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
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0503—Inert supplements
  • G03G5/051—Organic non-macromolecular compounds
  • G03G5/0521—Organic non-macromolecular compounds comprising one or more heterocyclic groups
• • 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
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0503—Inert supplements
  • G03G5/051—Organic non-macromolecular compounds
  • G03G5/0514—Organic non-macromolecular compounds not comprising cyclic groups
• • 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
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0503—Inert supplements
  • G03G5/051—Organic non-macromolecular compounds
  • G03G5/0517—Organic non-macromolecular compounds comprising one or more cyclic groups consisting of carbon-atoms only
• • 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
  • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
  • G03G5/0528—Macromolecular bonding materials
  • G03G5/0596—Macromolecular compounds characterised by their physical properties

Definitions

• the present invention relates to an electrophotographic copying material comprising a support and a photoconductive layer formed on one surface of said support by a water-emulsified resinous binder.
• the electrophotographic copying materials in the prior art were manufactured by a method wherein a metallic plate, or a special paper whose back had been processed to render it electroconductive, was used as a support.
• a light-sensitive or photoconductive layer-forming solution obtained by dispersing a photoconductive substance in a binder solution, prepared by dissolving a resin in an organic solvent, was applied onto the surface of said support and then dried.
• a water soluble resin was not generally used for said purpose because it does not provide the photoconductive layer formed on the support with the critical electrostatic characteristics-especially, high electric resistance required for photoconductive layers.
• the resin used for the binder is water-emulsive or water-dispersive
• the prior copying materials heretofore produced from these materials had such drawbacks as poor electrostatic characteristics. For example, when an electrostatic charge was impressed on the photoconductive layer by corona discharge, the charged potential become low. Also, the decay of the electric potential, i.e. the dark-decay when said materials were left in a dark place after being charged, was great. Accordingly, such materials have proven to be quite unsatisfactory for practical use.
• Another object of the invention is to provide a wateremulsified resinous binder which is suitable for forming a photoconductive layer having superior electrostatic characteristics in an electrophotographic copying material.
• the electrophotographic copying material of the present invention is obtained by the following process: a resinous binder having film-forming properties is emulsified with an aqueous emulsifier solution which comprises (1) at least one volatile basic compound selected from the group consisting of nitrogen-containing compounds and (2) at least one acidic compound selected from the group consisting of (a) a natural resin having an electric resistance of at least 10 t'Z-cm. and containing a resin acid, (b) a synthetic resin having an electric resistance of at least 10 Q-cm. and an acid value, i.e.
• the emulsion thus obtained has dispersed therein the photoconductive substance.
• the surface of a support is coated with said dispersion and dried thereafter.
• there are employed for the aforesaid resinous binder a variety of natural resins as well as synthetic resins having filmforming properties.
• the emulsion of the resin is produced by using the minimum quantity of organic solvent.
• the emulsion produced in such a way is characterized by being comprised of the resinous binder in the form of dispersed fine grains having a diameter of a few ,u, so that the resultant photoconductive layer is highly homogeneous.
• the water-emulsified resinous binder used to form a photoconductive layer is one member selected from the group consisting of the following members (a)-(f).
• (f) An emulsion produced by employing, as a filmforming resinous binder, a copolymer selected from the group consisting of a vinyl copolymer having an epoxy radical (O), and a vinyl copolymer having a hydroxyl radical (OH) in its molecular end, and by emulsifying said binder with an aqueous solution of a volatile basic compound and an acid compound such as are applied in (a)-(b).
• a copolymer selected from the group consisting of a vinyl copolymer having an epoxy radical (O), and a vinyl copolymer having a hydroxyl radical (OH) in its molecular end
• the photoconductive layer formed by employing an emulsion so obtained has too low an electric resistance to provide a sufficient electrostatic light-sensitivity and, therefore, is not of practical use.
• an aqueous solution of a volatile basic compound is a principal component of the emulsion of the resinous binder.
• these binders are emulsified by an emulsifier produced by the combination of said volatile basic compound and an acidic compound (such as a natural resin containing a resin acid in the case of (a), a carboxylic acid of an alicyclic compound in the case of (b), an organic acid group in the case of (c), and a synthetic resin having an acid value in the case of (d) as described in the foregoing).
• an acidic compound such as a natural resin containing a resin acid in the case of (a), a carboxylic acid of an alicyclic compound in the case of (b), an organic acid group in the case of (c), and a synthetic resin having an acid value in the case of (d) as described in the foregoing).
• nitrogen containing compounds such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, hexylamine, ethylenediamine, arylamine, morpholine, piperidine and hydrazine
• the applicable compounds for said purpose covers also a wide range of amine compounds, which are volatile and water-soluble, such as aliphatic primary amines, secondary amines, and tertiary amines.
• said volatile basic compounds are employed in the form of an aqueous solution.
• the acid compound i.e. a natural resin containing a resin acid
• a resin having an electric resistance of at least 10 n-cm. is selected lest its special quality should be deteriorated when applied in a photoconductive layer.
• Natural resins having such a property and considered suitable for use include, for example, elemi, Gurjun balsam, jalap, scammonia, amber, bdellium, sagapenum, Euphorbium, myrrh, Opopanax, various kinds of dammar (such as Benak, dead dammar, Melanty, Chan, yon banoun, papuan dammar), shellac, acaroid, dragon brad, mustic, styrax, Canada balsam, Mecca balsam, copai-ba balsam, Peru balsam, guaiac, tacamahac, galvanum, gamboge, olibanum, ammoniac, asafetida, various kinds of copal (such as kauri copal, soft manila copal, hard manila copal, congo copal, benguela copal, angora copal, Madagascar copal, Zanzibar copal, demera copal, hard borne
• Acid compounds for (b), i.e. carboxylic acids of alicyclic compounds include, for example, abietic acid, bisnorcholanic acid, fi-boswelic acid, chenodesoxylcholic acid, chenobic acid, cholanic acid, cholic acid, dehydrocholic acid, dioxylcoal acid, doisynolic acid, erythrophleinic acid, etiocholanic acid, glycocholic acid, glychyrrhizic acid, oleanolic acid, helvolic acid, hiodesoxycholic acid, isocholic acid, naphthenic acid, norcholanic acid, e-pimaric acid, quillaic acid, ursodesoxycholic acid, and ursolic acid.
• abietic acid bisnorcholanic acid, fi-boswelic acid
• chenodesoxylcholic acid chenobic acid
• cholanic acid cholic acid
• Acid compounds for (c), i.e. an aliphatic carboxylic acid, an aromatic carboxylic acid, and an acid anhydride of said carboxylic acids, include many applicable acids, and examples are enumerated as follows:
• Aliphatic saturated monocarboxylic acid caproic acid, heptanoic acid, caprylic 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, lignoceric acid, n-pentacosanoic acid, ceratic acid, n-heptacosanoic acid, montanic acid, n-nonacosanoic acid, melissic acid, n-hentriacontanoic acid, n-dotriacontanoic acid, n-tetratriacontanoic acid, ceroplastic
• Aliphatic olefin monocarboxylic acid 2-hexenoic acid, 3-hexenoic acid, 4hexenoic acid, S-hexenoic acid, 2- methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, 4- methyl-Z-pentenoic acid, 4-methylpentenoic acid, u-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-decenoic acid, 9- undecenoic acid, IO-undecenoic acid, 4-dodecenoic acid, S-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, cis-6-octadecenoic acid, 9-octadecenoic acid, oil acid, e
• Aliphatic diolefin carboxylic acid 2,4-hexadienoic acid, diallylacetic acid, geranium acid and 2,4decadienoic acid.
• Aliphatic higher unsaturated monocarboxylic acid hexadecatrienoic acid, linoleic acid, linolenic acid, 6,9,12- octadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, decosadienoic acid, decosatrienoic acid and heracodienoic acid.
• Aliphatic saturated dicarboxylic acid adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, brassylic acid and tetradecane dicarboxylic acid.
• Aromatic monocarbobylic acid benzoic acid, toluylic acid, m-toluylic acid, p-toluylic acid, dimethylbenzoic acid, o-ethylbenzoic acid, m-ethylbenzoic acid, pethylbenzoic 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, 3,4,5-trimethylbenzoic acid, cuminic acid, cinnamic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, 2,4-dim'trobenzoic acid, 3,5-dinitrobenzoic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-fluorobenzoic acid, m-fluorobenzoic acid, p-fluorobenzo
• Aromatic dicarboylic acid phthalic acid, isophthalic acid, terephthalic acid, S-chlorophthalic acid, 4-chlorophthalic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, tetraiodophthalic acid, naphthalic acid, naphthalene-l,2-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid and naphthalene-1,5- dicrboxylic acid.
• Aromatic tricarboxylic acid 1,2,3-hemimellitic acid and 1,2,4-trimellitic acid.
• the suitable synthetic resins include, for example, copolymer resins of acrylic ester, acrylic-alkyd resin, pure alkyd resin, epoxy ester resin, non-drying type pure alkyd resin, rosin-modified alkyd resin, phenol-modified alkyd resin, styrenated alkyd resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, natural resin-modified pentaerythritol resin, natural resin-modified fumaric acid resin, and so forth.
• one or two kinds of acidic compounds having the aforesaid emulsifier component are employed.
• a mixing ratio of 1 mol of at least one kind of acidic compound to 1-2 mols of at least one kind of basic compound will effect homogeneous emulsification of a resinous binder in water.
• resinous binder although a variety of resins having film-forming properties are applicable, such resins as enumerated hereunder are most suitable for the aforesaid (a)(d) in the present invention.
• A Natural resin and natural resin-modified resin: colophony (rosin), modified colophony, dammar resin, ethyl cellulose acetate, hydroxyethyl cellulose acetate, cellulose acetostearate, and ethylcellulose stearate
• B vinyl polymer and substituted vinyl polymer:
• Photoconductive vinyl polymer poly-N-vinylcarbazole, N-vinylcarbazole-ethylacrylate copolymer
• Polyvinyl ester vinylacetate resin, vinylacetatecrotonic acid copolymer, vinylacetate-vinylstearate copolymer, polyvinylstearate, vinylacetate-maleic acid copolymer
• Vinylchloride polymer or vinylchloride copolymer polyvinylchloride, vinylchloride-vinylisobutyl ether copolymer, vinylchloride vinylacetate-vinylalcohol copolymer, vinylchloride-vinylacetate-maleic anhydride copolymer, polyalkylmethacrylate
• Polyvinyl acetal and vinylacetal copolymer polyvinyl butyral, vinyl butyral-vinylacetate copolymer
• V Polystyrene or styrene copo
• the materials of the water-emulsified resinous binder to be employed in the present invention are as enumerated above.
• the materials other than said water-emulsified binder to be employed in forming a photoconductive layer can be any support, photoconductive substance, and
• sensitizer as conventionally used.
• the photoconductive substance for instance, zinc oxide, titanium oxide, cadmium sulfide, zinc selenide, and so forth may 'be cited, and above all, zinc oxide and titanium oxide are desirable.
• Phthalein dyes such as Fluorescein, Eosin, Erythrosine, and Rose Bengal
• Triphenylmethane dyes such as Malachite Green, Crystal Violet, Basic Fuchsin, Methyl Green, Brilliant Green, Bromophenol Blue, and Tetrabromophenol Blue
• Cyanine dyes such as Cryptocyanine and Pinacyanol
• Heterocyclic dyes such as Acridine Orange
• mixed dyes such as Methylene Grey
• Alizarine Red S for instance, zinc oxide, titanium oxide, cadmium sulfide, zinc selenide, and so forth may 'be cited, and above all, zinc oxide and titanium oxide are desirable.
• Phthalein dyes such as Fluorescein, Eosin,
• Alizarine, and Quinizarin may be cited.
• the support not only a metallic plate but also either paper or a sheet film whose back has been processed for electric conductivity can be employed, but it is desirable that the surface electroresistivity resulting from said process for electric conductivity be less than 10 Q-cm. and it is further advisable for it to be less than 10' Q-crn.
• a desirable impregnation of the aforesaid sensitizer in a photoconductive layer can be attained by mixing the sensitizer within the range of 0.01-5.0% per total weight of zinc oxide, for example, to be contained in the photoconductive layer.
• the copying material of the present invention is produced by the steps comprising: one member selected from the group consisting of emulsion members (a)-(f) as described above is dispersed with a photoconductive substance; the emulsion wherein said photoconductive substance is dispersed is applied as a coating to the surface of a support, by such methods as the centrifugal coating method, spray coating method and brush coating method. The surface thus coated with said emulsion is dried thereafter.
• the coated surface of the support that is to say, the photoconductive layer
• a volatile basic compound so that it is necessary to provide a sufiicient temperature for volatilization of said basic compound to expedite the drying of the layer. Therefore, it is desirable to take such measures as a. hot-air drying method or infrared ray drying method for the sake of rapid drying.
• the drying temperature though it may depend on the kind of the volatile basic compound employed, the most desirable drying temperature is not lower than 100 C. and also comes within the range of such temperatures as will not cause the resin contained in the photoconductive layer to deteriorate and thereby interfere with its character.
• the maximum temperature is ordinarily 250 C.
• the copying material having a photoconductive layer formed by the aforesaid (f) member is especially endowed with an excellent character.
• an epoxy radical or hydroxyl radical contained in a resinous binder shows a bridge-formation reaction in the drying process for formation of a photoconductive layer and thereby forms a network structure, so that the layer thus formed has outstanding weather-proofness.
• the copied picture as well as the characteristic obtained thereby is by no means inferior to those obtained in an atmosphere of normal humidity. This is attributable to the fact that a network structure formed by the resinous binder in the photoconductive layer impedes the adsorption of moisture from the atmosphere by the photoconductive substance.
• a bridge-formation reaction is readily expedited by the existence of a dibasic acid, a tertiary ammonium salt, and a quaternary ammonium salt in case of an epoxy radical; while in case of a hydroxyl radical at the end of a long-chain molecule it is expedited by the presence of a polybasic acid of an amino resin, and the like. Accordingly, a binder which has such a radical, an acid and a salt cause a bridge-formation reaction at the time of forming a photoconductive layer on the surface of a support as seen above.
• Example 1 3 gms. of Stabelite Resin (trade name of a product of Hercules Co. of U.S., having hydrogenated rosin as its principal component and containing abietic acid as a resin acid) is added to 70 gms. of a xylene solution of 70% silicone resin (manufactured by Shinetsu Kagaku Kogyo Kabushiki Kaisha in Japan, and named Silicone Resin KR-211), and then the mixture thus obtained is heated at 70 C.
• the substance thus treated is emulsified by adding steadily a solution obtained by dissolving 3 gms. of triethylamine in 100 gms. of water, while being agitated by a homomixer.
• Another solution is prepared by adding 100 gms. of photoconductive zinc oxide to 100 gms. of water and then dispersing same by a homomixer, and this solution is blended with 80 gms. of the aforesaid emulsion and then agitated.
• the solution thus processed is further blended with 5 cc. of a methanol solution comprising Bromophenol Blue 1%, Fluorescein 0.5 and Rose Bengal 0.1%, and agitated.
• the photoconductive layer forming solution thus obtained is applied to coat the surface of an art paper, whose back has been processed for electric conductivity, to such 8 an extent that the weight after the drying process will be 25 gms./m and thereafter is dried by the infrared-ray drying method.
• Example 2 When 100 gms. of Styrezol 4440 (50%-mineral turpentine solution of styrenated alkyd resin, manufactured by Dai Nippon Ink and Chemical Inc.) was employed in lieu of KR-Zl l, which was employed in Example 1 above, while otherwise following the processes as that in Example 1 for preparing an electrophotographic copying paper and producing a picture by an ordinary electrophotographic means, the resulting picture was superb.
• Styrezol 4440 50%-mineral turpentine solution of styrenated alkyd resin, manufactured by Dai Nippon Ink and Chemical Inc.
• Example 3 3 gms. of Dammar Gum (manufactured by Arakawa Rinsan Kagaku Kogyo Kabushiki Kaisha, and having dammarol acid as a resin acid component) is added as in Example 1 and the mixture is heated up to a temperature within the range of -80 C. to effect dissolution thereof.
• the solution thus obtained is agitated by a homomixer, while another solution prepared by dissolving 3 gms. of ethylamine in 100 gms. of water is added steadily, and is thereby emulsified.
• Example 2 gms. of the resultant emulsion is added to the zinc oxide dispersed solution, as prepared in the above Example 1, and is agitated.
• a sensitizing dye solution is also added in the same way as in Example 1 in producing the photoconductive layer forming solution.
• Example 4 In this case, 4 gms. of Ester Gum (Product of Hercules Co. in U.S., having abietic acid as a resin acid component) is added to gms. of Styrezol 4440, and the mixture is heated up to a temperature within the range of 7080 C. to elfect dissolution thereof. The solution thus obtained is agitated by a homomixer, while another solution prepared by dissolving 4 gms. of triethylamine in 100 gms. of water is added steadily, and is thereby emulsified. 80 gms. of the resultant emulsion is added to the zinc oxide dispersed solution, as prepared in Example 1, and agitated. A sensitizing dye solution is also added in the same way as in Example 1 in producing a photoconductive layer forming solution.
• Ester Gum Product of Hercules Co. in U.S., having abietic acid as a resin acid component
• Example 5 In this case, 2 gms. of Shellac (product of Japan Shellac Industrial Co., Ltd., containing aleuritic acid as its principal component) is added to 80 gms. of Beckozole 1341 (a 60%-Xylene Naphtha solution of phenolized alkyd resin, manufactured by Dai Nippon Ink and Chemicals Inc.), and the mixture thus obtained is heated up to a temperature within the range of 70-80 C. to effect dissolution thereof. The solution thus obtained is agitated by a homomixer, while another solution prepared by dissolving 8 gms. of 28% aqueous ammonia in 100 gms. of water is added steadily, and is thereby emulsified.
• Shellac product of Japan Shellac Industrial Co., Ltd., containing aleuritic acid as its principal component
• Beckozole 1341 a 60%-Xylene Naphtha solution of phenolized alkyd resin, manufactured by Dai Nippon Ink and Chemicals Inc.
• Another solution is prepared by adding 100 gms. of photoconductive zinc oxide into 100 gms. of water and then dispersing same by a homomixer, and thereafter 90 gms. of the aforesaid emulsion is added to this dispersed solution and agitated.
• the mixture thus obtained is further blended with 6 cc. of a methanol solution containing 2% Rose Bengal.
• the photoconductive layer forming solution thus obtained is applied to the surface of a baryta paper, Whose back has been processed for electric conductivity, to such an extent that the weight subsequent to the drying process will be 35 gms./m2, and thereafter is dried.
• An electrophotographic copying paper obtained as above is impressed with an electric charge by an ordinary method, and can be developed and fixed by dry-process development subsequent to exposure. This material produces a superb photographic effect, so that the picture obtained thereby may be used as a master for offset printing after making it hydrophilic.
• Example 6 In this case, 3 gms. of Polymer Rosin (product of Hercules Co. in US, having abietic acid as a resin acid component) is added to 100 gms. of Beckozole P-787 (a 45%-xylene solution of epoxide ester, manufactured by Dai Nippon Ink and Chemicals Inc.), and the mixture is heated up to a temperature within the range of 7080 C. to effect dissolution thereof. The solution thus obtained is agitated by a homomixer, While another solution prepared by dissolving 3 gms. of morpholine in 100 gms. of water is added steadily, and is thereby emulsified.
• Polymer Rosin product of Hercules Co. in US, having abietic acid as a resin acid component
• Example 1 100 gms. of the resultant emulsion is added into the zinc oxide dispersed solution, as prepared in Example 1 above, and is agitated. A sensitizing dye solution is also added in the same way as in Example 1.
• the photoconductive layer forming solution thus obtained is applied for coating the surface of an art paper, whose back has been processed for conductivity, to such an extent that the weight after the drying process will be 25 gms./m3, and is dried thereafter.
• This copying material when used for producing a picture thereon by an ordinary electrophotographic process, has brought about a superb effect.
• Example 7 In this case, 3 gms. of naphthenic acid is added to 100 gms. of Styrezol 4440, and the mixture is agitated by a homomixer, While a solution prepared by dissolving 3 gms. of morpholine in 100 gms. of water is added steadily, and is thereby emulsified. (The emulsion thus obtained is hereinafter referred to as the A solution.)
• the aforesaid B solution is blended with 80 gms. of the A solution and then is agitated.
• the conductive layer forming solution obtained by the above process is applied for coating the surface of an art paper, whose back has been processed for electric conductivity, to such an extent that the Weight after the drying process will be 25 gms./ m. and is dried thereafter.
• the resultant electrophotographic copying material when impressed with an electric charge by a conventional method and developed by the wet-process or the dryprocess, produced a superb picture in contrast to the fact that no such a picture has even been obtained by the employment of an emulsion produced by any conventional surface active agent.
• Example 8 In this case, 1 gr. of abietic acid is added to 70 gms. of KR-211 to be dissolved therein. The solution thus obtained is agitated by a homomixer, while another solu- 10 tion prepared by dissolving 2 gms. of triethylamine in 100 gms. of water is added thereto steadily, and is thereby emulsified.
• Example 9 In this case, except for the employment of 28 gms. of etiocholanic acid in lieu of abietic acid employed in Example 2, the same steps are applied in producing an electrophotographic copying paper. As for the photographic efficiency of the resultant copying paper, the same effect as in Example 1 is attained through the same conventional processes.
• Example 10 In this case, 3 gms. of oleanolic acid is added to 80 gms. of Beckozole 1341 (a 60% xylene naphtha solution of phenol-modified alkyd resin, manufactured by Dai Nippon Ink and Chemicals Inc.) and dissolved therein. The solution thus obtained is agitated by a homomixer, while another solution prepared by dissolving 3 gms. of morpholine in 100 gms. of water is added steadily, and is thereby emulsified.
• Beckozole 1341 a 60% xylene naphtha solution of phenol-modified alkyd resin, manufactured by Dai Nippon Ink and Chemicals Inc.
• Example 11 In this case, 3 gms. of napthenic acid is added to 110 gms. of Beckozole P-787. The mixture thus obtained is agitated by a homomixer, while another solution pre pared by dissolving 3 gms. of triethylamine in gms. of water is added steadily, and is thereby emulsified.
• 100 gms. of photoconductive zinc oxide is added to 100 gms. of water and dispersed by a homomixer. The dispersed solution thus obtained is mixed with 100 gms. of the aforesaid emulsion and is agitated. Next, 6 cc.
• the photoconductive layer forming solution thus produced is applied for coating the surface of a baryta paper, whose back has been processed for conductivity, to such an extent that its weight after the drying process will be 35 gms./m and is dried thereafter.
• the resultant electrophotographic copying material is impressed with an electric charge by a conventional method, and can be developed and fixed by the dry-process subsequent to exposure.
• This material produces a superb photographic image, so that a picture obtained thereby can be used as a master for an offset printing after making it hydrophilic.
• Example 12 In this case, 2 gms. of lauric acid was added to gms. of Beckozole P-787. The mixture thus obtained was agitated by a homomixer while another solution, which had been prepared by dissolving 3 gms. of triethylamine in 100 gms. of water, is added steadily, and thereby a binder solution comprising an emulsion of said resin was produced. 110 gms. of the thus produced binder solution was then added to a sensitizer solution comprising 100 gms. of photoconductive zinc oxide, 100 gms. of water, and 5 cc.
• a sensitizer solution a methanol solution consisting of 1% of Bromophenol Blue, 0.5% of Fluorescein, and 0.1% Rose Bengal
• the dispersed solution thus prepared was applied for coating the surface of a supportin the present case, an art paper-whose back had been processed for conductivity, to such an extent that the remainder of the applied solution on said surface subsequent to the drying process will be 25 gms./ m.
• an electrophotographic copying material was obtained.
• binder solution having the same composition as that of the aforesaid binder solution, except for substitution of 3 gms. of a surface active agent (such as Nissan Rapizole (dialkylsulfosuccinate manufactured by Nihon Yushi Kabushiki Kaisha)) for the lauric acid and triethylamine, was prepared and the same sensitizer solution as in the present invention described in the foregoing was added thereto, and the thus blended solution was further processed in the same way as in the present invention, thereby producing a copying material to serve for said comparison.
• a surface active agent such as Nissan Rapizole (dialkylsulfosuccinate manufactured by Nihon Yushi Kabushiki Kaisha)
• Example 13 In this case, except for the substitution of palmitic acid for the lauric acid employed for emulsification in the foregoing Example 12, the same components and processes as in case of Example 12 were applied in obtaining an electrophotographic copying material. The efiiciency and performance of the thus obtained copying material were equivalent to that of Example 12.
• Example 14 In this case, 3 gms. of stearic acid was added to 100 gms. of Styrezol 4440. The mixture thus obtained was agitated by a homomixer while another solution, which had been prepared by adding v3 gms. of morpholine to 100 gms. of water, was added steadily, and thereby a binder solution comprising an emulsion of said resin was produced. 100 gms. of the thus produced binder solution was then added to a sensitizer solution having the same composition as that of Example 12, and the thus blended solution was thereafer processed in the same way as in Example 12, thereby producing an electrophotographic copying material. The efficiency and performance of the thus obtained copying material were equivalent to that of Example 12 of the present invention.
• Example 15 In this case, 3 gms. of oleic acid was added to 70 gms. of Silicone Resin KR-211. The mixture thus obtained was agitated by a homomixer while another solution, which had been prepared by dissolving 3 gms. of triethylamine in 100 gms. of water, is added steadily, and thereby a binder solution comprising an emulsion of said resin was produced. 80 gms. of the thus produced binder solution was then added to a sensitizer solution having the same composition as that of Example 12, and the thus blended solution was thereafter processed in the same way as in Example 12, thereby producing an electrophotographic copying material. The efficiency and performance of the thus obtained sensitive material proved to be equivalent to that of Example 12 of the present invention.
• Example 16 In this case, 3 gms. of ricinoleic acid was added to gms. of Beckozole 1341. The mixture thus obtained was agitated by a homomixer while another solution, which had been prepared by blending 10 gms. of 28%-ammonia water with 100 gms. of water, was added steadily, and thereby a binder solution comprising an emulsion of said resin was produced. gms. of the thus produced binder solution was then added to a sensitizer solution having the same composition as that of Example 12, and the resultant solution was processed in the same Way as in Example 12, thereby producing an electrophotographic copying material. The copying material thus produced proved to be equivalent to that of Example 12 in its efficiency as well as performance.
• Example 17 In this case, there were prepared several binders:
• a binder which was obtained by emulsifying the same silicone resin as was employed in Example 15 by means of an emulsifier produced by combining phthalic anhydride with triethylamine,
• a binder which was obtained by emulsifying the same styrenated alkyd resin as was employed in Example 14 by means of an emulsifier produced through combination of cobalt naphthenate (a hardener), p-chlorobenzoic acid, and trirnethylamine,
• a binder which was obtained by emulsifying the aforesaid silicone resin by means of an emulsifier produced by combining naphthalic acid with triethylamine,
• a binder which was obtained by emulsifying the aforesaid silicone resin by means of an emulsifier produced by combining tetrachlorophthalic acid with triethylamine, and
• a binder which was obtained by emulsifying the aforesaid styrenated alkyd resin by an emulsifier produced by combining tetrachlorophthalic acid with trimethylamine.
• Example 18 In this case, 10 gms. of Styrezol J-718 (a 50%-high solvency mineral turpentine solution of styrenated alkyd resin, whose acid value is approximately 10, manufactured by Dai Nippon Ink and Chemicals Inc.) was added to gms. of Styrezol 4440, and the mixture thus obtained was agitated by a homomixer while another solution, which had been prepared by dissolving 3 gms. of triethylamine in 100 gms. of water, was added steadily, and thereby a binder solution comprising an emulsion of the aforesaid Styrezol 4440 resin was produced. On the other hand, 100 gms.
• Styrezol J-718 a 50%-high solvency mineral turpentine solution of styrenated alkyd resin, whose acid value is approximately 10, manufactured by Dai Nippon Ink and Chemicals Inc.
• photoconductive zinc oxide was added to 100 gms. of water, and furthermore, while this mixture was agitated by a homomixer, 5 cc. of a sensitizing dye solution (a methanol solution comprising 1% of Bro'mophenol Blue, 0.5% of Fluorescein, and 0.1% of Rose Bengal) was added, and thereby a photoconductive substance, that is, a sensitizer dispersed solution, was produced.
• a sensitizing dye solution a methanol solution comprising 1% of Bro'mophenol Blue, 0.5% of Fluorescein, and 0.1% of Rose Bengal
• 80 gms. of the aforesaid binder solution was added to said dispersed solution and, through thorough agitation, a photoconductive-layer forming solution was produced. Subsequently, by application of this solution and also following the same processes for forming a photoconductive layer as employed in Example 1, an electrophotographic copying material was Obtained.
• another binder was prepared by emulsifying the aforesaid resin by means of such a conventional surface active agent that will scarcely be volatilized even by drying, and by application of said binder, and through the same processes as in the present invention, an electrophotographic copying material was also prepared to serve for the test comparison.
• Example 19 In this case, 15 gms. of Beckozole 1341 was added to 70 gms. f Silicone Resin KR-2l1, and the mixture thus obtained was agitated by a homomixer while another solution, which had been prepared by dissolving 5 .gms. of morpholine in 100 gms. of water, was added steadily, and thereby a binder solution comprising an emulsion of said Silicone Resin KR-211 was produced. Then, 80 gms. of the thus obtained binder solution was added to a photoconductive substance, that is, a sensitizer dispersed solution having the same composition as that of Example 18, and was blended thoroughly by agitation, thereby producing a photoconductive layer forming solution. Subsequently, said solution was used in the same way as in Example 18, and an electrophotographic copying material was obtained thereby. The resultant coping material, when employed for the photographic reproduction by following the same processes as in Example 18, produced quite a clear copied image.
• Example 20 In this case, gms. of 70%-mineral turpentine solution of Super Beckozole 1351 (a pure alkyd resin whose acid value is approximately 20, manufactured by Dai Nippon Ink and Chemicals Inc.) was added to 70 gms. of a xylene solution of Silicone Resin (KR-211) which is the same as that of Example 19, and the mixture thus obtained was agitated by a homomixer while another solution, which had been prepared by dissolving 3 gms. of triethylamine in 100 gms. of water, was added steadily, and thereby a binder solution comprising an emulsion of said Silicone Resin KR-211 was produced. Subsequently, 80 gms. of the thus obtained binder solution was processed for application in the same way as in Example 18, and an electrophotographic copying material was produced thereby.
• KR-211 Silicone Resin
• Example 21 In this case, except for substitution of gms. of 50%-toluene solution of Aron S-lOOl (trade name of product of Toa Gosei Kagaku Kogyo Kabushiki Kaisha, whose acid value is approximately 12) which is a copolymer resin whose principal component is an acrylic ester, for the solution of a pure alkyd resin employed in the foregoing Example 20, the same components and processes of treatment as in Example were applied in obtaining an electrophotographic copying material. The efiiciency and performance of the resultant copying material were equivalent to that of Example 20.
• Example 22 In this case, except for substitution of 15 gms. of solution of a styrenated alkyd resin (i.e. the same as employed in Example 18) for the solution of a pure alkyd resin employed in Example 20, the same components and processes of treatment were applied in obtaining an elec- 14 trophotographic copying material. The efficiency and performance of the resultant copying material were equivalent to that of Example 20.
• Example 23 In this case, except for the substitution of 10 gms.
• Example 24 In this case, 0.5 gr. of manganese naphthenate (a hardener) was added to 100 gms. of a mineral turpentine solution of a styrenated alkyd resin (i.e. the same as employed in Example 18), and this mixture was agitated b a homomixer while another solution, which had been prepared by dissolving 3 gms. of triethylamine in 100 gms. of water, was added steadily, and thereby a binder solution comprising an emulsion of said resin was produced.
• 0.25 gr. of manganese naphthenate and 0.25 gr. of cobalt naphthenate were added to 100 gms. (50 gms.
• Example 25 In this case, 600 gms. of toluene, 270 gms. of styrene, 200 gms. of butyl methacrylate, 60 gms. of -hydroxypropylmethacrylate, 20 gms. of itaconic acid, and 12 gms. of azobisisobutyronitrile were put together in a three neck flask, and upon replacing the air within said flask by nitrogen, said mixture was polymerized over a period of 5 hours by heating at 100 C., and thereby a copolymerized resinous binder (hereinafter referred to as copolymer A) was obtained.
• copolymer A copolymerized resinous binder
• the photosensitive-layer forming solution thus produced was applied for coating the surface of an art paper, whose back had been processed for conductivity, to such an extent that the remainder of the applied sensitizer on said surface subsequent to the drying process was 30 gms./m1 Then, the thus coated support was dried at 120 C. for 10 min. and thereafter left in a dark place (temp. C., RH 65%) for modulation of the humidity for 24 hours, and thereby an electrophotographic copying material was obtained.
• Material of present invention 40 10 320 Compared material .9 35 30 360 Compared material b 5 100 Furthermore, as a result of putting the respective copying materials into practical use for the formation of copies, it was found that the material of the present invention was quite superior to the compared material a while the compared material b was conspicuously inferior to the compared material a in terms of the concentration of image and clearness of the produced copy.
• Example 26 In this case, except for containing the same amount of fi-hydroxyethylmethacrylate in lieu of 'y-hydroxypropylmethacrylate, a copolymer having the same composition as the copolymer A in the foregoing Example was prepared. This copolymer is hereinafter referred to as copolymer B. Then, said copolymer b was processed in the same way as in Example 25, and thereby an electrophotographic copying material was obtained.
• Example 27 In this case, 'y-hydroxypropylmethacrylate of the copolymer A in Example 25 was replaced with the same weight of p-hydroxyethylacrylate, while the composition ratio of other monomers was left the same.
• copolymer C Into 100 gms. of the copolymer thus prepared (hereinafter referred to as copolymer C) was added 3 gms. of phthalic acid, and this mixture was thoroughly agitated by a homomixer while 3% aqueous solution of trimethylamine was added steadily, to emulsify and produce a binder thereby.
• Example 28 In this case, a composition of monomers comprising 500 gms. of toluene, 200 gms. of styrene, 150 gms. of butyl methacrylate, 50 gms. of ethyl acrylate, 58 gms. of acrylonitrile, 40 gms. of glycidylmethacrylate, 2 gms. of acrylic acid, and 8 gms. of benzoyl peroxide was slowly agitated within a three neck flask, in which air had been replaced by nitrogen, while being heated at C. for a 6-hour polymerization. Subsequently, the thus polymerized product was cooled, and a 50% solid copolymer was obtained thereby. (This material is hereinafter referred to as copolymer D.)
• Rose Bengal were added to 80 gms. of said emulsion. This mixture was intensely agitated for blending for 10 min., and a photosensitive-layer forming solution was thus obtained.
• the back of an art paper was processed for electric conductivity.
• the surface of the thus processed art paper was then coated with the aforesaid photoconductive-layer forming solution to such an extent that the residue of coating substance (i.e. sensitizer) after drying will be 30 gms./11
• the art paper thus coated was dried at 120 C. for 10 min. and thereafter left hung in a dark place (temp. 20 0, RH 65%) for 12 hours for modulation of humidity, and hereby an electrophotographic copying material was obtained.
• the method of preparing an electrophotographic copying material comprising an electroconductive support having a photoconductive film layer on one surface thereof, the said material being capable of assuming and retaining an image-forming electrostatic charge, which method comprises forming an aqueous emulsion of a resinous binder and containing dispersed therein a finely divided photoconductive material, by emulsifying a resinous binder of a copolymer consisting of at least one member selected from the vinyl monomer group consisting of glycidyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 5-hydroxypentylvinyl ether (CHFCHOCHQCHZCHZCHZCHZOH) with at least one member selected from the monomer group consisting of styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl
• the volatile base is a member selected from the group consisting of ammonia, a lower aliphatic amine, an aromatic amine, morpholine and piperidine.
• the emulsifying step comprises mixing an organic solvent solution of said resinous binder and said acidic substance and an aqueous solution of said volatile base.
• An electrophotographic copying material comprising an electro-conductive support and having applied thereon a photoconductive film comprising a resinous binder having dispersed therein a photoconductive substance selected from the group consisting of zinc oxide, titanium oxide, cadmium sulfide and zinc selenide, said resinous binder consisting of a copolymer of at least one member selected from the vinyl monomer group consisting of glycidyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, S-hydroxypentylvinyl ether (CH CHOCH CH CH CH CH OH) with at least one member selected fom the monomer group consisting of styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid, methacrylic acid,
• the article of claim 4 which also contains a small amount not exceeding 0.5% per total weight of said photoconductive film of a volatile base.
• said photoconductive film contains a volatile base selected from the group consisting of ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, hexylamine, ethylenediamine, arylamine, morpholine, piperidine and hydrazine, said volatile base being present in said film within a range not exceeding 0.5% per total weight of said photoconductive film.
• a volatile base selected from the group consisting of ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, hexylamine, ethylenediamine, arylamine, morpholine, piperidine and hydrazine

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Photoreceptors In Electrophotography (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Cited By (11)

• 1968
  • 1968-12-03 GB GB1257186D patent/GB1257186A/en not_active Expired
  • 1968-12-06 NL NL6817529A patent/NL6817529A/xx unknown
  • 1968-12-06 BE BE725024D patent/BE725024A/xx not_active Expired
  • 1968-12-06 DE DE1813147A patent/DE1813147B2/de active Granted
  • 1968-12-06 FR FR1594214D patent/FR1594214A/fr not_active Expired
• 1971
  • 1971-06-10 US US151926A patent/US3704122A/en not_active Expired - Lifetime

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