US3772281A - Merocyanine dyes for sensitizing zinc oxide photoconductors - Google Patents

Merocyanine dyes for sensitizing zinc oxide photoconductors Download PDF

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Publication number
US3772281A
US3772281A US00161295A US3772281DA US3772281A US 3772281 A US3772281 A US 3772281A US 00161295 A US00161295 A US 00161295A US 3772281D A US3772281D A US 3772281DA US 3772281 A US3772281 A US 3772281A
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United States
Prior art keywords
acid
copying material
dispersion
prepared
copying
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US00161295A
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English (en)
Inventor
K Tubuko
T Kurotori
I Tashiro
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Ricoh Co Ltd
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Ricoh Co Ltd
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    • 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
    • G03G5/0666—Dyes containing a methine or polymethine group
    • G03G5/0672—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups
    • G03G5/0674—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups containing hetero rings

Definitions

  • the present invention relates to a sensitizer capable of manifesting superb sensitizing effect when applied to the pr'ocess'of preparing a copying material for use in electrophotography carrying a photoconductive layer from a ice photoconductive layer-formable dispersion in which water is used as the dispersion medium.
  • a copying material for use in electrophotography is generally prepared by forming a photoconductive layer consisting of a photoconductor such as zinc oxide, a resinous binder and a sensitizer on the surface of a support such as metallic plate or paper whose reverse side has been processed for conductivity.
  • the formation of the photoconductive layer is generally effected through the process of dispersing the foregoing components in an organic solvent such as toluene, applying the resulting dispersion onto the support and drying thereafter.
  • This process to use an organic solvent in forming the photoconductive layer is accompanied by various disadavntages such that: the organic solvent is "generally so expensive that it is necessary to recover it; it is hazardous due to high inflammability of said solvent; it calls for special cares in respect of the health control of workers concerned; it requires coating devices of special construction and therefore being expensive; because of the use of air knife as a coating head being impossible, high speed coating is infeasible; etc. Therefore, there have hitherto been proposed various processes intended for forming a photoconductive layer from a dispersion prepared by dispersing a photoconductor such as zinc oxide, a resinous binder and a sensitizer in water.
  • a photoconductor such as zinc oxide, a resinous binder and a sensitizer in water.
  • X: represents l (CHDECOOH (CI-Iflm COOH [provided that R and R each represents alkyl radical having carbon atoms in the range of 1-10; n, m, m and m each represent or a natural number in the range of 1-10; A and B each represents oxygen atom or sulfur atom and A may be the same as B; and indicates the position bonding to (CHCH )
  • these compounds when left standing in an aqueous dispersion for use in forming the photoconductive layer, they not only gradually get decolorized due to oxidation by a polymerization initiator present in the dispersion (this initiator is usually a peroxide and remains in the dispersion on the occasion of synthesis of an emulsion of resinous binder), resulting in deterioration of photosensitivity of the copying material, but also fade due to light even in the absence of the polymerization initiator within the copying material thereby to bring on a change in quality of the copy.
  • a polymerization initiator present in the dispersion
  • this initiator is usually a peroxide and remains in the dispersion on the occasion of synthesis of an emulsion of resinous binder
  • the primary object of the present invention is to provide a sensitizer which, when applied to the process of preparing a copying material for use in electrophotography using a photoconductive layer-forming dispersion in which water is contained as the dispersion medium, is
  • Another object of the present invention is to provide a sensitizer which has such characteristics that it is stable against a polymerization initiator and light, is capable of being sufficiently adsorbed to a photoconductor such as zinc oxide within an aqueous medium for dispersion and is superior in sensitization of the photoconductive layer formed thereby.
  • the inventors have conducted a seriesaof studies in search of such a sensitizer as being effective even when a small amount thereof is applied to the process of forming a photoconductive layer by using water as the dispersion medium, and, as a result, they havefound that specific merocyanine-type coloring matters are suitable for this purpose. In other words, they have found that the merocyanine-type coloring matters to be expressed by the following general formula are suitable for said purpose.
  • the merocyanine-type coloring matters expressed by the foregoing general formula are stable against the polymerization initiator and light, and the copying material for electrophotography containing these merocyanine-type coloring matters as the sensitizer in the photoconductive layer thereof shows very little deterioration of sensitivity in spite of a prolonged preservation.
  • a mixture consisting of 10 g. of the foregoing product expressed by the Formula IV, 4 g. of Z-methyl-S-carboxybenzothiazole and 4.5 g. of p-toluene methyl sulfonate is heated at C. for 3.5 hours for reaction.
  • the thus reacted mixture is cooled, mixed with cc. of pyridine, and boiled for 25 minutes.
  • the mixture treated as above is cooled again, there is obtained precipitate.
  • the merocyanine-type coloring matters prepared as above are applicable to (A): the photoconductive layerformable dispersion consisting mainly of water, a watersoluble resinous binder and such photoconductor as zinc oxide and (B): the photoconductive layer-formable dispersion consisting mainly of water, a water-dispersible binder and such photoconductor as zinc oxide, as described hereunder.
  • Type photoconductive layer-formable dispersion (a) A dispersion which is prepared by dissolving in water a water-soluble copolyrner obtained by treating a copolymer with ammonia or an organic amine, said copolymer being obtained by copolymerizing vinyl acetate with at least one vinyl monomer such as styrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate, and at least one unsaturated carboxylic acid such as methacrylic acid,
  • colophony (rosin), modified colophony, dammar resin, ethyl cellulose acetate, hydroxyethyl cellulose acetate, cellulose acetostearate, and ethylcellulose stearate poly-N-vinylcarbazole, N-vinylcarbazole-ethylacrylate copolymer polyvinylchloride, vinylchloride-vinylisobutyl ether cocopolymer, vinylchloride-vinylacetate-vinylalcohol copolymer, vinylchloride-vinylacetatemaleic anhydride copolymer, polyalkylmethacrylate vinylacetate resin, vinylacetate-crotonic aicd copolymer, vinylacetate-vinylstearate copolymer, polyvinylstearate, vinylacetatemaleic acid copolymerpolyvinyl butyral, vinyl butyral-vinylacetate copolymer polystyrene, s
  • Acidic compounds aliphatic saturated monocarboxylic acid such as caproic acid, heptanoic acid, capyrylic acid, pelargonic acid, capric acid, n-undecylenic acid, lauric acid, n-tridecylenic acid, myristic acid, n-pentadecylenic acid, palmitic acid, margaric acid, stearic acid, n-nonadecylenic acid, arachidic acid, n-heneicosanoic acid, behenic acid, n-tricosanoic acid.
  • aliphatic saturated monocarboxylic acid such as caproic acid, heptanoic acid, capyrylic acid, pelargonic acid, capric acid, n-undecylenic acid, lauric acid, n-tridecylenic acid, myristic acid, n-pentadecylenic acid, palmitic acid, margaric acid, stea
  • aliphatic unsaturated monocarboxylic acid such as 2-hexenoic acid, 3-hexenoic acid, 4-hexenoic acid, 5- hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, 4-methyl-2-pentenoic acid, 4- methylpentenoic acid, a-ethylcrotonic acid, 2,2- dimethyl-3-butenoic acid.
  • aliphatic diolefin carboxylic acid such as 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid.
  • aliphatic .higher unsaturated monocarboxylic acid such as hexadecatrienoic acid, linoleic acid, linolenic acid, 6,9,l2-octadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, docosadienoic acid, docosatrienoic acid.
  • aliphatic saturated dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, brassylic acid, and tetradecane dicarboxylic acid.
  • aromatic monocarboxylic acid such as benzoic acid, o-toluylic acid, m-toluylic acid, p-toluylic acid, dimethyl benzoic acid, o-ethylbenzoic acid, m-ethylbenzoic acid, p-ethylbenzoic acid, 2,3,4-trimethylbenzoic acid, 2,3,5-trimethylbenzoic acid, 2,3,6-trimethylbenzoic acid, 2,4,5-trimethylbenzoic acid, 2,4,6-trimethylbenzoic acid.
  • aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, 3- chlorophthalic acid, 4chlorophthalic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid.
  • aromatic tricarboxylic acid such as 1,2,3-hemimellitic acid and 1,2,4-trimellitic acid.
  • alicyclic carboxylic acid such as abietic acid, bisnorchonic acid, B-boswelic acid, chenodesoxycholic acid, quinovic acid, cholanic acid, cholic acid, dehydrocholic acid, dioxycohlic acid, doisynolic acid, erythrochlenic acid, etiocholanic acid, glycocholic acid, glycylrhezic acid, oleanolic acid, helvolic acid, hiodesoxycoalic acid, risocoalic acid, naphthenic acid.
  • abietic acid such as abietic acid, bisnorchonic acid, B-boswelic acid, chenodesoxycholic acid, quinovic acid, cholanic acid, cholic acid, dehydrocholic acid, dioxycohlic acid, doisynolic acid, erythrochlenic acid, etiocholanic acid, glycocholic acid, gly
  • vinyl copolymers having carboxyl radical such as styrene-maleic acid-methacrylic acid copolymer,
  • acrylic ester-acrylic acid copolymer vinyl acetatecrotonic acid copolymer and styrene-vinylacetatemaleic acid copolymer.
  • ammonia methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, hexylamine, ethylenediamine, anylamine, morpholine, piperidine and hydrazine.
  • vinyl acetate vinyl chloride, styrene, vinyl propionate, vinylidene chloride, crotonic acid, itaconic acid, maleic acid, fumalic acid, vinylstearate, vinyl isobutylether, vinyl alcohol, methacrylic acid, acrylic acid, butadiene, dimethyl itaconate, acrylonitrile, glycidyl methacrylate,
  • the surface active agent applicable in the dispersion (B) includes alkylbenzene sulfonic acid-triethanolamine, sodium benzenesulfonate, sodium lauryl sulfate, dialkylsulfosnccinate, sodium dodecylbenzenesulfonate, etc.
  • the appropriate amount of said acidic compound to be applied is in the range of 1-10 wt. percent or thereabout against said resin, and the appropriate amount of said volatile basic compound to be applied is in the range of 1-10 wt. percent or thereabout against the resin.
  • a mixture according to the foregoing prescription was stirred by a homomixer for 10 minutes for the sake of dispersion.
  • the dispersion thus prepared was applied to the reverse side of a paper support whose surface had been processed for conductivity and was dried for 10 minutes at 100 C., whereby there was obtained a copying material for electrophotography provided with a photoconductive layer having a thickness of about 20;/..
  • the appropriate amount of said surface active agent is in the range of 0.05-3 wt. percent or thereabout against the polymeric monomer.
  • the appropriate amount of said photoconductor such as zinc oxide to be applied is in the range of 1-l0 parts by weight or thereabout against said copolymer, resin and polymeric monomer of 1 part by weight, respectively, and the appropriate amount of the sensitizer according to' the present invention is in the range of 0.001-0.1 wt. percent or thereabout against zinc oxide.
  • Example 3 1% methanol solution (containing 0.001% of triethyl amine added thereto) of a compound expressed by the formula:
  • H drnooon A mixture according to the foregoing prescription was stirred by a homomixer for 10 minutes for the sake of dispersion. A dispersion thus prepared was applied to the reverse side of an art paper whose surface had been processed for conductivity and was dried, whereby there was obtained a copying material for electrophotography provided with a photoconductive layer having a thickness of about a.
  • the photoconductive layer-formable solution prepared as above was applied to the surface of an art paper whose reverse side had been processed for conductivity, to the extent of 30 g./m. in terms of dry weight of the coating.
  • the art paper thus coated was dried at 130 C. for 10 minutes and subsequently was subjected to humidity adjustment for 12 hours in a dark place with a humidity of 65% (RH), whereby a copying material for electrophotography was prepared.
  • Comparative copying material 50 1,020 Poor. y and 3 of naphthemc acld y a homo This proves that the copying material according to the present invention is superior to the comparative copying material both in sensitivity and clearness of image.
  • Example 4 G Vinyl acetate monomer 80.0 Crotonic acid 4.3 Styrene 2.0 Sodium dihydrogen phosphate 1.2 Sodium dodecyl sulfate 1.1 2, -azobisisobutylonitrile 1.5
  • Example 6 A mixture consisting of 70 g. of KR 211 (a 70% xylene solution of silicon resin, manufactured by Shinetsu Kagaku Kogyo K.K.) and 3 g. of Stebelite resin (a manufacture of Hercules Co., U.S.A.) was dissolved by heating at 70 C. Subsequently, while stirring the resulting solution by a homomixer, another solution prepared by dissolving 3 g. of triethyl amine in 100 g. of water was slowly added, thereby effecting emulsification.
  • KR 211 a 70% xylene solution of silicon resin, manufactured by Shinetsu Kagaku Kogyo K.K.
  • Stebelite resin a manufacture of Hercules Co., U.S.A.
  • a liquid was prepared by adding 100 g. of photoconductive zinc oxide to 100 g. of Water and dispersing by a homomixer. This liquid was then mixed with 80 g. of the foregoing emulsion by stirring.
  • a photoconductive layer-formable dispersion prepared as above was coated on the surface of an art paper, whose reverse side had been processed for conductivity, to the extent of g./m. in terms of dry weight of the coating. Then, by drying the thus coated art paper, a copying material for electrophotography Was obtained.
  • CHIC 0 0H (CHDQCO 0H 3% aqueous solution of triethyl amine was slowly added to emulsify said copolymer A, whereby a binder was prepared.
  • Example 8 1
  • Example 9 As the material, 60 parts of methyl ester acrylate, 20 parts of ethyl ester acrylate, 15 parts of glycidyl methacrylate, parts of acrylic acid, 4 parts of dammar, 0.1 part of triethanol amine salt of dodecylbenzene sulfonic acid, 0.3 part of ammonium persulfate and 150 parts of water were employed.
  • a 2-1. glass flask equipped with a stirrer, reflux condenser, inlet for introducing the material and thermometer was steeped in a hot bath, and the material according to the following composition (a) was stocked in said flask. Upon replacing the air within the flask by nitrogen, the stock was polymerized for 6 hours by heating at 60 C., whereby an O/W-type resin emulsion with about 40% of solid matter was obtained.
  • composition (a) G. Vinyl acetate Styrene 15 Crotonic acid 2 Abietic acid 13 Sodium dodecylbenzene sulfonate 0.08 Ammonium persulfate 0.3 Water 150 Further, another material according to the following composition (b) was stirred by a homomixer for 10-15 minutes, whereby a photoconductive layer-formable dispersion was prepared.
  • composition (b) Zinc oxide g Resin emulsion prepared as above g 50 1% methanol solution (containing 1% of trimethyl amine) expressed by the aforementioned Formula 2 cc 1 Water 2 60 TABLE 7 Lightfading Saturation (800 lux, potential Sensitivity Clearness 4hrs.), Copying material (v.) (lux sec.) of image percent Copying material under the presentinvention 424 304 Good 80.1 80.3 Comparative copying material 415 685 Poor 80.0 86, 1
  • Example 11 By applying the same process as in Example 8 except for substituting the following Composition (e) for said TABLE 8 Lightfading Saturation (800 lux potential Sensitivity Clearness 4hrs.) Copying material (v.) (lux sec.) of image percen Copying material under the present invention 466 311 Good 78. 3 78. 9 Comparative copying material 459 629 Poor 78.0 84.1
  • Example 10 Composition (a) and the following Composition (f) for By applying the same process as in Example 8 except for substituting the following Composition (c) for said Composition (a) and the following Composition (d) for said Composition (b), 2. copying material for electrophotograph was prepared.
  • composition (e) On the other hand, by applying the same process as above except for equivalently substituting a compound expressed by the following formula for the coloring matter used therein, a comparative copying material was prepared.
  • Example 12 EXAMPLE 13 By applying the same process as in Example 8 except for substituting the following Composition (g) for said Composition (a) and the following Composition (h) for said Composition (b), a copying material for electrophotography was prepared.
  • composition (g) On the other hand, by applying the same process as above except for equivalently substituting a compound expressed by the following formula for the coloring matter used therein, a comparative copying material was prepared.
  • composition (i) G. Ethyl acrylate 40 Styrene 55 Acrylic acid 5 Phthalic anhydride 4.5 Sodium lauryl sulfate 0.08 Ammonium persulfate 0.3 Water 150
  • Composition (5) Zinc oxide g 100 Resin emulsion prepared as above g 50 1% methanol solution (containing 1% of diethyl amine) expressed by the aforementioned formula 13 cc 1 Water 2
  • a comparative copying material was prepared.
  • the sensi- Y represents tizer according to the present invention is superior to the o a conventional ones in sensitizing effect, resistivity to llght- B fading and so forth.
  • N (HflmCOOH C: or I [wherein R, R and R" each represents alkyl radical having 1-10 carbon atoms; n, m, m' and m" each represents 0 or a natural number in the range of l-lO; A and B each represents oxygen atoms or sulfur atoms and A may be the same as B; and indicates the position bonding to (CHCH ) 2.
  • a sensitizer as in claim 1 represented by the formula:
  • a sensitizer as in claim 1 represented by the formula:
  • a sensitizer as in claim 1 represented by the formula:
  • a sensitizer as in claim 1 represented by the formula:
  • a sensitizer as in claim 1 represented by the formula:

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
US00161295A 1970-07-14 1971-07-09 Merocyanine dyes for sensitizing zinc oxide photoconductors Expired - Lifetime US3772281A (en)

Applications Claiming Priority (1)

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JP45061635A JPS4916067B1 (en, 2012) 1970-07-14 1970-07-14

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US (1) US3772281A (en, 2012)
JP (1) JPS4916067B1 (en, 2012)
CA (1) CA954859A (en, 2012)
DE (1) DE2135223A1 (en, 2012)
FR (1) FR2101746A5 (en, 2012)
GB (1) GB1361293A (en, 2012)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912507A (en) * 1973-06-04 1975-10-14 Itek Corp Polyrhodanine photoconductive materials
US4857431A (en) * 1986-11-14 1989-08-15 Fuji Photo Film Co., Ltd. Photoconductive composition
US20040241567A1 (en) * 2003-03-20 2004-12-02 Tsutomu Teraoka Liquid developer for image forming apparatus

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2902705C2 (de) * 1978-01-24 1982-12-30 Kinoshita Laboratory, Shizuoka Verfahren zur Herstellung eines sensibilisierten Zinkoxids und Verwendung des sensibilisierten Zinkoxids zur Herstellung lichtempfindlicher Schichten elektrostatographischer Aufzeichnungsmaterialien

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912507A (en) * 1973-06-04 1975-10-14 Itek Corp Polyrhodanine photoconductive materials
US4857431A (en) * 1986-11-14 1989-08-15 Fuji Photo Film Co., Ltd. Photoconductive composition
US20040241567A1 (en) * 2003-03-20 2004-12-02 Tsutomu Teraoka Liquid developer for image forming apparatus
US7141346B2 (en) 2003-03-20 2006-11-28 Ricoh Company, Ltd. Liquid developer for image forming apparatus

Also Published As

Publication number Publication date
DE2135223C3 (en, 2012) 1974-09-19
CA954859A (en) 1974-09-17
GB1361293A (en) 1974-07-24
DE2135223B2 (en, 2012) 1974-02-21
DE2135223A1 (de) 1972-01-20
FR2101746A5 (en, 2012) 1972-03-31
JPS4916067B1 (en, 2012) 1974-04-19

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