Vol.6Vol.6

20121017

URL http://www.yamakin-gold.co.jp 7838505

543-0015 TEL.(06)6761-4739()FAX.(06)6761-4743

ISO 9001/13485ISO 14001

QAIC/JP/0455

1.

2.

3.

4.

5.

6. TBBO

2

3

9

18

19

20

2 3

1.

0.1

1)

2)

2.

abc

a

OO

100

3)BPO

OO

( ) OO R 2 (

BPO 1

OO 1

3 g/mlBPO

4)BPO 25 1 BPO

HPLC BPO

C6H5CO2H

C6H5CO2CH3 0.91

C6H5COO

1

BPO

C

O

O O C

O

C

O

O-CO2

C

O

O O C

O

RC

O

O R O C

O

+

BPO

4 5

C6H5CO2C2H5

BPO BPO

79.81 2 28.5

43.0 5)BPO 1 kdT 3)

kd (s-1) = 1.20 x 1013exp(-120.5 kJ/RT)

BPO BPO

C6H5COOO

CH3CH()OCH2CH3 BPO 1

BPO

PEOBPO

3 PEO/ BPO PEO400

BPO

70PEG400 80PEG400

BPO [BPO]1.0

[BPO]1.5 6)

2590 22PEG

2,2AIBNBPO

2 NN 2 CN 1 AIBN

1 60

BPO kd 3)

kd (s-1) 1.58 x 1015 exp (-128.9 kJ/RT)

100

80

60

40

20

0

[BPO

] (%

)

0 2 4 6 8 10

125

BPO = 3g/ml

2 (, , ) (, , )25

BPO () (, )

3PEG400PEG400/BPO (0.5 mg/g) 25

0 2 4 6 8 10

12

16

12

4

0

BPO

(n

mol)

8

BPO (MeOH)

C6H5CO2Me (MeOH) C6H5CO2H (MeOH)

BPO (EtOH)

C6H5CO2Et (EtOH)

C6H5CO2H (EtOH)

PEG40090%PEG400

80%PEG400

70%PEG400

[BPO

]/[B

PO

] 0

1.0

0.8

0.6

0.4

0.2

0

0 20 40 60 80

2AIBN

H3C H3C H3C H3CC

CH3

CN

C

CH3

CN

C

CH3

CN

C

CH3

CN

C

CH3

CN

C

CH3

CN

N N CH3N2

CH3 H2C CH

CH3

CN

+ +

6 7

NN AIBN (CH3)2CCN CN

100CN

max 365 nm

AIBN

60 CN

BPO

AIBN AIBN

1/1000

AIBN AIBN

CN 2,2

AIBN

(b)

H2O2

HOHO- N,N1, X H

37), 8)

BPO pN,NMDMA, 1, X CH3 37pEDMAB, 2 BPO BisGMA (3)UDMA (4) TEGDMA (5) 8) MDMA 1,

X CH3 EDMAB (2) pCH3 pCO2C2H5 EDMAB (2) CQBPO

BPO/

< 0.1 0.2

Hammett

3 BPO

9)Hammett H 0

pCl 0.23pCH3 -0.17 "p"

2,2

H3C C

CH3

CN

N C C

CH3

CH3

H3C C

CH3

CO2CH3

N N C

CH3

CH3

CO2CH3

3

C

O

O O C

O

NCH3

CH3

C

O

O C

O

O N

CH3

CH3+ +

N

CH3

CH3N

CH3

CH2+ H

BPO

H3C

H3CCO2C2H5N

N

H3C

H3CX p N,N1

4N,NEDMAB, 2

O

O O O O

O

OH OH

O

OO N

O

H CH3 CH3

CH3

N O

H

O

O

O

O

O O O O

O

OC2H5 OC2H5

O

OO

OO

O

BisGMA3

UDMA4

TEGDMA5

BisEMA6

8 9

(c)

BPO AIBN

RCOR CO R R

R, R

70 80 kcal/molR

RCO

RCOR R R COR

COR

II CH3CH2D n*

RCOR

3.

CQ (max 460 nm, max

46 L/molcm10))

CQ

Vol. CQ

(RCH2)3N CQ

H+ CQH RCH()NRR

. CQ

0.1 0.2

m-CH3

p-CH3H

p-Br

p-Cl

-0.2 -0.1 0 0.3

Hammett

3.0

2.0

1.0

0.7

0.5

0.3

0.2

0.1

k d x

10

3 (L/

mols

)

4

2--2-

C C

CH3

OH

CH3

UVO

C C

CH3

OH

CH3

O*

C

O

C

CH3

OH

CH3

+

5

CUV

O

C

O*

C

OH

+

CH3CH2DCH3CHD

4BPO/

Hammett ()

5CQ

450

(nm)

350 400 500 550

40

30

20

10

0

(L

/mol

cm)

h

R

N CH2R''

R'

O

O

O

O

- +OH

O

+

R

N CHR''

R'

O

O

+

R

N CH2R''

R'

R

N CH2R''

R'

6

CQH

3

H+

CQ

10 11

CQ/ CQH

RCH()N(R)(R)

TEGDMA11) Bis-GMABis-EMA, 12) CQ/

Rp (s-1) Rp NNPG, 14, X H

N12, 2 CQ 7.32

MDMA1, X CH3 7.24

13, CQ

CQ/

N,N ff0 N,NfX 13)

Rp (kp/kt0.5)[M]I0.5i0.5

i H f

i H CQ f Rp2/H ( f Rp2/H).

CQ/

CQ

SOMO HOMO

CQ/p NPG14, X OCH3, C(CH3)3, CH3, H, C(O)CH3, CO2C2H5, CN TMPTA (15)/BisEMA (6)

Hammett 14)

6CQ/pN,N pXX = CN (1)C(O)C6H5 (2)C(O)C6H4CH(CH3)2 (3) CO2CH3 (4)H (5)CH3 (6)

1CQ/TEGDMA (3) Bis-EMA (6)

7, R = C4H9

8

N,N -9 N,N - (DMAEMA, 10)2,2,6,6-11, R = H

1,2,2,6,6-11, R = CH3

4- (N,N - ) 1, X = CHO4- (N,N - ) 1, X = CNMDMA1, X = CH3

N,N -1, X = HN -1213

NPG14, X = H

0

1.4

0

12.1

21.3

23.2

11.5

20

10

Rpmax x 104 a)(s-1)

0.4

4.0

37.9

40.7

44.4

46.9

4.3

0.5

1.2

Rpmax x 104 b)(s-1)

8.71

8.37

7.74

7.59

7.23

7.33

7.6

7.24

7.38

7.32

7.25

8.41

a) TEGDMA, [CQ] = 6 x 10-2 mol/L, [ ] = 6 x 10-3 mol/L11).

b ) Bis-EMA, [CQ] = 0.25 wt%, [ ] = 0.3 wt%12).

RNH2 (7) (8) (9) (10) (11)C2H5NCH3

CH3N R

CH3

CH3

CH3CH3

NHCH2CO2HCH3NH 12 13 14

CH2 C

CH3

CO2CH2CH2N

CH3

CH3

X

HNC2H5

C2H5

HN

(5)

(6)

(4)

(3)

(2)

(1)

3.0

2.0

1.0

0

-1.0

log (f x/f 0)

-0 .2 0 0.2 0.4 0.6 0.8

Hammett

H2C CHCO2

H2C CHCO2CH2

H2C CHCO2

CH2

C

CH2

C2H5 22( )1,3(TMPTA, 15)

12 13

CQ/

12)

7, R C4H9 2,2,6,611, R HCQ

CQ

CQ

Rp -d[M]/dt (kp2/kt)0.5{[A]I0CQ[CQ]/(k3 + kel[A])}0.5[M] 12kp kt [A] I0 CQ CQ 468 nm 40 L/molcmk3 CQ kel CQ k3

14 15

1 NPG14, X H CQ EDMAB2

NPG14, X H

6 15) NPG14, X

HCO2H CO2

C6H5NHCH2 , 17 CO2 CQ

NPG

NPG (14, X H)

15)EDMAB2CQ NPG

pC(CO)CH3pCOOH pCO2C2H5 EDMAB2

CQ , NPG18, X H

CO2 C6H5NHC()(CH3)2

(19) NPG (14) (17) NCH2

NPG14, X HpCH3C(O) pCO2H 15)

CQ/DMAEMA10 UDMA4BisGMA3 BisEMA6

10CQ/

CQ CQ

UDMA4 BisGMA3 BisEMA6

UDMA4

UDMA4 DAMEMA10 1116)

9EDMAB (2, ) NPG (14, X = H, ) CQ//

EAEPA (40%)DEBAAP (> 20%) (< 40%) pH (A)

(B)

(A)

0 2 4 6 8

pH

3

2

1

R p x

10

3 (m

ol/L

s)

0

(B)

0 10 20 30 40 50

(%)

4

3

2

1

0

R p x

10

3 (m

ol/L

s)

NPG14, X = H 17

8

CQ

NOH

OH

CQ

NO

OH

CQH

N

H

+ + +

H

H

H

2CQ/NPG

H, H

H, H

H, H

H, C6H5

CH3, CH3

CH3, CH3

19

21

20

19

11

9

4EDMAB (2)

H

C(=O)CH3

CO2H

H

H

COOC2H5

NPG a)

R1R2 pXRp x 103mol/Lsb)

2

95

47

5

15

73

hc)

aXC6H4NH(R1)(R2)CO2H

bEAEPA (40%), DEBAAP (20%), (40%), pH = 1.2, CQ (0.022 mmol/g), (0.022 mmol/g)

c42

O

O

OP

OOH

OH

O

N N

O

2[4( )2 ] (EAEPA)

N,N1,3 ( ) (DEBAAP)

9

,N18

19

HN

CC

OH

O

H3C CH3

CQ NHCQH+C

COH

O

H3C CH3

HN

CCH3

CH3

16 17

CQ CQ/

BisGMA (3) /TEGDMA (5) (50/50 wt/wt) 0.7 wt% CQ0.35 wt%

DAMEMA10 0.05 wt% 2,6t4BHTLED CQ

CQ 0.07 0.01 10)

11,2PPD (20), max 410 nm

LED 400 nm

PPD (20) CQ max 470 nmCQ

CQ PPD (20)

CQ/N,N21 PPD (20) CQ BisGMA (3), UDMA (4) TEGDMA (5)

CQ PPD (20) 17)

CQ/EDMAB (11) PPD (20) CQ/EDMAB (11)

18), 19)

CQ/

Ph2IPF6, 22 10 CQH

CQ 20)Ph2IF6 (22

TEGDMA (5) /CQ/TeMA16CQ Ph2IF6

(22) CQ

223

CQ/ Ph2IPF6 (22) 21)

CQ EDMAB2DMAEMA

(10)

10CQ1 wt%DMAEMA10

= 4 mW/cm2

11CQ

= 4 mW/cm2

UDMA (4)

BisGMA (3)

BisEMA (6)

s

0 20 40 60 80 100

0.8

0.6

0.4

0.2

0

s

UDMA4

BisEMA6

BisGMA3

0 20 40 60 80 100

0.8

0.6

0.4

0.2

0

C C

O O

CH3 N

CH2CH2CN

CH2CH2CN

11,PPD, 20 N,N (21)

10

+ + + +

+ + + +

OH

O

R

N CHR''

R'

IPF6-

O

O

I H+PF6-

H+PF6-IPF6-

I

R

N CHR''

R'

Ph2IPF6 (22)

Ph2IPF6 (22)

CQH CQ

H2CC

CH3

CO

CH2

H2C

OP

O

OH

OHO

223

18 19

4.

CQ/ EDMAB (2

2,4,6TMDPO, 24

11

(CH3)3C6H4C()O (C6H5)2P()O

0.5 0.7 22)C(O)P

ArC(O)P(C6H5)2

Ar C6H5< < 2

CH3C6H4 40 < 2,4,6(CH3)3C6H2 (24)>

2,4,6

BTMPO, 25 12

23)

(MMA) CQEDMAB (2

CQ 24)

5.

12

TMDPO24, max 381 nm, max 520 L/molcm BTMPO25, max

370 nm, max 300 L/molcmLED

PPD20 LED LED

CQ 470 nm 25), 26)

CQ

PPD20

CQ PPD20

PPD (20) CQ

( ) 0.05

wt% BHT BisGMA (3)/TEGDMA (5) (50/50 wt/wt)

(KHN) (Rpmax) (CIELab b ) 27)

11

C

O

P

O

CH3

CH3

H3C C

O

CH3

CH3

H3C P

O

+

TMDPO (24)

12

BTMPO, 25

C

O

P

O

C

CH3

CH3

H3C

OH3C

H3C

CH3 P

O

C

OH3C

H3C

CH3C

O

CH3

CH3

H3C +

TMDPO (24)

BTMPO (25)

PPD (20)

LED

600

400

200

0

(L

/molcm

)

350 400 450 500 550

nm

CQ

12

3 ()

(wt%)

0.33

0.33

0.17/0.17

0.17

0.17

0.17

EDMAB (2)

(wt%)

1

1

0.5/0.5

0.5

0.5

0.5

EDMAB (2)

CQ

PPD (20)

PPD (20)

20 21

FTIR (%)

CQ (%) Rpmax (%/s) KHN (kgf/mm2) CQ CQ 0.6 wt% CQ

CQ/

28)

0.1 1 ns

6.TBBO

Bu3B

Bu3B

Bu3B

29), 30)

Bu3B + O2 Bu2BOOBu (1)

Bu2BOOBu + Bu3B Bu3BBuO + Bu2BO (2)

Bu2O + Bu 3B BuOBBu2 + Bu (3)

Bu2BO + Bu3B Bu2BOBBu2 + Bu (4)

Bu3B MMA

75

BuOBBu23BuOBBu2 30)

(TBBO) (PMMA)/MMA

PMMA/MMATBBO 1), 31)

PMMA/MMATBBO

BPO/ 32)

20

20 / 0.3 0.5

30)

PMMA PMMA + MMA +

TBBOBPO/ MDMA (1, X CH3) CQ/ DMAEMA (10) PMMA/MMA

30 24 25

33)

CQ/DMAEMA (10) > BPO/MDMA (1, X CH3) >> TBBO

TBBO

MMATBBO MMA/

MMA

MMA MMA

PMMA/MMA 1), 31)BPO/

BPO MMA BPO

TBBO

MMA 34), 35) PMMA/MMATBBO

FeCl33 wt%10 wt%

MMA TBBO

FeCl3

5PMMA/MMATBBO

99

100

100

PMMA (%)

BPO (1%)

99

99

92

MMA (%)

DMA (1, X = CH3) (0.5%)

CQ (0.5%), DMAEMA (10) (0.5%)

TBBO (8%)

6TBBOPMMA/MMA

a) 5

30

24

1

4

MMA (%)

8.15

1.96

0.84

0.48

TBBOa)

8.39

4.50

3.67

3.45

BPO/MDMA (1, X = CH3) a)

9.19

7.99

7.28

6.79

CQ/DMAEMA (10) a)

4 ()

CQ ()

CQ ()

PPD (20) ()

PPD (20) ()

CQ/PPD (20) ()

CQ/PPD (20) ()

65.53

76.23

67.14

72.18

62.40

75.16

(%)

3.1

5.2

1.7

3.8

2.1

4.6

Rpmax (%/s)

26.67

37.89

24.50

34.73

25.58

38.65

KHN (kgf/mm2)

+1.5

+7.1

+0.7

+10.0

+1.7

+8.1

b-

22

FeCl3

FeCl3

FeCl3

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O

HO OH

OOHO

OH

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404

4

134

134

163

167176 ()

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2310

20121017

Vol.1 1200910

Vol.2 220102

Vol.3 20103

Vol.4 220107

Vol.5 20118

Vol.6 201210