method for manufacturing a resin-metal composite, resin-metal composite and lithium-ion battery cove

专利摘要:
METHOD FOR MANUFACTURING A METAL-RESIN COMPOSITE, METAL-RESIN COMPOSITE AND LITHIUM-ION BATTERY COVER A metal-resin composite having high gas-sealing properties is provided. An aluminum alloy structure having a shape around the copper (63) is first formed, and the bonded aluminum alloy is made to firmly contact the copper electrode (63) and additionally mesh with the copper electrode (63 ) by message or forge. This is then machined to a predetermined shape in order to prepare the copper alloy (63) connected to a piece of aluminum (61a). Subsequently, NMT or NMT 2 surface treatment is given to three members of an electrode (62), the copper electrode joined with the aluminum alloy part (61a), and an aluminum alloy cap (61) . These three members are inserted into an injection mold, and a thermoplastic resin composition (64) of PPS resin is injected. The cover of the lithium-ion battery (60) having a structure as shown in figure 11 is thus obtained.
公开号:BR112013013102B1
申请号:R112013013102-0
申请日:2011-11-25
公开日:2020-10-20
发明作者:Masanori Naritomi；Naoki Andoh
申请人:Taisei Plas Co., Ltd；
IPC主号:

专利说明:

Field of invention
[0001] The present invention relates mainly to a resin-metal compound that is composed of an aluminum alloy and a molded thermoplastic resin, such as polyphenylene sulfide (hereinafter referred to as "PPS"), and a method to manufacture it. In more detail, the present invention relates to a resin-metal composite that practically does not allow gaseous molecules to pass through a boundary joint between an aluminum alloy and a thermoplastic resin and that has good mechanical properties, and a method for manufacturing it. Background of the invention
[0002] Metal-to-metal adhesives and techniques for strongly bonding a metal to a synthetic resin are required in a wide range of industrial fields in addition to the manufacture of components for automobiles, appliances, industrial machines and the like, and many adhesives have been developed by this company. reason. That is, adhesion and bonding techniques are basic technology and applied in all manufacturing industries.
[0003] Previously, bonding methods without using adhesives have also been studied. Among these, it was the "NMT (short for nano-molding technology)" that was developed by the present inventors and that had a great impact on the manufacturing industries. NMT is a technique of joining an aluminum alloy to a resin composition (hereinafter, abbreviated as "injection joint") where a cast engineering resin is injected into a piece of aluminum that is previously inserted into a mold of injection, in such a way that a piece of resin is molded while the molded product is simultaneously joined to the aluminum alloy component. Patent literature 1 discloses a technique of injection-bonding a polybutylene terephthalate resin (hereinafter referred to as "PBT") to an aluminum alloy conformed to a specific surface treatment. Patent literature 2 discloses a technique for joining by injection of a polyphenylene sulfide resin (hereinafter referred to as "PPS") to an aluminum alloy with a specific surface treatment. In the following, the principle of union by injection in patent literature 1 and 2 will be briefly described. (NMT)
[0004] NMT requires two conditions for the aluminum alloy and one condition for the resin composition. The two conditions for the aluminum alloy are described below. (1) The surface of the aluminum alloy is covered with ultrafine roughness for a period of 20 to 80 nm or ultrafine recesses or ultrafine protrusions with a diameter of 20 to 80 nm. It is also preferred to be covered with ultrathin recesses or ultrathin protrusions having an Rz of 20 to 80 nm. In addition, it is also preferred to be covered with roughness having an RSm of 20 to 80 nm and an Rz of 20 to 80 nm. RSm represents the average width of profile elements defined by Japan Industrial Standards JIS B0601-2001, ISO 4287- 1997).
[0005] The aluminum alloy has a surface layer of an aluminum oxide film, having a thickness of 3 nm or more. (2) A compound of ammonia, hydrazine or water-soluble amine is chemically adsorbed on the surface of the aluminum alloy.
[0006] On the other hand, the condition of the resin composition is as follows. (3) The main component is a rigid crystalline thermoplastic resin that is capable of reacting with amine compounds in a broad sense from 150 ° C to 200 ° C such as ammonia, hydrazine and water-soluble amines. Specifically, the resin composition contains PBT, PPS, polyamide resin or the like as the main component.
[0007] When the resin composition contained PBT or PPS as the main component (i.e., it satisfied the condition of (3)) as well as 10 to 40% by weight of a glass fiber, it exhibited an unprecedented bond strength strong with an aluminum alloy that met conditions (1) and (2). In the condition where the aluminum alloy and resin composition were both plate-shaped and were bonded to each other in a certain area (0.5 cm2), the shear fracture was 20 to 25 MPa.
[0008] To achieve stronger bond strength by NMT, one more condition is additionally added to the resin composition. (4) A polymer other than the main component polymer is contained, and the majority of the different polymer is mixed with the base crystalline thermoplastic resin at the molecular level.
[0009] The purpose of adding this condition (4) is to reduce the rate of crystallization when the melted resin composition is rapidly cooled. This is based on the idea that a different polymer being mixed at the molecular level, this inhibits the arrangement during crystallization of the molten state, which eventually leads to reducing the crystallization rate during a rapid cooling. This was supposed to make it possible for the resin composition to sufficiently penetrate the ultra-fine roughness before solidifying, which would contribute to improving the bond strength. As a result, this assumption turned out to be true.
[0010] When the resin composition contained PBT or PPS as the main component (i.e., it satisfied the condition of (3)), it satisfied the condition of (4) (it was formulated with a different polymer) and additionally contained 10 to 40% by weight of a glass fiber, it exhibited a very strong bond strength with the aluminum alloy that met conditions (1) and (2). In the condition where the aluminum alloy and the resin composition were both plate-shaped and joined to each other over a certain area (0.5 to 0.8 cm2), the shear fracture was 25 to 30 MPa. In the case of a resin composition where different polyamides were formulated, the shear fracture was 20 to 30 MPa. (New NMT)
[0011] With regard to metal alloys, in addition to the aluminum alloy, the present inventors have also discovered the conditions in which such metal alloys can be strongly bonded with a thermoplastic resin such as PBT or PPS through injection bonding as described in the literature of patent 3, 4, 5, 6 and 7. The mechanism of union by injection in these conditions was denominated "new NMT". All of these inventions were made by the present inventors. The required conditions of this more widely applicable "new NMT" will be described below. There are conditions for both the alloy and the injection resin. First, the following conditions ((a), (b), and (c)) are required for metal alloys. (a) The first condition is that the metal alloys have a rough surface by chemical attack such that they have a period of 1 to 10 pm and a vertical interval of approximately half of the period, i.e., 0.5 to 5 pm. However, it is difficult to precisely cover the entire surface with such roughness by means of a non-uniform and variable chemical reaction. Therefore, it is specifically required that when measured with a roughness meter, the roughnesses have a roughness profile such as in an irregular period in the range of 0.2 to 20 pm, and a vertical interval in the range of 0.2 to 5 pm . Alternatively, when the alloy surface is scanned with a scanning probe microscope in the latest model dynamic mode, the above condition is considered to be substantially satisfied if the surface has a roughness such as an RSm of 0.8 to 10 pm and a Rz of 0.2 to 5 pm. Since an ideal rough surface has a roughness period of approximately 1 to 10 pm as described above, the present inventors have termed such surfaces "micron order rough surface" in simple terms. (b) The second condition is that ultrafine roughness having a period of 5 nm or more is additionally formed on the micron order roughness surface of the metal alloy. In other words, it is required to be a rough surface seen from the micron order. To satisfy this condition, the surface of the metal alloy above is subjected to a fine attack in order to form ultrafine roughness in the inner walls of roughness recesses of the micron order. The ultrafine roughnesses have a period of 5 to 500 nm, preferably 10 to 300 nm, more preferably 30 to 100 nm (the optimum value is 50 to 70 nm).
[0012] Describing these ultrafine roughnesses, if the roughness period is less than 10 nm, the resin component will clearly have difficulty penetrating them. Furthermore, since the vertical range normally becomes low in such cases, they are considered to be a smooth surface for the resin. As a result, they do not function as tips. If the period is approximately 300 to 500 nm or more (in this case, rough micron recesses are assumed to have a diameter or period of almost 10 pm), they become less effective since the number of tips in each rough micron recess it is drastically reduced. Hence it is required that the ultrafine asperities have a period ranging from 10 to 300 nm in principle. However, depending on the shape of the ultrafine roughness, the resin may penetrate the spaces even if the period is from 5 to 10 nm. For example, tangled rod-type crystals having a diameter of 5 to 10 nm fit in this case. Also, even if the period is from 300 to 500 nm, the ultrafine roughness of some shapes tend to have an anchoring effect. For example, a shape such as a perlite structure, which is composed of infinitely continuous steps having a height and depth of tens to 500 nm and width of hundreds to thousands of nm, fits in this case. Including these cases, the required period of ultrafine roughness is specified from 5 to 500 nm.
[0013] With respect to the first condition above, the RSm and Rz ranges are conventionally specified from 1 to 10 pm and 0.5 to 5 pm, respectively. However, when RSm and Rz respectively fall within the ranges of 0.8 to 1 pm and 0.2 to 0.5 pm, the bond strength is kept strong as long as the roughness of the ultrafine roughness is within a particularly preferred range. (approximately 30 to 100 nm). Hence, the RSm range has been extended to a certain lower point.
[0014] Specifically, the RSm and Rz were respectively specified in the ranges of 0.8 to 10 pm and 0.2 to 5 pm. (c) In addition, the third condition is that the metal alloy has a ceramic surface layer. Specifically, according to anticorrosive metal alloys, the surface layer is required to be a metal oxide layer having a thickness equal to or greater than its natural oxide layer. As for metal alloys having relatively low corrosion resistance 1 (eg, magnesium alloy, steels in general, and the like), the third condition is that the surface layer is a metal oxide film or metal phosphate that is produced by chemical conversion or the like.
[0015] On the other hand, the conditions for the resin are described below. (d) The resin is a rigid crystalline thermoplastic resin. Specifically, the resin composition contains PBT, PPS, polyamide resin or the like as a major component.
[0016] In addition, to achieve a high bond strength, the new NMT requires one more additional condition for the resin composition. (e) A polymer other than the main component polymer is contained, and most of the different polymer is mixed with the molecular level base crystalline thermoplastic resin.
[0017] Conditions (d) and (e) above are the same conditions as (3) and (4) of NMT. That is, the optimal injection resin is a PBT resin, a PPS resin or a polyamide resin that is formulated with a different polymer. These resin compositions start generating initial seed crystals when they are injected into a mold by an injection molding machine and cooled quickly in the mold to be crystallized and solidified. Through this property, an attempt was made to make an injection resin reach the bottom of the roughened recesses of the micron order. It was assumed that the heads of the flowing resin would also penetrate the recesses of the ultrafine roughness of the period from 5 to 500 nm that were present in the inner wall of these recesses, and then crystallize and solidify in the state of, so to speak, gluing the heads. In practice, when the resin above was injected into different metal alloys that had been pre-treated in order to meet conditions (a), (b) and (c), the resin was penetrated into the ultrafine roughnesses, which largely contributed for bond strength.
[0018] Magnesium alloy, aluminum alloy, copper alloy, titanium alloy, stainless steel alloy, steels in general and similar in plate shape were processed in such a way that their surfaces met conditions (a), (b ) and (c). PBT resin or PPS resin was injection molded into a plate format on the surfaces. Thus products were obtained joined plate-by-plate. In the condition where these metallic alloys and resin compositions were both plate-shaped and were joined together by a certain area (about 0.5 to 0.8 cm2), the shear fracture forces were 25 to 30 MPa . In these cases, the fracture was caused by the destruction of the cast resin side. Since the new NMT provided a very high bond strength and the fracture was therefore caused by the destruction of the resin side, the bond strengths were of the same level between the different metal alloys (patent literature 3 to 7).
[0019] Patent Literature 1: WO 03 / 064150A1 (aluminum alloy)
[0020] Patent Literature 2: WO 2004 / 041532A1 (aluminum alloy)
[0021] Patent Literature 3: WO 2008 / 069252A1 (magnesium alloy)
[0022] Patent Literature 4: WO 2008 / 047811A1 (copper alloy)
[0023] Patent Literature 5: WO 2008 / 078714A1 (titanium alloy)
[0024] Patent Literature 6: WO 2008 / 081933A1 (stainless steel)
[0025] Patent Literature 7: WO 2009 / 011398A1 (steels in general) Detailed description of the invention Problem to be solved by the invention
[0026] NMT and the new NMT were put into practice by the present inventors, and have already been applied to many products. They are currently applied to various pieces of electronic equipment. Specifically, parts of cell phones, notebook computers and projectors are the majority. Currently, NMT and the new NMT are used exclusively for the purpose of tightly integrating a metal alloy part with a molded resin (and thus for the purpose of reducing weight and number of parts).
[0027] Since NMT and the new NMT, which the present inventors have developed, enable a tight integration of a metal alloy part with a molded resin, they may be applicable in gas-sealable spaces between a metal part and a resin . For example, they may be applicable to seal electrodes from secondary lithium ion batteries. Secondary lithium ion batteries use a non-aqueous electrolyte, and include outlet electrodes that are composed of aluminum for the positive electrode and copper for the negative electrode. Since water penetration is absolutely unacceptable in this type of electrolyte, it is essential that it is sealed against gases including moisture. This is because water penetration is considered to cause degradation of battery performance and battery life. Currently, lithium ion battery outlet electrodes are sealed with O-rings.
[0028] However, the high bond strength between a metal alloy part and a molded resin is not directly linked to the improvement of the sealing properties. This is also evident from the experimental results described below. Therefore, it is uncertain whether superior gas-sealing properties are manifested compared to the O-ring that is used in secondary lithium-ion batteries. However, whether or not NMT and the new NMT or an improved technique based on these joining techniques provide good gas sealing properties, it would be possible to provide entirely new solution media with respect to gas sealing methods for lithium-ion batteries and similar. The present invention was made in view of such technological background, and its object is to provide a resin-metal composite that has high gas-sealing properties while achieving a firm resin-metal bond, and to provide a method for manufacturing the same. Means to Solve the Problem
[0029] The present inventors compared the sealing performance against gases by a conventional technique (sealing with an O-ring) with those with NMT and new NMT, and found that NMT provided the best sealing properties against gases. As shown in table 1 below, the amount of gas leakage has been reduced to approximately one hundredth by means of the NMT and to a fifth by means of the new NMT when compared to the conventional seal with an O-ring. The difference in gas-sealing properties between the NMT and the new NMT will now be described with reference to figures 1 and 2.
[0030] In the NMT example shown in figure 1, a resin is penetrated into the ultrathin recesses with a diameter of 20 to 80 nm that are formed on the surface of an aluminum alloy 10 phase. The ultrathin recesses are covered with an oxide film aluminum 30 having a thickness of 3 nm or more. An aluminum alloy with such a surface structure is inserted into an injection mold, and molten thermoplastic resin is injected under high pressure. At this point, the thermoplastic resin finds amine compound molecules adsorbed on the surface of the aluminum alloy in order to cause a chemical reaction. This chemical reaction suppresses a physical reaction where the thermoplastic resin crystallizes and solidifies when it is cooled quickly by contacting the aluminum alloy which is kept under a low mold temperature. As a result, this slows down the crystallization and solidification of the resin, and the resin penetrates the ultrathin recesses on the surface of the aluminum alloy at that time. After penetration, the resin is crystallized and solidified in order to bond to the hard thin layer of aluminum oxide 30. Due to this anchoring effect, the thermoplastic resin becomes resistant to peeling off the surface of the aluminum alloy even when subjected to an outside force. That is, the aluminum alloy is firmly attached to the formed molded resin. In practice, PBT and PPS, which are capable of chemically reacting with the amine compounds, are confirmed to be applicable for bonding by injection with this aluminum alloy.
[0031] Although NMT is published in patent literature 1 and 2, its summary will be described. A piece of conformed aluminum alloy is placed in a degreasing bath and treated by a degreasing process. It is subsequently immersed in a solution of several% sodium hydroxide to dissolve the surface, in order to remove residual contaminants that remain after the degreasing process together with the aluminum surface. It is subsequently immersed in a solution of several% nitric acid in order to neutralize and remove sodium or similar ions that are attached to the surface as a result of the previous step. These processes above aim to leave the surface of the aluminum alloy clean and stable in a chemical and structural sense, so to speak cleaning the face before putting on makeup. If the aluminum alloy part is so clean that it does not have any contamination or corrosion, these pretreatment processes can be omitted.
[0032] The following is an important treatment for NMT. At NMT, the aluminum alloy is immersed in an aqueous solution of water-soluble amine compound in its own condition such that it attacks the surface of the alloy in such a way as to form ultra-fine roughness with a period of 20 to 80 nm as well as to simultaneously leave there the chemically adsorbed amine compound. The present inventors conducted an experiment in which aluminum alloys with surface treatment under different conditions were each inserted into an injection mold, and the PBT resin or PPS resin for NMT was joined to that by injection. Hence, they found a condition in which the bond strength reaches the maximum value while the immersion time of the surface treatment was 1 to 2 min. This condition was used as the optimal production method. More specifically, hydrazine monohydrate was the water-soluble amine compound that was used for the surface treatment of aluminum alloys, the surface treatment was carried out under different conditions (concentration, solution temperature and immersion time) and the resistances of union between aluminum alloys and thermoplastic resin were measured. The optimal concentration, solution and immersion time were thus determined.
[0033] For example, an aluminum alloy part is immersed in solutions of several% hydrazine hydrate from 45 ° C to 65 ° C for 1 hour to several min in order to form the ultrafine rough surface from 20 to 40 nm by ultrathin attack. By this immersion treatment in the hydrazine hydrate solution, the entire face of the aluminum alloy part is corrosively attacked at the low basicity of the solution, while generating hydrogen gas. By adjusting the temperature, concentration and immersion time, the surface of the aluminum alloy is covered with an ultra-fine roughness with a period of 20 to 40 nm. After the ultrafine attack, the aluminum alloy part is washed well with ion-treated water and dried at 50 ° C to 70 ° C. The aluminum alloy is thus processed in order to be suitable for the injection joint, which has hydrazine chemically adsorbed. This is the "NMT" surface treatment. (New NMT)
[0034] Also in the example of the new NMT shown in figure 2, a resin phase 21 is penetrated into the ultrathin asperities formed on the surface of a metal alloy phase 11. The ultrathin recesses are covered with a film 31 of metal oxide or metal phosphate. Compared to NMT, the resin was penetrated into the ultrafine roughness (approximately 50 to 100 nm in diameter in this example) less deeply. This is probably because there is no chemical reaction between the thermoplastic resin and the amine compound molecules, and the crystallization and solidification of the resin cannot be delayed as much as is the case with NMT. That is, NMT is better in terms of the degree of resin penetration in the ultrafine roughness having a diameter of tenths of nm, and is consequently considered better also in terms of gas sealing properties. (NMT 2)
[0035] Improving NMT, the present inventors developed an injection joining technique that additionally provides better sealing properties against gases. This technique is called "NMT 2". Through NMT, an unprecedented strength bond can be established between an aluminum alloy and a resin composition. However, optimal conditions for bond strength are not always optimal conditions for gas-sealing properties. This improvement aims to increase the amount of amine compound adsorbed while the diameter of the ultrafine roughness is maintained at approximately 20 to 80 nm. That is, while the shape of the ultrafine roughness is kept undeformed in order to maintain the maximum level of bond strength, a greater amount of amine compound (eg, hydrazine) is adsorbed than would be the case with the NMT of in order to further delay the crystallization and solidification of the thermoplastic resin and thus increase the degree of penetration in the ultra-fine roughness.
[0036] The present inventors have improved the treatment process by this aspect. First, the ultrafine roughnesses were formed on a surface of the aluminum alloy by ultrafine attack under the same condition as NMT. It is then subjected to a treatment process to increase the amount of chemisorption of the amine compound, where it is immersed in an aqueous solution of a water-soluble amine compound that is more diluted and has a lower temperature than that used in NMT. For a specific example, the ultrathin recesses with a diameter of 20 to 40 nm are first formed on the surface by immersion in solutions of several% hydrazine at 45 ° C to 65 ° C for 1 to several min (the same treatment as in NMT) . In this treatment by immersion in the hydrazine solution, the entire face of the aluminum alloy is corrosively attacked due to the weak basicity of the solution while generating hydrogen gas. By adjusting the temperature, concentration and immersion time, the entire face is covered with ultrafine roughness with a period of 20 to 40 nm.
[0037] In NMT 2, after the above attack treatment (the same treatment as in NMT), the aluminum alloy is immersed in a 0.05 to 1% aqueous solution of an amine compound (eg, aqueous hydrazine hydrate solution) at 15 ° C to 45 ° C for 1 to 10 min, and then washed with water and dried at a low temperature of 50 ° C to 70 ° C. The purpose of this is to promote only the chemisorption of the amine compound (eg hydrazine) while moderating the attack with the use of the low-concentration aqueous solution with water-soluble amine compound (eg, aqueous solution of amine) hydrazine hydrate). In addition, the drying condition after washing with water is set as low as 50 ° C to 70 ° C. This low temperature drying is not intended to prevent hydroxylation of the aluminum alloy surface, but is a result of the search for an optimum temperature to fix the amine compound (eg hydrazine) adsorbed as a chemisorption substance. NMT may employ ammonia or a water-soluble amine in addition to hydrazine for the surface treatment of the aluminum alloy, as can NM 2 as well. In the experimental examples described below, it was confirmed that NMT 2 surface treatment can be carried out using any aqueous hydrazine hydrate solution, aqueous alkyl amine solution, and aqueous ethanol amine solution.
[0038] By the second immersion in the water-soluble amine compound solution, it was assumed that the amount of chemisorption of the amine compound can be increased while the attack rate is considerably reduced. From there, an experiment was carried out, and good results were obtained. The bond strength of the injection joint has not been reduced, while the gas sealing properties have been considerably improved compared to NMT. The thermoplastic resin that is injected into the surface of the aluminum alloy is almost completely penetrated into the bottoms of the ultrathin recesses with a diameter of 20 to 40 nm. As shown in figure 3, it is considered that little space remains between the thermoplastic resin and the aluminum oxide film on the surface of the aluminum alloy phase. This is probably the reason why the gas sealing properties are considerably improved in NMT 2 compared to NMT.
[0039] The reason why the bond strength remains unchanged between conventional NMT and NMT 2 is that the resin part fractures in both cases when subjected to a great external force. That is, a large part of the penetrated resin is left inside the ultrafine roughness even after the fracture, and the fracture is due to the destruction of the resin material itself. Hence, the bonding resistances are equal. As described above, the NMT 2 injection joining technique is totally the same as that of "NMT" at the point where an integrated aluminum alloy / molded resin product is obtained by giving a specific treatment to the aluminum alloy, inserting it into an injection mold, injecting improved thermoplastic resin, and releasing it from the matrix. However, its gas-sealing properties are apparently superior to those of NMT.
[0040] A composite obtained from NMT 2 does not differ from that of NMT except in terms of gas sealing properties. Its shear and tensile fracture forces are both approximately 25 to 30 MPa, which are the same as for molded resin. No difference is observed under an electron microscope between an aluminum alloy material with NMT surface treatment and one with NM 2 surface treatment. It is also difficult to identify the difference between NMT and NMT 2 when the joining part of the aluminum alloy piece of each composite is sliced to a thickness of 50 nm and observed under transmission analytical electron microscopy. Hence, a method is employed by which the structures described below are prepared, and the gas-sealing properties have been measured over several days to 1 week or more.
[0041] Another way is to analyze a piece of aluminum alloy superficially treated by XPS. However, it is difficult to identify whether the surface treatment is for NMT or for NMT 2 from a sample. XPS is an analytical technique that detects signals from almost all atoms present on the sample surface to a depth of several nm. The proportion of hydrazine molecules is thus low even if they are adsorbed on the entire face. This is because the chemisorption is composed of only a single layer of molecules, and the signal derived from the nitrogen atoms of the molecules is thus very low. Hence, if an NMT sample is treated or an NMT 2 sample is treated, it is necessary to integrate at least 5 or more irradiation data to distinguish a peak of noise signals to identify the presence of nitrogen atoms by XPS. On the other hand, damage by X-ray irradiation to the sample, and the chemically adsorbed hydrazine gradually decreases as a function of repetitive irradiation. Therefore, it is not always better to integrate a larger number of data, and the integration of approximately 15 data is the limit. As a result, XPS is difficult to use for the quantitative analysis of the adsorbed hydrazine, but on the other hand it is used for qualitative analysis. However, if a sample treated by NMT and a sample treated by NMT 2 are successively subjected to an XPS analysis under the same conditions and on the same day, the last sample will apparently have a higher nitrogen atom peak. (Resin composition used in NMT 2)
[0042] NMT 2 may employ the resin compositions that are used for NMT. That is, a resin composition including PBT, PPS, polyamide resin or the like may be used. A PPS resin is taken here as an example. For NMT, several types of PPS resins are commercially available from three companies. "SGX 120 (Tosoh Corp.)" Is one of the resins for NMT. This can also be used for NMT 2. Details of the resin compositions are described in patent literature 3, which will be cited here. The PPS resin composition for NMT is a composition whose resin component includes 70% to 97% PPS and 30% to 3% modified polyolefin resin. It is also preferable to contain a component that promotes compatibility between the two. In addition to the resin component, a load and the like are contained.
Preferred examples of the modified polyolefin resin include modified ethylene-maleic anhydride copolymers, modified ethylene-glycidyl methacrylate copolymers, ethylene-alkyl acrylate and the like copolymers. Copolymers of modified ethylene-maleic anhydride include, for example, grafted modified polyethylene maleic acid, ethylene-maleic anhydride copolymer, ethylene-acrylate-maleic anhydride and the like, of which the ethylene-acrylate-anhydride terpolymer is preferable. because particularly good composites are obtained from this. Specific examples of ethylene-acrylic ester-maleic anhydride terpolymer include "BONDINE (Arkema Corp.)" And the like. Copolymers of modified ethylene-glycidyl methacrylate include grafting modified polyethylene-glycidyl methacrylate, ethylene-glycidyl methacrylate copolymer and the like, of which the ethylene-glycidyl methacrylate copolymer is preferable since particularly good composites are obtained than particularly good composites are obtained. from it. Specific examples of the ethylene-glycidyl methacrylate copolymer include "BONFAST (Sumitomo Chemical Co., Ltd.)" And the like.
[0044] Copolymers of modified ethylene-glycidyl ether include, for example, graft-modified ethylene copolymer-glycidyl ether, ethylene-glycidyl ether copolymer and the like. Specific examples of ethylene-alkyl acrylate copolymers include "LOTRYL (Arkema Corp.)" And the like. In addition, ethylene-alkyl acrylate copolymers include ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers and the like, which are preferably used.
[0045] It is preferable to mix 0.1 to 6 parts by weight of a polyfunctional isocyanate compound and / or 1 to 25 parts by weight of an epoxy resin with 100 parts by weight of the above resin component, since the mixing property (mixing property at molecular level) in an extruder is improved. The polyfunctional isocyanate compound may be of the non-block or commercially available block type. Examples of non-block polyfunctional isocyanate compounds include, for example, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylpropane diisocyanate, toluene diisocyanate, phenylene bis (4-isocyanatophenyl) sulfone diisocyanate and the like. The block-type polyfunctional isocyanate compound includes two or more isocyanate groups in the molecule that are reacted with a volatile active hydrogen compound in order to be inactive at ordinary temperature. Although the type of block-type polyfunctional isocyanate compound is not particularly specified, it generally includes isocyanate groups that are masked with a blocking agent such as active alcohols, phenols, e-caprolactam, oximes or methylene compounds. Examples of block-like polyfunctional isocyanate compounds include, for example, "TAKENATE (Mitsui-Takeda Chemicals, Inc.)" and the like.
[0046] The epoxy resin may be an epoxy resin that is generally known as the bisphenol A type, novolaca cresol type and the like. Examples of bisphenol A-type epoxy resin include, for example, "EPICOTE (Japan Epoxy Resins Corp.)" and the like, and examples of novolac cresol-type epoxy resin include "EPICLON (Dainippon Ink and Chemicals Corp.)" and the like.
[0047] Examples of loads include reinforcing fibers, pulverized and similar loads. Reinforcement fibers include glass fibers, carbon fibers, aramid fibers and the like, and specific examples of glass fibers include a chopped filament having an average fiber size of 6 to 14 pm. In addition, pulverized fibers include, for example, calcium carbonate, mica, glass flakes, glass beads, magnesium carbonate, silica, talc, clay, ground products of carbon fiber or aramid fiber, and the like. These charges are preferably treated with a silane coupling agent or a titanate coupling agent. The filler content is from 0% to 60%, preferably from 20% to 40% of the final resin composition. (Injection joining process)
[0048] A piece of aluminum alloy with NMT 2 treatment is inserted into an injection mold, and the PPS resin is injected into it. The injection condition is the same as that of a common PPS resin. It is a common objective of NMT and NMT 2 to produce a strong bond strength in the ultrathin recesses on the ultrafine roughness surface of the aluminum alloy part. Therefore, gas bubbles, gas burning and the like are strictly unacceptable, and purging of mold gases is essential. Although the purging of gases causes small flashes, this is preferable on NMT 2 to inject constantly until the point where the small flashes occur. That is, injection molding conditions should not be determined just to achieve a beautiful appearance for molded products. The aim is to improve the sealing properties by constant injection splicing. If the occurrence of small flashes is problematic, such small flashes must be removed in a post-processing stage. Advantageous effect of the invention
[0049] The aluminum alloy composite and resin composition that is manufactured for "NMT 2" is integrated in such a way as not to separate easily from each other as well as presenting excellent sealing properties against gases. This "NMT 2" is an improved technique of "NMT". The composite has far better sealing properties against gases than a product joined by injection of aluminum alloy and thermoplastic resin by conventional "NMT", or has almost perfect sealing performance. There is substantially no space at the joining edge between the aluminum alloy and the molded resin, and gas molecules barely pass through the joining edge.
[0050] Therefore, if NMT 2 is applied in the manufacture of electrode caps for capacitors and batteries using non-aqueous electrolytes, the sealing properties against gases from the outside may be improved to the highest level. In particular, water penetration can be avoided. With respect to lithium ion batteries, the battery life can be extended since if water molecules penetrate the non-aqueous electrolyte from the outside, this is considered to cause deterioration in performance and a reduction in the capacity and recharge rate of the battery . By applying NMT 2 to the manufacture of electrode seals for capacitors and lithium ion batteries, which are expected to acquire great demand in the future, the durability of such batteries could be considerably improved. Brief description of the drawings
[0051] In the following the invention will be better described in relation to the attached drawings, in which:
[0052] Figure 1 is a view showing a joint piece of an aluminum alloy and a resin by NMT;
[0053] Figure 2 is a view showing a joining piece of an aluminum alloy and a resin by the new NMT;
[0054] Figure 3 is a view showing a joint piece of an aluminum alloy and a resin by NMT 2;
[0055] Figure 4 is a cross-sectional view of a structure in which the space between the pieces of aluminum alloy is sealed with an O-ring;
[0056] Figure 5 is a cross-sectional view of a structure in which the space between the pieces of aluminum alloy is sealed with a PPS resin;
[0057] Figure 6 is a cross-sectional view of a structure in which the space between the aluminum alloy parts is sealed with a PPS resin;
[0058] Figure 7 is a perspective view of a molded PPS resin;
[0059] Figure 8 is a schematic diagram of a test arrangement for testing gas sealing properties;
[0060] Figure 9 is a perspective view of a composite for measuring bond strength;
[0061] Figure 10 is a diagram showing the amounts of helium leakage from different composites; and
[0062] Figure 11 is a cross-sectional view showing an example of a cover structure for a lithium ion battery. Detailed description of the invention
[0063] Hereinafter, the best way to carry out the invention will be described on the basis of experimental examples. In the following experimental examples, an O-ring gas sealing properties test, an NMT gas sealing properties test, a new NMT gas sealing properties test, and a sealing properties test were conducted against gases by NMT 2. A structure 40a was used in the sealing test against gases with O-ring, a structure 40b was used in the sealing test against gases by NMT, a structure 40c was used in the sealing test against gases by the new NMT , and a 40d structure was used in the NMT 2 gas sealing test.
[0064] The structure 40a that was used for the gas sealing test with O-ring is shown in figure 4. The structure 40a includes a body 41a made of aluminum alloy A5052, a bottom 42a made of aluminum alloy A5052 and an O commercially available rubber ring-46. Body 41a was approximately cylindrical in shape, and was provided with a hole 48 in the center as shown in the cross-sectional view 4. A wall surrounding the upper part of hole 48 has a larger diameter than the wall surrounding the lower part of the orifice 48. That is, the wall surrounding the upper part of the orifice 48 is thinner, and the body 41a has a stepped cross section. A space between the bottom 42a and the body 41a is sealed with an O-ring 46 which is engaged in a groove 49. The O-ring has an outside diameter of 25 mm, an inside diameter of 19 mm and a central section of 3 mm <p. Screw holes 45 are provided in the vicinity of the side walls of the body 41a and the bottom 42a, respectively. In a condition where the O-ring is engaged in the groove 49 of the body 41a as well as the bottom end of the O-ring is in contact with the bottom 42a, screws are inserted through both screw holes 45 in the body 41a and bottom 42a, and are fastened with nuts on the upper body 41a and the bottom coffee 42a. Thus, the body 41a, the O-ring 46 and the bottom 42a will be integrated with each other. Figs. 5 and 6 show structure 40b that was used in the NMT gas sealing test. A body 41b is the same as body 41a of structure 40a in terms of shape and material, but is treated with NMT surface treatment. Also the bottom 42b is the same as the bottom 42a of the structure 40a in terms of shape and material, but is treated with the NMT surface treatment. The structure 40b does not include an O-ring, but a metal ring 43b having a rectangular cross section is engaged in the groove 49. This metal ring 43b is also made of aluminum alloy A5052 such as 41b and 42b, and treated with treatment surface of NMT. A resin member 47 seals a space between the body 41b and the metal ring 43b and a space between the metal ring 43b and the bottom 42b.
[0065] A method for manufacturing the 43b structure will be shown. As shown in figure 5, the metallic ring 43b is engaged in the groove 49, the bottom 42b is contacted with the lower face of the metallic ring 43b, these are inserted in an injection mold, and an intra-mold protrusion 50 is adapted in the orifice 48. A pin feeder 51 ("pin gate") is notched in the intra-cast protrusion 50. Here, the pin feeder 51 is positioned between the upper face of the bottom 42b and the lower face of the body 41b. With this arrangement, the resin composition is injected through the pin feeder 51 in such a way as to form a resin member 47 that joins the upper face of the bottom 42b, the lower face of the body 41b and the inner periphery of the metallic ring 43 to each other others. After injection molding, structure 40b is obtained as shown in figure 6.
[0066] Figure 7 shows a perspective view of the resin member 47. The resin member 47 is an injection molded product having a plate shape with a shallow center. The resin member 47 has an internal diameter of 15 mm, an external diameter of 19 mm and an edge width of 2 mm. The central recess coincides with hole 48 in order to form a cavity within the structure. The upper, lateral and lower faces of the rim of the resin member 47 are respectively joined to the lower face of the body 41b, the lateral face of the metal ring 43b and the upper face of the bottom 42b. The upper face (edge) of the resin member 47 is directly related to gas sealing. The amount of gas permeation is considered to be proportional to the inner circumference (15 mm x 3.14 = 4.71 cm) of this face, as well as being inversely proportional to the width between the inner and outer peripheries (edge width, 0, 2 cm).
[0067] Structure 40c, which is used in the gas sealing test of the new NMT, has the same shape as structure 40b. However, a body 41c of structure 40c is made of a different metallic alloy (copper alloy in the present example) with the surface treatment of the new NMT. A metallic bottom 42c and a metallic ring 43c are both made of aluminum alloy A5052 with NMT surface treatment.
[0068] Figs. 5 and 6 show the structure 40d that was used in the NMT 2 gas sealing test. A body 41d has the same shape and material as the body 41a of structure 40a, but is treated with the NMT 2 surface treatment. In the experimental example described below, a body 41b made of aluminum alloy A1050 has also been prepared. This body was also treated with the NMT 2 surface treatment. As for a bottom 42d and metallic ring 43d, these are made of aluminum alloy A5052 according to 42b and 43b, and are treated with the NMT surface treatment. A resin member 47 seals a space between the body 41d and the metal ring 43d and a space between the metal ring 43d and the bottom 42d. Arrangement for measuring sealing properties
[0069] Figure 8 shows a summary of an experimental arrangement for sealing properties against gases 100. The experimental arrangement for sealing properties against gases 100 is a measurement arrangement for measuring sealing properties against gases described above structures 40a, 40b, 40c and 40d. As shown in figure 8, the experimental arrangement for gas sealing properties 100 includes a helium cylinder 110 and a regulator 111 with a pressure gauge attached to it, an argon cylinder 120 and a regulator 121 with a connected pressure gauge to this, an autoclave 130, a Swagelok 131 pipe union, a mercury column vacuometer 140, a vacuum pump 150, a sampling vessel 160 and the like.
[0070] From outside to inside autoclave 130, as shown in figure 8, a pipe 132 connected to the helium cylinder 110 is inserted, a pipe 133 connected to the argon cylinder 110 is inserted, and a pipe 134 connected to the vacuometer 140, vacuum pump 150 and sampling vessel 160 are inserted. When measuring, the structures 40a, 40b, 40c and 40d are each placed inside the autoclave 130, an upper central end (projection) of the structure is connected to the pipe 132 by a union of pipes 131, and a gate is closed to place the interior of autoclave 130 in a sealed condition.
[0071] When measuring, the cavity (hole 48) inside the structure is pressurized to an absolute pressure of 0.61 MPa by the helium cylinder 110 through regulator 111 and pipe 132. A control is made to maintain the helium pressure at 0.61 MPa until the end of the measurement. In the meantime, the interior of autoclave 130 is filled with argon at an absolute pressure of 0.11 MPa (slightly higher than atmospheric pressure) of the argon cylinder 120 through regulator 121. The pressure difference between the interior of the structure and the interior of autoclave 130 is possibly 0.5 MPa.
[0072] At the beginning of the test, the interior of the autoclave is depressurized by the vacuum pump 150 while monitoring the vacuum pump 140, in order to create an atmosphere of 100% argon inside the autoclave. After 72 hours, the sampling vessel 160 and its inlet pipe are placed under vacuum by the vacuum pump 150, and approximately 30 cm3 are corrected from inside the autoclave to sampling vessel 160. The gas in the sampling vessel is then subjected to analysis to measure the amount of helium leakage into argon. That is, the structure cavity is filled with helium under high pressure of approximately 6 atm while the interior of the autoclave under an argon atmosphere at approximately atmospheric pressure (1 atm). A pressure difference of 0.5 MPa is thus created in order to let the helium seep out of the structure cavity into the autoclave. After a lapse of a predetermined time, the gas inside the autoclave is sampled and the amount of helium leakage is measured by gas analysis.
[0073] The present inventors have calculated that the helium leak rate from the amount of helium leaked in this way. The leak rate is a value obtained by dividing the amount of helium poured by the test time (table 1). However, when X mL / h of gas leaks per unit time of structure 40a with an O-ring due to the pressure difference, the value (X / 6.91) mL / cmh obtained by dividing this value by the circumferential length 6, 91 cm of the 22 mm central diameter of the O-ring is a suitable value that indicates the amount of leakage per unit length per unit of time (ie the leakage rate). As for structures 40b, 40c and 40d of injection connection, when X mL / h of gas leaks due to the pressure difference, the value (0.2X / 4.71) mL / h obtained by dividing this value by the circumferential length of 4 , 71 of the 15 mm internal diameter of the resin member 47 and additionally multiplying by the gas flow path 0.2 cm is an adequate value that indicates the amount of leakage per unit time (i.e., the leakage rate) . The structure 40a with the O-ring is different from the structures 40b, 40c and 40d by the union by injection in the format and the sealing technique. However, the general formats are similar and a superficial comparison can be made based on the values above. Experimental Examples
[0074] Hereinafter, a method of measuring sealing properties against gases by NMT, new NMT or NMT 2 of the present invention will be described with reference to the experimental examples. The following equipment was used for the experiments. (1) Electron microscopic observation
[0075] An electron microscope was used mainly for observing surfaces of aluminum alloys. This electron microscope was an electronic scanning microscope (SEM) "JSM-6700F (JEOL Ltd.)", and operated at 1 to 2 kV for observation. (2) X-ray photoelectronic spectroscopy (XPS observation)
[0076] A photoelectronic X-ray spectroscopic analyzer (XPS observation) was used, where a sample is irradiated with X-rays and the energy of the photoelectrons that are emitted from the sample is analyzed to perform the qualitative analysis of elements and the like. The qualitative analysis by XPS was conducted with respect to nitrogen atoms on aluminum alloys, and the presence of chemically adsorbed hydrazine was confirmed. An XPS "AXIS-Nova (Kratos Analytical Ltd., Shimadzu Corp.)" was used in the experiments. (3) Measurement of composite bond strength
[0077] A composite 50 shown in figure 9 was prepared in order to measure the bond strength of a composite of a metal alloy and resin composition. The composite 50 had a structure where an alloy plate 51 is joined to a molded resin 53 by injection joining and a joining piece 52 has an area of 0.5 cm2. As the bond strength of this composite 50, the breaking load was measured. Specifically, composite 50 was pulled by a tension tester in order to apply a shear force, and the fracture force at which composite 50 breaks was measured. A tension tester "AG-10kNX (Shimadzu Corp.)" Was used, and the shear fracture was caused at a tension rate of 10 mm / min. (4) Gas analyzer used to measure the sealing properties
[0078] For the quantitative analysis of helium concentration in argon and the like, a quadripolar mass spectrometer "JMS-Q1000GC (JEOL Ltd.)" was used. [Experimental example 1] Preparation of A5052 aluminum alloy parts (NMT 2)
[0079] To prepare the structure 40d shown in figure 5, aluminum alloy parts A5052 of the body 41d, bottom 42d and metallic ring 43d were prepared. Body 41d was treated with NMT 2 surface treatment. In contrast, bottom 42d and metal ring 43d were treated with NMT surface treatment. The surface treatment of NMT 2 was carried out as follows. First, an aqueous solution (solution temperature of 60 ° C) containing 7.5% of an aluminum degreasing agent "NE-6 (Meltex Inc.)" was prepared as a degreasing solution, and a degreasing bath was prepared with the degreasing solution. The piece of aluminum alloy A5052 (a piece shaped to be the body 41d for treatment) was immersed in it for 5 min, and then washed with spout (Ota city, Gunma). Subsequently, an aqueous solution (40 ° C) containing 1% hydrochloric acid was prepared in another pan in order to prepare an acid pre-cleaning bath. The piece was immersed in this acidic prewash bath for 1 min, and then washed with ion-treated water.
[0080] Subsequently, an aqueous solution (solution temperature 40 ° C) containing 1.5% sodium hydroxide was prepared in another pan, in order to prepare an attack bath. The piece was immersed in this attack bath for 1 min, and then washed with water treated with ion exchange. Subsequently, a 3% aqueous solution of nitric acid (40 ° C) was prepared in another pan. The piece was immersed in this neutralizing bath for 1 min, and then washed with water treated with ion exchange. Subsequently, an aqueous solution (60 ° C) containing 3.5% hydrazine hydrate was prepared in another pot, in order to prepare a first NMT treatment bath. The piece was immersed in this first NMT treatment bath for 1 min. Subsequently, an aqueous solution (40 ° C) containing 0.5% hydrazine hydrate was prepared in another pot, in order to prepare a second NMT treatment bath. The piece was immersed in this second treatment bath by NMT for 3 min, then being washed with water treated with exchanges. Subsequently, the part was left in a hot air dryer at 55 ° C for 40 min to dry. The obtained piece was firmly packed in aluminum laminate and additionally sealed in a plastic bag for storage.
[0081] The surface of the aluminum alloy A5052 with the above treatment was observed under an electron microscope. The surface was covered with countless ultrathin recesses, and these recesses had a diameter of 20 to 40 nm. Furthermore, the presence of nitrogen was confirmed by observation with XPS.
[0082] On the other hand, the bottom 42d and the metallic ring 43d were treated with the NMT surface treatment. The process of this treatment was totally the same as the NMT treatment described in [experimental example 2] below. [Experimental example 2] Preparation of A5052 aluminum alloy part (NMT)
[0083] To prepare the structure 40b shown in fig 5, aluminum alloy parts A5052 of the body 41b, bottom 42b and metallic ring 43b were prepared. Body 41b, bottom 42b and metal ring 43b were treated with NMT surface treatment. NMT surface treatment was performed as follows. First, an aqueous solution (solution temperature of 60 ° C) containing 7.5% of an aluminum degreasing agent "NE-6" was prepared as a degreasing solution, and a degreasing bath was prepared with the degreasing solution. The aluminum alloy parts A5052 (parts shaped to be the body 41b, bottom 42b and metal ring 43b for treatment) were immersed in it for 5 min, and then washed with spout (Ota city, Gunma) . Subsequently, an aqueous solution (40 ° C) containing 1% hydrochloric acid was prepared in another pan in order to prepare an acid pre-cleaning bath. The pieces were immersed in this acid pre-wash bath for 1 min, and then washed with ion-treated water.
[0084] Subsequently, an aqueous solution (solution temperature 40 ° C) containing 1.5% sodium hydroxide was prepared in another pan, in order to prepare an attack bath. The pieces were immersed in this attack bath for 1 min, and then washed with water treated with ion exchange. Subsequently, a 3% aqueous solution of nitric acid (40 ° C) was prepared in another pan. The pieces were immersed in this neutralizing bath for 1 min, and then washed with water treated with ion exchange. Subsequently, an aqueous solution (60 ° C) containing 3.5% hydrazine hydrate was prepared in another pot, in order to prepare a NMT treatment bath. The pieces were immersed in this NMT treatment bath for 1 min and then washed with water treated with ion exchange. Subsequently, the pieces were left in a hot air dryer at 67 ° C for 15 min to dry them. The pieces obtained were firmly packed in aluminum laminate and additionally sealed in a plastic bag for storage.
[0085] The surfaces of the A5052 aluminum alloys with the above treatment were observed under an electron microscope.
[0086] The surfaces were covered with countless ulltrafine recesses, and these recesses were 20 to 40 nm in diameter. Additionally, the presence of nitrogen was confirmed with XPS observation. The peak size of nitrogen atoms per XPS (the sum of the spectrum peaks of 10 measurements) was compared with that of the aluminum alloy A5052 from the NMT 2 treatment described in experimental example 1. The aluminum alloy in experimental example 1 had a value greater than that of experimental example 2. [Experimental example 3] Union by injection
[0087] The body 41d, bottom 42d and metallic ring 43d, which were treated with the surface treatment of experimental example 1, were assembled together as shown in figure 5, and inserted into an injection mold at a temperature of 140 ° Ç. The intra-mold projection 50 was fitted with a hole 48. The intra-mold projection 50 had a pin feeder 51 notched in it. After closing the injection mold and heating the body 41d, the bottom 42d and the metal ring 43d for approximately 10 sec, the PPS resin commercially available for NMT "SGX 120 (Tosoh Corp.)" Was injected. Injection molding was performed at an injection temperature of 300 ° C and a mold temperature of 140 ° C. This structure 40d shown in figure 6 was thus obtained. This is a sealing test composite manufactured by NMT 2.
[0088] According to structure 40d, structure 40b was prepared with body 41b bottom 42b and metal ring 43b, which were treated with the surface treatment of experimental example 2. This is a composite for the sealing test manufactured by NMT. Structures 40b and 40d as prepared above were annealed in a hot air dryer at 170 ° C for 1 hour. [Experimental example 4] Measurement of sealing properties (NMT, NMT 2)
[0089] The gas-sealing properties of structures 40b and 40d, which were prepared in experimental example 3, were measured by the arrangement shown in figure 8. The projection in the center of the upper face of structure 40b was connected to pipe 132 by the Swagelok joint 131, and the interior of autoclave 130 is put in a sealed condition. Valves are controlled in such a way that the cavity of structure 40b is replaced by helium, and the pressure in the cavity is adjusted to approximately 0.2 MPa. Subsequently, autoclave 130 is evacuated to produce a vacuum at a level of several mm Hg using the vacuum pump 150, and argon gas was then charged to bring the pressure back to approximately atmospheric pressure. This operation was repeated once more in such a way that the interior of autoclave 130 had almost 100% argon. Subsequently, the pressure of the autoclave was finely adjusted to 0.11 MPa of absolute pressure, which is slightly higher than atmospheric pressure. Subsequently, the pressure in the cavity of structure 40b was increased to 0.61 MPa. The gas sealing test was started in this condition.
[0090] The amount of helium contained in the gas inside the autoclave 130 after 3 days (72 hours) of the test start was calculated by analyzing the gas sampled in the sampling vessel 160. Three structures 40b were subjected to the same test, and the results are shown in table 1 (NMT) and figure 10. One of the structures 40b was subjected to the measurement of the amount of helium after 7 days (168 hours) from the start of the test. Likewise, three structures 40b were also subjected to the measurement of the amount of helium. The results are shown in table 1 (NMT 2) and figure 10.
[0091] As shown in table 1 and figure 10, structures 40b by NMT had a helium leak from 0.10 to 0.22 ml after 72 hours and 0.25 ml after 168 hours. In the case of O-ring sealing described below, the leakage was 17 to 19 mL after 72 hours, and there was a difference of approximately 100 times. Therefore, it can be said that the NMT gas sealing properties are very good.
[0092] Structure 40d was subjected to the same experiment as structure 40b. The structure 40d by NMT 2 has sealing properties against gases even superior to those of NMT. As shown in table 1 and figure 10, structure 40d by NMT 2 shows a helium leak of 0.01 mL after 72 hours. As described here, structure 40d by NMT 2 has a very low helium leakage that was less than a tenth of that by NMT. [Experimental example 5] Measurement of sealing properties (Extension of measurement period in the case of NMT 2)
[0093] It is demonstrated in experimental example 4 that NMT 2 provides sealing properties against very high gases. However, since the amount of helium leakage is very low, the reliability of the values is a concern. Therefore, one of the 40d structures by NMT 2 was subjected to measurement of the amount of helium leakage after 28 days (672 hours) since the start of the test. The result is shown in table 1 and figure 10. The leak rate was approximately 0.0002 mL / hour, and the value after format-based correction was 0.0002 x 0.2 / 4.71 = 8.5 x 10 -6 mL / h. However, if there is even a slight leak through the connection of Swagelok 131 pipes, the measured amount of leak may include it. Therefore, it may be impossible to accurately measure the sealing properties against gases by NMT 2 using this level experiment. [Experimental example 6] Preparation of C1100 copper alloy part (treated by the new NMT) and injection joining (Treatment by the new NM11 of copper alloy part C1100)
[0094] To prepare the structure 40c shown in figure 5, a piece of copper alloy C1100 of the body 41c, pieces of aluminum alloy A5052 with bottom 42c and metallic ring 43c were prepared. Body 41c was treated with the new NMT surface treatment for C1100, and the bottom 42c and metal ring 43c were treated with the new NMT surface treatment for C1100, and bottom 42c and metal ring 43c were treated with the treatment surface for NM50's A5052. The specific process for surface treatment of NMT was totally the same as that described in experimental example 2. The surface treatment of the new NMT for copper material C1100 was carried out as follows. First, an aqueous solution (solution temperature of 60 ° C) containing 7.5% of the aluminum degreasing agent "NE-6" was prepared, and a degreasing bath was prepared with the degreasing solution. The C1100 copper alloy body 43c was immersed in it for 5 min, and then washed with tap water (Ota city, Gunma). Subsequently, an aqueous solution (solution temperature 40 ° C) containing 1.5% sodium hydroxide was prepared in another pan, in order to prepare a basic pre-cleaning bath. The piece was immersed in this basic pre-cleaning bath for 1 min, and then washed with water treated with ion exchange.
[0095] Subsequently, an aqueous solution (solution temperature of 40 ° C) containing 10% nitric acid was prepared in another pan, and the piece was immersed in this neutralizing bath for 0.5 min. Subsequently, an aqueous solution containing 3% nitric acid was prepared in another pan, and the piece was immersed in this neutralizing bath for 10 min, and then washed with water treated with exchanges. Subsequently, an aqueous solution (25 ° C) of 10% sulfuric acid, 6% hydrogen peroxide and 0.3% trisodium phosphate hydrate was prepared in another pan, in order to prepare an attack bath. The piece was immersed in this attack bath for 1 min, and then washed with ion-exchange water. Subsequently, an aqueous solution containing 2% nitric acid was prepared in another pot, and the piece was immersed in it for 0.5 min and then washed well with water treated with ion exchange. Subsequently, a solution (70 ° C) containing 3% potassium hydroxide and 2% potassium permanganate was prepared in another pot, in order to prepare an oxidation treatment bath. The piece was immersed in this oxidation treatment bath for 3 min, and then washed well with water treated with ion exchange. Subsequently, the piece was left in a hot air dryer at 80 ° C for 15 min to dry. The obtained piece was firmly packed in aluminum laminate and additionally sealed in a plastic bag for storage. New NMT treatment of cllOO copper alloy part
[0096] A piece of copper alloy C1100 45 mm x 18 mm x 1.5 mm thick was treated with the Nova NMT treatment in accordance with the part described above. The PPS resin "SGX (Tosoh Corp.)" Was injected on the surface of this piece of copper alloy CllOO with the surface treatment, in order to obtain a molded product in the form of a plate. The composite 50 obtained has a structure in which a copper alloy plate C1100 is joined to a molded resin 53 by injection joining, and a joining piece 52 has an area of 0.5 cm2. After joining by injection, composite 50 was annealed at 170 ° C for approximately 1 hour, and then fractured by effective tensile stress. The shear fracture strength was 22 MPa in the average of three samples. The copper alloy part C1100 was integrated with the PPS resin molded with a very strong bond strength as high as that by NMT. Injection fitting
[0097] A body 41c with the new NMT surface treatment and a bottom 42c and a metallic ring 43c with the NMT surface treatment were mounted on each other as shown in figure 5 and inserted into an injection mold at a temperature of 140 ° C, and an intra-mold projection 50 was placed in a hole 48. The intra-mold projection 50 had a notched pin feeder 51. After closing the injection mold and heating the body 41c, the bottom 42c and the metal ring 43c for approximately 10 sec, the commercially available PPS resin "SGX 120 (Tosoh Corp.)" Was injected. Injection molding was performed at an injection temperature of 300 ° C and a mold temperature of 140 ° C. The structure 40c shown in fig 6 was thus obtained. This is a sealing test composite manufactured by the new NMT. Structure 40c as prepared above was annealed in a hot air dryer at 170 ° C for 1 hour. [Experimental example 7] Sealing property measurement (copper C1100)
[0098] The structure 40c that was prepared in the experimental example gases 6 was subjected to a measurement of sealing properties against gases in the same way as in the experimental example 4. The result is shown in table 1 and figure 10. As shown in table 1 and Figure 10, structure 40c by the new NMT had a helium leak of 2.6 ml after 72 hours and 3.9 ml. Consequently, structure 40c by the new NMT has a helium leakage 10 times higher than that of NMT, and its gas-sealing properties were lower than those of NMT 2 naturally, as well as those of NMT. The leak rate was 0.036 to 0.054 mL / h, which was reasonably lower than that of NMT. [Experimental example 8] Measurement of sealing properties (O-ring)
[0099] The structure 40a with an O-ring was subjected to the measurement of sealing properties against gases in the same way as in the experimental example 4. Three structures 40a were subjected to the measurement of sealing properties against gases, where the screws / nuts, that press the O-ring in the vertical direction, have been locked with different forces. The locking forces were of three levels "normal", "semi-strong" and "strong". The result is shown in table 1 and figure 10. As shown in table 1 and figure 10, structure 40a with an O-ring has a helium leak of 15 to 19 mL after 72 hours, and its sealing properties were by far even lower than those of structure 40c by the new NMT. Even when the O-ring is tightened more than "normal", the amount of helium leakage does not change considerably.
[Experimental example 9] NMT 2 gas sealing properties experiment (with dimethylamine)
[0101] The present inventors have also prepared a structure 40d which includes a body 41d made of aluminum alloy material A1050. In experimental example 9, the body 41d is a piece of aluminum alloy A1050 with the surface treatment of NMT 2, and a bottom 42d and a metal ring 43d are pieces of aluminum alloy A5052 with a surface treatment of NMT. The surface treatment of NMT for the aluminum alloy material A1050 was carried out as follows. First, an aqueous solution (solution temperature of 60 ° C) containing 7.5% of an aluminum degreasing agent "NE-6 (Meltex Inc.)" was prepared as a degreasing solution, and a degreasing bath was prepared with the degreasing solution. The aluminum alloy piece A1050 (a piece conformed to be the body 41d for the treatment) was immersed in it for 5 min, and then washed with tap water (Ota city, Gunma). Subsequently, an aqueous solution (40 ° C) containing 1% hydrochloric acid was prepared in another pan in order to prepare an acid pre-cleaning bath. The piece was immersed in this acidic prewash bath for 1 min, and then washed with ion-treated water.
[0102] Subsequently, an aqueous solution (solution temperature 40 ° C) containing 1.5% sodium hydroxide was prepared in another pan in order to prepare an attack bath. The piece was immersed in this attack bath for 4 min, and then washed with water treated with ion exchange. Subsequently, a 3% aqueous solution of nitric acid (40 ° C) was prepared in another pan. The piece was immersed in this neutralizing bath for 3 min, and then washed with water treated with ion exchange. Subsequently, an aqueous solution (60 ° C) containing 3.5% hydrazine hydrate was prepared in another pot, in order to prepare a first treatment bath. The piece was immersed in this first NMT treatment bath for 1 min. Subsequently, an aqueous solution (20 ° C) containing 0.1% dimethylamine was prepared in another pan, in order to prepare a second NMT treatment bath. The piece was immersed in this second treatment bath by NMT for 8 min, then being washed with water treated with exchanges. Subsequently, the part was left in a hot air dryer at 50 ° C for 40 min to dry. The obtained piece was firmly packed in aluminum laminate and additionally sealed in a plastic bag for storage.
[0103] The surface of the aluminum alloy A1050 with the above treatment was observed under an electron microscope. The surface was covered with countless ultrathin recesses, and these recesses had a diameter of 30 to 50 nm. Furthermore, the presence of nitrogen was confirmed by observation with XPS.
[0104] The 41d aluminum alloy body A1050 with the surface treatment described above, bottom 42d and metal ring 43d were mounted on each other as shown in figure 5 and inserted into an injection mold at 140 ° C, and an intra projection -mold 50 was mounted in a hole 48. Then, the PPS resin "SGX 120 (Tosoh Corp.)" was injected in a totally equal way to that of experimental example 3, in order to obtain the product joined by injection 40d. Subsequently, as in experimental example 3, it was annealed in a hot air dryer at 170 ° C for 1 hour.
[0105] Subsequently, the sealing properties against gases were measured with the measurement arrangement shown in figure 8 in a totally equal way to that of the experimental example 4. The amount of helium contained in the gas in autoclave 130 after 3 days (72 hours) a from the start of the test it was calculated by analyzing the gas sampled in the sampling vessel 160. As a result, the amount of helium leakage was 0.04 mL, which is extremely low. [Experimental example 10] NMT 2 gas sealing properties experiment (with ethanol amine)
[0106] An experiment was conducted in the same way as in experimental example 9, except for the surface treatment of the body 42. In the present experimental example, the surface treatment by NMT 2 for the aluminum piece A1050 (body 42d) was changed. Amine ethanol was used as the water-soluble amine compound of the second NMT treatment bath, and the immersion conditions were changed. Specifically, the solution of the second NMT treatment bath was a 0.15% aqueous solution of ethanol amine at a temperature of 40 ° C, and the immersion time was 1 min.
[0107] The body 41d of aluminum alloy 1050 with the surface treatment described above, a bottom 42d and a metallic ring 43d were assembled as shown in figure 5. The PPS resin "SGX 120 (Tosoh Corp.)" Was injected, in order to obtain the product joined by injection 40d. Subsequently, this was annealed in a hot air dryer at 170 ° C for 1 hour.
[0108] Subsequently, the sealing properties against gases were measured with the measurement arrangement shown in figure 8 in a totally equal way to that of the experimental example 4. The amount of helium contained in the gas in autoclave 130 after 3 days (72 hours) a from the start of the test it was calculated by analyzing the gas sampled in the sampling vessel 160. As a result, the amount of helium leakage was 0.04 mL, which is extremely low. [Comparison of bond strengths and gas sealing properties]
[0109] By means of NMT, the present inventors prepared 20 pieces of composites 50 of aluminum alloy A5052 and a product molded from PPS resin "SGX 120" having the shape shown in figure 9. Composites 50 were pulled by a tension tester in order to apply a shear force, and the fracture forces at which the composites 50 broke were measured. As a result, the shear fracture forces were approximately 25 to 30 MPa. Also, using NMT 2, 20 pieces of composites 50 of aluminum alloy A5052 and a product molded from PPS resin "SGX 120" having the shape as shown in figure 9 were prepared and subjected to the same experiment. The shear fracture forces were approximately 25 to 30 MPa. Therefore, NMT and NMT 2 provide the same bond strength. On the other hand, comparing the sealing properties against gases, structure 40b by NMT had a leakage rate of 0.0015 to 0.003 mL / h, while structure 40d by NMT 2 had a leakage rate from 0.0001 to 0.0002 mL / h (in the case where the body 41d is made of aluminum alloy A5052). Consequently, while NMT and NMT 2 provide the same bond strength, there is a difference of approximately ten times between their sealing performance against gases.
[0110] Including the case where the body 41d is made of aluminum alloy A5052, the structures 40d by NMT 2 have a leakage rate of 0.0001 to 0.0005 mL / h. The corrected value for the format described above obtained by multiplying it by the length of the flow path (0.2 cm) and further divided by the sealing length (4.71 cm) is (0.0001 to 0. 005) x 0, 2 / 4.7 1 = (4.2 to 21) x 10-6 ml / h. On the other hand, structure 40b by NMT has a leakage rate of 0.0015 to 0.003 ml / h. The value corrected by the format described above by multiplying it by the length of the flow path (0.2 cm) and additionally dividing by the sealing length (4.71 cm) is (0.0015 to 0.003) X 0.2 / 4.71 = (6.4 to 12.7 ) x 10 “5 mL / h. Through NMT 2, which the present inventors developed, the corrected value for format is considerably improved compared to conventional NMT. Comparing NMT to NMT 2 using the same material (A5052), there is a difference of approximately ten times between their gas sealing performances as described above. Such gas sealing techniques using a resin that provides a corrected value for the format of 3 x 10-5 mL / h or less was an unthinkable technique in the past. Through NMT 2, the helium leakage rate corrected for the format can be reduced to 3 x 10-5 mL / h or less. This is the characteristic of this invention.
[0111] The corrected leak rate is proportional to the pressure difference of up to 1 MPa, and is considered to be also affected by the test temperature. It is assumed that the rate of vibration and migration of the molecules will become more intense at a higher temperature, and the rate of leakage will thus increase. The present inventors conducted the experiments above 25 ° C to 30 ° C.
[0112] In contrast, structure 40a with the O-ring had a helium leak of 15 to 19 mL after 72 hours of the start of the experiment and a leak rate of 0.21 to 0.26 mL / h.
[0113] The amount of leakage is approximately 100 times as high as that of NMT, and approximately 1,000 as high as that of NMT 2. The value corrected for the format obtained by dividing the leakage rate by the circumferential length of 6.91 cm is (0.21 to 0.26 / 6.91) = (2.9 to 3.8) x 10-2 mL / cmh.
[0114] The 40c structure by the new NMT had a helium leakage of 2.6 to 3.9 ml after 72 hours of the start of the experiment and a rate of 0.036 to 0.054 ml / h. These data are values of the CHOO copper sample with the treatment of the new NMT as described in experimental example 6, and the values would be different depending on the metallic alloy and the process for the surface treatment of the new NMT if developed for the corresponding metallic alloy. However, the surface of the metal alloy with the new NMT surface treatment has a structure as shown in figure 2, where there are scattered spaces that are neither the metal phase including the surface coating layer nor the resin phase. It is evident that these spaces have a negative effect on the amount of leakage and the leakage rate, when compared to the characteristic of spaces shown in figure 1, which schematically shows a cross section of the product joined by injection by NMT. From such a perspective, it has been suggested that leakage rates would have different values ranging from approximately 0.01 to 0.1 mL / h if different metal alloys were subjected to the same experiment.
[0115] In any case, in the case of C1100 copper, the amount of leakage was approximately 10 times as high as that of NMT, and approximately 100 times as high as that of NMT 2. In contrast, when compared to the case of tightening with O-ring, the amount of leakage in the case of C1100 copper and the new NMT was approximately one fifth of that of an O-ring. In this case of copper C1100 and the new NMT, the corrected value for the format obtained by multiplying the leakage rate by the length of the flow path (0.2 cm) and additionally dividing by the sealing length (4.71 cm), is ( 0.036 to 0.054) X 0.2 / 4.71 = (1.5 to 2.3) X 10-3 mL / h. Lithium-ion battery cover structure
[0116] As shown in the above experimental results, NMT 2 provides the best gas-sealing properties, and NMT thereafter. However, NMT and NMT 2 are techniques for securely bonding an aluminum alloy to a resin. Lithium ion batteries use aluminum and copper for their output electrodes. Hence, while NMT and NMT 2 are applicable to aluminum electrodes, the new NMT should be applied to copper electrodes, which results in a problem that the gas-sealing properties by NMT and NMT 2 are impaired as a complete battery cover. Although the new NMT provides better sealing properties against gases than the O-ring technique, the low sealing properties of copper electrodes cancel out the best properties of aluminum electrodes.
[0117] To avoid the penetration of external moisture for a long time, it is preferable to seal the part between the metal and the resin with NMT or an NMT 2. As a result of considering the structure of the lithium ion battery covers in this respect, it was concluded that the optimal structure is the structure as shown in figure 11. According to the lithium 60 battery structure, a cap 61 is made of aluminum alloy, and a thermoplastic resin composition 64 seals a space between a hole through and an aluminum electrode 62, which is left after the lid 61 is closed, as well as a space through a hole and an aluminum alloy piece 61a, which is left after the lid 61 is closed. In order to eliminate a gap between the copper electrode 63 and the cap 61, the aluminum alloy piece 61a is wound around the copper electrode 63 and engaged with the copper surface. Once the cap 61, the aluminum alloy part 61a and the aluminum electrode 62 are treated with the NMT or NMT 2 surface treatment, a firm bond is established between the thermoplastic resin composition 64 and the cap 61 as well as between the thermoplastic resin composition 64 and the aluminum electrode 62, and sealing properties against very high gases are thus established. Also, the firm connection with NMT and NMT 2 is established between the thermoplastic resin composition 64 and the aluminum piece 61a which is engaged with the copper electrode 63, and very high gas sealing properties are thus established. In addition, the thermoplastic resin composition 64 seals a space between the aluminum alloy 61a and the cap 61. The thermoplastic resin composition 64 covers the part of the back face of the cap 61 and the aluminum part 61a that comes into contact with the electrolyte .
[0118] The key point of the lithium ion battery cover 60 shown in figure 11 is that the space between the aluminum electrode 62 and the cover 61 and the space between an outlet of the copper electrode 63 and the cover 61 are both sealed through NMT or NMT 2. In the lithium 60 battery cover, the gas-sealing properties are poor at the periphery of the copper electrode 63. To deal with this, an aluminum alloy structure having a contoured shape is formed copper 63, and the engaged aluminum alloy is made to contact copper electrode 63 closely and additionally engaged to electrode 63 by pressing or forging. It is then turned to a predetermined shape in order to prepare the copper alloy 63 connected to the aluminum alloy part 61a. Subsequently, NMT or NMT 2 surface treatment is given to the three members of the aluminum electrode 62, copper electrode 63 connected to the aluminum part 61a and aluminum alloy cap 61. These three members are inserted into an injection mold of metal, and the thermoplastic resin composition 64 such as PPS resin is injected. The lithium ion battery cover 60 having a structure as shown in fig 11 is thus obtained. With this configuration, the gas-sealing properties are considerably improved compared to O-ring sealing. With the structure shown in figure 11, the electrolyte will be able to maintain its composition when the battery is assembled for a long time, which makes it possible to extend the battery life. Industrial applicability
[0119] The present invention is a technique related to the union between an aluminum alloy and a thermoplastic resin, and is mainly applicable to the manufacture of electronic equipment and transportation equipment. In particular, the present invention is suitably applicable to the manufacture of lithium capacitors and batteries. Description of Reference Numbers 10- aluminum alloy 11- metallic alloy 20- resin 21- resin 30- aluminum oxide 31- metal oxide or metal phosphate 40a- structure with O-ring 40b- structure manufactured by NMT 40c- structure manufactured by new NMT 40d- structure manufactured by NMT 2.

权利要求:
Claims (6)
[0001]
1. Method for manufacturing a resin-metal composite, characterized by the fact that it comprises: - a step of attacking the surface by immersing an aluminum alloy in an aqueous solution of a first water-soluble amine compound, in order to cover a surface of the aluminum alloy with ultrafine roughness with a period of 20 to 80 nm or recesses or ultrafine protrusions with a diameter of 20 to 80 nm, as well as to leave an amine compound adsorbed on the surface; - a step of adsorbing or immersing the aluminum alloy obtained in the step of attacking the surface in an aqueous solution of a second water-soluble amine compound at a concentration of 0.05% to 1% at 15 ° C to 45 ° C for 1 to 10 min, in such a way as to increase an amount of the adsorbed amine compound; - a step of drying the aluminum alloy obtained in the adsorption step at 50 ° C to 70 ° C; an injection joining step by inserting the aluminum alloy obtained in the drying step into an injection mold and injecting a resin composition into the surface of the aluminum alloy, in such a way as to perform injection molding as well as to join a molded product from resin composition with the aluminum alloy, the resin composition comprising a rigid crystalline thermoplastic resin which is capable of reacting with the amine compound as a major component.
[0002]
2. Method for manufacturing a resin-metal composite according to claim 1, characterized in that the aqueous solution of the first water-soluble amine compound is an aqueous solution of hydrazine hydrate, and the second amine-soluble compound in water is any one selected from hydrazine hydrate solution, alkylamine solution and ethanol amine solution.
[0003]
3. Method for manufacturing a resin-metal composite according to claim 1, characterized in that the resin composition comprises one or more selected from polybutylene terephthalate, polyphenylene sulfide and polyamide resin as the main component.
[0004]
4. Method for manufacturing a resin-metal composite according to claim 2, characterized in that the resin composition comprises one or more selected from polybutylene terephthalate, polyphenylene sulfide and polyamide resin as the main component.
[0005]
5. Resin-metal composite, characterized by the fact that it comprises: - an aluminum alloy piece, the surface of which is covered with ultrafine roughness with a period of 20 to 80 nm or recesses or ultrafine protrusions with a diameter of 20 to 80 nm, and the surface comprises a surface layer mainly composed of an aluminum oxide film having a thickness of 3 nm or more; and - a molded product of a resin composition that is injected into the aluminum alloy part, the resin composition comprising one or more selected from polybutylene terephthalate, polyphenylene sulfide and polyamide resin as the main component, the rate of leakage of helium gas is 3 x 10-5 mL / h or less in a condition where the helium gas passes through through a pressure difference of 0.5 MPa from one space to another space that are separated from each other by a connecting piece of the aluminum alloy piece with the product molded in the resin-metal composite.
[0006]
6. Lithium ion battery cover, which comprises an aluminum electrode and an electrode other than aluminum, characterized in that the cover is made of an aluminum alloy, the surfaces of the cover and an outlet portion of the aluminum electrode each one being covered with ultrafine roughness with a period of 20 to 80 nm or recesses or protrusions of 20 to 80 nm in diameter, and the surfaces each comprising a surface layer predominantly composed of an aluminum oxide film having a thickness of 3 nm or more, - an electrode outlet portion other than aluminum being covered with an aluminum alloy member wrapped in the electrode other than aluminum, a surface of the aluminum alloy member being covered with ultrafine roughness with a period of 20 to 80 nm or recess or protrusions 20 to 80 nm in diameter, and the surface comprising a surface layer predominantly composed of an aluminum foil having a thickness of 3 nm or more, and - a space between a through hole in the cover and the aluminum electrode and a space between a through hole in the cover and an aluminum alloy member being sealed with a molded product of a resin composition that is injected into the surface of the cap, the resin composition comprising one or more of polybutylene terephthalate, polyphenylene sulfide and polyamide resin as a major component, with a helium leak rate of 3 x 10-5 ml / h or less in a condition where helium gas passes through a pressure difference of 0.5 MPa from one space to another space that are separated from each other by a connecting piece of the aluminum alloy piece with the product molded in the resin composite -metal.

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同族专利:

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公开号 | 公开日

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JPWO2012070654A1|2014-05-19|

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US9166212B2|2015-10-20|

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BR112013013102A2|2016-08-16|

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CN103228418A|2013-07-31|

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KR20130086357A|2013-08-01|

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US20140065472A1|2014-03-06|

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JP5728025B2|2015-06-03|

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DE112011103922B4|2019-11-14|

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CA2818160C|2016-01-26|

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CN103228418B|2015-07-01|

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CA2818160A1|2012-05-31|

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DE112011103922T5|2013-09-19|

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WO2012070654A1|2012-05-31|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

WO2003064150A1|2001-12-28|2003-08-07|Taisei Plas Co., Ltd.|Composite material of aluminum alloy and resin and production method therefor|

---

WO2004041532A1|2002-11-08|2004-05-21|Taisei Plas Co., Ltd.|Composite article of aluminum alloy with resin and method for production thereof|

---

JP5057422B2|2005-03-31|2012-10-24|日本ケミコン株式会社|Capacitor|

---

JP5124129B2|2005-12-08|2013-01-23|東レ株式会社|Aluminum alloy-resin composite and method for producing the same|

---

US8057890B2|2005-12-08|2011-11-15|Taisei Plas Co., Ltd.|Composite of aluminum alloy and resin and manufacturing method thereof|

---

US8273464B2|2006-10-16|2012-09-25|Taisei Plas Co., Ltd.|Metal and resin composite and method for manufacturing same|

---

JP2008131005A|2006-11-24|2008-06-05|Taisei Plas Co Ltd|Structure for electrical and electronic components having terminals, and method of manufacturing the same|

---

EP2103406B1|2006-12-06|2013-11-06|Taisei Plas Co., Ltd.|Process for production of highly corrosion-resistant composite|

---

CN101578170B|2006-12-22|2013-05-01|大成普拉斯株式会社|Metal/resin composition and process for producing the composition|

---

US20100028602A1|2006-12-28|2010-02-04|Taisei Plas Co., Ltd.|Composite of metal and resin and method for manufacturing the same|

---

WO2008114669A1|2007-03-12|2008-09-25|Taisei Plas Co., Ltd.|Aluminum alloy composite and method of bonding therefor|

---

US20100189958A1|2007-07-17|2010-07-29|Taisei Plas Co., Ltd.|Metal and resin composite and manufacturing method thereof|

---

JP5237303B2|2007-12-27|2013-07-17|大成プラス株式会社|Composite of steel and resin and method for producing the same|

---

WO2009151099A1|2008-06-12|2009-12-17|日本軽金属株式会社|Integrally injection-molded aluminum/resin article and process for producing the same|

---

CN101875251B|2009-04-30|2013-06-19|比亚迪股份有限公司|Aluminium alloy complex, preparation method thereof and lithium ion battery cover board|

---

JP5492653B2|2010-05-07|2014-05-14|日立ビークルエナジー株式会社|Secondary battery|DE69835366T2|1997-03-31|2007-07-19|Daikin Industries, Ltd.|PROCESS FOR THE PREPARATION OF PERFLUORVINYL ETHERSULFONIC ACID DERIVATIVES|

---

CN103862619A|2012-12-14|2014-06-18|宝理塑料株式会社|Insert metal member for metal resin composite molded body, and metal resin composite molded body|

---

JP6036350B2|2013-02-01|2016-11-30|王子ホールディングス株式会社|Aluminum coated composite panel|

---

US9655261B2|2013-03-21|2017-05-16|Htc Corporation|Casing of electronic device and method of manufacturing the same|

---

CN103341945B|2013-06-09|2015-06-03|东莞劲胜精密组件股份有限公司|Plastic-metal composite and manufacturing method thereof|

---

DE102014104475A1|2014-03-31|2015-10-01|Volkswagen Ag|Plastic-metal hybrid component and method of making the same|

---

CN107553815B|2014-05-20|2020-01-10|广东长盈精密技术有限公司|Preparation method of metal-resin composite|

---

KR102275333B1|2014-10-30|2021-07-09|삼성에스디아이 주식회사|Rechargeable battery|

---

CN104592757A|2014-12-24|2015-05-06|广东银禧科技股份有限公司|High-flowability glass-fiber-reinforced polyphenyl thioether composite material based on nano forming technology|

---

JP6224017B2|2015-02-18|2017-11-01|大成プラス株式会社|Method for producing CFRTP complex|

---

CN104846389B|2015-04-27|2018-02-06|深圳市澜博鑫纳米五金科技有限公司|A kind of preparation method of austenitic stainless steel compound resin body|

---

CN104910623B|2015-05-11|2017-10-17|深圳华力兴新材料股份有限公司|It is a kind of for PPS engineering plastics of NMT technologies and preparation method thereof|

---

US10243244B2|2015-11-04|2019-03-26|Johnson Controls Technology Company|Systems and methods for bonding metal parts to the polymer packaging of a battery module|

---

WO2017102943A1|2015-12-17|2017-06-22|Dsm Ip Assets B.V.|Process for plastic overmolding on a metal surface and plastic-metal hybrid part|

---

JP6657974B2|2016-01-12|2020-03-04|トヨタ紡織株式会社|Metal-resin integrated molded product and method of manufacturing the same|

---

CN107953505B|2016-10-14|2019-11-08|比亚迪股份有限公司|A kind of metal-resin composite and its preparation method and application|

---

JP6630297B2|2017-01-13|2020-01-15|大成プラス株式会社|An integrated product of metal and resin|

---

KR20200016256A|2017-06-14|2020-02-14|디에스엠 아이피 어셋츠 비.브이.|Plastic overmolding method and plastic-metal hybrid parts on metal surfaces|

---

WO2018228982A1|2017-06-14|2018-12-20|Dsm Intellectual Property|Process for plastic overmolding on a metal surface and plastic-metal hybride part|

---

KR20200016255A|2017-06-14|2020-02-14|디에스엠 아이피 어셋츠 비.브이.|Plastic overmolding method and plastic-metal hybrid parts on metal surfaces|

---

DE102017216886A1|2017-09-25|2019-03-28|Lithium Energy and Power GmbH & Co. KG|A method of preparing a bond of a lid assembly and lid assembly for a battery cell|

---

DE102018202627A1|2018-02-21|2019-08-22|Bayerische Motoren Werke Aktiengesellschaft|Method for producing an electric machine and system for electric motor production|

---

JP6717361B2|2018-11-27|2020-07-01|日亜化学工業株式会社|Light emitting device and manufacturing method thereof|

---

CN109774056A|2019-01-22|2019-05-21|深圳市小机灵精密机械有限公司|A kind of manufacture craft of the lithium battery cover plate of PPS nanometers of injection molding sealing|

---

CN111900292A|2019-05-07|2020-11-06|宁德时代新能源科技股份有限公司|Battery pack and vehicle|

---

DE102020106868A1|2020-03-12|2021-09-16|Kautex Textron Gmbh & Co. Kg|Functionalized and sealed component|

法律状态:
2016-09-20| B08F| Application fees: application dismissed [chapter 8.6 patent gazette]|Free format text: REFERENTE A 3A ANUIDADE. |

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2016-12-27| B08G| Application fees: restoration [chapter 8.7 patent gazette]|

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2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-02-18| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-07-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-10-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2010-263235|2010-11-26|

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JP2010263235|2010-11-26|

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JP2010-264652|2010-11-29|

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JP2010264652|2010-11-29|

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PCT/JP2011/077221|WO2012070654A1|2010-11-26|2011-11-25|Metal resin complex and process for production thereof|

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