JPS5845706B2 - organic electrophotographic film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic electrophotographic film, and in particular to an organic electrophotographic film using a polyester film as a support and providing an adhesive subbing layer to improve adhesion between the support and a conductive layer. This invention relates to an organic electrophotographic film.

Conventionally, electrophotographic photoreceptors generally have an inorganic or organic photoconductor layer provided on a support such as a metal plate, paper, or synthetic resin film.

In particular, when using an organic photoconductor, a synthetic resin film is often used as a support due to its transparency.As an organic electrophotographic film, it is used as a microfilm, a film for overhead projectors, or a film with a roughened surface.
Addition property is given and it is applied to the film for the second original drawing of industrial drawing.

In this way, when the support is an electrically insulating material such as a synthetic resin film, it is necessary to perform a conductive treatment on the surface of the support film from 10@9 Ω to below the contact plate.

To obtain an electrophotographic film, it is generally necessary to use a synthetic resin film having excellent mechanical strength, transparency, dimensional stability, and other physical properties as a support.

Polyester film satisfies these characteristics and is widely used as a support in fields that require durability.

This polyester film is an electrically insulating hydrophobic film having a volume resistivity of 1014 Ω or more.

Various methods are conventionally known for making such polyester films conductive, such as a method of vacuum-depositing a metal on the surface of the film, and a method of applying a conductive agent to the surface.

Vacuum deposition of the first metal provides very good conductivity, but it is extremely expensive, and although it is good for small area films such as microfilm, it is not suitable for large area electrophotographic films such as the second original. It cannot be manufactured cheaply.

Next, the method of applying a second conductive agent to the surface is the simplest method, but for inert surfaces such as polyester films, the conductive agent is simply attached to the surface.
Adhesion is poor, and even if a photoconductive layer is formed thereon, it peels off from the surface of the polyester film, making it unusable.

To compensate for this drawback, some kind of adhesive, such as polyvinyl acetate or epoxy resin, has traditionally been added to the conductive agent and applied to the film surface, but due to the high film-forming properties of the adhesive, the conductivity is low. Even if a photoconductive layer is provided thereon, a highly sensitive electrophotographic film cannot be obtained, and furthermore, when the support is a polyester film, the adhesive itself does not have sufficient adhesion.

Therefore, in order to make full use of the conductive properties of the conductive agent and to perform a conductive treatment with excellent adhesive properties at a relatively low cost, it is common to use a conductive agent and a support film for the purpose of increasing the adhesiveness between the conductive agent and the support film. It is common to provide an additional subbing layer that exhibits adhesive properties on both body films.

Particularly in the field of electrophotography, conductive agents used in conductive layers need to have higher conductivity than conductive agents generally used as antistatic agents. Quaternary ammonium salt type polymer conductive agent,
For example, polyvinyltrimethylammonium chloride,
Poly-N-acrylamidopropyl-3-trimethylammonium chloride, poly(N,N-dimethyl-3,
5-methylene)piperidinium chloride, poly-N-
Vinyl-2,3-dimethylimidazolinium chloride, polyvinylbenzyltrimethylammonium chloride, etc. are used.

When such a quaternary ammonium salt type polymer conductive agent is used as a conductive layer, it is used as an adhesive subbing layer for a silver salt photographic photosensitive layer.

For example, US Pat. No. 3,053,661, US Pat. No. 3,143,
No. 421, No. 3.501, 301 and Special Publication No. 43-2
An undercoat layer containing gelatin, which is described in Japanese Patent No. 603, No. 44-2597, etc., can be used.

However, gelatin itself easily absorbs water, becomes sticky and sticky at high humidity, and has insufficient adhesion to the conductive layer.

In addition, for electrophotographic film, a special public patent application was made in 1973, in which a polyester film base was treated with a sulfonating agent to form an adhesive layer.
There is a method described in No. 8-23450, but this method uses concentrated sulfuric acid, which is not only dangerous but also requires washing with water, making the process complicated.

Furthermore, in the method described in Japanese Patent Publication No. 49-16065, 120~
Conventional methods have drawbacks, such as requiring heat treatment at a high temperature of 130° C. for several minutes.

The present invention aims to provide an inexpensive electrophotographic film having excellent interlayer adhesion and based on a polyester film, which solves some of the above-mentioned drawbacks.

That is, the present invention provides an adhesive undercoat layer containing a vinyl chloride copolymer, a vinylidene chloride copolymer, or a mixture thereof and a swelling agent for the polyester film on a polyester film, and a quaternary The present invention provides an organic electrophotographic film comprising a conductive layer containing an ammonium salt type polymeric conductive agent as a main component, and a photoconductive layer containing an organic photoconductor as a main component on top of the conductive layer. be.

The present invention is an improvement of an electrophotographic film based on cellulose acetate film described in JP-A No. 51-3240 filed by the present applicant and applied to the base of a polyester film. The present invention provides an electrophotographic film having superior mechanical strength than that described in No. 3240.

Next, each layer constituting the electrophotographic film of the present invention will be explained in more detail.

The adhesive subbing layer constituting the present invention contains a vinyl copolymer and a polyester film swelling agent as essential components.

In particular, the vinyl copolymer used in the present invention is not a so-called hydrophilic substance but a substance that is insoluble in water and soluble in organic solvents, but the conductive layer is a quaternary ammonium salt type polymeric conductive agent. In some cases, strong adhesion occurs.

Examples of vinyl copolymers used in the present invention include vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinyl acetate/vinyl alcohol copolymer, vinyl chloride/vinyl acetate/maleic vinegar copolymer, and vinylidene chloride/acrylonitrile copolymer. Polymers etc. are effective.

These vinyl copolymers do not adhere to polyester films as they are, but when a swelling agent for polyester films is added, they become strongly adhesive. Strengthens the adhesion of the conductive layer of the polymeric conductive agent.

Swelling agents for the polyester film used in the present invention include known swelling agents, such as phenol, O-chlorophenol, P-chlorophenol, phenol derivatives such as cresol, and polyhydroxybenzenes such as resorcinol, catechol, and pyrogallol. However, in the present invention, in order to prevent pollution, it is preferable to use a material that does not contain halogen and is solid at room temperature.

Particularly in the present invention, resorcinol, catechol and the like are preferred.

The coating solution for the adhesive subbing layer is prepared by dissolving the vinyl copolymer in an organic solvent such as an ester solvent or a ketone solvent, and diluting it with an aromatic solvent if necessary.

The addition ratio of the swelling agent to the vinyl copolymer is preferably about 0.3 to 4 by weight.

If the amount of swelling agent added is too large or too small, the adhesion will deteriorate.

Furthermore, there is no particular limit to the thickness of the adhesive undercoat layer, but the thickness is 0.3
About 1 μm is sufficient.2 Next, as the conductive agent for the conductive layer used in the present invention, a quaternary ammonium salt type polymeric conductive agent which has excellent conductivity and film properties as described above is suitable.

In addition to the conductive agent, additives such as various resin emulsions, colloidal silica, etc. may be added to the conductive layer in order to further increase the adhesiveness with the photoconductive layer or to increase the hardness of the conductive layer. The amount added is preferably less than 50% by weight of the conductive layer.

The thickness of the conductive layer is not particularly limited, but is preferably about 0.5 to 5 μm.

Next, the photoconductor that can be used in the present invention includes, for example, a polymeric organic photoconductor that itself has film-forming properties, such as a polynuclear aromatic vinyl polymer, a vinyl polymer having a hetero side chain, or a photoconductor that itself has film-forming properties. Monomeric organic photoconductors without film-forming properties, such as oxadiazole-based, thiazole-based, thiadiazole-based, triazole-based, imidazole-based, imidasilone-based, oxazole-based, pyrazoline-based, imidacilline-based, pyrazine-based, triazine-based, In the case of oxacilone series, quinoxaline series, quinazoline series, furan series, acridine series, carbazole series, phenoazine series, acrylamine series, etc., other polymeric substances with suitable film-forming properties such as phenol resins, alkyd resins, polyester resins are used. , diaryl phthalate resin, epoxy resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, styrene resin, styrene copolymer resin, methacrylic resin, acrylic ester resin, polyamide resin, polyphenylene oxide resin, polysulfone resin, polycarbonate A resin or the like is used as a suitable binder, and as a sensitizing dye, for example, Victoria Blue 81 Crystal Violet, Ethyl Violet, Methyl Violet, Malachite Green, Rhodamine B10-Amine 6G is used.

Rose bengal, fluoreracene, methylene blue, etc. are used, and examples of chemical sensitizers include tetracyanoethylene, tetracyanoquinodimethine, chloranil, chloranil 1. Benzoquinone, naphthoquinone, anthraquinone and its derivatives, P-nitrophenol, picric acid,
1,3,5-trinitrobenzene, monochloroacetic acid, N
.

N'-diethylbarbylic acid, N,ni-diethylthiobarbylic acid, paranitrobenzoic acid, 2.4,7-)
Linitrofluorenone and the like are added.

In particular, in the present invention, it is preferable to use a monomeric organic photoconductor, and especially when using a quaternary ammonium salt type polymer conductive agent in the conductive layer, a monomeric organic photoconductor described in Japanese Patent Publication No. 49-26149 is used. Photoconductor, monomeric organic photoconductor described in Japanese Patent Publication No. 51-10983, monomeric organic photoconductor described in Japanese Patent Application Publication No. 49-60227, monomeric organic photoconductor described in Japanese Patent Application Publication No. 51-17442. Photoconductor and N, N, N', N'
-Tetrabenzyl-P-phenylenediamine, N-N.
A monomeric organic photoconductor based on phenylenediamine such as N'-N'-tetrabenzyl-m-phenylenediamine adheres firmly.

In order to impart film-forming properties to these monomeric organic photoconductors, prevent crystallization, and provide a hard film, hard resins with high softening points are generally selected from among the above-mentioned polymeric substances. The amount added is preferably 70% by weight or less based on the monomeric organic photoconductor.

Furthermore, when applied to a film for second original drawings for industrial drawings, in order to roughen the surface and provide ease of writing, for example, fine silica powder, fine low molecular weight polyethylene powder, fine polycarbonate powder can be used as a roughening agent. etc. may be added.

The thickness of the photoconductive layer is not particularly limited, but is suitably 3 to 10 microns.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 A transparent organic electrophotographic film was obtained by overcoating a commercially available polyester film (50 μm thick) in the following order: an adhesive subbing layer, a conductive layer, and a photoconductive layer.

Adhesion undercoat layer coating liquid> Vinyl chloride/vinyl acetate copolymer 10g resorcinol 10g n-butyl acetate
380g conductive layer coating solution> Polyvinylbenzyltrimethylammonium chloride (33% by weight aqueous solution) 60g methanol
340g Photoconductive layer coating solution> 1.1 Bis(4-N-N-dibenzylaminophenyl)propane 509N-N'
-Diethylthiobarbylic acid 5g polyphenylene oxide (average degree of polymerization 80) 4090-xylene
401 After dissolution, 1% N-N-dimethylformamide solution of crystal violet 20
Add ml.

Apply the above coating solution using a Dixon coater at a speed of 5 per minute.
Each was coated with m.

The dry coating amount and drying temperature were 0.5 g/m and 95°C for the adhesive subbing layer, 1F!/rri' and 105°C for the photoconductive layer, and 105°C for the photoconductive layer. In this case, it was 5g/rn' and 80°C.

In order to examine the interlayer adhesion of the thus obtained transparent organic electrophotographic film, a cellophane tape peeling test was carried out, and no interlayer peeling was observed, indicating that the adhesion was good.

For comparison, an electrophotographic film consisting of only a conductive layer and a photoconductive layer without an adhesive subbing layer was prepared using the coating solution with the above formulation, and a similar peel test was conducted. 100% peeled off from between.

Furthermore, based on the composition of the adhesive subbing layer, a subbing layer excluding vinyl chloride/vinyl acetate copolymer or resorcinol was applied, an organic electrophotographic film was prepared in the same manner, and the same peel test was conducted. When the former vinyl chloride/vinyl acetate copolymer was removed, the undercoat layer was destroyed and peeled off, and when the latter resorcinol was removed, 100% peeling occurred between the polyester film surface and the undercoat layer. .

Next, the above-mentioned transparent organic electrophotographic film of the present invention was subjected to negative corona charging in a dark room, and after image exposure, development was performed using a positively charging liquid developer, and a clear positive image with little background fog was obtained. .

Example 2 A transparent organic electrophotographic film was obtained by using the following coating solution instead of the adhesive subbing layer coating solution of Example 1.

Coating liquid for adhesive undercoat layer> Vinylidene chloride/acrylonitrile copolymer 10g Catechol 10g n-butyl acetate
□ 38-0. When the adhesion between the layers of the thus obtained transparent organic electrophotographic film was tested in the same manner as in Example 1, no peeling between the layers was observed and the adhesion was good.

Furthermore, the electrophotographic properties were excellent. Example 3 A transparent organic electrophotographic film was obtained by using the following coating solution in place of the adhesive subbing layer coating solution of Example 1.

Coating liquid for adhesive subbing layer> Vinyl chloride/vinyl acetate/vinyl alcohol copolymer 8g resorcinol 12g n-butyl acetate
The interlayer adhesion of 380 g of the thus obtained transparent organic electrophotographic film was tested in the same manner as in Example 1, and no peeling between the layers was observed, indicating that the adhesion was good.

Furthermore, the electrophotographic properties were also excellent. Example 4 A transparent organic electrophotographic film was obtained by using the following coating solution in place of the conductive layer coating solution of Example 1.

Conductive layer coating liquid> Poly(N,N-dimethyl-3,5-methylene)piperidinium chloride (40% by weight aqueous solution) 50.9 methanol 340 g The transparent organic electrophotographic film thus obtained was the same as in Example 1. It showed excellent adhesion and electrophotographic properties.

Example 5 A transparent organic electrophotographic film was obtained by using the following coating solution in place of the conductive layer coating solution of Example 1.

Conductive layer coating liquid> Poly-N-acrylamidopropyl-3-trimethylammonium chloride (30% by weight aqueous solution) 60 g methanol 340 g The transparent organic electrophotographic film thus obtained had excellent adhesiveness and electrophotographic properties similar to those in Example 1. showed that.

Example 6 A roughened organic electrophotographic film was obtained using a photoconductive layer coating solution prepared by adding 2.5 g of fine silica powder (average particle size 2.3 μm) to the photoconductive layer coating solution of Example 1. .

When the thus obtained organic electrophotographic film was tested for interlayer adhesion in the same manner as in Example 1, no peeling was observed, indicating excellent adhesion.

Further, the roughened organic electrophotographic film of the present invention was subjected to corona charging in a darkroom, a negative type microfilm of an industrial drawing was projected, image exposure was performed, and the image was developed with a negatively charged dry developer. A faithful second original drawing was obtained.

Example 7 A transparent electrophotographic film was obtained by using the following coating solution in place of the photoconductive layer coating solution of Example 1.

Coating liquid for photoconductive layer> N -N -N'-N'-tetraphenyl-m-xylylene diamine 50 g P-nitrobenzoic acid 5 g polyphenylene oxide (average degree of polymerization 80) 40 go-
Xylene 40 (Hi' Dissolve - 727801% N-N dimethylformamide solution 2
The transparent organic electrophotographic film thus obtained with the addition of 5WLl exhibited excellent adhesion and electrophotographic properties similar to those of Example 1.

Example 8 A transparent organic electrophotographic film was obtained by using the following coating solution in place of the photoconductive layer coating solution of Example 1.

Photoconductive layer coating liquid>N-N-N'-N'-tetrabenzyl-m-phenylenediamine 50gN-N
-Diethylthiobarbylic acid 5g Polymethyl methacrylate (softening point 100'C) 50g Xylene 400g After dissolving, 50ml of 0.5% N-N dimethylformamide solution of Victoria Blue was added.

The transparent organic electrophotographic film thus obtained exhibited excellent adhesion and electrophotographic properties similar to those of Example 1.

Claims (1)

[Claims] 1. An adhesive subbing layer containing a vinyl copolymer and a swelling agent for the polyester film is provided on a polyester film, and a conductive layer containing a polymer conductive agent as a main component is provided thereon. An organic electrophotographic film, further comprising a photoconductive layer containing an organic photoconductor as a main component on the layer. 2. The organic electrophotographic film according to claim 1, wherein the vinyl copolymer is a vinyl chloride copolymer. 3. The organic electrophotographic film according to claim 2, wherein the vinyl chloride copolymer is a vinyl chloride/vinyl acetate copolymer. 4. The organic electrophotographic film according to claim 2, wherein the vinyl chloride copolymer is a vinyl chloride/vinyl acetate/vinyl alcohol copolymer. 5. The organic electrophotographic film according to claim 2, wherein the vinyl chloride copolymer is a vinyl chloride/vinyl acetate/maleic acid copolymer. 6. The organic electrophotographic film according to claim 1, wherein the vinyl copolymer is a vinylidene chloride copolymer. 7. The organic electrophotographic film according to claim 6, wherein the vinylidene chloride copolymer is a vinylidene chloride acrylonitrile copolymer. 8. The organic electrophotographic film according to any one of claims 1 to 7, wherein the swelling agent of the polyester film is resorcinol. 9. The organic electrophotographic film according to any one of claims 1 to 7, wherein the swelling agent of the polyester film is catechol. 10. The organic electrophotographic film according to claim 8 or 9, wherein the polymeric conductive agent is a quaternary ammonium salt type polymeric conductive agent. 11. The organic electrophotographic film according to claim 10, wherein the organic photoconductor is a monomeric organic photoconductor.