TWI750148B - 樹脂組成物、導電性銅膏、以及半導體裝置 - Google Patents
樹脂組成物、導電性銅膏、以及半導體裝置 Download PDFInfo
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Abstract
本發明之目的係提供一種不論熱硬化性樹脂的種類為何,在硬化後比電阻低,且不會因銅粉的含量而大幅改變硬化後的比電阻之樹脂組成物、以及使用該樹脂組成物之導電性銅膏。
上述課題之解決手段為一種樹脂組成物及使用該樹脂組成物之導電性銅膏,該樹脂組成物含有:(A)氧含量為0.3質量%以下的銅粉、(B)熱硬化性樹脂、(C)脂肪酸、及(D)胺或胺化合物。其中,(A)成分的平均粒徑較佳為1至10μm的範圍。
Description
本發明係有關樹脂組成物、導電性銅膏及半導體裝置,尤其是有關比電阻低的樹脂組成物、導電性銅膏及半導體裝置。
由半導體元件的電極部與基板的導電部接著而成之半導體裝置係非常廣範地被使用,於半導體元件的電極部與基板的導電部之間的接著,係使用導電性接著劑或軟焊。導電性接著劑雖然具有可以較軟焊低的溫度進行接著之優點,但由於比電阻較焊料高,故正探討導電性接著劑的低電阻化。
以往的導電性接著劑係使用銀作為導電性填料。然而,由於銀的遷移性及價格高昂,故正探討使用銅作為導電性填料。使用該銅的導電性接著劑一般有比電阻較高之缺點。
就使用銅作為導電性填料的膏而言,已揭示有一種導電性銅膏,其係以具有預定的粒度分布與敲緊密度(tap density)的銅粉、熱硬化性樹脂、有機羧酸及螫合
劑、進一步包含聚丁二烯作為必須成分者(專利文獻1的請求項第1項、第0013、0022段落)。
該導電性銅膏之目的係可進行網版印刷,並且適合作為對應微間距的通孔(through hole)用之具有媲美導電性銀膏之良好的導電性,且應兼具有耐遷移性之導電性銅膏(專利文獻1的第0008段落),其中,有機羧酸之具體例可列舉水楊酸、苯甲酸、酒石酸、檸檬酸、順丁烯二酸、丁二酸、反丁烯二酸、丙二酸等(專利文獻1的第0018段落)。此外,該等有機羧酸在常溫均為固體。
又,已揭示有一種電路基板用導電性膏,其特徴為包含:含有銅的金屬粉、含有至少2個(甲基)丙烯醯基的化合物、及β-二羰基化合物,且實質上不含有偶氮化合物及過氧化物(專利文獻2的請求項第1項)。該電路基板用導電性膏中亦記載可包含具有助焊劑活性的化合物(專利文獻2的第0014段落),其中,具有助焊劑活性的化合物而言可列舉油酸等脂肪族羧酸(專利文獻2的第0038、0046段落)。
除此以外,尚揭示有一種導電性銅膏組成物,其含有在一分子中具有至少2個以上的羥基且包含1個以上的三級胺之預聚物、銅粉、胺基樹脂及還原劑,,為可藉由酸性蝕刻液進行蝕刻者(專利文獻3的請求項第1項),其中,還原劑而言可列舉油酸、亞麻油酸等碳數12至23的不飽和單羧酸(專利文獻3的第0016段落)。
然而,該等導電性銅膏中,由於比電阻容
易變高,因銅粉的含量使硬化後的導電性銅膏之比電阻大幅改變,故實質上可使用的樹脂受限制(專利文獻1中為可溶性酚醛樹脂型苯酚樹脂,在專利文獻2中為1分子內具有至少2個(甲基)丙烯醯基之化合物,在專利文獻3中為1分子中具有至少2個以上的羥基,且包含1個以上三級胺之預聚物與胺基樹脂),故會有能使用的用途受到限定之問題。
[專利文獻1]日本特開2008-130301號公報
[專利文獻2]日本特開2009-295895號公報
[專利文獻3]日本特開平10-064333號公報
本發明人等進行深入研究,結果發現,藉由併用特定的銅粉、熱硬化性樹脂、脂肪酸、胺或胺化合物,可得到一種不論熱硬化性樹脂的種類為何,比電阻較低,且不會因銅粉的含量而大幅改變硬化後的導電性銅膏之比電阻之樹脂組成物、以及使用該樹脂組成物之導電性銅膏。亦即,本發明之目的係提供一種不論熱硬化性樹脂的種類為何,在硬化後比電阻較低,且不會因銅粉的含量而大幅改變硬化後的比電阻之樹脂組成物、以及使用該樹脂組成物之導電性銅膏。
本發明係有關藉由具有下述的構成而解決上述問題之樹脂組成物、導電性銅膏、導電性銅膏的硬化物及半導體裝置。
[1]一種樹脂組成物,其含有:(A)氧含量為0.3質量%以下的銅粉、(B)熱硬化性樹脂、(C)脂肪酸、及(D)胺或胺化合物。
[2]如上述[1]記載之樹脂組成物,其中,(A)成分的平均粒徑為1至10μm的範圍。
[3]如上述[1]記載之樹脂組成物,其中,(B)成分係選自由環氧樹脂、苯酚樹脂、三聚氰胺樹脂、二甲苯樹脂及脲樹脂所組成群組之至少1種。
[4]如上述[1]記載之樹脂組成物,其中,(C)成分係選自由油酸、亞麻油酸、次亞麻油酸、硬脂酸、棕櫚酸及月桂酸所組成群組之至少1種。
[5]如上述[1]記載之樹脂組成物,其中,(D)成分含有三乙醇胺或4,4’-二胺基-3,3’-二甲基二苯基甲烷。
[6]一種導電性銅膏,係使用上述[1]記載之樹脂組成物。
[7]一種硬化物,其係上述[6]記載之導電性銅膏的硬化物。
[8]一種半導體裝置,其包含上述[1]記載之樹脂組成物的硬化物。
根據本發明[1],可提供一種不論熱硬化性樹脂的種類為何,在硬化後比電阻低,且不會因銅粉的含
量而大幅改變硬化後的比電阻(比電阻值未達1×10-4Ω‧cm)之樹脂組成物。
根據本發明[6],可提供一種使用樹脂組成物之導電性銅膏,該樹脂組成物係不論熱硬化性樹脂的種類為何,在硬化後比電阻低,且不會因銅粉的含量而大幅改變硬化後的比電阻(比電阻值未達1×10-4Ω‧cm)者。根據本發明[7],可提供一種用以得到可靠性高的半導體裝置之低電阻的導電性銅膏的硬化物。根據本發明[8],可得到一種例如半導體元件的電極部與基板的導電部之間的連接電阻值小之可靠性高的半導體裝置。
[樹脂組成物]
本發明之樹脂組成物(以下稱為樹脂組成物),其含有:(A)氧含量為0.3質量%以下的銅粉、(B)熱硬化性樹脂、(C)脂肪酸、及(D)胺或胺化合物。
相對於作為(A)成分之銅粉100%,氧含量為0.3質量%以下的銅粉係對硬化後的樹脂組成物賦予導電性。從不會因(A)成分的含量而大幅改變硬化後的比電阻之觀點而言,本樹脂組成物具有優勢。在此,銅粉的氧含量係以還原減量法進行測定。具體而言,係藉由堀場製作所(股)製的氧/氮分析裝置(型式:EMGA-623W)進行測定。此外,樹脂組成物中之銅粉的氧含量,係在以溶劑將銅粉由
樹脂組成物取出後測定。又,從氧含量及硬化後的樹脂組成物的比電阻之觀點而言,(A)成分的平均粒徑較佳為1至10μm的範圍。(A)成分可列舉棒狀、片狀、球狀的銅粉,(A)成分更佳為將粒子形狀的樹枝狀銅粉(電解銅粉)敲碎而得之棒狀的銅粉。又,從硬化後的樹脂組成物之比電阻的觀點而言,(A)成分以敲緊密度較高者為較佳。作為(A)成分的市售品,可列舉:三井金屬礦業(股)製的電解銅粉(ECY-4B,氧含量:0.11%,比表面積:0.223m2/g,敲緊密度:4.65g/cm3,平均粒徑:6.7μm)、三井金屬礦業(股)製的電解銅粉(品名:ECY-4B大粒徑品,氧含量:0.08%,比表面積:0.258m2/g,敲緊密度:3.77g/cm3,平均粒徑:10.9μm)、三井金屬礦業(股)製的液相還原銅粉(品名:CS-20D,氧含量:0.27%,比表面積:0.339m2/g,敲緊密度:3.85g/cm3,平均粒徑:2.9μm)、三井金屬礦業(股)製的液相還原銅粉(品名:CS-10D,氧含量:0.26%,比表面積:0.656m2/g,敲緊密度:4.55g/cm3、平均粒徑:1.0μm),其中,以氧含量較低之三井金屬礦業(股)製的電解銅粉(ECY-4B)、三井金屬礦業(股)製的電解銅粉(品名:ECY-4B大粒徑品)為較佳。在此,比表面積係藉由BET法進行測定,而敲緊密度係藉由振盪比重測定機(敲緊機)進行測定,平均粒徑係藉由雷射繞射/散射式粒子分布測定裝置進行測定。(A)成分可單獨使用或併用2種以上。
作為(B)成分之熱硬化性樹脂係對樹脂組成物賦予接著性、硬化性。本樹脂組成物不論熱硬化性樹脂
的種類為何,仍可使硬化後的樹脂組成物之比電阻降低。(B)成分並無特別限定,但從接著強度的觀點,以選自由環氧樹脂、苯酚樹脂、三聚氰胺樹脂、二甲苯樹脂及脲樹脂所組成群組之至少1種為較佳。(B)成分的市售品可列舉:DIC(股)製的雙酚F型環氧樹脂(品名:EPICLON EXA-835LV)、Asahi Kasei E-materials(股)製的雙酚A型環氧樹脂(品名:AER6072)、明和化成(股)製的酚醛清漆型苯酚樹脂(品名:MEH-8005)、群榮化學(股)製的酚醛清漆型苯酚樹脂(品名:RESITOP PSM4324)、昭和高分子(股)製的可溶性酚醛樹脂型苯酚樹脂(品名:Shonol CKM-908)、昭和高分子(股)製的可溶性酚醛樹脂型苯酚樹脂(品名:Shonol CKM-918A)。(B)成分可單獨使用或併用2種以上。此外,如可溶性酚醛樹脂型苯酚樹脂等之固形的樹脂,在製作膏時,可與後述的稀釋劑加熱混合而形成液狀後使用。
(C)成分係發揮作為使銅粉表面的氧化層溶出之助焊劑成分的功能。從與銅粉的潤濕性優異的觀點而言,(C)成分係選自由:油酸(CH3(CH2)7CH=CH(CH2)7COOH,(9Z)-十八碳-9-烯酸,液體)、亞麻油酸(CH3-(CH2)4-CH=CHCH2CH=CH(CH2)7COOH,(9Z,12Z)-十八碳-9,12-二烯酸,液體)、次亞麻油酸(CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH,(9Z,12Z,15Z)-十八碳-9,12,15-三烯酸,液體)、硬脂酸(CH3(CH2)16COOH,十八碳酸,白色固體)、
棕櫚酸(CH3(CH2)14COOH,十六碳酸,白色固體)、及月桂酸(CH3(CH2)10COOH,十二烷酸,白色固體)所組成群組之至少1種為較佳,以油酸為更佳。(C)成分可單獨使用或併用2種以上。
作為(D)成分之胺或胺化合物係可將因(C)成分的助焊劑效果而溶出的銅離子予以固定化,且可抑制在室溫下(25℃)的脂肪酸之羧基的作用。(D)成分係以含有三乙醇胺(TEA,N(CH2CH2OH)3)或4,4’-二胺基-3,3’-二甲基二苯基甲烷為較佳。4,4’-二胺基-3,3’-二甲基二苯基甲烷的市販品可列舉日本化藥製的胺化合物(品名:KAYAHARD AA)。(D)成分可單獨使用或併用2種以上。
從樹脂組成物的接著性、及硬化後的樹脂組成物之比電阻的觀點而言,相對於(A)成分與(B)成分的合計100質量份,(A)成分較佳為80至98質量份,更佳為85至95質量份。
又,在樹脂組成物的硬化物的情況時,相對於(A)成分與(B)成分的合計100質量份,(A)成分較佳為80至98質量份,更佳為85至95質量份。在此,由於樹脂組成物在硬化時減少的質量少至未達1%,故在硬化物中較佳的(A)成分之含量與在硬化前的(A)成分之含量相同。在此,(A)成分的定量分析係藉由熱重量分析裝置進行。
從樹脂組成物的硬化性、及硬化後的樹脂組成物的比電阻之觀點而言,相對於(A)成分與(B)成分的合計100質量份,(B)成分較佳為2至20質量份,更佳為5
至15質量份。
又,在樹脂組成物的硬化物的情況時,相對於(A)成分與(B)成分的合計100質量份,(B)成分較佳為2至20質量份,更佳為5至15質量份。在此,(B)成分的定量分析係藉由離子層析儀質量分析裝置進行。
相對於(A)成分與(B)成分的合計100質量份,(C)成分較佳為1至3質量份,更佳為1質量份。(C)成分低於1質量份時,硬化後的樹脂組成物之比電阻容易變高,而多於3質量份時,樹脂組成物的可使用期限容易變短。
又,在樹脂組成物的硬化物之情況時,相對於(A)成分與(B)成分的合計100質量份,(C)成分較佳為1至3質量份。在此,(C)成分的定量分析係藉由離子層析儀質量分析裝置進行。
相對於(A)成分與(B)成分的合計100質量份,(D)成分較佳為1至3質量份,更佳為3質量份。(D)成分低於1質量份時,樹脂組成物的可使用期限容易變短,而多於3質量份時,硬化後的樹脂組成物之比電阻值容易變高。
從(B)成分為固形時之熔融/液狀化及樹脂組成物的黏度調製之觀點而言,樹脂組成物可進一步使用稀釋劑。稀釋劑可考量熱硬化性樹脂的溶解性或硬化條件而作適當地選擇,具體而言,可列舉:乙基卡必醇(ethylcarbitol)、乙基卡必醇乙酸酯、丁基卡必醇、丁基卡
必醇乙酸酯、萜品醇(terpineol)、二氫萜品醇、乙基賽珞蘇(ethyl cellosolve)、丁基賽珞蘇、乙基賽珞蘇乙酸酯、丁基賽珞蘇乙酸酯、苯氧基乙醇等,從樹脂組成物的乾燥性之觀點而言,以使用東邦化學(股)製的苯氧基乙醇(品名:HYSORB EPH)較佳。
相對於樹脂組成物100質量份,稀釋劑較佳為10至20質量份。
在不損及本發明之目的之範圍內,本發明之樹脂組成物中可進一步視需要調配咪唑等的硬化促進劑(例如四國化成工業(股)製的2-苯基-4-甲基-5-羥基甲基咪唑(品名:CUREZOL 2P4MHZ-PW))、羧酸鹽等的濕潤分散劑(例如CRODA(股)製的分散劑(品名:Hypermer KD-57))、調平劑、著色劑、離子捕捉劑、消泡劑、阻燃劑、其他添加劑等。
本發明之樹脂組成物例如可藉由將(A)成分至(D)成分及其他添加劑等邊視需要施以加熱處理,邊同時或分別地進行攪拌、熔融、混合、分散而得到。該等混合、攪拌、分散等的裝置並無特別限定,可使用具備攪拌、加熱裝置的擂潰機、三輥研磨機、球磨機、行星式混合機、珠磨機等。又,亦可將該等裝置適當組合而使用。
從網版印刷性的觀點而言,樹脂組成物的初始黏度較佳為20至25Pa‧s的範圍。在此,樹脂組成物的初始黏度係在製作樹脂組成物後,於24小時以內使用Brookfield型黏度計(型號:HBDV-1,14號轉子),在25℃、
迴轉10次而測定者。
本發明之樹脂組成物係藉由網版印刷、點膠機等而形成/塗布於基板的導電部或半導體元件的電極部等電子零件之期望的位置上。
本發明之樹脂組成物的硬化條件,較佳為150至300℃、5至30分鐘,尤其適合在200至220℃、20至40分鐘的高溫短時間。樹脂組成物的硬化物為低比電阻者。
本發明之樹脂組成物以使用於導電性銅膏為較佳,其適合作為半導體元件的電極部與基板的導電部等電子零件用接著劑。
[半導體裝置]
本發明之半導體裝置係具有上述的樹脂組成物的硬化物,亦即具有導電性銅膏的硬化物。半導體裝置係包含例如具有導電部的基板及具有電極部的半導體元件,並利用屬於上述樹脂組成物的硬化物之樹脂組成物硬化膜,將基板的導電部與半導體元件的電極部予以接合。
本發明之半導體裝置係半導體元件的電極部與基板的導電部之間的連接電阻值小且可靠性高者。
針對本發明將藉由實施例來說明,但本發明並不限於該等實施例。此外,以下的實施例中,只要沒有特別的聲明,份、%表示質量份、質量%。
實施例、比較例中,
(A)成分係使用:三井金屬礦業(股)製的電解銅粉(品名:ECY-4B大粒徑品,氧含量:0.08%,比表面積:0.258m2/g,敲緊密度:3.77g/cm3,平均粒徑:10.9μm)、三井金屬礦業(股)製的電解銅粉(品名:ECY-4B,氧含量:0.11%,比表面積:0.223m2/g,敲緊密度:4.65g/cm3,平均粒徑:6.7μm)、三井金屬礦業(股)製的液相還原銅粉(品名:CS-20D,氧含量:0.27%,比表面積:0.339m2/g,敲緊密度:3.85g/cm3,平均粒徑:2.9μm)、三井金屬礦業(股)製的液相還原銅粉(品名:CS-10D,氧含量:0.26%,比表面積:0.656m2/g,敲緊密度:4.55g/cm3,平均粒徑:1.0μm)。此外,三井金屬礦業(股)製的電解銅粉(品名:ECY-4B)亦使用在大氣中進行100℃、15小時的氧化處理,作成氧含量:0.21%、比表面積:0.252m2/g,敲緊密度:4.44g/cm3者、以及大氣中進行100℃、550小時的氧化處理,作成氧含量:0.47%,比表面積:0.446m2/g,敲緊密度:4.08g/cm3者。
(B)成分係使用DIC(股)製的雙酚F型環氧樹脂(品名:EPICLON EXA-835LV)、Asahi Kasei E-materials(股)製的雙酚A型環氧樹脂(品名:AER6072)、明和化成(股)製的酚醛清漆型苯酚樹脂(品名:MEH-8005)、群榮化學(股)製的酚醛清漆型苯酚樹脂(品名:RESITOP PSM4324)、昭和電工(股)製的可溶性酚醛樹脂型苯酚樹脂(品名:Shonol CKM-908)、昭和電工(股)製的可溶性酚醛樹脂型苯酚樹脂(品名:Shonol CKM-918A)。
(C)成分係使用和光純藥工業(股)製的油酸、硬脂酸,
(D)成分係使用和光純藥工業(股)製的三乙醇胺(TEA,2,2’,2”-氮基三乙醇)、日本化藥製的胺4,4’-二胺基-3,3’-二甲基二苯基甲烷(品名:KAYAHARD AA),硬化促進劑係使用四國化成工業(股)製的咪唑(2-苯基-4-甲基-5-羥基甲基咪唑,品名:CUREZOL 2P4MHZ-PW),分散劑係使用CRODA(股)製的分散劑(品名:Hypermer KD-57),稀釋劑係使用東邦化學(股)製的稀釋劑(品名:HYSORB EPH)。
[實施例1至30、比較例1至8]
以表1至表5所示之比例將原料以三輥研磨機均勻地混練,調製成樹脂組成物。將(A)成分、(B)成分、(C)成分及(D)成分以三輥研磨機均勻地混練,調製成樹脂組成物。最後利用Brookfield型黏度計(型號:HBDV-1,14號轉子,10rpm)測定黏度,並以成為20至25Pa‧s的範圍之方式添加稀釋劑。此外,(B)成分為固體而難以進行混練時,將(B)成分預先以一部份的稀釋劑溶解後,再將其他成分混練。
[評估方法]
《初始黏度測定》
將樹脂組成物製成後,於24小時以內使用Brookfield型黏度計(HBDV-1,14號轉子),以25℃、迴轉10次來測定樹脂組成物。
《比電阻值測定》
於氧化鋁基板上將樹脂組成物以網版印刷機印刷出寬度:1mm、長度:71mm的圖案,再利用帶式運送機式硬化爐在氮環境中進行200℃×30分鐘加熱處理而使其硬化。使用東京精密(股)製的表面粗糙度形狀測定機(型號:Surfcom 1500SD-2)測定所得之樹脂組成物硬化膜的膜厚,並使用TFF Keithley Instruments(股)製的數位萬用電表(型號:2001)測定電阻值,以算出體積電阻率,作為比電阻值。
由表1至表3的結果可知,實施例1至24之所有硬化後的樹脂組成物之比電阻值均未達1×10-4Ω‧cm。相對於此,使用氧含量高的銅粉之比較例1至5,其硬化後的樹脂組成物之比電阻值均較高。
由表4的實施例2、25至26的結果可知,即使改變(B)成分、(C)成分、(D)成分,所有硬化後的樹脂組成物之比電阻值亦未達1×10-4Ω‧cm。
由表5的結果可知,實施例28至30之硬化
後的樹脂組成物之比電阻值未達1×10-4Ω‧cm。相對於此,不含(C)成分及(D)成分之比較例6、不含(D)成分之比較例7、及不含(C)成分之比較例8,其硬化後的樹脂組成物之比電阻值均較高。
如上所述,本發明之樹脂組成物由於不論熱硬化性樹脂的種類,在硬化後比電阻較低,且不會因銅粉的含量而大幅改變硬化後的比電阻,故作為導電性銅膏為非常實用。
Claims (8)
- 一種樹脂組成物,含有:(A)氧含量為0.2質量%以下的銅粉、(B)熱硬化性樹脂、(C)脂肪酸、及(D)胺或胺化合物,其中,相對於(A)成分與(B)成分的合計100質量份,(C)成分之含量為1至3質量份,(D)成分之含量為1至3質量份。
- 如申請專利範圍第1項所述之樹脂組成物,其中,(A)成分的平均粒徑為1至10μm的範圍。
- 如申請專利範圍第1項所述之樹脂組成物,其中,(B)成分係選自由環氧樹脂、苯酚樹脂、三聚氰胺樹脂、二甲苯樹脂及脲樹脂所組成群組之至少1種。
- 如申請專利範圍第1項所述之樹脂組成物,其中,(C)成分係選自由油酸、亞麻油酸、次亞麻油酸、硬脂酸、棕櫚酸及月桂酸所組成群組之至少1種。
- 如申請專利範圍第1項所述之樹脂組成物,其中,(D)成分含有三乙醇胺或4,4’-二胺基-3,3’-二甲基二苯基甲烷。
- 一種導電性銅膏,係使用申請專利範圍第1項所述之樹脂組成物。
- 一種硬化物,係申請專利範圍第6項所述之導電性銅膏的硬化物。
- 一種半導體裝置,包含申請專利範圍第1項所述之樹脂組成物的硬化物。
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CN107210085A (zh) * | 2015-03-05 | 2017-09-26 | 纳美仕有限公司 | 导电性铜浆料、导电性铜浆料固化膜和半导体装置 |
JP2017141330A (ja) * | 2016-02-08 | 2017-08-17 | ナミックス株式会社 | 樹脂組成物、導電性銅ペースト、導電性銅ペーストの硬化物、および半導体装置 |
JP6948111B2 (ja) * | 2016-02-09 | 2021-10-13 | ナミックス株式会社 | 樹脂組成物、導電性銅ペースト、および半導体装置 |
WO2020002890A1 (en) * | 2018-06-26 | 2020-01-02 | Alpha Assembly Solutions Inc. | Nano copper paste and film for sintered die attach and similar applications |
CN111205600B (zh) * | 2020-02-21 | 2023-04-21 | 中国石油化工股份有限公司 | 环氧树脂制剂、填充剂、管道修复材料及制备方法 |
WO2023080028A1 (ja) * | 2021-11-02 | 2023-05-11 | 昭栄化学工業株式会社 | 熱硬化型導電性樹脂組成物、電子部品の製造方法 |
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CN108473779B (zh) | 2022-02-25 |
TW201736496A (zh) | 2017-10-16 |
KR20180103875A (ko) | 2018-09-19 |
CN108473779A (zh) | 2018-08-31 |
US20200266170A1 (en) | 2020-08-20 |
KR102665528B1 (ko) | 2024-05-10 |
WO2017126382A1 (ja) | 2017-07-27 |
US10892242B2 (en) | 2021-01-12 |
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