理液中存在的氟樹脂軟質化。關於藉由所述黏結促進劑而軟質化的氟樹脂，構成乳液的粒子彼此容易更緊密地熔合，進一步形成不易浸透水的化學轉化處理皮膜。因此，認為由包含黏結促進劑的所述水系處理液所形成的化學轉化處理皮膜不易產生紅鏽，而化學轉化處理皮膜的耐腐蝕性進一步提高。另外，黏結促進劑藉由將氟樹脂軟質化並使構成乳液的粒子彼此容易更緊密地熔合，而進一步形成難以因紫外線等光而分解的化學轉化處理皮膜。因此，認為由含有黏結促進劑的所述水系處理液形成的化學轉化處理皮膜的耐候性亦進一步提高。 The adhesion promoter softens the fluororesin present in the water-based treatment solution. With regard to the fluororesin softened by the adhesion promoter, the particles constituting the emulsion are more likely to be fused together more closely to form a chemical conversion treatment film that is less permeable to water. Therefore, it is considered that the chemical conversion treatment film formed by the above-mentioned aqueous treatment solution containing an adhesion promoter is less likely to generate red rust, and the corrosion resistance of the chemical conversion treatment film is further improved. In addition, the adhesion promoter softens the fluororesin and makes it easier for the particles constituting the emulsion to fuse more tightly, thereby further forming a chemical conversion treatment film that is difficult to be decomposed by light such as ultraviolet rays. Therefore, it is considered that the weather resistance of the chemical conversion treatment film formed from the above-mentioned aqueous treatment solution containing the adhesion promoter is also further improved.

另外，藉由所述作用，所述黏結促進劑即便於常溫程度下亦可將氟樹脂良好地熔合。因此，關於所述包含黏結促進劑的水系處理液，可於加工現場不進行加熱而更容易地於藉由加工現場等的鍍敷鋼板的斷裂而生成的端面、或者鍍敷鋼板的端面等的露出部位形成化學轉化處理皮膜。 In addition, due to the above action, the adhesion promoter can well fuse the fluororesin even at about normal temperature. Therefore, the aqueous treatment solution containing the adhesion promoter can be more easily applied to the end surface generated by the fracture of the plated steel sheet at the processing site or the like, or the end surface of the plated steel plate, etc. without heating at the processing site. A chemical conversion treatment film is formed on the exposed part.

黏結促進劑可從己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮中適宜選擇使用。所述黏結促進劑的例子包含己二酸二甲酯、己二酸二乙酯、己二酸二(異)丙酯、己二酸二(異)丁酯、鄰苯二甲酸二甲酯、鄰苯二甲酸二乙酯、鄰苯二甲酸二(異)丙酯、鄰苯二甲酸二(異)丁酯及n-甲基-2-吡咯啶酮。該些黏結促進劑中，就耐腐蝕性、處理外觀的觀點而 言，較佳為己二酸二甲酯、己二酸二乙酯、己二酸二(異)丙酯及己二酸二(異)丁酯。再者，本發明中，所謂(異)丙基是指丙基及異丙基，所謂(異)丁基是指丁基及異丁基。 The adhesion promoter can be appropriately selected from ester compounds of adipic acid or phthalic acid and an alcohol having 1 to 3 carbon atoms, and n-methyl-2-pyrrolidone. Examples of the adhesion promoter include dimethyl adipate, diethyl adipate, di(iso)propyl adipate, di(iso)butyl adipate, dimethyl phthalate, Diethyl phthalate, di(iso)propyl phthalate, di(iso)butyl phthalate and n-methyl-2-pyrrolidone. Among these adhesion promoters, from the viewpoint of corrosion resistance and treatment appearance, For example, dimethyl adipate, diethyl adipate, di(iso)propyl adipate and di(iso)butyl adipate are preferred. Furthermore, in the present invention, the (iso)propyl group means propyl and isopropyl, and the (iso)butyl means butyl and isobutyl.

水系處理液中的黏結促進劑的含量例如可設為0.1g/L以上且50g/L以下，但就藉由所述作用而容易將氟樹脂進一步熔合，並進一步提高化學轉化處理皮膜的耐腐蝕性的觀點而言，較佳為0.5g/L以上且50g/L以下，更佳為0.7g/L以上且30g/L以下，進而佳為1g/L以上且15g/L以下。 The content of the adhesion promoter in the water-based treatment liquid can be set to, for example, not less than 0.1 g/L and not more than 50 g/L, but the fluororesin is easily further fused by this action, and the corrosion resistance of the chemical conversion treatment film is further improved. From the viewpoint of stability, it is preferably from 0.5 g/L to 50 g/L, more preferably from 0.7 g/L to 30 g/L, and still more preferably from 1 g/L to 15 g/L.

1-4.蝕刻劑 1-4. Etchant

蝕刻劑將基材鋼板的表面均一化及活性化，進一步提高化學轉化處理皮膜的密接性，抑制水自化學轉化處理皮膜朝鍍敷鋼板的浸透。因此，認為由包含黏結促進劑的所述水系處理液而形成的化學轉化處理皮膜不易產生紅鏽，而進一步提高化學轉化處理皮膜的耐腐蝕性。 The etchant uniformizes and activates the surface of the base steel sheet, further improves the adhesion of the chemical conversion treatment film, and suppresses the penetration of water from the chemical conversion treatment film into the plated steel sheet. Therefore, it is considered that the chemical conversion treatment film formed by the above-mentioned aqueous treatment solution containing an adhesion promoter is less likely to generate red rust, and the corrosion resistance of the chemical conversion treatment film is further improved.

具體而言，蝕刻劑溶解鍍敷層中所含的Zn及Al以及基材鋼板中所含的Fe等金屬成分，於化學轉化處理皮膜中滲入溶解的金屬成分，藉此提高形成有化學轉化處理皮膜的鍍敷鋼板的耐腐蝕性。此時，本發明中，所述經滲入的金屬成分藉由所述黏結促進劑被滲入至乳液狀的氟樹脂的更內部，亦進一步提高化學轉化處理皮膜的密接性，結果認為進一步提高形成有化學轉化處理皮膜的鍍敷鋼板的耐腐蝕性。 Specifically, the etchant dissolves metal components such as Zn and Al contained in the plating layer and Fe contained in the base steel sheet, and infiltrates the dissolved metal components into the chemical conversion treatment film, thereby improving the formation of chemical conversion treatment. Corrosion resistance of plated steel sheet with coating. At this time, in the present invention, the infiltrated metal component is infiltrated into the interior of the emulsion-like fluororesin through the adhesion promoter, and the adhesiveness of the chemical conversion treatment film is further improved. Corrosion resistance of plated steel sheet with chemical conversion treatment coating.

尤其就將基材鋼板的露出部位活性化的觀點而言，蝕刻 劑較佳為磷酸或磷酸鹽、以及氨或銨鹽。 In particular, from the viewpoint of activating the exposed portion of the base steel sheet, etching The agent is preferably phosphoric acid or a salt of phosphate, and ammonia or an ammonium salt.

磷酸或磷酸鹽將基材鋼板的露出部位的鐵(Fe)、或Zn系鍍敷中所含的鋅(Zn)均一化及活性化。因此，磷酸或磷酸鹽對於鋼板或Zn系鍍敷鋼板尤其有用。 Phosphoric acid or a phosphate salt homogenizes and activates iron (Fe) on the exposed portion of the base steel sheet or zinc (Zn) contained in the Zn-based plating. Therefore, phosphoric acid or phosphate is particularly useful for steel sheets or Zn-based plated steel sheets.

磷酸或磷酸鹽只要為具有磷酸根陰離子(PO4 3-)的水溶性化合物即可。磷酸鹽的例子中包含磷酸鈉、磷酸銨、磷酸氫銨、磷酸二氫銨、磷酸鎂、磷酸鉀、磷酸錳、磷酸鋅、正磷酸、偏磷酸、焦磷酸、三磷酸及四磷酸等。該些磷酸或磷酸鹽可單獨使用，亦可組合使用兩種以上。 Phosphoric acid or a phosphate salt should just be a water-soluble compound which has a phosphate anion ( PO43- ). Examples of phosphates include sodium phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, magnesium phosphate, potassium phosphate, manganese phosphate, zinc phosphate, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid. These phosphoric acid or phosphate salts may be used alone or in combination of two or more.

氨酸或銨鹽將基材鋼板的露出部位的鐵(Fe)、或Al系鍍敷或Zn-Al系鍍敷中所含的鋁(Al)均一化及活性化。因此，磷酸或磷酸鹽對於鋼板及Zn-Al系鍍敷鋼板尤其有用。 The acid or the ammonium salt homogenizes and activates iron (Fe) on exposed parts of the base steel sheet, or aluminum (Al) contained in Al-based plating or Zn—Al-based plating. Therefore, phosphoric acid or a phosphate salt is particularly useful for steel sheets and Zn—Al-based plated steel sheets.

銨鹽的例子中包含四級銨陽離子(NH4 +)的磷酸鹽、氟化物及金屬鹽等。該些中，較佳為包含四級銨陽離子的磷酸鹽，更佳為包含磷酸銨、磷酸氫銨及磷酸二氫銨。 Examples of ammonium salts include phosphate, fluoride, and metal salts of quaternary ammonium cations (NH 4 + ). Among these, phosphates containing quaternary ammonium cations are preferred, and ammonium phosphate, ammonium hydrogen phosphate, and ammonium dihydrogen phosphate are more preferred.

再者，就可利用單一的水系處理液而應用於各種鍍敷鋼板(Zn系、Al系、Zn-Al系及Zn-Al-Mg系等)中的觀點而言，水系處理液中較佳為包含磷酸或磷酸鹽、以及氨或銨鹽此兩者。另外，就進一步提高將基材鋼板的表面均一化及活性化的效果，進一步提高化學轉化處理皮膜的耐候性的觀點而言，水系處理液較佳為包含磷酸或磷酸鹽、以及氨或銨鹽此兩者。就該些觀點而言，蝕刻劑較佳為四級銨陽離子的磷酸鹽，更佳為磷酸銨、磷酸 氫銨及磷酸二氫銨。 Furthermore, from the viewpoint that a single water-based treatment solution can be applied to various plated steel sheets (Zn-based, Al-based, Zn-Al-based, Zn-Al-Mg-based, etc.), the water-based treatment solution is preferred. Both phosphoric acid or phosphate, and ammonia or ammonium salt are included. In addition, from the viewpoint of further improving the effect of uniformizing and activating the surface of the base steel sheet and further improving the weather resistance of the chemical conversion treatment film, it is preferable that the aqueous treatment liquid contains phosphoric acid or phosphate, and ammonia or ammonium salt. Both. From these points of view, the etchant is preferably a phosphate of quaternary ammonium cation, more preferably ammonium phosphate, phosphoric acid Ammonium hydrogen and ammonium dihydrogen phosphate.

水系處理液中的蝕刻劑的含量較佳為磷酸根陰離子(PO4 3-)的含量以磷酸根陰離子換算計為1g/L以上，進而佳為2g/L以上。或者，水系處理液中的蝕刻劑的含量較佳為四級銨陽離子(NH4+)的含量以四級銨陽離子換算計為1g/L以上，進而佳為2g/L以上。 The content of the etchant in the aqueous treatment solution is preferably 1 g/L or more in terms of phosphate anion (PO 4 3− ), more preferably 2 g/L or more. Alternatively, the content of the etchant in the aqueous treatment solution is preferably quaternary ammonium cation (NH 4+ ) content of 1 g/L or more in terms of quaternary ammonium cation, and more preferably 2 g/L or more.

於蝕刻劑包含磷酸或磷酸鹽以及氨或銨鹽此兩者時，水系處理液中的蝕刻劑的含量較佳為磷酸根陰離子(PO4 3)及四級銨陽離子(NH4+)的含量分別以磷酸根陰離子換算及四級銨陽離子換算計均為1g/L以上，進而佳為2g/L以上。 When the etchant contains both phosphoric acid or phosphate and ammonia or ammonium salt, the content of the etchant in the aqueous treatment solution is preferably the content of phosphate anion (PO 4 3 ) and quaternary ammonium cation (NH 4+ ) In terms of phosphate anion conversion and quaternary ammonium cation conversion, both are 1 g/L or more, and more preferably 2 g/L or more.

1-5.矽烷偶合劑 1-5. Silane coupling agent

矽烷偶合劑可進一步提高化學轉化處理皮膜的密接性。 The silane coupling agent can further improve the adhesion of the chemical conversion treatment film.

相對於氟樹脂100質量份，水系處理液中的矽烷偶合劑的含量較佳為0.5質量份以上且5質量份以下。若矽烷偶合劑的含量為0.5質量份以上，則可進一步提高化學轉化處理皮膜的密接性。另一方面，若矽烷偶合劑的含量為5質量份以下，則可抑制水系處理液的保存穩定性的下降。 The content of the silane coupling agent in the aqueous treatment liquid is preferably not less than 0.5 parts by mass and not more than 5 parts by mass relative to 100 parts by mass of the fluororesin. When the content of the silane coupling agent is at least 0.5 parts by mass, the adhesiveness of the chemical conversion treatment film can be further improved. On the other hand, if content of a silane coupling agent is 5 mass parts or less, the fall of the storage stability of an aqueous treatment liquid can be suppressed.

1-6.其他成分 1-6. Other ingredients

水系處理液亦可視需要添加所述以外的無機化合物、矽烷偶合劑以外的有機潤滑劑、無機潤滑劑、無機顏料、有機顏料及染料等作為其他成分。Mg、Ca、Sr、V、W、Mn、B、Si、Sn等無機化合物(氧化物、磷酸鹽等)將化學轉化處理皮膜緻密化而提 高耐水性。氟系、聚乙烯系及苯乙烯系等有機潤滑劑、以及二硫化鉬及滑石等無機潤滑劑使化學轉化處理皮膜的潤滑性提高。另外，藉由調配無機顏料、有機顏料及染料等，可對化學轉化處理皮膜賦予規定的色調。 Inorganic compounds other than those mentioned above, organic lubricants other than silane coupling agents, inorganic lubricants, inorganic pigments, organic pigments, and dyes may be added as other components to the water-based treatment liquid as needed. Inorganic compounds (oxides, phosphates, etc.) such as Mg, Ca, Sr, V, W, Mn, B, Si, Sn, etc. will densify the chemical conversion treatment film to improve High water resistance. Organic lubricants such as fluorine-based, polyethylene-based, and styrene-based lubricants, and inorganic lubricants such as molybdenum disulfide and talc improve the lubricity of the chemical conversion treatment film. In addition, by mixing inorganic pigments, organic pigments, dyes, etc., a predetermined color tone can be given to the chemical conversion treatment film.

再者，水系處理液較佳為釩(V)離子及鈦(Ti)離子的含量以金屬原子換算計為500ppm以下。包含V或Ti的化合物有時用作防鏽劑，藉由進一步減少該些離子的含量，可抑制V或Ti的光觸媒作用所導致的化學轉化處理皮膜的耐候性的下降。 Furthermore, the water-based treatment liquid preferably has a content of vanadium (V) ions and titanium (Ti) ions that is 500 ppm or less in terms of metal atoms. A compound containing V or Ti is sometimes used as an antirust agent, and by further reducing the content of these ions, the decrease in weather resistance of the chemical conversion treatment film caused by the photocatalytic action of V or Ti can be suppressed.

另外，水系處理液較佳為鉻(Cr)、尤其是六價鉻的含量以金屬原子換算計為100ppm以下。藉由進一步減少Cr(六價鉻)的含量，可形成對人體的影響少、安全性高的化學轉化處理皮膜。 In addition, the aqueous treatment liquid preferably has a content of chromium (Cr), especially hexavalent chromium, of 100 ppm or less in terms of metal atoms. By further reducing the Cr (hexavalent chromium) content, it is possible to form a chemical conversion treatment film that has less impact on the human body and is highly safe.

另外，就形成清晰的皮膜的觀點而言，水系處理液較佳為實質上不含無機顏料、有機顏料及染料等。水系處理液以氟樹脂作為主成分，因此與藉由磷酸的錳或鐵等的鹽而形成磷酸鹽皮膜的磷酸鹽處理(Parkerizing)、或者藉由大量的鋅粉末而形成犧牲防腐蝕層的富鋅漆(zinc rich paint)不同，可形成清晰的皮膜。 In addition, from the viewpoint of forming a clear film, it is preferable that the water-based treatment liquid does not substantially contain inorganic pigments, organic pigments, dyes, and the like. The water-based treatment liquid contains fluororesin as the main component, so it can be combined with phosphate treatment (Parkerizing) to form a phosphate film with manganese or iron salts of phosphoric acid, or to form a sacrificial anti-corrosion layer with a large amount of zinc powder. Unlike zinc rich paint, a clear film can be formed.

1-7.水系處理液的性狀 1-7. Properties of water system treatment liquid

相對於水系處理液的總質量，水系處理液較佳為除去水等溶媒的固體成分的含量(固體成分濃度)為20質量%以上。若固體成分的含量為20質量%以上，則可形成具有充分的膜厚、具有充分的耐候性的化學轉化處理皮膜。再者，就處理液穩定性的方面 而言，固體成分的含量的上限較佳為40質量%以下。 The aqueous treatment liquid preferably has a solid content (solid content concentration) of 20% by mass or more, excluding solvents such as water, relative to the total mass of the aqueous treatment liquid. When the solid content is 20% by mass or more, a chemical conversion treatment film having sufficient film thickness and sufficient weather resistance can be formed. Furthermore, in terms of the stability of the treatment fluid Specifically, the upper limit of the solid content is preferably 40% by mass or less.

水系處理液較佳為pH為7.0以上且9.5以下。若pH為7.0以上，則可適度調整Zn的蝕刻量，若pH為9.5以下，則可適度調整Al的蝕刻量。因此，若pH為7.0以上且9.5以下，則可抑制過剩的蝕刻所導致的外觀不良或耐腐蝕性的下降。 The aqueous treatment liquid preferably has a pH of not less than 7.0 and not more than 9.5. When pH is 7.0 or more, the etching amount of Zn can be adjusted moderately, and when pH is 9.5 or less, the etching amount of Al can be adjusted moderately. Therefore, when pH is 7.0-9.5, the external appearance defect and corrosion-resistant fall by excessive etching can be suppressed.

水系處理液可為單液型，亦可為於使用時將氟樹脂的乳液與包含黏結促進劑的溶液(或分散液)混合的雙液混合型。 The aqueous treatment solution may be a single-component type, or a two-component mixed type in which an emulsion of a fluororesin and a solution (or dispersion) containing an adhesion promoter are mixed at the time of use.

2.鍍敷鋼板的化學轉化處理方法 2. Chemical conversion treatment method of plated steel plate

所述水系處理液可用於鍍敷鋼板的化學轉化處理中。具體而言，可對鍍敷鋼板的端面賦予所述水系處理液，進行乾燥而形成化學轉化處理皮膜。 The water-based treatment solution can be used in chemical conversion treatment of plated steel sheets. Specifically, the above-mentioned aqueous treatment solution may be applied to the end surface of the plated steel sheet, and dried to form a chemical conversion treatment film.

實施了鍍敷的基材鋼板的種類並無特別限定。例如，鋼板可為包含低碳鋼、中碳鋼及高碳鋼等的碳鋼，亦可為含有Mn、Cr、Si、Ni等的合金鋼。另外，鋼板可為包含Al全靜鋼(killed steel)等的全靜鋼，亦可為未靜鋼(rimmed steel)。於需要良好的壓製成形性的情況下，包含添加Ti的低碳鋼及添加Nb的低碳鋼等的伸拉用鋼板作為鋼板而較佳。另外，亦可使用將P、Si、Mn等的量調整為特定的值的高強度鋼板。 The type of base steel plate to be plated is not particularly limited. For example, the steel plate may be carbon steel including low carbon steel, medium carbon steel, high carbon steel, etc., or alloy steel containing Mn, Cr, Si, Ni, etc. In addition, the steel plate may be killed steel including Al killed steel, or may be rimmed steel. When good press formability is required, a steel sheet for drawing including Ti-added low-carbon steel and Nb-added low-carbon steel is preferable as the steel sheet. In addition, high-strength steel sheets in which the amounts of P, Si, Mn, and the like are adjusted to specific values can also be used.

鍍敷鋼板只要將所述鋼板設為基材鋼板，實施公知的鍍敷即可。鍍敷可為熔融鍍敷亦可為蒸鍍鍍敷。鍍敷的種類並無特別限定，可使用Zn系鍍敷(Zn鍍敷、Zn-Al鍍敷、及Zn-Al-Mg鍍敷等)、Al系鍍敷、以及Ni系鍍敷等。該些中，較佳為Zn系 鍍敷及Al系鍍敷，更佳為Zn系鍍敷。 As for the plated steel sheet, the above-mentioned steel sheet may be used as a base steel sheet, and known plating may be performed. Plating may be either hot-dip plating or vapor deposition plating. The type of plating is not particularly limited, and Zn-based plating (Zn plating, Zn-Al plating, and Zn-Al-Mg plating, etc.), Al-based plating, and Ni-based plating can be used. Of these, Zn-based Plating and Al-based plating, more preferably Zn-based plating.

可於各種鍍敷層及基材鋼板兩者形成密接性高的化學轉化處理皮膜，因此可對鍍敷鋼板中其端面或藉由斷裂而生成的端面等的基材鋼板露出的部位賦予所述水系處理液，進行乾燥而形成化學轉化處理皮膜。 A chemical conversion treatment film with high adhesion can be formed on both the various plating layers and the base steel sheet, so it is possible to apply the above-mentioned coating to the exposed parts of the base steel sheet such as the end face of the plated steel sheet or the end face generated by fracture. The water-based treatment solution is dried to form a chemical conversion treatment film.

另外，亦可利用公知的方法對鍍敷鋼板實施預塗佈的基底化學轉化處理。 In addition, the base chemical conversion treatment of the pre-coating can also be performed on the plated steel sheet by a known method.

水系處理液的塗佈方法並無特別限定，只要根據鍍敷鋼板的形狀等適宜選擇即可。塗佈方法的例子中包含輥塗法、淋幕法、旋塗法、噴霧法、浸漬提拉法及滴加法等。水系處理液的液膜的厚度可藉由毛氈擠壓或壓縮空氣式刮水器(air wiper)等來調整。 The coating method of the water-based treatment liquid is not particularly limited, and may be appropriately selected according to the shape of the plated steel sheet and the like. Examples of the coating method include a roll coating method, a curtain method, a spin coating method, a spray method, a dipping method, and a dropping method. The thickness of the liquid film of the water-based treatment liquid can be adjusted by felt extrusion or compressed air wiper (air wiper).

水系處理液的塗佈量並無特別限定，較佳為以化學轉化處理皮膜的膜厚成為0.5μm以上且10μm以下的方式進行調整。若化學轉化處理皮膜的膜厚為0.5μm以上，則可對化學轉化處理皮膜充分賦予耐候性、耐腐蝕性及耐變色性等。另一方面，即便膜厚超過10μm，亦無法期待伴隨著膜厚的增加所帶來的性能提高。 The coating amount of the aqueous treatment liquid is not particularly limited, but is preferably adjusted so that the film thickness of the chemical conversion treatment film becomes 0.5 μm or more and 10 μm or less. When the film thickness of the chemical conversion treatment film is 0.5 μm or more, weather resistance, corrosion resistance, discoloration resistance, and the like can be sufficiently provided to the chemical conversion treatment film. On the other hand, even if the film thickness exceeds 10 μm, performance improvement accompanying the increase in film thickness cannot be expected.

所賦予的水系處理液可於常溫下乾燥而製成化學轉化處理皮膜。再者，亦可對所賦予的水系處理液進行加熱(例如加熱至50℃以上)並使其乾燥，此時，就抑制有機成分的熱分解所導致的化學轉化處理皮膜的性能下降的觀點而言，乾燥溫度較佳 為300℃以下。再者，就更容易地於加工現場等中藉由鍍敷鋼板的斷裂而生成的端面、或者鍍敷鋼板的端面等的基材鋼板的露出部位形成化學轉化處理皮膜的觀點而言，較佳為於常溫下使其乾燥。 The given aqueous treatment solution can be dried at normal temperature to form a chemical conversion treatment film. Furthermore, it is also possible to heat (for example, heat to 50° C. or higher) and dry the applied water-based treatment liquid. In other words, the drying temperature is better below 300°C. Furthermore, it is preferable from the viewpoint of easier formation of a chemical conversion treatment film on an end face generated by fracture of a plated steel sheet in a processing site or the like, or on an exposed portion of a base steel sheet such as an end face of a plated steel sheet. In order to make it dry at room temperature.

3.化學轉化處理鋼板及成形加工品 3. Chemical conversion treatment of steel plates and formed products

具有由所述水系處理液而形成的化學轉化處理皮膜的化學轉化處理鋼板具有：所述鍍敷鋼板、以及以被覆所述鍍敷鋼板的端面、較佳為所述鍍敷鋼板的端面的基材鋼板露出的部位的方式形成的所述化學轉化處理皮膜。所述化學轉化處理鋼板亦可為成形加工品。成形加工的方法並無特別限定，可自壓製加工、沖孔加工及拉伸加工等公知的方法中選擇。 The chemical conversion-treated steel sheet having the chemical conversion treatment film formed by the aqueous treatment liquid has: the above-mentioned plated steel sheet; The chemical conversion treatment film is formed in such a way that the steel plate is exposed. The chemical conversion-treated steel sheet may also be a formed product. The method of forming is not particularly limited, and can be selected from known methods such as pressing, punching, and stretching.

更具體而言，所述化學轉化處理皮膜包含：所述含有氟樹脂的有機樹脂、所述含有第4族元素的化合物或第4族元素的離子、選自由己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮所組成的群組中的一種以上的黏結促進劑、以及矽烷偶合劑。 More specifically, the chemical conversion treatment film includes: the organic resin containing fluororesin, the compound containing group 4 elements or ions of group 4 elements, selected from the group consisting of adipic acid or phthalic acid and One or more adhesion promoters and silane coupling agents selected from the group consisting of ester compounds of alcohols having 1 to 3 carbon atoms and n-methyl-2-pyrrolidone.

該些成分的含量比與水系處理液中所述比率相同。 The content ratios of these components are the same as those described in the aqueous treatment liquid.

化學轉化處理皮膜的膜厚較佳為0.5μm以上且10μm以下。若膜厚為0.5μm以上，則可對化學轉化處理皮膜充分賦予耐候性、耐腐蝕性及耐變色性等。另一方面，即便膜厚超過10μm，亦無法期待伴隨著膜厚的增加所帶來的性能提高。 The film thickness of the chemical conversion treatment film is preferably not less than 0.5 μm and not more than 10 μm. When the film thickness is 0.5 μm or more, weather resistance, corrosion resistance, discoloration resistance, and the like can be sufficiently provided to the chemical conversion treatment film. On the other hand, even if the film thickness exceeds 10 μm, performance improvement accompanying the increase in film thickness cannot be expected.

該化學轉化處理鋼板的耐候性、尤其是長期的耐候性優異。另外，關於在藉由鍍敷鋼板的成形加工等而生成的基材鋼板 的露出部位、即端面等具有所述化學轉化處理皮膜的化學轉化處理鋼板，由於所述基材鋼板的露出部位等的化學轉化處理皮膜的耐候性、尤其是長期的耐候性優異，因此較佳。另外，如上所述，關於在將鍍敷層熔化並熔接加工的熔接部具有所述化學轉化處理皮膜的化學轉化處理鋼板，明顯觀察到熔接部的耐腐蝕性提高的效果。 The chemical conversion-treated steel sheet is excellent in weather resistance, especially long-term weather resistance. In addition, regarding the base steel sheet produced by forming the plated steel sheet, etc. The chemical conversion treated steel sheet having the above-mentioned chemical conversion treatment film on the exposed part, that is, the end surface, etc., is preferable because the chemical conversion treatment film on the exposed part of the base steel sheet is excellent in weather resistance, especially long-term weather resistance. . In addition, as described above, the effect of improving the corrosion resistance of the welded portion was clearly observed for the chemically converted steel sheet having the above-mentioned chemical conversion treated film on the welded portion where the plating layer was melted and welded.

[實施例] [Example]

以下，參照實施例對本發明進行詳細說明，但本發明並不受該些實施例的限定。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by these examples.

1.水系處理液的製備 1. Preparation of aqueous treatment solution

將各成分混合，製備表1所示的水系處理液1~水系處理液15。 The components were mixed to prepare water-based treatment solutions 1 to 15 shown in Table 1.

再者，氟樹脂(Fluorine Resin，FR)使用氟系樹脂(Tg：-35℃~25℃、最低成膜溫度(Minimum Film Forming Temperature，MFT)：10℃)的水系乳液。所述氟樹脂乳液的固體成分濃度為38質量%，氟樹脂中的氟原子的含量為25質量%，乳液的平均粒徑為150nm。 Furthermore, as the fluororesin (Fluorine Resin, FR), an aqueous emulsion of a fluororesin (Tg: -35° C. to 25° C., minimum film forming temperature (MFT): 10° C.) is used. The solid content concentration of the fluororesin emulsion was 38% by mass, the content of fluorine atoms in the fluororesin was 25% by mass, and the average particle diameter of the emulsion was 150 nm.

關於丙烯酸樹脂(Acrylic Resin，AR)，準備作為丙烯酸樹脂乳液的DIC股份有限公司製造的「帕泰拉克(Patelacol)」(「帕泰拉克(Patelacol)」為DIC股份有限公司的註冊商標)。「帕泰拉克(Patelacol)」的固體成分濃度為40質量%，認為乳液的平均粒徑為10nm~100nm左右。 As an acrylic resin (Acrylic Resin, AR), "Patelacol" manufactured by DIC Corporation ("Patelacol" is a registered trademark of DIC Corporation) was prepared as an acrylic resin emulsion. The solid content concentration of "Patelacol" is 40% by mass, and the average particle diameter of the emulsion is considered to be about 10 nm to 100 nm.

胺基甲酸酯樹脂(Polyurethane，PU)使用作為胺基甲酸酯樹脂乳液的DIC股份有限公司製造的「海德藍(HYDRAN)」。「海德藍(HYDRAN)」的固體成分濃度為35質量%，認為乳液的平均粒徑為10nm~100nm左右。 As the urethane resin (Polyurethane, PU), "Hydran" manufactured by DIC Co., Ltd., which is a urethane resin emulsion, was used. The solid content concentration of "HYDRAN" is 35% by mass, and the average particle diameter of the emulsion is considered to be about 10nm to 100nm.

關於蝕刻劑，磷酸量以磷酸、磷酸氫二銨及磷酸二氫銨的合計量進行調整，銨量以氨(水溶液)、碳酸鋯銨、氟鋯銨、磷酸氫二胺、磷酸二氫銨及碳酸銨的合計量進行調整。 Regarding the etchant, the amount of phosphoric acid is adjusted by the total amount of phosphoric acid, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate, and the amount of ammonium is adjusted by the amount of ammonia (aqueous solution), ammonium zirconium carbonate, ammonium zirconium fluoride, diamine hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium dihydrogen phosphate. The total amount of ammonium carbonate was adjusted.

矽烷偶合劑(silicone coupling agent，SCA)使用日本邁圖高新材料(Japan Momentive Performance Materials)合同公司製造的「斯魯特(SILQUEST)A-186」。 As the silane coupling agent (silicone coupling agent, SCA), "SILQUEST A-186" manufactured by Japan Momentive Performance Materials contract company was used.

再者，表1的「F量」、「Zr量」、「添加量」、「磷酸量」、「銨量」及「SCA添加量」分別表示氟原子的量(質量%)、含有第4族元素的化合物或第4族元素的離子的以金屬原子換算計的量(g/L)、黏結促進劑的添加量(g/L)、磷酸或磷酸鹽的以磷酸根陰離子換算計的含量(g/L)、氨或銨鹽的以四級銨陽離子換算計的含量(g/L)、以及矽烷偶合劑的添加量(將氟樹脂的質量設為100質量%時的添加量)。 In addition, the "Amount of F", "Amount of Zr", "Amount of Addition", "Amount of Phosphoric Acid", "Amount of Ammonium" and "Amount of SCA Addition" in Table 1 respectively represent the amount of fluorine atoms (mass %), the amount containing 4 The amount (g/L) of the compound of the group element or the ion of the group 4 element in terms of metal atoms (g/L), the amount of the adhesion promoter added (g/L), the content of phosphoric acid or phosphate in terms of phosphate anion (g/L), the content (g/L) of ammonia or ammonium salt in terms of quaternary ammonium cations, and the amount of silane coupling agent added (the amount added when the mass of the fluororesin is 100% by mass).

另外，於在表1的「有機樹脂」的「種類」中記載有「FR/AR」時，表示將所述氟樹脂與所述丙烯酸樹脂摻合，以與其他化合物組合的水系處理液中的固體成分量成為「固體成分量」中記載的數值，且氟原子的量成為「F量」中記載的數值的方式進行調整。 In addition, when "FR/AR" is described in the "type" of "organic resin" in Table 1, it means that the above-mentioned fluororesin and the above-mentioned acrylic resin are blended and combined with other compounds in the water-based treatment liquid. The amount of solid content was adjusted so that it became the numerical value described in "amount of solid content", and the amount of fluorine atoms became the numerical value described in "amount of F".

Figure 108102631-A0305-02-0027-3
Figure 108102631-A0305-02-0027-3

2.評價 2. Evaluation

利用以下基準對水系處理液1~水系處理液15的保存穩定性及由水系處理液1~水系處理液15形成的皮膜的端面部耐腐蝕性進行評價。 The storage stability of the water-based treatment liquid 1 to the water-based treatment liquid 15 and the corrosion resistance of the end surface of the film formed by the water-based treatment liquid 1 to the water-based treatment liquid 15 were evaluated according to the following criteria.

2-1.保存穩定性 2-1. Storage stability

將水系處理液1~水系處理液15於常溫下保管180日。藉由福特黏度杯No.4測定各水系處理液的保管前後的黏度變化量(自保管後黏度減去保管前黏度而得的值)，利用以下基準對保存穩定性進行評價。 Store water-based treatment liquid 1 to water-based treatment liquid 15 at room temperature for 180 days. The viscosity change (the value obtained by subtracting the viscosity before storage from the viscosity after storage) before and after storage of each aqueous treatment solution was measured with a Ford viscosity cup No. 4, and the storage stability was evaluated using the following criteria.

A黏度變化量未滿10秒。 A Viscosity change amount is less than 10 seconds.

B黏度變化量為10秒以上，但使用上無問題。 The amount of change in viscosity of B is more than 10 seconds, but there is no problem in use.

C黏度變化量為30秒以上，因增黏而難以塗佈。 C The amount of change in viscosity is more than 30 seconds, and it is difficult to apply due to increased viscosity.

2-2.端面部耐腐蝕性 2-2. End face corrosion resistance

於板厚為0.6mm的普通鋼的表面形成熔融Zn-6.0質量%Al-3.0質量%Mg鍍敷層(鍍敷附著量為90g/m2)，並製成鍍敷鋼板。將所述鍍敷鋼板切成寬度50mm、長度100mm，結果於藉由斷裂而生成的端面的表面中約20%的面積被鍍敷層覆蓋，剩餘約80%的面積露出基底鋼。 A molten Zn-6.0% by mass Al-3.0% by mass Mg plating layer (plating deposition amount: 90g/m 2 ) was formed on the surface of ordinary steel with a plate thickness of 0.6mm to produce a plated steel sheet. The plated steel sheet was cut into a width of 50 mm and a length of 100 mm. As a result, about 20% of the surface of the end surface formed by fracture was covered by the plating layer, and the remaining about 80% of the area exposed the base steel.

於所述鍍敷鋼板的所述端面塗佈10ml/m2的水系處理液1~水系處理液15，於常溫下乾燥，並製成試驗片。 10 ml/m 2 of water-based treatment solution 1 to water-based treatment solution 15 was applied to the end surface of the plated steel sheet, dried at room temperature, and prepared as a test piece.

將試驗片於大氣下暴露2年，於經過1年後及經過2年後，測定試驗片端面所產生的紅鏽的面積率，求出端面的總面積 中紅鏽產生面積率WR(紅鏽產生面積/端面總面積)，利用以下基準對端面部耐腐蝕性進行評價。 Expose the test piece to the atmosphere for 2 years, measure the area ratio of red rust on the end surface of the test piece after 1 year and 2 years later, and calculate the total area of the end surface The medium red rust generation area ratio WR (red rust generation area/total end face area) was used to evaluate the corrosion resistance of the end face according to the following criteria.

A 紅鏽產生面積率WR為10%以下。 A Red rust generation area ratio WR is 10% or less.

B 紅鏽產生面積率WR超過10%且為30%以下。 B The red rust generation area ratio WR exceeds 10% and is 30% or less.

C 紅鏽產生面積率WR超過30%且為50%以下。 C The red rust generation area ratio WR exceeds 30% and is 50% or less.

D 紅鏽產生面積率WR超過50%。 D The red rust generation area ratio WR exceeds 50%.

將水系處理液1~水系處理液15的保存穩定性及端面部耐腐蝕性的評價結果示於表2中。 Table 2 shows the storage stability of the water-based treatment liquid 1 to the water-based treatment liquid 15 and the evaluation results of the corrosion resistance of the end surface.

Figure 108102631-A0305-02-0029-4
Figure 108102631-A0305-02-0029-4

關於包含含有氟樹脂的有機樹脂、含有第4族元素的化 合物或第4族元素的離子、蝕刻劑及黏結促進劑的水系處理液1~水系處理液10，水系處理液的保存穩定性及所形成的化學轉化處理皮膜的耐腐蝕性均良好。 Regarding organic resins containing fluororesins, chemicals containing Group 4 elements Compounds or ions of group 4 elements, etchant, and adhesion promoter are aqueous treatment solutions 1 to 10. The storage stability of the aqueous treatment solution and the corrosion resistance of the formed chemical conversion treatment film are good.

另外，若使用包含磷酸或磷酸鹽、以及氨或銨鹽中的任一者作為蝕刻劑的水系處理液4~水系處理液10而形成化學轉化處理皮膜，則耐腐蝕性進一步變高。 In addition, when the chemical conversion treatment film is formed using any one of phosphoric acid or phosphate, and ammonia or ammonium salt as an etchant, the corrosion resistance becomes higher.

另一方面，若使用含有氟樹脂以外的樹脂的水系處理液11~水系處理液13而形成化學轉化處理皮膜，則耐候性及耐腐蝕性低。 On the other hand, when the chemical conversion treatment film is formed using the water-based treatment liquid 11 to the water-based treatment liquid 13 containing resin other than the fluororesin, the weather resistance and corrosion resistance are low.

另外，若使用不包含含有第4族元素的化合物或第4族元素的離子的水系處理液14而形成化學轉化處理皮膜，則密接性低。 In addition, when the chemical conversion treatment film is formed using the aqueous treatment solution 14 that does not contain a compound containing a Group 4 element or an ion of a Group 4 element, the adhesion is low.

另外，若使用不含黏結促進劑的水系處理液15而形成化學轉化處理皮膜，則耐腐蝕性低。 In addition, if the chemical conversion treatment film is formed using the aqueous treatment solution 15 that does not contain an adhesion promoter, the corrosion resistance will be low.

本申請案是主張基於2018年1月24日提出申請的日本申請編號2018-009507號的優先權的申請，將該申請的申請專利範圍及說明書中記載的內容引用至本申請案中。 This application is an application claiming priority based on Japanese Application No. 2018-009507 filed on January 24, 2018, and the scope of claims of this application and the contents described in the specification are incorporated into this application.

[產業上之可利用性] [Industrial availability]

藉由本發明的水系處理液而製造的化學轉化處理皮膜可進一步提高鍍敷鋼板中藉由成形加工等而基材鋼板露出的端面的耐腐蝕性。例如，本發明的水系處理液可較佳地用於利用後塗佈而朝鍍敷鋼板形成化學轉化處理皮膜，所述鍍敷鋼板用於如下 用途：1)塑料大棚或農業暖窖用的鋼管、型鋼、支柱、橫樑、運輸用構件；2)遮音壁、隔音壁、吸音壁、防雪壁、護欄、欄杆、防護欄、支柱；3)鐵道車輛用構件、架線用構件、電氣設備用構件、安全環境用構件、結構用構件、太陽能光電(photovoltaic)支架等。 The chemical conversion treatment film produced by the aqueous treatment liquid of the present invention can further improve the corrosion resistance of the end surface of the base steel sheet exposed by forming processing or the like in the plated steel sheet. For example, the aqueous treatment solution of the present invention can be preferably used to form a chemical conversion treatment film on a plated steel sheet for the following by post-coating Uses: 1) Steel pipes, shaped steel, pillars, beams, and transportation components for plastic greenhouses or agricultural warm cellars; 2) Sound-insulating walls, sound-insulating walls, sound-absorbing walls, snow-proof walls, guardrails, railings, guardrails, and pillars; 3) Railway vehicles Components for wiring, components for electrical equipment, components for safety and environment, structural components, solar photovoltaic (photovoltaic) brackets, etc.

Claims (14)

一種鍍覆鋼板的端面防鏽處理液，其包含：含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子、蝕刻劑、選自由己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物、及n-甲基-2-吡咯啶酮所組成的群組中的一種以上的黏結促進劑、以及矽烷偶合劑。 An antirust treatment solution for the end surface of a plated steel plate, which comprises: an organic resin containing a fluororesin, a compound containing a group 4 element or an ion of a group 4 element, an etchant, and an etchant selected from adipic acid or phthalic acid and One or more adhesion promoters and silane coupling agents selected from the group consisting of ester compounds of alcohols having 1 to 3 carbon atoms and n-methyl-2-pyrrolidone. 如申請專利範圍第1項所述的鍍覆鋼板的端面防鏽處理液，其中相對於所述氟樹脂的總質量，所述氟樹脂包含6質量%以上的氟原子。 The antirust treatment solution for the end surface of a plated steel sheet according to claim 1, wherein the fluororesin contains 6% by mass or more of fluorine atoms relative to the total mass of the fluororesin. 如申請專利範圍第1項或第2項所述的鍍覆鋼板的端面防鏽處理液，其中所述含有第4族元素的化合物或第4族元素的離子的含量以金屬原子換算計為2g/L以上。 The antirust treatment solution for the end surface of plated steel sheet as described in item 1 or item 2 of the scope of application, wherein the content of the compound containing the group 4 element or the ion of the group 4 element is 2 g in terms of metal atoms /L above. 如申請專利範圍第1項或第2項所述的鍍覆鋼板的端面防鏽處理液，其中所述黏結促進劑的含量為0.5g/L以上且50g/L以下。 The anti-rust treatment solution for the end surface of plated steel sheet as described in item 1 or item 2 of the scope of the patent application, wherein the content of the adhesion promoter is not less than 0.5 g/L and not more than 50 g/L. 如申請專利範圍第1項或第2項所述的鍍覆鋼板的端面防鏽處理液，其中所述蝕刻劑為選自由磷酸及磷酸鹽、以及氨及銨鹽所組成的群組中的蝕刻劑。 The anti-rust treatment solution for the end surface of plated steel plate as described in item 1 or item 2 of the scope of application, wherein the etchant is an etchant selected from the group consisting of phosphoric acid and phosphate, and ammonia and ammonium salt agent. 如申請專利範圍第5項所述的鍍覆鋼板的端面防鏽處 理液，其中所述蝕刻劑包含磷酸或磷酸鹽、以及氨或銨鹽中的任一者。 Anti-rust part of the end face of the plated steel plate as described in item 5 of the scope of the patent application Liquid management, wherein the etchant comprises any one of phosphoric acid or phosphate salts, and ammonia or ammonium salts. 如申請專利範圍第6項所述的鍍覆鋼板的端面防鏽處理液，其中所述磷酸或磷酸鹽的含量以磷酸根陰離子PO4 3-換算計為1g/L以上，且所述氨或銨鹽的含量以四級銨陽離子NH4 +換算計為1g/L以上。 The end surface antirust treatment solution for plated steel sheets as described in item 6 of the patent scope of the application, wherein the content of phosphoric acid or phosphate is calculated as 1 g/L or more in terms of phosphate anion PO 4 3- , and the ammonia or The content of the ammonium salt is more than 1 g/L in terms of quaternary ammonium cation NH 4 + . 如申請專利範圍第1項或第2項所述的鍍覆鋼板的端面防鏽處理液，其中固體成分的含量為20%以上。 The antirust treatment solution for the end surface of plated steel sheet as described in item 1 or item 2 of the scope of the patent application, wherein the solid content is more than 20%. 如申請專利範圍第1項或第2項所述的鍍覆鋼板的端面防鏽處理液，其中pH為7.0以上且9.5以下。 The antirust treatment solution for the end surface of plated steel sheet as described in claim 1 or claim 2, wherein the pH is not less than 7.0 and not more than 9.5. 一種鍍覆鋼板的端面的化學轉化處理方法，其包括在鍍覆鋼板的端面賦予如申請專利範圍第1項或第2項所述的鍍覆鋼板的端面防鏽處理液的步驟。 A chemical conversion treatment method for the end face of a plated steel plate, which includes the step of applying the end face antirust treatment liquid of the plated steel plate as described in item 1 or item 2 of the scope of application to the end face of the plated steel plate. 如申請專利範圍第10項所述的鍍覆鋼板的端面的化學轉化處理方法，其中所述端面防鏽處理液被賦予至所述鍍敷鋼板的端面的、基材鋼板露出的部位。 The chemical conversion treatment method for the end surface of a plated steel sheet as described in claim 10, wherein the end surface antirust treatment liquid is applied to the exposed portion of the base steel plate on the end surface of the plated steel sheet. 一種化學轉化處理鋼板，其具有：鍍敷鋼板、以及形成於所述鍍敷鋼板的端面的化學轉化處理皮膜，並且所述化學轉化處理皮膜包含：含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子、 選自由己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物、及n-甲基-2-吡咯啶酮所組成的群組中的一種以上的黏結促進劑、以及矽烷偶合劑。 A chemical conversion treated steel sheet comprising: a plated steel sheet, and a chemical conversion treatment film formed on an end surface of the plated steel sheet, wherein the chemical conversion treatment film includes: an organic resin containing a fluororesin, an organic resin containing a group 4 element compounds or ions of group 4 elements, One or more adhesion promoters selected from the group consisting of an ester compound of adipic acid or phthalic acid and an alcohol having 1 to 3 carbon atoms, and n-methyl-2-pyrrolidone, and Silane coupling agent. 如申請專利範圍第12項所述的化學轉化處理鋼板，其中所述化學轉化處理皮膜以被覆所述鍍敷鋼板的端面的、基材鋼板露出的部位的方式形成。 The chemical conversion treated steel sheet according to claim 12, wherein the chemical conversion treatment film is formed to cover the exposed portion of the base steel sheet on the end surface of the plated steel sheet. 一種成形加工品，其藉由鍍敷鋼板的成形加工製作而成，並且所述成形加工品包含形成於所述鍍敷鋼板的端面的化學轉化處理皮膜，所述化學轉化處理皮膜包含：含有氟樹脂的有機樹脂、含有第4族元素的化合物或第4族元素的離子、選自由己二酸或鄰苯二甲酸與碳數1以上且3以下的醇的酯化合物及n-甲基-2-吡咯啶酮所組成的群組中的一種以上的黏結促進劑、以及矽烷偶合劑。 A formed product produced by forming a plated steel sheet, wherein the formed product includes a chemical conversion treatment film formed on an end surface of the plated steel plate, and the chemical conversion treatment film contains: Organic resins of resins, compounds containing group 4 elements or ions of group 4 elements, ester compounds selected from adipic acid or phthalic acid and alcohols having 1 to 3 carbon atoms, and n-methyl-2 - one or more adhesion promoters and silane coupling agents from the group consisting of pyrrolidone.
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