JP6669320B1 - 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板 - Google Patents
樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板 Download PDFInfo
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- JP6669320B1 JP6669320B1 JP2019552299A JP2019552299A JP6669320B1 JP 6669320 B1 JP6669320 B1 JP 6669320B1 JP 2019552299 A JP2019552299 A JP 2019552299A JP 2019552299 A JP2019552299 A JP 2019552299A JP 6669320 B1 JP6669320 B1 JP 6669320B1
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- styrene
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- printed wiring
- wiring board
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Abstract
Description
具体的には、積層板の耐薬品性が不十分であると積層板中の樹脂層が薬液に溶出することで薬液の汚染が生じ、汚染された薬液を使用することで積層板の品質の低下に繋がるという問題があるためである。
特にデスミア工程においては、メカニカルドリル加工やレーザードリル加工で生じるスミアを除去するため強いアルカリ性の薬品が用いられるので、積層板の耐薬品性が不十分であると、スミア以外のスルーホール内壁やプラスチック層の表面も溶出され、薬液が比較的に汚染されやすい傾向にある。
〔1〕
スチレン系エラストマー(A)、スチレンオリゴマー(B)、マレイミド化合物(C)及びシアン酸エステル化合物(D)を含有する、樹脂組成物。
〔2〕
上記スチレン系エラストマー(A)が、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−水添ブタジエン−スチレンブロック共重合体、スチレン−水添イソプレン−スチレンブロック共重合体およびスチレン−水添(イソプレン/ブタジエン)−スチレンブロック共重合体からなる群より選ばれる少なくとも1種である、〔1〕に記載の樹脂組成物。
〔3〕
上記スチレン系エラストマー(A)の含有量が、樹脂固形分100質量部に対して、1〜30質量部である、〔1〕又は〔2〕に記載の樹脂組成物。
〔4〕
上記スチレンオリゴマー(B)の含有量が、樹脂固形分100質量部に対して、1〜30質量部である、〔1〕〜〔3〕のいずれか1つに記載の樹脂組成物。
〔5〕
さらに、ポリフェニレンエーテル(E)を含有する、〔1〕〜〔4〕のいずれか1つに記載の樹脂組成物。
〔6〕
前記ポリフェニレンエーテル(E)が式(1)で表され、かつ数平均分子量が1000以上7000以下、最低溶融粘度が50000Pa・s以下である、〔5〕に記載の樹脂組成物。
〔7〕
前記ポリフェニレンエーテル(E)が式(11)で表される、〔5〕に記載の樹脂組成物。
〔8〕
さらに、無機充填材(F)を含有する、〔1〕〜〔7〕のいずれか1つに記載の樹脂組成物。
〔9〕
上記無機充填材(F)の含有量が、樹脂固形分100質量部に対して、50〜1600質量部である、〔8〕に記載の樹脂組成物。
〔10〕
基材と、〔1〕〜〔9〕のいずれか1つに記載の樹脂組成物から形成された層と、を有する、プリプレグ。
〔11〕
1枚以上積層された〔10〕に記載のプリプレグと、前記プリプレグの片面又は両面に配された金属箔と、を有する、金属箔張積層板。
〔12〕
〔1〕〜〔9〕のいずれか1つに記載の樹脂組成物から形成された層を含む、樹脂シート。
〔13〕
支持体と、前記支持体上に配された、〔1〕〜〔9〕のいずれか1つに記載の樹脂組成物から形成された層と、を有する、樹脂シート。
〔14〕
絶縁層と、前記絶縁層の表面に形成された導体層と、を有し、上記絶縁層が、〔1〕〜〔9〕のいずれか1つに記載の樹脂組成物から形成された層を含む、プリント配線板。
ここで、スチレン系エラストマーはスチレンを用いて合成されたエラストマーであることを意味するが、本実施形態においては、スチレンは置換基を有したものを用いてもよい。具体的には、α−メチルスチレン、3−メチルスチレン、4−プロピルスチレン、4−シクロヘキシルスチレン等のスチレン誘導体を用いることができる。
スチレン系エラストマー(A)は、末端に反応基を有していてもよいが、有していないことが好ましい。
なお、スチレン系エラストマー(A)は、後に詳述するスチレンオリゴマー(B)とは異なるものである。
スチレン系エラストマー(A)の数平均分子量は、1600超であることが好ましく、50000以上であることがより好ましく、80000以上であることが更に好ましい。上限は、300000以下であることが好ましく、200000以下であることがより好ましく、150000以下であることが更に好ましい。
ここで、樹脂組成物の樹脂固形分とは、樹脂組成物から無機充填材及び溶剤を除いた成分をいうものとする。また、樹脂固形分100質量部とは、樹脂組成物における無機充填材及び溶剤を除いた成分の総量が100質量部であることをいうものとする。
スチレンオリゴマー(B)は、数平均分子量が、178〜1600であることが好ましく、200〜1000であることがより好ましい。
また、スチレンオリゴマー(B)は、スチレン化率が90%以上であることが好ましい。スチレンオリゴマー(B)におけるスチレン化率とは、オリゴマーを構成する原料モノマーのうち、スチレン系モノマー(スチレン、メチルスチレン等をいう)の質量割合をいう。
本実施形態に係るスチレンオリゴマー(B)は、スチレン、上記したスチレン誘導体及びビニルトルエンからなる群より選ばれる少なくとも1種の化合物を重合してなり、その数平均分子量は、178〜1600、平均の芳香環数が2〜14、沸点が300℃以上である分岐構造のない化合物であることが好ましい。
本実施形態で用いられるスチレンオリゴマー(B)としては、例えば、スチレン重合体、ビニルトルエン重合体、α−メチルスチレン重合体、ビニルトルエン−α−メチルスチレン重合体、スチレン−α−スチレン重合体が挙げられる。
スチレン重合体としては、市販品を用いてもよく、例えば、ピコラスチックA5(イーストマンケミカル社製)、ピコラスチックA−75(イーストマンケミカル社製)、ピコテックス75(イーストマンケミカル社製)、FTR−8100(三井化学(株)製)、FTR−8120(三井化学(株)製)が挙げられる。
また、ビニルトルエン−α−メチルスチレン重合体としては、ピコテックスLC(イーストマンケミカル社製)が挙げられる。
また、α−メチルスチレン重合体としては、クリスタレックス3070(イーストマンケミカル社製)、クリスタレックス3085(イーストマンケミカル社製)、クリスタレックス(3100)、クリスタレックス5140(イーストマンケミカル社製)、FMR−0100(三井化学(株)製)、FMR−0150(三井化学(株)製)が挙げられる。
また、スチレン−α−スチレン重合体としてはFTR−2120(三井化学(株)製)が挙げられる。
これらのスチレンオリゴマーは1種単独又は2種以上を適宜混合して使用することも可能である。2種以上用いる場合は、合計量が上記範囲となることが好ましい。
マレイミド化合物(C)の具体例としては、例えば、N−フェニルマレイミド、N−ヒドロキシフェニルマレイミド、ビス(4−マレイミドフェニル)メタン、2,2−ビス{4−(4−マレイミドフェノキシ)−フェニル}プロパン、4,4’−ジフェニルメタンビスマレイミド、ビス(3,5−ジメチル−4−マレイミドフェニル)メタン、ビス(3,5−ジエチル−4−マレイミドフェニル)メタン、フェニルメタンマレイミド、o−フェニレンビスマレイミド、m−フェニレンビスマレイミド、p−フェニレンビスマレイミド、o−フェニレンビスシトラコンイミド、m−フェニレンビスシトラコンイミド、p−フェニレンビスシトラコンイミド、2,2−ビス(4−(4−マレイミドフェノキシ)−フェニル)プロパン、3,3’−ジメチル−5,5’−ジエチル−4,4’−ジフェニルメタンビスマレイミド、4−メチル−1,3−フェニレンビスマレイミド、1,6−ビスマレイミド−(2,2,4−トリメチル)ヘキサン、4,4’−ジフェニルエーテルビスマレイミド、4,4’−ジフェニルスルフォンビスマレイミド、1,3−ビス(3−マレイミドフェノキシ)ベンゼン、1,3−ビス(4−マレイミドフェノキシ)ベンゼン、4,4’−ジフェニルメタンビスシトラコンイミド、2,2−ビス[4−(4−シトラコンイミドフェノキシ)フェニル]プロパン、ビス(3,5−ジメチル−4−シトラコンイミドフェニル)メタン、ビス(3−エチル−5−メチル−4−シトラコンイミドフェニル)メタン、ビス(3,5−ジエチル−4−シトラコンイミドフェニル)メタン、下記式(2)で表されるマレイミド化合物、下記式(3)で表されるマレイミド化合物、及び下記式(4)で表されるマレイミド化合物、及びこれらマレイミド化合物のプレポリマー、又はマレイミド化合物とアミン化合物のプレポリマー等が挙げられる。
式(3)中、n2は平均値であり、1≦n2≦10である。n2は、溶剤溶解性がより一層優れる観点から、4以下であることが好ましく、3以下であることがより好ましく、2以下であることがさらに好ましい。マレイミド化合物(C)は、n2の異なる化合物を含んでいてもよい。
マレイミド化合物(C)は1種単独又は2種以上を適宜混合して使用することも可能である。2種以上用いる場合は、合計量が上記範囲となることが好ましい。
また、式(5)におけるアルキル基及びRaにおけるアリール基中の水素原子は、フッ素原子、塩素原子等のハロゲン原子、メトキシ基、フェノキシ基等のアルコキシ基、シアノ基等で置換されていてもよい。
アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、n−ブチル基、イソブチル基、tert−ブチル基、n−ペンチル基、1−エチルプロピル基、2,2−ジメチルプロピル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、トリフルオロメチル基等が挙げられる。
アリール基の具体例としては、フェニル基、キシリル基、メシチル基、ナフチル基、フェノキシフェニル基、エチルフェニル基、o−,m−又はp−フルオロフェニル基、ジクロロフェニル基、ジシアノフェニル基、トリフルオロフェニル基、メトキシフェニル基、o−,m−又はp−トリル基等が挙げられる。
アルコキシ基の具体例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、n−ブトキシ基、イソブトキシ基、tert−ブトキシ基等が挙げられる。
式(5)のZにおける2価の有機基の具体例としては、メチレン基、エチレン基、トリメチレン基、シクロペンチレン基、シクロヘキシレン基、トリメチルシクロヘキシレン基、ビフェニルイルメチレン基、ジメチルメチレン−フェニレン−ジメチルメチレン基、フルオレンジイル基、フタリドジイル基等が挙げられる。前記2価の有機基中の水素原子は、フッ素原子、塩素原子等のハロゲン原子、メトキシ基、フェノキシ基等のアルコキシ基、シアノ基等で置換されていてもよい。
式(5)のZにおける窒素数1〜10の2価の有機基としては、イミノ基、ポリイミド基等が挙げられる。
式(6)のAr2及び式(7)のAr3の具体例としては、1,4−フェニレン基、1,3−フェニレン基、4,4’−ビフェニレン基、2,4’−ビフェニレン基、2,2’−ビフェニレン基、2,3’−ビフェニレン基、3,3’−ビフェニレン基、3,4’−ビフェニレン基、2,6−ナフチレン基、1,5−ナフチレン基、1,6−ナフチレン基、1,8−ナフチレン基、1,3−ナフチレン基、1,4−ナフチレン基等が挙げられる。
式(6)のRb〜Rg及び式(7)のRh、Riにおけるアルキル基及びアリール基は式(5)で記載したものと同様である。
これらのシアン酸エステル化合物(D)は1種単独又は2種以上を適宜混合して使用することも可能である。2種以上用いる場合は、合計量が上記範囲となることが好ましい。
で表される構造単位の重合体を含む化合物であることが好ましい。
前記重合体は、式(9):
で表される構造、及び/又は、式(10):
末端が水酸基である変性ポリフェニレンエーテルとしては例えば、SABICイノベーティブプラスチックス社製SA90等が挙げられる。また、末端がメタクリル基であるポリフェニレンエーテルとしては例えば、SABICイノベーティブプラスチックス社製SA9000等が挙げられる。
で表される構造が挙げられる。
ここで、Xが表すアリール基は、上記のアリール基が酸素原子で結合されているジフェニルエーテル基等や、カルボニル基で結合されたベンゾフェノン基等、アルキレン基により結合された2,2−ジフェニルプロパン基等を含んでもよい。
また、アリール基は、アルキル基(好適には炭素数1〜6のアルキル基、特にメチル基)、アルケニル基、アルキニル基やハロゲン原子など、一般的な置換基によって置換されていてもよい。但し、前記「アリール基」は、酸素原子を介してポリフェニレンエーテル部分に置換されているので、一般的置換基の数の限界は、ポリフェニレンエーテル部分の数に依存する。
数平均分子量は、定法に従ってゲル浸透クロマトグラフィーを使用して測定される。数平均分子量は、1000〜3000であることがより好ましい。数平均分子量を1000以上7000以下とすることにより、成形性及び電気特性の両立という効果がより効果的に発揮される。
最低溶融粘度は、定法に従って動的粘弾性測定装置を使用して測定される。最低溶融粘度は、500〜50000Pa・sがより好ましい。最低溶融粘度を50000Pa・s以下とすることにより、成形性及び電気特性の両立という効果がより効果的に発揮される。
−(Y−O)m−及びmは、式(1)におけるものと同義である。
また、このような変性ポリフェニレンエーテルは市販品を用いることができ、例えば、三菱ガス化学(株)製OPE−2St1200、OPE−2st2200を好適に使用することができる。
これらのポリフェニレンエーテル(E)は1種単独又は2種以上を適宜混合して使用することも可能である。2種以上用いる場合は、合計量が上記範囲となることが好ましい。
本実施形態にかかる樹脂組成物は、スチレン系エラストマー(A)、スチレンオリゴマー(B)、マレイミド化合物(C)、シアン酸エステル化合物及び(D)ポリフェニレンエーテル(E)の総量が樹脂固形分の90質量%以上を占めることが好ましく、95質量%以上占めることがより好ましく、97質量%以上占めることがさらに好ましい。
これら基材は1種単独又は2種以上を組み合わせて使用することができる。基材の形状としては織布、不織布、ロービング、チョップドストランドマット、サーフェシングマットなど、織布の織り方としては、平織り、ななこ織り、綾織り等が知られており、これら公知のものから目的とする用途や性能により適宜選択して使用することができ、これらを開繊処理したものやシランカップリング剤などで表面処理したガラス織布が好適に使用される。基材の厚さや質量は、特に限定されないが、通常は0.01〜0.3mm程度のものが好適に用いられる。とりわけ、強度と吸水性の観点から、基材は、厚み200μm以下、質量250g/m2以下のガラス織布が好ましく、L−ガラスやNE−ガラス、Q−ガラス等の低誘電率性、低誘電正接性を示すガラス繊維からなる、低誘電ガラスクロスがより好ましい。
積層樹脂シートは、支持体と、前記支持体上に配された、本実施形態に係る樹脂組成物から形成された層とを有する。この積層樹脂シートは、常法にしたがって製造することができ、製造方法は特に限定されない。例えば、上記の本実施形態に係る樹脂組成物を溶剤に溶解させた溶液を支持体に塗布し乾燥することで得ることができる。
1−ナフトールアラルキル樹脂(新日鉄住金化学(株)製)300g(OH基換算1.28mol)及びトリエチルアミン194.6g(1.92mol)(ヒドロキシ基1molに対して1.5mol)をジクロロメタン1800gに溶解させ、これを溶液1とした。
スチレン−ブタジエン−スチレンブロック共重合体(TR2630、JSR(株)、スチレン化率32%、末端に反応基を有さない)10質量部、α−メチルスチレン重合体(クリスタレックス3085、イーストマンケミカル社製、数平均分子量:664)10質量部、マレイミド化合物(BMI−2300、大和化成工業(株)製)24質量部、合成例1より得られたシアン酸エステル化合物(SNCN)56質量部、球状シリカ(SC2050−MB、(株)アドマテックス製、平均粒子径0.5μm)150質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニス(樹脂組成物)を得た。
厚さ0.8mmの銅張積層板の銅箔を除去した試験片を使用し、空洞共振器摂動法(Agilent8722ES、アジレントテクノロジー製)にて10GHzの誘電率、誘電正接の測定を5回実施した。誘電率の評価については、誘電率の平均値が3.4未満の場合をAとし、3.4以上3.5未満の場合をBとし、3.5以上の場合をCとした。誘電正接の評価については、誘電正接の平均値が0.0026未満の場合をAとし、0.0026以上0.003未満の場合をBとし、0.003以上の場合をCとした。
(耐デスミア性)
厚さ0.2mmの銅張積層板の銅箔をエッチングにより除去し、得られた積層板を5cmx5cmサンプルとし、質量を測定した。その後、積層板を、膨潤液である、アトテックジャパン(株)のスウェリングディップセキュリガントPに80℃で10分間浸漬し、次に、粗化液である、アトテックジャパン(株)のコンセントレートコンパクトCPに80℃で8分間浸漬し、最後に中和液である、アトテックジャパン(株)のリダクションコンディショナーセキュリガントP500に45℃で10分間浸漬した。この処理を3回行った後の積層板の質量を測定し、処理前後の積層板の質量減少量(質量%)を算出した。耐デスミア性の評価は、4質量%未満をAとし、4質量%以上7質量%未満をBとし、7質量%以上をCとした。
(耐アルカリ性)
厚さ0.2mmの銅張積層板の銅箔をエッチングにより除去し、得られた積層板を5cmx5cmサンプルとし、質量を測定した。その後、積層板を、70℃の1N水酸化ナトリウム水溶液に60分浸漬した後の質量を測定し、処理前後の積層板の質量減少量(質量%)を算出した。耐アルカリ性の評価は、質量減少率が4質量%未満の場合をA、4質量%以上7質量%未満の場合をBとし、7質量%以上をCとした。
実施例1で用いたスチレン−ブタジエン−スチレンブロック共重合体(TR2630)を10質量部、α−メチルスチレン重合体(クリスタレックス3085)を20質量部、マレイミド化合物(BMI−2300)を15質量部、合成例1より得られたシアン酸エステル化合物(SNCN)を35質量部、球状シリカ(SC2050―MB)150質量部に加え、式(11)におけるXが、式(12)であり、−(Y−O)m−が、式(15)の構造単位が重合したものであるポリフェニレンエーテル(OPE−2St1200、三菱ガス化学(株)製、数平均分子量1187、ビニル基当量:590g/eq.、最低溶融粘度1000Pa・s)20質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。このワニスを使用する以外は実施例1と同様に各種特性試験を行った。得られた銅張積層板の物性値を表1に示す。
実施例1で用いたマレイミド化合物(BMI−2300)30質量部、合成例1より得られたシアン酸エステル化合物(SNCN)70質量部、球状シリカ(SC2050―MB)150質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。このワニスを使用する以外は実施例1と同様に各種特性試験を行った。得られた銅張積層板の物性値を表1に示す。
実施例1で用いたスチレン−ブタジエン−スチレンブロック共重合体(TR2630)10質量部、マレイミド化合物(BMI−2300)27質量部、合成例1より得られたシアン酸エステル化合物(SNCN)63質量部、球状シリカ(SC2050−MB)150質量部を混合し、メチルエチルケトンで固形分を65質量%に希釈しワニスを得た。このワニスを使用する以外は実施例1と同様に各種特性試験を行った。得られた銅張積層板の物性値を表1に示す。
以上より本発明により得られるプリプレグによる積層板は、誘電特性、耐アルカリ性、耐デスミア性に優れていることを確認した。
Claims (13)
- スチレン系エラストマー(A)、スチレンオリゴマー(B)、1分子中に2個以上のマレイミド基を有するマレイミド化合物(C)及びシアナト基が少なくとも1個置換された芳香族部分を分子内に2つ以上有するシアン酸エステル化合物(D)を含有し、
前記スチレン系エラストマー(A)が、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−水添ブタジエン−スチレンブロック共重合体、スチレン−水添イソプレン−スチレンブロック共重合体及びスチレン−水添(イソプレン/ブタジエン)−スチレンブロック共重合体からなる群より選ばれる少なくとも1種であるプリント配線板用樹脂組成物。 - 前記スチレン系エラストマー(A)の含有量が、樹脂固形分100質量部に対して、1〜30質量部である、請求項1に記載のプリント配線板用樹脂組成物。
- 前記スチレンオリゴマー(B)の含有量が、樹脂固形分100質量部に対して、1〜30質量部である、請求項1または2に記載のプリント配線板用樹脂組成物。
- さらに、ポリフェニレンエーテル(E)を含有する、請求項1〜3のいずれか1項に記載のプリント配線板用樹脂組成物。
- 前記ポリフェニレンエーテル(E)が式(1)で表され、かつ数平均分子量が1000以上7000以下、最低溶融粘度が50000Pa・s以下である、請求項4に記載のプリント配線板用樹脂組成物。
- 前記ポリフェニレンエーテル(E)が式(11)で表される、請求項4に記載のプリント配線板用樹脂組成物。
- さらに、無機充填材(F)を含有する、請求項1〜6のいずれか1項に記載のプリント配線板用樹脂組成物。
- 前記無機充填材(F)の含有量が、樹脂固形分100質量部に対して、50〜1600質量部である、請求項7に記載のプリント配線板用樹脂組成物。
- 基材と、
請求項1〜8のいずれか1項に記載のプリント配線板用樹脂組成物から形成された層と、を有する、プリント配線板用プリプレグ。 - 1枚以上積層された請求項9に記載のプリント配線板用プリプレグと、
該プリプレグの片面又は両面に配された金属箔と、を有する、プリント配線板用金属箔張積層板。 - 請求項1〜8のいずれか1項に記載のプリント配線板用樹脂組成物から形成された層を含むプリント配線板用樹脂シート。
- 支持体と、
該支持体上に配された、請求項1〜8のいずれか1項に記載のプリント配線板用樹脂組成物から形成された層と、を有する、プリント配線板用樹脂シート。 - 絶縁層と、該絶縁層の表面に形成された導体層と、を有し、
前記絶縁層が、請求項1〜8のいずれか1項に記載のプリント配線板用樹脂組成物から形成された層を含む、プリント配線板。
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EP (1) | EP3805293A4 (ja) |
JP (1) | JP6669320B1 (ja) |
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KR102400111B1 (ko) * | 2019-02-08 | 2022-05-19 | 주식회사 엘지화학 | 반도체 패키지용 열경화성 수지 조성물, 프리프레그 및 금속박 적층판 |
WO2020203320A1 (ja) * | 2019-03-29 | 2020-10-08 | パナソニックIpマネジメント株式会社 | 樹脂組成物、並びに、それを用いたプリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板及び配線基板 |
WO2022054864A1 (ja) * | 2020-09-11 | 2022-03-17 | パナソニックIpマネジメント株式会社 | 樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板 |
WO2022054303A1 (ja) * | 2020-09-11 | 2022-03-17 | パナソニックIpマネジメント株式会社 | 樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板 |
JPWO2022054862A1 (ja) * | 2020-09-11 | 2022-03-17 | ||
WO2022059167A1 (ja) * | 2020-09-18 | 2022-03-24 | 昭和電工マテリアルズ株式会社 | 半導体パッケージ用基板材料を製造する方法、プリプレグ、及び半導体パッケージ用基板材料 |
WO2022145377A1 (ja) * | 2020-12-28 | 2022-07-07 | 昭和電工マテリアルズ株式会社 | 樹脂組成物、プリプレグ、積層板、樹脂フィルム、プリント配線板及び半導体パッケージ |
JP2022161530A (ja) | 2021-04-09 | 2022-10-21 | エルジー・ケム・リミテッド | 熱硬化性樹脂組成物、その硬化物及びプリプレグ、硬化物又はプリプレグの硬化物を備えた積層板、金属箔張積層板、並びにプリント配線板 |
TW202317678A (zh) * | 2021-09-30 | 2023-05-01 | 日商三菱瓦斯化學股份有限公司 | 預浸體、積層板、及印刷配線板 |
CN115873406B (zh) * | 2022-12-01 | 2024-07-30 | 哈尔滨工业大学(深圳) | 一种改性bt树脂及其制备方法 |
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- 2019-05-31 EP EP19811496.9A patent/EP3805293A4/en active Pending
- 2019-05-31 US US17/059,563 patent/US20210229407A1/en not_active Abandoned
- 2019-05-31 TW TW108118865A patent/TWI820143B/zh active
- 2019-05-31 JP JP2019552299A patent/JP6669320B1/ja active Active
- 2019-05-31 CN CN201980036516.2A patent/CN112204076B/zh active Active
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EP3805293A1 (en) | 2021-04-14 |
US20210229407A1 (en) | 2021-07-29 |
CN112204076B (zh) | 2023-10-24 |
KR20210018307A (ko) | 2021-02-17 |
WO2019230943A1 (ja) | 2019-12-05 |
TW202003675A (zh) | 2020-01-16 |
KR102672360B1 (ko) | 2024-06-04 |
JPWO2019230943A1 (ja) | 2020-06-11 |
EP3805293A4 (en) | 2022-03-16 |
TWI820143B (zh) | 2023-11-01 |
CN112204076A (zh) | 2021-01-08 |
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