2011A1752

BL19B2ᮎ➃ࢆᐁ⬟ᇶಟ㣭ࡋࡓ㧗ᶵ⬟ࢦ࣒ᮦᩱࡢ㛤Ⓨ㻔7㻕
Development of Advanced Rubber Materials Having FunctionalizedPolymer Chain Ends 㻔7㻕‫‮‬ῦ Ẏ, ෠Ọ ဴ㞝, ᭮᰿ ༟⏨
Takeshi Yuasa, Tetsuo Tominaga, Takuo SoneJSR ᰴᘧ఍♫JSR Corporation┬⇞㈝ࢱ࢖ࣖ⏝ᮎ➃ኚᛶ SBR㸦ࢫࢳࣞࣥࣈࢱࢪ࢚ࣥࢦ࣒㸧ࡢ㛤Ⓨ࡟ྥࡅࡓᇶ♏᝟ሗࢆᚓࡿࡓࡵ㸪ࢦ࣒㓄ྜ≀୰࡛ࡢࢩࣜ࢝⢏Ꮚࡢᵓ㐀࣭ศᩓ≧ែࢆᑠゅ㸪࠾ࡼࡧ㉸ᑠゅ X ⥺ᩓ஘ἲ㻔SAXS,USAXS㻕࡟ࡼࡾゎᯒ୰࡛࠶ࡿ㸬௒ᅇࡢᐇ㦂࡛ࡣ㸪ศᏊ㔞ࡸᐁ⬟ᇶᑟධ⟠ᡤࡢ␗࡞ࡿኚᛶ SBR ࢆ⏝࠸ࡓࣔࢹࣝヨᩱࢆ ᐃࡋ㸪SBR ࡢᵓ㐀ࡀࢩࣜ࢝ࡢศᩓ≧ែ࡟ཬࡰࡍᙳ㡪ࢆ☜ㄆࡋࡓ㸬ࡑࡢ⤖ᯝ㸪ᐁ⬟ᇶ⃰ᗘࡸᑟධ⟠ᡤࡀ㸪ࢩࣜ࢝ࡢศᩓ⢏ᚄ࡜┦㛵㛵ಀࡀ࠶ࡿࡇ࡜ࡀࢃ࠿ࡗࡓ㸬࣮࣮࢟࣡ࢻ㸸 㧗ศᏊ㸪ྜᡂࢦ࣒㸪ࢱ࢖ࣖ㸪㉸ᑠゅ X ⥺ᩓ஘⫼ᬒ࡜◊✲┠ⓗ㸸㏆ᖺࡢ⎔ቃၥ㢟࡬ࡢྲྀࡾ⤌ࡳ࡜ࡋ࡚㸪 ᐊຠᯝ࢞ࢫࡢ㸯ࡘ࡛࠶ࡿ஧㓟໬Ⅳ⣲ࡢ᤼ฟ㔞๐ῶ࡟ྥࡅࡓ⮬ື㌴ࡢ⇞㈝ྥୖࡣᛴົࡢㄢ㢟࡛࠶ࡿ㸬⮬ື㌴ࡢ⇞㈝ྥୖࢆᅗࡿ࠺࠼࡛ࢱ࢖ࣖࡢ㌿ࡀࡾ᢬ᢠࢆపῶࡉࡏࡿࡇ࡜ࡣ㔜せ࡞ᅉᏊࡢ୍ࡘ࡛࠶ࡾ㸪࢚ࢿࣝࢠ࣮ࣟࢫࢆᢚ࠼ࡿࡓࡵࡢᮦᩱ㛤Ⓨࡀ㐍ࡵࡽࢀ࡚࠸ࡿ㸬⇞㈝࡬ࡢᐤ୚ࡀ኱ࡁ࠸ࢱ࢖ࣖࢺࣞࢵࢻ㒊ࡣ㸪୺࡟ྜᡂࢦ࣒࡜ࢩࣜ࢝➼ࡢࣇ࢕࣮ࣛ㸦⿵ᙉ๣㸧࡛ᵓᡂࡉࢀ࡚࠾ࡾ㸪ࢦ࣒୰࡛ࡢࣇ࢕࣮ࣛࡢศᩓ≧ែࡣࢱ࢖ࣖࡢᛶ⬟࡟኱ࡁࡃᙳ㡪ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ㸬ࡇࡢࡼ࠺࡞⫼ᬒ࠿ࡽ㸪ࢦ࣒୰࡛ࡢࣇ࢕࣮ࣛࡢศᩓᛶྥୖࢆ┠ⓗ࡜ࡋ࡚㸪ᮎ➃࡟ᐁ⬟ᇶࢆᑟධࡋࡓ㸦ᮎ➃ኚᛶ㸧⁐ᾮ㔜ྜ SBR ࡀ㛤Ⓨࡉࢀ࡚ࡁࡓ㸬ᮎ➃ኚᛶ SBR ࡣ㸪ࣇ࢕࣮ࣛ࡜࣏࣐࣮ࣜᮎ➃࡜ࡢ┦஫స⏝࡟ࡼࡾ㸪ΰ⦎᫬࡟ࣇ࢕࣮ࣛࢆࢦ࣒୰࡟ᚤศᩓࡉࡏࡿࡇ࡜ࡀ࡛ࡁࡿ㸬ࡑࡢ⤖ᯝ㸪ࣇ࢕࣮ࣛ⏤᮶ࡢࣟࢫࢆ኱ᖜ࡟పῶࡍࡿ࡜ྠ᫬࡟㸪࣏࣐࣮ࣜࡢ⮬⏤ᮎ➃ࡢ㐠ືࡶᢚไࡍࡿࡇ࡜࡛࣏࣐࣮ࣜ⏤᮶ࡢࣟࢫࢆపῶ࡛ࡁࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸬ᡃࠎࡣࡇࢀࡲ࡛㸪ᮎ➃ኚᛶ SBR ୰࡛ࡢࢩࣜ࢝ࡢᵓ㐀ࡸศᩓ≧ែࢆゎᯒࡍࡿࡓࡵ SPring-8
BL19B2 ࡟࡚ᩘࢼࣀ㹼ᩘⓒࢼࣀ࣓࣮ࢺࣝࡢᵓ㐀᝟ሗࡀᚓࡽࢀࡿ SAXS㸪USAXS ᐇ㦂ࢆ⾜࠸㸪ᮎ➃ኚᛶ SBR ࡀ㸪ྠࡌࡃࢩࣜ࢝ࡢศᩓࢆ┠ⓗ࡜ࡋ࡚⏝࠸ࡽࢀࡿࢩࣛࣥ࢝ࢵࣉࣜࣥࢢ๣࡟ẚ࡭࡚ࡼࡾ⣽࠿ࡃࢩࣜ࢝ࢆศᩓࡉࡏࡿ࡞࡝㸪㌿ࡀࡾ᢬ᢠࡢపῶ࡟ᑐࡋ㠀ᖖ࡟ඃࢀ࡚࠸ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸬ࡲࡓ㸪㹖⥺ᩓ஘⬟ࡢ㧗࠸໬ྜ≀ࢆ㝖࠸ࡓࣔࢹࣝ㓄ྜࢆ⏝࠸ࡿࡇ࡜࡛㸪ヲ⣽࡞ࣉࣟࣇ࢓࢖ࣝࡢゎᯒࡀྍ⬟࡛࠶ࡿࡇ࡜ࢆ♧ࡋ㸪SBR ࡟ᑟධࡋࡓᐁ⬟ᇶࡢ✀㢮࡟ࡼࡗ࡚ࢩࣜ࢝จ㞟యࡢ⢏ᚄศᕸࡀ␗࡞ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋࡓ㸬௒ᅇࡢᐇ㦂࡛ࡣ㸪ศᏊ㔞ࡸᐁ⬟ᇶᑟධ⟠ᡤࡢ␗࡞ࡿኚᛶ SBR ࢆ⏝࠸ࡓࣔࢹࣝ㓄ྜ≀ࢆస〇ࡋ㸪SAXS㸪USAXS ᐃࢆ⾜࠺ࡇ࡜࡛㸪SBR ࡢศᏊᵓ㐀࡜ࢩࣜ࢝ࡢศᩓ≧ែࡢ㛵ಀࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬ᐇ㦂㸸ศᏊ㔞࡜ᐁ⬟ᇶᑟධ⟠ᡤࡢ␗࡞ࡿ 6 ✀㢮ࡢ⁐ᾮ㔜ྜ SBR ࢆ୍⯡ⓗ࡞࢔ࢽ࢜ࣥ㔜ྜ࡟ࡼࡾྜᡂࡋ
ࡓ㸬ྜᡂࡋࡓ⁐ᾮ㔜ྜ SBR ࡣ㸪㔜ྜయࡢ⤊ᮎ➃࡟ᐁ⬟ᇶࢆࡶࡓ࡞࠸ Mw
20 ୓ࡢᮍኚᛶSBR㻔SBR[a]㻕࡜ᐁ⬟ᇶࢆᑟධࡋࡓᮎ➃ኚᛶ SBR㻔SBR[b]㻕㸪࠾ࡼࡧ Mw 40 ୓ࡢᮍኚᛶ SBR㻔SBR[c]㻕
࡜ᮎ➃ኚᛶ SBR㻔SBR[d]㻕㸪ࡉࡽ࡟」ᩘಶࡢᐁ⬟ᇶࢆ୺㙐࡟ࣛࣥࢲ࣒࡟ᑟධࡋࡓ SBR㻔SBR[e]㻕࡜」ᩘಶࡢᐁ⬟ᇶࢆᮎ➃࡟ࣈࣟࢵࢡⓗ࡟ᑟධࡋࡓ SBR㻔SBR[f]㻕࡛࠶ࡗࡓ㸬ࡇࢀࡽࡢ SBR ࡟㸪ࣇ࢕࣮ࣛ࡜ࡋ࡚ࡢࢩࣜ࢝㸪࠾ࡼࡧ◲㯤࡞࡝ࡢࢦ࣒㓄ྜ⸆ရࢆ㓄ྜࡋ㸪ࣂࣥࣂ࣮ࣜᆺ࣑࢟ࢧ࣮࡛ΰ⦎ࡾᚋ࡟ࣉࣞࢫຍ◲ࢆ⾜࠺ࡇ࡜࡛ࢩ࣮ࢺ≧ࡢ ᐃヨᩱࢆస〇ࡋࡓ㸬USAXS
࠾ࡼࡧ SAXS ᐃࡣ BL19B2 ࡛⾜ࡗࡓ㸬USAXS ࡣ࣓࢝ࣛ㛗 39.6 m㸪SAXS ࡣ࣓࢝ࣛ㛗ࢆ 2.7 m ࡟タᐃࡋࡓ㸬X ⥺࢚ࢿࣝࢠ࣮ࡣ 18 keV ࡜ࡋ㸪ࣆࢡࢭ᳨ࣝฟჾ PILATUS ࢆ⏝࠸ᩓ஘ࢹ࣮ࢱࢆᚓࡓ㸬⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
SBR[a] ~ [d]࠿ࡽస〇ࡋࡓࣔࢹࣝ㓄ྜヨᩱࡢ SAXS, USAXS ᐃ⤖ᯝࢆᅗ 1 ࡟♧ࡍ㸬඲࡚ࡢ SBRヨᩱ࠿ࡽ㸪ࡑࢀࡒࢀ 1 ḟ⢏Ꮚ㹼1 ḟจ㞟య㡿ᇦ࡟ࢃࡓࡿᩓ஘ࣉࣟࣇ࢓࢖ࣝࡀᚓࡽࢀࡓ㸬ᩓ஘࣋ࢡࢺࣝ q > 0.2 nm1 ࡢ㡿ᇦ࡟࠾࠸࡚ࡣ㸪ࢩࣜ࢝ࡢ 1 ḟ⢏Ꮚ⏤᮶ࡢᩓ஘ࡀほ ࡉࢀ㸪ࣉࣟࣇ࢓࢖ࣝࡢᙧ
≧ࡣ SBR ✀࡟౫Ꮡࡋ࡞࠿ࡗࡓ㸬ࡑࢀ࡟ᑐࡋ q < 0.2 nm1 ࡢࢩࣜ࢝ࡢ 1 ḟจ㞟య㡿ᇦ࡛ࡣ㸪SBR[a] ~[d]࡛ࡑࢀࡒࢀࢩࣙࣝࢲ࣮ࡢほ ఩⨨ࡀ኱ࡁࡃ␗࡞ࡗ࡚࠸ࡓ㸬ᅗ 1 ࠿ࡽࡣࢩࣜ࢝ࡢ 1 ḟจ㞟యࡢศᩓ⢏ᚄࡀ㸪SBR[a] > SBR[c] > SBR[d] >SBR[b]ࡢ㡰࡛⣽࠿࠸ࡇ࡜ࡀศ࠿ࡗࡓ㸬ᮍኚᛶ SBR ྠኈ࡛ࡢẚ㍑࡛ࡣ㸪ศᏊ㔞ࡢ㧗࠸ SBR[c]ࡢ᪉ࡀ SBR[a]ࡼࡾࡶΰ⦎᫬ࡢࡏࢇ᩿ຊࡀᙉࡃ㸪ࢩࣜ࢝ࡢจ㞟యࢆ⣽࠿ࡃ࡛ࡁࡓ࡜⪃࠼ࡽࢀࡿ㸬୍᪉㸪ኚᛶ SBR ྠኈࡢẚ㍑࡛ࡣ SBR[d]ࡢ᪉ࡀࡏࢇ᩿ຊࡣ㧗࠿ࡗࡓࡀ㸪ศᩓ⢏ᚄࡣ SBR[b]ࡢ᪉ࡀᑠࡉ࠿ࡗࡓ㸬ࡇࢀࡣศᏊ㔞ࡢ㐪࠸࡟ࡼࡿኚᛶᮎ➃ࡢᩘ㸪ࡍ࡞ࢃࡕᑟ
ධࡉࢀࡓᐁ⬟ᇶ㔞ࡢᕪ࡟㉳ᅉࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ㸪ࡼࡾከࡃࡢᐁ⬟ᇶࢆ᭷ࡍࡿ SBR[a]ࡢ᪉ࡀࢩࣜ࢝ࢆ⣽࠿ࡃศᩓ࡛ࡁࡓ࡜᥎ ࡋ࡚࠸ࡿ㸬ࡋࡓࡀࡗ࡚㸪ኚᛶ SBR ࡟࠾࠸࡚ࡣΰ⦎᫬ࡢࡏࢇ᩿ຊࡢ㧗ࡉࡼࡾࡶ㸪ࢩࣜ࢝࡜⤖ྜ࡛ࡁࡿᐁ⬟ᇶ㔞ࡀከ࠸࡯࠺ࡀ㸪ࢩࣜ࢝ࡢศᩓ≧ែ࡟୚࠼ࡿᙳ㡪ࡀ኱ࡁ࠸ࡇ࡜ࡀ♧၀ࡉࢀࡓ㸬ḟ࡟㸪SBR[e]࠾ࡼࡧ[f]࠿ࡽస〇ࡋࡓヨᩱࡢ ᐃ⤖ᯝࢆᅗ 2 ࡟♧ࡍ㸬ᅗ 1 ྠᵝ㸪ࢩࣜ࢝ࡢ 1 ḟ⢏Ꮚ㡿ᇦࡣࣉࣟࣇ࢓࢖ࣝࡢᙧ≧ࡣ SBR ✀࡟ࡣ౫Ꮡࡏࡎ㸪1 ḟจ㞟యࡢ㡿ᇦࡢࢩࣙࣝࢲ࣮ᙧ≧ࡀ␗࡞ࡗ࡚࠸ࡓ㸬ࣉࣟࣇ࢓࢖ࣝ࠿ࡽぢ✚ࡶࡽࢀࡿࢩࣜ࢝จ㞟యࡢศᩓ⢏ᚄࡣ SBR[f] > SBR[e]ࡢ㡰࡛⣽࠿ࡃ㸪୺㙐࡟ࣛࣥࢲ࣒࡟ᐁ⬟ᇶࢆᑟධࡋࡓ SBR ࡼࡾࡶᮎ➃࡟ࣈࣟࢵࢡⓗ࡟ᑟධࡋࡓ SBR ࡢ᪉ࡀ㸪ࢩࣜ࢝ࡢศᩓ⬟ຊ࡟ඃࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓ㸬ࡇࢀࡣ㸪ࢩࣜ࢝࡜ࡢ┦஫స⏝ࢆ᭷ࡍࡿᐁ⬟ᇶࢆᮎ➃࡟㞟୰ࡍࡿࡇ࡜࡛┦஫స⏝ࡢᙉࡉࢆ㧗ࡵࡿ࡜ඹ࡟㸪ΰ⦎᫬࡟ຠ⋡ࡼࡃࡏࢇ᩿ຊࢆຍ࠼ࡿࡇ࡜ࡀ࡛ࡁࡓࡓࡵ࡜⪃࠼࡚࠸ࡿ㸬௨ୖ࠿ࡽ㸪SBR ࡢศᏊᵓ㐀ࡢ㐪࠸࡟ࡼࡾࢩࣜ࢝ࡢ 1 ḟจ㞟యࡢ⢏ᚄࡀ␗࡞ࡿࡇ࡜ࡀ♧ࡉࢀ㸪ࢩࣜ࢝ࢆࡼࡾ⣽࠿ࡃศᩓࡉࡏࡿࡓࡵ࡟ࡣ㸪SBR ࡟ᑟධࡍࡿᐁ⬟ᇶࡢቑ㔞ࡸᑟධ⟠ᡤࡢ᭱㐺໬ࡀ᭷ຠ࡛࠶ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟ࡋ㸪ᮎ➃ኚᛶ SBR ࡢタィᣦ㔪ࢆ☜ㄆࡍࡿࡇ࡜ࡀ࡛ࡁࡓ㸬௒ᚋࡢㄢ㢟㸸௒ᅇࡢᐇ㦂࠿ࡽ㸪ᵝࠎ࡞ศᏊᵓ㐀ࢆࡶࡘ SBR ヨᩱࡢ SAXS, USAXS ᐃࢆᐇ᪋ࡍࡿࡇ࡜࡛㸪SBR࡟ᑟධࡋࡓᐁ⬟ᇶ㔞ࡸ㸪ᑟධ⟠ᡤ࡟ࡼࡾࣇ࢕࣮ࣛࡢ 1 ḟจ㞟యࡢ⢏ᚄࡀ␗࡞ࡿࡇ࡜ࢆ᫂ࡽ࠿࡟࡛ࡁࡓ㸬௒ᚋ㸪IR ࡸ BR ࢆࣈࣞࣥࢻࡋࡓ㸪ࡼࡾᐇ⏝࡟㏆࠸㓄ྜヨᩱࡢᩓ஘ࣉࣟࣇ࢓࢖ࣝ࡜࡜ࡶ࡟ヲ⣽࡟ゎᯒࡍࡿࡇ࡜࡛㸪࢚ࢿࣝࢠ࣮ࣟࢫ≉ᛶࡸ⪏ᦶ⪖ᛶ㸪⿵ᙉᛶ࡞࡝ࡢ≀ᛶ࡟ࡘ࠸࡚┦㛵㛵ಀࢆゎ᫂ࡋࡉࡽ࡞ࡿ㧗ᶵ⬟໬࣏࣐࣮ࣜࢆタィࡍࡿࡓࡵࡢᇶ♏᝟ሗࢆᚓ࡚࠸ࡃ㸬
SBR[e] (x10)SBR[f]

Intensity / a.u.

Intensity / a.u.

SBR[a] (x10)SBR[b]
SBR[c] (x10)SBR[d]

10-210-1

q / nm100-1

ᅗ 1 SBR[a] ~ [d]ࢆ⏝࠸ࡓࢩࣜ࢝㓄ྜヨᩱ
ࡢ SAXS-USAXS ࣉࣟࣇ࢓࢖ࣝ10-2

10-1

q / nm100-1

ᅗ 2 SBR[e],[f]䜢⏝䛔䛯䝅䝸䜹㓄ྜヨᩱ䛾SAXS-USAXS 䝥䝻䝣䜯䜲䝹