CN101846895B - Single-layer type electrophototgraphic photoreceptor and image forming device - Google Patents

Abstract

The invention provides a single-layer type electrophototgraphic photoreceptor capable of effectively preventing the generation of a dark spot in the high temperature and high humidity environment and effectively holding excellent photosensitivity characteristic in the low temperature and low humidity environment, as well as an image forming device. The single-layer type electrophototgraphic photoreceptor has a body, a photosensitive layer arranged on the body and an intermediate layer between the body and the photosensitive layer, characterized in that the intermediate layer contains a bonding resin and titanium oxide particles, and the titanium oxide particles have the following characteristics: (a) the number average primary particle size of the titanium oxide particles is in the range of 5 to 30 nm, (b) the surface treatment of the titanium oxide particles is performed by using aluminum oxide, silica and an organo-silicon compound, (c) the weight ratio X (weight%) of the organo-silicon compound on the surface of the titanium oxide particles meets the relation (1): 1 (weight%) <=X<4 (weight%).

Description

Mono-layer electronic photographic photoreceptor and image processing system

Technical field

The present invention relates to mono-layer electronic photographic photoreceptor and image processing system.Particularly relate to the generation that under hot and humid environment, can suppress stain effectively, even under the low temperature and low humidity environment, also can keep the mono-layer electronic photographic photoreceptor of excellent light sensitivity characteristic on the other hand effectively and use the image processing system of this mono-layer electronic photographic photoreceptor.

Background technology

In recent years, owing to require cheap and low environment pollution etc., used the Electrophtography photosensor that uses in the image processing system of xerography to use widely at duplicating machine or laser printer etc. and utilized organic Organophotoreceptor.

This Organophotoreceptor is known to have laminated electrophotographic photoreceptor that charge generating layer, charge transport laminated are formed and the mono-layer electronic photographic photoreceptor that is made up of simple layer.

Wherein, mono-layer electronic photographic photoreceptor is compared with laminated electrophotographic photoreceptor, and is simple in structure, therefore produces to be easy to simultaneously, and the cost aspect also is favourable.

In addition, mono-layer electronic photographic photoreceptor is different with laminated electrophotographic photoreceptor, also is favourable aspect the generation of the oxidizing gas in the time can suppressing to use through constituting positively charged type Electrophtography photosensor.

But, when using mono-layer electronic photographic photoreceptor, surpassing 100mm/s and carry out high speed image when forming to rouse peripheral speed, the influence of oxidizing gas increases, and the photographic layer surface is prone to deterioration.

In addition, be prone to produce the film forming that remaining toner causes on the photographic layer surface.

Its result because the resistance to pressure of photographic layer is prone to excessively reduce, particularly under hot and humid environment, exists to be prone to produce electric leakage or to form the problem that image is prone to produce stain.

Therefore, as solving the method that this resistance to pressure reduces, be widely used in the method that the middle layer is set between matrix and the photographic layer.

But when the middle layer was set, the animal migration of the electric charge in the photographic layer be prone to reduce, and therefore particularly under the low temperature and low humidity environment, had the problem that is difficult to obtain sufficient light sensitivity characteristic.

Therefore, even disclose when being provided with the middle layer,, make the middle layer contain the mono-layer electronic photographic photoreceptor of the particulate of regulation (for example, patent documentation 1 and 2) in order under the low temperature and low humidity environment, to obtain sufficient light sensitivity characteristic.

Promptly; In patent documentation 1; Disclose and made the middle layer contain titanium oxide microparticle; And the average primary particle diameter of this titanium oxide microparticle is in the scope of 10～30nm, and this titanium oxide microparticle is implemented surface treatment with aluminium oxide, silicon dioxide and organo-silicon compound, and the mono-layer electronic photographic photoreceptor of part by weight in the scope of 4～9.5 weight % of the organo-silicon compound on this titanium oxide microparticle surface.

In addition; In patent documentation 2; Disclose the Electrophtography photosensor with middle layer, this middle layer contains useful aluminium oxide, silicon dioxide and organo-silicon compound and has implemented the surface-treated titanium oxide microparticle, is 0V～0.6V with respect to the contact potential difference of aluminium-vapour deposition face.

Patent documentation 1: TOHKEMY 2007-286484 communique

Patent documentation 2: TOHKEMY 2002-287396 communique

But; Though patent documentation 1 disclosed mono-layer electronic photographic photoreceptor has successfully suppressed under the low temperature and low humidity environment, to carry out to a large amount of continuous letterings with paper, has been before the durable lettering and the variation of light sensitivity characteristic afterwards; But, there is the inadequate problem of initial stage light sensitivity characteristic itself because the part by weight of the organo-silicon compound in the titanium oxide microparticle is excessive.

In addition, patent documentation 2 disclosed Electrophtography photosensors have also that not only the particle diameter of titanium oxide microparticle excessively increases and also titanium oxide microparticle in the part by weight of organo-silicon compound excessively increase, be difficult to stably obtain the problem of sufficient initial stage light sensitivity.

Therefore, require under hot and humid environment, can to suppress effectively the generation of stain,, also can keep the mono-layer electronic photographic photoreceptor of the light sensitivity characteristic of excellence effectively even on the other hand under the low temperature and low humidity environment.

Summary of the invention

Promptly; The objective of the invention is to; Be provided at the generation that can suppress stain under the hot and humid environment effectively; Even under the low temperature and low humidity environment, also can keep the mono-layer electronic photographic photoreceptor and the image processing system that uses this mono-layer electronic photographic photoreceptor of the light sensitivity characteristic of excellence effectively on the other hand.

Through the present invention; Mono-layer electronic photographic photoreceptor is provided; Have matrix, be arranged on the photographic layer on the said matrix and be configured in said matrix and said photographic layer between the middle layer, it is characterized in that binding resin and titanium oxide microparticle are contained in the middle layer; And titanium oxide microparticle has property (a)～(c), thereby can address the above problem.(a) the number average primary particle size of titanium oxide microparticle is the value in 5～30nm scope.(b) titanium oxide microparticle is implemented surface treatment with aluminium oxide, silicon dioxide and organo-silicon compound.(c) the part by weight X (weight %) of the organo-silicon compound on titanium oxide microparticle surface satisfies following relational expression (1).

1 (weight %)≤X＜4 (weight %) (1)

That is, contain in the middle layer, can give the electric conductivity of proper range equably the middle layer through the surface-treated titanium oxide microparticle that makes particle diameter and implemented to stipulate with regulation.

Therefore, can improve the resistance to pressure of photographic layer and the balance between the charge migration property, therefore under hot and humid environment, can suppress the generation of stain effectively, even under the low temperature and low humidity environment, also can keep excellent light sensitivity characteristic on the other hand effectively.

In addition, when constituting mono-layer electronic photographic photoreceptor of the present invention, photographic layer preferably contains and has property (A) and titanyl phthalocyanine crystallization (B) as charge generating.

(A) in CuK α characteristic X ray diffracting spectrum, has main peak Bragg angle 2 θ ± 0.2 °=27.2 °.

(B) in differential scanning calorimetric analysis, except the peak that the gasification along with planar water produces, in 270～400 ℃ scope, has a peak.

Through such formation,, also can more effectively keep excellent light sensitivity characteristic even under the low temperature and low humidity environment.

In addition, when constituting mono-layer electronic photographic photoreceptor of the present invention, preferably on the surface-treated layer that carries out with aluminium oxide and silicon dioxide, implement with the surface treatment that organo-silicon compound carry out.

Through such formation, can give the more electric conductivity of proper range more equably to the middle layer.

In addition, when constituting mono-layer electronic photographic photoreceptor of the present invention, with respect to the binding resin in the middle layer of 100 weight portions, the content of preferred titanium oxide microparticle is in the scope of 120～450 weight portions.

Through such formation, can give the more electric conductivity of proper range more equably to the middle layer.

In addition, when constituting mono-layer electronic photographic photoreceptor of the present invention, the binding resin of preferred interlayer is a polyamide.

Through such formation, can improve the dispersiveness of the titanium oxide microparticle in middle layer, and also can improve the adaptation of matrix and photographic layer effectively.

In addition, when constituting mono-layer electronic photographic photoreceptor of the present invention, the thickness of preferred interlayer is the value in 0.1～50 mu m range.

Through such formation, can make the electric conductivity in middle layer more even, be more suitable scope.

In addition, other type of the present invention is an image processing system, it is characterized in that, possesses: above-mentioned mono-layer electronic photographic photoreceptor; Charged elements, said charged elements makes mono-layer electronic photographic photoreceptor charged; Exposing unit, said exposing unit makes public to utilizing the charged mono-layer electronic photographic photoreceptor of charged elements, thereby on mono-layer electronic photographic photoreceptor, forms electrostatic latent image; Developing cell, said developing cell develops to the electrostatic latent image that utilizes exposing unit to be formed on the mono-layer electronic photographic photoreceptor with developer, thereby on mono-layer electronic photographic photoreceptor, forms the developer image; The developer image that transfer printing unit, said transfer printing unit will utilize developing cell to be formed on the mono-layer electronic photographic photoreceptor arrives the recording medium of stipulating; And cleaning unit, said cleaning unit cleans the mono-layer electronic photographic photoreceptor of developer image to the recording medium of regulation to utilizing transfer printing unit.

Promptly; Image processing system of the present invention is owing to be equipped with above-mentioned specific mono-layer electronic photographic photoreceptor; Under hot and humid environment, can suppress the generation of stain effectively, even under the low temperature and low humidity environment, also can keep excellent light sensitivity characteristic on the other hand effectively.

In addition, when constituting image processing system of the present invention, preferred cleaning unit utilizes roller member that the surface of mono-layer electronic photographic photoreceptor is ground.

Through such formation, the part of oxidative degradation that can photographic layer is surperficial, the part that residual toner causes film forming are ground and are removed, thereby keep the resistance to pressure of photographic layer effectively.

In addition, when constituting image processing system of the present invention, preferred charged elements makes the surface charging of mono-layer electronic photographic photoreceptor become positive polarity.

Through such formation; Compare with the situation of charged one-tenth negative polarity; The oxidative degradation of the photographic layer that oxidizing gas such as ozone causes can be suppressed, therefore the resistance to pressure of photographic layer can be stably kept, even under hot and humid environment, also can more effectively suppress the generation of stain.

In addition, when constituting image processing system of the present invention, the peripheral speed of preferred single layer type Electrophtography photosensor is more than the 100mm/s.

Through such formation, though might be prone to produce the oxidative degradation on photographic layer surface, be prone to produce the film forming that residual toner causes, the resistance to pressure of photographic layer is prone to reduce, even the present invention also can suppress the generation of stain effectively under hot and humid environment.

In addition, even under the low temperature and low humidity environment, also can bring into play can be corresponding to the light sensitivity characteristic of this high-speed excellence.

Description of drawings

Fig. 1 is the figure that is used to explain the basic comprising of mono-layer electronic photographic photoreceptor of the present invention;

Fig. 2 is used for the figure that the relation to the generation of the part by weight of the organo-silicon compound on titanium oxide microparticle surface and light sensitivity characteristic under the low temperature and low humidity environment and the stain under the hot and humid environment describes;

Fig. 3 is used for the figure that the relation to the kind of charge generating and the light sensitivity characteristic under the low temperature and low humidity environment describes;

Fig. 4 is the figure that is used to explain the basic comprising of image processing system of the present invention;

Fig. 5 is the CuK α characteristic X ray diffracting spectrum of the titanyl phthalocyanine crystallization used among the embodiment 6 (in tetrahydrofuran, storage after 24 hours);

Fig. 6 is the differential scanning calorimetric thermogram of the titanyl phthalocyanine crystallization of use among the embodiment 6.

Embodiment

[first embodiment]

First embodiment provides mono-layer electronic photographic photoreceptor; Have matrix, be configured in the photographic layer on the matrix, and be configured in the middle layer between matrix and the photographic layer; It is characterized in that; When binding resin and titanium oxide microparticle were contained in the middle layer, titanium oxide microparticle had property (a)～(c), thereby can address the above problem.

(a) the number average primary particle size of titanium oxide microparticle is in the scope of 5～30nm.

(b) titanium oxide microparticle is implemented surface treatment with aluminium oxide, silicon dioxide and organo-silicon compound.

(c) the part by weight X (weight %) of the organo-silicon compound on titanium oxide microparticle surface satisfies following relational expression (1).

1 (weight %)≤X＜4 (weight %) (1)

Below to the mono-layer electronic photographic photoreceptor of first embodiment, specify each constitutive requirements.

1, basic comprising

As shown in Figure 1, the basic comprising of mono-layer electronic photographic photoreceptor 10 of the present invention does, middle layer 16 is set on matrix 12, and single photographic layer 14 is set above that.

Wherein, middle layer 16 can form as follows: the coating fluid that will in specified solvent, dissolve or be dispersed with specific titanium oxide microparticle and binding resin is coated on the matrix 12, makes its drying.

In addition, photographic layer 14 can form as follows: the coating fluid that will in specified solvent, dissolve or be dispersed with charge generating, electron transporting agent, cavity conveying agent and binding resin is coated on the above-mentioned middle layer 16, makes its drying.

This mono-layer electronic photographic photoreceptor 10 goes for positive and negative any one charged type, and layer constitutes simply the overlay film defective in the time of can suppressing to form photographic layer, so productivity excellence.In addition, because the interface of interlayer is few, has the advantage that can improve optical characteristics.

2, matrix

As the matrix 12 of example shown in Figure 1, can use various materials with electric conductivity.Can enumerate for example metals such as iron, aluminium, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel and brass; Vapor deposition or lamination the plastic material of above-mentioned metal; The glass that perhaps covers etc. with silver iodide, alumite, tin oxide and indium oxide etc.

In addition, the shape of matrix can be any one shapes such as sheet, drum type according to the structure of the image processing system that uses, and can be that matrix itself has electric conductivity, and perhaps the surface of matrix has electric conductivity.In addition, matrix is preferably the matrix that has sufficient mechanicalness intensity in use.

3, middle layer

As shown in Figure 1, mono-layer electronic photographic photoreceptor 10 is characterised in that, between matrix 12 and photographic layer 14, is provided with the middle layer 16 of containing binding resin and specific titanium oxide microparticle.

Below being divided into titanium oxide microparticle, binding resin etc. describes middle layer 16.

(1) titanium oxide microparticle

Middle layer 16 is characterised in that, contains titanium oxide microparticle.

Its reason is that titanium oxide microparticle has the electrical characteristics of regulation, therefore can the electric conductivity in middle layer 16 be adjusted to the scope of regulation.

Thus, can to since the balance that is provided with between the reduction of raising and charge migration property of middle layer 16 resistance to pressures that produce, photographic layer 14 regulate.

And the kind of titanium oxide microparticle can be used any one in crystalline, the noncrystalline matter.

In addition, when titanium dioxide was crystalline, its crystal formation can use any one in Detitanium-ore-type, rutile-type and the brookite type, but especially preferably used rutile-type.

(1)-1 number average primary particle size

The number average primary particle size of titanium oxide microparticle is in the scope of 5～30nm.

Its reason is, the number average primary particle size through making titanium oxide microparticle can improve the dispersiveness of the titanium oxide microparticle in the middle layer 16 in this scope.

That is,, state specific surface treatment after perhaps being difficult to titanium oxide microparticle implemented equably if the number average primary particle size of titanium oxide microparticle less than 5nm, then is prone to excessively cohesion between the titanium oxide microparticle.On the other hand,, then be difficult to be evenly dispersed in the middle layer 16, might become the reason of the photographic fog under the hot and humid environment if the number average primary particle size of titanium oxide microparticle surpasses 30nm.

Therefore, the number average primary particle size of the titanium oxide microparticle that middle layer 16 is contained is more preferably in the scope of 7～25nm, further preferably in the scope of 10～20nm.

In addition, titanium oxide microparticle also can condense in the scope of regulation, and the number average aggregate particle size of this moment is preferably in the scope of 30～100nm, more preferably in the scope of 30～50nm.

In addition, the number average primary particle size of titanium oxide microparticle can be measured through combination electron micrograph and image processing apparatus.

And the number average primary particle size of titanium oxide microparticle of the present invention refers to, and states the number average primary particle size of the titanium oxide microparticle after the surface treatment after having implemented.

(1)-2 surface treatment

(surface treatment of carrying out with aluminium oxide and silicon dioxide)

Titanium oxide microparticle is implemented surface treatment with aluminium oxide and silicon dioxide.

Its reason is, through with aluminium oxide (Al ₂O ₃), silicon dioxide (SiO ₂) implement surface treatment, can improve the basic dispersiveness of the titanium oxide microparticle in the middle layer 16.

In addition, after titanium oxide microparticle is implemented surface treatment with aluminium oxide and silicon dioxide, with after state organo-silicon compound and implement surface treatment, the part by weight of organo-silicon compound that can be easily that titanium oxide microparticle is surperficial is adjusted to the value in the specialized range.

In addition, as the surface treatment of titanium oxide microparticle being carried out with aluminium oxide, for example can carry out in order to following method.

At first, titanium oxide microparticle is dispersed in the WS of aluminium salt such as aluminum chloride, obtains dispersion liquid.Then, in the dispersion liquid that obtains, add alkaline matters such as NaOH, after hydrate of aluminium was separated out on the surface of titanium oxide microparticle, the temperature about calcination to 500 ℃ can be carried out surface treatment with aluminium oxide thus.

In addition, as the surface treatment of titanium oxide microparticle being carried out with silicon dioxide, for example can carry out in order to following method.

At first, titanium oxide microparticle is added in the water with alkaline matters such as NaOH, obtain the water paste of alkalescence.Then, in the water paste that obtains, add the silicasol or the silicate base WS, make the pH of water paste remain on alkalescence, can obtain being formed with the titanium oxide microparticle of silicon dioxide overlay film thus on the surface.Then, the titanium oxide microparticle that obtains is implemented processing such as washing, drying, can carry out surface treatment with silicon dioxide thus.

In addition, with respect to the titanium oxide microparticle of 100 weight portions, the addition of preferred aluminium oxide and silicon dioxide amounts in the scope of 0.1～50 weight portion.

Its reason is, if the total addition of aluminium oxide and silicon dioxide then might be difficult to fully improve the basic dispersiveness of titanium oxide microparticle less than 0.1 weight portion.On the other hand,, then might be difficult to titanium oxide microparticle is implemented surface treatment equably, or become excessive, its adjusting of the influence of the electric conductivity in middle layer is become difficult if the total addition of aluminium oxide and silicon dioxide surpasses 50 weight portions.

Therefore, with respect to the titanium oxide microparticle of 100 weight portions, the total addition of aluminium oxide and silicon dioxide is more preferably in the scope of 1～30 weight portion, further preferably in the scope of 5～20 weight portions.

(surface treatment of carrying out with organo-silicon compound)

Titanium oxide microparticle and then is implemented surface treatment with organo-silicon compound except above-mentioned aluminium oxide and silicon dioxide, and the part by weight X (weight %) of the organo-silicon compound on titanium oxide microparticle surface satisfies following relational expression (1).

1 (weight %)≤X＜4 (weight %) (1)

Its reason is, through implementing surface treatment with organo-silicon compound, can control the absorptive while of titanium oxide microparticle, can further improve dispersiveness.

Further, the part by weight of the organo-silicon compound through making titanium oxide microparticle surface can be with the dispersiveness of the titanium oxide microparticle in the middle layer and the balance adjustment between the electric conductivity to good state in above-mentioned scope.

Its result can improve the resistance to pressure of photographic layer and the balance between the charge migration property, therefore under hot and humid environment, can suppress the generation of stain effectively, even under the low temperature and low humidity environment, also can keep excellent light sensitivity characteristic on the other hand effectively.

That is, if the part by weight of organo-silicon compound is less than 1 weight %, then the dispersiveness of the titanium oxide microparticle in the middle layer reduces and excessively cohesion easily.At this moment, excessive cohesion partly forms the path of electric charge, produces small electric leakage, is prone to become the reason that the stain under hot and humid environment produces.On the other hand, if the part by weight of organo-silicon compound is that then the electric conductivity in middle layer excessively reduces more than the 4 weight %, thereby the residual charge in the photographic layer might be difficult to be discharged into the matrix side.Its result, the light sensitivity characteristic under the low temperature and low humidity environment are prone to excessively reduce.

Therefore, the part by weight X (weight %) of the organo-silicon compound on titanium oxide microparticle surface is more preferably in the scope of 1～3.5 weight %, further preferably in the scope of 1.5～3 weight %.

In addition, preferably use the fluorescent X-ray determinator, and measure the part by weight X (weight %) of the organo-silicon compound on titanium oxide microparticle surface by being described below.

That is, at first use the fluorescent X-ray determinator, the lubber-line of the mutual relationship of the weight of making expression organo-silicon compound and the peak intensity of silicon atom.

Then; Use the fluorescent X-ray determinator, to the peak intensity P1 of the silicon atom of implementing the titanium oxide microparticle surface before the surface treatment with organo-silicon compound, measure with the peak intensity P2 of the silicon atom of having implemented the titanium oxide microparticle surface after the surface treatment with organo-silicon compound.

Then, calculate peak intensity Pm=P2-P1 from the silicon atom of organo-silicon compound.

Then, through using the lubber-line of making in advance, calculate the weight (M) of having implemented the organo-silicon compound on surface treatment titanium oxide microparticle surface afterwards with organo-silicon compound.

At last, the weight (M) that obtains the surperficial organo-silicon compound of titanium oxide microparticle is with respect to the ratio (M/T=X) (weight %) of implementing the weight (T) of surface treatment titanium oxide microparticle before with organo-silicon compound.

Then; Use Fig. 2, to the part by weight of the organo-silicon compound on titanium oxide microparticle surface, with the mono-layer electronic photographic photoreceptor that uses the middle layer to contain titanium oxide microparticle measure the low temperature and low humidity environment under the light sensitivity characteristic (plain telegram potential difference) that obtains, and the relation of under hot and humid environment, carrying out the stain generation number of image when forming describe.

That is, Fig. 2 representes that transverse axis adopts the part by weight X (weight %) of the hydrogenated methyl polysiloxane (organo-silicon compound a kind of) on titanium oxide microparticle surface, and the left longitudinal axis adopts the family curve A of the plain telegram potential difference (V) under the low temperature and low humidity environment.

In addition, represent that the right longitudinal axis adopts the family curve B of the stain generation number (individual/as to open) under the hot and humid environment.

And the value that the plain telegram potential difference refers to the plain telegram position when being provided with the middle layer deducts the value that the value of the plain telegram position when not being provided with the middle layer obtains.In addition, the low more then light sensitivity of the value of plain telegram potential difference characteristic is more excellent.

In addition, the number average primary particle size of the titanium oxide microparticle that uses all is 10nm, and use is carried out with the hydrogenated methyl polysiloxane implementing identical surface-treated titanium oxide microparticle with aluminium oxide and silicon dioxide before the surface treatment.

In addition, with respect to binding resin 100 weight portions in middle layer, contain the titanium oxide microparticle of 300 weight portions.

In addition, plain telegram position, stain are produced concrete the records in an embodiment such as condition determination of number.

At first, can be known by family curve A that the plain telegram potential difference under the low temperature and low humidity environment is along with the increase of the part by weight (being designated hereinafter simply as X) of hydrogenated methyl polysiloxane, the temporary transient back of reducing increases.

More particularly, can know that the value along with X increases to 1 weight % from 0 weight %, the plain telegram potential difference sharply is reduced to volt more than 20 from volt more than 60, and the light sensitivity characteristic significantly improves.On the other hand; The value of X is when surpassing the scope of 1 weight %, and along with the increase of the value of X, the value of plain telegram potential difference continues increase more lentamente; But, then can the value of plain telegram potential difference be remained in the scope of allowing in the practicality about 40V if the value of X is the scope less than 4 weight %.

Then, can know that the stain under the hot and humid environment produces number to be reduced along with the increase of X by family curve B.

More particularly, can know that the value along with X increases to 1 weight % from 0 weight %, stain produce number from nearly 90/open sharply be reduced to more than 40/open, after this continue minimizing lentamente.

Therefore, if X is the above scope of 1 weight %, then can stain be produced number and remain in the scope of allowing in the practicality below more than 40/.

Know by above; Combined characteristic A and B judge; Then the value through making X is more than 1 weight % and in the scope less than 4 weight %, can realize maintenance and this opposite on the whole purpose of inhibition that the stain under the hot and humid environment produces of the plain telegram position of the excellence under the low temperature and low humidity environment effectively.

In addition, the surface treatment of carrying out with organo-silicon compound is preferably implemented on the surface-treated layer that carries out with aluminium oxide and silicon dioxide.

Its reason is, through carrying out like this, can give more suitable electric conductivity more equably to the middle layer.

That is, through carrying out like this, the part by weight that can bring into play to greatest extent like the organo-silicon compound on above-mentioned titanium oxide microparticle surface shown in Figure 2 is limited to the effect that obtains in the specialized range.

In addition; As the preferred organo-silicon compound that use among the present invention, can enumerate alkyl silane cpd, alkoxysilane compound containing trialkylsilyl group in molecular structure, contain vinyl silane compound, contain the hydrosulphonyl silane compound, contain amino silane compounds or their condensed polymer polysiloxane compound.

More particularly, be preferably silicone compounds such as hydrogenated methyl polysiloxane, dimethyl polysiloxane, be preferably the hydrogenated methyl polysiloxane especially.

And with respect to implemented surface-treated titanium oxide microparticle 100 weight portions with aluminium oxide and silicon dioxide, the addition of organo-silicon compound is preferably more than 1 weight portion and in the scope less than 4 weight portions.

Its reason is, if the addition of organo-silicon compound is the value less than 1 weight portion, then is difficult to obtain the treatment effect of organo-silicon compound, and dispersiveness might can not get improving.On the other hand, if the addition of organo-silicon compound is more than 4 weight portions, the amount of coating that then obtains with organo-silicon compound becomes excessive, might be difficult to bring into play effectively the electrical characteristics of titanium dioxide.

Therefore, with respect to implemented surface-treated titanium oxide microparticle 100 weight portions with aluminium oxide and silicon dioxide, the addition of organo-silicon compound is more preferably in the scope of 1.2～3.5 weight portions, further preferably in the scope of 1.5～3 weight portions.

(1)-3 content

With respect to the binding resin in the middle layer of 100 weight portions, the content of titanium oxide microparticle is preferably in the scope of 120～450 weight portions.

Its reason is, the content through making titanium oxide microparticle can be given the more electric conductivity of proper range to the middle layer more equably in this scope.

That is, with respect to the binding resin in the middle layer of 100 weight portions, if the content of titanium oxide microparticle is less than 120 weight portions, then the electric conductivity in middle layer becomes too small, and the residual charge in the photographic layer might be difficult to be discharged into the matrix side.On the other hand, with respect to the binding resin in the middle layer of 100 weight portions, if the content of titanium oxide microparticle surpasses 450 weight portions, then the electric conductivity in middle layer becomes excessive, or titanium oxide microparticle is prone to the cohesion in the middle layer, might be prone to produce stain.

Therefore, with respect to the binding resin in the middle layer of 100 weight portions, the content of titanium oxide microparticle is more preferably in the scope of 130～400 weight portions, and is further preferred in the scope of 150～350 weight portions.

And the addition of titanium oxide microparticle refers to the addition of having implemented surface treatment titanium oxide microparticle afterwards.

In addition, and during with titanium oxide microparticle among the present invention and titanium oxide microparticle in addition, the addition of titanium oxide microparticle refers to the total of their addition.

(2) adjuvant

Prevent to produce interference fringe in order to produce light scattering, improve dispersiveness etc., preferably in the middle layer, add the various adjuvants different (organic micropowder end or inorganic micro powder end) with charge-transporting pigment.

Particularly, Chinese whites such as zinc paste, zinc sulphide, white lead, lithopone, aluminium oxide, lime carbonate, barium sulphate etc. be as the inorganic pigment of extender pigment, or fluororesin particle, benzoguanamine resin particle, styrene resin particle etc. are preferred additives.

In addition, during adjuvants such as interpolation micropowder, its particle diameter is preferably in the scope of 0.01～3 μ m.Its reason is, if the concavo-convex increase in the excessive then middle layer of particle diameter of adjuvant, or produce electric uneven part, and then might be prone to produce the image quality defective.On the other hand, if the particle diameter of adjuvant is too small, then might can not get sufficient light scattering effect.

And, when adding adjuvant such as micropowder, its addition with respect to the solid constituent in middle layer in weight ratio, preferably at 1～70 weight %, more preferably in the scope of 5～60 weight %.

(3) binding resin

(3)-a kind

As the kind of binding resin, preferred use for example is selected from least a resin in polyamide, polyvinyl alcohol resin, polyvinyl butyral resin, vinyl-formal resin, vinyl acetate resin, phenoxy resin, vibrin, the acryl resin.

Wherein, especially preferably use polyamide.

Its reason is that polyamide can improve the dispersiveness of the titanium oxide microparticle in the middle layer, and can improve the adaptation of matrix and photographic layer effectively.

At this, when using polyamide, aspect the dissolubility solvent is excellent, consider as binding resin, preferably use pure soluble polyamide.As object lesson; The preferred resin that is called as multipolymer nylon that copolymerization such as nylon 6, nylon 66, NYLON610, nylon 11, nylon 12 are obtained that uses perhaps carries out the resin that is called as modification of nylon that chemical modification obtains like N-alkoxy methyl modification of nylon, N-alkoxyethyl modification of nylon etc. to nylon.

In addition; When using polyvinyl butyral resin and vinyl-formal resin, preferably use the resin that in its structure, contains 50～75 moles of % of vinyl acetal, 10～50 moles of % of polyvinyl alcohol (PVA) and 0～15 mole of % of polyvinyl acetate as binding resin.

And; Polyvinyl butyral resin can obtain through polyvinyl alcohol resin and butyraldehyde are reacted; Vinyl-formal resin can obtain through polyvinyl alcohol resin and formaldehyde are reacted; These resins are that the intermiscibility of resin is excellent with phenolic aldehyde particularly, are that reactivity, the cementability of resin is also excellent with phenolic aldehyde simultaneously, and institute thinks preferred resin.

(3)-2 number-average molecular weight

The number-average molecular weight of binding resin is preferably 1,000～60, in 000 the scope.

Its reason is, if the mean molecular weight of binding resin is less than 1,000, the viscosity of the coating fluid in the time of then might forming the middle layer significantly reduces, and is difficult to obtain uniform thickness, and perhaps mechanicalness intensity, film forming or cementability significantly reduce.On the other hand, if the mean molecular weight of binding resin surpasses 60,000, the viscosity of the coating fluid when then forming the middle layer significantly increases, and might be difficult to control the thickness in middle layer, or charge migration property reduces significantly.

Therefore, the mean molecular weight of binding resin is more preferably 2,000～40, in 000 the scope, further preferably 5,000～20, in 000 the scope.

And; The mean molecular weight of binding resin can use gel permeation chromatography (GPC:GelPermeation Chromatography), measure with the molecular weight form of polystyrene conversion; When perhaps binding resin is the condensation resinoid, can also be by its condensation degree through calculating.

(4) thickness

The thickness in middle layer is preferably in the scope of 0.1～50 μ m.

Its reason is, the thickness through making the middle layer in this scope, the electric conductivity that can make the middle layer more evenly, be more suitable scope.

That is, if the thickness in middle layer then might be difficult to fully improve the resistance to pressure of photographic layer less than 0.1 μ m.On the other hand, if the thickness in middle layer surpasses 50 μ m, then the charge migration property in the photographic layer might excessively reduce.

Therefore, the thickness in middle layer is more preferably in the scope of 0.5～40 μ m, further preferably in the scope of 1～30 μ m.

4, photographic layer

(1) charge generating

(1)-a kind

As charge generating, can use for example phthualocyanine pigment such as metal-free phthalocyanine, titanyl phthalocyanine, the perylene series pigments; Disazo pigment, no metal naphthalene phthalocyanine pigment, metal naphthalene phthalocyanine pigment; Side's sour series pigments (squaraine pigment), trisazo pigment, indigo pigment; Azulenes pigment (azuleniumpigment), phthalocyanine pigments, pyrans pigment; Anthanthrone pigment, triphenylmethane series pigments, intellectual circle's pigment, toluidine series pigments, pyrazoline series pigments, the such organic light-guide electricity body of quinacridone pigment; Selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, the so present known charge generating such as inorganic light conductive material of amorphous silicon.

The phthualocyanine pigment of more particularly, more preferably representing by following formula (1)～(4) (CGM-A～CGM-D).

Its reason is, when in having the image processing system of semiconductor laser, using as digit optical systems such as the laser beam printer of light source or facsimile recorders, and the photoreceptor that need the wavelength region may more than 600～800nm has light sensitivity.

And; When in the image processing system of simulated optical systems such as electrostatic duplicating machine, using with white light sources such as halide lamps; Therefore the photoreceptor that need have light sensitivity in visibility region for example can preferably use perylene series pigments, disazo pigment etc.

In addition, in above-mentioned phthualocyanine pigment, preferred especially the use has property (A) and titanyl phthalocyanine crystallization (B).

(A) in CuK α characteristic X ray diffracting spectrum, has main peak Bragg angle 2 θ ± 0.2 °=27.2 °.

(B) in differential scanning calorimetric analysis, except the peak that the gasification along with planar water produces, in 270～400 ℃ scope, has a peak.

Its reason is that the titanyl phthalocyanine crystallization through use has this specific character even under the low temperature and low humidity environment, also can more effectively keep excellent light sensitivity characteristic.

That is, the titanyl phthalocyanine crystallization has characteristic (A), thereby can significantly improve its crystallization-stable property, electric charge generating ability and dispersiveness.

In addition, the titanyl phthalocyanine crystallization has characteristic (B), thereby can further improve its crystallization-stable property, electric charge generating ability and dispersiveness.

And, for a peak the peak that produces except gasification, that in 270～400 ℃ scope, occur, more preferably in 280～390 ℃ scope, occur along with planar water, further preferably in 290～380 ℃ scope, occur.

And; When obtaining having above-mentioned characteristic (A) and titanyl phthalocyanine crystallization (B); Through adding alkoxytitanium such as four titanium butoxide or titanium tetrachloride, phthalonitrile or derivatives thereof, or 1,3-diimino isoindoline or derivatives thereof is as material substance, synthetic titanyl phthalocyanine compound.At this moment; Phthalonitrile or derivatives thereof with respect to 1 mole, or 1; 3-diimino isoindoline or derivatives thereof, the addition of alkoxytitanium such as four titanium butoxide or titanium tetrachloride is preferably in 0.40～0.53 mole scope, more preferably in 0.42～0.50 mole scope.

Further; The synthetic of this titanyl phthalocyanine compound preferably carries out in the presence of urea compounds; At this moment, the phthalonitrile or derivatives thereof with respect to 1 mole, or 1,3-diimino isoindoline or derivatives thereof; The addition of urea compounds is preferably in 0.1～0.95 mole scope, more preferably in 0.2～0.8 mole scope.

Then, use Fig. 3, the kind of charge generating and the relation of the light sensitivity characteristic under the low temperature and low humidity environment are described.

That is, Fig. 3 representes that transverse axis adopts the part by weight X (weight %) of the hydrogenated methyl polysiloxane (organo-silicon compound a kind of) on titanium oxide microparticle surface, and the longitudinal axis adopts the family curve A and the B of the plain telegram position (V) under the low temperature and low humidity environment.

Wherein, Family curve A for use have above-mentioned characteristic (A) with titanyl phthalocyanine crystallization (B) family curve during as charge generating, the family curve of the x type crystallization that family curve B does not have above-mentioned characteristic (A) and a metal-free phthalocyanine (B) for use during as charge generating.

And the number average primary particle size of the titanium oxide microparticle that use this moment all is 10nm, and use is carried out with the hydrogenated methyl polysiloxane implementing identical surface-treated titanium oxide microparticle with aluminium oxide and silicon dioxide before the surface treatment.

In addition,, contain the titanium oxide microparticle of 300 weight portions,, contain the charge generating of 3 weight portions with respect to the binding resin of the photographic layer of 100 weight portions with respect to the binding resin in the middle layer of 100 weight portions.

In addition, in an embodiment to concrete records such as the condition determinations of plain telegram position.

At first, can know by family curve A and B, with the kind of charge generating irrespectively, the value of plain telegram position is along with the value of X increases, the temporary transient back of reducing increases.

And can know, be more than the 1 weight % and in the scope less than 4 weight % in the value of X, the value that can make the plain telegram position is low value (as stated, the low more then light sensitivity of the value of plain telegram position characteristic is more excellent).

But in family curve A and B, the level of the value of whole plain telegram position separately is different.

More particularly, in family curve A, when the value of X is 0 weight %, when that is to say the surface treatment that titanium oxide microparticle is not carried out carrying out with organo-silicon compound, the value of plain telegram position is that 130V is many.

On the other hand, in family curve B, even when one of the value of X is the value of 3.5 weight %, plain telegram position when being minimum, the value of plain telegram position also is nearly 135V.

Therefore, can know to have characteristic (A) and titanyl phthalocyanine crystallization (B) as charge generating,, also can improve the light sensitivity characteristic of Electrophtography photosensor effectively even under the low temperature and low humidity environment through use by family curve A and B.

And can know that use between situation with characteristic (A) and titanyl phthalocyanine crystallization (B) and the situation of the using the general titanyl phthalocyanine crystallization that does not have these characteristics, the light sensitivity characteristic under the low temperature and low humidity environment produces significant difference (with reference to embodiment).

(1)-2 content

With respect to stating binding resin behind 100 weight portions, the content of preferred charge generating is in the scope of 0.1～50 weight portion.

Its reason is, the content through making charge generating is in this scope, and when made public in the photographic layer surface, charge generating can produce electric charge effectively.

That is, as if the binding resin with respect to 100 weight portions, the content of charge generating is less than 0.1 weight portion, and then the electric charge generating capacity is for possible insufficient the photographic layer surface forms electrostatic latent image.On the other hand, as if the binding resin with respect to 100 weight portions, the content of charge generating surpasses 50 weight portions, then might be difficult to be distributed to photographic layer equably with in the coating fluid.

Therefore, with respect to the binding resin of 100 weight portions, the content of charge generating is more preferably in the scope of 0.2～40 weight portion, further preferably in the scope of 0.5～30 weight portion.

(2) charge transport agent

(2)-a kind

As the charge transport agent that is used for charge transport layer (cavity conveying agent and electron transporting agent), can enumerate 2,5-two (to the diethylamino phenyl)-1,3; Oxadiazole derivants such as 4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1-[pyridine radicals-(2)]-3-(to the diethylamino styryl)-pyrazoline derivatives such as 5-(to the diethylamino styryl) pyrazoline; Triphenylamine, three (to methyl) aniline, N, aromatic series uncle amino-compounds such as N-two (3, the 4-3,5-dimethylphenyl) biphenyl-4-amine, dibenzyl aniline, N; N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-[1,1-biphenyl]-4, aromatic series uncle diamino compounds such as 4 '-diamines; 3-(4 '-dimethylaminophenyl)-5,6-two-(4 '-methoxyphenyl)-1,2,4-triazine etc. 1; 2,4-pyrrolotriazine derivatives, 4-diethyl amino benzaldehyde-1, hydazone derivatives such as 1-diphenyl hydrazone; 2-phenyl-quinazoline derivants such as 4-styryl-quinazoline, 6-hydroxyl-2, benzofuran derivatives such as 3-two (p-methoxyphenyl) coumarone; Right-(2, the 2-diphenylacetylene)-N, α-stilbene derivatives such as N-diphenyl aniline; Enamine derivates, carbazole derivates such as N-ethyl carbazole, cavity conveying materials such as poly-N-vinyl carbazole and derivant thereof; Quinone based compounds such as chloranil, bromine quinone, anthraquinone, four cyano quinone bismethane (tetracyano-quino-dimethan) based compound, 2; 4,7-TNF, 2,4; 5,7-tetranitro-Fluorenone compounds such as 9-Fluorenone, xanthone based compound; The thiophene based compound, electron transport materials such as diphenoquinone compound; And independent one or more the combination that has the polymkeric substance etc. of the group that above-claimed cpd constitutes at main chain or side chain.

(2)-2 content

With respect to the binding resin of the photographic layer of 100 weight portions, the content of preferred cavity conveying agent is in the scope of 10～100 weight portions, more preferably in the scope of 30～80 weight portions.

In addition, with respect to the binding resin of the photographic layer of 100 weight portions, the content of preferred electron agent delivery is in the scope of 10～100 weight portions, more preferably in the scope of 20～70 weight portions.

(3) adjuvant

For the deterioration of the ozone, oxidizing gas or the light that prevent to produce in the image processing system, photoreceptor that heat causes, preferably in photographic layer, add anti-oxidant, light stabilizer, thermal stabilizer etc.

For example, use hindered phenol, hindered amine, p-phenylenediamine (PPD), aromatic yl paraffin, quinhydrones, spiral shell chroman, spiral shell indone and their derivant, organosulfur compound, organic phosphorus compound etc. as anti-oxidant.In addition, use the derivant of benzophenone, benzotriazole, dithiocarbamate, tetramethyl piperidine etc. as light stabilizer.

(4) binding resin

Not restriction especially of kind to binding resin; But for example first-selected use polycarbonate resin, and can use thermoplastic resins such as vibrin, polyarylate resin, SB, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-propene acid copolymer, tygon, vinyl-vinyl acetate copolymer, haloflex, PVC, polypropylene, ionomer, vinyl chloride vinyl acetate copolymer, alkyd resin, polyamide, polyurethane, polysulfones, diallyl phthalate ester resin, ketone resin, polyvinyl butyral resin, polyether resin; Organic siliconresin, epoxy resin, phenolics, carbamide resin, melamine resin, other bridging property heat-curing resins; Resins such as light-cured type such as epoxy acrylate, polyurethane-acrylate resin.

(5) thickness

The thickness of photographic layer is preferably in the scope of 5.0～100 μ m.

Its reason is, if the thickness of photographic layer is then possible insufficient as the mechanicalness intensity of photoreceptor less than 5.0 μ m.On the other hand, then be prone to peel off, perhaps might be difficult to be formed uniformly from the middle layer if the thickness of photographic layer surpasses 100 μ m.Therefore, the thickness of photographic layer is more preferably in the scope of 10～80 μ m, further preferably in the scope of 20～40 μ m.

5, manufacturing approach

(1) preparation of matrix

In order to prevent to produce interference fringe, preferably use etching, anodic oxidation, wet blast method, sand-blast, rough cut, be not in the mood for methods such as cutting, the rough surface processing is carried out on the surface of matrix.

(2) formation in middle layer

(2)-1 the surface treatment of titanium oxide microparticle

As titanium oxide microparticle is implemented the surface-treated method; For example can use dry treatment method; In this method; Use comminutor and do not use solvent, make organo-silicon compound mix, disperse, thereby carry out the surface treatment of titanium oxide microparticle with the titanium oxide microparticle of separating out aluminium oxide and silicon dioxide on the surface.

In addition, can also use the wet processed method, in this method; Join after the surface is separated out in the slurry of the titanium dioxide that aluminium oxide and silicon dioxide are arranged being dissolved in organo-silicon compound in the appropriate solvent; Stir, make its drying then, thereby carry out the surface treatment of titanium dioxide.

And, in dry treatment method and the wet processed method, from carrying out surface treatment aspect consideration more uniformly, more preferably wet processed method.

In addition, the wet processed method is preferably used wet type medium decentralized device.

Its reason is that the dispersibility of wet type medium decentralized device is excellent, can effectively the aggregated particle of titanium dioxide be pulverized and disperse, and implements uniform surface treatment simultaneously.

Wherein, wet type medium decentralized device refers to, and in device, is filled with medium, and for example have can high speed rotating agitator disk etc. improve the device of the parts of dispersancy.

In addition, above-mentioned medium preferably uses ball or pearl etc., in order to carry out surface treatment more uniformly, preferably uses pearl.

In addition, the raw material of pearl preferably uses aluminium oxide, glass, zircon, zirconia, steel and preceding stone (Off ロ Application ト stone) etc.

In addition, the diameter of pearl is preferably in the scope of 0.3～2mm.

(2)-2 the middle layer is with the preparation of coating fluid

When forming the middle layer, preferably after in being dissolved with the solution of resinous principle, adding above-mentioned titanium oxide microparticle, carry out dispersion treatment, form the middle layer and use coating fluid.

In addition, to the not restriction especially of method of carrying out dispersion treatment, but preferred generally well-known roller mill, bowl mill, vibromill, vertical ball mill, sand mill, rubber mill, the coating vibrator etc. of using.

(2)-3 the middle layer is with the coating of coating fluid

To the coating process not especially restriction of middle layer, but can use rubbing methods such as dip coating, spraying process, drop rubbing method, knife coating, rolling method with coating fluid.

And, for more stably form the middle layer and on photographic layer, preferably after the coating middle layer is with coating fluid, under 30～200 ℃, implements 5 minutes～2 hours heat drying processing.

(3) formation of photographic layer

As the formation method of photographic layer, preferably prepare photosensitive layer coating liquid after, use rubbing methods such as dip coating, spraying process, drop rubbing method, knife coating, rolling method, form photographic layer, and carry out heat drying.In addition, the condition of heat drying for example is preferably under 30～200 ℃ the temperature, 5 minutes～2 hours scope.

[second embodiment]

As shown in Figure 4; Second embodiment of the present invention is an image processing system 100; When it has the mono-layer electronic photographic photoreceptor 10 of Fig. 1 of first embodiment, around mono-layer electronic photographic photoreceptor 10, having disposed charged elements 112, exposing unit 113, developing cell 114, transfer printing unit 115, cleaning unit 117 and having removed electric unit 102.

Below, omitted the content of explanation in the first embodiment, be the center with the part that is different from first embodiment record content, second embodiment is described.

Use Fig. 4 that the basic comprising and the work of image processing system 100 are described.

At first, the mono-layer electronic photographic photoreceptor 10 that makes image processing system 100 makes its surface charged to regulation current potential 119 (positive polarity) through charged elements 112 after the direction shown in the arrow A is rotated with predetermined process speed (peripheral speed).And, in Fig. 4, use charged roller as charged elements 112.

Then, the light of modulating according to image information through exposing unit 113 passes through irradiations such as catoptron, is made public in the surface of mono-layer electronic photographic photoreceptor 10.Through this exposure, form electrostatic latent image on the surface of mono-layer electronic photographic photoreceptor 10.

Then, based on this electrostatic latent image, carry out image development through developing cell 114.The inside of this developing cell 114 accommodates toner, the electrostatic latent images on the corresponding mono-layer electronic photographic photoreceptor of this toner 10 surfaces and adhering to, thus form toner image.

In addition, recording chart 120 is transported to mono-layer electronic photographic photoreceptor 10 bottoms along the transfer printing conveying channel of regulation.At this moment, through between mono-layer electronic photographic photoreceptor 10 and transfer printing unit 115, applying the transfer bias 122 of regulation, can be on recording chart 120 the transfer printing toner image.

Then, transfer printing has the recording chart 120 of toner image to pass through separative element (not shown) after mono-layer electronic photographic photoreceptor 10 surface isolation, is transported to fuser (not shown) through moving belt.Then, recording chart 120 carries out heating and pressurizing through this fuser to be handled, and toner image outputs to the outside of image processing system 100 through outlet roller behind the surface.

On the other hand; Mono-layer electronic photographic photoreceptor 10 former states ground behind the transfer printing toner image continues rotation, and the residual toner (attachment) that is not transferred to recording chart 120 during transfer printing is removed through the surface of cleaning unit 117 from mono-layer electronic photographic photoreceptor 10.In addition, the electric charge remaining on the surface of mono-layer electronic photographic photoreceptor 10 removed through removing electric unit 102, supplies to form in next image.

In image processing system of the present invention, to use of first embodiment, the mono-layer electronic photographic photoreceptor of specific titanium dioxide is contained in the middle layer.

Therefore, under hot and humid environment, can suppress the generation of stain effectively, on the other hand, even under the low temperature and low humidity environment, also can keep excellent light sensitivity characteristic effectively.

In addition, when constituting image processing system of the present invention, preferred charged elements 112 is the charged elements of contact.

Its reason is, compares with contactless charged elements, can not influenced by temperature and humidity and stably charged.

That is, contactless charged elements is owing to discharge and make photoreceptor charged through air, might receive air temperature or humidity influence and chargedly become unstable.On the other hand, the charged elements of contact can not produce this problem, can stably make photoreceptor charged.Further, the charged elements of contact electrification mode is compared with contactless charged elements, and whole formation is simple, and the generation of oxidizing gas such as ozone is also few, and environmental characteristics is also excellent.

In addition, charged elements is preferably the charged elements that the surface charging that makes mono-layer electronic photographic photoreceptor becomes the anodal sexual type of positive polarity.

Its reason is; The charged elements of anodal sexual type is compared with the charged elements of negative pole sexual type; The oxidative degradation that can suppress the photographic layer that oxidizing gas such as ozone cause; Therefore can stably keep the resistance to pressure of photographic layer, even under hot and humid environment, also can more effectively suppress the generation of stain.

In addition, cleaning unit 117 is preferably the cleaning unit that has adopted the roller cleaning system that the surface of mono-layer electronic photographic photoreceptor is ground through roller member.

Its reason is that the part of the oxidative degradation that this cleaning unit can be surperficial with photographic layer, the part that residual toner causes film forming are ground and removed, thereby keeps the resistance to pressure of photographic layer effectively.

On the other hand; If further carry out the grinding of photographic layer, then might be prone to reduce the resistance to pressure of photographic layer on the contrary, but among the present invention; Because the middle layer that mono-layer electronic photographic photoreceptor has regulation; Can address this is that,, also can suppress the generation of stain effectively even under hot and humid environment.

In addition, the peripheral speed of preferred single layer type Electrophtography photosensor (processing speed) is more than the 100mm/s.

Its reason is; Through the peripheral speed that makes mono-layer electronic photographic photoreceptor is this scope, though be prone to produce the oxidative degradation on photographic layer surface, is prone to produce the film forming that the residual toner causes; The resistance to pressure of photographic layer is prone to reduce; But among the present invention, because the middle layer that mono-layer electronic photographic photoreceptor has regulation, even under hot and humid environment, also can suppress the generation of stain effectively.

In addition, even under the low temperature and low humidity environment, also can bring into play can be corresponding to the light sensitivity characteristic of this high-speed excellence.

And from carrying out the viewpoint consideration that more stable image forms, the peripheral speed of mono-layer electronic photographic photoreceptor is more preferably in the scope of 100～400mm/s, further preferably in the scope of 100～300mm/s.

[embodiment]

Below through embodiment the present invention is explained more specifically, but the present invention be not limited to these the record content.

[embodiment 1]

1, the surface treatment of titanium oxide microparticle

To carry out surface-treated titanium oxide microparticle (TAYCA (strain) system with silicon dioxide and aluminium oxide; MT-05, number average primary particle size: 10nm) 100 weight portions, hydrogenated methyl polysiloxane (MHPS) 1 weight portion and toluene 100 weight portions dissolve in container, thereby obtain suspending liquid.Then, use stirring machine that the suspending liquid that obtains was stirred 20 minutes, obtain the slurry of titanium oxide microparticle.Then, use mixing roll with the slurry of the titanium oxide microparticle that obtains mixing after, the heating of reducing pressure removes desolvates, thereby obtains having carried out surface-treated titanium oxide microparticle (before the thermal treatment).Then, the titanium oxide microparticle (before the thermal treatment) that obtains is cured (thermal treatment) under 150 ℃, thereby obtains having carried out the surface-treated titanium oxide microparticle.

And the number average primary particle size that has carried out the surface-treated titanium oxide microparticle also is 10nm.

2, the mensuration of the part by weight of organo-silicon compound

To the carrying out that obtain the part by weight of hydrogenated methyl polysiloxane on surface of surface-treated Titanium particles measure.

That is, at first use the fluorescent X-ray determinator, the lubber-line of the mutual relationship of the weight of making expression hydrogenated methyl polysiloxane and the peak intensity of silicon atom.

Then; Use the fluorescent X-ray determinator, to the peak intensity P1 of the silicon atom of implementing the titanium oxide microparticle surface before the surface treatment with the hydrogenated methyl polysiloxane, the peak intensity P2 of surperficial silicon atom measures with implemented surface treatment titanium oxide microparticle afterwards with the hydrogenated methyl polysiloxane.

Then, calculate peak intensity Pm=P2-P1 from the silicon atom of hydrogenated methyl polysiloxane.

Then, through using the lubber-line of making in advance, calculate the weight (M) of having implemented the hydrogenated methyl polysiloxane on surface treatment titanium oxide microparticle surface afterwards with the hydrogenated methyl polysiloxane.

At last, the weight (M) that obtains the surperficial hydrogenated methyl polysiloxane of titanium oxide microparticle is with respect to the ratio (M/T=X) (weight %) of implementing the weight (T) of surface treatment titanium oxide microparticle before with the hydrogenated methyl polysiloxane.The result who obtains is as shown in table 1.

And the weight (T) of implementing surface treatment titanium oxide microparticle before with the hydrogenated methyl polysiloxane is for having implemented the weight of the titanium oxide microparticle of surface-treated state with aluminium oxide and silicon dioxide.

In addition, the mensuration of utilizing the fluorescent X-ray determinator to carry out is carried out as follows.

Promptly; Through sample pressure forming machine (BRE-32: preceding river testing machine is made institute (MAEKAWATESTING MACHINE) corporate system) to the titanium oxide microparticle of implementing the ormal weight before the surface treatment with organo-silicon compound give 3 second 20MPa plus-pressure, form round-shaped particle (diameter 40mm, thickness 5mm).Then, the fluorescent X-ray determinator RIX200 to this particle use RIGAKU society system measures (voltage: 50kV, electric current: 30mA, X-ray tube ball: Rh) to the fluorescent X-ray peak intensity (kcps) that belongs to Si.

In addition,, carry out similarly, the fluorescent X-ray peak intensity that belongs to Si is measured for the titanium oxide microparticle of implementing surface treatment ormal weight before with above-mentioned organo-silicon compound is implemented surface treatment titanium oxide microparticle afterwards with organo-silicon compound.

3, the formation in middle layer

Use bowl mill with the titanium oxide microparticle that obtains 300 weight portions, copolymer nylon (DAICEL-DEGUSSA (strain) system, X1010) 100 weight portions, ethanol 800 weight portions and butanols 300 weight portion mixed and dispersed 48 hours, obtain the middle layer and use coating fluid.

Then, the filtrator through 5 μ m filters the middle layer that obtains with coating fluid.Then, the aluminum pipe base (matrix) of diameter 30mm, long 254mm is made under the one of which end state up, is being impregnated into the middle layer that obtains with in the coating fluid with the speed of 5mm/s, thus to this matrix coating middle layer with coating fluid (dip coating).Then, for this matrix,, form the middle layer of thickness 3 μ m through under 130 ℃, 30 minutes condition, heat-treating.

4, the formation of photographic layer

Then, use ball mill, will be as the x type crystallization (x-H of the metal-free phthalocyanine (CGM-A) shown in the formula (1) of charge generating ₂Pc) 3 weight portions, as compound (HTM-1) 50 weight portions shown in the following formula (5) of cavity conveying agent, as the Z type polycarbonate resin shown in compound (ETM-1) 30 weight portions shown in the following formula (6) of electron transporting agent, the following formula (7) (Supreme Being people changes into (strain) system, TS2020) 100 weight portions and tetrahydrofuran 800 weight portion mixed and dispersed 50 hours, obtain photographic layer thus and use coating fluid.

Then, with dip coating the photographic layer that obtains is applied on the middle layer that has formed with coating fluid.

Then, under 130 ℃, 30 minutes condition, this matrix is heat-treated, forming thickness is the photographic layer of 30 μ m.Obtain mono-layer electronic photographic photoreceptor thus.

5, estimate

(1) evaluation of plain telegram position

Plain telegram position to the mono-layer electronic photographic photoreceptor that obtains is estimated.

Promptly; The mono-layer electronic photographic photoreceptor that obtains is assemblied in the printer (Kyocera Mita (strain) system, FS-1010 transformation apparatus); (temperature: 10 ℃, relative humidity: 20%) under the low temperature and low humidity condition; Surface potential is set at 400V, is equivalent to the exposure of (solid) on the spot image of lettering rate 100%.

Then, measure by the surface potential at exposure position as plain telegram position (V).The result who obtains is as shown in table 1.

In addition, except the middle layer was not set, the mono-layer electronic photographic photoreceptor that preparation and above-mentioned mono-layer electronic photographic photoreceptor are likewise made likewise carried out, and measured plain telegram position (V).

Further, the value of the plain telegram position the when value of calculating the plain telegram position when being provided with the middle layer deducts and is not provided with the middle layer and the value, the plain telegram potential difference (V) that obtain are estimated according to following benchmark.The result who obtains is as shown in table 1.

◎: the value of plain telegram potential difference is the value less than 20V.

Zero: the value of plain telegram potential difference is that 20V is above and less than the value of 50V.

*: the value of plain telegram potential difference is the above value of 50V.

(2) evaluation of stain

Stain when the mono-layer electronic photographic photoreceptor that then, use is obtained carries out image formation is estimated.

Promptly; The mono-layer electronic photographic photoreceptor that obtains is assemblied in the printer (Kyocera Mita (strain) system, FS-1010 transformation apparatus); (temperature: 35 ℃, relative humidity: 85%), behind 5000 blank sheet of paper images of continuous durable printing, placed a day under hot and humid environment.

Then, print 10 blank sheet of paper images, the generation of the stain in the 10th image number (individual/as to open) is counted, estimate according to following benchmark through visual.The result who obtains is as shown in table 1.

◎: it is the value less than 30/that stain produces number.

Zero: stain produce number be 30/open above and less than the 80/value of opening.

*: it is 80/above values that stain produces number.

(3) comprehensive evaluation

In addition, in order synthetically above-mentioned each evaluation result to be estimated, carry out comprehensive evaluation according to following benchmark.

◎: the evaluation that the evaluation of plain telegram potential difference and stain produce number all is ◎.

Zero: the evaluation that the evaluation of plain telegram potential difference and stain produce number not all be ◎, is zero perhaps ◎.

*: the evaluation of plain telegram potential difference and stain produce being evaluated as of number *.

[embodiment 2]

In embodiment 2, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 2 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 1 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 3]

In embodiment 3, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 3.5 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 1 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 4]

In embodiment 4; When forming photographic layer; The Y type crystallization of the titanyl phthalocyanine (CGM-B) shown in the use formula (2), have characteristic (A) but do not have the crystallization of characteristic (B); The common Y type crystallization of promptly all the time using (Y-TiOPc-1) is as charge generating, likewise makes mono-layer electronic photographic photoreceptor with embodiment 1 in addition and estimates.The result who obtains is as shown in table 1.

[embodiment 5]

In embodiment 5, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 3.5 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 4 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 6]

In embodiment 6; When forming photographic layer; The Y type crystallization of the titanyl phthalocyanine (CGM-B) shown in the use formula (2), have characteristic (A) and crystallization (B) (Y-TiOPc-2) as charge generating, likewise make mono-layer electronic photographic photoreceptor with embodiment 1 in addition and estimate.The result who obtains is as shown in table 1.

And this Y-TiOPc-2 is prepared as follows.

1, the titanyl phthalocyanine coarse crystallization is synthetic

At first, in the flask that argon replaces is crossed, add phthalonitrile 22g (0.17mol), four titanium butoxide 25g (0.073mol), quinoline 300g and urea 2.28g (0.038mol), be warming up to 150 ℃ in the time of stirring.

Then, the steam that produces distill to system outside from reaction system removes, be warming up to 215 ℃ simultaneously after, kept the also further stirring reaction of this temperature 2 hours.

Then, reaction is taken out reaction mixture in the moment that is cooled to 150 ℃ from flask after finishing, and filters through glass filter, and the solid that obtains is used N successively, after dinethylformamide and the methanol wash, carries out vacuum drying.Thus, obtain hepatic solid 24g as the titanyl phthalocyanine coarse crystallization.

2, operation before the acid treatment

The hepatic solid 10g that obtains in the preparation with above-mentioned titanyl phthalocyanine compound joins N, in 100 milliliters of the dinethylformamides, is heated to 130 ℃ in the time of stirring, stir process 2 hours.

Then, stop heating, and then stop to stir, under this state, leave standstill liquid and carried out stabilization processes in 12 hours in the moment that is cooled to 23 ± 1 ℃ in the moment through 2 hours.Then, filter the supernatant of the liquid after the stabilization through glass filter, the solid that obtains with methanol wash after, carry out vacuum drying.Thus, obtain the coarse crystallization 9.83g of titanyl phthalocyanine compound.

3, acid treatment operation

The coarse crystallization 5g of the titanyl phthalocyanine that obtains in the operation before the above-mentioned acid treatment is joined in 100 milliliters of the concentrated sulphuric acids and dissolves.

Then, be added to this drips of solution in the water under ice-cooled after, at room temperature stirred 15 minutes, and then near 23 ± 1 ℃, left standstill 30 minutes, carry out recrystallization thus.

Then, obtain solid through the solution behind the glass filter filtration and recrystallization, to the solid that obtains wash be neutrality to cleansing solution after, do not carry out drying, under the state that water exists, be distributed in 200 milliliters of the chlorobenzenes, be heated to 50 ℃, stirred 10 hours.

Then, the liquid that filter to stir through glass filter obtains solid, with the solid that obtains 50 ℃ of following vacuum drying 5 hours.Thereby crystallization (blue powder) 4.1g of the no substituted titanyl phthalocyanine shown in the formula of obtaining (2).

4, the evaluation of titanyl phthalocyanine crystallization

(X-ray diffraction mensuration)

The titanyl phthalocyanine crystallization 0.3g that obtains is dispersed among the tetrahydrofuran 5g, under the condition of 23 ± 1 ℃ of temperature, relative humidity 50～60%, in enclosed system, preserves after 24 hours and remove tetrahydrofuran, obtain test sample thus.Then, this test sample is filled into the sample holder of X-ray diffraction device (motor of science (strain) system RINT1100) and measures.The spectrogram that obtains is illustrated among Fig. 5.In addition, have from this spectrogram and to have main peak Bragg angle 2 θ ± 0.2 °=27.2 ° and can know that the titanyl phthalocyanine crystallization that obtains is the crystallization of Y type, have characteristic (A).

And the titanyl phthalocyanine crystallization before being dispersed in the tetrahydrofuran also is measured to and the same spectrogram of being represented by Fig. 5 of spectrogram.

The condition determination of this X-ray diffraction is described below.

X-ray tube ball: Cu

Tube voltage: 40kV

Tube current: 30mA

Beginning angle: 3.0 °

Stop angle: 40.0 °

Sweep velocity: 10 °/minute

(differential scanning calorimeter mensuration)

In addition, use differential scanning calorimeter (TAS-200 type, the DSC8230D of motor of science (strain) system), differential scanning calorimetric analysis is carried out in the titanyl phthalocyanine crystallization that obtains.The differential scanning analysis diagram that obtains is shown among Fig. 6.In addition, the peak of having confirmed in the figure to produce, have a peak, confirmed that thus the titanyl phthalocyanine crystallization that obtains has characteristic (B) at 296 ℃ except gasification along with planar water.

And condition determination is described below.

Sample disc: aluminum

Programming rate: 20 ℃/minute

[embodiment 7]

In embodiment 7, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 2 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 6 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 8]

In embodiment 8, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 3.5 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 6 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 9]

In embodiment 9, when forming photographic layer, use the compound (ETM-2) shown in the following formula (8) as electron transporting agent, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 10]

In embodiment 10, when forming photographic layer, use the compound (ETM-3) shown in the following formula (9) as electron transporting agent, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 11]

In embodiment 11, when forming photographic layer, use the compound (HTM-2) shown in the following formula (10) as the cavity conveying agent, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 12]

In embodiment 12, when forming photographic layer, use the compound (HTM-3) shown in the following formula (11) as the cavity conveying agent, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 13]

In embodiment 13; Use (MT-100SA) (number average primary particle size:, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate of TAYCA (strain) system 15nm) as having carried out the surface-treated titanium oxide microparticle with silicon dioxide and aluminium oxide.The result who obtains is as shown in table 1.

[embodiment 14]

In embodiment 14; Use (MT-500SA) (number average primary particle size:, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate of TAYCA (strain) system 30nm) as having carried out the surface-treated titanium oxide microparticle with silicon dioxide and aluminium oxide.The result who obtains is as shown in table 1.

[embodiment 15]

In embodiment 15; The X4685 (the low-molecular-weight article of X1010) that uses DAICEL-DEGUSSA (strain) system is as the copolymer nylon as binding resin in the middle layer, likewise makes mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimates.The result who obtains is as shown in table 1.

[embodiment 16]

In embodiment 16, make the content of the titanium oxide microparticle in the middle layer change into 120 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 17]

In embodiment 17, make the content of the titanium oxide microparticle in the middle layer change into 200 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 18]

In embodiment 18, make the content of the titanium oxide microparticle in the middle layer change into 380 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate.The result who obtains is as shown in table 1.

[embodiment 19]

In embodiment 19, when being implemented surface treatment, uses titanium oxide microparticle dimethyl polysiloxane (DMPS), and likewise make mono-layer electronic photographic photoreceptor with embodiment 7 in addition and estimate.The result who obtains is as shown in table 1.

[comparative example 1]

In comparative example 1, when titanium oxide microparticle is implemented surface treatment, implement the surface treatment carried out with the hydrogenated methyl polysiloxane, likewise make mono-layer electronic photographic photoreceptor with embodiment 6 in addition and estimate.The result who obtains is as shown in table 1.

[comparative example 2]

In comparative example 2, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 4 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 6 in addition and estimate.The result who obtains is as shown in table 1.

[comparative example 3]

In comparative example 3, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 6 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 6 in addition and estimate.The result who obtains is as shown in table 1.

[comparative example 4]

In comparative example 4, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 10 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 6 in addition and estimate.The result who obtains is as shown in table 1.

[comparative example 5]

In comparative example 5, when titanium oxide microparticle is implemented surface treatment, implement the surface treatment carried out with the hydrogenated methyl polysiloxane, likewise make mono-layer electronic photographic photoreceptor with embodiment 1 in addition and estimate.The result who obtains is as shown in table 1.

[comparative example 6]

In comparative example 6, when titanium oxide microparticle is implemented surface treatment, make the addition of hydrogenated methyl polysiloxane change into 10 weight portions, likewise make mono-layer electronic photographic photoreceptor with embodiment 1 in addition and estimate.The result who obtains is as shown in table 1.

According to mono-layer electronic photographic photoreceptor of the present invention and image processing system; In mono-layer electronic photographic photoreceptor; Between matrix and photographic layer, the middle layer is set, and makes this middle layer contain specific titanium oxide microparticle, thereby can eliminate the environmental factor dependence in the photoreceptor characteristic.

Its result can suppress the generation of stain effectively under hot and humid environment, even under the low temperature and low humidity environment, also can keep excellent light sensitivity characteristic on the other hand effectively.

Therefore, the expectation of mono-layer electronic photographic photoreceptor of the present invention and image processing system is made remarkable contribution to high-qualityization of various image processing systems such as duplicating machine, printer.

Claims (9)

1. mono-layer electronic photographic photoreceptor, have matrix, be arranged on the photographic layer on the said matrix and be configured in said matrix and said photographic layer between the middle layer, it is characterized in that,

Binding resin and titanium oxide microparticle are contained in said middle layer, and said titanium oxide microparticle has property (a)～(c):

(a) the number average primary particle size of said titanium oxide microparticle is in the scope of 5～30nm,

(b) said titanium oxide microparticle is implemented surface treatment with aluminium oxide, silicon dioxide and organo-silicon compound,

(c) the part by weight X (weight %) of the said organo-silicon compound on the surface of said titanium oxide microparticle satisfies following relational expression (1),

1 (weight %)≤X＜4 (weight %) (1),

And, said photographic layer contain the crystallization of X type metal-free phthalocyanine as charge generating, contain the HTM-1 shown in the formula (5) as the cavity conveying agent, contain the ETM-1 shown in the formula (6) as electron transporting agent,

2. mono-layer electronic photographic photoreceptor according to claim 1 is characterized in that, implements on the surface-treated layer that carries out with said aluminium oxide and said silicon dioxide with the surface treatment that said organo-silicon compound carry out.

3. mono-layer electronic photographic photoreceptor according to claim 1 is characterized in that, with respect to the said binding resin in the said middle layer of 100 weight portions, the content of said titanium oxide microparticle is in the scope of 120～450 weight portions.

4. mono-layer electronic photographic photoreceptor according to claim 1 is characterized in that, the said binding resin in said middle layer is a polyamide.

5. mono-layer electronic photographic photoreceptor according to claim 1 is characterized in that the thickness in said middle layer is in the scope of 0.1～50 μ m.

6. image processing system is characterized in that possessing:

Any described mono-layer electronic photographic photoreceptor of claim 1～5;

Charged elements, said charged elements make said mono-layer electronic photographic photoreceptor charged;

Exposing unit, said exposing unit makes public to utilizing the charged said mono-layer electronic photographic photoreceptor of said charged elements, thereby on said mono-layer electronic photographic photoreceptor, forms electrostatic latent image;

Developing cell, said developing cell develops to the said electrostatic latent image that utilizes said exposing unit to be formed on the said mono-layer electronic photographic photoreceptor with developer, thereby on said mono-layer electronic photographic photoreceptor, forms the developer image;

The said developer image that transfer printing unit, said transfer printing unit will utilize said developing cell to be formed on the said mono-layer electronic photographic photoreceptor arrives the recording medium of stipulating; With

Cleaning unit, said cleaning unit cleans the said mono-layer electronic photographic photoreceptor of said developer image to the recording medium of said regulation to utilizing said transfer printing unit.

7. image processing system according to claim 6 is characterized in that, said cleaning unit utilizes roller member that the surface of said mono-layer electronic photographic photoreceptor is ground.

8. image processing system according to claim 6 is characterized in that, said charged elements makes the surface charging of said mono-layer electronic photographic photoreceptor become positive polarity.

9. image processing system according to claim 6 is characterized in that, the peripheral speed of said mono-layer electronic photographic photoreceptor is more than the 100mm/s.

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