JP2012051983A - Polycarbonate copolymer for binder resin for electrophotographic photoreceptor - Google Patents
Polycarbonate copolymer for binder resin for electrophotographic photoreceptor Download PDFInfo
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- JP2012051983A JP2012051983A JP2010194081A JP2010194081A JP2012051983A JP 2012051983 A JP2012051983 A JP 2012051983A JP 2010194081 A JP2010194081 A JP 2010194081A JP 2010194081 A JP2010194081 A JP 2010194081A JP 2012051983 A JP2012051983 A JP 2012051983A
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 62
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 62
- 239000011230 binding agent Substances 0.000 title claims abstract description 32
- 108091008695 photoreceptors Proteins 0.000 title claims abstract description 23
- 229920005989 resin Polymers 0.000 title abstract description 20
- 239000011347 resin Substances 0.000 title abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 30
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000012695 Interfacial polymerization Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 63
- 239000010410 layer Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920005668 polycarbonate resin Polymers 0.000 description 10
- 239000004431 polycarbonate resin Substances 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 238000007664 blowing Methods 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- -1 carbonyl halide Chemical class 0.000 description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 3
- WUGKVYDVIGOPSI-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)-2-methylphenol Chemical group C1=C(O)C(C)=CC(C=2C=C(C)C(O)=CC=2)=C1 WUGKVYDVIGOPSI-UHFFFAOYSA-N 0.000 description 3
- SVOBELCYOCEECO-UHFFFAOYSA-N 4-[1-(4-hydroxy-3-methylphenyl)cyclohexyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(CCCCC2)C=2C=C(C)C(O)=CC=2)=C1 SVOBELCYOCEECO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- DLLHIOAWFNZHDO-UHFFFAOYSA-N OC1(CC(=CC=C1)C1=CC(=C(C=C1)O)C)C Chemical group OC1(CC(=CC=C1)C1=CC(=C(C=C1)O)C)C DLLHIOAWFNZHDO-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QLNFINLXAKOTJB-UHFFFAOYSA-N [As].[Se] Chemical compound [As].[Se] QLNFINLXAKOTJB-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PGEHNUUBUQTUJB-UHFFFAOYSA-N anthanthrone Chemical compound C1=CC=C2C(=O)C3=CC=C4C=CC=C5C(=O)C6=CC=C1C2=C6C3=C54 PGEHNUUBUQTUJB-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- UDYLZILYVRMCJW-UHFFFAOYSA-L disodium;oxido carbonate Chemical compound [Na+].[Na+].[O-]OC([O-])=O UDYLZILYVRMCJW-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Photoreceptors In Electrophotography (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、耐摩耗性および溶液保存安定性を両立した電子写真感光体バインダー用ポリカーボネート共重合体に関する。 The present invention relates to a polycarbonate copolymer for an electrophotographic photoreceptor binder that has both wear resistance and solution storage stability.
電子写真感光体分野において、感光層のバインダーポリマーとしてポリカーボネート樹脂が主に使用されている。当初は２，２−ビス（４−ヒドロキシフェニル）プロパン（通称ビスフェノールＡ）より得られるポリカーボネート樹脂（以下「ＰＣ−Ａ」と称することがある）が主流であったが、塗膜作成時に結晶化またはゲル化が起こってしまう事や、塗布時にソルベントクラックが発生してしまうといった問題があり、現在では１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（通称ビスフェノールＺ）より得られるポリカーボネート樹脂（以下「ＰＣ−Ｚ」と称する事がある）が主に用いられている。
ただ、近年の画質の向上要求に伴い、バインダーポリマーに対して、より高性能化が求められてきている。
In the electrophotographic photoreceptor field, a polycarbonate resin is mainly used as a binder polymer for a photosensitive layer. Initially, polycarbonate resin (hereinafter sometimes referred to as “PC-A”) obtained from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) was the mainstream, but crystallized at the time of coating film creation. Alternatively, there is a problem that gelation occurs and solvent cracks occur during coating. At present, a polycarbonate resin (hereinafter referred to as bisphenol Z) obtained from 1,1-bis (4-hydroxyphenyl) cyclohexane (commonly referred to as bisphenol Z). “PC-Z” is sometimes used.
However, with recent demands for improving image quality, higher performance has been demanded for binder polymers.
バインダー樹脂に求められる高性能化の特性の一つとしては、耐磨耗性がある。そこで、４，４’−ビフェノールをポリカーボネート樹脂に含有させ耐磨耗性を向上させるといった検討がなされている。（例えば、特許文献１，２参照）しかしながら、このようなビフェノール構造を含有するポリカーボネート樹脂は、先ず二価フェノールのみをホスゲンと反応させた後にビフェノールを添加する手法により重合されており、反応性の劣るビフェノールの共重合モル比率を３０ｍｏｌ％以上に向上させることが難しく、期待される耐磨耗性向上効果が小さいという問題があった。しかも、ビフェノールの共重合モル比率が３０ｍｏｌ％付近を超えると、感光体作製の際に溶媒への溶解性が低下するという問題があった。この溶解性が悪化すると、溶液保存安定性が低下して生産性が悪化したり、感光体を作製した際に、表面に凹凸を生じ画像欠陥を招き易くなる。そのため、従来から耐摩耗性と溶液保存安定性とを両立させるような電子写真感光体用バインダー樹脂の開発が望まれている。
One of the high performance characteristics required for the binder resin is wear resistance. Therefore, studies have been made to improve the abrasion resistance by adding 4,4'-biphenol to the polycarbonate resin. (For example, see
本発明は上記の耐刷性と溶解性の問題を解決するために、電子写真感光体用バインダー樹脂として耐摩耗性に優れ、且つ溶液保存安定性を併せ持つポリカーボネート共重合体を提供しようというものである。 In order to solve the above-mentioned problems of printing durability and solubility, an object of the present invention is to provide a polycarbonate copolymer having excellent wear resistance and solution storage stability as a binder resin for an electrophotographic photoreceptor. is there.
本発明者は、上記の目的を達成すべく、バインダー樹脂について鋭意検討を行った結果、前述のビフェノール化合物をランダムに且つ高濃度で共重合させることで上記特性を兼ね備える上、実用性に富んでいるポリカーボネート共重合体が得られることを見出し、本発明に至った。すなわち、本発明は、以下に示す電子写真感光体用ポリカーボネート共重合体に関する。 As a result of intensive studies on the binder resin in order to achieve the above object, the present inventor has the above characteristics by copolymerizing the above-mentioned biphenol compound at random and at a high concentration, and is highly practical. The present inventors have found that a polycarbonate copolymer can be obtained. That is, the present invention relates to the following polycarbonate copolymer for electrophotographic photoreceptors.
１．下記式（Ｉ）および下記一般式（ＩＩ）が主たる繰り返し単位で、式（Ｉ）および一般式（ＩＩ）のモル比率が、３０／７０〜６０／４０であるポリカーボネート共重合体からなり、該共重合体において、式（Ｉ）同士が隣り合う割合（ＮＩ−Ｉ）が下記数式（１）を満足することを特徴とした電子写真感光体バインダー用ポリカーボネート共重合体。
（ＮＩ−Ｉ）≦０．５×（ＮＩ）・・・（１）
（式中、（ＮＩ−I）は式（Ｉ）と（Ｉ）、一般式（ＩＩ）と（ＩＩ）及び式（Ｉ）と一般式（ＩＩ）が隣り合う場合の合計数を基準とした際の、式（Ｉ）と（Ｉ）とが隣り合う割合を表し、更に（ＮＩ）は、式（Ｉ）と一般式（ＩＩ）の合計モル数を基準とした場合の式（Ｉ）のモル分率を意味する。）
1. The following repeating formula (I) and the following general formula (II) are the main repeating units, and the molar ratio of the formula (I) and the general formula (II) is 30/70 to 60/40, and consists of a polycarbonate copolymer, In the copolymer, a polycarbonate copolymer for an electrophotographic photosensitive member binder, wherein a ratio (N I-I ) in which the formulas (I) are adjacent to each other satisfies the following formula (1).
(N I-I ) ≦ 0.5 × (N I ) (1)
(Wherein (N I-I ) is based on the total number of formulas (I) and (I), general formulas (II) and (II), and formula (I) and general formula (II)). The formulas (I) and (I) represent the ratio of adjacent to each other, and (N I ) represents the formula (I) based on the total number of moles of the formula (I) and the general formula (II). ) Means the mole fraction.)
２．該ポリカーボネート共重合体０．７ｇを１００ｍＬの塩化メチレンに溶解し、２０℃で測定した比粘度が０．３８〜１．５４の範囲である上記１記載の電子写真感光体バインダー用ポリカーボネート共重合体。 2. 2. The polycarbonate copolymer for an electrophotographic photoreceptor binder according to 1 above, wherein 0.7 g of the polycarbonate copolymer is dissolved in 100 mL of methylene chloride and the specific viscosity measured at 20 ° C. is in the range of 0.38 to 1.54. .
３．式（ｉ）および式（ｉｉ）で表される二価フェノールとホスゲンとを、水に不溶性の有機溶媒とアルカリ水溶液との混合液中において反応させ、得られたオリゴマー含有溶液を界面重合法により重合させ、得られる上記１または２記載の電子写真感光体バインダー用ポリカーボネート共重合体の製造方法。 3. The dihydric phenol represented by the formula (i) and the formula (ii) and phosgene are reacted in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution, and the resulting oligomer-containing solution is subjected to an interfacial polymerization method. 3. A process for producing a polycarbonate copolymer for electrophotographic photoreceptor binder according to 1 or 2 obtained by polymerization.
４．上記３記載の製造方法によって得られた電子写真感光体バインダー用ポリカーボネート共重合体を含有する電子写真感光体。 4). 4. An electrophotographic photoreceptor containing a polycarbonate copolymer for an electrophotographic photoreceptor binder obtained by the production method described in 3 above.
前述のビフェノール化合物をランダムに且つ高濃度で共重合させることで得られるポリカーボネート共重合体は、高い表面硬度を有し耐摩耗性に優れるとともに、複写機、レーザービームプリンター等の感光体作製時の溶媒中での保存安定性も高いため、バインダー樹脂として好適に用いられ、その奏する工業的効果は格別である。 The polycarbonate copolymer obtained by copolymerizing the above-mentioned biphenol compound randomly and at a high concentration has a high surface hardness and excellent wear resistance, and is suitable for the production of photoconductors such as copying machines and laser beam printers. Since the storage stability in a solvent is also high, it is suitably used as a binder resin, and its industrial effect is exceptional.
以下、本発明を詳細に説明する。
本発明において、ポリカーボネート共重合体は、主として下記式（Ｉ）と下記一般式（ＩＩ）からなる。
Hereinafter, the present invention will be described in detail.
In the present invention, the polycarbonate copolymer mainly comprises the following formula (I) and the following general formula (II).
本発明における下記式（Ｉ）は、４，４’−ジヒドロキシ−３，３’−ジメチルビフェニルに由来するものである。
また、本発明における一般式（ＩＩ）は、１，１−ビス（３−メチル−４−ヒドロキシフェニル）シクロヘキサン及び／又は、２，２−ビス（３−メチル−４ヒドロキシフェニル）プロパンに由来するものである。
The following formula (I) in the present invention is derived from 4,4′-dihydroxy-3,3′-dimethylbiphenyl.
The general formula (II) in the present invention is derived from 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane and / or 2,2-bis (3-methyl-4hydroxyphenyl) propane. Is.
（共重合体の組成比）
本発明のポリカーボネート共重合体は、前記式（Ｉ）で表される繰り返し単位と前記一般式（ＩＩ）で表される繰り返し単位のモル比率（（Ｉ）／（（ＩＩ））が、３０／７０〜６０／４０であり、好ましくは、３５／６５〜５５／４５であり、さらに好ましくは、４０／６０〜５０／５０である。
(Composition ratio of copolymer)
The polycarbonate copolymer of the present invention has a molar ratio ((I) / ((II)) of the repeating unit represented by the formula (I) and the repeating unit represented by the general formula (II) of 30 / It is 70-60 / 40, Preferably, it is 35 / 65-55 / 45, More preferably, it is 40 / 60-50 / 50.
一般式（ＩＩ）の割合は、式（Ｉ）と一般式（ＩＩ）との合計モル数を基準として４０〜７０モル％であることが必要である。
一般式（ＩＩ）の割合が下限未満では、溶剤に対する溶解性が低くなり溶液保存性が損なわれる。一方、一般式（ＩＩ）の割合が、上限を越えると共重合による本発明におけるフィルムの耐磨耗性効果が発現され難くなる。 ところで、本発明の特徴は、式（Ｉ）同士が隣り合う割合（ＮＩ−Ｉ）が下記数式（１）を満足していることにある。
（ＮＩ−Ｉ）≦０．５×（ＮＩ）・・・（１）
（式中、（ＮＩ−Ｉ）は式（Ｉ）と（Ｉ）、一般式（ＩＩ）と（ＩＩ）及び式（Ｉ）と一般式（ＩＩ）が隣り合う場合の合計数を基準とした際の、式（Ｉ）と（Ｉ）とが隣り合う割合を表し、更に（ＮＩ）は、式（Ｉ）と一般式（ＩＩ）の合計モル数を基準とした場合の式（Ｉ）のモル分率を意味する。）
The ratio of general formula (II) needs to be 40-70 mol% on the basis of the total number of moles of formula (I) and general formula (II).
When the ratio of the general formula (II) is less than the lower limit, the solubility in a solvent is lowered and the solution storage stability is impaired. On the other hand, if the ratio of the general formula (II) exceeds the upper limit, the wear resistance effect of the film in the present invention due to copolymerization is hardly exhibited. By the way, the feature of the present invention is that the ratio (N I-I ) where the formulas ( I ) are adjacent to each other satisfies the following formula (1).
(N I-I ) ≦ 0.5 × (N I ) (1)
(Wherein (N I-I ) is based on the total number of formulas (I) and (I), general formulas (II) and (II), and formula (I) and general formula (II)). The formulas (I) and (I) represent the ratio of adjacent to each other, and (N I ) represents the formula (I) based on the total number of moles of the formula (I) and the general formula (II). ) Means the mole fraction.)
つまり、前述の数式（１）の範囲にするということは、溶剤に対する溶解性を悪化させる式（Ｉ）同士が隣り合う割合（ＮＩ−Ｉ）を少なくすることを意味する。そして、前述の数式（１）の左辺値を上限より低くすることで、前記式（Ｉ）と前記一般式（ＩＩ）の組成比を適当にしただけでは、達成できなかった溶媒中での保存安定性も向上できることを見出したのが本発明である。 In other words, the range of the above formula (1) means that the ratio (N I-I ) of adjacent formulas (I) that deteriorate the solubility in the solvent is reduced. And by making the left side value of the above-mentioned numerical formula (1) lower than the upper limit, the storage in a solvent that could not be achieved only by making the composition ratio of the above formula (I) and the above general formula (II) appropriate. It was the present invention that the stability could be improved.
これまでに耐磨耗性向上の目的でビフェノールタイプのビスフェノールが検討されており、界面重縮合反応において、ビフェノールがホスゲン化されたオリゴマーは、ビフェノール同士の結合したオリゴマーとなるため、通常溶媒として使用されるハロゲン化溶媒には難溶となり、反応の不安定化を招き分子量調整が難しくなる。従ってビフェノールタイプのビスフェノールの共重合相手のビスフェノールをホスゲン化した後にビフェノールタイプのビスフェノールを添加して重合させている。この製造方法では、ビフェノールタイプのビスフェノールの含有率を高くすることは出来ない。
本発明のポリカーボネート共重合体は、ビフェノール構造の共重合比率が高くなっても、調整溶媒に溶解し保存安定性も保持している。
So far, biphenol type bisphenol has been studied for the purpose of improving abrasion resistance, and in the interfacial polycondensation reaction, the oligomer in which biphenol is phosgenated becomes an oligomer in which biphenols are combined, so it is usually used as a solvent. It becomes difficult to dissolve in the halogenated solvent, resulting in destabilization of the reaction and difficult to adjust the molecular weight. Accordingly, the bisphenol copolymerization partner of the biphenol type bisphenol is phosgenated, and then the biphenol type bisphenol is added for polymerization. In this production method, the content of biphenol type bisphenol cannot be increased.
The polycarbonate copolymer of the present invention dissolves in the adjustment solvent and retains storage stability even when the copolymerization ratio of the biphenol structure is increased.
（ポリカーボネート共重合体の製造方法）
本発明のポリカーボネート共重合体は、初期の段階から２種のジヒドロキシフェノール化合物を混合してオリゴマー化を開始するため、これまで反応性の劣るビフェノール構造の共重合比率を向上させることが出来るとともに、各ビスフェノールユニットがよりランダムに配されるため溶解性の低下を招くビフェノール構造のブロック化を防止することが出来る。
(Method for producing polycarbonate copolymer)
Since the polycarbonate copolymer of the present invention starts the oligomerization by mixing two kinds of dihydroxyphenol compounds from the initial stage, it can improve the copolymerization ratio of the biphenol structure which has been inferior in reactivity so far. Since each bisphenol unit is arranged more randomly, it is possible to prevent blocking of the biphenol structure that causes a decrease in solubility.
本発明の電子写真感光体バインダー用ポリカーボネート共重合体は、それぞれ通常のポリカーボネート樹脂を製造するそれ自体公知の反応手段、例えば二価フェノール成分にホスゲンや炭酸ジエステルなどのカーボネート前駆物質を反応させる方法により製造される。次にこれらの製造方法について基本的な手段を簡単に説明する。 The polycarbonate copolymer for an electrophotographic photoreceptor binder of the present invention is prepared by a reaction means known per se for producing a normal polycarbonate resin, for example, a method of reacting a dihydric phenol component with a carbonate precursor such as phosgene or carbonic acid diester. Manufactured. Next, basic means for these manufacturing methods will be briefly described.
カーボネート前駆体としてはカルボニルハライド、カーボネートエステルまたはハロホルメート等が使用され、具体的にはホスゲン、ジフェニルカーボネートまたは二価フェノールのジハロホルメート等が挙げられる。 As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
上記二価フェノールとホスゲンとを、水に不溶性の有機溶媒とアルカリ水溶液との混合液中において反応させ、得られたオリゴマー含有溶液を界面重合法により重合させ、得られることを特徴としており、一連の反応においては必要に応じて触媒、末端停止剤、二価フェノールの酸化防止剤等を使用してもよい。 The dihydric phenol and phosgene are reacted in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution, and the obtained oligomer-containing solution is polymerized by an interfacial polymerization method, and is obtained, In this reaction, a catalyst, a terminal terminator, a dihydric phenol antioxidant and the like may be used as necessary.
界面重合法による反応は、通常二価フェノールとホスゲンとの反応であり、酸結合剤および有機溶媒の存在下に反応させる。酸結合剤としては、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物またはピリジン等のアミン化合物が用いられる。有機溶媒としては、例えば塩化メチレン、クロロベンゼン等のハロゲン化炭化水素が用いられる。また、反応中の二価フェノールのアルカリ塩の酸化防止を目的として、例えばハイドロサルファイト等の酸化防止剤を添加したり、窒素を液相又は、気相に通したりすることが好ましい。さらに、反応促進のために例えばトリエチルアミン、テトラ−ｎ−ブチルアンモニウムブロマイド、テトラ−ｎ−ブチルホスホニウムブロマイド等の第三級アミン、第四級アンモニウム化合物、第四級ホスホニウム化合物等の触媒を用いることもできる。その際、反応温度は通常０〜４０℃、反応時間は１０分〜５時間程度、反応中のｐＨは９以上に保つのが好ましい。 The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. For the purpose of preventing the oxidation of the alkali salt of the dihydric phenol during the reaction, it is preferable to add an antioxidant such as hydrosulfite or to pass nitrogen through the liquid phase or the gas phase. Furthermore, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used for promoting the reaction. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.
かかる重合反応によって得られる反応液から有機溶媒溶液を分離し、該有機溶媒により希釈後水洗作業を行う。この際、残留モノマーの洗浄を強化する目的に、適宜水酸化ナトリウム水溶液で洗浄してもよい。さらに、酸洗浄及び水洗等によって残留触媒や無機塩等不純物を除去した後有機溶媒を除去することによって本発明のポリカーボネート共重合体が得られる。 An organic solvent solution is separated from the reaction solution obtained by such a polymerization reaction, diluted with the organic solvent, and washed with water. At this time, for the purpose of enhancing the cleaning of the residual monomer, it may be appropriately washed with an aqueous sodium hydroxide solution. Furthermore, the polycarbonate copolymer of the present invention can be obtained by removing the organic solvent after removing impurities such as residual catalyst and inorganic salt by acid washing and water washing.
（比粘度）
本発明に係るポリカーボネート共重合体の比粘度は、好ましくは、該ポリカーボネート
重合体０．７ｇを１００ｃｃの塩化メチレンに溶解し、２０℃で測定した比粘度が０．３
８〜１．５４の範囲であり、さらに、０．５８〜１．３５であり、特に、０．７７〜１．１６である。
比粘度が０．３８未満であると樹脂としての機械強度が低下し耐摩耗性が不足することがある。また、比粘度が、１．５４より大きいと、キャストフィルムを適当な膜厚に塗布して作製することが困難となり好ましくない。
(Specific viscosity)
The specific viscosity of the polycarbonate copolymer according to the present invention is preferably such that 0.7 g of the polycarbonate polymer is dissolved in 100 cc of methylene chloride and the specific viscosity measured at 20 ° C. is 0.3.
It is in the range of 8 to 1.54, more preferably 0.58 to 1.35, and particularly 0.77 to 1.16.
When the specific viscosity is less than 0.38, the mechanical strength as a resin is lowered, and the wear resistance may be insufficient. On the other hand, if the specific viscosity is greater than 1.54, it is difficult to produce a cast film by applying an appropriate film thickness.
（表面硬度）
本発明の電子写真感光体バインダー用ポリカーボネート共重合体は、感光体の表面層とした時の表面鉛筆硬度が２Ｈ以上である。
表面鉛筆硬度が、２Ｈより低い場合は、クリーニングブレード等感光体に当接している部材との圧接によりストレスクラックが入りやすくなる。
(surface hardness)
The polycarbonate copolymer for an electrophotographic photoreceptor binder of the present invention has a surface pencil hardness of 2H or more when used as a surface layer of a photoreceptor.
When the surface pencil hardness is lower than 2H, stress cracks easily occur due to pressure contact with a member that is in contact with the photosensitive member such as a cleaning blade.
（磨耗性）
本発明の電子写真感光体バインダー用ポリカーボネート共重合体はそれを用いて作製したキャストフィルムの磨耗輪ＣＳ−１７を使用し、荷重５００ｇｆで２０００回転磨耗を行ったテーバー試験の磨耗量が１２ｍｇ以下である。１０ｍｇ以下がより好ましく、８ｍｇ以下がさらに好ましい。
キャストフィルムのテーバー磨耗量が、１２ｍｇより大きい場合は、感光体の高耐久性化が困難となるため好ましくない。
(Abrasion)
The polycarbonate copolymer for an electrophotographic photosensitive member binder of the present invention uses a cast film wear wheel CS-17 produced by using the cast copolymer, and the wear amount of the Taber test in which 2000 rotation wear at a load of 500 gf is 12 mg or less. is there. 10 mg or less is more preferable, and 8 mg or less is more preferable.
If the Taber wear amount of the cast film is larger than 12 mg, it is difficult to make the photoreceptor more durable, which is not preferable.
（溶解性）
一般式（ＩＩ）の割合は、式（Ｉ）と一般式（ＩＩ）との合計モル数をを基準として４０〜７０モル％であることが必要である。
一般式（ＩＩ）の割合が４０未満では、溶剤に対する溶解性が低くなり溶液保存性が損なわれる。また、一般式（ＩＩ）の割合が７０より大きいと溶解性は良好であるが、鉛筆硬度が低くなる。
(Solubility)
The ratio of general formula (II) needs to be 40-70 mol% on the basis of the total number of moles of formula (I) and general formula (II).
If the ratio of general formula (II) is less than 40, the solubility with respect to a solvent will become low, and solution preservability will be impaired. Further, when the ratio of the general formula (II) is larger than 70, the solubility is good, but the pencil hardness is lowered.
次に、本発明の電子写真感光体は、複写機やプリンターに用いられ、導電性基体とその上に形成された感光層よりなり、この感光層中に上記本発明のポリカーボネート共重合体を含有させたものである。本発明の電子写真感光体は、導電性基体上に電荷発生層と電荷輸送層を順次積層した積層負帯電型、この積層負帯電型の電荷輸送層上に保護層を形成した負帯電型、導電性基体上に電荷輸送層と電化発生層を順次積層した正帯電型、バインダー樹脂中に電荷輸送物質と電荷発生物質を分散させた単層構造の感光層を導電性基体上に形成した単層正帯電型のいずれにも適用できる。具体的には、積層負帯電型の場合は電荷輸送層や保護層に上記ポリカーボネート共重合体を含有させ、積層正帯電型の場合には電荷発生層に上記ポリカーボネート共重合体を含有させ、単層構造の感光層の場合にはバインダー樹脂中に上記ポリカーボネート樹脂組成物を含有させる。 Next, the electrophotographic photosensitive member of the present invention is used in a copying machine or a printer, and is composed of a conductive substrate and a photosensitive layer formed thereon, and the photosensitive layer contains the polycarbonate copolymer of the present invention. It has been made. The electrophotographic photosensitive member of the present invention is a laminated negatively charged type in which a charge generation layer and a charge transport layer are sequentially laminated on a conductive substrate, a negatively charged type in which a protective layer is formed on this laminated negatively charged charge transport layer, A positively charged type in which a charge transport layer and a charge generation layer are sequentially laminated on a conductive substrate, and a single layer photosensitive layer in which a charge transport material and a charge generation material are dispersed in a binder resin. It can be applied to any of the positively charged layers. Specifically, in the case of the laminated negative charge type, the above-mentioned polycarbonate copolymer is contained in the charge transport layer and the protective layer, and in the case of the laminated positive charge type, the above-mentioned polycarbonate copolymer is contained in the charge generation layer. In the case of a photosensitive layer having a layer structure, the polycarbonate resin composition is contained in a binder resin.
更に具体的に説明すると、積層負帯電型の場合、電荷発生層は電荷発生物質を溶媒中で粉砕分散し、好ましくは平均粒径を０．３ミクロン以下にして、導電性基体上に膜厚０．０５〜５ミクロン程度に製膜する。また、分散液にバインダー樹脂を配合する代わりに、導電性基体と電荷発生層の間にバインダー樹脂層を設けてもよい。次いで電荷発生層の上に膜厚１５〜５０ミクロン程度の電荷輸送物質と上記本発明のポリカーボネート樹脂組成物からなる電荷輸送層を、電荷発生層と同様にして製膜する。この際上記本発明のポリカーボネート共重合体１０重量部に対して電荷輸送物質５〜５０重量部になる割合が好ましい。また製膜方法としては例えば浸漬法、スプレー法、ロール法等任意の方法が採用される。保護層を形成するときは保護層の樹脂として膜厚０．５〜１０ミクロン程度の上記本発明のポリカーボネート樹脂共重合体からなる層を設ける。 More specifically, in the case of a laminated negatively charged type, the charge generation layer pulverizes and disperses the charge generation material in a solvent, and preferably has an average particle size of 0.3 microns or less to form a film thickness on the conductive substrate. The film is formed to about 0.05 to 5 microns. Moreover, you may provide a binder resin layer between an electroconductive base | substrate and a charge generation layer instead of mix | blending binder resin with a dispersion liquid. Next, a charge transport layer comprising a charge transport material having a thickness of about 15 to 50 microns and the polycarbonate resin composition of the present invention is formed on the charge generation layer in the same manner as the charge generation layer. In this case, a ratio of 5 to 50 parts by weight of the charge transport material is preferable with respect to 10 parts by weight of the polycarbonate copolymer of the present invention. Moreover, as a film forming method, for example, an arbitrary method such as a dipping method, a spray method, or a roll method is adopted. When the protective layer is formed, a layer made of the polycarbonate resin copolymer of the present invention having a film thickness of about 0.5 to 10 microns is provided as the protective layer resin.
積層正帯電型の場合、電荷発生層が表層にあるので、上記ポリカーボネート共重合体を
電荷発生層に含有させる。電荷発生物質を溶媒中で粉砕分散した後上記ポリカーボネート
共重合体を配合するかまたは電荷発生物質と上記ポリカーボネート共重合体を溶媒中粉砕
分散し、膜厚１５〜５０ミクロン程度の電荷輸送層の上に膜厚０．５〜１０ミクロン程度の電荷発生層を形成する。この際上記ポリカーボネート樹脂１０ 重量部に対して電荷発生物質２〜３０重量部になる割合が好ましい。なお、電荷輸送層には電荷輸送物質と共に該ポリカーボネート共重合体をバインダー樹脂として用いる。
In the case of the laminated positively charged type, since the charge generation layer is on the surface layer, the polycarbonate copolymer is contained in the charge generation layer. After the charge generating material is pulverized and dispersed in a solvent, the polycarbonate copolymer is blended, or the charge generating material and the polycarbonate copolymer are pulverized and dispersed in a solvent, and the charge transporting layer having a film thickness of about 15 to 50 microns is formed. Then, a charge generation layer having a thickness of about 0.5 to 10 microns is formed. At this time, a ratio of 2 to 30 parts by weight of the charge generating substance with respect to 10 parts by weight of the polycarbonate resin is preferable. In the charge transport layer, the polycarbonate copolymer is used as a binder resin together with a charge transport material.
単層正帯電型の場合、上記ポリカーボネート共重合体１０重量部に対して電荷輸送物質０．５〜５重量部になる割合で用いるのが好ましい。導電性基体上に形成される感光層は、単層構造であっても、電荷発生層と電荷輸送層とに機能分離された積層構造であってもよい。積層構造の場合、電荷発生層と電荷輸送層の積層順序は任意でよい。感光層は、電荷発生物質、電化輸送物質、又はそれ等両者がバインダー樹脂中に含有された塗膜により構成される。電荷発生物質としては、例えば非晶質セレン、結晶性セレン、セレンーテルル合金、セレンーヒ素合金等セレンを主成分とした各種合金材料、酸化亜鉛、酸化チタン等の無機系光導電体、フタロシアニン系、スクエアリウム系、アントアントロン系、ペリレン系、アゾ系、アントラセン系、ピレン系、ピリチウム塩、チアピリリウム塩等の有機顔料及び染料が使用される。 In the case of a single-layer positively charged type, it is preferably used at a ratio of 0.5 to 5 parts by weight of the charge transport material with respect to 10 parts by weight of the polycarbonate copolymer. The photosensitive layer formed on the conductive substrate may have a single-layer structure or a laminated structure in which the functions of the charge generation layer and the charge transport layer are separated. In the case of a stacked structure, the order of stacking the charge generation layer and the charge transport layer may be arbitrary. The photosensitive layer is constituted by a coating film in which a charge generating material, an electrotransport material, or both are contained in a binder resin. Examples of charge generating materials include amorphous selenium, crystalline selenium, selenium-tellurium alloys, selenium-arsenic alloys and other alloy materials mainly composed of selenium, inorganic photoconductors such as zinc oxide and titanium oxide, phthalocyanine-based, square Organic pigments and dyes such as lithium, anthanthrone, perylene, azo, anthracene, pyrene, pyrithium salt and thiapyrylium salt are used.
また、電荷輸送物質としては、例えばカルバゾール、インドール、イミダゾール、チアゾール、ピラゾール、ピラゾリン等の複素環化合物、アニリン誘導体、スチルベン誘導体又はこれらの化合物からなる基本側鎖を有する重合体等の電子供与性物質が使用され、特にヒドラゾン誘導体、アニリン誘導体、スチルベン誘導体が好ましい。 Examples of the charge transport material include electron donating materials such as heterocyclic compounds such as carbazole, indole, imidazole, thiazole, pyrazole, pyrazoline, aniline derivatives, stilbene derivatives, or polymers having a basic side chain composed of these compounds. In particular, hydrazone derivatives, aniline derivatives, and stilbene derivatives are preferred.
以下、実施例を挙げて詳細に説明するが、本発明はその趣旨を超えない限り、何らこれに限定されるものではない。なお評価は下記の方法に従った。 Hereinafter, although an example is given and explained in detail, the present invention is not limited to this unless it exceeds the purpose. Evaluation was according to the following method.
（１）耐磨耗性評価
塩化メチレンにポリカーボネート共重合体８ｇを溶解させ、固形分濃度１０重量％の溶液を調製した。その溶液を１５０ｍｍφのシャーレ内に流し込み、一晩室温、４０℃で３時間、６０℃で３時間、溶媒を除去した後、１２０℃で２４時間乾燥し、２５０μｍ厚の透明キャストフィルムを得た。該キャストフィルムを直径１２０ｍｍの円盤状に切り出したものを使用し、東洋精機（株）社製 テーバー摩耗試験機を用いて摩耗評価を行った。試験条件は２３℃、５０％ＲＨの雰囲気下、摩耗輪ＣＳ−１７を用いて荷重５００ｇｆ（摩耗輪の自重を含む）で２０００回転後の摩耗量を試験前後の重量を比較することにより測定した。
(1) Evaluation of abrasion resistance 8 g of a polycarbonate copolymer was dissolved in methylene chloride to prepare a solution having a solid content concentration of 10% by weight. The solution was poured into a petri dish with a diameter of 150 mm, and after removing the solvent overnight at room temperature, 40 ° C. for 3 hours, and at 60 ° C. for 3 hours, it was dried at 120 ° C. for 24 hours to obtain a transparent cast film having a thickness of 250 μm. The cast film was cut into a disk shape having a diameter of 120 mm, and the wear was evaluated using a Taber abrasion tester manufactured by Toyo Seiki Co., Ltd. The test conditions were 23 ° C., 50% RH atmosphere, wear wheel CS-17 was used to measure the amount of wear after 2000 rotations with a load of 500 gf (including the own weight of the wear wheel) by comparing the weight before and after the test. .
（２）溶解性評価
得られたポリカーボネート共重合体を、トルエンとＴＨＦの２種の溶媒でそれぞれ２０ｗｔ％となるように溶解させた溶液を調整し、暗所で一週間保管した後、目視で透明性を確認した。
評価基準： ○；透明性維持、△；わずかに濁りが発生、×；白化
(2) Solubility evaluation A solution in which the obtained polycarbonate copolymer was dissolved in two solvents of toluene and THF so as to be 20 wt% each was prepared, stored for one week in the dark, and then visually. The transparency was confirmed.
Evaluation criteria: ○: Transparency maintenance, Δ: Slight turbidity occurred, ×: Whitening
（３）鉛筆硬度（樹脂）
（１）と同様にして得られたキャストフィルムを使用し、ＪＩＳ Ｋ５７００（ 鉛筆： 三菱Ｕｎｉ 、鉛筆角度： ４５度、荷重： ７５０ｇｆ ）に準じて鉛筆引っかき試験により測定した。
(3) Pencil hardness (resin)
The cast film obtained in the same manner as in (1) was used and measured by a pencil scratch test according to JIS K5700 (pencil: Mitsubishi Uni, pencil angle: 45 degrees, load: 750 gf).
（４）鉛筆硬度（電子写真感光体）
次に下記式［ＩＩＩ］で示されるヒドラジン化合物１０部及びバインダー樹脂としてポリカーボネート共重合体１０部をＴＨＦ６０部に溶解し、この溶液を電荷発生層の上に浸漬法によって塗布し、乾燥して２０ミクロンの電荷輸送層を形成した電子写真感光体を得た。ＪＩＳ Ｋ５７００（ 鉛筆： 三菱Ｕｎｉ 、鉛筆角度： ４５度、荷重： ７５０ｇｆ ）に準じて鉛筆引っかき試験により測定した。
(4) Pencil hardness (electrophotographic photoreceptor)
Next, 10 parts of a hydrazine compound represented by the following formula [III] and 10 parts of a polycarbonate copolymer as a binder resin are dissolved in 60 parts of THF, and this solution is applied onto the charge generation layer by a dipping method and dried. An electrophotographic photoreceptor having a micron charge transport layer was obtained. It was measured by a pencil scratch test according to JIS K5700 (pencil: Mitsubishi Uni, pencil angle: 45 degrees, load: 750 gf).
（５）ポリカーボネート共重合体の共重合組成分析
ポリマー３０ｍｇを重クロロホルム１．０ｍｌに溶解し、日本電子社製ＪＮＭ−ＡＬ４００の１Ｈ−ＮＭＲを用いて、積算回数１２８回で測定した。具体的に示すと、実施例１及び３においては、４，４’−ジヒドロキシ−３，３’−ジメチルビフェニル（以後ＯＣ−ＢＰと称することがある）の芳香族部位４H相当に起因するピーク（７．００〜７．１７ｐｐｍ）及び１，１−ビス（３−メチル−４−ヒドロキシフェニル）シクロヘキサン（以後ＯＣ−Ｚと称することがある）の芳香族部位６H相当に起因するピーク（７．３３〜７．５１ｐｐｍ）の積分比から求めた。
実施例２及び４においては、ＯＣ−ＢＰのメチル基６Ｈ相当に起因するピーク（２．３３〜２．４５ｐｐｍ）及び２，２−ビス（３−メチル−４ヒドロキシフェニル）プロパン（以後Ｂｉｓ−Ｃと称することがある）のメチル基６Ｈ相当に起因するピーク（２．２１〜２．３３ｐｐｍ）の積分比から求めた。
(5) Copolymer composition analysis of polycarbonate copolymer 30 mg of polymer was dissolved in 1.0 ml of deuterated chloroform, and the number of integration was measured 128 times using 1 H-NMR of JNM-AL400 manufactured by JEOL. Specifically, in Examples 1 and 3, the peak due to the aromatic portion 4H corresponding to 4,4′-dihydroxy-3,3′-dimethylbiphenyl (hereinafter sometimes referred to as OC-BP) ( (7.03 to 7.17 ppm) and 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane (hereinafter, sometimes referred to as OC-Z) peaks (7.33) ˜7.51 ppm).
In Examples 2 and 4, the peak (2.33 to 2.45 ppm) and 2,2-bis (3-methyl-4hydroxyphenyl) propane (hereinafter referred to as Bis-C) attributed to the methyl group 6H equivalent of OC-BP. It was calculated | required from the integral ratio of the peak (2.21-2.33 ppm) resulting from the methyl group 6H equivalency of the (sometimes called).
（６）ポリカーボネート共重合体のシーケンス評価（１３Ｃ−ＮＭＲ）
式（Ｉ）同士が隣り合う割合（ＮＩ−Ｉ），一般式（ＩＩ）同士が隣り合う割合（ＮＩＩ−ＩＩ），式（Ｉ）と一般式（ＩＩ）が隣り合う割合（ＮＩ−ＩＩ）試料１００ｍｇを重クロロホルム１ｍｌに溶解させ日本電子社製ＪＮＭ−ＡＬ４００にて積算回数２０４８回で測定した。具体的に示すと、実施例１及び３においては、１３Ｃ−ＮＭＲより、ＯＣ−ＢＰ同士が隣り合っている構造の中心カーボネート結合側のｏ−メチル基（１６．１４ｐｐｍ）と、ＯＣ−Ｚ同士が隣り合っている構造の中心カーボネート結合側のｏ−メチル基（１６．２９ｐｐｍ）と、ＯＣ−ＢＰ及びＯＣ−Ｚが隣り合っている構造の中心カーボネート結合側のｏ−メチル基（１６．１０ｐｐｍ、１６．３２ｐｐｍ）とではピークのケミカルシフトが異なる。従って、（ＮＩ−Ｉ），（ＮＩＩ−ＩＩ），（ＮＩ−ＩＩ）の割合は、検出位置の異なるＯＣ−ＢＰ成分とＯＣ−Ｚ成分のｏ−メチル基のピーク面積より求めた。
実施例２及び４においては、実施例１及び３と同様に、Ｂｉｓ−Ｃ同士が隣り合っている構造の中心カーボネート結合側のｏ−メチル基（１６．２０ｐｐｍ）と、ＯＣ−ＢＰ及びＢｉｓ−Ｃが隣り合っている構造の中心カーボネート結合側のｏ−メチル基（１６．１１ｐｐｍ、１６．１８ｐｐｍ）とではピークのケミカルシフトが異なる。従って、（ＮＩ−Ｉ），（ＮＩＩ−ＩＩ），（ＮＩ−ＩＩ）の割合は、検出位置の異なるＯＣ−ＢＰ成分とＢｉｓ−Ｃ成分のｏ−メチル基のピーク面積より求めた。
(6) Sequence evaluation of polycarbonate copolymer ( 13 C-NMR)
Ratio of adjacent formulas (I) (N I-I ), ratio of adjacent general formulas (II) (N II-II ), ratio of adjacent formula (I) and general formula (II) (N I -II ) 100 mg of a sample was dissolved in 1 ml of deuterated chloroform and measured with JNM-AL400 manufactured by JEOL Ltd. with a cumulative number of 2048 times. Specifically, in Examples 1 and 3, from 13 C-NMR, OC-BP is adjacent to the central carbonate bond-side o-methyl group (16.14 ppm), and OC-Z. The o-methyl group (16.29 ppm) on the central carbonate bond side of the structure adjacent to each other and the o-methyl group (16.29 ppm) on the central carbonate bond side of the structure where OC-BP and OC-Z are adjacent to each other. 10 ppm and 16.32 ppm), the chemical shift of the peak is different. Therefore, the ratio of (N I-I ), (N II-II ), and (N I-II ) was determined from the peak areas of the o-methyl groups of the OC-BP component and the OC-Z component having different detection positions. .
In Examples 2 and 4, as in Examples 1 and 3, the o-methyl group (16.20 ppm) on the central carbonate bond side of the structure in which Bis-C are adjacent to each other, OC-BP and Bis- The chemical shift of the peak is different from the o-methyl group (16.11 ppm, 16.18 ppm) on the central carbonate bond side of the structure in which C is adjacent. Therefore, the ratios of (N I-I ), (N II-II ), and (N I-II ) were determined from the peak areas of the o-methyl groups of the OC-BP component and the Bis-C component having different detection positions. .
［実施例１］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコに窒素雰囲気下にて１,１−ビス（３−メチル−４−ヒドロキシフェニル）シクロヘキサン（以下ＯＣ−Ｚと称する）５２．４ｇ（０．１７７モル）、４,４’−ジヒドロキシ−３,３’−ジメチルビフェニル（以下ＯＣ−ＢＰと称する）３７．９ｇ（０．１７７モル）、ハイドロサルファイト０．２７ｇ、９．１％水酸化ナトリウム水溶液５５０ｍｌ（水酸化ナトリウム１．３４５モル）、塩化メチレン３４０ｍｌを仕込んで溶解し、攪拌下１８〜２０℃に保持し、ホスゲン５０．８ｇ（０．５１３モル）を７０分要して吹込みホスゲン化反応させた。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．７４ｇ（０．００５０モル）および２５％水酸化ナトリウム水溶液３６ｍｌ（水酸化ナトリウム０．１７７モル）を加え撹拌し、途中トリエチルアミン０．１２ｍＬ（０．０００８９モル）を添加し、３０〜３５℃の温度で２時間反応させた。分離した塩化メチレン相を無機塩類及びアミン類がなくなるまで酸洗浄及び水洗した後、塩化メチレンを除去して共重合ポリカーボネートを得た。このポリカーボネートは、ＯＣ−ＺとＯＣ−ＢＰとの構成単位の比がモル比で５２：４８であり、比粘度は０．９６、ガラス転移温度は１４７℃であった。
[Example 1]
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 52.4 g (0.177 mol) of 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane (hereinafter referred to as OC-Z) in a nitrogen atmosphere. ) 3,4'-dihydroxy-3,3'-dimethylbiphenyl (hereinafter referred to as OC-BP) 37.9 g (0.177 mol), hydrosulfite 0.27 g, 9.1% aqueous sodium hydroxide solution 550 ml (Sodium hydroxide 1.345 mol) and 340 ml of methylene chloride were charged and dissolved, maintained at 18 to 20 ° C. with stirring, and 50.8 g (0.513 mol) of phosgene was required for 70 minutes for blowing phosgenation. I let you. After completion of the phosgenation reaction, 0.74 g (0.0050 mol) of p-tert-butylphenol and 36 ml of 25% aqueous sodium hydroxide solution (0.177 mol of sodium hydroxide) were added and stirred, and 0.12 mL (0.00089) of triethylamine was added along the way. Mol) was added and reacted at a temperature of 30-35 ° C. for 2 hours. The separated methylene chloride phase was washed with acid and water until inorganic salts and amines disappeared, and then methylene chloride was removed to obtain a copolymer polycarbonate. This polycarbonate had a molar ratio of OC-Z to OC-BP of 52:48, a specific viscosity of 0.96, and a glass transition temperature of 147 ° C.
［実施例２］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコに窒素雰囲気下にて２,２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン（以下Ｂｉｓ−Ｃと称する）７８．６ｇ（０．３０７モル）、４,４’−ジヒドロキシ−３,３’−ジメチルビフェニル（以下ＯＣ−ＢＰと称する）６５．６ｇ（０．３０７モル）、ハイドロサルファイト０．４３ｇ、９．８％水酸化ナトリウム水溶液８３７ｍｌ（水酸化ナトリウム２．２０７モル）、塩化メチレン５９０ｍｌを仕込んで溶解し、攪拌下１８〜２０℃に保持し、ホスゲン８５．０ｇ（０．８５８モル）を７０分要して吹込みホスゲン化反応させた。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール１．４７ｇ（０．００９８モル）および２５％水酸化ナトリウム水溶液４９ｍｌ（水酸化ナトリウム０．３０６モル）を加え撹拌し、途中トリエチルアミン０．１１ｍＬ（０．０００７６モル）を添加し、３０〜３５℃の温度で２時間反応させた。分離した塩化メチレン相を無機塩類及びアミン類がなくなるまで酸洗浄及び水洗した後、塩化メチレンを除去して共重合ポリカーボネートを得た。このポリカーボネートは、Ｂｉｓ−ＣとＯＣ−ＢＰとの構成単位の比がモル比で５２：４８であり、比粘度は０．９９、ガラス転移温度は１３３℃であった。
[Example 2]
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 78.6 g (0.307 mol) of 2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as Bis-C) in a nitrogen atmosphere. ) 65.6 g (0.307 mol) of 4,4′-dihydroxy-3,3′-dimethylbiphenyl (hereinafter referred to as OC-BP), 0.43 g of hydrosulfite, 837 ml of 9.8% aqueous sodium hydroxide solution (Sodium hydroxide 2.207 mol) and 590 ml of methylene chloride were charged and dissolved, and kept at 18 to 20 ° C. with stirring, and 85.0 g (0.858 mol) of phosgene was required for 70 minutes to blow phosgenation reaction I let you. After completion of the phosgenation reaction, 1.47 g (0.0098 mol) of p-tert-butylphenol and 49 ml of 25% aqueous sodium hydroxide solution (0.306 mol of sodium hydroxide) were added and stirred, and 0.11 mL (0.00076) of triethylamine was added along the way. Mol) was added and reacted at a temperature of 30-35 ° C. for 2 hours. The separated methylene chloride phase was washed with acid and water until inorganic salts and amines disappeared, and then methylene chloride was removed to obtain a copolymer polycarbonate. This polycarbonate had a molar ratio of Bis-C to OC-BP of 52:48, a specific viscosity of 0.99, and a glass transition temperature of 133 ° C.
［実施例３］
仕込みのモノマー量を、ＯＣ−Ｚ４１．９ｇ（０．１４２モル）、ＯＣ−ＢＰ４５．５ｇ（０．２１２モル）に変更した以外は、実施例１における手順を繰り返した。このポリカーボネートは、ＯＣ−ＺとＯＣ−ＢＰとの構成単位の比がモル比で４２：５８であり、比粘度は０．９４、ガラス転移温度は１４９℃であった。
[Example 3]
The procedure in Example 1 was repeated except that the monomer amount charged was changed to OC-Z 41.9 g (0.142 mol) and OC-BP 45.5 g (0.212 mol). The polycarbonate had a molar ratio of OC-Z to OC-BP of 42:58, a specific viscosity of 0.94, and a glass transition temperature of 149 ° C.
［実施例４］
仕込みのモノマー量を、Ｂｉｓ−Ｃ９４．３ｇ（０．３６８モル）、ＯＣ−ＢＰ５２．５ｇ（０．２４６モル）に変更した以外は、実施例２における手順を繰り返した。このポリカーボネートは、Ｂｉｓ−ＣとＯＣ−ＢＰとの構成単位の比がモル比で６１：３９であり、比粘度は１．００、ガラス転移温度は１３１℃であった。
[Example 4]
The procedure in Example 2 was repeated except that the amount of monomer charged was changed to Bis-C 94.3 g (0.368 mol) and OC-BP 52.5 g (0.246 mol). This polycarbonate had a molar ratio of Bis-C and OC-BP of 61:39, a specific viscosity of 1.00, and a glass transition temperature of 131 ° C.
［比較例１］
特開平４−１７９９６１の実施例２の追試を実施した。
仕込みモノマー量を１,１−ビス（４−ヒドロキシフェニル）シクロヘキサン（以下Ｂｉｓ−Ｚと称することがある）９３．２ｇ（０．３４８モル）を、６％濃度の水酸化ナトリウム水溶液に溶解した溶液と、塩化メチレン２５０ｍＬとを混合して撹拌しながら、冷却下、ホスゲン６３．０ｇ（０．６３６モル）を１５分要して吹込みホスゲン化反応させた。得られたオリゴマー溶液に塩化メチレンを加えて全量を４５０ｍＬとした後、４,４’−ジヒドロキシビフェニル（以下ＢＰと称することがある）２３．３ｇ（０．１２５モル）を８％濃度の水酸化ナトリウム水溶液１５０ｍＬに溶解した溶液およびｐ−ｔｅｒｔ−ブチルフェノール０．８９ｇ（０．００６０モル）を加えた。次いでこの混合液を激しく撹拌し、７％濃度のトリエチルアミン２ｍＬを加え、２８℃において撹拌下１．５時間反応を行った。反応後の操作は、実施例と同様に行った。このポリカーボネートは、Ｂｉｓ−ＺとＢＰとの構成単位の比がモル比で７５：２５であり、比粘度は０．９８、ガラス転移温度は１８４℃であった。
[Comparative Example 1]
A supplementary test of Example 2 of JP-A-4-179961 was carried out.
A solution prepared by dissolving 93.2 g (0.348 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter sometimes referred to as Bis-Z) in a 6% strength aqueous sodium hydroxide solution. Then, 250 mL of methylene chloride was mixed and stirred, and under cooling, 63.0 g (0.636 mol) of phosgene was required for 15 minutes to perform a blowing phosgenation reaction. Methylene chloride was added to the resulting oligomer solution to bring the total amount to 450 mL, and then 23.3 g (0.125 mol) of 4,4′-dihydroxybiphenyl (hereinafter sometimes referred to as BP) was hydroxylated at 8% concentration. A solution dissolved in 150 mL of an aqueous sodium solution and 0.89 g (0.0060 mol) of p-tert-butylphenol were added. The mixture was then vigorously stirred, 2 mL of 7% strength triethylamine was added, and the reaction was carried out at 28 ° C. with stirring for 1.5 hours. The operation after the reaction was performed in the same manner as in the example. This polycarbonate had a molar ratio of the constituent units of Bis-Z and BP of 75:25, a specific viscosity of 0.98, and a glass transition temperature of 184 ° C.
［比較例２］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコに窒素雰囲気下にてＢｉｓ−Ｃ４１．０ｇ（０．１６０モル）、ＢＰ１９．８ｇ（０．１０７モル）、８．５％水酸化ナトリウム水溶液３５６ｍｌ（水酸化ナトリウム０．８００モル）、塩化メチレン２５７ｍｌを仕込んで溶解し、攪拌下１８〜２０℃に保持し、ホスゲン３５．６ｇ（０．３６０モル）を７０分要して吹込みホスゲン化反応させた。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．５２ｇ（０．００３５モル）および２５％水酸化ナトリウム水溶液１７ｍｌ（水酸化ナトリウム０．１３３モル）を加え撹拌し、途中トリエチルアミン０．０９ｍＬ（０．０００６７モル）を添加し、３０〜３５℃の温度で２時間反応させた。分離した塩化メチレン相を無機塩類及びアミン類がなくなるまで酸洗浄及び水洗した後、塩化メチレンを除去して共重合ポリカーボネートを得た。このポリカーボネートは、Ｂｉｓ−ＣとＢＰとの構成単位の比がモル比で６０：４０であり、比粘度は０．９８、ガラス転移温度は１４１℃であった。
[Comparative Example 2]
A flask equipped with a phosgene blowing tube, a thermometer and a stirrer was charged with 41.0 g (0.160 mol) of Bis-C, 19.8 g (0.107 mol) of BP, and 356 ml of an aqueous 8.5% sodium hydroxide solution in a nitrogen atmosphere ( Sodium hydroxide (0.800 mol) and methylene chloride (257 ml) were charged and dissolved, and the mixture was kept at 18 to 20 ° C. with stirring, and 35.6 g (0.360 mol) of phosgene was required for 70 minutes to perform the blowing phosgenation reaction. It was. After completion of the phosgenation reaction, 0.52 g (0.0035 mol) of p-tert-butylphenol and 17 ml of 25% aqueous sodium hydroxide solution (0.133 mol of sodium hydroxide) were added and stirred, and 0.09 mL (0.00067) of triethylamine was added along the way. Mol) was added and reacted at a temperature of 30-35 ° C. for 2 hours. The separated methylene chloride phase was washed with acid and water until inorganic salts and amines disappeared, and then methylene chloride was removed to obtain a copolymer polycarbonate. This polycarbonate had a molar ratio of Bis-C and BP of 60:40, a specific viscosity of 0.98, and a glass transition temperature of 141 ° C.
［比較例３］
仕込みのモノマー量を、ＯＣ−Ｚ３１．４ｇ（０．１０７モル）、ＯＣ−ＢＰ５３．１ｇ（０．２４７モル）に変更した以外は、実施例１における手順を繰り返した。このポリカーボネートは、ＯＣ−ＺとＯＣ−ＢＰとの構成単位の比がモル比で３３：６７であり、ガラス転移温度は１４６℃であったが、比粘度は測定時の塩化メチレン濃度では溶解しなかったため測定できなかった。
[Comparative Example 3]
The procedure in Example 1 was repeated except that the monomer amount charged was changed to OC-Z 31.4 g (0.107 mol) and OC-BP 53.1 g (0.247 mol). In this polycarbonate, the ratio of the constituent units of OC-Z and OC-BP was 33:67 in terms of molar ratio, and the glass transition temperature was 146 ° C., but the specific viscosity was dissolved at the methylene chloride concentration at the time of measurement. It was not possible to measure because there was not.
［比較例４］
仕込みのモノマー量を、Ｂｉｓ−Ｃ１１７．９ｇ（０．４６０モル）、ＯＣ−ＢＰ３２
．８ｇ（０．１５４モル）に変更した以外は、実施例２における手順を繰り返した。このポリカーボネートは、Ｂｉｓ−ＣとＯＣ−ＢＰとの構成単位の比がモル比で７５：２５であり、比粘度は０．９９、ガラス転移温度は１２８℃であった。
[Comparative Example 4]
The amount of monomers charged was Bis-C117.9 g (0.460 mol), OC-BP32
. The procedure in Example 2 was repeated except that the amount was changed to 8 g (0.154 mol). In this polycarbonate, the ratio of the constituent units of Bis-C and OC-BP was 75:25 in terms of molar ratio, the specific viscosity was 0.99, and the glass transition temperature was 128 ° C.
［比較例５］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコに窒素雰囲気下にてＯＣ−ＢＰ１５．６ｇ（０．０７３モル）、１１．６％水酸化ナトリウム水溶液１１０ｍｌ（水酸化ナトリウム０．３２８モル）、ハイドロサルファイト０．０５ｇ、塩化メチレン７０ｍｌを仕込んで溶解し、攪拌下１８〜２０℃に保持し、ホスゲン１０．８ｇ（０．１０９モル）を７０分要して吹込みホスゲン化反応させ、ＯＣ−ＢＰオリゴマーを得た。一方で、ホスゲン吹込管、温度計及び攪拌機を備えたフラスコに窒素雰囲気下にてＯＣ−Ｚ２１．６ｇ（０．０７３モル）、ハイドロサルファイト０．０６ｇ、９．１％水酸化ナトリウム水溶液１１４ｍｌ（水酸化ナトリウム０．２７７モル）、塩化メチレン７０ｍｌを仕込んで溶解し、攪拌下１８〜２０℃に保持し、ホスゲン９．５ｇ（０．０９６モル）を７０分要して吹込みホスゲン化反応させ、ＯＣ−Ｚオリゴマーを得た。これら２種類のオリゴマーを混合させ、ｐ−ｔｅｒｔ−ブチルフェノール０．３１ｇ（０．００２１モル）および２５％水酸化ナトリウム水溶液１５ｍｌ（水酸化ナトリウム０．０７３モル）を加え撹拌し、途中トリエチルアミン０．０５ｍＬ（０．０００３７モル）を添加し、３０〜３５℃の温度で２時間反応させた。分離した塩化メチレン相を無機塩類及びアミン類がなくなるまで酸洗浄及び水洗した後、塩化メチレンを除去して共重合ポリカーボネートを得た。このポリカーボネートは、ＯＣ−ＺとＯＣ−ＢＰとの構成単位の比がモル比で５０：５０であり、比粘度は０．９６、ガラス転移温度は１４５℃であった。
以上、得られた各樹脂の物性を下記表１に示す。
[Comparative Example 5]
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 15.6 g (0.073 mol) of OC-BP, 110 ml of 11.6% aqueous sodium hydroxide solution (0.328 mol of sodium hydroxide), hydro 0.05 g of sulfite and 70 ml of methylene chloride were charged and dissolved, and the mixture was kept at 18 to 20 ° C. with stirring, and 10.8 g (0.109 mol) of phosgene was blown into the phosgenation reaction for 70 minutes. A BP oligomer was obtained. Meanwhile, in a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 21.6 g (0.073 mol) of OC-Z, 0.06 g of hydrosulfite, and 114 ml of a 9.1% aqueous sodium hydroxide solution in a nitrogen atmosphere ( Sodium hydroxide (0.277 mol) and methylene chloride (70 ml) were charged and dissolved, and the mixture was kept at 18 to 20 ° C. with stirring, and phosgene (9.5 g (0.096 mol)) was required for 70 minutes to blow phosgenation reaction. OC-Z oligomer was obtained. These two kinds of oligomers are mixed, and 0.31 g (0.0021 mol) of p-tert-butylphenol and 15 ml of 25% aqueous sodium hydroxide solution (0.073 mol of sodium hydroxide) are added and stirred. (0.00037 mol) was added and reacted at a temperature of 30 to 35 ° C. for 2 hours. The separated methylene chloride phase was washed with acid and water until inorganic salts and amines disappeared, and then methylene chloride was removed to obtain a copolymer polycarbonate. This polycarbonate had a molar ratio of OC-Z to OC-BP of 50:50, a specific viscosity of 0.96, and a glass transition temperature of 145 ° C.
The physical properties of the obtained resins are shown in Table 1 below.
本発明の特定の構造を含有するポリカーボネート共重合体は、耐摩耗性に優れるとともに、複写機、レーザービームプリンター等の感光体作製時の溶媒中での保存安定性も高く、耐摩耗性に優れる上、高い表面硬度も有していることから電子写真感光体用バインダー樹脂として好適に用いられ、その奏する工業的効果は格別である。 The polycarbonate copolymer containing the specific structure of the present invention is excellent in abrasion resistance, and also has high storage stability in a solvent when producing a photoreceptor such as a copying machine and a laser beam printer, and is excellent in abrasion resistance. In addition, since it also has a high surface hardness, it is suitably used as a binder resin for electrophotographic photoreceptors, and the industrial effects that it exhibits are exceptional.
Claims (4)
（ＮＩ−Ｉ）≦０．５×（ＮＩ）・・・（１）
（式中、（ＮＩ−Ｉ）は式（Ｉ）と（Ｉ）、一般式（ＩＩ）と（ＩＩ）及び式（Ｉ）と一般式（ＩＩ）が隣り合う場合の合計数を基準とした際の、式（Ｉ）と（Ｉ）とが隣り合う割合を表し、更に（ＮＩ）は、式（Ｉ）と一般式（ＩＩ）の合計モル数を基準とした場合の式（Ｉ）のモル分率を意味する。）
(N I-I ) ≦ 0.5 × (N I ) (1)
(Wherein (N I-I ) is based on the total number of formulas (I) and (I), general formulas (II) and (II), and formula (I) and general formula (II)). The formulas (I) and (I) represent the ratio of adjacent to each other, and (N I ) represents the formula (I) based on the total number of moles of the formula (I) and the general formula (II). ) Means the mole fraction.)
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