Aluminum resin bonded body and method for producing same

Abstract

Provided is an aluminum-resin bonded body that expresses excellent bonding strength and does not show a reduction in the strength after a durability test, thus being able to keep the excellent bonding strength over a long period of time. The aluminum-resin bonded body includes: an aluminum substrate formed of aluminum or an aluminum alloy; an oxygen-containing film containing oxygen, the oxygen-containing film being formed on a surface of the aluminum substrate; and a resin molded body formed of a thermoplastic resin composition containing a thermoplastic resin and an additive, the resin molded body being bonded onto the oxygen-containing film, in which the thermoplastic resin composition contains any one or both of: a thermoplastic resin containing an element having an unshared electron pair in a repeat unit and/or at an end; and an additive containing an element having an unshared electron pair.

Claims

1. An aluminum-resin bonded body, comprising: an aluminum substrate formed of aluminum or an aluminum alloy; an oxygen-containing film containing oxygen, the oxygen-containing film being formed on a surface of the aluminum substrate; and a resin molded body formed of a thermoplastic resin composition containing a thermoplastic resin and an additive, the resin molded body being bonded onto the oxygen-containing film, wherein the oxygen-containing film formed on the surface has an oxygen content measured with an EPMA within a range of from 0.1 wt % or more to 20 wt % or less, wherein the thermoplastic resin in the thermoplastic resin composition comprises any one kind or two or more kinds of resins selected from the group consisting of a polyphenylene sulfide-based resin, a polyether-based resin, a polyphenylene ether-based resin, a sulfone-based resin, and a polyphenylene oxide-based resin, wherein the additive in the thermoplastic resin composition is a carbonyl compound having a carbonyl group, wherein the resin molded body has a carbonyl group (CO) as resulted from the additive, and wherein the oxygen-containing film comprises any one kind or two or more kinds of aluminum compound-containing films selected from: a film containing any one kind or two or more kinds of aluminum compounds selected from the group consisting of Al(OH).sub.3, AlO(OH), Al(PO.sub.4), Al.sub.2(HPO.sub.4).sub.3, and Al(H.sub.2PO.sub.4).sub.3 derived from an aluminum film-forming treatment; a film containing a hydrogen bond between a hydroxy group on the aluminum substrate and a silanol group derived from the aluminum film-forming treatment; and a film containing an AlOSi bond derived from the aluminum film-forming treatment.

2. The aluminum-resin bonded body according to claim 1, wherein the oxygen-containing film comprises a film formed on the surface of the aluminum substrate by laser treatment.

3. The aluminum-resin bonded body according to claim 1, wherein a surface of the oxygen-containing film has a contact angle of 70 or less.

4. The aluminum-resin bonded body according to claim 1, wherein the resin molded body is bonded onto the oxygen-containing film by a bonding method based on injection molding or thermocompression bonding.

5. The aluminum-resin bonded body according to claim 1, wherein the carbonyl compound comprises any one kind or two or more kinds of compounds selected from the group consisting of carboxylic acids, esters, and acid amides.

6. A method of producing the aluminum-resin bonded body of claim 1, comprising: a film-forming step of forming an oxygen-containing film on a surface of an aluminum substrate formed of aluminum or an aluminum alloy; and a resin-molding step of forming a resin molded body on the oxygen-containing film of the surface-treated aluminum substrate obtained in the film-forming step, by injection molding of a thermoplastic resin composition containing a thermoplastic resin and an additive, so that the aluminum substrate and the resin molded body are bonded through intermediary of the oxygen-containing film, wherein the oxygen-containing film formed on the surface has an oxygen content measured with EPMA within a range of from 0.1 wt % or more to 20 wt % or less, wherein the thermoplastic resin in the thermoplastic resin composition comprises any one kind or two or more kinds of resins selected from the group consisting of a polyphenylene sulfide-based resin, a polyether-based resin, a polyphenylene ether-based resin, a sulfone-based resin, and a polyphenylene oxide-based resin, wherein the additive in the thermoplastic resin composition is a carbonyl compound having a carbonyl group, wherein the resin molded body has a carbonyl group (CO) as resulted from the additive, and wherein the oxygen-containing film comprises any one kind or two or more kinds of aluminum compound-containing films selected from: a film containing any one kind or two or more kinds of aluminum compounds selected from the group consisting of Al(OH).sub.3, AlO(OH), Al(PO.sub.4), Al.sub.2(HPO.sub.4).sub.3, and Al(H.sub.2PO.sub.4).sub.3 derived from an aluminum film-forming treatment; a film containing a hydrogen bond between a hydroxy group on the aluminum substrate and a silanol group derived from the aluminum film-forming treatment; and a film containing an AlOSi bond derived from the aluminum film-forming treatment.

7. The method of producing an aluminum-resin bonded body of claim 6, further comprising an aluminum-resin-bonding step of bonding the resin molded body obtained in the resin-molding step onto the oxygen-containing film of the surface-treated aluminum substrate obtained in the film-forming step, by thermocompression bonding.

8. The method of producing an aluminum-resin bonded body according to claim 6, wherein the film-forming step comprises forming, on the surface of the aluminum substrate formed of aluminum or an aluminum alloy, the oxygen-containing film containing any one kind or two or more kinds of aluminum compounds selected from Al(OH).sub.3, AlO(OH), Al(PO.sub.4), Al.sub.2(HPO.sub.4).sub.3, and Al(H.sub.2PO.sub.4).sub.3 by treating the aluminum substrate by any one kind of the aluminum film-forming treatment selected from: warm water immersion treatment involving immersion in warm water at 50 C. or more for 60 seconds or more; water vapor treatment involving exposure to a water vapor atmosphere under pressurized conditions of 0.1 MPa or more and 1 minute or more; phosphoric acid treatment involving immersion in a phosphoric acid-based aqueous solution containing any one kind or two or more kinds of phosphate ion species selected from the group consisting of a phosphate ion, a monohydrogen phosphate ion, and a dihydrogen phosphate ion in a range of from 0.1 to 100 g/L for from 30 seconds to 30 minutes, followed by drying with hot air at from 80 to 400 C. for from 30 seconds to 30 minutes; and anodic oxidation treatment.

9. The method of producing an aluminum-resin bonded body according to claim 6, wherein the film-forming step comprises forming, on the surface of the aluminum substrate formed of aluminum or an aluminum alloy, an oxygen-containing film containing a hydrogen bond between an hydroxy group on an aluminum substrate and a silanol group and/or an oxygen-containing film containing an AlOSi bond by treating the aluminum substrate by any one kind of the aluminum film-forming treatment selected from silane coupling treatment and/or a silica treatment involving immersion in a solution containing 0.1 to 100 g/L of a silane coupling agent and/or colloidal silica for from 30 seconds to 30 minutes, followed by drying with hot air at from 80 to 400 C. for from 30 seconds to 30 minutes.

10. The method of producing an aluminum-resin bonded body according to claim 6, wherein the film-forming step comprises forming an oxygen-containing film by a laser treatment involving heating a vicinity of the surface of the aluminum substrate formed of aluminum or an aluminum alloy.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an explanatory diagram for illustrating an aluminum-resin bonded body produced in Example 1 of the present invention.

(2) FIG. 2 is an explanatory diagram for illustrating a method for an evaluation test for bonding strength between aluminum and a resin carried out in Example 1 of the present invention.

DESCRIPTION OF EMBODIMENTS

(3) An aluminum-resin bonded body and method of producing the same of the present invention are specifically described below on the basis of Examples and Comparative Examples.

Example 1

(1) Production of Surface-Treated Aluminum Substrate

(4) An aluminum substrate measuring 40 mm40 mm was cut out of a commercially available aluminum plate (A5052; plate thickness: 2.0 mm). In addition, a zinc ion-containing aqueous solution of sodium having a sodium hydroxide concentration of 100 g/L and a zinc oxide concentration of 25 g/L (20 g/L in terms of Zn.sup.+) was prepared as a film-forming treatment agent. Next, the aluminum substrate was immersed in the zinc ion-containing aqueous solution of sodium under room temperature for 3 min, and then washed with water to produce a surface-treated aluminum substrate for tests having formed on its surface an oxygen-containing film containing a zinc element.

(2) Measurement of Thickness of Oxygen-Containing Film

(5) The obtained surface-treated aluminum substrate was embedded and fixed in an epoxy resin, and then the surface-treated aluminum substrate was Cut together with the epoxy resin. The cross-section was subjected to wet polishing with emery paper and mirror-finished by buff polishing using a magnesium oxide-based polish. After that, the resultant cross-section after the wet polishing was observed with an SEM (FE-SEM manufactured by Carl Zeiss; 50,000) and the thickness of its film portion was measured.

(6) Table 1 shows the result.

(3) Measurement of Oxygen Content in Film

(7) The obtained surface-treated aluminum substrate was subjected to mapping analysis with an EPMA (manufactured by SHIMADZU: EPMA1610) involving measurement in 512 steps in each of vertical and horizontal directions at an irradiation diameter of 40 m/step. Here, the measurement area is 20.48 mm20.48 mm, the sampling time per step is 20 ms, the accelerating voltage is 15 kV, and the resolution of oxygen in a depth direction is 3 m or less. Next, the detected oxygen intensity was calculated in terms of weight percentage (wt %) on the basis of a calibration curve prepared in advance. It should be noted that the calibration curve used was prepared on the basis of the following two points: the oxygen intensity of an Al.sub.2O.sub.3 standard sample (oxygen content: 48 wt %) and the oxygen intensity of a high-purity Al foil.

(8) Table 1 shows the result.

(4) Measurement of Contact Angle of Surface-Treated Aluminum Substrate

(9) The surface (oxygen-containing film) of the obtained surface-treated aluminum substrate was measured for its contact angle with a water droplet. The contact angle was measured by a droplet method involving using an automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). About 2 L of pure water were dropped onto the surface of the surface-treated aluminum substrate, and a contact angle in this case was measured. As a result, the contact angle with the water droplet was found to be 20.

(10) Table 1 shows the result.

(5) Measurement of Substance Present in Outermost Surface Layer of Oxygen-Containing Film

(11) A substance present in the outermost surface layer of the oxygen-containing film of the obtained surface-treated aluminum substrate was analyzed by GD-OES analysis (elemental analysis involving using a glow discharge-optical emission spectrometer; see A. Bengtson: J. Anal. At. Spectrom, 18(2003), 1066). As a result, a Bi element was detected. In the elemental analysis by GD-OES, the Bi element is known to correspond to an OH group. The Al alloy and each treatment liquid used contain no Bi, and hence the detection of Bi means the presence of an OH group.

(12) Table 1 shows the result.

(6) Production of Aluminum-Resin Bonded Body

(13) PPS (manufactured by POLYPLASTICS CO., LTD., trade name: FORTRON, grade name: RSF10719, CO group: present) was used as a thermoplastic resin, the surface-treated aluminum substrate for tests obtained in the foregoing was set in a die of an injection molding machine, and injection molding of PPS was performed under the injection molding conditions of a die temperature of 150 C., a resin temperature of 320 C., an injection speed of 100 mm/s, a dwell pressure of 50 MPa, and a pressure dwell time of 3 sec. Thus, as illustrated in FIG. 1, a PPS molded body 3 measuring 5 mm10 mm30 mm was molded, and the PPS molded body 3 was bonded onto the zinc-containing film (not shown) of a surface-treated aluminum substrate 2 in an area of 5 mm10 mm to produce an aluminum-resin bonded body 1 for tests.

(7) IR Analysis of Resin Portion of Aluminum-Resin Bonded Body

(14) The aluminum-resin bonded bodies 1 for tests thus produced were each subjected to IR analysis of a resin molded body portion using an IR analysis apparatus (Agilent Technologies 660 FastImage-IR) by a micro-ATR method to confirm the presence or absence of a peak derived from a carbonyl group (CO) (around 1,730 cm.sup.1). The result was as shown in Table 1. Specifically, a peak derived from a carbonyl group (CO) was detected.

(8) Evaluation Test for Bonding Strength of Aluminum-Resin Bonded Body Before and after Durability Test

(15) The aluminum-resin bonded bodies for tests thus produced were each subjected to a durability test for an aluminum-resin bonded body involving: leaving the aluminum-resin bonded body to stand under an environment having a temperature of 85 C. and a humidity of 85% for 1,000 hr; and evaluating the corrosion resistance of the aluminum-resin bonded body. The aluminum-resin bonded bodies after the durability test were each subjected to an evaluation test for bonding strength between aluminum and the resin by the following method.

(16) As illustrated in FIG. 2, a test for evaluating the shear strength of the bonded portion of an aluminum-resin bonded body was carried out by a method involving: fixing the surface-treated aluminum substrate 2 of the aluminum-resin bonded body 1 to a jig 4; and applying a load 5 to the upper end of the PPS molded body 3 from thereabove at a speed of 1 mm/min. to break the bonded portion between the surface-treated aluminum substrate 2 and the PPS molded body 3. The fracture surface in that case was observed, and the bonding strength of the aluminum-resin bonded body before and after the durability test was evaluated in accordance with the following criteria: : the case where the entire bonded surface was broken through the cohesive failure of the resin; : the case where part of the bonded surface was broken through the cohesive failure of the resin; and x: the case where the bonded portion was broken at the interface between the aluminum substrate and the PPS molded body.

(17) Table 1 shows the result.

(9) Surface Hardness Measurement and Bending Evaluation of Aluminum-Resin Bonded Body

(18) The produced aluminum-resin bonded body for tests was measured for its Vickers hardness (Hv) as a surface hardness in conformity with the Vickers hardness test method of JIS 22244, and was investigated for the presence or absence of a film defect in conformity with the press bending method of JIS 22248.

(19) Table 1 shows the results.

Examples 2 to 9

(20) Aluminum-resin bonded bodies for tests were produced in the same manner as in Example 1 except that: as the aluminum substrate, the same aluminum plate as that of Example 1 (A5052; plate thickness: 2.0 mm) was used in each of Examples 2 to 7, an aluminum plate (A1050; plate thickness: 2.0 mm) was used in Example 8, and an aluminum plate (ADC12; plate thickness: 2.0 mm) was used in Example 9; and aqueous solutions having liquid compositions shown in Table 1 were used as the zinc ion-containing alkali aqueous solution, and the alkali hydroxide concentration and the zinc ion concentration were set to concentrations shown in Table 1. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(21) Table 1 shows the results.

Examples 10 and 11

(22) As the aluminum substrate, the same aluminum plate as that of Example 1 (A5052; plate thickness: 2.0 mm) was used in Example 10, and the same aluminum plate as that of Example 9 (ADC12; plate thickness: 2.0 mm) was used in Example 11. The aluminum substrate was subjected to pretreatment involving immersion in a 30 wt % aqueous solution of nitric acid at normal temperature for 5 min, followed by sufficient water washing with ion-exchanged water, subsequent immersion in a 5 wt % solution of sodium hydroxide at 50 C. for 1 min, followed by water washing, and further immersion in a 30 wt % aqueous solution of nitric acid at normal temperature for 3 min, followed by water washing. Next, hydration treatment involving immersion in hot water at 91 C. for 5 min was performed. Thus, aluminum film-forming treatment was performed to form an oxygen-containing film containing an aluminum compound AlO(OH) on the surface of the aluminum substrate. Aluminum-resin bonded bodies for tests were produced in the same manner as in Example 1 except for the foregoing. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(23) Table 1 shows the results.

Example 12

(24) The same aluminum plate as that of Example 1 (A5052; plate thickness: 2.0 mm) was used as the aluminum substrate. The aluminum substrate was subjected to degreasing treatment with 2% SURFCLEANER 53S (manufactured by Nippon Paint Co., Ltd.) at 60 C. for 30 sec, followed by water washing, and was dried at 80 C. Colloidal silica ST-O (manufactured by Nissan Chemical Industries, Ltd.) was used as SiO.sub.2 and phosphoric acid having a purity of 85% (manufactured by Wako Pure Chemical Industries, Ltd.) was used as H.sub.3PO.sub.4 to produce a surface treatment liquid blended at a ratio shown in Table 1, and aluminum film-forming treatment was performed, which involved immersing the aluminum substrate in the surface treatment liquid at room temperature for 10 sec, followed by drying at 80 C. Thus, an oxygen-containing film containing an aluminum compound Al(PO.sub.4) and a hydrogen bond between an hydroxy group on an aluminum substrate and a silanol group was formed on the surface of the aluminum substrate. An aluminum-resin bonded body for tests was produced in the same manner as in Example 1 except for the foregoing. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(25) Table 1 shows the results.

Example 13

(26) The same aluminum plate as that of Example 1 (A5052; plate thickness: 2.0 mm) was used as the aluminum substrate. The aluminum substrate was subjected to degreasing treatment with 2% SURFCLEANER 53S (manufactured by Nippon Paint Co., Ltd.) at 60 C. for 30 sec, followed by water washing, and was dried at 80 C. Colloidal silica ST-O (manufactured by Nissan Chemical Industries, Ltd.) was used as SiO.sub.2, phosphoric acid having a purity of 85% (manufactured by Wako Pure Chemical Industries, Ltd.) was used as H.sub.3PO.sub.4, and a silane coupling agent (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) was used to produce a surface treatment liquid blended at a ratio shown in Table 1, and aluminum film-forming treatment was performed, which involved immersing the aluminum substrate in the surface treatment liquid at room temperature for 10 sec, followed by drying at 120 C. Thus, an oxygen-containing film containing an aluminum compound Al(PO.sub.4), a hydrogen bond between an hydroxy group on an aluminum substrate and a silanol group, and an AlOSi bond was formed on the surface of the aluminum substrate. An aluminum-resin bonded body for tests was produced in the same manner as in Example 1 except for the foregoing. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(27) Table 1 shows the results.

Examples 14 and 15

(28) Aluminum-resin bonded bodies for tests were produced in the same manner as in Example 1 except that: as the aluminum substrate, the same aluminum plate as that of Example 1 (A5052; plate thickness: 2.0 mm) was used in Example 14, and the same aluminum plate as that of Example 9 (ADC12; plate thickness: 2.0 mm) was used in Example 15; and the aluminum substrate was irradiated in a single direction at a pitch of 50 m by laser etching treatment (apparatus name: Miyachi Technos/ML-7112A, laser light wavelength: 1,064 nm, spot diameter: 50 to 60 m, oscillation mode: Q-switch pulse, frequency: 10 kHz) to form a thermally oxidized film (oxygen-containing film) in the surface layer. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(29) Table 1 shows the results.

Example 16

(30) As the aluminum substrate, the same aluminum plate as that of Example 1 (A5052; plate thickness: 2.0 mm) was used. The aluminum substrate was subjected to pretreatment involving immersion in a 30 wt % aqueous solution of nitric acid at normal temperature for 5 min, followed by sufficient water washing with ion-exchanged water, subsequent immersion in a 5 wt % solution of sodium hydroxide at 50 C. for 1 min, followed by water washing, and further immersion in a 30 wt % aqueous solution of nitric acid at normal temperature for 3 min, followed by water washing. Next, aluminum film-forming treatment was performed, which involved anodic oxidation in a solution having a sulfuric acid concentration of 160 g/L at a melting temperature of 18 C. and a DC voltage of 20 V so as to achieve a film thickness of 10 m, followed by water washing, and drying with hot air at 120 C. for 5 min. Thus, an oxygen-containing film containing an aluminum compound Al.sub.2O.sub.3 was formed on the surface of the aluminum substrate. An aluminum-resin bonded body for tests was produced in the same manner as in Example 1 except for the foregoing. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

Example 17

(31) An oxygen-containing film containing an aluminum compound AlO(OH) was formed on the surface of an aluminum substrate in the same manner as in Example 10 except that the conditions of the hydration treatment of Example 10 were changed to the conditions of immersion in hot water at 80 C. for 5 min. After that, an aluminum-resin bonded body for tests was produced in the same manner as in Example 1. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(32) Table 1 shows the results.

Example 18

(33) Anodic oxidation was performed in a solution having a sulfuric acid concentration of 160 g/L at a melting temperature of 18 C. and a DC voltage of 20 V so as to achieve a film thickness of 2 m. Thus, an oxygen-containing film containing an aluminum compound Al.sub.2O.sub.3 was formed on the surface of an aluminum substrate. After that, an aluminum-resin bonded body for tests was produced in the same manner as in Example 1. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(34) Table 1 shows the results.

Comparative Examples 1 and 2

(35) Aluminum-resin bonded bodies for tests according to Comparative Examples 1 and 2 were produced in the same manner as in Example 1 above except that materials shown in Table 2 were used as the thermoplastic resin. In addition, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(36) Table 2 shows the results.

Comparative Example 3

(37) An aluminum-resin bonded body for tests was produced in the same manner as in Example 10 above except that a material shown in Table 2 was used as the thermoplastic resin. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(38) Table 2 shows the results.

Comparative Example 4

(39) An aluminum-resin bonded body for tests was produced in the same manner as in Example 1 except that: the same aluminum plate as that of Example 1 (A5052; plate thickness: 2.0 mm) was used as the aluminum substrate; and the aluminum substrate was immersed in a 30 wt % aqueous solution of nitric acid at normal temperature for 5 min, followed by sufficient water washing with ion-exchanged water, and was dried, to form an aluminum substrate having a naturally oxidized film on the surface of the aluminum substrate. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(40) Table 2 shows the results.

Comparative Example 5

(41) An aluminum-resin bonded body for tests was produced in the same manner as in Example 1 except that: a material shown in Table 2 was used as the thermoplastic resin; and a thermally oxidized film was formed in the surface layer by laser treatment in the same manner as in Example 14 above. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(42) Table 2 shows the results.

Comparative Example 6

(43) An aluminum-resin bonded body for tests was produced in the same manner as in Example 1 above except that: a material shown in Table 2 was used as the thermoplastic resin; and an oxygen-containing film containing a zinc element was formed on the surface, followed by heat treatment at 150 C. for 1 hr. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(44) Table 2 shows the results.

Comparative Example 7

(45) An aluminum-resin bonded body for tests was produced in the same manner as in Example 1 above except that: a material shown in Table 2 was used as the thermoplastic resin; and aluminum film-forming treatment was performed by changing the hydration treatment of Example 10 above to treatment involving immersion in hot water at 70 C. for 5 min to form an oxygen-containing film containing an aluminum compound AlO(OH) on the surface of the aluminum substrate. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(46) Table 2 shows the results.

Comparative Example 8

(47) An aluminum-resin bonded body for tests was produced in the same manner as in Example 1 above except that: a material shown in Table 2 was used as the thermoplastic resin; and aluminum film-forming treatment was performed by changing the hydration treatment of Example 10 above to treatment involving immersion in hot water at 60 C. for 10 min to form an oxygen-containing film containing an aluminum compound AlO(OH) on the surface of the aluminum substrate. Then, IR analysis of a resin portion and an evaluation test for bonding strength were performed in the same manner as in Example 1.

(48) Table 2 shows the results.

(49) TABLE-US-00001 TABLE 1 Oxygen-containing film Bending Composition Substance Resin molded body Evaluation for Surface evaluation of treatment present in Kind of Presence bonding strength hardness Presence Exam- liquid for Thickness Oxygen Contact outermost resin or absence Fracture Vickers or absence ple film Kind of of film content angle surface compo- of CO load Form of hardness of film No. formation film (m) (wt %) () layer sition group (N) fracture (Hv) defect 1 NaOH: 100 g/L; ZnO 0.5 3 20 OH RSF10719 Present 1,800 81 Absent Zn.sup.2+: 20 g/L (*1) 2 NaOH: 100 g/L; ZnO 1 8 10 OH RSF10719 Present 1,800 82 Absent Zn.sup.2+: 100 g/L 3 NaOH: 500 g/L; ZnO 0.2 0.8 30 OH RSF10719 Present 1,400 81 Absent Zn.sup.2+: 10 g/L 4 NaOH: 300 g/L; ZnO 0.4 2.4 25 OH RSF10719 Present 1,700 82 Absent Zn.sup.2+: 30 g/L 5 NaOH: 10 g/L; ZnO 0.2 0.1 60 OH RSF10719 Present 1,300 80 Absent Zn.sup.2+: 1 g/L 6 LiOH: 100 g/L; ZnO 0.4 1.6 45 OH RSF10719 Present 1,500 81 Absent Zn.sup.2+: 20 g/L 7 KOH: 100 g/L; ZnO 0.4 1.6 46 OH RSF10719 Present 1,550 82 Absent Zn.sup.2+: 20 g/L 8 NaOH: 100 g/L; ZnO 0.4 1.6 44 OH RSF10719 Present 1,600 80 Absent Zn.sup.2+: 20 g/L 9 NaOH: 100 g/L; ZnO 0.5 0.3 55 OH RSF10719 Present 900 91 Absent Zn.sup.2+: 20 g/L 10 H.sub.2O AlO(OH) 0.5 8 9 OH RSF10719 Present 1,800 81 Absent 11 H.sub.2O AlO(OH) 0.5 0.2 18 OH RSF10719 Present 1,100 92 Absent 12 H.sub.3PO.sub.4: 0.5 Al (PO.sub.4) 0.5 3 11 OH RSF10719 Present 1,500 80 Absent g/L; SiO.sub.2: 4.5 g/L (*2) 13 H.sub.3PO.sub.4: 0.25 Al(PO.sub.4) 0.5 4 11 OH RSF10719 Present 1,500 80 Absent g/L SiO.sub.2: 2.25 (*2) (*6) g/L KBM-803 (*3): 1.25 g/L 14 Dry (laser) Al.sub.2O.sub.3 1 8 15 OH RSF10719 Present 1,800 80 Absent 15 Dry (laser) Al.sub.2O.sub.3 1 8 16 OH RSF10719 Present 1,800 80 Absent 16 H.sub.2SO.sub.4: 160 g/L Al.sub.2O.sub.3 10 53 10 OH RSF10719 Present 900 250 Present 17 H.sub.2O AlO(OH) 0.3 4 20 OH RSF10719 Present 1,100 81 Absent 18 H.sub.2SO.sub.4: 160 g/L Al.sub.2O.sub.3 2 12 10 OH RSF10719 Present 900 250 Present (Note) (*1): PPS manufactured by POLYPLASTICS CO., LTD., (*2): hydrogen bond between hydroxy group on an aluminum substrate and silanol group, (*3): silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., (*6): AlOSi bond.

(50) TABLE-US-00002 TABLE 2 Oxygen-containing film Bending Composition Substance Resin molded body Evaluation for Surface evaluation Compar- of treatment present in Kind of Presence bonding strength hardness Presence ative liquid for Thickness Oxygen Contact outermost resin or absence Fracture Vickers or absence Exam- film Kind of of film content angle surface compo- of CO load Form of hardness of film ple No. formation film (m) (wt %) () layer sition group (N) fracture (Hv) defect 1 NaOH: 100 ZnO 0.5 3 20 OH 1140 Absent 200 x 81 Absent g/L (*4) Zn.sup.2+: 20 g/L 2 NaOH: 100 ZnO 0.5 3 20 OH A575W20 Absent 300 x 81 Absent g/L (*5) Zn.sup.2+: 20 g/L 3 H.sub.2O AlO(OH) 0.5 8 9 OH A575W20 Absent 700 x 82 Absent 4 30 wt %-HNO.sub.3 Al.sub.2O.sub.3 0.005 0.02 90 N RSF10719 Present 50 x 81 Absent (*1) 5 Dry (laser) Al.sub.2O.sub.3 1 8 15 OH A575W20 Absent 600 x 80 Absent 6 NaOH: 100 ZnO 0.5 5 120 Zn RSF10719 Present 600 x 80 Absent g/L Zn.sup.2+: 20 g/L 7 H.sub.2O AlO(OH) 0.01 0.05 18 OH RSF10719 Present 400 x 81 Absent 8 H.sub.2O AlO(OH) 0.01 0.05 20 OH RSF10719 Present 300 x 80 Absent (Note) (*1): PPS manufactured by POLYPLASTICS CO., LTD., (*4): PPS manufactured by POLYPLASTICS CO., LTD., (*5): PPS manufactured by TORAY INDUSTRIES, INC.

INDUSTRIAL APPLICABILITY

(51) The aluminum-resin bonded body of the present invention has excellent bonding strength both before and after a durability test, and hence can be suitably utilized in the production of various components such as various sensor components for automobiles, components for household electrical appliances, and components for industrial equipment.

REFERENCE SIGNS LIST

(52) 1 . . . aluminum-resin bonded body, 2 . . . surface-treated aluminum substrate, 3 . . . PPS molded body (resin molded body), 4 . . . jig, 5 . . . load.