Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)

BL08B2

2015B3389

খ֯ X ઢࢄཚ๏ʹΑΔφϊϑΟϥʔͷ෼ࢄঢ়ଶղੳ

Distribution Analysis of Nano Size Hollow Particles Dispersed inPolymer Matrix by Small-Angle X-ray Scatteringࡾࠜੜ ৾ 1 , ੴ௡ Յࢠ 1 , ‫ݹ‬լ ޿೭ 1 , ֯ౡ ৴࢘ 1 , ‫܂‬ຊ ࣎ੜ 2 , ࣫‫ྑ ݪ‬ণ 2 , ཥ ཕ 2 ,໺੉ ૜ࢢ 2 ɼԣࢁ ࿨࢘ 2 , ॅా ߂༞ 1
Susumu Mineoi1 , Yoshiko Ishizu1 , Hiroyuki Koga1 , Shinji Kadoshima1 , Shigeo Kuwamoto2
Yoshimasa Urushihara2 , Lei Li2 , Souichi Nose2 , Kazushi Yokoyama2 , Hirosuke Sumida111Ϛπμ‫ࣜג‬ձࣾ ٕज़‫ॴڀݚ‬ɼ2 ฌ‫ཱݝݿ‬େֶ์ࣹޫφϊςΫηϯλʔ

Mazda Motor Corporation Technical Research Center, 2 Synchrotron Radiation Nanotechnology
Laboratory, University of Hyogo֓ཁɿதۭφϊϑΟϥʔΛथࢷʹఴՃͨ͠ෳ߹ࡐྉΛ༻͍ͯɺϑΟϥʔͷ෼ࢄঢ়ଶΛখ֯ X ઢࢄཚ๏ʹΑΓධՁͨ͠ɻࢄཚ‫ۂ‬ઢͷղੳʹதۭφϊϑΟϥʔͷ‫ܗ‬ঢ়Λ൓өͤ͞ΔͨΊɺಁաిࢠ‫ݦ‬ඍ‫ڸ‬ʢTEMʣ‫࡯؍‬Λߦͬͯ‫ܗ‬ঢ়Λ֬ೝ͠ɺதۭφϊϑΟϥʔͷಛ௃తͳ‫ܗ‬ঢ়Λද‫͢ݱ‬ΔͨΊԁ൘ϞσϧΛద༻ͨ͠ɻԁ൘ϞσϧΛ༻͍ͨղੳʹΑΓɺྑ޷ͳϑΟοςΟϯάͱ෼ࢄঢ়ଶʹؔ͢Δύϥϝʔλ͕ಘΒΕͨɻখ֯ X ઢࢄཚख๏͸ɺࢄཚମ͕ಛҟͳߏ଄Λ΋ͭதۭφϊϑΟϥʔͷ෼ࢄঢ়ଶղੳʹ͓͍ͯ༗ޮͰ͋Δ͜ͱ͕෼͔ͬͨɻ
Ωʔϫʔυɿখ֯ X ઢࢄཚ, தۭφϊϑΟϥʔ, ෳ߹ࡐྉ, ಁաిࢠ‫ݦ‬ඍ‫࡯؍ڸ‬എ‫ڀݚͱܠ‬໨తʹద༻͢Δ͜ͱͰɼখ֯ X ઢࢄཚख๏ʹΑΔφϊཻ࣋ଓՄೳͳࣾձͷ࣮‫͚ࣗͯ޲ʹݱ‬ಈंͰ͸ΤωϧΪʔར༻ޮ཰޲্͕ඞཁͰ͋Δɽಈྗ‫ؔػ‬ͷੑೳ޲্ɼిಈσόΠε౥ࡌʹΑΔΤωϧΪʔϩε௿‫Ͳͳݮ‬ࢠ෼ࢄঢ়ଶධՁͷ༗ޮੑΛ‫ݕ‬౼ͨ͠ɽ࣮‫ݧ‬ʹՃ͑ͯɼंମͷܰྔԽ͸ඞਢͰ͋Δɽۙ೥ɼࣗಈं

φϊαΠζཻࢠͱͯ͠தۭφϊϑΟϥʔʢࡐ࣭ɿγΛ‫ؚ‬Ή͞·͟·ͳ੡඼Ͱ୸ૉણҡ΍ΨϥεણҡΛ෼ࢄϦΧɼϝʔΧʔΧλϩάฏ‫ܘۉ‬ɿ100 nmʣΛ༻͍ɼෳͤͨ͞थࢷෳ߹ࡐྉΛۚଐ෦඼ʹஔ͖‫͑׵‬ɼ‫౓ڧ‬΍߶߹ࡐྉ͸தۭφϊϑΟϥʔΛथࢷʢ‫ؚ‬τϧΤϯ༹ഔʣੑΛҡ࣋ͭͭܰ͠ྔԽ͕ਤΒΕ͍ͯΔɽथࢷෳ߹ࡐྉ

ʹɼ10vol%ఴՃ֧ͯ͠፩ɾࠞ߹ͨ͠‫ޙ‬ɼۚଐ൘্ʹ੒ͷ‫ػ‬ցతಛੑʹண໨͢Δͱɼણҡ΍ཻࢠͷ෼ࢄ഑ஔ͕

ບ͠ɼ೤ॲཧΛߦ͏͜ͱͰ࡞੡ͨ͠ɽͳ͓ɼ೤ॲཧ‫ޙ‬ಛੑ޲্ͷͨΊʹॏཁͳ੍‫ޚ‬ཁҼͰ͋ΓɼߋʹఴՃ͞ͷࢼྉް͞͸໿ 0.5 mm Ͱ͋Γɼ໿ 10 mm×10 mm

ΕΔણҡ΍ཻࢠαΠζ͕ϚΠΫϩ͔Βφϊεέʔϧ΁ʹ੾Γग़ͯ͠ଌఆࢼྉͱͨ͠ɽൺֱͷͨΊɼ೤ॲཧ·ͱඍࡉԽ͍ͯ͠Δɽ͔͠͠ͳ͕Βɼ୯७ʹఴՃࡐͷඍͰෳ߹ࡐྉͱಉ͡޻ఔΛ‫ͨܦ‬थࢷ୯ମɼϙϦΠϛυ

ࡉԽͷΈΛߦͬͯࠞ߹ͨ͠৔߹ɼथࢷ฼ࡐதͰ‫͠ूڽ‬ϑΟϧϜͰ‫ڬ‬Έ͜ΜͩதۭφϊϑΟϥʔΛଌఆࢼྉͱ

ͯմঢ়ଶͱͳΓқ͘ɼ‫ۉ‬Ұ΋͘͠͸ૂͬͨ෼ࢄঢ়ଶ͕

ͨ͠ɽಘΒΕͣ෦ࡐಛੑͱͯ͠΋ૂͬͨಛੑ͕ಘΒΕͳ͍ɽ࣮‫ݧ‬͸ SPring-8 ฌ‫ݝݿ‬ϏʔϜϥΠϯ BL08B2 ʹ͓ͦͷͨΊɼφϊαΠζͷఴՃࡐͷ෼ࢄঢ়ଶΛධՁ͠ɼ͍ͯೋ࣍‫ݩ‬൒ಋମ‫ݕ‬ग़‫ ث‬PILATUS Λ༻͍ɼX ઢΤωथࢷෳ߹ࡐྉͷಛੑͱϞϧϑΥϩδʔΛ݁ͼ෇͚ͨ‫ݚ‬ϧΪʔɿ8 keVʢ೾௕ɿ0.155 nmʣɼΧϝϥ௕ɿ6 m ͓‫ڀ‬ɼ‫͕ূݕ‬ඞཁͰ͋Δɽຊ݅Ͱ͸ɼφϊαΠζͷཻࢠΑͼ 0.5 m ͷ৚݅ͰଌఆΛߦͬͨɽΛथࢷʹ෼ࢄͤͨ͞ࢼྉΛখ֯ X ઢࢄཚख๏Ͱ෼ੳ

औಘͨ͠ 2 ࣍‫ݩ‬σʔλ͸ղੳιϑτ Fit2D [3] Λ༻͠ɼཻࢠ‫ܗ‬ঢ়Λߟྀͨ͠ϞσϧΛࢄཚ‫ۂ‬ઢͷղੳ [1,2]͍ͯԁपํ޲ੵ෼ͱࢄཚ‫౓ڧ‬-ࢄཚ֯ (2θ) ·ͨ͸ࢄཚ– 24 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
ϕΫτϧ (q) ͷग़ྗΛߦ͍ɼΧϝϥ௕ 6 m ͷࢄཚ‫౓ڧ‬Λิਖ਼͠ɼΧϝϥ௕ 0.5 m ͷσʔλͱ࿈݁ͨ͠ɽΧϝϥ௕ 6 m ͱ 0.5 m ͷ࿈݁ͨ͠ࢄཚ‫ۂ‬ઢʹ͍ͭͯղੳ
ιϑτ NanoSolverʢϦΨΫ੡ʣΛ༻͍ͯϑΟοςΟϯ
άΛߦͬͨɽ
தۭφϊϑΟϥʔͷ‫ܗ‬ঢ়‫࡯؍‬͸ɼಁաిࢠ‫ݦ‬ඍ‫ڸ‬

JEM-3000Fʢ೔ຊిࢠ੡ʣΛ༻͍ͯߦͬͨɽ
݁Ռ͓Αͼߟ࡯

Fig.1 ʹɼTEM Λ༻͍ͯதۭφϊϑΟϥʔͷ‫ܗ‬ঢ়‫؍‬࡯ͨ݁͠ՌΛࣔ͢ɽφϊϑΟϥʔͷ‫ܗ‬ঢ়͸‫Ͱܗٿ‬͸ͳ

Fig. 2. SAXS profile of nanoparticles.

͘ɼ֯ுཱͬͨํମʹ͍ۙ‫ܗ‬ঢ়Ͱ͋Δ͜ͱΛ֬ೝͨ͠ɽ

ϊϑΟϥʔͷน໘Λԁ൘ϞσϧͰද‫͠ݱ‬ɼࢄཚ‫ۂ‬ઢΛ

log(q) = −1.3 ∼ 0.4 ͷൣғͰϑΟοςΟϯάͨ͠ɽԁ൘ϞσϧϑΟοςΟϯάʹΑΓಘΒΕͨ‫ۂ‬ઢΛ Fig. 2

ͷଌఆσʔλʹॏͶͯࣔ͠ɼԁ൘௚‫ܘ‬αΠζ͓ΑͼαΠζ෼෍ͷඪ४ภࠩΛ Table. 1 ʹࣔ͢ɽͳ͓ɼαΠζ෼෍ʹ͸ Γ ؔ਺Λద༻͠ɼΞεϖΫτൺ͸ 0.1 Λઃఆ͍ͯ͠ΔɽϞσϧϑΟοςΟϯά͔ΒಘΒΕͨԁ൘௚‫ܘ‬αΠζ͸ 90 nm Ͱ͋ΓɼTEM ‫֬Ͱ࡯؍‬ೝ͞ΕͨதۭφϊϑΟϥʔαΠζͱରԠ͢Δ݁Ռ͕ಘΒΕͨɽͳ͓ɼ
தۭφϊϑΟϥʔͷࢄཚ‫ۂ‬ઢʹରͯ͠ log(q) = −1.3

ΑΓ௿ q ଆ͸ԁ൘ϞσϧͰϑΟοςΟϯάͰ͖ͣɼࢄ

Fig. 1. TEM image of nanoparticles.

ཚ‫ۂ‬ઢ্ཱ͕͕͍ͪͬͯΔ͜ͱ͔ΒதۭφϊϑΟϥʔෳ਺ࢹ໺ͷ‫͔࡯؍‬Βɼཻࢠ֎‫ܘ‬͸ 50∼150 nm Ͱ͋Γ୯෼ࢄͰ͸ͳ͍͕ɼཻࢠนް͞͸໿ 10nm Ͱཻࢠʹ‫د‬Βͣൺֱత‫ۉ‬ҰͰ͋ͬͨɽ

Fig.2 ʹதۭφϊϑΟϥʔ୯ମͷখ֯ X ઢࢄཚଌఆ

͸‫͍ͯ͠ूڽ‬Δͱߟ͑ΒΕΔɽ

Table 1. Particle size and size distribution of
nanoparticles.

ʹΑΓಘΒΕͨࢄཚ‫ۂ‬ઢΛࣔ͢ɽͳ͓ɼFig.2 ͷࢄཚ‫ۂ‬ઢ͸ɼதۭφϊϑΟϥʔค຤Λ‫ڬ‬ΈࠐΉͨΊʹ࢖༻άϥ΢ϯυॲཧΛߦ͍ͬͯΔɽΒΕΔɽࢄཚϕΫτϧ q ͱߏ଄ͷେ͖͞ʢ΋͘͠͸ߏ଄ͷ‫܁‬Γฦִؒ͠ dʣͷؔ܎ࣜ (1) ΑΓ d =100 nm ͕
ಘΒΕΔɽ

90

αΠζඪ४ภࠩ (nm) ˞11˞෼෍͸ Γ ؔ਺Λద༻ͨ͠ϙϦΠϛυϑΟϧϜͷଌఆσʔλΛ༻͍ͯόοΫ͜ͷࢄཚ‫ۂ‬ઢͰ͸ɼlog(q) = −1.2 ෇ۙʹ‫͕ݞ‬ೝΊԁ൘௚‫ܘ‬αΠζ (nm)࣍ʹɼதۭφϊϑΟϥʔ෼ࢄෳ߹ࡐྉͱɼൺֱͷͨΊʹதۭφϊϑΟϥʔͷΈͷࢄཚ‫ۂ‬ઢΛ Fig.3 ʹࣔ͢ɽͳ͓ɼෳ߹ࡐྉͷࢄཚ‫ۂ‬ઢ͸थࢷ୯ମϑΟϧϜͷσʔλΛ༻͍όοΫάϥ΢ϯυॲཧ͍ͯ͠Δɽ
ෳ߹ࡐྉͱதۭφϊϑΟϥʔ୯ମͷଌఆࢼྉ಺Ͱத

q = 2π/d(1)͜ͷ஋ͱ TEM ‫࡯؍‬ͷ݁Ռ͔Βɼཱ๏ମ‫ܗ‬ঢ়ͷதۭφϊϑΟϥʔͰ޲͔͍߹ͬͨน໘ͷେ͖͕͞ࢄཚମͷߏ଄ಛ௃ͱͯ͠‫ݱ‬Ε͍ͯΔͱߟ͑Δɽͦ͜ͰɼதۭφۭφϊϑΟϥʔʢࢄཚମʣͷଘࡏྔ͕ҟͳΔͨΊɼࢄཚ‫౓ڧ‬ͷઈର஋ൺֱ͸ࠔ೉Ͱ͋ΔͨΊߦΘͳ͍ɽ྆ࢄ
ཚ‫ۂ‬ઢͷ log(q) = −1.2 ∼ 0.3 ͷൣғͰ‫ݞ‬ͷग़‫ݱ‬ҐஔʢࢄཚϕΫτϧ஋ʣΛൺֱ͢Δͱɼෳ߹ࡐྉͷ‫ݞ‬͸ߴ qଆʹ͋Γɼࢄཚମͷେ͖͞ͳͲʹมԽ͕ੜ͍ͯ͡Δͱ

– 25 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)ϑΟοςΟϯάͷ݁ՌΛ Fig.5 ʹɼಘΒΕͨύϥϝʔλΛ Table 2 ʹࣔ͢ɽෳ߹ࡐྉதͷதۭφϊϑΟϥʔน໘Λද‫͍ͯͤ͞ݱ‬Δ੒෼ 1 ͷฏ‫ۉ‬αΠζ͸ɼϑΟϥʔ୯ମͷ஋ΑΓ΋খ͘͞ͳ͓ͬͯΓɼαΠζͷେ͖ͳ΋ͷ͕ഁଛ͍ͯ͠ΔՄೳੑ͕ߟ͑ΒΕΔɽ·ͨɼഁଛʹΑΓੜͨ͡খยΛ TEM ‫Ͱ࡯؍‬͸໌֬ʹଊ͑ΒΕ͍ͯͳ͍͕ɼࢄཚ‫ۂ‬ઢͷղੳ݁Ռ͔Β෼ࢄମͷαΠζ͸ 10 nm ఔ౓ͱਪ࡯͞ΕΔɽ
·ͨɼෳ߹ࡐྉͷࢄཚ‫ۂ‬ઢ΋ log(q) = −1.3 ΑΓ௿q ଆʹ͓͍ͯɼதۭφϊϑΟϥʔ୯ମͷࢄཚ‫ۂ‬ઢͱಉ༷ʹࢄཚ‫ۂ‬ઢ্ཱ͕͕͍ͪͬͯΔͨΊɼ‫ߏूڽ‬଄͕ଘࡏ͍ͯ͠Δͱߟ͑Δɽ

Fig. 3. SAXS profile of composite material.

෼͔Δɽ͜ΕΒͷ‫ܗ‬ঢ়มԽ͕ੜ͡ΔՄೳੑͱͯ͠ɼ֧
፩ɾࠞ߹࣌ͷ‫ػ‬ցతͳ֎ྗʹΑΔதۭφϊϑΟϥʔͷഁଛ͕ߟ͑ΒΕΔɽ͜ͷӨ‫ڹ‬Λ֬ೝ͢ΔͨΊɼதۭφϊϑΟϥʔΛτϧΤϯʢ༹ഔʣʹՃ͑ͯෳ߹ࡐྉௐ੡
ͱಉ࣌ؒ͡ͷ֧፩ɾࠞ߹Λߦ͍ɼ‫ס‬૩ͤͨ͞‫ ʹޙ‬TEM‫࡯؍‬Λߦͬͨɽ‫ࣸ࡯؍‬ਅΛ Fig.4 ʹࣔ͢ɽFig.1 ͱൺֱͯ͠ɼน໘ͷഁଛ͍ͯ͠ΔதۭφϊϑΟϥʔ͕ࢄ‫ݟ‬͞Εͨɽ

Fig. 5. SAXS profile fitting of composite material.

Table 2.

Particle size and size distribution of

nanoparticles dispersed in matrix.
੒෼ 1

੒෼ 2

ԁ൘௚‫ܘ‬αΠζ (nm)7810αΠζඪ४ภࠩ (nm)92Fig. 4. TEM image of nanoparticles after stirring
processing.

·ͱΊͱࠓ‫ޙ‬ͷ՝୊

TEM ‫࡯؍‬ͷ݁Ռ͔Βɼഁଛͨ͠தۭφϊϑΟϥʔͷഁย͕ෳ߹ࡐྉ಺ʹଘࡏ͍ͯ͠ΔͱԾఆ͠ɼதۭφϊϑΟϥʔ୯ମͷղੳʹ༻͍ͨ੒෼ 1ʢԁ൘ϞσϧʣͱഁยΛ૝ఆͨ͠੒෼ 2ʢԁ൘ϞσϧʣΛద༻ͯ͠ɼ

log(q) = −1.3 ∼ 0.4 ͷൣғͰࢄཚ‫ۂ‬ઢͷϑΟοςΟ
ϯάΛߦͬͨɽͳ͓ɼ੒෼ 1 ʹ͍ͭͯ͸ɼதۭφϊϑΟϥʔ୯ମͱಉ༷ͷ૬ରඪ४ภࠩʹ‫ݻ‬ఆ͍ͯ͠Δɽ

தۭφϊϑΟϥʔ෼ࢄෳ߹ࡐྉΛϞσϧࡐྉͱͯ͠
খ֯ X ઢࢄཚख๏ʹΑΓ෼ੳղੳΛߦͬͨɽຊෳ߹ࡐ
ྉͰ͸ɼφϊϑΟϥʔͷҰ෦͸‫͠ूڽ‬ɼ·ͨϑΟϥʔͷׂΕ͕ൃੜ͍ͯ͠Δͱਪ࡯͞ΕΔ݁Ռ͕ಘΒΕͨɽෳ߹ࡐྉதͷϑΟϥʔ‫ूڽ‬ମͳͲͷߋʹେ͖ͳߏ଄Λ‫ݕ‬౼͢ΔͨΊɼ௒খ֯ X ઢࢄཚख๏ͷద༻ɼαΠζ΍‫ܗ‬ঢ়ͷҟͳΔϑΟϥʔ͕ࠞࡏ͢Δ‫ܥ‬ͷղੳٕज़ཱ֬

– 26 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
͕ඞཁͰ͋Δɽ·ͨɼҟͳΔϓϩηεͰ࡞੡͞Εͨෳࢀߟจ‫ݙ‬

߹ࡐྉ΍ͦͷ଱‫ࢼޙݧࢼٱ‬ྉʹ͍ͭͯ΋෼ੳղੳΛ[1] Ӎ‫ ޾ܚٶ‬ଞɿ์ࣹޫ 19, 338 (2006).
[2] দԬलथɿ೔ຊ݁থֶձࢽ 41, 213 (1999).
[3] http://www.esrf.eu/computing/scientific/FIT2D/

ਐΊΔ͜ͱͰɼෳ߹ࡐྉͷಛੑൃ‫ݱ‬ϝΧχζϜ΍ม࣭ʹ൐͏ಛੑมԽΛৄࡉʹ‫ূݕ‬ՄೳͱͳΔ͜ͱ͕‫ظ‬଴͞ΕΔɽࣄ‫΁ۀ‬ͷߩ‫ݙ‬ຊ‫͔ڀݚ‬ΒಘΒΕٕͨज़ʹΑΓ, थࢷʹఴՃ͞ΕͨφϊϑΟϥʔͷ෼ࢄঢ়ଶ΍ߏ଄มԽΛղੳ͢Δ͕Ͱ͖
Δɽं͔྆Β‫ٻ‬ΊΒΕΔܰྔ‫ػߴͭ׌‬ೳΛ࣮‫͍ͯ͠ݱ‬ͨ͘Ίʹࡐྉߏ଄Λৄࡉʹղੳ͠, ࡐྉ੍‫ޚ‬Ҽࢠͷ໌֬Խ΍‫ػ‬ೳൃ‫ݱ‬ϝΧχζϜͷղ໌ʹར༻͢Δ༧ఆͰ
͋Δ.

– 27 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)

BL08B2

2016A3330, 2016B3330

cos α ๏ʹΑΔ൒ಋମύοέʔδ༻೤ߗԽੑ෧ࢭथࢷ/ಔք໘ͷྫྷ೤࣌࢒ཹԠྗͦͷ৔ղੳ
In-situ residual stress analysis at the interface between
semiconductor package encapsulation resins and copper during
heating and cooling process by using cos α methodՃʑྑ ߶ࢤɼ௕ౡ େɼ࿨ઘ ಞ࢜
Takeshi Kakara, Dai Nagashima, Atsushi Izumi
ॅ༑ϕʔΫϥΠτ‫ࣜג‬ձࣾ

Sumitomo Bakelite Co., Ltd.
֓ཁɿ X ઢճં๏Λ༻͍ͨ൒ಋମύοέʔδ༻෧ࢭथࢷ/Cu ք໘ͷ࢒ཹԠྗධՁٕज़ʹ͍ͭͯ‫ݕ‬౼ͨ͠ɽCuഩ/෧ࢭथࢷ/Cu ഩͷࡾ૚ߏ଄͔ΒͳΔࢼྉΛ൒ಋମύοέʔδͷϞσϧࡐͱͯ͠༻͍ɼΠϝʔδϯάϓϨʔτʹΑΓଌఆͨ͠ Cu(331) ໘ͷ 2 ࣍‫ݩ‬ճં‫؀‬ͷ࿪ΈΛ cos α ๏ʹΑΓղੳͨ͠ɽ·ͨɼՃ೤ྫྷ٫εςʔδΛ༻͍ͨྫྷ೤࣌ͦͷ৔‫ʹ࡯؍‬ΑΓɼྫྷ೤ϓϩηεաఔ (−40 ∼ 250◦ C) ʹ͓͚Δथࢷ/Cu ք໘ͷ࢒ཹԠྗมԽ‫ڍ‬ಈͷ໌֬Խʹ੒ޭ͠ɼྫྷ٫࣌ʹԠྗ૿େ͢Δ͜ͱΛ֬ೝͨ͠ɽߋʹ͸ɼथࢷͱ Cu ͷີண৴པੑ͕ྫྷ٫࣌Ԡྗͱ
Α͍૬ؔΛࣔ͠ɼ࢒ཹԠྗͷଘࡏ͕ີண৴པੑʹӨ‫͍ͯ͠ڹ‬Δ͜ͱ͕ࣔࠦ͞ΕͨɽΩʔϫʔυɿresidual stress, in-situ analysis, semiconductor package, resin-copper-interfaceഎ‫ڀݚͱܠ‬໨త໘ʹ͓͚Δ࢒ཹԠྗͷධՁٕज़ͷཱ֬ɼ͓Αͼ࢒ཹԠ൒ಋମύοέʔδͷߴ৴པੑɾബ‫ܕ‬Խɾߴີ౓࣮૷
ԽΛ࣮‫͢ݱ‬Δ্Ͱɼ൒ಋମύοέʔδ༻෧ࢭथࢷ͸ඞਢͷࡐྉͰ͋Δɽ൒ಋମͷߴੑೳԽʹ൐͍ɼͦͷ൒ಋମύοέʔδ༻෧ࢭथࢷʹ΋͞ΒͳΔੇ๏҆ఆੑɼ௿೤๲ு཰ɼ଱೤ੑɼి‫ؾ‬ઈԑੑɼ೤఻ಋੑɼ଱࣪ੑͳ
Ͳͷಛੑ͕‫ٻ‬ΊΒΕɼ͜ΕΒ͸൒ಋମύοέʔδͷ௕‫ظ‬৴པੑʹ΋Ө‫͢ڹ‬ΔॏཁҼࢠͰ͋Δɽ
൒ಋମύοέʔδ͸ओʹɼγϦΧͳͲͷແ‫ػ‬ϑΟϥʔΛ‫ؚ‬༗ͨ͠೤ߗԽੑथࢷͱɼͦΕʹΑΓ෧ࢭ͞ΕΔ഑ઢ΍ϦʔυϑϨʔϜͱ͍ͬͨۚଐ͔ΒͳΔෳ߹෦ࡐͰ
͋Δɽ൒ಋମύοέʔδ͸ɼͦͷ੡଄޻ఔʹ͓͍ͯथࢷ੒‫ܗ‬ɾ೤ߗԽɾ൒ాϦϑϩʔͳͲͷෳ਺ͷՃ೤ྫྷ٫ϓϩηεΛ‫ܦ‬ΔͨΊɼथࢷͱۚଐͱ͍ͬͨ஄ੑ཰΍ઢྗൃੜϝΧχζϜͷղ໌͸ɼ൒ಋମύοέʔδͷෆྑൃੜΛ཈੍͠ɼߴ৴པੑ੡඼ͷ։ൃʹ͓͍ͯ‫ۃ‬Ίͯॏཁͳ՝୊ͱͳΔɽզʑ͸͜Ε·Ͱʹଟ࣠ճં‫ ͱܭ‬0 ࣍‫ݩ‬γϯνϨʔγϣϯΧ΢ϯλʔΛ༻͍ɼsin2 Ψ ๏ʹΑΔ൒ಋମύοέʔδʹ͓͚Δथࢷ/Cu ք໘ͷ࢒ཹԠྗධՁΛ‫ݕ‬౼͖ͯͨ͠ɽsin2 Ψ ๏͸ɼࢼྉද໘ͱ Cu ݁থ֨ࢠ໘๏
ઢͷͳ֯͢ Ψ ͱ X ઢճં֯ͷؔ܎Λղੳ͢ΔධՁख
๏Ͱ͋Δ [1–3]ɽ͔͠͠ͳ͕Βɼෳ਺ͷ Ψ ʹର͢Δճ
ંϓϩϑΟʔϧΛεΩϟϯ͢Δඞཁ͕͋ΔͨΊɼ1 ଌఆʹ਺े෼ؒ΋ͷ࣌ؒΛཁ͠ɼ਺–਺े෼Φʔμʔͷ೤ϓϩηεͷ֤޻ఔʹ͓͚ΔԠྗมԽΛৄࡉʹղੳ͢ΔͨΊʹ͸ɼଌఆ࣌ؒΛ਺෼Φʔμʔʹ୹ॖ͢Δ͜ͱ

๲ு܎਺ (CTE) ͳͲͷ෺ੑ஋͕େ͖͘ҟͳΔࡐྉؒ

͕՝୊Ͱ͋Δɽͦ͜Ͱɼ0 ࣍‫ݕݩ‬ग़‫ث‬Λ༻͍ͨ sin2 Ψͷք໘ʹ͸೤Ԡྗ͕࢒ཹԠྗͱͯ͠஝ੵ͢Δɽ࢒ཹԠ๏ʹ୅ΘΔ୹࣌ؒͰͷԠྗධՁख๏ͱͯ͠ɼ2 ࣍‫ݕݩ‬ྗ͸൒ಋମύοέʔδͷ࿪Έ΍൓Γͱͳͬͯ‫ݱ‬Εɼքग़‫ث‬Λ༻͍ͨ cos α ๏ʹ஫໨ͨ͠ [4, 5]ɽcos α ๏͸ 2໘ണ཭ͱ͍͏൒ಋମύοέʔδʹ͓͚Δக໋తͳෆྑ

࣍‫ݕݩ‬ग़‫Ͱث‬ಘΒΕΔճં‫؀‬શମͷ࿪Έ৘ใΑΓԠྗϞʔυͷཁҼͱͳΔɽ൒ಋମύοέʔδʹ͓͚Δ഑ઢ

Λࢉग़͢Δख๏Ͱ͋Γɼߋʹ 1 छྨͷ X ઢೖࣹ֯Ͱ

΍ϦʔυϑϨʔϜ͸ओʹ Cu Ͱ͋ΔͨΊɼथࢷ/Cu քͷճંσʔλͷΈͰղੳՄೳͰ͋ΔͨΊɼେ෯ͳଌఆ

– 28 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
࣌ؒ୹ॖ͕ՄೳͰ͋Δɽ՝୊φϯόʔ 2015A3330 ͓‫ٻ‬ΊΔͨΊͷඪ४ࢼྉͱͯ͠Ξϧϛχ΢Ϝค຤ͷճં

Αͼ 2015B3330 ͷ࣮‫͍͓ͯʹݧ‬ɼCu ഩ/൒ಋମύο‫؀‬Λଟॏ࿐ޫͨ͠ɽଌఆࢼྉͱඪ४ࢼྉͷަ‫࡞ૢ׵‬͸έʔδ༻೤ߗԽੑ෧ࢭथࢷ/Cu ഩͷࡾ૚ߏ଄͔ΒͳΔ

ࣗಈ X ࣠εςʔδΛར༻͢Δ͜ͱͰϋον֎ΑΓߦͬ൒ಋମύοέʔδϞσϧࡐྉΛ༻͍ͯධՁٕज़‫ূݕ‬Λͨɽଌఆʹ༻͍ͨ X ઢͷΤωϧΪʔ͸ 8.0 keVɼϏʔߦ͍ɼࢼྉ΁ͷ X ઢ࿐ޫ࣌ؒ 2 ෼ͱ͍͏୹࣌ؒͰͷϜαΠζ͸ 0.3 mm × 0.4 mm ͱ͠ɼX ઢরࣹ࣌ؒ͸࢒ཹԠྗධՁʹ੒ޭͨ͠ɽߋʹՃ೤ࢼྉεςʔδΛ༻ଌఆࢼྉ 2 minɼඪ४ࢼྉ 3 min ͱͨ͠ɽ◦͍ͨ 40 ∼ 250 C ͷ೤ϓϩηεաఔʹ͓͚Δ࢒ཹԠྗଌఆԹ౓͸ྫྷ೤িܸࢼ‫ݧ‬Λ૝ఆ͠ɼ40◦ C ͔Β 250◦ CมԽͦͷ৔‫ʹ࡯؍‬ΑΓɼथࢷͷߴ࣍ߏ଄มԽͱ࢒ཹԠ
ྗͷ૬ؔղੳʹ੒ޭͨ͠ [6]ɽ͔͠͠ͳ͕Βɼ൒ಋମύοέʔδͷྫྷ೤িܸࢼ‫Ͱݧ‬͸ −40◦ C ΄Ͳͷ௿Թ‫؀‬‫ڥ‬ԼͰͷධՁ΋࣮ࢪ͞ΕΔͨΊɼຊ‫ݕ‬౼Ͱ͸ cos α ๏Λ༻͍ͨ −40 ∼ 250◦ C Ͱͷྫྷ೤ϓϩηεͷ࢒ཹԠྗͦͷ৔‫ٕ࡯؍‬ज़ʹ͍ͭͯ‫ݕ‬౼ͨ͠ɽ࣮‫ݧ‬൒ಋମύοέʔδͷϞσϧࡐྉͱͯ͠ɼCu ഩ (12µm)/൒ಋମύοέʔδ༻೤ߗԽੑ෧ࢭथࢷ (1.3 mm)/Cu ഩ (12 µm) ͷࡾ૚ߏ଄͔ΒͳΔฏ൘ঢ়ࢼྉΛ 200◦ CͰͷՃ೤ѹॖ੒‫ʹܗ‬ΑΓ࡞੡͠ɼ20 mm × 20 mm ʹ੾Γग़ͨ͠ (Fig. 1)ɽ೤ߗԽੑ෧ࢭ༻थࢷ͸γϦΧϑΟϥʔΛ‫ؚ‬༗͓ͯ͠Γɼຊ‫ݕ‬౼Ͱ͸γϦΧϑΟϥʔ‫ؚ‬༗཰ͷҟͳΔ 3 ਫ४ͷथࢷΛ࢖༻ͨ͠ɽͦΕͧΕΛγϦΧϑΟϥʔ‫ؚ‬༗཰͝ͱʹथࢷ-a (‫ؚ‬༗཰ 88 wt%)ɼ
थࢷ-b (84 wt%)ɼथࢷ-c (80 wt%) ͱ͠ɼͦΕΛ༻

Fig. 1. (a) Schematic image of Semiconductor package model for residual stress analysis comprising of
Cu/Resin/Cu three-layered sample. (b) Photo image of the specimen for the residual stress analysis.

͍ͯ࡞੡ͨ͠ϞσϧࡐྉΛ֤ʑsample-Aɼsample-Bɼ

sample-C ͱ͢Δɽ͜͜Ͱɼ൒ಋମύοέʔδͷྫྷ೤িܸࢼ‫͚͓ʹݧ‬Δ Cu ͱͷີண৴པੑ͸ɼथࢷ-a< थࢷ-b< थࢷ-c ͷॱͰथࢷ-c ͕࠷΋ྑ޷Ͱ͋Δɽ·֤ͨथࢷͷ 250◦ C ߗԽ෺ͷ CTE ͸ɼ−50◦ C ͔Β 150◦ C෇ۙ·Ͱ͸͓͓ΑͦҰఆ஋Λࣔ͠ɼ200◦ C ͔Βେ্͖͘ঢ͠ɼΨϥεసҠԹ౓ (Tg) ͸ 250◦ C ෇ۙͱ‫ੵݟ‬΋ͬͨɽ֤Թ౓ʹ͓͚ΔߗԽ෺ͷ CTE ͷେ͖͞͸थࢷ-a< थࢷ-b< थࢷ-c ͷॱͰ͋Δ (Fig. 2 )ɽଌఆͷϨΠΞ΢τΛ Fig. 3 ʹࣔ͢ɽࢼྉՃ೤࿍ʹ͸ϏʔϜϥΠϯอ༗ͷখ‫ܕ‬ηϥϛοΫώʔλʔΛ༻͍ɼೖࣹ X ઢͱࢼྉද໘๏ઢͷͳ֯͢ (ϕ) ͕ 30◦ ͱͳΔΑ͏ʹઃஔͨ͠ɽࢼྉՃ೤࿍ʹ͸ӷମ஠ૉλϯΫΛ઀ଓ͠ɼӷମ஠ૉʹΑΔྫྷ٫ͱώʔλʔʹΑΔՃ೤ʹΑΓɼ࿈ଓతͳԹ౓มԽ͕ՄೳͱͳΔΑ͏ઃ‫ͨ͠ܭ‬ɽࢼ
ྉද໘ Cu ഩ͔Βͷճં X ઢ͸ɼࢼྉΑΓ্ྲྀଆʹ

Fig. 2. CTE of resin-a, resin-b and resin-c cured
at 250◦ C as a function of temperature obtained byઃஔͨ͠ X ઢಁա݀Λ༗͢ΔΠϝʔδϯάϓϨʔτ

TMA analyses. The value of copper (16.8 ppm/K)(IP)(BAS-SR2025) Λ༻͍ͯഎ໘൓ࣹ഑ஔͰଌఆͨ͠ɽ

is from literature data.

ଓ͚ͯಉ͡ IP ʹແ࿪ճં‫͓؀‬ΑͼϏʔϜηϯλʔΛ– 29 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)ࢼྉ 83 mm ͓Αͼඪ४ค຤ 77 mm ͱ͠ɼࣜ (1) ʹ͓͚Δඪ४ค຤ͷճં֯ 2θ0,std ͸ɼඪ४ค຤ʔ‫ݕ‬ग़‫཭ڑؒث‬Λ 77 mm ͱԾఆͨ͠‫ֻ͚ݟ‬ͷճં֯ 141.4◦
Λ༻͍ͨɽIP σʔλͷಡऔΓʹ͸ BAS-1800II Λ༻͍ɼಡऔը૾ͷϐΫηϧαΠζ͸ɼIP ΛαΠζ‫ط‬஌ͷ Al ഩͰϚεΫͨ͠ঢ়ଶͰ X ઢΛ࿐ޫͯ͠ಘͨը૾
σʔλ͔Βࢉग़ͨ͠ߍਖ਼஋ (49.95 µm/pixel × 49.56µm/pixel) Λ࢖༻ͨ͠ɽ
Fig. 3. Instrumental setup for residual stress measurements with an imaging plate detector by usingcos α method.

݁Ռ͓Αͼߟ࡯

Fig. 4 ʹ sample-A ͷ −40◦ C ʹ͓͚Δ 2 ࣍‫ݩ‬ճંϓϩϑΟʔϧΛࣔ͢ɽߋʹɼFig. 5 ʹ Al(422) ໘͓Α΁ͷঢԹɼ250◦ C ͔Β −40◦ C ΁ͷ߱Թɼ−40◦ C ͔Β

ͼ Cu(331) ໘͔ΒͷճંϓϩϑΟʔϧʹ͍ͭͯ 1 ࣍

40◦ C ΁ͷঢԹͱ͍͏ྲྀΕͰԹ౓มԽͤͨ͞ɽࢼྉશ

‫ݩ‬Խͨ͠΋ͷΛ α ͷؔ਺ͱͯࣔ͢͠ɽࢼྉ͸ Cu ഩ/ମΛ‫ۉ‬ҰՃ೤͢ΔͨΊʹɼࢼྉͱώʔλʔΛΧϓτϯ

थࢷ/Cu ഩͷࡾ૚ߏ଄Ͱ͋Δ͕ɼϐʔΫ෼྾ͷͳ͍໌ϑΟϧϜͰ෴͍ɼࢼྉԹ౓͸γʔτঢ়೤ిରΛ༻͍ͯྎͳ Cu ͷճં‫͕؀‬ಘΒΕ͍ͯΔ͜ͱΑΓɼཪ໘ Cu

Cu ഩ্ͷԹ౓ͱͯ͠‫ܭ‬ଌͨ͠ɽഩ͔Βͷ X ઢճંͷ‫د‬༩͸γϦΧϑΟϥʔΛ‫ؚ‬༗͢थࢷ/Cu ഩք໘ͷ࢒ཹԠྗ (σ) ͸ࣜ (1) Λ༻͍ͯࢉΔथࢷ૚Ͱͷ X ઢ‫ٵ‬ऩʹΑͬͯແࢹͰ͖Δͱߟ͑Βग़ͨ͠ [5]ɽԠྗූ߸͕ਖ਼ͷ৔߹͸ҾுԠྗɼෛͷ৔

ΕΔɽFig. 5 ͓Αͼࣜ (2) ΑΓ‫ٻ‬Ίͨ ∆L − cos α ઢ߹͸ѹॖԠྗͰ͋Δɽ E
cos2 2θ0 tan 2θ0,std·
σ=
2Lstd tan θ0
1+


 ν
1
d∆L
·
(1)
·
d cos αsin2 (ϕ − η) − sin2 (ϕ + η)ਤΛ Fig. 6 ʹࣔ͢ɽ∆L − cos α ઢਤ͸શͯͷํҐ֯αɼ͢ͳΘͪ cos α = 0 ∼ 1 ͷൣғͰΑ͍௚ઢੑΛࣔ͠ɼઢ‫ܗ‬ϑΟοςΟϯάΑΓ‫ٻ‬Ίͨ܏͖ 0.95 ± 0.01mm ͓Αͼࣜ (1) ΑΓ࢒ཹԠྗ͸ 95.9 ± 0.8 MPa ͱ͜͜Ͱɼ2θ0 ͓Αͼ 2θ0,std ͸ଌఆࢼྉ (Cu) ͓Αͼඪ४ค຤ (Al) ͷແ࿪ঢ়ଶͷճં֯ɼLstd ͸ඪ४ค຤ճ
ં‫؀‬൒‫ܘ‬ɼE ͓Αͼ ν ͸ Cu ഩͷ஄ੑ཰ (65.0 GPa) ͓ΑͼϙΞιϯൺ (0.343)ɼ2η ͸ଌఆࢼྉͷճં֯ 2θ0ͷิ֯Ͱ͋Δɽα ͸ Fig. 3 ͓Αͼ Fig. 4 ʹ −η ଆͱͯࣔͨ͠͠‫ݕ‬ग़໘ʹ͓͚Δ 9 ࣌ํ޲͔Β࣌‫ܭ‬ճΓͷํҐ֯ɼ∆L ͸ࣜ (2) Ͱఆٛ͞ΕΔύϥϝʔλͰ͋Γɼࣜ(2) தͷ ∆L ͸ఴࣈͰࣔ͢ํҐ֯ʹ͓͚Δඪ४ࢼྉͱ
ଌఆࢼྉͷճંϐʔΫτοϓͷಈ‫͋Ͱࠩ཭ڑܘ‬ΓɼํҐ֯ α ʹ͓͚ΔճંϐʔΫτοϓ͸ɼํҐ֯ α ± 0.5◦ͷൣғͰηΫλʔฏ‫ͯ͠ۉ‬ಘͨ 1 ࣍‫ݩ‬ϓϩϑΟʔϧͷϩʔϨϯπؔ਺ϑΟοςΟϯάʹΑΓࢉग़ͨ͠ɽ

∆L =(∆lα − ∆lπ+α ) + (∆l−α − ∆lπ−α )2(2)Fig. 4. Two-dimensional diffraction profiles of Cuղੳʹ͸ Al(422) ໘ͱ Cu(331) ໘ͷճં‫؀‬Λ༻͍ɼ8.0

keV ʹ͓͚Δ 25◦ C ແ࿪ঢ়ଶͰͷճં֯Λ֤ʑ139.3◦
͓Αͼ 138.2◦ ͱͨ͠ɽࢼྉʔ‫ݕ‬ग़‫཭ڑؒث‬͸ɼଌఆ(sample-A at −40◦ C) and Al-powder measured on asingle imaging plate at different sample-to-detector
distances of 83 and 77 mm, respectively.

– 30 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

Fig. 7. Change in residual stress at the resin/Cu
Fig. 5.

Diffraction peak profiles of Cu(311) andinterface during heating and cooling processes.

Al(422) as a function of azimutial angle Ћ forsample-A at −40◦ C.

Fig. 8. Strain quantity at the resin/Cu interface.

Fig. 6. ∆L−cos α plot for cured sample-A at −40◦ C.
ࢉग़͞Εͨɽ͜ͷ݁ՌΑΓɼ−40◦ C ͷ௿Թ‫ڥ؀‬Լʹ͓͍ͯ΋ɼथࢷ/Cu ഩք໘ʹ͸ҾுԠྗ͕ଘࡏ͢Δ͜ͱ͕໌Β͔ͱͳͬͨɽIP ͓Αͼ cos α ๏Λ༻͍ɼߋʹ͸Ճ೤ྫྷ٫εςʔδʹΑΔଌఆԹ౓੍‫ʹޚ‬ΑΓɼ௿Թ‫ڥ؀‬ԼͰͷथࢷ/Cu ഩք໘ʹ͓͚Δ࢒ཹԠྗΛɼࢼྉ΁ͷ X ઢরࣹ࣌ؒ 2 min ͱ͍͏୹࣌ؒͰղੳՄೳͱ
ͳͬͨɽ࣍ʹྫྷ೤ϓϩηεաఔʹ͓͚Δ֤ sample ͷथࢷ/Cuഩք໘ͷ࢒ཹԠྗมԽͷղੳ݁ՌΛ Fig. 7 ʹࣔ͢ɽ֤

sample ͱ΋ଌఆԹ౓ʹΑΓԠྗมԽ͕ੜ͡Δ݁ՌΛಘͨɽଌఆ։࢝࣌ͷ 40◦ C Ͱ͸ 40∼60 MPa ͷҾுԠྗΛࣔ͠ɼͦͷ‫ޙ‬ͷ 250◦ C ͷՃ೤࣌ʹ͸ 25∼30 MPa
ʹ·ͰԠྗ؇࿨͢Δ͜ͱ͕֬ೝ͞Εͨɽ·ͨ −40◦ Cͷ௿Թ࣌ʹ͸ sample-A ͕ 95.9 ± 0.8 MPaɼsample-B͕ 78.8 ± 0.6 MPaɼsample-C ͕ 64.6 ± 0.5 MPa ͱͳΓɼଌఆԹ౓Լʹ͓͍ͯ࠷΋ sample ؒͷԠྗ͕ࠩ

େ͖͘ͳΔ݁Ռͱͳͬͨɽ·ͨɼ࠶౓ 40◦ C ʹঢԹ͢Δͱɼଌఆ։࢝࣌ͷԠྗ஋ͱ͸ 2∼8 MPa ΄ͲมԽ͍ͯ͠Δ͕ɼ͓͓Αͦಉ͡Ԡྗ஋ʹ໭Δ͜ͱΛ֬ೝͨ͠ɽ
͜ͷԹ౓ʹର͢ΔԠྗ‫ڍ‬ಈʹ͍ͭͯɼߗԽ‫ޙ‬ͷ֤थࢷͷ CTE ΑΓ࿪ΈྔΛࢉग़ͨ݁͠ՌΛ Fig. 8 ʹࣔ͢ɽଌఆͷ೤ॲཧϓϩηεʹै͍ɼ֤Թ౓ʹ͓͚ΔथࢷͱCu ഩͷ࿪ΈྔΛͦΕͧΕࢉग़͠ɼͦͷࠩΛ‫ٻ‬ΊΔ͜ͱʹΑΓɼथࢷ/Cu ഩք໘ʹੜ͡Δ࿪Έྔͱͨ͠ɽͳ
͓ɼූ߹͕ਖ਼ͷ৔߹͸ Cu ഩʹҾு࿪Έ͕ɼෛͷ৔߹͸ѹॖ࿪Έ͕ੜ͍ͯ͡Δ͜ͱΛҙຯ͢Δɽ250◦ C ͷ৔߹ɼ͍ͣΕͷ sample ΋࿪Έྔ͸খ͍͜͞ͱ͕࢕͑ΔɽҰํͰɼ−40◦ C ͷ৔߹ʹ͸ɼsample-A ͕ 2660 ppmɼ– 31 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)͔Β‫ٻ‬Ίͨ࿪Έྔ͔Β΋ɼಉ༷ͷԠྗ‫ڍ‬ಈΛࣔ͢͜ͱ͕ࢧ࣋͞Εͨɽ͔͠͠ͳ͕Β 250◦ C ࣌ͷ݁ՌΑ͏ʹɼԠྗղੳ݁ՌͰ͸Ҿுํ޲ͷɼ࿪Έྔ‫͔ࢉܭ‬Β͸ѹॖํ޲ͷԠྗ஋͕‫ੵݟ‬΋ΒΕɼԠྗͷઈର஋͕ରԠͯ͠
͍ͳ͍ͱ͍͏՝୊͕࢒͍ͬͯΔɽࠓ‫ޙ‬͸ sin2 Ψ ๏ͳͲͷଞख๏ධՁʹΑΔɼcos α ๏ͷԠྗઈର஋ͷ֬ೝ΍ɼԠྗ஋ͷ৴པੑΛ‫ݕ‬౼͢Δ͜ͱ͕՝୊Ͱ͋Δɽࣄ‫΁ۀ‬ͷߩ‫ݙ‬ࠓճ‫ݕ‬౼ͨ͠ cos α ๏ʹΑΔ࢒ཹԠྗධՁٕज़͸ɼ൒ಋମύοέʔδ༻೤ߗԽੑ෧ࢭथࢷ/Cu ഩք໘ͷ

Fig. 9. Residual stress analysis results for sample-A࿪Έঢ়ଶΛඇഁյͰղੳ͢Δ͜ͱ͕Մೳͳ‫ۃ‬Ίͯ༗ޮͳख๏Ͱ͋Δɽߋʹ਺෼Φʔμʔͱ͍͏୹࣌ؒͰͷ(sample size: 15 mm × 15 mm).

ଌఆ͕ՄೳͰ͋ΔͨΊɼྫྷ೤িܸࢼ‫ݧ‬ͷΑ͏ͳԹ౓‫؀‬

sample-B ͕ 2050 ppmɼsample-C ͕ 1500 ppm ͱɼ
Cu ഩʹ͸Ҿுํ޲ͷ࿪Έ͕ੜ͍ͯ͡Δ͜ͱ͕ࣔࠦ͞
Εɼղੳͨ͠Ԡྗ஋ͷେখؔ܎ͱ΋Ұகͨ͠ɽ͜ͷ͜ͱ͔Β΋ cos α ๏ʹΑΓࢉग़͞Εͨ࢒ཹԠྗղੳ஋͸ଥ౰ͳ݁ՌͰ͋Δͱߟ͑ΒΕΔɽ
·ͨ sample-A ʹ͍ͭͯ͸ɼΑΓৄࡉͳԠྗධՁΛ‫ڥ‬ԼͰ΋൒ಋମύοέʔδͷߏ଄มԽΛਝ଎ʹଊ͑Δ͜ͱ͕ՄೳͰ͋Δɽࠓ‫ޙ‬ɼฐࣾͷ൒ಋମύοέʔδ༻෧ࢭथࢷࡐྉ։ൃʹຊධՁٕज़Λల։͍ͯ͘͠༧ఆͰ
͋Δɽ

ँ࣮ࣙࢪͨ͠ (Fig. 9)ɽ40◦ C Ҏ্ͷߴԹ৚݅ԼͰ͸ 50◦ CຊଌఆΛߦ͏ʹ͋ͨΓฌ‫ཱݝݿ‬େֶ์ࣹޫφϊςΫ͝ͱʹɼ0◦ C ҎԼͷ௿Թ৚݅ԼͰ͸ 20◦ C ͝ͱʹଌఆηϯλʔͷ‫܂‬ຊ࣎ੜത࢜ɼ࣫‫ྑݪ‬ণത࢜ɼཥཕത࢜ɼ

Λߦͬͨɽଌఆʹ༻͍ͨϞσϧࡐ͸্‫ํه‬๏ͱಉ༷ʹͦͷଞؔ܎ऀͷօ༷ΑΓଟ਺ͷٕज़‫ݴॿ͝ͱྗڠ‬Λ͍੒‫͠ܗ‬ɼ੾Γग़͠αΠζ͸ 15 mm × 15 mm ͱͯ͠

͖ͨͩ·ͨ͠ɽ‫ँײ‬ਃ্͛͠·͢ɽғͰ͸ɼԠྗ͸Թ౓ʹର͠௚ઢతʹมԽ͠ɼ250◦ C Ͱࢀߟจ‫ݙ‬

࡞੡ͨ͠ɽԠྗղੳͷ݁Ռɼ −40 ∼ 200◦ C ͷԹ౓ൣ͸΍΍Ԡྗ૿େ͢Δ͜ͱ͕໌Β͔ͱͳͬͨɽ͜Ε͸थࢷͷ Tg ෇ۙͰ CTE ͕େ͖͘มԽ͍ͯ͠ΔͨΊʹੜͨ͡ͱߟ࡯͍ͯ͠Δɽ·ͨྫྷ೤ϓϩηεԼʹ͓͍ͯɼ࠷΋Ԡྗ؇࿨͢ΔԹ౓͕ 200◦ Cɼ࠷େԠྗ஋Λࣔ͢Թ౓͕ −40◦ C Ͱ͋Δ͜ͱ΋໌Β͔ͱͳͬͨɽҎ্ͷ݁ՌΑΓɼྫྷ೤ϓϩηεԼʹ͓͍ͯथࢷ/Cu ഩք໘ʹ࠷΋Ԡྗ͕ੜ͡Δͷ͸ sample-A Ͱ͋ΓɼͦͷԹ౓͸

−40◦ C Ͱ͋Δ͜ͱ͕໌Β͔ͱͳͬͨɽ·֤ͨ sample

ͷ −40◦ C ʹ͓͚ΔԠྗ஋͸ɼथࢷͷ Cu ͱͷີண৴[1] ాத‫ܒ‬հɹଞɿʮ์ࣹޫʹΑΔԠྗͱͻͣΈͷධՁʯཆ‫ݡ‬ಊ, ౦‫( ژ‬2009).
[2] K. Nakamae et al.: J. Appl. Polym. Sci. 40, 2231
(1990).
[3] T. Nishino et al.: J. Appl. Polym. Sci. 45, 1239
(1992).
[4] ࠤʑ໦හ඙ ଞɿࡐྉ 44, 1138 (1995).
[5] Ԧ ଞɿ೔ཱධ࿦ 95, 454 (2013).
[6] Ճʑྑ߶ࢤ ଞɿฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
5, 7 (2017).

པੑͱ΋Α͘Ұக͓ͯ͠Γɼ࢒ཹԠྗͷଘࡏ͕ີண৴
པੑʹӨ‫͍ͯ͠ڹ‬Δ͜ͱ͕ࣔࠦ͞Εͨɽࠓ‫ޙ‬ͷ՝୊
ຊ‫ݕ‬౼ʹΑΓɼ−40 ∼ 250◦ C ͷྫྷ೤ϓϩηεԼʹ͓͚Δ࢒ཹԠྗΛධՁ͢Δ͜ͱ͕ՄೳͱͳΓɼ֤Թ౓Ͱ
ͷԠྗ‫ڍ‬ಈΛ໌֬Խ͢Δ͜ͱʹ੒ޭͨ͠ɽ·ͨɼCTE– 32 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

BL24XU

2016A3271, 2016B3271

थࢷࣹग़੒‫ܗ‬඼ͷ൘ްஅ໘ํ޲ͷ݁থԽ౓෼෍ղੳ

Distribution of Crystallinity for Injection Molded Resin in the
Thickness Directionसຊ ࡾ‫ ܙ‬1 , দӬ ୓࿠ 2 , ԣా ສཬѥ 2
Mie Funamoto1 , Takuro Matsunaga2 , Maria Yokota2
1ΞΠγϯਫ਼‫ ػ‬2 ๛ాதԝ‫ॴڀݚ‬
1

2

AISIN SEIKI Co., Ltd.

Toyota Central R&D Labs., Inc.

֓ཁɿϙϦΞηλʔϧࣹग़੒‫ܗ‬඼ͷ൘ްஅ໘ํ޲ͷ݁থԽ౓෼෍ΛɼX ઢϚΠΫϩϏʔϜΛ༻͍ͯղੳͨ͠ɽ
அ໘Λ‫͢࡯؍‬ΔͨΊʹɼ੒‫ܗ‬඼த৺෦෼Λ୹࡭ঢ়ʹ੾࡟͠ɼ൘ްํ޲ʹࢼྉΛ૸ࠪ͠ͳ͕Β޿֯ X ઢࢄཚଌఆ
Λߦͬͨɽ֤ଌఆҐஔͰಘΒΕͨࢄཚεϖΫτϧΛϐʔΫ෼཭͢Δ͜ͱʹΑΓ૬ର݁থԽ౓Λࢉग़͠ɼ൘ްํ
޲ͷ෼෍Λಘͨɽͦͷ݁Ռɼ थࢷද໘ 100 – 400 µmʢۚ‫ܕ‬ଆʣʹ௿݁থԽྖҬ͕‫؍‬ଌ͞Εɼͦͷ಺ଆ͸΄΅Ұఆͷ݁থԽ౓Ͱ͋Δ͜ͱ͕Θ͔ͬͨɽ·ͨɼࠓճͷଌఆର৅Ͱ͋Δ 40 – 90 ◦ C ۚ‫ܕ‬Թ౓ൣғͰಘΒΕͨ੒‫ܗ‬඼ʹ͍ͭͯɼ௿݁থԽྖҬ͸ۚ‫ܕ‬Թ౓ʹର͠ઢ‫ݮʹܗ‬গ͢Δ܏޲͕‫ݟ‬ΒΕͨɽΩʔϫʔυɿࣹग़੒‫ܗ‬ɼϚΠΫϩϏʔϜɼ޿֯ X ઢࢄཚɼ݁থԽ౓

എ‫ڀݚͱܠ‬໨త

͢Δɽैͬͯɼࣹग़੒‫ܗ‬৚݅ͷ࠷దԽ͕ෆՄܽͰ͋Δ

ۙ೥ɼ஍‫ٿ‬ԹஆԽରࡦʹΑΔ CO2 ഉग़ྔ࡟‫ݮ‬ͷͨΊͷ‫ڧ੍ن‬Խ΁ͷରԠͱͯ͠ɼࣗಈं‫ۀ‬քͰ͸ഉΨεΛ཈੍͠ CO2 ͷ࡟‫͢ݙߩʹݮ‬Δं྆ॏྔͷܰྔԽʹऔΓ૊ΜͰ͍Δ [1,2]ɽ͜Ε·Ͱ࢖༻͍ͯͨۚ͠ଐࡐྉ
͔Βൺॏ͕͍ܰࡐྉ΁ͷஔ‫͕׵‬ਐΊΒΕ͍ͯΔதͰɼ
थࢷࡐྉ͸ࠓ‫ޙ‬Ұ૚ద༻ൣғͷ֦େ͕‫·ࠐݟ‬Εɼߴਫ਼౓ɾ௿ίετɾߴੜ࢈ੑͳͲͷཁ‫·ߴ͕ٻ‬Δ܏޲ʹ͋Δɽಛʹ੡඼඼࣭ʹେ͖ؔ͘܎͢Δ‫ܗ‬ঢ়ɾੇ๏ਫ਼౓ͷ໰୊͸ɼղܾ͢΂͖՝୊ͷҰͭͰ͋Δɽ‫ࡏݱ‬थࢷࡐྉͷ੡଄ํ๏ͱͯ͠Ұൠతʹ༻͍ΒΕ͍ͯΔࣹग़੒‫ʹܗ‬͓͍ͯ΋ɼ‫ܗ‬ঢ়ɾੇ๏ਫ਼౓ͷ޲্͕‫ٻ‬ΊΒΕ͍ͯΔɽ
थࢷࡐྉͷ੒‫͍͓ͯʹܗ‬ɼࣹग़੒‫ܗ‬͸ɼෳࡶ‫ܗ‬ঢ়ͷ੒‫͕ܗ‬ՄೳͰ͋Δ͜ͱͱɼੜ࢈ੑ͕ߴ͍͜ͱ͔Βࠓ‫ޙ‬΋޿͘‫·ࠐݟ͕༻׆‬ΕΔɽࣹग़੒‫ܗ‬ͷϓϩηεʹ͓͍ͯथࢷࡐྉ͸ɼ༹༥ঢ়ଶͰࣹग़ʹΑΔͤΜஅྗΛड͚ͳ͕Βɼۚ‫ܕ‬ද໘ΑΓ‫ٸ‬଎ʹྫྷ٫͞ΕΔͨΊɼ݁থԽͱඇথྖҬͷ‫ݻ‬Խ͕ಉ࣌ʹਐߦ͢Δ [3]ɽඇฏߧঢ়ଶ
Ͱͷߏ଄‫ܗ‬੒Λ൐͏ͨΊɼ੒‫ܗ‬඼ͷ෺ੑ΍඼࣭ͷਖ਼֬ͳ༧ଌ͸೉͍͠ɽ࣮ࡍʹɼΫϥοΫ · ϘΠυ · ൓Γ · ώ͕ɼͦͷଟ͘ͷ৔߹͸‫ݧܦ‬తɾ࢑ఆతʹߦΘΕΔͱ͍͏ͷ͕‫ݱ‬ঢ়Ͱ͋Δɽࣹग़੒‫ܗ‬඼ͷੇ๏ਫ਼౓΍֎‫্޲؍‬ͷϝΧχζϜΛ
ཧղ͢ΔͨΊʹ͸ɼथࢷද໘૚ʢεΩϯ૚ʣΛղੳ͢
Δ͜ͱ͕ॏཁͰ͋ΔɽεΩϯ૚͸ɼͤΜஅྗ΍ྫྷ٫࣌ͷԹ౓ޯ഑ʹ‫͘ڧ‬Ө‫ڹ‬Λड͚ΔͨΊɼࣹग़੒‫ܗ‬৚݅ͷӨ‫͘ڧ͕ڹ‬൓ө͞Ε͍ͯΔɽ͔͠͠ɼεΩϯ૚͸ද૚

100 µm ఔ౓Ͱ͋ΔͨΊɼͦͷߏ଄Λ‫࡯؍‬ɾධՁ͢Δ
͜ͱ͸೉͘͠ɼ͜Ε·Ͱภޫ‫ݦ‬ඍ‫Ͳͳڸ‬Λ༻͍ͨఆੑ
తͳ‫࡯؍‬ख๏͕ओͰ͋ͬͨɽͱ͜Ζ͕ୈࡾੈ୅์ࣹޫ
ࢪઃ͕‫ݐ‬ઃ͞ΕɼϚΠΫϩϏʔϜ X ઢΛ༻͍ͨߏ଄ղ
ੳख๏ཱ͕֬͞Ε͔ͯΒ͸ɼఆྔతʹߏ଄৘ใʢྫ͑
͹ɼ݁থԽ౓΍഑޲౓ͳͲʣΛධՁͰ͖ΔΑ͏ʹͳ͖ͬͯͨ [4–6]ɽ
ຊ࣮‫Ͱݧ‬͸ɼࣹग़੒‫ܗ‬৚݅ͱ੒‫ܗ‬඼ͷ֎‫؍‬඼࣭ͷؔ܎ੑΛ໌֬Խ͢Δ͜ͱΛ໨తͱͯ͠ɼϚΠΫϩϏʔϜX ઢΛ༻͍ͨߏ଄ղੳΛߦͬͨɽಛʹۚ‫ܕ‬Թ౓͕εΩϯ૚ߏ଄ʹ༩͑ΔӨ‫ڹ‬Λଊ͑ΔͨΊɼ൘ްํ޲ͷ݁থԽ౓ͷ෼෍ͱۚ‫ܕ‬Թ౓ʹର͢Δ‫ܥ‬౷తͳ࣮‫ݧ‬Λߦͬͨɽέ౳ͱ͍ͬͨ੒‫ܗ‬඼֎‫؍‬΋ࣹग़੒‫ܗ‬৚݅ʹେ͖͘ґଘ– 33 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)࣮‫ݧ‬‫ࡐࢼڙ‬ɿ ඇ‫ڧ‬ԽϙϦΞηλʔϧίϙϦϚʔ (POMɿ

polyoxymethylene) Λࣹग़੒‫͢ܗ‬Δ͜ͱʹΑΓࢼ‫ݧ‬ยΛ࡞੡ͨ͠ɽࣹग़੒‫ʹܗ‬͸ɼ200 × 50 × 2(t) mm ͷฏ൘‫ܗ‬ঢ়༻ۚ‫ܕ‬Λ༻͍ɼ‫ݻ‬ఆɾՄಈۚ‫ܕ‬ͷԹ౓Λม͑ͯࢼ‫ݧ‬ยΛ࡞੡ͨ͠ɽ޿֯ X ઢࢄཚʢWAXSʣ࣮‫ݧ‬͸ɼ

Fig.1 ʹࣔ͢ Through ํ޲ͱ Edge ํ޲͔Βߦͬͨɽ
Through ํ޲‫ʹ༻࡯؍‬͸ɼۚ‫ܕ‬Թ౓ 45, 55, 65, 75, 85◦ Cʢ‫ݻ‬ఆɾՄಈۚ‫ͱܕ‬΋ʹʣͰࣹग़੒‫ͨ͠ܗ‬੒‫ܗ‬඼ͷத৺෦Λ༻͍ͨɽEdge ํ޲‫ʹ༻࡯؍‬͸ɼۚ‫ܕ‬Թ౓ʹΑΔӨ‫ڹ‬Λ‫͢࡯؍‬ΔͨΊʹɼ‫ݻ‬ఆ-Մಈۚ‫Ͱؒܕ‬Թ౓ࠩΛ͚ͭͨɽ‫ݻ‬ఆۚ‫ܕ‬Թ౓ͱՄಈۚ‫ܕ‬Թ౓͕ͦΕͧΕ 40◦ C: 90◦ Cɼ45◦ C : 85◦ Cɼ50◦ C : 80◦ Cɼ55◦ C : 75◦ Cɼ
60◦ C : 70◦ Cɼ65◦ C : 65◦ C ͷ৚݅Ͱࢼ‫ݧ‬ยΛ࡞੡ͨ͠ɽۚ‫ܕ‬Թ౓Ҏ֎ͷࣹग़ · อ࣋ѹྗͳͲͷࣹग़੒‫ܗ‬৚݅͸Ұఆͱͨ͠ɽ

Through ํ޲‫࡯؍‬ɿ Through ํ޲ͷ WAXS ࣮‫ݧ‬͸ɼSPring-8 BL33XUʢ๛ాϏʔϜϥΠϯʣʹ࣮ͯࢪͨ͠ɽ‫ݕ‬ग़‫ث‬͸ɼPILATUS-300KɼX ઢΤωϧΪʔ͸ 15 keVɼϏʔϜαΠζ͸ɼ໿ 300 µm ֯Λ༻͍ͨɽࢼྉ‫ݕ‬ग़‫཭ڑؒث‬͸ɼ157.5 mm ͱͨ͠ɽEdge ํ޲ʢ൘ްஅ໘ʣ‫࡯؍‬ɿ SPring-8 BL24XUʹͯϚΠΫϩϏʔϜ޿֯ X ઢࢄཚʢµB-WAXSʣଌఆΛߦͬͨɽFig.1 ʹࣔ͢Α͏ʹ X ઢϏʔϜಁաްΈ͕

0.5 mm ͱͳΔΑ͏੒‫ܗ‬඼தԝ෦Λ୹࡭ঢ়ʹ੾࡟͠ɼ൘
ްํ޲ͷஅ໘Λ‫ݻ‬ఆۚ‫ܕ‬ଆ͔ΒՄಈۚ‫ܕ‬ଆ·Ͱ 10 µm
εςοϓͰ૸ࠪ͠ɼµB-WAXS ଌఆΛߦͬͨɽ‫ݕ‬ग़‫ث‬͸ϑϥοτύωϧσΟςΫλʔɼX ઢΤωϧΪʔ͸ 10

keVɼϏʔϜαΠζ͸ɼ5.0(W)×4.6(H) µm Λ༻͍ͨɽφΠϑΤοδεΩϟϯʹΑΔ൒஋શ෯ΛϏʔϜαΠζͱͨ͠ɽࢼྉ-‫ݕ‬ग़‫཭ڑؒث‬͸ɼ45.6 mm ͱͨ͠ɽಘ
ΒΕͨࢄཚ૾Λथࢷྲྀಈํ޲ͱਫฏํ޲ʹ ± 5◦ Ͱઔ‫ܗ‬ฏ‫ࢄۉ‬ཚ‫౓ڧ‬Λࢉग़͠ɼಘΒΕͨεϖΫτϧΛϐʔΫ෼཭͢Δ͜ͱʹΑΓ૬ର݁থԽ౓ΛධՁͨ͠ɽ

Fig. 1. Schematic image of a cut-out position of
injection molded samples and a measurement position for µB-WAXS.
ग़ͨ͠ WAXS εϖΫτϧΛࣔ͢ɽશͯͷεϖΫτϧ
͕ॏͳ͓ͬͯΓɼThrough ํ޲Ͱͷ‫Ͱ࡯؍‬͸ۚ‫ܕ‬Թ౓ʹΑΔҧ͍͸‫ݟ‬ΒΕͳ͔ͬͨɽ

Fig.3 ʹ‫ݻ‬ఆۚ‫ܕ‬:40◦ CɼՄಈۚ‫ܕ‬:90◦ C Ͱ࡞੡ͨ͠
੒‫ܗ‬඼൘ްํ޲அ໘ͷ (a) ۚ‫ۙܕ‬๣ҐஔʢεΩϯ૚ɿՄಈۚ‫ܕ‬ଆʣ͓Αͼ (b) த৺ҐஔʢίΞ૚ʣʹ͓͚ΔµB-WAXS ࢄཚ૾Λࣔ͢ɽίΞ૚͸౳ํతͳࢄཚ૾Ͱ
͋Δͷʹର͠ɼۚ‫ܕ‬ද໘ۙ๣ͷεΩϯ૚Ͱ͸ҟํੑΛ༗͢Δࢄཚ૾͕ಘΒΕͨɽFig.2 ʹࣔͨ͠Α͏ʹɼฏ൘‫ܗ‬ঢ়੒‫ܗ‬඼ʹର͠ Through ํ޲ʹ X ઢΛಁաͤͨ͞৔߹ʹ͸ɼҟํੑͷ͋Δ૾͸ಘΒΕͳ͔ͬͨɽͦͷཧ༝ͱͯ͠ɼۚ‫ۙܕ‬๣ͷ෼ࢠ഑޲૚͕ඇৗʹബ͍͜ͱ͕ߟ͑ΒΕɼϚΠΫϩϏʔϜ X ઢΛ༻͍ͨஅ໘ํ޲
ͷ‫ߏॴہ‬଄‫࡯؍‬Λߦ͏͜ͱͰॳΊͯͦͷଘࡏΛ֬ೝ͢
Δ͜ͱ͕Ͱ͖ͨɽ
࣍ʹɼEdge ํ޲ͷ݁থԽ౓ͷ෼෍Λ‫ٻ‬Ίͨɽࢄཚ૾͸ҟํੑ͕ଘࡏ͢ΔͨΊɼथࢷྲྀಈํ޲ʹର͠ਫฏํ޲ ±5◦ ͷൣғͰઔ‫ܗ‬ฏ‫ࢄۉ‬ཚ‫౓ڧ‬εϖΫτϧΛ‫ٻ‬Ί༻͍ͨɽFig.4 ʹίΞ૚ͷ µB-WAXS εϖΫτϧͷ
ϐʔΫ෼཭݁ՌΛࣔ͢ɽϐʔΫ෼཭ͷϑΟοςΟϯά
ൣғ͸ɼ1 – 2 Å

−1−1ͱͨ͠ɽࢄཚϕΫτϧ 1.6 Å෇ۙͷϐʔΫΛ Voigt ؔ਺ʢ݁থ༝དྷͷϐʔΫʣͱ Gauss݁Ռ͓Αͼߟ࡯

ؔ਺ʢඇথ༝དྷͷϋϩʔʣΛ༻͍ͯϑΟοςΟϯάΛ

Fig.2(A)ɼ(B) ʹ Through ํ޲͔Β X ઢΛೖࣹ͠ଌఆͨ͠ WAXS ͷೋ࣍‫૾ݩ‬Λࣔ͢ɽ(A) ͱ (B) ͸ͦߦ͍ɼશࢄཚ‫݁ͱ౓ڧ‬থ༝དྷͷϐʔΫ໘ੵͷൺ͔Β૬ର݁থԽ౓Λࢉग़ͨ͠ɽ

ΕͧΕ‫ݻ‬ఆɾՄಈۚ‫ܕ‬Թ౓͕ಉҰͷ 45 Cɼ85 C Ͱ

Fig.4 ͱಉ༷ͷղੳΛ‫ݻ‬ఆۚ‫ ܕ‬40◦ CɼՄಈۚ‫ ܕ‬90◦ C࡞੡ͨ͠ࢼྉͷ݁ՌͰ͋Δ͕ɼ྆ऀͱ΋౳ํతͳࢄ

ͷ৚݅Ͱ࡞੡ͨ͠ࢼྉͷஅ໘ํ޲͢΂ͯͷଌఆ఺Ͱ࣮

ཚ૾Ͱ͋ΓɼϐʔΫ‫ʹ౓ڧ‬΋ҧ͍͸‫ݟ‬ΒΕͳ͔ͬͨɽ

ࢪ͠ɼಘΒΕͨ૬ର݁থԽ౓ͷްΈํ޲ͷ෼෍Λ Fig.5

◦

◦

◦

Fig.2(C) ʹɼۚ‫ܕ‬Թ౓ 45 - 85 C ͷԁ‫؀‬ฏ‫ʹۉ‬ΑΓࢉʹࣔ͢ɽۚ‫ۙܕ‬๣Ͱ͸ɼ݁থԽ౓ͷ௿͍εΩϯ૚ྖҬ– 34 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
!"#

$""

"

!""

!""

%""

%""

6""

6""

&""

!"##

&""

$%&'()*+,-(.(/0129"""!"#$$%&'()*'($%(+'$, '()*+*

<>=

$""

!"#$$%&'()*'($%(+'$, &'()*)

"

$""

!""

%""

./01(2345*(?(;&78

9""

6""

"

$""

!""

%

#
!"##

$"
&

$*&

!*"

!*&

!"#$$%&'()*-%"$.& '(,

-$

!

$##

6""

01(<'=>'(4=20D=*@
AE(*@@'>5)C%##01(<'=>':2?@6(7AB=396'>5)C##./01(2345*
6&(78
&&(78
9&(78
:&(78
;&(78

$&

./01234156(78366359':*2;1

%##

<8=

!"#$"

$*"

%""

$##

!)#

!)+

")#

")+
-!

!"#$$%&'()*-%"$.& &',Fig. 4. Scattering intensity vs. scattering vector
for core layer of POM, and the peak fitting result.

%*"ʹΑΔҧ͍͕‫؍‬ଌ͞Εͳ͔ͬͨͱߟ͑ΒΕΔɽ·ͨɼۚ‫ܕ‬Թ౓ 40◦ C ͱ 90◦ C ͷۚ‫ܕ‬ද໘ଆ͔Β಺෦ํ޲΁

Fig. 2. WAXS 2D images and 1D spectra of injection molded POM plate from through direction.

ͷ݁থԽ౓ͷ෼෍Λൺֱ͢Δͱɼ40◦ C ͷํ͕݁থԽ
౓ͷ্ঢ͕ͳͩΒ͔Ͱ͋ͬͨɽPOM ͸ɼΨϥεసҠԹ౓͕໿ −50◦ Cɼ݁থ༥఺͕໿ 180◦ C Ͱ͋ΓɼͦͷதؒͷԹ౓Ͱ͋Δ 65◦ C ۙ๣Ͱ݁থԽ଎౓͕ߴ͘ͳΔ
ͱߟ͑ΒΕΔɽ40◦ C ͱ 90◦ C Ͱ͸ɼ݁থԽ଎౓ʹ΄ͱΜͲࠩ͸ͳ͍͕ɼ௿ԹଆͰ͸֩ੜ੒଎౓্͕ঢ͢ΔͨΊ 40◦ C Ͱ͸ɼଟ͘ͷ݁থ͕֩ൃੜ͠ɼ࠷ऴతͳ݁
থԽ౓͕ߴ͘ͳΒͣɼ಺෦ํ޲΁ͷ݁থԽ౓ͷ্ঢ͕ͳͩΒ͔ʹͳͬͨͱߟ͑ΒΕΔɽ

Fig. 3. µB-WAXS patterns of injection molded
POM in the (a) surface layer and (b) core layer!"#$""%&'%($)*+,--./.+) ()*!"#͕‫؍‬ଌ͞Ε͓ͯΓɼۚ‫ܕ‬Թ౓ʹΑͬͯɼεΩϯ૚ްΈʹҧ͍͕͋Δ͜ͱ͕Θ͔ͬͨɽFig.5 ΑΓεΩϯ૚ް͞ΛఆྔԽ͢Δʹ͋ͨΓɼ݁থԽ౓͸࿈ଓతʹมԽ͢ΔͨΊɼεΩϯ૚ͱίΞ૚Λ໌֬ʹ۠ผ͢Δ͜ͱ͕Ͱ͖ͳ͍ͨΊɼۚ‫ܕ‬ද໘Ґஔ͔Β໿ 1 mmʢࢼྉத৺Ґ#"$?<@2A5,BC2B/1
D5BB5CE)0F)G5E,-53);C",-./012),-13)4532
67#)89:;5<23),-13)4532
6&#)89:

#"%
#"&
#"'

ஔʣͷൣғΛ Sigmoid ؔ਺ͰϑΟοςΟϯά͠ɼؔ਺ͷ&!# !!
!,#"#

൒஋‫× ཭ڑ‬2 ΛεΩϯ૚ްΈͱͯ͠਺஋Խͨ͠ɽ‫ݻ‬ఆۚ‫ ܕ‬40◦ CɼՄಈۚ‫ ܕ‬90◦ C ͷ৚݅Ͱ࡞੡ͨ͠ࢼྉ͸ɼ#"#!=> !!
!,

#"+

!"#

!"+

'"#

0",*1$./#%2&*.+.&/ (),,

40◦ C ‫ݻ‬ఆۚ‫ܕ‬ଆʹ໿ 410 µmɼ90◦ C Մಈۚ‫ܕ‬ଆʹ໿
170 µm ͷεΩϯ૚͕ଘࡏ͢Δ͜ͱ͕Θ͔ͬͨɽίΞ◦૚ྖҬʢ಺ଆͷ໿ 1.4 mmʣͰ͸ɼۚ‫ܕ‬Թ౓͕ 40 C,

Fig. 5. Distribution of crystallinity in the platethickness cross section.

90◦ C ͷҧ͍ʹΑΒͣɼ݁থԽ౓͸΄΅ҰఆͰ͋Δ͜ͱ͕Θ͔ͬͨɽ2 mm ްͷࢼྉͷ৔߹ɼ໿ 70% ͕౳ํతͳίΞ૚Ͱ͋Γɼ·ͨ෼ࢠ഑޲ͷ͋ΔεΩϯ૚͸݁থੑ͕௿͍ͨΊʹɼThrough ํ޲ͷ‫Ͱ࡯؍‬͸ίΞ૚ͷ݁থ༝དྷͷϐʔΫ͕‫ڧ‬ௐ͞Εͯ‫؍‬ଌ͞Εɼۚ‫ܕ‬Թ౓্‫ه‬ղੳʹΑΓಘΒΕͨۚ‫ܕ‬Թ౓ͱεΩϯ૚ްΈͷؔ܎Λ Fig.6 ʹࣔ͢ɽଌఆΛߦͬͨ 40◦ C ͔Β 90◦ C ͷൣғͰ͸ɼۚ‫ܕ‬Թ౓্͕ঢ͢ΔͱεΩϯ૚ްΈ͸ઢ‫ܗ‬ʹ‫ݮ‬গ͢Δ͜ͱ͕ଊ͑ΒΕͨɽPOM ͸ΨϥεసҠԹ

– 35 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)౓͕໿ −50◦ C Ͱ͋ΓɼࣨԹʹ͓͍ͯ΋݁থԽ͕ਐߦ

ࣄ‫΁ۀ‬ͷߩ‫ݙ‬͢Δͱߟ͑ΒΕΔɽ͔͠͠ɼۚ‫͔ܕ‬ΒऔΓग़ͨ͠੒‫ܗ‬඼ͷεΩϯ૚ްΈ͸੒‫࣌ܗ‬ͷۚ‫ܕ‬Թ౓ʹґଘͨ͠มԽ
͕ΈΒΕͨɽ͜Ε͸ɼۚ‫಺ܕ‬෦Ͱड͚Δྫྷ٫࣌ͷԹ౓ޯ഑ʹΑΓ‫ܗ‬੒͞Εͨ݁থߏ଄ʢ݁থ෼෍ʣ͕ɼͦͷ‫ޙ‬ͷ݁থԽ౓ͷਐߦʹ΋Ө‫ڹ‬Λ‫͍ͯ͠΅ٴ‬Δ͜ͱΛ͍ࣔͯ͠ΔɽࠓճಘΒΕͨฏ൘ࢼ‫ݧ‬ย‫ܗ‬ঢ়Ͱͷ஌‫ݟ‬Λ΋ͱʹ͢Δ͜ͱͰɼΑΓෳࡶͳ‫ܗ‬ঢ়ʢ੡඼‫ܗ‬ঢ়ʣʹ͓͍ຊ‫Ͱڀݚ‬ಘΒΕͨ੒Ռ͸ɼࣹग़੒‫ܗ‬඼ͷ֎‫؍‬඼࣭ͷ޲্ʹ‫͕ܨ‬Δ͚ͩͰ͸ͳ͘ɼ࠷దͳ੒‫ܗ‬৚݅Λ༧ଌ͢
Δ͜ͱͰ੒‫ܗ‬αΠΫϧ୹ॖ΍ೋ࣍Ճ޻ʹ͓͚Δෆྑ཰ͷ௿‫Ͳͳݮ‬ϓϩηεશମͷվળɾ޲্΁ͷߩ‫ظ͕ݙ‬଴͞ΕΔɽࢀߟจ‫ݙ‬

ͯ΋ɼεΩϯ૚ްΈΛ µB-WAXS ख๏͔Β‫ٻ‬Ίɼ͔ͦ͜Β࣮ࡍͷྫྷ٫ʢۚ‫ܕ‬ʣԹ౓Λ‫ੵݟ‬΋Δ͜ͱ͕Ͱ͖
Δͱߟ͑ΒΕΔɽ

!"#$%&'(()*+)(%#&),-.'/'('µ)

!"#
!##
$"#
$##
%"#
%##
&"#
&##

!#

"#

-#

,#

+#

*#

0*,1)!'23'/-45/''('./

Fig. 6. Mold temperature dependence of skin layer
thickness for POM.

ࠓ‫ޙ‬ͷ՝୊
੒‫ܗ‬඼ͷ݁থߏ଄෼෍ͱࣹग़੒‫ܗ‬৚݅ͱͷ૬ؔΛղ໌͢Δ͜ͱͰɼࣹग़੒‫ܗ‬৚݅ͷ࠷దԽʹ༗ޮͳࢦ਑͕
ಘΒΕΔ͜ͱ͕Θ͔ͬͨɽࠓ‫ޙ‬ɼۚ‫ܕ‬Թ౓͚ͩͰͳ͘ɼ
ࣹग़଎౓ (ϓϥϯδϟʔ)ɼ͞Βʹ͸ۚ‫ܕ‬෦Ґ΍੒‫ܗ‬඼ްΈΛม͑ͯࢼ‫ݧ‬ยΛ࡞੡͠ɼ‫ૅج‬σʔλΛऩू͢Δ
͜ͱʹΑΓɼ࣮੡඼ʹ͓͚Δෳࡶͳ‫ܗ‬ঢ়΁ͷղੳٕज़΁ͷల։͕‫ظ‬଴͞ΕΔɽ

– 36 –[1] JETRO ϢʔϩτϨϯυ 2007 ೥ 4 ݄߸ 3. ࣗಈंͷ CO2 ഉग़‫੍ن‬.
[2] தଜकɿ࢈૯‫ ݚ‬TODAY 2006.1 VOL.6-1.
[3] ࠇ࡚Ꮼ෉ɼࠤ౻‫܄‬ɼੴҪߒҰ࿠ɿ೔ຊ‫ػ‬ցֶձ࿦จू C ฤɼ56 ‫ ר‬522 ߸ɼ504-511 (1990).
[4] N. E. Zaheiropoulos, R. J. Davies, S. V. Roth,
M. Burghammer, K. Schneider and C. Stamm:
Macromol. Rapid Commun., 26, 1547-1551(2005).
[5] ໺຤Ղ৳ɼӍ‫޾ܚٶ‬ɿ์ࣹޫ Nov. 2006 Vol.19,
No.6, 356-363.
[6] Y. Shinohara, K. Yamazoe, T. Sakurai, S. Kimata, T. Maruyama, and Y. Amemiya: Macromolecules, 45, 1398-1407 (2012).

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

BL08B2, BL24XU

2014B3256, 2016A3352

์ࣹޫΛར༻ͨ͠ΰϜ֊૚ߏ଄௥੻ (4)Analysis of hierarchical structure of rubber using ultra small angle
X-ray scattering৓ग़ ݈༎ɼେߐ ༟জɼ࡝୩ ஐɼඛ઒ ༃ߒɼࡾӜ ૱Ұ࿠ɼ੢઒ ༝ਅ
Kensuke Shirode, Hiroaki Oe, Satoshi Sagitani, Yasuhiro Hishikawa,
Souichiro Miura, Yuma Nishikawa౦༸ΰϜ޻‫ࣜגۀ‬ձࣾ

TOYO TIRE ˍ RUBBER CO., LTD.
֓ཁɿ์ࣹޫΛޫ‫ ͨ͠ͱݯ‬X ઢখ֯ࢄཚ๏ͱ X ઢϥϛϊάϥϑΟʔΛ૊߹ΘͤɼλΠϠ༻ΰϜࡐྉதิ‫ࡎڧ‬ͷ֊૚ߏ଄ΛධՁͨ͠ɽҟͳΔଌఆεέʔϧΛ࣋ͭख๏ͷ૊߹ΘͤʹΑͬͯɼ෼ࢄॲཧํ๏ʹΑΔิ‫֊ࡎڧ‬૚ߏ଄ͷҧ͍Λ‫ݟ‬ग़͢͜ͱ͕Ͱ͖ɼΰϜ෺ੑͱͷ૬ؔߟ࡯Λߦ͏͜ͱ͕Մೳͱͳͬͨɽ
Ωʔϫʔυɿখ֯ࢄཚɼϥϛϊάϥϑΟʔ๏ɼCTɼΰϜɼϑΟϥʔɼ‫ूڽ‬ɼ෼ࢄɼ֊૚ߏ଄

࣮‫ݧ‬എ‫ڀݚͱܠ‬໨తΰϜࡐྉ͸ɼ֤छΰϜ੡඼ʹ‫ٻ‬ΊΒΕΔੑೳΛຬ଍

SAXS ଌఆ͸ɼBL08B2 Ͱߦͬͨɽଌఆ৚݅͸ɼX

ͤ͞ΔͨΊʹଟ਺ͷҟͳΔఴՃࡎΛࠞ߹͢Δ͕Ώ͑ɼઢͷ೾௕Λ 1.5 ÅɼΧϝϥ௕Λ 6182 mmɼ࿐ޫ࣌ؒΛछʑͷ૬͔Β‫ܗ‬੒͞ΕΔߏ଄Λ࣋ͬͨෳࡶࡐྉͰ͋Δɽ1 sɼσΟςΫλʔʹ͸ Pilatus–100K Λ࢖༻ͨ͠ɽऔ

ͦͷ༷ʑͳ‫ڍ‬ಈ΍‫ݱ‬৅͸ɼۙ೥ͷ෼ੳɾղੳٕज़ͷਐ

ಘͨ͠ 2 ࣍‫ࢄݩ‬ཚ૾͔Βਫฏํ޲ʹ෯ 40◦ ͷൣғͰԁาʹ΋͔͔ΘΒͣɼࡐྉ͕ෆ‫ۉ‬Ұ͔ͭ 3 ࣍‫ݩ‬ͷ֊૚ߏ‫؀‬ฏ‫ ͠ۉ‬1 ࣍‫ݩ‬σʔλʹม‫׵‬ɼࢄཚ‫ۂ‬ઢΛಘͨɽຊ৚

଄Λ༗͍ͯ͠ΔͨΊɼ͍·ͩϒϥοΫϘοΫεతͳཁ݅Ͱͷ q Ϩϯδ͸ 0.015∼0.3 nm−1 Ͱ͋ͬͨɽ

ૉ͕ଟ͍ɽҰํͰΰϜ੡඼ͷ‫ڥ؀‬ɾ҆શʹର͢Δχʔ

X ઢϥϛϊάϥϑΟʔଌఆ͸ɼBL24XU–B2 ϋοζ͸ߴ·ΓɼࡐྉͷߴੑೳԽɾߴ‫ػ‬ೳԽʹ޲͚ͨ։ൃ

νͰߦͬͨɽরࣹ X ઢΤωϧΪʔ 10 keVɺΧϝϥ௕͕‫ٸ‬຿Ͱ͋Δ͜ͱ͔ΒɼΑΓਫ਼ີͳ෼ੳɾղੳٕज़͕

42 mm ͱ͠ɼΰϜαϯϓϧ͸ճసεςʔδʹ‫ݻ‬ఆɼඞཁෆՄܽͰ͋Δɽ

γϯνϨʔλ͸ GAGG; Ce(Ce ఴՃ Gd3 (Al,Ga)5 O12͜Ε·Ͱʹɼ์ࣹޫখ֯ X ઢࢄཚ๏ʢSAXSʣΛ༻୯݁থ) Λ࢖༻ͨ͠ɽը૾ͷϐΫηϧ਺͸ 1920×1440

͍ͯɼΰϜ෺ੑʹେ͖͘Ө‫ڹ‬Λ‫͢΅ٴ‬ҼࢠͷҰͭͰ͋

pixelsɼࡱӨϐΫηϧαΠζ͸ 0.65 µm Ͱ͋ͬͨɽಘΒΔิ‫ࡎڧ‬ʢΧʔϘϯϒϥοΫɼγϦΧ౳ʣʹؔͯ͠ɼΕͨ౤Өσʔλ͸ઐ༻ιϑτΛ༻͍ͯ࠶ߏ੒Λߦͬͨɽྗֶతࢼ‫ݧ‬Լʹ͓͚Δɼ෼ࢄɾ‫ߏूڽ‬଄ධՁΛߦͬͯΰϜαϯϓϧ͸ɼενϨϯϒλδΤϯΰϜʹɼิ‫ڧ‬͖ͨ [1]ɽ͔͠͠ɼิ‫ࡎڧ‬͸φϊ ∼ ϚΠΫϩϝʔτϧࡎʢϑΟϥʔʣͱͯ͠γϦΧ 20 vol%ఴՃΛ‫ج‬ຊͱ͠ΦʔμʔͰ֊૚ߏ଄Λ‫ܗ‬੒͍ͯ͠Δ͕ɼ͜Ε·ͰͷͨɽΰϜͱγϦΧ͸ਫͱ༉ͷؔ܎ʹ͋Γɼͦͷ··ࠞ

SAXS ධՁͰ͸ಈత৚݅ԼͰͷߏ଄ղੳʹओ‫؟‬Λ͓͍ͥͯ΋‫ۉ‬Ұʹ෼ࢄͤ͞Δ͜ͱ͸ࠔ೉ͳͨΊɼ෼ࢄॲཧ

͍ͯͨͨΊɼϚΠΫϩϝʔτϧΦʔμʔͷߏ଄ධՁ͕

Λࢪ͢͜ͱ͕ҰൠతͰ͋Δɽ̍ͭ໨͸ϙϦϚʔͱγϦे෼ʹͰ͖͍ͯͳ͔ͬͨɽͦ͜Ͱɼຊ‫Ͱڀݚ‬͸ SAXSΧͷؒΛऔΓ࣋ͭ෼ࢄࡎʢγϥϯΧοϓϦϯάࡎʣΛʹՃ͑ͯɼX ઢϥϛϊάϥϑΟʔʹΑΔγϦΧ௚઀‫؍‬

ఴՃ͢Δํ๏ʢSilane coupling agentʣɼ̎ͭ໨͸ϙ࡯Λߦ͍ɼ࣮/‫ۭؒٯ‬ͷ྆໘͔ΒϚϧνεέʔϧͰͷϦϚʔ࠯຤୺ʹγϦΧͱ૬ੑͷྑ͍‫׭‬ೳ‫ج‬Λมੑ͢Δ

ิ‫ߏࡎڧ‬଄ධՁΛߦ͍ɼ‫ػ‬ցಛੑͱͷ૬͔ؔΒߴੑೳ

ํ๏ʢEnd modified polymerʣͰ͋Δɽ͜ΕΒ෼ࢄॲλΠϠ։ൃʹ‫͕ܨ‬Δ৽஌‫ݟ‬ΛಘΔ͜ͱΛ໨తͱͨ͠ɽ

ཧͷ༗ແΛ૊Έ߹Θͤͨ 4 छྨͷαϯϓϧΛ༻ҙ͠

– 37 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)
ͨɽTable. 1 ʹࣔ͢ɽnn ͸γϥϯΧοϓϦϯάࡎͱ͜ͱΛࣔ͠ɼώεςϦγεϩεͷগͳ͍ࡐྉͱͳΔɽ

຤୺มੑϙϦϚʔෆ࢖༻ɼsn ͸γϥϯΧοϓϦϯάࡎ

Table. 2 ʹࠓճଌఆʹ༻͍ͨαϯϓϧͷώεςϦγε

ͷΈ࢖༻ɼne ͸຤୺มੑϙϦϚʔͷΈ࢖༻ɼse ͸γϩεͱϖΠϯޮՌΛࣔ͢ɽʢnn ͷ஋Λ 100 ͱͯ͠ indexϥϯΧοϓϦϯάࡎͱ຤୺มੑϙϦϚʔ࢖༻Ͱ͋Δɽ

දࣔͱ͍ͯ͠Δɽʣαϯϓϧ࡞੡͸ɼີดࣜࠞ߹‫ʹػ‬ΑͬͯΰϜͱ഑߹ࡎΛࠞ࿅͠ɼۚ‫ܕ‬ϞʔϧυͰϓϨεՃ޻͢Δ͜ͱͰɼSAXS ଌఆ༻ʹ 1.0 mm ްɼCT ଌఆ༻ʹ 0.5 mm ް

Table 2.
samples.

Viscoelastic properties of measurementͷγʔτঢ়ʹ੒‫ͨ͠ܕ‬ɽ

Hysteresys loss
Payne effect

Table 1. Measurement samples.
Silane coupling agent
End modified polymer

nn

sn

ne

se

×

◦

×

◦

×

×

◦

nn

sn

ne

se

100
100

93
33

84
51

67
11

γϦΧ෼ࢄॲཧΛࢪ͍ͯ͠ͳ͍ nn ͕ώεςϦγε

◦ϩεɼϖΠϯޮՌͱ΋ʹେ͖͘ɼγϦΧ෼ࢄ͕ѱ͍ͱߟ͑ΒΕΔɽ࣍ʹγϥϯΧοϓϦϯάࡎॲཧͨ͠ snͰ͸ώεςϦγεϩεɼϖΠϯޮՌͱ΋ʹ௿‫͞ݮ‬Εޮ݁Ռ͓Αͼߟ࡯
ҰൠʹλΠϠͷస͕Γ఍߅͸ΰϜ഑߹෺ͷώεςϦ
γεϩεͱͷؔ܎͕‫͘ڧ‬ɼώεςϦγεϩεʹ͸ϑΟϥʔ෼ࢄঢ়ଶ͕Ө‫ڹ‬Λ‫͢΅ٴ‬ɽΰϜதϑΟϥʔ෼ࢄΛ‫ੵݟ‬΋Δํ๏ͱͯ͠ɼಈత஄ੑ཰ͷৼ෯ґଘੑʢϖΠϯޮՌʣΛଌఆ͢Δํ๏͕͋Δɽ͋ΔൣғͰͷৼ෯૿ՃʹΑΓɼϑΟϥʔ‫ूڽ‬ମؒͷ෺ཧ݁߹͕੾அ͞Ε஄ੑ཰͕‫ݮ‬গ͢Δɽ͜ͷ‫ूڽ‬ମͷ่ΕʹΑΔ஄ੑ཰ͷ‫ݮ‬গ෯Λൺֱ͢Δ͜ͱͰΰϜதϑΟϥʔͷ෼ࢄੑΛٞ࿦
͢Δ͜ͱ͕Ͱ͖ΔɽFig. 1 ʹϖΠϯޮՌͷΠϝʔδਤΛࣔ͢ɽ

sample 1 ͸ɼ࿪ྖҬ಺ͷ࠷େ஄ੑ཰ͱ࠷খ஄ੑ཰ͷ͕ࠩେ͖͘ɼ‫ूڽ‬ମͷׂ߹͕ଟ͍ͱ‫͑ݴ‬Δɽ‫ʹٯ‬ϖΠϯޮՌͷখ͍͞ sample 2 ͸ɼ෼ࢄঢ়ଶ͕ྑ޷Ͱ͋Δ

Fig. 1. Image of Payne effect.

Ռ͕֬ೝͰ͖Δɽ຤୺มੑϙϦϚʔΛ࢖༻ͨ͠ neɼγϥϯΧοϓϦϯάࡎͱ຤୺มੑϙϦϚʔͱ΋ʹ࢖༻ͨ͠ se ʹ͓͍ͯ΋ɼώεςϦγεϩεͱϖΠϯޮՌͷ௿‫ݮ‬Λ֬ೝͨ͠ɽ௿‫ޮݮ‬Ռ͸ɼώεςϦγεϩεʹ͓͍ͯ͸ sn>ne>seɼϖΠϯޮՌʹ͓͍ͯ͸ ne>sn>seͱͳΓɼ྆ऀ͸ҟͳΔ௿‫ॱݮ‬ংͱͳͬͨɽͭ·ΓɼώεςϦγεϩε௿‫ʹݮ‬͸຤୺มੑϙϦϚʔͷ‫د‬༩͕େ͖͘ɼϖΠϯޮՌͷ௿‫ʹݮ‬͸γϥϯΧοϓϦϯάࡎॲཧͷ‫د‬༩͕େ͖͍ɽϖΠϯޮՌ͸ϑΟϥʔ෼ࢄΛ‫ੵݟ‬΋Δํ๏Ͱ͸͋Δ͕ɼ͠͹͠͹ώεςϦγεϩεͱ૬͕ؔऔΕͳ͍৔߹͕‫ݟ‬ड͚ΒΕΔɽ͜ͷ݁Ռ͔ΒɼγϦΧ෼ࢄޮՌ͕‫ظ‬଴͞ΕΔ 2 ͭͷख๏͕ͩɼϝΧχζϜͷҧ͍ʹΑͬͯಘΒΕΔ෼ࢄঢ়ଶ͕ҟͳΔͨΊʹɼώεςϦγεϩεͱϖΠϯޮՌͷ‫ٯ‬స‫ݱ‬৅͕‫ͱ͖ͨى‬Fig. 2. SAXS profiles of silica compounded rubbers.

– 38 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

Table 3. Filler dispersion parameters obtained from SAXS profiles.
R / nmNr / The number of aggregates
Vr / nm−3

nn

sn

ne

se

98.7
5.11×1010
1.46×10676.5
6.16×1010
6.62×105

73.7
6.15×1010
7.21×105

64.3
8.09×1010
4.39×105ਪଌͨ͠ɽͦ͜ͰɼSAXS ͱ X ઢϥϛϊάϥϑΟʔ͕‫ݟ‬ΒΕΔ͕ɼse ʹ͸େ͖ͳཻ͸‫ݟ‬ΒΕͣɼ෼ࢄঢ়ଶ

Λ૊߹ΘͤͨϑΟϥʔͷ֊૚ߏ଄ղੳΛߦͬͨɽFig.

͕ྑ޷ͩͱߟ͑ΒΕΔɽγϥϯΧοϓϦϯάࡎͱɼ຤2 ʹҰ࣍‫ݩ‬Խͨ͠ SAXS ϓϩϑΝΠϧΛࣔ͢ɽ୺มੑϙϦϚʔΛซ༻͢Δ͜ͱͰɼϚΠΫϩΦʔμʔq > 0.1 nm−1ʹ͓͍ͯϓϩϑΝΠϧʹେ͖ͳࠩ͸−1ͷཻࢠ௿‫ʹݮ‬େ͖ͳޮՌ͕͋ΓɼώεςϦγεϩεɼʹ͓͍ͯ͸γϣϧμʔҐϖΠϯޮՌʹ΋޷Ө‫͍ͯ͠ڹ‬Δɽ෼ࢄॲཧ͍ͯ͠ͳ͍

ஔʹҧ͍͕‫ݟ‬ΒΕɼγϦΧ෼ࢄॲཧ͍ͯ͠ͳ͍ nn ͸

nn ͱɼ෼ࢄॲཧ͍ͯ͠Δ sn ͱ ne Ͱ͸ɼ‫ͨݟ‬໨ʹ͸໌‫ݟ‬ΒΕͳ͍ɽq < 0.1 nm−1෇ۙʹγϣϧμʔΛࣔ͠ɼ෼ࢄॲཧ

֬ͳࠩ͸֬ೝͰ͖ͳͬͨɽͦ͜ͰɼϑϦʔιϑτͰ͋ͨ͠ snɼne Ͱ͸γϣϧμʔ͕ߴ q Ϩϯδଆ΁ͱγϑ

ΔʮImageJʯΛ༻͍ͯɼཻ౓෼෍ղੳΛߦͬͨɽखॱ

τɼse ʹ͓͍ͯ͸͞Βʹߴ q Ϩϯδଆ΁γϑτ͠ɼҰͱͯ͠ɼը૾Λೋ஋Խͨ͠‫ʹޙ‬ɼanalyze particle ‫ػ‬࣍‫ूڽ‬ମαΠζ͕௿‫͞ݮ‬Εͨͱߟ͑ΒΕΔɽ͔͠͠ɼ

ೳΛར༻ཻͯ͠ࢠͷ໘ੵΛࢉग़ͨ͠ɽͦͯ͠ɼཻࢠΛsn ͱ ne ͰγϣϧμʔҐஔʹେ͖ͳҧ͍͸‫ݟ‬ΒΕͣɼਅԁͱԾఆͯ͠ɼཻࢠ໘ੵΛཻࢠ௚‫΁ܘ‬ม‫ͨ͠׵‬ɽͳ྆ऀͷҰ࣍‫ूڽ‬ମαΠζ͸ಉఔ౓ͱߟ͑ΒΕΔɽ͓ͨͩɼࡱӨϐΫηϧαΠζͱɼೋ஋Խͨ͠ࡍͷϊΠζΛ

q = 0.04 nm−1ʹ͓͍ͯϓϩϑΝΠϧʹ͕ࠩ‫ݟ‬ΒؑΈͯɼ௚‫ ܘ‬3.5 µm Ҏ্Λཻࢠͱͯ͠‫ͨ͠ͳݟ‬ɽ·Εɼߴ࣍ߏ଄ʹ͕ࠩ͋Δ͜ͱ͕ࣔࠦ͞ΕΔɽߏ଄৘ใ

ͨෳ਺ຕͷஅ໘૾Λղੳ͠ɼฏ‫ۉ‬஋Λࢉग़ͨ͠ɽཻࢠ

ΛΑΓఆྔతʹධՁ͢ΔͨΊɼUnified function [2, 3]௚‫ܘ‬Λԣ࣠ʹɼཻࢠ਺Λॎ࣠ͱͯ͠ϓϩοτཻͨ͠౓͠ɼq < 0.3 nmΛར༻ͯ͠ղੳͨ݁͠ՌΛ Table. 3 ʹࣔ͢ɽҰ࣍‫ूڽ‬ମαΠζ R ͸ɼnn>snne>se ͱͳΓɼ෼ࢄॲཧʹΑͬͯҰ࣍‫ूڽ‬ମαΠζ͸‫ݮ‬গͨ͠ɽ·ͨɼҰ࣍‫ूڽ‬ମαΠζͷ௿‫ʹݮ‬൐ͬͯɼҰ࣍‫ूڽ‬ମ਺ Nr͸૿Ճ͠ɼҰ࣍‫ूڽ‬ମ͕઎ΊΔମੵ Vr ͸‫ݮ‬গͨ͠ɽҎ্ͷ݁ՌΑΓɼγϦΧ෼ࢄॲཧʹΑΓҰ࣍‫ूڽ‬ମαΠζ R ͕খ͘͞ͳΓɼ෼ࢄੑ͕޲্ͨ͜͠ͱ͕֬ೝͰ
͖ͨɽͨͩ͠ɼ෼ࢄॲཧํ๏͕ҟͳΔ sn ͱ ne ʹߏ଄͕ࠩ‫ݟ‬ΒΕͳ͔ͬͨʹ΋ؔΘΒͣɼώεςϦγεϩε
ͱϖΠϯޮՌʹ͕ࠩ͋Γɼ෺ੑࠩΛઆ໌͢Δʹ͸ࢸΒͳ͔ͬͨɽ͔͠͠ɼSAXS ϓϩϑΝΠϧͷ௿ q ϨϯδྖҬʹΘ͔ͣͳ͕ࠩ͋Δ͜ͱ͔Βߴ࣍ߏ଄ʹҧ͍͕͋
Δ͜ͱ͕ࣔࠦ͞Εͨɽͦ͜ͰɼX ઢϥϛϊάϥϑΟʔ๏Λ༻͍ͯɼϚΠΫϩΦʔμʔͰͷγϦΧ෼ࢄධՁΛߦͬͨɽ

Fig. 3 ʹ X ઢϥϛϊάϥϑΟʔଌఆͰಘΒΕͨஅ໘૾Λࣔ͢ɽଌఆ৚݅͸ɼ1 ౤Өͷ࿐ޫ࣌ؒ=0.15 sɼ౤Ө਺=3000 ຕɼαϯϓϦϯά਺=1920×1440 pixels
Ͱ͋ͬͨɽFig. 3. Cross-sectional images of silica compoundedࠇ͍ࣸͬͯ͘Δ෦෼͕ΰϜ૚ɼനཻ͍͕γϦΧ‫ूڽ‬rubbers using X-ray Laminography.

մͰ͋Δɽnnɼsnɼneɼʹ͸ͱ͜ΖͲ͜Ζʹେ͖ͳཻ– 39 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5, 6 (2016, 2017)

Fig. 4. Particle size distribution of silica in rubbers.

Fig. 5. The total number of particles with a diameter
larger than 7.5 µm.

෼෍ΛɼFig. 4 ʹࣔ͢ɽ·ͨ Fig. 5 ʹ 7.5 µm Ҏ্ͷཻࢠ਺ͷ߹‫ܭ‬Λࣔ͢ɽࠓ‫ޙ‬ͷ՝୊

෼ࢄॲཧ͍ͯ͠ͳ͍ nn ʹରͯ͠ɼͦͷଞ෼ࢄॲཧ
αϯϓϧ͸ɼ͢΂ͯͷ௚‫ݮ͕਺ࢠཻͰܘ‬গ͍ͯ͠Δɽ͜Ε͸෼ࢄॲཧʹΑͬͯɼγϦΧ‫ूڽ‬մ͕খ͘͞ͳΓɼࡱӨϐΫηϧαΠζҎԼͷ‫ूڽ‬մ͕૿Ճͨͨ͠Ίͩͱߟ͑ΒΕΔɽଓ͍ͯɼ෼ࢄॲཧͨ͠αϯϓϧ಺Ͱൺֱ
͢Δͱɼ4 µm ҎԼͷཻࢠʹେ͖ͳ͕ࠩ‫ݟ‬ΒΕɼཻࢠ਺͸ sn>ne>se ͱͳΓɼ຤୺มੑϙϦϚʔͷޮՌ͕େ͖͍͜ͱ͕Θ͔ͬͨɽ·ͨଌఆ෼ղೳͷؔ܎͔Β 3.5µm ҎԼͷཻࢠ͸ධՁͰ͖ͳ͍͕ɼཻ౓෼෍ͷ܏޲͔Β༧ଌ͢Δͱɼ਺ඦ nm∼ ਺ µm ͷཻࢠ਺‫ݮ‬গʹɼγSAXS ͱϥϛϊάϥϑΟʔΛ૊߹ΘͤͯϑΟϥʔ֊૚ߏ଄ղੳΛߦͬͨɽϑΟϥʔ෼ࢄॲཧํ๏ʹΑΔ֊
૚ߏ଄ͷҧ͍Λ໌Β͔ʹ͢Δͱͱ΋ʹɼ෺ੑͱͷ૬ؔ
ߟ࡯·Ͱͭͳ͛Δ͜ͱ͕Ͱ͖ͨɽࠓ‫ޙ‬͸ɼSAXSɼϥϛϊάϥϑΟʔͷΈͳΒͣɼଟ֯తͳߏ଄ධՁΛߦ͍ࡐྉߏ଄ͱ෺ੑͱͷ૬ؔؔ܎Λղ໌͠ɼߴੑೳλΠϠ։ൃ΁ͱల։͍ͨ͠ɽ
ࣄ‫΁ۀ‬ͷߩ‫ݙ‬ϥϯΧοϓϦϯάࡎͱൺֱͯ͠຤୺มੑϙϦϚʔͷํຊ‫ڀݚ‬੒Ռ͸ɼΰϜ෺ੑͱߏ଄ͷ૬ؔཧղʹࢿ͢Δ

͕ޮՌ͸େ͖͍ͱࣔࠦ͞ΕΔɽ7.5 µm Ҏ্ͷཻࢠ਺΋ͷͰ͋ΓɼλΠϠ༻ΰϜࡐྉ։ൃ΁ͷߩ‫͕ͨͬ͋ݙ‬ɽΛ‫ݟ‬Δͱɼne>sn>se ͱͳΓɼγϥϯΧοϓϦϯάࡎʹΑΔޮՌ͕େ͖͍͜ͱ͕Θ͔ͬͨɽΑͬͯɼ෼ࢄॲ

ࢀߟจ‫ݙ‬

ཧํ๏ʹΑΒͣ਺ඦ nm∼ ਺े µm ͷεέʔϧͰཻࢠ[1] େߐ༟জɼ৓ग़݈༎ɼඛ઒༃ߒɼࡾӜ૱Ұ࿠ɿฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू 4ɼ24-26 (2015).
[2] G. Beaucage, J. Appl. Cryst. 28, 717-728 (1995).
[3] T. Koga et al., Macromolecules 41, 453-464(2008).

਺ͷ‫ݮ‬গ͕‫ݟ‬ΒΕΔ͕ɼ෼ࢄॲཧํ๏ʹΑͬͯޮՌ͕
͋Δཻࢠ‫ʹܘ‬͸͕ࠩ͋ΓɼγϥϯΧοϓϦϯάࡎॲཧ͸ɼ7.5 µm Ҏ্ͷཻࢠʹޮՌ͕େ͖͘ɼ຤୺มੑϙϦϚʔ͸਺ඦ nm∼ ਺ µm ͷཻࢠʹޮՌ͕େ͖͍ͱߟ
͑ΒΕΔɽ·ͨΰϜ෺ੑͱরΒ͠߹Θͤͯߟ͑Δͱɼ

7.5 µm Ҏ্ͷཻࢠΛ‫ݮ‬গͤ͞ΔͱϖΠϯޮՌ͕௿‫ݮ‬͞Εɼ਺ඦ nm∼ ਺ µm ͷཻࢠΛ‫ݮ‬গͤ͞Δ͜ͱ͸ώεςϦγεϩεͷ௿‫͕ͳͭʹݮ‬Δ͜ͱ͕ࣔࠦ͞ΕΔɽ
ͨͩ͠ɼώεςϦγεϩεͷ௿‫ݮ‬͸୯ʹγϦΧ෼ࢄͷվળ͚ͩͰͳ͘ɼϙϦϚʔ຤୺มੑʹΑͬͯɼϙϦϚʔ຤୺ͷӡಈ͕཈੍͞ΕͨޮՌ΋ߟ͑ΒΕΔɽΑΓਂ͍ٞ࿦΁ൃలͤ͞ΔͨΊʹ͸ɼϑΟϥʔ෼ࢄධՁͷΈͳΒͣଟ֯తͳධՁ͕ඞཁͱͳͬͯ͘Δɽ

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