JPS63270654A - Bis(diazonium) salt compound and production thereof - Google Patents
Bis(diazonium) salt compound and production thereofInfo
- Publication number
- JPS63270654A JPS63270654A JP10548887A JP10548887A JPS63270654A JP S63270654 A JPS63270654 A JP S63270654A JP 10548887 A JP10548887 A JP 10548887A JP 10548887 A JP10548887 A JP 10548887A JP S63270654 A JPS63270654 A JP S63270654A
- Authority
- JP
- Japan
- Prior art keywords
- bis
- compound
- diazonium
- formula
- decapentaene
- 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.)
- Granted
Links
- -1 diazonium) salt compound Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 abstract description 3
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 3
- FFCMQWQQUMRRRC-UHFFFAOYSA-N 1-nitro-4-[10-(4-nitrophenyl)deca-1,3,5,7,9-pentaenyl]benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1C=CC=CC=CC=CC=CC1=CC=C([N+]([O-])=O)C=C1 FFCMQWQQUMRRRC-UHFFFAOYSA-N 0.000 abstract description 2
- FVKHZYMNMKZOMV-UHFFFAOYSA-N 4-[10-(4-aminophenyl)deca-1,3,5,7,9-pentaenyl]aniline Chemical compound C1=CC(N)=CC=C1C=CC=CC=CC=CC=CC1=CC=C(N)C=C1 FVKHZYMNMKZOMV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 3
- 150000001450 anions Chemical group 0.000 abstract 1
- HCWFRUHIOMLJCH-UHFFFAOYSA-L dichlorotin;hydrochloride Chemical compound Cl.Cl[Sn]Cl HCWFRUHIOMLJCH-UHFFFAOYSA-L 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- 108091008695 photoreceptors Proteins 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012954 diazonium Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BOBLSBAZCVBABY-WPWUJOAOSA-N 1,6-diphenylhexatriene Chemical compound C=1C=CC=CC=1\C=C\C=C\C=C\C1=CC=CC=C1 BOBLSBAZCVBABY-WPWUJOAOSA-N 0.000 description 1
- GUPMCMZMDAGSPF-UHFFFAOYSA-N 1-phenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1[C](C=C[CH2])C1=CC=CC=C1 GUPMCMZMDAGSPF-UHFFFAOYSA-N 0.000 description 1
- CVHQMEAEIHOKQW-UHFFFAOYSA-N 2-nitro-3-phenylprop-2-enal Chemical compound [O-][N+](=O)C(C=O)=CC1=CC=CC=C1 CVHQMEAEIHOKQW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- G03G5/0664—Dyes
- G03G5/0675—Azo dyes
- G03G5/0679—Disazo dyes
- G03G5/0683—Disazo dyes containing polymethine or anthraquinone groups
Abstract
Description
【発明の詳細な説明】
投宜分互
本発明は新規なビス（ジアゾニウム）塩化合物及びその
製造法に関し、更に詳しくは有機光導電体として有用な
ビスアゾ化合物を製造するための中間体であるビス（ジ
アゾニウム）塩化合物及びその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel bis(diazonium) salt compound and a method for producing the same, and more particularly to a bis(diazonium) salt compound which is an intermediate for producing a bisazo compound useful as an organic photoconductor. (Diazonium) salt compound and its manufacturing method.
災米技権
従来より、ある種のアゾ化合物が電子写真感光体の一つ
の形態である積層型感光体に用いられる有機光導電体、
特に電荷発生顔料として有用であることが知られている
。この積層型感光体は周知のように導電性支持体上に光
によって電荷担体を発生する能力を有する電荷発生顔料
を主成分とする電荷発生層とその上に電荷発生層で発生
した電荷担体を効率よく注入し、更にこれを搬送する能
力を有する電荷搬送物質を主成分とする電荷搬送層とを
設けた感光体である。Traditionally, certain azo compounds have been used as organic photoconductors for laminated photoconductors, which is one form of electrophotographic photoconductor.
It is known to be particularly useful as a charge-generating pigment. As is well known, this laminated photoreceptor has a charge generation layer containing a charge generation pigment as a main component having the ability to generate charge carriers by light on a conductive support, and a charge carrier generated by the charge generation layer on top of the charge generation layer. This photoreceptor is provided with a charge transport layer mainly composed of a charge transport substance that can efficiently inject and further transport charge.
従来、このような感光体に使用されるアゾ化合物として
は、例えば特開昭４７−３７５４３号公報、同５２−５
５６４３号公報等に記載されるベンジジン系ビスアゾ化
合物や特開昭５２−８８３２号公報に記載されるスチル
ベン系ビスアゾ化合物、特開昭５８−２２２１５２号公
報に記載されるジフェニルヘキサトリエン系ビスアゾ化
合物、特開昭５８−２２２１５３号公報に記載されるジ
フェニルブタジェン系ビスアゾ化合物等が知られている
。Conventionally, azo compounds used in such photoreceptors include, for example, those disclosed in JP-A-47-37543 and JP-A-52-5.
Benzidine-based bisazo compounds described in JP-A No. 5643, etc., stilbene-based bisazo compounds described in JP-A-52-8832, diphenylhexatriene-based bisazo compounds described in JP-A-58-222152, etc. Diphenylbutadiene-based bisazo compounds described in JP-A-58-222153 are known.
しかし従来のアゾ化合物を用いた積層型感光体は一般に
感度が低いため、高速複写機用感光体としては不満足で
ある。一方、近年レーザープリンター用感光体として特
に半導体レーザーの波長域をカバーできるような高感度
感光体の開発が望まれているが、前述の積層型感光体は
同様な理由からこのような目的に応じ得ないのが実状で
ある。そこで従来の欠点を克服した有機光導電体として
有用なアゾ化合物の製造が望まれている。However, conventional laminated photoreceptors using azo compounds generally have low sensitivity and are unsatisfactory as photoreceptors for high-speed copying machines. On the other hand, in recent years, there has been a desire to develop high-sensitivity photoconductors that can cover the wavelength range of semiconductor lasers as photoconductors for laser printers. The reality is that you can't get it. Therefore, it is desired to produce an azo compound useful as an organic photoconductor that overcomes the conventional drawbacks.
目 的
本発明の目的は高速複写機用としては勿論、レーザープ
リンター用としても実用的な高感度の電子写真感光体、
特に積層型感光体に用いられる有機光導電体として有用
なビスアゾ化合物を製造するための中間体であるビス（
ジアゾニウム）塩化合物及びその製造法を提供すること
である。Purpose The purpose of the present invention is to provide a highly sensitive electrophotographic photoreceptor that is practical not only for high-speed copying machines but also for laser printers.
Bis(
An object of the present invention is to provide a diazonium salt compound and a method for producing the same.
碧−一」叉
本発明の１つは一般式（Ｉ）
Ｘｏ・Ｎ２゜−◎＋ＣＨ＝ＣＨ）、−◎−Ｎ２゜・Ｘｏ
（Ｉ）（但し又はアニオン官能基を表わす）
で示されるビス（ジアゾニウム）塩化合物であり、他の
１つは式（ｎ）
Ｈ，Ｎ−■＋ＣＨ＝ＣＨ）、−◎−ＮＨ，（Ｉｔ）で示
される１、１０−ビス（４−アミノフェニル）−１，３
゜５．７．９−デカペンタエンをジアゾ化することを特
徴とする前記一般式（Ｉ）で示されるビス（ジアゾニウ
ム）塩化合物の製造法である。こ−で一般式（Ｉ）にお
けるアニオン官能基Ｘの代表例とＬ／ テＩｔＣＱ’、
Ｂｒ”、 Ｉ’、 ＢＦ４゜、 ＰＦ、。、 Ｂ（Ｃ
，Ｈ，）４゜。One of the present invention is the general formula (I) Xo・N2゜−◎+CH=CH), −◎−N2゜・Xo
(I) (representing or anionic functional group) is a bis(diazonium) salt compound represented by formula (n) H,N-■+CH=CH), -◎-NH, (It ) 1,10-bis(4-aminophenyl)-1,3
5. A method for producing a bis(diazonium) salt compound represented by the general formula (I), which comprises diazotizing 7.9-decapentaene. Here, representative examples of the anionic functional group X in general formula (I) and L/teItCQ',
Br", I', BF4゜, PF,., B(C
,H,)4°.
Ｃ４０，”、 ＳＯｌ”、 Ｈ，Ｃ−◎−５ｏ３゜、
ＡｓＦ−、ＳｂＦ、。等が挙げられ、好ましくはＢＦ４
”である。C40,”, SOl”, H,C-◎-5o3゜,
AsF-, SbF,. etc., preferably BF4
” is.
本発明の一般式（Ｉ）で示されるビス（ジアゾニウム）
塩化合物はカップラーとのカップリング反応により形成
される下記一般式（ｍ）で示されるビスアゾ化合物を得
るための有用な中間体である〔本発明のビス（ジアゾニ
ウム）塩（Ｉ）を使用したビスアゾ化合物の製造につい
ては本出願人の「ビスアゾ化合物及びその製造法」と題
する同日付出願に詳細に記載されている〕。Bis(diazonium) represented by general formula (I) of the present invention
The salt compound is a useful intermediate for obtaining a bisazo compound represented by the following general formula (m) formed by a coupling reaction with a coupler [bisazo compound using the bis(diazonium) salt (I) of the present invention] The preparation of the compound is described in detail in the applicant's application dated the same date entitled ``Bisazo Compound and Process for Preparing the Same''].
Ａｒ−Ｎ＝Ｎ−◎＋ＣＨ＝ＣＨ）ｓ−■−Ｎ＝Ｎ−Ａｒ
（ｍ）〔但しＡｒはＡ ｒ Ｈで示されるカップラ
ー（例えば水酸基及び／又はアミノ基を有する芳香族炭
化水素化合物；水酸基及び／又はアミノ基を有する複素
環式化合物；脂肪族又は芳香族のエノール性ケトン基を
有する化合物、即ち活性メチレン基を有する化合物等）
の残基を表わす、〕
次に本発明のビス（ジアゾニウム）塩化合物の製造法に
ついて説明する。まずこの製造法で使用される式（ＩＩ
）の、１．１０−ビス（４−アミノフェニル）−１，３
，５，７，９−デカペンタエンは１，１ｏ−ビス（４−
二トロフェニル）−Ｌ３ｙ５ｙ７ｔ９−７カペンタエン
を還元することによって得られる８
１．１０−ビス（４−ニトロフェニル） −１，３，５
，７，９−デカペンタエンは例えば１，４−ビス（トリ
フェニルホスホニウムブロマイド）−２−ブテンと４−
ニトロシンナムアルデヒドとを塩基性触媒の存在下で縮
合させる、いわゆるウィティッヒ反応によって製造でき
る。この反応によって生成するジ二′トロ化合物には３
−モノシス体あるいは３，７−ジシス体が一部含まれる
が、これは反応粗製品をそのまへ或いは精製後、触媒量
の沃素と共にトルエン、キシレン等の芳香族炭化水素系
溶媒中で加熱処理することによりオールトランス体に変
換することができる（Ｉ，１０−ビス（４−ニトロフェ
ニル） −１，３，５，７，９−デカペンタエンについ
ては本出願人のｒｌ、１０−ビス（４−ニトロフェニル
） −１，３，５，７，９−デカペンタエン及びその製
造法」と題する同日付出願に詳細に記載されている〕。Ar-N=N-◎+CH=CH)s-■-N=N-Ar
(m) [However, Ar is a coupler represented by A r H (for example, an aromatic hydrocarbon compound having a hydroxyl group and/or an amino group; a heterocyclic compound having a hydroxyl group and/or an amino group; an aliphatic or aromatic enol) compounds with active ketone groups, i.e. compounds with active methylene groups, etc.)
represents a residue of ]] Next, the method for producing the bis(diazonium) salt compound of the present invention will be explained. First, the formula (II
), 1.10-bis(4-aminophenyl)-1,3
,5,7,9-decapentaene is 1,1o-bis(4-
1.10-Bis(4-nitrophenyl) -1,3,5 obtained by reducing capentaene
,7,9-decapentaene is, for example, 1,4-bis(triphenylphosphonium bromide)-2-butene and 4-
It can be produced by the so-called Wittig reaction, in which nitrocinnamaldehyde is condensed in the presence of a basic catalyst. The di-2'tro compound produced by this reaction has 3
-Contains some monocis or 3,7-dicis isomers, which can be obtained by heating the reaction crude product as is or after purification in an aromatic hydrocarbon solvent such as toluene or xylene with a catalytic amount of iodine. (I,10-bis(4-nitrophenyl)-1,3,5,7,9-decapentaene can be converted to the all-trans form by Nitrophenyl)-1,3,5,7,9-decapentaene and process for its production”, filed in the same application in detail].
次にこうして得られた１、１０−ビス（４−二トロフェ
ニル） −１，３，５，７，９−デカペンタエンの還元
は通常、鉄−塩酸、塩化第−錫一塩酸等を還元剤として
７０〜１２０℃の温度に加熱することにより行なわれ１
反応は約０．５〜３時間で完結する。Next, the 1,10-bis(4-nitrophenyl)-1,3,5,7,9-decapentaene thus obtained is usually reduced using iron-hydrochloric acid, tin-tinychloride monohydrochloride, or the like as a reducing agent. It is carried out by heating to a temperature of 70-120 °C1
The reaction is completed in about 0.5-3 hours.
なお鉄−塩酸還元剤を用いた場合はＮ、Ｎ−ジメチルホ
ルムアミドのような有機溶媒中で行なうことが好ましい
。In addition, when an iron-hydrochloric acid reducing agent is used, it is preferable to carry out the reaction in an organic solvent such as N,N-dimethylformamide.
なお以上のようにして得られるジニトロ化合物及びジア
ミノ化合物（ＩＩ）はいずれも新規物質である〔なお、
ジアミノ化合物（ｆｆ）の１，１０−ビス（４−アミノ
フェニル） −１，３，５，７，９−デカペンタエンに
ついては本出願人のｒｌ、１０−ビス〔４−アミノフェ
ニル） −１，３，５，７，９−デカペンタエン及びそ
の製造法」と題する同日付出願に詳細に記載されている
〕。Note that the dinitro compound and diamino compound (II) obtained as described above are both new substances.
Regarding the diamino compound (ff) 1,10-bis(4-aminophenyl)-1,3,5,7,9-decapentaene, the applicant's rl, 10-bis[4-aminophenyl)-1,3 , 5,7,9-Decapentaene and Process for Preparing the Same].
次にこうして得られた式（ＩＩ）の１，１０−ビス（４
−アミノフェニル） −１，３，５，７，９−デカペン
タエンのジアゾ化はこのジアミノ化合物（ｎ）を塩酸、
硫酸等の無機酸中に分散し、これに、−１０〜２０℃の
温度で亜硝酸ナトリウムを添加することにより行なわれ
、反応は約０．５〜３時間で完結する。Next, the 1,10-bis(4) of formula (II) obtained in this way
-aminophenyl) -1,3,5,7,9-decapentaene is diazotized by diazotizing this diamino compound (n) with hydrochloric acid,
The reaction is carried out by dispersing in an inorganic acid such as sulfuric acid and adding sodium nitrite at a temperature of -10 to 20°C, and the reaction is completed in about 0.5 to 3 hours.
この反応により一般式（Ｉ）のビス（ジアゾニウム）塩
が得られるが、更にこのジアゾ化反応液に例えば硼弗化
水素酸、硼弗化ナトリウム等の水溶液を加えて塩交換す
ることにより一般式（Ｉ）のビス（ジアゾニウム）塩を
得ることができる。By this reaction, a bis(diazonium) salt of the general formula (I) is obtained, and by further adding an aqueous solution of borofluoric acid, sodium borofluoride, etc. to this diazotization reaction solution for salt exchange, the general formula A bis(diazonium) salt of (I) can be obtained.
以下に本発明を実施例及び応用例によって説明する。The present invention will be explained below using examples and application examples.
実施例
ビス ジアゾニウム の ゛
１．１０−ビス（４−７ミノフエニル） −１，３，５
，７，９−デカペンタエン３０．０ｇを１５ｖｏ１％硫
酸水溶液４２５ｍＱに加え、５０℃で９０分攪拌した。Example bis diazonium ゛1.10-bis(4-7minophenyl)-1,3,5
, 30.0 g of 7,9-decapentaene was added to 425 mQ of a 15 vol. 1% aqueous sulfuric acid solution, and the mixture was stirred at 50° C. for 90 minutes.
−５℃まで急冷した後、亜硝酸ナトリウム１４．４６ｇ
を水４５ｍΩに溶解した溶液を一５℃〜−３℃で９０分
を要して滴下した。その後−５℃で３０分攪拌した後生
成物を濾過し、た、濾渣を冷水１０ｇに溶解し、微量の
不溶物をセライトと共に濾過除去した後、濾液に４２％
硼弗化水素酸水溶液を加え、析出した結晶を濾取、乾燥
して陪席色のビス（ジアゾニウム）塩４２．１ｇ（収率
８６．０幻を得た０分解点１２０℃ビス（ジアゾニウム
）塩の赤外線吸収スペクトル（ＫＢｒＢｒ法）を第１図
に示したが、２２３０ａｍ−″にジアゾニウム塩の伸縮
振動が、１０１０ａａ−”にトランスオレフィンの面外
変角振動に基づく吸収が認められた。After rapidly cooling to -5℃, 14.46g of sodium nitrite
A solution prepared by dissolving . After stirring at -5℃ for 30 minutes, the product was filtered, and the filter residue was dissolved in 10 g of cold water, and a trace amount of insoluble material was filtered off with Celite.
An aqueous solution of borohydrofluoric acid was added, and the precipitated crystals were collected by filtration and dried to give 42.1 g of bis(diazonium) salt (yield: 86.0%, 0 decomposition point: 120°C, bis(diazonium) salt). The infrared absorption spectrum (KBrBr method) is shown in FIG. 1, and the stretching vibration of the diazonium salt was observed at 2230 am-'', and the absorption based on the out-of-plane bending vibration of the trans-olefin was observed at 1010 aa-''.
応用例
本発明のビス（ジアゾニウム）塩から得られたビスアゾ
化合物を使用して下記のように積層型感光体を製造した
。Application Example A laminated photoreceptor was manufactured as follows using the bisazo compound obtained from the bis(diazonium) salt of the present invention.
電荷発生物質として上式で表わされるビスアゾ化合物７
．５部及びポリエステル樹脂〔（株）東洋紡績製バイロ
ン２００〕の０．５％テトラヒドロフラン溶液５００部
をボールミル中で粉砕、混合し、得られた分散液をアル
ミニウム蒸着ポリエステルフィルム上にドクターブレー
ドで塗布し、自然乾燥して約１μｍ厚の電荷発生層を形
成した。Bisazo compound 7 represented by the above formula as a charge generating substance
．． 5 parts and 500 parts of a 0.5% tetrahydrofuran solution of polyester resin [Vylon 200 manufactured by Toyobo Co., Ltd.] were ground and mixed in a ball mill, and the resulting dispersion was applied onto an aluminum-deposited polyester film using a doctor blade. , and air-dried to form a charge generation layer with a thickness of about 1 μm.
次に電荷輸送物質として９−エチルカルバゾール−３−
アルデヒド−１−メチル−１−フェニルヒドラゾン２部
をポリカーボネート樹脂〔（株）今人製パンライトに−
１３００）の１０％テトラヒドロフラン溶液２０部に溶
解し、この溶液を前記電荷発生層上にドクターブレード
で塗布し、８０”Ｃで２分間。Next, as a charge transport substance, 9-ethylcarbazole-3-
Add 2 parts of aldehyde-1-methyl-1-phenylhydrazone to polycarbonate resin [Panlite manufactured by Konjin Co., Ltd.]
1300) in 20 parts of a 10% tetrahydrofuran solution, and this solution was applied onto the charge generating layer with a doctor blade at 80''C for 2 minutes.
ついで１２０℃で５分間乾燥して厚さ約２０μｍの電荷
輸送層を形成した。Then, it was dried at 120° C. for 5 minutes to form a charge transport layer with a thickness of about 20 μm.
次にこうして得られた積層型電子写真感光体の可視域で
の感度を調べるため、この感光体について静電複写紙試
験装置〔（株）川口電機製作所製５Ｐ４２８型〕を用い
て暗所で一６ＫＶのコロナ放電を２０秒間行なって帯電
せしめた後、２０秒間着減衰せしめ、この時の表面電位
Ｖｏ（ボルト）を測定し、ついで感光体表面の照度が４
゜５ｆｌｕｘになるようにタングステンランプ光を照射
してその表面電位がＶｏの１／２になるまでの時間（ｓ
ｅｃ）を求め、可視域での感度として半減露光量Ｅ １
／２（Ｉ２ｕｘ−ｓｅｃ）を算出した。この結果、Ｖ
ｏ ＝ ３０６ボルト、Ｅ １／２＝１．１３Ｑｕｘ・
ｓｅｃであった。Next, in order to examine the sensitivity of the laminated electrophotographic photoreceptor thus obtained in the visible range, this photoreceptor was tested in a dark place using an electrostatic copying paper tester (Model 5P428, manufactured by Kawaguchi Denki Seisakusho Co., Ltd.). After charging with 6KV corona discharge for 20 seconds, it was allowed to decay for 20 seconds, and the surface potential Vo (volt) at this time was measured.
The time (s
ec), and the half-reduced exposure amount E 1 as the sensitivity in the visible range.
/2 (I2ux-sec) was calculated. As a result, V
o = 306 volts, E 1/2 = 1.13 Qux・
It was sec.
このように本発明のテトラゾニウム塩化合物から誘導さ
れるビスアゾ化合物を用いた感光体゛ は可視域での感
度が、高いことが判る。Thus, it can be seen that the photoreceptor using the bisazo compound derived from the tetrazonium salt compound of the present invention has high sensitivity in the visible region.
勿−−−釆一
以上の説明から判るように本発明のビス（ジアゾニウム
）塩化物は高速複写機用としても、またレーザープリン
ター用としても高い感度を示す電子写真感光体、特に積
層型感光体に用いられる有機光導電体であるビスアゾ化
合物の中間体としてきわめて有用である。As can be seen from the above explanation, the bis(diazonium) chloride of the present invention can be used in electrophotographic photoreceptors, especially laminated photoreceptors, which exhibit high sensitivity for use in high-speed copying machines and laser printers. It is extremely useful as an intermediate for bisazo compounds, which are organic photoconductors used in
第１図は本発明のビス（ジアゾニウム）塩化合物の赤外
線吸収スペクトルを示す。FIG. 1 shows the infrared absorption spectrum of the bis(diazonium) salt compound of the present invention.
Claims (1)
，３，５，７，９−デカペンタエンをジアゾ化すること
を特徴とする一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （但しＸはアニオン官能基を表わす） で示されるビス（ジアゾニウム）塩化合物の製造法。[Claims] 1. A bis(diazonium) salt compound represented by the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (where X represents an anionic functional group). 2. Formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) 1,10-bis(4-aminophenyl)-1 shown by
, 3,5,7,9-decapentaene is diazotized.General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, X represents an anionic functional group) Method for producing bis(diazonium) salt compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10548887A JPH0825978B2 (en) | 1987-04-28 | 1987-04-28 | Bis (diazonium) salt compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10548887A JPH0825978B2 (en) | 1987-04-28 | 1987-04-28 | Bis (diazonium) salt compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63270654A true JPS63270654A (en) | 1988-11-08 |
| JPH0825978B2 JPH0825978B2 (en) | 1996-03-13 |
Family
ID=14408978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10548887A Expired - Lifetime JPH0825978B2 (en) | 1987-04-28 | 1987-04-28 | Bis (diazonium) salt compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0825978B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081233A (en) * | 1986-05-15 | 1992-01-14 | Ricoh Company, Ltd. | Bisazo compounds and electrophotographic photoconductors comprising the bisazo compounds |
-
1987
- 1987-04-28 JP JP10548887A patent/JPH0825978B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081233A (en) * | 1986-05-15 | 1992-01-14 | Ricoh Company, Ltd. | Bisazo compounds and electrophotographic photoconductors comprising the bisazo compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0825978B2 (en) | 1996-03-13 |
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