CN116635549A - Aluminum alloy and aluminum alloy casting material - Google Patents
Aluminum alloy and aluminum alloy casting material Download PDFInfo
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- CN116635549A CN116635549A CN202080107953.1A CN202080107953A CN116635549A CN 116635549 A CN116635549 A CN 116635549A CN 202080107953 A CN202080107953 A CN 202080107953A CN 116635549 A CN116635549 A CN 116635549A
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- aluminum alloy
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- casting material
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 75
- 238000005266 casting Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000004378 air conditioning Methods 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 229910052710 silicon Inorganic materials 0.000 abstract description 14
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 28
- 239000010949 copper Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000956 alloy Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004512 die casting Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/002—Castings of light metals
- B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
Abstract
The present invention provides an aluminum alloy and an aluminum alloy casting material which have excellent castability and can exhibit high mechanical properties without performing heat treatment. More specifically, an aluminum alloy and an aluminum alloy casting material having excellent castability, and having high 0.2% yield strength and excellent ductility without heat treatment are provided. The aluminum alloy of the present invention is characterized by comprising Si:7.0 to 9.0 mass% of Cu:2.0 to 4.0 mass percent of Mg:0.8 to 1.2 mass percent of Fe:0.3 to 0.5 mass% of Mn:0.3 to 0.5 mass% and Zn:2.0 to 4.0 mass% of an aluminum alloy comprising Al and unavoidable impurities in the balance.
Description
Technical Field
The present invention relates to an aluminum alloy for castings and an aluminum alloy casting material composed of the aluminum alloy.
Background
Aluminum alloy materials are lightweight and have excellent texture, and therefore are used in housings of portable electronic devices and electronic terminals. The demands for thinness and weight reduction of these portable electronic devices have been increasing year by year, and aluminum alloys used for housings have been demanded to have higher strength.
In particular, smartphones are often placed in pockets or the like when not in use, in which case the smartphones are often subjected to bending stresses. That is, an aluminum alloy used for a housing of a portable electronic device is also indispensable to have high strength and ductility (toughness) in addition to excellent castability.
In contrast, for example, patent document 1 (japanese unexamined patent publication No. 48-32719) discloses a high-strength aluminum alloy for castings, which is excellent in castability, and which is composed of, by weight, 7.5 to 1.2% of silicon, 4.0 to 5.5% of copper, 0.2 to 1.0% of magnesium, and the balance of aluminum and impurities, in order to effectively utilize the excellent castability of al—cu—si-based or al—si—cu—mg-based alloys and to obtain an alloy having strength equivalent to that of conventional high-strength aluminum alloys for casting.
It is generally considered that the high-strength aluminum alloy for castings described in patent document 1 can provide excellent mechanical properties to aluminum alloy castings by subjecting the alloy to solution treatment at about 500 ℃ and then allowing the alloy to age-harden.
Further, patent document 2 (japanese patent application laid-open No. 60-57497) discloses a heat-resistant high-strength aluminum alloy which contains, by weight, more than 6% and up to 13% of silicon, more than 3% and up to 5.5% of copper, more than 1% and up to 4% of zinc, more than 0.2% and up to 1% of magnesium, and more than 0.03% and up to 1% of antimony, with the remainder being composed of aluminum and impurities, with the aim of obtaining a heat-treated high-strength aluminum alloy which has good castability and is high in toughness and excellent in heat resistance.
It is generally considered that in the heat-resistant high-strength aluminum alloy described in patent document 2, when more than 3% of copper is contained in the al—si—cu—zn—mg alloy, if antimony is added to the alloy, the age hardening property of the alloy can be promoted at the time of aging treatment, the toughness is not so lowered, the alloy strength can be remarkably improved, and the heat shock resistance of the alloy can be remarkably improved.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 48-32719
Patent document 2: japanese patent laid-open No. 60-57497
Disclosure of Invention
Problems to be solved by the invention
In the high-strength aluminum alloy for castings described in patent document 1 and the heat-resistant high-strength aluminum alloy described in patent document 2, excellent mechanical properties can be imparted in addition to excellent castability, but in order to achieve the mechanical properties, heat treatment such as artificial aging is necessary.
However, the heat treatment process not only increases the manufacturing cost and time, but also affects the size and shape of the aluminum alloy casting material. In particular, since a housing of a portable electronic device is required to be thin and also to have high dimensional accuracy, it is desired that high strength and excellent ductility be achieved without performing heat treatment.
In view of the above problems in the prior art, an object of the present invention is to provide an aluminum alloy and an aluminum alloy casting material that have excellent castability and can exhibit high mechanical properties without heat treatment. More specifically, the present invention aims to provide an aluminum alloy and an aluminum alloy casting material having excellent castability, and having high 0.2% yield strength and excellent ductility without heat treatment.
Means for solving the problems
The present inventors have conducted intensive studies on the composition range of an aluminum alloy in order to achieve the above object, and as a result, have found that it is extremely effective to strictly control the addition amounts of Si, cu, mg, fe, mn and Zn, and the present invention has been achieved.
That is, the present invention provides an aluminum alloy comprising:
si:7.0 to 9.0 mass percent,
Cu:2.0 to 4.0 mass percent,
Mg:0.8 to 1.2 mass percent,
Fe:0.3 to 0.5 mass percent,
Mn:0.3 to 0.5 mass percent
Zn:2.0 to 4.0 mass percent,
the remainder consists of Al and unavoidable impurities.
The aluminum alloy of the present invention preferably contains any one or more of the following components:
sr:0.008 to 0.04 mass percent,
Be:0.001 to 0.004 mass percent,
Ti:0.05 to 0.005 mass%
B:0.01 to 0.005 mass%.
In addition, the invention also provides an aluminum alloy casting material, which is characterized in that,
is composed of the aluminum alloy of the present invention,
the 0.2% yield strength is more than 230MPa,
the elongation at break is 2.5% or more.
The aluminum alloy casting material of the present invention can exhibit a 0.2% yield strength of 230MPa or more and an elongation at break of 2.5% or more after being cast into a desired shape without heat treatment. More preferably, the 0.2% yield strength is 240MPa or more, and still more preferably, the elongation at break is 3.0% or more.
Effects of the invention
According to the present invention, an aluminum alloy and an aluminum alloy casting material having excellent castability and capable of exhibiting high mechanical properties without performing heat treatment can be provided. More specifically, according to the present invention, an aluminum alloy and an aluminum alloy casting material having excellent castability, and having high 0.2% yield strength and excellent ductility without heat treatment can be provided.
Detailed Description
Representative embodiments of the aluminum alloy and aluminum alloy casting materials of the present invention are described in detail below, but the present invention is not limited to these.
1. Aluminum alloy
The aluminum alloy of the present invention is an aluminum alloy comprising Si:7.0 to 9.0 mass% of Cu:2.0 to 4.0 mass percent of Mg:0.8 to 1.2 mass percent of Fe:0.3 to 0.5 mass% of Mn:0.3 to 0.5 mass% and Zn:2.0 to 4.0 mass% and the balance of Al and unavoidable impurities. The components are described in detail below.
(1) Necessary additive elements
Si:7.0 to 9.0 mass percent
Si has a property of improving the castability of aluminum and has an effect of improving mechanical properties such as tensile strength. This effect becomes remarkable when Si is 7.0 mass% or more. Conversely, if Si is 9.0 mass% or more, the crystallized eutectic Si or primary crystal Si tends to coarsen. When these compounds coarsen, these compounds tend to become the starting points at the time of fracture, and thus tend to cause a decrease in elongation. The more preferable addition amount of Si is 7.5 to 8.5 mass%.
Cu:2.0 to 4.0 mass percent
Cu has an effect of improving mechanical properties such as tensile strength. This effect becomes remarkable when Cu is 2.0 mass% or more. Conversely, when the amount is more than 4.0 mass%, the Cu-based crystal precipitate tends to coarsen and the elongation tends to decrease. In addition, when the Cu content increases, the corrosion resistance also decreases. Further, when the alumina film treatment (alumite treatment) is performed, the color tends to be yellow. The amount of Cu added is more preferably 2.5 to 3.7 mass%, and still more preferably 3.5 mass% or less.
Mg:0.8 to 1.2 mass percent
Mg has an effect of improving mechanical properties such as tensile strength. This effect becomes remarkable when Mg is 0.8 mass% or more. Conversely, when the amount exceeds 1.2% by mass, coarse compounds tend to be formed, and the elongation tends to be lowered.
Si, mg, and Cu are elements that precipitate as compounds by aging treatment and contribute to the precipitation strength, but the aluminum alloy of the present invention is mainly used as a non-heat-treated material, and a strengthening mechanism based on these elements is basically solid solution strengthening.
Fe:0.2 to 0.5 mass%
Fe has the effect of improving mechanical properties such as tensile strength. This effect becomes remarkable when Fe is 0.2 mass% or more. In addition, the effect of preventing the sticking of the mold is also obtained in the die casting such as the die casting. When the content exceeds 0.5 mass%, coarse needle-like Al- (Si, fe, mn) -based compounds serving as starting points of fracture are easily formed.
Mn:0.3 to 0.5 mass%
Mn has the effect of improving mechanical properties such as tensile strength. This effect becomes remarkable when Mn is 0.3 mass% or more. In addition, the Al- (Si, fe, mn) compound is also granulated. Conversely, when the content exceeds 0.5 mass%, the Al- (Si, fe, mn) compound tends to coarsen.
Zn:2.0 to 4.0 mass percent
Zn has the effect of improving mechanical properties such as tensile strength. This effect becomes remarkable when Zn is 2.0 mass% or more. Conversely, when it exceeds 4.0 mass%, stress corrosion cracking is liable to occur. Further, discoloration and color unevenness are likely to occur when the anodic oxidation coating treatment is performed.
(2) Arbitrary additive element
Sr:0.008 to 0.04 mass%
Sr has an effect of refining and granulating eutectic Si, and the effect becomes remarkable when Sr is 0.008 mass% or more. Even if the content exceeds 0.04 mass%, the effect is not significantly improved, and therefore, the content is preferably less than 0.04 mass%.
Be:0.001 to 0.004 mass%
Be has the effect of forming an oxide film on the surface of the molten metal during melting and suppressing the consumption of other elements such as Mg. In addition, the effect of suppressing blackening of the surface of the casting is also obtained. This effect becomes remarkable when Be is 0.001 mass% or more. Even if the amount exceeds 0.004 mass%, the effect is not significantly improved, and therefore, the amount is preferably less than 0.004 mass%.
Ti:0.05 to 0.005 mass%
Ti mainly contributes to toughness by refining the structure. When the content is less than the lower limit, the effect is small, and even if the content exceeds the upper limit, the effect is sufficiently reduced, and when the content is excessively added, coarse crystal precipitates are formed to adversely affect the ductility, so that the content needs to be limited to the above range.
B:0.01 to 0.005 mass%
B contributes mainly to toughness by miniaturizing the structure. When the amount is less than the lower limit, the effect is small, and even if the amount exceeds the upper limit, the effect is sufficiently reduced, and when the amount is excessively added, coarse crystal precipitates are formed to adversely affect the ductility, so that the range needs to be limited.
The method for producing the aluminum alloy of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and various conventionally known methods may be used.
2. Aluminum alloy casting material
The aluminum alloy casting material of the present invention is characterized by comprising the aluminum alloy of the present invention, wherein the 0.2% yield strength is 230MPa or more, and the elongation at break is 2.5% or more. More preferably, the 0.2% yield strength is 240MPa or more, and still more preferably, the elongation at break is 3.0% or more.
The excellent mechanical properties are basically achieved by strictly optimizing the composition, and do not depend on the shape and size of the aluminum alloy casting material, nor on the location and orientation of the aluminum alloy casting material.
In addition, in the aluminum alloy casting material of the present invention, the 0.2% yield strength of 230MPa or more and the elongation at break of 2.5% or more can be exhibited without performing heat treatment such as aging treatment.
The shape and size of the aluminum alloy casting material are not particularly limited as long as the effects of the present invention are not impaired, and the aluminum alloy casting material can be used as various conventionally known members. As this member, for example, an electronic terminal housing can be cited.
The method for producing the aluminum alloy casting material of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and the aluminum alloy of the present invention may be used for casting by various methods known in the art. Furthermore, the casting material using the alloy of the present invention has excellent mechanical properties, particularly toughness, even without heat treatment, but may be subjected to heat treatment such as aging treatment. When aging is performed, higher mechanical properties can be obtained by precipitation strengthening of compounds such as Si, mg, cu, zn.
While the above description has been made of the representative embodiments of the present invention, the present invention is not limited to these, and various design changes can be made, and these design changes are all included in the technical scope of the present invention.
Examples
Examples
Aluminum alloys having the compositions described in examples 1 to 5 in table 1 were melted, and die casting was performed at a casting pressure of 120MPa, a molten metal temperature of 730 ℃, and a die temperature of 170 ℃. The mold was in the shape of a plate 55 mm. Times.110 mm. Times.3 mm. The aluminum alloy has excellent die-casting property, and a good aluminum alloy casting material (die-casting material) is obtained. The unit of the numerical values shown in table 1 is the mass% concentration.
TABLE 1
Using each of the obtained aluminum alloy cast materials, a test piece No. 14B specified in JIS-Z2241 was selected, and a tensile test was performed at room temperature, and as a result, the tensile strength, 0.2% yield strength and elongation at break were values shown in Table 2. Further, the Rockwell hardness of the obtained cast aluminum alloy material was measured, and the results were the values shown in Table 2. Here, the aluminum alloy casting material is directly cast, and heat treatment such as aging treatment is not performed.
TABLE 2
Comparative example
A comparative aluminum alloy casting material (die casting material) was obtained in the same manner as in example except that the melting materials were adjusted so as to be the components described in comparative examples 1 to 22 in table 1. Further, tensile properties and Rockwell hardness were measured in the same manner as in examples. The obtained values are shown in Table 2. In addition, the case where no numerical value is described means that measurement is not performed.
When the tensile properties of each of the aluminum alloy casting materials obtained in the examples and comparative examples were compared, it was found that only the aluminum alloy casting materials obtained in the examples had both a 0.2% yield strength of 230MPa or more and an elongation at break of 2.5% or more. In the examples, it was found that the tensile strength and elongation of example 1 in which Sr was added were higher than those of example 4 in which Sr was not added (Sr content was extremely small).
The aluminum alloy casting materials having the compositions of comparative examples 1 to 5, in which the contents of Si, cu and Mn were large, exhibited high 0.2% yield strength, but the elongation at break was 2.0% or less. The elongation at break of the aluminum alloy casting materials having the compositions of comparative examples 6 to 10 and comparative examples 13 to 19, in which the content of Fe was large, was also less than 2.5%.
Further, it was found that the hardness of the aluminum alloy casting materials having the compositions of comparative example 11 in which the addition amount of Mg was small and comparative example 12 in which the addition amount of Mg was small was low, and sufficient strength was not obtained.
Further, the aluminum alloy casting material having the composition of comparative example 20 in which the contents of Si and Cu were small had an elongation at break of 2.5% or more, but the 0.2% yield strength was low. Further, comparative example 21, in which the contents of Si and Zn were small and the contents of Cu and Mn were large, had a high tensile strength and 0.2% yield strength, but the elongation at break was a low value of less than 2.5%. In comparative example 22 in which Cu and Mn were contained in large amounts, the 0.2% yield strength did not reach 230MPa, except for the low value of elongation at break of less than 2.5%.
From the above results, it was found that in order to enable the aluminum alloy casting material to exhibit a 0.2% yield strength of 230MPa or more and an elongation at break of 2.5% or more without heat treatment, it was necessary to strictly control the addition amounts of Si, cu, mg, fe, mn and Zn.
Claims (3)
1. An aluminum alloy is characterized in that,
comprising:
si:7.0 to 9.0 mass percent;
cu:2.0 to 4.0 mass percent;
mg:0.8 to 1.2 mass percent;
fe:0.3 to 0.5 mass percent;
mn:0.3 to 0.5 mass percent; a kind of electronic device with high-pressure air-conditioning system
Zn:2.0 to 4.0 mass percent,
the remainder consists of Al and unavoidable impurities.
2. The aluminum alloy according to claim 1, comprising any one or more of the following components:
sr:0.008 to 0.04 mass percent;
be:0.001 to 0.004 mass%;
ti:0.05 to 0.005 mass%; a kind of electronic device with high-pressure air-conditioning system
B:0.01 to 0.005 mass%.
3. An aluminum alloy casting material is characterized in that,
an aluminum alloy according to claim 1 or claim 2, wherein the 0.2% yield strength is 230MPa or more,
the elongation at break is 2.5% or more.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2020/046678 WO2022130484A1 (en) | 2020-12-15 | 2020-12-15 | Aluminum alloy and aluminum alloy casting material |
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| Publication Number | Publication Date |
|---|---|
| CN116635549A true CN116635549A (en) | 2023-08-22 |
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| CN202080107953.1A Pending CN116635549A (en) | 2020-12-15 | 2020-12-15 | Aluminum alloy and aluminum alloy casting material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20240018632A1 (en) |
| JP (1) | JP7472318B2 (en) |
| CN (1) | CN116635549A (en) |
| WO (1) | WO2022130484A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117646138A (en) * | 2024-01-30 | 2024-03-05 | 鸿劲新材料研究(南通)有限公司 | Explosion-proof aluminum alloy material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4713724B1 (en) * | 1968-02-20 | 1972-04-25 | ||
| JPS5142567B2 (en) * | 1971-05-15 | 1976-11-16 | ||
| KR101955993B1 (en) * | 2017-02-17 | 2019-03-08 | 주식회사 지.에이.엠 | High strength aluminium alloy and high strength aluminium alloy casting |
| CN108754250A (en) * | 2018-06-03 | 2018-11-06 | 深圳市鑫申新材料科技有限公司 | A kind of high strength die-casting aluminum alloy and its manufacturing method |
| CN110952001A (en) * | 2019-12-19 | 2020-04-03 | 山东泰来铸铝科技有限公司 | High-strength and high-toughness Al-Si-Cu-Mg cast aluminum alloy added with Mn and Zn and heat treatment method thereof |
-
2020
- 2020-12-15 JP JP2022569355A patent/JP7472318B2/en active Active
- 2020-12-15 US US18/039,829 patent/US20240018632A1/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117646138A (en) * | 2024-01-30 | 2024-03-05 | 鸿劲新材料研究(南通)有限公司 | Explosion-proof aluminum alloy material and preparation method thereof |
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| JP7472318B2 (en) | 2024-04-22 |
| WO2022130484A1 (en) | 2022-06-23 |
| US20240018632A1 (en) | 2024-01-18 |
| JPWO2022130484A1 (en) | 2022-06-23 |
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