COATED ALUMINUM MATERIAL FOR JOINING AND ALUMINUM RESIN COMPOSITE MATERIAL

Abstract

Provided is a coated aluminum material for joining having an adhesion layer on a surface, and can exert excellent adhesion strength and corrosion resistance performance even under severe use conditions while being chromium-free. Provided is a coated aluminum material capable of producing the coated aluminum material for joining, and an aluminum resin composite material using the coated aluminum material for joining. Disclosed are a coated aluminum material for joining having an adhesion layer on a surface thereof and including a coated aluminum material and a silica-containing film formed on a surface of the aluminum material, the silica-containing film including 0.5 to 35 mass % of a silane coupling agent and having Si and P contents of 2 to 60, and 0.1 to 6.0 mg/m.sup.2, respectively, and P/Si mass ratio of P content and Si content of 0.02 to 0.15, and a coated aluminum material capable of producing the coated aluminum material for joining, and an aluminum resin composite material obtained using the coated aluminum material for joining.

Claims

1. A coated aluminum material comprising: an aluminum material including aluminum or an aluminum alloy, and a silica-containing film, as a joining undercoat film, formed on a surface of the aluminum material, the silica-containing film containing a water dispersible silica, phosphoric acid, and a silane coupling agent, wherein the silica-containing film includes the silane coupling agent in a ratio of 0.5 to 35 mass %, and has a Si content falling within the range of 2 to 60 mg/m.sup.2, a P content falling within the range of 0.1 to 6.0 mg/m.sup.2, and a mass ratio (P/Si mass ratio) of the P content to the Si content falling within the range of 0.02 to 0.15.

2. A coated aluminum material for joining comprising: an aluminum material including aluminum or an aluminum alloy, and an adhesion layer formed on a surface of the aluminum material with a silica-containing film that contains a water dispersible silica, phosphoric acid, and a silane coupling agent provided therebetween, wherein the silica-containing film includes the silane coupling agent in a ratio of 0.5 to 35 mass %, and has a Si content falling within the range of 2 to 60 mg/m.sup.2, a P content falling within the range of 0.1 to 6.0 mg/m.sup.2, and a mass ratio (P/Si mass ratio) of the P content to the Si content falling within the range of 0.02 to 0.15.

3. The coated aluminum material for joining according to claim 2, wherein the adhesion layer is a coating film made of a thermoplastic resin having a reactive functional group.

4. The coated aluminum material for joining according to claim 3, wherein the coating film made of a thermoplastic resin is a coating film including one or more resins selected from an acid modified polyolefin type resin and an acid modified chlorinated polyolefin type resin.

5. The coated aluminum material for joining according to claim 2, wherein the adhesion layer is a coating film made of a thermosetting resin.

6. The coated aluminum material for joining according to claim 5, wherein the coating film made of a thermosetting resin is a coating film including an epoxy resin adhesive.

7. The coated aluminum material for joining according to claim 2, wherein a coating film layer is formed between the silica-containing film and the adhesion layer.

8. The coated aluminum material for joining according to claim 7, wherein the coating film layer is a coating film including a thermosetting resin.

9. The coated aluminum material for joining according to claim 7, wherein the total film thickness of the sum of the film thickness of the adhesion layer and the film thickness of the coating film layer is 5 m or more and 200 m or less.

10. The coated aluminum material for joining according to claim 2, wherein the coated aluminum material for joining is a precoated material before machining.

11. An aluminum resin composite material, comprising: the coated aluminum material for joining according to claim 2; and a resin molded body joined to the adhesion layer of the coated aluminum material for joining.

12. The aluminum resin composite material according to claim 11, comprising: a metal-resin integrally molded product including the coated aluminum material for joining and the resin molded body joined with each other by injection molding, coextrusion molding, or thermocompression.

13. The aluminum resin composite material according to claim 11, wherein the coated aluminum material for joining is a precoated material having adhesion layers on two surfaces thereof, respectively, and a resin molded body is joined to the adhesion layer on any one surface of the two surfaces.

14. The aluminum resin composite material according to claim 11, wherein the coated aluminum material for joining is a precoated material having an adhesion layer on one surface thereof and having a coating film layer on the other surface, and a resin molded body is joined to the adhesion layer.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0064] FIG. 1 is an explanatory view for illustrating a testing method of tensile shear strength evaluation according to the ISO 19095 testing method, wherein (a) in FIG. 1 shows a joining aluminum specimen for tensile shear strength evaluation, and (b) in FIG. 1 shows a testing method for tensile shear strength evaluation.

[0065] FIG. 2 is an explanatory view of an adhesion specimen for use in a testing method of an adhesive evaluation according to the JIS K 6829 testing method.

DESCRIPTION OF EMBODIMENTS

[0066] Hereinafter, preferred embodiments of the present invention will be specifically described by way of Examples and Comparative Examples. [Examples 1 to 22 and Comparative Examples 1 to 12]

[0067] As an aluminum material, an aluminum sheet (JIS 5052-H18) with dimensions of 70 mm150 mm1.0 mm was prepared. Each prepared aluminum sheet of respective Examples and Comparative Examples was subjected to a pretreatment, a film-forming treatment of a silica-containing film, and formation of a coating film shown below, thereby preparing each aluminum coated material of respective Examples and Comparative Examples.

[0068] [Pretreatment]

[0069] In respective Examples and Comparative Examples, each of the aluminum sheets was subjected to the following pretreatment.

[0070] Namely, a degreasing treatment in which the aluminum sheet was immersed in a 2 mass % aqueous solution of a degreasing agent (trade name: SURFCLEANER 155 manufactured by NIPPON PAINT Co., Ltd.) containing sodium metasilicate under the conditions of 60 C. and 30 seconds was performed, followed by water washing and drying.

[0071] [Film-Forming Treatment]

[0072] As a treatment solution for forming a silica-containing film, using the colloidal silicas and additive resins, and the like shown in Table 1, the phosphorus compounds, the silane coupling agents, and water or isopropanol (iso-PrOH) as a solvent shown in Table 2, a film-forming treatment solution with each composition shown in Table 2 and Table 3 was prepared.

TABLE-US-00001 TABLE 1 Colloidal silica Solid content Average concen- particle tration Size Dispersion Manufacturer (wt %) (nm) medium Colloidal ST-C Nissan Chemical 20 10-20 Water silica Corporation ST-O Nissan Chemical 20 10-21 Water Corporation ST-UP Nissan Chemical 20 40-300 Water Corporation chain- shaped ST-OL Nissan Chemical 20 40-50 Water Corporation ST-40 Nissan Chemical 40 10-20 Water Corporation IPA-ST Nissan Chemical 30 10-20 iso-PrOH Corporation

TABLE-US-00002 TABLE 2 Composition of film-forming treatment solutions of Examples 1-11 and Comparative Examples 1-8 Examples 1 2 3 4 5 6 7 8 9 10 Colloidal ST-C 4.5 silica ST-O 15 15 15 ST-OL 48 ST-UP 0.9 9 ST-40 IPA-ST 15 15 15 Phosphorus Phosphoric 1.8 0.3 0.13 0.02 0.4 0.4 0.2 0.4 0.4 0.2 compound acid Silane KBE403(epoxy 0.2 0.1 coupling group) agent KBE803(thiol 0.3 0.03 1 0.1 1.6 1 0.1 group) KBE903(amino 0.05 group) Resin polyacrylic acid Pentalite MODEPICS302 The Water 50 84.4 95.32 90.5 84.7 10 84.7 balance iso-PrOH 99.05 83.6 73 83.6 Example Comparative Examples 11 1 2 3 4 5 6 7 8 Colloidal ST-C silica ST-O 2 15 50 50 ST-OL 12 ST-UP 4.5 9 ST-40 50 IPA-ST 3.5 phosphorus phosphoric 0.1 0.1 3 0.1 0.3 0.3 0.5 0.3 compound acid Silane KBE403(epoxy 0.1 coupling group) agent KBE803(thiol 0.5 0.9 0.3 0.3 group) KBE903(amino 10 group) Resin Polyacrylic 0.1 acid Pentalite 0.003 MODEPICS302 50 The Water 44.9 97.9 81.1 49.4 49.4 90.4 87.6 balance iso-PrOH 50 96.4

TABLE-US-00003 TABLE 3 Composition of film-forming treatment solutions of Examples 12-22 and Comparative Examples 9-12 Examples 12 13 14 15 16 17 18 19 Colloidal ST-C 4.5 silica ST-O 15 15 ST-OL 48 ST-UP 0.9 9 ST-40 IPA-ST 15 15 Phosphorus Phosphoric 1.8 0.3 0.13 0.02 0.26 0.4 0.2 0.4 compound acid Silane KBE403(epoxy 0.2 0.3 0.03 coupling group) agent KBE803(thiol 0.1 1 0.1 1.6 group) KBE903(amino 0.05 group) Resin Polyacrylic acid Pentalite MODEPICS302 The Water 50 84.4 95.32 90.64 84.7 10 balance iso-PrOH 99.05 83.6 73 Examples Comparative Examples 20 21 22 9 10 11 12 Colloidal ST-C silica ST-O ST-OL ST-UP 9 9 9 9 9 ST-40 50 50 IPA-ST Phosphorus Phosphoric 0.26 0.26 0.26 0.26 0.26 compound acid Silane KBE403(epoxy Coupling group) agent KBE803(thiol 0.1 0.1 0.1 0.1 0.1 group) KBE903(amino 10 10 group) Resin Polyacrylic acid Pentalite MODEPICS302 50 50 The Water 90.64 90.64 90.64 90.64 90.64 balance iso-PrOH

[0073] [Manufacturing of Aluminum Coated Material]

[0074] In each of Examples 1, 3, 5 to 9, 12, 14, and 16 to 22, and Comparative Examples 1 to 4, 6 to 7, and 10 to 12, after completion of the pretreatment, using a bar coater, the film-forming treatment solution with each composition shown in Table 2 or Table 3 was coated so as to achieve a coating amount of 1 g/m.sup.2. Then, at a peak temperature (PMT: Peak metal temperature) of 180 C., drying was performed for 1 minute, thereby forming a silica-containing film on a surface of the aluminum sheet.

[0075] Further, in Examples 2 and 13, after completion of the pretreatment, using a bar coater, the film-forming treatment solution with each composition shown in Table 2 or Table 3 was coated so as to achieve a coating amount of 2.5 g/m.sup.2. Then, at a PMT of 180 C., drying was performed for 1 minute, thereby forming a silica-containing film on a surface of the aluminum sheet.

[0076] Further, in Examples 4 and 15, after completion of the pretreatment, using a spray gun, the film-forming treatment solution with each composition shown in Table 2 or Table 3 was coated so as to achieve a coating amount of 25 g/m.sup.2. Then, at a PMT of 180 C., drying was performed for 1 minute, thereby forming a silica-containing film on a surface of the aluminum sheet.

[0077] Further, in Example 10, after completion of the pretreatment, using a bar coater, the film-forming treatment solution with each composition shown in Table 2 was coated so as to achieve a coating amount of 2 g/m.sup.2. Then, at a PMT of 220 C., drying was performed for 1 minute, thereby forming a silica-containing film on a surface of the aluminum sheet.

[0078] Further, in Example 11, after completion of the pretreatment, using a bar coater, the film-forming treatment solution with each composition shown in Table 2 was coated so as to achieve a coating amount of 10 g/m.sup.2. Then, at a peak temperature (PMT: Peak metal temperature) of 220 C., drying was performed for 1 minute, thereby forming a silica-containing film on a surface of the aluminum sheet.

[0079] Further, in Comparative Example 5, after completion of the pretreatment, using a bar coater, the film-forming treatment solution with each composition shown in Table 2 (the same as that in Comparative Example 4) was coated so as to achieve a coating amount of 2 g/m.sup.2. Then, at a PMT of 180 C., drying was performed for 1 minute, thereby forming a silica-containing film on a surface of the aluminum sheet.

[0080] Then, in Comparative Examples 8 and 9, after completion of the pretreatment, using a bar coater, the film-forming treatment solution with each composition shown in Table 2 or Table 3 was coated so as to achieve a coating amount of 1 g/m.sup.2. Then, at a PMT of 100 C., drying was performed for 1 minute, thereby forming a silica-containing film on a surface of the aluminum sheet.

[0081] As for each aluminum coated material of respective Examples and Comparative Examples formed in the foregoing manner, the silicon content (Si content: mg/m.sup.2) and the phosphorus content (P content: mg/m.sup.2) of the silica-containing film formed on a surface thereof were measured by fluorescent X ray analysis, respectively. For this measurement, a silica-containing film was prepared on a 99.999% pure aluminum sheet by the same method as that in respective Examples and Comparative Examples. Thus, the silicon content (Si content: mg/m.sup.2) and the phosphorus content (P content: mg/m.sup.2) contained in unit area of the silica-containing film were subjected to quantitative analysis.

[0082] [Manufacturing of Joining Aluminum Coated Material]

[0083] Then, on a surface of each aluminum coated material of respective Examples and Comparative Examples, an adhesion layer, or a coating film layer and an adhesion layer were stacked with the silica-containing film provided therebetween, thereby manufacturing each joining aluminum material of respective Examples and Comparative Examples. Herein, for the coating film layer and the adhesion layer, the coating film layer forming paint and the adhesion layer forming adhesion paint shown in Table 4 shown below were used, and were coated so that the coating film layer becomes the lower layer, and the adhesion layer becomes the upper layer by the following method, thereby forming a coating film with each film thickness shown in Table 5 and Table 6.

TABLE-US-00004 TABLE 4 Coating film layer forming paint and adhesion layer forming paint Paint name Manufacturer Resin type Coating A Precolor TX4427 BASF Polyester type Thermosetting film B V nit #120 DAI NIPPON TORYO Co., Epoxy type Thermosetting layer Ltd. forming G V nit #500 DAI NIPPON TORYO Co., Polyester type Thermosetting paint Ltd. Si-E silica-added MITSUI CHEMICAL Inc. Acid modified olefin Thermoplastic UNISTOLE R-300 type Adhesion C Hardlen TD-15B TOYOBO Co., Ltd. Maleic anhydride- Thermoplastic layer modified olefin type forming D Hardlen NZ-1022 TOYOBO Co., Ltd. Maleic anhydride- Thermoplastic adhesion modified olefin type paint E UNISTOLE R-300 MITSUI CHEMICAL Inc. Acid modified olefin Thermoplastic type F EP106NL CEMEDINE Co., Ltd. Epoxy type Thermosetting

[0084] In Example 1, a paint A was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a 5-m coating film (coating film layer). Then, an adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a 25-m coating film (adhesion layer). As a result, a specimen (joining aluminum coated material) with a total film thickness of 30 m was prepared.

[0085] In Example 2, a paint B was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a 10-m coating film (coating film layer). Then, an adhesion paint D was subjected to bar coat coating, thereby forming a 5-m coating film (adhesion layer), and was subjected to a baking treatment at a PMT of 150 C. for 60 seconds to be dried, thereby preparing a specimen (joining aluminum coated material) with a total film thickness of 15 m.

[0086] In Example 3, an adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 15 m, resulting in preparation of a specimen (joining aluminum coated material).

[0087] In Example 4, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 40 m, resulting in preparation of a specimen (joining aluminum coated material).

[0088] In Example 5, the adhesion paint D was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 150 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 20 m, resulting in preparation of a specimen (joining aluminum coated material).

[0089] In Example 6, an adhesion paint E was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 35 m, resulting in preparation of a specimen (joining aluminum coated material.

[0090] In Example 7, the adhesion paint E was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 20 m, resulting in preparation of a specimen (joining aluminum coated material).

[0091] In Example 8, an adhesion paint F was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 150 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 35 m, resulting in preparation of a specimen (joining aluminum coated material).

[0092] Note that, in Examples 9 to 11, without forming either of the coating film layer and the adhesion layer, the aluminum coated material was used as an Example as it was.

[0093] In Example 12, the paint A was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a 10-m coating film (coating film layer). Then, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a 5-m coating film (adhesion layer), thereby preparing a specimen (joining aluminum coated material) with a total film thickness of 15 m.

[0094] In Example 13, the paint B was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a coating film (coating film layer) with a film thickness of 10 m. Then, the adhesion paint D was subjected to bar coat coating, thereby forming a 2-m coating film (adhesion layer), and was subjected to a baking treatment at a PMT of 150 C. for 60 seconds to be dried, thereby preparing a specimen (joining aluminum coated material) with a total film thickness of 12 m.

[0095] In Example 14, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 10 m, resulting in preparation of a specimen (joining aluminum coated material).

[0096] In Example 15, the adhesion paint D was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 150 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 40 m, resulting in preparation of a specimen (joining aluminum coated material).

[0097] In Example 16, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 20 m, resulting in preparation of a specimen (joining aluminum coated material).

[0098] In Example 17, an adhesion paint G was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 10 m. The adhesion paint E was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 10 m, resulting in preparation of a specimen (joining aluminum coated material).

[0099] In Example 18, the adhesion paint E was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 20 m, resulting in preparation of a specimen (joining aluminum coated material).

[0100] In Example 19, the adhesion paint F was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 120 C. for 60 seconds to be dried, thereby vaporizing the solvent, and forming a coating film (adhesion layer) with a film thickness of 50 m, resulting in preparation of a specimen (joining aluminum coated material).

[0101] In Example 20, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a 5-m coating film (adhesion layer), resulting in preparation of a specimen (joining aluminum coated material).

[0102] In Example 21, the adhesion paint G was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a 4-m coating film (adhesion layer). Then, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a 1-m coating film (adhesion layer), resulting in preparation of a specimen (joining aluminum coated material) with a total film thickness of 5 m.

[0103] In Example 22, the paint G was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a 9-m coating film (coating film layer). Then, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a 1-m coating film (adhesion layer), resulting in preparation of a specimen (joining aluminum coated material) with a total film thickness of 10 m.

[0104] In Comparative Example 1, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a 20-m coating film (adhesion layer), resulting in preparation of a specimen (joining aluminum coated material). The joining aluminum coated material of Comparative Example 1 has a silica-containing film with substantially the same P/Si mass ratio as that described in Example 2 of PTL 5, and is free from a silane coupling agent.

[0105] In Comparative Example 2, the adhesion paint D was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 150 C. for 60 seconds to be dried, thereby forming a 2-m coating film (adhesion layer), resulting in preparation of a specimen (joining aluminum coated material). The silane coupling agent content exceeds the upper limit value.

[0106] In Comparative Example 3, the paint A was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a 5-m coating film (coating film layer). Then, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a 30-m coating film (adhesion layer), resulting in preparation of a specimen (joining aluminum coated material) with a total film thickness of 35 m. The aluminum coated material of Comparative Example 3 has a silica-containing film with substantially the same P/Si mass ratio as that described in Example 9 of PTL 5, and is free from a silane coupling agent.

[0107] In Comparative Example 4, the paint B was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a coating film (coating film layer) with a film thickness of 5 m. Then, the paint D was subjected to bar coat coating, thereby forming a 30-m coating film (adhesion layer), and was subjected to a baking treatment at a PMT of 150 C. for 60 seconds to be dried, thereby forming a specimen (joining aluminum coated material) with a total film thickness of 35 m. The P/Si mass ratio is less than the lower limit value.

[0108] In Comparative Example 5, the adhesion paint E was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 20 m, resulting in preparation of a specimen (joining aluminum coated material). The P/Si mass ratio is smaller than the lower limit value.

[0109] In Comparative Example 6, the paint B was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a coating film (coating film layer) with a film thickness of 5 m. Then, the adhesion paint E was subjected to bar coat coating, thereby forming a 30-m coating film (adhesion layer), and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby forming a specimen (joining aluminum coated material) with a total film thickness of 35 m. The P/Si mass ratio exceeds the upper limit value.

[0110] In Comparative Example 7, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a 40-m coating film (adhesion layer), resulting in preparation of a specimen (joining aluminum coated material). The joining aluminum coated material of Comparative Example 7 has a silica-containing film with substantially the same P/Si mass ratio as that described in Example 2 of PTL 6, and is free from a silane coupling agent.

[0111] In Comparative Example 8, the adhesion paint E was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 20 m, resulting in preparation of a specimen (joining aluminum coated material). The aluminum coated material of Comparative Example 8 is the chemical conversion film (silica-containing film) of PTL 1 in which a phosphorus compound is not added, the P/Si mass ratio is zero (0), and a silane coupling agent is added in an amount exceeding 21 mass %.

[0112] In Comparative Example 9, the adhesion paint E was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 40 m, resulting in preparation of a specimen (joining aluminum coated material).

[0113] In Comparative Example 10, the adhesion paint C was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby forming a coating film (adhesion layer) with a film thickness of 4 m, resulting in preparation of a specimen (joining aluminum coated material).

[0114] In Comparative Example 11, the paint G was subjected to bar coat coating, and was subjected to a baking treatment at a PMT of 210 C. for 60 seconds to be dried, thereby forming a coating film (coating film layer) with a film thickness of 2 m. Then, the adhesion paint C was subjected to bar coat coating, thereby forming a 2-m coating film (adhesion layer), and was subjected to a baking treatment at a PMT of 130 C. for 60 seconds to be dried, thereby preparing a specimen (joining aluminum coated material) with a total film thickness of 4 m.

[0115] In Comparative Example 12, further, for the paint Si-E for forming the coating film layer shown in Table 4, a paint Si-E obtained by adding a fine powder silica (calcium-ion exchanged silica; trade name: Sylomask 52 manufactured by FUJI SILYSIA CHEMICAL LTD.) in an amount equivalent to 10 mass % of the solid content of the adhesion paint E in the adhesion layer forming adhesion paint E (solid content 18%) shown in Table 4 was used, and subjected to bar coat coating. Then, a baking treatment at a PMT of 220 C. for 60 seconds was performed for drying, thereby forming a coating film (coating film layer) with a film thickness of 10 m. Then, the adhesion paint E was subjected to bar coat coating, thereby forming a 10-m coating film (adhesion layer), and was subjected to a baking treatment at a PMT of 220 C. for 60 seconds to be dried, thereby preparing a specimen (joining aluminum coated material) with a total film thickness of 20 m.

[0116] [Preparing of Aluminum Resin Composite Material (Injection Integrally Molded Product)]

[0117] The joining aluminum coated materials of Examples 1 to 7, and 12 to 22, and the joining aluminum coated materials of Comparative Examples 1 to 12 were prepared in required numbers, respectively. From the joining aluminum coated materials or the aluminum coated materials, in Examples 1 to 7 and Comparative Examples 1 to 8, in order to measure three tensile shear strengths (tensile shear strength, tensile shear strength after wetting test, and tensile shear strength after salt spray test (SST)) described later with the number of tests N=3, respectively, nine joining aluminum specimens each including the resin part (resin molded body) joined thereto were prepared, and in Examples 12 to 22 and Comparative Examples 9 to 12, in order to measure four tensile shear strengths (tensile shear strength, tensile shear strength after wetting test, tensile shear strength after salt spray test (SST), and tensile shear strength after PCT test) described later with the number of tests N=3, respectively, twelve joining aluminum specimens each including the resin part (resin molded body) joined thereto were prepared.

[0118] Namely, each of the joining aluminum coated materials 2 of Examples 1 to 7 and 12 to 22, and Comparative Examples 1 to 12 was set in a mold of an injection molding machine. Thus, using a polypropylene resin (GCS 30 NOVATEC prepared by Japan Polypropylene Corporation), a joining aluminum specimen (aluminum resin composite material) for tensile shear strength evaluation according to the ISO 19095 testing method shown in (a) in FIG. 1 was prepared. For the prepared joining aluminum specimen, while the dimensions of the joining aluminum coated material 2 were 20 mm45 mm1 mmt, the dimensions of the resin part 1 were 10 mm45 mm3 mmt; the area of the junction part 3 between the joining aluminum coated material 2 and the resin part 1 was 10 mm5 mm; and the injection molding conditions for manufacturing each specimen were a resin temperature of 250 C., a mold temperature of 50 C., an injection speed of 40 mm/s, a holding pressure of 30 MPa, and an injection time of 8 seconds.

[0119] Of the nine joining aluminum specimens (aluminum resin composite materials) of Examples 1 to 7 and Comparative Examples 1 to 8 thus prepared, three specimens were used as it were for the tests, and the remaining six specimens were used as for the corrosion resistance tests (three for the salt spray test, and three for the wetting test). After conducting each test, the tensile shear strength evaluation and the appearance evaluation of the coated part were performed. Further, of the twelve joining aluminum specimens (aluminum resin composite materials) of Examples 12 to 22 and Comparative Examples 9 to 12 thus prepared, three specimens were used as it were for the tests, further, the remaining nine specimens were used as for the corrosion resistance tests (three for the salt spray test, and three for the wetting test, and three for the PCT test). After conducting each test, the tensile shear strength evaluation and the appearance evaluation of the coated part were performed.

[0120] [Tensile Shear Strength Evaluation of Aluminum Resin Composite Material (Injection Integrally Molded Product)]

[0121] As for the tensile shear strength, with the method according to the ISO 19095 testing method shown in (b) in FIG. 1, there was carried out a test in which the aluminum resin composite material (specimen) was fixed at a jig 4, and the upper end of the resin molded body was applied with a load 5 from above at a speed of 10 mm/min, thereby breaking the junction part between the aluminum material and the resin molded body. The breaking force of the aluminum resin composite material (injection integrally molded product) of the specimen was taken as the tensile shear strength. The tensile shear strength test was carried out with N=3 as it was, for after the salt spray test (JIS K 5600 7-1), and for after the wetting test (JIS K 5600 7-2), respectively. Each resulting average strength is shown as the tensile shear strength in Table 5 and Table 6.

[0122] [Manufacturing of Aluminum/Aluminum Adhesion Product]

[0123] In Example 8, as shown in FIG. 2, joining aluminum coated materials were prepared in a required number. From the joining aluminum coated materials, 18 specimens having dimensions of 25 mm150 mm were cut out. A support body 6 with dimensions of an area (grab area 6a) of 25 mm38 mm was attached to one end of each specimen. Further, the specimens thus obtained were used in pairs of two thereof. With each pair of specimens, respective adhesion layers on the other end without the support body 6 were stacked one on another. A junction part 7 was fixed with a clip so that the area (junction area 7a) of the stacked junction part 7 becomes 25 mm25 mm, and was baked and dried in an oven under the conditions of a set temperature of 150 C. and for 20 minutes, thereby manufacturing nine adhesion specimens according to the JIS K 6829 testing method.

[0124] Further in Example 19, joining aluminum coated materials were prepared in a required number. From the joining aluminum coated materials, 24 specimens having dimensions of 25 mm150 mm were cut out. In the same manner as in the case of Example 8, 12 adhesion specimens according to the JIS K 6829 testing method were prepared.

[0125] Further, in Example 9, as shown in FIG. 2, aluminum coated materials were prepared in a required number. From the aluminum coated materials, 18 specimens having dimensions of 25 mm150 mm were cut out. A support body 6 with dimensions of an area (grab area 6a) of 25 mm38 mm was attached to one end of each specimen for grasping the specimen. Further, the specimens thus obtained were used in pairs of two thereof. Roughly in the same manner as in the case of Example 8, with one specimen of each pair, on the end on the side without the support body 6, 2.5 g of normal temperature setting adhesive (main agent: curing agent=10:5; Araldite 2014-1 manufactured by HUNTSMAN Co.) was uniformly coated to the portion (junction part 7) with an area (junction area 7a) of 25 mm25 mm. On the portion coated with the adhesive, the end on the side without the support body 6 of the other specimen was stacked, thereby forming a junction part 7. The junction part 7 was fixed with a clip, and was dried under the conditions of a set temperature of 60 C. and for 3 hours, thereby manufacturing 9 adhesion specimens according to the JIS K 6829 testing method.

[0126] [Shear Strength Evaluation of Aluminum/Aluminum Adhesion Product]

[0127] As for adhesion specimens of Examples 8, 9, and 19 prepared in the manner described up to this point, a tensile test was conducted under the conditions of a LOAD SPEED of 50 mm/min and a grab area of 38 mm25 mm according to the JIS K 6829 testing method, thereby measuring the breaking force when the junction part 7 of the adhesion specimen was broken. The measured value was referred to as the tensile shear strength. For the adhesion specimen before the following corrosion resistance test, for the adhesion specimen after the following corrosion resistance test (salt spray test), and for the adhesion specimen after the following corrosion resistance test (wetting test), the shear strength tests were conducted with N=3, respectively. Each obtained average strength was referred to as the tensile shear strength, and is shown in Table 5 and Table 6.

[0128] [Corrosion Resistance Test (Salt Spray Test (SST): 500 Hr, Wetting Test: 500 hr)]

[0129] As for the joining aluminum specimens and adhesion specimens of respective Examples and Comparative Examples prepared in the manner described up to this point, the following salt spray test (JIS K 5600 7-1) was conducted for 500 hours, and the wetting test (JIS K 5600 7-2) was conducted for 500 hours. As for Examples 1 to 9, and 12 to 22, and Comparative Examples 1 to 11, for the junction part between the aluminum material and the resin molded body, the tensile shear strength was evaluated after the corrosion resistance test, and further, for the coated surface except for the junction part, the adhesion (cross-cut adhesion) was evaluated by the adhesion evaluation method (cross-cut method) of JIS K 5600. Further, the appearance was evaluated, and was taken as the evaluation of the corrosion resistance performance.

[0130] Further, for Examples 10 and 11, each resulting aluminum coated material was used as it was, and the appearances after the salt spray test and the wetting test were evaluated, and were taken as the evaluation of the corrosion resistance performance. The results are shown in Table 5 and Table 6.

[0131] [High Temperature High Humidity Acceleration Test (High Acceleration Life Test, PCT Test (Pressure Cooker Test)]

[0132] Further, for Examples 12 to 22, and Comparative Examples 9 to 12, using a high acceleration life test apparatus [EHS-411(M) manufactured by ESPEC Co.], a PCT test ranked as a high temperature high humidity acceleration test was conducted under the conditions of 95% RH, at 150 C., and for 5 hours, thereby evaluating the tensile shear strength after the high temperature high humidity test. Further, for the coated surface except for the junction part, the adhesion (cross-cut adhesion) was evaluated by the method (cross-cut method) of the adhesion evaluation of JIS K 5600. Further, the appearance was evaluated, and was taken as the evaluation of the corrosion resistance performance.

[0133] <Corrosion Resistance Evaluation of Coating Film>

[0134] With the salt spray test, the coated surface except for the junction part of each specimen (N=3) of the joining aluminum specimens and adhesion specimens obtained in respective Examples and Comparative Examples was cross-cut, and a 500-hour test was carried out. With the salt spray test, evaluation was performed with the evaluation criteria of : corrosion, swelling, and the like are not caused at the cut part at all, and the adhesion of the cut part was good, : the corrosion of the cut part is equal to or smaller than 1 mm in size, and swelling was not caused, and the adhesion was good, and X: the corrosion of the cut part was 1 mm or more in size, or abnormal condition such as occurrence of swelling or poor adhesion was caused, in the coating film after 500 hours. The results are shown in Table 5 and Table 6.

[0135] With the wetting test, there was evaluated the adhesion of the coated surface except for the junction part of each specimen (N=3) of the joining aluminum specimens and adhesion specimens obtained in respective Examples and Comparative Examples. The adhesion of the coating film was evaluated by rating the case where the area of the cross cut part which had undergone peeling was 5% or less (classification 1 or less) as ; the case of more than 5% and 15% or less as , the case of more than 15% and 35% or less as ; and the case of more than 35% as X with the method of adhesion (cross-cut method) of JIS K 5600. The results are shown in Table 5 and Table 6.

TABLE-US-00005 TABLE 5 Examples 1-11 and Comparative Examples 1-8 Example 1 2 3 4 5 6 7 8 9 10 Layer Coating A B configuration film layer Adhesion C D C C D E E F layer Film Coating 5 10 thickness film layer (m) Adhesion 25 5 15 40 20 35 20 35 layer Total film 30 15 15 40 20 35 20 35 thickness Composition Film mass 112.1 88.9 10.6 56.75 22.4 60.4 32.7 64.4 60.4 65.4 of silica (mg/m.sup.2) containing Si content 44.9 36.1 4.26 22.1 8.53 22.7 14.14 23.3 22.7 28.29 film (mg/m.sup.2) P content 4.84 2.01 0.35 1.34 1.07 1.07 0.54 1.07 1.07 1.07 (mg/m.sup.2) P/Si mass 0.108 0.056 0.082 0.061 0.125 0.047 0.038 0.046 0.047 0.038 ratio Si content 40.04 40.58 40.20 38.89 38.06 37.60 43.25 36.15 37.60 43.25 ratio (mass %) P content 4.31 2.27 3.29 2.37 4.80 1.78 1.64 1.66 1.78 1.64 ratio (mass %) Silane 0.71 8.43 4.71 13.21 4.46 19.87 3.06 24.84 19.87 3.06 coupling agent content ratio (mass %) Evaluation of Tensile shear 13.7 13.2 14.4 15.2 14.7 11.2 10.7 25.4 7.8 adhesion strength (MPa) strength with Tensile shear 12.5 12.8 14.2 14.8 13.5 10.8 10.5 24.5 7.8 resin strength after wetting test (MPa) Tensile shear 12.2 12.5 13.6 14.7 13.6 10.5 10.4 24.2 7.4 strength after SST 500 hrs (MPa) Evaluation of Appearance corrosion after SST 500 resistance hrs except for Cross-cut junction part adhesion after wetting test 500 hrs Comprehensive evaluation Example Comparative Example 11 1 2 3 4 5 6 7 8 Layer Coating film A B B configuration layer Adhesion C D C D E E C E layer Film Coating film 5 5 5 thickness layer (m) Adhesion 20 2 30 30 20 30 40 20 layer Total film 20 2 35 35 20 35 40 20 thickness Composition Film mass 148.5 4.85 64.5 11.35 105.6 211.1 23.3 26.83 465 of silica (mg/m.sup.2) containing Si content 49.1 1.87 15.28 4.9 47.1 94.2 8.53 11.2 106 film (mg/m.sup.2) P content 2.68 0.27 8.06 0.27 0.81 1.61 1.34 0.81 0 (mg/m.sup.2) P/Si mass 0.055 0.144 0.527 0.055 0.017 0.017 0.157 0.072 0.000 ratio Si content 33.08 38.48 23.69 43.17 44.62 44.62 36.67 41.74 22.79 ratio(mass %) P content 1.81 5.54 12.49 2.37 0.76 0.76 5.78 3.00 0.00 ratio(mass %) Silane 33.67 0.00 13.95 0.00 2.84 2.84 4.30 0.00 21.51 coupling agent content ratio (mass %) Evaluation of Tensile shear 13.5 2.1 13.9 14.2 11.4 11.8 1.2 10.5 adhesion strength (MPa) strength Tensile shear 0 0 0 0 0 0 0 5.2 with resin strength after wetting test (MPa) Tensile shear 0 0 0 0 0 0 0 0 strength after SST 500 hrs (MPa) Evaluation of Appearance X X X corrosion after SST 500 resistance hrs except for Cross-cut X X X X X X junction part adhesion after wetting test 500 hrs Comprehensive evaluation X X X X X X X X

TABLE-US-00006 TABLE 6 Examples 12-22 and Comparative Examples 9-12 Example 12 13 14 15 16 17 18 19 Layer Coating film layer A B G configuration Adhesion layer C D C D C E E F Film Coating film layer 10 10 10 thickness Adhesion layer 5 2 10 40 20 10 20 50 (m) Total film thickness 15 12 10 40 20 20 20 50 Composition Film mass(mg/m.sup.2) 112.1 88.9 10.6 56.75 21.21 60.4 32.7 64.4 of silica Si content (mg/m.sup.2) 44.9 35.75 4.26 21.75 8.54 22.7 14.14 23.3 containing P content (mg/m.sup.2) 4.84 2.01 0.35 1.34 0.70 1.07 0.54 1.07 film P/Si mass ratio 0.108 0.056 0.082 0.062 0.082 0.047 0.038 0.046 Si content ratio (mass %) 40.04 40.23 40.20 38.33 40.28 37.60 44.25 36.15 P content ratio (mass %) 4.31 2.27 3.29 2.37 3.29 1.78 1.64 1.66 Silane coupling agent 0.71 8.43 4.71 13.21 4.71 19.87 3.06 24.84 content ratio (mass %) Evaluation Tensile shear strength 13.5 13.0 13.8 15.4 14.5 11.5 11.2 25.1 of adhesion (MPa) strength Tensile After wetting 13.0 12.5 13.5 14.9 13.8 11.2 10.9 24.3 with Resin shear test strength After SST 500 12.7 12.5 13.0 14.5 13.6 11.0 10.2 24.5 (MPa) hrs After PCT 12.0 12.5 0 10.5 3.5 11.0 3.8 24.3 test 5 hrs Evaluation Appearance after SST 500 of corrosion hrs resistance Cross-cut adhesion after except for wetting test 500 hrs junction part Cross-cut adhesion after X PCT test 5 hrs Comprehensive evaluation Example Comparative Example 20 21 22 9 10 11 12 Layer Coating film layer G G G Si-E configuration Adhesion layer C C C E C C E Film Coating film layer 4 9 2 10 thickness Adhesion layer 5 1 1 40 4 2 10 (m) Total film thickness 5 5 10 40 4 4 20 Composition Film mass(mg/m.sup.2) 21.21 21.21 21.21 465 21.21 21.21 465 of silica Si content (mg/m.sup.2) 8.54 8.54 8.54 106 8.54 8.54 106 containing P content (mg/m.sup.2) 0.70 0.70 0.70 0 0.70 0.70 0 film P/Si mass ratio 0.082 0.082 0.082 0.000 0.082 0.082 0.000 Si content ratio (mass %) 40.28 40.28 40.28 22.79 40.28 40.28 22.79 P content ratio (mass %) 3.29 3.29 3.29 0.00 3.29 3.29 0.00 Silane coupling agent 4.71 4.71 4.71 21.51 4.71 4.71 21.51 content ratio (mass %) Evaluation of Tensile shear strength 13.8 12.8 13.5 10.9 9.5 7.3 9.8 adhesion (MPa) strength Tensile After wetting 12.1 11.5 12.6 6.0 9.1 6.2 8.7 with Resin shear test strength After SST 500 11.9 11.3 12.8 0 9.2 4.5 9.4 (MPa) hrs After PCT 0 11.2 12.3 0 0 0 0 test 5 hrs Evaluation of Appearance after SST 500 X corrosion hrs resistance Cross-cut adhesion after except for wetting test 500 hrs junction part Cross-cut adhesion after X X X X X PCT test 5 hrs Comprehensive evaluation X X X X

REFERENCE SIGNS LIST

[0136] 1: Resin part (resin molded body) [0137] 2: joining aluminum coated material [0138] 3: Junction part [0139] 4: Jig [0140] 5: Load [0141] 6: Support body [0142] 6a: Grab area [0143] 7: Junction part [0144] 7a: Junction area