ポリマーナノコンポジットII― 飛躍する高機能ナノテク材料とその評価・用途の動向 ―2007年9月発行
定価104,500円（消費税込み）
住ベリサーチの調査研究レポート
住ベリサーチ株式会社
技術調査部〒140-0002 品川区東品川2-5-8
天王洲パークサイドビル16F
TEL 03-5462-7036
FAX 03-5462-7040

目

次はじめに ········································································································································· 1
第 １章 ポリマーナノコンポジット材 料 用 ナノ素 材 ······························································ 2
１.１ ポリマー ······························································································································ 2
1.1.1 リビングラジカル重 合 、立 体 特 異 性 リビングラジカル重 合 によるポリマー ····················· 2
1.1.2 リビングアニオン重 合 によるポリマー ············································································· 2
1.1.3 リビングカチオン重 合 によるポリマー ············································································· 3
1.1.4 リビング配 位 重 合 によるポリマー ·················································································· 4
1.1.5 開 環 メタセシス重 合 によるポリマー ··············································································· 4
1.1.6 連 鎖 重 縮 合 によるポリマー ··························································································· 4
1.1.7 高 次 制 御 重 縮 合 によるポリマー ··················································································· 5
1.1.8 精 密 高 分 子 技 術 プロジェクト ························································································ 5
１.２ 金 属 、セラミックスのナノ粒 子 素 材 ····················································································· 6
1.2.1 ナノ粒 子 の合 成 と機 能 化 技 術 プロジェクト ···································································· 6
1.2.2 大 気 圧 プラズマによるジルコニアナノ粒 子 ···································································· 8
1.2.3 ジルコニアナノ粒 子 の分 散 液 ························································································ 8
1.2.4 高 周 波 熱 プラズマによる金 属 ナノ粒 子 ········································································· 9
1.2.5 AlN球 状 複 合 粒 子 ······································································································ 10
１.３ カーボン系 ナノ素 材 ·········································································································· 10
1.3.1 単 層 CNT ····················································································································· 10
1.3.2 多 層 CNT ····················································································································· 11
1.3.3 フラーレン ···················································································································· 11
1.3.4 カーボン系 ナノ粒 子 のトピックス ·················································································· 12
1.3.5 カーボンナノファイバー ································································································ 13
１.４ シリカ系 ナノ粒 子 ·············································································································· 13
1.4.1 コロイダルシリカ ·········································································································· 13
1.4.2 シルセスキオキサン ····································································································· 14
1.4.3 多 孔 質 シリカ ··············································································································· 14

第 ２章 ポリマーコンポジット材 料 ························································································· 16
２.１ ポリマー／ポリマー系 ナノコンポジット材 料 ······································································· 16
2.1.1 コポリマー ···················································································································· 16
2.1.1.1 ラジカルリビング重 合 によるコポリマー ·································································· 16
2.1.1.2 アニオンリビング重 合 によるコポリマー ·································································· 17
2.1.1.3 アニオンリビング重 合 による共 重 合 用 モノマー ····················································· 18
2.1.1.4 開 環 メタセシス重 合 によるコポリマー ···································································· 19
2.1.1.5 連 鎖 重 縮 合 によるコポリマー ················································································ 19
2.1.1.6 プラズマ重 合 によるコポリマー＜参 考 ＞ ······························································· 20－i－2.1.1.7 オレフィン系 コポリマー＜参 考 ＞ ··········································································· 21
2.1.1.8 温 度 応 答 型 コポリマー ·························································································· 22
2.1.1.9 ロッドコイル型 コポリマー ······················································································· 25
2.1.1.10 両 親 媒 性 コポリマー ···························································································· 26
2.1.2 グラフト重 合 ················································································································ 28
2.1.2.1 塩 化 ビニルのグラフト重 合 ···················································································· 28
2.1.2.2 ポリアミドのグラフト重 合 ······················································································· 28
2.1.2.3 リビングラジカル重 合 によるグラフト重 合 ······························································ 29
2.1.2.4 リビングラジカル重 合 による高 分 子 微 粒 子 へのグラフト ······································· 30
2.1.2.5 フッ素 系 樹 脂 への光 グラフト重 合 ········································································· 31
2.1.2.6 フッ素 系 樹 脂 への放 射 線 グラフト重 合 ································································· 31
2.1.2.7 放 射 線 グラフト重 合 で化 学 修 飾 したポリシラン ····················································· 32
2.1.3 エラストマー ················································································································· 33
2.1.3.1 PVDF／アクリルゴム系 ························································································· 33
2.1.3.2 架 橋 型 エラストマー ······························································································· 34
2.1.3.3 1,3-シクロヘキサジエン(CHD)／ブタジエンのトリブロック共 重 合 体 ······················ 34
2.1.3.4 低 立 体 規 則 性 ポリプロピレン ················································································ 36
2.1.3.5 ポリウレタン－ロタキサンエラストマー ··································································· 36
2.1.3.6 ポリカプロラクトン／アラミド系 ··············································································· 37
2.1.3.7 ナイロン6(PA6)／変 性 ブチルゴム(BIMS)共 重 合 体 ·············································· 38
2.1.4 ポリマーアロイ ············································································································· 39
2.1.4.1 エポキシアロイ ······································································································ 39
2.1.4.2 PPEのアロイ ·········································································································· 41
2.1.4.3 PBTのアロイ ········································································································· 42
2.1.4.4 ポリベンゾオキサジン／ポリイミドアロイ ································································ 43
2.1.4.5 ポリマーアロイ用 相 溶 化 剤 ··················································································· 44
2.1.4.6 ポリマーアロイのトピックス ···················································································· 45
2.1.4.7 ポリマーアロイのシミュレーションソフト ·································································· 46
2.1.5 結 晶 性 制 御 ················································································································ 47
2.1.5.1 結 晶 性 －結 晶 性 重 合 体 の結 晶 化 挙 動 （１） ························································· 47
2.1.5.2 結 晶 性 －非 晶 性 重 合 体 の結 晶 化 挙 動 （２） ························································· 48
2.1.5.3 結 晶 性 および他 の要 因 による構 造 制 御 ······························································· 48
2.1.5.4 配 向 による結 晶 性 制 御 ························································································ 50
2.1.6 ナノ粒 子 、ナノシート ···································································································· 51
2.1.6.1 コポリマーナノ粒 子 ································································································ 51
2.1.6.2 コアシェル型 ナノ粒 子 ···························································································· 52
2.1.6.3 ナノカプセル ·········································································································· 54
2.1.6.4 ナノ粒 子 の集 積 ···································································································· 56
2.1.6.5 ナノ多 層 シート ······································································································ 57
2.1.7 DNA／ポリマー ············································································································ 58－ii－

2.1.8 ゲル ····························································································································· 61
２.２ ポリマー／金 属 、金 属 化 合 物 粒 子 系 ナノコンポジット材 料 ·············································· 64
2.2.1 高 分 子 ／金 属 錯 体 蒸 気 （乾 式 ） ················································································· 64
2.2.2 高 分 子 ゲル／金 属 粒 子 （湿 式 ） ·················································································· 65
2.2.3 水 溶 性 高 分 子 ／金 属 イオン（湿 式 ） ··········································································· 66
2.2.4 ターチオフェンチオレート／金 属 ·················································································· 66
2.2.5 デンドリマー／金 属 ····································································································· 67
2.2.6 ポリイミド／金 属 ナノ粒 子 ···························································································· 68
2.2.7 CR39／銀 ナノ粒 子 ····································································································· 69
2.2.8 層 状 の結 晶 性 高 分 子 ／金 属 ····················································································· 69
2.2.9 高 分 子 ナノシート／金 ナノ粒 子 ··················································································· 70
2.2.10 刺 激 応 答 性 粒 子 ／金 属 ··························································································· 71
2.2.11 両 親 媒 性 高 分 子 ／金 属 、金 属 錯 体 ········································································· 71
2.2.12 DNA／金 属 ··············································································································· 72
2.2.13 延 伸 PI／銀 ··············································································································· 72
2.2.14 配 位 高 分 子 ／金 属 錯 体 系 ······················································································· 73
2.2.15 核 に金 属 錯 体 を持 つ星 型 ポリマー ··········································································· 74
2.2.16 表 面 積 層 型 ナノ金 属 錯 体 ························································································ 74
2.2.17 環 状 ヘキサペプチド／金 属 錯 体 ··············································································· 74
2.2.18 高 分 子 微 粒 子 ／金 属 錯 体 系 ··················································································· 75
2.2.19 ポリアミド／銀 ／ヨウ素 ····························································································· 75
2.2.20 樹 脂 ／金 属 ナノ配 線 ································································································ 75
２.３ ポリマー／カーボン系 ······································································································· 77
2.3.1 ポリマー／カーボンブラック ························································································· 77
2.3.1.1 ゴム／カーボンブラック ·························································································· 77
2.3.1.2 ポリウレタン／カーボンブラック ············································································· 77
2.3.1.3 ポリエチレン／カーボンブラック ············································································· 78
2.3.1.4 ポリオレフィン／カーボンブラック ··········································································· 78
2.3.1.5 PMMA／PEO／カーボンブラック ··········································································· 81
2.3.2 ポリマー／カーボンナノチューブ ·················································································· 81
2.3.2.1 導 電 性 高 分 子 ／CNT ··························································································· 82
2.3.2.2 イオン性 液 体 ／CNT ····························································································· 83
2.3.2.3 樹 脂 ／CNTコンポジット材 料 の量 産 状 況 ····························································· 84
2.3.2.4 透 明 樹 脂 ／CNT ··································································································· 84
2.3.2.5 樹 脂 ／CNT複 合 材 料 ··························································································· 85
2.3.2.6 ポリイミド／CNT ···································································································· 85
2.3.2.7 ゴム／CNT ············································································································ 86
2.3.2.8 ゴム／CNT系 補 強 メカニズム ················································································ 86
2.3.2.9 PC／CNT ·············································································································· 87
2.3.2.10 DNA／CNT ·········································································································· 88－iii－

2.3.2.11 ポリマー／CNT関 連 進 行 中 の研 究 ·································································· 88
2.3.3 ポリマー／カーボンナノホーン、カーボンナノポッド ······················································ 89
2.3.3.1 樹 脂 ／カーボンナノホーン ···················································································· 89
2.3.3.2 樹 脂 ／カーボンナノポッド ······················································································ 89
2.3.4 ポリマー／フラーレン ··································································································· 90
2.3.4.1 ポリメタクリル酸 フランエステル／フラーレン ·························································· 90
2.3.4.2 導 電 性 高 分 子 ／フラーレン ·················································································· 91
2.3.4.3 樹 脂 ／フラーレン複 合 体 ······················································································ 91
2.3.4.4 DNA／フラーレン ··································································································· 92
2.3.4.5 ホストゲスト錯 体 ··································································································· 92
2.3.4.6 アクリル系 樹 脂 ／フラーレン誘 導 体 ······································································ 93
2.3.4.7 フラーレン誘 導 体 ·································································································· 94
2.3.4.8 フラーレンポリマー＜参 考 ＞ ················································································· 95
2.3.5 樹 脂 ／カーボンナノファイバー、炭 素 繊 維 ·································································· 96
2.3.5.1 樹 脂 ／CNF複 合 材 料 ··························································································· 96
2.3.5.2 ポリウレタン／CNF ································································································ 96
2.3.5.3 不 飽 和 ポリエステル／CNF ··················································································· 97
2.3.5.4 エポキシ、ポリイミド／CNF ···················································································· 98
2.3.5.5 ポリプロピレン／CNF ····························································································· 99
2.3.5.6 フラン樹 脂 ／CNF ································································································ 100
2.3.5.7 エポキシ／CNF ··································································································· 100
２.４ ポリマー／無 機 系 ナノコンポジット材 料 ·········································································· 101
2.4.1 ポリマー／シリカ ········································································································ 101
2.4.1.1 エポキシ／シリカ微 粒 子 ····················································································· 101
2.4.1.2 フェノール／シリカ ······························································································· 103
2.4.1.3 アクリル系 ポリマー／シリカ ················································································· 104
2.4.1.4 ウレタン／シリカ ·································································································· 107
2.4.1.5 その他 ポリマー／シリカ ······················································································· 108
2.4.2 ポリマー／Si系 ハイブリッド材 料 ··············································································· 110
2.4.2.1 ポリマー／シルセスキオキサン ············································································ 110
2.4.2.2 ポリマー／その他 Si系 ハイブリッド材 料 ······························································ 113
2.4.2.2.1 エポキシ／Si系 ハイブリッド ··········································································· 113
2.4.2.2.2 フェノール／Si系 ハイブリッド ········································································· 115
2.4.2.2.3 ポリイミド／Si系 ハイブリッド ·········································································· 116
2.4.2.2.4 アクリル／Si系 ハイブリッド ············································································ 117
2.4.2.2.5 ウレタン／Si系 ハイブリッド ············································································ 119
2.4.2.2.6 エラストマー／Si系 ハイブリッド ······································································ 120
2.4.2.2.7 ヒドロキシプロピルセルロース／Si系 ハイブリッド ·········································· 121
2.4.3 ポリマー／クレイ ········································································································ 121
2.4.3.1 エポキシ／クレイ ································································································· 121－iv－

2.4.3.2 アクリル／クレイ ·································································································· 125
2.4.3.3 フェノール／クレイ ······························································································· 126
2.4.3.4 ポリオレフィン／クレイ ························································································· 127
2.4.3.5 熱 可 塑 性 樹 脂 ／クレイ ······················································································· 130
2.4.3.6 ハイドロゲル／クレイ ··························································································· 134
2.4.4 ポリマー／その他 の無 機 系 材 料 ·············································································· 135
2.4.4.1 ポリマー／アルミナ ······························································································ 135
2.4.4.2 ポリマー／酸 化 チタン ························································································· 137
2.4.4.3 ポリマー／ジルコン、チタン酸 バリウム、酸 化 セリウム ········································ 139
2.4.4.4 ポリマー／水 酸 化 マグネシウム、炭 酸 カルシウム ··············································· 142

第 ３章 コンポジット関 連 プロセス製 造 技 術 ···································································· 145
３.１ せん断 、圧 力 ·················································································································· 145
3.1.1 三 本 ロール ················································································································ 145
3.1.2 微 量 型 高 せん断 成 形 加 工 機 ··················································································· 145
3.1.3 押 出 機 ······················································································································ 146
3.1.3.1 ２軸 押 出 機 （１） ··································································································· 146
3.1.3.2 ２軸 押 出 機 （２） ··································································································· 147
3.1.3.3 ２軸 押 出 機 の改 造 ······························································································ 147
3.1.3.4 押 出 機 の開 発 状 況 ····························································································· 148
3.1.4 低 温 せん断 ··············································································································· 149
3.1.4.1 二 軸 押 出 機 による低 温 せん断 混 練 ··································································· 149
3.1.4.2 プレスによる固 相 せん断 混 練 ············································································· 150
3.1.4.3 混 練 機 による低 温 固 相 せん断 ··········································································· 150
3.1.5 混 練 機 ······················································································································ 151
３.２ リアクティブプロセッシング ······························································································ 152
3.2.1 ポリアミド系 ··············································································································· 152
3.2.2 ポリオレフィンの動 的 脱 架 橋 ／動 的 架 橋 ································································· 154
3.2.3 PPE／EGMA、四 軸 押 出 機 ······················································································· 155
3.2.4 ポリブチレンサクシネート／クレイ ·············································································· 155
3.2.5 鎖 延 長 剤 ／PET＜参 考 ＞ ························································································ 155
3.2.6 水 素 化 アクリロニトリル／ブタジエン共 重 合 体 ·························································· 156
3.2.7 PBT／反 応 性 ポリマー ······························································································ 156
3.2.8 リアクティブプロセッシング用 添 加 剤 ········································································· 157
３.３ 相 分 離 と自 己 組 織 化 ····································································································· 159
3.3.1 PEO／液 晶 性 ＰＭＡ ·································································································· 159
3.3.2 フィンガリング不 安 定 性 ···························································································· 161
3.3.3 自 己 組 織 化 アルキメデスタイリング ·········································································· 162
3.3.4 階 層 構 造 フィルム ····································································································· 163
3.3.5 相 分 離 構 造 からのパターン形 成 ··············································································· 164－v－

3.3.6 ミクロ相 分 離 による多 孔 性 材 料 ················································································ 166
3.3.7 光 重 合 誘 起 相 分 離 ·································································································· 166
3.3.8 ミクロ相 分 離 構 造 の光 制 御 ······················································································ 167
３.４ 電 場 、磁 場 の印 可 ·········································································································· 168
3.4.1 エポキシ／カーボンナノフィラーに電 場 ····································································· 168
3.4.2 アクリル系 ブロック共 重 合 体 に電 場 ·········································································· 168
3.4.3 スチレン系 ブロック共 重 合 体 に磁 場 ········································································· 169
3.4.4 液 晶 ／非 晶 ブロック共 重 合 体 に磁 場 ······································································· 169
3.4.5 アクリル系 ／有 機 結 晶 に磁 場 ·················································································· 170
3.4.6 ポリスチレン／CNTに磁 場 ························································································ 170
3.4.7 ポリスチレン微 粒 子 ／シリカ粒 子 の配 列 を磁 場 で ···················································· 171
3.4.8 アクリル系 樹 脂 ／酸 化 亜 鉛 に磁 場 ·········································································· 171
3.4.9 高 分 子 に高 磁 場 ＜参 考 ＞ ························································································ 172
３.５ 超 臨 界 利 用 ···················································································································· 172
3.5.1 各 種 樹 脂 のCO 2 による発 泡 ······················································································ 172
3.5.2 ポリスチレン系 ブレンドの超 臨 界 CO 2 発 泡 ································································ 173
3.5.3 PP／クレイナノコンポジットの超 臨 界 CO 2 発 泡 ·························································· 174
3.5.4 超 臨 界 CO 2 によるポリマーの表 面 処 理 ····································································· 174
3.5.5 超 臨 界 CO 2 と押 出 機 による熱 可 塑 性 樹 脂 の混 練 ···················································· 175
3.5.6 超 臨 界 CO 2 と有 機 溶 媒 の併 用 によるポリスチレン／CNT ········································· 175
3.5.7 ナノカプセルのプラスチック添 加 剤 ············································································ 176
3.5.8 超 臨 界 乾 燥 、超 臨 界 延 伸 による材 料 調 整 ＜参 考 ＞ ··············································· 176
3.5.9 超 臨 界 水 熱 合 成 法 による高 分 子 ／ナノ粒 子 系 材 料 ··············································· 177
３.６ プロセス装 置 ·················································································································· 177
3.6.1 マイクロリアクタ ········································································································· 177
3.6.2 湿 式 分 散 機 ·············································································································· 179
3.6.3 機 械 的 複 合 化 装 置 ·································································································· 179
3.6.4 気 相 化 学 的 手 法 のための装 置 ················································································ 180
3.6.5 エアロゾルデポジション法 （AD法 ）用 装 置 ＜参 考 ＞ ·················································· 180

第 ４章 ポリマーナノコンポジットの加 工 技 術 ·································································· 182
４.１ ポリマーナノコンポジットの微 細 加 工 ·············································································· 182
４.２ ポリマーナノコンポジットを鋳 型 とした材 料 の創 製 ·························································· 185
4.2.1 シリカ多 孔 質 体 ········································································································· 185
4.2.2 ブロックコポリマーを鋳 型 とするメソポーラスシリカの創 製 ········································ 186
4.2.3 ポリマーナノコンポジットの焼 成 による材 料 の創 製 ··················································· 187
４.３ ナノ加 工 装 置 ·················································································································· 187
4.3.1 熱 リソグラフィー応 用 ナノ加 工 装 置 ··········································································· 187
4.3.2 電 子 ビームリソグラフィによる三 次 元 ナノ加 工 ·························································· 188
4.3.3 レーザーマイクロナノ加 工 ························································································· 188－vi－

第 ５章 ポリマーナノコンポジットの表 面 、界 面 、薄 膜 ··················································· 189
５.１ 表 面 処 理 ························································································································ 189
5.1.1 無 機 ／樹 脂 コンポジットの表 面 処 理 に関 する問 題 点 ··············································· 189
5.1.2 無 機 ／樹 脂 コンポジットの表 面 処 理 剤 による処 理 効 果 の違 い ································ 189
5.1.3 樹 脂 の直 接 表 面 処 理 によるポリイミド／金 属 コンポジット材 料 ································ 190
5.1.4 樹 脂 ／セラミックス系 の表 面 処 理 例 ········································································· 191
5.1.5 有 機 化 処 理 無 機 材 料 によるナノコンポジットの例 ···················································· 191
5.1.6 新 しい手 法 による表 面 改 質 の例 ·············································································· 191
５.２ 界 面 ································································································································ 193
5.2.1 ポリペプチド系 LB膜 ·································································································· 193
５.３ 親 水 性 ・撥 水 性 材 料 ······································································································ 194
5.3.1 シリコーンアクリル共 重 合 体 薄 膜 ············································································· 194
5.3.2 アクリルシリコーン／シリカ複 合 材 料 ········································································ 194
5.3.3 フッ素 系 ブロック共 重 合 体 ························································································ 195
5.3.4 フッ素 系 高 分 子 ナノ粒 子 による表 面 処 理 ································································· 195
5.3.5 微 細 孔 による撥 水 性 発 現 ························································································ 196
５.４ 薄 膜 ································································································································ 196
5.4.1 アクリル／ジルコニア ナノ薄 膜 ················································································ 196
5.4.2 交 互 吸 着 法 ·············································································································· 197
5.4.3 アクリルアミド系 共 重 合 体 薄 膜 ················································································· 197
5.4.4 フッ素 化 ポリイミド薄 膜 ······························································································ 198
5.4.5 ポリジメチルシロキサン薄 膜 ····················································································· 198

第 ６章 ポリマーナノコンポジットのナノ計 測 技 術 ·························································· 200
６.１ TEM＋コンピュータトモグラフィー ···················································································· 200
6.1.1 TEMT ························································································································ 200
6.1.2 TEMTのナノコンポジット応 用 例 ················································································ 200
6.1.3 TEMT＋SCFシミュレーションの研 究 ········································································· 203
６.２ X線 CT ···························································································································· 204
6.2.1 ポリスチレン／ポリメチルメタクリレート系 （１） ··························································· 204
6.2.2 ポリスチレン／ポリメチルメタクリレート系 （２） ··························································· 205
６.３ NMR ································································································································ 205
６.４ ポリマー／無 機 コンポジットの高 輝 度 放 射 光 による計 測 技 術 ······································· 206
６.５ ポリマー材 料 の陽 電 子 消 滅 法 による計 測 技 術 ····························································· 207
６.６ 界 面 計 測 技 術 ················································································································ 208
6.6.1 電 子 分 光 結 像 法 による高 分 子 接 着 界 面 の計 測 ····················································· 208
6.6.2 SIMSによるポリエチレン／ポリアミド系 界 面 の計 測 ·················································· 209

第 ７章 ポリマーナノコンポジットのナノ性 能 評 価 技 術 ················································· 210－vii－

７.１ ナノ力 学 物 性 ·················································································································· 210
7.1.1 その場 観 察 と試 験 ···································································································· 210
7.1.2 AFMによるナノレオロジー力 学 特 性 ·········································································· 211
７.２ トライボロジー ················································································································· 213
7.2.1 ナノトライボロジー ····································································································· 213
7.2.2 ナノコンポジット材 料 のトライボロジー評 価 ································································ 214
７.３ ガスバリア性 ··················································································································· 216
７.４ 難 燃 性 ···························································································································· 218
7.4.1 エポキシ／水 酸 化 マグネシウム系 の難 燃 性 評 価 ···················································· 218
7.4.2 熱 可 塑 性 樹 脂 ／金 属 水 和 物 系 ナノコンポジットの難 燃 性 評 価 ······························· 219

第 ８章 ポリマーナノコンポジットのエレクトロニクス、光 関 連 分 野 への応 用 ·········· 220
８.１ 低 誘 電 率 材 料 ················································································································ 220
8.1.1 プラズマ共 重 合 法 ····································································································· 220
8.1.2 多 孔 性 ポリイミド／ポリイミド系 ················································································· 221
８.２ 高 誘 電 率 材 料 ················································································································ 222
8.2.1 樹 脂 ／チタン酸 バリウム系 ······················································································· 222
８.３ 光 硬 化 材 料 ···················································································································· 224
8.3.1 F 2 レジスト向 けTFE-ノルボルネン誘 導 体 共 重 合 体 ·················································· 224
8.3.2 ArFレジスト向 けノルボルナンラクトン構 造 のアクリレート３種 の３元 共 重 合 体 ········· 224
8.3.3 低 誘 電 率 ネガ型 感 光 性 樹 脂 ···················································································· 225
8.3.4 光 酸 化 誘 起 重 縮 合 によるフラーレン－ポリイミドコンポジット ·································· 225
8.3.5 エン－チオール硬 化 型 ハイブリッド材 料 ··································································· 226
8.3.6 UVナノインプリント用 有 機 無 機 ナノコンポジット材 料 ················································· 226
8.3.7 共 重 合 ポリイミドのレジスト材 料 ··············································································· 226
８.４ 実 装 用 材 料 ···················································································································· 227
8.4.1 ダイボンディング材 料 フィルム ·················································································· 227
8.4.2 ナノペースト·············································································································

229

8.4.3 異 方 導 電 材 料 ACF ··································································································· 231
8.4.4 透 明 導 電 材 料 ·········································································································· 232
8.4.5 電 波 吸 収 材 ·············································································································· 232
8.4.5.1 エポキシ／ナノ金 属 金 属 酸 化 物 複 合 微 粒 子 ····················································· 232
8.4.5.2 電 磁 抑 制 シートの磁 性 粉 末 に対 するシラン処 理 とシート物 性 ＜参 考 ＞ ············ 233
8.4.6 実 装 基 板 用 接 着 剤 ·································································································· 233
8.4.6.1 フレキシブル銅 張 積 層 板 用 接 着 剤 ···································································· 233
8.4.6.2 実 装 基 板 用 接 着 剤 ···························································································· 234
８.５ 電 子 デバイス ·················································································································· 235
8.5.1 有 機 半 導 体 関 連 ······································································································ 235··········································································································

238··················································································································

239

8.5.2 電 子 ペーパー8.5.3 センサー

－viii－

8.5.4 光 電 変 換 素 子 ·········································································································· 240
8.5.5 導 電 性 材 料 ·············································································································· 241
8.5.6 ジブロックコポリマーテンプレートによるパターン形 成 利 用 ········································ 242
8.5.6.1 ハードディスク ···································································································· 242
8.5.6.2 自 己 組 織 化 法 パターンの半 導 体 への利 用 ························································ 242
８.６ 電 池 ································································································································ 243
8.6.1 燃 料 電 池 ·················································································································· 243
8.6.1.1 フッ素 樹 脂 系 電 解 質 （イオン交 換 膜 ）·······························································

243

8.6.1.2 PEFC燃 料 電 池 ··································································································· 244
8.6.1.3 DMFC燃 料 電 池 ·································································································· 246
8.6.1.4 燃 料 電 池 の電 極 ································································································· 247
8.6.2 リチウム二 次 電 池 ····································································································· 248
8.6.3 有 機 ラジカル電 池 ····································································································· 249
8.6.4 プラスチック太 陽 電 池 ······························································································· 249
8.6.4.1 プラスチック太 陽 電 池 （１） ················································································· 249
8.6.4.2 プラスチック太 陽 電 池 （２） ················································································· 250
8.6.4.3 プラスチック太 陽 電 池 （３）＜参 考 ＞ ·································································· 250
８.７ 一 般 電 気 絶 縁 材 料 用 途 向 けポリマーナノコンポジット ··················································· 251
8.7.1 電 力 機 器 用 絶 縁 材 料 ······························································································· 251
8.7.2 成 形 材 料 ·················································································································· 253
8.7.3 電 線 被 覆 材 料 ·········································································································· 254
8.7.3.1 ABSセンサーケーブル·······················································································

254

8.7.3.2 スイッチング電 源 トランス対 応 電 線 ····································································· 255
8.7.3.3 エナメル線 絶 縁 皮 膜 材 料 および電 子 回 路 用 フィルム想 定 材 料 ························ 255
８.８ 光 学 材 料 ························································································································ 257
8.8.1 透 明 材 料 ·················································································································· 257
8.8.1.1 PMMA／シリカ透 明 材 料 ····················································································· 257
8.8.1.2 アクリル系 光 散 乱 ポリマー導 光 体 ······································································ 258
8.8.1.3 アクリル系 透 明 材 料 ··························································································· 259
8.8.1.4 ポリイミド系 透 明 材 料 ·························································································· 260
8.8.1.5 ポリオレフィン系 透 明 材 料 ·················································································· 260
8.8.1.5.1 シクロオレフィンコポリマー···········································································

260

8.8.1.5.2 ノルボルネン系 コポリマー ············································································ 260
8.8.1.6 ポリマー／バイオナノファイバーコンポジット······················································

261

8.8.2 屈 折 率 制 御 材 料 ······································································································ 261
8.8.2.1 ゼロ配 向 複 屈 折 性 光 学 用 樹 脂 材 料 ································································· 261
8.8.2.2 屈 折 率 制 御 ········································································································ 262
8.8.2.3 高 屈 折 率 材 料 ···································································································· 262
8.8.2.3.1 PHEMA/TiO 2·······························································································

262

8.8.2.3.2 エポキシ/TiO 2 ······························································································ 263－ix－

8.8.2.4 低 屈 折 率 ナノ多 孔 性 薄 膜 ·················································································· 263
８.９ 光 回 路 用 材 料 ················································································································ 264
8.9.1 プラスチック光 ファイバー（POF）材 料 ········································································ 264
8.9.2 光 導 波 回 路 用 材 料 ·································································································· 265
8.9.2.1 アクリル／エポキシ系 ·························································································· 265
8.9.2.2 PMMA／シリカ系 ································································································· 265
8.9.2.3 ポリイミド共 重 合 体 ····························································································· 266
8.9.2.4 ポリイミド／CNT ·································································································· 267
8.9.2.5 ポリイミド共 重 合 体 ／銀 ナノ粒 子 ········································································ 267
8.9.3 フォトニック結 晶 、非 線 形 光 回 路 用 材 料 ·································································· 268
8.9.3.1 酸 化 セリウム／ポリマー系 ·················································································· 268
8.9.3.2 PMMA／アゾ色 素 ······························································································· 268
8.9.3.3 光 硬 化 樹 脂 ／金 属 錯 体 ····················································································· 268
8.9.3.4 フォトニック結 晶 関 連 材 料 ··················································································· 269
８.10 光 機 能 材 料 ·················································································································· 270
8.10.1 ポリイミド系 発 光 材 料 ······························································································ 270
8.10.2 光 応 答 性 材 料 ········································································································ 270
8.10.2.1 センサー、フォトニックペーパー ········································································ 270
8.10.2.2 構 造 色 ゲル·····································································································

8.10.2.3 光 応 答 性 コポリマー························································································

271
272

8.10.2.3.1 色 素 担 持 コポリマー ··················································································· 272
8.10.2.3.2 光 応 答 性 コンポジット ················································································· 273
8.10.3 光 学 活 性 ポリマー·································································································

273

8.10.4 応 力 発 光 材 料 ········································································································ 274
8.10.5 光 触 媒 材 料 ············································································································ 274
8.10.5.1 光 触 媒 性 微 粒 子 分 散 液 ··················································································· 275
8.10.5.2 光 触 媒 コート剤 ································································································· 275
8.10.5.3 光 触 媒 コート用 成 分 傾 斜 膜 ＜参 考 ＞ ····························································· 276

第 ９章 ポリマーナノコンポジットのバイオ、医 療 分 野 への応 用 ································· 277
９.１ 概 要 ································································································································ 277
9.1.1 ポリマーナノコンポジットのバイオ、医 療 分 野 への応 用 状 況 ····································· 278
9.1.2 実 用 化 に近 いポリマーナノコンポジットによるDDS開 発 研 究 例 ································ 279
9.1.2.1 高 分 子 ナノ粒 子 DDSの開 発 例 （１） ····································································· 279
9.1.2.2 高 分 子 ナノ粒 子 DDSの開 発 例 （２） ····································································· 280
9.1.2.3 高 分 子 ミセルDDSの開 発 例 ················································································ 280
9.1.2.4 バイオナノカプセルによるDDS＜参 考 ＞ ···························································· 281
9.1.2.5 高 分 子 ハイドロゲルDDSの開 発 例 ····································································· 282
9.1.3 ポリマーナノコンポジットによるDDS研 究 例 ······························································· 283
9.1.3.1 コアコロナ型 高 分 子 ナノスフェアDDS－x－································································

283

9.1.3.2 温 度 応 答 性 DDS ································································································· 284
9.1.3.3 リポソームによるDDS························································································

284

9.1.3.4 天 然 高 分 子 由 来 の高 分 子 材 料 によるDDS ······················································ 285
9.1.4 遺 伝 子 DDS ··············································································································· 285
９.２ 生 体 適 合 材 料 による医 療 デバイス ················································································ 287
9.2.1 抗 血 栓 性 材 料 ·········································································································· 287
9.2.1.1 ポリメタクリロイルオキシエチルホスホリルコリン(MPCポリマー)関 連 ················· 287
9.2.1.2 セグメント化 ポリウレタン ····················································································· 288
9.2.1.3 樹 脂 ／ナノカーボン ····························································································· 289
9.2.1.3.1 樹 脂 ／CNT ··································································································· 289
9.2.1.3.2 イオン性 液 体 ／ナノカーボン ········································································· 290
9.2.2 人 工 骨 ······················································································································ 291
9.2.2.1 コラーゲン／アパタイト系 （１） ·············································································· 291
9.2.2.2 コラーゲン／アパタイト系 （２） ·············································································· 292
9.2.2.3 PE／酸 化 チタン ·································································································· 293
９.３ 各 種 医 療 ・バイオ用 複 合 材 料 ························································································ 293
9.3.1 三 元 複 合 材 料 による経 皮 材 料 ················································································· 293
9.3.2 再 生 治 療 用 材 料 細 胞 培 養 、細 胞 シート ··································································· 295
9.3.3 バイオ用 ゲル ············································································································ 296
9.3.3.1 ナノゲル ·············································································································· 296
9.3.3.2 アクリルアミド型 ゲル ··························································································· 297
9.3.3.3 高 圧 法 によるコンポジットゲル ············································································ 297
9.3.3.4

PEG系 ナノゲル ································································································· 297

9.3.4 各 種 バイオ分 野 用 ナノコンポジット材 料 ···································································· 298
9.3.4.1 PEG系 トリブロック共 重 合 体 ··············································································· 298
9.3.4.2 ヘテロ2官 能 性 PEG ····························································································· 299
9.3.4.3 ナノファイバー系 ·································································································· 299
9.3.4.4 PEG／デンドリマー ······························································································ 300
９.４ DNA関 連 材 料 ················································································································ 300
9.4.1 DNA／シリカ ·············································································································· 300
9.4.2 DNA／金 属 ··············································································································· 301
9.4.2.1 金 属 含 有 DNAワイヤー ······················································································· 301
9.4.2.2 DNA／金 属 （２） ·································································································· 301
9.4.2.3 DNA／金 属 （３） ·································································································· 302
9.4.3 DNA／カーボンナノチューブ ······················································································ 302
9.4.3.1 DNA内 包 CNT ····································································································· 302
9.4.3.2 DNA／CNT系 ······································································································ 303
9.4.4 DNAチップ ················································································································· 303

第 10章 ポリマーナノコンポジットの構 造 材 料 への応 用 ·············································· 304－xi－

10.１ ポリマーナノコンポジット材 料 メーカーの開 発 例 ···························································· 304
10.２ 構 造 部 材 用 ポリマーナノコンポジットの研 究 例 ····························································· 305
10.2.1 ポリアミド／反 応 性 ポリオレフィン ············································································ 305
10.2.2 アクリル／シリカまたはポリカーボネート／シリカ ····················································· 305
10.2.3 樹 脂 ／ナノフィラー系 の特 性 ··················································································· 306
10.2.4 PC／PBT系 ············································································································ 307
10.2.5 PP／クレイ発 泡 構 造 体 ··························································································· 307
10.2.6 タイヤ向 けナノコンポジット材 料 ·············································································· 308
10.2.6.1 ゴム／カーボンブラック ······················································································ 308
10.2.6.2 シリカタイヤ用 変 性 溶 液 重 合 SBR／シリカ ······················································· 309
10.2.7 航 空 宇 宙 用 複 合 材 料 ····························································································· 310
10.2.7.1 ポリイミド／炭 素 繊 維 ························································································ 310
10.2.7.2 エポキシ／カーボンナノチューブ ······································································· 311
10.2.7.3 次 世 代 航 空 機 用 構 造 部 材 創 製 ・加 工 技 術 開 発 関 連 ＜参 考 ＞ ······················ 311

第 11章 ポリマーナノコンポジットの塗 料 、接 着 剤 、分 離 膜 への応 用 ······················ 313
11.１ 接 着 剤 ·························································································································· 313
11.1.1 半 導 体 装 置 用 接 着 剤 ····························································································· 313
11.1.2 自 動 車 用 接 着 剤 ···································································································· 313
11.1.3 導 電 性 接 着 剤 ········································································································ 314
11.1.4 解 体 性 接 着 剤 ········································································································ 314
11.1.5 生 体 用 接 着 剤 ········································································································ 314
11.２ 塗 料 、コーティング剤 ····································································································· 315
11.2.1 水 系 建 築 用 塗 料 ···································································································· 315
11.2.2 水 性 塗 料 （１） ·········································································································· 316
11.2.3 水 性 塗 料 （２） ·········································································································· 316
11.2.4 PP系 塗 料 ··············································································································· 317
11.2.5 各 種 樹 脂 コンポジット塗 料 ······················································································ 317
11.３ 分 離 膜 ·························································································································· 318
11.3.1 ポリイミド／Agを焼 成 した分 離 膜 ············································································ 318
11.3.2 ポリイミド／Pdを焼 成 した分 離 膜 ············································································ 318
11.3.3 ポリイミド／シリカ系 気 体 分 離 膜 ············································································· 319
11.3.4 ポリアリーレンエーテル系 イオン交 換 膜 ·································································· 319
11.3.5 PVA／オリゴシラン系 液 体 分 離 膜 ·········································································· 320

第 12章 省 エネルギー、リサイクル、環 境 対 応 ポリマーナノコンポジット ·················· 321
12.１ ポリマーナノコンポジット製 造 工 程 の省 エネルギー対 策 ··············································· 321
12.1.1 ポリプロピレン共 重 合 体 の製 造 工 程 ······································································ 321
12.1.2 PP／炭 素 繊 維 材 料 ································································································ 321
12.1.3 樹 脂 ／金 属 複 合 化 技 術 ························································································· 322－xii－

12.２ リサイクル関 連 ·············································································································· 323
12.2.1 汎 用 樹 脂 のリサイクル ···························································································· 323
12.2.2 発 泡 PS ··················································································································· 324
12.2.3 植 物 由 来 剛 直 材 料 ································································································ 324
12.2.4 リサイクル技 術 ＜参 考 ＞ ························································································ 325
12.３ 生 分 解 性 材 料 ··············································································································· 326
12.3.1 ポリ乳 酸 系 ·············································································································· 326
12.3.2 PBS関 連 ················································································································· 329
12.3.3 一 般 生 分 解 性 材 料 ································································································ 333
12.４ 環 境 対 応 材 料 ··············································································································· 336
12.4.1 ノンハロゲン材 料 ···································································································· 336
12.4.2 有 害 物 質 捕 集 材 料 ································································································ 339
12.4.2.1 ゲル状 捕 集 剤 ··································································································· 339
12.4.2.2 キトサン系 吸 着 剤 ····························································································· 340
12.4.2.3 光 触 媒 関 連 有 害 物 質 処 理 材 料 ······································································· 340

第 13章 ポリマーナノコンポジットの安 全 性 ····································································· 342
13.１ 2005年 度 ナノテクノロジーの社 会 受 容 促 進 に関 するプロジェクト概 要 ························· 342
13.２ ナノマテリアルのリスク評 価 に関 する状 況 ····································································· 342
13.３ ナノ材 料 の安 全 性 評 価 ································································································· 343

第 14章 終言 ····················································································································· 345

略 語 表 ·································································································································· 346
参 考 文 献 ·································································································································· 349－xiii－