Title
高分子固体中及び液体中のマイクロ・ナノ孔の自己圧壊( 本
文(Fulltext) )
Author(s)
宮田, 利彰
Report No.(Doctoral
Degree)
博士(工学) 工博甲第519号
Issue Date
2017-03-25
Type
博士論文
Version
ETD
URL
http://hdl.handle.net/20.500.12099/56179
※この資料の著作権は、各資料の著者・学協会・出版社等に帰属します。࣐ࢡ࣭ࣟࢼࣀᏍࡢ⮬ᕫᅽቯ
Self-collapsing of micro/nano pore in
polymer solid and water
2016 ᖺ㸦ᖹᡂ 28 ᖺ㸧ᗘ
ᒱ㜧ᏛᏛ㝔ᕤᏛ◊✲⛉
≀㉁ᕤᏛᑓᨷ
┠ḟ- i
┠ḟ
➨1 ❶ ⥴ㄽ ··· 1 1.1 ࢼࣀ࣓࣮ࢺࣝࢧࢬࡢᵓ㐀ࢆ᭷ࡍࡿᮦᩱ ··· 1 1.2 ᅛయ୰ࡢࢼࣀᏍ 㸫ࢡ࣮ࣞࢬ୰ࡢ࣎ࢻ㸫 ··· 2 1.3 ᾮయ୰ࡢࢼࣀᏍ 㸫࣐ࢡ࣭ࣟࢼࣀࣂࣈࣝࡢᛶ㉁㸫 ··· 5 1.4 ᮏㄽᩥࡢ┠ⓗ ··· 7 ➨2 ❶ ᅛయ୰ࡢࢼࣀ࣎ࢻࡢࣄ࣮ࣜࣥࢢ ··· 9 2.1 ᗎㄽ ··· 9 2.2 ᐇ㦂 ··· 10 2.2.1 ヨᩱ ··· 10 2.2.1.1 ࣏ࣜࣉࣟࣆࣞࣥ ··· 10 2.2.1.2 ࣏ࣜࢫࢳࣞࣥ ··· 11 2.2.1.3 ࣏࣓ࣜࢳ࣓ࣝࢱࢡ࣮ࣜࣞࢺ ··· 12 2.2.1.4 ࣏ࣜ L-ங㓟 ··· 13 2.2.2 ࢟ࣕࢫࢺἲࡼࡿࣇ࣒ࣝసᡂ ··· 14 2.2.3 ຊᏛ≉ᛶ ··· 15 2.2.4 ⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞ࡢ ᐃ ··· 16 2.2.5 ࢡ࣮ࣞࢬ⏕ᡂ ··· 18 2.2.5.1 ࢡ࣮ࣞࢬฎ⌮ࡢᴫせ ··· 18 2.2.5.2 ࢡ࣮ࣞࢬฎ⌮᮲௳ ··· 19 2.2.6 ࢡ࣮ࣞࢬࣄ࣮ࣜࣥࢢ㛤ጞ ᗘࡢホ౯ ··· 20 2.2.6.1 ගᏛ㢧ᚤ㙾ࡼࡿホ౯ ··· 20 2.2.6.2 㟼ⓗගᩓࡼࡿホ౯ ··· 21 2.2.6.3 ࢡ࣮ࣜࣉヨ㦂ࡼࡿホ౯ ··· 22┠ḟ- ii 2.3.2 ࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢ ᗘࡢ ᐃ ··· 27 2.3.2.1 ගᏛⓗᡭἲࡼࡿ┤᥋ほᐹ ··· 27 2.3.2.2 㟼ⓗගᩓࡼࡗ࡚ồࡵࡓ┦㛵㛗ኚ ··· 39 2.3.2.3 ࢡ࣮ࣞࢬࣄ࣮ࣜࣥࢢࡢぢࡅࡢάᛶ࢚ࢿࣝࢠ࣮ࡢኚ ··· 47 2.3.3 ࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢෆ㒊ᛂຊࡀ࠼ࡿᙳ㡪 ··· 52 2.3.3.1 ࢡ࣮ࣞࢬฎ⌮࠾ࡅࡿᙳ㡪 ··· 52 2.3.3.2 ᛂຊ⦆ࡉࡏࡓࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢ ··· 54 2.3.4 ࢡ࣮ࣞࢬⓎ⏕ᶵᵓࡢ᳨ウ ··· 56 2.3.5 ⤡ࡳྜ࠸ࢭࢢ࣓ࣥࢺࡀࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢ࠼ࡿᙳ㡪··· 59 2.4 ࡲࡵ ··· 65 ➨3 ❶ ࣏࢚ࣜࢫࢸࣝ⧄⥔ࡢᨵ㉁ ··· 66 3.1 ᗎㄽ ··· 66 3.1.1 ࣐ࢡࣟࣂࣈࣝࡢ≉ᚩ ··· 66 3.1.2 ࢜ࢰࣥࡢᛶ㉁ ··· 69 3.1.3 ࣏࢚ࣜࢫࢸࣝ⧄⥔ࡢᨵ㉁ ··· 70 3.2 ᐇ㦂 ··· 72 3.2.1 ヨᩱ ··· 72 3.2.2 ࢜ࢰ࣐ࣥࢡࣟࣂࣈࣝࡢⓎ⏕᮲௳ ··· 73
┠ḟ- iii 3.2.3 ࢜ࢰࣥ⃰ᗘ ᐃ ··· 74 3.2.4 ࣐ࢡࣟࣂࣈࣝᚄ ᐃ ··· 75 3.2.5 ᰁⰍࡼࡿホ౯ ··· 76 3.2.6 X ⥺ග㟁Ꮚศගἲ㸦XPS㸧ࡼࡿホ౯ ··· 77 3.3 ⤖ᯝ⪃ᐹ ··· 79 3.3.1 ⁐Ꮡ࢜ࢰࣥ⃰ᗘ࣐ࢡࣟࣂࣈࣝᚄ ··· 79 3.3.2 OMB ฎ⌮ࡼࡗ࡚⏕ࡌࡓ⾲㠃ᐁ⬟ᇶࡢホ౯ ··· 83 3.3.3 ࢺࣜࢭࢸ࣮ࢺࢆ⏝࠸ࡓ㏥Ⰽヨ㦂 ··· 86 3.3.4 ୍ᐃ⁐Ꮡ࢜ࢰࣥ⃰ᗘ࠾ࡅࡿฎ⌮ ᗘ౫Ꮡᛶ ··· 89 3.4 ࡲࡵ ··· 93 ➨4 ❶ Ⅳ⣲⧄⥔ࡢᨵ㉁ࡼࡿCFRP ࡢᙉᗘྥୖ ··· 94 4.1 ᗎㄽ ··· 94 4.2 ᐇ㦂 ··· 95 4.2.1 ヨᩱ ··· 95 4.2.2 ࣐ࢡࣟࣂࣈࣝฎ⌮ ··· 96 4.2.3 ⏺㠃ࡏࢇ᩿ᙉᗘࡢ ᐃ ··· 96 4.2.4 ⾲㠃ᵓ㐀ࡢほ ··· 98 4.2.5 ⾲㠃ᙧែࡢほ ··· 98 4.2.6 ⇕ࣉࣞࢫࡼࡿCFRP ᡂᙧయࡢసᡂ ··· 99 4.2.7 CFRP ᡂᙧయࡢຊᏛ≉ᛶ ··· 99 4.2.8 CFRP ᡂᙧయࡢ᩿㠃ほᐹ ··· 99 4.3 ⤖ᯝ⪃ᐹ ··· 100 4.3.1 ⏺㠃ࡏࢇ᩿ᙉᗘ⾲㠃ࡢኚ ··· 100 4.3.2 CFRP ᡂᙧయࡢຊᏛ≉ᛶ ··· 108
┠ḟ- iv 5.2.3 ヨ㦂∦సᡂ ··· 117 5.2.4 ヨ㦂∦ࡢ┦ศ㞳ᵓ㐀ホ౯ ··· 117 5.2.5 ヨ㦂∦ࡢ⾲㠃࢚ࢿࣝࢠ࣮ホ౯ ··· 118 5.2.6 ࣂࣈࣝ྾╔ᣲືほᐹ ··· 119 5.2.7 ࢜ࢰ࣐ࣥࢡࣟࣂࣈࣝࡼࡿ࢚ࢵࢪࣥࢢ ··· 120 5.3 ⤖ᯝཬࡧ⪃ᐹ ··· 121 5.3.1 ┦ᐜࡢホ౯ ··· 121 5.3.2 ヨ㦂∦ほᐹ ··· 125 5.3.3 ࣂࣈࣝ྾╔ᣲືほᐹ ··· 128 5.3.4 ࢜ࢰ࣐ࣥࢡࣟࣂࣈࣝࡼࡿ࢚ࢵࢪࣥࢢ ··· 133 5.4 ࡲࡵ ··· 135 ➨6 ❶ ⤖ㄽ ··· 136 ㅰ㎡ ··· 139 ཧ⪃ᩥ⊩ ··· 140 ᏛⓎ⾲ ··· 143 Ⓨ⾲ㄽᩥ ··· 144
1
➨1❶ ⥴ㄽ
1.1 䝘䝜䝯䞊䝖䝹䝃䜲䝈䛾ᵓ㐀䜢᭷䛩䜛ᮦᩱ ᮦᩱᕤᏛ࠾࠸࡚ᮦᩱ⮬యࡀࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮࡛ࣝ࠶ࡿࠊᡈࡣࠊࢼࣀ࣓࣮ࢺࣝࢧࢬࡢ ᵓ㐀ࢆ᭷ࡍࡿ㏻ᖖࡣ␗࡞ࡿᛶ㉁ࢆ♧ࡍࠋ๓⪅ࡣࠊࢭ࣮ࣝࣟࢫࢼࣀࣇࣂ࣮ࠊ࣮࢝࣎ࣥ ࢼࣀࢳ࣮ࣗࣈ➼ࠊᚋ⪅ࡣ㧗ศᏊࢼࣀࢥ࣏ࣥࢪࢵࢺࠊ࣮ࣟࢱࢫຠᯝࢆ⏝࠸ࡓ㉸᧕Ỉ➼ࡀᣲࡆࡽ ࢀࡿࠋ ᮦᩱ⮬యࡢᑡ࡞ࡃࡶ୍ḟඖ᪉ྥࡢࡁࡉࡀ100 nm ௨ୗࡢᮦᩱࡣࢼࣀ࣐ࢸࣜࣝࡤ ࢀࡿࠋ࠼ࡤࢭ࣮ࣝࣟࢫࢼࣀࣇࣂ࣮ࡣ㗰㕲ࡢ5 ศࡢ 1 ࡢ㔜ࡉ࡛ࠊ5 ಸ௨ୖࡢᙉᗘࢆ᭷ࡍ ࡿ1ࠋྠࡌࢫࢣ࣮ࣝࢧࢬࡢ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࡣ㗰㕲ࡢ16 ศࡢ 1 ࡢ㔜ࡉ࡛ࠊ⣙ 100 ಸ ࡢᙉᗘࢆ᭷ࡍࡿ2ࠋࡲࡓ㟁ὶᐜ㔞ࡣ109 A/cm2࡛࠶ࡾࠊࡇࡢ್ࡣ㖡ࠊ㔠௨ୖ࡛࠶ࡿ3ࠋࡇࢀࡽ ࡀ≉ᚩⓗ࡞ᣲືࢆ♧ࡍࡢࡣࠊᮦᩱࡀࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮ࣝ࡞ࡿ⤖ᬗḞ㝗ࡸ⣧≀࡞ࡢ ᵓ㐀Ḟ㝗ࡀᑡ࡞ࡃ࡞ࡿࡽ࡛࠶ࡿࠋ ᮦᩱ⮬యࡀࢼࣀ࣓࣮ࢺࣝᵓ㐀࡛↓ࡃ࡚ࡶࠊᮦᩱ୰ࢼࣀ࣓࣮ࢺࣝᵓ㐀ࢆ᭷ࡍࡿࡢࡳ࡛ࡶ ࡁࡃ≉ᚩࡀኚࡍࡿࠋ㧗ศᏊࢼࣀࢥ࣏ࣥࢪࢵࢺࡣࠊ㧗ศᏊ࣐ࢺࣜࢵࢡࢫ୰ࢼࣀ࣓࣮ࢺࣝ ࣮࢜ࢲ࣮ࡢࣇ࣮ࣛ㸦↓ᶵ⢏Ꮚ㸧ࢆῧຍࡋࡓᮦᩱࡢࡇ࡛࠶ࡾࠊ⌧ᅾ࡛ࡶࢱࣖ࡞ࡢࢦ࣒ 〇ရᗈࡃ⏝ࡉࢀ࡚࠸ࡿ4ࠋࣇ࣮ࣛࡢῧຍ㔜㔞ࢆኚࡏࡎࠊ⢏ᚄࡀ1 ȝm ࡽ 100 nm ኚ᭦ࡋࡓሙྜࠊ࣐ࢺࣜࢵࢡࢫࡢ᥋ゐ㠃✚㸦ࣇ࣮ࣛࡢ⾲㠃✚㸧ࡣ10 ಸ࡞ࡾࠊࣇ࣮ࣛ ࡢಶᩘࡣ1000 ಸ࡞ࡾࠊ⢏Ꮚ㛫㊥㞳ࡣ 10 ศࡢ 1 ῶᑡࡍࡿࠋFU ࡽࡣ⢏Ꮚᚄࠊࡉࡽࡣ⢏ Ꮚ⾲㠃㛫㊥㞳ࢆ⦰ᑠࡉࡏࡿࡇ࡛ࠊ⾪ᧁᙉᗘࡢྥୖࢆሗ࿌ࡋ࡚࠸ࡿ 5ࠋࡇࢀࡽࡢࡇࡽࠊ 㧗ศᏊࢼࣀࢥ࣏ࣥࢪࢵࢺࡣࣇ࣮ࣛ⣔」ྜᮦᩱࡢ᭱⤊ᙧゝ࠼ࡿࠋ ♧ࡋࡓࠊࢭ࣮ࣝࣟࢫࢼࣀࣇࣂ࣮ࠊ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈࠊ㧗ศᏊࢼࣀࢥ࣏ࣥࢪࢵࢺ ࡢࣇ࣮ࣛ࡞ࡣ⮬㌟ᙉᗘࢆ᭷ࡍࡿࠋࡇࡇ࡛ࠊ㧗ศᏊከᏍᮦᩱࡣࠊ㧗ศᏊ࣐ࢺࣜࢵࢡࢫ ✵Ẽࢆ」ྜࡋࡓࡶࡢ⪃࠼ࡿࡇࡀ࡛ࡁࡿࠋ✵Ẽࡣᙉᗘࡀ↓࠸ࡢ࡛ࠊࢼࣀ࣓࣮ࢺࣝࢧࢬ ࡢ✵㝽ࢆᣢࡘ㧗ศᏊࢼࣀࢥ࣏ࣥࢪࢵࢺࡣࣇ࣮ࣛ⣔ࡣ␗࡞ࡿᣲືࢆ♧ࡍྍ⬟ᛶࡀ࠶ࡿࠋ୍ ᪉ࠊ࣐ࢺࣜࢵࢡࢫࢆᾮయ㸦Ỉ㸧ࡋࡓሙྜࠊ࣐ࢡ࣭ࣟࢼࣀࣂࣈࣝ㸦௨ᚋࠊ࣐ࢡࣟࣂࣈࣝ㸧 ࡋ࡚ぢࡿࡇࡀ࡛ࡁࡿࠋࢼࣀ࣓࣮ࢺࣝࢧࢬࡢẼἻࢆᣢࡘᅛయ㸭Ẽయ⏺㠃ཬࡧᾮయ㸭Ẽయ ⏺㠃ࡢ≉ᚩὀ┠ࡋࠊ◊✲╔ᡭࡋࡓࠋ2 ⏝ࡉࢀ࡚࠾ࡾࠊ㉥ࡉࡧࡸ⃮ࡾࠊ⣽⳦➼ࢆ㝖ཤࡋ࡚࠸ࡿ ࠋ⣽ᏍᚄࠊከᏍ⋡ࢆไᚚࡍࡿࡇ ࡛ࠊᵝࠎ࡞⏝㏵ᛂ⏝ࡉࢀ࡚࠸ࡿࠋ ✀ࠎࡢ⏝㏵࡛⏝ࡉࢀ࡚࠸ࡿ㧗ศᏊከᏍἲࡢ〇ἲࡣࠊ┦ศ㞳ἲࠊᢳฟἲࠊ↷ᑕ࢚ࢵࢪࣥ ࢢἲࠊⓎἻἲࠊ⼥╔ἲࠊᘏఙἲ࡞ࡀ࠶ࡿ8ࠋ┦ศ㞳ἲࡣࠊ㧗ศᏊࡢ┦ศ㞳⌧㇟ࢆ⏝ࡍࡿ ᪉ἲࠊ㔜ྜ⣽Ꮝࢆᙧᡂࡉࡏࡿ᪉ἲࡀ࠶ࡾࠊ๓㏙ࡋࡓPS/DVB ࡣᚋ⪅ࡢᡭἲ┦ᙜࡍࡿࠋ ᢳฟἲࡣࠊᚋฎ⌮࡚㝖ཤྍ⬟࡞ῧຍࢆΰྜࡋࠊᡂᙧᚋࠊ⸆ရ➼࡛㝖ཤࡋࠊከᏍᮦᩱࢆᚓ ࡿ᪉ἲ࡛࠶ࡿࠋᘏఙἲࡣࠊ࣏࢚ࣜࢳࣞࣥࠊ࣏ࣜࣉࣟࣆࣞࣥࠊ࣏ࣜࢸࢺࣛࣇ࢚ࣝ࢜ࣟࢳࣞࣥ࡞ ࡢ⤖ᬗᛶ㧗ศᏊࡢࡳ㐺⏝࡛ࡁࡿᡭἲ࡛࠶ࡾࠊᘏఙࡼࡾ㠀ᬗᛶ㒊ศࡀᘬࡁఙࡤࡉࢀࠊᚤ⣽ ᵓ㐀ࡀᙧᡂࡉࢀࡿࠋ ḟ㧗ศᏊࡢ◚ቯࢆ⏝ࡋࡓከᏍࡢࢆ♧ࡍࠋ㧗ศᏊ◚ቯࡢከࡃࡣᘏᛶ◚ቯ࡛࠶ࡿࠋኚ ᙧࡢ㐣⛬࡚ࢡ࣮ࣞࢬኚᙧࡏࢇ᩿㝆అࡢ࠸ࡎࢀࡀ㉳ࡇࡿ9ࠋࢡ࣮ࣞࢬࡣࠊ㧗ศᏊᮦᩱ ຊᏛⓗ㈇Ⲵࠊᡈ࠸ࡣ⁐፹ࡀ᥋ࡋࡓ10つ๎Ⓨ⏕ࡍࡿࠋᘏఙἲ࡚ᚓࡽࢀࡓ㧗ศᏊከᏍ ᮦᩱࡣࢡ࣮ࣞࢬࢆⓎ⏕ࡉࡏࡓࡶࡢ࡛࠶ࡿࠋFigure 1.1 ࡣ SEM ୰࡚ప㏿ᘏఙ࡚Ⓨ⏕ࡉࡏࡓ ࢡ࣮ࣞࢬࡢ⾲㠃SEM ⏬ീ࡛࠶ࡿࠋᑦࠊࢡ࣮ࣞࢬࡢⓎ⏕⨨ࢆㄪ⠇ࡍࡿࡓࡵࠊᘏఙ᧯సࡢ ࠊⓎ⏕⨨ࢆ㡬Ⅼࡍࡿ᭤ࡆࡀຍ࠼ࡽࢀ࡚࠸ࡿࠋ⏬ീࡢኳᆅ᪉ྥࡀᘏఙ᪉ྥ࡛࠶ࡿࠋࢡ ࣮ࣞࢬࡣ㧗ศᏊ㙐ࡀຊᏛⓗ㈇Ⲵࡼࡾᘬࡁᢤࢀࠊ㓄ྥศᏊ㙐ࡀ㞟ࡲࡗࡓࣇࣈࣜࣝ㸦⧄⥔ ᮰㸧ࣇࣈࣜࣝ㛫⏕ᡂࡋࡓ࣎ࢻ㸦✵㝽㸧ࡼࡗ࡚ᵓᡂࡉࢀࡿࠋࡇࡢࢡ࣮ࣞࢬࡢෆ㒊ᵓ 㐀ࡣ࣐ࢡ࣭ࣟࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮࡛ࣝ࠶ࡿࠋࡑࡢⅭࠊධᑕගࢆᑕࡉࡏࡿࡓࡵࠊࢡ࣮ࣞ ࢬࡀⓎ⏕ࡋࡓ㧗ศᏊᮦᩱࡣⓑࡋࠊ〇ရࡢእほࢆᦆ࡞࠺ࠋࡲࡓࠊࢡ࣮ࣞࢬࡀⓎ⏕ࡋࡓ〇ရ ᭦࡞ࡿⲴ㔜ࡀຍࢃࡿࠊࣇࣈࣜࣝࡀษ᩿ࡉࢀࠊᕧどⓗ࡞ட㸦ࢡࣛࢵࢡ㸧ᡂ㛗ࡋࠊ〇ရ ࡢ◚ቯࡘ࡞ࡀࡿࠋᕤᴗⓗࡣࢡ࣮ࣞࢬࡢⓎ⏕ࢆ㜵Ṇࡍࡿࡓࡵࠊ㐺ᗘ࡞ࡁࡉࡢࢦ࣒⢏Ꮚ ࢆῧຍࡋࠊ〇ရࡢⓑࢆ㜵Ṇࡍࡿ〇ἲࡶ࠶ࡿ11ࠋ
3
Figure 1.1 SEM image of surface of crazed PP film.
ୖグࡋࡓࡼ࠺ࠊࢡ࣮ࣞࢬࡣ≉ᚩⓗ࡞ෆ㒊ᵓ㐀ࢆ᭷ࡍࡿࡀࠊᕤᴗⓗࡣḞ㝗࡛࠶ࡿࡓࡵࠊ ᢚไࡍࡁ⌧㇟࡛࠶ࡿࠋࡋࡋࠊ➹⪅ඹྠ◊✲⪅ࡣ᭤ࡆࢆ⏝ࡋࡓᡭἲ࡚㧗ศᏊᮦᩱ୰ ฎ⌮᪉ྥᑐࡋ࿘ᮇⓗ⦤≧ࡢࢡ࣮ࣞࢬࢆⓎ⏕ࡉࡏࡿࡇᡂຌࡋ࡚࠸ࡿ12ࠋFigure 1.2 ࡣ ࿘ᮇࢡ࣮ࣞࢬࢆⓎ⏕ࡉࡏࡓ࣏ࣜࣉࣟࣆࣞࣥ㸦PP㸧ࣇ࣒ࣝࡢගᏛ㢧ᚤ㙾┿࡛࠶ࡿࠋ┿ࡢ ᕥྑ᪉ྥࡀࣇ࣒ࣝࡢ᭤ࡆ᪉ྥ࡛࠶ࡾࠊ᭤ࡆ᪉ྥᑐࡋᖹ⾜࿘ᮇⓗ㯮ࡃᏑᅾࡍࡿࡢࡀࢡ ࣮ࣞࢬ࡛࠶ࡿࠋࡇࡢ࿘ᮇⓗࢡ࣮ࣞࢬࢆࣇ࣒᩿ࣝ㠃᪉ྥ㈏㏻ࡉࡏࡓࣇ࣒ࣝࡣࠊ≉␗ⓗ࡞ ෆ㒊ᵓ㐀ࢆᣢࡘࢡ࣮ࣞࢬࢆ࿘ᮇⓗ᭷ࡍࡿࡇࡼࡾᵝࠎ࡞ࡇᛂ⏝࡛ࡁࡿࠋ࠼ࡤࠊࢡ ࣮ࣞࢬࡀ㠃ⓗⓎ⏕ࡋࡓࣇ࣒ࣝࡣࣇ࣒ࣝయࡀⓑࡍࡿࠋ୍᪉ࠊࢡ࣮ࣞࢬ㡿ᇦ㠀ࢡ ࣮ࣞࢬ㡿ᇦࡀ࿘ᮇⓗᏑᅾࡍࡿࢡ࣮ࣞࢬࣇ࣒ࣝࡣࠊⓑࡋࡓᒙ㏱᫂ᒙࡀᏑᅾࡍࡿ ᙧ࡞ࡿࠋⓑࡋࡓᒙࡀࣈࣛࣥࢻࡢ⩚ࡢࡼ࠺࡞ാࡁࢆࡍࡿࡓࡵࠊṇ㠃ࡽࡣ㏱࡛᫂࠶ࡿࡀࠊ ᩳࡵࡽぢࡿ㏱᫂ぢ࠼ࡿど⏺ไᚚᛶࣇ࣒ࣝᛂ⏝࡛ࡁࡿ13ࠋࡲࡓࠊࢡ࣮ࣞࢬࡣ⇕ ฎ⌮ࡼࡗ࡚⦆ࡍࡿࡇࡀሗ࿌ࡉࢀ࡚࠸ࡿ14, 15ࠋ࿘ᮇࢡ࣮ࣞࢬࡶ⇕ฎ⌮ࡼࡾ⦆ࡍࡿࡇ ࡀྍ⬟࡛࠶ࡿࠋࡇࡢ≉ᚩࢆ⏝ࡋ࡚ࠊ࣏ࣜࣉࣟࣆࣞࣥ⧄⥔ࡢᚋᰁࡵࡸᰠࢆ⏝ࡋࡓᢠ⳦ ⧄⥔ࡢసᡂᡂຌࡋ࡚࠸ࡿ16ࠋ
5 1.3 ᾮయ୰䛾䝘䝜Ꮝ㻌 䠉䝬䜲䜽䝻䞉䝘䝜䝞䝤䝹䛾ᛶ㉁䠉 ከᏍᮦᩱࡣ㏻ᖖᅛయ࡛࠶ࡿࡀࠊᾮయࡶࢼࣀᏍࡣᏑᅾࡍࡿࠋỈ୰ࢆ⁻࠺ࣂࣈࣝ㸦Ἳ㸧ࡘ ࠸࡚ࡣ௨๓ࡽ◊✲ࡉࢀ࡚࠸ࡿࠋ࠼ࡤࠊỈฎ⌮࠾࠸࡚ࠊຍᅽᾋୖἲࡤࢀࡿᡭἲࡀ࠶ ࡿࠋ⏺㠃άᛶࢆ᭷ࡍࡿ⁐㉁ࠊỈᛶࢆ᭷ࡍࡿᾋ㐟≀ࡣࠊỈ⁐ᾮ୰ࡢࣂࣈࣝ⾲㠃྾╔ࡋࡸࡍ ࠸ᛶ㉁ࢆ᭷ࡍࡿࠋࡇࡢ≉ᚩࢆ⏝ࡋࠊࡑࢀࡽࢆ྾╔ࡉࡏࠊᾋୖࡋࡓࡇࢁ࡛ᅇࡋࠊỈࡢί ࢆᅗࡿᡭἲ࡛࠶ࡿࠋࡇࡢᢏ⾡ࡣ㐜ࡃࡶ1965 ᖺሗ࿌ࡉࢀ࡚࠾ࡾࠊᚑ᮶ࡽ⏝ࡉࢀ࡚ ࠸ࡿࡇࡀศࡿ17ࠋỈฎ⌮ࡢᢏ⾡ࡣάᛶởἾἲࡶ࠶ࡿࠋࡇࢀࡣࠊฎ⌮ᑐ㇟ᾮ୰ዲẼᛶ ᚤ⏕≀ࢆῧຍࡋࠊ✵Ẽ㸦㓟⣲㸧ࢆ࠼࡚᭷ᶵ≀ࢆฎ⌮ࡉࡏࡿ᪉ἲ࡛࠶ࡿࠋ࠸ࡎࢀࡢᡭἲࡶ͆ᚤ ⣽࡞ẼἻ͇ࡀᚲせ࡛࠶ࡿࠋ ᚑ᮶ࡽ“ᚤ⣽࡞ẼἻ”ࢆ⏝࠸ࡓ◊✲ࡉࢀ࡚࠸ࡓࡶࢃࡽࡎࠊ࣐͆ࢡࣟࣂࣈࣝ”ࡘ࠸ ࡚ࡢ◊✲ࡣࠊ2000 ᖺ๓ᚋࡽᛴ⃭◊✲ሗ࿌ࡀቑຍࡋࡓࠋ࣐ࢡࣟࣂࣈࣝࡣẼἻᚄ 50 μm ௨ୗࠊࢼࣀࣂࣈࣝࡣẼἻᚄ 1 ȝm ᮍ‶ࡢࣂࣈࣝࡢἻࡢࡇࢆ♧ࡍࡇࡀከ࠸ࠋ࣐ࢡࣟࣂ ࣈࣝࡣ㧗ศᏊࢼࣀࢥ࣏ࣥࢪࢵࢺྠᵝࠊᾮయ㸭Ẽయ⏺㠃ࡢ㠃✚ࡀࡁ࠸ࠋࡲࡓࠊ㠀ᖖᑠࡉ ࠸⢏Ꮚࡶぢ࠼ࡿࡓࡵࠊỈ୰㛗㛫␃࡛ࡁࡿࠋࡇࡢᵝᵝࠎ࡞≉ᚩࢆ᭷ࡍࡿ࣐ࢡࣟࣂ ࣈࣝࡣᵝࠎ࡞ศ㔝࡛⏝ࡉࢀ࡚࠸ࡿ18, 19, 20ࠋ࠼ࡤࠊ㒊ရࡢ⬺⬡࡛࠶ࡿࠋ⌧ᅾࠊ⎔ቃၥ㢟➼ ࡼࡾࠊ᭷ᶵ⣔⁐፹ࡢ⏝ࡀ๐ῶࠊᗫṆࡉࢀ࡚࠸ࡿࠋỈ⣔ࡢ⏺㠃άᛶኚ᭦ࡉࢀࡘࡘ࠶ࡿ ࡀࠊὙίຊࡢపୗࡀㄢ㢟࡛࠶ࡿࠋࡑࡢ௦᭰ࡋ࡚࣐ࢡࣟࣂࣈࣝࡢὙίࡀᥦࡉࢀ࡚࠸ࡿࠋ ࣐ࢡࣟࣂࣈࣝࡣẼయࡢศᩓయ࡛࠶ࡿࡓࡵࠊ⾲㠃ࡣỈᛶ࡛࠶ࡿࠋࡑࡢⅭࠊ⾲㠃╔ࡋࡓ Ἔศ࣐ࢡࣟࣂࣈࣝࡀ╔ࡍࡿࠊ࣐ࢡࣟࣂࣈࣝࡢ⾲㠃Ἔศࡀᒎ㛤ࡉࢀࡿࠋ࣐ࢡࣟ ࣂࣈࣝ1 ಶ࡛㝖ཤ࡛ࡁࡿἜศࡣഹ࡛࠶ࡿࡀࠊ࣐ࢡࣟࣂࣈࣝࡢᑠࡉࡉࠊẚ⾲㠃✚ࡢࡁ ࡉࡼࡾ⣽㒊ࡲ࡛ຠ⋡ࡼࡃὙίࡀྍ⬟࡛࠶ࡿࠋࡑࡢࠊẼయࡢຠ⋡ⓗ࡞⁐ゎࢆ⏝ࡋ᳜≀ ⫱ᡂࠊ㈅㢮ࡢ㣴Ṫࡢศ㔝࡛ࡶ⏝ࡉࢀ࡚࠸ࡿࠋ㉸㡢Ἴࡼࡗ࡚⏕ᡂࡍࡿ࣐ࢡࣝࣂࣈࣝࡀᅽ ቯࡍࡿࡁࠊ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡀⓎ⏕ࡍࡿࠋ࢟ࣕࣅࢸ࣮ࢩࣙࣥࡣ⯪⯧ࡢࢫࢡ࣮ࣜࣗࡢቯ㣗ࡀ ㉳ࡇࡍࠋ⯪⯧ࡢ㧗ᛶ⬟క࠸⏕ࡌࡓၥ㢟࡛࠶ࡿࡀࠊࡇࡢᛶ㉁ࢆ⏝࠸࡚㔠ᒓ⾲㠃ࡢࢼࣀ࣭࣐ ࢡࣟࢫࢣ࣮ࣝࡢ⾲㠃ᨵ㉁⏝ࡉࢀ࡚࠸ࡿ21ࠋࡑࡢࠊ࢞ࣛࢡࢺ࣮ࢫࡢ㢛⢏ࡀ⁐ゎࡍࡿ㝿 ࣐ࢡࣟࣂࣈࣝࢆⓎ⏕ࡉࡏࡿ᪉ἲࡶ࠶ࡾࠊ་⒪ศ㔝ࡢ㐀ᙳ⏝ࡉࢀ࡚࠸ࡿ19ࠋ ࣐ࢡࣟࣂࣈࣝࡢⓎ⏕᪉ἲࡣୖグࡋࡓ㉸㡢Ἴᘧ௨እࡶᩘከࡃ࠶ࡿ22ࠋ࠸ࡃࡘࡢⓎ⏕᪉ ἲࢆୗグ♧ࡍࠋ
6 ࡑࢀࡒࢀࡢⓎ⏕ἲ≉ᚩࡀ࠶ࡿࠋ࠼ࡤࠊẼᾮࡏࢇ᩿ἲࡣࠊࢫࢡ࣮࡚ࣜࣗẼᾮ⏺㠃ࢆ᧠ ᢾࡍࡿ࠸࠺⡆᫆࡞ᵓ㐀ࡼࡗ࡚సᡂྍ⬟࡛࠶ࡿࡀࠊ୍ᐃࡢࡁࡉࡢ࣐ࢡࣟࣂࣈࣝ࡞ࡿ ࡏࢇ᩿ຊࡀ↓ࡃ࡞ࡾࠊᚤ⣽ࡀᅔ㞴࡛࠶ࡿࠋຍᅽῶᅽᘧࡣࠊῶᅽ࣐ࢡࣟࣂࣈࣝࡀⓎ ⏕ࡍࡿࡓࡵࠊ࣐ࢡࣟࣂࣈࣝᚄࡢศᕸࡀẚ㍑ⓗ⊃࠸ࡀࠊࣂࢵࢳ༢࡛ࡢ᧯సࡢⅭࠊຠ⋡ࡀ ᝏ࠸ࠋ⣽Ꮝᘧࠊ࣋ࣥࢳ࣮ࣗࣜᘧࡣෆໟẼయࢆ㑅ᢥࡋࡸࡍ࠸≉ᚩࢆ᭷ࡍࡿࠋ㉸㡢Ἴᘧࡣࠊ㉸㡢 Ἴࡢ㝜ᅽⓎ⏕ࡋࡓ࣐ࢡࣟࣂࣈࣝࡀḟࡢຍᅽ⦰ᑠࡉࢀࡿࡓࡵࠊ࣐ࢡࣟࣂࣈࣝࡢᅽ ቯࡀ㉳ࡇࡾࡸࡍ࠸ࠋࡑࢀࡒࢀࡢ⏝㏵ᛂࡌࡓⓎ⏕ἲࡢ㑅ᢥࡀᚲせ࡛࠶ࡿࠋ
7 1.4 ᮏㄽᩥ䛾┠ⓗ ᮏㄽᩥ࡛ࡣࠊ㧗ศᏊᅛయ࠾ࡼࡧỈ୰ᏑᅾࡍࡿࢼࣀᏍࡢᣢࡘຠᯝࡘ࠸࡚ㄽࡌ࡚࠸ࡿࠋ≉ ࡑࡢ⏺㠃ࡢᐤ╔┠ࡋ࡚࠸ࡿࠋ㧗ศᏊᅛయ୰ࡢࢼࣀᏍ㛵ࡋ࡚ࡣࠊ≉ࢡ࣮ࣞࢬࢆྲྀࡾ ᢅࡗ࡚࠸ࡿࠋࢡ࣮ࣞࢬࡢ⦆ࡢ◊✲ࡣ௨๓ࡽሗ࿌ࡉࢀ࡚࠸ࡿࠋࡋࡋࠊࡑࢀࡽࡢከࡃࡣศ Ꮚࡢᣑᩓὀ┠ࡋࡓ◊✲࡛࠶ࡾࠊࢡ࣮ࣞࢬࡢᙧែὀ┠ࡋࡓ◊✲ࡣᑡ࡞࠸ࠋ➹⪅ࡽࡣࠊ ⊂⮬ࡢ᪉ἲ࡛ࢡ࣮ࣞࢬࢆⓎ⏕ࡉࡏࡿࡇᡂຌࡋ࡚࠸ࡿ12ࠋࡉࡽࠊࢡ࣮ࣞࢬࡢ⦆ࢆ⏝ ࡋࠊᶵ⬟ᡂຌࡋ࡚࠸ࡿ16ࠋࡋࡋࠊ➹⪅ࡽࡀᡂຌࡋࡓ࣏ࣜࣉࣟࣆࣞࣥ⧄⥔ࡢᶵ⬟ࡢ㝿 ᚓࡓ▱ぢẚ㍑ࡍࡿ᫂ࡽ࡞▩┪ࡀ⏕ࡌࡿࠋ࣏ࣜࣉࣟࣉࣞࣥࡢ࢞ࣛࢫ㌿⛣ ᗘ㸦Tg㸧ࡣ ᐊ ௨ୗ࡛࠶ࡾࠊ㠀ᬗ㡿ᇦⓎ⏕ࡋࡓࢡ࣮ࣞࢬࡢ⦆ࡣ┤ࡕ㉳ࡇࡿ⪃࠼ࡽࢀࡿࠋࡋࡋࠊ ඛࡢᐇ㦂࡛ࡣ࠶ࡿ ᗘࢆ㉸࠼ࡿࢡ࣮ࣞࢬࡢ⦆ࡀᛴ⃭㏿ࡃ࡞ࡿࡇࡀᚓࡽࢀࡓࠋࡲࡓࠊ ♧ᕪ㉮ᰝ⇕㔞 ᐃ࠾࠸࡚ࡇࡢ ᗘࡀ㌿⛣Ⅼ࡛࡞࠸ࡇࡶุ᫂ࡋ࡚࠸ࡿࠋ༶ࡕࠊࢡ࣮ࣞࢬࡢ ⦆ࡀࢡ࣮ࣞࢬࡢᵓ㐀ࡀࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮࡛ࣝ࠶ࡿࡇ⏤᮶ࡍࡿ≉᭷ࡢ⌧㇟࡛࠶ࡿྍ⬟ ᛶࢆ♧ࡋ࡚࠸ࡿࠋࡇࡇ࡛ࠊ⦆ࡣศᏊࡢᣑᩓࡼࡗ࡚⏕ࡌࡿ⌧㇟࡛࠶ࡿࡓࡵࠊศᏊᣑᩓ௨ እࡢせᅉࡀ⪃࠼ࡽࢀࡿᮏ◊✲ࡢࢡ࣮ࣞࢬࡢ⦆ࡣࠊᐃ⩏ୖࡢ͆⦆͇␗࡞ࡿࠋᚑࡗ࡚ࠊศ Ꮚᣑᩓ௨እࡢせᅉࢆᣢࡘࢡ࣮ࣞࢬࡢ⦆ࢆ͆ࣄ࣮ࣜࣥࢢ͇ࡋ࡚༊ูࡋࡓࠋ ๓㏙ࡋࡓࡀࠊࢼࣀ࣓࣮ࢺࣝࢧࢬࡢẼయࡀྵࡲࢀࡿᅛయ㸭Ẽయ⏺㠃ࠊᾮయ㸭Ẽయ⏺㠃ࡣ≉ ᚩ࠶ࡿᛶ㉁ࢆ᭷ࡍࡿྍ⬟ᛶࡀ࠶ࡿࠋ≉ࠊ⾲㠃ᙇຊࡼࡗ࡚⾲㠃✚ࢆ᭱ᑠࡍࡿຊ࡛࠶ࡿ /DSODFH ᅽࡣࠊࢼࣀ࣓࣮ࢺࣝࢧࢬ࡛ࡣ↓ど࡛ࡁ࡞࠸⪃࠼ࡽࢀࡿࠋᮏㄽᩥ࡛ࡣࠊᅛయ㸭Ẽ య⏺㠃ࠊᾮయ㸭Ẽయ⏺㠃ാࡃ/DSODFH ᅽὀ┠ࡋࠊᮦᩱࡢᨵ㉁ࡢྍ⬟ᛶࡘ࠸᳨࡚ウࡋࡓࠋ ලయⓗࡣࠊ㏻ᖖ⇕⦆⌧㇟ࡋ࡚ㄝ᫂ࡉࢀ࡚࠸ࡿࢡ࣮ࣞࢬࡢ⦆⌧㇟ࡀࢡ࣮ࣞࢬࡢෆ㒊ᵓ 㐀ࡀᙳ㡪ࡋ࡚࠸ࡿࡇࢆゎ᫂ࡍࡿࠋ࣐ࢡࣟࣂࣈࣝ࠾ࡅࡿ /DSODFH ᅽࡣࠊẼἻᚄࡢ⦰ᑠࠊ Ẽయࡢ⁐Ꮡ㔞ࡢቑຍᐤࡍࡿࠋ࣐ࢡࣟࣂࣈࣝࡣ⌧ᅾࠊᵝࠎ࡞ศ㔝࡛⏝ࡉࢀ࡚࠸ࡿࠋࡑ ࡢከࡃࡀ࣐ࢡࣟࣂࣈࣝࢆẼయࡢ⁐ゎᗘࢆୖࡆࡿᡭẁ⏝࠸ࡿࠊᡈࡣࠊ⾲㠃ࡢὙί⏝㏵⏝ ࠸ࡽࢀࡿ࡞ࡋ࡚࠸ࡿࠋࡋࡋࠊ࣐ࢡࣟࣂࣈࣝࢆ⾲㠃ᨵ㉁ࡢᡭἲࡋ࡚࠸ࡿ◊✲ࡣᑡ࡞ ࠸ࠋࡑࡇ࡛ࠊᮏㄽᩥ࡛ࡣࠊ࣐ࢡࣟࣂࣈࣝࢆ⏝࠸ࡓ⾲㠃ᨵ㉁ࡢࡘ࠸࡚ᥦࡍࡿࠋࡑࡢ 㐣⛬࠾࠸࡚ࠊ/DSODFH ᅽࡼࡿᙳ㡪ࡘ࠸࡚ࡶ᳨ウࡍࡿࠋࡇࢀࡽ࣐ࢡࣟࣂࣈࣝฎ⌮ࢆຠ ⋡ⓗ⾜࠺ࡓࡵࡣࠊ⿕ฎ⌮≀ᑐࡍࡿ࣐ࢡࣟࣂࣈࣝࡢ྾╔ᛶࡀ㔜せ࡞ࡿࡓࡵࠊࡇࡢⅬ ࡘ࠸࡚ࡶゝཬࡍࡿࠋ ᮏㄽᩥࡣ6 ❶ࡽ࡞ࡿࠋ➨ 1 ❶ࡢᗎㄽጞࡲࡾࠊ➨ 2 ❶࡛ࡣࢡ࣮ࣞࢬᵓ㐀ࡀࢡ࣮ࣞࢬࡢ ࣄ࣮ࣜࣥࢢཬࡰࡍᙳ㡪ࡘ࠸࡚ࠊ➨3 ❶ཬࡧ➨ 4 ❶࡛ࡣ࢜ࢰ࣐ࣥࢡࣟࣂࣈࣝࢆ⏝࠸ࡓ⾲㠃 ᨵ㉁ࡘ࠸࡚ࠊ➨5 ❶࡛ࡣࣝࢦ࣐ࣥࢡࣟࣂࣈࣝࡢ㧗ศᏊ⾲㠃ࡢ྾╔ᣲືࡢほᐹࡘ࠸ ࡚ㄽࡌ࡚࠸ࡿࠋࡲࡎࠊ➨2 ❶࡛ࡣࠊࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢ ᗘࡘ࠸᳨࡚ウࡋࡓࠋඛࡢ◊✲ ࠾࠸࡚ࠊࣄ࣮ࣜࣥࢢ ᗘࡘ࠸᳨࡚ドࡉࢀ࡚࠸ࡿࡀࠊ ᐃࡣᶵ⬟ࡢ᭷↓ࡘ࠸ุ࡚᩿ࡉ
9
➨2❶ ᅛయ୰䛾䝘䝜䝪䜲䝗䛾䝠䞊䝸䞁䜾
2.1 ᗎㄽ ࢡ࣮ࣞࢬࡣࡍ࡚ࡢ㧗ศᏊⓎ⏕ࡍࡿ⌧㇟࡛ࡣ࡞࠸ࠋ㠀ᬗᛶ࢞ࣛࢫ≧㧗ศᏊࡢ࣏ࣜࢫࢳࣞ ࣥ㸦PS㸧ࡸ࣏࣓ࣜࢳ࣓ࣝࢱࢡ࣮ࣜࣞࢺ㸦PMMA㸧ࡣ⾲ࢀࡸࡍ࠸ࡀࠊྠࡌ㠀ᬗᛶ࢞ࣛࢫ≧㧗 ศᏊࡢ࣏࣮ࣜ࢝࣎ࢿ࣮ࢺ㸦PC㸧ࡣࡏࢇ᩿㝆అࡀඃඛࡋ࡚㉳ࡇࡿࡇࡀከ࠸ࠋࡇࡢ㐪࠸ࡣ㧗 ศᏊࡢᵓ㐀ࡼࡗ࡚Ỵࡲࡾࠊ⤡ࡳྜ࠸ᐦᗘȞeศᏊ㙐ࡢᰂ㌾ࡉࢆ♧ࡍ≉ᛶẚCࡽண࡛ ࡁࡿ23ࠋࡇࡢPPࠊ࣏࢚ࣜࢳࣞࣥࢸࣞࣇࢱ࣮ࣞࢺ㸦PET㸧ࠊ࣏ࣜ L-ங㓟㸦PLLA㸧࡞ࡢ⤖ ᬗᛶ㧗ศᏊࡶࢡ࣮ࣞࢬࢆ」ྜࡍࡿࡇࡀྍ⬟࡛࠶ࡿࠋ 㧗ศᏊᮦᩱ࠾ࡅࡿࢡࣛࢵࢡࡣ⦆ࡉࡏࡿࡇࡀ࡛ࡁࡿࠋ-XG ࡽࡣ PMMA ࢫࢳࣞࣥ- ࢡࣜࣟࢽࢺࣜࣝඹ㔜ྜయࡢࢡࣛࢵࢡ1 EDU ࡢᅽຊࢆຍ࠼ࠊTgࡼࡾ㧗࠸ ᗘ࡛⇕ฎ⌮ࢆ⾜࠸ࠊ ヨᩱࡢᙉᗘࡘ࠸࡚ㄪᰝࡋ࡚࠸ࡿ24ࠋࡑࡢ⤖ᯝࠊศࡋࡓ⾲㠃࡚ศᏊ㙐ࡢ┦ᣑᩓࢆక࠺ ≀⌮ⓗ࡞⤡ࡳྜ࠸ࡀᙧᡂࡉࢀࡓࡇࢆሗ࿌ࡋ࡚࠸ࡿࠋTgࢆ㉸࠼ࡓ᮲௳ୗࡢ㧗ศᏊ㙐ࡣࣞࣉ ࢸ࣮ࢩࣙࣥ㐠ືࡼࡾศᏊᣑᩓࡀ㉳ࡇࡿࠋࡇࢀࡽࡀࢡࣛࢵࢡ⦆ࡢ㥑ືຊ࡞ࡗ࡚࠸ࡿࠋࡲ ࡓࠊ%RLNR ࡽࡣ✀ࠎࡢ᮲௳ࡢ PET ࢆᑐ㇟ྠᵝ࡞◊✲ࢆ⾜ࡗ࡚࠸ࡿ25ࠋྠࡌPET Ⓨ⏕ࡉ ࢀࡓࢡࣛࢵࢡࡢ⦆㛫ࡣ⤖ᬗᗘࡀప࠸᪉ࡀ▷࠸ࠋࡇࢀࡣࠊ⤖ᬗࡼࡾศᏊࡢᣑᩓᛶࡀᢚ ไࡉࢀࡿࡓࡵ࡛࠶ࡿࠋࡲࡓࠊࡲࡓࠊศᏊ㔞ࡀࡁ࠸ࠊ⦆ࡀ㐜ࡃ࡞ࡿࡇࢆేࡏ࡚ሗ࿌ ࡋ࡚࠸ࡿࠋࡇࢀࡣศᏊࡢᣑᩓᛶࡣศᏊ㔞౫Ꮡᛶࡍࡿࡓࡵ࡛࠶ࡿࠋᅵ࢚̿ࢻ࣮࣡ࢬࡢ⟶ᶍ ᆺ࡛ࡣࠊࣞࣉࢸ࣮ࢩࣙࣥ㛫ࡣศᏊ㔞ࡢ3 ẚࡍࡿᥦゝࡉࢀ࡚࠸ࡿ26ࠋ ࢡ࣮ࣞࢬࡢ⦆ࡣ⏺㠃㸦ࣇࣈࣜࣝ㸧ࡢ᥋ྜࡢほⅬࡽࢡࣛࢵࢡࡢ⦆ࢇኚࢃࡽ ࡞࠸ࠋࢡ࣮ࣞࢬࢆ⦆ࡉࡏࡿࡓࡵࡣ⇕ฎ⌮ࡼࡾศᏊ㐠ືᛶࢆ୍ⓗ㧗ࡵࡿ᪉ἲࡀ᭷ຠ ࡛࠶ࡿࡀࠊ⁐፹ࢆᾐ㏱ࡉࡏࡿࡇࡼࡾࠊTgࢆపୗࡉࡏ㧗ศᏊ㙐ࡢ㐠ືᛶࢆ㧗ࡵࡿࡇࡶྍ ⬟࡛࠶ࡿ27ࠋࡇࡇ࡛ࠊPS ⾲㠃ࡢ࢞ࣛࢫ㌿⛣ ᗘ㸦T g㸧ࡣ⣙30ºC ୗࡀࡿࡇࡀሗ࿌ࡉࢀ࡚࠸ ࡿ28ࠋ ࡲࡓࠊ3RFKDQ ࡽࡣ㔜Ỉ⣲⨨ࡋࡓ PS ࡢ୰ᛶᏊᩓἲࢆ⏝࠸ࡓศᯒ࡚ࠊ⾲㠃ᒙ ࡽ35-60 nm ࡢ⇕⭾ᙇಀᩘࡀࠊࣂࣝࢡ␗࡞ࡿࡇࢆ♧ࡋࡓ29ࠋࢡ࣮ࣞࢬࡢࣇࣈࣜࣝࡣ㧗 ศᏊ㙐ࡀᩘᮏ㹼ᩘ10 ᮏ⛬ᗘࡢࡁࡉ࡛࠶ࡿࡓࡵࠊ⾲㠃ྠࡌࡼ࠺࡞ᣲືࢆ♧ࡍࠋᚑࡗ࡚ࢡ ࣮ࣞࢬࡣࣂࣝࢡࡢTg௨ୗ࡛⦆ࡀ㉳ࡇࡿࠋࡲࡓࠊ3OXPPHU ࡽࡼࡾ࢞ࣛࢫ㌿⛣ ᗘᑐࡍ ࡿ⇕ฎ⌮ ᗘࡢẚ㸦T/Tg㸧ࡀࡁ࠸ࠊࢡ࣮ࣞࢬࡢᾘ⁛㛫ࡀ▷࠸ࡇࡀሗ࿌ࡉࢀ࡚࠸ࡿ30ࠋ ࡲࡓࠊࡇࡢഴྥࡣ㧗ศᏊ✀ࡼࡽ࡞࠸ゝࢃࢀ࡚࠸ࡿࠋ༶ࡕࠊTgࡀ␗࡞ࡿ㧗ศᏊ࡛࠶ࡗ࡚ࡶࠊ T/Tgࡢ್ࡀྠࡌ࡛࠶ࢀࡤࢡ࣮ࣞࢬࡢᾘ⁛㛫ࡶྠࡌ࡛࠶ࡿࠋ ௨ୖࡢࡇࡽࠊࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢ㛵ࡋ࡚ࡣࠊTgࡢ౫Ꮡᛶࡀ࠶ࡿ⪃࠼ࡽࢀࡿࠋࡲ ࡓࠊ⏺㠃ࡢ⦆ࡢ㥑ືຊࢆ⪃៖ࡍࡿࠊศᏊ㔞౫Ꮡᛶࡀ࠶ࡿ⪃࠼ࡽࢀࡿࠋᮏ◊✲࡛ࡣࢡ࣮ࣞ ࢬࡢࣄ࣮ࣜࣥࢢࡢTg౫ᏑᛶࠊศᏊ㔞౫Ꮡᛶࡘ࠸᳨࡚ウࡋࡓࠋ10
ᐩࢇ࡛࠸ࡿ㸦80-90%㸧ࠋࡉࡽࠊỗ⏝ࣉࣛࢫࢳࢵࢡࡢ୰࡛ࠊẚ㔜ࡢᑠࡉࡉ㸦ẚ㔜 0.93-0.96㸧 ࡣࢺࢵࣉࢡࣛࢫ࡛࠶ࡾࠊຊᏛ≉ᛶࠊ⪏⸆ᛶඃࢀ࡚࠸ࡿࠋ7DEOH ୍⯡ⓗ࡞ PP ࡢ≀ᛶࢆ ♧ࡍࠋ
ᮏ◊✲࡛ࡣᢲࡋฟࡋᙧᡂࡉࢀࡓཌࡉ30 ȝm ࡢᮍᘏఙࣇ࣒ࣝࢆ⏝࠸ࡓࠋ
Figure 2.1 Chemical structure of PP.
Table 2.1 Property of PP31 3URSHUW\ 8QLW 7HVWPHWKRG 9DOXH 'HQVLW\ g/cm3 D792 0.930 7HQVLOHVWUHQJWK 03D D638 35.5 7HQVLOHPRGXOXV *3D D638 1.38 )OH[XUDOPRGXOXV *3D D638 1.69 1RWFKHGL]RGDW57 J/m D256 37 +DUGQHVV D785 100 /LQHDUFRHIILFLHQWRIWKHUPDOH[SDQVLRQ mm/(mm࣭K) D696 90×10-6 :DWHUDEVRUSWLRQK % D570 <0.03 0HOWLQJSRLQW ºC D3418 164 *ODVVWUDQVLWLRQWHPS ºC D3418 -20
11 2.2.1.2 ࣏ࣜࢫࢳࣞࣥ ࣏ࣜࢫࢳࣞࣥ㸦PS㸧ࡣࢫࢳࣞࣥࡢ㔜ྜయ࡛࠶ࡾࠊPP ྠᵝỗ⏝ࣉࣛࢫࢳࢵࢡ࡛࠶ࡿࠋFigure 2.2 PS ࡢᏛᵓ㐀ࢆ♧ࡋࡓࠋ㏻ᖖࠊPS ࡣࣛࢪ࢝ࣝ㔜ྜࡼࡗ࡚ᚓࡽࢀࡿࡓࡵࢱࢡࢳࢵ ࢡᵓ㐀࡛࠶ࡾࠊ㠀ᬗᛶ㧗ศᏊศ㢮ࡉࢀࡿࠋࢱࢡࢳࢵࢡPS ࡣࠊᏳ౯࡞⇕ྍረᛶ㧗ศᏊ࡛ ࠶ࡾࠊᐜ᫆ᑕฟᡂᆺ࡛ࡁࡿࡇࡽ㔞ࢃࢀ࡚࠸ࡿࠋ7DEOH ୍⯡ⓗ࡞ PS ࡢ≀ᛶ ࢆ♧ࡍࠋ ᮏ◊✲࡛ࡣ6FLHQWLILF3RO\PHU 〇ࠊ㔜㔞ᖹᆒศᏊ㔞㸦Mw㸧210,000㸦௨ᚋࠊ210k㸧ࡢ PS ࢆ⏝ ࠸ࡓࠋ
Figure 2.2 Chemical structure of PS.
Table 2.2 Property of PS31 3URSHUW\ 8QLW 7HVWPHWKRG 9DOXH 'HQVLW\ g/cm3 D792 1.04 7HQVLOHVWUHQJWK 03D D638 46 7HQVLOHPRGXOXV *3D D638 2.89 )OH[XUDOPRGXOXV *3D D638 3.18 1RWFKHGL]RGDW57 J/m D256 93 +DUGQHVV D785 M60-M80 /LQHDUFRHIILFLHQWRIWKHUPDOH[SDQVLRQ mm/(mm࣭K) D696 90×10-6 :DWHUDEVRUSWLRQK % D570 0.05-0.07 0HOWLQJSRLQW ºC D3418 - *ODVVWUDQVLWLRQWHPS ºC D3418 74-110
12 ᮏ◊✲࡛ࡣከศᩓ࡛࠶ࡿ $OGULFK 〇 Mw=350,000 (௨ᚋࠊ350k)ࠊ୕⳻ࣞࣚࣥ〇 MW= 2250,000 (௨ᚋࠊ2250k), 60,000 (௨ᚋࠊ60k)ࠊSCIENTIFC POLYMER 〇 Mw=40,000㸦௨ᚋࠊ 40k㸧ཬࡧ༢ศᩓ࡛࠶ࡿ 3RO\PHU6RXUFH 〇 Mw=1825,600 (௨ᚋࠊ1825.6k)㸦Mw/Mn=1.4㸧, 640,00 (௨ᚋࠊ640k)㸦Mw/Mn =2.0㸧, 442,000 (௨ᚋࠊ442k)㸦Mw/Mn =1.7㸧, 132,000 (௨ᚋࠊ132k)㸦Mw/Mn =1.2㸧ࡢ PMMA ࢆ⏝ࡋࡓࠋ
Figure 2.3 Chemical structure of PMMA.
Table 2.3 Property of PMMA31
3URSHUW\ 8QLW 7HVWPHWKRG 9DOXH 'HQVLW\ g/cm3 D792 1.17-1.20 7HQVLOHVWUHQJWK 03D D638 55-76 7HQVLOHPRGXOXV *3D D638 2.4-3.1 )OH[XUDOPRGXOXV *3D D638 2.8-3.4 1RWFKHGL]RGDW57 J/m D256 16-32 +DUGQHVV D785 M80-M100 /LQHDUFRHIILFLHQWRIWKHUPDOH[SDQVLRQ mm/(mm࣭K) D696 5-9×10-5 :DWHUDEVRUSWLRQK % D570 0.2-0.4 0HOWLQJSRLQW ºC D3418 - *ODVVWUDQVLWLRQWHPS ºC D3418 105 O O n
13 2.2.1.4 ࣏ࣜ L-ங㓟
࣏ࣜங㓟㸦PLLA㸧ࡣங㓟ࡢ㔜ྜయ࡛࠶ࡾࠊ᳜≀ࡽ࡛ࡁࡿ㧗ศᏊࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࠋ Figure 2.4 PLLA ࡢᵓ㐀ࢆ♧ࡋࡓࠋங㓟ࡣ 1 ࡘࡢᩧⅣ⣲ࡀ࠶ࡿࡓࡵࠊ࣏ࣜங㓟ࡣ L యࡢࡳ࡛㔜ྜࡋࡓࡶࡢ㸦PLLA㸧ࠊD యࡢࡳ࡛㔜ྜࡋࡓࡶࡢ㸦PDLA㸧ࠊL య D యΰྜ࡛㔜ྜࡋ ࡓࡶࡢ㸦PDLLA㸧ࡢ 3 ✀㢮࠶ࡿࠋPLLA PDLA ࡣࡽࡏࢇᵓ㐀ࢆࡋ࡚࠾ࡾࠊ⤖ᬗᛶࡀ࠶ࡿࠋ
ࡲࡓࠊࡇࢀࡽࡢࡽࡏࢇᵓ㐀ࡣ࠸㏫ྥࡁ࡛࠶ࡾࠊPLLA PDLA ࢆ⤌ࡳྜࢃࡏࡿࡇࡼ
ࡾ㧗࠸⪏⇕ᛶࢆᣢࡘࢫࢸࣞ࢜ࢥࣥࣉࣞࢵࢡࢫPLA㸦SC-PLA㸧ࡀసᡂ࡛ࡁࡿࠋ7DEOH ୍
⯡ⓗ࡞PLA ࡢ≀ᛶࢆ♧ࡋࡓࠋ
ᮏ◊✲࡛ࡣ୍⯡ⓗ࡞PLLA ࡛࠶ࡿ୕Ꮫ〇 LACEA H-400 ࢆ⏝ࡋࡓࠋ
Figure 2.4 Chemical structure of PLLA.
Table 2.4 Property of PLA31
3URSHUW\ 8QLW 7HVWPHWKRG 'HQVLW\ g/cm3 D792 1.25 7HQVLOHVWUHQJWK 03D D638 53 7HQVLOHPRGXOXV *3D D638 3.45 )OH[XUDOPRGXOXV *3D D638 - 1RWFKHGL]RGDW57 J/m D256 16 +DUGQHVV D785 - /LQHDUFRHIILFLHQWRIWKHUPDOH[SDQVLRQ mm/(mm࣭K) D696 - :DWHUDEVRUSWLRQK % D570 <0.5 0HOWLQJSRLQW ºC D3418 178 *ODVVWUDQVLWLRQWHPS ºC D3418 63
14
Figure 2.5 Casting procedure of sample films.
ୖグᡭἲ࡛〇⭷ࡋࡓPLLA ࢆ DSC ᐃࡋࠊPLLA ࡢ⼥ゎ࢚ࣥࢱࣝࣆ࣮㸦93 J/g㸧32ࡼࡾ⤖ ᬗᗘTgࢆ⟬ฟࡋࡓࠋࡑࡢ⤖ᯝࠊ〇⭷ࡋࡓPLLA ࡣ⤖ᬗᗘࡀ 3%࡛࠶ࡾࠊTgࡶ54.4ºC ᩥ⊩್ẚ10ºC ௨ୖపࡗࡓࠋࡇࢀࡣࠊPLLA ࡢ⤖ᬗࡀ㐜࠸ࡓࡵ࡛࠶ࡾࠊḟࡢࡼ࠺ ࢟ࣕࢫࢺἲࢆᨵⰋࡋࡓࠋ ZW3//$ࢡ࣒ࣟࣟ࣍ࣝ⁐ᾮࢆ࢞ࣛࢫᯈୖὶࡋ㎸ࡳ 45ºC ࡛ 1 ᪥⇱ࡉࡏࡓࠋࡑࡢᚋࠊ ࣇ࣒ࣝࢆ࢞ࣛࢫᯈୖࡽࡀࡋࠊFigure 2.6 ♧ࡍ ᗘ࡛┿✵⇱ࡉࡏࡓࠋࡇࢀࡽ᧯స ࡼࡾ⤖ᬗᗘࡀ16%ࠊTgࡀ82.9ºC ࡲ࡛ୖ᪼ࡋࡓࠋᚋࠊ⤖ᬗᗘࢆୖࡆࡿ᧯సࢆࡋ࡚࠸࡞
࠸PLLA ࢆ PLLAC3ࠊ⤖ᬗᗘࢆୖࡆࡓ PLLA ࢆ PLLAC16 ⾲グࡍࡿࠋ
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Figure 2.6 Annealing temperature procedure in vacuum condition as to after treatment of PLLA casting film.
2.2.3 ຊᏛ≉ᛶ
ᮏ◊✲࡛⏝ࡋࡓPPࠊPSࠊPMMAࠊ PLLAC3 ཬࡧ PLLAC16 ࡢᐊ ࡛ࡢຊᏛ≀ᛶࡣ㟼ⓗ
ᘬᙇヨ㦂ࢆ⾜࠺ࡇࡼࡾホ౯ࡋࡓࠋ PP ヨᩱࡣᢲฟ᪉ྥ㸦0' 0HFKDQLFDO'LUHFWLRQ㸧ᑐࡋᆶ┤᪉ྥ㸦7' 7UDQVYHUVH'LUHFWLRQ㸧 㛗ࡉ50 mmࠊᖜ 10 mm ࡢ▷≧ษࡾฟࡋࡓࠋࡑࡢ 4 ✀㢮ࡢ㧗ศᏊࡣ㓄ྥᛶࡀ↓࠸ࡓ ࡵᙧ≧ࡢࡳࢆPP ⤫୍ࡋࡓࠋ▷≧ษࡾฟࡋࡓࣇ࣒ࣝࢆࢤ࣮ࢪ㛗ࡀ 30 mm ࡞ࡿࡼ࠺ ⬟ヨ㦂ᶵ㸦ᓥὠ〇సᡤ 〇, ༟ୖᆺ⬟ヨ㦂ᶵ EZ-L㸧ྲྀࡾࡅࠊࢡࣟࢫ࣊ࢵࢻࢫࣆ࣮ ࢻ 10 mm/min ࡛ᘬᙇヨ㦂ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓ 6WUHVV-6WUDLQ ᭤⥺ࡽྛࣇ࣒ࣝࡢࣖࣥࢢ⋡ࠊ ◚᩿ᙉᗘཬࡧ◚᩿ࡦࡎࡳࢆ⟬ฟࡋࡓࠋ Time (h)㻌 7H P SHUDWXUH & 㻌 R.T.㻌 55㻌 90㻌 17㻌 17.5㻌 22.5㻌 24㻌 0㻌
16 ࠼ࡿṇᘻἼᛂຊࡢ࿘Ἴᩘࢆኚࡉࡏࡿࡇ࡛ࠊ▐㛫ⓗ࡞ᛂ⟅ࡽ㛗㛫ᚋࡢᛂ⟅ࡲ࡛ ᐃ ࡛ࡁࡿࠋ DMA ࡣࡇࢀࡽࡢ ᐃࡀ ᗘࢆไᚚࡋ࡚⾜࠼ࡿࠋ ᗘࡢไᚚ᪉ἲࡣࠊᛴ⃭࡞ ᗘኚࠊ ୍ᐃࡢ᪼ ࣭㝆 ㏿ᗘࠊ ᗘ⥔ᣢ࡞ࡀ࠶ࡾࠊ⤌ࡳྜࢃࡏ࡛ᵝࠎ࡞ ᗘไᚚࡀ࡛ࡁࡿࠋFigure 2.7 DMA ࡢᴫ␎ᅗ D ィ⟬ἲ(b)ࢆ♧ࡋࡓࠋᮏ◊✲࡛ࡣࠊ7HQVLRQ-)LOP ࢡࣛࣥࣉࢆ⏝ࡋࠊ ᐃ᮲௳ࡣࠊᐊ ࡽ200ºC ࡲ࡛ࠊ᪼ ㏿ᗘࢆ 5 ºC/minࠊ㟼ⓗᙇຊࢆ 0.01 Nࠊᖜࢆ 1 ȝmࠊ ࿘Ἴᩘࢆ+] ࡋࡓࠋ D 0HFKDQLFDOVFKHPDWLFRI'0$ E &DOFXODWLRQRIDQDO\VLV
Figure 2.7 Schematic drawings of Dynamic Mechanical Analyzer.
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VLVFRHODVWLFERG\ ( iǚ E’ ǚ E” ǚ Dž ( iǚ &RPSOH[PRGXOXVRIHODVWLFLW\ (ӇE’ ǚ) + i E” ǚ E’ ǚ) : 6WRUDJHPRGXOXV E” ǚ /RVVPRGXOXV WDQț /RVVIDFWRU ӇE” ǚ / E’ ǚ)) Ȱ : Angular frequency Clamp
17
Figure 2.8 Typical DMA curves of polymer materials around Tg.
Figure 2.8 DMA ゎᯒࡼࡗ࡚ᚓࡽࢀࡿ DMA ᭤⥺ࡢࢆ♧ࡍࠋWDQțࡀ᭱࡞ࡿ ᗘ
ࡀTg࡛࠶ࡿࠋTg௨ୖࡢ ᗘ࠾࠸࡚ࠊ ᗘࡀୖࡀࡗ࡚ࡶᙎᛶ⋡ࡀࢇኚࡋ࡞࠸㡿ᇦ ࡀ⌧ࢀࡿࠋࡇࡢ㡿ᇦࢆࢦ࣒≧ᖹᆠ㡿ᇦࡧࠊ㙐ࡀ࣑ࢡࣟࣈࣛ࢘ࣥ㐠ືࢆ㉳ࡇࡍࡀࠊ⤡ࡳ ྜ࠸ࡀ⥔ᣢ࡛ࡁࡿ㡿ᇦ࡛࠶ࡿࠋࢦ࣒≧ᖹᆠ㡿ᇦ࡛ࡢᙎᛶ⋡ࢆࢦ࣒≧ᖹᆠᙎᛶ⋡EN0ࡪࠋ ࢦ࣒≧ᖹᆠᙎᛶ⋡GN0⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞Meࡢ㛵ಀࢆᘧ㸦2.4㸧♧ࡋࡓࠋࡲࡓࠊࡏࢇ᩿ ᙎᛶ⋡ࡽᘬᙇᙎᛶ⋡ࡢኚࡢ㝿⏝ࡍࡿ࣏ࢯࣥẚࡣ0.5 ᅛᐃࡋࡓࠋࡇࡇ࡛ࠊᘧ୰ ࡢɏࡣᐦᗘࠊR ࡣ࢞ࢫᐃᩘࠊT ࡣ ᗘ࡛࠶ࡿࠋ 0 0 e
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࣭࣭࣭㸦2.5㸧 7HPSHUDWXUH E’ E” Tg EN0 WD Q 䃓 7HPSHUDWXUH E’ E” Tg EN0 WD Q 䃓18 ࡆࡀຍ࠼ࡽࢀ࡞ࡀࡽ⛣ືࡍࡿࠋࣇ࣒ࣝࡢ᭤ࡆࡢእ࿘ഃࡣࠊᘬᙇᛂຊຍ࠼᭤ࡆᛂຊࡼ ࡿᛂຊࡀຍࢃࡿࠋࡇࡢᛂຊࡀࢡ࣮ࣞࢬⓎ⏕ᛂຊࢆ㉸࠼ࡓࡁࢡ࣮ࣞࢬࡀⓎ⏕ࡍࡿ㸦Figure 2.9 D 㸧ࠋ ࡇࡢࢡ࣮ࣞࢬⓎ⏕ᛂຊࡣ㧗ศᏊࡢ⤡ࡳྜ࠸Ⅼ㛫ᐦᗘࡼࡗ࡚Ỵࡲࡿࡓࡵࠊ㧗ศᏊࡼࡗ࡚ኚ ࢃࡿࠋࢡ࣮ࣞࢬࡀᡂ㛗ࡍࡿᙎᛶ⋡ࡀపୗࡍࡿࡓࡵࠊ᭤ࡆࡼࡿᛂຊࡀⴭࡋࡃపୗࡍࡿ㸦Figure 2.9(b)㸧ࠋࡑࡢ⤖ᯝࠊࣇ࣒ࣝࡿᛂຊࡣࢡ࣮ࣞࢬⓎ⏕ᛂຊ௨ୗ࡞ࡾࠊࡧᛂຊ㞟୰ࡍ ࡿࡲ࡛ࢡ࣮ࣞࢬࡣⓎ⏕ࡋ࡞࠸㸦Figure2.9 (c)㸧ࠋࡑࡢࡓࡵࠊࢡ࣮ࣞࢬࡣࢡࣛࢵࢡࡑࡋ࡚◚᩿ 㐍⾜ࡍࡿࡇࡀ࡞ࡃࠊ⮬Ⓨⓗ⧞ࡾ㏉ࡋ⏕ࡌࡿࠋࡲࡓࠊࢡ࣮ࣞࢬฎ⌮࠾࠸࡚ኚ᭦࡛ࡁࡿࡢ ࡣࠊฎ⌮㏿ᗘ㸦㏦ࡾ㏿ᗘ㸧ࠊฎ⌮ゅᗘ㸦᭤ࡆࡢࡁࡉ㸧ࠊฎ⌮ᛂຊ㸦ᘬᙇᛂຊ㸧࠾ࡼࡧฎ⌮ᅇ ᩘ࡛࠶ࡾࠊࡇࢀࡽࢆㄪ⠇ࡍࡿࡇ࡛ࢡ࣮ࣞࢬᙧែࢆไᚚ࡛ࡁࡿࠋ
Figure 2.9 Schematic diagram of crazing process: (a) Craze is generated if stress concentration at tip of blade is over craze generation stress. (b) Craze is grown and stress is released because modulus is decreased. (c) Film is moved until further craze is generated.
&UD]LQJEODGH 5ROOHU Tension D (b) (c) 3RO\PHUILOP &UD]H 3RO\PHU ILOP
19 2.2.5.2 ࢡ࣮ࣞࢬฎ⌮᮲௳ 㓄ྥᛶࡢ࠶ࡿPP ࡣ TD ᖜ 10 mmࠊ࢟ࣕࢫࢺἲ࡛〇⭷ࡋࡓ PSࠊPMMA ཬࡧ PLA ࡣ௵ព ࡢ᪉ྥᖜ10 mm ษࡾฟࡋࡓࠋࢡ࣮ࣞࢬฎ⌮⨨タ⨨ࡍࡿࡢᚲせ࡞㛗ࡉ࡞ࡿࡼ࠺ ࠊษࡾฟࡋࡓࣇ࣒ࣝࡢ୧➃⣬ࢆྲྀࡅヨ∦ࡢ㛗ࡉࢆᘏ㛗ࡋࠊฎ⌮ลᙜࡓࡿࡼ࠺࣮ࣟ ࣮ࣛࢆ㏻ࡋࢡ࣮ࣞࢬฎ⌮⨨タ⨨ࡋࡓࠋࡑࡢᚋࠊ∦᪉ࡢ࣮࣮ࣟࣛࡢࡳࣇ࣒ࣝࢆᢲࡉ࠼ࡿ ࡼ࠺ࡋࠊᑐഃࡢඛ➃㗽ࢆྞࡿࡋᙇຊࢆࡅࡓࠋࡑࡢᚋࠊ࣮࣮ࣟࣛࢆᅇ㌿ࡉࡏࣇ࣒ࣝ ࢆ㏦ࡾࠊࢡ࣮ࣞࢬฎ⌮ࢆ⾜ࡗࡓࠋ7DEOH5 ᮏ◊✲࡛ࡢࢡ࣮ࣞࢬฎ⌮᮲௳ࢆ♧ࡍࠋ
Table 2.5 Conditions of crazing process
3DUDPHWHU PP PS PMMA PLA
5DWH PPPLQ 20 20 20 20
$QJOH 80 120 80 80
6WUHVV 03D 22 15 22 22
20 ගᏛ㢧ᚤ㙾㸦(ᰴ) 1LNRQ 〇㸪 MEASURING MICROSCOPE MM-400㸧ࡼࡿࢡ࣮ࣞࢬᙧ ែࡢほᐹࡣࣇ࣒ࣝࢆຍ⇕ࡋ࡞ࡀࡽ⾜ࡗࡓࠋࢫࢸ࣮ࢪୖ⨨ࢀࡓ㏱᫂ᑟ㟁ᛶ࢞ࣛࢫୖほ ᐹᑐ㇟ࡢࣇ࣒ࣝࢆタ⨨ࡋࡓࠋࡑࡢᚋࠊ㏱᫂ᑟ㟁ᛶ࢞ࣛࢫࡢ୧➃ࢫࣛࢲࢵࢡࢆ⏝࠸᪼ ㏿ᗘࡀ5 |C/min ⛬ᗘ࡞ࡿࡼ࠺௵ពࡢ㟁ᅽࢆ༳ຍࡋࠊࢪ࣮ࣗࣝ⇕ࡼࡾࣇ࣒ࣝࢆຍ⇕ ࡋࡓࠋࡇࡢࡢ࢞ࣛࢫᯈୖࡢ ᗘࡣࠊ㉥እ⥺ࢧ࣮ࣔࢢࣛࣇ㸦1(&$YLR ㉥እ⥺ࢸࢡࣀࣟࢪ࣮ (ᰴ) 〇ࠊThermR*($5*(;㸧ࢆ⏝࠸࡚ ᐃࡋࡓࠋࡇࡇ࡛ࠊࣇ࣒ࣝࡣ༑ศⷧ࠸ࡓࡵࠊ࢞ ࣛࢫᯈୖࡢ ᗘࣇ࣒ࣝࡢ ᗘࡣྠࡌ⪃࠼ࡿࠋගᏛ㢧ᚤ㙾ࡢග※ࡣ㏱㐣ගࢆ⏝ࡋࡓࠋ ࡑࡢࡓࡵࠊࢡ࣮ࣞࢬࡣࢡ࣮ࣞࢬ୰ࡢ࣎ࢻࡼࡾᩓࡉࢀ㏱㐣ࡋ࡞࠸ࡓࡵᙳ࡞ࡾ㯮࠸⥺ ࡋ࡚⾲ࢀࡿࠋ ගᏛ㢧ᚤ㙾┿ࡣࠊCMOS ࣓࢝ࣛ㸦(ᰴ) ᓥὠ⌮ 〇㸪 0RWLFDP㸪 03L[HO㸧ࢆ ⏝࠸࡚ᙳࡋࡓࠋᚓࡽࢀࡓ⏬ീࢆࠊࢯࣇࢺࢆ⏝࠸࡚ࢡ࣮ࣞࢬᙧែࢆホ౯ࡋࡓࠋFigure 2.10 ࢡ࣮ࣞࢬᙧែࡢᐃ⩏ࢆ♧ࡋࡓࠋ
Figure 2.10 Definition of craze interval and craze width.
&UD]HLQWHUYDO
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21 2.2.6.2 㟼ⓗගᩓࡼࡿホ౯ ගᏛ㢧ᚤ㙾࡛ࡢほᐹ࡛ࡣ㏱㐣ගࢆ⏝࠸ࡓࠋࡋࡋࠊࢡ࣮ࣞࢬࡣࣇ࣒᩿ࣝ㠃ᑐࡋᆶ┤ Ꮡᅾࡍࡿࡣ㝈ࡽ࡞࠸ࠋࡑࡢࡓࡵࠊഴᩳࡋࡓࢡ࣮ࣞࢬࡀᏑᅾࡍࡿࡑࡢศࢡ࣮ࣞࢬࡢᖜࡀ ࡁࡵほᐹࡉࢀࡿྍ⬟ᛶࡀ࠶ࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࡉࡽṇ☜ࢡ࣮ࣞࢬᖜࢆ ᐃࡍࡿࡓ ࡵ㟼ⓗගᩓἲࢆ⏝࠸ࡓࠋ ᐃࡣࠊ㟼ⓗගᩓ⨨ࡢ1 ࡘ࡛࠶ࡿ㧗ศᏊࣇ࣒ࣝࢲࢼ࣑ࢵࢡࢫゎᯒ⨨㸦ሯ㟁 Ꮚ((ᰴ)) 〇㸪 DYNA-300㸧ࢆ⏝ࡋࡓࠋࡇࡢ DYNA-3000 ࡣ㧗 ຍ⇕ࢫࢸ࣮ࢪࢆᦚ㍕ࡋ࡚ ࠾ࡾࠊගᏛ㢧ᚤ㙾ほᐹྠᵝࠊࣜࣝࢱ࣒࡛ࡢฎ⌮ ᗘ౫Ꮡᛶࡢ ᐃࡀྍ⬟࡛࠶ࡿࠋ ࢡ࣮ࣞࢬฎ⌮ࡋࡓࣇ࣒ࣝࢆࢡ࣮ࣞࢬࡀゎᯒ᪉ྥᑐࡋᆶ┤࡞ࡿࡼ࠺⨨タ⨨ࡋࠊ He-Ne ࣮ࣞࢨ࣮㸦Ἴ㛗 632.8 nm㸧ࢆ↷ᑕࡋࡓࠋࡑࡢࡢ೫ගಖᣢᩓീࢆ 2 ḟඖ CCD ࣓࢝ ࡛ࣛᙳࡋࡓ㸦Figure 2.11 D 㸧ࠋᚓࡽࢀࡓᩓീࡼࡾ 'HE\H ࣉࣟࢵࢺ㸦Figure 2.11(b)㸧ࢆసᡂ
ࡋࡓࠋ'HE\H ࣉࣟࢵࢺࡀ┤⥺㛵ಀ࡛࠶ࡿ㛫࡛ᘧ㸦2.1㸧ࡼࡾ┦㛵㛗ࢆ⟬ฟࡋࡓࠋᘧ୰ࡢ Isࡣ
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ᗘࡣ⣙10 |C/min ࡛᪼ ࡋࠊ ᐃࡣᐊ 40|C ࡽ 100|C ࡲ࡛ 10|C ẖ⾜ࡗࡓࠋ
(a) CCD image of light
scattering. (b) Debye plot. Figure 2.11 Example of static light scattering results.
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D &UHHSFXUYHRIWHPSHUDWXUHFKDQJH. E $UUKHQLXVSORW.
Figure 2.12 Calculation of apparent activation energy due to creep test
2.2.7 ᜏ ฎ⌮䛻䛚䛡䜛ศᏊ㔞౫Ꮡᛶ ๓㡯ࡲ࡛ࡣࠊTCHࡘ࠸᳨࡚ウࡋࡓࠋᮏ㡯࡛ࡣTCH௨ୖࡢ ᗘ࡛⇕ฎ⌮ࡋࡓࡢࢡ࣮ࣞࢬ ⤒ኚࡘ࠸᳨࡚ウࡍࡿࠋ ᚑ᮶ࡢࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡣࠊศᏊ㐠ືࡼࡗ࡚㉳ࡇࡿ⪃࠼ࡽࢀ࡚࠸ࡿࠋࡋࡋࠊࢡ ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡣศᏊ㐠ື௨እࡶせᅉࡀ࠶ࡿ⪃࠼ࡽࢀࡿࠋࡑࡇ࡛ࠊᮏ㡯࡛ࡣࠊศᏊ 㔞ࡢ␗࡞ࡿPMMA Ⓨ⏕ࡉࡏࡓࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢᣲືࢆ㟼ⓗගᩓἲ࡛ほᐹࡍࡿࡇ ࡼࡾࠊࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢᑐࡍࡿศᏊ㐠ືᛶࡢᐤࡘ࠸᳨࡚ウࡋࡓࠋ ヨᩱࡣከศᩓࡢMw = 350k ཬࡧ༢ศᩓࡢ Mw = 1825.6k㸦Mw/Mn = 1.4㸧, 640k 㸦Mw/Mn = 2.0㸧, 442k㸦Mw/Mn = 1.7㸧, 132k㸦Mw/Mn = 1.2㸧ࢆ⏝ࡋࡓࠋ ᐃࡣ 2.2.6.2 ࡛♧ࡋࡓ㟼ⓗග ᩓࢆ⏝࠸ࡓࠋ ᐃ ᗘࡣࠊPMMA 㸦Mw = 350k㸧ࡢ TCH + 5|C ࡋࠊᙳࡣ 1 min ẖ 20 min ⾜ࡗࡓࠋ
24 ࢡ࣮ࣞࢬฎ⌮ࡣ2.2.5.1 ♧ࡋࡓ᪉ἲࢆ⏝࠸ࡓࠋヨᩱࡣ PP ࣇ࣒ࣝࢆ⏝ࡋࡓࠋฎ⌮ᛂ ຊࡣ03Dࠊฎ⌮㏿ᗘࡣ 20 mm/minࠊฎ⌮ᅇᩘࡣ 1 ᅇࡋࠊฎ⌮ゅᗘࢆ 80ºࠊ100ºࠊ120º ࡍࡿࡇ࡛ࠊṧ␃ᛂຊࡢไᚚࢆ⾜ࡗࡓࠋTCHࡢ ᐃࡣ2.2.6.3 ♧ࡋࡓࢡ࣮ࣜࣉヨ㦂ࡼࡿ᪉ ἲࡼࡗ࡚⾜ࡗࡓࠋ 2.2.8.2 ᚋฎ⌮ࡼࡿෆ㒊ᛂຊ⦆ 2.2.8.1 ࡛ࡣࢡ࣮ࣞࢬࡢⓎ⏕ࡢฎ⌮᮲௳ࡼࡾṧ␃ᛂຊࢆไᚚࡋࡓࠋḟࠊࢡ࣮ࣞࢬⓎ⏕ ᚋࡢᚋฎ⌮࠾࠸࡚ࣇ࣒ࣝࡿṧ␃ᛂຊࢆไᚚࡋࡓࠋ ࢡ࣮ࣞࢬฎ⌮ࡣ2.2.5.1 ♧ࡋࡓ᪉ἲࢆ⏝࠸ࡓࠋヨᩱࡣ PP ࣇ࣒ࣝࢆ⏝ࡋࡓࠋฎ⌮ᛂ ຊࡣ03Dࠊฎ⌮㏿ᗘࡣ 20 mm/minࠊฎ⌮ᅇᩘࡣ 1 ᅇࠊฎ⌮ゅᗘࡣ 80º ࡋࡓࠋࡑࡢᚋࠊᘬ
ᙇヨ㦂ᶵ㸦TENSION UTM-4-200ࠊTOYO BALDWIN (ᰴ) 〇㸧ྲྀࡾࡅࠊࢡ࣮ࣞࢬࡀࣄ࣮
ࣜࣥࢢࡋ࡞࠸ᵝᙎᛶ㡿ᇦෆࡢ3%ࡢࡦࡎࡳࢆຍ࠼ࡓࠋࡑࡢᚋࠊ㟁Ẽ⅔ࢆ⏝࠸࡚ 100ºC ຍ ⇕ࡋࠊ5 min ಖᣢࡋࡓࠋಖᣢᚋࠊ⅔ࡢᡞࢆ㛤ᨺࡋࠊᐊ ࡞ࡿࡲ࡛⣙ 30 min 㛫෭༷ࡋࡓࠋࡑ ࡢᚋࠊࡦࡎࡳࢆ㛤ᨺࡋࠊヨ㦂∦ࢆᚓࡓࠋ ࿘ᮇࢡ࣮ࣞࢬࡣࣜࢳ࣒࢘㟁ụ⏝ࡢࢭࣃ࣮ࣞࢱࡋ࡚ࡢ⏝ࡘ࠸᳨࡚ウࡉࢀ࡚࠸ࡿ37ࠋࣜ ࢳ࣒࢘㟁ụࡢࢭࣃ࣮ࣞࢱࡣࣜࢳ࣒࢘࢜ࣥࡢ⇕ᭀ㉮࢜ࣥࡢ㏱㐣ࢆ㐽᩿ࡍࡿᛶ⬟ࡀồࡵ ࡽࢀࡿࠋࡲࡓࠊࢭࣃ࣮ࣞࢱࡢ࢜ࣥ㏱㐣ᛶࡣẼయ㏱㐣ᛶ࡚ホ౯ࡉࢀࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ ࡣࠊTCHࢆẼయࡢ㏱㐣ᛶ࡚ホ౯ࡋࡓࠋ ୖグᡭἲ࡚సᡂࡋࡓ PP ࣇ࣒ࣝࢆ┤ᚄ 13 mm ࡢᙧษ᩿ࡋࠊࢫࢸࣥࣞࢫ࣍ࣝࢲ࣮ 㸦(ᰴ)ࢻࣂࣥࢸࢵࢡ〇ࠊ KS-13㸧タ⨨ࡋࡓࠋ࢞ࢫ₃ࢀࡀ↓࠸ࡼ࠺ᘱࡳὀពࡋࠊᅵྎ ⨨ࡁࠊࢦ࣒ࣃࢵ࡛࢟ࣥᅛᐃࡋࡓࠋ࢞ࢫࡣ❅⣲࢞ࢫࢩࣜࣥࢲ࣮ࡼࡾ౪⤥ࡋࠊᅽຊࡣ03D ࡋࡓࠋࣇ࣒ࣝࢆ㏱㐣ࡋࡓ࢞ࢫࡣࢹࢪࢱࣝὶ㔞ィ㸦ࢪ࣮࢚ࣝࢧ࢚ࣥࢫ(ᰴ) 〇ࠊࣥࢸࣜ ࢪ࢙ࣥࢺࣇ࣮࣓࣮ࣟࢱ࣮ ADM1000㸧ࢆ⏝࠸ࡓࠋᚓࡽࢀࡓ࢞ࢫὶ㔞ࡽᘧ㸦2.5㸧ࡼࡾẼయ㏱ 㐣ಀᩘP ࢆ⟬ฟࡋࡓࡇࡇ࡛ࠊᘧ୰ࡢ F ࡣẼయὶ㔞ࠊt ࡣࣇ࣒ࣝཌࠊp ࡣ࢞ࢫὶ㔞ࠊA ࡣẼ యࡢ㏱㐣㠃✚㸦0.9 cm2㸧࡛࠶ࡿࠋ ᐃ⣔ࡢᴫ␎ᅗࢆFigure 2.13 ♧ࡍࠋ
25
A
p
t
F
P
࣭࣭࣭㸦2.5㸧Figure 2.13 Schematic diagram of gas permeability measurement.
TCHࡣࢡ࣮ࣞࢬࢆⓎ⏕ࡉࡏࡓPP ࣇ࣒ࣝࢆ✀ࠎࡢ ᗘ࡛ᜏ ⇱ჾෆ࡚ 1h ⇕ฎ⌮ࢆ ࡋࠊẼయ㏱㐣ಀᩘࡢῶᑡ⋡ࡽホ౯ࡋࡓࠋ N2 JDVF\OLQGHU㻌 33ILOP㻌 3UHVVXUHJDXJH
㻌
䠄03D 㻌 6WDLQOHVV㻌
OLQHKROGHU㻌 KS-13㻌 %DVH㻌 Rubber㻌 SDFNLQJ㻌
,QWHOOLJHQWIORZPHWHU㻌 ADM1000㻌26 ࢆࡅࡿࡇࡼࡾ⁐፹࡛࠶ࡿࢡ࣒ࣟࣟ࣍ࣝࡀᛴ㏿Ⓨࡍࡿࠋࡑࡢࡓࡵࠊࣇ࣒ࣝ⾲㠃ࡀ ኚᙧࡋࠊᒁᡤⓗ⭷ཌࡀⷧ࠸ᆅⅬࡀ⏕ᡂࡉࢀࡿࠋࣖࣥࢢ⋡ࡣᘬᙇヨ㦂࠾ࡅࡿึᮇࡢᣲື࡛ ࠶ࡿ࡛࠶ࡿࡓࡵࠊ⭷ཌࡢⷧ࠸ᆅⅬࡢ್ࡀᫎࡉࢀࡿࠋࡲࡓࠊ࣐ࢡ࣓࣮ࣟࢱ࣮ࡼࡿ⭷ཌ ᐃ࠾࠸࡚ࠊ⭷ཌࡀ᭱ࡶཌ࠸Ⅼࡀ ᐃࡉࢀࡿࠋࣖࣥࢢ⋡ࡢồࡵࡿ㝿ࠊ⭷ཌࡢ࣒ࣛࡘ࠸࡚ ࡣ⪃៖࡛ࡁ࡞࠸Ⅽࠊ࣐ࢡ࣓࣮ࣟࢱ࣮ࡼࡾᚓࡽࢀࡓ್ࢆ⏝ࡋࡓࠋᚑࡗ࡚ࠊ⤖ᬗࡉࡏࡓࡢ ࡶࢃࡽࡎࣖࣥࢢ⋡ࡀୖ᪼ࡋ࡞ࡗࡓࠋ
Table 2.6 Mechanical properties of sample films
<RXQJ¶VPRGXOXV *3D %UHDNLQJVWUHVV 03D %UHDNLQJVWUDLQ
Ave. ± S.D. Ave. ± S.D. Ave. ± S.D.
PP 1.30 ± 0.14 39.0 ± 2.3 12.0 ± 3.9
PS 3.02 ± 0.18 30.4 ± 5.9 2.28 ± 0.61
PMMA 2.32 ± 0.19 43.6 ± 4.6 5.05 ± 0.88
PLLAC6 2.90 ± 0.42 44.7 ± 10.1 6.75 ± 1.13
PLLAC16 2.73 ± 0.23 46.8 ± 2.28 4.26 ± 0.55
Thickness: PP: P RWKHUV: P :LGWK PP *DJH OHQJWK PP &URVVKHDG VSHHG mm/min.
27 2.3.2 䜽䝺䞊䝈䛾䝠䞊䝸䞁䜾 ᗘ䛾 ᐃ ᮏ◊✲࡛ࡣTCHࢆගᏛ㢧ᚤ㙾┿ࠊ㟼ⓗගᩓἲࠊࢡ࣮ࣜࣉヨ㦂ࡼࡾồࡵࡓࠋගᏛ㢧ᚤ 㙾ࡣࢡ࣮ࣞࢬࢆ┤᥋ほᐹ࡛ࡁࡿࠊ㟼ⓗගᩓࡣㄏ㟁⋡ࡢᦂࡽࡂࡼࡾࢡ࣮ࣞࢬࢆほᐹࡍࡿࡓ ࡵࠊࡼࡾṇ☜ ᐃ࡛ࡁࡿࠊࢡ࣮ࣜࣉヨ㦂ࡣගᏛ㢧ᚤ㙾ࠊ㟼ⓗගᩓ␗࡞ࡾࠊ≀⌮ⓗࢡ ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࢆほᐹ࡛ࡁࡿࠋᮏ㡯࡛ࡣࠊྛᡭἲ࡛ồࡵࡓTCHࡘ࠸᳨࡚ウࡋࡓࠋ 2.3.2.1 ගᏛⓗᡭἲࡼࡿ┤᥋ほᐹ ࡲࡎࠊගᏛ㢧ᚤ㙾ࡼࡾホ౯ࢆ⾜ࡗࡓࠋගᏛ㢧ᚤ㙾ࡼࡿ ᐃ࡛ࡣࠊࢡ࣮ࣞࢬࡢᖜ㛫㝸 ࡀ┤᥋ほᐹ࡛ࡁࠊࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢᑐࡍࡿ㠀ࢡ࣮ࣞࢬ㡿ᇦࡢᙳ㡪ࡘ࠸࡚ࡶ᳨ウࡍࡿ ࡇࡀྍ⬟࡛࠶ࡿࠋ
ྛ㧗ศᏊࣇ࣒ࣝࢆ⣙ 5 ºC/min ࡛᪼ ࡋࡓࡢගᏛ㢧ᚤ㙾┿ࢆ Figure2.14 ࡽ Figure
2.18 ♧ࡍࠋPS ࡣ㠌ᛶࡀపࡃࡢ㧗ศᏊྠᵝࡢࢡ࣮ࣞࢬฎ⌮᮲௳࡛ࡣ◚᩿ࡋࡓࠋࡑࡢࡓ ࡵPS ࢆ㝖ࡁࢡ࣮ࣞࢬࡢฎ⌮᮲௳ࢆ⤫୍ࡋࡓࡀࠊࢡ࣮ࣞࢬࡢᙧែࡣࡑࢀࡒࢀ␗࡞ࡗࡓࠋࡇࢀ ࡣࠊྛ㧗ศᏊࣇ࣒ࣝࡢ⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞ࡀ␗࡞ࡿࡽ࡛࠶ࡿࠋྛ㧗ศᏊࣇ࣒ࣝࡢ7DEOH 2.7 ᐊ 㸦&D&㸧࡛ࡢࢡ࣮ࣞࢬᙧែྛ㧗ศᏊࡢ⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞ࢆ♧ࡋࡓࠋᑦࠊ⤡ ࡳྜ࠸Ⅼ㛫ศᏊ㔞࠾࠸࡚⤖ᬗᛶ㧗ศᏊ࡛࠶ࡿPP ཬࡧ PLLA ࡣ᥎ᐃᘧࡼࡾ⟬ฟ40ࡋࠊPS ཬ ࡧPMMA ࡣ DMA ᐃࢆ⾜࠸ࠊ160ºC ࡛ࡢ㈓ⶶᙎᛶ⋡ࡽ⟬ฟࡋࡓࠋ ⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞ࢆᐇ ࡋࡓPS ཬࡧ PMMA ࡣᩥ⊩್␗࡞ࡿ್࡞ࡗࡓࠋࡇࢀࡣࠊ ࣏ࢯࣥẚࢆ㧗ศᏊ౫ࡽࡎ0.5 ᅛᐃࡋࡓⅬࠊ⌮ㄽୖࡣࢦ࣒≧ᖹᆠ㡿ᇦ࠾ࡅࡿ㈓ⶶᙎᛶ ⋡ࡣ ᗘẚࡋ࡚పୗࡍࡿࡀࠊᐇ ࡛ࡣࡑࡢࡼ࠺࡞ࡽ࡞࠸ࠋࡲࡓࠊࢦ࣒≧ᖹᆠᙎᛶ⋡ ࡀPS ࡛⣙ 03Dࠊ PMMA ࡛⣙ 03D ᑠࡉࡃࠊィ⟬ᘧࡢศẕ࠶ࡿࡇࡽᑡࡋࡢㄗ ᕪࡀࡁ࡞ㄗᕪ࡞ࡗࡓࠋ
28
݉ : Function of isotactic
݊ : Number of atoms in repeat unit on main strand
: Flory constant(= 2.51 × 10ଶଷ cmଷή molଵ ଶΤ ή gିଷ ଶΤ )
ܯ௩ : Molecular weight per statistical skeletal unit(= ܯΤ݊௩)
݊௩ : Number of statistical skeletal units in a repeat unit
ۃ݈௩ଶۄ : Mean square length of statistical skeletal unit (cm)
ܰ௩= 3ܥஶଶ
ܰ௩ : Number of statistical skeletal units in an entanglement strand
ܯ= ܰ௩ܯ௩
ܯ= 3ܯ௩ܥஶଶ
Table 2.7 Craze morphology and entanglement molecular weight of sample polymers
&UD]HPRUSKRORJ\ ȝP (QWDQJOHPHQWPROHFXODUZHLJKW JPRO
,QWHUYDO :LGWK ([SHULPHQWDO 5HIHUHQFH
PP 15.2 1.2 5,200 6,900 (ϸ) PS 11.1 1.0 23,000 17,900 (Ϲ) PMMA (Mw=350k) 8.2 1.2 5,900 9,880 (Ϲ) PLLAC3 10.5 1.3 8,290 8,700 (Ϻ) PLLAC16 3.4 1.0
Thickness: PP: PRWKHUV: 25 μm, cUD]LQJFRQGLWLRQ 36: 15 03DPPPLQDQGWLPH RWKHUV 03DPPPLQDQGWLPH.
(ϸ)$(FNVWHLQ-6XKP&)ULHGULFKHWDOMacromolecules 31 (4), 1335 (1998).
(Ϲ)S. Wu, Polym. Eng. Sci., 30, 753(1990).
29 ྠࡌฎ⌮᮲௳࡛ࢡ࣮ࣞࢬฎ⌮ࡋࡓPPࠊPMMA ཬࡧ PLLAC3 ࡘ࠸࡚ẚ㍑ࡍࡿࠋࡇࢀࡽࡢ ࣇ࣒ࣝࡢࢡ࣮ࣞࢬᖜࡣ࠸ࡎࢀࡶ⣙ ȝP ࡛࠶ࡿࠋࡇࢀࡣࠊฎ⌮ᛂຊࡀྠࡌ࡛࠶ࡾࠊ⤡ࡳ ྜ࠸Ⅼ㛫ศᏊ㔞ࡶ㏆࠸ⅭࠊⓎ⏕ࡋࡓࢡ࣮ࣞࢬࡀᡂ㛗ࡍࡿ㝿ࠊྠ⛬ᗘࡢ㊥㞳ࢆศᏊ㙐ࡀ⛣ື ࡋࡓࡓࡵ⪃࠼ࡽࢀࡿࠋࡋࡋࠊࡑࡢࢡ࣮ࣞࢬ㛫㝸ࡣᩥ⊩್ࡢ⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞ࡀቑຍࡍ ࡿᚑ࠸ࢡ࣮ࣞࢬ㛫㝸ࡀ⊃ࡃ࡞ࡗ࡚࠸ࡿࠋ༶ࡕࠊ⤡ࡳྜ࠸ᐦᗘࡀ࡞ࡿࡘࢀ࡚ࢡ࣮ࣞࢬ ࡀⓎ⏕ࡋࡸࡍࡃ࡞ࡗ࡚࠸ࡿࡇࡀศࡿࠋࡇࢀࡽࡢࡇࡽࠊᮏᡭἲࡼࡿࢡ࣮ࣞࢬⓎ⏕ ࠾࠸࡚ࠊ⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞ࡣࠊࢡ࣮ࣞࢬⓎ⏕ࡁࡃᙳ㡪ࢆཬࡰࡋࠊⓎ⏕ࡋࡓࢡ࣮ࣞࢬࡢ ᡂ㛗࠾࠸࡚ࡣᙳ㡪ࡀᑠࡉ࠸ࠋ ࡲࡓࠊ⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞ࡀྠࡌ PLLAAC3 PLLAC16 ࢆẚ㍑ࡍࡿࠊࢡ࣮ࣞࢬᖜࡣ PLLAC16 ࡢ᪉ࡀ⊃࠸ࠋྠࡌฎ⌮ᙇຊ࡛࠶ࡗࡓࡓࡵࠊ⤖ᬗక࠸ศᏊ㙐ࡢ⛣ືࡀᢚไࡉࢀ ࡿࠋࢡ࣮ࣞࢬ㛫㝸ࡶࠊPLLAC16 ࡢ᪉ࡀ PLLAC3 ẚ⊃ࡃ࡞ࡗ࡚࠸ࡿࠋᮏᡭἲࡼࡿࢡ࣮ࣞ ࢬⓎ⏕ࡣࠊ᭤ࡆࢆ⏝ࡋ࡚࠾ࡾࠊ᭤ࡆࡢእ㠃ࡀࢡ࣮ࣞࢬⓎ⏕ᛂຊ㐩ࡋࡓ㝿ࢡ࣮ࣞࢬࡀⓎ ⏕ࡍࡿࠋ⤖ᬗ㡿ᇦࡢᙎᛶ⋡ቑຍࡣࠊ᭤ࡆࡢእ㠃ࡢᛂຊࡢఏࡋࡸࡍࡃ࡞ࡿࡓࡵࠊࢡ࣮ࣞࢬ Ⓨ⏕ᛂຊ㐩ࡍࡿࢧࢡࣝࡀ▷ࡃ࡞ࡾࠊࢡ࣮ࣞࢬ㛫㝸ࡀ⊃ࡃ࡞ࡿࠋࡲࡓࠊPPࠊPMMA ཬࡧ PLLAC3 ࠾࠸࡚⤡ࡳྜ࠸ᐦᗘࡀ࡞ࡿࢡ࣮ࣞࢬࡀⓎ⏕ࡋࡸࡍ࠸ࡇࡽࠊ⤖ᬗ క࠸㠀ᬗ㡿ᇦࡢ⤡ࡳྜ࠸ࡀ࡞ࡗ࡚࠸ࡿྍ⬟ᛶࡶ⪃࠼ࡽࢀࡿࠋ ௨ୖࡢࡇࡽࠊPPࠊPMMA ཬࡧ PLLAC3 ࡢẚ㍑࠾࠸࡚ࠊ⤡ࡳྜ࠸Ⅼ㛫ศᏊ㔞ࡶẚ㍑ ⓗ㏆ࡃࠊࢡ࣮ࣞࢬᙧែࡀྠࡌ࡛࠶ࡿࡇࡽࠊࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡢTg౫Ꮡᛶࡘ࠸࡚ ㄪᰝࡀྍ⬟࡛࠶ࡿࠋࡲࡓࠊPLLAC3 PLLAC16 ࡢẚ㍑࠾࠸࡚ࠊ⤖ᬗᗘࡢ౫Ꮡᛶࡘ࠸ ࡚ㄪᰝࡀྍ⬟࡛࠶ࡿࠋ ࡇࢀࡽࡢ┿ࡽồࡵࡓࢡ࣮ࣞࢬᖜཬࡧࢡ࣮ࣞࢬ㛫㝸ࡢ ᗘ౫Ꮡࢆ Figure2.19 ࡽ Figure2.23 ♧ࡍࠋ
30
Figure 2.14 Temperature dependence of craze morphology for PP film by optical microscope.
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Figure 2.15 Temperature dependence of craze morphology for PS film by optical microscope.
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Figure 2.16 Temperature dependence of craze morphology for PMMA film by optical microscope.
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Figure 2.17 Temperature dependence of craze morphology for PLLAC3 film by optical microscope.
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Figure 2.18 Temperature dependence of craze morphology for PLLAC16 film by optical microscope.
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Figure 2.19 Temperature dependence of craze morphology for PP film by optical microscope.
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Figure 2.20 Temperature dependence of craze morphology for PS film by optical microscope.
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Figure 2.21 Temperature dependence of craze morphology for PMMA film by optical microscope
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Figure 2.22 Temperature dependence of craze morphology for PLLAC3 film by optical microscope. Thickness: ȝPFUD]LQJFRQGLWLRQ 03DPPPLQDQGWLPHKHDWLQJUDWH FD&PLQ. 0.0 0.5 0.6 0 20 40 60 80 100 120 7HPSHUDWXUH & :LWGK ,QWHUYDO 0.0 5.0 10.0 15.0 20.0 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 0 20 40 60 80 100 120 ,QWHUYDO (ȝP :LWGK ȝP 7HPSHUDWXUH & :LWGK ,QWHUYDO
37
Figure 2.23 Temperature dependence of craze morphology for PLLAC16 film by optical microscope. 7KLFNQHVV ȝPFUD]LQJFRQGLWLRQ 03DPPPLQDQGWLPHKHDWLQJUDWH FD&PLQ. 0.0 5.0 10.0 15.0 20.0 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 0 20 40 60 80 100 120 ,QWHUYDO (ȝP :LWGK ȝP 7HPSHUDWXUH & :LWGK ,QWHUYDO
38 ࡢ⥺⭾ᙇಀᩘ9.0×10 mm/(mm࣭K)ࢡ࣮ࣞࢬ㛫㝸 ȝP ࢆ⪃៖ࡍࡿࠊ⎔ቃ ᗘࡀ 70ºC 㧗ࡃ࡞ࡗࡓࡢቑຍศࡣȝP ⛬ᗘ࡛࠶ࡿࠋࢡ࣮ࣞࢬᖜࡢῶᑡࡀࢡ࣮ࣞࢬ㛫㝸ࡢ⇕⭾ᙇ ᑐࡋࡁࡃࠊ௵ពࡢ ᗘࡼࡾࢡ࣮ࣞࢬᖜࡀᛴῶࡍࡿࡇࡽࠊࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡣ㠀 ࢡ࣮ࣞࢬ㡿ᇦࡢ⇕⭾ᙇࡼࡿࡶࡢ࡛ࡣ࡞࠸ࠋ PLLA ࡢࡳ⤖ᬗ᧯సࡢ᭷↓㛵ࢃࡽࡎࢡ࣮ࣞࢬ㛫㝸ࡣ⇕ฎ⌮ ᗘࡢቑຍక࠸ቑຍࡋࡓࠋ ๓㏙ࡋࡓࡼ࠺⇕⭾ᙇࡼࡿቑຍࡣගᏛ㢧ᚤ㙾࡛ࡣ᳨ฟ࡛ࡁࡎࠊࡢせᅉࡀᏑᅾࡍࡿࠋ⇕ฎ ⌮క࠸ࢡ࣮ࣞࢬ୰ࡢ࣎ࢻࡀ⦰࣭ᾘ⁛ࡋࠊගᏛ㢧ᚤ㙾ࡢ㏱㐣ගࡢᩓ⬟ຊࡀపୗࡍࡿࠋ ࢡ࣮ࣞࢬࡢ≉ᚩࡀෆ㒊ࡢ࣎ࢻ࡛࠶ࡿࡓࡵࠊ࣎ࢻࡢᾘ⁛ࡣࢡ࣮ࣞࢬࡢᾘ⁛್ࡍࡿࠋᚑࡗ ࡚┦ᑐⓗࢡ࣮ࣞࢬ㛫㝸ࡀᗈࡀࡿࠋPLLA ࡣࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡢ┤๓ࡢ⌧㇟ࡋ࡚ ⪃࠼ࡽࢀࠊࡢ㧗ศᏊẚ≉Ṧᛶࡀ㧗࠸ࠋ ࢡ࣮ࣞࢬᖜࡢኚࡽồࡵࡓTCHࡣPP ཬࡧ PS ࡀ⣙ 60ºCࠊPMMA ࡀ⣙ 50ºCࠊPLLA ࡀ⤖ ᬗ㛵ࢃࡽࡎ⣙35ºC ࡛࠶ࡗࡓࠋࡇࢀࡽ ᗘࡣ PP ࡀ Tg௨ୖTm௨ୗࠊPS ཬࡧ PMMA ࡀ Tg ௨ୗࠊPLLAC3 ཬࡧ PLLAC16 ࡀ Tg௨ୗTm௨ୗ࡛࠶ࡾࠊ⇕ຊᏛⓗ࡞㌿⛣ ᗘࡢ㛵㐃ᛶࡀ ぢࡽࢀ࡞࠸Ⅼࡀ≉ᚩⓗ࡛࠶ࡿࠋࡇࡇ࡛ࠊྛ㧗ศᏊࡢᐇ⏝ ᗘࢆぢࡿࠊPPࠊPS ཬࡧ PMMA ࡀ⣙90ºC ࡛࠶ࡿࡢᑐࡋࠊPLLA ࡣ Tg㏆ࡉࢀ࡚࠸ࡿࠋPLLA 㛵ࡋ࡚ࡣ⤖ᬗᗘࡢୖ ᪼ࡼࡿ⪏⇕ᛶࡢྥୖࡘ࠸࡚◊✲ࡀ⾜ࢃࢀ࡚࠸ࡿ41ࡀࠊࢡ࣮ࣞࢬࡣ㠀ᬗ㡿ᇦⓎ⏕ࡋ࡚࠸ ࡿ⪃࠼ࡽࢀࡿࡓࡵࠊ⤖ᬗᗘࡢᙳ㡪ࢆཷࡅ࡞࠸ࠋࡇࢀࡽࡢࡇࡽࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢ 㧗ศᏊࡢᐇ⏝ᙉᗘࡀྵࡲࢀࡿྍ⬟ᛶࡀ㧗࠸ࠋ PLLAC3 ࡣ᪼ క࠸⤖ᬗࡋࠊᐦᗘࡶኚࡍࡿࠋࡲࡓࠊPLLAC16 ࡣ⾲㠃ࡀ⢒ࡃຊᏛⓗ ࡶᆒ୍࡛࡞࠸ࠋࡑࡢࡓࡵࠊ㟼ⓗගᩓཬࡧࢡ࣮ࣜࣉヨ㦂ࡣᅔ㞴࡛࠶ࡿࠋᚑࡗ࡚ࠊᚋࡢᐇ 㦂ࡽPLLA ࢆ㝖እࡋࡓࠋ
39 2.3.2.2 㟼ⓗගᩓࡼࡗ࡚ồࡵࡓ┦㛵㛗ኚ ๓㏙ࡋࡓࡼ࠺ࠊගᏛ㢧ᚤ㙾ほᐹ࡛ࡣഴᩳࡋࡓࢡ࣮ࣞࢬࡢᙳࢆㄆ㆑ࡋࠊࢡ࣮ࣞࢬᖜࡀࡁ ࡃ ᐃࡉࢀࡿࡇࡀ࠶ࡿࠋࡲࡓࠊࣇ࣒ࣝᆶ┤࡞ࢡ࣮ࣞࢬ࡛ࡶ㏱㐣ගࢆ⏝࠸ࡓගᏛ㢧ᚤ㙾 ほᐹ࡛ࡣ࣎ࢻࡼࡾගࡀᩓࡉࢀࢡ࣮ࣞࢬᖜࡀࡁࡃ ᐃࡉࢀࡿࠋ୍᪉ࠊ㟼ⓗගᩓἲ࡛ ࡣㄏ㟁⋡ࡢᦂࡽࡂࡼࡗ࡚ ᐃࡉࢀࡿࠋࡑࡢࡓࡵࠊࢡ࣮ࣞࢬ୰ࡢ࣎ࢻࡼࡿගᩓࡢᙳ㡪 ࢆཷࡅࡃ࠸ࠋࡲࡓࠊࣇ࣒ࣝ⾲㠃࡛ගᩓࡀ㉳ࡇࡿࡓࡵࢡ࣮ࣞࢬࡀഴᩳࡋ࡚࠸࡚ࡶṇ☜ ᐃ࡛ࡁࡿࠋ㟼ⓗගᩓἲ࡛⟬ฟࡉࢀࡓ┦㛵㛗ࡣᆒ୍ᵓ㐀ࡢࡁࡉࡢ┠Ᏻ࡞ࡾᮏ◊✲࡛ ࡣࢡ࣮ࣞࢬᖜ┦ᙜࡍࡿࠋ Figure 2.24 ࡽ Figure 2.27 PPࠊࢡ࣮ࣞࢬฎ⌮ PPࠊ ࢡ࣮ࣞࢬฎ⌮ PS ཬࡧࢡ࣮ࣞࢬฎ⌮ PMMA ࡢḟඖ೫ගಖᣢᩓീࢆ♧ࡍࠋPS ཬࡧ PMMA ࡣ㠀ᬗᛶ㧗ศᏊ࡛࠶ࡿࡓࡵࠊࢡ࣮ࣞ ࢬᮍฎ⌮ࣇ࣒࡛ࣝࡣᩓീࡣࢇᚓࡽࢀ࡞࠸ࠋ୍᪉ࠊPP ࡣ⤖ᬗᛶ㧗ศᏊ࡛࠶ࡿࡓࡵ ࢡ࣮ࣞࢬᮍฎ⌮ࡶ㛵ࢃࡽࡎ⤖ᬗࡼࡿගᩓࡀ㉳ࡇࡿࠋࡋࡋࠊࡇࡢࣇ࣒ࣝࡢ⤖ᬗࡣ ␗᪉ᛶࡀ࡞࠸ࡓࡵࠊᩓගࡣᨺᑕ≧ᩓࡋ࡚࠸ࡿࠋࡲࡓࠊࢡ࣮ࣞࢬฎ⌮PP PP ࡢ⣙ 30ºC ࡛ࡢᩓീࢆẚ㍑ࡍࡿࢡ࣮ࣞࢬฎ⌮PP ࡢᩓീࡢ᪉ࡣ PP ࡢᩓീࡢ࠶ࡗࡓᨺᑕ⥺ ≧ࡢᩓࡀ↓ࡃ࡞ࡗ࡚࠸ࡿࠋࡇࡢࡇࡽࠊࢡ࣮ࣞࢬࡼࡿᩓࡣ⤖ᬗࡢᩓẚ༑ศ ࡁࡃ⤖ᬗࡢᙳ㡪ࡣ↓ど࡛ࡁࡿࠋ
41
Figure 2.25 Temperature dependence of 2D CCD images for crazed PP film by SLS.
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42 Ⓨ⏕ࡍࡿࡇࡽࠊࡇࡢᵓ㐀ࡣฎ⌮ἲᑐࡋᖹ⾜Ꮡᅾࡍࡿࠋᚑࡗ࡚ࠊࡇࡢᵓ㐀ࡣࢡ࣮ࣞ ࢬฎ⌮ลࡢᦶ᧿ࡼࡗ࡚⏕ࡌࡓ⾲㠃ࡢയ࡛࠶ࡿࠋࡋࡋࠊ'HE\H ࣉࣟࢵࢺࡢゎᯒ⠊ᅖࢆ Ỉᖹ᪉ྥࡢࡳ㝈ᐃࡋ࡚࠸ࡿࡓࡵࠊࢡ࣮ࣞࢬⓎ⏕ࡢയࡀࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢ࠼ࡿᙳ 㡪ࡣ↓ど࡛ࡁࡿࠋ PS PMMA ࡛ࡣ ᗘୖ᪼క࠸ࠊᩓᙉᗘࡀᙅࡃ࡞ࡗࡓࠋධᑕࡋࡓ࣮ࣞࢨ࣮ᙉᗘࡣ ᗘ ౫ࡽࡎ୍ᐃࡢࡓࡵࡇࡢኚࡣࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡼࡾᵓ㐀ࡢᆒ୍ࡀ㐍⾜ࡋ࡚࠸ࡿࡇ ࢆ♧ࡍࠋࡇࢀࡽࡢᩓീࡽ┦㛵㛗ࢆ⟬ฟࡋࡓ⤖ᯝࢆFigure 2.28 ࡽ Figure 2.30 ♧ࡍࠋ
43
Figure 2.27 Temperature dependence of 2D CCD images for crazed PMMA film by SLS.
7KLFNQHVV ȝPFUD]LQJFRQGLWLRQ 03DPPPLQ DQGWLPHKHDWLQJUDWH FD&PLQ D FD& E & F & G & H & I & J &DQG K 100ºC. Figure 2.28 ࡣ PPࠊࢡ࣮ࣞࢬฎ⌮ PP ࠾ࡅࡿ┦㛵㛗ࡢ ᗘ౫Ꮡᛶࢆ♧ࡍࠋ๓㏙ࡋࡓࡀࠊPP ࡣ⤖ᬗᛶ㧗ศᏊ࡛࠶ࡿࡓࡵࢡ࣮ࣞࢬࡼࡿᩓ⤖ᬗࡼࡿᩓࡀぢࡽࢀࡿࠋࡋࡋࠊᚓࡽ ࢀࡓ┦㛵㛗ࢆẚ㍑ࡍࡿ⤖ᬗࡼࡿᩓീࡀᚓࡽࢀࡿPP ࡀࢡ࣮ࣞࢬࡼࡿᩓࡀ࡞ࡿ ࢡ࣮ࣞࢬฎ⌮PP ࡢ್ࡼࡾᖖᑠࡉࡃࠊ༊ูࡉࢀࡿࠋࡲࡓࠊPP ࡢᩓീࡽᚓࡽࢀࡿ┦㛵㛗 ࡣࠊ⼥Ⅼ௨ୗ࡛ࡣ ᗘ౫Ꮡᛶࡀ࡞࠸ࡇࡽࡶࠊࢡ࣮ࣞࢬฎ⌮ࣇ࣒ࣝࡢ㟼ⓗගᩓࡽ ᚓࡽࢀࡿ┦㛵㛗ࡢኚࡣࢡ࣮ࣞࢬࡼࡿࡶࡢゝ࠼ࡿࠋ ࢡ࣮ࣞࢬฎ⌮PP ࡣ⣙ 30ºC ࡽ 60ºC ࡅ࡚┦㛵㛗ቑຍഴྥࡀぢࡽࢀࡓࠋቑຍ್ࡣ⇕ ⭾ᙇಀᩘࡽ᥎ᐃࡉࢀࡿቑຍẚ㐣࡛࠶ࡿࠋᮏㄽᩥ࠾ࡅࡿࢡ࣮ࣞࢬࡢⓎ⏕ἲࡣࠊᛂຊ ࢆࡅ࡞ࡀࡽ᭤ࡆࡿ᪉ἲ࡛࠶ࡿࠋᚑࡗ࡚ࠊᛂຊゎᨺ⏕ᡂࡋࡓࢡ࣮ࣞࢬࡢࣇࣈࣜࣝࡀᙎ ᛶࡼࡾኚᙧࡋࠊᘱࡳࡀ⏕ࡌࡿྍ⬟ᛶࡀ࠶ࡿࠋ┦㛵㛗ࡢቑຍࡣࠊᘱࢇࡔ≧ែࡢࣇࣈࣜࣝࡢ ⇕⭾ᙇࡀ⪃࠼ࡽࢀࡿࠋࡇࡢࠊࢡ࣮ࣞࢬࢆⓎ⏕ࡉࡏࡓ㡿ᇦࡣ⤡ࡳྜ࠸ࡀ࡞㡿ᇦ࡛࠶ࡿࡓ ࡵ⇕⭾ᙇࡋࡸࡍ࠸࡞ࡢせᅉࡀ⪃࠼ࡽࢀࡿࠋ60ºC ࡽ 90ºC ࡅ࡚┦㛵㛗ࡣῶᑡࡋࡓࠋࡑ
44 ࡞ࡗࡓࠋణࡋࠊࣇ࣒ࣝయᑐࡋࣇࣈࣜࣝࡣᩘ%⛬ᗘ࡛࠶ࡾࠊDSC ࡢឤᗘ௨ୗ࡛࠶ࡿྍ ⬟ᛶࡀ࠶ࡿࠋ㠀ᬗᛶࡢPS ཬࡧ PMMA ࡛ࡣࡇࡢࡼ࠺࡞⌧㇟ࡣ☜ㄆ࡛ࡁࡎࠊ⤖ᬗᛶ㧗ศᏊࡢ ࢡ࣮ࣞࢬ≉᭷ࡢ⌧㇟࡛࠶ࡿࠋࡑࡢᚋࠊ130ºC ㏆࡚ῶᑡ㌿ࡌࠊ᭱ᚋࠊTm㏆࠸150ºC ࡞ࡿࢡ࣮ࣞࢬࣇ࣒ࣝࡢ┦㛵㛗ࡣPP ࣇ࣒ࣝࡢ┦㛵㛗ྠ➼࡞ࡗࡓࠋᩓീ࡛ࡣࢡ ࣮ࣞࢬྠ᪉ྥࡢᩓീᑐࡋᕥྑ᪉ྥᩓࡀ☜ㄆ࡛ࡁࡿࡀࠊࡇࢀࡣࢡ࣮ࣞࢬࢆⓎ⏕ࡉࡏ ࡓࡢ᭤ࡆࡢ᭱እ㠃࡛ࡁࡓࣇࣈࣜࣝࡀษࢀࢡࣛࢵࢡࡶⓎ⏕ࡍࡿࡽ࡛࠶ࡿࠋ
Figure 2.28 Temperature dependence of correlation length for original and crazed PP film by SLS. 7KLFNQHVV ȝP, cUD]LQJFRQGLWLRQ 03DPPPLQDQGWLPH, hHDWLQJUDWH FD&PLQ. 0.50 0.55 0.60 0.65 0.70 0.75 20 40 60 80 100 120 140 160 &RUUHODWLRQ OHQJWK ȝ m) 7HPSHUDWXUH & 2ULJLQDO33 &UD]HG33
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Figure 2.29 Temperature dependence of correlation length for crazed PS film by SLS.
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Figure 2.30 Temperature dependence of correlation length for crazed PMMA film by SLS.
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46 ᑐࡋࠊ㟼ⓗගᩓࡣㄏ㟁⋡ࡢᦂࡽࡂࡼࡾ ᐃࡍࡿࡓࡵࠊᑡ࡞࠸࣎ࢻ࡛ࡶᩓࡍࡿࡓࡵ࡛ ࠶ࡿࠋࡇࡢࡇࡽࠊ㟼ⓗගᩓἲࢆ⏝࠸ࡓࢡ࣮ࣞࢬᖜࡢ ᐃࡣගᏛ㢧ᚤ㙾ࢆ⏝࠸ࡿࡼࡾṇ ☜ ᐃ࡛ࡁࡿࠋ ගᏛ㢧ᚤ㙾ࡼࡾṇ☜ࢡ࣮ࣞࢬᖜࢆ ᐃ࡛ࡁࡿ㟼ⓗගᩓἲࡼࡾồࡵࡓTCHࡣ㧗ศᏊ✀ ౫ࡽࡎ60ºC ࡛࠶ࡗࡓࠋࡇࢀࡣࠊගᏛ㢧ᚤ㙾࡛ồࡵࡓ್ࡰ୍⮴ࡍࡿࠋ
47 2.3.2.3 ࢡ࣮ࣞࢬࣄ࣮ࣜࣥࢢࡢぢࡅࡢάᛶ࢚ࢿࣝࢠ࣮ࡢኚ ๓㡯ࡲ࡛ࡣගᏛⓗࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡘ࠸᳨࡚ウࡋࡓࠋࡑࡢ⤖ᯝࠊPLLA ࡢ௨እࡢ 㧗ศᏊ✀ཬࡧᡭἲ౫ࡽࡎTCHࡣ60ºC ࡛࠶ࡗࡓࠋࡲࡓࠊගᏛ㢧ᚤ㙾ࡼࡾồࡵࡓࢡ࣮ࣞࢬ㛫 㝸ࢆᇶ⟬ฟࡋࡓ⇕⭾ᙇ㔞ཬࡧ㟼ⓗගᩓἲ࡚ồࡵࡓࣄ࣮ࣜࣥࢢࡼࡿࢡ࣮ࣞࢬᖜࡢῶ ᑡ㔞ࢆ⪃៖ࡋࡓ㝿ࠊࢡ࣮ࣞࢬᖜࡢῶᑡࡢ᪉ࡀࡁࡗࡓࠋ༶ࡕࠊࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡀ㠀 ࢡ࣮ࣞࢬ㡿ᇦࡢ⇕⭾ᙇࡼࡗ࡚㉳ࡇࡗ࡚࠸ࡿࡢ࡛ࡣ࡞࠸ࠋᚑࡗ࡚ࠊࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࡣ ࢡ࣮ࣞࢬ┦⮬యࡀ⦰ࡋ࡚࠸ࡿࠋࡑࡇ࡛ࠊᮏ⠇࡛ࡣࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢࢆヨᩱࡢ㛗ࡉኚ ࡽ⟬ฟࡍࡿࡇࢆヨࡳࡓࠋ ࡇࡇ࡛ࠊ୍ᐃ㏿ᗘࡢ᪼ ࠾ࡅࡿࢡ࣮ࣜࣉヨ㦂࡛ࡣ ᗘ㛫ࡢ2 ࡘࡢኚᩘࢆྵࡴࠋࡑࡢ ࡓࡵࠊṇ☜࡞TCHࡣ⟬ฟ࡛ࡁ࡞࠸ࠋᮏ◊✲࡛ࡣ㛫ࡢࣃ࣓࣮ࣛࢱ࣮ࢆ㝖ࡍࡿࡓࡵࠊ⎔ቃ ᗘࢆᛴ⃭ኚࡉࡏ࡚ぢࡅࡢάᛶ࢚ࢿࣝࢠ࣮ኚࡽTCHࢆ⟬ฟࡍࡿࡇࢆヨࡳࡓࠋྛ ࢡ࣮ࣜࣉヨ㦂࠾࠸࡚ࠊึᮇࡢࡦࡎࡳ㏿ᗘࡢ᭱ഴࡁࢆ⟬ฟࡋࠊ ᗘูࡢࡦࡎࡳ㏿ᗘࡢ⤯ᑐ ್ࢆᚓࡓࠋࡑࡢᚋࠊᶓ㍈┠ᶆ ᗘࡢ㏫ᩘࠊ⦪㍈ᚓࡽࢀࡓ᭱ࡦࡎࡳ㏿ᗘࡢ⮬↛యᩘ್ࢆ ࣉࣟࢵࢺࡋࠊഴࡁࡼࡾぢࡅࡢάᛶ࢚ࢿࣝࢠ࣮ࢆ⟬ฟࡋࡓࠋFigure 2.31 ࡽ Figure 2.33 ྛ㧗ศᏊࡢArrhenius ࣉࣟࢵࢺࢆ♧ࡍࠋ
Figure 2.31 Arrhenius plot for uncraze region and craze region of crazed PP.
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Figure 2.32 Arrhenius plot for uncraze region and craze region of crazed PS.
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Figure 2.33 Arrhenius plot for craze region of crazed PMMA.
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49 PMMA ࡢࡳࢡ࣮ࣞࢬᮍฎ⌮ࡢ Arrhenius ࣉࣟࢵࢺࢆᚓࡿࡇࡀ࡛ࡁ࡞ࡗࡓࠋࡇࢀࡣࢡ࣮ࣞ ࢬᮍฎ⌮ࡶ㛵ࢃࡽࡎ60ºC ㏆ࡼࡾࣇ࣒ࣝࡢ⦰ࡀጞࡲࡿࡓࡵ࡛࠶ࡿࠋࡑࡢࡓࡵࠊࡦࡎ ࡳ㏿ᗘࡢṇ㈇ࡀ㏫㌿ࡋࠊ⮬↛ᑐᩘ್ࡀᚓࡽࢀ࡞࠸ࠋ୍᪉ࠊࢡ࣮ࣞࢬ㡿ᇦࡣࠊ㠀ࢡ࣮ࣞࢬ㡿ᇦ ࡢ⦰ࢆ⪃៖ࡋ࡚⟬ฟࡋࡓࡢ࡛ ᗘ౫ࡽࡎࡦࡎࡳ㏿ᗘࡣ㈇ࡢ್ࢆᚓࡿࠋᚑࡗ࡚ Arrhenius ࣉࣟࢵࢺࢆసᡂࡍࡿࡇࡀྍ⬟࡛࠶ࡿࠋ ୍᪉ࠊPP ཬࡧ PS ࡣ㠀ࢡ࣮ࣞࢬ㡿ᇦࡘ࠸࡚ Arrhenius ࣉࣟࢵࢺࢆసᡂࡍࡿࡇࡀ࡛ࡁࡓࠋ PP ཬࡧ PS ࡢ㠀ࢡ࣮ࣞࢬ㡿ᇦࡣ ᗘ㡿ᇦ࡛ࠊࡦࡎࡳ㏿ᗘࡢ⮬↛యᩘ್ࡣ ᗘࡢ㏫ᩘᑐࡋ ୍ḟ㛵ᩘ࡞ࡗࡓࠋArrhenius ࣉࣟࢵࢺࡽồࡵࡓぢࡅࡢάᛶ࢚ࢿࣝࢠ࣮ࡣ PP ࣇ࣒ࣝ ࡀ48 N-PROࠊPS ࣇ࣒ࣝࡀ N-PRO ࡞ࡗࡓࠋ୍⯡ⓗ㧗ศᏊ⇕ࢆຍ࠼࡚ࡶࢇࡀ ෆ㒊࢚ࢿࣝࢠ࣮ࡋ࡚㈓ࡉࢀࠊ⇕⭾ᙇࡣഹࡋࢃࢀ࡞࠸ࠋࡇࡢぢࡅࡢάᛶ࢚ࢿࣝ ࢠ࣮ࡣ⇕⭾ᙇ࣭⇕⦰せࡍࡿ࢚ࢿࣝࢠ࣮࡛࠶ࡾࠊᐇ㝿ࡣࡇࢀ௨ୖࡢ࢚ࢿࣝࢠ࣮ࡀࣇࣝ ࣒ࡣຍ࠼ࡽࢀ࡚࠸ࡿࠋ⇕⭾ᙇ࣭⇕⦰⏝ࡉࢀ࡞ࡗࡓഃ㙐ࡢ㐠ືࠊ㙐ࡢᒁᡤⓗ࡞㐠 ື࡞⏝ࡉࢀࡿࠋ PP ཬࡧ PS ࡢ㠀ࢡ࣮ࣞࢬ㡿ᇦࡣ ᗘ㡿ᇦ࡛ 1 ᮏࡢ୍ḟ㛵ᩘ࡞ࡗࡓࡢᑐࡋࠊࢡ࣮ࣞࢬ ฎ⌮ࡋࡓPPࠊPS ཬࡧ PMMA ࡣ Arrhenius ࣉࣟࢵࢺ୰ኚ᭤Ⅼࡀ 1 ⅬࡢᏑᅾࡍࡿ 2 ᮏࡢ୍ḟ 㛵ᩘ࡞ࡗࡓࠋ༶ࡕࠊぢࡅࡢάᛶ࢚ࢿࣝࢠ࣮ࡀኚࡍࡿ ᗘࡀᏑᅾࡍࡿࠋྛ㧗ศᏊࡢぢ ࡅࡢάᛶ࢚ࢿࣝࢠ࣮ኚࡍࡿ ᗘࢆ7DEOH2.8 ♧ࡍࠋ
Table 2.8 Apparent activation energy of sample polymer films and inflection point
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