CN1940736A - Electrophotographic photoconductor and manufacturing method of electrophotographic photoconductor - Google Patents

Abstract

The invention provides an electrophotographic photoreceptor which generates less fog in a high temperature and high humidity environment and is easily manufactured, and a method for manufacturing such an electrophotographic photoreceptor. The electrophotographic photoreceptor includes a supporting substrate, an intermediate layer and a photosensitive layer, wherein the intermediate layer comprises titanium oxide and a binder resin and delta A of the intermediate layer is set to <=0.055 or between 0 and -5.0, and delta L of the same is set to between 0 and -5.0, wherein delta L is the difference of the L value which is measured in state of forming an intermediate layer on the support substrate to the L value of the support substate measured individually (based on JIS Z 8722 standard, the parameter measured by color-difference meter). and delta A is the difference of the reflection absorbance value which is measured in state of forming an intermediate layer on the support substrate to the reflection absorbance value of the support substate measured individually (the parameter is measured by color-difference meter).

Description

The manufacture method of Electrophtography photosensor and Electrophtography photosensor

Technical field

The present invention relates to the manufacture method of Electrophtography photosensor and Electrophtography photosensor.Particularly, the manufacture method that relates to a kind of Electrophtography photosensor and such Electrophtography photosensor of the high image quality of in image processing systems such as printer, duplicating machine, facsimile unit, using.

Background technology

In the Electrophtography photosensor that in image processing system, has, be extensive use of by the charge generating that produces electric charge by illumination, that constitute, the so-called Organophotoreceptors such as binding resin carrying the charge transport agent of the electric charge that produces and constitute the layer that disperses these materials., in Organophotoreceptor, found following problem.

(1) in charged operation, be accompanied by photoreceptor is applied positive and negative any one electric charge, on support matrices, produce the electric charge of opposite polarity, but when not having the middle layer, because the electric charge of its generation is injected in the photoreceptor layers, become the reason of the charging property reduction of photoreceptor.

When (2) directly being coated with photoreceptor layers on support matrices, according to the kind or the coating condition of binding resin, photoreceptor layers can be not bonding with support matrices fully.

(3) when defectives such as support matrices surface existence damage, on image, produce stain easily.

Therefore, in order to solve such problem, proposed on support matrices, to be provided with and contained the middle layer (prime coat) of binding resin, and the method for photoreceptor layers has been set thereon.

For example, a kind of image processing system with Electrophtography photosensor has been proposed, described Electrophtography photosensor has support matrices, middle layer (prime coat) and photoreceptor layers, it is characterized in that, phenolic resin, polyvinyl acetal resin and electron transport organic pigment (for example, with reference to patent documentation 1) are contained in the middle layer.

In addition, in order to make the thickness homogenization in middle layer, a kind of Electrophtography photosensor has also been proposed, described Electrophtography photosensor has support matrices, middle layer and photoreceptor layers, it is characterized in that, the middle layer is contained phenolic resin and is had the charge-transporting material (for example, with reference to patent documentation 2) of the molecular weight of regulation.

[patent documentation 1] spy opens flat 9-258468 communique (claim)

[patent documentation 2] spy opens 2002-341570 communique (claim)

Summary of the invention

, find that there is following problems in the image processing system that possesses the Electrophtography photosensor that contains the middle layer of record in the patent documentation 1: owing in the middle layer, used the electron transport organic pigment, therefore lack the initial stage light sensitivity, and lack permanance.

In addition, there is following problems in the Electrophtography photosensor with middle layer of finding record in the patent documentation 2: though electrical characteristics and picture characteristics excellence, but the mean molecular weight of the charge transport agent that can use is limited in 400～1000 scope, is difficult to use the charge transport agent in addition of this scope.

In addition, there is following problems in the Electrophtography photosensor of also finding record in patent documentation 1 and the patent documentation 2: owing to used heat cured phenolic resin in a large number, easily brownization or heavy colourization are difficult to judge by the gimmick of optics the homogeneity of the thickness etc. in middle layer.

Therefore, inventor of the present invention has carried out the result of further investigation, found a kind of Electrophtography photosensor with support matrices, middle layer and photoreceptor layers, this Electrophtography photosensor is by containing titanium dioxide and binding resin in the middle layer, and make the whiteness (Δ L value) or the reflection absorbance (Δ A value) measured with colour difference meter based on JIS Z 8722 standards in this middle layer be the value in the specialized range, when even environmental baseline on every side changes, also can obtain excellent picture characteristics.

That is, the objective of the invention is to, provide a kind of and seldom image fog takes place down hot and humid, and the manufacture method of the Electrophtography photosensor of making easily and such Electrophtography photosensor.

According to the present invention, a kind of Electrophtography photosensor is provided, can address the above problem, described Electrophtography photosensor has support matrices, middle layer and photoreceptor layers, it is characterized in that titanium dioxide and binding resin are contained in the middle layer, simultaneously, Δ L value in this middle layer is to satisfy the value of following relational expression (1), and perhaps Δ A value is to satisfy the value of following relational expression (2).

-5.0≤ΔL≤0 (1)

ΔA≤0.055 (2)

Δ L value: deduct the difference DELTA A value that the L value of independent mensuration support matrices obtains: deduct the difference that the reflection absorbance of independent mensuration support matrices obtains with the reflection absorbance (with the parameter value of colour difference meter mensuration) of the state estimating in formation middle layer on support matrices with the L value of the state estimating that on support matrices, forms the middle layer (based on JIS Z 8722 standards, the parameter value of measuring with colour difference meter)

That is, make Δ L value or Δ A value middle layer, the dispersiveness of the titanium dioxide in this middle layer is become well, and can reduce in the Electrophtography photosensor generation image fog under hot and humid for the value in the specialized range by having.In addition, owing to improved the storage stability of the coating fluid that is used for the middle layer etc., not only can be easily and stably make the middle layer, but also can be easily and stably make photoreceptor layers, thereby the stable Electrophtography photosensor of electrical characteristics can be obtained economically.

In addition, the Δ L value in the middle layer satisfies relational expression (1), and Δ A value can also become the state of the favorable dispersibility of titanium dioxide when satisfying relational expression (2).

In addition, when constituting Electrophtography photosensor of the present invention, preferably will deduct the difference (Δ a value) that a value of independent mensuration support matrices obtains and be set at the interior value of-1.2～0 scopes with a value in the middle layer of the state estimating that on support matrices, forms the middle layer (based on JIS Z 8722 standards, the parameter value of measuring with colour difference meter).

By such formation, the kind of the parameter of measuring with colour difference meter becomes many, thus the dispersiveness of the titanium dioxide that can judge rightly more.Therefore, become better, and can further reduce in the hot and humid image fog that produces down with the balance of electrical insulating property.

In addition, when constituting Electrophtography photosensor of the present invention, preferably will deduct the difference (Δ b value) that the b value of independent mensuration support matrices obtains and be set at the interior value of 0～10 scope with the b value in the middle layer of the state estimating that on support matrices, forms the middle layer (based on JIS Z 8722 standards, the parameter value of measuring with colour difference meter).

By such formation, the kind of the parameter of measuring with colour difference meter becomes more, thus the dispersiveness of the titanium dioxide that can judge rightly more.

In addition, when constituting Electrophtography photosensor of the present invention, preferably the addition of the titanium dioxide that contains in the middle layer being set at respect to 100 weight portion binding resins is value in 150～350 weight portion scopes.

By such formation, the dispersiveness of titanium dioxide and become well with the balance of electrical insulating property, and further reduce more in the hot and humid image fog that produces down.

In addition, when constituting Electrophtography photosensor of the present invention, preferably the average primary particle diameter of titanium dioxide is set at the value in the scope of 0.001～0.1 μ m, is more preferably the value that is set in 0.001～0.015 mu m range.

By such formation, can further improve the dispersiveness of titanium dioxide.

In addition, the average primary particle diameter of such titanium dioxide can make up electron micrograph and image processing apparatus is measured.

In addition, when constituting Electrophtography photosensor of the present invention, the titanium dioxide that contains in the preferred interlayer is coated by organo-silicon compound.

By such formation, can control the water absorptivity of titanium dioxide, can further improve the dispersiveness in binding resin simultaneously.

In addition, when constituting Electrophtography photosensor of the present invention, preferably the mean molecular weight of the binding resin that contains in the middle layer is set at the value in 1000～50000 scopes.

Like this, be set at value in the specialized range, can make the viscosity of the coating fluid when forming the middle layer more suitable, thereby may be controlled to the thickness of homogeneous by mean molecular weight with binding resin.In addition, be set at value in such specialized range by mean molecular weight with binding resin, can be so that the physical strength in the middle layer of arriving and cementability be excellent more.Therefore, not only can significantly improve the mar proof and the permanance in middle layer, and can significantly improve the mar proof and the permanance of photoreceptor layers.

In addition, when constituting Electrophtography photosensor of the present invention, preferably be the value in 0.1～50 mu m range with the thickness setting in middle layer.

By such formation, can make the electronics that in photoreceptor, forms move to support matrices one side rapidly, can make simultaneously and photoreceptor layers between adaptation and better with the balance of mechanical property.

In addition, when constituting Electrophtography photosensor of the present invention, preferably on support matrices, form the lamination-type Electrophtography photosensor of middle layer, charge generating layer, charge transport layer successively.

By such formation, can in the serious lamination-type Electrophtography photosensor of the deterioration that is considered to electrical characteristics usually, obtain to have the excellent light sensitivity and the Electrophtography photosensor of permanance.

In addition, another way of the present invention is a kind of manufacture method of Electrophtography photosensor, this manufacture method is to have support matrices, the manufacture method of the Electrophtography photosensor of middle layer and photoreceptor layers, it is characterized in that, comprise: titanium dioxide is dispersed in contains in the binding resin solution of binding resin and organic solvent, manufacturing is used to form the operation of the coating fluid that is used for the middle layer in middle layer, use this coating fluid that is used for the middle layer to form the operation in middle layer, Δ L value in the described middle layer satisfies following relational expression (1), and perhaps the Δ A value in this middle layer satisfies following relational expression (2).

-5.0≤ΔL≤0 (1)

ΔA≤0.055 (2)

Δ L value: deduct the difference DELTA A value that the L value of independent mensuration support matrices obtains: deduct the difference that the reflection absorbance of independent mensuration support matrices obtains with the reflection absorbance (with the parameter value of colour difference meter mensuration) of the state estimating in formation middle layer on support matrices with the L value of the state estimating that on support matrices, forms the middle layer (based on JIS Z 8722 standards, the parameter value of measuring with colour difference meter)

By making in this wise, can improve the storage stability of the coating fluid that is used to form the middle layer, thereby can be easily and stably form the middle layer of regulation, can make the Electrophtography photosensor of rare image fog under hot and humid simultaneously effectively.

Description of drawings

[Fig. 1] is the figure that is used to illustrate the schematic configuration of the mono-layer electronic photographic photoreceptor that the present invention relates to (a) and (b).

[Fig. 2] is the figure that is used to illustrate the schematic configuration of the lamination-type Electrophtography photosensor that the present invention relates to (a) and (b).

[Fig. 3] is used for illustrating the Δ L value in middle layer and uses the photoreceptor with such middle layer to carry out the figure of relation of the value of the image fog ID of image when forming.

[Fig. 4] is the figure of relation that is used for the bright current potential of the photoreceptor that the Δ L value in middle layer is described and has such middle layer.

[Fig. 5] is used for illustrating the Δ A value in middle layer and uses the photoreceptor with such middle layer to carry out the figure of relation of the value of the image fog ID of image when forming.

[Fig. 6] is the figure of relation that is used for the bright current potential of the photoreceptor that the Δ A value in middle layer is described and has such middle layer.

[Fig. 7] is the figure that is used to illustrate the schematic configuration of the image processing system with Electrophtography photosensor that the present invention relates to.

[Fig. 8] (a) and (b) is the figure of assay method that is used to illustrate the L value in middle layer.

[Fig. 9] (a) and (b) is the figure of assay method that is used to illustrate the reflection absorbance in middle layer.

[Figure 10] is to use the image of the interlayer surfaces of electron microscope observation.(embodiment 8)

[Figure 11] is to use the image of the interlayer surfaces of electron microscope observation.(embodiment 9)

[Figure 12] is to use the image of the interlayer surfaces of electron microscope observation.(embodiment 10)

[Figure 13] is to use the image of the interlayer surfaces of electron microscope observation.(comparative example 4)

[Figure 14] is to use the image of the interlayer surfaces of electron microscope observation.(comparative example 5)

[Figure 15] is to use the image of the interlayer surfaces of electron microscope observation.(comparative example 6)

[Figure 16] is to use the image of the interlayer surfaces of electron microscope observation.(comparative example 7)

Embodiment

[the 1st kind of embodiment]

The 1st kind of embodiment of the present invention be as Fig. 1 (a) with (b), can make have support matrices 13, the mono-layer electronic photographic photoreceptor 10 of middle layer 12 and photoreceptor layers 11., also can be lamination-type Electrophtography photosensor 10 perhaps with support matrices 13, middle layer 12, charge generating layer 34 and charge transport layer 32 as Fig. 2 (a) with (b).And, a kind of Electrophtography photosensor is provided, can address the above problem, it is characterized in that, titanium dioxide and binding resin are contained in middle layer 12 in these Electrophtography photosensors, simultaneously, the Δ L value in this middle layer satisfies following relational expression (1), and perhaps the Δ A value in this middle layer satisfies following relational expression (2).

-5.0≤ΔL≤0 (1)

ΔA≤0.055 (2)

Δ L value: deduct the difference that the L value of the above-mentioned support matrices of independent mensuration obtains with the L value (based on JIS Z 8722 standards, with the parameter value of colour difference meter mensuration) of the state estimating that on support matrices, forms above-mentioned middle layer;

Δ A value: deduct the difference that the reflection absorbance of the above-mentioned support matrices of independent mensuration obtains with the reflection absorbance of the state estimating that on support matrices, forms above-mentioned middle layer (parameter value of measuring with colour difference meter).

At this, as Electrophtography photosensor of the present invention, can be the mono-layer electronic photographic photoreceptor that on support matrices, has middle layer and photographic layer, but be more preferably at the lamination-type Electrophtography photosensor that has formed middle layer, charge generating layer and charge transport layer on the support matrices successively.

Its reason is because can obtain to have the excellent light sensitivity and the Electrophtography photosensor of permanance in the serious lamination-type Electrophtography photosensor of the deterioration that is considered to electrical characteristics usually.

Therefore, below, describe particularly for the situation of using the lamination-type Electrophtography photosensor as the Electrophtography photosensor of the 1st kind of embodiment of the present invention.

1. support matrices

As the illustrative support matrices 13 of Fig. 2, except metal materials such as copper, aluminium, nickel, iron, can also use in surperficial evaporation metal or formation and disperse filming of conducting powder etc. to carry out the stupalith of conductionization processing or polymeric material etc.

2. middle layer

In addition, as illustrated in Fig. 2, it is characterized in that on support matrices 13, being provided with the middle layer 12 of containing binding resin and titanium dioxide.Below, divide binding resin and titanium dioxide to wait the middle layer is described.

(1) binding resin

As binding resin, the 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 acrylic resin.

Here, when using polyamide-based resin, excellent this point of dissolubility to solvent preferably uses pure soluble polyamide resin.As object lesson, preferably use copolymerization nylon 6, nylon 66, NYLON610, nylon 11, nylon 12 etc. be called as the material of copolymer nylon or make the material that is called as modification of nylon of nylon chemical modification as N-alkoxy methyl modification of nylon, N-alkoxyethyl nylon etc.

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

And, polyvinyl butyral resin can obtain by making the reaction of butyraldehyde and polyvinyl alcohol resin, vinyl-formal resin can obtain by making the reaction of formaldehyde and polyvinyl alcohol resin, particularly, because the intermiscibility excellence of these resins and phenolic resin, also excellent with the reactivity and the cementability of phenolic resin simultaneously, be preferred resin therefore.

In addition, preferably the mean molecular weight of binding resin (number-average molecular weight, down with) is set at value in 1000～50000 the scope.

Its reason be because, during the mean molecule quantity not sufficient 1000 of binding resin, the viscosity of the coating fluid when forming the middle layer significantly reduces, according to the mean molecular weight of the cavity conveying agent of adding, sometimes be difficult to obtain the thickness of homogeneous, perhaps physical strength or film forming or cementability significantly reduce.On the other hand, be that perhaps the electric charge movability significantly reduces because when the mean molecular weight of binding resin surpassed 50000, the viscosity of the coating fluid when forming the middle layer significantly increased, and is difficult to control the thickness in middle layer sometimes.

Therefore, be more preferably mean molecular weight with binding resin and be set at value in 2000～30000 the scope, further preferably the mean molecular weight of binding resin is set at the value in 5000～15000 the scope.

In addition, the mean molecular weight of binding resin can use gel permeation chromatography (GPC), as the polystyrene conversion molecular weight determination, perhaps, when binding resin is the condensation resinoid, can be calculated by calculating by condensation degree.

In addition, preferably the solution viscosity (in ethanol/toluene=1/1 solvent, 5 weight % concentration) of binding resin is set at value in 10～200mPasec. scope.

Its reason be because, during the solution viscosity of binding resin is not enough 10mPasec, the film forming in middle layer reduces and makes the film thickness difference become big sometimes, perhaps the physical strength in middle layer or cementability significantly reduce, perhaps the dispersiveness to pigment etc. also reduces.On the other hand, be because when the solution viscosity of binding resin during above 200mPasec., be difficult to form the middle layer of homogeneous thickness etc. sometimes.

Therefore, the solution viscosity (in ethanol/toluene=1/1 solvent, 5 weight % concentration) that is more preferably binding resin is set at the interior value of 30～180mPasec. scope, further is preferably set to the value in 50～150mPasec. scope.

In addition, binding resin is when having the epithelium formation resin of hydroxyl, preferably its amount of hydroxyl groups to be set at the value in 10～40mol% scope.

Its reason be because, when the epithelium with hydroxyl formed the not enough 10mol% of the amount of hydroxyl groups of resin, the physical strength in middle layer or film forming or cementability significantly reduced sometimes, perhaps the dispersiveness to pigment etc. also reduces.On the other hand, be because the amount of hydroxyl groups that forms resin when epithelium during above 40mol% with hydroxyl, the easy gelation that becomes sometimes perhaps is difficult to form the middle layer of homogeneous thickness.

Therefore,, when the epithelium that has a hydroxyl in use forms resin, be more preferably its amount of hydroxyl groups is set at value in 20～38mol% scope, further preferably its amount of hydroxyl groups is set at the value in 25～35mol% scope as binding resin.

(2) titanium dioxide

In addition, it is characterized in that, in the middle layer, when adding above-mentioned binding resin, add titanium dioxide.

Its reason is because because titanium dioxide has the electrical characteristics of regulation, therefore by adding such titanium dioxide, can remove electric charge unnecessary in the photoreceptor layers.Therefore, by adding titanium dioxide, can prevent effectively in the hot and humid image fog that produces down.

Be in addition because, by adding titanium dioxide, can come together to improve the physical strength and the adaptation in middle layer with binding resin.

In addition because, though the light of titanium dioxide is disguised high, by disperseing the titanium dioxide of regulation particle diameter equably, the transparency that can obtain stipulating, and can measure film thickness etc. by the optics gimmick.

Here, with respect to 100 weight portion binding resins, preferably the addition of the titanium dioxide that contains in the middle layer is set at the value in 150～350 weight portion scopes.

Its reason is because by such formation, the dispersiveness of titanium dioxide and the balance of electrical insulating property are become well, and can further reduce in the hot and humid image fog that takes place down.

Therefore, put from the balance of the dispersiveness that can make titanium dioxide and electrical insulating property good this that become, be more preferably with respect to 100 weight portion binding resins, the addition of the titanium dioxide that contains in the middle layer is set at value in 180～320 weight portion scopes, further is preferably set to the value in 200～300 weight portion scopes.

In addition, adopt Electrophtography photosensor of the present invention, consider the occasion of dispersiveness in the middle layer etc., the average aggregate particle size of preferred control titanium dioxide, but also can obtain good dispersiveness etc. by the average primary particle diameter of control titanium dioxide, its result can be adjusted to the L value in middle layer the value in the specialized range.

More specifically, preferably the average primary particle diameter of titanium dioxide is controlled at value in 0.001～0.1 mu m range.

Its reason is because have the titanium dioxide of such average primary particle diameter by use, the transparency that can obtain stipulating, and can measure film thickness etc. by the optics gimmick.That is, if having the titanium dioxide of such average primary particle diameter, then can obtain good dispersiveness, and can be dispersed in the binding resin equably.

Therefore, a mean grain size that is more preferably the titanium dioxide that will contain in the middle layer is set at the value in 0.005～0.05 mu m range, further is preferably set to the value in 0.01～0.015 mu m range.

In addition, the average primary particle diameter of such titanium dioxide or average aggregate particle size can make up electron micrograph and image processing apparatus is calculated.

In addition, the titanium dioxide that contains in the middle layer is preferably coated by organo-silicon compound.

Its reason be because, by such formation, can control the water absorptivity of titanium dioxide, simultaneously can further improve dispersiveness.

At this,, preferably the treatment capacity of organo-silicon compound is set at the value in 1～50 weight portion scope with respect to titanium dioxide 100 weight portions that contain in the middle layer.

Its reason is because during treatment capacity less than 1 weight portion of such organo-silicon compound, be difficult to obtain the treatment effect of organo-silicon compound sometimes, and dispersiveness can not improve.On the other hand, be because when the treatment capacity of such organo-silicon compound surpasses 50 weight portions, be difficult to bring into play effectively the electrical characteristics of titanium dioxide sometimes.

Therefore, put from the balance of the dispersiveness that can make titanium dioxide and electrical insulating property good this that become, be more preferably with respect to titanium dioxide 100 weight portions that contain in the middle layer, the treatment capacity of organo-silicon compound is set at value in 5～40 weight portion scopes, further is preferably set to the value in 10～30 weight portion scopes.

In addition, as the organo-silicon compound that preferably use in the present invention, can enumerate, alkyl silane cpd, alkoxysilane compound containing trialkylsilyl group in molecular structure, contain vinyl silane compound, contain sulfydryl silane compound, contain amino silane compound or as their polysiloxane compound of condensed polymer.

As more concrete organo-silicon compound, can preferably use dimethyl siloxane or as dimethyl silicone polymer of its condensed polymer etc.

(3) Δ L value (based on JIS Z 8722 standards)

In addition, it is characterized in that, when constituting Electrophtography photosensor of the present invention, deduct the difference (Δ L value) that the L value of independent mensuration support matrices obtains with the L value (based on JIS Z 8722 standards, with the parameter value of colour difference meter mensuration) in the middle layer of the state estimating that on support matrices, forms the middle layer and satisfy following relational expression (1).

-5.0≤ΔL≤0 (1)

Its reason is because by possessing the middle layer of the Δ L value with such scope, the dispersiveness of the titanium dioxide in this middle layer is become well, and reduce Electrophtography photosensor in the hot and humid image fog that produces down.

In addition also because, remain on proper state by dispersiveness with the titanium dioxide in the middle layer, can improve the storage stability of the coating fluid that is used for the middle layer etc.Therefore, not only can be easily and stably make the middle layer, but also can be easily and stably make photoreceptor layers, thereby can obtain the stable Electrophtography photosensor of electrical characteristics economically.

In addition, as the optical characteristics in middle layer,, can confirm that the dispersiveness of the titanium dioxide in the middle layer is preferred state as long as any one of above-mentioned Δ L value and Δ A value described later is the value in the specialized range.But when Δ L value satisfies relational expression (1), and Δ A value can make the dispersiveness of titanium dioxide become good state more when satisfying relational expression (2).

At this, to the Δ L value in this middle layer and the relation of using photoreceptor to carry out the image fog ID of image when forming with such middle layer describe.That is, specifically describe Δ L value (-) in the middle layer and the relation of image fog ID (-) with reference to Fig. 3.

Fig. 3 is the family curve of image fog ID (-), the transverse axis of the longitudinal axis when adopt forming image when adopting Δ L value (-) in the middle layer that constitutes such photoreceptor.

From this family curve as can be known, along with the Δ L value in the middle layer by-7.0 near 0, the value of image fog ID diminishes.Therefore as can be known, for the value that makes image fog ID is little value, keeping the Δ L value in the middle layer is effective for bigger value.

More specifically, be the value in-5.0～0 scope by making the Δ L value in the middle layer, the value that can make image fog ID is 0.008 or littler value.Therefore, be more preferably this Δ L value is set at value in-4.0～0 scopes, further be preferably set to the value in-3.0～0 scopes.

In addition, because the assay method of the Δ L value in the middle layer and the assay method of image fog ID elaborate in embodiment described later, therefore here omit.

In addition, Δ L value in this middle layer and relation with the bright current potential in the photoreceptor in such middle layer are described.That is, specifically describe the Δ L value (-) in the middle layer and the relation of bright current potential (V) with reference to Fig. 4.

Fig. 4 is the family curve of absolute value (V), the transverse axis of the bright current potential of the longitudinal axis when adopt forming image when adopting Δ L value (-) in the middle layer that constitutes such photoreceptor.

From this family curve as can be known, along with the Δ L value in the middle layer by-7.0 near 0, the absolute value of bright current potential (V) diminishes.Therefore as can be known, for the absolute value (V) that makes bright current potential diminishes, keeping the Δ L value in the middle layer is effective for bigger value.

More specifically, be the value in-5.0～0 scope by making the Δ L value in the middle layer, the value that can make the absolute value (V) of bright current potential is about 30 (V) or littler value.Therefore, be more preferably this Δ L value is set at value in-4.0～0 scopes, further be preferably set to the value in-3.0～0 scopes.

In addition, the assay method of bright current potential (V) elaborates in embodiment described later, therefore here omits.

(4) Δ a value (based on JIS Z 8722 standards)

In addition, when constituting Electrophtography photosensor of the present invention, preferably will deduct the difference (Δ a value) that a value of independent mensuration support matrices obtains and be set at the interior value of-1.2～0 scopes with a value in the middle layer of the state estimating that on support matrices, forms the middle layer (based on JIS Z 8722 standards, the parameter value of measuring with colour difference meter).

Its reason is because by considering the Δ a value of such scope, the kind change of the parameter of measuring with colour difference meter is many, the dispersiveness of the titanium dioxide that can judge rightly more.Its result becomes better with the balance of electrical insulating property, and can further reduce in the hot and humid image fog that produces down.Therefore, be more preferably this Δ a value is set at value in-0.8～-0.2 scope, further be preferably set to the value in-0.6～-0.3 scope.

(5) Δ b value (based on JIS Z 8722 standards)

In addition, when constituting Electrophtography photosensor of the present invention, preferably will deduct the difference (Δ b value) that the b value of independent mensuration support matrices obtains and be set at the interior value of 0～10 scope with the b value in the middle layer of the state estimating that on support matrices, forms the middle layer (based on JIS Z 8722 standards, the parameter value of measuring with colour difference meter).

Its reason is because by considering the Δ b value of such scope, the kind change of the parameter of measuring with colour difference meter is many, the dispersiveness of the titanium dioxide that can judge rightly more.Its result becomes better with the balance of electrical insulating property, and can further reduce in the hot and humid image fog that produces down.Therefore, be more preferably this Δ b value is set at value in 1～6 scope, further be preferably set to the value in 2～4 scopes.

(6) reflection absorbance (Δ A value)

In addition, it is characterized in that, when constituting Electrophtography photosensor of the present invention, (root thickness: the reflection absorbance in the middle layer of state estimating 2 μ m) (parameter value of measuring with colour difference meter) deducts the difference (Δ A value) that the reflection absorbance of independent mensuration support matrices obtains and satisfies following relational expression (2) to form the middle layer on above-mentioned support matrices.

ΔA≤0.055 (2)

Its reason be because, be 0.055 or littler value by the reflection absorbance in the middle layer that makes specific thickness (Δ A value), the disperse state that can judge the titanium dioxide in this middle layer is preferred state.

That is, the disperse state of the titanium dioxide in the middle layer is inhomogeneous more, and the aggregated particle of white more can be residual, and the scattering during to the middle layer irradiates light becomes many more.Therefore, the reflection absorbance in the middle layer (Δ A value) becomes big value.On the other hand, because the disperse state of the titanium dioxide in the middle layer is even more, the aggregated particle of white more can be not residual, and therefore, the scattering during to the middle layer irradiates light becomes few more.Therefore, the reflection absorbance in the middle layer (Δ A value) becomes little value.

Therefore, the reflection absorbance in the middle layer (Δ A value) can judge as long as be 0.055 or littler value, and when content of titanium dioxide etc. was specialized range, the disperse state of the titanium dioxide in the middle layer was preferred state.And by using such middle layer, the electrical characteristics in the photoreceptor improve, and can prevent in the hot and humid image fog that produces down.In addition, because the storage stability that is used to form the coating fluid that is used for the middle layer in such middle layer also improves, not only the manufacturing in middle layer becomes easily, and can be easily and stably make photoreceptor layers.

But, the reductions such as content of the titanium dioxide that in the middle layer, contains, the reflection absorbance in the middle layer (Δ A value) is difficult to electric charge residual in the photographic layer is discharged in the conductive base effectively when too diminishing sometimes.Therefore, about the lower limit of the reflection absorbance in the middle layer (Δ A value), be preferably set to 0.005 or bigger value.

Therefore, be more preferably the reflection absorbance in the middle layer (Δ A value) is set at the interior value of 0.008～0.05 scope, be more preferably the value in 0.01～0.045 scope that is set at.

In addition, when the thickness in middle layer changes, can be assumed to the value that root thickness is adjusted the reflection absorbance.For example, when the thickness in middle layer is 4 μ m, the value of the reflection absorbance that obtains can be adjusted into 1/2.

In addition,, can confirm that as long as above-mentioned Δ L value and Δ A value or any one are the interior value of specialized range, then the dispersiveness of the titanium dioxide in the middle layer is preferred state as the optical characteristics in middle layer.But explanation is again, and when Δ L value satisfies relational expression (1), and Δ A value can make the dispersiveness of titanium dioxide become good state more when satisfying relational expression (2).

At this, to (Δ A) value of the reflection absorbance in such middle layer and the relation of using photoreceptor to carry out the image fog ID of image when forming with such middle layer describe.That is, specifically describe the relation of reflection absorbance (Δ A value) (-) and image fog (ID) (-) in the middle layer with reference to Fig. 5.

Fig. 5 is the family curve of image fog (ID) (-), the transverse axis of the longitudinal axis when adopt forming image when adopting Δ A value (-) in the middle layer that constitutes such photoreceptor.

From this family curve as can be known, along with the Δ A value in the middle layer becomes big, it is big that the value of image fog ID also becomes.Therefore as can be known, for the value that keeps image fog ID is a low value, keeping the Δ A value in the middle layer is effective for low value.More specifically, be 0.055 or littler value by making Δ A value in the middle layer as can be known, the value that can make image fog ID is the value of less than 0.008.

In addition, because the assay method of the Δ A value in the middle layer and the assay method of image fog ID elaborate in embodiment described later, therefore here omit.

Then, the reflection absorbance in the above-mentioned middle layer (Δ A value) and the relation of electrical characteristics with the photoreceptor in such middle layer are described.That is, specifically describe the Δ A value (-) in the middle layer and the relation of bright current potential (V) with reference to Fig. 6.

Fig. 6 is absolute value, transverse axis that the longitudinal axis adopts the bright current potential in the photoreceptor family curve when adopting Δ A value (-) in the middle layer that constitutes such photoreceptor.

From this family curve as can be known, along with the Δ A value in the middle layer becomes big, it is big that the absolute value of bright current potential also becomes.Therefore as can be known, for the absolute value that makes bright current potential is a low value, and the light sensitivity height of maintenance photoreceptor, keeping the Δ A value in the middle layer is effective for low value.More specifically, be 0.055 or littler value by making Δ A value in the middle layer as can be known, can make the absolute value of the bright current potential of photoreceptor be the value of not enough approximately 30V.

In addition, because the assay method of the Δ A value in the middle layer and the assay method of the bright current potential in the photoreceptor elaborate in embodiment described later, therefore here omit.

(7) adjuvant

In addition, to interfere striped in order preventing to produce light scattering and to improve dispersiveness, preferably in the middle layer, add the various adjuvants (organic attritive powder or inorganic attritive powder) different with electron transport pigment.

Particularly, preferred additives is: Chinese white such as zinc paste, zinc white, zinc sulphide, white lead, lithopone or aluminium oxide, lime carbonate, barium sulphate etc. are as the inorganic pigment of filler pigment or fluororesin particle, benzo guanamine resin particle, styrene resin particle etc.

In addition, during adjuvants such as interpolation attritive powder, preferably its particle diameter is set at the value in 0.01～3 mu m range.Its reason is because when this particle diameter was excessive, the concavo-convex change in middle layer sometimes was big, or produces electric uneven part, perhaps is easy to generate the image quality defective.On the other hand, be owing to when this particle diameter is too small, can not obtain sufficient light scattering effect sometimes.

In addition, when adding adjuvant such as fine powder, its addition, is preferably set to 1～70 weight %, is more preferably the value in 5～60 weight % scopes that are set in weight ratio with respect to the solid constituent in middle layer.

In addition, also preferably in the middle layer, add the cavity conveying agent.That is,, can make the electronics that forms at charge generating layer promptly move to the matrix side, can prevent that electronics from accumulating in the middle layer and residual electric potential is risen, thereby can show stable electric characteristics by containing the cavity conveying agent.

As such cavity conveying agent, can use known in the past all cpds, particularly, can enumerate the diphenyl amine compound, the phenylenediamine compound, the naphthylenediamine compounds, luxuriant and rich with fragrance diamine compounds,  diazoles compound, compound of styryl, carbazole compound, pyrazoline compounds, hydrazone compounds, the triphenylamine compounds, Benzazole compounds, the  azole compounds, different  azole compounds, thiazole compound, thiadiazole compound, glyoxaline compound, pyrazole compound, triazole class compounds, butadiene compounds, pyrene-hydrazone compounds, the acryl aldehyde compounds, carbazole-hydrazone compounds, quinoline-hydrazone compounds, stilbenes compound, Stilbene-hydrazone compounds, and diphenylene diamine compounds a kind of or the combination of two or more.

(8) film thickness

In addition, because the middle layer, can be improved the concavo-convex disguise of supporting in the base material by thickening film thickness, therefore, be preferred aspect the image quality defective that reduces point-like, but in contrast, having the tendency of electrical characteristics such as the rising reduction of residual electric potential.

Therefore, preferably the film thickness in middle layer is set at the value in 0.1～50 mu m range, is more preferably the value that is set in 1～30 mu m range.

3. photoreceptor layers

(1) charge generating layer

Charge generating layer preferably forms by the vacuum evaporation charge generating, perhaps disperses with organic solvent and binding resin, and forms by coating.

As such charge generating, can enumerate, noncrystalline selenium, crystallinity selenium, selenium-tellurium alloy, selenium-arsenic alloy, other selenium compound and various phthalocyanine colors such as mineral-type light conductive material, metal-free phthalocyanine, phthalocyanine titanium, CuPc, phthalocyanine tin, phthalocyanine gallium, chlorination phthalocyanine indium, side's acid such as selenium alloy, zinc paste, titanium dioxide in  salt (squarylium) class, aromatic series polycyclic compund class, azo class, pyrans  salt, thiapyran  salt etc. a kind of or the combination of two or more.

In addition, these organic pigments have multiple crystal habit, particularly phthalocyanine pigment usually, and the known various crystal habits that have headed by α, the β etc. so long as can obtain being fit to the pigment of the light sensitivity of purpose, then can use any crystal habit.

In addition, as the binding resin that uses in the charge generating layer, can enumerate bisphenol A-type, polycarbonate resins such as bisphenol Z type or bisphenol-c type, vibrin, methacrylic resin, acrylic resin, Corvic, polystyrene resin, polyvinyl acetate resins, the Styrene-Butadiene resin, the vinylidene chloride-acrylonitrile copolymer resin, chloroethylene-vinyl acetate-maleic acid acid anhydride resin, silicones, polysiloxane-alkyd resin, phenolics, styrene-alkyd resin, N-vinylcarbazole etc. a kind of or the combination of two or more.

In addition, when adding these binding resins, preferably the match ratio (weight ratio) with charge generating and binding resin is set at 10: 1～1: 10 interior value of scope.

In addition, the film thickness of charge generating layer is set at 0.01～5 μ m usually, is preferably set to the value in 0.05～2.0 mu m range.

In addition, as making charge generating be dispersed in method in the binding resin, can use the method for roller mill, bowl mill, vibromill, vertical ball mill, Dai Nuomo, sand mill, colloid mill etc.

(2) charge transport layer

In addition, as the charge transport agent of using in the charge transport layer (cavity conveying agent and electron transporting agent), can enumerate, 2, two (to the diethylamino phenyl)-1 of 5-, 3,  oxadiazole derivatives such as 4- diazole, 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) phenyl amine, N, N-two (3, the 4-3,5-dimethylphenyl) biphenyl-4-amine, aromatic uncle amine compounds such as dibenzyl aniline, N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-[1, the 1-xenyl]-4, aromatic series tertiary diamine compounds such as 4 '-diamines, 3-(4 '-dimethylaminophenyl)-5,6-two (4 '-methoxyphenyl)-1,2,4-triamine etc. 1,2, the 4-triamine derivative, 4-dimethylamino 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, to (2, the 2-diphenylacetylene)-and N, α-stilbene derivatives such as N-diphenyl aniline, enamine derivates, carbazole derivates such as N-vinylcarbazole, cavity conveying materials such as poly N-vinyl carbazole and derivant thereof; Quinones, tetra cyanogen subculture dimethyl benzene quinone compounds, 2 such as chloranil, tetrabromoquinone, anthraquinone, 4,7-trinitro-fluorenone, 2,4,5, electron transport materials such as Fluorenone compounds such as 7-tetranitro-9-Fluorenone, xanthone compounds, thiophene compound, connection 1,4-benzoquinone compound; And have polymkeric substance etc. a kind of of the group that comprises above-claimed cpd or a combination of two or more at main chain or side chain.

In addition, as the binding resin that uses in the charge transport layer, particularly, can enumerate electrical polymkeric substance of organic light-guide such as insulative resin such as polycarbonate resin, polystyrene, acrylonitritrile-styrene resin, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfones, polyacrylamide, polyamide, chlorinated rubbers such as acrylic resin, polyarylate, vibrin, bisphenol A-type, bisphenol Z type or bisphenol-c type or Polyvinyl carbazole, polyvinyl anthracene, polyvinyl pyrene etc. and their copolymer resin.

In addition, charge transport layer can form by dry after coating is dissolved in charge transport agent and binding resin solution in the appropriate solvent.

The solvent that uses during as such formation charge transport layer, can enumerate, for example, ring-type or straight chain shape ether or their mixed solvents etc. such as halogenated aliphatic hydrocarbon classes such as ketone, methylene chloride, chloroform, vinyl chloride such as aromatic hydrocarbon such as benzene, toluene, chlorobenzene, acetone, 2-butanone, tetrahydrofuran, two  alkane, ethylene glycol, ether.

In addition, preferred 10: 1～1: 5 scope of the match ratio of charge transport agent and binding resin.In addition, the film thickness of charge transport layer is set at 5～50 μ m usually, is preferably set to the value in 10～40 mu m ranges.

In addition, in order to prevent because the deterioration of the photoreceptor that the ozone that produces or oxidizing gas or light, heat cause in the electro-photography apparatus is preferably added antioxidant, light stabilizer, thermal stabilizer etc. in photoreceptor layers.

For example, as antioxidant, can use hindered phenol, hindered amine, p-phenylenediamine (PPD), aryl alkane, quinhydrones, volution chroman, volution indone and their derivant, organosulfur compound, organic phosphorus compound etc.In addition, as light stabilizer, can enumerate the derivant of benzophenone, benzotriazole, dithiocarbamate, tetramethyl piperidine etc.

4. mono-layer electronic photographic photoreceptor

In addition, when constituting Electrophtography photosensor of the present invention, photographic layer preferably has the mono-layer electronic photographic photoreceptor 10 of support matrices 13, middle layer 12 and photoreceptor layers 11 as illustrated in Fig. 1 (a).

And, shown in Fig. 1 (b), also preferably on photographic layer 11, protective seam 11 ' is set.

In addition, in mono-layer electronic photographic photoreceptor, with the lamination-type Electrophtography photosensor similarly, the middle layer can be set.On the other hand, as the photographic layer that on the middle layer, is provided with, can be by preparing the coating fluid that is used for photographic layer with the dispersion medium dispersing and mixing with the same charge generating of lamination-type Electrophtography photosensor, charge transport agent, binding resin etc., then this coating fluid is coated on the middle layer and and forms by dry.

In addition, with respect to binding resin 100 weight portions, preferably the content with the charge generating in such single-layer type photoreceptor is set at the interior value of 0.1～50 weight portion scope, is more preferably the value in 0.5～30 weight portion scope that is set at.

In addition,,, be preferably set to the value in 1～120 weight portion scope, be more preferably the value in 5～100 weight portion scopes that are set at respect to 100 weight portion binding resins for the content of cavity conveying agent.

In addition, for the content of electron transporting agent, with the cavity conveying agent similarly, with respect to 100 weight portion binding resins, be preferably set to the value in 1～120 weight portion scope, be more preferably the value in 5～100 weight portion scopes that are set at.

In addition,, be preferably set to the value in 5.0～100 mu m ranges, be more preferably the value that is set in 10～80 mu m ranges for the thickness of photographic layer.

5. image processing system

(1) basic structure

Then, the basic structure of the image processing system that the present invention relates to 50 shown in Figure 7.The structure of this image processing system 50 is, photoreceptor 10 with drum-shape, around this photoreceptor 10, dispose once charged device 14a, exposure device 14b, developer 14c, transfer belt electrical equipment 14d, separating belt electrical equipment 14e, cleaning device 18 successively and remove electrical equipment 23 along the sense of rotation of representing with arrow A.

In addition, along the throughput direction shown in the arrow B, swim side from it and carry recording materials P by feed roll 19a, 19b and conveying belt 21 successively, and in its way, dispose fixing roller 22a and the backer roll 22b that is used to make toner fixing and forms image.

And photoreceptor 10 has the middle layer 12 of afore mentioned rules on support matrices 13.Therefore, be middle layer with homogeneous thickness, simultaneously,, still can show excellent electrical characteristics or picture characteristics through long-time.

(2) operation

The basic operation of image processing system 50 then, is described with reference to Fig. 7.

At first, the photoreceptor 10 that makes this image processing system 50 by drive unit (not shown) is in process speed (peripheral speed) rotation of the direction shown in the arrow A with regulation, makes the polarity and the current potential of its surface charging regulation simultaneously by Charging system 14a.For example, under the situation of the mode that conductive elastic roller is contacted with photosensitive surface, preferably apply the DC voltage about 1～2KV, make it just charged 50～2000V.

Then, carry out optical modulation according to image information by exposure device 14b such as laser, LED, simultaneously by irradiates lights such as catoptrons, the surface of exposure photoreceptor 10.By this exposure, form electrostatic latent image on the surface of photoreceptor 10.

Then, based on electrostatic latent image by the developer 14c developer (toner) that develops.That is, in developer 14c, by the development sleeve that holds and have a toner being applied the development bias voltage of regulation, toner adheres to corresponding to the electrostatic latent image of photoreceptor 10, thereby forms toner image.

Then, be transferred on the recording materials P at the toner image that forms on the photoreceptor 10.These recording materials P after give carton (not shown) paper feeding, adjusts the toner image and regularly synchronously on the photoreceptor 10 by feed roll 19a, 19b, supplies to the transfer printing portion between photoreceptor 10 and the transfer belt electrical equipment 14d.And the toner image on the photoreceptor 10 can be by applying the transfer bias of regulation to transfer belt electrical equipment 14d and positively being transferred on the recording materials P.

Then, the recording materials P after the toner image transfer printing, is transported in the fuser by conveying belt 21 from photoreceptor 10 surface isolation by separating belt electrical equipment 14e.At this, carry out heat treated and pressurized treatments by fixing roller 22a and backer roll 22b, toner image is discharged to the outside of image processing system 50 by distributing roller (not shown) after surperficial photographic fixing.

On the other hand, photoreceptor 10 after the toner image transfer printing continues rotation with keeping intact, the remaining toner (attachment) that is not transferred to when transfer printing on the recording materials P is removed from the surface of photoreceptor 11 by cleaning device 18, and photoreceptor 10 is supplied with image formation next time simultaneously.

And as mentioned above, photoreceptor 10 is owing to the middle layer 12 that has regulation on support matrices 13, through still showing for a long time excellent electrical characteristics and picture characteristics.

[the 2nd kind of embodiment]

The 2nd kind of embodiment of the present invention is a kind of manufacture method of Electrophtography photosensor, this manufacture method is to have support matrices, the manufacture method of the Electrophtography photosensor of middle layer and photoreceptor layers, it is characterized in that, comprise: titanium dioxide is dispersed in contains in the binding resin solution of binding resin and organic solvent, manufacturing is used to form the operation of the coating fluid that is used for the middle layer in above-mentioned middle layer, with the operation of using this coating fluid that is used for middle layer formation middle layer, Δ L value in the described middle layer satisfies following relational expression (1), perhaps the Δ A value in this middle layer satisfies following relational expression (2)

-5.0≤ΔL≤0 (1)

ΔA≤0.055 (2)

Δ L value: deduct the difference that the L value of independent mensuration support matrices obtains with the L value (based on JIS Z 8722 standards, with the parameter value of colour difference meter mensuration) of the state estimating that on support matrices, forms the middle layer;

Δ A value: deduct the difference that the reflection absorbance of independent mensuration support matrices obtains with the reflection absorbance of the state estimating that on support matrices, forms the middle layer (parameter value of measuring with colour difference meter).

Below, be that the center describes particularly with explanation difference with the 1st kind of embodiment.

1. the preparation of support matrices

In order to prevent to produce interference fringe, method is carried out the asperities processing to the surface of support matrices preferably to use etching, anodic oxidation, wet shotcrete technology method, sand-blast, rough cut, be not in the mood for cutting etc.

2. the formation in middle layer

(1) is used for the preparation of the coating fluid in middle layer

In addition, when forming the middle layer, preferably in the solution that has dissolved resinous principle, add cavity conveying agent etc., and carry out dispersion treatment, form coating fluid.

In addition, the method for carrying out dispersion treatment is not particularly limited, preferred usually known roller mill, bowl mill, vibromill, vertical ball mill, sand mill, colloid mill, the coating wobbler etc. of using.

In addition, when manufacturing is used for the coating fluid in middle layer, preferably divide the multistage to make the binding resin dissolving, mix with titanium dioxide simultaneously.

More specifically, when manufacturing is used for the coating fluid in middle layer, preferably comprise following operation (A)～(B).

(A) titanium dioxide is added to the binding resin of 31～65 weight % that dissolved the total binding resin amount that is equivalent to constitute the middle layer and in the binding resin solution that forms, make the operation of a dispersion liquid

(B) dissolving is equivalent to the binding resin of 35～69 weight % of total binding resin amount in dispersion liquid, makes the operation of the coating fluid that is used for the middle layer

Its reason be because, be regardless of the multistage, initial when just the titanium dioxide of the binding resin of total amount, total amount and organic solvent being mixed with a stage, Titanium particles surperficial with resin the ratio that contacts, with the ratio that contacts of the organic solvent heterogeneity that becomes easily.Therefore, this be because, the character of titania surface that is used for the coating fluid in middle layer changes the dispersiveness deterioration of titanium dioxide sometimes etc.When mixing, when particularly using average primary particle diameter to be 0.015 μ m or littler titanium dioxide, dispersedly sometimes significantly reduce with a stage.

On the other hand also because, when being provided with (A), (B) two operations, at first, because the titanium dioxide in dispersion liquid becomes very high concentration in (A) operation, therefore, the ratio that contacts of each Titanium particles surface and resin, with the ratio that contacts of the organic solvent homogeneous that becomes easily.Therefore, in (B) operation of following, even added the state of total interpolation amount of resin, the dispersiveness of titanium dioxide also can keep under certain state.Its result, the storage stability that is used for the coating fluid in middle layer improves, can be easily and stably form the middle layer of regulation, simultaneously, use this coating fluid that is used for the middle layer, can make the Electrophtography photosensor of rare image fog under hot and humid effectively.

Therefore, preferably the amount of the binding resin that will add in operation (A) is set at the component of 35～60 weight % that are equivalent to total binding resin, is more preferably and is set at the component that is equivalent to 40～55 weight %.

(2) be used for the coating process of the coating fluid in middle layer

In addition, be not particularly limited, can use rubbing methods such as dip coated method, spraying process, drop rubbing method, scraper rubbing method, rolling method for the coating process of the coating fluid that is used for the middle layer.

In addition, for more stably form the middle layer with and on photographic layer, wish after coating is used for the coating fluid in middle layer, handle at 30～200 ℃ of heat dryings of implementing down 5 minutes～2 hours.

3. the formation of photographic layer

In addition, preferably after preparing the photoreceptor layers coating fluid, use rubbing methods such as dip coated method, spraying process, drop rubbing method, scraper rubbing method, rolling method to form photoreceptor layers.In addition, do not use when adding wet processing methods, carry out heat drying behind the preferred dry to touch at room temperature.And, as the condition of heat drying, for example, be preferably set under 30～200 ℃, 5 minutes～2 hours scope.

Embodiment

Below, more specifically describe the present invention by embodiment, but the present invention is not subjected to the qualification of these record contents.

1. be used for the making of the coating fluid A in middle layer

Adding 150 weight portions in container carries out carrying out (the TAYCA manufacturing of surface-treated titanium dioxide with the hydrogenated methyl polysiloxane again after the surface treatment with aluminium oxide and silicon dioxide, SMT-02, number average primary particle size: 10nm), 100 weight portions carry out the surface-treated titanium dioxide with aluminium oxide and silicon dioxide, and (TAYCA makes, MT-05, number average primary particle size: 10nm), 600 weight portion methyl alcohol, 150 weight portion butanols, (make in east beautiful (strain) to be dissolved in the Amilan CM8000 of 50 weight portions in the butanols of the methyl alcohol of 200 weight portions and 50 weight portions in advance, quarternary copolymerized polyamide) after, use ball mill (medium: the zirconium oxide bead of diameter 0.5mm) mixed 1 hour, make dispersion soln 1 time.

Then, behind the Amilan CM8000 of 50 weight portions in the butanols that adds the methyl alcohol be dissolved in 200 weight portions in advance and 50 weight portions, use the coating wobbler to mix 1 hour, carry out 2 times and disperse, make the coating fluid A that is used for the middle layer.

In addition, about the addition of each constituent material of the above-mentioned coating fluid that is used for the middle layer, with the total amount of the Amilan CM8000 that joins the coating fluid that is used for the middle layer as datum quantity (100 weight portion).At the following coating fluid that is used for the middle layer also is same.

2. be used for the making of the coating fluid B in middle layer

The coating fluid B that is used for the middle layer disperses except carrying out adopting 1 time of ball mill in 2 hours, and carries out adopting in 2 hours beyond 2 dispersions of coating wobbler, similarly makes with the coating fluid A that is used for the middle layer.

3. be used for the making of the coating fluid C in middle layer

The coating fluid C that is used for the middle layer similarly makes with the coating fluid A that is used for the middle layer except 2 dispersions carrying out 0.5 hour employing coating wobbler.

4. be used for the making of the coating fluid D in middle layer

The coating fluid D that is used for the middle layer similarly makes with the coating fluid A that is used for the middle layer except 1 dispersion carrying out 0.5 hour employing ball mill.

5. be used for the making of the coating fluid E in middle layer

The coating fluid E that is used for the middle layer disperses except carrying out adopting 1 time of ball mill in 0.5 hour, and to adopting beyond 2 times of coating wobbler disperse also to carry out 0.5 hour, similarly makes with the coating fluid A that is used for the middle layer.

6. be used for the making of the coating fluid F in middle layer

SMT-500SAS (the number average primary particle size: 35nm) replace SMT-02 (number average primary particle size: 10nm) as with aluminium oxide and silicon dioxide carry out surface treatment after again with hydrogenated methyl polysiloxane carry out surface-treated titanium dioxide of coating fluid F that is used for the middle layer except using TAYCA to make, simultaneously, MT-600BS (the number average primary particle size: 35nm) replace MT-05 (number average primary particle size: that uses TAYCA to make 10nm) as only carrying out the surface-treated titanium dioxide with aluminium oxide and silicon dioxide, and, carry out adopting in 2 hours and disperse for 1 time of ball mill, and carry out adopting in 2 hours beyond 2 dispersions of coating wobbler, similarly make with the coating fluid A that is used for the middle layer.

7. be used for the making of the coating fluid G in middle layer

The coating fluid G that is used for the middle layer disperses except carrying out adopting 1 time of ball mill in 1 hour, and to adopting beyond 2 times of coating wobbler disperse also to carry out 1 hour, similarly makes with the coating fluid F that is used for the middle layer.

8. be used for the making of the coating fluid H in middle layer

The coating fluid H that is used for the middle layer is except adding 250 weight portions as SMT-02 (the number average primary particle size: 10nm) and not add as MT-05 (the number average primary particle size: 10nm), similarly make with the coating fluid A that is used for the middle layer that only carries out the surface-treated titanium dioxide with aluminium oxide and silicon dioxide that carries out carrying out with the hydrogenated methyl polysiloxane again after the surface treatment surface-treated titanium dioxide with aluminium oxide and silicon dioxide.

9. be used for the making of the coating fluid I in middle layer

The coating fluid I that is used for the middle layer disperses except carrying out adopting 1 time of ball mill in 0.5 hour, and to adopting beyond 2 times of coating wobbler disperse also to carry out 0.5 hour, similarly makes with the coating fluid H that is used for the middle layer.

10. be used for the making of the coating fluid J in middle layer

The coating fluid J that is used for the middle layer disperses except carrying out adopting 1 time of ball mill in 1 hour, and carries out adopting in 0.5 hour beyond 2 dispersions of coating wobbler, similarly makes with the coating fluid H that is used for the middle layer.

In addition, be used for the composition of coating fluid A～J in middle layer and the summary of manufacturing process and be shown in table 1.

11. be used for the making of the coating fluid K in middle layer

The coating fluid K that is used for the middle layer is dissolved in the butanols of the methyl alcohol of 140 weight portions and 35 weight portions except use the Amilan CM8000 of 35 weight portions is dissolved in Amilan CM8000 in the solvent in advance as what add when once disperseing, and the Amilan CM8000 that uses 65 weight portions in the butanols of the methyl alcohol be dissolved in 260 weight portions and 65 weight portions is dissolved in Amilan CM8000 in the solvent in advance as interpolation when secondary disperses, and the mixing when secondary is disperseed is same the use beyond ball mill carries out when once disperseing, and similarly makes with the coating fluid A that is used for the middle layer.

12. be used for the making of the coating fluid L in middle layer

The coating fluid L that is used for the middle layer is except the medium of the zirconium oxide bead that the uses diameter 1mm ball mill when once disperseing, and the mixing when secondary is disperseed is same the use beyond ball mill carries out when once disperseing, and similarly makes with the coating fluid A that is used for the middle layer.

13. be used for the making of the coating fluid M in middle layer

The coating fluid M that is used for the middle layer uses the Amilan CM8000 of 60 weight portions of the butanols of the methyl alcohol be dissolved in 240 weight portions and 60 weight portions to be dissolved in Amilan CM8000 in the solvent in advance as what add when once disperseing, and the medium of the ball mill of the zirconium oxide bead that uses diameter 1mm when once disperseing.In addition, the Amilan CM8000 that use is dissolved in 40 weight portions in the butanols of the methyl alcohol of 160 weight portions and 40 weight portions is dissolved in Amilan CM8000 in the solvent in advance as what add when secondary disperses, and the mixing when secondary is disperseed and similarly use ball mill to carry out when once disperseing.In addition, similarly make with the coating fluid A that is used for the middle layer.

14. be used for the making of the coating fluid N in middle layer

The coating fluid N that is used for the middle layer is that (medium: the zirconium oxide bead of diameter 1mm) titanium dioxide, 1000 weight portion methyl alcohol, 250 weight portion butanols, the 100 weight portion Amilan CM8000 of the titanium dioxide identical type same amount that will use with the coating fluid A that is used for the middle layer mix 10 hours, and do not carry out secondary and make dispersedly with ball mill.

15. be used for the making of the coating fluid O in middle layer

The coating fluid O that is used for the middle layer is that (medium: the zirconium oxide bead of diameter 0.5mm) titanium dioxide, 600 weight portion methyl alcohol, the 150 weight portion butanols of the titanium dioxide identical type same amount that will use with the coating fluid A that is used for the middle layer mixed 1 hour, made dispersion soln 1 time with ball mill.

Then, add the CM8000 of 100 weight portions in the butanols of the methyl alcohol be dissolved in 400 weight portions in advance and 100 weight portions after, and once disperse similarly to use ball mill to mix 1 hour, carry out 2 dispersions, make the coating fluid O that is used for the middle layer.

16. be used for the making of the coating fluid P in middle layer

The coating fluid P that is used for the middle layer is to use the Amilan CM8000 of 10 weight portions of the butanols of the methyl alcohol that is dissolved in 40 weight portions and 10 weight portions to be dissolved in Amilan CM8000 in the solvent in advance as what add when once disperseing, and the medium of the ball mill of the zirconium oxide bead that uses diameter 1mm when once disperseing.In addition, the Amilan CM8000 that use is dissolved in 90 weight portions in the butanols of the methyl alcohol of 360 weight portions and 90 weight portions is dissolved in Amilan CM8000 in the solvent in advance as what add when secondary disperses, and the mixing when secondary is disperseed and similarly use ball mill to carry out when once disperseing.In addition, similarly make with the coating fluid A that is used for the middle layer.

17. be used for the making of the coating fluid Q in middle layer

The coating fluid Q that is used for the middle layer adds 250 weight portions as SMT-02 (the number average primary particle size: 10nm) and not add as MT-05 (the number average primary particle size: 10nm) that only carries out the surface-treated titanium dioxide with aluminium oxide and silicon dioxide that carries out carrying out with the hydrogenated methyl polysiloxane again after the surface treatment surface-treated titanium dioxide with aluminium oxide and silicon dioxide.In addition, add such titanium dioxide, 500 weight portion methyl alcohol, 125 weight portion butanols, in advance be dissolved in the Amilan CM8000 of 10 weight portions in the butanols of the methyl alcohol of 40 weight portions and 10 weight portions after, use ball mill (medium: the zirconium oxide bead of diameter 0.5mm) mixed 1 hour, make dispersion soln 1 time.

Then, add the Amilan CM8000 of 90 weight portions in the butanols of the methyl alcohol be dissolved in 460 weight portions in advance and 115 weight portions after, and once disperse similarly to use ball mill to mix 1 hour, carry out 2 dispersions, make the coating fluid Q that is used for the middle layer.

In addition, be used for the composition of coating fluid K～Q in middle layer and the summary of manufacturing process and be shown in table 2.

[table 1]

Table 1

Coating fluid	Once disperse					Secondary disperses
								Titanium dioxide 1	Titanium dioxide 2	Methyl alcohol/butanols (weight portion)	Resin solution	Mix	Resin solution	Mix
	Kind/particle diameter (nm)/addition (weight portion)	Kind/particle diameter (nm)/addition (weight portion)	Amilan/methyl alcohol/butanols (weight portion)	Method/incorporation time (hour)	Amilan/methyl alcohol/butanols (weight portion)	Method/incorporation time (hour)
							A	SMT-02 /10 /150	MT-05 /10 /100		600 /150	50 /200 /50	Ball mill (particle diameter: 0.5mm)/1	50 /200 /50	Coating wobbler/1
B	Ball mill (particle diameter: 0.5mm)/2	Coating wobbler/2
			C	Ball mill (particle diameter: 0.5mm)/1	Coating wobbler/0.5
D	Ball mill (particle diameter: 0.5mm)/0.5	Coating wobbler/1
			E	Coating wobbler/0.5
F		SMT- 500SAS /35 /150			MT-600BS /35 /100	Ball mill (particle diameter: 0.5mm)/2	Coating wobbler/2
	G		Ball mill (particle diameter: 0.5mm)/1	Coating wobbler/1
H						SMT-02 /10 /250	-
	I	Ball mill (particle diameter: 0.5mm)/0.5			Coating wobbler/0.5
J			Ball mill (particle diameter: 0.5mm)/1

[table 2]

Table 2

Coating fluid	Once disperse					Secondary disperses
								Titanium dioxide 1	Titanium dioxide 2	Methyl alcohol/butanols (weight portion)	Resin solution	Mix	Resin solution	Mix
	Kind/particle diameter (nm)/addition (weight portion)	Kind/particle diameter (nm)/addition (weight portion)	Amilan/methyl alcohol/butanols (weight portion)	Method/incorporation time (hour)	Amilan/methyl alcohol/butanols (weight portion)	Method/incorporation time (hour)
							K	SMT-02 /10 /150	MT-05 /10 /100		600 /150	35 /140 /35	Ball mill (particle diameter: 0.5mm)/1	65 /260 /65	Ball mill (particle diameter: 0.5mm)/1
L	50 /200 /50	Ball mill (particle diameter: 1mm)/1	50 /200 /50	Ball mill (particle diameter: 1mm)/1
					M	60 /240 /60	40 /160 /40
N	1000 /250		100 /- /-							Ball mill (particle diameter: 1mm)/10		-	-
		O		600 /150	-	Ball mill (particle diameter: 0.5mm)/1	100 /400 /100				Ball mill (particle diameter: 0.5mm)/1
P	10 /40 /10		Ball mill (particle diameter: 1mm)/1							90 /360 /90		Ball mill (particle diameter: 1mm)/1
		Q			SMT-02 /10 /250	-	500 /125				Ball mill (particle diameter: 0.5mm)/1		90 /460 /115	Ball mill (particle diameter: 0.5mm)/1

[embodiment 1]

1. the making of lamination-type Electrophtography photosensor

(1) formation in middle layer

Behind the coating fluid A that is used for the middle layer that obtains among 5 microns the filtrators filtration embodiment 1, with an end of the aluminum substrate (support matrices) of diameter 30mm, length 238.5mm up, in the speed dip coated of the coating fluid that is used for the middle layer that obtains with 5mm/sec.Then, be cured processing under 130 ℃, 30 minutes condition, forming film thickness is the middle layer of 2 μ m.

(2) formation of photoreceptor layers

Then, mix 1 weight portion as the phthalocyanine titanium of making according to following order of charge generating, 1 weight portion polyvinyl acetal (ponding chemical industry as binding resin, S-LECKS-5), as the propylene glycol monomethyl ether of 60 weight portions of dispersion medium and the tetrahydrofuran of 20 weight portions, disperseed 48 hours with bowl mill, make the coating fluid that is used for charge generating layer.

Filter after the coating fluid that is used for charge generating layer that obtains with 3 microns filtrators, be coated on the middle layer with the dip coated method, drying is 5 minutes under 80 ℃, and forming film thickness is the charge generating layer of 0.3 μ m.

Then, (Supreme Being people changes into as the polycarbonate resin of binding resin as the stilbene compounds (HTM-1) of the following formula (1) of cavity conveying agent expression, 100 weight portions with 70 weight portions, TS2020), 460 weight portions are as the tetrahydrofuran mixed dissolution of solvent, preparation is used for the coating fluid of charge transport layer.

[Chemical formula 1]

Coating fluid that is used for charge transport layer that obtains and the coating fluid that is used for charge generating layer similarly are coated on charge generating layer, after drying under 130 ℃, 30 minutes the condition, forming film thickness is the charge transport layer of 20 μ m, makes the lamination-type Electrophtography photosensor.

In addition, the phthalocyanine titanium of use is synthetic according to following order.

At first, in the flask that argon replaces is crossed, add 25g as the phthalonitrile of reaction raw materials, 28g four titanium butoxide, 300g quinoline after, the limit is used stirring apparatus to stir the limit and is warming up to 150 ℃.

Then, heat up in a steamer the steam that produces by the reaction raw materials in the flask, be warmed up to 215 ℃ more simultaneously.Then, while keep this temperature and stir again and made reaction raw materials reaction 2 hours.

Reaction in the moment that is cooled to 150 ℃, is taken out reactant after finishing from flask, filter with glass filter.The solid shape material that obtains is used N successively, after dinethylformamide and the methanol wash, carry out vacuum drying, obtain the hepatic solid of 24g.(pigmentation pre-treatment)

Then, add hepatic solid, 100 milliliters of N that 10g obtains in having the flask of stirring apparatus, dinethylformamide is heated to 130 ℃, carries out 2 hours stir process, makes reactant liquor.

Then, stop the heating, be cooled to 23 ± 1 ℃ after, reactant liquor was left standstill 12 hours, carry out stabilization processes.

Then, after the reactant liquor of stabilization filtered with glass filter, the solid that obtains with methanol wash again.Then, with its vacuum drying, obtain the coarse crystallization of 9.83g phthalocyanine titanium compound.

Then, coarse crystallization and 100 milliliters of concentrated sulphuric acids of the phthalocyanine titanium that adding 5g obtains in having the flask of stirring apparatus make it dissolving equably.

Then, the drips of solution that obtains is added in the ice-cooled water, then, at room temperature stirred 15 minutes, under 23 ± 1 ℃, left standstill 30 minutes again, make it recrystallization.

Then, use the solution of glass filter isolated by filtration recrystallization, and the solid water that obtains is washed till cleansing solution for neutral.Then, moist and make it to be distributed to the state that has water in 200 milliliters the chlorobenzene, be heated 50 ℃, stirred 10 hours.

Then, the solution that obtains with the glass filter isolated by filtration, and with the solid that obtains 50 ℃ of following vacuum drying 5 hours, as the crystallization of phthalocyanine titanium, obtain the 4.1g blue powder.

Confirmed in addition, even the phthalocyanine titanium that obtains in the early stage and be impregnated into 1, in 3-two oxa-s penta ring or the tetrahydrofuran 7 days, locate not produce the peak Prague angle 2 θ ± 0.2 °=7.4 ° and 26.2 °, and except near the peak 90 ℃ of the gasification that is accompanied by planar water, at the peak that does not show that in 50 ℃ to 400 ℃ temperature range crystallization changes.

2. estimate

(1) disperse state 1 of titanium dioxide (state that is used for the coating fluid in middle layer)

The dispersiveness of the titanium dioxide of the coating fluid that is used for the middle layer before being coated on the support matrices with visualization is estimated with reference to following benchmark.What obtain the results are shown in table 3.

Zero: do not observe owing to disperse the aggregate of the bad titanium dioxide that causes

△: observe a little owing to disperse the aggregate of the bad titanium dioxide that causes

*: observe owing to disperse the aggregate of the bad titanium dioxide that causes

(2) disperse state 2 of titanium dioxide (Δ L value, Δ a value and Δ b value)

(Minolta (strain) is made, and CM1000), (root thickness: support matrices 2 μ m) is to the L value (L of the light of wavelength 550nm to measure the middle layer that obtains stacked to use colour difference meter ₁).Then, similarly measure the L value (L of the support matrices in stacked middle layer not to the light of wavelength 550nm ₂).

That is, use Fig. 8 (a) and (b) when more specifically describing, Fig. 8 (a) shows the stacked state in middle layer 12 on support matrices 13, and it is the state of support matrices that Fig. 8 (b) shows.And, Fig. 8 (a) and (b) in H ₀Expression is to the light (incident light) of each support matrices irradiation, H ₁And H ₂Expression is to the reflection of incident light light of each support matrices irradiation.

Therefore,, obtain the L value (Δ L value) in the middle layer in the middle layer in order to get rid of the influence of support matrices, can be from the L value (L of the catoptrical H1 that is mixed with middle layer and support matrices ₁) deduct the H of independent support matrices ₂Value (L ₂), as corrected value.

That is, based on the L value (L that obtains ₁, L ₂), calculate the correction L value (Δ L value) in middle layer by following mathematical expression (1).

In addition, when measuring the L value,, also similarly measure with the L value for a value and b value.In addition, with by the L value (L that obtains ₁, L ₂) calculate Δ L value similarly, calculate Δ a value and Δ b value.What obtain the results are shown in table 3.

In addition, by measuring such Δ L value, Δ a value and Δ b value, can easily confirm the disperse state of the titanium dioxide in the middle layer.That is each characteristic such as image fog ID in the time of, can easily confirming to use Electrophtography photosensor and bright current potential with such middle layer.

[mathematical expression 1]

ΔL＝L ₁-L ₂ (1)

(3) disperse state 3 of titanium dioxide (reflection absorbance (Δ A value))

Use colour difference meter (Minolta (strain) is made, colour difference meter CM1000), (root thickness: support matrices 2 μ m) is to the reflection of light absorbance (A of wavelength 550nm to measure the middle layer that obtains stacked ₁).Then, similarly measure the reflection of light absorbance (A of the support matrices in stacked middle layer not to wavelength 550nm ₂).

That is, use Fig. 9 (a) and (b) when more specifically describing, Fig. 9 (a) shows the stacked state in middle layer 12 on support matrices 13, and it is the state of support matrices that Fig. 9 (b) shows.And, Fig. 9 (a) and (b) in I ₀Expression is to the intensity of the light (incident light) of each support matrices irradiation, I ₁And I ₂Expression is to the intensity of reflected light in the incident light of each support matrices irradiation.Therefore,, obtain the reflection absorbance (Δ A value) in the middle layer in order to get rid of the influence of support matrices, can be from the A of the reflection absorbance that is mixed with middle layer and support matrices ₁Deduct the reflection absorbance A of support matrices ₂

Therefore, based on the value (A of the reflection absorbance that obtains ₁, A ₂), calculate the reflection absorbance (Δ A value) in middle layer by following mathematical expression (2), simultaneously, reflect the evaluation that absorbance (Δ A value) is implemented the dispersiveness of the Titanium particles in the middle layer by this with reference to following benchmark.What obtain the results are shown in table 3.

In addition, calculate reflection absorbance (A among Fig. 9 (a) by following mathematical expression (3) ₁), similarly, calculate reflection absorbance (A among Fig. 9 (b) by following mathematical expression (4) ₂).And the reflection absorbance in this middle layer (Δ A value) is more little, shows that the scattering of light in the middle layer is few more.That is, the dispersiveness of the Titanium particles in the demonstration middle layer is high more.

[mathematical expression 2]

ΔA＝A ₁-A ₂ (2)

[mathematical expression 3]

$A_1=-\mathrm{Log}\frac{I_1}{I_0}---\left(3\right)$

[mathematical expression 4]

$A_2=-\mathrm{Log}\frac{I_2}{I_0}---\left(4\right)$

○：A≤0.055

△：0.055＜A≤0.08

×：A＞0.08

(4) mensuration of bright current potential

With the Electrophtography photosensor that obtains be installed in adopted negative charging reverse developing process printer (strokes per minute is made according to (strain), Microline-22N) in, carry out the mensuration of bright current potential under the low temperature and low humidity environment.

That is, under the low temperature and low humidity environment (temperature: 10 ℃, humidity: after carrying out 1000 printings 20%), with the current potential of developing location as bright current potential (V).In addition, according to following benchmark, implement the evaluation of light sensitivity by the value of the bright current potential that obtains.What obtain the results are shown in table 3.In addition, as the measured value of bright current potential, represent the absolute value of bright current potential.

Zero: the absolute value of bright current potential is the value of not enough 25V

△: the absolute value of bright current potential is to be equal to or greater than 25V but the value of not enough 35V

*: the absolute value of bright current potential is 35V or bigger value

(5) evaluation of image fog ID

With the Electrophtography photosensor that obtains be installed in adopted negative charging reverse developing process printer (strokes per minute is made according to (strain), Microline-22N) in, carry out hot and humid environment (temperature: 35 ℃, humidity: the image fog picture appraisal 85%).

That is, under such hot and humid environment, the picture appraisal pattern that lettering is 100,000, and, estimate 100,000 later image fogs of printing according to following benchmark.In addition, said here image fog is meant that ID by the lettering image deducts the meaning of difference of the ID of blank sheet of paper.

Therefore, (Tokyo electricity look company makes, and TC-6D) measures the ID of blank sheet of paper lettering image and the ID of blank sheet of paper to use reflection of the concentration.More specifically, be the concentration determination of carrying out any 9 places in the blank sheet of paper lettering image, calculate its mean value, as the benchmark of image fog ID evaluation.What obtain the results are shown in table 3.

Zero: concentration difference is the value of less than 0.005

△: concentration difference is to be equal to or greater than 0.005 but the value of less than 0.010

*: concentration difference is 0.010 or bigger value

[embodiment 2～7 and comparative example 1～3]

In embodiment 2～7 and comparative example 1～3, during except the middle layer in forming the lamination-type Electrophtography photosensor, as shown in table 3, be used for the coating fluid B in middle layer～J respectively as being used for beyond the coating fluid in middle layer, make the lamination-type Electrophtography photosensor similarly to Example 1 and estimate.What obtain the results are shown in table 3.

[table 3]

Table 3

	The middle layer							Electrical characteristics
												Coating fluid	Δ L value (-)	Δ a value (-)	Δ b value (-)	Reflection absorbance (Δ A value) measured value		Liquid status	Bright current potential		Image fog ID
	(-)	Estimate	Measured value (V)	Estimate	Measured value (-)	Estimate
							Embodiment 1	A	-2.8	-1.11	3.88					0.032	○		○	15	○	0.003	○
Embodiment 2	B	-3.0	-0.61	2.34	0.038	○						○	20	○	0.004			○
							Embodiment 3	C	-3.7	-0.57	2.20					0.053	○		○	18	○	0.003	○
Embodiment 4	F	-3.8	-0.33	1.56	0.046	○						○	18	○	0.003			○
							Embodiment 5	H	-2.1	-0.55	0.99					0.024	○		○	19	○	0.002	○
Embodiment 6	I	-4.8	0.12	-1.64	0.063	△						△	33	△	0.006			△
							Embodiment 7	J	-4.5	-0.33	7.30					0.064	△		△	30	△	0.007	△
Comparative example 1	D	-5.3	-1.60	-0.35	0.072	△						△	41	×	0.006			△
							Comparative example 2	E	-5.1	-0.23	-3.50					0.085	×		×	38	×	0.011	×
Comparative example 3	G	-6.5	-0.85	-0.56	0.091	×						×	37	×	0.021			×

[embodiment 8～10 and comparative example 4～7]

In embodiment 8～10 and comparative example 4～7, during except the middle layer in forming the lamination-type Electrophtography photosensor, as shown in table 4, coating fluid K～the Q that is used for the middle layer respectively is as being used for making the lamination-type Electrophtography photosensor similarly to Example 1 beyond the coating fluid in middle layer.In addition, similarly to Example 1, implement to be used for the mensuration of state, the reflection absorbance (Δ A value) of the coating fluid in middle layer, bright current potential and for the evaluation of image fog ID, simultaneously, as shown below, observe the surface in the middle layer that forms with the electronics photomicroscope, and estimate.

That is, scan microscope JSM-7401F, the FE-SEM that uses NEC company to make observes the surface in the middle layer that forms on support matrices, and according to the disperse state of following benchmark evaluation titanium dioxide.What obtain the results are shown in table 4.In addition, Figure 10～16 illustrate the image with the interlayer surfaces of electron microscope observation respectively.

Zero: confirm as the state that disperses homogeneous.

△: observe a little and disperse inhomogenous part.

*: confirm as and disperse inhomogenous state.

[table 4]

Table 4

	The middle layer					Electrical characteristics
										Coating fluid	Reflection absorbance (Δ A value)		Liquid status	Electron microscope observation	Bright current potential		Image fog ID
	Measured value (-)	Estimate	Measured value (V)	Estimate	Measured value (-)	Estimate
							Embodiment 8	K	0.027		○	○			○	15	○	0.003	○
Embodiment 9	L	0.018	○	○	○	20				○			0.002	○
							Embodiment 10	M	0.041		○	○			○	18	○	0.005	△
Comparative example 4	N	0.112	×	△	×	38				×			0.028	×
							Comparative example 5	○	0.092		×	Gel state			△	-	-	-	-
Comparative example 6	P	0.072	△	△	△	40				×			0.016	×
							Comparative example 7	Q	0.075		△	○			△	30	△	0.018	×

[embodiment 11]

1. the making of mono-layer electronic photographic photoreceptor

(1) making in middle layer

The coating fluid A that is used for the middle layer that obtains among the embodiment 11 filters with 5 microns filtrator and obtains being used for the coating fluid in middle layer, then, with an end of the aluminum substrate (support matrices) of diameter 30mm, length 254mm up, in the speed dip coated of the coating fluid that is used for the middle layer that obtains with 5mm/sec.Then, be cured processing under 130 ℃, 30 minutes condition, forming film thickness is the middle layer of 2 μ m.

(2) formation of photographic layer

Then, (Supreme Being people changes into as the polycarbonate of binding resin as the compound (ETM-1) of following formula (2) expression of electron transporting agent, 100 weight portions as the compound (HTM-1) of formula (1) expression of cavity conveying agent, 30 weight portions as the phthalocyanine titanium of making according to similarly to Example 1 order of charge generating, 70 weight portions with 5 weight portions, TS2020), the tetrahydrofuran one of 800 weight portions reinstates ultrasonic dispersing machine and mixes, disperses, and makes the coating fluid that is used for the single-layer type photographic layer.

Then, the coating fluid that is used for the single-layer type photographic layer that obtains is coated on above-mentioned middle layer with the dip coated method in manufacturing in back 60 minutes, then, heat-treat under 130 ℃, 30 minutes condition, forming film thickness is the mono-layer electronic photographic photoreceptor of 25 μ m.

[Chemical formula 2]

2. estimate

(1) evaluation of the disperse state of titanium dioxide

In addition, similarly to Example 1, implement to be used for the evaluation of dispersiveness of the titanium dioxide in the coating fluid in middle layer and middle layer.What obtain the results are shown in table 5.

(2) mensuration of bright potential change

In addition, the mensuration of bright potential change is to use the printer that has adopted just charged reverse developing process, and (Kyocera Mita (strain) is made, FS1010) as the image processing system that loads Electrophtography photosensor, simultaneously, (temperature: 10 ℃ under the low temperature and low humidity environment, humidity: 20%), measure respectively after 1000 of initial stage and the printings at the current potential of developing location as bright current potential (V).Then, deduct the bright current potential (V) at initial stage by the bright current potential (V) of printing after 1000, as bright potential change (V).In addition, according to following benchmark, implement the light sensitivity evaluation by the value of the bright potential change that obtains.What obtain the results are shown in table 5.

Zero: bright potential change is the value of not enough 10V.

△: bright potential change is to be equal to or greater than 10V but the value of not enough 20V.

*: bright potential change is 20V or bigger value.

(3) evaluation of image fog ID

In addition, printer (Kyocera Mita (strain) manufacturing of just charged reverse developing process has been adopted in the evaluation of image fog ID except use, FS1010), use similarly to Example 1 method and benchmark to implement as beyond the image processing system that loads Electrophtography photosensor.What obtain the results are shown in table 5.

[embodiment 12～17 and comparative example 8～10]

In embodiment 12～17 and comparative example 8～10, during except the middle layer in forming mono-layer electronic photographic photoreceptor, as shown in table 5, be used for the coating fluid B in middle layer～J respectively as being used for beyond the coating fluid in middle layer, make mono-layer electronic photographic photoreceptor similarly to Example 11 and estimate.What obtain the results are shown in table 5.

[table 5]

Table 5

	The middle layer							Electrical characteristics
												Coating fluid	Δ L value (-)	Δ a value (-)	Δ b value (-)	Reflection absorbance (Δ A value)		Liquid status	Bright potential change		Image fog ID
	Measured value (-)	Estimate	Measured value (V)	Estimate	Measured value (-)	Estimate
							Embodiment 11	A	-2.8	-1.11	3.88					0.032	○		○	6	○	0.003	○
Embodiment 12	B	-3.0	-0.61	2.34	0.038	○						○	8	○	0.004			○
							Embodiment 13	C	-3.7	-0.57	2.20					0.053	○		○	6	○	0.003	○
Embodiment 14	F	-3.8	-0.33	1.56	0.046	○						○	6	○	0.003			○
							Embodiment 15	H	-2.1	-0.55	0.99					0.024	○		○	5	○	0.002	○
Embodiment 16	I	-4.8	0.12	-1.64	0.063	△						△	11	△	0.006			△
							Embodiment 17	J	-4.5	-0.33	7.30					0.064	△		△	12	△	0.007	△
Comparative example 8	D	-5.3	-1.60	-0.35	0.072	△						△	20	×	0.012			×
							Comparative example 9	E	-5.1	-0.23	-3.50					0.085	×		×	21	×	0.011	×
Comparative example 10	G	-6.5	-0.85	-0.56	0.091	×						×	29	×	0.021			×

Industrial applicibility

Adopt Electrophtography photosensor of the present invention, by having the L value or the reflection absorbance is intermediate layer in the prescribed limit, can reduce Electrophtography photosensor in hot and humid lower generation image fog.

In addition, adopt the manufacture method of Electrophtography photosensor of the present invention, owing to can improve the storage stability for the coating fluid in intermediate layer etc., not only can be easily and stably make the intermediate layer, and can be easily and stably make photoreceptor layers. Therefore, can obtain economically the stable Electrophtography photosensor of electrical characteristics.

Claims (10)

1. Electrophtography photosensor, it has support matrices, middle layer and photoreceptor layers, it is characterized in that, titanium dioxide and binding resin are contained in described middle layer, and simultaneously, the Δ L value in this middle layer satisfies following relational expression (1), perhaps the Δ A value in this middle layer satisfies following relational expression (2)

-5.0≤ΔL≤0 (1)

ΔA≤0.055 (2)

Δ L value: deduct the difference that the L value of the described support matrices of independent mensuration obtains with the L value of the state estimating that forms described middle layer on described support matrices, the L value here is based on JIS Z 8722 standards and with the parameter value of colour difference meter mensuration;

Δ A value: deduct the difference that the reflection absorbance of the described support matrices of independent mensuration obtains with the reflection absorbance of the state estimating that forms described middle layer on described support matrices, the reflection absorbance here is the parameter value of measuring with colour difference meter.

2. Electrophtography photosensor according to claim 1, it is characterized in that, deducting difference DELTA a value that a value of the above-mentioned support matrices of independent mensuration obtains with a value in the middle layer of the state estimating that forms above-mentioned middle layer on above-mentioned support matrices is value in-1.2～0 scope, and a value here is based on JIS Z 8722 standards and with the parameter value of colour difference meter mensuration.

3. Electrophtography photosensor according to claim 1, it is characterized in that, deducting difference DELTA b value that the b value of the above-mentioned support matrices of independent mensuration obtains with the b value in the middle layer of the state estimating that forms above-mentioned middle layer on above-mentioned support matrices is value in 0～10 scope, and the b value here is based on JIS Z 8722 standards and with the parameter value of colour difference meter mensuration.

4. Electrophtography photosensor according to claim 1 is characterized in that, with respect to the above-mentioned binding resin of 100 weight portions, the addition of the titanium dioxide that contains in the above-mentioned middle layer is the value in 150～350 weight portion scopes.

5. Electrophtography photosensor according to claim 1 is characterized in that, the average primary particle diameter of above-mentioned titanium dioxide is the value in 0.001～0.1 mu m range.

6. Electrophtography photosensor according to claim 1 is characterized in that the titanium dioxide that contains in the above-mentioned middle layer is coated by organo-silicon compound.

7. Electrophtography photosensor according to claim 1 is characterized in that, the mean molecular weight of the binding resin that contains in the above-mentioned middle layer is the value in 1000～50000 scopes.

8. the described Electrophtography photosensor of claim 1 is characterized in that, the thickness in above-mentioned middle layer is the value in 0.1～50 mu m range.

9. the described Electrophtography photosensor of claim 1 is characterized in that, above-mentioned photoreceptor is the lamination-type Electrophtography photosensor that forms middle layer, charge generating layer, charge transport layer on above-mentioned support matrices successively.

10. the manufacture method of an Electrophtography photosensor, this manufacture method is the manufacture method with Electrophtography photosensor of support matrices, middle layer and photoreceptor layers, it is characterized in that, comprises:

Titanium dioxide is dispersed in contains in the binding resin solution of binding resin and organic solvent, make the coating fluid that is used for the middle layer be used to form described middle layer operation and

Use this coating fluid that is used for the middle layer to form the operation in middle layer, the Δ L value in the described middle layer satisfies following relational expression (1), and perhaps the Δ A value in this middle layer satisfies following relational expression (2),

-5.0≤ΔL≤0 (1)

ΔA≤0.055 (2)

Δ L value: deduct the difference that the L value of the described support matrices of independent mensuration obtains with the L value of the state estimating that forms described middle layer on described support matrices, the L value here is based on JIS Z 8722 standards and with the parameter value of colour difference meter mensuration;

Δ A value: deduct the difference that the reflection absorbance of the described support matrices of independent mensuration obtains with the reflection absorbance of the state estimating that forms described middle layer on described support matrices, the reflection absorbance here is the parameter value of measuring with colour difference meter.

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