JP6844115B2 - 感放射線樹脂組成物及び電子部品 - Google Patents
感放射線樹脂組成物及び電子部品 Download PDFInfo
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- JP6844115B2 JP6844115B2 JP2016063924A JP2016063924A JP6844115B2 JP 6844115 B2 JP6844115 B2 JP 6844115B2 JP 2016063924 A JP2016063924 A JP 2016063924A JP 2016063924 A JP2016063924 A JP 2016063924A JP 6844115 B2 JP6844115 B2 JP 6844115B2
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- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- YOKZJDRCZXTECO-UHFFFAOYSA-N tricyclo[5.2.1.02,6]deca-3,8-diene-2-carboxylic acid Chemical compound C1=CC2CC1C1(C(=O)O)C2CC=C1 YOKZJDRCZXTECO-UHFFFAOYSA-N 0.000 description 1
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Description
〔1〕バインダー樹脂(A)、感放射線化合物(B)、軟化点が30℃以下であり、かつ、4官能以下であるエポキシ系架橋剤(C)、及びビスフェノール型ノボラック樹脂(D)を含有する感放射線樹脂組成物、
〔2〕前記バインダー樹脂(A)が、カルボキシル基を含有する環状オレフィン重合体である前記〔1〕に記載の感放射線樹脂組成物、
〔3〕前記ビスフェノール型ノボラック樹脂(D)の重量平均分子量が500〜2,000である前記〔1〕または〔2〕に記載の感放射線樹脂組成物、
〔4〕前記ビスフェノール型ノボラック樹脂(D)の含有量が、前記バインダー樹脂(A)100重量部に対して、5〜70重量部である前記〔1〕〜〔3〕のいずれかに記載の感放射線樹脂組成物、ならびに、
〔5〕前記〔1〕〜〔4〕のいずれかに記載の感放射線樹脂組成物からなる樹脂膜を備える電子部品、
が提供される。
本発明で用いるバインダー樹脂(A)としては、特に限定されないが、プロトン性極性基を有する環状オレフィン重合体(A1)、アクリル樹脂(A2)、ポリイミド(A3)、カルド樹脂(A4)又はポリシロキサン(A5)であることが好ましく、これらの中でも、プロトン性極性基を有する環状オレフィン重合体(A1)が特に好ましい。
これらのバインダー樹脂(A)は、それぞれ単独で用いてもよく、又は2種以上を併用してもよい。
本発明において、プロトン性極性基を有する環状オレフィン重合体に結合しているプロトン性極性基の数に特に限定はなく、また、相異なる種類のプロトン性極性基が含まれていてもよい。
これら単量体(b2)は、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
これら単量体(b3)は、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
プロトン性極性基を有しない重合体は、上述した単量体(b1)及び(b2)のうち少なくとも一種と、必要に応じて単量体(b3)とを任意に組み合わせて重合することによって得ることができる。
このような化合物の具体例としては、アクリル酸、メタクリル酸、アンゲリカ酸、チグリン酸、オレイン酸、エライジン酸、エルカ酸、ブラシジン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、アトロパ酸、ケイ皮酸等の不飽和カルボン酸;アリルアルコール、メチルビニルメタノール、クロチルアルコール、メタリルアルコール、1−フェニルエテン−1−オール、2−プロペン−1−オール、3−ブテン−1−オール、3−ブテン−2−オール、3−メチル−3−ブテン−1−オール、3−メチル−2−ブテン−1−オール、2−メチル−3−ブテン−2−オール、2−メチル−3−ブテン−1−オール、4−ペンテン−1−オール、4−メチル−4−ぺンテン−1−オール、2−ヘキセン−1−オール等の不飽和アルコール;等が挙げられる。
これら変性剤を用いた重合体の変性反応は、常法に従えばよく、通常、ラジカル発生剤の存在下で行われる。
アクリル基を有するカルボン酸無水物の具体例としては、無水マレイン酸、シトラコン酸無水物等が挙げられる。
エポキシ基含有アクリレート化合物の具体例としては、アクリル酸グリシジル、メタクリル酸グリシジル、α−エチルアクリル酸グリシジル、α−n−プロピルアクリル酸グリシジル、α−n−ブチルアクリル酸グリシジル、アクリル酸−3,4−エポキシブチル、メタクリル酸−3,4−エポキシブチル、アクリル酸−6,7−エポキシヘプチル、メタクリル酸−6,7−エポキシヘプチル、α−エチルアクリル酸−6,7−エポキシヘプチル、アクリル酸−3,4−エポキシシクロヘキシルメチル、メタクリル酸−3,4−エポキシシクロヘキシルメチル等が挙げられる。
オキセタン基含有アクリレート化合物の具体例としては、(メタ)アクリル酸(3−メチルオキセタン−3−イル)メチル、(メタ)アクリル酸(3−エチルオキセタン−3−イル)メチル、(メタ)アクリル酸(3−メチルオキセタン−3−イル)エチル、(メタ)アクリル酸(3−エチルオキセタン−3−イル)エチル、(メタ)アクリル酸(3−クロロメチルオキセタン−3−イル)メチル、(メタ)アクリル酸(オキセタン−2−イル)メチル、(メタ)アクリル酸(2−メチルオキセタン−2−イル)メチル、(メタ)アクリル酸(2−エチルオキセタン−2−イル)メチル、(1−メチル−1−オキセタニル−2−フェニル)−3−(メタ)アクリレート、(1−メチル−1−オキセタニル)−2−トリフロロメチル−3−(メタ)アクリレート、及び(1−メチル−1−オキセタニル)−4−トリフロロメチル−2−(メタ)アクリレート等が挙げられる。
これらのうち、(メタ)アクリル酸、無水マレイン酸、(メタ)アクリル酸グリシジル、メタクリル酸−6,7−エポキシヘプチル等が好ましい。
これらのなかでも、メチル(メタ)アクリレート、ブチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、2−メチルシクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、トリシクロ[5.2.1.0 2 , 6 ]デカン−8−イル(メタ)アクリレート、N−フェニルマレイミド及びN−シクロヘキシルマレイミド等が好ましい。
これらの化合物は、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
上記単量体の重合方法は、常法に従えばよく、例えば、懸濁重合法,乳化重合法,溶液重合法等が採用される。
環状構造を構成している4級炭素原子に二つの環状構造が結合した骨格構造の具体例としては、フルオレン骨格、ビスフェノールフルオレン骨格、ビスアミノフェニルフルオレン骨格、エポキシ基を有するフルオレン骨格、アクリル基を有するフルオレン骨格等が挙げられる。
本発明で用いるカルド樹脂(A4)は、このカルド構造を有する骨格がそれに結合している官能基間の反応等により重合して形成される。カルド樹脂(A4)は、主鎖と嵩高い側鎖が一つの元素で繋がれた構造(カルド構造)をもち、主鎖に対してほぼ垂直方向に環状構造を有している。
カルド樹脂(A4)は、カルド構造を有する単量体を重合して得られる重合体であるが、その他の共重合可能な単量体との共重合体であってもよい。
上記単量体の重合方法は、常法に従えばよく、例えば、開環重合法や付加重合法等が採用される。
(R4)p−Si−(OR5)4−p (4)
これらのオルガノシランのうち、得られる樹脂膜の耐クラック性や硬度の点から3官能性シランが好ましく用いられる。これらのオルガノシランは単独で使用しても、2種以上を組み合わせて使用してもよい。
また、バインダー樹脂(A)の分子量分布は、重量平均分子量/数平均分子量(Mw/Mn)比で、通常、4以下、好ましくは3以下、より好ましくは2.5以下である。
バインダー樹脂(A)の重量平均分子量(Mw)や分子量分布(Mw/Mn)は、テトラヒドロフラン等の溶媒を溶離液としたゲル・パーミエーション・クロマトグラフィー(GPC)により、ポリスチレン換算値として求められる値である。
感放射線化合物(B)は、紫外線や電子線等の放射線の照射により、化学反応を引き起こすことのできる化合物である。本発明において感放射線化合物(B)は、感放射線樹脂組成物から形成されてなる樹脂膜のアルカリ溶解性を制御できるものが好ましく、特に、光酸発生剤を使用することが好ましい。
これらの感放射線化合物は、それぞれ単独で、又は2種以上を組み合わせて用いることができる。
本発明の感放射線樹脂組成物は、上述したバインダー樹脂(A)及び感放射線化合物(B)に加えて、軟化点が30℃以下であり、かつ、4官能以下であるエポキシ系架橋剤(C)を含有する。
また、本発明の感放射線樹脂組成物は、上述したバインダー樹脂(A)、感放射線化合物(B)、及びエポキシ系架橋剤(C)に加えて、ビスフェノール型ノボラック樹脂(D)を含有する。上述したように、本発明においては、エポキシ系架橋剤(C)とともに、ビスフェノール型ノボラック樹脂(D)を配合することで、本発明の感放射線樹脂組成物を用いて樹脂膜を形成した場合に、得られる樹脂膜を、白濁等することなく外観が良好であり、金属層に対する密着性が高く、耐薬品性及び現像性に優れたものとすることができる。特に、本発明においては、ビスフェノール型ノボラック樹脂(D)は、感放射線樹脂組成物中において、エポキシ系架橋剤(C)と反応することで、硬化剤として作用するものであり、これにより、得られる樹脂膜を、耐薬品性に優れたものとしながら、金属層に対する密着性を高めることができるものであり、しかも、水酸基を2つ有する、ビスフェノール構造の作用により、エポキシ系架橋剤(C)と反応した後においても、アルカリ可溶性にも優れることから、得られる樹脂膜を、現像性にも優れたものとすることができるものである。
また、本発明の感放射線樹脂組成物には、さらに、溶剤が含有されていてもよい。溶剤としては、特に限定されず、樹脂組成物の溶剤として公知のもの、例えばアセトン、メチルエチルケトン、シクロペンタノン、2−ヘキサノン、3−ヘキサノン、2−ヘプタノン、3−ヘプタノン、4−ヘプタノン、2−オクタノン、3−オクタノン、4−オクタノンなどの直鎖のケトン類;n−プロピルアルコール、イソプロピルアルコール、n−ブチルアルコール、シクロヘキサノールなどのアルコール類;エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジオキサンなどのエーテル類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルなどのアルコールエーテル類;ギ酸プロピル、ギ酸ブチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、酪酸エチル、乳酸メチル、乳酸エチルなどのエステル類;セロソルブアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピルセロソルブアセテート、ブチルセロソルブアセテートなどのセロソルブエステル類;プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルなどのプロピレングリコール類;ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテルなどのジエチレングリコール類;γ−ブチロラクトン、γ−バレロラクトン、γ−カプロラクトン、γ−カプリロラクトンなどの飽和γ−ラクトン類;トリクロロエチレンなどのハロゲン化炭化水素類;トルエン、キシレンなどの芳香族炭化水素類;ジメチルアセトアミド、ジメチルホルムアミド、N−メチルアセトアミドなどの極性溶媒などが挙げられる。これらの溶剤は、単独でも2種以上を組み合わせて用いてもよい。溶剤の含有量は、バインダー樹脂(A)100重量部に対して、好ましくは10〜10000重量部、より好ましくは50〜5000重量部、さらに好ましくは100〜1000重量部の範囲である。なお、感放射線樹脂組成物に溶剤を含有させる場合には、溶剤は、通常、硬化膜形成後に除去されることとなる。
混合の方法は特に限定されないが、感放射線樹脂組成物を構成する各成分を溶剤に溶解又は分散して得られる溶液又は分散液を混合するのが好ましい。これにより、感放射線樹脂組成物は、溶液又は分散液の形態で得られる。
次いで、本発明の電子部品について、説明する。本発明の電子部品は、上述した本発明の感放射線樹脂組成物からなる樹脂膜を有する。
潜像パターンを有する樹脂膜に現像液を接触させる方法としては、例えば、パドル法、スプレー法、ディッピング法等の方法が用いられる。現像は、通常、0〜100℃、好ましくは5〜55℃、より好ましくは10〜30℃の範囲で、通常、30〜180秒間の範囲で適宜選択される。
さらに、必要に応じて、感放射線樹脂組成物に含有させた感放射線化合物(B)を失活させるために、電子部品全面に、活性放射線を照射することもできる。活性放射線の照射には、上記潜像パターンの形成に例示した方法を利用できる。照射と同時に、又は照射後に樹脂膜を加熱してもよい。加熱方法としては、例えば、電子部品をホットプレートやオーブン内で加熱する方法が挙げられる。温度は、通常、80〜300℃、好ましくは100〜200℃の範囲である。
このようにして、パターン化された樹脂膜を備える電子部品は製造することができる。
なお、各特性の定義及び評価方法は、以下のとおりである。
各実施例及び各比較例において作製した感放射線樹脂組成物を、基板上に塗布した際における塗膜の外観を光学顕微鏡により観察して、以下の基準で評価した。なお、塗膜の外観が良好であると、塗膜と下地の基板との密着性が均一であると評価でき、一方、塗膜の外観に劣ると、塗布による方法のみならず、スピンコート等の他の方法にて樹脂膜を形成した場合においても、各種特性の評価を行うことができるような樹脂膜を得ることができないものと評価できる。
○:下記の評価「×」において例示したような現象が確認されず、塗膜外観が良好であった。
×:塗膜が白く濁る、塗膜に気泡跡が残る、塗膜に放射状の筋が残る、膜厚が均一でない等の塗膜外観が損なわれていたものであった。
スパッタリング装置を用いて、50nm厚のチタン膜上に、銅を100nmの膜厚で形成したシリコンウエハ上に、各実施例及び各比較例において作製した感放射線樹脂組成物をスピンコートした後、ホットプレートを用いて120℃で2分間プリベークして、樹脂膜を形成した。次いで、窒素中において230℃で1時間加熱することにより、3μm厚の樹脂膜が形成された樹脂膜付きシリコンウエハを得た。そして、得られた樹脂膜付きシリコンウエハを用いて、以下に説明する表面−界面切削法(SAICAS法)により、形成された樹脂膜の、銅に対する密着性の評価を行った。
○:剥離強度Pが100N/m以上
△:剥離強度Pが100N/m以上、70N/m未満
×:剥離強度Pが70N/m未満
シリコンウエハ上に、各実施例及び各比較例において作製した樹脂組成物をスピンコートしたのち、ホットプレートを用いて120℃で2分間加熱乾燥し、次いで、窒素雰囲気下、230℃で1分間の条件で硬化させることで、樹脂膜を形成することで、評価用サンプルを得た。そして、得られた評価用サンプルを、テトラヒドロフラン中に、25℃で30分間浸漬し、浸漬前後の樹脂膜の厚みの変化率を測定することで、耐薬品性の評価を行った。なお、浸漬前後の樹脂膜の厚みの変化率は、「浸漬前後の樹脂膜の厚みの変化率(%)=(|浸漬後の樹脂膜の厚み−浸漬前の樹脂膜の厚み|/浸漬前の樹脂膜の厚み)×100」に従って算出した。また、耐薬品性は、以下の基準で評価した。
○:浸漬前後の樹脂膜の厚みの変化率が1%未満
△:浸漬前後の樹脂膜の厚みの変化率が1%以上、3%未満
×:浸漬前後の樹脂膜の厚みの変化率が3%以上
シリコンウエハ上に、各実施例及び各比較例において作製した感放射線樹脂組成物をスピンコートした後、ホットプレートを用いて120℃で2分間加熱乾燥して、厚さ3μmの樹脂膜を形成した。次いで、g線(436nm)、h線(405nm)、及びi線(365nm)の波長の光を発する高圧水銀ランプを用い、400mJ/cm2にて露光を行った。そして、露光後の試料を23℃の2.38%テトラメチルアンモニウムヒドロキシド水溶液(アルカリ現像液)にて3分間浸漬した後、超純水で30秒間リンスを行い、現像後の試料の表面状態を目視にて観察し、以下の基準にて現像性の評価を行った。樹脂膜の不溶解、あるいは膨潤が発生しないものが、ポジ型の樹脂膜としての現像性に優れるものと判断することができる。
○:樹脂膜が完全に溶解していた。
×:樹脂膜が全く溶解していない、あるいは、膨潤していた。
<環状オレフィン重合体(A−1)の調製>
N−フェニル−ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド(NBPI)40モル%、及び4−ヒドロキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ−9−エン(TCDC)60モル%からなる単量体混合物100部、1,5−ヘキサジエン2.0部、(1,3−ジメシチルイミダゾリン−2−イリデン)(トリシクロヘキシルホスフィン)ベンジリデンルテニウムジクロリド(Org.Lett.,第1巻,953頁,1999年 に記載された方法で合成した)0.02部、及びジエチレングリコールエチルメチルエーテル200部を、窒素置換したガラス製耐圧反応器に仕込み、攪拌しつつ80℃にて4時間反応させて重合反応液を得た。
バインダー樹脂(A)として、合成例1で得られた環状オレフィン重合体(A−1)の重合体溶液291部(環状オレフィン重合体(A−1)として100部)、感放射線化合物(B)として、4,4’−[1−[4−[1−[4−ヒドロキシフェニル]−1−メチルエチル]フェニル]エチリデン]ビスフェノール(1モル)と1,2−ナフトキノンジアジド−5−スルホン酸クロライド(2.5モル)との縮合物)35部、エポキシ系架橋剤(C)として、エポキシ化ブタンテトラカルボン酸テトラキス(3−シクロヘキセニルメチル)修飾ε−カプロラクトン(商品名「エポリードGT401」、ダイセル化学工業社製、脂肪族環状4官能性のエポキシ樹脂、エポキシ当量:220、常温で液状)30部、ビスフェノール型ノボラック樹脂(D)として、ビスフェノールA型ノボラック樹脂(商品名「PAPS−BPAN」、旭有機材工業社製、重量平均分子量(Mw):940、数平均分子量(Mn):670、分子量分布(Mw/Mn):1.4、軟化点:124℃)20部、及び、溶剤として、ジエチレングリコールエチルメチルエーテル160部を混合し、溶解させた後、孔径0.45μmのポリテトラフルオロエチレン製フィルターでろ過して感放射線樹脂組成物を調製した。
ビスフェノールA型ノボラック樹脂(商品名「PAPS−BPAN」、旭有機材工業社製)の配合量を20部から60部に変更した以外は、実施例1と同様にして、感放射線樹脂組成物を調製し、同様に測定・評価を行った。結果を表1に示す。
エポキシ化ブタンテトラカルボン酸テトラキス(3−シクロヘキセニルメチル)修飾ε−カプロラクトン(商品名「エポリードGT401」、ダイセル化学工業社製)30部に代えて、ビスフェノールF型エポキシ化合物(商品名「jER YL983U」、三菱化学社製、2官能のエポキシ化合物、エポキシ当量:170、軟化点:常温で液状)23部を使用するとともに、ビスフェノールA型ノボラック樹脂(商品名「PAPS−BPAN」、旭有機材工業社製)の配合量を20部から40部に変更した以外は、実施例1と同様にして、感放射線樹脂組成物を調製し、同様に測定・評価を行った。結果を表1に示す。
ビスフェノールA型ノボラック樹脂(商品名「PAPS−BPAN」、旭有機材工業社製)を配合しなかった以外は、実施例1と同様にして、感放射線樹脂組成物を調製し、同様に測定・評価を行った。結果を表1に示す。
ビスフェノールA型ノボラック樹脂(商品名「PAPS−BPAN」、旭有機材工業社製)40部に代えて、フェノールノボラック樹脂(商品名「EPR5010G」、旭有機材工業社製、重量平均分子量(Mw):9500)60部を使用した以外は、実施例3と同様にして、感放射線樹脂組成物を調製し、同様に測定・評価を行った。結果を表1に示す。
ビスフェノールA型ノボラック樹脂(商品名「PAPS−BPAN」、旭有機材工業社製)20部に代えて、ビフェニルアラルキル樹脂(商品名「MEH−7851−4H」、明和化成社製、重量平均分子量(Mw):9900)60部を使用した以外は、実施例1と同様にして、感放射線樹脂組成物を調製し、同様に測定・評価を行った。結果を表1に示す。
エポキシ化ブタンテトラカルボン酸テトラキス(3−シクロヘキセニルメチル)修飾ε−カプロラクトン(商品名「エポリードGT401」、ダイセル化学工業社製)30部に代えて、グリシジルエーテル型エポキシ化合物(商品名「エピクロンHP7200HH」、DIC社製、多官能のエポキシ化合物、エポキシ当量:280、軟化点:92℃)38部を使用するとともに、ビスフェノールA型ノボラック樹脂(商品名「PAPS−BPAN」、旭有機材工業社製)の配合量を20部から40部に変更した以外は、実施例1と同様にして、感放射線樹脂組成物を調製し、同様に測定・評価を行った。結果を表1に示す。
ビスフェノール型ノボラック樹脂(D)の代わりに、高分子量フェノールノボラック樹脂を使用した場合には、感放射線樹脂組成物中において、各成分の混合が不十分となり、そのため、塗膜とした場合に白濁が発生してしまい(外観不良)、各種特性の評価を行うことができるような樹脂膜を得ることができなかった(比較例2)。
また、ビスフェノール型ノボラック樹脂(D)の代わりに、ビフェニルアラルキル樹脂を使用した場合には、得られる樹脂膜は、金属層(銅)に対する密着性に劣り、さらには、アルカリ可溶性を示さず、現像性に劣るものであった(比較例3)。
さらに、軟化点が30℃以下であり、かつ、4官能以下であるエポキシ系架橋剤(C)の代わりに、軟化点が30℃超であるエポキシ化合物を使用した場合には、得られる樹脂膜は、金属層(銅)に対する密着性及び耐薬品性に劣り、さらには、アルカリ可溶性を示さず、現像性に劣るものであった(比較例4)。
Claims (3)
- バインダー樹脂(A)、感放射線化合物(B)、軟化点が30℃以下であり、かつ、4官能以下であるエポキシ系架橋剤(C)、及びビスフェノール型ノボラック樹脂(D)を含有し、
前記バインダー樹脂(A)が、カルボキシル基を含有する環状オレフィン重合体であり、
前記ビスフェノール型ノボラック樹脂(D)の含有量が、前記バインダー樹脂(A)100重量部に対して、15〜50重量部である感放射線樹脂組成物。 - 前記ビスフェノール型ノボラック樹脂(D)の重量平均分子量が500〜2,000である請求項1に記載の感放射線樹脂組成物。
- 請求項1または2に記載の感放射線樹脂組成物からなる樹脂膜を備える電子部品。
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