Metal Surface Treatment Agent, Metal Surface Treatment Method, and Metal Material

Abstract

The present invention addresses a problem of providing, for example, a metal surface treatment agent capable of forming a coating film that exhibits good corrosion resistance at edges, such as cut portions, of a coated metal material. The problem is solved by a metal surface treatment agent comprising: an ion (A) containing at least one kind of metal selected from zirconium, titanium and hafnium at a metal-equivalent molar concentration of 0.1 mmol/L or higher; and an aqueous urethane resin (B) having a weight-average molecular weight of 50,000 or higher at a solid mass concentration of 0.5 to 10 g/L, in which the ratio of a solid mass (B.sub.M) of the resin (B) to a metal-equivalent mass (A.sub.M) of the ion (A), [B.sub.M/A.sub.M], is 0.7 or higher.

Claims

1. A metal surface treatment agent, comprising: an ion (A) comprising at least one kind of metal selected from zirconium, titanium and hafnium at a metal-equivalent molar concentration of 0.1 mmol/L or higher; and an aqueous urethane resin (B) having a weight-average molecular weight of 50,000 or higher at a solid mass concentration of 0.5 to 10 g/L, wherein the ratio of a solid mass (B.sub.M) of the resin (B) to a metal-equivalent mass (A.sub.M) of the ion (A), [B.sub.M/A.sub.M] is 0.7 or higher.

2. The metal surface treatment agent according to claim 1, further comprising at least one kind of metal (C) selected from aluminum, magnesium, zinc, and iron.

3. The metal surface treatment agent according to claim 1, further comprising at least one kind of acid radical (E) selected from a nitric acid radical, a sulfuric acid radical, a formic acid radical, an acetic acid radical, and an alkanesulfonic acid radical.

4. A metal surface treatment method, comprising the step of bringing the metal surface treatment agent according to claim 1 into contact with a metal surface.

5. A metal material, having a surface treatment coating layer formed on/over a surface of the metal material by the surface treatment method according to claim 4.

Description

EXAMPLES

[0125] The present invention will now be described in more detail by way of Examples and Comparative Examples thereof. It is noted here, however, that the present invention is not restricted to the below-described Examples.

[Preparation of Test Pieces]

<Metal Material>

[0126] As a metal material, a cold-rolled mild steel sheet specified in JIS G3141 (SPCC: thickness=0.8 mm) or a hot-dip zinc-coated steel sheet defined in JIS G3302 (SGCC: thickness=0.8 mm) was used. The metal material was cut into a size of 70 mm in length×150 mm in width. The below-described evaluations of each test piece were performed on a surface having burrs generated by the cutting. The burr's height was about 100 μm.

Synthesis of Resins

Synthesis Example 1

[0127] First, 100 g of a bisphenol A-polyoxyethylene 2-mol adduct (NEWPOL BPE-20T, manufactured by Sanyo Chemical Industries, Ltd.; the below-described b2-1), 105 g of a polyethylene glycol (PEG1000, manufactured by DKS Co., Ltd.; the below-described b3-1), 15 g of trimethylolpropane (TMP, manufactured by Perstorp Holding AB; the below-described b4-1), 30 g of N-methyldiethanolamine (aminoalcohol MDA, manufactured by Nippon Nyukazai Co., Ltd.; the below-described b5-1), and 250 g of dicyclohexylmethane-4,4′-diisocyanate (DESMODUR W, manufactured by Bayer AG; the below-described b1-1) were added to and sufficiently dissolved in 400 g of methyl ethyl ketone. After allowing the resulting mixed solution to react at 80° C. for about 2 hours, it was confirmed that the reaction solution contained 3% by mass or less of isocyanate groups, and 8 g of formic acid (the below-described ionizing agent b6-1) was further added thereto (production of a urethane prepolymer). It is noted here that, in accordance with JIS K7301:1995, the content ratio of isocyanate groups can be calculated by the following equation after dissolving 2 g of the reaction solution in dimethylformamide, adding thereto 10 ml of an n-dibutylamine-toluene solution, and subsequently titrating the resultant with a 0.5-mol/L hydrochloric acid solution using bromophenol blue as an indicator:

[00001]$\mathrm{NCO}\left(\%\right)=\frac{\left(A-B\right)\times f\times N\times 4.Math.2.0.Math.2}{S\times 1.Math.0.Math.0.Math.0}\times 1.Math.0.Math.0$

[0128] (wherein, A means the volume of the hydrochloric acid solution required for titrating the amount (mass) of isocyanate used in the preparation of a reaction solution in a prescribed amount (═S); B means the volume of the hydrochloric acid solution required for titrating the prescribed amount (═S) of the reaction solution; f means “1”; N means the molar concentration of hydrochloric acid standard solution; and S means the mass of the reaction solution respectively).

[0129] Subsequently, 1,000 g of deionized water was added to prepare a urethane emulsion. From the thus obtained urethane emulsion, methyl ethyl ketone was removed by vacuum distillation, whereby a urethane resin having a urethane resin concentration of 25% by mass was prepared.

Synthesis Examples 2 to 18

[0130] Urethane resins of Synthesis Examples 2 to 18 were prepared by the same synthesis method as in Synthesis Example 1, except that the added amounts (% by mass) of the respective components were adjusted as prescribed in Table 1.

TABLE-US-00001 TABLE 1 Polyisocyanate(b1) Polyol(b2) Diol(b3) Diol(b4) Synthesis Added Added Added Added Added Added Example Type amount Type amount Type amount Type amount Type amount Type amount Synthesis b1-1 50% b2-1 20% b3-1 21% b4-1 3% Example1 Synthesis b1-1 50% b2-1 20% b3-1 21% b4-1 3% Example2 Synthesis b1-1 50% b2-1 20% b3-1 21% b4-1 3% Example3 Synthesis b1-1 50% b2-1 20% b3-2 21% b4-1 3% Example4 Synthesis b1-1 55% b2-1 16% b3-1 17% b4-1 2% Example5 Synthesis b1-1 56% b2-2 10% b3-1 24% b4-1 3% Example6 Synthesis b1-1 50% b2-1 20% b3-1 21% b4-1 3% Example7 Synthesis b1-1 50% b2-1 20% b3-1 21% b4-1 3% Example8 Synthesis b1-1 46% b2-1 23% b3-1 25% b4-1 3% Example9 Synthesis b1-2 38% b2-1 23% b3-1 25% b4-1 3% Example10 Synthesis b1-1 52% b2-3 14% b3-2 22% b4-1 3% Example11 Synthesis b1-1 57% b2-1 13% b3-1 13% b4-1 2% Example12 Synthesis b1-1 67% b2-1 15% b3-1 16% b4-1 2% Example13 Synthesis b1-1 50% b2-1 20% b3-1 21% b4-1 3% Example14 Synthesis b1-1 50% b2-1 20% b3-1 10.5%   b3-2 10.5% b4-1 3% Example15 Synthesis b1-1 50% b2-1 20% b3-1 14% b4-1 3% b4-2 7% Example16 Synthesis b1-1 50% b2-1 20% b3-1 14% b4-1 3% b4-3 7% Example17 Synthesis b1-1 50% b2-1 20% b3-1 21% b4-1 3% Example18 Tertiary amine compound(b5) Neutralizer(b6) Neutral- Synthesis Added ization Reaction Example Type amount Type rate time Synthesis b5-1 6% b6-1 70% 2 h Example1 Synthesis b5-1 6% b6-1 70% 4 h Example2 Synthesis b5-1 6% b6-1 70% 6 h Example3 Synthesis b5-1 6% b6-1 70% 6 h Example4 Synthesis b5-1 11% b6-1 70% 6 h Example5 Synthesis b5-1 7% b6-1 70% 6 h Example6 Synthesis b5-1 6% b6-2 70% 6 h Example7 Synthesis b5-1 6% b6-3 70% 6 h Example8 Synthesis b5-1 3% b6-1 70% 6 h Example9 Synthesis b5-1 11% b6-1 70% 6 h Example10 Synthesis b5-1 9% b6-1 70% 6 h Example11 Synthesis b5-1 15% b6-1 70% 6 h Example12 Synthesis b5-1 1% b6-1 70% 6 h Example13 Synthesis b5-1 6% b6-1 70% 1 h Example14 Synthesis b5-1 6% b6-1 70% 6 h Example15 Synthesis b5-1 6% b6-1 70% 6 h Example16 Synthesis b5-1 6% b6-1 70% 6 h Example17 Synthesis b5-2 6% b6-1 70% 6 h Example18

[0131] The components shown in Table 1 are as follows. The added amount (% by mass) of each component shown in Table 1 indicates the mass ratio of the component with respect to the total amount of the components (b1) to (b5). It is noted here that the urethane prepolymers obtained in all Synthesis Examples contained isocyanate groups.

<Polyisocyanates (b1; Some of the Following Polyisocyanates has a Cyclohexane Ring Structure)>

[0132] b1-1: dicyclohexylmethane-4,4′-diisocyanate (DESMODUR W, manufactured by Bayer AG)

[0133] b1-2: hexamethylene diisocyanate (50M-HDI, manufactured by Asahi Kasei Corporation)

<Polyols (b2)>

[0134] b2-1: bisphenol A-polyoxyethylene 2-mol adduct (NEWPOL BPE20T, manufactured by Sanyo Chemical Industries, Ltd.)

[0135] b2-2: cyclohexane dimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) b2-3: bisphenol A (manufactured by Mitsubishi Chemical Corporation)

<Diols (b3)>

[0136] b3-1: polyethylene glycol (PEG1000, Mw: 1,000, manufactured by Sanyo Chemical Industries, Ltd.)

[0137] b3-2: polyester polyol (NIPPOLLAN 4040, Mw: 2,000, manufactured by Tosoh Corporation)

<Diols (b4)>

[0138] b4-1: trimethylolpropane (TMP, manufactured by Perstorp Holding AB) b4-2: polyethylene glycol (PEG400, Mw: 400, manufactured by Sanyo Chemical Industries, Ltd.)

[0139] b4-3: diethylene glycol (manufactured by Nippon Shokubai Co., Ltd.)

<Tertiary Amine Compounds (b5)>

[0140] b5-1: N-methyldiethanolamine (aminoalcohol MDA, manufactured by Nippon Nyukazai Co., Ltd.)

[0141] b5-2: DMPA (dimethylol propionic acid, manufactured by Perstorp Holding AB)

<Ionizing Agents (b6)>

[0142] Ionizing agent b6-1: formic acid (manufactured by Asahi Chemical Co., Ltd.) Ionizing agent b6-2: methanesulfonic acid (manufactured by Tosoh Corporation) Ionizing agent b6-3: dimethyl sulfate (manufactured by Tsujimoto Chemical Co., Ltd.)

<Preparation of Metal Surface Treatment Agents>

[0143] Metal surface treatment agents of Examples 1 to 264 and Comparative Examples 1 to 10 were each prepared by adding various components to water at the respective prescribed concentrations shown in Tables 2-1 to 2-5. As a supply source of the ion (A), hexafluorozirconic acid, hexafluorotitanic acid or hexafluorohafnic acid was used in Examples 1 to 66 and Comparative Examples 1 to 10; zirconium oxysulfate, titanium oxysulfate or hexafluorohafnic acid was used in Examples 67 to 132; zirconium oxynitrate, titanium oxynitrate or hexafluorohafnic acid was used in Examples 133 to 198; and zirconium hydroxide (R zirconium hydroxide, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.), titanium (IV) oxide or hexafluorohafnic acid was used in Examples 199 to 264 respectively. As an aluminum-containing metal compound, aluminum nitrate nonahydrate was used; as a supply source of nitric acid radicals, the above-described zirconium oxynitrate, the above-described titanium oxynitrate, the above-described aluminum nitrate nonahydrate, nitric acid or the like was used; and, as a supply source of alkanesulfonic acid radicals, methanesulfonic acid (shown as “MSA” in Tables) was used. In Examples 19, 52, 85, 118, 151, 184, 217 and 250, aluminum oxide was used in place of aluminum nitrate nonahydrate. Further add an allylamine polymer (PAA-03, manufactured by Nittobo Medical Co., Ltd.) in examples 29, 62, 95, 128, 161, 194, 227 and 260, an allylamine hydrochloride-diallylamine hydrochloride copolymer (PAA-D11-HCL, manufactured by Nittobo Medical Co., Ltd.) in examples 30, 63, 96, 129, 162, 195, 228 and 261, a diallylamine hydrochloride polymer (PAS-21CL, manufactured by Nittobo Medical Co., Ltd.) in examples 31, 64, 97, 130, 163, 196, 229 and 262, a diallylamine hydrochloride-sulfur dioxide copolymer (PAS-92, manufactured by Nittobo Medical Co., Ltd.) in examples 32, 65, 98, 131, 164, 197, 230 and 263, and a methyldiallylamine hydrochloride polymer (PAS-M-1, manufactured by Nittobo Medical Co., Ltd.) in examples 33, 66, 99, 132, 165, 198, 231 and 264, in an amount of 0.1 g/L, respectively. Moreover, as the resin (B), each resin synthesized in Synthesis Examples 1 to 18 was used. The pH was adjusted with an aqueous solution of nitric acid or sodium hydroxide. In Examples 19, 52, 85, 118, 151, 184, 217 and 250, however, the pH was adjusted with an aqueous solution of methanesulfonic acid or sodium hydroxide.

TABLE-US-00002 TABLE 2-1 ResinB Presence or Added amount [mmol/L] absence of Added Acid radical (E) Treatment Synthesis Molecular Amine cyclohexane amount Ion (A) Ion (C) Nitric Other solution Example weight value ring [mg/L] Zr Ti Hf Al acid MSA HF Example1 2 120000 30.0 Present 547.20 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example2 2 120000 30.0 Present 510.72 8.00 0.00 0.00 6.00 47.62 0.00 18.00 Example3 2 120000 30.0 Present 528.00 0.00 2.00 0.00 6.00 47.62 0.00 18.00 Example4 2 120000 30.0 Present 765.60 1.00 1.00 0.00 6.00 47.62 0.00 18.00 Example5 2 120000 30.0 Present 1483.35 1.00 0.00 1.00 6.00 47.62 0.00 18.00 Example6 1 70000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example7 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example8 3 1200000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example9 9 120000 14.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example10 5 120000 52.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example11 12 120000 71.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example12 13 120000 4.7 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example13 6 120000 34.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example14 10 120000 52.0 Absent 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example15 2 120000 30.0 Present 500.00 0.40 0.00 0.00 6.00 47.62 0.00 18.00 Example16 2 120000 30.0 Present 4900.00 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example17 2 120000 30.0 Present 5472.00 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example18 2 120000 30.0 Present 9500.00 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example19 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 0.00 20.83 18.00 Example20 2 120000 30.0 Present 500.00 0.10 0.00 0.00 6.00 47.62 0.00 18.00 Example21 7 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example22 8 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example23 4 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example24 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example25 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example26 16 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example27 17 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example28 2 120000 30.0 Present 500.00 1.00 0.00 0.00 0.00 0.00 0.00 0.00 Example29 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example30 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example31 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example32 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example33 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example34 2 120000 30.0 Present 547.20 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example35 2 120000 30.0 Present 510.72 8.00 0.00 0.00 6.00 47.62 0.00 18.00 Example36 2 120000 30.0 Present 528.00 0.00 2.00 0.00 6.00 47.62 0.00 18.00 Example37 2 120000 30.0 Present 765.60 1.00 1.00 0.00 6.00 47.62 0.00 18.00 Example38 2 120000 30.0 Present 1483.35 1.00 0.00 1.00 6.00 47.62 0.00 18.00 Example39 1 70000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example40 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example41 3 1200000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example42 9 120000 14.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example43 5 120000 52.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example44 12 120000 71.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example45 13 120000 4.7 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example46 6 120000 34.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example47 10 120000 52.0 Absent 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example48 2 120000 30.0 Present 500.00 0.40 0.00 0.00 6.00 47.62 0.00 18.00 Example49 2 120000 30.0 Present 4900.00 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example50 2 120000 30.0 Present 5472.00 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example51 2 120000 30.0 Present 9500.00 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example52 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 0.00 20.83 18.00 Example53 2 120000 30.0 Present 500.00 0.10 0.00 0.00 6.00 47.62 0.00 18.00 Example54 7 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example55 8 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example56 4 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example57 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example58 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example59 16 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example60 17 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example61 2 120000 30.0 Present 500.00 1.00 0.00 0.00 0.00 0.00 0.00 0.00 Example62 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example63 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example64 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example65 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example66 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 [B.sub.M Treatment mass]/ solution pH [A.sub.M mass] Example1 4.0 3.00 Example2 4.0 0.70 Example3 4.0 5.50 Example4 4.0 5.50 Example5 4.0 5.50 Example6 4.0 5.48 Example7 4.0 5.48 Example8 4.0 5.48 Example9 4.0 5.48 Example10 4.0 5.48 Example11 4.0 5.48 Example12 4.0 5.48 Example13 4.0 5.48 Example14 4.0 5.48 Example15 4.0 13.71 Example16 4.0 26.86 Example17 4.0 30.00 Example18 4.0 52.08 Example19 4.0 5.48 Example20 4.0 54.82 Example21 4.0 5.48 Example22 4.0 5.48 Example23 4.0 5.48 Example24 4.0 5.48 Example25 4.0 5.48 Example26 4.0 5.48 Example27 4.0 5.48 Example28 4.0 5.48 Example29 4.0 5.48 Example30 4.0 5.48 Example31 4.0 5.48 Example32 4.0 5.48 Example33 4.0 5.48 Example34 3.6 3.00 Example35 3.6 0.70 Example36 3.6 5.50 Example37 3.6 5.50 Example38 3.6 5.50 Example39 3.6 5.48 Example40 3.6 5.48 Example41 3.6 5.48 Example42 3.6 5.48 Example43 3.6 5.48 Example44 3.6 5.48 Example45 3.6 5.48 Example46 3.6 5.48 Example47 3.6 5.48 Example48 3.6 13.71 Example49 3.6 26.86 Example50 3.6 30.00 Example51 3.6 52.08 Example52 3.6 5.48 Example53 3.6 54.82 Example54 3.6 5.48 Example55 3.6 5.48 Example56 3.6 5.48 Example57 3.6 5.48 Example58 3.6 5.48 Example59 3.6 5.48 Example60 3.6 5.48 Example61 3.6 5.48 Example62 3.6 5.48 Example63 3.6 5.48 Example64 3.6 5.48 Example65 3.6 5.48 Example66 3.6 5.48

TABLE-US-00003 TABLE 2-2 ResinB Presence or absence of Added Added amount [mmol/L] Treatment Synthesis Molecular Amine cyclohexane amount Ion (A) Ion (C) Acid radical (E) Other solution Example weight value ring [mg/L] Zr Ti HF Al Nitric acid MSA HF Example67 2 120000 30.0 Present 547.20 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example68 2 120000 30.0 Present 510.72 8.00 0.00 0.00 6.00 47.62 0.00 50.00 Example69 2 120000 30.0 Present 528.00 0.00 2.00 0.00 6.00 47.62 0.00 26.00 Example70 2 120000 30.0 Present 765.60 1.00 1.00 0.00 6.00 47.62 0.00 26.00 Example71 2 120000 30.0 Present 1483.35 1.00 0.00 1.00 6.00 47.62 0.00 22.00 Example72 1 70000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example73 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example74 3 1200000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example75 9 120000 14.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example76 5 120000 52.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example77 12 120000 71.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example78 13 120000 4.7 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example79 6 120000 34.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example80 10 120000 52.0 Absent 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example81 2 120000 30.0 Present 500.00 0.40 0.00 0.00 6.00 47.62 0.00 19.60 Example82 2 120000 30.0 Present 4900.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example83 2 120000 30.0 Present 5472.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example84 2 120000 30.0 Present 9500.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example85 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 0.00 20.83 22.00 Example86 2 120000 30.0 Present 500.00 0.10 0.00 0.00 6.00 47.62 0.00 18.40 Example87 7 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example88 8 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example89 4 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example90 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example91 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example92 16 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example93 17 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example94 2 120000 30.0 Present 500.00 1.00 0.00 0.00 0.00 0.00 0.00 4.00 Example95 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example96 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example97 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example98 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example99 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example100 2 120000 30.0 Present 547.20 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example101 2 120000 30.0 Present 510.72 8.00 0.00 0.00 6.00 47.62 0.00 50.00 Example102 2 120000 30.0 Present 528.00 0.00 2.00 0.00 6.00 47.62 0.00 26.00 Example103 2 120000 30.0 Present 765.60 1.00 1.00 0.00 6.00 47.62 0.00 26.00 Example104 2 120000 30.0 Present 1483.35 1.00 0.00 1.00 6.00 47.62 0.00 22.00 Example105 1 70000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example106 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example107 3 1200000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example108 9 120000 14.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example109 5 120000 52.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example110 12 120000 71.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example111 13 120000 4.7 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example112 6 120000 34.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example113 10 120000 52.0 Absent 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example114 2 120000 30.0 Present 500.00 0.40 0.00 0.00 6.00 47.62 0.00 19.60 Example115 2 120000 30.0 Present 4900.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example116 2 120000 30.0 Present 5472.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example117 2 120000 30.0 Present 9500.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example118 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 0.00 20.83 22.00 Example119 2 120000 30.0 Present 500.00 0.10 0.00 0.00 6.00 47.62 0.00 18.40 Example120 7 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example121 8 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example122 4 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example123 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example124 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example125 16 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example126 17 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example127 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 0.00 0.00 4.00 Example128 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example129 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example130 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example131 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example132 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Treatment [B.sub.M mass]/ solution pH [A.sub.M mass] Example67 4.0 3.00 Example68 4.0 0.70 Example69 4.0 5.50 Example70 4.0 5.50 Example71 4.0 5.50 Example72 4.0 5.48 Example73 4.0 5.48 Example74 4.0 5.48 Example75 4.0 5.48 Example76 4.0 5.48 Example77 4.0 5.48 Example78 4.0 5.48 Example79 4.0 5.48 Example80 4.0 5.48 Example81 4.0 13.71 Example82 4.0 26.86 Example83 4.0 30.00 Example84 4.0 52.08 Example85 4.0 5.48 Example86 4.0 54.82 Example87 4.0 5.48 Example88 4.0 5.48 Example89 4.0 5.48 Example90 4.0 5.48 Example91 4.0 5.48 Example92 4.0 5.48 Example93 4.0 5.48 Example94 4.0 5.48 Example95 4.0 5.48 Example96 4.0 5.48 Example97 4.0 5.48 Example98 4.0 5.48 Example99 4.0 5.48 Example100 3.6 3.00 Example101 3.6 0.70 Example102 3.6 5.50 Example103 3.6 5.50 Example104 3.6 5.50 Example105 3.6 5.48 Example106 3.6 5.48 Example107 3.6 5.48 Example108 3.6 5.48 Example109 3.6 5.48 Example110 3.6 5.48 Example111 3.6 5.48 Example112 3.6 5.48 Example113 3.6 5.48 Example114 3.6 13.71 Example115 3.6 26.86 Example116 3.6 30.00 Example117 3.6 52.08 Example118 3.6 5.48 Example119 3.6 54.82 Example120 3.6 5.48 Example121 3.6 5.48 Example122 3.6 5.48 Example123 3.6 5.48 Example124 3.6 5.48 Example125 3.6 5.48 Example126 3.6 5.48 Example127 3.6 5.48 Example128 3.6 5.48 Example129 3.6 5.48 Example130 3.6 5.48 Example131 3.6 5.48 Example132 3.6 5.48

TABLE-US-00004 TABLE 2-3 ResinB Presence or Added amount [mmol/L] absence of Added Acid radical (E) Treatment Synthesis Molecular Amine cyclohexane amount Ion (A) Ion (C) Nitric Other solution Example weight value ring [mg/L] Zr Ti Hf Al acid MSA HF Example133 2 120000 30.0 Present 547.20 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example134 2 120000 30.0 Present 510.72 8.00 0.00 0.00 6.00 47.62 0.00 50.00 Example135 2 120000 30.0 Present 528.00 0.00 2.00 0.00 6.00 47.62 0.00 26.00 Example136 2 120000 30.0 Present 765.60 1.00 1.00 0.00 6.00 47.62 0.00 26.00 Example137 2 120000 30.0 Present 1483.35 1.00 0.00 1.00 6.00 47.62 0.00 22.00 Example138 1 70000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example139 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example140 3 1200000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example141 9 120000 14.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example142 5 120000 52.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example143 12 120000 71.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example144 13 120000 4.7 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example145 6 120000 34.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example146 10 120000 52.0 Absent 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example147 2 120000 30.0 Present 500.00 0.40 0.00 0.00 6.00 47.62 0.00 19.60 Example148 2 120000 30.0 Present 4900.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example149 2 120000 30.0 Present 5472.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example150 2 120000 30.0 Present 9500.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example151 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 2.00 20.83 22.00 Example152 2 120000 30.0 Present 500.00 0.10 0.00 0.00 6.00 47.62 0.00 18.40 Example153 7 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example154 8 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example155 4 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example156 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example157 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example158 16 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example159 17 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example160 2 120000 30.0 Present 500.00 1.00 0.00 0.00 0.00 2.00 0.00 4.00 Example161 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example162 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example163 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example164 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example165 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example166 2 120000 30.0 Present 547.20 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example167 2 120000 30.0 Present 510.72 8.00 0.00 0.00 6.00 47.62 0.00 50.00 Example168 2 120000 30.0 Present 528.00 0.00 2.00 0.00 6.00 47.62 0.00 26.00 Example169 2 120000 30.0 Present 765.60 1.00 1.00 0.00 6.00 47.62 0.00 26.00 Example170 2 120000 30.0 Present 1483.35 1.00 0.00 1.00 6.00 47.62 0.00 22.00 Example171 1 70000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example172 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example173 3 1200000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example174 9 120000 14.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example175 5 120000 52.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example176 12 120000 71.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example177 13 120000 4.7 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example178 6 120000 34.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example179 10 120000 52.0 Absent 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example180 2 120000 30.0 Present 500.00 0.40 0.00 0.00 6.00 47.62 0.00 19.60 Example181 2 120000 30.0 Present 4900.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example182 2 120000 30.0 Present 5472.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example183 2 120000 30.0 Present 9500.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example184 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 2.00 20.83 22.00 Example185 2 120000 30.0 Present 500.00 0.10 0.00 0.00 6.00 47.62 0.00 18.40 Example186 7 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example187 8 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example188 4 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example189 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example190 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example191 16 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example192 17 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example193 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 2.00 0.00 4.00 Example194 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example195 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example196 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example197 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example198 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Treatment [B.sub.M mass]/ solution pH [A.sub.M mass] Example133 4.0 3.00 Example134 4.0 0.70 Example135 4.0 5.50 Example136 4.0 5.50 Example137 4.0 5.50 Example138 4.0 5.48 Example139 4.0 5.48 Example140 4.0 5.48 Example141 4.0 5.48 Example142 4.0 5.48 Example143 4.0 5.48 Example144 4.0 5.48 Example145 4.0 5.48 Example146 4.0 5.48 Example147 4.0 13.71 Example148 4.0 26.86 Example149 4.0 30.00 Example150 4.0 52.08 Example151 4.0 5.48 Example152 4.0 54.82 Example153 4.0 5.48 Example154 4.0 5.48 Example155 4.0 5.48 Example156 4.0 5.48 Example157 4.0 5.48 Example158 4.0 5.48 Example159 4.0 5.48 Example160 4.0 5.48 Example161 4.0 5.48 Example162 4.0 5.48 Example163 4.0 5.48 Example164 4.0 5.48 Example165 4.0 5.48 Example166 3.6 3.00 Example167 3.6 0.70 Example168 3.6 5.50 Example169 3.6 5.50 Example170 3.6 5.50 Example171 3.6 5.48 Example172 3.6 5.48 Example173 3.6 5.48 Example174 3.6 5.48 Example175 3.6 5.48 Example176 3.6 5.48 Example177 3.6 5.48 Example178 3.6 5.48 Example179 3.6 5.48 Example180 3.6 13.71 Example181 3.6 26.86 Example182 3.6 30.00 Example183 3.6 52.08 Example184 3.6 5.48 Example185 3.6 54.82 Example186 3.6 5.48 Example187 3.6 5.48 Example188 3.6 5.48 Example189 3.6 5.48 Example190 3.6 5.48 Example191 3.6 5.48 Example192 3.6 5.48 Example193 3.6 5.48 Example194 3.6 5.48 Example195 3.6 5.48 Example196 3.6 5.48 Example197 3.6 5.48 Example198 3.6 5.48

TABLE-US-00005 TABLE 2-4 ResinB Added amount [mmol/L] Presence or Acid absence of Added radical (E) Treatment Synthesis Molecular Amine cyclohexane amount Ion (A) Ion (C) Nitric Other solution Example weight value ring [mg/L] Zr Ti Hf Al acid MSA HF Example199 2 120000 30.0 Present 547.20 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example200 2 120000 30.0 Present 510.72 8.00 0.00 0.00 6.00 47.62 0.00 50.00 Example201 2 120000 30.0 Present 528.00 0.00 2.00 0.00 6.00 47.62 0.00 26.00 Example202 2 120000 30.0 Present 765.60 1.00 1.00 0.00 6.00 47.62 0.00 26.00 Example203 2 120000 30.0 Present 1483.35 1.00 0.00 1.00 6.00 47.62 0.00 22.00 Example204 1 70000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example205 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example206 3 1200000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example207 9 120000 14.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example208 5 120000 52.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example209 12 120000 71.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example210 13 120000 4.7 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example211 6 120000 34.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example212 10 120000 52.0 Absent 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example213 2 120000 30.0 Present 500.00 0.40 0.00 0.00 6.00 47.62 0.00 19.60 Example214 2 120000 30.0 Present 4900.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example215 2 120000 30.0 Present 5472.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example216 2 120000 30.0 Present 9500.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example217 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 0.00 20.83 22.00 Example218 2 120000 30.0 Present 500.00 0.10 0.00 0.00 6.00 47.62 0.00 18.40 Example219 7 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example220 8 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example221 4 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example222 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example223 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example224 16 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example225 17 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example226 2 120000 30.0 Present 500.00 1.00 0.00 0.00 0.00 0.00 0.00 4.00 Example227 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example228 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example229 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example230 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example231 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example232 2 120000 30.0 Present 547.20 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example233 2 120000 30.0 Present 510.72 8.00 0.00 0.00 6.00 47.62 0.00 50.00 Example234 2 120000 30.0 Present 528.00 0.00 2.00 0.00 6.00 47.62 0.00 26.00 Example235 2 120000 30.0 Present 765.60 1.00 1.00 0.00 6.00 47.62 0.00 26.00 Example236 2 120000 30.0 Present 1483.35 1.00 0.00 1.00 6.00 47.62 0.00 22.00 Example237 1 70000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example238 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example239 3 1200000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example240 9 120000 14.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example241 5 120000 52.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example242 12 120000 71.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example243 13 120000 4.7 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example244 6 120000 34.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example245 10 120000 52.0 Absent 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example246 2 120000 30.0 Present 500.00 0.40 0.00 0.00 6.00 47.62 0.00 19.60 Example247 2 120000 30.0 Present 4900.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example248 2 120000 30.0 Present 5472.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example249 2 120000 30.0 Present 9500.00 2.00 0.00 0.00 6.00 47.62 0.00 26.00 Example250 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 0.00 20.83 22.00 Example251 2 120000 30.0 Present 500.00 0.10 0.00 0.00 6.00 47.62 0.00 18.40 Example252 7 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example253 8 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example254 4 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example255 2 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example256 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example257 16 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example258 17 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example259 2 120000 30.0 Present 500.00 1.00 0.00 0.00 0.00 0.00 0.00 4.00 Example260 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example261 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example262 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example263 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Example264 15 120000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 22.00 Treatment [B.sub.M mass]/ solution pH [A.sub.M mass] Example199 4.0 3.00 Example200 4.0 0.70 Example201 4.0 5.50 Example202 4.0 5.50 Example203 4.0 5.50 Example204 4.0 5.48 Example205 4.0 5.48 Example206 4.0 5.48 Example207 4.0 5.48 Example208 4.0 5.48 Example209 4.0 5.48 Example210 4.0 5.48 Example211 4.0 5.48 Example212 4.0 5.48 Example213 4.0 13.71 Example214 4.0 26.86 Example215 4.0 30.00 Example216 4.0 52.08 Example217 4.0 5.48 Example218 4.0 54.82 Example219 4.0 5.48 Example220 4.0 5.48 Example221 4.0 5.48 Example222 4.0 5.48 Example223 4.0 5.48 Example224 4.0 5.48 Example225 4.0 5.48 Example226 4.0 5.48 Example227 4.0 5.48 Example228 4.0 5.48 Example229 4.0 5.48 Example230 4.0 5.48 Example231 4.0 5.48 Example232 3.6 3.00 Example233 3.6 0.70 Example234 3.6 5.50 Example235 3.6 5.50 Example236 3.6 5.50 Example237 3.6 5.48 Example238 3.6 5.48 Example239 3.6 5.48 Example240 3.6 5.48 Example241 3.6 5.48 Example242 3.6 5.48 Example243 3.6 5.48 Example244 3.6 5.48 Example245 3.6 5.48 Example246 3.6 13.71 Example247 3.6 26.86 Example248 3.6 30.00 Example249 3.6 52.08 Example250 3.6 5.48 Example251 3.6 54.82 Example252 3.6 5.48 Example253 3.6 5.48 Example254 3.6 5.48 Example255 3.6 5.48 Example256 3.6 5.48 Example257 3.6 5.48 Example258 3.6 5.48 Example259 3.6 5.48 Example260 3.6 5.48 Example261 3.6 5.48 Example262 3.6 5.48 Example263 3.6 5.48 Example264 3.6 5.48

TABLE-US-00006 TABLE 2-5 ResinB Presence or Added amount [mmol/L] absence of Added Acid radical(E) Treatment Synthesis Molecular Amine cyclohexane amount Ion (A) Ion (C) Nitric Other solution Example weight value ring [mg/L] Zr Ti Hf Al acid MSA HF Comparative — 0.00 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example1 Comparative 2 120000 30.0 Present 500.00 0.00 0.00 0.00 6.00 47.62 0.00 18.00 Example2 Comparative 2 120000 30.0 Present 127.68 2.00 0.00 0.00 6.00 47.62 0.00 18.00 Example3 Comparative 2 120000 30.0 Present 11673.60 8.00 0.00 0.00 6.00 47.62 0.00 18.00 Example4 Comparative 14 30000 30.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example5 Comparative 2 120000 30.0 Present 500.00 #### 0.00 0.00 6.00 47.62 0.00 18.00 Example6 Comparative 2 120000 30.0 Present 500.00 0.03 0.00 0.00 6.00 47.62 0.00 18.00 Example7 Comparative 11 120000 45.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example8 Comparative 18 120000 45.0 Present 500.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example9 Comparative — 0.00 1.00 0.00 0.00 6.00 47.62 0.00 18.00 Example10 Treatment [B.sub.M mass]/ solution pH [A.sub.M mass] Comparative 4.0 0.00 Example1 Comparative 4.0 — Example2 Comparative 4.0 0.70 Example3 Comparative 4.0 64.00 Example4 Comparative 4.0 5.48 Example5 Comparative 4.0 0.55 Example6 Comparative 4.0 182.75 Example7 Comparative 4.0 5.48 Example8 Comparative 4.0 5.48 Example9 Comparative 4.0 0.00 Example10

<Pretreatment of Metal Materials>

[0144] Metal materials (SPCC: cold-rolled steel sheet, and SGCC: hot-dip zinc-coated steel sheet) were immersed in an alkali degreasing agent [a solution obtained by mixing agent A and agent B of FINE CLEANER E2093 (manufactured by Nihon Parkerizing Co., Ltd.) with water at concentrations of 13 g/L and 11 g/L, respectively] at 45° C. for 2 minutes to remove oil and dirt from the surface of each metal material. Then, the surface of each metal material was washed with water.

[0145] Next, the thus water-washed metal materials were immersed in metal surface treatment agents (the respective metal surface treatment agents of Examples 1 to 264 and Comparative Examples 1 to 10) at 40° C. for 2 minutes.

[0146] After the water-wash of the metal materials immersed in the respective metal surface treatment agents, 180-second constant-voltage cathodic electrolysis was subsequently performed using an electrodeposition coating agent (GT-100, manufactured by Kansai Paint Co., Ltd.) with each metal material being set as a cathode, thereby allowing a coating film component to precipitate on the entire surface of each metal material. Thereafter, the metal materials were washed with water and then baked at 170° C. (PMT: highest temperature of each metal material during baking) for 20 minutes to prepare test pieces, and the following evaluations were performed. It is noted here that the coating film's thickness was adjusted to be 20 μm.

[Evaluation of Test Pieces]

<Corrosion Resistance>

[0147] In order to verify the corrosion resistance of the test pieces (test pieces of No. 1 to 274) at their edges, the test pieces were each set in a composite cycle tester, and a composite cycle test was conducted in accordance with JASO-M609-91 for 100 cycles. After the 100 cycles, the maximum blister width from a burr generated at the time of cutting was measured, and the corrosion resistance was evaluated based on the following evaluation criteria. The results thereof are shown in Tables 3-1 to 3-5.

(Evaluation Criteria)

[0148] S: The maximum blister width was less than 1.5 mm.

[0149] A: The maximum blister width was 1.5 mm to less than 2.5 mm.

[0150] B: The maximum blister width was 2.5 mm to less than 5.0 mm.

[0151] C: The maximum blister width was 5.0 mm or greater.

<Adhesion Performance>

[0152] In order to verify the coating film adhesion performance of the test pieces (test pieces of Nos. 1 to 274), cuts were made on each test piece in a grid form at 1-mm intervals (10×10=100 cuts), and each test piece was subsequently immersed in boiling water for 1 hour. Thereafter, water on the surface was wiped off and a cellophane tape was pasted to the grid-form cuts, after which the cellophane tape was peeled off, and the number of grids where the coating film was not removed was measured to evaluate the adhesion performance based on the following evaluation criteria. The results thereof are shown in Tables 3-1 to 3-5.

(Evaluation Criteria)

[0153] A: The number of grids where the coating film was not removed was 100.

[0154] B: The number of grids where the coating film was not removed was 80 to 99.

[0155] C: The number of grids where the coating film was not removed was 79 or less.

TABLE-US-00007 TABLE 3-1 Test Corrosion Adhesion piece Steel sheet Treatment solution resistance performance 1 SPCC Example1 S A 2 SPCC Example2 S A 3 SPCC Example3 S A 4 SPCC Example4 S A 5 SPCC Example5 S A 6 SPCC Example6 A A 7 SPCC Example7 S A 8 SPCC Example8 S A 9 SPCC Example9 S A 10 SPCC Example10 A B 11 SPCC Example11 B A 12 SPCC Example12 B B 13 SPCC Example13 S A 14 SPCC Example14 B A 15 SPCC Example15 S A 16 SPCC Example16 S A 17 SPCC Example17 B A 18 SPCC Example18 B A 19 SPCC Example19 S A 20 SPCC Example20 B A 21 SPCC Example21 S A 22 SPCC Example22 S A 23 SPCC Example23 S A 24 SGCC Example24 S A 25 SPCC Example25 A A 26 SPCC Example26 S A 27 SPCC Example27 S A 28 SPCC Example28 S A 29 SPCC Example29 S A 30 SPCC Example30 S A 31 SPCC Example31 S A 32 SPCC Example32 S A 33 SPCC Example33 S A 34 SPCC Example34 S A 35 SPCC Example35 S A 36 SPCC Example36 S A 37 SPCC Example37 S A 38 SPCC Example38 S A 39 SPCC Example39 A A 40 SPCC Example40 S A 41 SPCC Example41 S A 42 SPCC Example42 S A 43 SPCC Example43 A B 44 SPCC Example44 B A 45 SPCC Example45 B B 46 SPCC Example46 S A 47 SPCC Example47 B A 48 SPCC Example48 S A 49 SPCC Example49 S A 50 SPCC Example50 B A 51 SPCC Example51 B A 52 SPCC Example52 S A 53 SPCC Example53 B A 54 SPCC Example54 S A 55 SPCC Example55 S A 56 SPCC Example56 S A 57 SGCC Example57 S A 58 SPCC Example58 A A 59 SPCC Example59 S A 60 SPCC Example60 S A 61 SPCC Example61 S A 62 SPCC Example62 S A 63 SPCC Example63 S A 64 SPCC Example64 S A 65 SPCC Example65 S A 66 SPCC Example66 S A

TABLE-US-00008 TABLE 3-2 Test Corrosion Adhesion piece Steel sheet Treatment solution resistance performance 67 SPCC Example67 S A 68 SPCC Example68 S A 69 SPCC Example69 S A 70 SPCC Example70 S A 71 SPCC Example71 S A 72 SPCC Example72 A A 73 SPCC Example73 S A 74 SPCC Example74 S A 75 SPCC Example75 S A 76 SPCC Example76 A B 77 SPCC Example77 B A 78 SPCC Example78 B B 79 SPCC Example79 S A 80 SPCC Example80 B A 81 SPCC Example81 S A 82 SPCC Example82 S A 83 SPCC Example83 B A 84 SPCC Example84 B A 85 SPCC Example85 S A 86 SPCC Example86 B A 87 SPCC Example87 S A 88 SPCC Example88 S A 89 SPCC Example89 S A 90 SGCC Example90 S A 91 SPCC Example91 A A 92 SPCC Example92 S A 93 SPCC Example93 S A 94 SPCC Example94 S A 95 SPCC Example95 S A 96 SPCC Example96 S A 97 SPCC Example97 S A 98 SPCC Example98 S A 99 SPCC Example99 S A 100 SPCC Example100 S A 101 SPCC Example101 S A 102 SPCC Example102 S A 103 SPCC Example103 S A 104 SPCC Example104 S A 105 SPCC Example105 A A 106 SPCC Example106 S A 107 SPCC Example107 S A 108 SPCC Example108 S A 109 SPCC Example109 A B 110 SPCC Example110 B A 111 SPCC Example111 B B 112 SPCC Example112 S A 113 SPCC Example113 B A 114 SPCC Example114 S A 115 SPCC Example115 S A 116 SPCC Example116 B A 117 SPCC Example117 B A 118 SPCC Example118 S A 119 SPCC Example119 B A 120 SPCC Example120 S A 121 SPCC Example121 S A 122 SPCC Example122 S A 123 SGCC Example123 S A 124 SPCC Example124 A A 125 SPCC Example125 S A 126 SPCC Example126 S A 127 SPCC Example127 S A 128 SPCC Example128 S A 129 SPCC Example129 S A 130 SPCC Example130 S A 131 SPCC Example131 S A 132 SPCC Example132 S A

TABLE-US-00009 TABLE 3-3 Test Corrosion Adhesion piece Steel sheet Treatment solution resistance performance 133 SPCC Example133 S A 134 SPCC Example134 S A 135 SPCC Example135 S A 136 SPCC Example136 S A 137 SPCC Example137 S A 138 SPCC Example138 A A 139 SPCC Example139 S A 140 SPCC Example140 S A 141 SPCC Example141 S A 142 SPCC Example142 A B 143 SPCC Example143 B A 144 SPCC Example144 B B 145 SPCC Example145 S A 146 SPCC Example146 B A 147 SPCC Example147 S A 148 SPCC Example148 S A 149 SPCC Example149 B A 150 SPCC Example150 B A 151 SPCC Example151 S A 152 SPCC Example152 B A 153 SPCC Example153 S A 154 SPCC Example154 S A 155 SPCC Example155 S A 156 SGCC Example156 S A 157 SPCC Example157 A A 158 SPCC Example158 S A 159 SPCC Example159 S A 160 SPCC Example160 S A 161 SPCC Example161 S A 162 SPCC Example162 S A 163 SPCC Example163 S A 164 SPCC Example164 S A 165 SPCC Example165 S A 166 SPCC Example166 S A 167 SPCC Example167 S A 168 SPCC Example168 S A 169 SPCC Example169 S A 170 SPCC Example170 S A 171 SPCC Example171 A A 172 SPCC Example172 S A 173 SPCC Example173 S A 174 SPCC Example174 S A 175 SPCC Example175 A B 176 SPCC Example176 B A 177 SPCC Example177 B B 178 SPCC Example178 S A 179 SPCC Example179 B A 180 SPCC Example180 S A 181 SPCC Example181 S A 182 SPCC Example182 B A 183 SPCC Example183 B A 184 SPCC Example184 S A 185 SPCC Example185 B A 186 SPCC Example186 S A 187 SPCC Example187 S A 188 SPCC Example188 S A 189 SGCC Example189 S A 190 SPCC Example190 A A 191 SPCC Example191 S A 192 SPCC Example192 S A 193 SPCC Example193 S A 194 SPCC Example194 S A 195 SPCC Example195 S A 196 SPCC Example196 S A 197 SPCC Example197 S A 198 SPCC Example198 S A

TABLE-US-00010 TABLE 3-4 Test Corrosion Adhesion piece Steel sheet Treatment solution resistance performance 199 SPCC Example199 S A 200 SPCC Example200 S A 201 SPCC Example201 S A 202 SPCC Example202 S A 203 SPCC Example203 S A 204 SPCC Example204 A A 205 SPCC Example205 S A 206 SPCC Example206 S A 207 SPCC Example207 S A 208 SPCC Example208 A B 209 SPCC Example209 B A 210 SPCC Example210 B B 211 SPCC Example211 S A 212 SPCC Example212 B A 213 SPCC Example213 S A 214 SPCC Example214 S A 215 SPCC Example215 B A 216 SPCC Example216 B A 217 SPCC Example217 S A 218 SPCC Example218 B A 219 SPCC Example219 S A 220 SPCC Example220 S A 221 SPCC Example221 S A 222 SGCC Example222 S A 223 SPCC Example223 A A 224 SPCC Example224 S A 225 SPCC Example225 S A 226 SPCC Example226 S A 227 SPCC Example227 S A 228 SPCC Example228 S A 229 SPCC Example229 S A 230 SPCC Example230 S A 231 SPCC Example231 S A 232 SPCC Example232 S A 233 SPCC Example233 S A 234 SPCC Example234 S A 235 SPCC Example235 S A 236 SPCC Example236 S A 237 SPCC Example237 A A 238 SPCC Example238 S A 239 SPCC Example239 S A 240 SPCC Example240 S A 241 SPCC Example241 A B 242 SPCC Example242 B A 243 SPCC Example243 B B 244 SPCC Example244 S A 245 SPCC Example245 B A 246 SPCC Example246 S A 247 SPCC Example247 S A 248 SPCC Example248 B A 249 SPCC Example249 B A 250 SPCC Example250 S A 251 SPCC Example251 B A 252 SPCC Example252 S A 253 SPCC Example253 S A 254 SPCC Example254 S A 255 SGCC Example255 S A 256 SPCC Example256 A A 257 SPCC Example257 S A 258 SPCC Example258 S A 259 SPCC Example259 S A 260 SPCC Example260 S A 261 SPCC Example261 S A 262 SPCC Example262 S A 263 SPCC Example263 S A 264 SPCC Example264 S A

TABLE-US-00011 TABLE 3-5 Test Corrosion Adhesion piece Steel sheet Treatment solution resistance performance 265 SPCC Comparative Example1 C C 266 SPCC Comparative Example2 C C 267 SPCC Comparative Example3 C B 268 SPCC Comparative Example4 C A 269 SPCC Comparative Example5 C B 270 SPCC Comparative Example6 C A 271 SPCC Comparative Example7 C C 272 SPCC Comparative Example8 C C 273 SPCC Comparative Example9 C C 274 SGCC Comparative Example10 C C

[0156] The present invention has been described in detail referring to concrete embodiments and examples thereof; however, it is obvious to those skilled in the art that various modifications and changes can be made without departing from the gist and the scope of the present invention.