JPH01156752A - Carrier generating material and preparation of same - Google Patents
Carrier generating material and preparation of sameInfo
- Publication number
- JPH01156752A JPH01156752A JP62316462A JP31646287A JPH01156752A JP H01156752 A JPH01156752 A JP H01156752A JP 62316462 A JP62316462 A JP 62316462A JP 31646287 A JP31646287 A JP 31646287A JP H01156752 A JPH01156752 A JP H01156752A
- Authority
- JP
- Japan
- Prior art keywords
- generating material
- rhodanine
- carrier generating
- polymer
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 2
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 125000001424 substituent group Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000969 carrier Substances 0.000 abstract description 9
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 108091008695 photoreceptors Proteins 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000007857 hydrazones Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- JGRMXPSUZIYDRR-UHFFFAOYSA-N 2-(4-oxo-2-sulfanylidene-1,3-thiazolidin-3-yl)acetic acid Chemical compound OC(=O)CN1C(=O)CSC1=S JGRMXPSUZIYDRR-UHFFFAOYSA-N 0.000 description 3
- -1 carbonyloxyethyl Chemical group 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 150000003219 pyrazolines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZBUUHLDYMKTVLT-UHFFFAOYSA-N 3-amino-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound NN1C(=O)CSC1=S ZBUUHLDYMKTVLT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006363 carbonyl oxy alkylene group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002382 photo conductive polymer Polymers 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/07—Polymeric photoconductive materials
- G03G5/075—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/07—Polymeric photoconductive materials
- G03G5/071—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、電子写真感光体などに用いる電荷発生材料、
とくに可視光でキャリアを生成するとともに成膜性に優
れた電荷発生材料およびその製法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a charge generating material used in an electrophotographic photoreceptor, etc.
In particular, the present invention relates to a charge generating material that generates carriers using visible light and has excellent film forming properties, and a method for producing the same.
（従来技術）
有機光導電性化合物を用いた実用的なデバイスとしては
電子写真感光体がある。このような有機光導電性化合物
のうち、ポリビニルカルバゾール（ＰＶＣｚ）等の高分
子系の光導電性物質は成膜性が高く、電子写真感光体の
ように広面積を必要とするデバイスに適している。しか
し、これらの高分子系の物質は、いずれも主鎖または側
鎖に大きな芳香環や複素環を有しており、π電子系の連
なりを利用して紫外光の吸収で励起された励起子の解離
によって生じたキャリアが移動して光導電性が得られる
ものであるので、可視光領域ではキャリアの発生効率が
低く、そのため電荷輸送材料として利用されるか、ある
いは有機顔料、染料など可視光に怒度を有する物質とと
もに利用されることが多い。また、ヒドラゾン誘導体等
の低分子系の光導電性物質は電気伝導性は高いが可視光
領域のキャリア発生効率は高分子系と同様に低く、また
成膜性にやや劣るため、樹脂や前述の増感剤とともに電
荷輸送材料として用いられている。−方、可視光領域に
吸収域を有しキャリアの発生効率の高い物質として有機
顔料、染料がある。これらの物質は電気伝導性、成膜性
がほとんど無いため電荷発生材料として樹脂に分散させ
たり、前述の電荷輸送材料に分散させたりして用いられ
ている。(Prior Art) An electrophotographic photoreceptor is a practical device using an organic photoconductive compound. Among these organic photoconductive compounds, polymeric photoconductive substances such as polyvinylcarbazole (PVCz) have high film-forming properties and are suitable for devices that require a large area such as electrophotographic photoreceptors. There is. However, all of these polymeric substances have large aromatic rings or heterocycles in their main chains or side chains, and utilize the chain of π-electron systems to generate excitons excited by absorption of ultraviolet light. Photoconductivity is obtained by the movement of carriers generated by the dissociation of , so the generation efficiency of carriers is low in the visible light region, so it is used as a charge transport material, or it is used as a material for visible light such as organic pigments and dyes. It is often used in conjunction with substances that have a degree of anger. Furthermore, although low-molecular-weight photoconductive materials such as hydrazone derivatives have high electrical conductivity, their carrier generation efficiency in the visible light region is as low as polymer-based materials, and their film-forming properties are somewhat inferior. It is used as a charge transport material together with a sensitizer. On the other hand, organic pigments and dyes are substances that have an absorption region in the visible light region and have a high carrier generation efficiency. Since these substances have almost no electrical conductivity or film-forming properties, they are used as charge-generating materials by being dispersed in resins or in the aforementioned charge-transporting materials.
（発明が解決しようとする問題点）
前述したように、光導電性高分子は可視光に対して導電
性を示さず、またヒドラゾン誘導体等の低分子導電性化
合物はキャリアを発生しないため電子写真感光体として
用いる場合には単独で使用することができず可視光に感
光性や増感性を有する染料、顔料の添加が必要である。(Problems to be Solved by the Invention) As mentioned above, photoconductive polymers do not show conductivity to visible light, and low-molecular conductive compounds such as hydrazone derivatives do not generate carriers, so they are not suitable for electrophotography. When used as a photoreceptor, it cannot be used alone and requires the addition of dyes or pigments that are sensitive or sensitizing to visible light.
従ってこれらの方法はいずれも顔料の結着樹脂中への分
散が必要であるため、その分散方法、分散液安定性等に
問題があった。Therefore, since all of these methods require dispersion of the pigment into the binder resin, there are problems with the dispersion method, stability of the dispersion, and the like.
即ち、結着樹脂中に溶剤に不溶な顔料を均一に分散する
ことは難しく、また、分散液の安定性に問題があるため
塗布液の寿命が短くなる等の問題点があった。That is, it is difficult to uniformly disperse a pigment insoluble in a solvent in a binder resin, and there are also problems in that the stability of the dispersion liquid is poor, resulting in a shortened lifespan of the coating liquid.
さらに、顔料は凝集体であるために顔料製造工程の条件
の差が作成する感光体の電子写真特性に大きく影響する
。それを解決するための顔料の物性制御に技術的課題が
あった。Furthermore, since pigments are aggregates, differences in the conditions of the pigment manufacturing process greatly affect the electrophotographic characteristics of the photoreceptor produced. To solve this problem, there was a technical problem in controlling the physical properties of pigments.
従って、本発明の目的は可視光でキャリアを生成すると
ともに、成膜性に優れた電荷発生材料およびその製法を
提供するにある。Therefore, an object of the present invention is to provide a charge-generating material that generates carriers using visible light and has excellent film-forming properties, and a method for producing the same.
（問題点を解決するための手段）
即ち、本発明によれば鎖状高分子の側鎖にローダニン誘
導体を具備した電荷発生材料が提供される。(Means for Solving the Problems) That is, according to the present invention, there is provided a charge generating material comprising a rhodanine derivative in the side chain of a chain polymer.
さらに、側鎖に反応性置換基を有する高分子化合物と、
反応性置換基を有するローダニン誘導体とを反応させ、
鎖状高分子の側鎖にローダニン誘導体を結合させること
を特徴とする電荷発生材料の製法が提供される。Furthermore, a polymer compound having a reactive substituent in its side chain,
reacting with a rhodanine derivative having a reactive substituent,
A method for producing a charge generating material is provided, which is characterized by bonding a rhodanine derivative to the side chain of a chain polymer.
（作用）
本発明の可視光でキャリヤを発生させる重合体は、分子
鎖にローダニン環とローダニン環の５位にベンジリデン
基を有する。上記重合体はローダニン環部が電子受容体
、ベンジリデン部が電子供与体と考えられ、可視光によ
り分子内電荷移動型錯体を形成する。 つまり、基底状
態の電子供与体に非局在化していたπ電子が基ｒ＝Ｃ＝
ＣＨ−」を通じて電子受容体の空軌道に遷移する際に光
エネルギーを吸収して発色する。光キャリアは、この光
励起により発生する。(Function) The polymer of the present invention that generates carriers with visible light has a rhodanine ring in its molecular chain and a benzylidene group at the 5-position of the rhodanine ring. In the above polymer, the rhodanine ring part is considered to be an electron acceptor, and the benzylidene part is considered to be an electron donor, and forms an intramolecular charge transfer type complex when exposed to visible light. In other words, the π electrons delocalized in the electron donor in the ground state become the group r=C=
When it transfers to the empty orbit of an electron acceptor through CH-, it absorbs light energy and develops color. Photocarriers are generated by this photoexcitation.
このように光キャリアを発生させる本発明の電荷発生材
料は、それ自身で成膜性や透光性に優れ−た重合体とな
っている。それゆえ、この電荷発生材料は例えば、ヒド
ラゾン誘導体、トリフェニルアミン誘導体、ピラゾリン
誘導体のようなホール輸送材料を組み合わせることによ
り重合体で発生した光キャリアを重合体中に相溶させた
ホール輸送材料を通して移動可能なポリマー型の光Ｗ電
性材料とすることができるものである。The charge-generating material of the present invention that generates photocarriers in this manner is itself a polymer with excellent film-forming properties and translucency. Therefore, this charge-generating material can be used, for example, by combining hole-transporting materials such as hydrazone derivatives, triphenylamine derivatives, and pyrazoline derivatives to transfer photocarriers generated in the polymer through hole-transporting materials that are made compatibilized in the polymer. It can be made into a mobile polymer type photoconductor material.
この場合、光導電性材料そのものに顔料等を分散させて
いないので成膜性はもとより透光性並びに安定性に優れ
た光導電性材料となるのである。In this case, since no pigment or the like is dispersed in the photoconductive material itself, the photoconductive material has excellent film-forming properties, light transmittance, and stability.
（発明の好適態様）
本発明の重合体としての電荷発生材料は、反応性置換基
を有するローダニン誘導体と、反応性置換基を有する高
分子化合物とを反応させ結合させることにより得られる
。(Preferred Embodiment of the Invention) The charge generating material as a polymer of the present invention can be obtained by reacting and bonding a rhodanine derivative having a reactive substituent with a polymer compound having a reactive substituent.
かかる重合体の成分であるローダニン誘導体は、下記一
般式
Ｓ
（式中Ｂは反応性を有する置換基、Ｃは２価の有機基、
Ｒ，は低級アルキル基、水酸基を示す）で表される。Ｃ
は炭素数４以下のアルキレン基、フェニレン基等のアリ
ーレン基、カルボニルオキシエチル、カルボニルオキシ
プロピレン基等のカルボニルオキシアルキレン基が例示
される。Ｒ１には、アルキル基としては、メチル、エチ
ル、プロピル、イソプロピル、ブチル、イソブチル、ｔ
ｅｒｔ−ブチル、ペンチル、ヘキシル基等の低級アルキ
ル基が例示される。The rhodanine derivative, which is a component of such a polymer, has the following general formula S (where B is a reactive substituent, C is a divalent organic group,
R represents a lower alkyl group or a hydroxyl group. C
Examples include alkylene groups having 4 or less carbon atoms, arylene groups such as phenylene groups, and carbonyloxyalkylene groups such as carbonyloxyethyl and carbonyloxypropylene groups. R1 has an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t
Examples include lower alkyl groups such as ert-butyl, pentyl, and hexyl groups.
具体的には、
Ｓ
上記具体例に示すように反応性置換基Ｂとしては、−（
、ＯＯＨ−ＣＨ２Ｃｌ −０１１−ＣＯＣＩ−ＮＨＫ等
が例示される。Specifically, S As shown in the above specific example, the reactive substituent B is -(
, OOH-CH2Cl-011-COCI-NHK and the like.
これらのローダニン誘導体は、種々の方法、例えば下記
反応式により合成することができる。These rhodanine derivatives can be synthesized by various methods, such as the following reaction formula.
Ｓ （１）
（式中Ｂ及びＲ１は前記と同じ）
すなわち、ローダニン誘導体は（２）で表される３−置
換ローダニンと、（３）で表されるＰ−置換ベンズアル
デヒドを等モル反応させることにより得ることができる
。S (1) (In the formula, B and R1 are the same as above) That is, the rhodanine derivative is obtained by reacting equimolar amounts of 3-substituted rhodanine represented by (2) and P-substituted benzaldehyde represented by (3). It can be obtained by
上述したローダニン誘導体を結合させる反応性置換基を
有する高分子としては例えば
下記反復単位
→ＣＨ２−ＣＨ←
（ＣＨｚ）−
Ｈ２
（式中ｍは０〜３の整数を示す）で表されるポリアリル
アミン、
下記反復単位
→ＣＨＩ−ＣＨ←
（式中Ｒ２は−ＣＨ２Ｃ１，−ＮＨｚ、−３ｏ□Ｃ１，
−ＣｏｏＨを示す）で表されるスチレン系重合体、
下記反復単位
、Ｒ３
→ＣＨ２−Ｃ←
ＯＯＨ
→ＣＨ２−Ｃ←
Ｃ；Ｏ
Ｈ２
→ＣＨ２−Ｃ←
Ｃ＝０
（ＣＨ２）。An example of a polymer having a reactive substituent to which the rhodanine derivative described above is bonded is polyallylamine represented by the following repeating unit → CH2-CH← (CHz)-H2 (in the formula, m represents an integer of 0 to 3). , the following repeating unit → CHI-CH← (in the formula, R2 is -CH2C1, -NHZ, -3o□C1,
-CooH), the following repeating unit: R3 → CH2-C← OOH → CH2-C← C; O H2 → CH2-C← C=0 (CH2).
Ｈ２
（式中Ｒ８は水素原子又はメチル基、ｍは０〜３の整数
を示すで表されるアクリルまたはメタクリル系重合体や
これらの共重合体、
下記反復単位
で表されるポリカーボネート樹脂、
さらに、前記スチレン系重合体やボリカーボふ一ト樹脂
のように主鎖または側鎖にフェニル環を有した高分子に
対してＣＨｚ ＣＯＣＨｚ Ｃ１を反応させ、反応性置
換基として−ＣＨ２Ｃ１を有した高分子が例示される。H2 (in the formula, R8 is a hydrogen atom or a methyl group, m is an integer of 0 to 3, an acrylic or methacrylic polymer or a copolymer thereof, a polycarbonate resin represented by the following repeating unit, and A polymer having a phenyl ring in the main chain or side chain, such as the styrene polymer or polycarbonate resin, is reacted with CHHz COCHz C1 to form a polymer having -CH2C1 as a reactive substituent. Illustrated.
これらの重合体とローダニン誘翼体との反応は、例えば
下記反応によって達成される。The reaction between these polymers and rhodanine derivatives is achieved, for example, by the following reaction.
（以下余白）
Ｎｌ＋□
Ｒ７
（５）Ｓ
Ｉ
上記具体例中ｎは、２０．０００〜２００，０００の整
数を示す。(The following is a blank space) Nl+□ R7 (5) S I In the above specific examples, n represents an integer of 20.000 to 200,000.
（発明の効果）
本発明による重合体は、可視光でキャリアを発生するの
で従来公知のＰＶＣ２等の高分子系の光導電性物質の様
に可視光増感の必要性がないためキャリア発生顔料と組
み合わせて用いなくてもよく、また必要に応じてヒドラ
ゾンＢＡ ’Ａ体、トリフェニルアミンｆＡｍ体、ピラ
ゾリン誘導体等従来公知の電荷輸送材料と容易に固溶体
を形成する。(Effects of the Invention) The polymer according to the present invention generates carriers with visible light, so there is no need for visible light sensitization unlike conventionally known polymeric photoconductive materials such as PVC2, so it is a carrier-generating pigment. It does not need to be used in combination with hydrazone BA'A form, triphenylamine fAm form, pyrazoline derivatives, and other conventionally known charge transport materials as needed to easily form a solid solution.
従って、溶媒に溶解し塗布するだけで分子分散された均
一な薄膜が容易に作成できる。Therefore, a uniform thin film with molecularly dispersed molecules can be easily created by simply dissolving it in a solvent and applying it.
更に、高分子化合物であるので低分子化合物に比べて衛
生釣書が少ない。Furthermore, since it is a high-molecular compound, there are fewer sanitary fishing records compared to low-molecular compounds.
（実施例） 以下に、実施例に基づき本発明をより詳細に説明する。(Example) Hereinafter, the present invention will be explained in more detail based on Examples.
■光体■作威
実施例１
〔ローダニン誘導体の合成〕
３−カルボキシメチル−５−（Ｐ−エチルベンジリデン
）ローダニンの合成
３−カルボキシメチルローダニン１９．１ｇと、Ｐ−エ
チルベンズアルデヒド１７．７ｇをＤＭＦ中、１００℃
で反応させた。３時間後、反応溶液・を水に加え、得ら
れる沈澱を水洗後、アセトンで再結晶することにより上
記化合物を得た（収率８７％）。■Light body■Production Example 1 [Synthesis of rhodanine derivative] Synthesis of 3-carboxymethyl-5-(P-ethylbenzylidene) rhodanine 19.1 g of 3-carboxymethyl rhodanine and 17.7 g of P-ethylbenzaldehyde were added. 100℃ in DMF
I reacted with After 3 hours, the reaction solution was added to water, and the resulting precipitate was washed with water and then recrystallized with acetone to obtain the above compound (yield: 87%).
ポリクロルメチルスチレン１５．２ｇと３−カルボキシ
メチル−５−（Ｐ−エチルベンジリデン）ローダニン３
５ｇとトリエチルアミン１２ｍ１を１００ ｍ ｌのジ
メチルホルムアミドに溶解し、１００℃で３時間反応さ
せる。15.2 g of polychloromethylstyrene and 3-carboxymethyl-5-(P-ethylbenzylidene) rhodanine
5 g of triethylamine and 12 ml of triethylamine were dissolved in 100 ml of dimethylformamide and reacted at 100°C for 3 hours.
反応後、溶液をメタノール中に注ぎ生じた沈澱を水洗メ
タノール洗浄後、ＴＨＦ／メタノールで再沈澱し減圧乾
燥することにより、ポリスチレンの側鎖にＮ−置換−５
−（Ｐ−エチルベンジリデン）ローダニンを担持した電
荷発生材料を得た。After the reaction, the solution was poured into methanol, the resulting precipitate was washed with water, washed with methanol, reprecipitated with THF/methanol, and dried under reduced pressure to add N-substituted -5 to the side chain of polystyrene.
A charge generating material carrying -(P-ethylbenzylidene)rhodanine was obtained.
得られたローダニン誘導体を側鎖に担持した電荷発生材
料７重量部、４−ジエチルアミノベンズアルデヒド−１
，２−ジフェニルヒドラゾン３重量部をＴＨＦ １００
重量部に溶解し、アルミシート上にドクターブレードを
用いて塗布し、１００℃で３０分間乾燥し、２０μｍの
電子写真感光体を作製した。7 parts by weight of a charge generating material carrying the obtained rhodanine derivative on its side chain, 4-diethylaminobenzaldehyde-1
, 3 parts by weight of 2-diphenylhydrazone in THF 100
The solution was dissolved in parts by weight, applied onto an aluminum sheet using a doctor blade, and dried at 100° C. for 30 minutes to produce a 20 μm electrophotographic photoreceptor.
実施例２
〔ローダニン誘導体の合成〕
３−アミノ−５−（Ｐ−エチルベンジリデン）ローダニ
ンの合成
上記実施例１の３−カルボキシメチルローダニンに変え
て、３−アミノローダニンを用いて前記実施例１と同様
にして上記化合物を得た（収率７３％）。Example 2 [Synthesis of rhodanine derivative] Synthesis of 3-amino-5-(P-ethylbenzylidene)rhodanine 3-aminorhodanine was used in place of 3-carboxymethylrhodanine in Example 1 above. The above compound was obtained in the same manner as in 1 (yield 73%).
ポリメタクリル酸クロライド１０．５ｇと３＝アミノ−
５−（Ｐ−エチルベンジリデン）ローダニン３０．７ｇ
を１００ｍ１のピリジン中８０°Ｃで３時間反応させる
。反応後、溶液をメタノール中に注ぎ生じた沈澱を水洗
、メタノール洗浄後、ＴＨＦ／メタノールで再沈澱し減
圧乾燥することにより、ポリメタクリル酸の側鎖にＮ−
置換−５−（Ｐ−エチルベンジリデン）ローダニン誘導
体した電荷発生材料を得た。10.5 g of polymethacrylic acid chloride and 3=amino-
5-(P-ethylbenzylidene)rhodanine 30.7g
are reacted in 100 ml of pyridine at 80°C for 3 hours. After the reaction, the solution was poured into methanol and the resulting precipitate was washed with water and methanol, then reprecipitated with THF/methanol and dried under reduced pressure to add N- to the side chains of polymethacrylic acid.
A charge generating material containing a substituted-5-(P-ethylbenzylidene)rhodanine derivative was obtained.
電荷発生材料を上記化合物とした以外は、実施例１と同
様にして感光体を作製した。A photoreceptor was produced in the same manner as in Example 1 except that the above compound was used as the charge generating material.
実施例３
〔ローダニン誘導体の合成〕
３−（Ｐ−クロルメチルフェニル）−５−（Ｐ−エチル
ベンジリデン）ローダニンの合成前記実施例１の３−カ
ルボキシメチルローダニンに変工て、３−（Ｐ−クロル
メチルフェニル）ローダニンを用いて、前記実施例１と
同様にして上記化合物を得た（収率７０％）。Example 3 [Synthesis of rhodanine derivative] Synthesis of 3-(P-chloromethylphenyl)-5-(P-ethylbenzylidene)rhodanine Modified to 3-carboxymethylrhodanine of Example 1, 3-(P- -Chlormethylphenyl)rhodanine was used to obtain the above compound in the same manner as in Example 1 (yield 70%).
ポリメタクリル酸８．６ｇと３−（Ｐ−クロルメチルフ
ェニル）−５−（Ｐ−エチルベンジリデン）ローダニン
４１．２ｇとトリエチルアミン１２ｍ１を１００ｍ１の
ジメチルホルムアミド解し、１００°Ｃで３時間反応さ
せる。反応後、溶液をメタノール中に注ぎ生じた沈澱を
水洗、メタノール洗浄後、ＴＨＦ／メタノールで再沈澱
し減圧乾燥することにより、ポリメタクリル酸の側鎖ニ
Ｎ ｆ換５ （Ｐ−エチルベンジリデン）ローダニ
ンを担持した電荷発生材料を得た。8.6 g of polymethacrylic acid, 41.2 g of 3-(P-chloromethylphenyl)-5-(P-ethylbenzylidene)rhodanine, and 12 ml of triethylamine were dissolved in 100 ml of dimethylformamide and reacted at 100°C for 3 hours. After the reaction, the solution was poured into methanol, the resulting precipitate was washed with water, washed with methanol, reprecipitated with THF/methanol, and dried under reduced pressure to obtain Nf-converted 5 (P-ethylbenzylidene) rhodanine in the side chain of polymethacrylic acid. A charge-generating material carrying the was obtained.
電荷発生材料を上記化合物とした以外は、実施例１と同
様にして感光体を作製した。A photoreceptor was produced in the same manner as in Example 1 except that the above compound was used as the charge generating material.
電子− 感 体の評価
上記電子写真感光体の帯電特性、感光特性を調べるため
、静電複写紙試験装置（川口電機社製、ＳＩ”４ ２
Ｂ型）を用いて、＋６．０ｋＶの条件で５秒間コロナ放
電を行うことにより、前記各感光体を正に帯電させ、こ
の時の表面電位■。を測定した。次いで、タングステン
ランプを用いて、感光体表面の照度が２０１ｕｘになる
ように調整すると共に、タングステンランプにより露光
し、上記表面電位ｖ０が１／２となるまでの時間を求め
、半減露光量Ｅ１／２を算出した。Evaluation of the electrophotographic photoreceptor In order to investigate the charging characteristics and photosensitive characteristics of the electrophotographic photoreceptor described above, an electrostatic copying paper tester (manufactured by Kawaguchi Electric Co., Ltd., SI"4 2) was used.
By performing corona discharge for 5 seconds at +6.0 kV using Type B), each of the photoreceptors was positively charged, and the surface potential at this time was . was measured. Next, using a tungsten lamp, adjust the illuminance on the surface of the photoreceptor to 201ux, and expose it to light using the tungsten lamp.The time until the surface potential v0 becomes 1/2 is determined, and the half-reduced exposure amount E1/ 2 was calculated.
各感光体の帯電特性および感光特性の測定結果を表１に
示す。Table 1 shows the measurement results of the charging characteristics and photosensitive characteristics of each photoreceptor.
表１
表１かられかるように本発明の電荷発生材料を用いた感
光体は帯電性に優れ、半減露光量も小さく、良好な電子
写真特性を示した。Table 1 As can be seen from Table 1, the photoreceptor using the charge generating material of the present invention had excellent charging properties, had a small half-decrease exposure amount, and exhibited good electrophotographic properties.
特許出願人 三田工業株式会社Patent applicant: Sanda Kogyo Co., Ltd.
Claims (2)
を示す）を有するローダニン誘導体を具備した電荷発生
材料。(1) A rhodanine derivative having the following general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (in the formula, R_1 represents a lower alkyl group having 1 to 6 carbon atoms or a hydroxyl group) in the side chain of a chain polymer. Charge generating material.
造式 ▲数式、化学式、表等があります▼ （式中Ｂは反応性を有する置換基、Ｃは２価の有機基、
Ｒ＿１は炭素数１〜６の低級アルキル基、水酸基、Ｐは
０または１を示す）を有するローダニン誘導体とを反応
させることを特徴とする電荷発生材料の製法。(2) A chain polymer with a reactive substituent in its side chain and the following structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, B is a reactive substituent, and C is a divalent organic group. ,
R_1 is a lower alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and P represents 0 or 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62316462A JPH01156752A (en) | 1987-12-14 | 1987-12-14 | Carrier generating material and preparation of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62316462A JPH01156752A (en) | 1987-12-14 | 1987-12-14 | Carrier generating material and preparation of same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01156752A true JPH01156752A (en) | 1989-06-20 |
Family
ID=18077365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62316462A Pending JPH01156752A (en) | 1987-12-14 | 1987-12-14 | Carrier generating material and preparation of same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01156752A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235573B2 (en) | 2002-09-30 | 2007-06-26 | The Regents Of The University Of California | Methods of treating secretory diarrhea using cystic fibrosis transmembrane conductance regulator protein inhibitors |
-
1987
- 1987-12-14 JP JP62316462A patent/JPH01156752A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235573B2 (en) | 2002-09-30 | 2007-06-26 | The Regents Of The University Of California | Methods of treating secretory diarrhea using cystic fibrosis transmembrane conductance regulator protein inhibitors |
| US7638543B2 (en) | 2002-09-30 | 2009-12-29 | The Regents Of The University Of California | Cystic fibrosis transmembrane conductance regulator protein inhibitors and uses thereof |
| US8058295B2 (en) | 2002-09-30 | 2011-11-15 | The Regents Of The University Of California | Cystic fibrosis transmembrane conductance regulator protein inhibitors and uses thereof |
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