CN1082252C - An electrophotographic photoconductor and a method for forming the same - Google Patents

Abstract

An electrophotographic photoconductor comprising a conductive support, an undercoating layer provided on the conductive support and a photosensitive layer provided on the undercoating layer, in which the undercoating layer comprises a needle-like titanium oxide particles and a binder resin. The needle-like titanium oxide particles in the undercoating layer show a volume resistance in the range from 10<5> OMEGA*cm to 10<10> OMEGA*cm when a loading pressure of 100 Kg/cm2 is applied and have a short axis S having a length of 0.5 mu m or less and a long axis L having a length of 10 mu m or less and the aspect ratio of L/S ranging from 2 to 10. Further, the needle-like titanium oxide particles are contained in the undercoating layer in the range from 50 wt % to 95 wt % and the surface thereof remains untreated.

Description

Electronic photography photoconductor and manufacture method thereof

The present invention relates to a kind of electronic photography photoconductor particularly, the present invention relates to a kind of electronic photography photoconductor that comprises conductive substrates, priming coat and photosensitive layer.

Adopt the electronic photography processing of photoconductor may further comprise the steps: photoconductor is placed on the dark place and passes through corona discharge uniform charging in its surface; Expose a zone to discharge selectively and in this zone, to form electrostatic latent image; And, by electrostatic attraction colored charged particle (toner) is deposited on the latent image making it and becomes as seen, thereby form image.

The key property that photoconductor must have in above-mentioned a series of processing is as follows:

(1) it must in the dark be arrived suitable electromotive force by uniform charging.

(2) it in the dark has very high chargeable property and is not easy discharge.

(3) it has excellent light sensitivity and can discharge immediately by exposure.

In addition, also require photoconductor to have: stability and durability for example have little residual electromotive force owing to photoconductor surface discharges easily; Excellent mechanical strength and flexibility; Stable electric characteristics is even the variation on also can not occurring aspect charging property, light sensitivity, residual electromotive force or the like after reusing; And, heat-resisting, light, temperature, wet, ozone layer destroying or the like.

The electronic photography photoconductor has obtained actual use at present.This photoconductor is easy to generate from the charge carrier on the surface of conductive substrates and injects, thereby owing to the disappearance or the minimizing of microcosmic surface charges caused image deflects.In order to address this is that, and further covering surfaces defective, improve charge characteristic and improve adhering to and applying characteristic of photosensitive layer, between conductive substrates and photosensitive layer, be provided with a priming coat.

Traditional priming coat comprises various types of resin materials and comprises the material of titanium dioxide powder or the like.The known material that is used for the priming coat that constitutes by single layer, comprise: resin material, such as polyethylene, polypropylene, polystyrene, acrylic acid (class) resin, vinyl chloride resin, vinyl acetate resin, polyurethane resin, epoxy resin, mylar, melamine resin, silicone resin, polyvinyl butyral resin, polyamide; And the copolymer that contains above-mentioned resin repetitive more than two; Casein, gelatin, polyvinyl alcohol, ethyl cellulose or the like.Wherein, polyamide be preferably (day the disclosure specially permit clear 51 (1976)-114132 and a day disclosure specially permit in clear 52 (1977)-25638 announce).Yet, this have constitute by polyamide etc., as the electronic photography photoconductor of the single layer of priming coat, have the big defective of residual electromotive force, this has reduced sensitivity and has caused the overlapping of image.It is more obvious that this tendency becomes under low humidity.

Therefore, in order to prevent image deflects and improve residual electromotive force that a day disclosure is speciallyyed permit clear 56 (1981)-52757 and announced a kind of priming coat that comprises surperficial untreated titanium oxide.In addition, day disclosure specially permit clear 59 (1984)-93453 and day disclosure special permission flat 2 (1990)-181158 in announced a kind of priming coat, this priming coat comprises the titan oxide particles that is coated with aluminium oxide etc. from the teeth outwards, and the purpose that is coated with aluminium oxide etc. is to improve the dispersiveness of titanium dioxide powder.In addition, day disclosure is speciallyyed permit clear 63-(1988)-234261 and a day disclosure and is speciallyyed permit clear 63 (1988)-298251 and proposed a kind of priming coat, this priming coat comprises titan oxide particles and binder resin, and wherein the mixing ratio of titanium oxide has obtained optimization, to prolong the useful life of photoconductor.

In the above-mentioned priming coat that comprises titanium dioxide powder, adopted to have microspheric titanium oxide.

The painting method that is used to form the electronic photography photoconductor comprises spraying method, bar painting method, roller coat coating method, scraping blade method, ring method, painting method or the like drips.According to the painting method that drips shown in Figure 1, the electronic photography photoconductor is the coating storage tank that has been full of the coating solution that is used for photosensitive layer by conductive substrates is immersed in, and the conductive substrates of soaking is made to draw on average rate or the speed change.This painting method that drips often is used to make the electronic photography photoconductor, because it is fairly simple and all very excellent aspect output and cost.

The best difficulty of resin that is used for priming coat is dissolved in the coating solution that is used for photosensitive layer.Usually, adopt the resin that dissolves in alcohol or water.Priming coat is by the preparation alcoholic solution of resin or the dispersion soln coating solution as priming coat, and is coated to by this coating solution that will be used for priming coat and makes in the substrate.

When priming coat comprise titanium dioxide powder and binder resin and wherein the ratio of titanium oxide compare with binder resin when very little, the carrier that the volume resistance of priming coat increases and exposure produces is carried controlled or is prevented.Its result, residual electromotive force rises, thereby has formed overlapping image.In addition, when the electronic photography photoconductor was repeated to use, they had been subjected to the appreciable impact of residual electromotive force accumulation, temperature and humidity.Especially, the accumulation of residual electromotive force becomes obviously under low humidity, thereby has reduced stability and enough photoconductor characteristics can't be provided.

Along with the increase of the content of titanium oxide, these problems have obtained solution.But if the electronic photography photoconductor is repeated to use, residual electromotive force tends to be stored, and especially, this tendency becomes when low humidity obviously, thereby can't solve stability in long-term use and the problem aspect the environmental characteristics fully.

In addition, if the content of titanium oxide increases to the content degree of vanishing almost that makes binder resin, adhering between the film-strength reduction of priming coat and priming coat and the conductive substrates has been subjected to weakening, consequently after photoconductor is repeated to use, its light sensitivity is owing to the fracture of film has been subjected to reduction, and image has been subjected to adverse influence.In addition, photoconductor has volume resistance and reduces suddenly and the low shortcoming of chargeable property.

The titanium dioxide powder that is used for the priming coat of conventional art in microscopic has more than or equal to 0.01 μ m, and smaller or equal to the particle size of 1 μ m, and its average aspect ratio more than or equal to 1 to smaller or equal to 1.3 scope.Particle has roughly spherical shape (granular hereinafter referred to as class), though some is inhomogeneous.Titanium oxide in being dispersed in priming coat has class when granular, these particles contact with each other on one point and its contact area very little.Therefore, unless the content of titanium oxide has surpassed certain value, the very high and photoconductor characteristic of the resistance of priming coat-particularly sensitivity and residual electromotive force have obtained reduction.Therefore, under the situation of the granular titanium oxide of class, in priming coat, need bigger titanium oxide content.

Although along with the increase of titanium oxide content, characteristic has had improvement, because the contact between the particle is very weak, photoconductor always is damaged after long-term the repeated use.

When the content of titanium oxide increased, titanium oxide was to the dispersion of binder resin, and the dispersion and the stability that are used for the coating solution of priming coat, all has been subjected to influence.When in the manufacturing process at photoconductor during coating base coat, this has caused the inhomogeneous of layer, thereby excellent image characteristics can't be provided.Therefore, need to satisfy the coating solution of enough dispersions and stability.

Fig. 1 is a schematic diagram, has shown an example of the coating unit that drips that is used to form the electronic photography photoconductor, 11 expression cydariform conductive substrates among the figure; 12 expression cydariform conductive substrates bearings; 13 expression motors; 14,17 expressions apply bath; 15 expression coating solutions; 16 expression pumps; 18 expression blenders.

Fig. 2 is the cutaway view of the electronic photography photoconductor in the example of the present invention, and this electronic photography photoconductor has the function separated structures.

The invention provides a kind of electronic photography photoconductor, it comprises conductive substrates, be arranged on the priming coat on this conductive substrates and be arranged on photosensitive layer on this priming coat, and wherein priming coat comprises needle-like titan oxide particles and binder resin.When having applied 100Kg/cm ²The load pressure the time, the needle-like titan oxide particles in priming coat presents 10 ⁵Ω cm to 10 ¹⁰The volume resistance of Ω cm.The aspect ratio L/S of the longitudinal axis L of this needle-like titan oxide particles and minor axis S is 1.5 or bigger.

The present invention further provides a kind of method that is used to form this electronic photography photoconductor, wherein by adopting a kind of coating solution to adopt the formation priming coat, this coating solution comprises needle-like titan oxide particles, binder resin and a kind of organic solvent, this binder resin is a kind of polyamide, and this organic solvent is C _1-3Lower alcohol be selected from carrene, chloroform, 1,2-dichloroethanes, 1, the azeotropic mixture that the another kind of organic solvent of 2-dichloropropane, toluene and oxolane is formed.

Above-mentioned azeotropic mixture is so a kind of mixture solution, and promptly its liquid phase composition overlaps each other with the vapour phase composition under certain pressure, thereby has provided the mixture with constant boiling point.This is made up of C _1-3Lower alcohol be selected from carrene, chloroform, 1,2-dichloroethanes, 1, the combination of the another kind of organic solvent of 2-dichloropropane, toluene and oxolane determines that this organic solvent is that those skilled in the art are known.For example, a kind of by 35 parts of weight methyl alcohol and 65 parts of weight 1, the mixture that the 2-dichloroethanes is formed is an azeotropic solution.This azeotropic compound has caused uniform evaporation, thereby has formed uniform priming coat that does not have defective and the storage stability that has improved the coating solution that is used for priming coat.

One object of the present invention, provide a kind of electronic photography photoconductor, it has such as the good chargeable property and the advantageous feature of low-residual electromotive force, and it is all very excellent on stability after reusing and the environmental characteristics, thereby have residual electromotive force seldom to accumulate, and the performance reduction can not appear in this electronic photography photoconductor after reusing.

Another object of the present invention provides a kind of electronic photography photoconductor, and wherein the surface of priming coat is very smooth, thereby can apply photosensitive layer equably, thereby has overcome the defective of conductive substrates basically.

A further object of the present invention provides a kind of method that is used to form the electronic photography photoconductor, and wherein photosensitive layer is applied and provide excellent image characteristics uniformly.

Another purpose of the present invention provides a kind of coating solution that is used for priming coat, and this priming coat has excellent storage stability, and it can form uniform coat film for a long time under the situation that does not occur assembling.

The titan oxide particles that is used for priming coat of the present invention has needle-like shape.The meaning of " needle-like " is long and narrow shape, comprises rod and rod, and it is that the aspect ratio L/S of the length S of the length L of major axis and minor axis is 1.5 or bigger shape.It does not need to have very long and thin shape or has sharp-pointed end.The mean value of aspect ratio is preferably in from 1.5 to 300 scope, is preferably in 2 to 10 scope.The minor axis of the diameter of needle-like titan oxide particles and major axis are respectively 1 μ m or littler and 100 μ m or littler, are more preferably to be respectively 0.5 μ m or littler and 10 μ m or littler.

Such as natural sedimentation and light extinction method etc., can be used to measure diameter and aspect ratio.As titan oxide particles, preferably adopt microscopic observation, to measure its diameter and aspect ratio with needle-like shape.Priming coat comprises titanium oxide and binder resin.The content of needle-like titan oxide particles is in the scope from 30 weight % to 99 weight % in the scope from 10 weight % to 99 weight % better, preferably in the scope from 50 weight % to 95 weight %.In the present invention, the needle-like titan oxide particles can use with having the granular titanium oxide of class.

Titanium oxide has two kinds of crystal forms, comprises anatase and rutile, and they can be by separately or one be used from the present invention.

At 100Kg/cm ²Load pressure under, the needle-like titanium oxide fine particle must have from 10 ⁵Ω cm to 10 ¹⁰The volume resistance of Ω cm scope.Below, will apply 100Kg/cm ²Load pressure under volume resistance be called powder resistance simply.

When the powder resistance of needle-like titan oxide particles less than 10 ⁵During Ω cm, the resistance of priming coat reduces and can not play the effect of electric charge barrier layer.

For example, when using the SnO that is doped with antimony ₂When conductive layer carried out conductive processing, titanium oxide presented such as 10 ⁰Ω cm or 10 ¹The low-down powder resistance of Ω cm.In the case, titanium oxide can not be used as priming coat, because it can not play the effect of electric charge barrier layer, and the chargeable property of photoconductor has been subjected to reduction.On the other hand, if the powder resistance of titanium oxide has reached 10 ¹⁰Ω cm or higher, thus reached the volume resistance identical or higher with binder resin, and the caused carrier transport that then exposes has been subjected to control or has stoped.This has caused the increase of residual electromotive force, thereby is worthless.

In addition, as long as the powder resistance of needle-like titan oxide particles is in the above-mentioned scope, just can not handle on the surface of titan oxide particles, or use Al ₂O ₃, SiO ₂, ZnO etc. or their mixture handle, to improve dispersing characteristic and surface smoothing.

The binder resin that is included in the priming coat can be made of the identical materials of the priming coat that forms as single resin bed.Wherein, preferably adopt polyamide, because it satisfies the desired various conditions of binder resin, such as in the solution of the photosensitive layer of (i) polyamide on being used to form priming coat neither dissolving do not expand yet, and (ii) polyamide and conductive substrates have the tack and the flexibility of excellence.In polyamide, the solvable nylon resin of ethanol is best, for example by 6-nylon, 6, and the copolymer nylon that 6-nylon, 610-nylon, 11-nylon, 12-nylon etc. aggregate into, and the nylon of chemical modification, such as N-alkoxy methyl modification of nylon and N-alkoxyethyl modification of nylon.

Priming coat is made by following steps: preparation comprises the mixed solvent of lower alcohol and above-mentioned organic solvent, and this organic solvent is azeotropic solvent preferably; Polyamide and titan oxide particles are dispersed in the mixed solvent to be formed for the coating solution of priming coat; Be coated in this coating solution on the conductive substrates and make its drying.This organic solvent obtains combination, with improve dispersed in alcohol solvent and prevent coating solution along with the past of time gel.In addition, this azeotropic solvent is used to prevent that the composition of coating solution from changing along with the past of time, thereby the storage stability of coating solution can be improved and coating solution can access regeneration.Storage is by fate (hereinafter referred to as the pot life) expression of counting from the date of the coating solution that is formed for priming coat.

The thickness of priming coat is preferably in from the scope of 0.01 μ m to 10 μ m, is the scope at 0.05 μ m to 5 μ m better.

The coating solution of priming coat obtains disperseing by adopting ball milling, husky mill, grinding, vibration mill or ultrasonic mill etc., and uses the conventional method such as the above-mentioned painting method that drips to apply.

Being used for conductive substrates of the present invention comprises: metal drum or the sheet material made by aluminium, aluminium alloy, copper, zinc, stainless steel, nickel or titanium or the like; And, by handle such as the polymeric material surface of PETG, nylon, polystyrene or the like or drum, sheet material or do not have the seam band or be stacked with metal forming or metallized cardboard.

Be formed on the photosensitive layer on the priming coat, have and comprise the charge generating layer that function wherein obtains separating and the function separated structures or the single layer structure of charge-transport layer.

Under the situation of function separated light electric conductor, charge generating layer at first is formed on the priming coat.The charge generation material that is included in the charge generating layer comprises bis-azo compound such as chlorodiane blue, polynucleation quinone compound such as dibromo dibenzo [cd, jk] pyrene-5,10-diketone, pyrene compound, quinoline a word used for translation ketonic compound, phthalocyanine compound and Azulene salt, they can be used singly or in combination.This charge generating layer can form by directly form this compound under vacuum evaporation.Perhaps, it can form by electric charge generation material is distributed in the binder resin solution.As a kind of method that is used to form this charge generating layer, back one method is to adopt usually.In a kind of processings in back, electric charge generation material is mixed or be distributed in the binder resin solution and the step of coating, identical with the step that is used for priming coat.Binder resin of the present invention can be traditional resin, and it can be used alone or in combination.Preferred melamine resin, epoxy resin, silicone resin, polyurethane resin, the poly-carbon resin of acrylic resin, poly-aryl resin phenoxy resin and the copolymer resins of forming by the repetitive of two or more above-mentioned resin.As copolymer, can adopt insulating resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-styrene copolymerized resin.

The solvent that is used to dissolve these resins comprises: such as the halogenated hydrocarbon of carrene and dichloroethanes; Ketone is such as acetone, methylethylketone and cyclohexanone; Ketone is such as ethyl acetate and butyl acetate; Ethers, such as oxolane with diox; Arene is such as benzene, toluene and dimethylbenzene; Non-protonization polar solvent, such as N, dinethylformamide, N, N-dimethylacetylamide and dimethyl formamide.The thickness of charge generating layer is in the scope from 0.05 μ m to 5 μ m preferably, is in the scope from 0.1 μ m to 1 μ m better.

Be included in the charge transport material in the charge-transport layer that is formed on the charge generating layer, comprise hydrazone compound, pyrazoline compounds, triphenylamine compound, triphenyl methane compound, stilbene compounds, oxadiazole compound or the like.The coating solution that is used for charge-transport layer is by forming the charge transport substance dissolves in binder resin solution.

The coating step of charge transport material is the method identical with the coating step of priming coat.The thickness of charge-transport layer is in the scope from 5 μ m to 50 μ m preferably, is in the scope from 10 μ m to 40 μ m better.

When photosensitive layer is when being made of single structure, the thickness of photosensitive layer is in the scope from 5 μ m to 50 μ m preferably, is in the scope from 10 μ m to 40 μ m better.

Since priming coat be used as stop from the charge carrier of conductive substrates inject the barrier layer, no matter and have high sensitivity and durability and the type of structure how, therefore negative photosensitive layer is preferably.

For improve sensitivity, reduce residual electromotive force and prevent to reuse after fatigue, join in the photoconductor to a kind of electron acceptor of major general.The example of electron acceptor comprises: naphtoquinone compounds, and such as 1,4-benzoquinone, tetrachloroquinone, tetrachloro-1,2-benzoquinones, quinhydrones, 2,6-phlorone, methyl 1,4-benzoquinones, α-Nai Kun and beta-naphthoquinone; Nitro compound, such as 2,4,7-trinitro--9-Fluorenone, 1,3,6,8-tetranitrocarbazol, p-nitro benzophenone, 2,4,5,7-tetranitro-9-Fluorenone and 2-nitryl fluorenone; Cyano compound, such as TCNE, 7,7,8,8-four cyano quino bismethane, 4-(p-p-nitrobenzoic acid-base)-2 ', 2 '-dicyano vinyl benzene, 4-(m-p-nitrobenzoic acid-base)-2 ', 2 '-dicyano vinyl benzene.Wherein, comprise electronics and extract composition (such as Cl, CN and NO ₂) fluorene compound, naphtoquinone compounds and benzene derivative be preferably.Photosensitive layer can further comprise UV assimilate or antioxidant, such as benzoic acid, stilbene compounds and derivative thereof, and comprises nitrogen compound, such as triazole compounds, imidazolium compounds, oxadiazole compound, thiazole and derivative thereof.

In addition, if desired, on photosensitive layer, can form a protective layer, to protect the surface.As this protective layer, can adopt thermoplastic resin, light-cured resin or thermosetting resin.This protective layer can comprise: UV absorbent or antioxidant; Inorganic material is such as metal oxide; Organo-metallic compound; Electron-acceptor material or the like.In addition, can add plasticizer if desired,,, and improve physical property with increase disposal ability and plasticity such as dibasic acid ester, fatty acid ester, phosphate, phthalic acid ester and chlorinated paraffin wax.In addition, can add levelling agent such as silicone resin.

Because the needle-like titan oxide particles has long and narrow shape, these particles contact with each other easily and these particles between contact area greater than the contact area of granular solid matter.Therefore, even the content of the titanium oxide in priming coat is lower than the content of granular solid matter, also can produce priming coat easily with identical performance.Adopt less titanium oxide, for improve film-strength and with the tack of conductive substrates, all be favourable.Comprise the photoconductor of needle-like titan oxide particles because the contact between the particle is strong, so its performance can not reduce after reusing, thereby obtain excellent stability.

When being provided with two priming coats and one and comprising needle-like titan oxide particles and another and comprise the granular titan oxide particles of same amount, the priming coat that comprises the needle-like titan oxide particles has the resistance littler than the priming coat that comprises granular titan oxide particles.This feasible thickness that comprises the priming coat of needle-like titan oxide particles can be thicker than the primer thickness that comprises granular titan oxide particles.Its result is comprising the blemish that occurs conductive substrates on the priming coat surface of needle-like titanium oxide hardly, this means that the needle-like titanium oxide is favourable for the smooth surface that obtains priming coat.

In addition, the priming coat that comprises elongated piece, even without carrying out any special surface treatment, with respect to the mixed solvent of the lower alcohol that is used for primer-layer-coated solution and other organic solvent or comprise the mixed solvent of their azeotropic component, show highly stable dispersive property, thus can stable for extended periods of time and the surface energy of substrate access uniform coating.Its result can obtain even and favourable image performance.

Below in conjunction with the example in the accompanying drawing, describe the present invention in detail, but the present invention is not limited only to these examples.In these examples, adopted the electronic photography photoconductor of function type of separation.Yet, adopt the electronic photography photoconductor of single layer structure also can obtain similar effects.

Example 1 to 5

Fig. 2 is the schematic sectional view of having represented according to the example of function divergence type electronic photography photoconductor of the present invention.This electronic photography photoconductor comprises priming coat 2 that is formed on the conductive substrates 1 and the photosensitive layer 5 that is formed on this priming coat.This photosensitive layer comprises charge generating layer 3 that comprises electric charge generation material 30 and the charge-transport layer 4 that comprises charge transport material 40.

With weight 1.8 parts needle-like titanium oxide STR-60N (Sakai ChemicalIndustry Co., Ltd. make) and binder resin copolymer polyamide resin (the Toray Industries of 16.2 parts of weight, Inc.:CM8000) be mixed into 1 of the methyl alcohol that comprises 28.7 parts of weight and 53.3 parts of weight, in the mixed solvent of 2-dichloroethanes, this STR-60N does not pass through surface treatment, and has about 9 * 10 ⁵The minor axis length of the long axis length of the powder resistance of Ω cm, L=0.05 μ m, S=0.01 μ m, and its aspect ratio is 5.With the pigment shaking machine this mixture was disperseed 8 hours, to be formed for the coating solution of priming coat.With sprinkler the coating solution that forms being coated to thickness is on the aluminum conductive substrates 100 μ m, as conductive substrates 1, and subsequently with hot-air under 110 ℃ with the substrate drying that applies 10 minutes, with the priming coat 2 that the dry thickness with 3.0 μ m is provided.When coating solution was dry, solvent was evaporated, and had stayed needle-like titanium oxide and copolymer polyamide resin as priming coat, and the content of needle-like titanium oxide is set at 10 weight %.

In addition, phenoxy resin (Union Carbide:PKHH manufacturing) with disazo pigment 1.5 parts of weight, that have following Chemical formula 1 (chlorodiane blue) and 1.5 parts of weight, with 1 of 97 parts of weight, the 2-dimethoxy-ethane mixes, disperseed 8 hours with the pigment shaking machine subsequently, to be formed for the coating solution of charge generating layer.This coating solution that will be used for charge generating layer with sprinkler is coated in priming coat 2.Subsequently, with hot-air this coating solution was descended dry 10 minutes at 90 ℃, with the charge generating layer 3 that the dry thickness with 0.8 μ m is provided.

Further, poly-carbon resin (Mitsubishi Gas Chemical Company with hydrazone compound 1 part of weight, that have Chemical formula 2,0.5 part of weight, Ltd. make: Z-200) (Unichika makes: U-100) carrene with 8 parts of weight mixes mutually with the poly-aryl resin of 0.5 part of weight, and stir with magnetic stirrer subsequently and the dissolving mixing, to be formed for the coating solution of charge-transport layer.This coating solution that will be used for charge-transport layer with sprinkler is coated in charge generating layer 3.With hot-air under 80 ℃ with dry 1 hour of this coating solution, with the charge-transport layer 4 that the dry thickness with 20 μ m is provided, thereby form function divergence type electronic photography photoconductor shown in Figure 2.

Chemical formula 1

Chemical formula 2

This electronic photography photoconductor is added in actual device, and (Sharp KabushikiKaisha makes: SF-8870), to measure surface potential, for example except the surface potential (V in the dark of photoconductor exposure-processed at the photoconductor of the part of developing _O)-be used to check charging ability, the surface potential (V of photoconductor after discharge _R) and when when exposure the surface potential (V in blank parts _L)-be used to checked sensitivity.At initial point with after 20000 times are reused, measure these photoconductor characteristics under the following conditions: the high temperature/high humidity of the normal temperature/normal humidity of low temperature/low humidity of 5 ℃/20%RH (below be abbreviated as " L/L "), 25 ℃/60%RH (below be abbreviated as " N/N ") and 35 ℃/85%RH (below be abbreviated as H/H).The example 1 of table 1 has shown the result of this measurement.

The example 2 to 5 of electronic photography photoconductor is made in the mode identical with example 1, just the mixing ratio of needle-like titanium oxide and copolymer polyamide resin changes to some extent, thereby the content that makes titanium oxide is 50,80,95 and 99 weight %, so that priming coat and measuring light electric conductor characteristic to be provided.The result who in the example 2 to 5 of table 1, has shown these measurements in an identical manner.

Example 6 to 10

With STR-60N (the Sakai Chemical Industry Co. identical with example 1 to 5, Ltd. make), utilize N-methoxy nylon resin (Teikoku ChemicalIndustry Co., Ltd.) as the binder resin in the priming coat, and change the mixing ratio of N-methoxy nylon resin in the mode identical with example 1 to 5, form the example 6 to 10 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 1 has shown the result of these measurements.

The result of table 1, make it possible to 10 to 99 weight %, do not apply surface treatment and have in the needle-like titanium oxide scope of aspect ratio 5 photoconductor with favourable photoconductor characteristic is provided, and under various environment, have excellent repetition stability.

Example 11 to 15

Adopt FTL-100 (Ishihara Sangyo Kaisha, Ltd. makes) as the needle-like titanium oxide-it is not subjected to surface treatment and has about 3 * 10 ⁵The powder resistance of Ω cm, L=3 to 6 μ m, S=0.05 to 0.1 μ m also have 30 to 120 aspect ratio, adopt copolymer polyamide resin (Toray Industries, Inc. make: CM8000) as the binder resin in the priming coat, and by changing mixing ratio in the mode identical with example 1 to 5, make the example 11 to 15 of electronic photography photoconductor, thereby priming coat and measuring light electric conductor characteristic are provided.Table 2 has shown the result of these measurements.

Example 16 to 20

Adopt with example 11 to 15 in identical FTL-100 (Ishihara Sangyo Kaisha, Ltd. make), adopt N-methoxy nylon resin (Teikoku ChemicalIndustry Co., Ltd. make: EF-30T) as the binder resin in the priming coat, and change mixing ratio in the mode identical with example 1 to 5, form the example 16 to 20 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 2 has shown the result of these measurements.

The result of table 2, make it possible to 10 to 99 weight %, do not apply surface treatment and have in the needle-like titanium oxide scope of 30 to 120 aspect ratio the photoconductor with favourable photoconductor characteristic is provided, and under various environment, have excellent repetition stability.

Example 21 to 25

Utilize STR-60N (Sakai Chemical Industry Co., Ltd. make) as the needle-like titanium oxide-its on be coated with Al ₂O ₃And have about 4 * 10 ⁶The powder resistance of Ω cm, L=0.05 μ m, S=0.01 μ m also have aspect ratio 5, utilize copolymer polyamide resin (Toray Industries, Inc. make: CM8000) as the binder resin in the priming coat, and change mixing ratio in the mode identical with example 1 to 5, form the example 21 to 25 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 3 has shown the result of these measurements.

Example 26 to 30

With STR-60N (the Sakai Chemical IndustryCo. identical with example 21 to 25, Ltd. make) as the needle-like titanium oxide, utilize N-methoxy nylon resin (Teikoku Chemical Industry Co., Ltd.) as the binder resin in the priming coat, and change the mixing ratio of N-methoxy nylon resin in the mode identical with example 1 to 5, form the example 26 to 30 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 3 has shown the result of these measurements.

The result of table 3, make it possible to 10 to 99 weight %, carried out surface treatment and had in the needle-like titanium oxide scope of aspect ratio 5 photoconductor with favourable photoconductor characteristic is provided, and under various environment, have excellent repetition stability.

Comparative example 1 to 5

Adopt TTO-55N (Ishihara Sangyo Kaisha, Ltd. makes) as granular titanium oxide-it is not subjected to surface treatment and has about 5 * 10 ⁵The powder resistance of Ω cm and the average particulate diameter of 0.03 μ m, adopt copolymer polyamide resin (Toray Industries, Inc. make: CM8000) as the binder resin in the priming coat, and by becoming mixing ratio in the mode identical with example 1 to 5, make the comparative example 1 to 5 of electronic photography photoconductor, thereby priming coat and measuring light electric conductor characteristic are provided.Table 4 has shown the result of these measurements.

Comparative example 6 to 10

Adopt with comparative example 1 to 5 in identical TTO-55N (Ishihara SangyoKaisha, Ltd. make) as granular titanium oxide, utilize N-methoxy nylon resin (Teikoku Chemical Industry Co., Ltd. make: EF-30T) as the binder resin in the priming coat, and change mixing ratio in the mode identical with example 1 to 5, form the comparative example 6 to 10 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 4 has shown the result of these measurements.

The result of table 4 demonstrates, and is not subjected under the situation of the granular titanium oxide of surface-treated in employing, when the content of titanium oxide is 10 and 50 weight %, after 20000 times are reused, has stored a large amount of residual electromotive force V _RAnd sensitivity V _LBe subjected to reducing greatly.Along with the content increase of titanium oxide, the reduction of photoconductor characteristic makes moderate progress.When content was 95 and 99 weight %, the electronic photography photoconductor presented more favourable photoconductor characteristic under environmental condition N/N and H/H.Yet, in the L/L environment, experienced after 20000 repeated uses, stored a large amount of residual electromotive force V _RAnd sensitivity V _LReduce.

Comparative example 11 to 15

Utilize TTO-55A (Ishihara Sangyo Kaisha, Ltd. make) as granular titanium oxide-its on be coated with Al ₂O ₃And have about 4 * 10 ⁷The powder resistance of Ω cm and the average particulate diameter of 0.03 μ m, utilize copolymer polyamide resin (Toray INdustries, Inc. make: CM8000) as the binder resin in the priming coat, and change mixing ratio in the mode identical with example 1 to 5, form the comparative example 11 to 15 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 5 has shown the result of these measurements.

Comparative example 16 to 20

Adopt with comparative example 11 to 15 in identical TTO-55A (Ishihara SangyoKaisha, Ltd. make) as granular titanium oxide, adopt N-methoxy nylon resin (Teikoku Chemical Industry Co., Ltd. make: EF-30T) as the binder resin in the priming coat, and change mixing ratio in the mode identical with example 1 to 5, form the comparative example 16 to 20 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 5 has shown the result of these measurements.

The result of table 5 demonstrates, and is coated with Al in employing ₂O ₃The situation of non-conductive granular titanium oxide under, when the content of titanium oxide is 10 and 50 weight %, after 20000 times are reused, stored a large amount of residual electromotive force V _RAnd sensitivity V _LBe subjected to reducing greatly.Along with the content increase of titanium oxide, the reduction of photoconductor characteristic makes moderate progress.When content was 95 and 99 weight %, the electronic photography photoconductor presented more favourable photoconductor characteristic under environmental condition N/N and H/H.Yet, in the L/L environment, experienced after 20000 repeated uses, stored a large amount of residual electromotive force V _RAnd sensitivity V _LReduce.

Comparative example 21 to 25

Utilize FTL-1000 (Ishihara Sangyo Kaisha, Ltd. make) as needle-like titanium oxide-its surface by using SnO ₂(being doped with antimony) handled and had conductivity and have about 1 * 10 ¹The powder resistance of Ω cm, L=3 to 6 μ m, S=0.05 to 0.1 μ m and aspect ratio are 30 to 120, utilize copolymer polyamide resin (Toray INdustries, Inc. make: CM8000) as the binder resin in the priming coat, and change mixing ratio in the mode identical with example 1 to 5, form the comparative example 21 to 25 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 6 has shown the result of these measurements.

Comparative example 26 to 30

Adopt with comparative example 21 to 25 in identical FTL-1000 (Ishihara SangyoKaisha, Ltd. make) as the needle-like titanium oxide, adopt N-methoxy nylon resin (Teikoku Chemical Industry Co., Ltd. make: EF-30T) as the binder resin in the priming coat, and change mixing ratio in the mode identical with example 1 to 5, form the comparative example 26 to 30 of electronic photography photoconductor, so that priming coat to be provided, thus measuring light electric conductor characteristic.Table 6 has shown the result of these measurements.

The result of table 6 demonstrates, and has carried out in employing under the situation of needle-like titanium oxide of conductive processing, along with the content of titanium oxide increases charge characteristic V _OReduce, and after 20000 times are reused, be reduced to and make the electronic photography photoconductor be difficult to obtain charging degree.

Example 31

The example 31 of function divergence type electronic photography photoconductor is to use the mode identical with example 1 to make, different is by as shown in Figure 1 the coating unit that drips, a kind of coating solution dripped be coated on the aluminum cydariform conductive substrates, this conductive substrates is of a size of 1mm (t) * 80mm (φ) * 348mm and maximum surface roughness is 0.5 μ m, the dry thickness that this is used for the coating solution of priming coat and has 3.0 μ m, and be to utilize the needle-like titanium oxide of 17.1 parts of weight and copolymer polyamide resin being prepared into as binder resin of 0.9 part of weight; This conductive substrates is coated with by dripping subsequently and is covered with coating solution that is used for charge generating layer and the coating solution that is used for charge-transport layer.So the conductive substrates that applies is installed into actual device (Sharp Kabushiki Kaisha manufacturing: SF-8870), to carry out image evaluation.Table 7 has shown the result who estimates.

Example 32 to 35

Example 32 to 35 usefulness of electronic photography photoconductor and example 31 identical modes are made, different is to use 1 respectively, 2-dichloropropane, chloroform, toluene and oxolane have replaced the organic solvent 1 of the coating solution of the priming coat that is used for example 31, the 2-dichloroethanes, so that the mixing ratio of azeotropic composition and methyl alcohol is as shown in table 7, and carry out image evaluation in the mode identical with example 31.Table 7 has shown the result who estimates.

Example 36 to 40

Example 36 to 40 usefulness of electronic photography photoconductor and example 31 to 35 identical modes are made, different is is used for the coating solution methyl alcohol of priming coat and the ratio of various organic solvents was set to 41: 41 in the example 31 to 35, carry out image evaluation in the mode identical with example 31.Table 7 has shown the result who estimates.

Comparative example 31

The comparative example 31 of electronic photography photoconductor is made in the mode identical with example 31, just the methyl alcohol of 82 parts of weight is used alone as the solvent of the coating solution of the priming coat that is used for example 31, carries out image evaluation in the mode identical with example 31.Table 7 has shown the result who estimates.

Example 41 to 50

Example 41 to 50 usefulness of electronic photography photoconductor and example 31 to 40 identical modes are made, and gone over 30 days pot life that just is used for the coating solution of priming coat, to carry out image evaluation.Table 8 has shown the result who estimates.

Comparative example 32

The comparative example 32 of electronic photography photoconductor is made in the mode identical with example 31, and gone over 30 days pot life that just is used for the coating solution of priming coat, to carry out image evaluation.Table 8 has shown the result who estimates.

Example 51

(Mitsubishi Chemical Industries Ltd. makes: SEPPT-501D) measure the turbidity of the coating solution of the priming coat that is used for example 31, to carry out evaluation dispersed and stability with the muddy instrument that has integrating sphere.Table 9 has shown the result of this evaluation.

Example 52

After having gone over 30 days pot life, measure the turbidity of the coating solution of priming coat used in the example 51, to carry out dispersiveness and estimation of stability.Table 9 has shown the result who estimates.

Example 53

The electronic photography photoconductor uses the mode identical with example 31 to make, and just solvent comprises 1 of the ethanol of 41 parts of weight and 41 parts of weight, and the 2-dichloropropane is measured turbidity in the mode identical with example 51, carries out dispersiveness and estimation of stability.Table 9 has shown the result who estimates.

Example 54

With with example 51 in identical mode, measure the turbidity of the coating solution be used in the priming coat in the example 53, just gone over 30 days pot life, to carry out dispersiveness and estimation of stability.Table 9 has shown the result who estimates.

Comparative example 33

With with example 51 in identical mode, measure the turbidity of the coating solution be used in the priming coat in the comparative example 31, to carry out dispersiveness and estimation of stability.Table 9 has shown the result who estimates.

Comparative example 34

With the mode identical with example 51, measure the priming coat that is used in the comparative example 32, gone over 30 days the turbidity of coating solution pot life, to carry out dispersiveness and estimation of stability.Table 9 has shown the result who estimates.

Comparative example 35

With not passing through surface treatment and having 10 ⁷The granular titanium oxide of the powder resistance of Ω cm and the average particulate diameter of 0.03 μ m (Ishihara Sangyo Kaisha, Ltd. make: TIO-55N), replace being used for example 31 primer-layer-coated solution without surface treatment needle-like titanium oxide.Use the mode identical to measure turbidity subsequently, to carry out dispersiveness and estimation of stability with example 51.Table 9 has shown the result who estimates.

According to the result of example 31 to 54, adopt according to not surface treated needle-like titanium oxide of the present invention and mixed solvent, can improve the dispersed and stable of coating solution.

Example 55 to 56

With with example 31 and 32 identical modes, make the electronic photography photoconductor example 55 to 56-they have the priming coat that dry thickness is 1.0 μ m, the coating solution that just is used for priming coat drips and is coated to aluminum cydariform conductive substrates; Identical in this conductive substrates and example 31 and 32, the maximum surface roughness that just has 0.2 μ m, with respectively under the environmental condition of the H/H of the N/N of the L/L of 5 ℃/20%RH, 25 ℃/60%RH, 35 ℃/85%RH, at initial point with after reusing for 20000 times, in the mode identical, carry out image evaluation with example 31.

Example 55 and 56 result are that excellent image quality is provided under all environmental conditions, and it is irregular and that defective causes is visual irregular to have eliminated the coating that causes owing to conductive substrates.In addition, after 20000 times were reused, the quality of image was good the samely with initial point.

Example 57 and 58

The example 57 of electronic photography photoconductor and 58 usefulness and example 55 identical modes are made, the binder resin of coating solution of priming coat that just is used for example 31 and 32 is by N-methoxy nylon resin (Teikoku Chemical Industry Co., Ltd. make: EF-30T) replace, to carry out image evaluation.

Example 57 and 58 result are to have obtained excellent image quality, and image can not appear in these images under all environmental conditions irregular.In addition, Tu Xiang quality is the same good with at initial point the time after 20000 times are reused.

Comparative example 36

Comparative example 36 usefulness of electronic photography photoconductor and example 55 identical modes are made, (DenkiKagaku Kogyo Kabushiki Kaisha makes: 3000K by butyral resin just to be used for the binder resin of coating solution of priming coat of example 31, it is not a copolymer polyamide resin) replace, to carry out image evaluation.

The result of comparative example 36 shows, when applying charge generating layer when dripping, priming coat is dissolved in the solvent that is used for charge generating layer, caused under the fluid drips and the coat film of charge generating layer irregular.This coating is irregular further to have caused the irregular of image.Especially, after 20000 times were reused, image is irregular to become obvious.

Comparative example 37

Form the comparative example 37 of electronic photography photoconductor with the mode identical with example 55, just utilize FTL-1000 (Ishihara Sangyo Kaisha, Ltd. makes) as needle-like titanium oxide-its surface by using SnO ₂(being doped with antimony) handled and had conductivity and have about 1 * 10 ¹The powder resistance of Ω cm, L=3 to 6 μ m, S=0.05 to 0.1 μ m and aspect ratio are 30 to 120, to carry out image evaluation.

The result of comparative example 37 has shown the charge characteristic of non-constant and the picture tone that greatly reduces in the solid black part.Especially, after 20000 times are reused tangible decline has appearred.

Comparative example 38

Comparative example 38 usefulness of electronic photography photoconductor and example 55 identical modes are made, and have just removed the titanium oxide in the priming coat that is used in example 55, and the content of copolymer polyamide resin is 18 parts of weight, to carry out image evaluation.

The result of comparative example 38 has shown the sensitivity of very high residual electromotive force, non-constant and at the picture overlapping of white part.Especially, after only reusing for 1000 times, under low temperature and low humidity condition tangible picture overlapping has just appearred.

Can obviously see from The above results, by adopting mixed solvent according to the present invention as the solvent and the needle-like titanium oxide that are used for the coating solution of priming coat, can improve the dispersed and stable of coating solution, thereby the electronic photography photoconductor that has favourable image characteristics and do not apply scrambling is provided.

Example 59 to 61

Example 59 usefulness of function divergence type electronic photography photoconductor and example 31 identical modes are made, 10 weight %) and 16.2 parts of weight just needle-like titanium oxide and the binder resin that is used for the coating solution of priming coat are set to 1.8 parts of weight (content of titanium oxide:, carry out image evaluation in the mode identical with example 31 respectively.The results are shown in the table 10 of example 59.

In addition, make the example 60 and 61 of function divergence type electronic photography photoconductor with the mode identical with example 31, just change the mixing ratio of the binder resin in needle-like titanium oxide and the priming coat, respectively the content of titanium oxide being set at 30 and 50 weight %, carry out image evaluation in the mode identical with example 31.Example 60 and 61 result are as shown in table 10.

Example 62 to 64

Make the example 62 to 64 of function divergence type electronic photography photoconductor with the mode identical with example 31, just with N-methoxy nylon resin (Teikoku ChemicalIndustry Co., Ltd. make: the binder resin that EF-30T) has replaced being used for the coating solution of priming coat, and change the mixing ratio of the needle-like titanium oxide in the priming coat in the mode identical, so that carry out image evaluation in the mode identical with example 31 with example 59 to 61.Table 10 has shown its result.

Comparative example 39 to 41

Make the comparative example 39 to 41 of function divergence type electronic photography photoconductor with the mode identical with example 31, just adopted not surface treated, have about 10 ⁷TTO-55N (the Ishihara SangyoKaisha of the powder resistance of Ω cm and the average particulate diameter of 0.03 μ m, Ltd. make), and according to example 59 to 61 in identical mode change the mixing ratio of the granular titanium oxide in priming coat so that carry out image evaluation in the mode identical with example 31.Table 10 has shown its result.

Comparative example 42 to 44

Make the example 42 to 44 of function divergence type electronic photography photoconductor with the mode identical with example 31, just with comparative example 39 to 41 in identical mode adopt granular titanium oxide, and employing N-methoxy nylon resin (Teikoku Chemical Industry Co., Ltd. make: EF-30T) as binder resin and with example 59 to 61 in identical mode change the mixing ratio of the granular titanium oxide in the priming coat so that with example 31 in identical mode carry out image evaluation.Table 10 has shown its result.

Example 65 to 67

With with example 32 in identical mode make the example 65 to 67 of function divergence type electronic photography photoconductor, just the mixing ratio of the binder resin in needle-like titanium oxide and the priming coat is set to 10,30 and 50 weight % respectively, so that carry out image evaluation in the mode identical with example 31.Table 11 has shown its result.

Example 68 to 70

Make the example 68 to 70 of function divergence type electronic photography photoconductor in the mode identical with example 32, just with N-methoxy nylon resin (Teikoku ChemicalIndustry Co., Ltd. make: EF-30T) as binder resin, and with example 65 to 67 in identical mode change the needle-like titanium oxide in the priming coat and the mixing ratio of binder resin so that carry out image evaluation in the mode identical with example 31.Table 11 has shown its result.

Example 71 to 73

Make the example 71 to 73 of function divergence type electronic photography photoconductor with the mode identical with example 31, the needle-like titanium oxide and the binder resin that just are used in the coating solution that is used for priming coat are set to 9 parts of weight respectively, and the solvent that is included in the coating solution that is used for priming coat is respectively by the chloroform of the methyl alcohol that comprises 10.33 parts of weight and 71.67 parts of weight, comprise the methyl alcohol of 25.50 parts of weight and the oxolane of 56.50 parts of weight, and the azeotropic composition that comprises the toluene of the methyl alcohol of 58.30 parts of weight and 23.70 parts of weight makes, so that carry out image evaluation in the mode identical with example 31.Table 11 has shown its result.

The object lesson of needle-like titanium oxide used in this invention, except above-mentioned, also comprise: not surface treated Titanium Dioxide Rutile Top grade, such as FTL-100 (L=3 to 6 μ m, S=0.05 to 0.1 μ m, aspect ratio is 30 to 120) and FTL-200 (L=4 to 12 μ m, S=0.05 to 0.15 μ m, aspect ratio is 27 to 240) (IshiharaSangyo Kaisha, Ltd. makes); STR-60N (aspect ratio is 5 for L=0.05 μ m, S=0.01 μ m) (Sakai Chemical Industry Co., Ltd. makes); Be coated with Al ₂O ₃, Titanium Dioxide Rutile Top grade, such as STR-60 (aspect ratio is 5 for L=0.05 μ m, S=0.01 μ m), use Al ₂O ₃And SiO ₂Carry out surface-treated STR-60A (aspect ratio is 5 for L=0.05 μ m, S=0.01 μ m) and used SiO ₂Carried out surface-treated STR-60S (aspect ratio is 5 for L=0.05 μ m, S=0.01 μ m) (Sakai ChemicalIndustry Co., Ltd. makes).

In addition, except above-mentioned, the specific product of binder resin comprises: and CM4000 (Toray Industries, Inc. makes), F-30 and MF-30 (Teikoku ChemicalIndustry Co., Ltd.).Have high sensitivity by utilizing a kind of coating solution that priming coat is provided, the invention enables and can providing, long life and the good electronic photography photoconductor that is not applied the irregular image that influences; This coating solution is a kind of mixed solvent, when priming coat comprises when not being subjected to surface-treated needle-like titanium oxide fine particle, the lower alcohol that this mixed solvent is preferably selected from the group that comprises methyl alcohol, ethanol, isopropyl alcohol and n-propyl alcohol and from comprising carrene, chloroform, 1,2-dichloroethanes, 1, the Azeotrope compositions mixed solvent that a kind of organic solvent of selecting in the group of 2-dichloropropane, toluene and oxolane forms.[table 1]

Example	TiO 2		Binder resin	Environment	Initial value (V)			After 20000 times (V)
											Type	W％	V O	V R	V L	V O	V R	V L
	1	A			10	a	L/L N/N H/H	702 710 710	21 14 13	148 143 142									705 714 715	32 20 18	156 148 147
2			″	50							″	L/L N/N H/H	705 709 711	16 12 11	144 143 142	712 713 710	27 16 14	154 146 145
	3	″			80	″	L/L N/N H/H	705 707 706	12 10 10	143 142 142									707 708 707	17 11 11	147 144 143
4			″	95							″	L/L N/N H/H	704 704 703	9 8 7	139 139 138	702 705 702	8 9 7	138 139 138
	5	″			99	″	L/L N/N H/H	700 702 703	9 9 8	138 138 137									696 700 704	7 8 9	134 135 138
6			″	10							b	L/L N/N H/H	703 709 710	20 14 12	148 142 142	705 713 716	33 19 19	156 147 148
	7	″			50	″	L/L N/N H/H	709 712 709	12 11 10	142 143 141									715 713 710	25 15 14	156 146 144
8			″	80							″	L/L N/N H/H	704 706 705	10 8 8	140 139 138	712 707 707	16 10 11	147 141 140
	9	″			95	″	L/L N/N H/H	702 703 701	8 7 7	138 138 136									700 704 703	7 7 8	138 139 138
10			″	99							″	L/L N/N H/H	699 701 702	7 7 6	136 137 137	694 698 699	5 6 6	132 136 137

TiO ₃A ... Sakai ChemicalIndustry Co..Ltd. makes: STR-60N.

Needle-like is not carried out surface treatment .0.05 * 0.01 μ m binder resin a ... Toray Industries, the copolymer resins that Inc makes: CM-8000

B ... N-methoxy nylon Teikoku Chemical

Industry Co., Ltd. makes: EF-30T[table 2]

Example	TiO 2		Binder resin	Environment	Initial value (V)			After 20000 times (V)
											Type	W％	V O	V R	V L	V O	V R	V L
	11	B			10	a	L/L N/N H/H	705 712 711	24 16 13	150 144 142									713 716 714	35 22 20	159 149 148
12			″	50							″	L/L N/N H/H	706 709 710	19 14 12	146 145 142	714 716 713	29 19 15	153 147 145
	13	″			80	″	L/L N/N H/H	704 706 704	11 10 10	143 142 141									709 707 706	18 12 11	147 144 142
14			″	95							″	L/L N/N H/H	702 701 700	9 8 8	140 139 139	700 703 701	8 8 9	139 139 140
	15	″			99	″	L/L N/N H/H	698 701 700	8 8 7	135 138 137									696 703 701	7 8 8	134 136 137
16			″	10							b	L/L N/N H/H	707 706 707	25 15 13	150 144 142	711 714 712	33 20 19	157 151 149
	17	″			50	″	L/L N/N H/H	706 712 706	18 14 11	147 143 142									715 716 712	29 20 14	154 146 145
18			″	80							″	L/L N/N H/H	704 707 704	13 11 9	144 143 140	710 711 706	19 13 12	148 145 142
	19	″			95	″	L/L N/N H/H	701 703 705	10 8 8	141 139 140									701 704 706	9 8 8	140 141 141
20			″	99							″	L/L N/N H/H	699 701 703	9 8 7	136 136 135	697 703 704	7 8 7	134 136 136

TiO ₂B ... Ishihara Sangyo Kaisha.Ltd. makes: FTL-100.

Needle-like is not carried out surface treatment, 3 to 6 * 0.05 to 0.1 μ m binder resin a ... Toray Industries, the copolymer resins that Inc. makes: CM-8000

B ... N-methoxy nylon Teikoku Chemical

Industrys Co., Ltd makes: EF-30T[table 3]

Example	TiO 2		Binder resin	Environment	Initial value (V)			After 20000 times (V)
											Type	W%	V O	V R	V L	V O	V R	V L
	21	C			10	a	L/L N/N H/H	701 710 709	20 13 13	147 142 142									703 713 715	30 20 17	154 149 146
22			″	50							″	L/L N/N H/H	706 712 710	15 10 10	144 141 142	714 715 714	24 14 13	150 145 144
	23	″			80	″	L/L N/N H/H	705 707 708	13 9 9	143 142 141									708 709 710	17 12 12	146 145 144
24			″	95							″	L/L N/N H/H	704 705 703	10 8 8	139 140 139	701 703 702	9 9 8	139 140 138
	25	″			99	″	L/L N/N H/H	701 705 704	10 8 7	138 140 139									698 700 705	8 7 7	136 139 140
26			″	10							b	L/L N/N H/H	703 712 710	19 12 11	146 144 143	709 716 714	27 19 14	152 148 145
	27	″			50	″	L/L N/N H/H	706 709 709	11 10 10	143 142 141									714 712 711	19 13 12	148 143 142
28			″	80							″	L/L N/N H/H	704 707 706	11 10 9	137 143 140	707 710 707	15 13 11	143 146 141
	29	″			95	″	L/L N/N H/H	703 706 704	10 9 7	139 140 138									701 702 705	9 9 8	139 139 138
30			″	99							″	L/L N/N H/H	700 705 704	10 8 7	138 139 139	697 701 704	7 6 7	136 137 140

TiO ₂C ... Sakai Chenical Industry Co., Ltd makes: STR-60.

Needle-like is coated with Al ₂O ₃.0.05 * 0.01 μ m.

Binder resin a ... Toray Industries, the copolymer resins that Inc. makes: CM-8000

B ... N-methoxy nylon Teikoku Chemical

Industry Co., Ltd. makes: EF-30[table 4]

Comparative example	TiO 2		Binder resin	Environment	Initial value (V)			After 20000 times (V)
											Type	W％	V O	V R	V L	V O	V R	V L
	1	D			10	a	L/L N/N H/H	715 712 709	98 19 17	216 152 150									833 751 714	362 63 25	479 197 157
2			″	50							″	L/L N/N H/H	707 709 711	67 19 19	214 156 146	815 737 713	241 50 23	391 187 148
	3	″			80	″	L/L N/N H/H	705 708 712	19 12 11	153 144 141									798 712 715	126 18 13	256 150 142
4			″	95							″	L/L N/N H/H	705 707 706	16 10 10	148 143 142	769 713 708	84 15 13	220 149 144
	5	″			99	″	L/L N/N H/H	703 706 705	16 10 8	147 142 140									749 708 706	60 11 10	199 143 141
6			″	10							b	L/L N/N H/H	718 714 715	89 19 18	212 153 451	811 754 717	302 60 21	434 191 152
	7	″			50	″	L/L N/N H/H	710 709 712	66 18 17	209 157 145									809 733 716	226 41 24	371 179 152
8			″	80							″	L/L N/N H/H	703 709 711	19 12 10	154 143 142	789 711 713	122 16 12	251 145 143
	9	″			95	″	L/L N/N H/H	709 706 705	21 12 12	157 144 143									771 708 706	83 15 14	216 145 142
10			″	99							″	L/L N/N H/H	706 703 702	15 8 9	148 140 140	754 704 703	61 11 10	195 142 140

TiO ₂D ... Ishihara sangyo Kaisha.Ltd. makes: TTO-55N

Granular, do not do the surface and handle .0.03 μ m

Binder resin a ... Toray Industries, the copolymer resins that Inc. makes: CM-8000

B ... N-methoxy nylon Teikoku Chemical

Industry Co., Ltd. makes: EF-30T[table 5]

Comparative example	TiO 2		Binder resin	Environment	Initial value (V)			After 20000 times (V)
											W%	Resin	V O	V R	V L	V O	V R	V L
	11	E			10	a	L/L N/N H/H	712 714 713	104 21 19	224 153 154									821 740 715	354 59 23	482 198 157
12			″	50							″	L/L N/N H/H	709 708 712	70 19 18	213 155 147	804 741 718	224 51 24	369 187 152
	13	″			80	″	L/L N/N H/H	708 707 710	19 12 10	156 143 141									783 713 715	129 17 12	261 149 143
14			″	95							″	L/L N/N H/H	706 708 706	18 11 10	154 143 142	775 707 708	86 16 13	221 150 144
	15	″			99	″	L/L N/N H/H	702 705 704	15 9 8	147 142 140									750 704 702	61 12 10	203 144 142
16			″	10							b	L/L N/N H/H	716 715 715	84 17 15	226 146 144	789 742 718	261 49 23	408 218 150
	17	″			50	″	L/L N/N H/H	712 711 713	65 17 16	208 144 145									794 731 716	184 39 22	342 172 149
18			″	80							″	L/L N/N H/H	706 708 707	18 11 11	154 141 142	768 716 708	106 19 12	243 150 143
	19	″			95	″	L/L N/N H/H	707 704 705	20 13 11	155 144 141									765 708 706	82 17 14	218 150 142
20			″	99							″	L/L N/N H/H	705 706 706	14 8 8	150 141 140	749 701 703	59 12 9	197 144 141

TiO ₂E ... Ishihara Sangyo Kaisha.Ltd. makes: TTP-55A.

Granular, be coated with Al ₂O ₃.0.03 μ m

Binder resin a ... Toray Industries, the copolymer resins that Inc. makes: CM-8000

B ... N-methoxy nylon Teikoku Chemical

Industry Co., Ltd. makes: EF-30T[table 6]

Comparative example	TiO 2		Binder resin	Environment	Initial value (V)			After 20000 times (V)
											Type	W％	V O	V R	V L	V O	V R	V L
	21	F			10	a	L/L N/N H/H	659 662 658	18 10 9	109 101 102									125 139 146	2 2 2	18 15 12
22			″	50							″	L/L N/N H/H	621 631 635	15 9 8	92 85 86	101 97 99	2 1 1	13 14 12
	23	″			80	″	L/L N/N H/H	601 624 621	7 6 6	82 80 81									83 79 81	1 1 1	10 12 11
24			″	95							″	L/L N/N H/H	593 598 595	5 4 4	79 78 79	80 81 83	1 0 1	11 10 12
	25	″			99	″	L/L N/N H/H	536 524 528	4 3 4	75 72 74									75 72 76	1 0 0	10 9 9
26			″	10							b	L/L N/N H/H	662 667 665	19 11 9	108 103 102	126 124 131	2 2 2	13 12 10
	27	″			50	″	L/L N/N H/H	617 624 621	16 10 10	94 87 86									100 89 93	2 1 1	9 10 11
28			″	80							″	L/L N/N H/H	597 615 620	9 7 6	81 82 80	82 81 79	1 1 1	10 10 11
	29	″			95	″	L/L N/N H/H	591 601 598	7 6 6	78 77 76									82 79 80	1 0 0	10 10 9
30			″	99							″	L/L N/N H/H	536 526 525	5 5 4	72 71 73	75 71 74	0 0 0	9 9 9

TiO ₂F ... Ishihara Sangyo Kaisha.Ltd. makes: FTL-1000.

Needle-like is by using SnO ₂(being doped with sb) handled and made surface conductance,

3 to 6 * 0.05 to 0.1 μ m.

Binder resin a ... Toray Industries, the copolymer resins that Inc makes: CM-8000

B ... N-methoxy nylon by Teikoku Chemical

Industrys Co., Ltd. makes: EF-30T[table 7]

Photoconductor	Needle-like TiO 2Weight %	The solvent that is used for the coating solution of priming coat		The coating solution that is used for priming coat		The degree of irregularity of priming coat		The image degree of irregularity
											Composition (part weight)	Composition (part weight)	Disperse	Pot life	Under the fluid drips	Irregular	Under the fluid drips	Irregular	The structure fineness
		Example 31	95	Methyl alcohol 28.70	-1,2-dichloroethanes 53.30	○	0 day	○	○	○										○	○
Example 32	95										Methyl alcohol 43.46	1,2 cbloropropane isopropyl chloride 38.54	○	0 day	○	○	○	○	○
		Example 33	95	Methyl alcohol 10.33	Chloroform-71.67	○	0 day	○	○	○										○	○
Example 34	95										Methyl alcohol 25.50	Oxolane 56.50	○	0 day	○	○	○	○	○
		Example 35	95	Methyl alcohol 58.30	Toluene 23.70	○	0 day	○	○	○										○	○
Example 36	95										Methyl alcohol 41	1,2-dichloroethanes 41	○	0 day	○	○	○	○	○
		Example 37	95	Methyl alcohol 41	1,2 cbloropropane isopropyl chloride 41	○	0 day	○	○	○										○	○
Example 38	95										Methyl alcohol 41	Chloroform 41	○	0 day	○	○	○	○	○
		Example 39	95	Methyl alcohol 41	Oxolane 41	○	0 day	○	○	○										○	○
Example 40	95										Methyl alcohol 41	Toluene 41	○	0 day	○	○	○	○	○
		Comparative example 31	95	Methyl alcohol 82	-	×	0 day	××	×	×										×	××

Disperse to estimate: zero good irregular evaluation: zero is no irregular

△ can accept △ and can accept

* gathering * have irregular arranged

* * very poor [table 8]

Photoconductor	Primer-layer-coated solution		The priming coat degree of irregularity		The image degree of irregularity
								Storage stability	Pot life	Under the fluid drips	Degree of irregularity	Under the fluid drips	Degree of irregularity	The fineness of group structure
	Example 41	○	30 days	○	○	○	○								○
Example 42								○	30 days	○	○	○	○	○
	Example 43	○	30 days	○	○	○	○								○
Example 44								○	30 days	○	○	○	○	○
	Example 45	○	30 days	○	○	○	○								○
Example 46								○	30 days	○	○	○	○	○
	Example 47	○	30 days	○	○	○	○								○
Example 48								○	30 days	○	○	○	○	○
	Example 49	○	30 days	○	○	○	○								△
Example 50								○	30 days	○	○	○	○	△
	Comparative example 32	×	30 days	××	×	×	×								××

Storage capacity is estimated: zero good irregular evaluation: zero is no irregular

△ can accept △ and can accept

* gathering * have irregular arranged

* * very poor

Photoconductor	Pot life	Turbidity
			Example 51	0 day	53
Example 52	30 days	58
			Example 53	0 day	60
Example 54	30 days	67
			Comparative example 33	0 day	395
Comparative example 34	30 days	Part is assembled and precipitation
			Comparative example 35	0 day	Assemble fully and precipitate

Photoconductor	TiO 2		Binder resin	The degree of irregularity of priming coat		The image degree of irregularity
										Type	wt％
	Under the fluid drips	Degree of irregularity										Under the fluid drips	Degree of irregularity	Group structure fineness	Part is overlapping in vain
				Example 59	A	10	a	○	○							○	○	○	○
Example 60	A	30	a							○	○	○	○	○	○
				Example 61	A	50	a	○	○							○	○	○	○
Example 62	A	10	b							○	○	○	○	○	○
				Example 63	A	30	b	○	○							○	○	○	○
Example 64	A	50	b							○	○	○	○	○	○
				Comparative example 39	B	10	a	△	×							△	×	××	××
Comparative example 40	B	30	a							×	×	×	×	×	××
				Comparative example 41	B	50	a	×	×							×	×	×	×
Comparative example 42	B	10	b							△	×	△	×	×	××
				Comparative example 43	B	30	b	×	×							×	×	××	××
Comparative example 44	B	50	b							×	×	×	×	×	×

TiO ₂A:Sakai Chcmical Industry Co., Ltd. makes: STR-60N.

Needle-like is not done the surface and is handled:

B:Ishihara Sangyo Kaisha, Ltd. makes: TTO-55N.

Granular, do not do the surface and handle the copolymer resins that binder resin a:Toray Industries.Inc. makes: CM-8000

B:N-methoxyl group nylon Teikoku Chemical Industry Co..Ltd. makes: EF-30T

Irregular evaluation: zero do not have irregular

△ can accept

* have irregular

* * extreme difference [table 11]

Photoconductor	TiO 2		The solvent of primer-layer-coated solution		Binder resin	The degree of irregularity of priming coat		The image degree of irregularity
												Type	wt％	Become portioning weight	Become portioning weight	Under the fluid drips	Degree of irregularity	Under the fluid drips	Degree of irregularity	Group structure fineness	Overlapping in the white part
	Example 65	A	10	Methyl alcohol 43.46		1,2-dichloropropane 38.54	a	○	○	○	○											○	○
Example 66					A							30	Methyl alcohol 43.46	1,2-dichloropropane 38.54	a	○	○	○	○	○	○
	Example 67	A	50	Methyl alcohol 43.46		1,2-dichloropropane 38.54	a	○	○	○	○											○	○
Example 68					A							10	Methyl alcohol 43.46	1,2-dichloropropane 38.54	b	○	○	○	○	○	○
	Example 69	A	30	Methyl alcohol 43.46		1,2-dichloropropane 38.54	b	○	○	○	○											○	○
Example 70					A							50	Methyl alcohol 43.46	1,2-dichloropropane 38.54	b	○	○	○	○	○	○
	Example 7l	A	50	Methyl alcohol 10.33		Chloroform 71.67	a	○	○	○	○											○	○
Example 72					A							50	Methyl alcohol 25.50	Oxolane 56.50	a	○	○	○	○	○	○
	Example 73	A	50	Methyl alcohol 58.30		Toluene 23.70	a	○	○	○	○											○	○

TiO ₂A:Sakai Chcmical Industry Co..Lid. makes: STR-60N.

Needle-like is not done the surface and is handled: binder resin a:Toray Industries, the copolymer resins that Inc. makes: CM-8000

B:N-methoxy nylon Teikoku Chcmical Industry Co., Ltd. makes: EF-30T

Irregular evaluation: zero do not have irregular

△ can accept

* have irregular

* * very poor

Claims (6)

1. electronic photography photoconductor, it comprises conductive substrates, be arranged on the priming coat on this conductive substrates and be arranged on photosensitive layer on this priming coat, wherein priming coat comprises needle-like titan oxide particles and binder resin, the aspect ratio L/S of the longitudinal axis L of this needle-like titan oxide particles and minor axis S is 1.5 or bigger, and at 100Kg/cm ²Load pressure under present from 10 ⁵Cm to 10 ¹⁰The volume resistance of Ω cm scope.

2. according to the electronic photography photoconductor of claim 1, wherein to have length be that 1 μ m or shorter minor axis S and length are 100 μ m or shorter longitudinal axis L and the aspect ratio L/S that is in from 1.5 to 300 scopes to the needle-like titan oxide particles.

3. according to the electronic photography photoconductor of claim 1, wherein to have length be that 0.5 μ m or shorter minor axis S and length are 10 μ m or shorter longitudinal axis L and the aspect ratio L/S that is in from 2 to 10 scopes to the needle-like titan oxide particles.

4. according to the electronic photography photoconductor of claim 1, wherein be included in needle-like titan oxide particles in the priming coat in scope from 10 weight % to 99 weight %.

5. according to the electronic photography photoconductor of claim 1, wherein be included in needle-like titan oxide particles in the priming coat in scope from 30 weight % to 99 weight %.

6. according to the electronic photography photoconductor of claim 1, wherein be included in needle-like titan oxide particles in the priming coat in scope from 50 weight % to 95 weight %.

7. according to the electronic photography photoconductor of claim 1, wherein the surface of needle-like titan oxide particles is not through handling.

8. according to the electronic photography photoconductor of claim 1, wherein binder resin is a polyamide.

9. according to the electronic photography photoconductor of claim 1, wherein to have length be that 0.5 μ m or shorter minor axis S and length are 10 μ m or shorter length by L and the aspect ratio L/S that is in from 2 to 10 scopes to the needle-like titan oxide particles, is included in needle-like titanium oxide in the priming coat and is in from the scope of 50 weight % to 95 weight % and is not subjected to surface treatment.

10. be used to form the method for the electronic photography photoconductor of claim 1, wherein priming coat is made by adopting a kind of coating solution, this coating solution comprises needle-like titan oxide particles, binder resin and a kind of organic solvent, and this binder resin is that polyamide and this organic solvent comprise C _1-3Lower alcohol and or from by carrene, chloroform, 1,2-dichloroethanes, 1, the another kind of organic solvent of selecting in the group that 2-dichloropropane, toluene and oxolane are formed.

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