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Nippon Steel Chemical Co.,Ltd.
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Nippon Steel Chemical Co.,Ltd.
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Nippon Steel Chemical Co.,Ltd.
(A)
(B)
(C)
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Nippon Steel Chemical Co.,Ltd.
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Nippon Steel Chemical Co.,Ltd.
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Nippon Steel Chemical Co.,Ltd.
200
0 100 200 300
T g
PIPBIPBO
300
400
500
400
T
d
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Nippon Steel Chemical Co.,Ltd.
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Nippon Steel Chemical Co.,Ltd.
N N O
O
O
O
O
N N
O
O
O
O
N N
OO
O
O
O
O
O
N N
O
O O
O O
NC
CF3
CF3
N
O
O
O
O
O C
CF3
CF3
O
N N
OO
O O
O O O
N N O O
O
O
O
O
N N
O
O
O
O
O C
CH3
CH3
C
CH3
CH3
O
Sky Bond
LARC-TPI
LARC-CPI
NR-150
AURUM
KAPTON
UPILEX
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Nippon Steel Chemical Co.,Ltd.
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Nippon Steel Chemical Co.,Ltd.
Si OH2C SiCH3CH3
CH2O SiCH3
CH3Ar1 N
O
O
NAr2
O
Ar1 N
O
O
N
O
OO
3 3lx
yCH3CH3
1) 2)1) 2)
Ar1 Ar2 : Aromatic structure
1)N. Furukawa, M. Yuasa, F. Omori and Y. Yamada, J. Adhesion, 59
(1996) 281 .2)N. Furukawa, M. Yuasa, J. Adhesion Society .Japan.,
33(2), (1997) 63 .
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Nippon Steel Chemical Co.,Ltd.
1.0
(kgf/mm2)
(1MHz)
(wt%)
Film
.. ..
..
Poor Good
Poor Good
Virnish Poor Exellent
..
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Nippon Steel Chemical Co.,Ltd.
SPISPI
Poly amic acid
at 25 in NMP / Xylen
Solution imidization at 160in NMP / Xylen
Aromatic carboxlic dianhydride
Aromatic diamine
SPIsolution
Si OH2C Si
CH3CH3
CH2 NH2O Si
CH3
CH3
3lCH3CH3
H2N 3
Cast on glass plate and dry at 100Heat at 150
SPISPI--A,BA,Bfilmsfilms
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Nippon Steel Chemical Co.,Ltd.
SLSS(Mpa)Initial (F.M)*1
SLSS(Mpa)Initial (F.M)
- 0 28.4 (co) 12.7 (co)10 28.9 (co) 29.4 (co)20 18.1 (co/ad) 9.8
(ad)30 14.2 (co/ad) 4.9 (ad)10 28.6 (co)20 20.2 (co/ad)30 6.5
(ad)
Siloxanecontent(wt%)
Mw ofSiloxanediamine
SPI (Type A) SPI (Type B )
750
1200
SPISPI))
Table 2Single lap shear strength of SPI at initial
Single lap shear strength(SLSS) (JIS K 6850)
Adhesive filmSteel (JIS G 3141)
Bonding pressure:196MpaBonding temperature:Tg + 50
*1 Fracture mode of SPI films (co:cohesive, ad:adhesive)
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Nippon Steel Chemical Co.,Ltd.
Fig.2Fig.2Relationship between the content of Relationship
between the content of Siloxane diamineSiloxane diamine and and
TgTg , Tensile modulus of SPI, Tensile modulus of SPI
0
50
100
150
200
250
0 10 20 300
10
20
30
40
Tg(
)
Tens
ile m
odul
us (M
pa)
Siloxane content (%)
Tg
SPISPI--
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Nippon Steel Chemical Co.,Ltd.
SPISPI--
4
6
8
10
12
14
0 2 4 6 8 10Ar sputtering time (min)
Rel
ativ
e pe
ak a
rea
of S
i (%
)
750-15wt% (4.6%)
750-30wt% (8.6%)
1200-30wt% (9.6%)Siloxane
Fig.3 Results of XPS analysis of SPI filmsFig.3 Results of XPS
analysis of SPI films
(Ar sputtering rate : 30-40 /min)
(Si bulk %)
Si
2020wtwt
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Nippon Steel Chemical Co.,Ltd.
SLSS(Mpa)After treatment*1 (F.M)
SLSS(Mpa)initial
- 0 17.6 (co) 28.410 28.0 (co/ad) 28.920 13.7 (co/ad) 18.130 7.8
(ad) 14.210 27.2 (co) 28.620 4.3 (ad) 20.230 1.5 (ad) 6.5
SPI (Type A)
1200
Siloxanecontent(wt%)
Mw ofSiloxanediamine
750
SPISPI))
Table 3Single lap shear strength of SPI after treatment
*1 After 72hr at 25, 90%RH(JIS K 6856)
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Nippon Steel Chemical Co.,Ltd.
SPISPI--22
Siloxanecontent(wt%)
Mw ofSiloxanediamine
Moisturesorption(wt%)
WVPC*1Retention ofSLSS (%)*2
0 - 0.6 0.4 66
750
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Nippon Steel Chemical Co.,Ltd.
PolysiloxanePolysiloxane contentcontent
(Surface tension)
Elastic propertyFluidity (Viscosity)
(stress relaxation)
Lap shear strength
Surface Property
Sing
le la
p sh
ear
stre
ngth
Sing
le la
p sh
ear
stre
ngth
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Nippon Steel Chemical Co.,Ltd.
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Nippon Steel Chemical Co.,Ltd.
Si OH2C SiCH3CH3
CH2O SiCH3
CH3Ar1 N
O
O
NAr2
O
Ar1 N
O
O
N
O
OO
3 3lx
yCH3
Functional groupFunctional group
-)
1)M.Yuasa,et al., J.Photopolym. Sci. Technol., Vol.16,
No.2,227-232 (2003).
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Nippon Steel Chemical Co.,Ltd.
SiCH3
OH2C SiCH3
CH3CH3CH2O Si
CH3O Si
CH3
CH3Ar1 N
O
O
NAr2
O
O
Ar1 N
O
O
N
O
O
3 3l mx y
HC CH2VmPI
Si-(OCH2CH3)2HCH3
/ H2PtCl6
SiCH3
OH2C SiCH3
CH3CH3CH2O Si
CH3O Si
CH3
CH3Ar1 N
O
O
NAr2
O
O
Ar1 N
O
O
N
O
O
3 3l mx y
CH2CH2SiH3C (OCH2CH3)2SSmmPIPI
DEMS
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Nippon Steel Chemical Co.,Ltd.
SmPI
SiCH3
OH2C SiCH3
CH3CH3CH2O Si
CH3O Si
CH3
CH3Ar1 N
O
O
NAr2
O
O
Ar1 N
O
O
N
O
O
3 3l mx y
CH2CH2SiH3C (OCH2CH3)2
SmPIH2O
CH3CH2OH
SiCH3
OH2C SiCH3
CH3CH3CH2O Si
CH3O Si
CH3
CH3CH2
Ar1 N
O
O
SiCH3
OH2C SiCH3
CH3CH3CH2O Si
CH2O Si
CH3
CH3CH3
Ar1 N
O
O
CH2
CH2
NAr2
O
O
Ar1 N
O
O
N
O
O
NAr2
O
O
Ar1 N
O
O
N
O
O
3 3l mx y
3 3l mx y
SiOSi
H3C
CH3O
O
CC--SSmmPIPI
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Nippon Steel Chemical Co.,Ltd.
Table 5 Solubility of VmPI and C-SmPI films
Polymer DEMS 1)(wt%) (mol/mol) NMP THF CHCL3
V2PI-10 V2PSX 10 - S S SCC--SS22PIPI--1010--22 10 2.0 ISIS ISIS
ISISV2PI-30 30 - S S SCC--SS22PIPI--3030--22 30 2.0 ISIS ISIS
ISISV2PI-50 50 - S S SCC--SS2PIPI--5050--22 50 2.0 ISIS ISIS
ISISV4PI-30 V4PSX 30 - S S SCC--SS4PIPI--3030--11 30 1.0 ISIS ISIS
ISISV4PI-50 50 - S S SCC--SS44PIPI--5050--11 50 1.0 ISIS ISIS
ISIS
Polysiloxane Solvent solubility 2)
1) DEMS=[DEMS (mol)] / [Vinyl group (mol)].]
2) S : Soluble, IS : Insoluble
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Nippon Steel Chemical Co.,Ltd.
Fig. 4 Temperature-dependent changes in storage modulus(E)and
loss modulus (E) of the polyimide film of V4PI-30 and
C-S4PI-30-1.
DMA
0.0001
0.001
0.01
0.1
1
10
-200 -100 0 100 200 300 400Temperature ()
V4PI-30
C-S4PI-30-10
E, E
(G
Pa)
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Nippon Steel Chemical Co.,Ltd.
Table 6 Thermal and mechanical property of VmPI and C-SmPI
films
TMA
a) Thermal deformation temperature determined by TMAb)
Determined by TMA (Temperature range; 50-100)c) Determined by TMA
(Temperature range; Thd-Thd+50)
Polymer Thda)
1b)
2c) Tensile
modulusTensile
strength() (ppm/) (ppm/) (Gpa) (Mpa)
V2PI-10 192 116 >5000 2.62 79.4C-S2PI-10-2 199 130 23002300
2.65 83.3V2PI-30 150 155 >5000 1.17 41.2C-S2PI-30-2 158 132
601601 1.23 35.3V2PI-50 98 204 >5000 0.35 11.8C-S2PI-50-2 100
189 354354 0.610.61 23.523.5V4PI-30 154 105 >5000 1.22
47C-S4PI-30-1 156 109 740 1.35 50V4PI-50 97 201 >5000 0.36
11.8C-S4PI-50-1 102 185 348348 0.590.59 27.427.4
1
2
Thd
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Nippon Steel Chemical Co.,Ltd.
1) mol%= [H2O (mol)]/[DEMS(mol)]2) Determined by TMA
(Temperature range; 50-100)3) Determined by TMA (Temperature range;
Thd-Thd+50)4) Caluculted from Monny-Revins equation
Table 7 Effect of water addition on the thermal properties of
C-SmPI films.
Polymer Amount of H2O1)
12)
23) Cross linking
density4)
(mol%) (ppm/) (ppm/) (10-3 mol/cm3 )C-S4PI-30-2 0 105 740
0.40C-S4PI-30-2' 20 109 243243 0.890.89
C-S4PI-30-5 0 109 362 0.61C-S4PI-30-5' 20 106 161161
1.661.66
C-S4PI-30-10 0 106 250 1.10C-S4PI-30-10' 20 115 108108
1.681.68
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Nippon Steel Chemical Co.,Ltd.
Test condition : 250Test condition : 250, 100hr, 100hr Test
condition : 25Test condition : 25, 95%RH, 72hr, 95%RH, 72hr
Figure 5 Adhesive property of VmPI and C-SmPI on glass after
treatment (a) V2PI-10,(b)S2PI-10-2, (c)S2PI-10-5, (d) S2PI-30-2,
(e)S2PI-30-5
0
20
40
60
80
100
( a ) ( b ) ( c ) ( d ) ( e )
Res
udur
e (%
)
0
20
40
60
80
100
120
( a ) ( b ) ( c ) ( d ) ( e )R
esud
ure
(%)
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Nippon Steel Chemical Co.,Ltd.
SmPISilicate compound /H2O
-HOR
SiCH3
OH2C SiCH3
CH3CH3CH2O Si
CH3O Si
CH3
CH3CH2
Ar1 N
O
O
SiCH3
OH2C SiCH3
CH3CH3CH2O Si
CH2O Si
CH3
CH3CH3
Ar1 N
O
O
CH2Si
O
Si
H3C
O
O
CH2
Si
Si
NAr2
O
O
Ar1 N
O
O
N
O
O
NAr2
O
O
Ar1 N
O
O
N
O
O
3 3l mx y
3 3l mx y
OO
OO
OSiO
O
SiOO
O
CH3
SiO O
O
Si
O
Si
O
O
O
Si
O
O OO
Si OO
SiO
OO
Si OO
Si(OR)4
PolyimidePolyimide--siloxanesiloxane //Silica hybrid
materialsSilica hybrid materials
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Nippon Steel Chemical Co.,Ltd.
Material Polymer(2.0g)TEOS(mmol) Transparency
( a ) S4PI-50-2 - TransparentTransparent( b ) S4PI-50-2 0.7
TransparentTransparent( c ) S4PI-50-2 2.0 TransparentTransparent( d
) S4PI-50-2 3.3 TransparentTransparent( e ) V4PI-50 3.3 Opaque
SPI/Silica hybrid film
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Nippon Steel Chemical Co.,Ltd.
SPI/Silica hybrid films
Temperature /0.0001
0.001
0.01
0.1
1
10
-100 0 100 200 300
E
, E
/ GPa
( b )( d )
Material Polymer (2.0g) TEOS (mmol)
( a ) S4PI-50-2 0.0S4PI-50-2 0.7S4PI-50-2 3.3
---100 0 100 200 3000.0001
0.001
0.01
0.1
1
10
tan
Temperature /
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Nippon Steel Chemical Co.,Ltd.
--//
X O
N
O
NR
R
BXZ)BXZ) 1)1)
TdTdTgTg
1)T.Takeichi, R.Zeidam, T. Agag, Polymer, Vol.43, 45(2002) .
OH
N
R
OH
X X
N
R
OHOH n
((
SPISPI
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Nippon Steel Chemical Co.,Ltd.
BXZBXZSPISPI
X OHHO
R-NH2X O
N
O
NR
R
HCOH
100120
X=SPI/BXZSPI/BXZ
SPIsolution
Cast on glass plate and dryed at 100 Heated at 150
BXZ
SPI/BXZSPI/BXZfilmsfilms
BXZBXZ
BXZ-x
CCH3
CH3CH2 S O
y:80%
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Nippon Steel Chemical Co.,Ltd.
SPI/BXZSPI/BXZ
Fig.6 Glass transition temperature of SPI/BXZ filmsFig.6 Glass
transition temperature of SPI/BXZ films
020406080
100120140160180200
0 10 20 30 40BXZ content (wt%)
Tg
()
200Cure
150Cure
C O
N
O
N
CH3
CH3
BXZ-C(CH3)2
OH
N
Ph
OH
C C
N
Ph
OHOH
H3C CH3 H3C CH3
n
>150
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Nippon Steel Chemical Co.,Ltd.
SPI/BXZSPI/BXZ
BXZ-C(CH3)2
Fig.7 Single lap shear strength of SPI/BXZ filmsFig.7 Single lap
shear strength of SPI/BXZ films
C O
N
O
N
CH3
CH3
02468
101214161820
0 10 20 30 40BXZ content (wt%)
SLSS
(Mpa
)
Single lap shear strength(SLSS) (JIS K 6850)
Adhesive filmSteel (JIS G 3141)
Bonding pressure:196MpaBonding temperature:Tg + 50
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Nippon Steel Chemical Co.,Ltd.
SPI/BXZSPI/BXZ
SLSS
(Mpa
)
BXZ-X(30wt%)
Fig.8 Single lap shear strength of SPI/BXZ filmsFig.8 Single lap
shear strength of SPI/BXZ films
X ON
O
N
0
2
4
6
8
10
12
14
16
18
20
non CH2 S - O
