CFRP ᡂᙧయ䛾ຊᏛ≉ᛶ

99

4.2.6 ⇕䝥䝺䝇䛻䜘䜛CFRPᡂᙧయ䛾సᡂ

CFRPᡂᙧయࡣῶᅽ⇕ࣉࣞࢫ࡟࡚ᡂᙧࡋࡓࠋPPࡣணࡵTࢲ࢖ࢆ⏝࠸࡚30 ȝm⛬ᗘࡢࣇ࢕

࣒ࣝ࡜ࡋࠊCF࡜PPࣇ࢕࣒ࣝࢆ✚ᒙࡉࡏࡓ≧ែ࡛㔠ᆺ㸦60 mm™ 77.5 mm ™ ཌࡉ1 mm㸧

࡟ࢭࢵࢺࡋࠊ࣮ࣟࢱ࣮࣏ࣜࣥࣉ㸦⌮ㄽ฿㐩┿✵ᗘ㸸⣙3D㸧࡟ࡼࡾ┿✵࡟ࡋࡓ≧ែ࡛ῶᅽ

⇕ࣉࣞࢫࢆ⾜ࡗࡓࠋCFࡢᢞධ㔞ࡣCFRP඲య࡟ᑐࡋZW࡛࠶ࡿࠋᑦࠊῶᅽ⇕ࣉࣞࢫࡢ᮲

௳ࡣ200ºCࠊ15 03Dࠊ10 min࡛࠶ࡿࠋ

ᐇᢞධ㔞ࡣCFRPᡂᙧయࢆ400|C࡛↝ࡁࠊPPࢆ⇕ศゎࡍࡿࡇ࡜࡛⟬ฟࡋࡓࠋヨᩱࡢᐦᗘ ࡣ࣓ࢺ࣮ࣛࢺࣞࢻᅛయᐦᗘ/ẚ㔜 ᐃ⏝࢟ࢵࢺ㸦࣓ࢺ࣮ࣛࢺࣞࢻ(ᰴ) 〇㸪ATኳ⛗⏝210485㸧

ࢆ⏝࠸࡚࢔࣓ࣝ࢟ࢹࢫἲ࡟࡚⟬ฟࡋࡓࠋ

CFࡢᐇᢞධ㔞ࡣࠊ⇕ศゎ๓ࡢ㔜㔞࠿ࡽ⇕ศゎᚋࡢ㔜㔞ࢆᘬ࠸ࡓ್࡜࡞ࡿࠋPPࡢᐇᢞධ㔞 ࡣ⇕ศゎ๓ࡢ㔜㔞࠿ࡽࠊCFࡢᐇᢞධ㔞ࢆᘬ࠸ࡓ್࡜࡞ࡿࠋࡇࢀࡽ࠿ࡽᘧ㸦4.2㸧࡟♧ࡍᘧ࡟

ࡼࡗ࡚✵㝽⋡ࢆ⟬ฟࡋࡓࠋ

CFRP CFRP PP

PP CF

CF W W

V W

U U

U

^¸¸_¹

¨¨ ·

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§

1 ^{࣭࣭࣭㸦4.2㸧}

ࡇࡇ࡛ࠊᘧ୰ࡢVࡣ✵㝽⋡ࠊWCFࠊWPPࠊWCFRPࡣCFࠊPPࡢᐇᢞධ㔞ࠊཬࡧCFRPࡢᐇ㔜 㔞ࠊɏCFࠊɏPPࠊɏCFRPࡣCFࠊPPࠊCFRPࡢᐦᗘࢆ♧ࡋ࡚࠸ࡿࠋ

100

OMBࠊ❅⣲ࢆෆໟẼయ࡜ࡋࡓ࣐࢖ࢡࣟࣂࣈࣝฎ⌮㸦௨ᚋࠊNMBฎ⌮㸧ࢆ⾜࠺ࡇ࡜࡛⏺㠃

ࡏࢇ᩿ᙉᗘࡀྥୖࡋࡓࠋάᛶ࢞ࢫࠊ୙άᛶ࢞ࢫ࡜ࡶ࡟ୖ᪼ࡋ࡚࠾ࡾࠊୟࡘࠊ࢞ࢫ✀࡟ࡼࡗ࡚

ୖ᪼ࡢ⛬ᗘࡀ␗࡞ࡿࡇ࡜࠿ࡽࠊ⏺㠃ࡏࢇ᩿ᙉᗘࡢୖ᪼ࡢせᅉ࡜ࡋ࡚ࠊ࣐࢖ࢡࣟࣂࣈࣝࡢ≉᭷

ࡢຠᯝ࡜ෆໟẼయࡢຠᯝࡀ࠶ࡿࠋࡇࡇ࡛ࠊ࣐࢖ࢡࣟࣂࣈࣝࡢ≉᭷ࡢຠᯝ࡜ࡋ࡚ᣲࡆࡽࢀࡿࡢ ࡣෆ㒊ᅽຊ㸦/DSODFHᅽ㸧࡟ࡼࡿ⮬ᕫᅽቯຠᯝ࡛࠶ࡿࠋ࣐࢖ࢡࣟࣂࣈࣝࡀỈ୰࡛⮬ᕫ཰⦰࣭

ᾘ⁛ࡍࡿ࡜ࡁࠊ࣐࢖ࢡࣟࣂࣈࣝෆ㒊ࡢᅽຊࡣᩘⓒᗘࠊᩘ03D࡜㧗 ࣭㧗ᅽ࡟࡞ࡿ࡜⪃࠼ࡽ

ࢀ࡚࠸ࡿࠋࡲࡓࠊᾘ⁛᫬࡟ࡣࣇ࣮ࣜࣛࢪ࢝ࣝࡢⓎ⏕ࡀ☜ㄆࡉࢀ࡚࠸ࡿ¹⁸ࠋࡇࢀࡽᾘ⁛᫬ࡢ㧗  ࣭㧗ᅽ཯ᛂሙࡢᙳ㡪ཪࡣࣇ࣮ࣜࣛࢪ࢝ࣝࡢ⏕ᡂ࡟ࡼࡾ⾲㠃ᵓ㐀ࡸᙧែࡢኚ໬ࡀ᥎ᐃࡉࢀࡿࠋ

Figure 4.2 Interfacial shear strength of modified CF: Error bar is shown standard deviation.

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0 2 4 6 8 10 12 14

'HVL]LQJ OMB NMB

,QWHUIDFLDOVKHDUVWUHQJWK03D

101

ྛ✀࢞ࢫ࡟ࡼࡿ࣐࢖ࢡࣟࣂࣈࣝฎ⌮࡟ࡼࡗ࡚ᵓ㐀ࠊᙧែࡢኚ໬ࡀண᝿ࡉࢀࡓⅭࠊSEM ࡟

ࡼࡿ⾲㠃ほᐹࠊ࢞ࢫ྾╔࡟ࡼࡿẚ⾲㠃✚ࡢ ᐃཬࡧXPS࡟ࡼࡿO/Cẚࡢ ᐃࢆ⾜ࡗࡓࠋ

2ULJLQDO 'HVL]LQJ

OMB NMB

Figure 4.3 SEM images of surface of CF.

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Figure 4.3ࡣࠊࢧ࢖ࢪࣥࢢ๣㝖ཤCFࠊOMBฎ⌮CFࠊNMBฎ⌮CFࡢ⾲㠃SEM⏬ീ࡛࠶

ࡿࠋ࢔ࢭࢺࣥ࡟ࡼࡿࢧ࢖ࢪࣥࢢ๣㝖ཤ࡟ࡼࡾࠊࢧ࢖ࢪࣥࢢ๣࡟ࡼࡗ࡚ᇙࡲࡗ࡚࠸ࡓ⧄⥔᪉ྥ

ࡢ⁁ࡀ㩭᫂࡟⌧ࢀࡿࠋࢧ࢖ࢪࣥࢢ๣㝖ཤᚋࡢSEM⏬ീ࡟ࡣࠊ⧄⥔᪉ྥࡢ⁁௨እ࡟ࡶ CF⾲ 㠃࡟พฝࡀ࠶ࡿࡢࡀ☜ㄆ࡛ࡁࡿࠋࡇࢀࡣࠊ࢔ࢭࢺࣥฎ⌮࡟ࡼࡗ࡚ྲྀࡾ㝖ࡃࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗ ࡓࢧ࢖ࢪࣥࢢ๣࡛࠶ࡾࠊ࢔ࢭࢺࣥฎ⌮࡛ࡣ᏶඲࡟ࢧ࢖ࢪࣥࢢ๣㝖ཤࡀ࡛ࡁ࡞࠸ࠋࡇࡢพฝࡣ OMBฎ⌮ᚋ࡛ࡣ☜ㄆ࡛ࡁࡎࠊOMB࡟ࡼࡾࢧ࢖ࢪࣥࢢ๣ࡀ࢜ࢰࣥ㓟໬࡟ࡼࡾศゎ࣭㝖ཤ࡛ࡁ ࡓࠋࡲࡓࠊNMB࡟࠾࠸࡚ࡣOMB࡜ẚ࡭ࡿ࡜᏶඲࡛ࡣ࡞࠸ࡀࠊࢧ࢖ࢪࣥࢢ๣㝖ཤᚋࡼࡾพ ฝࡀῶᑡࡋ࡚࠾ࡾࠊࢧ࢖ࢪࣥࢢ๣ࡀ㝖ཤ࡛ࡁࡓࠋ㓟໬ຊࡢஈࡋ࠸NMB࡛ࡉ࠼ࡶ࢔ࢭࢺࣥฎ

102

ᅽຊࠊp0ࡣ㣬࿴ᅽຊࠊVDࡀẼయࡢ྾╔㔞ࠊVmࡀ༢ศᏊᒙ྾╔㔞ࠊCࡣ⇕࡟㛵ࡍࡿࣃ࣓࣮ࣛ

ࢱ࣮ࢆ♧ࡋ࡚࠸ࡿࠋࡑࡢᚋࠊᘧ㸦3.4㸧࡟ࡼࡗ࡚ẚ⾲㠃✚ࢆ⟬ฟࡍࡿࠋࡇࡇ࡛ࠊᘧ୰ࡢAࡣ ẚ⾲㠃✚ࠊNAࡣ࢔࣎࢞ࢻࣟᐃᩘࠊDࡣศᏊ༨᭷᩿㠃✚㸦0.162 nm²㸧࡛࠶ࡿࠋࡇࡢᘧࡣࠊ༢ศ Ꮚᒙ྾╔㔞ࡢࣔࣝᩘࢆ⟬ฟࡋࠊศᏊᩘ࡟ኚ᥮ࡋࠊศᏊ1ಶᙜࡓࡾࡢ㠃✚ࢆ஌ࡌ࡚࠸ࡿࠋࡇࡢ ᘧ࡟ࡼࡗ࡚ẚ⾲㠃✚ࢆ⟬ฟࡋࡓ⤖ᯝࢆ7DEOH 4.2࡟♧ࡍࠋ

Figure 4.4 BET plot of CF: Each plot is shown follows: circle plot is original, square plot is desizing, cross plot is OMB, and triangle plot is NMB.

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_m ^¨¨_©^§ _m ^¸¸_¹^·¨¨_©^§ ₀^¸¸_¹^·

D

1 1

p p C V C C V p p V

p _{࣭࣭࣭㸦4.3㸧}

0 1.0 2.0 3.0 4.0 5.0

0 0.1 0.2 0.3

p/VD(p0-p) [cm-3(STP)࣭g]

p/p₀

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A D

muN u

A V ࣭࣭࣭㸦4.4㸧

ẚ⾲㠃✚ࡣᮏ ᐃ࡛⏝࠸ࡓ⿦⨨ࡀಖドࡍࡿẚ⾲㠃✚2 m²/g࡟ᒆ࠸࡚࠸࡞࠸ࠋࡑࡢⅭࠊẚ⾲

㠃✚ࡢ್ࡣ⤯ᑐ್࡜ࡋ࡚ࡣಖド࡛ࡁ࡞࠸ࠋࡋ࠿ࡋࠊ4ヨᩱ࡜ࡶྠ᮲௳࡛ ᐃࡋ࡚࠾ࡾࠊヨᩱ

㛫ࡢ┦ᑐホ౯ࡣྍ⬟࡛࠶ࡿࠋ⾲ࡼࡾࠊẚ⾲㠃✚ࡢ኱ࡁࡉࡣOMBฎ⌮㸼NMBฎ⌮㸼ࢧ࢖ࢪ

ࣥࢢ๣㝖ཤ㸼ᮍฎ⌮ࡢ㡰࡛࠶ࡾࠊSEM ⏬ീࡢഴྥ࡜୍⮴ࡍࡿࠋ๓㏙ࡋࡓࡀࠊ ᐃ್ࢆಖド ࡍࡿẚ⾲㠃✚ࢆᚓࡽࢀ࡚࠸࡞࠸ࡓࡵࠊ᭷ពᕪ࡟ࡘ࠸࡚㆟ㄽࡍࡿᚲせࡀ࠶ࡿࠋẚ⾲㠃✚ࡢ⟬ฟ ࡣᘧ㸦4.3㸧ཬࡧ㸦4.4㸧࡟ࡼࡗ࡚⾜ࢃࢀࡿࠋẚ⾲㠃✚࡜༢ศᏊᒙ྾╔㔞ࡣẚ౛㛵ಀ࡛࠶ࡿࡢ

࡛ࠊ༢ศᏊᒙ྾╔㔞࡟ඃ఩ᛶࡀぢࡽࢀࡿ࠿ࢆ㆟ㄽࡍࡿᚲせࡀ࠶ࡿࠋࡇࡇ࡛ࠊᘧ㸦3.3㸧࡟ὀ┠

ࡍࡿ࡜ࠊBETࣉࣟࢵࢺࡢษ∦ࡀ1㸭VmCࠊഴࡁࡀ㸦C-1㸧㸭VmC࡛࠶ࡿࠋVmࡀ༢ศᏊᒙ྾╔

㔞࡛࠶ࡿ࠿ࡽVm࡟ࡘ࠸࡚ゎࡃ࡜ 1㸭㸦ษ∦㸩ഴࡁ㸧࡜࡞ࡿࠋࢢࣛࣇࡼࡾࠊᮍฎ⌮ࢆ㝖࠸࡚

ษ∦ࡣ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠸ࠋ୍᪉ࠊഴࡁࡣOMB㸺NMB㸺ࢧ࢖ࢪࣥࢢ㝖ཤࡢ㡰࡛࠶ࡾࠊ᫂ࡽ

࠿࡞᭷ពᕪࡀ࠶ࡿࠋᚑࡗ࡚ࠊ⾲࡟♧ࡉࢀࡓẚ⾲㠃✚ࡢヨᩱ㛫ࡢᕪ࡟᭷ពᕪࡀ࠶ࡿ࡜ゝ࠼ࡿࠋ

Table 4.2 Specific surface area of CF

&RQGLWLRQV 6SHFLILFVXUIDFHDUHD (m²/g) 2ULJLQDO 0.35

'HVL]LQJ 0.51

OMB 0.60

NMB 0.55

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ࡇࡇ࡛ࠊ᥋╔ᛶ࡟⪃࠼ࡿ࡜ࠊぢ࠿ࡅࡢ᥋╔㠃✚㸦ࢻࣟࢵࣉࣞࢵࢺࡢ኱ࡁࡉ㸧ࡀྠ୍࡛࠶ࡿ

ሙྜࠊCF࡜᥋ࡋ࡚࠸ࡿ㠃✚ࡀ኱ࡁ࠸࡯࡝⏺㠃ࡏࢇ᩿ᙉᗘࡣᙉࡃ࡞ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ ẚ⾲㠃✚ࡢୖ᪼ࡣSEM࡛ࡣ☜ㄆ࡛ࡁ࡞࠸⛬ࡢᑠࡉ࡞พฝࡀ⏕ᡂࡋࡓྍ⬟ᛶࡀ࠶ࡾࠊ࢔࣮ࣥ࢝

ຠᯝ࡟ࡼࡿ⏺㠃ࡏࢇ᩿ᙉᗘࡢྥୖࡶᮇᚅ࡛ࡁࡿࠋࡋ࠿ࡋࠊ ᐃࡋࡓ⏺㠃ࡏࢇ᩿ᙉᗘࡢ್ࡣࠊ OMBฎ⌮ࡼࡾNMBฎ⌮ࡢ᪉ࡀ኱ࡁࡃࠊẚ⾲㠃✚ࡢ⤖ᯝ࡜▩┪ࡍࡿࠋࡑࡇ࡛ࠊḟ࡟⾲㠃ࡢ

໬Ꮫⓗᵓ㐀࡟ࡘ࠸᳨࡚ウࡋࡓࠋ

Figure 4.5ࡣྛ✀CF࡟ࡘ࠸࡚XPS ᐃ࡟ࡼࡗ࡚ᚓࡽࢀࡓC1sࣆ࣮ࢡࢆ♧ࡋ࡚࠸ࡿࠋ࢔ࢭ

ࢺࣥὙί࡟ࡼࡾࠊᮍฎ⌮࡟㢧ⴭ࡟⾲ࢀ࡚࠸ࡓࢧ࢖ࢪࣥࢢ๣⏤᮶࡜⪃࠼ࡽࢀࡿ286 eV௜㏆ࡢ CO⤖ྜࡢࣆ࣮ࢡࡀῶᑡࡋ࡚࠸ࡿࠋࡋ࠿ࡋࠊࢩࣙࣝࢲ࣮࡜ࡋ࡚☜ㄆ࡛ࡁࡿࡇ࡜࠿ࡽࢧ࢖ࢪࣥ

ࢢ๣ࡢṧ␃ࡀ♧၀ࡉࢀࡿࠋࡋ࠿ࡋࠊOMBฎ⌮ࢆ⾜࠺࡜ࢩࣙࣝࢲ࣮ࡶ☜ㄆ࡛ࡁ࡞ࡃ࡞ࡾࠊࢧ

104

105 (D) 2ULJLQDO

(b) 'HVL]LQJ

275 280

285 290

295 300

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275 280

285 290

295 300

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106 (c) 20%WUHDWPHQW

(d) NMB

Figure 4.5 C1s Peak of CF surface by XPS.

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275 280

285 290

295 300

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107

Figure 4.6ࡣྛ✀CFࡢO/Cẚࢆ♧ࡋ࡚࠸ࡿࠋ๓㏙ࡋࡓࡼ࠺࡟OMBฎ⌮࡟ࡼࡾCF࡟࢝ࣝ

࣎࢟ࢩᇶ࡜ᛮࢃࢀࡿᐁ⬟ᇶࡀᑟධࡉࢀࡓⅭࠊOMBฎ⌮ࡣO/Cẚࡀቑຍࡋࡓࠋ୍᪉ࠊ⏺㠃ࡏ

ࢇ᩿ᙉᗘࡀ᭱ࡶ㧗࠿ࡗࡓNMBฎ⌮࡛ࡣO/Cẚࡣࢧ࢖ࢪࣥࢢ๣㝖ཤᚋ࡜࡯࡜ࢇ࡝ኚ໬ࡋ࡞ࡗ ࡓࠋ୍⯡ⓗ࡟ࠊCFRPࢆసᡂࡍࡿ࡜ࡁPPࡢࡠࢀᛶࡀ㔜どࡉࢀࠊPPࢆ࣐ࣞ࢖ࣥ㓟ኚᛶࡍࡿࡇ

࡜࡛ᙉᗘࡀୖ᪼ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊᮏ◊✲࡛ࡣCFࡢぶỈ໬ࡣࠊPP࡜ࡢ᥋╔

ᛶࢆᝏࡃࡍࡿഴྥࡀ࠶ࡿࠋOMBฎ⌮࡛ࡶCF࡟ᑐࡍࡿPPࡢࡠࢀᛶࡣྥୖࡍࡿࡢ࡛ྠᵝࡢ⤖

ᯝࡀᚓࡽࢀࡿࡇ࡜ࡀண᝿࡛ࡁࡿࡀࠊ⏺㠃ࡏࢇ᩿ᙉᗘࡢほⅬ࠿ࡽࡣࡠࢀᛶࢆኚ໬ࡉࡏࡎࠊẚ⾲

㠃✚ࡢࡳࢆቑຍࡉࡏࡿNMBฎ⌮ࡢ᪉ࡀ㐺ࡋ࡚࠸ࡿࠋ

Figure 4.6 O/C ratio of modified CF.

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0 5 10 15 20 25 30 35

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108

3Ⅼ᭤ࡆヨ㦂⤖ᯝࡢᖹᆒ್࡜✵㝽⋡ཬࡧCFࡢᐇᢞධ㔞࡛࠶ࡿࠋࢢࣛࣇ࠿ࡽOMBฎ⌮CFRP ᡂᙧయࡣࢧ࢖ࢪࣥࢢ๣㝖ཤCFRPᡂᙧయ࡟ẚ࡭ᙉᗘࠊᙎᛶ⋡࡜ࡶ࡟ୖ᪼ࡋ࡚࠸ࡿࠋ୍᪉ࠊ⏺

㠃ࡏࢇ᩿ᙉᗘࡀ᭱ࡶⰋ࠿ࡗࡓNMBฎ⌮CFRPᡂᙧయࡣࠊᐇ㦂Ỉ‽ෆ࡛ࡣ᭱ࡶᝏ࠿ࡗࡓࠋCF ࡢᐇᢞධ㔞ࡣ᧯సᢞධ㔞࡜࡯ࡰྠࡌ࡛࠶ࡾࠊỈ‽㛫࡟࠾࠸࡚ࡶᕪࡣ࡞࠸ࠋᚑࡗ࡚ࠊCFRPᡂ ᙧయࡢᙉᗘ࡜⏺㠃ࡏࢇ᩿ᙉᗘࡀ୍⮴ࡋ࡞࠸ࠋࡇࢀࡣCFRPᡂᙧయࡢෆ㒊ᵓ㐀࡟ࡼࡿᙳ㡪ࡀ኱

ࡁ࠸ࠋࡑࡇ࡛ࠊᙉᗘపୗࡢせᅉ࡜࡞ࡿ✵㝽⋡࡟ὀ┠ࡋࡓࠋྛ✀CFࢆ⏝࠸ࡓCFRPᡂᙧయ࡟

ࡘ࠸࡚✵㝽⋡ࢆ ᐃࡋࡓ⤖ᯝࠊOMBฎ⌮CFRPᡂᙧయࡀ᭱ࡶ✵㝽⋡ࡀపࡃࠊNMBฎ⌮CFRP ᡂᙧయࡀ᭱ࡶ✵㝽⋡ࡀ㧗࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊOMBฎ⌮CFRPᡂᙧయࡢࡳࡀᙉᗘୖ᪼ࡋ ࡓࡢࡣࠊCFࡢࡠࢀᛶྥୖ࡟ࡼࡿྵᾐᛶࡢୖ᪼࡟㉳ᅉࡍࡿࠋ

Figure 4.7 S-S curves of CFRP at 3-point bending.

)XOFUXP GLVWDQFH PP FURVVKHDG VSHHG PPPLQDHVL]LQJ: DFHWRQH rinsing, OMB, NMB: WUHDWPHQWWHPSUHWXUH s 1 ºCWUHDWPHQWWLPH h.

'HVL]LQJ OMB

NMB

0 10 20 30 40 50 60 70

0 1 2 3 4 5 6 7 8 9

6WUHVV03D

6WUDLQ (%)

109

Table 4.3 Mechanical properties of CFRP

&RQGLWLRQV

)OH[XUDO PRGXOXV

*3D

0D[LPXP VWUHVV 03D

9RLG UDWLR (%)

&)UDWLR ZW 'HVL]LQJ 2.96 51.8 2.1 9

OMB 4.03 59.2 2.0 10

NMB 2.41 44.8 2.5 9

)XOFUXP GLVWDQFH PP FURVVKHDG VSHHG PPPLQDHVL]LQJ: DFHWRQH rinsing, OMB, NMB: WUHDWPHQWWHPSUHWXUH s 1 ºC, WUHDWPHQWWLPH h

OMBฎ⌮CFRPࡢྵᾐᛶࡢ㧗ࡉࠊNMBฎ⌮CFRPࡢྵᾐᛶࡢపࡉࡣCFRPࡢ᩿㠃ほᐹ࡟

ࡼࡗ࡚ศ࠿ࡿࠋFigure 4.8ࡣྛ✀ฎ⌮CFRPᡂᙧయࡢ᩿㠃ࡢ㢧ᚤ㙾෗┿࡛࠶ࡿࠋᕥഃࡀ3Ⅼ

᭤ࡆヨ㦂๓ࠊྑഃࡀ3Ⅼ᭤ࡆヨ㦂ᚋࡢ෗┿࡛࠶ࡿࠋᑦࠊヨ㦂ᚋࡢ෗┿ࡣ᭤ࡆヨ㦂ࡢⲴ㔜Ⅼࡢ

఩⨨࡛ほᐹࡋࡓࠋ෗┿࡟࡚ⓑࡃほᐹࡉࢀ࡚࠸ࡿࡢࡀCFࠊ㯮ࡃほᐹࡉࢀࡿࡢࡀ࣎࢖ࢻ࡛࠶ࡿࠋ ࡇࢀࡽ෗┿ࢆぢࡿ࡜ࠊOMBฎ⌮CFRPᡂᙧయ࡜ࢧ࢖ࢪࣥࢢ๣㝖ཤCFRPᡂᙧయ࡛ࡣ3Ⅼ

᭤ࡆヨ㦂๓࡛ࡣCF࿘ࡾ࡟࣎࢖ࢻࡣ࡯࡜ࢇ࡝ほᐹ࡛ࡁ࡞࠸ࠋ୍᪉ࠊNMBฎ⌮CFRPᡂᙧయ ࡣ3Ⅼ᭤ࡆヨ㦂๓࡛ࡶ⧄⥔᮰ෆ㒊࡟࣎࢖ࢻࡀ☜ㄆ࡛ࡁࠊᶞ⬡ࡀྵᾐࡉࢀ࡚࠸࡞࠸ࡇ࡜ࡀศ࠿

ࡿࠋ3Ⅼ᭤ࡆヨ㦂ᚋࡣࠊNMBฎ⌮CFRPᡂᙧయࡣ⧄⥔᮰ෆ㒊ࡢ࣎࢖ࢻࡢᣑ኱ࡀ☜ㄆ࡛ࡁࠊ ࢧ࢖ࢪࣥࢢ๣㝖ཤCFRPᡂᙧయ࡟ࡘ࠸࡚ࡶCF࿘ࡾ࡟࣎࢖ࢻࡢⓎ⏕ࡀ☜ㄆ࡛ࡁࡿࠋ୍᪉ࠊOMB ฎ⌮CFRPᡂᙧయࡣ3Ⅼ᭤ࡆヨ㦂ᚋ࡛ࡶCF࿘ࡾ࡟࣎࢖ࢻࡢⓎ⏕ࡣ☜ㄆ࡛ࡁ࡞࠸ࠋࡇࡢࡇ࡜

࠿ࡽࡶNMBฎ⌮CFRPᡂᙧయࡣᶞ⬡ࡢྵᾐᛶࡀప࠸ࡇ࡜ࡀ♧ࡉࢀࡿࠋࡲࡓࠊࢧ࢖ࢪࣥࢢ๣

㝖ཤCFRPᡂᙧయࡣ3Ⅼ᭤ࡆヨ㦂ᚋ࡟࣎࢖ࢻࡀⓎ⏕ࡋࡓࡢ࡟ᑐࡋࠊOMBฎ⌮CFRPᡂᙧయ

࡛ࡣⓎ⏕ࡋ࡞࠿ࡗࡓࡇ࡜࠿ࡽOMBฎ⌮࡟ࡼࡾCF㸫PP㛫ࡢ᥋╔ᙉᗘࡀྥୖࡋ࡚࠸ࡿࡇ࡜ࢆ

♧ࡍࠋ

110

20%EHIRUH-SRLQWEHQGLQJ 20%DIWHU-SRLQWEHQGLQJ

10%EHIRUH-SRLQWEHQGLQJ NMB DIWHU-SRLQWEHQGLQJ Figure 4.8 Micrograph of each CFRP: Micrographs of left hand are before 3-point bending testing and them of other are after testing.

)XOFUXP GLVWDQFH PP FURVVKHDG VSHHG PPPLQDHVL]LQJ: DFHWRQH rinsing, OMB, NMB: WUHDWPHQWWHPSUHWXUH s 1 ºCWUHDWPHQWWLPH h

111

NMBฎ⌮CFRPࡢྵᾐᛶࡢపࡉࡢせᅉࡘ࠸࡚⪃࠼ࡿࠋྵᾐᛶࢆᕥྑࡍࡿࡢࡣCFࡢ⾲㠃

࢚ࢿࣝࢠ࣮࡛࠶ࡿࠋᮏ◊✲࡛⏝࠸ࡓ᥋ゐゅィ࡛ࡣCFࡢࡼ࠺࡞⧄⥔ᙧែࡢヨᩱ࡟ࡘ࠸࡚ ᐃ

࡛ࡁ࡞࠿ࡗࡓࡢ࡛ࠊCF࡟⾲㠃ᵓ㐀ࡀ㢮ఝࡋ࡚࠸ࡿࢢࣛࣇ࢙ࣥࢆ⏝࠸᳨࡚ウࡋࡓࠋFigure 4.9 ࡣྛฎ⌮ࢆ⾜ࡗࡓࢢࣛࣇ࢙ࣥࡢ᥋ゐゅࢆ♧ࡋ࡚࠸ࡿࠋOMBฎ⌮ࡣXPSࡢ⤖ᯝࡼࡾ࢝ࣝ࣎࢟

ࢩᇶࡢᑟධࡀ♧၀ࡉࢀ࡚࠾ࡾࠊ᥋ゐゅࡀపୗࡋࡓࠋ୍᪉ࠊNMB ࡣ᥋ゐゅࡀୖ᪼ࡋࡓࠋ2 ᡂ ศ⣔ࡢ᥋ゐゅࡣᘧ㸦4.5㸧࡛♧ࡋࡓ&DVVLHࡢᘧ࡟ࡼࡗ࡚⾲グ࡛ࡁࡿࠋࡇࡇ࡛ࠊ✵Ẽࡢ᥋ゐゅ ࡣ0࡜ࡉࢀ࡚࠸ࡿࠋᚑࡗ࡚ࠊ✵Ẽ┦ࢆྵࡴ⣔࡛ࡣ᥋ゐゅࡀୖ᪼ࡍࡿࠋXPS࡟ࡼࡿ࡜NMBฎ

⌮ࡣࢧ࢖ࢪࣥࢢ๣㝖ཤ࡜⾲㠃ᵓ㐀ࡣ࡯࡜ࢇ࡝ኚ໬ࡋ࡚࠸࡞࠸ࠋࡲࡓࠊSEM ⏬ീࡼࡾ࢔ࢭࢺ

ࣥ࡟ࡼࡿࢧ࢖ࢪࣥࢢ๣㝖ཤ࡟ẚ࡭ഹ࠿࡟ࢧ࢖ࢪࣥࢢ๣ࡀ㝖ཤࡉࢀࡓࡶࡢࡢ኱ࡁ࡞ᵓ㐀ኚ໬ࡣ ぢࡽࢀ࡞࠸ࠋࡋ࠿ࡋࠊ࢞ࢫ྾╔࡟ࡼࡿ⾲㠃✚ቑຍཬࡧ᥋ゐゅࡢቑຍ࠿ࡽ⪃៖ࡍࡿ࡜ࠊ⾲㠃ࡀ ഹ࠿࡟⢒࡟࡞ࡾ✵Ẽ┦ࡀ⏕ᡂࡋ࡚࠸ࡿࠋࡇࡢࡇ࡜࠿ࡽࠊNMBࡣ⾲㠃ࢆ≀⌮ⓗ࡟࢚ࢵࢪࣥࢢ ࡍࡿ⬟ຊࡀ࠶ࡿ࡜♧၀ࡉࢀࡿࠋ

PPࡣỈࡼࡾࡶ⾲㠃࢚ࢿࣝࢠ࣮ࡀప࠸ⅭࠊNMBฎ⌮ᚋ࡛ࡶ༑ศ࡟⃿ࢀࡿྍ⬟ᛶࡀ࠶ࡿࠋࡋ

࠿ࡋࠊ⁐⼥ࡋࡓ PP ࡣ⢓ᗘࡀ㧗࠸Ⅽࡀ⏕ᡂࡋࡓ✵Ẽ┦࡟༑ศ࡟ྵᾐ࡛↓࠿ࡗࡓⅭࠊNMB ฎ

⌮CFRPࡢᙉᗘࡣప࠸ࠋࡋ࠿ࡋࠊࢧ࢖ࢪࣥࢢ๣㝖ཤࢆ᏶඲࡟⾜࠺ࡇ࡜࡟ࡼࡾᙉᗘྥୖࡍࡿ࡜

࠸࠺ሗ࿌౛ࡀ࠶ࡾ⁶⁷ࠊCF⾲㠃ࢆ␯Ỉᛶ࡟⥔ᣢࡋࡓ≧ែ࡛ࠊ࣮࢜ࢺࢡ࣮ࣞࣈᡂᙧἲࢆ⏝࠸ࡿ

࡞࡝ᡂᙧ᫬࡟ྵᾐᛶࢆୖࡆࡿࡇ࡜࡛OMBฎ⌮௨ୖࡢຊᏛ≉ᛶࡀᚓࡽࢀࡿྍ⬟ᛶࡀ࠶ࡿࠋ

&RVȟ = f FRVȟ₁㸩 㸦 1-f 㸧FRVȟ₂ ࣭࣭࣭㸦4.5㸧

112

Figure 4.9 Contact angle measurements of graphite MB processing:

Error bar is shown standard deviation.

7UHDWPHQWWHPSUHWXUH s 1 ºCWUHDWPHQWWLPH h 70

75 80

2ULJLQDO OMB NMB

&RQWDFW

113 4.4 䜎䛸䜑

ᮏ❶࡛ࡣࠊCFࢆOMBฎ⌮ࠊNMBฎ⌮ࢆ⾜࠸ࠊ⏺㠃ࡏࢇ᩿ᙉᗘࡢྥୖࠊCFRPᡂᙧయࡢ ᙉᗘྥୖࢆ᳨ウࡋࡓࠋࡑࡢ⤖ᯝࠊ௨ୗࡢ▱ぢࢆᚓࡓࠋ

㸦1㸧ẚ⾲㠃✚ࡣࠊOMBฎ⌮ࠊNMBฎ⌮ࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊ࢔ࢭࢺࣥฎ⌮ᚋ࡜ẚ㍑ࡋࠊࡑ

ࢀࡒࢀࡀ⣙20%ࠊ8%ྥୖࡍࡿࠋ

㸦2㸧O/CẚࡣࠊOMBฎ⌮ࢆ⾜࠺ࡇ࡜࡛࢔ࢭࢺࣥฎ⌮ᚋ࡜ẚ㍑ࡋ⣙32%ྥୖࡋࡓࡀࠊNMB ฎ⌮ࢆ⾜ࡗ࡚ࡶ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠸ࠋ

㸦3㸧⏺㠃ࡏࢇ᩿ᙉᗘࡣࠊOMBฎ⌮ࠊNMBฎ⌮ࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊ࢔ࢭࢺࣥฎ⌮ᚋ࡜ẚ㍑

ࡋࠊࡑࢀࡒࢀࡀ⣙19%ࠊ55%ྥୖࡍࡿࠋ

㸦4㸧OMBฎ⌮ࢆ⾜ࡗࡓCFࡢࢡࣟࢫࢆ⏝࠸࡚ᡂᙧࡋࡓCFRPࡣࠊ࢔ࢭࢺࣥฎ⌮ࡋࡓCFࢆ

⏝࠸࡚ᡂᙧࡋࡓCFRP࡜ẚ࡭ࠊ᭱኱ᛂຊ࣭᭤ࡆᙎᛶ⋡ࡀ⣙14%ࠊ36%ྥୖࡍࡿࠋ୍᪉ࠊNMB ฎ⌮ࢆ⾜ࡗࡓ CF ࢡࣟࢫࢆ⏝࠸࡚ᡂᙧࡋࡓ CFRP ࡟㛵ࡋ࡚ࡣࠊ᭱኱ᛂຊ࣭᭤ࡆᙎᛶ⋡ࡀ⣙

16%ࠊ32%ῶᑡࡍࡿࠋ

㸦5㸧ᡂᙧࡋࡓCFRPࡢ✵㝽⋡ࡣࠊOMBฎ⌮ࠊ࢔ࢭࢺࣥฎ⌮ࠊNMBฎ⌮ࡢ㡰࡛࠶ࡾࠊ᩿㠃 ࡢගᏛ㢧ᚤ㙾෗┿࠿ࡽࡶࠊࡇࢀࡽࡢഴྥࡀ☜ㄆ࡛ࡁࡿࠋ

௨ୖࡢࡇ࡜࠿ࡽࠊCF ࡟OMBฎ⌮ࢆ⾜࠺ࡇ࡜࡟ࡼࡾࠊ⾲㠃ࡠࢀᛶࡢᨵ㉁࡟ࡼࡿ⏺㠃ࡏࢇ

᩿ᙉᗘཬࡧྵᾐᛶྥୖࠊẚ⾲㠃✚ࡢୖ᪼ࡀ㉳ࡇࡿࡓࡵࠊCFRPᡂᙧయࡢᙉᗘࡀྥୖࡍࡿࠋࡋ

࠿ࡋࠊ⏺㠃ࡏࢇ᩿ᙉᗘࡣNMBࡀ᭱ࡶୖ᪼ࡋ࡚࠾ࡾࠊCFRPᡂᙧ᫬ࡢᡂᙧ᪉ἲ࡟ࡼࡗ࡚ࡣ᭦

࡞ࡿᙉᗘྥୖࡀぢ㎸ࡲࢀࡿࠋ

114

ࡃࠊࣇ࣮ࣜࣛࢪ࢝ࣝⓎ⏕࠿ࡽCFࡲ࡛ࡢ᥋ࡍࡿࡲ࡛㛗࠸࡜཯ᛂ๓࡟ࣇ࣮ࣜࣛࢪ࢝ࣝࡀᾘ⁛ࡍ

ࡿࠋ᭱ࡶฎ⌮ຠᯝࡀᚓࡽࢀࡿ࡜ᮇᚅࡉࢀࡿ≧ἣࡣCF⾲㠃࡟࣐࢖ࢡࣟࣂࣈࣝࡀ௜╔ࡋࠊࡑࡢ ሙ࡟࡚⦰ᑠ࣭ᾘ⁛ࡍࡿࡇ࡜࡛࠶ࡿࠋ

๓㏙ࡋࡓࡼ࠺࡟ࠊ࣐࢖ࢡࣟࣂࣈࣝࢆ⏝࠸ࡓ᳜≀ࡢ⫱ᡂಁ㐍ࠊᶵᲔ㒊ရࡢὙίࠊỈࡢί໬࡞

࡝ᵝࠎ࡞◊✲ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ࣐࢖ࢡࣟࣂࣈࣝࡢฎ⌮࡟㛵ࡋ࡚ࡣ⿕ฎ⌮≀࡟ᑐࡍࡿ྾╔ᛶ ࡀ㔜せ࡜࡞ࡿ࡟ࡶ࠿࠿ࢃࡽࡎࠊ◊✲ሗ࿌౛ࡣഹ࠿࡛࠶ࡿ⁷³ࠋࡑࡇ࡛ࠊᮏ❶࡛ࡣ࣐࢖ࢡࣟࣂࣈ

ࣝࡢ྾╔ᛶ࡟ࡘ࠸᳨࡚ウࡋࡓࠋ

࣐࢖ࢡࣟࣂࣈࣝࡣẼἻᚄ50 ȝm௨ୗ࡜ࡉࢀ࡚࠸ࡿࡓࡵࠊᆒ୍⾲㠃࡬ࡢ྾╔ࡔࡅ࡛ࡣ࡞ࡃ࣑

ࢡࣟࢧ࢖ࢬ࡟┦ศ㞳ࡋࡓࣇ࢕࣒ࣝ࡟㑅ᢥⓗ࡟྾╔࡛ࡁࡿྍ⬟ᛶࡀ࠶ࡿࠋᮏ◊✲࡛ࡣࠊẚ㍑ⓗ

࡟␯Ỉᛶ㧗ศᏊ࡛࠶ࡿ࣏ࣜࢫࢳࣞࣥ㸦PS㸧࡜ẚ㍑ⓗ࡟ぶỈᛶ㧗ศᏊ࡛࠶ࡿ࣏࣓ࣜࢳ࣓ࣝࢱࢡ

࣮ࣜࣞࢺ㸦PMMA㸧ࢆ࣑ࢡࣟࢧ࢖ࢬ࡟┦ศ㞳ࡉࡏࡓࣇ࢕࣒ࣝࢆసᡂࡋࠊỈᬗ᣺ືᏊ࣐࢖ࢡࣟ

ࣂࣛࣥࢫἲ࡟࡚྾╔ᣲືࢆほᐹࡋࡓࠋࡑࡢᚋࠊ྾╔≉ᛶࢆ฼⏝ࡋࠊ≉␗ⓗ࡞⾲㠃ᵓ㐀ࢆ᭷ࡍ

ࡿࣇ࢕࣒ࣝࡢసᡂࢆ᳨ウࡋࡓࠋ

115 5.2 ᐇ㦂

5.2.1 ┦ᐜ໬๣䛾ྜᡂ

ᮏ◊✲࡛⏝࠸ࡓPS-PMMA⣔ࡣ㠀┦ᐜ⣔࡛࠶ࡾࠊ୧⪅ࡢ༢⣧࡞ΰྜࡢࡳ࡛ࡣᾏᓥᵓ㐀ࢆᣢ ࡘࣇ࢕࣒ࣝࡀᚓࡽࢀ࡞࠸ࠋࡑࡇ࡛ࠊ┦ᐜ໬๣࡜ࡋ࡚PS-EORFN-PMMAࡢඹ㔜ྜయࡢసᡂࢆヨ

ࡳࡓࠋࡋ࠿ࡋࠊ୍⯡ⓗ࡟PS-EORFN-PMMAࢆྜᡂࡍࡿࣜࣅࣥࢢ࢔ࢽ࢜ࣥ㔜ྜࡣ༑ศ࡟⬺Ỉ࣭

⬺㓟⣲ࡉࢀࡓ⣔࡛ྜᡂࡋ࡞࠸࡜㔜ྜᗘࡀ༑ศ࡟኱ࡁࡃ࡞ࡽ࡞࠸࡜ሗ࿌ࡉࢀ࡚࠸ࡿ⁷⁴ࠋࡑࡇ࡛ࠊ ᮏ◊✲࡛ࡣ࣐ࢡࣟࣔࣀ࣐࣮ࢆ⏝࠸࡚ࢢࣛࣇࢺඹ㔜ྜయࡢྜᡂࢆヨࡳࡓࠋࡇࡇ࡛ࠊ࣐ࢡࣟࣔࣀ

࣐࣮࡜ࡣᮎ➃࡟㔜ྜྍ⬟࡞ᐁ⬟ᇶࢆ᭷ࡍࡿ࣏࣐࣮࡛ࣜ࠶ࡾࠊࣔࣀ࣐࣮࡜ඹ㔜ྜࡍࡿࡇ࡜࡛ᐜ

᫆࡟ࣈࣟࢵࢡඹ㔜ྜయࡀྜᡂྍ⬟࡛࠶ࡿࠋ

ࢢࣛࣇࢺඹ㔜ྜయࡣ࣓ࢱࢡࣜࣝ㓟࣓ࢳࣝ㸦࿴ග⣧⸆ᕤᴗ㸦ᰴ㸧〇㸧ࢆᖿᡂศ࡜ࡋ࡚ࠊᮎ➃

࡟࣓ࢱࢡࣜࣟ࢖ࣝᇶࢆ᭷ࡍࡿࢫࢳ࣏࣐࣮ࣞࣥࣜ㸦ᮾவྜᡂ㸦ᰴ㸧 〇ࠊAS-6 ࠊMn = 6,000㸧

ࢆᯞᡂศ࡜ࡋ࡚㔜ྜࡋࡓࠋࡑࢀࡒࢀࢆ25 g⛗㔞ࡋࠊ⁐፹࡜ࡋ࡚࢟ࢩࣞࣥ㸦࿴ග⣧⸆ᕤᴗ㸦ᰴ㸧

〇㸧50 gࠊ2-ࣈࢱࣀࣥ㸦࢟ࢩࢲ໬Ꮫ㸦ᰴ㸧 〇㸧50 gࡢΰྜᾮ࡟⁐ゎࡋࡓࠋ㔜ྜ㛤ጞ๣࡜ࡋ࡚

㐣㓟໬࣋ࣥࢰ࢖ࣝ㸦᪥Ἔ㸦ᰴ㸧 〇㸧0.15 gࢆῧຍࡋࠊ❅⣲ࣂࣈࣜࣥࢢୗ࡛80|C࡟᪼ ࡋࠊ 㑏ὶࢆ⾜࠸࡞ࡀࡽ㔜ྜࡋࡓࠋ6 h⤒㐣ᚋࠊ100|Cࡲ࡛᪼ ࡋࠊ㔜ྜࢆ⤊஢ࡉࡏࡓࠋࡑࡢᚋࠊ ࢩࢡࣟ࣊࢟ࢧࣥ㸦࿴ග⣧⸆ᕤᴗ㸦ᰴ㸧〇㸧ࠊn-࣊࢟ࢧࣥ㸦࿴ග⣧⸆ᕤᴗ㸦ᰴ㸧 〇㸧ࡢయ✚ẚ 9:1ࡢΰྜᾮ࡟㔜ྜ⁐ᾮࢆᩛ໬ࡋࠊ෌ỿ᧯సࢆ⾜࠸ࠊ྾ᘬࢁ㐣࡟࡚ỿẊ≀ࢆᚓࡓࠋᚓࡽࢀࡓ ỿẊ≀ࢆ㔜ྜ⁐፹࡟෌ᗘ⁐ゎࡋࠊ෌ỿ᧯సࢆྜィ3ᅇ⾜ࡗࡓࠋ

116

ࣇ࢕ࣝࢱ࣮㸦Ꮝᚄ0.2 ȝm㸧ࢆ㏻ࡋ࡚⣙1.5 mL ධࢀ࡚࣮࢜ࢺࢧࣥࣉ࣮ࣛ㸦ᮾࢯ࣮㸦ᰴ㸧 〇

AS-8020㸧࡟ࢭࢵࢺࡋࡓࠋ࢜ࣥࣛ࢖ࣥࢹ࢕࢞ࢵࢧ㸦ᮾࢯ࣮㸦ᰴ㸧 〇ࠊSD-8022㸧࡟ࡼࡾ⬺Ẽ

ࡋࡓࢡ࣒ࣟࣟ࣍ࣝࢆࢹࣗ࢔࣏ࣝࣥࣉ㸦ᮾࢯ࣮㸦ᰴ㸧 〇ࠊDP-8020㸧࡟ࡼࡾ1 mL/minࡢ㏿ᗘ

࡛㏦ᾮࡋࡓࠋヨᩱࡣ࣮࢜ࢺࢧࣥࣉ࣮ࣛ࡟ࡼࡗ࡚100 ȝLὀධࡋࡓࠋ࣒࢝ࣛࡣPS㸭DVBࢆ඘ሸ

๣࡜ࡍࡿ࣒࢝ࣛ㸦ᮾࢯ࣮㸦ᰴ㸧 〇 TSKJHOGMHHR-M㸦᤼㝖㝈⏺PSศᏊ㔞 400,000㸧ࢆ౑⏝

ࡋࡓࠋ♧ᕪᒅᢡ⋡ࡣ ᗘ࡟ࡼࡿᙳ㡪ࢆ኱ࡁࡃཷࡅࡿࡓࡵࠊ᳨ฟჾࡢ ᗘࢆ40|C࡟ᜏ ࡋࡓࠋ

࣒࢝ࣛ࢟ࣕࣜࣈ࣮ࣞࢩࣙࣥ࡟ࡣ6FLHQWLILF 3RO\PHUࡢM_wࡀ1,100࠿ࡽ451,000ࡢ༢ศᩓ PS 㸦ᰯṇⅬᩘ13Ⅼ㸧ࢆ⏝࠸࡚⾜ࡗࡓࠋ

GPCࢆ⏝࠸ࡓศᏊ㔞 ᐃࡣࠊศᏊ㔞ࡀቑຍࡋ㔜ྜࡀ㐍⾜ࡋ࡚ࡶࠊᡤᮃࡢࢢࣛࣇࢺ㔜ྜయࡀ ᚓࡽࢀࡓ࡜࠿㝈ࡽ࡞࠸ࠋ୍⯡ⓗ࡞Ỉ⣲NMR࡛ࡣࠊ໬Ꮫࢩࣇࢺࡢ࡯࠿࡟✚ศ್ࡸࣆ࣮ࢡࡢศ

⿣ࣃࢱ࣮ࣥࡀᵓ㐀ゎᯒࡢࡓࡵࡢ㔜せ࡞᝟ሗ࡜࡞ࡿࠋᮏ◊✲࡛ࡣᯞᡂศ࡛࠶ࡿPSࡢࣇ࢙ࢽࣝ

ᇶ⏤᮶ࡢࣆ࣮ࢡ㠃✚࡜ᖿᡂศ࡛࠶ࡿPMMAࡢ࣓ࢳ࢚ࣝࢫࢸࣝ⏤᮶ࡢࣆ࣮ࢡ㠃✚ࢆồࡵࠊ㔜

ྜ≀ࡢ⤌ᡂẚࢆ⟬ฟࡋࡓࠋ

ᮏ◊✲࡛ࡣFT-NMR㸦᪥ᮏ㟁Ꮚ㸦ᰴ㸧 〇ࠊ(&;S㸧ࢆ⏝࠸ࡓࠋ ᐃヨᩱࡣࢸࢺ࣓ࣛࢳ

ࣝࢩࣛࣥࢆῧຍࡋࡓ㔜Ỉ⣲໬ࢡ࣒ࣟࣟ࣍ࣝ⁐ᾮ㸦HXULVR-WRS 〇㸧࡟ZW࡛㔜ྜ≀ࢆ⁐ゎࡋࠊ ヨᩱ⟶ࡢ㧗ࡉ4 cm࡯࡝ࡲ࡛ධࢀࡓࡶࡢ࡜ࡋࡓࠋ¹H NMRࡢ64ᅇࡢ ᐃࢆ ᐃ⤖ᯝ࡜ࡋࡓࠋ

117 5.2.3 ヨ㦂∦సᡂ

PS㸦Mw = 210k㸧ཬࡧPMMA㸦Mw = 350k㸧ࢆ✀ࠎࡢ๭ྜ࡛ΰྜࡋࠊࢡ࣒ࣟࣟ࣍ࣝ㸦࿴ග⣧

⸆ᕤᴗ(ᰴ) 〇㸧࡟ᑐࡋࠊ5 ZW࡟࡞ࡿࡼ࠺࡟⁐ゎࡋࡓࠋࡲࡓࠊPS/PMMAࣈࣞࣥࢻ⣔࡟ࡣ๓

⠇࡛ྜᡂࡋࡓ┦ᐜ໬๣ࢆ඲࣏࣐࣮ࣜ㔜㔞ࡢ10%ῧຍࡋࡓࠋ

ࡇࢀࡽ⁐ᾮ࡟࢝ࣂ࣮࢞ࣛࢫࠊỈᬗ᣺ືᏊࢆᾐₕࡋࠊᘬᢤ㏿ᗘ20 mm/min࡛ᘬࡁୖࡆࡓࠋࡑ ࡢᚋࠊ┿✵஝⇱ჾ࡛ᖖ 24᫬㛫┿✵஝⇱ࡋࠊ⁐፹ࢆ㝖ཤࡋࡓࠋ

5.2.4 ヨ㦂∦䛾┦ศ㞳ᵓ㐀ホ౯

๓⠇࡛సᡂࡋࡓヨ㦂∦ࡢ┦ศ㞳ᵓ㐀ࡀᡤᮃࡍࡿᾏᓥᵓ㐀ࢆᙧᡂࡋ࡚࠸ࡿ࠿ࢆ᳨ウࡍࡿࡓࡵ

࡟ࠊࡲࡓࠊᚓࡽࢀࡓࢻ࣓࢖ࣥᚄࢆホ౯ࡍࡿࡓࡵ࡟ගᏛ㢧ᚤ㙾ほᐹ㸦(ᰴ1LNRQ〇ࠊMEASURING

MICROSCOPE MM-400㸧ࢆ⾜ࡗࡓࠋࡇࡇ࡛ࠊPS/PMMAࣇ࢕࣒ࣝࡣ୧⪅࡟ከᑡࡢᒅᢡ⋡ࡢᕪ

ࡀ࠶ࡿࡶࡢࡢࠊ↓Ⰽ㏱࡛᫂࠶ࡿࡓࡵ࡟ホ౯ࡣᅔ㞴࡛࠶ࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ㔜㔠ᒓᰁⰍࢆ

⾜ࡗࡓࠋ㔜㔠ᒓᰁⰍࡣ୍⯡ⓗ࡟㟁Ꮚ㢧ᚤ㙾ࡢ๓ฎ⌮࡜ࡋ࡚⏝࠸ࡽࢀ࡚࠾ࡾ౑⏝ࡍࡿ㔠ᒓ✀࡟

ࡼࡗ࡚ᰁⰍࡢྍྰࡀ࠶ࡿ^{75, 76, 77}ࠋᮏ◊✲࡛ࡣPSࡢࡳࢆ㑅ᢥⓗ࡟ᰁⰍࡍࡿ0.5%ᅄ㓟໬ࣝࢸࢽ

࣒࢘㸦6WUHP&KHPLFDOV〇㸧Ỉ⁐ᾮࡢ⵨Ẽ࡟ᚓࡽࢀࡓヨ㦂∦ࢆ60 min᭚㟢ࡋࡓࠋ

118

⾲㠃ࡢࡠࢀᛶࡢ ᐃ࡟ࡣࠊࡠࢀᛶホ౯⿦⨨㸦(ᰴ)ࢽࢵࢡ 〇ࠊLSE-B100W㸧ࢆ⏝࠸ࠊゎᯒ

࡟ࡣྠ♫ࡢ⏬ീゎᯒࢯࣇࢺ࢙࢘࢔i2winࢆ⏝࠸ࡓࠋࡲࡓࠊ ᐃ⁐፹࡟ࡣࡠࢀᙇຊヨ㦂⏝ΰྜ

ᾮ㸦࿴ග⣧⸆ᕤᴗ(ᰴ) 〇㸧 30.0 mN/mࠊ35.0 mN/mࠊ40.0 mN/mࠊ50.0 mN/mࠊ60.0 mN/m,

70.0 mN/mཬࡧ㉸⣧Ỉࢆ౑⏝ࡋࡓࠋࡇࢀࡽᾮయࢆ⣙1.5 ȝL⁲ୗࡋࠊ100 msᚋࡢ᥋ゐゅࢆ 

ᐃࡋࡓࠋ

119

5.2.6 䝞䝤䝹྾╔ᣲືほᐹ

ࣈࣞࣥࢻࣇ࢕࣒ࣝ࡟࣐࢖ࢡࣟࣂࣈࣝࡀ྾╔ࡋࡓ㝿ࠊࡑࡢ᫬ࡢ㔜㔞ኚ໬ࡣ㠀ᖖ࡟ഹ࠿࡛࠶ࡿࠋ ࡑࡇ࡛ࠊ㠀ᖖ࡟ᑠࡉ࠸㔜㔞ኚ໬ࢆ ᐃ࡛ࡁࡿỈᬗ᣺ືᏊ࣐࢖ࢡࣟࣂࣛࣥࢫ㸦QCM㸧ἲࢆ⏝࠸

ࡓ⁷⁸ࠋ

QCMἲࡣࠊỈᬗ࡟஺ὶ㟁ᅽࢆ༳ຍࡍࡿࡇ࡜࡛㉳ࡇࡿඹ᣺ࢆ฼⏝ࡋࡓ㔜㔞ኚ໬ ᐃἲ࡛࠶

ࡿࠋ㔜㔞ኚ໬࡜࿘Ἴᩘኚ໬ࡣᘧ㸦5.1㸧࡛♧ࡋࡓ 6DXHUEUH\ᘧ࡟ࡼࡗ࡚㛵㐃௜ࡅࡽࢀ࡚࠸ࡿࠋ

^F

F N

ȝ ȡ

m S u '

u u

u

' u

₂

ࠉ 2

࣭࣭࣭㸦5.1㸧

ࡇࡇ࡛ࠊǼmࡣ㔜㔞ኚ໬ࠊǼFࡀ㔜㔞ኚ໬ࠊSࡀ㟁ᴟ㠃✚ࠊȡࡀỈᬗࡢᐦᗘࠊȝࡀỈᬗࡢࡏ

ࢇ᩿ᙎᛶ⋡ࠊNࡀ࣮࢜ࣂ࣮ࢺ࣮ࣥḟᩘࠊFࡀⓎ᣺࿘Ἴᩘ࡛࠶ࡿࠋᮏሗ࡛⏝࠸ࡓQCM㸦SEIKO

EG&G 〇ࠊQCA922ࠊAT࢝ࢵࢺỈᬗ᣺ືᏊ㸧࡟࠾࠸࡚ࡣ᭱ᑠឤᗘࡀ⣙ -QJ+]࡜࡞ࡿࠋࡲ

ࡓࠊࡇࡢᘧ࠿ࡽศ࠿ࡿࡼ࠺࡟⤯ᑐ㔜㔞ࡣ ᐃ࡛ࡁ࡞࠸ࡓࡵࠊᖹ⾮᫬࠿ࡽࡢ࿘Ἴᩘኚ໬ࡼࡾ㔜 㔞ኚ໬ࢆ⟬ฟࡋࡓࠋ

࣐࢖ࢡࣟࣂࣈࣝࡢⓎ⏕ἲࡣࠊ3.2.2࡛⏝࠸ࡓ⿦⨨࡛⾜ࡗࡓࠋෆໟẼయࡣ࢔ࣝࢦࣥࠊ౪⤥࢞ࢫ

ὶ㔞ࡣ80 mL/min࡜ࡋࡓࠋࡲࡓࠊ࣐࢖ࢡࣟࣂࣈࣝࡣ㛤ཱྀ㒊⣙390 mm™⣙290 mm㸦ᾮ㔞18

L㸧ࡢỈᵴࢆ⏝࠸ࡓࠋసᡂࡋࡓ࣐࢖ࢡࣟࣂࣈࣝᚄࡢホ౯ࡣ3.2.4࡜ྠ➼࡛࠶ࡿࠋ

5.2.3࡛ࢹ࢕ࢵࣉࢥ࣮ࢺࡋࡓỈᬗ᣺ືᏊࢆࢹ࢕ࢵࣉࢭࣝ㸦QA-CL3ࠊ᭷ຠ㠃✚12.6 mm²㸧࡟

ᅛᐃࡋࠊ࣐࢖ࢡࣟࣂࣈࣝࢆⓎ⏕ࡉࡏࡿ๓ࡢỈᵴ࡟ᾐₕࡋࡓࠋ࣏࣐࣮ࣜࢆỈ࡟ᾐₕࡍࡿ࡜‵₶

ᙇຊ⦆࿴ࡀ㉳ࡇࡿࠋQCMἲ࡛ࡣഹ࠿࡞㔜㔞ኚ໬ࢆ᳨▱ࡍࡿࡓࡵ࡟ࠊᖹ⾮≧ែ࡟ࡍࡿࡓࡵ࡟

3 hᨺ⨨ࡋࡓࠋࡑࡢᚋࠊ࣐࢖ࢡࣟࣂࣈࣝࢆⓎ⏕ࡉࡏࠊ㔜㔞ኚ໬ࢆ ᐃࡋࡓࠋ

120

ࣞࣥࢻࣇ࢕࣒ࣝࢆᾐₕࡋࠊ✀ࠎࡢ᫬㛫ฎ⌮ࡋࡓࠋ

ホ౯ࡣⓑⰍᖸ΅ィ㸦᪥❧ࣁ࢖ࢸࢡࢧ࢖࢚ࣥࢫ 〇ࠊAFM5400L㸧ࢆ⏝࠸ࡓࠋ

121 5.3 ⤖ᯝཬ䜃⪃ᐹ

5.3.1 ┦ᐜ໬๣䛾ホ౯

ྜᡂࡋࡓ┦ᐜ໬๣ࡀ༑ศ࡟ྜᡂࡉࢀࡓ࠿ࢆศᏊ㔞࡜ᵓ㐀࠿ࡽホ౯ࡋࡓࠋศᏊ㔞ࡣGPCࢆ⏝

࠸࡚ホ౯ࡋࡓࠋFigure 5.1ࡣGPC࡛ồࡵࡓᚤศศᏊ㔞ศᕸ᭤⥺ࢆ♧ࡋ࡚࠸ࡿࠋ

Figure 5.1 Differential molecular weight distribution curve of macromonomer and synthesized copolymer.

&RQFHQWUDWLRQ J/PRYLQJSKDVHFKORURIRUP.

ᅗࡼࡾࠊᘧ㸦5.2㸧ࢆ⏝࠸࡚ᩘᖹᆒศᏊ㔞Mn࡜㔜㔞ᖹᆒศᏊ㔞Mwࢆ⟬ฟࡋࡓ⁷⁹ࠋࡇࡇ࡛ࠊ ᘧ୰ࡢHiࡣศᏊ㔞Mi࡟࠾ࡅࡿࣄࢫࢺࢢ࣒ࣛࡢ㧗ࡉ࡛࠶ࡿࠋྛᘧ࡛⟬ฟࡋࡓ⤖ᯝࢆ7DEOH 5.1

࡟♧ࡍࠋ

° °

¿

° °

¾

½

¦ ¦

¦ ¦

i i i W

i i

i n

H M M H

M H M H

࣭࣭࣭㸦5.2㸧 0

0.2 0.4 0.6 0.8 1.0 1.2

1E+02 1E+03 1E+04 1E+05 1E+06 1E+07

GWGORJM)

MJPRO

0DFURPRQRPHU 6\QWKHVL]HGFRSRO\PHU

122

ᕸࢆ♧ࡍMw/Mnࡣ㔜ྜ๓ࡢ2ಸ⛬ᗘ࡟ቑຍࡋࡓࠋᮏ◊✲⣔ࡣࣛࢪ࢝ࣝ㔜ྜ࡛࠶ࡿࡓࡵࠊẚ

㍑ⓗศᕸࡢᑠࡉ࠸㔜ྜ≀ࡀᚓࡽࢀࡿ࡜ண᝿ࡋࡓࡀࠊ෌ỿ᧯స࡟ࡼࡿᙳ㡪ࡀ኱ࡁ࠸ࠋࡋ࠿ࡋࠊ

┦ᐜ໬๣࡜ࡋ࡚⏝࠸ࡿࡓࡵࠊࡇࢀ௨ୖࡢ෌ỿ᧯సࡣ⾜ࢃ࡞࠿ࡗࡓࠋࡇࡇ࡛ࠊඹ㔜ྜయࡀ PS-JUDIW-PMMAࡢᵓ㐀ࢆᙧᡂࡋ࡚࠸ࡿࡇ࡜ࡣศᏊ㔞ቑຍ࠿ࡽࡣ᩿ᐃ࡛ࡁ࡞࠸ࠋࡑࡇ࡛ࠊNMR࡟

ࡼࡗ࡚ᵓ㐀ࢆ᥎ᐃࡋࠊPS/PMMA⤌ᡂẚࢆ⟬ฟࡋࡓࠋFigure 5.2ࡣ¹H NMRࡢࢫ࣌ࢡࢺࣝࢆ

♧ࡋ࡚࠸ࡿࠋ

(a) PS -0.2

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

-2 0

2 4

6 8

Abundance

Parts per Million : ¹H

123 (b) PMMA

(C) Synthesized copolymer

Figure 5.2 NMR spectrum of each polymer.

-0.2 0.3 0.8 1.3 1.8 2.3 2.8 3.3

-2 0

2 4

6 8

Abundance

Parts per Million : ¹H

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

-2 0

2 4

6 8

Abundance

Parts per Million : ¹H 120

100

124

3 100 5 66

120 u

u n

^{࣭࣭࣭㸦5.3㸧}

ࡇࡢᘧࡢn࡟ࡘ࠸࡚ゎࡃ࡜n = 92࡜࡞ࡿࠋᚑࡗ࡚ࠊඹ㔜ྜయࡣPMMAࡢ༢఩ᵓ㐀92࡟ ᑐࡋࠊ࣐ࢡࣟࣔࣀ࣐࣮ࡀ1ಶࠊ༶ࡕࠊࢫࢳࣞࣥࡢ༢఩ᵓ㐀ࡀ66Ꮡᅾࡍࡿᵓ㐀ࢆ᭷ࡍࡿࠋᚑࡗ

࡚ࠊPS࣐ࢡࣟࣔࣀ࣐࣮࡜࣓ࢱࢡࣜࣝ㓟ࡢ㔜㔞ẚࡣ43㸸57࡜࡞ࡾࠊᢞධ㔞ࡢ50㸸50࡟㏆࠸

್ࡀᚓࡽࢀࡓࠋ

㧗࠸㔜ྜᗘࡀᚓࡽࢀࠊPS/PMMAࡢ⤌ᡂẚࡀ⣙4㸸6࡜࡞ࡗ࡚࠸ࡿࡇ࡜࠿ࡽᚓࡽࢀࡓඹ㔜

ྜయࡣ┦ᐜ໬๣࡜ࡋ࡚⏝࠸ࡿࡇ࡜ࡀྍ⬟࡞ᵓ㐀ࢆ᭷ࡍࡿࠋ

125 5.3.2 ヨ㦂∦ほᐹ

๓㡯࡛సᡂࡋࡓ┦ᐜ໬๣ࢆῧຍࡋࠊPS/PMMAࣇ࢕࣒ࣝࢆసᡂࡋࡓࠋᮏ㡯࡛ࡣࠊගᏛ㢧ᚤ 㙾ほᐹཬࡧ᥋ゐゅ ᐃ࡟ࡼࡾ࣑ࢡࣟࢧ࢖ࢬࡢ┦ศ㞳ᵓ㐀ࡀᚓࡽࢀࡓ࠿ࢆ☜ㄆࡍࡿࠋ

Figure 5.3ࡣ〇⭷ࡋࡓࣇ࢕࣒ࣝ࡟ࠊᅄ㓟໬ࣝࢸࢽ࣒࢘ฎ⌮ࡋࡓ᫬ࡢගᏛ㢧ᚤ㙾෗┿࡛࠶ࡿࠋ

PS/PMMA ࣈࣞࣥࢻ⣔࡟࠾࠸࡚ࠊ⃰Ⰽ࡟ぢ࠼ࡿ㡿ᇦࡀ PS ࡛࠶ࡿࠋᅗࡼࡾ┦ᐜ໬๣ࢆྵࡴ

PS/PMMAࣇ࢕࣒ࣝࡣᾏᓥᵓ㐀ࢆᙧᡂࡍࡿࠋࡲࡓࠊPS ⤌ᡂࡀ 50%௨ୗࡢሙྜࡣࠊPS ࡀᓥࠊ

50%ࡼࡾከ࠸ሙྜࡣ PMMAࡀᓥ࡜࡞ࡿࠋࡇࢀࡽ㢧ᚤ㙾෗┿ࡼࡾࠊࢻ࣓࢖ࣥᚄཬࡧ⤌ᡂẚࢆ

ồࡵࡓ⤖ᯝࢆFigure 5.4࡟♧ࡍࠋࢻ࣓࢖ࣥᚄࡣᾏᓥࡀ཯㌿ࡍࡿPS⤌ᡂ50%ࡢ᫬࡟᭱ࡶ኱ࡁ ࡃ࡞ࡾࠊࢻ࣓࢖ࣥᚄࡀᖹᆒ⣙ 4.7 ȝm࡛࠶ࡿࡇ࡜࠿ࡽࠊ඲PS⤌ᡂẚ࡟࠾࠸࡚ࠊ࣑ࢡࣟࢧ࢖ࢬ ࡢᾏᓥᵓ㐀ࢆᙧᡂࡋ࡚࠸ࡿࠋࡲࡓࠊᢞධࡋࡓPS⤌ᡂẚ࡜⏕ᡂࡋࡓᾏᓥᵓ㐀ࡢPS㡿ᇦࡢ㠃

✚ẚࡣ࡯ࡰ୍⮴ࡋࡓࠋ

36FRPSRVLWLRQ 10% 30%

50% 70% 90%

100%

Figure 5.3 Optical micrograph of PS/PMMA coated slide glass: Each blend films is stained by ruthenium tetroxide. Dark area is PS.

126

Figure 5.4 Structure of PS/PMMA coated slide glass: Circle plots are shown domain diameter and square plots are shown region area of PS. Error bars are shown standard deviation of domain diameter.

ࡇࡇ࡛ࠊᾏᓥᵓ㐀ࡣ3ḟඖᵓ㐀࡛࠶ࡿࠋFigure 5.3࡟♧ࡋࡓගᏛ㢧ᚤ㙾෗┿ࡣࠊ㏱㐣ගࢆ

⏝࠸࡚ほᐹࡋ࡚࠸ࡿࡓࡵ࡟ࠊPS/PMMAࣈࣞࣥࢻࣇ࢕࣒ࣝࡢ⾲㠃ࡀ┦ศ㞳ࡋ࡚࠸ࡿ࡜ࡣ㝈ࡽ

࡞࠸ࠋࡑࡇ࡛ࠊྛࣈࣞࣥࢻࣇ࢕࣒ࣝ࡟࠾࠸࡚ࠊ⮫⏺⾲㠃ᙇຊࢆ⟬ฟࡍࡿࡇ࡜࡛⾲㠃ࡢᙧែࢆ

☜ㄆࡋࡓࠋࡇࡇ࡛㹫ࠊ=LPDQࣉࣟࢵࢺࡣᘧ㸦5.4㸧࡟ࡼࡗ࡚⾲♧ࡉࢀࡿࠋ

&RVɅ Dɀ + b ࣭࣭࣭㸦5.4㸧

ᘧ୰ࡢȟࡣ⾲㠃ᙇຊȚࡢᾮయ࡛ ᐃࡋࡓ᫬ࡢ᥋ゐゅ࡛࠶ࡾࠊDཬࡧbࡣᐃᩘ࡛࠶ࡿࠋ7DEOH 5.2ࡣ=LVPDQࣉࣟࢵࢺࡢྛ್ࢆ♧ࡋ࡚࠸ࡿࠋᑦࠊ⾲୰ࡢr²ࡣ┦㛵ࢆ♧ࡍࠋ

0 20

0

0 20 40 60 80 100

36FRPSRVLWLRQ

127

Table 5.2 Value of Zisman plot 36FRPSRVLWLRQ D b r²

0 % -0.0133 1.32 0.97

10% -0.0137 1.34 0.97

30% -0.0135 1.31 0.97

50% -0.0125 1.28 0.96

70% -0.0130 1.28 0.94

90% -0.0132 1.28 0.93

100% -0.0167 1.35 0.92

⾲ࡼࡾ඲PS⤌ᡂẚ⠊ᅖ࡟࠾࠸࡚ࠊr²ࡀ0.9ࢆ㉸࠼࡚࠾ࡾࠊ༑ศ࡟┤⥺㏆ఝ࡛ࡁࡿࠋࡇࢀ

ࡽ್ࢆ⏝࠸࡚ྛヨᩱࡢ⮫⏺⾲㠃ᙇຊࢆồࡵࡓ⤖ᯝࢆFigure 5.5࡟♧ࡋࡓࠋᅗࡼࡾࠊPS⤌ᡂẚ ࡀቑຍࡍࡿ࡟క࠸⮫⏺⾲㠃ᙇຊࡀపୗࡋ࡚࠾ࡾࠊ୍ḟࡢ㛵ᩘ࡟ᅇᖐ࡛ࡁࡿࠋࡲࡓࠊ〇⭷ࡋࡓ

⭷ཌࡀ⣙2 ȝm࡛࠶ࡾࠊࢻ࣓࢖ࣥᚄ࡜࡯ࡰྠࡌ࡛࠶ࡿࡇ࡜࠿ࡽࠊᾏᓥᵓ㐀ࡀ⭷ཌ᪉ྥ࡟ᙧᡂ

࡛ࡁ࡞࠸ࠋ௨ୖࡢࡇ࡜࠿ࡽPSࠊPMMAࡢ୧ᡂศࡣ೫ᅾࡍࡿࡇ࡜ࡣ࡞ࡃࠊ⾲㠃ࡶPS/PMMA ࡢᾏᓥᵓ㐀ࡀᙧᡂࡉࢀ࡚࠸ࡿࠋ

Figure 5.5 Dependence of critical surface tension on PS composition.

20 21 22 23 24 25

0 20 40 60 80 100

&ULWLFDOVXUIDFHWHQVLRQP1P

36FRPSRVLRQ

128

ࡢ㞳⬺ࠊࣂࣈࣝࡢ཰⦰࣭ᾘ⁛➼ࢆࡍ࡭࡚ྵࢇࡔ್࡛࠶ࡿࠋࡇࡇ࡛ࠊQCMἲࡣ⤯ᑐ㔜㔞ࢆ 

ᐃ࡛ࡁ࡞࠸ࠋࡑࡇ࡛ࠊ࣐࢖ࢡࣟࣂࣈࣝⓎ⏕┤ᚋࡢ࿘Ἴᩘࢆᇶ‽࡜ࡋࡓࠋࡲࡓࠊ࣐࢖ࢡࣟࣂࣈ

ࣝⓎ⏕┤ᚋࡣࠊ࣐࢖ࢡࣟࣂࣈࣝⓎ⏕ჾ࡟ࡼࡗ࡚Ⓨ⏕ࡍࡿỈᵴෆࡢ஘ὶ࡟ࡼࡾ࿘Ἴᩘࡀ୙Ᏻᐃ

࡛࠶ࡿࡇ࡜࠿ࡽࠊ600 sᚋ࠿ࡽࢹ࣮ࢱࡢࡳ࡟ὀ┠ࡋࡓࠋ

Figure 5.6 Change of weight by adsorption of argon micro bubble on PS/PMMA surface.

ᅗࡼࡾࠊྛPS⤌ᡂẚ࡟࠾࠸࡚᫬㛫ࡢ⤒㐣࡜࡜ࡶ࡟㔜㔞ࡀῶᑡࡋ࡚࠸ࡿࠋࡇࢀࡣࠊỈࡼࡾ

ᐦᗘࡢప࠸ࣂࣈࣝࡀ྾╔ࡋࡓࡓࡵ࡛࠶ࡿࠋྛPS⤌ᡂẚ࡟࠾࠸࡚ࠊ㔜㔞ኚ໬ࡢഴࡁࠊ༶ࡕ྾

╔㏿ᗘࢆ⟬ฟࡋࡓ⤖ᯝࡀFigure 5.7࡛࠶ࡿࠋPS⤌ᡂẚࡀቑຍࡍࡿ࡟ࡘࢀ࡚྾╔㏿ᗘࡀ㏿ࡃ࡞

ࡿഴྥࡣぢࡽࢀࡿࡀࠊ┤⥺࡟ᅇᖐࡏࡎࠊ྾╔㜼ᐖࡍࡿPS⤌ᡂẚࡀ࠶ࡿࠋFigure 5.5࡛♧ࡋࡓ

⮫⏺⾲㠃ᙇຊࡣPS⤌ᡂẚ࡟ᑐࡋ┤⥺ⓗ࡟ῶᑡࡋ࡚࠸ࡿࡇ࡜࠿ࡽࠊࣂࣈࣝࡢ྾╔㏿ᗘࡣ⮫⏺

⾲㠃ᙇຊ௨እࡢࣇ࢓ࢡࢱ࣮ࢆᣢࡘࠋࡇࡇ࡛ࠊ⮫⏺⾲㠃ᙇຊ࡜ࣂࣈࣝࡢ྾╔㏿ᗘࡢࢫࢣ࣮ࣝࡢ 0%

10%

30%

50%

70%

90%

-100 100%

-80 -60 -40 -20 0

600 1100 1600 2100 2600 3100 3600

ǻm(ng)

Time (s)

36FRPSRVLWLRQ

129

㐪࠸࡟ࡘ࠸᳨࡚ウࡍࡿࠋ⮫⏺⾲㠃ᙇຊࡣ␗࡞ࡿ⾲㠃ᙇຊࡢᾮయࢆ⁲ୗࡋࠊࡑࡢ᫬ࡢ᥋ゐゅࢆ

 ᐃࡍࡿࠋࡑࡢ㝿ࡢᾮ⁲ࡢ኱ࡁࡉࡣᩘmm࡜࡞ࡿࠋPS/PMMAࡢᾏᓥᵓ㐀ࡢࢫࢣ࣮ࣝ࡟ᑐࡋ

༑ศ࡟኱ࡁ࠸Ⅽࠊ&DVVLHࡢᘧࡀᡂ❧ࡍࡿࡓࡵࠊ⮫⏺⾲㠃ᙇຊࡣPS⤌ᡂ࡟ᑐࡋ୍ḟࡢ㛵ᩘ࡜

࡞ࡿࠋ୍᪉ࠊ྾╔㏿ᗘࡣ᭱ࡶ㏿࠸ࡀPS⤌ᡂẚ100%࡟࠾ࡅࡿ0.035 ng/s࡛ࡣ⣙31000 ȝm³/s ࡢẼయࡀ྾╔ࡋ࡚࠾ࡾࠊ1ಶࡢࣂࣈࣝ࡜௬ᐃࡍࡿ࡜ࣂࣈࣝᚄࡣഹ࠿⣙40 ȝm࡛࠶ࡿࠋᐇ㝿࡟

ࡣࠊ」ᩘಶࡢࣂࣈࣝࡀ྾╔ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ྾╔ࡍࡿࣂࣈࣝᚄࡣࡉࡽ࡟ᑠࡉࡃ࡞ࡿࠋ྾╔

ࡍࡿࣂࣈࣝᚄ࡜ᾏᓥᵓ㐀ࡢࢫࢣ࣮ࣝࡀ㏆ఝࡋ࡚࠸ࡿࡓࡵࠊࣂࣈࣝࡢ྾╔㏿ᗘࡣᾏᓥᵓ㐀ࡢᵓ 㐀࡟ᙳ㡪ࢆཷࡅࠊPS⤌ᡂẚ࡟ᑐࡋ୍ḟࡢ㛵ᩘ࡜࡞ࡽ࡞࠸ࠋ

Figure 5.7 Dependence of PS composition on adsorption rate of argon micro bubble on PS/PMMA surface.

ࡇࡇ࡛ࠊࣇ࢕࣒ࣝ࡟྾╔ࡋࡓ࣐࢖ࢡࣟࣂࣈࣝࡣẚ⾲㠃✚ࢆᑠࡉࡃࡋࡼ࠺࡜ࡍࡿࡓࡵࠊࣂࣈ

ࣝࡀྜ୍ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋᓥᵓ㐀㒊࡬྾╔ࡋࡓሙྜࠊࢻ࣓࢖ࣥ㡿ᇦࡀࣂࣈࣝࡢ྾╔ྍ⬟㠃

✚࡜࡞ࡿࠋ୍᪉ࠊᾏᵓ㐀㒊࡬྾╔ࡋࡓሙྜࠊ㏆᥋ࡍࡿࢻ࣓࢖ࣥ࡟ෆ᥋ࡍࡿ෇ࡢ㡿ᇦࡀࣂࣈࣝ

ࡢ྾╔ྍ⬟㠃✚࡜࡞ࡿࠋࡇࡢෆ᥋෇ࡢ┤ᚄࢆ௬᝿ࢻ࣓࢖ࣥᚄ࡜ࡋࠊFigure 5.4࡟♧ࡋࡓࢻ࣓

࢖ࣥᚄ࡜PS㠃✚ẚ࠿ࡽᗄఱᏛⓗ࡟᥎ᐃࡋࡓࠋᑦࠊᐃ⩏ࢆFigure 5.8࡟ࠊ᥎ᐃࡢ࢔ࣝࢦࣜࢬ

࣒ࡣୗグ࡟♧ࡍࠋ 0

0.01 0.02 0.03 0.04

0 20 40 60 80 100

$GVRUSWLRQUDWHQJV

36FRPSRVLWLRQ

130

Figure 5.8 Definition of terms

௬᝿ࢻ࣓࢖ࣥᚄࡢ᥎ᐃࡢ࢔ࣝࢦࣜࢬ࣒

1. 0௨ୖ1௨ୗࡢ஘ᩘࢆⓎ⏕ࡉࡏࠊᘧ㸦5.5㸧࡟♧ࡍ⣼✚ศᕸ㛵ᩘࡼࡾࠊࢻ࣓࢖ࣥᚄD1ࠊ D2ཬࡧD3ࢆ⟬ฟࡍࡿࠋ

¸¸ ¹

·

¨¨ ©

§

₂ ²

1 2 2 1

V P erf x

P

࣭࣭࣭(5.5)

ࡇࡇ࡛ࠊPࡣ☜⋡ࠊx^{ࡀኚᩘࠊȝࡀᖹᆒ್ࠊ}Ȫࡀᶆ‽೫ᕪ࡛࠶ࡿࠋⓎ⏕ࡋࡓ஘ᩘࢆP

࡟ࠊȝ࡟Figure 5.4ࡼࡾồࡵࡓࢻ࣓࢖ࣥᚄࠊȪ࡟ᶆ‽೫ᕪࢆ௦ධࡋࠊx࡛♧ࡋࡓD₁ࠊD₂

ཬࡧD3ࢆ⟬ฟࡍࡿࠋ

2. 1.࡜ྠᵝ࡟ゅᗘDࠊbࢆⓎ⏕ࡉࡏࠊ୕ゅᙧࡢෆゅࡢ⥲࿴ࡼࡾゅᗘcࢆ⟬ฟࡍࡿࠋࡇࡇ࡛ࠊ

ࢻ࣓࢖ࣥࡀᆒ୍࡟㓄ิࡋ࡚࠸ࡓሙྜࠊᖹᆒ್ࡣ60º࡛࠶ࡿࠋࡲࡓࠊᾏᓥᵓ㐀࡟࠾࠸࡚ࠊ 3ࡘࡢࢻ࣓࢖ࣥ࡟ࡼࡗ࡚ᥥ࠿ࢀࡿ୕ゅᙧࡣ㗦ゅ୕ゅᙧ࡛࠶ࡿࠋᚑࡗ࡚ࠊゅᗘࡢ᭱኱ࡀ90º

࡛࠶ࡾࠊ᭱ᑠࡀ 30º࡜௬ᐃ࡛ࡁࡿࠋᶆ‽೫ᕪศᕸ࡟࠾࠸࡚ ȝs3Ȫ⠊ᅖ࡟ධࡿྍ⬟ᛶࡀ

99.73%ࡢ☜⋡࡛࠶ࡿࡇ࡜࠿ࡽࠊᶆ‽೫ᕪࢆ10º࡜௬ᐃࡋࡓࠋ

3. ࢻ࣓࢖ࣥ㠃✚SDࡣࠊ◚⥺࡟ࡼࡗ࡚ᥥ࠿ࢀࡓ୕ゅᙧࡢ㠃✚࡜ࠊࢻ࣓࢖ࣥ࡜୕ゅᙧࡢ㔜࡞ࡗ

D b

D

₁

L

_c

D

₂

131

࡚࠸ࡿ㒊ศࡢ㠃✚ẚ࡜࡞ࡾࠊᘧ㸦5.6㸧࡟ࡼࡗ࡚♧ࡉࢀࡿࠋࡇࡢᘧࡢ L_c࡟ࡘ࠸࡚ゎࡁࠊ ࡑࡢᚋLb࡟ࡘ࠸࡚ࡶゎࡃࠋ

2 2 sin 2

360 4

sin 2

sin 2 sin

360 4

3 1 C 2 1

3 2 1

2 2 C

1

3 2 1 D

a D L

L D D D

c D b D a D

c b

c b D L

D

c D b D a D S

b¸

¹

¨ ·

©

§

¸¹

¨ ·

©

§

u

¸¹

¨ ·

©

§

u

S S

࣭࣭࣭㸦5.6㸧

4. LbࠊLcࡼࡾྛࢻ࣓࢖ࣥࡢᗙᶆࢆ⟬ฟࡋࠊࡑࢀࡒࢀࡢࢻ࣓࢖ࣥ࡟ෆ᥋ࡍࡿ௬᝿ࢻ࣓࢖ࣥᚄ Dsࢆ⟬ฟࡍࡿࠋ

Figure 5.9 Dependence of virtual domain diameter on PS composition: Error bars show standard deviation of virtual domain diameter.

0 2 4 6 8

0 20 40 60 80 100

9LUWXDOGRPDLQGLDPHWHUȝP

36FRPSRVLWLRQ

PMMA island PS island

132

⏕ࡌࡿPS⤌ᡂẚࡀᏑᅾࡍࡿࠋࡲࡓࠊPS⤌ᡂẚࡀ50%௨እࡣ௬᝿ࢻ࣓࢖ࣥᚄࡀࢻ࣓࢖ࣥᚄࡼ

ࡾ኱ࡁ࠸Ⅽࠊ࣐࢖ࢡࣟࣂࣈࣝࡢ྾╔ࡣᓥ㡿ᇦࡼࡾᾏ㡿ᇦࡢ᪉ࡀ㉳ࡇࡾࡸࡍ࠸࡜᥎ᐃࡉࢀࡿࠋ

133

5.3.4 䜸䝌䞁䝬䜲䜽䝻䝞䝤䝹䛻䜘䜛䜶䝑䝆䞁䜾

๓⠇ࡲ࡛ࡣάᛶࡀప࠸࢔ࣝࢦࣥࢆෆໟẼయ࡜ࡋࠊPS/PMMAࣈࣞࣥࢻࣇ࢕࣒ࣝ࡬ࡢ࣐࢖ࢡ

ࣟࣂࣈࣝࡢ྾╔ࢆ᳨ウࡋࡓࠋࡑࡢ⤖ᯝࠊᓥᵓ㐀㒊࡬ࡢ྾╔ࡣᾏᵓ㐀㒊࡬ࡢ྾╔࡟ẚ࡭୙฼࡛

࠶ࡿྍ⬟ᛶࢆ♧ࡋࡓࠋࡇࡇ࡛ࠊOMBࡣ࢜ࢰࣥࡢ㧗࠸㓟໬ຊ࡜ࠊ࣐࢖ࢡࣟࣂࣈࣝࡢẼయࡢ㧗

࠸⁐ゎᛶࢆᣢࡗ࡚࠾ࡾࠊ᭷ᶵ≀ࡢศゎὙίࡸ⾲㠃ࡢᨵ㉁࡞࡝࡟⏝࠸ࡽࢀ࡚࠸ࡿࠋ➨3❶࡛♧

ࡋࡓࡼ࠺࡟࢜ࢰࣥࡣ஧㔜⤖ྜ࡜཯ᛂࡋࡸࡍ࠸࡜⪃࠼ࡽࢀࡿࠋ➨3❶࡛ᢅࡗࡓ࣏࢚ࣜࢫࢸࣝ࡜

ྠᵝ࡟ࠊOMBฎ⌮࡟࠾࠸࡚஧㔜⤖ྜࢆྵࡴPSࡣ⾲㠃ࡀ㓟໬ฎ⌮ࡉࢀࠊPMMAࡣ࡯࡜ࢇ࡝

ኚ໬ࡋ࡞࠸ࡇ࡜ࡀணഛᐇ㦂࡟࡚☜ㄆ࡛ࡁࡓࠋᚑࡗ࡚ࠊ⣲ᮦ࡟ᑐࡍࡿOMBࡢฎ⌮ຠᯝࡢ㐪࠸

࡜ࠊ࣐࢖ࢡࣟࣂࣈࣝࡢ྾╔ຠ⋡ࡢ㐪࠸ࢆ⏝࠸࡚ࠊ≉␗ⓗ࡞⾲㠃ᵓ㐀ࡢᙧᡂ࡛ࡁࡿྍ⬟ᛶࡀ࠶

ࡿࠋࡑࡇ࡛ࠊ๓⠇ࡲ࡛࡟౑⏝ࡋࡓྛPS⤌ᡂẚࡢPS㸭PMMAࣈࣞࣥࢻࣇ࢕࣒ࣝࢆOMBฎ⌮

ࡋࠊᚓࡽࢀࡿᵓ㐀࡟ࡘ࠸᳨࡚ウࡋࡓࠋ

Figure 5.10ࡣྛPS⤌ᡂẚ࡟࠾ࡅࡿⓑⰍᖸ΅ἲ࡟ࡼࡗ࡚ồࡵࡓ⾲㠃⢒ࡉࢆ♧ࡋࡓ⏬ീ࡛࠶

ࡿࠋྛ⏬ീࡢᕥഃࡀฎ⌮๓ࠊྑഃࡀOMBỈ࡟5 hᾐₕࡋࡓᚋࡢ⏬ീࢆ♧ࡋ࡚࠸ࡿࠋฎ⌮๓ ࡢ⏬ീ࠿ࡽᩘ༑ nm࠿ࡽⓒᩘ༑nm⛬ᗘ࡛࠶ࡿࡀࠊྛ⤌ᡂẚ࡟࠾࠸࡚พฝᵓ㐀ࢆ᭷ࡍࡿࠋࡋ

࠿ࡋࠊ࣐࢖ࢡࣟࣂࣈࣝࡢࢫࢣ࣮ࣝ࡟ᑐࡋᑠࡉ࠸Ⅽ࡟↓ど࡛ࡁࡿࠋ

PSࢆࢻ࣓࢖ࣥ࡜ࡍࡿPS⤌ᡂẚ10㸣ࠊ30%ࠊ50%࡟ࡘ࠸᳨࡚ウࡍࡿࠋOMBฎ⌮ᚋࡢ⏬ീ

࡟ࡘ࠸࡚ࡳࡿ࡜PS⤌ᡂẚ 10%ࡢ᫬ࡣ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠸ࠋPS ⤌ᡂẚ30%ࡢ᫬ࡣࠊฎ⌮๓ ᚋ࡛พฝᵓ㐀࡟ࡣኚ໬ࡀ࡞࠸ࡀࠊࣇࣝࢫࢣ࣮ࣝࡢ㐪࠸ࡼࡾฝࡢ㧗ࡉࡀῶᑡࡋ࡚࠾ࡾࠊPS ࡀ

࢚ࢵࢪࣥࢢࡉࢀ࡚࠸ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡿࠋPS⤌ᡂẚ50%࡛ࡣPSࡢ࢚ࢵࢪࣥࢢࡀࡼࡾ㢧ⴭ࡟

⾲ࢀࠊฎ⌮๓ࡢฝᵓ㐀࡛࠶ࡗࡓ㒊ศࡀฎ⌮ᚋ࡛ࡣพᵓ㐀࡜ኚ໬ࡋ࡚࠸ࡿࠋྠࡌฎ⌮᫬㛫࡛ࡶࠊ

PS⤌ᡂẚ10%࡛ࡣPSࡀ࡯࡜ࢇ࡝࢚ࢵࢪࣥࢢࡉࢀ࡚࠾ࡽࡎࠊPS⤌ᡂẚ50%ࡢ᪉ࡀPS⤌ᡂ

ẚ30%࡟ẚ࡭࢚ࢵࢪࣥࢢࡀ㏿࠸ࡇ࡜࠿ࡽࠊPSࢻ࣓࢖ࣥ࡬ࡢ྾╔ຠ⋡ࡣPS⤌ᡂẚ50%ࠊ30%ࠊ

10%ࡢ㡰࡜࡞ࡿࠋ

ࡇࡇ࡛ࠊᓥ㡿ᇦࠊᾏ㡿ᇦ࡬ࡢ྾╔ຠ⋡ࡀ࡜ࡶ࡟100%࡟㏆࠸PS⤌ᡂẚ50%࡟ࡘ࠸࡚ὀ┠

ࡍࡿࠋOMBฎ⌮࡟࢚ࢵࢳࣥࢢ㏿ᗘࡀPS࡜PMMAࡀྠࡌሙྜࠊ⾲㠃ࡀᆒ୍࡟࢚ࢵࢪࣥࢢࡉ

ࢀࡿࡓࡵࠊพฝᵓ㐀ࡢᙧែࠊ㧗ࡉ࡞࡝ࡣ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠸ࠋࡋ࠿ࡋࠊᐇ ࡛ࡣฎ⌮๓ฝᵓ 㐀࡛࠶ࡗࡓ PS ࡀฎ⌮ᚋ࡛ࡣพᵓ㐀࡟ኚ໬ࡋ࡚࠸ࡿࠋࡇࡢ⤖ᯝࡣࠊPS ࡢ࢚ࢵࢪࣥࢢ㏿ᗘࡣ PMMAࡢ࢚ࢵࢪࣥࢢ㏿ᗘ࡟ẚ࡭㠀ᖖ࡟㏿࠸ࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋ

ḟ࡟ࠊPMMAࢆࢻ࣓࢖ࣥ࡜ࡍࡿPS⤌ᡂẚ70%ࠊ90%࡟ࡘ࠸᳨࡚ウࡍࡿࠋ୧⤌ᡂẚ࡜ࡶฎ

⌮ᚋࡢ⏬ീࡼࡾࢻ࣓࢖ࣥ㒊ศ࡟෇ᰕ≧ࡢᵓ㐀ࡀᙧᡂࡋ࡚࠸ࡿࠋPS ⤌ᡂẚ 10%ࠊ30%ྠᵝ࡟

ࢻ࣓࢖࡛ࣥ࠶ࡿPMMAࡀ࢚ࢵࢪࣥࢢࡉࢀࡎࠊᓥࡢPSࡢࡳࡀ࢚ࢵࢪࣥࢢࡉࢀࡓࡓࡵ࡛࠶ࡿࠋ ௨ୖࡢࡇ࡜࠿ࡽࠊPS⤌ᡂẚࢆไᚚࡍࡿࡇ࡜࡟ࡼࡾࠊ⾲㠃ࡀพᵓ㐀ࡢࣇ࢕࣒ࣝࠊฝᵓ㐀ࡢ

ࣇ࢕࣒ࣝࡢసᡂࡀྍ⬟࡛࠶ࡿࠋ

134 30%

)XOOVFDOH “QP )XOOVFDOH “QP

50%

)XOOVFDOH “QP )XOOVFDOH “QP

70%

)XOOVFDOH ± 28 nm )XOOVFDOH “QP

90%

)XOOVFDOH “QP )XOOVFDOH “QP Figure 5.10 Surface roughness image of ozone microbubble treated PS/PMMA blend films.

135 5.4 䜎䛸䜑

ᮏ❶࡛ࡣࠊPSࠊPMMA ཬࡧࡑࢀࡽ࡟ࡼࡗ࡚ᙧᡂࡋࡓᾏᓥᵓ㐀࡬ࡢ࣐࢖ࢡࣟࣂࣈࣝࡢ྾╔

≉ᛶࢆホ౯ࡋࡓࠋࡑࡢ⤖ᯝࠊ௨ୗࡢ▱ぢࢆᚓࡓࠋ

㸦1㸧࣐࢖ࢡࣟࣂࣈࣝࡢ྾╔㏿ᗘࡣ⾲㠃ࡀ␯Ỉᛶ࡛࠶ࡿ᪉ࡀ㏿࠸ഴྥࡀ࠶ࡿࠋ

㸦2㸧࣐࢖ࢡࣟࢧ࢖ࢬࡢᾏᓥᵓ㐀ࢆᣢࡘࣇ࢕࣒ࣝࡣࠊ⮫⏺⾲㠃ᙇຊࡣPS⤌ᡂẚ࡟ᑐࡋࠊ୍

ḟࡢ㛵ಀ࡛ኚ໬ࡍࡿࡀࠊ྾╔㏿ᗘࡣPS⤌ᡂẚࡀቑຍࡍࡿ࡜㏿ࡃ࡞ࡿഴྥࡀࡳࡽࢀࡿࡶࡢ ࡢࠊ୍ḟࡢ㛵ಀ࡛ࡣ࡞࠸ࠋ

㸦3㸧࣐࢖ࢡࣟࣂࣈࣝࡢᓥ㡿ᇦ࡬ࡢ྾╔ࡣᾏ㡿ᇦ࡬ࡢ྾╔࡟ẚ࡭୙Ᏻᐃ࡛࠶ࡿࠋ

㸦4㸧ෆໟẼయࢆάᛶ࢞ࢫ࡛࠶ࡿ࢜ࢰࣥ࡟ኚ᭦ࡋࡓሙྜࠊ⾲㠃࡟พฝᵓ㐀ࢆ᭷ࡍࡿࣇ࢕ࣝ

࣒ࡢసᡂࡀྍ⬟࡛࠶ࡿࠋ

௨ୖࡢࡇ࡜࠿ࡽࠊ2ᡂศ⣔௨ୖࡢ⾲㠃ࢆ᭷ࡍࡿᮦᩱ࡟OMBฎ⌮ࢆ⾜࠺࡜ࠊ࣐࢖ࢡࣟࣂ

ࣈࣝࡢ྾╔ᛶࡢせᅉཬࡧ࢜ࢰࣥ࡟ᑐࡍࡿ⪏㓟໬ᛶࡢᙳ㡪࡟ࡼࡗ࡚ฎ⌮ࡢຠᯝ࡟ࣂࣛࡘࡁࡀ

⏕ࡌࡿྍ⬟ᛶࡀ࠶ࡿࠋࡋ࠿ࡋࠊࡑࢀࡽࡢ≉ᚩࢆ฼⏝ࡍࡿࡇ࡜࡟ࡼࡾࠊ⾲㠃࡟พฝᵓ㐀ࢆᣢ ࡘࣇ࢕࣒ࣝࡢసᡂࡀྍ⬟࡜࡞ࡿࠋ

136

௨ୖ࡟ຍ⇕ࡍࡿࡇ࡜࡛ࣄ࣮ࣜࣥࢢࡍࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋࡑࢀࡽࡢ㥑ືຊࡣศᏊᣑᩓᛶ

࡛࠶ࡾࠊศᏊ㔞౫Ꮡᛶࡀ࠶ࡿ࡜ሗ࿌ࡉࢀ࡚࠸ࡓࠋࡋ࠿ࡋࠊ➹⪅ࡽࡢ௨๓ࡢ◊✲࡟࠾࠸࡚ࠊTg

ࡀᐊ ௨ୗࡢPP࡟Ⓨ⏕ࡉࡏࡓࢡ࣮ࣞࢬࡣᐊ ࡛ࣄ࣮ࣜࣥࢢࡋ࡞࠿ࡗࡓࠋࡇࡢ⤖ᯝࡣࠊ᪂ࡓ

࡞ࢡ࣮ࣞࢬࡢࣄ࣮ࣜࣥࢢᶵᵓࡢᏑᅾࢆ♧၀ࡍࡿࠋࡑࡇ࡛ࠊᮏ❶࡛ࡣPP௨እࡢ㧗ศᏊࡢࢡ࣮ࣞ

ࢬࡢࣄ࣮ࣜࣥࢢ㛤ጞ ᗘࠊPMMAࡢ⦆࿴᫬㛫ࡢศᏊ㔞౫Ꮡᛶ࡟ࡘ࠸᳨࡚ウࡋࡓࠋࡑࡢ⤖ᯝࠊ ࢡ࣮ࣞࢬࣄ࣮ࣜࣥࢢ㛤ጞ ᗘࡣPPࠊPSࠊPMMA࡛60ºCࠊPLLA࡛40-50ºC࡜࡞ࡗࡓࠋT/Tg

ࡀྠࡌ᫬ࠊࣄ࣮ࣜࣥࢢࡢ⛬ᗘࡣྠࡌ࡛࠶ࡿ࡜ሗ࿌ࡉࢀ࡚࠾ࡾࠊࡇࡢ⤖ᯝࡣ௨๓ࡢሗ࿌౛࡟཯

ࡍࡿࠋࡲࡓࠊศᏊ㔞౫Ꮡᛶ࡟ࡘ࠸᳨࡚ウࡋࡓ⤖ᯝࠊ⦆࿴᫬㛫࡟ศᏊ㔞౫Ꮡᛶࡣ࡞ࡃࠊศᏊᣑ ᩓᛶ௨እ࡟ࡶ㥑ືຊࡀ࠶ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋࢡ࣮ࣞࢬ୰ࡢ࣎࢖ࢻࡣࢼࣀ࣓࣮ࢺࣝࢫࢣ࣮࡛ࣝ

࠶ࡿࡓࡵࠊ/SODceᅽࡢᙳ㡪ࡀ↓ど࡛ࡁ࡞࠸ࡇ࡜ࡀ♧ࡉࢀࡓࠋ

࣏࢚ࣜࢫࢸࣝ⧄⥔ࡢᨵ㉁㸦➨3❶㸧

ከࡃࡢ⾰ᩱ࡟౑⏝ࡉࢀ࡚࠸ࡿ࣏࢚ࣜࢫࢸࣝࡣ཯ᛂᇶࢆ᭷ࡉ࡞࠸ࠋ୍᪉ࠊᕷሙࡣᶵ⬟໬ࡀồ

ࡵࡽࢀ࡚࠾ࡾࠊ⪏ஂᛶྥୖࡢࡓࡵ࡟ࡣ཯ᛂᇶࡢᑟධࡀᚲ㡲࡛࠶ࡿࠋ➨2❶࡛ࡣ࣏࢚ࣜࢫࢸࣝ

࡟OMBฎ⌮ࢆ⾜࠸ࠊ⏕ᡂࡋࡓᐁ⬟ᇶཬࡧ㧗ຠ⋡໬࡟ࡘ࠸᳨࡚ウࡋࡓࠋࡑࡢ⤖ᯝࠊ࣏࢚ࣜࢫ ࢸࣝ࡟OMBฎ⌮ࢆࡍࡿ࡜㓟⣲ࢆྵࡴ཯ᛂᇶࡀᑟධࡉࢀࠊࡑࡢ1㒊ࡀ࢝ࣝ࣎࢟ࢩᇶ࡛࠶ࡿࡇ

࡜ࡀุ᫂ࡋࡓࠋࡲࡓࠊ࣏࢚ࣜࢫࢸࣝࡢ༢఩ᵓ㐀୰࡟࠶ࡿⰾ㤶᪘⎔࡜཯ᛂࡋ࡚࠸ࡿྍ⬟ᛶࡀ♧

၀ࡉࢀࡓࠋⰾ㤶᪘⎔ࢆྵࡴᰁᩱࢆ⏝࠸࡚ᰁⰍࡋࡓࢺࣜ࢔ࢭࢸ࣮ࢺࡢኚ㏥Ⰽヨ㦂࡟࠾࠸࡚ࠊS+

ࡀప࠸᪉ࡀࠊࡼࡾኚ㏥Ⰽࡀ኱ࡁ࠸ࡇ࡜࠿ࡽࠊⰾ㤶᪘⎔ࡣ࢜ࢰࣥศゎ᫬࡟⏕ᡂࡍࡿOHࣛࢪ࢝

࡛ࣝࡣ࡞ࡃࠊ࢜ࢰࣥ࡜┤᥋཯ᛂࡋ࡚࠸ࡿࠋࡲࡓࠊOMBࡢⓎ⏕Ỉ ࡢ౫Ꮡᛶ࡟ࡘ࠸࡚ㄪᰝࡋ ࡓ⤖ᯝࠊ⁐Ꮡ࢜ࢰࣥ⃰ᗘ࡜ࢺࣜ࢔ࢭࢸ࣮ࢺࡢኚ㏥Ⰽࡢ⛬ᗘࡣ୍⮴ࡋ࡞࠿ࡗࡓࠋỈ పୗ࡟ࡼ

ࡾ⁐Ꮡ࢜ࢰࣥ⃰ᗘୖ᪼ࡢせᅉࡼࡾ཯ᛂ㏿ᗘపୗࡢせᅉࡀ኱ࡁ࠸ࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊ㧗⁐Ꮡ

࢜ࢰࣥ⃰ᗘ࡜㧗཯ᛂ㏿ᗘࢆ୧❧࡛ࡁࡿ⿦⨨㸦ᒁᡤຍ⇕⿦⨨㸧ࢆ㛤Ⓨࡋࡓࠋࡇࡢ⿦⨨ࢆ⏝࠸ࡿ

ࡇ࡜࡟ࡼࡾࠊ࣏࢚ࣜࢫࢸࣝ࡜࢜ࢰࣥࡢ཯ᛂ࡟࠾ࡅࡿぢ࠿ࡅࡢάᛶ໬࢚ࢿࣝࢠ࣮ࡢ⟬ฟ࡟ᡂຌ

ࡋࡓࠋࡲࡓࠊᒁᡤຍ⇕⿦⨨ࢆ⏝࠸ࡿࡇ࡜࡛ࠊᒁᡤຍ⇕⿦⨨ࢆ⏝࠸࡞࠸᭱ࡶⰋዲ࡞᮲௳࡟ẚ࡭ࠊ ฎ⌮ຠ⋡ࡀ4.5ಸྥୖࡉࡏࡿࡇ࡜࡟ᡂຌࡋࡓࠋ

137

Ⅳ⣲⧄⥔ࡢᨵ㉁࡟ࡼࡿCFRPࡢᙉᗘྥୖ㸦➨4❶㸧

CFRPࢆỗ⏝〇ရ࡟⏝࠸ࡿࡓࡵ࡟ࡣࢱࢡࢺࢱ࢖࣒ࡀ㛗࠸ࡇ࡜ࡀḞⅬ࡜࡞ࡗ࡚࠸ࡿࠋࡑࡇ࡛ࠊ ࢱࢡࢺࢱ࢖࣒ࡀ▷⦰ฟ᮶ࡿCFRTPࡀὀ┠ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ⌧ᅾࠊୖᕷࡉࢀ࡚࠸ࡿCFࡢ

ከࡃࡣࠊCFRTS⏝ࡢࢧ࢖ࢪࣥࢢ๣ࡀሬᕸࡉࢀ࡚࠸ࡿࠋࡑࡢⅭࠊCF-ᶞ⬡⏺㠃࡛ࡢ᥋╔ᛶࡀஈ

ࡋࡃࠊ㧗ᛶ⬟⬟ࡢCFRPࡢసᡂࡀㄢ㢟࡛࠶ࡿࠋᮏ◊✲࡛ࡣࠊCFࢆOMBฎ⌮ࠊNMBฎ⌮ࢆ

⾜࠸ࠊᙉᗘྥୖࢆヨࡳࡓࠋ⏺㠃ࡏࢇ᩿ᙉᗘࢆㄪᰝࡋࡓ⤖ᯝࠊOMBฎ⌮ࡼࡾNMBฎ⌮ࡢ᪉ ࡀຠᯝࡀ኱ࡁ࠿ࡗࡓࠋẚ⾲㠃✚ࡢቑຍ⋡ࠊO/Cẚࡢቑຍ⋡ࡣOMBฎ⌮ࡢ᪉ࡀ኱ࡁ࠿ࡗࡓⅭࠊ

⏺㠃ࡏࢇ᩿ᙉᗘࡢᙉᗘࢆྥୖࡉࡏࡿࡓࡵ࡟ࡣࠊ⾲㠃ࢆ␯Ỉᛶ࡟⥔ᣢࡋࡓ≧ែ࡛ẚ⾲㠃✚ࢆᣑ

኱ࡍࡿࡇ࡜ࡀᮃࡲࡋ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡋ࠿ࡋࠊCFࢡࣟࢫࢆ⏝࠸࡚CFRPᡂᙧయࢆసᡂࡋࠊ 3Ⅼ᭤ࡆヨ㦂ࢆ⾜ࡗࡓ⤖ᯝࠊOMB ฎ⌮ࡀ᭱ࡶຠᯝࡀ࠶ࡗࡓࠋࡑࡢせᅉ࡟ࡘ࠸࡚ㄪᰝࡍࡿࡓ

ࡵ࡟ࠊCFRPᡂᙧయࡢ✵㝽⋡ࡢ ᐃ࡜᩿㠃ࡢගᏛ㢧ᚤ㙾෗┿ࡢ᧜ᙳࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊNMB ฎ⌮ࢆ⾜ࡗࡓCF࡛సᡂࡋࡓCFRPࡣ✵㝽⋡ࡀ㧗ࡃࠊ᭤ࡆヨ㦂๓ࡢ≧ែ࡛ࡶ✵㝽ࡀ☜ㄆ࡛ࡁ ࡓࠋ⏺㠃ࡏࢇ᩿ᙉᗘ࡟ᶞ⬡ࡢྵᾐᛶࡢᴫᛕࡀ࡞࠸Ⅽ⏕ࡌࡓ㏫㌿⌧㇟࡛࠶ࡾࠊ࣮࢜ࢺࢡ࣮ࣞࣈ

ἲ࡞࡝ࡢ᭦࡟✵㝽ࡀฟ᮶࡟ࡃ࠸ᡂᙧἲ࡟࡚సᡂࡍࡿࡇ࡜࡛᭦࡞ࡿᙉᗘྥୖࡀぢ㎸ࡲࢀࡿࠋ୍

᪉ࠊOMBฎ⌮ࢆ⾜ࡗࡓCF࡛సᡂࡋࡓCFRPࡢ✵㝽⋡ࡣపࡃࠊ᭤ࡆヨ㦂๓ᚋࡢගᏛ㢧ᚤ㙾

෗┿࡛ࡶ✵㝽ࡣ☜ㄆ࡛ࡁ࡞࠿ࡗࡓࠋ௨ୖࡢࡇ࡜࠿ࡽࠊOMBฎ⌮ࡣྵᾐᛶࠊ⏺㠃ࡢ᥋╔ᙉᗘ

ࢆྠ᫬࡟ྥୖ࡛ࡁࡿฎ⌮ἲ࡜ゝ࠼ࡿࠋ

㧗ศᏊ⾲㠃࡬ࡢ࣐࢖ࢡࣟࣂࣈࣝࡢ྾╔ࡢほᐹ㸦➨5❶㸧

➨2❶ࠊ➨3❶࡛ࡣࠊ࣏࢚ࣜࢫࢸࣝࠊCFࡢᨵ㉁࡟ࡘ࠸᳨࡚ウࡋࡓࠋఱࢀࡶ࣐࢖ࢡࣟࣂࣈ

ࣝ࡜⿕ฎ⌮≀ࡀ᥋ゐࡍࡿᚲせࡀ࠶ࡿࠋࡋ࠿ࡋࠊ࣐࢖ࢡࣟࣂࣈࣝࡢຠᯝ࡟ࡘ࠸࡚ࡢሗ࿌౛ࡣᩘ

ከ࠸ࡀࠊ⿕ฎ⌮≀࡬ࡢ྾╔≉ᛶࡢホ౯ࡢ◊✲౛ࡣഹ࠿࡛࠶ࡿࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊ2ᡂศ

⣔ࡢࣇ࢕࣒ࣝ࡬ࡢ࣐࢖ࢡࣟࣂࣈࣝࡢ྾╔≉ᛶ࡟ࡘ࠸࡚ホ౯ࡋࡓࠋẚ㍑ⓗ␯Ỉᛶ࡞PS࡜ẚ㍑

ⓗぶỈᛶࡢPMMAࢆ࣑ࢡࣟࢧ࢖ࢬ࡟┦ศ㞳ࡉࡏࡿࡓࡵ࡟ࠊ┦ᐜ๣࡜ࡋ࡚PS-JUDIW-PMMAࢆ 㔜ྜࡋࡓࠋ┦ᐜ໬๣ࢆῧຍࡋࡓPS/PMMA⁐ᾮࢆࢹ࢕ࢵࣉࢥ࣮ࢺࡍࡿࡇ࡜࡛ᡤᮃࡢᾏᓥᵓ㐀

ࢆᣢࡘࣇ࢕࣒ࣝࡢసᡂ࡟ᡂຌࡋࡓࠋỈᬗ᣺ືᏊ࡟ࢹ࢕ࢵࣉࢥ࣮ࢺࡋࠊQCMἲ࡟࡚࣐࢖ࢡࣟ

ࣂࣈࣝࡢ྾╔≉ᛶࢆホ౯ࡋࡓ࡜ࡇࢁࠊPS ᡂศࡀቑຍࡍࡿ࡟ࡘࢀ࡚྾╔㏿ᗘࡀ㏿ࡃ࡞ࡿഴྥ

ࡀぢࡽࢀࡓࠋࡋ࠿ࡋࠊ⮫⏺⾲㠃ᙇຊࡣ PS ⤌ᡂẚ࡟ᑐࡋ୍ḟࡢ㛵ಀࢆ♧ࡍࡀࠊ྾╔㏿ᗘࡣࠊ

PS⤌ᡂẚ50%௨እࠊPS࡜PMMAࡢ྾╔㏿ᗘࢆ⤖ࢇࡔ⥺ࡼࡾୗᅇࡗࡓࠋᾏᓥᵓ㐀ࡢࢧ࢖ࢬ

ࢫࢣ࣮ࣝࡀ࣐࢖ࢡࣟࣂࣈࣝࡢࢧ࢖ࢬࢫࢣ࣮ࣝ࡜㏆࠸Ⅽࠊ⾲㠃ࡢᵓ㐀࡟ࡼࡿᙳ㡪ࢆཷࡅ࡚࠸ࡿࠋ ࡑࡢⅭࠊᾏෆ࡟྾╔࡛ࡁࡿ࣐࢖ࢡࣟࣂࣈࣝᚄ࡜ࡋ࡚௬᝿ࢻ࣓࢖ࣥᚄࢆ⟬ฟࡋࠊ᭦࡞ࡿ᳨ウࢆ

⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊᓥ㡿ᇦࡢ᪉ࡀᾏ㡿ᇦ࡟ẚ࡭྾╔ࡋ࡟ࡃ࠸ࡇ࡜ࡀศ࠿ࡗࡓࠋࡇࡢ≉ᚩ࡜≀

㉁ࡢ⪏࢜ࢰࣥᛶࡢ㐪࠸ࢆ฼⏝ࡋ࡚ࠊ⾲㠃ࡀ≉␗ⓗ࡞ᵓ㐀ࢆ᭷ࡍࡿࣇ࢕࣒ࣝࡢసᡂ࡟ᡂຌࡋࡓࠋ

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