JP6182398B2 - 透明絶縁膜形成用組成物 - Google Patents
透明絶縁膜形成用組成物 Download PDFInfo
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- JP6182398B2 JP6182398B2 JP2013182588A JP2013182588A JP6182398B2 JP 6182398 B2 JP6182398 B2 JP 6182398B2 JP 2013182588 A JP2013182588 A JP 2013182588A JP 2013182588 A JP2013182588 A JP 2013182588A JP 6182398 B2 JP6182398 B2 JP 6182398B2
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- QKFJVDSYTSWPII-UHFFFAOYSA-N tris(4-methylphenyl)sulfanium Chemical compound C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 QKFJVDSYTSWPII-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006679 α-naphthoxycarbonyl group Chemical group 0.000 description 1
- 125000006680 β-naphthoxycarbonyl group Chemical group 0.000 description 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
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- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Formation Of Insulating Films (AREA)
- Organic Insulating Materials (AREA)
Description
本発明の透明絶縁膜形成用組成物(以下、膜形成用組成物とも記す)は、基底状態において4f軌道又は5d軌道に電子を収容する元素の、単体、酸化物、キレート化合物、塩、及び合金からなる群より選択される1種以上を(A)充填材として含む。また、本発明の透明絶縁膜形成用組成物は、厚さ2μmの試料を用いて測定を行う場合に波長400nmの光の透過率が90%以上である膜を形成可能なものである。
(A)充填材は、基底状態において4f軌道又は5d軌道に電子を収容する元素の、単体、酸化物、キレート化合物、塩、及び合金からなる群より選択される。基底状態において4f軌道又は5d軌道に電子を収容する元素とは、原子番号57〜86の元素である。このような元素は、具体的には、La(57)、Ce(58)、Pr(59)、Nd(60)、Pm(61)、Sm(62)、Eu(63)、Gd(64)、Tb(65)、Dy(66)、Ho(67)、Er(68)、Tm(69)、Yb(70)、Lu(71)、Hf(72)、Ta(73)、W(74)、Re(75)、Os(76)、Ir(77)、Pt(78)、Au(79)、Hg(80)、Tl(81)、Pb(82)、Bi(83)、Po(84)、At(85)、及びRn(86)である。括弧内の数は、各元素の原子番号を表す。これらの元素は、電子密度が高い。このため、これらの元素の、単体、酸化物、キレート化合物、塩、及び合金は誘電率が高い。また、このような元素の、単体、酸化物、キレート化合物、塩、及び合金は、膜形成用組成物を用いて形成される膜において、膜を構成するマトリックス中に分散された状態で、可視光の透過を阻害しない。このため、上述の(A)充填材を含む膜形成用組成物を用いて形成される透明絶縁膜は、誘電率が高く、透明性に優れる。
以下、(A)充填材、(B1)脂環式エポキシ基を有する化合物、及び(C)酸発生剤を含む膜形成用組成物に含まれる成分について説明する。なお、(A)充填材については、説明を割愛する。
(B1)脂環式エポキシ基を有する化合物を(C)酸発生剤から発生する酸の作用で硬化させると、透明性の高い硬化物が得られる。(B1)脂環式エポキシ基を有する化合物の硬化物中に前述の特定の(A)充填材を分散させると、透明性を損なうことなく硬化物の誘電率を高めることができる。このため、(A)充填材、(B1)脂環式エポキシ基を有する化合物、及び(C)酸発生剤を含む膜形成用組成物を用いると、透明性に優れ、誘電率の高い、透明絶縁膜を形成することができる。(B1)脂環式エポキシ化合物の分子量は、100〜800が好ましく、500以下がより好ましい。膜形成用組成性物の固形分中の(B1)脂環式エポキシ基を有する化合物の含有量と(C)酸発生剤の含有量との合計は、20〜99質量%が好ましく、30〜80質量%がより好ましく、40〜70質量%がさらに好ましい。
酸発生剤としては、活性光線又は放射線の照射により酸を発生する光酸発生剤、又は加熱により酸を発生する熱酸発生剤が好適に使用される。
以下、(A)充填材、(B2)樹脂を含む膜形成用組成物に含まれる成分について説明する。なお、(A)充填材については、説明を割愛する。
膜形成用組成物を用いて透明絶縁膜を製膜可能である必要があるため、樹脂を含む膜形成用組成物は、透明性と製膜性との観点から(B2)樹脂として、シリコーン樹脂、ポリアミドイミド、ポリイミド、ポリカーボネート、ポリエーテル、ポリチオエーテル、及びエチレン性不飽和二重結合を有する単量体の重合体からなる群より選択される1種以上が使用される。膜形成用組成性物の固形分中の(B2)樹脂の含有量は、20〜99質量%が好ましく、30〜80質量%がより好ましく、40〜70質量%がさらに好ましい。
(A)充填材と、(B2)樹脂とを含む膜形成用組成物に、(D)光重合性化合物と、(E)光重合開始剤とを含有させ、膜形成用組成物に感光性を付与することもできる。特に、(B2)樹脂がアルカリ可溶性の樹脂である場合、(A)充填材と、(B2)樹脂と、(D)光重合性化合物と、(E)光重合開始剤とを、透明絶縁膜を形成する対象となる基材に塗布した後に、塗布膜に対して、選択的露光と、テトラメチルアンモニウムヒドロキシドの水溶液のようなアルカリ現像液とを行うことで、パターニングされた透明絶縁膜を形成することができる。
(D)光重合性化合物とともに使用される(E)光重合開始剤は、従来から(D)光重合性化合物用の重合開始剤として使用されている種々の光重合開始剤を用いることができる。
以下、(E)光重合開始剤として好適な下記式(E1)で表されるオキシムエステル化合物について説明する。
以下(E)光重合開始剤として好適な、下記式(E2)で表されるオキシムエステル化合物について説明する。
(A)充填材と、(B2)樹脂とを含む膜形成用組成物は、塗布性の改善や、粘度調整のため、(S)有機溶剤(以下、「(S)成分」ともいう。)を含んでいてもよい。
(A)充填材と(B2)樹脂とを含む膜形成用組成物には、必要に応じて、界面活性剤、密着性向上剤、熱重合禁止剤、消泡剤等の添加剤を含有させることができる。いずれの添加剤も、従来公知のものを用いることができる。界面活性剤としては、アニオン系、カチオン系、ノニオン系等の化合物が挙げられ、密着性向上剤としては、従来公知のシランカップリング剤が挙げられ、熱重合禁止剤としては、ヒドロキノン、ヒドロキノンモノエチルエーテル等が挙げられ、消泡剤としては、シリコーン系、フッ素系化合物等が挙げられる。
透明絶縁膜形成用組成物の製造方法は特に限定されない。透明絶縁膜形成用組成物は、以上説明した、各成分を、公知の混合装置により均一に混合することにより製造できる。透明絶縁膜形成用組成物が、室温で固体であったり高粘度のゲルであったりする場合には、ニーダーや、二本ロール、及び三本ロールのような溶融混練装置を用いて、各成分を混合してもよい。
以上説明した透明絶縁膜形成用組成物を用いて、透明絶縁膜を形成する対象となる基材の表面に膜形成症組成物の膜を形成した後、膜形成用組成物の組成に応じて、形成された膜を処理することで、透明絶縁膜を形成することができる。膜形成用組成物の膜を基材の表面に形成する方法は、特に限定されない。膜形成用組成物が固体や高粘度のゲルである場合、所定量の膜形成用組成物を基材上に供給した後、膜形成用組成物を加熱しながらプレスする方法で、膜形成用組成物の膜を形成することができる。膜形成用組成物が液体である場合、例えば、ロールコーター、リバースコーター、バーコーター、スリットコーター等の接触転写型塗布装置や、スピンナー(回転式塗布装置)、カーテンフローコーター等の非接触型塗布装置を用いる方法により、膜形成用組成物の膜を形成することができる。
各実施例及び比較例の膜形成用組成物をガラス基板上にスピンコートした。次いで、ガラス基板上の膜形成用組成物の塗布膜をホットプレート上で80℃120秒加熱乾燥させた後、ブロードバンド光で塗布膜を露光して、膜厚2μmの硬化膜を形成させた。
分光測定器(MCPD−3000、大塚電子株式会社製)を用いて、測定波長範囲400nmで、得られた透明絶縁膜の透過率の測定を行った。
透過率について、95%以上を◎と判定し、90%以上95%未満を○と判定し、90%未満を×と判定した
Siウェハー(結晶面方向(100)N型、抵抗率0.01〜0.03Ω・cm、信越半導体株式会社製)を基板として用いた。各実施例及び比較例の膜形成用組成物を基板にスピンコートして塗布膜を形成し、透過率の測定方法と同様にして塗布膜を硬化させて、膜厚0.9μmの透明絶縁膜を形成した。形成された透明絶縁膜の比誘電率を、周波数0.1MHzの条件下で、誘電率測定装置(SSM−495、日本セミラボ株式会社製)を用いて測定した。
誘電率(比誘電率)について、10以上を◎と判定し、7以上10未満を○と判定し、7未満を×と判定した。
透過率の測定と同様にして形成された透明絶縁膜について、JIS K5600に準じて、8H鉛筆を用いて、荷重1kg、45度法、測定距離30mmの条件で、5回の硬度試験を行い、荷重印加後の傷の有無を観察した。
5回の試験中3回以上傷が付かなかった場合を○と判定し、3回以上傷が付いた場合を×と判定した。
実施例9〜16、及び比較例4〜6では、下記式で表される構造単位I〜IVからなる樹脂を用いた。下記式において、各構成単位のモル比率(I/II/III/IV)は、14/11/40/35である。実施例9〜16、及び比較例4〜6で用いた樹脂の質量平均分子量は12,000である。
各実施例及び比較例の膜形成用組成物をガラス基板上にスピンコートした。次いで、ガラス基板上の膜形成用組成物の塗布膜をホットプレート上で80℃300秒加熱乾燥させた後、ミラープロジェクションアライナー(製品名:TME−150RTO、株式会社トプコン製)を使用し、露光量20mJ/cm2で塗布膜を露光して、膜厚2μmの硬化膜を形成させた。
分光測定器(MCPD−3000、大塚電子株式会社製)を用いて、測定波長範囲400nmで、得られた透明絶縁膜の透過率の測定を行った。
透過率について、95%以上を◎と判定し、90%以上95%未満を○と判定し、90%未満を×と判定した
Siウェハー(結晶面方向(100)N型、抵抗率0.01〜0.03Ω・cm、信越半導体株式会社製)を基板として用いた。各実施例及び比較例の膜形成用組成物を基板にスピンコートして塗布膜を形成し、透過率の測定方法と同様にして塗布膜を硬化させて、膜厚0.9μmの透明絶縁膜を形成した。形成された透明絶縁膜の比誘電率を、周波数0.1MHzの条件下で、誘電率測定装置(SSM−495、日本セミラボ株式会社製)を用いて測定した。
誘電率(比誘電率)について、10以上を◎と判定し、7以上10未満を○と判定し、7未満を×と判定した。
透過率の測定と同様にして形成された透明絶縁膜について、JIS K5600に準じて、8H鉛筆を用いて、荷重1kg、45度法、測定距離30mmの条件で、5回の硬度試験を行い、荷重印加後の傷の有無を観察した。
5回の試験中3回以上傷が付かなかった場合を○と判定し、3回以上傷が付いた場合を×と判定した。
Siウェハー(結晶面方向(100)N型、抵抗率0.01〜0.03Ω・cm、信越半導体株式会社製)の表面に、誘電率の測定と同様の方法で、各実施例及び比較例の膜形成用組成物を用いて膜厚0.9μmの透明絶縁膜を形成した。形成された絶縁膜に対して、30ボルトの電圧を印加してリーク電流を計測した。リーク電流値が1.0×10−9A/cm2以下である場合を◎と判定し、リーク電流値が1.0×10−9A/cm2超1.0×10−7A/cm2以下である場合を○と判定し、リーク電流値が1.0×10−7A/cm2超1.0×10−6A/cm2以下である場合を△と判定した。
膜形成用組成物の調製に用いた樹脂の構造単位I〜IVの比率を、実施例9で用いた樹脂についての比率から、下記表5に記載の比率に変更することの他は、実施例9と同様にして、実施例17〜19の膜形成用組成物を調製した。実施例17〜19の膜形成用組成物を用いて形成された透明絶縁膜の、透過率、誘電率、鉛筆硬度、及びリーク電流について、実施例9と同様の方法で評価した。これらの評価結果を表5に記す。
Claims (11)
- 基底状態において4f軌道又は5d軌道に電子を収容する元素の酸化物を(A)充填材として含み、(B1)脂環式エポキシ基を有する化合物及び(B2)樹脂よりなる群から選択される少なくともいずれかを含み、厚さ2μmの試料を用いて測定を行う場合に波長400nmの光の透過率が90%以上である膜を形成できる、透明絶縁膜形成用組成物であって、
前記酸化物の含有量が、前記組成物中の固形分の質量に対して1〜80質量%であり、
前記(B2)樹脂が、シリコーン樹脂、ポリアミドイミド、ポリイミド、ポリカーボネート、ポリエーテル、ポリチオエーテル、及びエチレン性不飽和二重結合を有する単量体の重合体からなる群より選択される少なくとも1種である、透明絶縁膜形成用組成物。 - 前記酸化物の一次粒子径が50μm以下である、請求項1に記載の透明絶縁膜形成用組成物。
- 前記(A)充填材に含まれる前記元素が、5d軌道に収容される電子数が5d軌道が半閉殻となる電子数以下である元素か、4f軌道に収容される電子数が4f軌道が半閉殻となる電子数以下である元素である、請求項1又は2に記載の透明絶縁膜形成用組成物。
- 前記(A)充填材、(B1)脂環式エポキシ基を有する化合物、及び(C)酸発生剤を含む、請求項1〜3のいずれか1項に記載の透明絶縁膜形成用組成物。
- 前記(B2)樹脂が、(メタ)アクリル酸及び(メタ)アクリル酸エステルから選択される1種以上を含む単量体の重合体である、請求項1〜5のいずれか1項に記載の透明絶縁膜形成用組成物。
- 前記(B2)樹脂が、(メタ)アクリル酸及び(メタ)アクリル酸エステルから選択される1種以上を含む単量体の重合体であり、エポキシ基を有する基を有する(メタ)アクリル酸エステルに由来する単位を含む樹脂である、請求項6に記載の透明絶縁膜形成用組成物。
- 前記(B2)樹脂が、(メタ)アクリル酸及び(メタ)アクリル酸エステルから選択される1種以上を含む単量体の重合体であり、脂環式骨格を有する基を有する(メタ)アクリル酸エステルに由来する単位を含む樹脂である、請求項6に記載の透明絶縁膜形成用組成物。
- 前記(B2)樹脂が、(メタ)アクリル酸及び(メタ)アクリル酸エステルから選択される1種以上を含む単量体の重合体であり、(メタ)アクリル酸に由来する単位と、脂環式炭化水素基を有する(メタ)アクリル酸エステルに由来する単位と、脂環式エポキシ基を有する基を有する(メタ)アクリル酸エステルに由来する単位とを含む樹脂である、請求項7又は8に記載の透明絶縁膜形成用組成物。
- 請求項1〜9のいずれか1項に記載の透明絶縁膜形成用組成物を用いて得られる透明絶縁膜。
- 請求項10に記載の透明絶縁膜を備える、表示装置。
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