Polycarbonate copolymer, coating fluid using same, electrophotographic photoreceptor, and method for producing polycarbonate copolymer
This invention relates to a polycarbonate copolymer having a structure formed of a repeating unit represented by the following formula (100): in which a molar copolymer composition represented by Ar 1 /(Ar 1 +Ar 2 ) is in a range of 50 mol % to 67 mol %, a reduced viscosity [ηsp/C] is in a range of 0.60 dl/g to 4.0 dl/g, and a ratio of a hydroxyl group in all ends is 20 mol % or less.
1. A polycarbonate copolymer, comprising a structure formed of a repeating unit represented by formula (100):
wherein:
a molar copolymer composition represented by Ar 1 /(Ar 1 +Ar 2 i) is in a range of 50 mol % to 67 mol %;
a reduced viscosity [ηsp/C] of the polycarbonate copolymer is in a range of 0.60 dl/g to 4.0 dl/g;
a ratio of a hydroxyl group at all ends is 20 mol % or less;
Ar 2 represents a divalent group having an aromatic group;
Ar 1 represents a group represented by the following formula (2):
chain ends are terminated by a monovalent aromatic group or a monovalent fluorine-containing aliphatic group;
n represents an average repeating number of an Ar 1 block and is a numeral of 1.0 to 1.99; and
Ar 1 and Ar 2 are not the same,
R 1 and R 2 each represent a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 ring carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
p1 and p2 each represent an integer of 0 to 4; and
when the aromatic ring is substituted by two or more of R 1 or R 2 (p1, p2>2), the two or more of R 1 or R 2 are optionally different groups.
2. A polycarbonate copolymer, comprising a structure formed of a repeating unit represented by formula (1),
wherein:
a molar copolymer composition represented by Ar 1 /(Ar 1 +Ar 2 +Ar 3 ) is in a range of 47 mol % to 67 mol %;
a reduced viscosity [ηsp/C] is in a range of 0.60 dl/g to 4.0 dl/g;
a ratio of a hydroxyl group at all ends is 20 mol % or less;
Ar 2 and Ar 3 each represent a divalent group having an aromatic group;
Ar 1 represents a group represented by the following formula (2):
chain ends are terminated by a monovalent aromatic group or a monovalent fluorine-containing aliphatic group;
n represents an average repeating number of an Ar 1 block and is a numeral of 1.0 to 1.99;
m represents an average repeating number of an Ar 3 block and is a numeral of 1.0 to 4.0; and
Ar 2 and Ar 3 are optionally the same or different, but Ar 1 is not the same as Ar 2 and Ar 3 ;
R 1 and R 2 each represent a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 ring carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
p1 and p2 each represent an integer of 0 to 4; and
when the aromatic ring is substituted by two or more of R 1 or R 2 (p1, p2>2), the two or more of R 1 or R 2 are optionally different groups.
3. The polycarbonate copolymer according to claim 1 , wherein
Ar 2 represents a group represented by at least one of the following formulae (3) and (4):
wherein:
X 2 represents —O—, —CO—, —S—, —SO—, —SO 2 —, —CONH—, —CR 6 R 7 — in which R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, —O—R 8 —O— in which R 8 is a carbonyl group, an alkyl chain having 1 to 6 carbon atoms, or a trifluoroalkyl chain and is optionally branched, a substituted or unsubstituted cycloalkylidene group having 5 to 12 ring carbon atoms, a substituted or unsubstituted adamantane-2,2-diyl group, a substituted or unsubstituted adamantane-1,3-diyl group, a substituted or unsubstituted α,ω-alkylene group having 2 to 12 carbon atoms, a substituted or unsubstituted 9,9-fluorenylidene group, a 1,8-menthanediyl group, a 2,8-menthanediyl group, a substituted or unsubstituted pyrazylidene group, or a substituted or unsubstituted arylene group having 6 to 12 ring carbon atoms;
R 3 , R 4 and R 5 each represent a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 ring carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
p3 and p4 represents an integer of 0 to 4 and p5 represents an integer of 0 to 6;
a repeating unit number n 0 is in a range of 0 to 2, wherein R 3 , p3 and X 2 are selected in each of the repeating unit;
when an aromatic ring is substituted by two or more of R 3 or R 4 (p3, p4>2), the two or more of R 3 or R 4 are optionally different groups; and
when an aromatic ring is substituted by two or more of R 5 (p5>2), the two or more of R 5 are optionally different groups.
4. The polycarbonate copolymer according to claim 3 , wherein:
Ar 2 is a group represented by the following formula (3′):
X 2 is —O—, —CR 6 R 7 — in which R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, a substituted or unsubstituted cycloalkylidene group having 5 to 12 ring carbon atoms, a substituted or unsubstituted adamantane-2,2-diyl group, a substituted or unsubstituted adamantane-1,3-diyl group, or a substituted or unsubstituted α,ω-alkylene group having 2 to 12 carbon atoms;
n 0 is 1; and
R 3 , R 4 , p3 and p4 are the same as those in the formula (3).
5. The polycarbonate copolymer according to claim 2 , wherein:
Ar 2 and Ar 3 each are a group represented by at least one of the following formulae (3) and (4):
X 2 represents —O—, —CO—, —S—, —SO—, —SO 2 —, —CONH—, —CR 6 R 7 — in which R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, —O—R 8 —O— in which R 8 is a carbonyl group, an alkyl chain having 1 to 6 carbon atoms, or a trifluoroalkyl chain and is optionally branched, a substituted or unsubstituted cycloalkylidene group having 5 to 12 ring carbon atoms, a substituted or unsubstituted adamantane-2,2-diyl group, a substituted or unsubstituted adamantane-1,3-diyl group, a substituted or unsubstituted α,ω-alkylene group having 2 to 12 carbon atoms, a substituted or unsubstituted 9,9-fluorenylidene group, a 1,8-menthanediyl group, a 2,8-menthanediyl group, a substituted or unsubstituted pyrazylidene group, or a substituted or unsubstituted arylene group having 6 to 12 ring carbon atoms;
R 3 , R 4 and R 5 each represent a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 ring carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
p3 and p4 represents an integer of 0 to 4 and p5 represents an integer of 0 to 6;
a repeating unit number n 0 is in a range of 0 to 2, wherein R 3 , p3 and X 2 are selected in each of the repeating unit;
when an aromatic ring is substituted by two or more of R 3 or R 4 (p3, p4≧2), the two or more of R 3 or R 4 are optionally different groups; and
when an aromatic ring is substituted by two or more of R 5 (p5≧2), the two or more of R 5 are optionally different groups.
6. The polycarbonate copolymer according to claim 5 , wherein:
Ar 2 and Ar 3 each are a group represented by formula (3′):
wherein:
X 2 represents —O—, —CR 6 R 7 — in which R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, a substituted or unsubstituted cycloalkylidene group having 5 to 12 ring carbon atoms, a substituted or unsubstituted adamantane-2,2-diyl group, a substituted or unsubstituted adamantane-1,3-diyl group, or a substituted or unsubstituted α,ω-alkylene group having 2 to 12 carbon atoms;
n 0 is 1; and
R 3 , R 4 , p3 and p4 are the same as those in the formula (3).
7. The polycarbonate copolymer according to claim 6 , wherein Ar 2 and Ar 3 are the same group.
8. The polycarbonate copolymer according to claim 1 , further comprising:
a divalent organic siloxane modified phenylene group for Ar 2 .
9. The polycarbonate copolymer according to claim 8 , wherein:
the divalent organic siloxane modified phenylene group is a group represented by formula (3A) or (3B):
R 21 and R 22 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms;
R 23 each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms;
n1 is an integer of 2 to 4; and
n2 is an integer of 1 to 600, or
wherein:
R 31 each independently represents a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms;
R 32 each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms;
R 33 represents a monovalent hydrocarbon group having no aliphatic unsaturated bond, the monovalent hydrocarbon being the same or different;
R 34 represents a monovalent hydrocarbon group having no aliphatic unsaturated bond, the monovalent hydrocarbon group being the same or different;
Y and Y′ are an alkylene group having 2 or more carbon atoms, alkyleneoxyalkylene group or an oxygen atom;
na is 0 or 1, nb is 1 or 2, and nc is 1 or 2, with the proviso that na+nb+nc=3;
n1 to n4 each represent an integer of 0 or more, with the proviso that a sum of n1, n2, n3 and n4 is an integer of 2 to 600, and a sum of n3 and n4 is an integer of 1 or more; and
a is an integer of 0 to 4.
10. The polycarbonate copolymer according to claim 1 , wherein Ar 1 represented by the formula (2) is a divalent group derived from a group selected from 4,4′-biphenol and 3,3′-dimethyl-4,4′-biphenol.
11. A manufacturing method of a polycarbonate copolymer, the method comprising reacting a bischloroformate oligomer represented by formula (5) or a combination of formulae (5) and (6) with a divalent phenol monomer represented by formula (7) in the presence of an acid binding agent:
wherein:
when a mole number of the bischloroformate oligomer is represented by Mc (mol), a mole number of the divalent phenol monomer is represented by Mp (mol), a mole number of the acid binding agent is represented by Mo (mol), and a valence of the acid binding agent is represented by Y, an acid binding value X represented by the following formula is in a range of 1.1 to 1.3:
X=Mo·Y/(2Mc−2Mp),
Ar 1 is a group represented by formula (2):
Ar 2 and Ar 3 are a divalent group having an aromatic group;
Ar 2 and Ar 3 are optionally the same or different, but Ar 1 is not the same as Ar 2 and Ar 3 ;
n′ is a numeral of 1.0 to 1.99;
n″ is 0 or a numeral of 1.0 to 4.0;
R 1 and R 2 each represent a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 ring carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
p1 and p2 each represent an integer of 0 to 4; and
when the aromatic ring is substituted by two or more of R 1 or R 2 (p 1, p2≧2), the two or more of R 1 or R 2 are optionally different groups.
12. A coating liquid, comprising:
the polycarbonate copolymer according to claim 1 ; and
an organic solvent.
13. A coating liquid, comprising:
the polycarbonate copolymer manufactured by the manufacturing method of claim 11 ; and
an organic solvent.
14. An electrophotographic photoreceptor, comprising:
a conductive substrate; and
a photosensitive layer provided on the conductive substrate,
wherein the photosensitive layer comprises the polycarbonate copolymer according to claim 1 .
15. An electrophotographic photoreceptor, comprising:
a conductive substrate; and
a photosensitive layer provided on the conductive substrate,
wherein the photosensitive layer comprises the polycarbonate copolymer manufactured by the manufacturing method of claim 11 .
16. The polycarbonate copolymer according to claim 2 , further comprising:
a divalent organic siloxane modified phenylene group for Ar 2 .
17. The polycarbonate copolymer according to claim 16 ,
wherein:
the divalent organic siloxane modified phenylene group is a group represented by formula (3A) or (3B):
R 21 and R 22 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms;
R 23 each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms;
n1 is an integer of 2 to 4; and
n2 is an integer of 1 to 600, or
R 31 each independently represents a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms;
R 32 each independently represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 ring carbon atoms;
R 33 represents a monovalent hydrocarbon group having no aliphatic unsaturated bond, the monovalent hydrocarbon being the same or different;
R 34 represents a monovalent hydrocarbon group having no aliphatic unsaturated bond, the monovalent hydrocarbon group being the same or different;
Y and Y′ are an alkylene group having 2 or more carbon atoms, alkyleneoxyalkylene group or an oxygen atom;
na is 0 or 1, nb is 1 or 2, and nc is 1 or 2, with the proviso that na+nb+nc=3;
n1 to n4 each represent an integer of 0 or more, with the proviso that a sum of n1, n2, n3 and n4 is an integer of 2 to 600, and a sum of n3 and n4 is an integer of 1 or more; and
a is an integer of 0 to 4.
18. The polycarbonate copolymer according to claim 2 , wherein Ar 1 represented by the formula (2) is a divalent group derived from a group selected from 4,4′-biphenol and 3,3′-dimethyl-4,4′-biphenol.
19. A coating liquid, comprising:
the polycarbonate copolymer according to claim 2 ; and
an organic solvent.
20. An electrophotographic photoreceptor, comprising:
a conductive substrate; and
a photosensitive layer provided on the conductive substrate,
wherein the photosensitive layer comprises the polycarbonate copolymer according to claim 2 as a component.