JPS6113221B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic electrophotographic photosensitive film, and particularly relates to a glass transition temperature (hereinafter referred to as "Tg").
The present invention provides an organic electrophotographic photosensitive film with excellent adhesiveness, characterized by using an organic photoconductor photosensitive layer containing an acrylic resin at a temperature of 10 to 60°C.

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, and organic electrophotographic photosensitive films include microfilm, film for overhead projectors,
Alternatively, the surface may be roughened to give it the ability to be written on, and the film may be applied to a film for second original drawings for industrial drawings. In this way, when the support is an electrically insulating material such as a synthetic resin film, the surface of the support film is
A conductive treatment must be applied to provide a conductivity of 10 ⁹ Ω-cm or less.

Various methods have been known for making synthetic resin films conductive, such as vacuum-depositing a gold layer on the surface of the film, kneading a conductive agent into the film, and coating the surface with a conductive agent. There is. Vacuum deposition of the first metal provides very good conductivity, but is extremely expensive and
Good for small areas such as microfilm, but
In the case of a large-area electrophotographic photosensitive film such as the second original image, it cannot be manufactured at low cost. Next, when kneading a conductive agent into the inside of the second film, when melting the synthetic resin and molding the film, add the conductive agent at the time of melting, apply the conductive agent into the film, and apply the conductive agent from the inside. conductivity is imparted by leaching (called bleed).
In general, conductivity is poor, and if high conductivity is expected, the amount of conductive agent will naturally increase, making it extremely easy to bleed, resulting in extremely sticky film surfaces, blocking, and poor adhesion of the photoconductor layer. There are drawbacks. The method of applying the third conductive agent to the surface is the simplest conductive treatment method, but the conductive agent is merely attached to the surface, and even if a photoconductor layer is provided on top of it, it will not be removed from the supporting film. It will peel off and become unusable. In order to compensate for this drawback, some kind of adhesive such as polyvinyl acetate or epoxy resin is traditionally added to the conductive agent and applied to the film surface, but the conductivity deteriorates significantly due to the high film-forming properties of the adhesive. However, even if a photoconductor layer is provided on top of the photoconductor layer, a highly sensitive electrophotographic photosensitive film cannot be obtained, and when the amount of conductive agent is increased until conductivity appears, the adhesion with the support film deteriorates significantly. It becomes unusable. Therefore, in order to make full use of the conductive properties of conductive agents and to conduct conductive treatment with excellent adhesive properties at a relatively low cost, new methods are generally used to increase the adhesive properties between the conductive layer and the support film. It is common to provide a subbing layer for adhesion. When conductive treatment is performed with such a structure, an appropriate adhesive subbing layer is provided depending on the conductive agent used for the conductive layer and the type of support film. There are many known conductive agents, but recently polymer conductive agents such as quaternary ammonium salt type polymer conductive agents [e.g. 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.) ], and other polymer conductive agents (e.g. polyvinyl sulfonic acid and its salts, salts of polystyrene sulfonates, etc.) are often used.When the support film is a polyester film for such conductive agents, there is no adhesion. For example, the subbing layer may be a layer treated with a sulfonating agent described in Japanese Patent Publication No. 48-23450, or a layer treated with a sulfonating agent described in
A polymer layer obtained by chemically reacting a substance selected from vinyl isocyanate, propenyl isocyanate, and isopropenyl isocyanate described in No. 16065 with a substance selected from dihydroxy compounds is used. Furthermore, cellulose propionate and mixtures of gelatin and nitrocellulose used in the hydrophilic treatment of polyester films can also be effective adhesive subbing layers. In addition, when the support is a triacetic acid cellulose film, for example, the patent application
The vinyl chloride copolymer, vinylidene chloride copolymer, and vinyl acetate copolymer described in No. 72983 can be used as an adhesive subbing layer.

When a synthetic resin film is used as a support in this way, a conductive treatment is performed and an organic photoconductor layer is provided on it to make an organic electrophotographic photosensitive film. Examples of the body include polymeric organic photoconductors that themselves have film-forming properties (e.g., polynuclear aromatic vinyl polymers,
(e.g., vinyl polymers with hetero side chains), or monomeric organic photoconductors that do not have film-forming properties by themselves (e.g., oxadiazole-based, thiazole-based, thiadiazole-based, triazole-based, etc.) are used.
imidazole series, imidazolone series, oxazole series, pyrazoline series, imidazoline series, pyrazine series, triazine series, oxazolone series, quinoxaline series, quinazoline series, furan series, acridine series,
Carbazole-based, phenoazine-based, acrylamine-based organic photoconductors, etc.) are used, and if necessary, sensitizing dyes such as Victoria Blue B, Crystal Violet, Ethyl Violet, Methyl Violet, Malachite Green, Rhodamine B are used. , rhodamine 6G, rose bengal, fluorescein, methylene blue, capri blue, etc. are added, and chemical sensitizers such as tetracyanoethylene, tetracyanoquinodimethane, bromanil, chloranil, benzoquinone, naphthoquinone, anthraquinone and its derivatives, P- Nitrophenol, picric acid, 1,3,5-trinitrobenzene, monochloroacetic acid, N,N'-diethylbarbituric acid, N,N'-diethylthiobarbituric acid, paranitrobenzoic acid, 2,4,7-
Trinitrofluorenone, etc. are added. Particularly in the case of monomeric organic photoconductors, various binders are added to provide film-forming properties, but in order to prevent crystallization and obtain a hard film without deteriorating the sensitivity, Generally, binders with high softening points,
Hard resins such as polycarbonate resins, polysulfone resins, polyphenylene oxide resins, diallyl phthalate resins, polystyrene resins, polymethyl methacrylate resins, phenolic resins, etc. are used. An organic electrophotographic photosensitive film is produced by disposing a polymer or monomeric organic photoconductor having such a structure as a photosensitive layer on a conductive layer mainly composed of the above-mentioned polymeric conductive agent. However, because the conductive layer is a hydrophilic substance, the adhesion of the photosensitive layer is poor.
It peels off easily and is unusable. In order to increase the adhesion between the photosensitive layer and the conductive layer, a new adhesive intermediate layer such as polyvinyl acetate, polyvinyl chloride, etc.
Although it is effective to provide a thin layer of polyvinylidene chloride or the like, these adhesive interlayers have extremely poor electrical conductivity, which significantly deteriorates the electrophotographic properties.

The present invention aims to improve the above-mentioned various drawbacks and provide an inexpensive organic electrophotographic photosensitive film with excellent adhesiveness of the photosensitive layer even over a large area.

That is, the present invention provides a conductive layer mainly composed of a polymeric conductive agent on a support film provided with an adhesive subbing layer, and further contains an acrylic resin having a Tg of 10 to 60°C on top of the conductive layer. An organic electrophotographic photosensitive film characterized by being provided with an organic photoconductor photosensitive layer, the organic electrophotographic photosensitive film having a conductive layer with excellent conductivity and excellent adhesive properties. This makes it possible to inexpensively produce a large-area organic electrophotographic photosensitive film used for second original drawings and the like.

Next, the present invention will be explained in more detail.

As the support film used in the present invention, known commercially available synthetic resin films can be used. For example, films of polyester, polystyrene, polypropylene, polyvinyl chloride, cellulose acetate, etc. can be used. Furthermore, composite films made by taking advantage of the characteristics of these films can also be used.

In the present invention, an adhesive subbing layer is provided on these support films, and a conductive layer is provided thereon, but such an adhesive subbing layer varies depending on the types of the support film and the conductive agent. All known conductive agents can be used as the conductive agent for the conductive layer of the present invention, but the above-mentioned polymeric conductive agents are particularly preferred from the viewpoint of their excellent conductivity and film properties. When such a polymer conductive agent is used, the undercoating adhesive layer may be, for example, the material described in Japanese Patent Publication No. 48-23450, the material described in Japanese Patent Publication No. 49-16065, or the material described in Japanese Patent Application No. 49-1989.
72983, cellulose propionate, a mixture of gelatin and nitrocellulose, etc. are preferred, but are not limited thereto. There is no particular limit to the thickness of the adhesive undercoat layer, and a thickness of about 0.1 to 10 μm is sufficient. Furthermore, the thickness of the conductive layer is not particularly limited, but is preferably about 0.1 to 10 μm;
In particular, about 0.5 to 2μ is appropriate. If the conductive layer is too thin, the conductivity will deteriorate, and if it is too thick, the photosensitive layer may peel off, which is not preferable.

Although the various organic photoconductors mentioned above can be used in the photosensitive layer of the present invention, the present invention is characterized in that these photosensitive layers contain an acrylic resin having a Tg of 10 to 60°C. It is something.

As such an acrylic resin, a carboxyl group-containing copolymer is particularly preferable, and a carboxyl group-containing copolymerizable monomer such as acrylic acid,
At least one of methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, crotonic acid, aconitic acid, etc. and an acrylic copolymerizable monomer, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylic An acrylic multi-component copolymer with at least one monomer selected from n-butyl methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, lauryl methacrylate, etc. Furthermore, these copolymerizable monomers are copolymerized with other copolymerizable monomers, such as styrene, α-methylstyrene, β-chlorostyrene, vinyltoluene, vinyl acetate, acrylonitrile, etc., as necessary. Polymer copolymers are suitable. The Tg of these acrylic resins is preferably in the range of 10 to 60°C; anything below this range may cause blocking or crystal precipitation, especially when a monomeric organic photoconductor is used. Yes, it's not good. or,
If Tg exceeds this range, the effect on adhesiveness will be poor. Such a carboxyl group-containing acrylic resin has an acid value. There is no particular restriction on the acid value, but it is preferably about 1 to 30, and for products with a large acid value, such as methacrylic acid homopolymer, the Tg
= 130°C, which is not only not effective for adhesion but also causes deterioration of sensitivity, which is undesirable. There is no particular restriction on the content of the acrylic resin used in the present invention in the photosensitive layer, but it is
20% by weight is suitable. If the content is too low, there will be no effect on adhesion; if the content is too high, for example, when the acrylic resin used in the present invention is used as a binder for monomeric photoconductors, blocking and crystal precipitation may occur. etc., which is not desirable.

The various polymer or monomeric organic photoconductors described above can be used in the photosensitive layer of the present invention, and the acrylic resin described above exhibits an effect on adhesiveness no matter which photoconductor is used. , especially monomeric organic photoconductors such as N,N,N',N'-tetrabenzyl-m-
Phenylenediamine, N,N,N',N'-tetrabenzyl-P-phenylenediamine, Special Publication 1977-
Monomeric organic photoconductor described in 26049 JP-A-49-
A photosensitive layer obtained by adding the above-mentioned hard resin with a high softening point as a binder to the monomer organic photoconductor described in No. 60227 exhibits a strong adhesive effect. Even if the acrylic resin used in the present invention is used as a binder in a monomeric organic photoconductor, it is effective in adhesion, but it also causes the damage described above, and the hard resin with a high softening point described above It is possible to obtain an organic electrophotographic film with higher practicality by adding . Furthermore, when used as a second original image, in order to roughen the surface of the photosensitive layer and provide additional writing ability, fine inorganic powder such as silica alumina and fine organic powder such as low molecular weight polyethylene or polycarbonate are added to the photosensitive layer. However, even if these are added, the adhesive effect of the acrylic resin used in the present invention does not change.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 An adhesive undercoat layer of vinyl chloride-vinyl acetate (weight ratio 70:30) copolymer was provided on a commercially available cellulose triacetate film (200μ thick), and a conductive layer of polyvinylbenzyltrimethylammonium chloride was formed on top of it. , and then apply the following photosensitive layer coating solution on top of it.
A photosensitive layer was formed by coating with a 0.6 mmφ wire bar to obtain a transparent organic electrophotographic photosensitive film.

Photosensitive layer coating liquid 1,1-bis(4-N-benzyl-N-2-phenylethylaminophenyl)propane 8g N,N'-diethylthiobarbituric acid 1.6g Polymethyl methacrylate resin (Tg=105℃ )
7g Ethyl acrylate/styrene/maleic anhydride copolymer (weight ratio 35:68:2, Tg=47℃)
1g toluene 70g 1% N of crystal violet after dissolving,
Add 4 ml of N'-dimethylformamide solution.

When the adhesiveness of the thus obtained transparent organic electrophotographic photosensitive film was examined by cellophane tape peeling test, no peeling of the photosensitive layer was observed. For comparison, we prepared a photosensitive layer coating solution that did not contain the above ethyl acrylate/styrene/maleic anhydride copolymer and made a prototype film, and the photosensitive layer was
100% peeled off. Next, when the film of this example was copied using a wet type copying machine, a clear image without background fog was obtained.

Example 2 A transparent organic electrophotographic photosensitive film was prepared using polyphenylene oxide resin (softening point: 175°C) in place of the polymethyl methacrylate resin in the photosensitive layer coating solution of Example 1, but the same result as in Example 1 was obtained. The photosensitive layer showed excellent adhesion. For comparison, a film containing no ethyl acrylate/styrene/maleic anhydride copolymer was produced in the same manner as in Example 1, and the photosensitive layer was 100% peeled off.

Example 3 Polystyrene resin (Tg=100
℃), a transparent organic electrophotographic photosensitive film exhibiting the same excellent adhesive properties as in Example 1 was obtained.

Example 4 A conductive layer of polyvinylbenzyltrititylammonium chloride was provided on a polyester film (thickness 75μ) provided with a thin layer of a mixture of gelatin and nitrocellulose as an adhesive sublayer, and the following photosensitive layer was placed on top of the polyester film (thickness 75μ). The coating solution was applied using a 0.6 mm diameter wire bar to form a photosensitive layer, thereby obtaining an organic electrophotographic photosensitive film for second original drawings.

Photosensitive layer coating liquid N,N,N',N'-tetraphenyl-m-phenylenediamine 10g P-nitrophenol 2g Polyquenylene oxide resin (softening point 175℃)
8g Ethyl acrylate/styrene/maleic anhydride copolymer (weight ratio 35:68:2, Tg=47℃)
1g Chlorbenzene 80g After dissolving, add high-density, low-molecular-weight polyethylene fine powder (softening point 132°C), disperse it ultrasonically, and then add 4ml of a 1% N,N'-dimethylformamide solution of crystal violet.

When the adhesion of the organic electrophotographic photosensitive film for the second original image thus obtained was examined by cellophane tape peeling test, no peeling of the photosensitive layer was observed. For comparison, a photosensitive layer coating solution containing no ethyl acrylate/styrene/maleic anhydride copolymer was prepared and a prototype film was made, and 100% of the photosensitive layer was peeled off. Next, when the A-2 size drawing was copied onto the A-2 size film of this example using a dry type electronic copying machine, Canon Jumbo Printer 500FX, a clear second original drawing could be obtained.

Example 5 Ethyl acrylate of the photosensitive layer coating solution of Example 4
Styrene/maleic anhydride copolymer (Tg=47
℃) instead of methyl methacrylate/acrylic acid 2
-Ethylhexyl/acrylic acid copolymer (weight ratio
65:30:5, Tg=37°C), a second original organic electrophotographic photosensitive film having excellent adhesion of the photosensitive layer as in Example 4 was obtained. Commercially available methacrylic acid copolymer (Tg=82℃) for comparison
When using the photosensitive layer, 100% of the photosensitive layer was peeled off.

Example 6 Ethyl acrylate of the photosensitive layer coating solution of Example 4
Methyl methacrylate/n-butyl acrylate/methacrylic acid copolymer instead of styrene/maleic anhydride copolymer (weight ratio 58:39:3Tg=21℃)
As in Example 4, an organic electrophotographic photosensitive film for second original images having excellent adhesiveness of the photosensitive layer was obtained. For comparison, a commercially available methyl acrylate polymer (Tg = 5°C) was used, and the photosensitive layer was 100
% peeled off.

Example 7 Polycarbonate resin (softening point:
220° C.), an organic electrophotographic photosensitive film for second original images with good adhesion of the photosensitive layer was obtained. In this case, when copies were made using the dry type electronic copying machine described in Example 4, the adhesion was particularly improved after heat fixing, and no peeling of the photosensitive layer was observed in the cellophane tape peeling test.

Example 8 N, N, N', N' of the photosensitive layer coating solution of Example 4
When N,N,N',N'-tetraphenyl-m-xylylene diamine was used instead of tetrabenzyl-m-phenylene diamine, the second original image with good adhesion of the photosensitive layer was obtained as in Example 4. An organic electrophotographic photosensitive film was obtained.

Example 9 Even if poly(N,N-dimethyl-3.5-methylene)piperidinium chlorite was used instead of polyvinylbenzyltrimethylammonium chloride in the conductive layer of Example 4, the adhesion of the photosensitive layer was the same as in Example 4. An organic electrophotographic photosensitive film for second original images with excellent properties was obtained.

Example 10 A commercially available polyester film (thickness:
The same conductive layer as in Example 4 was provided on top of the second
When an original organic electrophotographic photosensitive film was prepared, an organic electrophotographic photosensitive film having excellent adhesion of the photosensitive layer as in Example 4 was obtained.

Claims (1)

[Claims] 1. A conductive layer mainly composed of a polymeric conductive agent is provided on a support film provided with an adhesive subbing layer, and an organic photoconductive layer containing an acrylic resin with a glass transition temperature (Tg) of 10 to 60°C is placed on top of the support film. An organic electrophotographic photosensitive film characterized by being provided with a photosensitive layer.