(19)
(11)EP 3 239 355 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
06.05.2020 Bulletin 2020/19

(21)Application number: 15873271.9

(22)Date of filing:  25.12.2015
(51)Int. Cl.: 
C23C 22/34  (2006.01)
C23C 22/53  (2006.01)
C23C 22/46  (2006.01)
C23C 22/78  (2006.01)
(86)International application number:
PCT/JP2015/086229
(87)International publication number:
WO 2016/104703 (30.06.2016 Gazette  2016/26)

(54)

TRIVALENT CHROMIUM CHEMICAL CONVERSION LIQUID FOR ZINC OR ZINC ALLOY BASES

AUF DREIWERTIGEM CHROM BASIERENDE CHEMISCHE UMWANDLUNGSFLÜSSIGKEIT FÜR ZINK- ODER ZINKLEGIERUNGSGRUNDSTOFFE

LIQUIDE DE CONVERSION CHIMIQUE À BASE DE CHROME TRIVALENT POUR BASES DE ZINC OU D'ALLIAGE DE ZINC


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 26.12.2014 JP 2014266254

(43)Date of publication of application:
01.11.2017 Bulletin 2017/44

(73)Proprietor: Dipsol Chemicals Co., Ltd.
Chuo-ku Tokyo 1040028 (JP)

(72)Inventors:
  • SAITO Ayumi
    Nagareyama-shi Chiba 270-0121 (JP)
  • ISHIKAWA Masatoshi
    Nagareyama-shi Chiba 270-0121 (JP)
  • KOIKE Takashi
    Nagareyama-shi Chiba 270-0121 (JP)

(74)Representative: Carpmaels & Ransford LLP 
One Southampton Row
London WC1B 5HA
London WC1B 5HA (GB)


(56)References cited: : 
JP-A- 2006 316 334
JP-A- 2012 036 469
JP-A- 2012 528 251
US-A1- 2006 240 191
JP-A- 2006 316 334
JP-A- 2012 036 469
US-A1- 2002 053 301
US-B1- 6 375 726
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to a novel chemical conversion treatment solution for imparting an excellent corrosion resistance to a zinc- or zinc alloy-metal surface, and a method for chemical conversion treatment using the solution.

    Background Art



    [0002] A chemical conversion treatment is a technique having been utilized from the past to impart a corrosion resistance to metal surfaces. At present also, this technique is used in the surface treatments for aircrafts, construction materials, automotive parts, and so forth. Meanwhile, a coating obtained by a chemical conversion treatment represented by chromic acid/chromate chemical conversion treatment partially contains harmful hexavalent chromium.

    [0003] Hexavalent chromium is restricted by the WEEE (Waste Electrical and Electronic Equipment) Directive, the RoHS (Restriction of Hazardous Substances) Directive, the ELV (End of Life Vehicles) Directive, and so forth. Chemical conversion treatment solutions using trivalent chromium instead of hexavalent chromium are actively studied for the industrialization.

    [0004] Nevertheless, a trivalent chromium chemical conversion treatment solution for a zinc or zinc alloy substrate is generally supplemented with a cobalt compound to enhance the corrosion resistance.

    [0005] Cobalt is one of what is called a rare metal. It cannot necessarily be said that the cobalt supply system stable because the usage and application of cobalt are increasing or the countries where cobalt is produced are limited, for example. Moreover, cobalt chloride, cobalt sulfate, cobalt nitrate, and cobalt carbonate are listed as SVHCs (Substances of Very High Concern) in REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) regulation. The uses of these compounds are likely to be restricted.

    [0006] Meanwhile, as environmentally-friendly chemical conversion treatment solutions for a zinc or zinc alloy substrate, several chromium-free chemical conversion treatment solutions have been reported. For example, there have been known: a treatment agent containing a compound selected from zirconium and titanium, a compound selected from vanadium, molybdenum, and tungsten, and further an inorganic phosphorus compound (Japanese Patent Application Publication No. 2010-150626); and a fluorine- and chromium-free chemical conversion treatment agent containing a compound selected from water-soluble titanium compounds and water-soluble zirconium compounds, and an organic compound having functional groups (International Publication No. WO2011/002040).

    [0007] However, such chromium-free chemical conversion treatment agents are inferior to conventional cobalt-containing chemical conversion treatment agents for zinc or zinc alloys in chemical conversion treatment coating performances such as corrosion resistance. An improvement in this respect has been desired.

    [0008] US 2002/053301 discloses an aqueous composition for post-treating metal coated substrates comprising an acidic aqueous solution having a pH ranging from about 2.5 to 4.5 containing trivalent chromium salts, an alkali metal hexafluorozirconate, at least one alkali metal fluoro-compound, and water soluble thickeners and/or surfactants.

    [0009] US 2006/240191 discloses an acidic aqueous solution for treating metal substrates which comprises water soluble trivalent chromium compounds, fluorozirconates, fluorometallic compounds, zinc compounds, thickeners, surfactants, and at least about 0.001 mole per liter of the acidic solution of at least one polyhydroxy and/or carboxylic compound as the stabilizing agent for the aqueous solution.

    [0010] US 6,375,726 discloses the treatment of aluminum substrates with an acidic aqueous solution containing at least one trivalent chromium salt such as a trivalent chromium sulfate, at least one alkali metal hexafluorazirconate such as potassium hexafluorozirconate in combination with at least one water soluble or dispersible thickening agent such as a cellulose compound and at least one water soluble surfactant.

    [0011] JP2012036469 (A) discloses a protective film formed of a liquid composition containing (A) trivalent chromium, (B) zirconium, (C) one or more selected from groups consisting of chlorine ions, sulfate ions and nitrate ions, (D) aromatic sulfonic acid, and (E) fluorine ions.

    [0012] JP2006316334 (A) discloses a hexavalent chrome-free chemical conversion treatment liquid containing a trivalent chromium compound, a zirconium compound and a dicarboxylic acid.

    Summary of Invention



    [0013] In view of the circumstances as described above, an object of the present invention is to provide a chemical conversion treatment solution for a zinc or zinc alloy substrate as defined in the claims, the solution containing substantially no cobalt compound and being excellent in corrosion resistance and capable of forming a chemical conversion coating while taking the environment also into consideration.

    [0014] The present inventors have intensively studied a chemical conversion treatment solution which is excellent in corrosion resistance without incorporating hexavalent chromium ions and cobalt ions, and which is capable of forming a chemical conversion coating while taking the environment also into consideration. As a result, the inventors have found out that the above object is achieved by a chemical conversion treatment solution containing both zirconium ions and trivalent chromium ions, and further containing fluorine ions and water-soluble carboxylic acids or salts thereof. This finding has led to the completion of the present invention. Specifically, the present invention provides a chemical conversion treatment solution for a zinc or zinc alloy substrate, the solution comprising:

    2 to 200 mmol/L of trivalent chromium ions;

    1 to 300 mmol/L of zirconium ions;

    fluorine ions; and

    1 g/L - 5 g/L of water-soluble carboxylic acids or salts thereof, wherein the water soluble dicarboxylic acids or salts thereof comprise oxalic acid or salts thereof, or combinations of oxalic acid or salts thereof and malonic acid or salts thereof,

    wherein the solution comprises fluorozirconic acid for providing the zirconium ions and the fluorine ions and wherein the solution does not comprise Co ions and hexavalent chromium ions.



    [0015] Moreover, the present invention provides a chemical conversion treatment method for a zinc or zinc alloy substrate, the method comprising bringing the chemical conversion treatment solution into contact with a zinc or zinc alloy substrate.

    [0016] Also described is a chemical conversion treatment coating formed from the chemical conversion treatment solution, the coating comprising trivalent chromium and zirconium but not comprising hexavalent chromium and cobalt.

    [0017] The present invention makes it possible to provide a chemical conversion treatment solution for a zinc or zinc alloy substrate, the solution not containing hexavalent chromium and cobalt but being excellent in corrosion resistance and capable of forming a chemical conversion coating while taking the environment also into consideration.

    Description of Embodiments



    [0018] A substrate used in the present invention includes substrates of metals and alloys such as various metals including iron, nickel, and copper, alloys thereof, and aluminum subjected to a zincate conversion treatment, which are in various shapes such as plate, cuboid, solid cylinder, hollow cylinder, or sphere.

    [0019] The substrate is plated with zinc and a zinc alloy in a usual manner. To deposit zinc plating on the substrate, it is possible to use any one of acidic or neutral baths such as a sulfuric acid bath, a fluoborate bath, a potassium chloride bath, a sodium chloride bath, and an ammonium chloride eclectic bath; and alkaline baths such as a cyanide bath, a zincate bath, and a pyrophosphate bath. Especially, a zincate bath is preferable. Moreover, the zinc alloy plating may be conducted by using any alkaline bath such as an ammonium chloride bath or an organic chelate bath.

    [0020] In addition, the zinc alloy plating includes zinc-iron alloy plating, zinc-nickel alloy plating, zinc-cobalt alloy plating, tin-zinc alloy plating, and the like. Zinc-iron alloy plating is preferable. The zinc or zinc alloy plating may be deposited on the substrate to any thickness, but the thickness should be 1 µm or more, preferably 5 to 25 µm.

    [0021] In the present invention, after the zinc or zinc alloy plating is deposited on the substrate as described above, the resultant is optionally subjected as appropriate to a pretreatment, for example, washing with water, or washing with water and then activation treatment with nitric acid. Then, a chemical conversion treatment is conducted by a method, for example, such as an immersion treatment, using a chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention.

    [0022] The chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention contains 2 to 200 mmol/L of trivalent chromium ions, 1 to 300 mmol/L of zirconium ions, and fluorine ions and water-soluble carboxylic acids or salts thereof as defined in the claims, but does not contain Co ions and hexavalent chromium ions.

    [0023] The type of a trivalent chromium compound for providing the trivalent chromium ions is not particularly limited, but the trivalent chromium compound is preferably water soluble. Examples of the trivalent chromium compound include Cr(NO3)3·9H2O, Cr(CH3COO)3, Cr2(SO4)3.18H2O, CrK(SO4)2.12H2O, and the like. These trivalent chromium compounds may be used alone, or two or more thereof may be used in combination. The content of the trivalent chromium ions is 2 to 200 mmol/L, preferably 5 to 100 mmol/L, and more preferably 10 to 80 mmol/L. When the content of the trivalent chromium ions is within such ranges, an excellent corrosion resistance can be obtained.

    [0024] The zirconium compound for providing the zirconium ions is zirconium hydrofluoric acid (H2ZrF6). The content of the zirconium ions is 1 to 300 mmol/L, preferably 5 to 150 mmol/L, and more preferably 10 to 100 mmol/L. When the content of the zirconium ions is within such ranges, an excellent corrosion resistance can be obtained.

    [0025] A molar ratio between the trivalent chromium ions and the zirconium ions (trivalent chromium ions/zirconium ions) is preferably 2. 5 or less, more preferably 0.1 to 2.5, furthermore preferably 0.2 to 2.1, and most preferably 0.3 to 2.0. When the molar ratio between the trivalent chromium ions and the zirconium ions is within such ranges, an excellent corrosion resistance can be obtained.

    [0026] The chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention further contains fluorine ions and water-soluble carboxylic acids or salts thereof as defined in the claims.

    [0027] The fluorine-containing compound for providing the fluorine ions is hexafluorozirconic acid. The content of the fluorine ions is preferably 5 to 500 mmol/L, and more preferably 60 to 300 mmol/L. The fluorine ions serve as counterions of the zirconium ions. When the content of the fluorine ions is within such ranges, the zirconium ions can be stabilized.

    [0028] The water-soluble carboxylic acids or salts thereof comprise oxalic acid or salts thereof, or combinations of oxalic acid or salts thereof and malonic acid or salts thereof. Further water-soluble carboxylic acids include dicarboxylic acids which can be represented by R1-(COOH)2[R1=C0 to C8] such as succinic acid, glutaric acid, adipic acid, and suberic acid. Examples of the salts of the water-soluble carboxylic acids include salts of alkali metals such as potassium and sodium, salts of alkaline earth metals such as calcium and magnesium, ammonium salts, and the like. These water-soluble carboxylic acids or salts may be used alone, or two or more thereof may be used in combination. The content of the water-soluble carboxylic acid (s) or the salt (s) is 1 g/L to 5 g/L. When the content of the water-soluble carboxylic acid (s) or the salt (s) is within such ranges, Cr3+ can be stabilized through the complex formation with the chromium ions.

    [0029] The chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention contains the water-soluble zirconium compound and the fluorine-containing compound in the form of fluorozirconic acid.

    [0030] The chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention may further contain one or more selected from the group consisting of: i) water-soluble metal salts each containing a metal selected from the group consisting of Al, Ti, Mo, V, Ce and W; ii) Si compounds; and iii) phosphorus compounds.

    [0031] Examples of the water-soluble metal salts include K2TiF6, and the like. These water-soluble metal salts may be used alone, or two or more thereof may be used in combination. The content of the water-soluble metal salt (s) is preferably 0.1 g/L to 1.5 g/L, and more preferably 0.2 g/L to 1.0 g/L.

    [0032] Examples of the Si compounds include SiO2 (colloidal silica), and the like. These Si compounds may be used alone, or two or more thereof may be used in combination. The content of the Si compound(s) is preferably 0.1 g/L to 10 g/L, more preferably 0.5 g/L to 5.0 g/L, and furthermore preferably 1.0 g/L to 3.0 g/L.

    [0033] Examples of the phosphorus compounds include NaH2PO2 (sodium hypophosphite), and the like. These phosphorus compounds may be used alone, or two or more thereof may be used in combination. The content of the phosphorus compound(s) is preferably 0.01 g/L to 1.0 g/L, and more preferably 0.1 g/L to 0.5 g/L.

    [0034] The chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention has a pH preferably within a range of 1 to 6, and more preferably within a range of 1.5 to 4.

    [0035] The balance of the chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention other than the above-described components is water.

    [0036] In a method for forming a trivalent chromium chemical conversion coating on the zinc or zinc alloy plating by using the chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention, a substrate plated with zinc or a zinc alloy is generally immersed in the chemical conversion treatment solution. In the event of the immersion, the temperature of the chemical conversion treatment solution is preferably 20 to 60°C, and more preferably 30 to 40°C. The immersion time is preferably 5 to 600 seconds, and more preferably 30 to 300 seconds. Note that, to activate the zinc- or zinc alloy-plated surface, the substrate may be immersed in a diluted nitric acid solution (such as 5% nitric acid), a diluted sulfuric acid solution, a diluted hydrochloric acid solution, a diluted hydrofluoric acid solution, or the like before the trivalent chromium chemical conversion treatment. Conditions and treatment operations other than those described above may follow conventional methods for hexavalent chromate conversion treatment.

    [0037] The trivalent chromium chemical conversion coating thus formed on the zinc or zinc alloy plating by using the chemical conversion treatment solution for a zinc or zinc alloy substrate of the present invention contains trivalent chromium and zirconium, but does not contain hexavalent chromium and cobalt. In the trivalent chromium chemical conversion coating, the proportion of zirconium (Zr/(Cr+Zr)) is preferably 60 to 90% by weight.

    [0038] Next, the present invention will be described based on Examples and Comparative Examples. However, the present invention is not limited to Examples.

    [Examples]



    [0039] As test pieces, 0.5 mm × 50 mm × 70 mm SPCC steel plates were used, and the surfaces were subjected to zincate/zinc plating. The zinc platings had film thicknesses of 9 to 10 micrometers.

    [0040] The zinc plated test pieces were immersed in an aqueous solution of 5% nitric acid at normal temperature for 10 seconds, and then the test pieces were sufficiently rinsed with running tap water to clean the surfaces. Additionally, alkaline immersion, washing with hot water, or the like may be conducted depending on the surface states of the test pieces.

    [0041] The methods for conducting a chemical conversion treatment are described in Examples and Comparative Examples below.

    [0042] After the chemical conversion treatment, the test pieces were sufficiently washed with tap water and ion-exchanged water, then left standing for 10 minutes in an electric drying furnace kept at 80°C, and dried.

    [0043] The chemical conversion coatings were evaluated for the appearances in terms of color tone and uniformity.

    Favorable = appearance with even color tone of pale blue to pale yellow, and with glossiness and uniformity

    Fair = appearance with somewhat uneven color tone of pale blue to pale yellow, and with less uniformity

    Poor = appearance with color tone outside the range of pale blue to pale yellow, and/or with no uniformity and less glossiness.



    [0044] After the chemical conversion treatment, the test pieces were subjected to a salt spray test (hereinafter SST) in accordance with JIS Z-2371, and evaluated for the corrosion resistances according to the area of white rust formed after 72 hours, 120 hours, and 240 hours. The test results were categorized into four groups and evaluated: o = no white rust was formed; Δ = white rust accounted for less than 5%; ▲ = white rust accounted for 5% or more; and × = red rust was formed. 1. Metal Concentration Evaluation

    (Example 1)



    [0045] As shown below, a chemical conversion treatment solution was prepared, and a caustic soda solution was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 5.2 g/L (Zr was 10 mmol/L)
    3. (C) Oxalic acid: 1.4 g/L (15 mmol/L)
      Malonic acid: 1.6 g/L (15 mmol/L)
    The balance is water.

    (Example 2)



    [0046] As shown below, a chemical conversion treatment solution was prepared, and a caustic soda solution was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 10.4 g/L (Zr was 20 mmol/L)
    3. (C) Oxalic acid: 1.4 g/L (15 mmol/L)
      Malonic acid: 1.6 g/L (15 mmol/L)
    The balance is water.

    (Example 3)



    [0047] As shown below, a chemical conversion treatment solution was prepared, and a caustic soda solution was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 15.6 g/L (Zr was 30 mmol/L)
    3. (C) Oxalic acid: 1.4 g/L (15 mmol/L)
      Malonic acid: 1.6 g/L (15 mmol/L)
    The balance is water.

    (Example 4)



    [0048] As shown below, a chemical conversion treatment solution was prepared, and a caustic soda solution was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 26 g/L (Zr was 50 mmol/L)
    3. (C) Oxalic acid: 1.4 g/L (15 mmol/L)
      Malonic acid: 1.6 g/L (15 mmol/L)
    The balance is water.

    (Comparative Example 5)



    [0049] As shown below, a chemical conversion treatment solution was prepared, and 62% nitric acid was used to make the pH = 4.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 3 g/L (Cr was 5 mmol/L)
    2. (B) Fluorozirconic acid: 5.2 g/L (Zr was 10 mmol/L)
    The balance is water.

    (Comparative Example 6)



    [0050] As shown below, a chemical conversion treatment solution was prepared, and 62% nitric acid was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Ammonium zirconium carbonate solution (ZrO2 20%: 6.2 g/L (Zr was 10 mmol/L)
    3. (C) 50% Lactic acid: 3.6 g/L (lactic acid was 20 mmol/L) The balance is water.

    (Comparative Example 1)



    [0051] As shown below, a chemical conversion treatment solution was prepared, and a caustic soda solution was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 48 g/L (Cr was 80 mmol/L)
    2. (B) Cobalt nitrate: Co was 1.0 g/L
    3. (C) Oxalic acid: 1.4 g/L (15 mmol/L)
      Malonic acid: 1.6 g/L (15 mmol/L)
    The balance is water.

    (Comparative Example 2)



    [0052] As shown below, a chemical conversion treatment solution was prepared, and a caustic soda solution was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 24 g/L (Cr was 40 mmol/L)
    2. (B) Cobalt nitrate: Co was 1.0 g/L
    3. (C) Oxalic acid: 1.4 g/L (15 mmol/L)
      Malonic acid: 1.6 g/L (15 mmol/L)
    The balance is water.

    [0053] Table 1 summarizes the composition of each treatment solution in Examples 1 to 6 and Comparative Examples 1 and 2. Table 2 shows the evaluation results. Table 3 shows the trivalent chromium and zirconium contents in the coating.
    Table 1: Treatment solution composition
     Treatment solution composition (mmol/L)Cr3+/Zr4+ molar ratioDicarboxylic acid (g/L)
    Cr3+Zr4+F-Co2+
    Example 1 20 10 60 - 2.0 oxalic acid 1.4 + malonic acid 1.6
    Example 2 20 20 120 - 1.0
    Example 3 20 30 180 - 0.6
    Example 4 20 50 300 - 0.4
    Comparative Example 5 5 10 60 - 0.5 -
    Comparative Example 6 20 10 - - 2.0
    Comparative Example 1 80 - - 20 - oxalic acid 1.4 + malonic acid 1.6
    Comparative Example 2 40 - - 20 -
    Table 2: Corrosion resistance evaluation result
     AppearanceGeneral corrosion resistance
    72 h120 h240 h
    Example 1 favorable
    Example 2 favorable
    Example 3 favorable
    Example 4 favorable
    Comparative Example 5 favorable Δ Δ
    Comparative Example 6 favorable Δ Δ
    Comparative Example 1 favorable
    Comparative Example 2 favorable Δ
    Table 3: Trivalent chromium and zirconium contents in the coating
     Cr (mg/dm2)Zr (mg/dm2)Zr/(Cr+Zr)
    Example 1 0.33 0.54 0.62
    Example 2 0.34 0.66 0.66
    Example 3 0.34 0.73 0.68
    Example 4 0.34 0.88 0.72
    Comparative Example 5 0.34 0.88 0.72
    Comparative Example 6 0.34 0.88 0.72


    [0054] From the result in Table 2, Examples 1 to 6 successfully formed coatings having performances equivalent to those in Comparative Examples 1 and 2 containing cobalt.

    2. Dicarboxylic Acid Evaluation


    (Example 7)



    [0055] As shown below, a chemical conversion treatment solution was prepared, and an aqueous solution of caustic soda was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 10.4 g/L (Zr was 20 mmol/L)
    3. (C) Oxalic acid: 1.8 g/L (20 mmol/L)
    The balance is water.

    (Comparative Example 8)



    [0056] As shown below, a chemical conversion treatment solution was prepared, and an aqueous solution of caustic soda was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 10.4 g/L (Zr was 20 mmol/L)
    3. (C) Malonic acid: 2.0 g/L (20 mmol/L)
    The balance is water.

    (Comparative Example 9)



    [0057] As shown below, a chemical conversion treatment solution was prepared, and an aqueous solution of caustic soda was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 10.4 g/L (Zr was 20 mmol/L)
    3. (C) Succinic acid: 2.4 g/L (20 mmol/L)
    The balance is water.

    (Comparative Example 10)



    [0058] As shown below, a chemical conversion treatment solution was prepared, and an aqueous solution of caustic soda was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 10.4 g/L (Zr was 20 mmol/L)
    3. (C) Glutaric acid: 2.7 g/L (20 mmol/L)
    The balance is water.

    (Comparative Example 11)



    [0059] As shown below, a chemical conversion treatment solution was prepared, and an aqueous solution of caustic soda was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 10.4 g/L (Zr was 20 mmol/L)
    3. (C) Adipic acid: 3.0 g/L (20 mmol/L)
    The balance is water.

    (Comparative Example 12)



    [0060] As shown below, a chemical conversion treatment solution was prepared, and an aqueous solution of caustic soda was used to make the pH = 2.0. Then, the above-described test pieces were subjected to the immersion treatment at 30°C for 40 seconds.
    1. (A) 40% Chromium nitrate: 12 g/L (Cr was 20 mmol/L)
    2. (B) Fluorozirconic acid: 10.4 g/L (Zr was 20 mmol/L)
    3. (C) Suberic acid: 3.5 g/L (20 mmol/L)
    The balance is water.

    [0061] Table 4 summarizes the composition of each treatment solution in Examples 7 to 12. Table 5 shows the evaluation results.
    Table 4: Treatment solution composition
     Treatment solution composition (mmol/L)Cr3+/Zr4+ molar ratioDicarboxylic acid (20 mmoL/L)
    Cr3+Zr4+F-Co2+
    Example 7 20 20 120 - 1.0 oxalic acid
    Comparative Example 8 20 20 120 - 1.0 malonic acid
    Comparative Example 9 20 20 120 - 1.0 succinic acid
    Comparative Example 10 20 20 120 - 1.0 glutaric acid
    Comparative Example 11 20 20 120 - 1.0 adipic acid
    Comparative Example 12 20 20 120 - 1.0 suberic acid
    Table 5: Corrosion resistance evaluation result
     AppearanceGeneral corrosion resistance
    72 h120 h240 h
    Example 7 favorable
    Comparative Example 8 favorable
    Comparative Example 9 favorable Δ Δ
    Comparative Example 10 favorable Δ Δ
    Comparative Example 11 favorable Δ Δ
    Comparative Example 12 favorable Δ


    [0062] From the above, it was demonstrated that when oxalic acid CO - (COOH)2 and malonic acid C1 - (COOH)2 were used, the corrosion resistances were particularly favorable.


    Claims

    1. A chemical conversion treatment solution for a zinc or zinc alloy substrate, the solution comprising:

    2 to 200 mmol/L of trivalent chromium ions;

    1 to 300 mmol/L of zirconium ions;

    fluorine ions; and

    1 g/L - 5 g/L of water-soluble dicarboxylic acids or salts thereof,

    wherein the solution comprises fluorozirconic acid for providing the zirconium ions and the fluorine ions and wherein the solution does not comprise Co ions and hexavalent chromium ions;

    characterised in that the water soluble dicarboxylic acids or salts thereof comprise oxalic acid or salts thereof, or combinations of oxalic acid or salts thereof and malonic acid or salts thereof.


     
    2. The chemical conversion treatment solution according to claim 1, wherein a molar ratio of the trivalent chromium ions to the zirconium ions (trivalent chromium ions/zirconium ions) is 2.5 or less.
     
    3. The chemical conversion treatment solution according to claim 1 or 2, wherein a further zirconium compound for providing the zirconium ions is an inorganic zirconium compound or a salt thereof, or an organic zirconium compound.
     
    4. The chemical conversion treatment solution according to any one of claims 1 to 3, further comprising one or more selected from the group consisting of:

    i) water-soluble metal salts each containing a metal selected from the group consisting of Al, Ti, Mo, V, Ce and W;

    ii) Si compounds; and

    iii) phosphorus compounds.


     
    5.  A method for chemical conversion treating a zinc or zinc alloy substrate, the method comprising bringing the chemical conversion treatment solution according to any one of claims 1 to 4 into contact with a zinc or zinc alloy substrate.
     


    Ansprüche

    1. Behandlungslösung für die chemische Konversion für ein Zink- oder Zinklegierungssubstrat, wobei die Lösung Folgendes umfasst:

    2 bis 200 mmol/L dreiwertige Chromionen,

    1 bis 300 mmol/L Zirconiumionen,

    Fluorionen und

    1 g/L - 5 g/L wasserlösliche Dicarbonsäuren oder Salze davon,

    wobei die Lösung Fluorozirconiumsäure zur Bereitstellung der Zirconiumionen und der Fluorionen umfasst und wobei die Lösung keine Co-Ionen und sechswertigen Chromionen umfasst;

    dadurch gekennzeichnet, dass die wasserlöslichen Dicarbonsäuren oder Salze davon Oxalsäure oder Salze davon oder Kombinationen von Oxalsäure oder Salzen davon und Malonsäure oder Salzen davon umfassen.


     
    2. Behandlungslösung für die chemische Konversion nach Anspruch 1, wobei das Molverhältnis von dreiwertigen Chromionen zu Zirconiumionen (dreiwertige Chromionen/Zirconiumionen) 2,5 oder weniger beträgt.
     
    3. Behandlungslösung für die chemische Konversion nach Anspruch 1 oder 2, wobei es sich bei einer weiteren Zirconiumverbindung zur Bereitstellung der Zirconiumionen um eine anorganische Zirconiumverbindung oder ein Salz davon oder eine organische Zirconiumverbindung handelt.
     
    4. Behandlungslösung für die chemische Konversion nach einem der Ansprüche 1 bis 3, ferner umfassend eines oder mehrere aus der Gruppe bestehend aus:

    i) wasserlöslichen Metallsalzen, die jeweils ein Metall aus der Gruppe bestehend aus Al, Ti, Mo, V, Ce und W enthalten,

    ii) Si-Verbindungen und

    iii) Phosphorverbindungen.


     
    5. Verfahren zur Behandlung eines Zink- oder Zinklegierungssubstrats zur chemischen Konversion, bei dem man die Behandlungslösung für die chemische Konversation nach einem der Ansprüche 1 bis 4 mit einem Zink- oder Zinklegierungssubstrat in Kontakt bringt.
     


    Revendications

    1. Solution de traitement de conversion chimique pour un substrat de zinc ou d'alliage de zinc, la solution comprenant :

    2 à 200 mmol/L d'ions chrome trivalents ;

    1 à 300 mmol/L d'ions zirconium ;

    des ions fluor ; et

    1 g/L à 5 g/L d'acides dicarboxyliques solubles dans l'eau ou des sels correspondants,

    la solution comprenant de l'acide fluorozirconique pour la fourniture des ions zirconium et des ions fluor et la solution ne comprenant pas d'ions Co ni d'ions chrome hexavalents ;

    caractérisée en ce que les acides dicarboxyliques solubles dans l'eau ou les sels correspondants comprennent de l'acide oxalique ou des sels correspondants, ou des combinaisons d'acide oxalique ou de sels correspondants et d'acide malonique ou de sels correspondants.


     
    2. Solution de traitement de conversion chimique selon la revendication 1, un rapport molaire des ions chrome trivalents aux ions zirconium (ions chrome trivalents/ions zirconium) étant de 2,5 ou moins.
     
    3. Solution de traitement de conversion chimique selon la revendication 1 ou 2, un composé de zirconium supplémentaire pour la fourniture des ions zirconium étant un composé inorganique de zirconium ou un sel correspondant, ou un composé organique de zirconium.
     
    4. Solution de traitement de conversion chimique selon l'une quelconque des revendications 1 à 3, comprenant en outre l'un ou plusieurs choisis dans le groupe constitué par :

    i) des sels métalliques solubles dans l'eau, chacun contenant un métal choisi dans le groupe constitué par Al, Ti, Mo, V, Ce et W ;

    ii) des composés de Si ; et

    iii) des composés de phosphore.


     
    5. Procédé pour un traitement de conversion chimique d'un substrat de zinc ou d'alliage de zinc, le procédé comprenant la mise en contact de la solution de traitement de conversion chimique selon l'une quelconque des revendications 1 à 4 avec un substrat de zinc ou d'alliage de zinc.
     




    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description