JPWO2019146807A1 - 熱可塑性樹脂組成物及び成形品の製造方法 - Google Patents
熱可塑性樹脂組成物及び成形品の製造方法 Download PDFInfo
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- JPWO2019146807A1 JPWO2019146807A1 JP2019536113A JP2019536113A JPWO2019146807A1 JP WO2019146807 A1 JPWO2019146807 A1 JP WO2019146807A1 JP 2019536113 A JP2019536113 A JP 2019536113A JP 2019536113 A JP2019536113 A JP 2019536113A JP WO2019146807 A1 JPWO2019146807 A1 JP WO2019146807A1
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- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- C—CHEMISTRY; METALLURGY
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
Description
また、本発明者は、このようにポリカーボネート樹脂とポリエステル樹脂を併用したガラス強化熱可塑性樹脂組成物を特定の方法で射出成形することにより、透明性をより一層改善することができることを見出した。
本発明の熱可塑性樹脂組成物及びその成形品によれば、自動車や建物等の窓等を含めたガラス代替材料として、その他透明性が要求される用途に、ガラス強化熱可塑性樹脂組成物の適用範囲を大幅に拡大することができる。
本発明の熱可塑性樹脂組成物は、粘度平均分子量が13,000〜22,000のポリカーボネート樹脂(A)と、テレフタル酸残基、1,4−シクロヘキサンジメタノール残基、及び2,2,4,4−テトラメチル−1,3−シクロブタンジオール残基を含むポリエステル樹脂(B)とを含有する熱可塑性樹脂成分と、ガラス充填剤(C)とを含む熱可塑性樹脂組成物であって、ポリカーボネート樹脂(A)とポリエステル樹脂(B)の合計100質量部中にポリカーボネート樹脂(A)を25〜65質量部、ポリエステル樹脂(B)を75〜35質量部含み、該熱可塑性樹脂成分100質量部に対してガラス充填剤(C)を10〜45質量部含むことを特徴とする。
本発明の熱可塑性樹脂組成物では、テレフタル酸残基、1,4−シクロヘキサンジメタノール残基、及び2,2,4,4−テトラメチル−1,3−シクロブタンジオール残基を含むポリエステル樹脂(B)をポリカーボネート樹脂(A)に対して所定の割合で混合して用いることにより、樹脂マトリクスの屈折率をガラスの屈折率に近づけることができ、樹脂マトリクスの屈折率とガラス充填剤(C)の屈折率の差に起因する透明性の低下の問題を軽減することができる。
本発明で用いるポリカーボネート樹脂(A)としては、透明性、耐衝撃性、耐熱性等の面から、芳香族ポリカーボネート樹脂が好ましい。
本発明で用いるポリエステル樹脂(B)は、テレフタル酸残基、1,4−シクロヘキサンジメタノール(以下「CHDM」と称す場合がある。)残基、及び2,2,4,4−テトラメチル−1,3−シクロブタンジオール(以下「TMCD」と称す場合がある。)残基を含む非晶性ポリエステル樹脂(B)である。
ポリエステル樹脂は、ジカルボン酸成分(ジカルボン酸或いはその誘導体)とジオールとをエステル化反応又はエステル化交換反応して得られるものであるが、本発明で用いるポリエステル樹脂(B)は、ジカルボン酸成分として少なくともテレフタル酸成分(テレフタル酸或いはその誘導体)を用い、ジオールとして少なくともCHDMとTMCDを用いて製造されたものである。
本発明の熱可塑性樹脂組成物は、ポリカーボネート樹脂(A)とポリエステル樹脂(B)とを、これらの合計100質量部中にポリカーボネート樹脂(A)を25〜65質量部、ポリエステル樹脂(B)を75〜35質量部含む。この範囲よりもポリカーボネート樹脂(A)が多く、ポリエステル樹脂(B)が少なくても、逆にポリエステル樹脂(B)が多く、ポリカーボネート樹脂(A)が少なくても、樹脂マトリクスの屈折率をガラス充填剤(C)の屈折率に近づけることができず、透明性に優れた成形品を得ることができない。
本発明の熱可塑性樹脂組成物は、本発明の効果を損なわない範囲において、熱可塑性樹脂成分として、ポリカーボネート樹脂(A)及びポリエステル樹脂(B)以外の他の熱可塑性樹脂を含有していてもよい。
本発明で用いるガラス充填剤(C)の形態には特に制限はなく、ガラス繊維、ガラスパウダー、ガラスフレーク、ミルドファイバー、ガラスビーズなど様々な形態のものを用いることができる。ガラス充填剤(C)はこれらの1種のみを用いてもよく、2種以上を組み合わせて用いてもよい。透明性と補強効果の観点からガラス繊維及び/又はガラスフレークを用いることが好ましく、ガラス繊維又はガラスフレークを用いることがより好ましく、ガラス繊維を用いることが特に好ましい。
本発明の熱可塑性樹脂組成物は、本発明の効果を損なわない範囲で、更に種々の添加剤を含有していても良い。このような添加剤としては、リン系熱安定剤等の安定剤(D)、離型剤(E)、紫外線吸収剤、帯電防止剤、着色剤(染顔料)、防曇剤、滑剤、アンチブロッキング剤、流動性改良剤、摺動性改質剤、耐衝撃性改良剤、可塑剤、分散剤、抗菌剤、難燃剤、滴下防止剤などが挙げられる。これらは2種以上を併用してもよい。以下、本発明の熱可塑性樹脂組成物に好適な添加剤の一例について具体的に説明する。
安定剤(D)としては、以下のリン系熱安定剤、フェノール系酸化防止剤、有機リン酸エステル化合物等が挙げられる。
本発明の熱可塑性樹脂組成物は、リン系熱安定剤を含有していてもよい。リン系熱安定剤は一般的に、樹脂成分を溶融混練する際、高温下での滞留安定性や樹脂成形品使用時の耐熱安定性の向上に有効である。
本発明の熱可塑性樹脂組成物はフェノール系酸化防止剤を含有していてもよい。フェノール系酸化防止剤を含有することで、色相劣化や、熱滞留時の機械物性の低下を抑制することができる。
本発明の熱可塑性樹脂組成物は、熱安定性の向上のために下記一般式(1)で表される有機リン酸エステル化合物を含有していてもよい。
(RO)nP(O)(OH)3−n …(1)
一般式(1)中、Rは総炭素数が2〜25の、置換基を有していてもよいアルキル基を表す。nは1又は2を表す。nが2の場合に2つのRは同一であってもよく、相互に異なっていてもよい。
離型剤(E)としては、脂肪族カルボン酸、脂肪族カルボン酸とアルコールとのエステル、数平均分子量200〜15000の脂肪族炭化水素化合物、及びポリシロキサン系シリコーンオイルの群から選ばれる少なくとも1種の化合物が挙げられる。
本発明の熱可塑性樹脂組成物は、紫外線吸収剤を含有していてもよい。紫外線吸収剤を含有することで、本発明の熱可塑性樹脂組成物の耐候性を向上させることができ、耐候性の向上で透明性の低下を防止することができる。
ベンゾトリアゾール化合物の市販品としては、例えば、シプロ化成社製「シーソーブ701」、「シーソーブ705」、「シーソーブ703」、「シーソーブ702」、「シーソーブ704」、「シーソーブ709」、共同薬品社製「バイオソーブ520」、「バイオソーブ582」、「バイオソーブ580」、「バイオソーブ583」、ケミプロ化成社製「ケミソーブ71」、「ケミソーブ72」、サイテックインダストリーズ社製「サイアソーブUV5411」、アデカ社製「LA−32」、「LA−38」、「LA−36」、「LA−34」、「LA−31」、チバ・スペシャリティケミカルズ社製「チヌビンP」、「チヌビン234」、「チヌビン326」、「チヌビン327」、「チヌビン328」等が挙げられる。
ベンゾフェノン化合物の市販品としては、例えば、シプロ化成社製「シーソーブ100」、「シーソーブ101」、「シーソーブ101S」、「シーソーブ102」、「シーソーブ103」、共同薬品社製「バイオソーブ100」、「バイオソーブ110」、「バイオソーブ130」、ケミプロ化成社製「ケミソーブ10」、「ケミソーブ11」、「ケミソーブ11S」、「ケミソーブ12」、「ケミソーブ13」、「ケミソーブ111」、BASF社製「ユビヌル400」、BASF社製「ユビヌルM−40」、BASF社製「ユビヌルMS−40」、サイテックインダストリーズ社製「サイアソーブUV9」、「サイアソーブUV284」、「サイアソーブUV531」、「サイアソーブUV24」、アデカ社製「アデカスタブ1413」、「アデカスタブLA−51」等が挙げられる。
サリシレート化合物の市販品としては、例えば、シプロ化成社製「シーソーブ201」、「シーソーブ202」、ケミプロ化成社製「ケミソーブ21」、「ケミソーブ22」等が挙げられる。
シアノアクリレート化合物の市販品としては、例えば、シプロ化成社製「シーソーブ501」、共同薬品社製「バイオソーブ910」、第一化成社製「ユビソレーター300」、BASF社製「ユビヌルN−35」、「ユビヌルN−539」等が挙げられる。
オキザリニド化合物の市販品としては、例えば、クラリアント社製「サンデュボアVSU」等が挙げられる。
マロン酸エステル化合物の市販品としては、例えば、クラリアントジャパン社製「PR−25」、チバ・スペシャリティケミカルズ社製「B−CAP」等が挙げられる。
本発明の熱可塑性樹脂組成物は、所望によって帯電防止剤を含有していてもよい。帯電防止剤は特に限定されないが、好ましくは下記一般式(2)で表されるスルホン酸ホスホニウム塩が挙げられる。
本発明の熱可塑性樹脂組成物は、所望によって着色剤として各種の染顔料を含有していてもよい。染顔料を含有することで、本発明の熱可塑性樹脂組成物の隠蔽性、耐候性を向上させることができる。また、着色剤を含有することで、本発明の熱可塑性樹脂組成物を成形して得られる成形品のデザイン性を向上させることができる。
本発明の熱可塑性樹脂組成物を製造するための混練条件は、熱可塑性樹脂組成物に用いる各成分の種類や配合割合により異なり、一概に言えないが、ガラス充填剤(C)として特にガラス繊維を用いる場合は、これを他の成分とは別に溶融混練することが好ましい。特に、ガラス繊維は、押出機を用いて溶融混練する際にサイドフィード法を用いてポリカーボネート樹脂(A)及びポリエステル樹脂(B)等他の成分が十分に溶融混練された溶融混練物に対して押出機の途中から供給して溶融混練することが、溶融混練時のガラス繊維の切断や折曲を防止してガラス繊維の形状を維持することができ好ましい。
本発明の熱可塑性樹脂組成物から成形品を製造する方法は、特に限定されるものではなく、熱可塑性樹脂について一般に採用されている成形法、すなわち一般的な射出成形法、超高速射出成形法、射出圧縮成形法、多色射出成形法、ガスアシスト射出成形法、断熱金型を用いた成形法、急速加熱冷却金型を用いた成形法、発泡成形(超臨界流体も含む)、インサート成形、IMC(インモールドコーティング成形)成形法、押出成形法、シート成形法、熱成形法、回転成形法、積層成形法、プレス成形法などを採用することができる。各種射出成形法においてはホットランナー方式を用いた成形法を選択することもできる。
表面粗さRaが0.1μm以下の平滑表面の面積は、大きい程透明性の観点から好ましく、成形品の全表面の50%以上の面積であることがより好ましい。透明性の観点からこの面積は、成形品の形状や用途によっても異なるが、成形品の全表面の面積の70%以上であれば十分であるが、その上限は通常100%である。
本発明の成形品の製造方法の一態様は、本発明の熱可塑性樹脂組成物を断熱金型、即ち、キャビティ表面にセラミックス層を具備する金型、或いは、キャビティ表面側から、金属層、次いで熱硬化性樹脂層を具備する金型で射出成形することを特徴とする。
上記いずれの成形品の製造方法においても、成形品表面へのガラス充填剤(C)の浮きが防止され、平滑表面が形成されることで成形品表面の光の散乱が抑制される結果、透明性が改善される。
本発明で用いる断熱金型は、キャビティ表面にセラミックス層を有する金型(以下「セラミックス断熱金型」と称す場合がある。)、或いはキャビティ側から金属層、次いで熱硬化性樹脂層が形成された金型(以下「樹脂断熱金型」と称す場合がある。)である。
ヒート&クール成形法で用いる急速加熱冷却金型とは、金型温調装置により、金型の媒体通路に循環させる熱媒体と冷媒体の切り換えを瞬時に行うことができるものである。ヒート&クール成形法は、このような急速加熱冷却金型を用いて、少なくとも型開き後から溶融樹脂の充填完了前までの間に金型の媒体通路に熱媒体を供給し、少なくとも溶融樹脂の充填完了後から型開き前までの間に金型の媒体通路に冷媒体を供給することで、所定の金型キャビティ温度以上で射出工程を行い、射出工程終了と同時に熱媒体を冷媒体に切り換えて所定の金型キャビティ温度以下で型開き工程を行うものである。
本発明の熱可塑性樹脂組成物及びその射出成形品は、ガラス充填剤(C)を配合したことによる優れた寸法安定性、剛性(曲げ強度)、耐熱性等の各種特性を得た上で、透明性にも優れる。
本発明のシートは、本発明の熱可塑性樹脂組成物よりなるものである。
[実施例I−1〜26、比較例I−1〜18]
<熱可塑性樹脂組成物ペレットの製造>
表1A,1Bに記したガラス充填剤(C)以外の各成分を、表2〜7に記した割合(質量部)で配合し、タンブラーにて20分混合した後、1ベントを備えた東芝機械社製二軸押出機(TEM26SX)に上流のフィーダーより供給し、さらにガラス充填剤(C)をバレルの途中より供給して(押出機の上流(ホッパー部位)から、バレル長さLの3/5の下流位置)、回転数250rpm、吐出量25kg/時間、バレル温度280℃の条件で混練した。押出機からストランド状に押出された溶融樹脂を水槽にて急冷し、ペレタイザーを用いてペレット化して熱可塑性樹脂組成物のペレットを得た。なお、比較例I−8、16については、ストランドの振動が大きく、引き取りが困難であったため、ペレットを得ることができなかった。
上述の製造方法で得られたペレットを100℃で5時間乾燥させた後、住友重機械工業社製射出成形機(SE50DUZ型)を用いて、シリンダー温度290℃、金型温度100℃の条件で射出成形し、長さ50mm、幅40mm、厚さ2mmの平板を成形した。金型として、固定側キャビティ及び可動側キャビティを構成する入れ子の材質がSUS420J2である金型を使用した。
上述の製造方法で得られたペレットを100℃で5時間乾燥させた後、ファナック社製射出成形機(S−2000i150B型)を用いて、シリンダー温度290℃、金型温度100℃の条件で射出成形し、長さ100mm、幅100mm、厚さ2mmの平板を成形した。金型として、固定側キャビティ及び可動側キャビティ表面に、100mm×100mm×3mmの酸化ジルコニウム(ZrO2)の板を備えた断熱金型を使用した。
上述の製造方法で得られたペレットを100℃で5時間乾燥させた後、ファナック社製射出成形機(S−2000i150B型)を用いて、シリンダー温度290℃の条件で射出成形し、長さ50mm、幅40mm、厚さ2mmの平板を成形した。このとき、金型温調装置として松井製作所社製MCJ−OM−250AAを用いた急速加熱冷却金型により、300℃の油を金型流路に循環させ、金型のキャビティ表面温度が160℃に到達したときに300℃の油の循環を止め、その後射出工程を行った。射出工程終了と同時に、40℃の油を金型流路に循環させ、金型のキャビティ表面温度が80℃に到達したときに型開き工程を行い、上述の形状の成形品を得た。金型として、固定側キャビティ及び可動側キャビティを構成する入れ子の材質がSUS420J2である金型を使用した。射出工程終了から型開きまでの保持時間は25秒であった。
日本電色工業社製ヘーズメーターNDH4000を用い、上述の方法で得られた平板のヘイズを測定した。ヘイズが小さい程透明性が優れることを意味している。断熱金型を用いて成形した射出成形品、及びヒート&クール成形で得られた射出成形品の場合、ヘイズは15%以下であることが好ましい。一般金型を用いて成形した射出成形品の場合、ヘイズは55%以下であることが好ましい。
ヘイズの測定結果を表2〜7に示す。
比較例I−18は白濁し、測定不可であった。
東京精密社製SURFCOM 3000Aを用い、カットオフ波長λcを0.8mm、カットオフ種別をガウシアン、λsを2.67μm、評価長さを8mmに設定し、上述の方法で得られた平板の表面粗さRaを測定した。Raが小さい程成形品表面が平滑であることを意味しており、透明性に優れた成形品を得るためにはRaを0.1μm以下にすることが好ましい。
ポリエステル樹脂(B)の配合量が本発明の範囲を超えて多過ぎる比較例I−4,11でも、少な過ぎる比較例I−3,10でも、樹脂マトリクスの屈折率をガラス充填剤(C)の屈折率に近づけることができず、透明性が悪い。
いずれの実施例においても、一般金型で射出成形するよりも断熱金型を用いたり、ヒート&クール成形で射出成形したりすることで、透明性は格段に改善されることが分かる。
実施例I−23〜26より、ガラス充填剤(C)としてガラスフレークを用いた場合も、良好な透明性が得られることが分かる。
比較例I−18はポリエステル樹脂(B)を用いていないため、白濁した。
〔実施例II−1〜11、比較例II−1〜7〕
<熱可塑性樹脂組成物ペレットの製造>
熱可塑性樹脂組成物の配合を表8,9に記した割合(質量部)としたこと以外は実施例I−1と同様にして熱可塑性樹脂組成物のペレットを得た。
上述の製造方法で得られたペレットを100℃で5時間乾燥させた後、単軸押出機を用いて厚み1.0mmのシートを成形した。単軸押出機のスクリューとして、φ30mm、L/D=38のフルフライトスクリューを使用した。Tダイはリップ幅300mmのものを使用した。Tダイより吐出された樹脂を鏡面仕上げした2本の冷却ロールで挟み、更に一方の冷却ロールに沿わせることで冷却した。冷却ロールの温度はいずれも120℃であった。
日本電色工業社製SH7000を用い、上述の方法で得られたシートのヘイズを測定した。ヘイズが小さい程透明性が優れることを意味している。シートのヘイズは70%以下であることが好ましい。
ヘイズの測定結果を表8、9に示す。
実施例II−11は、実施例I−15に対して離型剤(E)を含まず、同一配合の射出成形品の実施例がないものである。
本出願は、2018年7月11日付で出願された日本特許出願2018−131658及び2019年1月23日付で出願された日本特許出願2019−009474に基づいており、その全体が引用により援用される。
Claims (9)
- 粘度平均分子量が13,000〜22,000のポリカーボネート樹脂(A)と、テレフタル酸残基、1,4−シクロヘキサンジメタノール残基、及び2,2,4,4−テトラメチル−1,3−シクロブタンジオール残基を含むポリエステル樹脂(B)とを含有する熱可塑性樹脂成分と、ガラス充填剤(C)とを含む熱可塑性樹脂組成物であって、
ポリカーボネート樹脂(A)とポリエステル樹脂(B)の合計100質量部中にポリカーボネート樹脂(A)を25〜65質量部、ポリエステル樹脂(B)を75〜35質量部含み、該熱可塑性樹脂成分100質量部に対してガラス充填剤(C)を10〜45質量部含むことを特徴とする熱可塑性樹脂組成物。 - ガラス充填剤(C)が、扁平率1.5〜8の断面形状を持つガラス繊維と、平均厚みが0.1〜10μmのガラスフレークのいずれか一方又は双方であることを特徴とする請求項1に記載の熱可塑性樹脂組成物。
- 請求項1又は2に記載の熱可塑性樹脂組成物を射出成形してなる成形品。
- 該成形品の全表面の30%以上の面積を占める成形品表面の表面粗さRaが0.1μm以下であることを特徴とする請求項3に記載の成形品。
- 請求項1又は2に記載の熱可塑性樹脂組成物からなるシート。
- 厚みが0.2〜2mmであることを特徴とする請求項5に記載のシート。
- 請求項1又は2に記載の熱可塑性樹脂組成物を、キャビティ表面にセラミックス層を具備する金型で射出成形することを特徴とする成形品の製造方法。
- 請求項1又は2に記載の熱可塑性樹脂組成物を、キャビティ表面側から、金属層、次いで熱硬化性樹脂層を具備する金型で射出成形することを特徴とする成形品の製造方法。
- 請求項1又は2に記載の熱可塑性樹脂組成物を射出成形して成形品を製造する方法であって、急速加熱冷却金型を用い、金型キャビティ表面温度が130℃以上のときに射出工程を行い、金型キャビティ表面温度が80℃以下のときに型開き工程を行うことを特徴とする成形品の製造方法。
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EP3822319A2 (en) | 2021-05-19 |
CN112352016A (zh) | 2021-02-09 |
EP3822319A4 (en) | 2022-04-13 |
CN112352016B (zh) | 2022-12-16 |
JP6607335B1 (ja) | 2019-11-20 |
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