Surface treatment agent for metal material, method of producing the same, metal material having a surface treatment coating, and method of producing the same

Abstract

A surface treatment agent for metal material may include a compound (A) that is obtained by modifying a silicic acid (a) with a hydrolysate (b) of an epoxy group-having silane coupling agent, a silicic acid (B) represented by M.sub.2O.SiO.sub.2 (wherein a mass ratio of M.sub.2O to SiO.sub.2 is 0.1 to 1 and M represents an alkali metal), and water. A mass ratio (B/A) of the silicic acid (B) to the compound (A) is 1.1 to 17.9.

Claims

1. A surface treatment agent for metal material comprising: a compound (A) obtained by modifying a silicic acid (a) with a hydrolysate (b) of an epoxy group-having silane coupling agent; a silicic acid (B) represented by M.sub.2O.Math.SiO.sub.2; and water, wherein a mass ratio (B/A) of the silicic acid (B) to the compound (A) is within a range of 1.1 to 17.9, and wherein a mass ratio (M.sub.2O/SiO.sub.2) of M.sub.2O to SiO.sub.2 in the silicic acid (B) is within a range of 0.1 to 1 and M represents an alkali metal.

2. The surface treatment agent for metal material according to claim 1, wherein the hydrolysate (b) of the epoxy group-having silane coupling agent is obtained by ring-opening the epoxy group-having silane coupling agent with a carboxylic acid, and the surface treatment agent for metal material contains the carboxylic acid.

3. The surface treatment agent for metal material according to claim 1, wherein a mass ratio (a/b) of the silicic acid (a) to the hydrolysate (b) of the epoxy group-having silane coupling agent is within a range of 0.07 to 6.36.

4. The surface treatment agent for metal material according to claim 1, wherein the agent is for a metal material that is used for an electronic component and a micro device component.

5. A method of producing a surface treatment agent for metal material according to claim 1, comprising: adding a silicic acid (a), an epoxy group-having silane coupling agent, an acid catalyst (C) to water and mixing them to form an aqueous dispersion containing a compound (A) obtained by modifying the silicic acid (a) with a hydrolysate (b) of the epoxy group-having silane coupling agent; and adding the aqueous dispersion and a silicic acid (B) represented by M.sub.2O.SiO.sub.2 to water and mixing them, wherein a mass ratio (B/A) of the silicic acid (B) to the compound (A) is within a range of 1.1 to 17.9, and wherein a mass ratio (M.sub.2O/SiO.sub.2) of M.sub.2O to SiO.sub.2 in the silicic acid (B) is within a range of 0.1 to 1 and M represents an alkali metal.

6. The method of producing a surface treatment agent for metal material according to claim 5, wherein the hydrolysate (b) of the epoxy group-having silane coupling agent is obtained by ring-opening the epoxy group-having silane coupling agent with a carboxylic acid, and the surface treatment agent for metal material contains the carboxylic acid.

7. The method of producing a surface treatment agent for metal material according to claim 5, wherein the mass ratio (a/b) of the silicic acid (a) to the hydrolysate (b) of the epoxy group-having silane coupling agent is within a range of 0.07 to 6.36.

8. The method of producing a surface treatment agent for metal material according to claim 5, wherein the agent is for a metal material that is used for an electronic component and a micro device component.

9. A metal material having a surface treatment coating, the coating obtained by bringing the surface treatment agent for metal material according to claim 1 into contact with a metal material.

10. A method of producing a metal material having a surface treatment coating comprising bringing the surface treatment agent for metal material according to claim 1 into contact with a metal material.

11. The surface treatment agent for metal material according to claim 2, wherein a mass ratio (a/b) of the silicic acid (a) to the hydrolysate (b) of the epoxy group-having silane coupling agent is within a range of 0.07 to 6.36.

12. The surface treatment agent for metal material according to claim 2, wherein the agent is for a metal material that is used for an electronic component and a micro device component.

13. The surface treatment agent for metal material according to claim 3, wherein the agent is for a metal material that is used for an electronic component and a micro device component.

14. The surface treatment agent for metal material according to claim 11, wherein the agent is for a metal material that is used for an electronic component and a micro device component.

15. The method of producing a surface treatment agent for metal material according to claim 6, wherein the mass ratio (a/b) of the silicic acid (a) to the hydrolysate (b) of the epoxy group-having silane coupling agent is within a range of 0.07 to 6.36.

16. The method of producing a surface treatment agent for metal material according to claim 6, wherein the agent is for a metal material that is used for an electronic component and a micro device component.

17. The method of producing a surface treatment agent for metal material according to claim 7, wherein the agent is for a metal material that is used for an electronic component and a micro device component.

18. The method of producing a surface treatment agent for metal material according to claim 15, wherein the agent is for a metal material that is used for an electronic component and a micro device component.

19. The surface treatment agent for metal material according to claim 1, wherein the mass ratio (B/A) of the silicic acid (B) to the compound (A) is within a range of 1.1 to 8.9.

20. The surface treatment agent for metal material according to claim 1, wherein the surface treatment agent is a dried coating layer provided on the metal material.

Description

EXAMPLES

(1) Hereinafter, effects of the present invention will be specifically described by examples. However, the following examples do not limit the present invention.

(2) (1) Sample Material (Material)

(3) The following commercially available material was used as a sample material:

(4) (M1) Cold rolled steel sheet SPCC-SD: 0.8 mm in thickness

(5) (2) Pretreatment (Washing)

(6) Hereinafter, the method of producing a test plate will be explained. The surface of the sample material was treated using a fine cleaner E6406 manufactured by Nihon Parkerizing Co., Ltd. to remove oil and impurities on the surface. Then, the resulting material was washed with tap water and 100% of the surface was confirmed to be wet with water. After that, pure water was poured thereon, water was removed in an oven at 100 C., and the resulting product was used as the test plate.

(7) (3) Preparation of Surface Treatment Agent for Metal Material

(8) <Compound A>

(9) The silicic acid of Table 1 (a), the hydrolysate (b) of the epoxy group-having silane coupling agent of Table 2, and the acid catalyst (C) of Table 3 were used to prepare a compound A. The average particle diameters in the following Tables were values measured by a laser diffraction/scattering type particle size distribution meter: LA-920 (manufactured by HORIBA, Ltd.).

(10) TABLE-US-00001 TABLE 1 Symbol Silicic acid (a) Characteristics a1 Hydrolysate of tetraethoxysilane Average particle diameter: 3 nm, (manufactured by Shin-Etsu Shape: spherical shape Chemical Co., Ltd.) a2 Hydrolysate of tetraethoxysilane Average particle diameter: 1 nm, (manufactured by Shin-Etsu Shape: spherical shape Chemical Co., Ltd.) a3 Hydrolysate of tetraethoxysilane Average particle diameter: 9 nm, (manufactured by Shin-Etsu Shape: spherical shape Chemical Co., Ltd.) a4 Hydrolysate of tetraethoxysilane Average particle diameter: 15 nm, (manufactured by Shin-Etsu Shape: spherical shape Chemical Co., Ltd.) a5 Hydrolysate of tetraethoxysilane Average particle diameter: 50 nm, (manufactured by Shin-Etsu Shape: spherical shape Chemical Co., Ltd.) a6 Hydrolysate of tetraethoxysilane Average particle diameter: 70 nm, (manufactured by Shin-Etsu Shape: spherical shape Chemical Co., Ltd.) a7 Snowtech OS (manufactured by Average particle diameter: 3 nm, Nissan Chemical Industries, Ltd.) Shape: spherical shape a8 Potassium silicate (manufactured by Average particle diameter: 3 nm, Nippon Chemical Industries, Co., Ltd.) Shape: spherical shape a9 Aerosil 200 (manufactured by Average particle diameter: 3 nm, NIPPON AEROSIL CO., LTD.) Shape: spherical shape a10 Hydrolysate of tetraethoxysilane Average particle diameter: 3 nm, (manufactured by Shin-Etsu Shape: non-spherical shape Chemical Co., Ltd.)

(11) TABLE-US-00002 TABLE 2 Hydrolysate (b) of an epoxy group-having silane Symbol coupling agent b1 Hydrolysate of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) b2 Hydrolysate of 3-glycidoxyoctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(12) TABLE-US-00003 TABLE 3 Symbol Compound C C1 Tartaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) C2 Sulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) C3 Phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd.)
<Method of Preparing Compound A>

(13) The compound (A) was produced by adding the silicic acid (a) of Table 1, the epoxy group-having silane coupling agent of Table 2, and the acid catalyst (C) of Table 3 to deionized water in accordance with the compound A preparation conditions (A1 to A14) shown in Table 4. The epoxy group-having silane coupling agent was hydrolyzed by rotating an eggplant type flask equipped with a refluxing pipe at a reflux temperature of 20 C. on a water bath at 60 C. in the atmosphere. At that time, the measurements of both the epoxy equivalent and the free alcohol amount were continued until when both the ring-opening of an epoxy group and the hydrolysis to a silanol group were completely (100%) performed.

(14) TABLE-US-00004 TABLE 4 Production conditions of Compound A Symbol pH Concentration (%) Temperature ( C.) A1 3.8 25 60 A2 2.5 25 60 A3 5 25 60 A4 2 25 60 A5 6 25 60 A6 1.5 25 60 A7 10 25 60 A8 11 25 60 A9 3.8 10 60 A10 3.8 40 60 A11 3.8 5 60 A12 3.8 50 60 A13 3.8 1 60 A14 3.8 60 60
<Silicic Acid (B)>

(15) The silicic acid (B): potassium silicate (manufactured by Nippon Chemical Industrial CO., LTD.), Snowtech N (manufactured by Nissan Chemical Industries, Ltd.), and K.sub.2O (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and adjusted to have a mass ratio of M.sub.2O to SiO.sub.2 shown in Table 5. Each of the average particle diameters was 10 to 12 nm. The average particle diameter measurement conditions are as the same as those of the silicic acid (a).

(16) TABLE-US-00005 TABLE 5 Symbol Ratio of M.sub.2O to SiO.sub.2 B1 0.23 B2 0.15 B3 0.3 B4 0.13 B5 0.4 B6 0.1 B7 1.0 B8 0.05 B9 2

(17) Table 6 is a table showing surface treatment agents for metal material according to the present examples and the present comparative examples (ingredients and the ratio of each ingredients and pH). Here, the silicic acid (a) and the hydrolysate (b) of the epoxy group-having silane coupling agent as a constituents of the compound (A) and the silicic acid (B) were added at the ratios (% by mass) shown in Table 6 based on the total solid content of the surface treatment agent for metal material {the total of the solid contents of the silicic acid (a), the hydrolysate (b) of the epoxy group-having silane coupling agent, the silicic acid (B), and the acid catalyst (C)}, and the resulting mixture was adjusted with deionized water to form surface treatment agents for metal material according to the present examples and the present comparative examples (solid content concentration: 5 to 10% by mass). A main ingredient other than the silicic acid (a), the hydrolysate (b) of the epoxy group-having silane coupling agent, the silicic acid (B), and the acid catalyst (C) shown in Table 6 is water. In Table 6, % by mass indicates % by mass based on the total solid content in the surface treatment agent for metal material. Further, in Table 6, B/A or a/b represents a mass ratio. Since the acid catalyst is not added in Comparative example 7, the value described in the item of the hydrolysate (b) of the epoxy group-having silane coupling agent in Comparative example 7 indicates not the hydrolysate (b) of the epoxy group-having silane coupling agent, but a non-hydrolyzed epoxy group-having silane coupling agent.

(18) TABLE-US-00006 TABLE 6 Surface treatment agent for meta1 materia1 Compound (A) Hydrolysate (b) of an epoxy group-having Acid silane cata1yst Example/ Silicic acid (a) coupling agent Mass Silicic acid (B) (C) Mass Comparative Production % by % by ratio % by % by ratio Example method Kind mass Kind mass a/b Kind mass Kind mass B/A pH Example 1 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 2 A1 a2 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 3 A1 a3 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 4 A1 a4 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 5 A1 a5 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 6 A1 a6 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 7 A1 a7 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 8 A1 a8 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 9 A1 a9 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 10 A1 a10 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 11 A2 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 12 A3 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 13 A4 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 14 A5 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 15 A6 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 16 A7 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 17 A8 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 18 A9 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 19 A10 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 20 A11 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 21 A12 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 22 A13 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 23 A14 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 24 A1 a1 9.1% b2 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 25 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C2 0.5% 4.4 9.8 Example 26 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C3 0.5% 4.4 9.8 Example 27 A1 a1 9.1% b1 9.3% 0.98 B2 81.1% C1 0.5% 4.4 9.8 Example 28 A1 a1 9.1% b1 9.3% 0.98 B3 81.1% C1 0.5% 4.4 9.8 Example 29 A1 a1 9.1% b1 9.3% 0.98 B4 81.1% C1 0.5% 4.4 9.8 Example 30 A1 a1 9.1% b1 9.3% 0.98 B5 81.1% C1 0.5% 4.4 9.8 Example 31 A1 a1 9.1% b1 9.3% 0.98 B6 81.1% C1 0.5% 4.4 9.8 Example 32 A1 a1 9.1% b1 9.3% 0.98 B7 81.1% C1 0.5% 4.4 9.8 Example 33 A1 a1 15.3% b1 15.6% 0.98 B1 68.6% C1 0.5% 2.2 9.8 Example 34 A1 a1 6.5% b1 6.6% 0.98 B1 86.4% C1 0.5% 6.6 9.8 Example 35 A1 a1 19.9% b1 20.4% 0.98 B1 59.2% C1 0.5% 1.5 9.8 Example 36 A1 a1 5.0% b1 5.1% 0.98 B1 89.4% C1 0.5% 8.9 9.8 Example 37 A1 a1 23.4% b1 24.0% 0.98 B1 52.1% C1 0.5% 1.1 9.8 Example 38 A1 a1 2.6% b1 2.7% 0.96 B1 94.2% C1 0.5% 4.4 9.8 Example 39 A1 a1 5.0% b1 13.4% 0.37 B1 81.1% C1 0.5% 4.4 9.8 Example 40 A1 a1 10.7% b1 7.7% 1.39 B1 81.1% C1 0.5% 4.4 9.8 Example 41 A1 a1 2.3% b1 16.1% 0.14 B1 81.1% C1 0.5% 4.4 9.8 Example 42 A1 a1 13.0% b1 5.4% 2.41 B1 81.1% C1 0.5% 4.4 9.8 Example 43 A1 a1 1.2% b1 17.2% 0.07 B1 81.1% C1 0.5% 4.4 9.8 Example 44 A1 a1 15.9% b1 2.5% 6.36 B1 81.1% C1 0.5% 4.4 9.8 Example 45 A1 a1 0.1% b1 18.3% 0.01 B1 81.1% C1 0.5% 4.4 9.8 Example 46 A1 a1 16.7% b1 1.8% 9.28 B1 81.0% C1 0.5% 4.4 9.8 Example 47 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.0 Example 48 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 10.5 Example 49 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 8.5 Example 50 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 11.0 Example 51 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 8.0 Example 52 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 11.5 Example 53 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 54 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 55 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 56 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 57 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 58 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 59 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 60 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 61 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 62 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 63 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Example 64 A1 a1 9.1% b1 9.3% 0.98 B1 81.1% C1 0.5% 4.4 9.8 Comparative A1 b1 10.2% B1 89.3% C1 0.5% 9.8 Example 1 Comparative A1 a1 10.0% B1 89.5% C1 0.5% 9.8 Example 2 Comparative A1 a1 49.3% b1 50.2% 0.98 C1 0.5% 9.8 Example 3 Comparative A1 B1 99.5% C1 0.5% 9.8 Example 4 Comparative A1 b1 99.5% C1 0.5% 9.8 Example 5 Comparative A1 a1 99.5% C1 0.5% 9.8 Example 6 Comparative A1 a1 9.2% b1 9.4% 0.98 B1 81.4% 9.8 Example 7 Comparative A1 a1 9.1% b1 9.3% 0.98 B8 81.1% C1 0.5% 4.4 9.8 Example 8 Comparative A1 a1 9.1% b1 9.3% 0.98 B9 81.1% C1 0.5% 4.4 9.8 Example 9 Comparative A1 a1 28.4% b1 29.1% 0.98 B1 42.0% C1 0.5% 0.7 9.8 Example 10 Comparative A1 a1 2.1% b1 2.1% 0.98 B1 95.3% C1 0.5% 22.3 9.8 Example 11
Upper Layer Coating

(19) T1: methylphenyl-based silicone resin (KR-311, manufactured by Shin-Etsu Chemical Co., Ltd.)

(20) T2: epoxy-based silicone resin (ES-1002T, manufactured by Shin-Etsu Chemical Co., Ltd.)

(21) T3: alkyd-based silicone resin (KR-5206, manufactured by Shin-Etsu Chemical Co., Ltd.)

(22) T4: polyester-based silicone resin (KR-5230, manufactured by Shin-Etsu Chemical Co., Ltd.)

(23) (4) Surface Treatment Method

(24) The surface treatment agent for metal material was applied onto each test plate by a bar coating method and each plate was directly placed in an oven without washing with water and dried at each drying temperature shown in Table 7 to form each coating with each coating amount shown in Table 7. The coating amount indicates a coating amount per one side of the steel sheet. The surface treatment for the upper layer coating is also performed in the same manner and the coating thickness indicates a coating thickness per one side of the steel sheet.

(25) TABLE-US-00007 TABLE 7 Conditions of test plate production Upper layer film Example/ Coating Film Comparative Steel amount PMT thickness PMT Example sheet g/m2 C. Kind m C. Example 1 M1 1.0 250 Example 2 M1 1.0 250 Example 3 M1 1.0 250 Example 4 M1 1.0 250 Example 5 M1 1.0 250 Example 6 M1 1.0 250 Example 7 M1 1.0 250 Example 8 M1 1.0 250 Example 9 M1 1.0 250 Example 10 M1 1.0 250 Example 11 M1 1.0 250 Example 12 M1 1.0 250 Example 13 M1 1.0 250 Example 14 M1 1.0 250 Example 15 M1 1.0 250 Example 16 M1 1.0 250 Example 17 M1 1.0 250 Example 18 M1 1.0 250 Example 19 M1 1.0 250 Example 20 M1 1.0 250 Example 21 M1 1.0 250 Example 22 M1 1.0 250 Example 23 M1 1.0 250 Example 24 M1 1.0 250 Example 25 M1 1.0 250 Example 26 M1 1.0 250 Example 27 M1 1.0 250 Example 28 M1 1.0 250 Example 29 M1 1.0 250 Example 30 M1 1.0 250 Example 31 M1 1.0 250 Example 32 M1 1.0 250 Example 33 M1 1.0 250 Example 34 M1 1.0 250 Example 35 M1 1.0 250 Example 36 M1 1.0 250 Example 37 M1 1.0 250 Example 38 M1 1.0 250 Example 39 M1 1.0 250 Example 40 M1 1.0 250 Example 41 M1 1.0 250 Example 42 M1 1.0 250 Example 43 M1 1.0 250 Example 44 M1 1.0 250 Example 45 M1 1.0 250 Example 46 M1 1.0 250 Example 47 M1 1.0 250 Example 48 M1 1.0 250 Example 49 M1 1.0 250 Example 50 M1 1.0 250 Example 51 M1 1.0 250 Example 52 M1 1.0 250 Example 53 M1 1.0 60 Example 54 M1 1.0 80 Example 55 M1 1.0 280 Example 56 M1 1.0 300 Example 57 M1 0.5 250 Example 58 M1 5.0 250 Example 59 M1 0.1 250 Example 60 M1 10.0 250 Example 61 M1 1.0 250 T1 20 200 Example 62 M1 1.0 250 T2 20 200 Example 63 M1 1.0 250 T3 20 200 Example 64 M1 1.0 250 T4 20 200 Comparative M1 1.0 250 Example 1 Comparative M1 1.0 250 Example 2 Comparative M1 1.0 250 Example 3 Comparative M1 1.0 250 Example 4 Comparative M1 1.0 250 Example 5 Comparative M1 1.0 250 Example 6 Comparative M1 1.0 250 Example 7 Comparative M1 1.0 250 Example 8 Comparative M1 1.0 250 Example 9 Comparative M1 1.0 250 Example 10 Comparative M1 1.0 250 Example 11
(5) Evaluation Test Method
(5-1) Water Resistance

(26) Each test plate was cut out into a size of 70150 mm, the backside and the edge were sealed with a cellophane tape, and the resulting test piece was evaluated at a temperature of 50 C. and a humidity of 85% until when 5% of rust occurred (area rate).

(27) : it took 120 hours or more until 5% rust was generated;

(28) : it took 72 hours or more and less than 120 hours until 5% rust was generated;

(29) : it took 48 hours or more and less than 72 hours until 5% rust was generated;

(30) : it took 24 hours or more and less than 48 hours until 5% rust was generated; and

(31) x: it took less than 24 hours until 5% rust was generated.

(32) (5-2) Adhesion

(33) 100 grids with 1 mm square were formed in the coating of each test plate in accordance with JIS K5400 and the tape was peeled off and the number of remained squares (where the coating was not peeled off) was evaluated as the grid residual ratio.

(34) : the residual ratio was 95% to 100%;

(35) : the residual ratio was 90% or more and less than 95%;

(36) : the residual ratio was 70% or more and less than 90%;

(37) : the residual ratio was 50% or more and less than 70%; and

(38) x: the residual ratio was 0% or more and less than 50%.

(39) (5-3) Water Resistance After Heat Test

(40) Each test plate was cut out into a size of 70150 mm and heated in an oven at 700 C. for 24 hours, followed by being allowed to stand at room temperature for 24 hours. Thereafter, the backside and the edge were sealed with a cellophane tape, and the resulting test piece was evaluated at a temperature of 50 C. and a humidity of 85% until when 5% (area rate) of rust occurred.

(41) : it took 120 hours or more until 5% rust was generated;

(42) : it took 96 hours or more and less than 120 hours until 5% rust was generated;

(43) : it took 72 hours or more and less than 96 hours until 5% rust was generated;

(44) : it took 48 hours or more and less than 72 hours until 5% rust was generated;

(45) : it took 24 hours or more and less than 48 hours until 5% rust was generated; and

(46) x: it took less than 24 hours until 5% rust was generated.

(47) (5-4) Water Resistance After Heat Test

(48) Each test plate was cut out into a size of 70150 mm and heated in an oven at 700 C. for 24 hours, followed by being allowed to stand at room temperature for 24 hours. Thereafter, as for the resulting test piece in which the backside and the edge were sealed with a cellophane tape, the number of remained squares (where the coating was not peeled off) was evaluated as the grid residual ratio.

(49) : the residual ratio was 95% to 100%;

(50) : the residual ratio was 90% or more and less than 95%;

(51) : the residual ratio was 70% or more and less than 90%;

(52) : the residual ratio was 50% or more and less than 70%; and

(53) x: the residual ratio was 0% or more and less than 50%.

(54) (5-5) Solution Stability

(55) The treatment agent tightly sealed was stored in a thermostat bath at 40 C. for three months and the solution appearance was visually evaluated.

(56) : the solution was not changed or slightly thickened, and no precipitates were observed;

(57) : the solution was slightly thickened and slight precipitates were observed; and

(58) x: the solution was thickened or precipitates were observed.

(59) The metal materials obtained by using the surface treatment agent for metal materials of the Examples and Comparative Examples were subjected to the evaluations (5-1) to (5-3) above, and the results are shown in Table 8. From a practical viewpoint, it is required that there is no x in the evaluation items.

(60) TABLE-US-00008 TABLE 8 Water Example/ resistance Adhesion Comparative Water after heat after heat Solution Example resistance Adhesion test test stability Example 1 + Example 2 + Example 3 + Example 4 + Example 5 + Example 6 + Example 7 + Example 8 + Example 9 + Example 10 + Example 11 + Example 12 + Example 13 + Example 14 + Example 15 + Example 16 + Example 17 + Example 18 + Example 19 + Example 20 + Example 21 + Example 22 + Example 23 + Example 24 + Example 25 Example 26 Example 27 + Example 28 + Example 29 + Example 30 + Example 31 + Example 32 + Example 33 + Example 34 + Example 35 Example 36 Example 37 Example 38 Example 39 + Example 40 + Example 41 + Example 42 + Example 43 + Example 44 + Example 45 + Example 46 + Example 47 + Example 48 + Example 49 + Example 50 + Example 51 + Example 52 + Example 53 + Example 54 + Example 55 + Example 56 + Example 57 + Example 58 + Example 59 Example 60 Example 61 Example 62 Example 63 Example 64 Comparative X X Example 1 Comparative X X X Example 2 Comparative X Example 3 Comparative X X X X Example 4 Comparative X X X Example 5 Comparative X X Example 6 Comparative X Example 7 Comparative X X Example 8 Comparative X X Example 9 Comparative X X Example 10 Comparative X X Example 11

(61) As shown in Table 8, it is found that the metal material treated with the surface treatment agent for metal material as specified in the present invention has excellent heat resistance in high-temperature environments and excellent adhesion and water resistance for a long period of time.