JPS6113588B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polymer base material in which only the surface of the base material is electrically conductive. In general, polymer base materials have extremely high electrical resistance;
As a result, frictional static electricity and dust adhesion are likely to occur, and it is hoped that improvements can be made to these drawbacks. It can also be used as a transparent conductive base material for microfilm or transparent electrophotographic film used as a second original, or as a conductive base material for panel boards and electrostatic recording films for electrical measuring instruments. It is desired to develop a polymeric base material that has high properties. Many studies have been conducted to date on methods of making polymeric base materials conductive. The main ones are the following two methods. 1. Blend a conductive substance into a polymer resin. 2. Apply conductive polymer to the surface of the polymer base material. However, in order to blend a conductive material with a polymer resin and impart sufficient conductivity to the polymer resin base material, a large amount of the conductive material must be added, and the basic properties of the polymer resin, such as Mechanical properties etc. will be impaired. Furthermore, in the method of imparting conductivity to a polymer resin by applying a conductive polymer to the surface of a polymer base material, it is not possible to adhere a hydrophilic conductive polymer to a hydrophobic polymer base material. In order to bond the polymer base material and the conductive polymer well, a method of treating the surface of the polymer base material with a sulfonating agent (for example, Japanese Patent Publication No. 48-23450) or a method of roughening the surface of the polymer base material (for example, JP-A-51-32334) has been proposed, but even after these treatments, the adhesion between the conductive polymer and the polymer base material may still be insufficient, or the conductive polymer may be damaged by solvents such as methanol. The polymer easily dissolves and flows away, resulting in a loss of conductivity, and film properties such as transparency must be sacrificed, so that a durable and excellent conductive polymer base material has not yet been obtained. To give an example of the current state of conductive polymer base materials in the above applications,
For example, regarding electrophotographic photosensitive materials, electrophotographic photoreceptors generally consist of a conductive base material and a photoconductive layer, and the conductive base material must have a surface resistivity of 10 ⁹ Ω/□ or less. It won't happen. Conventionally, such conductive substrates include metal plates, substrates formed by providing a vapor-deposited metal layer on a polymer film, and substrates formed by impregnating paper with an organic conductive polymer. In recent years, the development of organic photoconductive materials has improved their performance and made it possible to apply them to electrophotography. A characteristic of organic photoconductive substances is that they are extremely transparent, and it is desirable to develop transparent electrophotographic films that take advantage of this characteristic in microfilms, slide films, slide films for overhead projectors, second original images, etc. It is rare. In the case of such a transparent electrophotographic film, the conductive base material is naturally required to be a transparent conductive base material. Conventionally, as a transparent conductive base material,
A method of forming an extremely thin metal layer on a transparent polymer substrate by vapor deposition or sputtering, and a method of coating a conductive polymer on a transparent polymer substrate have been proposed. In the former case, a certain thickness of the metal layer is required to obtain adequate conductivity as an electrophotographic photoreceptor, which reduces the transparency of the substrate.
Generally, in order to obtain a surface resistivity of 10 ⁹ Ω/□ or less, the light transmittance of the substrate must be reduced to 70% or less, and when an organic photoconductive layer is provided on the conductive substrate, the electron Reduce the light transmittance of the photographic photoreceptor to 60% or less. This level of transparency is insufficient for the above-mentioned uses, and it is generally desired that the electrophotographic photoreceptor has a transparency of 70% or more for such uses. Another major drawback is that the processing cost for vacuum vapor deposition while controlling the thickness of such an ultra-thin metal layer is extremely high. In the latter case, the organic conductive polymer has extremely excellent transparency, the processing cost is low, and the conductive base material obtained by this method can be said to be extremely excellent. However, organic conductive polymers generally do not adhere to hydrophilic and hydrophobic polymer substrates and are easily peeled off from the substrate, making them unusable. For this reason, a method has been proposed in which the surface of a polymer substrate is treated with a corona discharge treatment or a sulfonating agent (for example, Japanese Patent Publication No. 48-23450) to make the surface of the polymer substrate hydrophilic and improve its adhesion with organic conductive polymers. ing. However, such methods reduce the transparency of the substrate and cannot bond the organic conductive polymer to the polymer substrate sufficiently strong enough to withstand use. Transparent conductive substrates have not yet been provided. Next, regarding photographic materials, polymer films, especially hydrophobic plastic films, have traditionally been widely used as photographic substrates, but photographic emulsions are mostly made of hydrophilic polymers, such as gelatin. In order to use it as a binding resin, it must be subbed at least once or several times. In particular, in order to bond the base material and the photographic emulsion sufficiently strongly, it is necessary to at least first apply a subbing process with a resin that adheres well to the base material, and then apply an undercoat process with a resin that adheres well to the resin and the photographic emulsion. It is necessary to carry out the underlining process two or more times. That is, it is almost impossible to find a resin that adheres well to both the hydrophobic polymer base material and the hydrophilic photographic emulsion layer, which are generally used as the base material for photographic light-sensitive materials. Resins are selected that adhere well and are compatible with other resins. Next, a resin for bonding the undercoat layer and the base material is selected to form the second undercoat layer. Generally, polymers used for photographic light-sensitive material substrates have difficulty adhering to other resins, so a solvent that corrodes the substrate is added to the resin solvent to coat the undercoat layer resin. However, this adhesive is generally bonded using a so-called anchor effect, and does not form a chemical bond with the base material, so its adhesive strength with the base material is weak. In addition, in order to prevent the hydrophilic resin used for the first undercoat layer from dissolving and washing away during fixing and washing with water, the resin is crosslinked, and for this reason, the resin layer and the photographic emulsion layer adhere to each other. This results in a decrease in Furthermore, these methods require a large amount of equipment and generally involve the use of chemicals that attack the substrate, such as acetic acid, trichloroacetic acid, etc., which are used to increase the adhesion to the substrate when subbing resins that adhere well to the substrate. The cost of undercoating is extremely high because it requires undercoating equipment made of corrosion-resistant and expensive materials to prevent corrosion of the undercoating equipment, and the photographic materials obtained in this way are expensive. Become something. In addition, the current situation is that it tends to cause various troubles such as a decrease in transparency due to the occurrence of scratches during the multiple undercoating processes. In view of the current situation, the present inventors conducted research to overcome such conventional drawbacks and provide an excellent conductive polymer base material that has extremely excellent conductivity and durability, and as a result, the present invention has been completed. Reached. That is, the present invention provides a conductive polymer base material formed by laminating an organic conductive substance and a polymer base material, in which the organic conductive substance is chemically bonded to a high voltage discharge active site on the surface of the polymer base material. It is. In the present invention, the polymer base material includes, for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl acetate, and acetate resins such as nitrocellulose, diacetate, and triacetate. , polyolefins such as polyethylene and polypropylene, nylon 6, nylon
66, polyamide such as nylon 10, polyimide, polystyrene, polycarbonate, acrylic resin, polyether, polysulfone, ABS resin,
It is a base material made of ordinary organic polymers such as phenolic resin, urea resin, urethane resin, melamine resin, and epoxy resin, and these can have any polymer composition such as homopolymers, copolymers, blends, etc. The form of the polymer base material is not particularly limited, and may take various forms depending on the field of application, such as fiber, woven fabric, nonwoven fabric, film, plate shape, block shape, etc. can. The organic conductive substance as used in the present invention refers to a radically polymerizable monomer substance having a substituent that contributes to conductivity and a polymer substance thereof. Such a radically polymerizable monomer is a compound having a carbon-carbon double bond, and is a monomer that polymerizes using a radical as a propagating terminal in a chain mechanism, and such a monomer is a monomer that is capable of coordinating with a base material. ,Join. For example, para-styrene sulfonic acid, sulfopropyl methacrylate, sodium para-styrene sulfonate, sodium vinyl sulfonate, sodium sulfopropyl acrylate, sulfopropyl methacrylate, sulfoethyl acrylate, sodium sulfoethyl methacrylate, etc. Monomers containing Gotoku-SO ₃ M (where M is H or an alkali metal), -PO such as acid phosphooxyethyl methacrylate, vinyl sodium phosphate, etc.
(OM) ₂ (where M is H or an alkali metal) radically polymerizable monomers, radically polymerizable monomers having an amino group such as diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, 2-hydroxy 3 -methacryloxypropyltrimethylammonium chloride,
Dimethyldiallylammonium chloride, 2-acryloxytrimethylammonium chloride,
Radically polymerizable monomers having a quaternary amino group such as vinylbenzyltrimethylammonium chloride, radically polymerizable monomers having an amide group such as acrylamide and N-methylolacrylamide, vinylpyridine, N-methyl 4- vinylpyridium chloride, vinylpyrrolidone,
Radically polymerizable monomers containing nitrogen and heterocyclic groups such as N/N-dimethyl 3,5-methylpiperidium chloride, polyethylene glycol monoacrylate, polyethylene glycol diacrylate, methoxypolyethylene glycol acrylate, polyalkylene glycol Radically polymerizable monomers containing an alkylene oxide chain with 4 to 25 repeating units such as monomethacrylate, polyalkylene glycol dimethacrylate, methoxypolyalkylene glycol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Radically polymerizable monomers containing hydroxyl groups such as hydroxypropyl methacrylate, copolymers of polyethylene glycol and polypropylene glycol,
Examples include monomers containing conductive polymer chains such as monoacrylate and diacrylate, monomethacrylate and dimethacrylate, and the like.
Such monomers can be used in either gaseous or liquid form (hereinafter referred to as monomer solution). Among them, sulfonates, phosphates, quaternary ammonium salts, monomers having alkylene oxide chains, and their polymers have particularly excellent conductivity (surface resistivity: 10 ³ Ω/□, 10 ¹² Ω/ □). Polymeric materials of these monomers, such as poly(sodium parastyrene sulfonate), poly(sodium vinylsulfonate), poly(sodium sulfopropyl acrylate), poly(sodium sulfopropyl methacrylate), poly(sodium sulfopropyl acrylate), poly(sodium sulfopropyl methacrylate), conductive polymers with sulfonic acid groups such as sodium sulfoethyl acrylate), poly(sodium sulfoethyl methacrylate), poly(sodium vinyl phosphate), poly(acid phosphooxyethyl methacrylate), etc. Conductive polymers with phosphoric acid groups, poly(vinylbenzyltrimethylammonium chloride), poly(N-methyl 4-vinylpyridium chloride), poly(2-acryloxytrimethylammonium chloride), poly(2-
Examples include conductive polymers having quaternary ammonium salts such as (methacryloxytrimethylammonium chloride) and poly(N·N-dimethyl3,5-methylpiperidium chloride). Such polymers are usually applied in the form of solvent solutions, but are not limited thereto. The high-voltage discharge active sites as used in the present invention are chemically active radicals generated on the surface of a substrate by high-voltage discharge, and such active sites are generated as follows. That is, the base material is Ar, He, H ₂ , N ₂ ,
The active points are generated on the surface of the substrate by exposing it to high voltage discharge in a gas such as NO ₂ , O ₂ , air, carbon fluoride, carbon halogonide, or a mixture thereof. . Although the gas pressure when performing high voltage discharge in the above method for generating active sites is not particularly limited, it is preferably 0.2 mmHg or more and 10 mmHg or less. In this gas pressure range, the generation efficiency of active points on the surface of the base material is high, and the discharge energy does not cause heppin holes or thermal contraction of the base material. The power supply and electrodes for performing high voltage discharge are not particularly limited, and any power source and electrode that can form a uniform discharge and form active points on the surface of the base material during the discharge may be used. The above method of generating active points on the surface of a substrate by high voltage discharge generates active points in the substrate like radiation and generates voids, or sulfonates the substrate to generate active points by functional groups. It does not damage the base material or cause loss of transparency, and does not impair various properties of the base material, such as mechanical properties. The substrate having such active sites is then capable of chemically bonding an organic conductive substance in either liquid or gaseous state to the active sites. In this case, when the base material is subjected to the discharge treatment described above in an oxygen-free gas, the active sites are radicals, but when the base material is treated in an oxygen-containing system, the active sites take the form containing peroxide. Even the above radicals change into peroxide when exposed to oxygen gas. In order for such peroxide to react with the substance, it is important to expose it to a temperature of 40°C or higher (preferably 40°C to 80°C) to regenerate radicals. The timing of this regeneration may be before, during, or after applying the organic conductive substance to the substrate.
Either of the latter may be used, but it is usually regenerated in the drying step after application. Moreover, when it is in the form of a radical, it can be easily chemically bonded by adding various substances as it is. The method for bonding the conductive substance to a substrate having such active sites includes introducing the substrate into a treatment liquid made of the conductive substance, or applying the treatment liquid to the surface of the substrate. Alternatively, a method such as introducing the base material into a gas atmosphere made of the conductive substance can be applied. Such a method can be appropriately selected depending on the properties of the organic conductive substance used. The conductivity of the conductive polymer base material of the present invention thus obtained exhibits humidity dependence, and the conductivity decreases as the humidity decreases. This seems to be because the moisture contained in the organic conductive polymer graft polymerization layer contributes to the conductivity, and the amount of moisture contained decreases as the humidity decreases. The electrically conductive polymer base material of the present invention, which uses a quaternary ammonium salt, a radically polymerizable monomer having a hydroxyl group, and a polymer made of these, showed little decrease in electrical conductivity even at low humidity. This is probably because it contains a large amount of water even at low humidity because it has hydroxyl groups. In particular, 2-hydroxy 3-methacryloxypropyltrimethylammonium chloride and 2-hydroxy 3-acryloxypropyltrimethylammonium chloride easily form a conductive graft polymerization layer by discharge graft polymerization, and the present invention using these monomers The conductive polymer base material of the invention has a surface resistivity value of
It showed excellent conductivity of 16 ⁶ Ω/□ to 10 ⁹ Ω/□.
Similarly, a polymer of the monomer also showed excellent conductivity. The conductive polymer base material made of the above monomer has a surface resistivity increase of two digits or less under low humidity, whereas the conductive polymer base material of the present invention using other monomers The surface resistivity value of the material increases by about three orders of magnitude under low humidity. That is, the material made of the above-mentioned specific monomer is an extremely excellent conductive polymer base material with little change in conductivity due to humidity. The monomer solution in the present invention refers to one or more monomers or a solution in which the monomers are dissolved in a solvent such as water. By using a monomer solution in which a monomer that imparts conductivity is mixed with other monomers that can be radically polymerized, such as acrylic acid, the organic conductive polymer graft polymerization layer can be given other properties, such as the upper layer. When a resin layer is formed on the material, performance such as improved adhesion with the resin can be imparted. When a mixed monomer containing a monomer other than a monomer having conductivity is used, the conductive polymer base material of the present invention has a surface resistivity value.
10 To provide conductivity of ¹⁰ Ω/□ or less, it depends on the ease of radical polymerization of the monomers added, but 30
It needs to be less than mol%. The conductive polymer base material of the present invention is, for example, one in which an organic conductive polymer graft layer is provided on at least one side of the polymer base material, and both sides of the base material are organic conductive polymers formed from different monomers. It may be a polymer graft polymer layer. An electrophotographic film can be obtained by providing a photoconductor material layer directly or via an insulating layer on the conductive polymer base material of the present invention, or by further providing an insulating layer on top of the photoconductor material layer. What is photoconductor material?
Inorganic photoconductive materials such as Se, Se-Te alloys, CdS or ZnO bonded with resin, poly-N-vinyl carbazole, halogenated poly-N-vinyl carbazole, nitrated poly-N-vinyl carbazole, anthracene, polyvinyl anthracene, etc. Sen,
These are organic photoconductive substances such as N.N.N'.N'-tetrabenzyl-p-phenylenediamine and N.N.N'.N'-tetrabenzyl-m-phenylenediamine. When a polymer base material with excellent transparency such as polyethylene terephthalate is used, the conductive polymer base material of the present invention becomes a transparent conductive base material with extremely excellent transparency, and it can be used as a transparent conductive base material with excellent transparency such as poly(N-vinylcarbazole). By using a conductive substance, a transparent electrophotographic film with excellent transparency and mechanical strength can be obtained. This transparent electrophotographic film has excellent performance as a micro film, a slide film, an overhead slide film, and an electrophotographic film for second original drawings. Furthermore, an excellent electrostatic recording film can be obtained by providing a dielectric resin such as a vinyl chloride/vinyl acetate copolymer, acrylic resin, or methacrylic resin on the conductive polymer base material of the present invention. As described above, the electrical conductivity of the conductive polymer base material of the present invention decreases with a decrease in humidity. This effect results in an increase in the acceptance potential in the electrophotographic properties, which manifests itself as an increase in the dark decay rate. But 2
-hydroxy 3-methacryloxypropyltrimethylammonium chloride, 2-hydroxy 3-methacryloxypropyltrimethylammonium chloride
- When the conductive polymer base material of the present invention using acryloxypropyltrimethylammonium chloride as a monomer is used, this effect can be reduced. Generally, in electrofax type electrophotographic paper or electrostatic recording paper, paper is impregnated with a conductive polymer and used as a conductive base paper. However, since the base material is paper, it has drawbacks such as opacity and low mechanical strength. In contrast, the electrophotographic film and electrostatic recording film of the present invention have excellent transparency, strong mechanical strength, and excellent durability. There are also electrophotographic films (for example, Japanese Patent Publication No. 48-23450) that are made by coating a conductive polymer on a polymer base material and then providing an organic photoconductive layer on top. The electrophotographic film has poor durability because of its weak adhesion to the conductive polymer, and when the organic photoconductive layer is applied onto the conductive polymer, the conductive polymer is eluted by the solvent of the organic photoconductive layer resin. When mixed into the organic photoconductive layer resin, the dark decay of the electrophotographic film increases or the organic photoconductive layer becomes white, resulting in a decrease in the transparency of the electrophotographic film. On the other hand, in the electrophotographic film using the conductive polymer base material of the present invention, the organic conductive polymer graft polymer layer is chemically bonded to the base material as described above, so it is different from the conventional electrophotographic film. This transparent electrophotographic film is extremely durable and highly transparent, without causing any of the problems described above. Such a conductive polymer base material is preferably applied to applications requiring conductivity and antistatic properties, and the application will be described in more detail below by citing an example. First, the photographic material will be explained. As the base material used in the photographic light-sensitive material, materials with excellent dimensional stability, mechanical properties, and transparency, such as triacetate film, polyvinyl chloride film, and polyethylene terephthalate film, can be selected. Such a base material is subjected to the above-mentioned high voltage discharge treatment to form active sites on its surface, and the following three methods are applicable. 1 After activating the base material surface by high voltage discharge,
A method of graft polymerization in which the vapor of a monomer capable of radical polymerization is exposed without exposure to oxygen. 2 After activating the base material surface by high voltage discharge,
A method of graft polymerization by exposing a monomer solution capable of radical polymerization to a radically polymerizable monomer solution without exposing it to oxygen. 3 After activating the base material surface by high voltage discharge,
It is brought into contact with oxygen or an oxygen-containing mixed gas to react with the active sites on the surface of the substrate. Next, the base material is brought into contact with a radically polymerizable monomer solution to carry out graft polymerization. As specified in the above method, among the organic conductive substances of the present invention, radically polymerizable monomers are preferably applied to the photographic light-sensitive material, and it is preferable to graft-polymerize these onto a substrate. The reason for this is the durability of the organic conductive polymer and organic conductive monomer of the present invention against solvents such as water, and as will be understood from the following experiment, the monomer is more durable than the polymer. has excellent durability. That is, since photographic materials are processed with water during development, fixing, washing, etc., they cannot be considered practical unless they have excellent water resistance. Experiment 1 2-Hydroxy-3-methacryloxypropyltrimethylammonium chloride (A) and its polymer (B) were used as a conductive substance, using polyethylene terephthalate film as a base material, and subjected to high voltage discharge (glow discharge) treatment. After imparting active points, two types of substances, a monomer (A) and a polymer (B), were applied to form conductive films each having a thickness of 0.3μ on the base material. When the obtained conductive films of the present invention were extracted with a Soxhlet extractor using methanol, which has a better solvent ability than water, the conductivity (surface specific resistance) of each film showed the results as shown in Table 1. . For comparison, the results obtained when (B) was applied to an untreated substrate are also shown (comparative example).

[Table] From Table 1, when monomer (A) is used, (A) graft polymerizes with the active sites of the base material, can withstand long-term extraction, and is virtually conductive with the base material. It is clear that it is integrated with the sexual substance layer. If the same (A) is used, but a polymerized product (B) is used,
Although the conductivity before extraction is superior to the case of graft polymerization in (A), the durability against extraction is inferior to the case of (A). However, in any case, it can be seen that the durability is extremely excellent compared to the untreated comparative example. In view of the durability required of photographic materials, monomers are more suitable for the conductive substance than polymers. Among such monomers, the following conductive monomers are applied to photographic materials. That is, a photographic light-sensitive material has a photographic emulsion layer on a base material,
Therefore, it is also a desirable requirement to have strong adhesion to such an emulsion layer. Among the monomers capable of radical polymerization, -
Monomers having SO ₃ M or -PO(OM) ₂ (where M is H or an alkali metal), and monomers containing nitrogen such as amino groups, quaternary amino groups, and amide groups, and alkylene Monomers containing oxide groups (with 4 to 25 repeating units) or hydroxyl groups can be applied. Especially para-styrene sulfonic acid, sulfoethyl methacrylate, sulfopropyl methacrylate, sodium para-styrene sulfonate, sodium sulfoethyl methacrylate,
Sodium sulfopropyl methacrylate, acid phosphooxyethyl methacrylate, 2-hydroxy 3-methacryloxypropyl trimethylammonium chloride, acrylamide, N-
Methyloracrylamide, vinylpyrrolidone,
Vinylpyridine easily forms a discharge graft polymerized layer by the above-mentioned discharge grafting method and adheres extremely firmly to the upper photographic emulsion layer. Further, when a solution of two or more types of monomers is used in the discharge graft polymerization method, a discharge graft polymerization layer of two or more types of monomers or a discharge graft polymerization layer of a copolymer of these monomers can be formed. Such a discharge graft polymerization layer may be used as the discharge graft polymerization layer used in the present invention. For example, a graft layer formed using a monomer solution in which acrylic acid and methacrylic acid were added to these monomers was firmly adhered to the upper photographic emulsion layer. Although the discharge graft layer formed using only acrylic acid or methacrylic acid as a monomer had good adhesion to the photographic emulsion immediately after coating, it was extremely susceptible to peeling during development, fixing, or after these treatments. It got easier. This is thought to be because the graft layer was converted to sodium polyacrylate due to the sodium ions contained in these treatment solutions. In fact, the base material on which the discharge graft layer was formed was immersed in a NaOH solution before emulsion coating, and the base material in which the discharge graft layer was made of sodium polyacrylate did not adhere firmly to the photographic emulsion. The photographic emulsion of the photographic recording material is an ordinary silver salt photographic emulsion whose main components are silver halide, gelatin, polyvinyl alcohol, etc., and its composition or the structure of the photographic emulsion layer, such as a protective layer, a photosensitive layer, an antihalation layer, etc. The configuration is determined depending on each application and is not particularly limited. In general, in photographic light-sensitive materials, light that has passed through an emulsion layer is reflected or scattered at the interface of layers other than the emulsion layer, such as an undercoat layer or a base material, and returns to the emulsion layer again, causing halation and a decrease in resolution. For this reason, in conventional photographic light-sensitive materials, an antihalation layer in which a red dye or a dark green dye is dispersed in gelatin or the like is provided below the photosensitive layer in the emulsion layer. The discharge graft layer of the photographic light-sensitive material according to the present invention, which is formed from monomers other than monomers containing polyalkylene oxide chains, can be dyed red or dark green with acid dyes or basic dyes. Since this layer is extremely thin, the dyed layer is easily reductively decolored by the developing agent in the developer and the hypo in the fixer. Therefore, a discharge graft layer dyed in a color suitable for preventing halation can bind the base material and the photographic emulsion layer and at the same time serve as an anti-halation layer.Therefore, it is necessary to provide an anti-halation layer in the photographic emulsion layer. This eliminates various obstacles associated with the antihalation layer coating process. Further, since conventional antihalation layers are made by dispersing dyes in gelatin, uniform dispersion in a microscopic sense is difficult to occur and the antihalation effect is poor. On the other hand, since the dyed discharge graft polymerization layer is dyed, the dye is very uniformly adsorbed into the discharge graft polymerization layer, and the halation prevention effect is extremely good. However, in the photographic light-sensitive materials of the present invention, the discharge graft polymerization layer is not necessarily all dyed so that it also serves as an antihalation layer, and the antihalation layer is not excluded from the photographic emulsion layer. Depending on the application, a conventional antihalation layer may be provided. For example, when a roll film requires a backing layer to prevent roll-up, a dye may be dispersed in this layer to serve as an anti-halation layer. The basic structure of the photographic light-sensitive material according to the present invention is to have a discharge graft polymerization layer on a base material, and a photographic emulsion layer on top of the discharge graft polymerization layer. Furthermore, the discharge graft polymerization layer and the photographic emulsion layer may be provided not only on one side of the substrate but also on both sides. When discharge graft polymerization layers are provided on both sides, discharge graft polymerization layers made of different monomers may be provided on both surfaces. The discharge graft polymerization layer of the photographic light-sensitive material according to the present invention is hydrophilic and has antistatic properties, and when the discharge graft polymerization layer is used on both sides, fogging due to frictional static electricity, which is a serious problem during emulsion coating, can be avoided. Occurrence can be prevented. Therefore, a photographic material having discharge graft polymerization layers on both sides is an extremely excellent photographic material free from fog. To summarize the features of the photographic light-sensitive material according to the present invention, 1. The photographic light-sensitive material according to the present invention does not undergo the expensive undercoating process that is carried out in ordinary photographic light-sensitive materials, and the base material and photographic emulsion are It is an inexpensive photographic material that is extremely strongly bonded because it is not due to the anchor effect, but is chemically bonded (coordination bond). 2. Since an undercoat layer is not required, optical properties deteriorate due to light scattering and refraction at layer interfaces that occur when multiple undercoat layers are formed, and optical properties deteriorate due to scratches that occur during undercoat processing. It is a photographic material with extremely excellent optical properties without deterioration. 3. It is a photographic light-sensitive material that can impart antihalation performance by dyeing the discharge graft polymerization layer, has no antihalation layer in the photographic emulsion layer, and has an extremely excellent antihalation effect. 4 When the discharge graft polymerization layer is formed on both sides,
It imparts antistatic properties to the base material and prevents the generation of sparks due to frictional electrification that occurs when coating photographic emulsions. Therefore, the photographic light-sensitive material according to the present invention has extremely excellent characteristics, such as being an excellent photographic light-sensitive material with extremely little fog compared to conventional photographic light-sensitive materials. Next, an example in which the conductive polymer base material of the present invention is applied to a transparent electrophotographic material will be described in more detail. Electrophotographic materials are required to have surface resistivity of 10 ⁹ Ω/□ or less, electrical conductivity, and transparency. Furthermore, unlike photosensitive photography, electrophotography is not treated with water or alcohol, so there is no problem of conductive substances being dissolved and washed away due to water treatment. Due to these characteristics, the conductive polymer base material of the present invention does not need to be graft polymerized using the above monomer as a conductive substance, and it is sufficient to use a conductive polymer. . Of course, it goes without saying that graft polymerization using the above-mentioned conductive monomer provides a product with better durability. Generally, the conductivity of organic conductive polymers decreases as humidity decreases. This is thought to be because water contained in the organic conductive polymer contributes to conductivity, and the amount of water contained in the organic conductive polymer decreases as the humidity decreases. Organic conductive polymers containing quaternary ammonium salts and hydroxyl groups, such as poly(2-hydroxy 3-methacryloxypropyltrimethylammonium chloride) and poly(2-hydroxy 3-methacryloxypropyltrimethylammonium chloride), are There was little decrease in conductivity even at low humidity. This is probably because it contains a large amount of water even at low humidity because it has hydroxyl groups. A decrease in the electrical conductivity of the conductive substrate of an electrophotographic film is undesirable because it causes a decrease in the maximum acceptance potential and an increase in dark decay of electrophotographic properties.
From this point of view, poly(2-hydroxy 3-methacryloxypropyltrimethylammonium chloride) and poly(2-hydroxy 3-acryloxypropyltrimethylammonium chloride) are preferred conductive polymers. Furthermore, by using a conductive polymer composition that is a mixture of these conductive polymers and other polymers such as poly(methacrylic acid), it is possible to improve the adhesion with the upper photoconductive layer. . The conductive polymer film of the conductive support base material in the present invention is preferably an extremely thin layer. Even if the conductive polymer film is an extremely thin layer, the conductive support substrate has sufficient conductivity, and has no adverse effect on the electrophotographic properties, and surprisingly, its transparency is This is improved compared to using only polymer film.
For example, the light transmittance of the conductive support substrate used in the present invention, which is a glow discharge-treated polyethylene terephthalate film provided with poly(2-hydroxy 3-methacryloxypropyltrimethylammonium chloride), is the light transmittance of the polyethylene terephthalate film. compared to 84%
It showed 89%. This shows that the transparent electrophotographic film according to the present invention has extremely high transparency and is an excellent transparent electrophotographic film. Further, the conductive base material used for this has no stickiness on the surface of the base material, although it is not clear whether this is due to the fact that the conductive polymer film is an extremely thin layer. Generally, hydrophilic polymers become sticky due to moisture in the atmosphere, causing blocking. Particularly in a high humidity atmosphere, the polymer film may break due to blocking, which poses a very serious problem in handling the film. The conductive supporting base material of the present invention does not cause any blocking and maintains extremely excellent workability. The thickness of the conductive polymer film of the conductive support base material in the present invention depends on various factors.
0.1μ or more 2μ or more (more preferably 0.3 to 0.6μ)
is preferred. The organic conductive layer constituting such a transparent electrophotographic film includes a known monomeric or polymeric organic photoconductive material, and a photoconductive material containing a bonding resin, a plasticizer, and a photosensitizer to the organic photoconductive material. Conductive compositions can be used. As an organic photoconductive substance, N.
N・N′・N′-tetrabenzyl P-phenylenediamine, N・N・N′・N′-tetrabenzyl m-
Phenyl diamine, poly N-vinyl carbazole, halogenated poly N-vinyl carbazole, nitrated poly N-vinyl carbazole, polyvinylanthracene, etc. can be used. In particular, the poly-N-vinylcarbazole-based organic photoconductor strongly adheres to the conductive support, and the sensitizer, such as 2.4.
7-trinitrofluorenone, 2, 4, 5, 7-
It easily becomes a highly sensitive organic photoconductor with tetranitro-9-fluorenone and the like, and is an extremely excellent photoconductor for the transparent electrophotographic film of the present invention. Further, the transparent electrophotographic film according to the present invention may have an insulating resin layer between the conductive support and the organic photoconductive layer or on the organic photoconductive layer depending on the electrophotographic method. The present invention will be explained in detail in the following examples. Before that, the data measurement method and judgment criteria in the examples will be explained. 1 Surface potential decay characteristics (electrophotographic characteristics) ELECTROSTATIC PAPER ANALYZER
It was measured using SP-428 (manufactured by Kawaguchi Electric). 2 Surface specific resistance ELECTROMETER 610 (KEITHLEY IN
(manufactured by STRUMENTS). 3 Peeling test during drying A razor blade is applied to the laminate surface of a film having an organic conductive material layer, a dry film having a developed and fixed emulsion layer, and a dry film having a photoconductive coarse material layer, for example, to the emulsion surface. Make 100 squares by making a mesh-like line with a spacing of about 4 mm using the adhesive tape, then apply adhesive tape that adheres well (Permacel adhesive tape manufactured by Scotchi) on top of the scratches, and instantly peel it off. In this method, a peeled portion of 0 to 5% is graded A, a peeled portion of 5 to 30% is graded B, and a peeled portion of 30 to 100% is graded C. Alternatively, the surface specific resistance of the peeled portion of the sample after the peel test was measured, and the value was determined by comparing it with the resistance value before the test or the resistance value of the blank film. 4 Peeling test during wet processing This test is particularly suitable for determining the durability of the emulsion layer of photographic light-sensitive materials. That is, at each stage of development, fixing, and washing, two scratches are made on the emulsion surface of the film in the processing solution using an iron pen, and the scratches are rubbed with the tip of a finger in a direction perpendicular to the line to remove the emulsion layer. Class A if there is no peeling beyond the scratches.
If the maximum peeling is within 5 mm, it is classified as B class, and if it is larger than this, it is classified as C class. Example 1 A polymethyl methacrylate plate (“Torre Glass”) was exposed to a high voltage discharge in air at 0.6 Torr, then taken out into the atmosphere and transferred into a glass container, and the container was vacuum degassed and nitrogen gas was removed. Introduced. Next, the monomer solution shown in Table 1, which had been degassed and heated to 60°C, was introduced into the container and allowed to react for 15 minutes. The treated substrate was taken out, thoroughly washed with running water, and then dried. The surface resistivity of the conductive polymer base material thus obtained was 2×10 ⁸ Ω/□ in an atmosphere of 20°C and 60% RH.
It was hot. In order to examine the antistatic performance, we investigated the surface potential attenuation characteristics and found that the surface potential was zero, no charge was accumulated on the surface of the conductive polymer base material, and it had extremely excellent antistatic performance. Ta. Table 1 Sodium sulfopropyl methacrylate (manufactured by Sanyo Chemical Co., Ltd.) 10g Distilled water 990g Example 2 LP record (manufactured by CBS Sony) was heated to 0.8 Torr.
It was exposed to high voltage discharge in Ar gas, then exposed to the monomer solution shown in Table 1 for 5 minutes without being exposed to oxygen, and then vacuum dried. In order to examine the antistatic performance of the conductive polymer base material obtained in this way, after rubbing the conductive polymer base material with a Tetron cloth, the base material was held in a space 1 cm above the cigarette ash to check for ash adhesion. I looked into it. It was shown that the conductive polymer substrate did not have any ash adhesion at all and had extremely excellent antistatic performance. Commercially available LP records were found to have a large amount of ash attached to them during this test. When the record of the present invention was played on a player and the signal voltage from the pickup was observed with an oscilloscope, it was found that there was no difference at all from the record used as the base material. Example 3 A polyethylene terephthalate film ("Lumirror") was exposed to a high voltage discharge in _N2 gas at 0.6 Torr, then exposed to the monomer solution in Table 2 for 2 minutes without exposure to oxygen, and then vacuum dried. did. The surface resistivity of the conductive polymer base material obtained in this way is 20
The resistance was 6×10 ⁷ Ω/□ in an atmosphere of 60% RH. After subjecting the conductive polymer base material to a peel test and measuring the surface resistivity of the peeled part, no change was observed in the resistivity value, indicating that the conductive polymer base material has excellent durability. I found out that there was. This conductive polymer base material was thoroughly washed with running water, and then dyed with an acid dye (Acid Orang) in hot water at 90°C for 1 hour. As a result, it was dyed orange and the base material was dyed with the monomer. It was determined that it had a conductive polymer graft polymer layer. In this way, the conductive polymer layer does not dissolve or wash away even in running water or hot water, so the conductive polymer base material has an organic chemical bond between the base material and the conductive polymer goft polymer layer. It was shown that the material was extremely durable. Table 2 2-Hydroxy 3-methacryloxypropyltrimethylammonium chloride (trade name Bremma Q, manufactured by NOF Corporation) 10g Distilled water 990g Comparative example 1 A polyethylene terephthalate film ("Lumirror") was immersed in a concentrated sulfuric acid solution at 35°C for 2 seconds. The surface was then thoroughly washed with running water and dried. This film turns white the moment it is washed under running water, and a thick layer of low-molecular substances generated by hydrolysis with concentrated sulfuric acid is formed on the film surface, reducing the light transmittance to less than 20% and making the film smooth. The properties were completely lost due to the formed low molecular weight layer. A 1% methyl alcohol solution of a homopolymer of 2-hydroxy 3-methacryloxypropyltrimethylammonium chloride was applied onto this surface-treated substrate using a wire bar and dried. The coating thickness after drying is approximately 1μ, and the surface resistivity is 8×10 ⁶ Ω/□ in an atmosphere of 20℃ and 60%RH.
It was hot. Scotchi tape was pasted on the coating film of the base material and peeled off in the same manner as in Example 3. As a result,
The coating film was peeled off extremely easily together with the low molecular weight substances formed on the surface of the substrate. As a result, it was found that the conductive base material thus obtained was completely unusable for practical purposes. Example 4 Table 3 was printed on the conductive polymer base material obtained in Example 3.
The solution was applied with a wire bar and dried. The coating film thickness after drying was 8μ. The light transmittance and electrophotographic properties of the electrophotographic film thus obtained were measured, and the results shown in Table 4 were obtained. These results showed that this electrophotographic film had excellent properties. The electrophotographic characteristics were measured under the following conditions: +6 kV corona application, application time 10 seconds, and exposure amount 20 Lux. Table 3 Poly N-vinylcarbazole (trade name Rubican M-170 manufactured by BASF) 100 parts 2,4,7-trinitrofluorenone (manufactured by Tokyo Kasei Co., Ltd.) 4 parts polycarbonate (A2200 manufactured by Idemitsu Petrochemical Co., Ltd.) 10 parts Dibenzyltoluene (Marosam S, manufactured by Huels) 20 parts Monochlorobenzene 844 parts Tetrahydrofuran 362 parts

[Table] Example 5 A dielectric resin layer of a copolymer of 80 parts of methyl methacrylate and 20 parts of ethyl acrylate with a thickness of 5 μm was provided on the conductive polymer base material obtained in Example 3, and electrostatic recording was carried out. A film was produced. A corona of -6 kV was applied to the electrostatic recording film, and its charging characteristics were measured, and the results shown in Table 5 were obtained. These results showed that this electrostatic recording film had excellent properties.

[Table] Example 6 A polyethylene terephthalate film ("Lumirror") with a thickness of 100 μm was subjected to glow discharge treatment in air at 0.6 Torr using a 2 kW intermittent oscillation type high voltage power supply at a discharge treatment speed of 1 m/min. Next, a 0.5 homopolymer of 2-hydroxy 3-methacryloxypropyltrimethylammonium chloride (trade name: Bremma Q, manufactured by NOF Corporation) was polymerized using ammonium persulfate in a conventional manner.
A composition prepared by dissolving 100 parts of methanol was coated on the treated film using a bar coater until the film thickness after drying was 0.6.
It was applied to a thickness of μ and dried. The photoconductive composition shown in Table 6 was applied onto the conductive substrate thus prepared using a bar coater so that the film thickness after drying was 8 μm, and then dried. The electrophotographic film thus obtained has the electrophotographic properties and transparency shown in Table 7, and is an extremely transparent electrophotographic film. Further, as a result of an adhesion test, it was found that neither the photoconductive layer nor the conductive polymer layer peeled off, and each layer had sufficient adhesion as an electrophotographic film. The electrophotographic characteristics were measured under the following conditions: +6 kV corona application, application time 10 seconds, and exposure amount 20 Lux. Table 6 Poly N-vinylcarbazole (trade name Rubican M-170 manufactured by BASF) 100 parts 2,4,7-trinitrofluorenone (manufactured by Tokyo Kasei Co., Ltd.) 4 parts polycarbonate (A2200 manufactured by Idemitsu Petrochemical Co., Ltd.)
10 parts Dibenzyltoluene (Marosam S, manufactured by Huels) 20 parts Monochlorobenzene 844 parts Tetrahydrofuran 362 parts

[Table] Comparative Example 2 A polyethylene terephthalate film ("Lumirror") with a thickness of 100 μm was subjected to corona discharge treatment in the atmosphere using a 2 kW intermittent oscillation type high voltage power supply at a discharge treatment speed of 10 m/min. During the corona discharge treatment, a strong local discharge occurred and pinholes were formed in some areas. In the same manner as in Example 6, a conductive polymer composition was applied to the treated film and dried to produce a conductive base material. Next, Table 6 was prepared in the same manner as in Example 6.
A transparent electrophotographic film was prepared by coating the photoconductive composition. As a result of a peel test between each layer of this transparent electrophotographic film, peeling occurred between the polymer film and the conductive layer polymer, and the transparent electrophotographic film could not withstand actual use. Comparative Example 3 A conductive group was prepared by coating (0.3 μ) a polymer of 2-hydroxy 3-methacryloxypropyl trimethylammonium chloride on an untreated polyethylene terephthalate film, a corona discharge treated polyethylene terephthalate film, and a glow discharge treated polyethylene terephthalate film. A conductive substrate prepared by glow discharge graft polymerization of the material and the monomer was extracted with methyl alcohol using a Soxhlet extractor, and changes in the surface resistivity and concentration (dye Acid Orange) of the substrate were examined. The results shown in Table 8 were obtained.

[Table] Light transmittance was measured at 480 mμ, which is the maximum absorption wavelength of the dye Acid Orang. As a reference sample for measurement, a polyethylene terephthalate film ("Lumirror" 75μ), which is the base film of the treated substrate, was extracted at the same time.
Surface resistivity was measured at 20℃ and 60%RH atmosphere. As can be seen from Table 8, the conductive layer produced by glow discharge graft polymerization is completely chemically bonded to the base material through covalent bonds, so that the conductive layer does not dissolve or disappear due to extraction or the like. In addition, in the case of conductive substrates prepared by applying a homopolymer of 2-hydroxy 3-methacryloxypropyltrimethylammonium chloride to a glow discharge-treated substrate, the homopolymer dissolves and disappears during extraction, but the homopolymer remains in an extremely thin layer. It can be seen from Table 8 that the remaining on the surface of the base material. This is thought to be due to the chemical bonding between the homopolymer and the active sites generated on the surface of the base material due to glow discharge.
This seems to provide strong adhesive force between the homopolymer and the base material, as seen in Table 9. Table 9 shows the results of a peel test between the conductive substrate and the conductive layer produced by each of the above methods.

[Table] Example 7 A polyethylene terephthalate film (“Lumirror”) with a thickness of 70 μ was heated at 4 kW in N ₂ gas at 0.6 Torr.
Glow discharge treatment was performed at a discharge treatment speed of 10 m/min using a 110 kHz tuned self-oscillation high voltage power supply. Then 0.5 part of a homopolymer of 2-hydroxy 3-methacryloxypropyltrimethylammonium chloride and 0.05 part of polymethacrylic acid
A composition prepared by dissolving 100 parts of methanol was coated on the treated film using a bar coater until the film thickness after drying was 0.6.
It was applied to a thickness of μ and dried. The photoconductive composition shown in Table 10 was coated onto the conductive substrate thus prepared using a bar coater so that the film thickness after drying was 8 μm, and then dried. The electrophotographic film thus obtained had the electrophotographic properties and transparency shown in Table 11. Further, as a result of a peel test, it was found that neither the photoconductive layer nor the conductive polymer layer peeled off, and each layer had sufficient adhesion as an electrophotographic film. Note that the measurement conditions for electrophotographic properties are the same as in Example 6. Table 10 Poly N-vinylcarbazole (trade name Rubican M-170 manufactured by BASF) 100 parts 2,4,7-trinitrofluorenone (manufactured by Tokyo Kasei Co., Ltd.) 4 parts Saturated polyester resin (Vylon-200 manufactured by Toyo Co., Ltd.) 10 parts Dibenzyltoluene (Marosum S, manufactured by Huels) 20 parts Monochlorobenzene 844 parts Tetrahydrofuran 362 parts

[Table] Example 8 One side of a polyethylene terephthalate film (“Lumirror”) with a thickness of 75 mm was exposed to a high voltage discharge in N ₃ gas of 0.6 mmHg, and the surface of the base material was activated and then exposed without being exposed to oxygen. 12 was brought into contact with the monomer solution for 1 minute to form a graft polymerized layer of the monomer on the surface of the substrate. Gelatin is placed on the polyethylene terephthalate film provided with this graft polymerization layer.
A silver halide emulsion was coated and dried to produce a photographic material. The results of a peel test between the base material and the photographic emulsion of this photographic light-sensitive material were A grade both when dry and when wet. Table 12 Sodium sulfopropyl methacrylate (manufactured by Sanyo Kasei Co., Ltd.) 5 g Distilled water 995 g Comparative example 4 After polymerizing sodium sulfopropyl methacrylate in an aqueous solvent system using ammonium persulfate,
A large amount of acetone was added to precipitate, and the precipitate was washed with acetone and dried. The homopolymer thus obtained was dissolved in methyl alcohol, and a thickness of 75 μm was obtained.
Coated on polyethylene terephthalate film,
After drying, a gelatin-silver halide emulsion was applied and dried to prepare a photographic material. The adhesive strength between the base material and the photographic emulsion of this photographic light-sensitive material was grade C both when dry and when wet. Comparative Example 5 A 75 μm thick polyethylene terephthalate film (“Lumirror”) was surface treated by exposing it to a high voltage discharge in N ₂ gas at 0.6 mmHg. A gelatin-silver halide emulsion was coated on the surface-treated film and dried to prepare a photographic material. The result of the peel test between the base material of this photographic light-sensitive material and the photographic emulsion was A when dry.
It was grade C when wet. Example 9 One side of a 75 μm thick polyethylene terephthalate film (“Lumirror”) was exposed to a high voltage discharge in air at 0.8 mmHg, and the substrate surface was activated and then taken out into the atmosphere to react with oxygen. Next, the treated film was placed in a glass container, and after purging the inside of the container with nitrogen, the monomer solution shown in Table 13 heated to 60°C and vacuum degassed was introduced into the container and allowed to react for 15 minutes. The monomer was reacted with. The base material on which this graft polymerization layer is formed is dyed with a basic dye (Astrazon Blue BG) to impart antihalation properties to the graft polymerization layer, and then a gelatin-silver halide emulsion is applied and dried to form a photographic light-sensitive material. was created. As a result of the peel test, the adhesive strength between the base material of this photographic light-sensitive material and the photographic emulsion was found to be
It was grade A even when wet. Table 13 Sodium sulfopropyl methacrylate (manufactured by Sanyo Chemical Co., Ltd.) 10 g Distilled water 990 g Example 10 Both sides of a 100 μm thick polyethylene terephthalate film (“Lumirror”) were exposed to high voltage discharge in Ar gas at 0.6 mmHg. After that, the base material was brought into contact with the monomer solution shown in Table 14 for 1 minute without being brought into contact with oxygen to form a graft polymerized layer of the monomer on the surface of the base material. The surface resistivity of the polyethylene terephthalate film provided with this graft polymerization layer was 2×10 ⁸ Ω/□ under an atmosphere of 25° C. and 60% RH, showing extremely excellent antistatic performance. The surface resistivity of untreated polyethylene terephthalate film is greater than or equal to 10 ¹⁴ Ω/□. A gelatin-silver halide emulsion was coated on the polyethylene terephthalate film provided with the graft polymerization layer and dried to prepare a photographic material. The results of a peel test between the base material and the photographic emulsion of this photographic light-sensitive material were A grade both when dry and when wet. Table 14 Sodium ballastyrene sulfonate (manufactured by Toyo Soda Co., Ltd.) 10 g Distilled water 990 g Example 11 One side of a 75 μm thick polyethylene terephthalate film (“Lumirror”) was exposed to high pressure discharge in N ₂ gas at 0.6 mmHg. Thereafter, the base material was exposed to the monomer solution shown in Table 14 for 1 minute without being exposed to oxygen to form a graft polymerized layer of the monomer on the surface of the base material. Next, the other side of the treated substrate provided with the graft polymerization layer was
After being exposed to high voltage discharge in N ₂ gas at 0.6 mmHg, the sample was exposed to the monomer solution shown in Table 15 for 1 minute without being exposed to oxygen to form a graft polymerized layer of the monomer. The base material on which graft polymerization layers were provided on both sides was dyed with a basic dye (Astrazon Blue BG), and antihalation performance was imparted only to the surface on which sodium p-styrene sulfonate was graft-polymerized. The surface resistivity of the other side of this base material is 60% at 25℃
It was 9×10 ⁷ Ω/□ in an RH atmosphere. A gelatin-silver halide emulsion was coated onto the surface of the base material having antihalation properties and antistatic properties and dried to prepare a photographic light-sensitive material. The adhesive strength between the substrate of this photographic light-sensitive material and the photographic emulsion was grade A both when dry and when wet. Table 15 2-Hydroxy 3-methacryloxypropyltrimethylammonium chloride (manufactured by NOF Corporation) 5 g Distilled water 995 g Example 12 One side of a 90 μm thick triacetate film was exposed to high voltage discharge in Ar gas at 1 mmHg. After the surface of the base material was activated, it was exposed to the monomer solution shown in Table 16 for 1 minute without being exposed to oxygen to form a graft polymerized layer of the monomer on the surface of the base material. A gelatin-silver halide emulsion was coated on the triacetate film provided with the graft polymerization layer and dried to prepare a photographic material. The adhesive strength between the substrate of this photographic light-sensitive material and the photographic emulsion was grade A both when dry and when wet. Table 16 Vinylpyridine 27g Acrylic acid 3g N・N-dimethylformamide 970g Comparative Example 6 A triacetate film subjected to discharge treatment under the same conditions as in Example 12 was exposed to the monomer solution shown in Table 17 for 5 minutes, and acrylic acid was applied to the surface of the substrate. A graft polymer layer was formed. A gelatin-silver halide emulsion was coated on the triacetate film provided with the graft polymerization layer and dried to prepare a photographic material. As a result of a peel test, the adhesive strength between the base material and the photographic emulsion of this photographic light-sensitive material was grade A when the photographic emulsion was applied and dried, grade B when dry after fixing and development, and grade C when wet. Table 17 Acrylic acid 10g N・N-dimethylformamide 990g

Claims (1)

[Claims] 1. A conductive polymer base material formed by laminating an organic conductive substance and a polymer base material, characterized in that the organic conductive substance is chemically bonded to high voltage discharge active sites on the surface of the polymer base material. conductive polymer base material.