Surface Treatment Agent, Metal Material Having Surface-Treated Coating Film and Method for Producing Same

Abstract

The present invention is aimed at providing: a surface treatment agent that is capable of forming a surface-treated coating film having excellent antifouling properties; a metal material that includes a surface-treated coating film using the surface treatment agent; and a method of producing the metal material. The present invention provides a surface treatment agent containing: a silicone resin (A); a compound (B) containing a metal element selected from titanium, platinum, rhodium and palladium; and an aromatic hydrocarbon-based solvent (C). In the surface treatment agent, (I) a content of the silicone resin (A) is in a range of 90% by mass to 99.9% by mass with respect to a total solid mass of the silicone resin (A) and the compound (B), and (II) a ratio (B.sub.M/A.sub.M) of a mass (B.sub.M) of the compound (B) to a mass (A.sub.M) of the silicone resin (A) is in a range of 0.001 to 0.111.

Claims

1. A surface treatment agent, comprising: a silicone resin (A); a compound (B) containing a metal element selected from the group consisting of titanium, platinum, rhodium, and palladium; and an aromatic hydrocarbon-based solvent (C), wherein (I) a content of the silicone resin (A) is in a range of 90% by mass to 99.9% by mass with respect to a total solid mass of the silicone resin (A) and the compound (B), and (II) a ratio (B.sub.M/A.sub.M) of a mass (B.sub.M) of the compound (B) to a mass (A.sub.M) of the silicone resin (A) is in a range of 0.001 to 0.111.

2. The surface treatment agent according to claim 1, further comprising a vinyl group-containing silane coupling agent and/or an epoxy group-containing silane coupling agent, wherein a ratio (D.sub.M/A.sub.M) of a total mass (D.sub.M) of the vinyl group-containing silane coupling agent and the epoxy group-containing silane coupling agent to the mass (A.sub.M) is in a range of 0.005 to 0.251.

3. A method of producing a metal material comprising a surface-treated coating film, the method comprising: a first step of contacting the surface treatment agent according to claim 1 on/over a surface of a metal material; and a second step of drying the surface treatment agent contacted with the metal material and thereby forming a surface-treated coating film.

4. The method according to claim 3, further comprising, prior to the first step: a step of contacting a base treatment agent, comprising an amino group-containing silane coupling agent, a polymer of the silane coupling agent or a copolymer formed with the polymer, on/over the surface of the metal material; and a step of drying the base treatment agent contacted with the metal material and thereby forming a base coating.

5. A metal material comprising a surface-treated coating film obtained by the method according to claim 3, wherein the surface-treated coating film has a film thickness in a range of 10 m to 400 m.

6. A metal material comprising a surface-treated coating film obtained by the method according to claim 4, wherein the surface-treated coating film has a film thickness in a range of 10 m to 400 m, and a Si content in the base coating is in a range of 0.1 mg/m.sup.2 to 50 mg/m.sup.2 in terms of SiO.sub.2 mass.

7. A metal material comprising a surface-treated coating film on/over a surface of the metal material, wherein the surface-treated coating film comprises: a silicone resin (A); and a compound (B) containing a metal element selected from the group consisting of titanium, platinum, rhodium, and palladium, (I) a content of the silicone resin (A) is in a range of 90% by mass to 99.9% by mass with respect to a total solid mass of the silicone resin (A) and the compound (B), and (II) a ratio (B.sub.M/A.sub.M) of a mass (B.sub.M) of the compound (B) to a mass (A.sub.M) of the silicone resin (A) is in a range of 0.001 to 0.111.

8. The metal material comprising a surface-treated coating film according to claim 7, further comprising a base coating between the metal material and the surface-treated coating film, wherein the base coating comprises an amino group-containing silane coupling agent, a polymer of the silane coupling agent, or a copolymer formed with the polymer.

9. The metal material comprising a surface-treated coating film according to claim 7, wherein the surface-treated coating film has a film thickness in a range of 10 m to 400 m.

10. The metal material comprising a surface-treated coating film according to claim 8, wherein the surface-treated coating film has a film thickness in a range of 10 m to 400 m, and a Si content in the base coating is in a range of 0.1 mg/m.sup.2 to 50 mg/m.sup.2 in terms of SiO.sub.2 mass.

11. The metal material comprising a surface-treated coating film according to claim 5, wherein the metal material is stainless steel.

Description

EXAMPLES

[0067] The actions and effects of the present invention will now be described concretely by way of Examples. It is noted here, however, that the below-described Examples do not limit the present invention.

(1) Test Materials (Raw Materials)

[0068] The following commercially available materials were used as test materials. [0069] (M1) cold-rolled steel sheet SPCC-SD: sheet thickness=0.8 mm [0070] (M2) stainless steel SUS304: sheet thickness=0.8 mm

(2) Pretreatment (Alkali Degreasing)

[0071] The surfaces of the test materials were subjected to a degreasing treatment in which the test materials were immersed in a 2% aqueous solution of an alkali degreasing agent (FINE CLEANER E6406, manufactured by Nihon Parkerizing Co., Ltd.) at 60 C. for 30 seconds, whereby oil and dirt were removed from the surfaces. Subsequently, the thus pretreated test materials were washed with tap water, and pure water was further poured over the test materials, after which the surfaces of the test materials were dried at 100 C.

(3) Preparation of Surface Treatment Agents

[0072] The components shown in Table 1 were mixed at the respective prescribed mass ratios to prepare surface treatment agents of Examples 1 to 23 and Comparative Examples 1 to 5. Further, in order to adjust the viscosity of each of the thus prepared surface treatment agents to be 7.0, a vapor-phase silica (fumed silica; AEROSIL R974, manufactured by Nippon Aerosil Co., Ltd.) was added as a thickening agent. The viscosity was adjusted using a vibration-type viscometer (VM Series, manufactured by Sekonic Corporation) at 25 C. In Table 1, the values in the columns of % by mass under Silicone resin (A), Compound (B) and Silane coupling agent (D) each indicate the mass ratio of each component with respect to a total mass of these components. Further, in Table 1, the values in the column of % by mass under Aromatic hydrocarbon-based solvent (C) each indicate the mass ratio of the aromatic hydrocarbon-based solvent (C) with respect to a total mass of the corresponding surface treatment agent. In Table 1, B.sub.M/A.sub.M represents a ratio of the total mass (B.sub.M) of the compound (B) to the total mass (A.sub.M) of the silicone resin (A). Moreover, in Table 1, D.sub.M/A.sub.M represents a ratio of the total mass (D.sub.M) of the silane coupling agent (D) to the total mass (A.sub.M) of the silicone resin (A). Tables 2 to 5 show the types of the respective components shown in Table 1.

TABLE-US-00001 TABLE 1 Formulation of Surface Treatment Agent Surface treatment agent Example/ Silicone resin Compound Aromatic hydrocarbon- Silane coupling Comparative (A) (B) based solvent (C) agent (D) Mass ratio Mass ratio Example Type % by mass Type % by mass Type % by mass Type % by mass B.sub.M/A.sub.M D.sub.M/A.sub.M Example 1 A2 90.0% B1 10.0% C1 70.0% 0.111 Example 2 A2 95.0% B1 5.0% C1 70.0% 0.053 Example 3 A2 98.0% B1 2.0% C1 70.0% 0.020 Example 4 A2 99.6% B1 0.4% C1 70.0% 0.004 Example 5 A2 99.7% B1 0.3% C1 70.0% 0.003 Example 6 A2 99.8% B1 0.2% C1 70.0% 0.002 Example 7 A2 99.9% B1 0.1% C1 70.0% 0.001 Example 8 A1 99.6% B1 0.4% C1 70.0% 0.004 Example 9 A3 99.6% B1 0.4% C1 70.0% 0.004 Example 10 A2 99.6% B2 0.4% C1 70.0% 0.004 Example 11 A2 99.6% B2 0.4% C2 70.0% 0.004 Example 12 A2 99.6% B1 0.4% C1 40.0% 0.004 Example 13 A2 99.6% B1 0.4% C1 50.0% 0.004 Example 14 A2 99.6% B1 0.4% C1 60.0% 0.004 Example 15 A2 99.6% B1 0.4% C1 75.0% 0.004 Example 16 A2 99.6% B1 0.4% C1 80.0% 0.004 Example 17 A2 99.6% B1 0.4% C1 90.0% 0.004 Example 18 A2 99.1% B2 0.4% C1 70.0% D1 0.5% 0.004 0.005 Example 19 A2 98.6% B2 0.4% C1 70.0% D1 1.0% 0.004 0.010 Example 20 A2 96.6% B2 0.4% C1 70.0% D1 3.0% 0.004 0.031 Example 21 A2 89.6% B2 0.4% C1 70.0% D1 10.0% 0.004 0.112 Example 22 A2 79.6% B2 0.4% C1 70.0% D1 20.0% 0.005 0.251 Example 23 A2 96.6% B2 0.4% C1 70.0% D2 3.0% 0.004 0.031 Comparative A2 80.0% B1 20.0% C1 70.0% 0.250 Example 1 Comparative A2 100.0% C1 70.0% Example 2 Comparative B2 100.0% C1 70.0% Example 3 Comparative A2 99.6% B1 0.4% C1 30.0% 0.004 Example 4 Comparative A2 99.6% B1 0.4% C1 95.0% 0.004 Example 5

TABLE-US-00002 TABLE 2 Symbol Silicone resin (A) A1 Epoxy resin-based silicone resin (product name: ES-1002T, manufactured by Shin-Etsu Chemical Co., Ltd.) A2 Mixture of a polydimethylsiloxane having a dimethylvinylsiloxane group at each of both terminals of its molecular chain and a methyl hydrogen siloxane-dimethyl siloxane copolymer having a trimethylsilyl group at each of both terminals of its molecular chain (product name: KR-165, manufactured by Shin-Etsu Chemical Co., Ltd.) A3 Polyester resin-based silicone resin (product name: KR-5230, manufactured by Shin-Etsu Chemical Co., Ltd.)

TABLE-US-00003 TABLE 3 Symbol Compound (B) B1 H.sub.2PtC1.sub.4nH.sub.2O (product name: D-168, manufactured by Shin-Etsu Chemical Co., Ltd.) B2 Ti(C.sub.3H.sub.7O).sub.2(C.sub.5H.sub.7O.sub.2).sub.2 (product name: ORGATIX TC-100, manufactured by Matsumoto Fine Chemical Co., Ltd.)

TABLE-US-00004 TABLE 4 Aromatic hydrocarbon- Symbol based solvent (C) C1 Xylene (SP value: 8.9) C2 Benzene (SP value: 9.2)

TABLE-US-00005 TABLE 5 Symbol Silane coupling agent (D) D1 Vinyltrimethoxysilane (product name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) D2 3-glycidoxypropyltrimethoxysilane (product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(4) Metal Materials Having Surface-Treated Coating Film

[0073] As shown in Table 6, various surface treatment agents were contacted with the surfaces of the pretreated test materials. Subsequently, without washing the test materials with water, the surface treatment agents contacted with the test materials were dried at the respective drying temperatures shown in Table 6 to produce test materials (test sheets) each having a surface-treated coating film of a prescribed thickness. Further, with regard to No. 35 to 39 shown in Table 6, the pretreated test materials, before a surface treatment agent was contacted therewith, were immersed in a base treatment agent that contained the amino group-containing silane coupling agent shown in Table 6 at 25 C., whereby a base coating was formed on the surface of each test material. It is noted here that 2-propanol was used as a solvent for the preparation of the base treatment agent. The mass concentration of the base treatment agent and the immersion time were adjusted as appropriate such that the Si content in the resulting base coating in terms of SiO.sub.2 mass would be the respective values shown in Table 6. The type of Amino group-containing silane coupling agent in base treatment agent and the types of Contact method used for each surface treatment agent, which are shown in Table 6, are described in Tables 7 and 8, respectively.

TABLE-US-00006 TABLE 6 Production of Test Sheet Base coating-forming step Amino group- containing silane Surface-treated coating film-forming step coupling agent Si Surface Drying Film Test Steel in base content treatment Contact temperature thickness Sheet sheet treatment agent mg/m.sup.2 agent method C. m No. 1 M2 Example1 T1 150 100 No. 2 M2 Example2 T1 150 100 No. 3 M2 Example3 T1 150 100 No. 4 M2 Example4 T1 150 100 No. 5 M2 Example5 T1 150 100 No. 6 M2 Example6 T1 150 100 No. 7 M2 Example7 T1 150 100 No. 8 M2 Example8 T1 150 100 No. 9 M2 Example9 T1 150 100 No. 10 M2 Example10 T1 150 100 No. 11 M2 Example11 T1 150 100 No. 12 M2 Example12 T1 150 100 No. 13 M2 Example13 T1 150 100 No. 14 M2 Example14 T1 150 100 No. 15 M2 Example15 T1 150 100 No. 16 M2 Example16 T1 150 100 No. 17 M2 Example17 T1 150 100 No. 18 M2 Example18 T1 150 100 No. 19 M2 Example19 T1 150 100 No. 20 M2 Example20 T1 150 100 No. 21 M2 Example21 T1 150 100 No. 22 M2 Example22 T1 150 100 No. 23 M2 Example23 T1 150 100 No. 24 M1 Example4 T1 150 100 No. 25 M2 Example4 T1 150 10 No. 26 M2 Example4 T1 150 20 No. 27 M2 Example4 T1 150 300 No. 28 M2 Example4 T1 150 400 No. 29 M2 Example4 T1 40 100 No. 30 M2 Example4 T1 60 100 No. 31 M2 Example4 T1 180 100 No. 32 M2 Example4 T1 250 100 No. 33 M2 Example4 T1 150 100 No. 34 M2 Example4 T2 150 100 No. 35 M2 S1 0.1 Example4 T1 150 100 No. 36 M2 S1 1 Example4 T1 150 100 No. 37 M2 S1 10 Example4 T1 150 100 No. 38 M2 S1 40 Example4 T1 150 100 No. 39 M2 S1 50 Example4 T1 150 100 No. 40 M2 Comparative T1 150 100 Example1 No. 41 M2 Comparative T1 150 100 Example2 No. 42 M2 Comparative T1 150 100 Example3 No. 43 M2 Comparative T1 150 100 Example4 No. 44 M2 Comparative T1 150 100 Example5

TABLE-US-00007 TABLE 7 Symbol Amino group-containing silane coupling agent S1 3-aminopropyltriethoxysilane (product name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

TABLE-US-00008 TABLE 8 Symbol Contact method T1 Dispenser (desktop-type robot) (product name: ML-808GX, SM4000 MEGAX-3A-SS, manufactured by Musashi Engineering, Inc.) T2 Immersion method

(5) Evaluation Tests

[0074] For each test sheet, the following evaluation tests were conducted. The results of the evaluation tests are shown in Table 9. From a practical standpoint, the test sheets without D in any of the evaluated items shown in Table 9 were regarded as satisfactory.

Insulation Test after Heating

[0075] The test sheets (No. 1 to 44) were each cut into a size of 70 mm150 mm, subsequently heated in an oven at 300 C. for 24 hours, and then left to stand at room temperature (25 C.) for 24 hours. Thereafter, in accordance with JIS C2110-1:2016, a voltage was applied to each test sheet at a voltage increase rate of 10 V/s, and the maximum voltage with which each test sheet was electrified was measured to evaluate the post-heating insulation based on the following evaluation criteria.

(Evaluation Criteria)

[0076] S: The maximum voltage was 1,000 V or higher.

[0077] A: The maximum voltage was 500 V or higher but lower than 1,000 V.

[0078] B: The maximum voltage was 300 V or higher but lower than 500 V.

[0079] C: The maximum voltage was 200 V or higher but lower than 300 V.

[0080] D: The maximum voltage was lower than 200 V.

Adhesion Test after Heating

[0081] The test sheets were each cut into a size of 70 mm150 mm, subsequently heated in an oven at 300 C. for 24 hours, and then left to stand at room temperature (25 C.) for 24 hours. Next, on each test sheet, 11 cuts were made at 1-mm intervals both in the lengthwise and the widthwise directions to form a grid (1010=100 cells). Thereafter, a cellophane tape was pasted to the grid-form cuts and then peeled off, and the number of remaining cells among the 100 cells was measured. The residual ratio was calculated from the measurement results to evaluate the post-heating adhesion based on the following evaluation criteria.

(Evaluation Criteria)

[0082] S: The residual ratio was 95% to 100%.

[0083] A: The residual ratio was 90% or higher but lower than 95%.

[0084] B: The residual ratio was 70% or higher but lower than 90%.

[0085] C: The residual ratio was 50% or higher but lower than 70%.

[0086] D: The residual ratio was 0% or higher but lower than 50%.

Test of Antifouling Properties

[0087] The test sheets were each cut into a size of 70 mm150 mm and then maintained such that each test sheet had a surface temperature of 300 C., after which three drops of a simulated contaminant liquid (a mixture of acrylic resin and carbon black) were applied dropwise to each test sheet. After the simulated contaminant liquid was dried, each test sheet was cooled at room temperature (25 C.). Thereafter, each test sheet was wiped with a piece of dry gauze, and the area ratio (residual ratio) of remaining dry matter (burnt matter such as soot) with respect to the area of the dried contaminant liquid was measured to evaluate the antifouling properties based on the following evaluation criteria.

(Evaluation Criteria)

[0088] S: The residual ratio was 0% or lower.

[0089] A: The residual ratio was 1% or higher but lower than 5%.

[0090] B: The residual ratio was 5% or higher but lower than 10%.

[0091] C: The residual ratio was 10% or higher but lower than 30%.

[0092] D: The residual ratio was 30% or higher.

TABLE-US-00009 TABLE 9 Evaluation Results Evaluation results Test Post-heating Post-heating Antifouling Sheet insulation adhesion properties No. 1 B A B No. 2 B A A No. 3 A A A No. 4 A A A No. 5 A A A No. 6 B A A No. 7 B A B No. 8 A B A No. 9 A B A No. 10 A A B No. 11 A A A No. 12 B A A No. 13 A A A No. 14 A A A No. 15 A A A No. 16 A A A No. 17 B A A No. 18 A A S No. 19 A A S No. 20 A S S No. 21 A A S No. 22 A A S No. 23 A S A No. 24 B A B No. 25 B A A No. 26 A A A No. 27 A A A No. 28 A B A No. 29 A B A No. 30 A A A No. 31 A A A No. 32 A B A No. 33 A A A No. 34 A B A No. 35 A S A No. 36 S S S No. 37 S S S No. 38 S S S No. 39 A S A No. 40 D C D No. 41 D C D No. 42 D D D No. 43 D C C No. 44 D C C

[0093] The present invention has been described above in detail referring to concrete 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.