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    • 5. 发明授权
      US3948657A Photosensitive matter for electrophotography and method of the production thereof 失效
    • Photosensitive matter for electrophotography and method of the production thereof
    • 电摄影的感光性物质及其生产方法
    • US3948657A
    • 1976-04-06
    • US868135
    • 1969-10-21
    • Hideo Yoshikawa , Umi Tosaka , Takehiko Matsuo , Hirokazu Negishi
    • Hideo Yoshikawa , Umi Tosaka , Takehiko Matsuo , Hirokazu Negishi
    • G03G5/05 , G03G5/14 , G03G5/147 , B32B31/06 , B32B31/12 , G03G5/087
    • G03G5/0525 , G03G5/14 , G03G5/147
    • An electrophotographic photosensitive member is produced by a method in which a photoconductive layer is provided on a base, a polymeric solventless-type liquid resin adhesive is placed between said photoconductive layer and an overlying insulating layer and, by applying pressure on said insulating layer to spread said resin, said insulating layer is secured closely to the photoconductive layer through said adhesive layer. Fine grains of photoconductive material may be dispersed in said adhesive to provide a second photoconductive layer.This invention relates to a method for producing an electrophotographic photosensitive member and further to a method for obtaining a novel photosensitive member by employing said method. More particularly, this invention relates to an electrophotographic photosensitive body comprising basically three layers, a base layer, a photoconductive layer, and an insulating (insulative) layer, and offers a method for producing a photosensitive member whereby excellent results both in smoothness and in uniformity are effectively obtained when installing the photoconductive layer or the insulating layer, and a photosensitive member obtainable through said method.Furthermore, this invention relates to a method by which an adhesive layer is placed between two layers to be bound, with said two layers then being made to adhere to each other by squeezing.There have been suggested general methods of installing an insulating layer on a photoconductive layer such as; (1) the insulating film is simply placed on the surface of the photoconductive layer; (2) the insulating film is caused to contact closely the photoconductive layer to laminate them by utilizing the stickiness of the resin binder contained in the photoconductive layer; (3) an adhesive layer is placed between the photoconductive layer and the insulating layer to make them adhere to each other in layers.However, in the case of method (1), since two layers are only piled in layers, such defects as the trapping of bubbles, an uneven surface, and wrinkles are liable to be produced and since these defects are difficult to remove once they occur, this method can not be said to be an advantageous one.In the case of method (2), the physical properties of the photosensitive layer itself are affected greatly by the selection of the binder and, even if the selection is appropriate, still there occur many defects especially when the amount of binder selected is small. For example, since the photoconductive layer itself has a porous surface, when coating or bonding an insulating substance on said surface, there occurs easily such conditions as bubbles remaining in the interface between said coating layer and said photoconductive layer, said coating layer being formed unevenly in thickness, and twists or wrinkles being formed partially on the coated surface. When an insulating layer is formed directly on a photoconductive layer, there is the fear that the solvent in the insulating layer will permeate the photoconductive layer to deteriorate the photoconductive body itself or, depending on the kind of solvent, a large amount of solvent permeates the photoconductive layer not only impairing the function of the photoconductive body but also making its surface uneven.The same phenomena are observed when organic semiconductors are used for the photoconductive layer.When such phenomena as mentioned above have occurred, a uniform photosensitive element cannot be obtained and, therefore, not only is the function of the photosensitive element reduced, but also nonuniformity in image density and nonuniformity in charging occurs and can not be avoided.In the case of (3) mentioned above, a photosensitive member excellent in performance as compared with the foregoing two cases can be obtained. However, since the binding agents normally used are sticky at normal temperatures, it is very hard to apply a thin insulating film to the surface of the photoconductive layer without causing wrinkles or bubbles to be produced.Especially in the case of a tubular insulating film being shrunk by heat upon a drum-shaped photoconductive layer with a sticky adhesive therebetween, since the thermoshrinkage of the insulating film invariably is accompanied by local unevenness, the thermoshrinkage tends to produce wrinkles and capture bubbles produced by the sticky adhesive. A photosensitive member that had experienced the formation of such wrinkles or bubbles was hard to correct and could not be practically used.Although there are many known kinds of electrophotographic systems, the characteristics of the photosensitive member affects, to a great extent, image formation. By way of example, the present invention is particularly applicable to the electrophotographic systems using a photosensitive element comprising basically three layers, an insulating layer, a photoconductive layer, and a base, such as disclosed, for example, in Japanese Patent Publication No. 23910/1967 and No. 24748/1968, U.S. Ser. No. 571,538 filed Aug. 10, 1966, abandoned in favor of continuation application Ser. No. 116,557 filed Feb. 18, 1971, now U.S. Pat. No. 3,666,363 issued May 30, 1972, July U.S. Ser. No. 563,899 filed Jul. 8, 1966, divided by the filing of divisional application Ser. No. 133,789 filed Apr. 14, 1971, now U.S. Pat. No. 3,801,317 issued Apr. 2, 1974, all owned by the assignee of the present application. The photoconductive layer and the insulating layer must be in very close contact with each other at the interface in these examples.The charging states in these cases are as follows. The surface of the insulating layer is charged to one polarity by a first charging step and a charge opposite in polarity to the above is bound either to the interface between the photoconductive layer and the contacting insulating layer or in the neighborhood of said interface. Under the influence of this charge, the image of the original is projected onto the photosensitive element simultaneously with further charging through the application of charge of opposite polarity to said one polarity or AC corona discharge, and, when required, a radiation to which the photoconductive layer is sensitive is irradiated over the entire surface of the photosensitive member (i.e., unpatterned radiation) to obtain an electrostatic image on the insulating layer with high contrast.Therefore, the conditions under which charging occurs determine the quality of the electrostatic image, and such charging conditions at that time are a function of the characteristic of the photosensitive member itself. In a photosensitive member comprising basically a base, a photoconductive layer, and an insulating layer, when the photoconductive layer and the insulating layer are not laminated in close contact with each other, such deficiencies as reduction in the contrast of the electrostatic image, uneven image, and unstable image appear due to the effect of nonuniformity in charge and so forth.An essential object of this invention is, taking into consideration the above-mentioned facts, to offer a means to bind closely in layers the photoconductive layer and the insulating layer in order to obtain an excellent image.Specific objects of this invention will be described below. Further objects will also appear from reading the detailed description which follows.An object of this invention is to provide a photosensitive member having a photoconductive layer and an insulating layer closely bound in layers with a polymer-nonsolvent type synthetic resin and a method for producing same.A further object of this invention is to provide a method for providing a permeation preventing layer on a photoconductive layer and closely bonding on said permeation preventing layer an insulating layer by using a polymer-nonsolvent type synthetic resin bonding agent and the photosensitive member thus produced.Another object of this invention is to provide a bonding method with which a polymer-nonsolvent type bonding agent is spread by squeezing and to provide the photosensitive member thus produced.A still further object of this invention is to provide a method in which, for example, a liquid hotmelt is used as the bonding agent and to provide a photosensitive member produced by using such method.A specific object of this invention is to provide a way of making a protecting layer to use when squeezing which is peeled off later.Another specific object of this invention is to provide a way by which the base of the photosensitive member forms a layered structure with the insulating layer and the photoconductive layer in either the stated or reverse order to obtain a multilayered photosensitive member.This invention will be described in detail in the following.In providing an insulating layer on the photoconductive layer it is necessary as the most important condition that the insulating layer be bound closely to the photoconductive layer. Laminating with the aid of a bonding agent is one available way to meet this requirement. However, this method heretofore has been limited in its application by the characteristics of the bonding agent itself and by the nature of the insulating layer and the photoconductive layer to be laminated.In the present invention the conditions set forth for bonding in layers avoids such restrictions. In other words, the feature of this invention lies in the fact that a polymeric solventless-type adhesive is used as the bonding agent.When photoconductive fine particles are dispersed in a binder resin to form a photoconductive layer, if a solvent type adhesive is used, the solvent of the adhesive permeates into the photoconductive layer and causes local decrease in electrical resistance and disturbs the image quality.Accordingly, in this invention, affect of adhesive on the photoconductive layer is prevented by the use of a solventless and polymeric adhesive, and at the same time, since polymerization and hardening are accelerated by the presence of a hardener or heat, not only can the photosensitive member itself be in close laminar contact but also mechanical strength of the insulating layer can be achieved.The solventless polymeric adhesives used here are generally those which give rise to a polymerization reaction and adhesive on heating or through the addition of a hardener or by reaction between the polymer and some constituent of the air or by isolating the polymer from the air. Examples of such adhesives are epoxy resin, unsaturated polyester resin, cyanoacrylate resin, and various kinds of polymeric monomers. Moreover, there are adhesives, called hotmelt type adhesives, such as polyvinylbutyral, polyvinylacetate, vinyl chloride-vinylacetate copolymer resin, vinylacetate-polyethylene copolymer resin, acrylic resin, rosin, phenolic resin, modified phenol resin, maleic acid resin, modified fumaric acid, and dammar rubber having softening points ranging from about 70.degree. to 150.degree.C, and which are transparent and highly insulating. These low-temperature softening resins show no adhesion at normal temperatures. However, they melt by heating them up to the above-mentioned temperatures with infrared rays etc. and become adhesive in character.As a way of placing the insulating layer on the photoconductive layer in close contact using these adhesives, it is possible to employ the general method by which the insulating layer is merely laid upon the photoconductive layer. However, the following method is provided by this invention to prevent the trapping of bubbles and the occurrence of twists, wrinkles, etc. between the insulating layer and the photoconductive layer.
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