Phthalocyanine

chr chromopho chromophore chromophore 20 ! 20 # 20 20 1928 &'( chromopho 20 20 chr 20 1928 0

chromophore 1928 & 20 7& 20 1928 87: 20 1928 chr0 20 1928 chromophore 1907 Braun 7
Tcherniac C(( 20 1928 20 1928 chromopho 20 1928 chromophore 20 1928 o-cyanobenzamide 20 20 1928 !& 20 1928 &'(' 20
J chromopho7 20 1928 C( 20 1928 7 chromopho chromophore Metal-free phthalocyanine chromophore 1927, de Diesbach
70 chromopho chromopho 20 ! 20 1928 treat coppercyanine chromophore 1,2-dibromobenzene boiling
quinoline 20 8 V chromopho !& 20 1928 Copperphthalocyanine C( chr 20
J07 20 1928 #7 chr 20 0 20 1928 chromopho 20 chr 20 20
20 1928 '' 7 chromopho J7 20 1928 Scottish Dyes (J7 20 1928 7 chromophore chromophoJ(' ICI)
20 1928 7& phthalimide chromopho phthalic anhydride chromopho ammonia glass linter reactor 7 20 1928 &
!& chromophore '( 7 20 1928 chromophore !&' 7 20 1928 chromophore 7( 20 1928 20 chr77 chromopho 20 !
77 C( 20 20 1928 &'( 20 &7 chromopho chromophore ironphthalocyanine 20 iron 20 1928 ' reactor 20 chromophore
J7 20 1928 chromophore 20 1928 20 1928 J:( 20 1928 20 7 ammonia chromophore phthalic anhydride
chromopho 20 iron 0 20 1928 chr 20 J7 20 1928 20 1928 20 1928 20 1928 chromophore V: 20
20 1928 20 1928 20 phthalocyanine chr chromopho chromophore chromophore 20 20 1928 ( 20 1928 20 1928 20 #J( 20 1928 chromopho
chromopho7 chromopho 20 20 0 20 1928 20 20 1928 J: chr 20 7& 20 1928 isomer
chromophore (Unique molecular structure) C(0 chromophore
0B

N
CONH2

NH

N
N

N
N

CN

o-cyanobenzamide

N
Cu

HN

N
N

metal-free phthalocyanine

copperphthalocyanine

phthalo phthalocyanine
' phthalocyanine chromophore 20 1928 chromophore chromopho tetraaza derivative ' tetrabenzoporphin
7 20 1928 chromophore C( chromophore 16-membered ring 20 7 20 1928 chromophore ' carbon 7 nitrogen 20 1928 20 1928 &
7J0 20 1928 7 '&' chromophore 0 chromophore J7# &
chromopho chromopho7 20 1928 V&V chlorophyll 7 haem C( 20 1928 chromophore Porphyrin
derivative 20 chromopho chr!0 chromophore
R
H3C
N

CH3
C2H5

H3C
N

Mg
N

N
CH3

H3C

H3COOC

N
FeCl
N
CH3

H3C

R = CH3 : chlorophyll A
R = CHO : chlorophyll B

COOH

COOH
Haem

' 20 phthalocyanine chromopho chr0 20 1928 (0 20 # 20 20 1928 J:

20 J7 20 1928 ) 20 1928 0 chromophore ' copperphthalocyanine chromopho chromophore 20 1928 chromophore chromopho benzenoid 3 J chromopho
7 o-quinonoid 20 1928 1 J chromopho 20 1928 chr chromopho7 20 1928 #7 centrosymmetric 7 20 1928 J chromopho chromopho
0 chromophore chromophore 1 CC: 20 20 1928 ' C( 20 1928 chromophore 7 20 !J chromopho
chr 20 0 20 1928 20 1928 chromophore 20 1928 20 ' phthalocyanine chr chromopho chromophore aromatic 20 1928 electron 18 chromopho ( 20 1928 4n+2) & 20 !J chromopho chr 20 1928 &'(
chromophore 20 1928 7J' phthalocyanine chrJ' 20 1928 0 20 1928 7 UV/Visible '
metal-free phthalocyanine 1-chloronaphthalene JV chromopho7 20 1928 0 20 1928 7 2 V chromopho 20 20 1928 7 699 7
664 nm. ' 20 chromophore 20 1928 7J' phthalocyanine JV chromopho7 20 1928 0 20 1928 7V chromopho chromopho7
20 1928 7 20 0 20 1928 20 1928 chromopho metal-free compound. 20 chromopho chromophore ' 20
chromophore chromophore phthalocyanine chrJV chromopho!&-! 20 7-' chromopho 7 20 1928 20 1928
20 1928 J chr0 20 1928 7V chromopho near-infrared chromopho
Phthalocyanine chromophore 20 1928 7# chromophore 20 chromophore polyene 20 1928 20 1928 chromopho 20 chromophore electron donoracceptor chromogenic type.
V chromopho7' 20 1928 0 20 1928 7' chromophore 20 1928 7J' phthalocyanine '(0 20 1928 V&'7J
20 0 20 1928 7, J0 20 20 20 0 20 1928 chromopho 7! chromopho' chromopho 20 20 1928 & annelation chromopho 20 1928 20 1928 ( 20 1928
chromophoV&'7J 20 20 1928 20 1928 chromophore 7V chromopho7 20 1928 0 20 1928 77 20 1928 chromopho 20 1928 0V chromopho 670685 nm 20 chromopho 20 hypsochromic 20 1928 20 # PtPc ( 652 nm) 7 bathochromic shift 20 1928 20 #
PbPc ( 714 nm)
J0 20 20 20 0 20 1928 chromopho 20 1928 20 !J 20 1928 & bathochromic shift V copper hexadecachlorophthalocyanine 1-chloronaphthalene chr0 20 1928 7V chromopho 720 nm 20 !JJ chromophore ' chromopho
(C.I. Pigment Green 7)
! chromopho chromopho 20 20 1928 & annelation 20 1928 20 !J 20 1928 & bathochromic shift 20 20 1928 20 # 20 & 20 1928 0
20 1928 7' copper naphthalocyanine 20 784 nm (C( chromophore V chromopho near infrared V!J 20 1928 20 1928
'07 CD J security printing ) 20
max

max

max

max

max

N
N

N
Cu

N
N

N
N

copper naphthalocyanine

' 20 20 & 20 20 1928 7 20 1928 V 20 '! 20 1928 20 V chromophore

V chromopho!&-! 20 7-' chromopho 20 chromopho 20 V 20 1928 20 # copper phthalocyanine (C.I. Pigment Blue
15) C( chromophore 20 20 1928 chromopho7& 20 1928 V chromophore 20 J( 20 1928 &: 7 chromopho 20 1928 7& 7
20 1928 chromopho chromophore pigment !& 20 chromopho! 20 # 20 1928 J!& 7J&V& 20 1928
V 20 chr 20 20 chromopho 20 !77 7 chromopho chr 20 20

 20 1928 J& chr( 500C 7 chr 20 77 20 1928 20 1928 ! chr'' 20 1928 20 !7

C( chr 20 ! 20 1928 7VJ 20 1928 20 1928 20 # 20 1928 7& 20 1928 ! 20 1928 20 1928 chromopho chr
J:7J yield 20 0 20 1928
Copper phthalocyanine polymorphism 20 7( 20 1928 20 ! 2 - 7 -form
7 20 1928 3 20 - 7 -form 20 1928 chromopho 20 1928 0 chromophore

-form

-form

20 2 chromopho! 20 20 1928 20 1928 20 -form (parallel form) J!&

7 -form (herring bone form) J! 20 77 chromopho chr0# chromopho& chromopho 20 !
77 chr! -form chromopho 20 !77 20 J 20 1928 20 !J chr 20 chromophore 70 chromophore chromophore -form
( 20 1928 & single chlorine substituent 7 chromophore '' chromopho 20 1928 chromophore 70 chromophore
20 1928 20 1928 20 1928 20 1928 20 ! chlorination ' phthalocyanine J 16 !JJ C.I.
Pigment Green 7 7 20 1928 20 ! bromination J bromo- J bromochloro-copper phthalocyanine
(C.I. Pigment Green 36) C( phthlocyanine green chr 20 J& 20 1928
chromopho phthalocyanine chr 20 1928 & complex 20 1928 7J 20 1928 20 # 20 1928 V& copper
phthalocyanine 20 1928 chromophore 20 & 20 1928 20 # 20 1928 chromopho chr 20 J7#& 20 J 20 1928 20 1928 V
20 & 20 20 # 20 1928 20 1928 V metal-free phthalocyanine chromophore pigment ! 20 7
20 chromopho chr0 chromopho
20 1928 V chromophore ' chromopho'V (! chromophore V) 20 1928 chromopho'
7 20 1928 #7 20 J 20 1928 & 20 1928 chromopho 20 20 20 1928 C('0 &J:! chromopho 20 1928 acrylic
J polyester 20 1928 20 1928 20 1928 V 20 1928 V& 20 J chromopho 20 20 0 20 1928
chromopho 20 20 1928 C 20 1928 ! 20 1928 chromophoV C.I. Direct Blue 86 C( chromophore #: disulfonate ' copper
phthalocyanine 0 chromophore
NaO3S
N
N

N
Cu

N
N

N
N

N
SO3Na

7 20 1928 20 1928 20 1928 20 1928 V chromophore reactive ! 20 7 cotton 20 1928 chromopho

 phthalocy# phthalocyanine
20 1928 J: 20 1928 7#! chromophore : chromophore 20 1928 3 chromopho
1. Phthalic acid derivative V phthalic anhydride, phthalimide, phthalonitrile J
o-cyanobenzamide
2. Nitrogen source 20 1928 20 V phthalic acid derivative 20 N chromophore : chromophore 20 1928
20 1928 ' phthalic anhydride V ammonia
3. Appropriate metal derivative V Copper cyanine 20 1928 J Cu ion
20 chromopho chromophore 20 1928 20 ! 20 1928 chromophore & 20 1928 && 20 #J0&0V chromopho 20 !77 20 #0 J 20 !
20 1928 chromopho 20 1928 Dry-bake process 7 chr chromophore 20 1928 substituted phthalocyanine 20 1928 V
substituted starting material J! phthalocyanine 20 ! 20 1928 &J0 20 20 20 J7 20 1928 chromopho 20 &
20 1928 copperphthalocyanine 2 chromopho& 20 1928 20 & 20 1928 20 #!
1. Phthalic anhydride route:
O

NH

NH

NH
O

N
N

N
Cu

N
N

x 4, Cu2+
N

NH2
NH

N
N

NH

chromophore chromopho& 20 1928 20 & 20 1928 20 1928 20 ! 20 1928 heat phthalic anhydride 20 1928 urea 20 1928 copper (I)
chloride 7V ammonium molybdate chromophore catalyst high boiling point solvent 20 1928 urea chromophore chromopho
J nitrogen 7 carbonyl ' 20 1928 7 chromopho chromophore CO2 chromophore C( nitrogen 20 1928 ' chromophore 20 20 O atom '
phthalic anhydride JJ7 20 1928 20 1928 20 1928 7 chromophore 1-amino-3iminoisoindoline J7 20 1928 '
ammoniummolybdate 20 1928 20 !J 20 chromophore catalyst 20 !J 20 1928 & 20 1928 tetramerisation 20 1928 20 1928 chromophore & chromopho chromopho Cu
ion 20 1928 & chromophore copper phthalocyanine

2. Phthlonitrile route
-

Cu2+
C N

Y
N Cu2+
N

2+
N Cu

C N
C

Y NN
N

etc.

N
Cu2+

N Cu2+

C N
N
N

Route 1: 2e , Y-

Cu

N
N

N
+

N
N

N
CuPc

Cu
N

N
+

Route 2: Y

Y (Y=Cl)
CuPc

ClCuPc

20 ! 20 1928 heat phthalonitrile 20 200C chromopho7J copper J 20 1928 7' V chromopho

20 !77JV 20 1928 20 1928 7 20 1928 20 1928 20 1928 & 20 1928 & 20 nucleophile (Y-) C( chromophore counter ion ' Cu 20 J0 CN
' phthalonitrile J0 20 1928 J7 20 1928 20 1928 20 1928 & 20 1928 chromophore & chromopho chromophore isoindoline derivative 7 chromopho( 20 ! 20 1928 attack
20 1928 phthalonitrile chromopho chromophore chromophore & 20 1928 &&C!V& 4 J chromopho chr copper V0 chromophore '7J 20 1928
&7 20 1928 20 7J copper J'0 20 !J 20 1928 & 20 1928 J7# 20 1928 ' Y- 20 !J chromophore copper phthalocynine
7J7 20 1928 Cu(0) chr0 20 1928 20 1928 C&C: chromophore Cu(II) 20 20 !J 20 1928 & chromophore & 20 1928 &&!& chromophore ( route 20 1)
chr copper 20 V00 chromophore ' copper salt ( route 20 2) 20 1928 chr 20 20 !J Y 20 1928 & chromophore Y+
(Chloromium ion 20 1928 20 chromophore CuCl2) 20 chr0 20 1928 20 1928 ! 20 1928 7 20 1928 20 1928 20 1928 & chromophore electrophilic
substitution 20 1928 & chromophore monochloro derivative C( chromophore 7 20 !J 20 1928 & -crystal 20 chr

7&: 20 20 1928 20 2 chromopho&J 20 1928 chromophore blue crude product 20 chrV chromophore
pigment (! chromophore 20 ! acid pasting chromophore 20 1928 7''# 20 1928 77 crude
product 20 1928 20 1928 ! chr'' 7 chromophoJ7 20 1928 20 ! 20 1928 20 1928 20 1928 C! chromopho! 20 1928 chromopho& chrJ -form
20 chromopho7 chromopho 20 1928 V& 20 1928 7 (Mechanical grinding) chr 20 chromopho 20 1928 inorganic salt
V NaCl J CaCl2 20 product 20 chromophore ' 20 7 -form C( 20 1928 chr 20
chromophore 7 20 1928 7 chromophore chromophore -form 20 &# 20 & w 20 1928 heat 77 20 J chromopho&(J
!J 20 1928 -form 20 chromopho7
20 1928 #:' phthalocyanine V phthalocyanine green pigment 20 1928 chr 20
20 ! direct exhaustive halogenation crude copper phthalocyanine chromopho Cl J Br chromopho 20 !77 20
J V molten AlCl3/NaCl 20 1928 phthalocyanine chromophore chromophore 20 1928 & 20 1928 0:(
chr 20 1928 & Electrophilic substitution chromophore & 20 1928 &&
X

X
N

Cu

N
N

X2 : X = Cl or Br

Cu

N
N
N

N
X

X
X

C( Crude green product 20 20 ! 20 1928 chromopho 20 1928 V organic solvent 20 J J 20 !

treat chromopho aqueous surfactant solution C( 20 1928 chromopho 20 1928 20 1928 7 chromopho 20 1928 20 1928 chr 20 20 !J'
#'777 chromopho 20 !J chr chromopho 20 1928 chromophore 7( 20 1928 '( 20 !J chromopho chr 20 1928 20 20
20 1928 '( chromopho