CN100456171C - Cleaning blade, and cleaning apparatus, process cartridge, and image forming apparatus using the same - Google Patents

Abstract

The invention provides a cleaning blade, which cleans the parts by contacting the surface of parts needing cleanness with the blade, and it is characterized in that the material of contact site of said cleaning blade and said parts surface satisfies at least the following inequality (1)-(3): inequality (1)3.92<=M<=29.42 ;inequality (2)0<=alpha<=0.294; inequality (3)S>=250, ( in the inequality (1)-(3), M represents 100% modulus (MPa); alpha represents the ratio of stress variation (delta stress) to strain variation (delta strain) [delta stress/delta strain= (the stress under 200% degree of strain - the stress under 100% degree of strain)/ (200-100) ] (MPa%)in the rang of 100%-200% strain degree and in stress-strain curve; furthermore, s represents elongation at break (%). The invention also provides a cleaning arrangement containing a cleaning blade, a processing box and an image-forming device.

Description

Cleaning device, handle box and the imaging device of cleaning balde and this cleaning balde of use

Technical field

The present invention relates to be used for forming the cleaning balde and the cleaning device, handle box and the imaging device that use this cleaning balde of the duplicating machine of image by xerography.

Background technology

Usually, the imaging of xerography or electrostatic recording is to carry out in the following manner: form electrostatic latent image on image carrier such as photoreceptor, use developer to make described latent electrostatic image developing to form toner image, then with toner image transfer printing and photographic fixing to recording medium.Use in the imaging device of above-mentioned formation method and be typically provided with cleaning device, so that cleaning remains in the toner on the image carrier behind the transfer printing toner image.

Known have polytype cleaning device, usually, use the scraper plate cleaning method under many circumstances, in this method, cleaning balde (using the contact plate with elastic force usually) is set so that it contacts with image carrier, thereby scrapes off any toner that remains on this image carrier.

With regard to middle low speed device, widely used as the charging unit of image carrier is for example charging roller of contact-type charging device.The reason that is extensive use of the contact-type charging device is, compare with the non-contact type charging device that uses corona tube to charge, the ozone that is accompanied by the contact-type device and produces is few, therefore comparatively environmental protection of contact-type device, and because the contact-type device does not need ozone filter or air blast, so the contact-type device takes up space little and with low cost.

On the other hand, the problem that has of contact-type charging device is that the discharging product amount that is deposited on the photoreceptor is more much more than the described product amount of the non-contact type charging device that uses corona tube to charge.Although this be because the absolute magnitude of the discharging product that produced of contact-type charging device less than the amount that is produced under the situation of using the non-contact type charging device, its region of discharge is but very near apart from photoreceptor.Therefore, under the situation that is used in combination contact-type charging device and cleaning balde, the problem of existence is to cause these cleaning balde wearing and tearing, generation gap and curling owing to friction factor increases, and causes the moment of torsion of photoreceptor drive system to increase.

In order to prevent these problems, the device that has proposed to remove the lip-deep discharging product of image carrier and reduced the friction force on the cleaning balde.For example, proposed to remove the method (opening flat 1-090479 number) of discharging product referring to for example Japanese kokai publication hei 10-143039 number and spy by slip Magnetic brush on the image carrier surface and the sponge roller that comprises lapping compound.In addition, also proposed by selecting suitable material to make cleaning balde have other method of advantages of good abrasion, for example will hang down friction, high hardness material and be used for the method (referring to for example TOHKEMY 2001-343874 number) of the part that contacts with image carrier on the cleaning balde, and the method (referring to for example TOHKEMY 2003-241599 number) that high-modulus (high rigidity) material is used for the part that contacts with image carrier on the cleaning balde.

Under the situation that adopts the bi-component development method that uses the developer that comprises magnetic carrier and toner, carry out toner development in the following manner: apply predetermined visualization and be biased into developer roll, and between developer roll and image carrier, apply the development electric field thus, to be used for that toner is transferred to electrostatic latent image, in this process, (Bead Carry Over: the bead displacement) phenomenon, promptly the part of magnetic carrier is transferred to the surface of image carrier owing to electrostatic attraction BCO to occur.

On the other hand, different with general carrier roughly spherical in shape, the micro mist carrier that produces in developer production run or developing apparatus (carrier of pulverizing) usually has sharp keen chip shape.Therefore, if BCO takes place, when toner image is transferred to the toner acceptor, owing to be subjected to the influence of the transfer pressure between transfer electric field or image carrier and the toner acceptor, the micro mist carrier is easy to imbed the surface of image carrier, and in a single day the micro mist carrier adheres to the surface that its surface just anchors at image carrier securely simultaneously.

Along with the rotation of image carrier, the carrier that adheres to the image carrier surface by this way contacts with the cleaning balde on contact image supporting body surface repeatedly, makes like this edge gap to occur in the cleaning balde.In order to prevent this phenomenon, proposed to be used to capture the device of the carrier that adheres to the image carrier surface.For example proposed by capturing the device (referring to Japanese kokai publication sho 62-262074 number) that forms electric field between parts and the photoreceptor and capture carrier, capturing the device (referring to Japanese kokai publication hei 3-120577 number and real public clear 53-32599 number) of carrier by magnetic attraction.

Yet, consider miniaturization and reduce cost, in imaging device, add and be used to remove the unit of discharging product with the mar proof that improves cleaning balde, and it is all not ideal enough to add the methods such as carrier capture unit be used to capture the micro mist carrier, and described micro mist carrier is the micro mist carrier that adheres to the surface of image carrier along with the generation of BCO and cause the edge gap.In addition, need prevent that the carrier that will have sharp-pointed chip shape in the transfer printing toner image is transferred to the image carrier surface and imbeds this surface.In the case, between development step and transfer step, must remove the carrier that adheres to the image carrier surface, and not destroy toner image in the image carrier surface development with sharp-pointed chip shape.

Therefore, in order to capture the carrier of having that adheres to the image carrier surface, need have stronger magnetic field or electric field under the situation of carrier of common particle diameter than capture than small particle diameter and sharp-pointed chip shape.In order to produce stronger magnetic field or electric field, need be provided with capture unit nearer from photoreceptor.Yet, if be arranged to from photoreceptor capture unit nearer simply, toner image on the carrier meeting scrub images supporting body that is then captured during transmitting, therefore, it is very difficult thoroughly removing the carrier of transferring on the image carrier under the situation of not destroying toner image.

On the other hand, if use the material of high rigidity or high-modulus to improve the mar proof of cleaning balde as the used material of the part that contacts with image carrier on the cleaning balde with this, usually, mar proof can improve, but elasticity but can descend.If flexibility decrease will be lost the performance of rubber like, and can make this cleaning balde be difficult to extend.Because this cleaning balde is difficult to extend, when the foreign matters such as carrier fragment of for example imbedding the image carrier surface during by the contact site between cleaning balde edge and the image carrier surface along with the generation of BCO, the end at described edge can not be out of shape along with the power of the foreign matter that makes this edge deformation, is easy to produce gap.

Therefore, in order to prevent that cleaning balde from producing the edge gap, advantageously, use to a certain degree low-durometer material to form the end at described edge, so that at foreign matter during by the contact site between cleaning balde edge and the image carrier surface described edge can deform (extension).Yet the material of soft is relatively poor aspect mar proof, and this makes it can not keep good clean-up performance for a long time.

Summary of the invention

The present invention has considered the above-mentioned fact and has finished the cleaning device, handle box and the imaging device that cleaning balde are provided and have used described cleaning balde.

＜1〉a kind of cleaning balde, this cleaning balde by with the surface that is used to clean the described parts that are cleaned that contacts on the surface of the parts that are cleaned, wherein, the material of the part that contacts with the surface of the described parts that are cleaned at least on the described cleaning balde satisfies following inequality (1)～(3):

Inequality (1) 3.92≤M≤29.42;

Inequality (2) 0＜α≤0.294; With

Inequality (3) S 〉=250,

In inequality (1)～(3), M represents 100% modulus, and unit is MPa; α is illustrated in the stress-strain curve, answer in the variation scope 100%～200%, STRESS VARIATION be Δ stress for strain variation be the Δ strain ratio { Δ stress/Δ is answered variation=(answering stress under the variation-at 100% stress of answering under the variation 200%)/(200-100) } (MPa/%); And S represents breaking elongation, and unit is %.

＜2〉as＜1〉described cleaning balde, wherein, described breaking elongation S is less than or equal to 500.

＜3〉as＜1〉described cleaning balde, wherein, the glass transition temperature of the part that contacts with the surface of the described parts that are cleaned is less than or equal to 10 ℃.

＜4〉as＜1〉described cleaning balde, wherein, be greater than or equal in temperature under 10 ℃ the environment, the rebound resilience of the material of the part that contacts with the surface of the described parts that are cleaned is more than or equal to 10%.

＜5〉as＜1〉described cleaning balde, wherein, described material is the elastomeric material that comprises hard segment and soft chain segment, and in the general assembly (TW) of material that constitutes described hard segment and the material that constitutes described soft chain segment, the weight ratio that constitutes the material of described hard segment is the 46 weight %～96 weight % of described general assembly (TW).

＜6〉as＜5〉described cleaning balde, wherein, described hard segment comprises urethane resin.

＜7〉as＜5〉described cleaning balde, wherein, described soft chain segment comprises a kind of resin, this resin comprises isocyanate group is had reactive functional group, glass transition temperature is for being less than or equal to 0 ℃, viscosity in the time of 25 ℃ is 600mPas～35000mPas, and weight-average molecular weight is 700～3000.

＜8〉as＜7〉described cleaning balde, wherein, described resin comprises acryl resin with two or more hydroxyls or the polybutadiene with two or more hydroxyls.

＜9〉as＜7〉described cleaning balde, wherein, described resin comprises the epoxy resin with two or more epoxy radicals.

＜10〉as＜1〉described cleaning balde, described cleaning balde is by two-layer or constitute more than two-layer layer, described two-layer or more than comprise in the two-layer layer contact with the surface of the described parts that are cleaned layer, wherein, the surfaces described and parts that are cleaned contact the layer make by the material that satisfies inequality (1)～(3).

＜11〉a kind of comprising＜1〉cleaning device of described cleaning balde.

＜12〉as＜11〉described cleaning device, wherein, described breaking elongation S is less than or equal to 500.

＜13〉as＜11〉described cleaning device, wherein, the glass transition temperature of the part that contacts with the surface of the described parts that are cleaned is less than or equal to 10 ℃.

＜14〉as＜11〉described cleaning device, wherein, be greater than or equal in temperature under 10 ℃ the environment, the rebound resilience of the material of the part that contacts with the surface of the described parts that are cleaned is more than or equal to 10%.

＜15〉a kind of handle box, described handle box comprises image carrier and cleaning device, described cleaning device has the cleaning balde that contacts with the surface of described image carrier with the surface that is used to clean described image carrier, and this handle box is made the form that can load and unload on imaging device, wherein, described cleaning balde be＜1〉described cleaning balde.

＜16〉as＜15〉described handle box, wherein, described breaking elongation S is less than or equal to 500.

＜17〉as＜15〉described handle box, wherein, the glass transition temperature of the part that contacts with the surface of the described parts that are cleaned is less than or equal to 10 ℃.

＜18〉as＜15〉described handle box, wherein, be greater than or equal in temperature under 10 ℃ the environment, the rebound resilience of the material of the part that contacts with the surface of the described parts that are cleaned is more than or equal to 10%.

＜19〉as＜15〉described handle box, wherein, the surface of described image carrier is the layer that contains fluororesin.

＜20〉as＜15〉described handle box, wherein, the surface of described image carrier is the layer that comprises resin, described resin comprises the structural unit with charge transport ability and has cross-linked structure.

＜21〉as＜20〉described handle box, wherein, described resin is the resin that is selected from the group of being made up of phenol resin, urethane resin and silicone resin.

＜22〉a kind of imaging device, described imaging device comprises at least one be cleaned parts and one or more cleaning device, described cleaning device has the cleaning balde that contacts with the surface of the described parts that are cleaned with the surface that is used to clean these parts that are cleaned, wherein, at least one cleaning device have＜1〉described cleaning balde.

＜23〉as＜22〉described imaging device, wherein, described breaking elongation S is less than or equal to 500.

＜24〉as＜22〉described imaging device, wherein, the glass transition temperature of the part that contacts with the surface of the described parts that are cleaned is less than or equal to 10 ℃.

＜25〉as＜22〉described imaging device, wherein, be greater than or equal in temperature under 10 ℃ the environment, the rebound resilience of the material of the part that contacts with the surface of the described parts that are cleaned is more than or equal to 10%.

＜26〉as＜22〉described imaging device, wherein, the material of the part that contacts with the surface of the described parts that are cleaned at least on the described cleaning balde is an elastomeric material, described material comprises hard segment and soft chain segment, and in the general assembly (TW) of material that constitutes described hard segment and the material that constitutes described soft chain segment, the weight ratio that constitutes the material of described hard segment is the 46 weight %～96 weight % of described general assembly (TW).

＜27〉as＜26〉described imaging device, wherein, described hard segment comprises urethane resin.

＜28〉as＜26〉described imaging device, wherein, described soft chain segment comprises a kind of resin, this resin comprises isocyanate group is had reactive functional group, glass transition temperature is for being less than or equal to 0 ℃, viscosity in the time of 25 ℃ is 600mPas～35000mPas, and weight-average molecular weight is 700～3000.

＜29〉as＜28〉described imaging device, wherein, described resin comprises acryl resin with two or more hydroxyls or the polybutadiene with two or more hydroxyls.

＜30〉as＜28〉described imaging device, wherein, described resin comprises the epoxy resin with two or more epoxy radicals.

＜31〉as＜22〉described imaging device, wherein, described cleaning balde is by two-layer or constitute more than two-layer layer, described two-layer or more than comprise in the two-layer layer contact with the surface of the described parts that are cleaned layer, wherein, the surfaces described and parts that are cleaned contact the layer make by the material that satisfies inequality (1)～(3).

As mentioned above, the invention provides a kind of cleaning balde with good mar proof and splitting resistance, this cleaning balde can keep favourable cleaning performance for a long time, and the present invention also provides cleaning device, handle box and the imaging device that uses this cleaning balde.

Description of drawings

Describe the preferred embodiment of inventing in detail according to following diagram, described figure is:

Fig. 1 is the synoptic diagram that shows an example of imaging device of the present invention;

Fig. 2 is the synoptic diagram that shows an example of cleaning device of the present invention;

Fig. 3 is the synoptic diagram that shows an example of cleaning balde of the present invention;

Fig. 4 is the synoptic diagram of an example that shows the fixing means of cleaning balde of the present invention; And

Fig. 5 is the chart of answering mutual relationship between variation and the stress that shows the cleaning balde of embodiment 1～3 and Comparative Examples 1～3.

Embodiment

(cleaning balde)

Cleaning balde of the present invention is contacted to be used to clean the surface of the described parts that are cleaned with the surface of the parts that are cleaned, this cleaning balde is characterised in that the material of the part that contacts with the surface of the described parts that are cleaned at least on the described cleaning balde satisfies following inequality (1)～(3):

Inequality (1) 3.92≤M≤29.42;

Inequality (2) 0＜α≤0.294; With

Inequality (3) S 〉=250,

(in inequality (1)～(3), M represents 100% modulus (MPa); α is illustrated in the stress-strain curve, answer in the variation scope 100%～200%, STRESS VARIATION (Δ stress) for the ratio of strain variation (Δ strain) { Δ stress/Δ is answered variation=(answering stress under the variation-at 100% stress of answering under the variation 200%)/(200-100) } (MPa/%); And S represents the breaking elongation (%) according to JIS K6251 (using No. 3 test films of dumbbell shape) mensuration).

For cleaning balde of the present invention, (followingly sometimes this part is called edge part or edge termination because the material of the part that contacts with the surface of the parts that are cleaned on this cleaning balde, the material that perhaps will constitute this part is called edge part material or edge termination material) satisfy inequality (1), so this cleaning balde also demonstrates good mar proof when showing good clean-up performance.

If 100% modulus M is less than 3.92MPa (40kgf/cm ²), it is not enough that mar proof becomes, and can not keep favourable cleaning performance for a long time.On the other hand, if 100% modulus M surpasses 29.42MPa (300kgf/cm ²), to such an extent as to the edge part material is followed too firmly and describedly is cleaned parts and shape is taken place

The servo-actuated performance that becomes descends, thereby good clean-up performance can not be provided, and in addition, the surface of the parts that are cleaned sometimes may be by scratch.

100% modulus M is preferably in the scope of 5MPa～20MPa, more preferably in the scope of 6.5MPa～15MPa.

Because described edge part material satisfies inequality (2) and inequality (3), so this cleaning balde has excellent splitting resistance.α in inequality (2) surpasses under 0.294 the situation, the flexibility deficiency of this edge part material.Therefore, generation along with BCO, the foreign matter (just as the foreign matter of imbedding and anchor at the image carrier surface) of particularly imbedding or be bonded to described surface when the foreign matter that is present in the parts surface that is cleaned is the contact portion by be cleaned parts and cleaning balde repeatedly, therefore and apply heavily stressed repeatedly to the edge termination of this cleaning balde, at this moment, described edge termination can't be out of shape so that efficiently spread this stress, so gap can appear in this edge in the short period of time.As a result, owing to produce gap too early, can not keep good clean-up performance for a long time.

The α value is preferably and is less than or equal to 0.2, more preferably is less than or equal to 0.1, and the α value is near more good more from the limit lower limit 0 of this physical property.

In addition, if the breaking elongation S that is limited by inequality (3) is lower than 250%, when the foreign matter in the above-mentioned parts surface that is cleaned and edge termination bumped against with brute force, this edge termination will be stretched, and can not be out of shape thereupon, therefore can occur the edge gap in the short period of time.As a result, owing to produce gap too early, can not keep good clean-up performance for a long time.

Described breaking elongation S is preferably and is greater than or equal to 300%, more preferably be greater than or equal to 350%, high more preferred more at the described breaking elongation of edge gap, but breaking elongation S is higher than at 500% o'clock, servo-actuated performance (adaptation) to the parts that are cleaned increases, increase with the friction force of the parts that are cleaned, edge abrasion as a result becomes sometimes and is easy to increase.So from the viewpoint of edge abrasion, preferred breaking elongation S is less than or equal to 500%, more preferably less than or equal 450%, further preferably be less than or equal to 400%.

In addition, the cleaning balde peripheral temperature of imaging device promptly uses environment temperature generally 10 ℃～60 ℃ scopes.Therefore,, will lose the performance of rubber like, and the contact pressure of cleaning balde becomes unstable if the glass transition temperature Tg of the material of the part that contacts with the parts surface that is cleaned surpasses the environment for use temperature.So the glass transition temperature Tg of the material of the part that preferably contacts with the parts surface that is cleaned is less than or equal to the lower limit (10 ℃) of environment for use temperature.

On the other hand, for the rebound resilience R of the material partly that contacts with the parts surface that is cleaned, when the glass transition temperature Tg of described material was less than or equal to 10 ℃, temperature low-repulsion more had more little tendency.Particularly rebound resilience R was less than 10% o'clock, and the adhesion of edge termination and slip behavior dull are easy to generate the friction portion that is in the state that deforms with certain contact posture sometimes.

Contact posture if can not discharge, then to keep the posture of edge termination and cause friction, so be easy to take place the distortion of part by adhesion and slip behavior.If the plastic yield of this part takes place, then edge termination and the adaptation that is cleaned between the parts reduce, and it is bad to be easy to generate cleaning sometimes.In order to suppress the plastic yield of this part, preferred edge termination is adhered and the slip behavior always, for this reason, under the environment of 10 ℃ of the essence lower limit temperature that is greater than or equal to the environment for use temperature, preferred rebound resilience R is more than or equal to 10%, more preferably greater than or equal 15%, further be preferably greater than or equal 20%.

Rebound resilience is measured based on JIS K6255.Wherein the technical standard of being mentioned is incorporated herein by reference.

The 100% modulus M that is limited by inequality (1) reaches 100% o'clock Stress calculation by strain to obtain, and this strain is to record 500mm/ minute haulage speed by using No. 3 test films of dumbbell shape according to JIS K6251.As measurement mechanism, use be the Strograph AE elastomer that makes by the smart machine of Japan (strain).

α value that inequality (2) limits is calculated by stress-strain curve, and through the following steps with method calculate the stress and strain degree.That is, carry out described mensuration by using No. 3 test films of dumbbell shape 500mm/ minute haulage speed according to JIS K6251, to record at stress under 100% strain and the stress under 200% strain.As measurement mechanism, use be the Strograph AE elastomer that makes by the smart machine of Japan (strain).

In addition, calculate the S value that inequality (3) limits according to JIS K6251 (using No. 3 test films of dumbbell shape).

In addition, the glass transition temperature of glass transition temperature, soft chain segment material described later and the hard segment materials of the material of the part that contacts with the parts surface that is cleaned among the present invention is to utilize the determination of viscoelasticity device to measure temperature dispersion, tries to achieve as the peak temperature of tan δ (loss tangent).

Wherein tan δ value is to utilize the storage modulus of following explanation and the value that loss modulus derives.Linear elastomer is constant when giving sinusoidal wave strain quiveringly, and stress is represented with formula (4).| E*| is called as complex modulus.By rheology theory, the elastic body composition is with formula (5) expression, and the viscoid composition is represented with formula (6).Herein, E ' is called as storage modulus, E " be called as loss modulus.δ represents the phasic difference angle of stress and strain, and it is called as " mechanics angle of loss ".

The identical E that uses of tan δ value with formula (7) "/E ' expression, be called as " loss tangent ", this value is big more, and its linear elastomer just has caoutchouc elasticity more.

Formula (4) δ=| E ^*| γ cos (ω t)

Formula (5) E '=| E ^*| cos δ

Formula (6) E "=| E ^*| sin δ

Formula (7) tan δ=E "/E '

Tan δ value be utilize レ オ ペ Network ト ラ one-DVE-V4 (manufacturing of レ オ ロ ジ one company) to static strain 5%, 10Hz sinusoidal wave stretch to excite to measure-60 ℃ to 100 ℃ temperature range obtain.

As mentioned above, cleaning balde of the present invention has good mar proof and splitting resistance, and can keep good clean-up performance for a long time.

Therefore, different with regular situation is, the new equipment that need not additionally to be provided for to improve mar proof and splitting resistance in imaging device is present in the problem of the foreign matter of the parts surface that is cleaned with solution, particularly imbed and be bonded to the problem of the foreign matter (just as the foreign matter on the surface of imbedding and be bonded to image carrier along with the generation of BCO) on described surface, therefore can avoid device volume to enlarge and the cost increase.

In addition, owing to prolonged the life-span of cleaning balde, comprise that therefore handle box, cleaning device and the imaging device of cleaning balde of the present invention can have the long life-span, and be easy to reduce their maintenance cost.Particularly, if handle box or imaging device comprise the image carrier and the cleaning balde of the present invention of the surface abrasion resistance with improvement, then this handle box or imaging device will be more favourable at above-mentioned aspect of performance.

For cleaning balde of the present invention, described at least edge part material is the material that satisfies inequality (1)～(3), and still edge part and other parts can not made by the material that satisfies inequality (1)～(3) yet.

The material that satisfies inequality (1)～(3) is not particularly limited,, and especially preferably comprises the elastomeric material of hard segment and soft chain segment so long as elastomeric material gets final product.When described elastomeric material comprises hard segment and soft chain segment, can satisfy the physical property that limits by inequality (1)～(3) etc. at an easy rate, and high abrasion resistance and high cracking resistance can be provided simultaneously.

In addition, " hard segment " and " soft chain segment " is meant that the material that constitutes the former is to compare to constitute the latter's the hard material of material, and the material that constitutes the latter is the material of the material softer that constitutes the former of comparing.

The glass transition temperature that comprises the elastomeric material of hard segment and soft chain segment is preferably-50 ℃～30 ℃, more preferably-30 ℃～10 ℃.If glass transition temperature surpasses 30 ℃, then described cleaning balde becomes fragile in the practical application temperature range of cleaning balde.If glass transition temperature is lower than-50 ℃, then cleaning balde may not possess enough hardness and stress sometimes in practical ranges.

Therefore, in order to reach above-mentioned glass transition temperature, the glass transition temperature that constitutes the material (hereinafter being called hard segment materials) of hard segment in the elastomeric material is preferably 35 ℃～100 ℃, more preferably 30 ℃～60 ℃, and the glass transition temperature that constitutes the material (hereinafter being called the soft chain segment material) of soft chain segment in elastomeric material is preferably-100 ℃～-50 ℃, more preferably-90 ℃～-60 ℃.

In addition, have in use under the hard segment materials and soft chain segment material situation of above-mentioned glass transition temperature, the weight of hard segment materials is preferably 46 weight %～96 weight % with respect to the ratio (hereinafter being sometimes referred to as the hard segment materials ratio) of the general assembly (TW) of hard segment materials and soft chain segment material, more preferably 50 weight %～90 weight % are preferably 60 weight %～85 weight % again.

If the hard segment materials ratio is less than 46 weight %, it is not enough that the mar proof of edge termination becomes, to such an extent as to cause wearing and tearing too early, therefore can not keep good clean-up performance for a long time sometimes.If hard segment materials is than surpassing 96 weight %, it is too hard that edge termination can become, to such an extent as to can not keep enough flexibility and tensilities, occurs gap too early, therefore can not keep good clean-up performance for a long time sometimes.

Combination to hard segment materials and soft chain segment material does not have particular restriction, and this material can be selected from known resin material usually, as long as a kind of material and hard or a kind of material of another kind of material compared and another kind of material compared are soft.Preferred following combination among the present invention.

That is,, preferably use urethane resin as described hard segment materials.In this case, the weight-average molecular weight of polyurethane is preferably in 1000～4000 scope, more preferably in 1500～3500 scope.

Be lower than in its weight-average molecular weight under 1000 the situation, if cleaning balde is used under the low temperature environment, the urethane resin that then constitutes hard segment will be lost elasticity, and it is bad often to occur cleaning sometimes easily.If weight-average molecular weight surpasses 4000, the permanent strain that constitutes the urethane resin of hard segment can become seriously, thereby edge termination can not keep causing cleaning bad with the contact force of the parts that are cleaned sometimes.

As urethane resin, can enumerate ChemicalIndustries, Placcel 205 and Placcel 240 that Ltd. produces by Daicel as above-mentioned hard segment materials.

Equally, use urethane resin as the hard segment materials situation under, as described soft chain segment material, preferred use (1) have can with the resin of the functional group of isocyanates radical reaction.In addition, the physical property that preferably has of this resin is: (2) glass transition temperature is for being less than or equal to 0 ℃; Viscosity in the time of (3) 25 ℃ is 600mPas～35000mPas; (4) weight-average molecular weight is in 700～3000 scope.If can not satisfy these physical properties, the mouldability deficiency when causing producing cleaning balde sometimes, or cause the performance deficiency of cleaning balde sometimes.

Described physical property is more preferably as follows: glass transition temperature is for being less than or equal to-10 ℃; Viscosity in the time of 25 ℃ is in the scope of 1000mPas～3000mPas; Weight-average molecular weight is in 900～2800 scope.Produced under the situation of cleaning balde by centrifugal casting, the viscosity in the time of preferred 25 ℃ is in the scope of 600mPas～3500mPas.

The structure of above-mentioned as satisfying (1)～(4) and the soft chain segment material of physical property can suitably be selected usually known resin, preferably have at least endways can with the resin of the functional group of isocyanate reaction.In addition, consider flexibility, this resin preferably has the group aliphatic resin of linear chain structure.As concrete example, the preferred use has the acrylic resin of two or more hydroxyls, the epoxy resin that has the polybutadiene of two or more hydroxyls or have two or more epoxy radicals.

As acrylic resin with two or more hydroxyls, can enumerate by always grinding the Actflow (grade: UMB-2005B, UMB-2005P, UMB-2005 and UME-2005 etc.) that chemical society produces, as the polybutadiene with two or more hydroxyls, adducible is the R-45HT that produced by the emerging product of bright dipping society etc.

As the epoxy resin with two or more epoxy radicals, preferably they are different with conventional epoxy resin hard and that enbrittle, and are more soft more tough and tensile than conventional epoxy resin.

As such epoxy resin, with regard to molecular structure, preferably, the epoxy resin that in backbone structure, has the structure (flexibility skeleton) of high pliability main chain, as the flexibility skeleton, can enumerate alkylidene skeleton, naphthenic hydrocarbon skeleton and polyoxy alkylidene skeleton, especially preferred polyoxy alkylidene skeleton.

With regard to physical property, compare with common epoxy resin, preferably have the low-viscosity epoxy resin with respect to molecular weight.More particularly, preferably in about 900 ± 100 scope, the viscosity in the time of 25 ℃ is preferably in the scope of 15000 ± 5000mPas, more preferably in the scope of 15000 ± 3000mPas for weight-average molecular weight.As epoxy resin, can enumerate the EPLICON EXA-4850-150 that produces by big Japanese ink chemical industry society etc. with these performances.

Cleaning balde of the present invention is not particularly limited, as mentioned above, need only described at least edge part and make, and the integral body of cleaning balde also can be made by this material by the material that satisfies inequality (1)～(3).Under cleaning balde had situation by layer structure two-layer or that forms more than two-layer layer, what contact with the surface of the parts that are cleaned layer was preferably made by the material that satisfies inequality (1)～(3).

Method as production cleaning balde of the present invention, can adopt known method usually according to the raw material that is used to produce cleaning balde, for example form sheet material by centrifugal casting or extrusion moulding, then this sheet material is cut or processes and make it form reservation shape or with two or fit together, can make described cleaning balde thus more than two sheet material.

Using cleaning balde of the present invention to clean under the situation of the parts that are cleaned, as the object that is cleaned, parts are not particularly limited for being cleaned, so long as the parts that need the his-and-hers watches face to clean in the imaging device promptly can be used as the parts that are cleaned, can enumerate intermediate transfer body, charging roller, transfer roll, the travelling belt that is used to be transferred material, paper-feed roll and be used for from what the cleaning brush of removing the toner on the image carrier was removed toner removing toner roller (detoning roll), among the present invention, the preferred especially described parts that are cleaned are image carriers.

Use cleaning balde of the present invention can suppress appearance by the gap due to the foreign matter, this foreign matter is for for example imbedding and be bonded to the carrier on the surface of image carrier because of generation BCO, simultaneously, can remove following material steadily in the long term: at the toner of the surface attachment of the above-mentioned various parts that are cleaned, outside reagent, discharging product, talcum powder and the paper powder that adds.

(cleaning device, handle box and imaging device)

Next, will cleaning device, handle box and the imaging device that use cleaning balde of the present invention be described.

Cleaning device of the present invention is not particularly limited, as long as this device comprises cleaning balde of the present invention as the cleaning balde that contacts with the surface of the parts that are cleaned with the surface that is used to clean these parts that are cleaned.For example, configuration example as described cleaning device, adducible is following cleaning device: this cleaning device comprises the cleaning balde that is fixed in the cleaning housing, this cleaning housing has the peristome facing to parts one side that is cleaned, the fixed form of described cleaning balde is that edge termination is positioned at this side of peristome; Be used for foreign matter is imported the transmission spiral of foreign matter returnable, this foreign matter is for example by the toner used of cleaning doctor from the surface collection of the parts that are cleaned.Cleaning device of the present invention can comprise two or more cleaning baldes.

In addition, when cleaning balde of the present invention is applied to the cleaning of image carrier, image flows when looking like in order to be suppressed to, preferred cleaning balde is pressed in power NF (NormalForce) on the image carrier in 2.0gf/mm～6.0gf/mm scope, more preferably in 4.0gf/mm～5.0gf/mm scope.The cleaning balde terminal part is nipped the length d of image carrier preferably in 0.4mm～1.6mm scope, more preferably in 0.8mm～1.4mm scope.The angle W/A of the contact site between cleaning balde and the image carrier (Working Angle) is preferably 6.0 °～14.0 ° scope, more preferably 8.0 °～12.0 ° scope.The Young modulus E of the every 1mm of cleaning balde direction of principal axis is preferably at 60gf/mm ²～130gf/mm ²Scope, more preferably at 90gf/mm ²～110gf/mm ²Scope.

During cleaning, exist between cleaning balde and the image carrier under the situation of lapping compound or lubricant, if NF, the length of nipping, angle W/A, Young modulus E are adjusted in the above-mentioned scope, cleaning balde of the present invention will be followed the image carrier rotation and be shown good stretch characteristics, so the lapping compound of the driving fit portion that is maintained at cleaning balde and image carrier or the amount of lubricant are increased.

Like this, if being maintained at the amount of the lapping compound of driving fit portion increases, its result can make the producing property raising as the discharging product of the mobile reason of image, in addition, if being maintained at the amount of the lubricant of driving fit portion increases, its result not only can make the producing property raising of discharging product, and can reduce the wearing and tearing of scraper plate terminal part and photoreceptor.

In addition, as the supply source of lapping compound or lubricant, can utilize the lapping compound that is applied in the toner or lubricant or utilize and be connected the contacted solid abrasive agent of media such as brush on the image carrier etc.

In addition, sense of rotation with respect to image carrier, preferably on sense of rotation, be positioned at the position that image carrier is provided with the upstream side of cleaning balde side and is positioned at the transcription portion downstream of toner image, the toner holding member be set in the mode of contact image supporting body.

In this case, because toner holding member and can remove image carrying discharging product, flow so can significantly reduce the image that discharging product causes to the surface attached to the toner on this toner holding member.And, owing to the friction that has reduced between cleaning balde and the image carrier, so can reduce the scraper plate wearing and tearing for a long time.

In addition, preferably make the parallel or vertical vibration of sense of rotation of the relative image carrier of toner holding member.By the vibration of toner holding member, can more effectively remove discharging product, further suppress image and flow.

And then, with respect to the sense of rotation of image carrier, on sense of rotation, form the toner aggregation and also be fit to being positioned at zone that the image carrier surface is provided with the downstream of cleaning balde side and is positioned at the upstream side that is provided with cleaning balde.Like this, because the absorption of the toner in toner aggregation discharging product flows so can further suppress image.

Constituent material as the part that contacts with image carrier of toner holding member for example can use non-woven or brush etc., also can use other by fibroplastic cloth etc.Use under the situation of non-woven, stick sponge and then this sponge is fixed on the axle etc. of SUS or metal in the bottom of non-woven and use, non-woven also can be made the roller shape.

Power as making toner holding member vibration can use external power supplys such as motor, perhaps also the driving force of image carrier or other imaging devices can be sent on the toner holding member by gear etc.In addition, the vibration period be preferably 0.1 second～5 seconds to guarantee that toner does not break away from from the toner holding member.

In addition, when cleaning balde is fixed on the cleaning device main body with the direction that is directed upwardly with respect to gravity by metal laminated spring, by ribbon that resins such as polyester are formed to be attached on the sheet metal, to form the toner gathering with the axially consistent direction of cleaning balde.Herein, the end of ribbon is mounted to than the terminal outstanding form of cleaning balde.

Like this, if the region clustering that the toner of being removed by cleaning balde marks off at above-mentioned ribbon a certain amount of or accumulate in the zone that this marks off more than a certain amount of toner, then contacts with image carrier.

Toner is assembled like this and the toner accumulated, its a part of contact image supporting body, and the discharging product on absorption image carrier surface, and the result can suppress the image that discharging product causes and flow.

In addition, by material, length or the thickness that changes above-mentioned ribbon, can adjust the toner maintenance dose of toner aggregation, and, by the logical hole of leaking of toner is set on ribbon, make the toner circulation of toner aggregation, form the toner aggregation, so also can make the producing property raising of discharging product by the new toner that pours at any time.In addition, in the occasion of actively utilizing the toner aggregation to the producing property of discharging product, reduce the pressure of toner holding member to image carrier, removing with toner holding member and toner aggregation only is a certain amount of discharging product.

On the other hand, image carrier charged is that the discharge that utilizes Charging system such as charged roller to produce is carried out, and image carrier surface charging to the needed discharge capacity of regulation current potential can be changed according to the humiture of the mould of image carrier, imaging device periphery.

For the thickness of image carrier, general thickness is more little then more little for obtaining the needed discharge capacity of certain specific charged current potential, thus adjust discharge capacity according to thickness, thus the generation of discharging product can be suppressed at necessary irreducible minimum.In addition, temperature, humidity are high more, and is then more little for obtaining the needed discharge capacity of certain specific charged current potential, thus adjust discharge capacity according to temperature or humidity, thus the generation of discharging product can be suppressed at necessary irreducible minimum.

Therefore, detecting the thickness or the humiture of image carrier with certain means, serves as the discharge capacity that necessary minimum is determined on the basis with its result, thereby also can effectively suppress to become the generation that the image stream movable property is given birth to the discharging product of reason.Whereby, flow even produce image, the degree of its generation is also low weight, and utilizes cleaning balde of the present invention with this state, and it also is easy suppressing image significantly mobile.

On the other hand, handle box of the present invention is not had particular determination, need only the cleaning device of the present invention that it comprises image carrier and is used to clean the surface of this image carrier, and this handle box can load and unload on imaging device.Imaging device of the present invention is not had particular determination, as long as it comprises at least one cleaning device of the present invention, this cleaning device is used to clean at least one parts that are cleaned that is arranged in the imaging device, as image carrier and intermediate transfer body etc.For example, under use has situation with the so-called tandem arrangement of the corresponding a plurality of image carriers of each colour toners, can cleaning device of the present invention be set respectively at each image carrier.In addition, except cleaning device of the present invention, if necessary, can be used in combination cleaning brush etc.

-image carrier (photoreceptor)-

As the image carrier that is used for handle box and imaging device, can use known photoreceptor such as organic photoreceptor and inorganic photoreceptors such as for example amorphous silicon photoconductor and selenium type photoreceptor usually, preferably use at the Organophotoreceptor that has outstanding advantage aspect cost, productivity and the disposability.

Organophotoreceptor is not particularly limited, as long as it is included in the photographic layer on the conductive base at least, and in the present invention, preferably comprise the Organophotoreceptor of function divergence type photographic layer so that effectively show clean-up performance, described function divergence type photographic layer is by the charge generation layer of lamination and charge transport layer are formed successively on conductive base.In addition, if necessary, can on the surface of photographic layer, form sealer, can also form the middle layer between photographic layer and the conductive base or between photographic layer and sealer.

The example of described conductive base can comprise for example made metal drum (metal drum) of aluminium, copper, iron, stainless steel, zinc and nickel; By will be for example metals such as aluminium, copper, gold, silver, platinum, palladium, titanium, nickel-chromium, stainless steel, copper-indium deposit to the conductive base that obtains on the base materials such as sheet material, paper, plastics, glass for example; By depositing to the conductive base that obtains on the above-mentioned base material as conductive metal compounds such as indium oxide, tin oxide; By metal foil layer being pressed onto the conductive base that obtains on the above-mentioned base material; And by carbon black, indium oxide, tin oxide-antimony oxide powder, metal powder and cupric iodide being distributed in the adhesive resin and this potpourri being coated to the conductive base that obtains on the above-mentioned base material.The shape of this conductive base can be drum type, sheet or tabular.

In addition, as under the situation of conductive base, the surface of the tubular matrix that is made of metal can be without polishing at the tubular matrix that will be made of metal, and perhaps in advance this matrix surface carried out surface roughening and handle.As under the situation of exposure light source, this surface roughening can prevent that the contingent grain of wood shape of the event density unevenness of photoreceptor internal cause interference light is even in jamming light source such as for example laser beam.As being used for described surface-treated method, can enumerate mirror-finish cutting, etching, anodic oxidation, rough cut, centerless grinding, sandblast, wet type honing etc.

Specifically, just improve with regard to the stickability and film forming of photographic layer, preferably with the surface through anodised aluminum substrate as described conductive base.

By charge generating material is deposited or apply the solution that comprises charge generating material, organic solvent or adhesive resin with vacuum vapor deposition method, to form charge generation layer.

As charge generating material, can use: for example amorphous selenium, crystallinity selenium, selenium-tellurium alloy, selenium-arsenic alloy, other inorganic photoconductors such as selenium compound, selenium alloy, zinc paste and titanium dioxide; These materials are carried out dye sensitization and the material that obtains; Various phthalocyanine compounds such as for example metal-free phthalocyanine, titanyl phthalocyanine, copper phthalocyanine, tin phthalocyanine and gallium phthalocyanine; For example squarilium, flower anthrone (various organic pigments such as anthoanthrone), perylene, azo, anthraquinone, pyrene, pyralium salt, thiapyran salt; Or dyestuff.

Organic pigment has multiple crystal structure usually, and particularly for the situation of phthalocyanine compound, known have for example multiple crystal formation such as α type and β type, so long as provide light sensitivity and with the pigment of corresponding other performance of purpose, can adopt any crystal formation.

In above-mentioned charge generating material, preferred phthalocyanine compound.In this case, when photographic layer was subjected to the irradiation of light, the phthalocyanine compound that is included in the photographic layer can absorb photon, and produced charge carrier.At this moment, because phthalocyanine compound has high quantum efficiency, this compound can absorb the photon that is absorbed efficiently and produce charge carrier.

As the adhesive resin that is used for charge generation layer, can enumerate following example.That is, bisphenol A-type or bisphenol z-polycarbonate resin and multipolymer thereof, polyarylate resin, vibrin, methacrylic resin, acrylic resin, poly-(vinyl chloride) resin, polystyrene resin, poly-(vinyl acetate) resin, Styrene-Butadiene resin, vinylidene chloride-acrylonitrile compolymer resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin and poly-(N-vinylcarbazole).

These adhesive resins can use separately or two or more mixing in them is used.The mixed weight of charge generating material and adhesive resin is than (charge generating material: adhesive resin) preferably in 10: 1 to 1: 10 scope.The thickness of charge generation layer is preferred usually in the scope of 0.01 μ m～5 μ m, more preferably in the scope of 0.05 μ m～2.0 μ m.

In order to improve light sensitivity, to reduce rest potential and fatigue when using repeatedly, charge generation layer can comprise at least a electron acceptor material.As the electron acceptor material that is used for charge generation layer, can enumerate: for example, succinic anhydride, maleic anhydride, dibromomaleic acid acid anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, four cyanogen paraquinones bismethanes, o-dinitrobenzene, meta-dinitro-benzent, chloranil, dinitroanthraquinone, trinitro-fluorenes, trinitrophenol, o-nitrobenzoic acid, paranitrobenzoic acid and phthalic acid.Wherein preferred especially Fluorenone type, quinoid or have as Cl, CN, NO ₂Benzene derivative Deng electron-withdrawing substituent.

The method that charge generating material is scattered in resin can be to use the method for roll mill, bowl mill, vibromill, masher, ball mill (Dyno-mill), sand mill, colloid mill etc.

As the solvent of the coating solution that forms charge generation layer, can use known organic solvent usually, aromatic hydrocarbon type solvent for example is as toluene, chlorobenzene etc.; Fatty alcohol type solvent, for example methyl alcohol, ethanol, n-propanol, isopropyl alcohol and normal butyl alcohol; Ketone type solvent, for example acetone, cyclohexanone and 2-butanone; The aliphatic solvent of halogenation is methylene chloride, chloroform and ethylene dichloride for example; Cyclic ethers type or linear type solvent, for example tetrahydrofuran, diox, ethylene glycol, ether; With ester type solvent, for example methyl acetate, ethyl acetate and n-butyl acetate.

As charge transport layer, can use the charge transport layer that forms by common known method.Described charge transport layer can be by using charge transport materials and adhesive resin or using polymer charge-conveying materials to form.

The example of charge transport materials can comprise the electric transmission compound, and quinonoid compound for example is as 1,4-benzoquinone, chloranil, tetrabromoquinone and anthraquinone; Tetracyano-p-quinodimethane type compound; The Fluorenone compound, for example 2,4, the 7-trinitro-fluorenone; Xanthone type compound, diphenyl ketone type compound, cyano group vinyl-type compound and ethylene type compound; The electron hole transport compound is as triarylamine type compound, benzidine compound, aromatic yl paraffin type compound, have the ethylene type compound of aryl substituent; Stilbene type compound, anthracene type compound and hydrazone type (hydazone type) compound.

These charge transport materials can use separately or two or more form with potpourri in them is used, but described material is not limited to above-mentioned example.These charge transport materials can use separately or two or more form with potpourri in them is used, and consider flowability, the material shown in preferred use following structural formula (1)～(3).

Structural formula (1)

In the structural formula (1), R ¹⁴Expression hydrogen or methyl; N represents 1 or 2; Ar ₆And Ar ₇Independently the expression have substituting group (or not having substituting group) aryl or-C (R ¹⁸)=C (R ¹⁹) (R ²⁰) ,-CH=CH-CH=C (Ar) ₂, and described substituting group can be halogen atom, have 1～5 carbon atom alkyl, have the alkoxy of 1～5 carbon atom or have the amino of the alkyl substituent that contains 1～3 carbon atom.

Structural formula (2)

In the structural formula (2), R ¹⁵And R ¹⁵' can be identical or different, and represent hydrogen, halogen atom independently, have the alkyl of 1～5 carbon atom or have the alkoxy of 1～5 carbon atom; R ¹⁶, R ¹⁶', R ¹⁷And R ¹⁷' can be identical or different, and represent hydrogen, halogen atom independently, have 1～5 carbon atom alkyl, have 1～5 carbon atom alkoxy, have the alkyl substituent that contains 1～2 carbon atom amino, have substituting group (or not having substituting group) aryl or-C (R ¹⁸)=C (R ¹⁹) (R ²⁰) ,-CH=CH-CH=C (Ar) ₂

In structural formula (1) and (2), R ¹⁸, R ¹⁹And R ²⁰Represent hydrogen independently, have substituting group (or not having substituting group) alkyl or have the aryl of substituting group (or not having substituting group); M and n represent 0～2 integer independently.

Structural formula (3)

In the structural formula (3), R ₂₁The expression hydrogen atom, have 1～5 carbon atom alkyl, have 1～5 carbon atom alkoxy, have substituting group (or not having substituting group) aryl or-CH=CH-CH=C (Ar) ₂R ₂₂And R ₂₃Can be identical or different, and represent hydrogen atom, halogen atom independently, have 1～5 carbon atom alkyl, have 1～5 carbon atom alkoxy, have the amino of the alkyl substituent that contains 1～2 carbon atom or have the aryl of substituting group (or not having substituting group).

With regard to the substituting group in structural formula (1)～(3), Ar represents the to have substituting group aryl of (or not having substituting group).

Can be polycarbonate resin as charge transport layer with the example of adhesive resin, vibrin, methacrylic resin, acrylic resin, poly-(vinyl chloride) resin, poly-(vinylidene chloride) resin, polystyrene resin, poly-(vinyl acetate) resin, Styrene-Butadiene, vinylidene chloride-acrylonitrile copolymer, vinyl chloride vinyl acetate copolymer, vinyl chloride-vinyl acetate-copolymer-maleic anhydride, silicones, silicon-alkyd resin, phenolics, styrene-alkyd resin; Polymer charge-conveying materials, for example poly-(N-vinylcarbazole), polysilane and Japanese kokai publication hei 8-176293 number and specially open the polyester polymer charge transport materials described in flat 8-208820 number.These adhesive resins can use separately, or two or more form with potpourri in them is used.The mixed weight ratio of charge transport materials and adhesive resin is preferably 10: 1 to 1: 5.

Polymer charge-conveying materials can use separately.As polymer charge-conveying materials, can adopt known material usually, as poly-(N-vinylcarbazole) and polysilane with charge transport properties.Specifically, Japanese kokai publication hei 8-176293 number and special open the polyester polymer charge transport materials shown in flat 8-208820 number and have high charge transport properties, therefore especially preferred.Polymer charge-conveying materials can be directly used in charge transport layer, also can be used in combination with above-mentioned adhesive resin to form charge transport layer.

The thickness of charge transport layer is preferably 5 μ m～50 μ m usually, more preferably 10 μ m～30 μ m.As coating process, can adopt conventional method, for example knife coating, Mel (Mayor) rod are coated with method, spraying process, dip coating, Tu Bianfa (bead coating), airblade coating method and curtain coating method.In addition, as the solvent that is used to form charge transport layer, can use or be used in combination in the following solvent two or more separately: aromatic hydrocarbon, for example benzene,toluene,xylene and chlorobenzene; Ketone, for example acetone and 2-butanone; The fat hydrocarbon solvent of halogenation, for example methylene chloride, methenyl choloride and ethylene dichloride; Cyclic ethers type solvent or linear type solvent are as tetrahydrofuran and ether.

Aging in order to prevent the photoreceptor that causes by the ozone that in duplicating machine, produces or oxidizing gas or light or heat, can in photographic layer, add adjuvant, for example antioxidant, light stabilizer or thermal stabilizer etc.For example can enumerate hindered phenol, hindered amine, p-phenylenediamine (PPD), aromatic yl paraffin, quinhydrones, volution benzodihydropyran, volution indenone and their derivant as antioxidant; Organic sulfide and organic phosphorus compound.The example of light stabilizer can be benzophenone, benzotriazole, dithiocarbamate, tetramethyl piperidine and their derivant.

In order to improve light sensitivity, the fatigue when reduction residual electric potential and inhibition are used repeatedly can add at least a electron acceptor material.The example that can be used as described electron acceptor material among the present invention can be the compound of succinic anhydride, maleic anhydride, dibromomaleic acid acid anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyano-p-quinodimethane, o-dinitrobenzene, meta-dinitro-benzent, chloranil, dinitroanthraquinone, trinitro-fluorenone, trinitrophenol, o-nitrobenzoic acid, m-Nitrobenzoic Acid and phthalic acid and general formula (1) definition.Wherein, particularly preferably be Fluorenone type, quinoid or have for example Cl, CN or NO ₂Benzene derivative Deng electron-withdrawing substituent.

The outermost surface of image carrier preferably contains for example layer and the layer that comprises the resin with cross-linked structure of the fluorinated resin particle of polytetrafluoroethylene (PTFE).

By on the conductive base successively under the situation of the function divergence type photographic layer formed of the charge generation layer of lamination and charge transport layer, described charge transport layer can comprise fluorinated resin particle at the photographic layer of image carrier.Perhaps, the sealer that forms on charge transport layer can comprise the resin with cross-linked structure.

Forming on the image carrier surface under the situation of the charge transport layer that comprises described fluorinated resin particle, friction force between cleaning balde and the image carrier surface reduces, these the feasible scratch and abrasion that can suppress the image carrier surface, and can suppress cleaning balde edge termination wearing and tearing and produce gap, to prolong the life-span of image carrier itself, can be suppressed between image carrier and the cleaning balde simultaneously and form the space, thus the service time of prolongation cleaning capacity.

Fluorinated resin particle is being added under the situation of charge transport layer, general assembly (TW) with respect to the material that constitutes this charge transport layer, the content of fluorinated resin particle 0.1 weight %～40 weight % preferably in this charge transport layer, be more preferably 1 weight %～30 weight %, to be more preferably be 3 weight %～10 weight %.If this content is lower than 0.1 weight %, be under the situation of contact-type charger at the charger of image carrier, disperse fluorinated resin particle to become not enough sometimes with the effect of reducing friction.On the other hand, if this content surpasses 40 weight %, the transmitance and the charge transport properties of charge transport layer obviously reduce, sometimes because of using residual electric potential to increase repeatedly.

As being used for fluorinated resin particle of the present invention, preferably suitably be selected from one or more resins and polymkeric substance in tetrafluoroethylene resin, trifluorochlorethylene resin, hexafluoropropylene resin, fluoride-based resin, vinylidene fluoride resin, dichloro difluoroethylene resin and their multipolymer, particularly preferably be tetrafluoroethylene resin and vinylidene fluoride resin.

The initial mean grain size of fluorinated resin particle is preferably 0.05 μ m～1 μ m, more preferably 0.1 μ m～0.5 μ m.If initial mean grain size tends to impel its aggegation, if greater than 1 μ m, often produce the image quality defective less than 0.05 μ m when disperseing.

Forming under the situation of the sealer that comprises resin on the image carrier surface,, can enumerate phenol resin, urethane type resin and silicone-type resin as resin with cross-linked structure with cross-linked structure.Because these resins with cross-linked structure have excellent mar proof, so wearing and tearing take place on the image carrier surface or form scratch even after long-term the use, still can suppress.

In addition, the resin that more preferably has a cross-linked structure further contains the charge transfer material.As resin with cross-linked structure, can use various materials, but preferred phenol resin, urethane resin and silicone resin etc. on the characteristic, the material that preferred especially siloxane-based resin forms.Wherein, particularly have by the general formula (I) or (II) material of structure of the compound deriving of expression, intensity, stable aspect excellence, so be particularly preferred.

F-[D-Si(R ²) _(3-a)Q _a] _b (I)

In the general formula (I), F represents that D represents pliability subelement, R by the organic group of the compound deriving with cavity conveying energy ²The aryl of expression hydrogen, alkyl, replacement or non-replacement, Q represents hydrolization group; A represents 1～3 integer, and b represents 1～4 integer.

Pliability subelement as representing with D in the general formula (I) must contain-(CH ₂) _n-group, also can be on this group combination-COO-,-O-,-CH=CH-,-CH=N-group and the divalent straight chain group that obtains.-(CH ₂) _nThe n of-group represents 1～5 integer.In addition, as the hydrolization group of representing with Q, expression-OR group (wherein, R represents alkyl).

F-((X)nR ₁-ZH)m (II)

In the general formula (II), F represents the organic group by the compound deriving with cavity conveying energy, R ₁The expression alkylidene, Z represents-O-,-S-,-NH-or-COO-, m represents 1～4 integer.X represents-O-or-S-, n represents 0 or 1.

As the preferred material of compound, can enumerate the material that organic group F especially uses the group of following general formula (III) expression with general formula (I), (II) expression.

Chemical formula 4

In the general formula (III), Ar ₁～Ar ₄The aryl of representing replacement or non-replacement respectively independently, Ar ₅The aryl or the arlydene of expression replacement or non-replacement, and Ar ₁～Ar ₅In 2～4 have with in general formula (I)-D-Si (R ²) _(3-a)Q _aThe binding groups of expression.D represents pliability subelement, R ²The aryl of expression hydrogen, alkyl, replacement or non-replacement, Q represents hydrolization group, a represents 1～3 integer.

Ar in the general formula (III) ₁～Ar ₄The aryl of representing replacement or non-replacement respectively independently, the group shown in the preferred particularly following structural group 1.

Chemical formula 5

Structural group 1

In addition, the Ar shown in the structural group 1 is preferably the group of selecting from following structural group 2, and Z ' is preferably the group of selecting from following structural group 3.

Chemical formula 6

Structural group 2

Chemical formula 7

Structural group 3

-(CH ₂)q--(CH ₂CH ₂O) _r-

In the structural group 1～3, R ⁶Be selected from hydrogen, have alkyl, the alkyl of 1～4 carbon atom or have phenyl or the unsubstituted phenyl that the alkoxy of 1～4 carbon atom replaces, aralkyl with 7～10 carbon atoms through having 1～4 carbon atom.

R ⁷～R ¹³Phenyl that be selected from hydrogen, have the alkyl of 1～4 carbon atom, the alkoxy with 1～4 carbon atom, the alkoxy through having 1～4 carbon atom replaces or unsubstituted phenyl, aralkyl, halogen with 7～10 carbon atoms.

M and s represent 0 or 1, and q and r represent 1～10 integer, and t represents 1～3 integer.Herein, X represent with shown in general formula (I)-D-Si (R ²) _(3-a)Q _aThe group of expression.

W shown in the structural group 3 is preferably the group of representing with following structural group 4.In addition, in the structural group 4, the integer of s ' expression 0～3.

Chemical formula 8

Structural group 4

-CH ₂--C(CH ₃) ₂--O--S--C(CF ₃) ₂--Si(CH ₃) ₂-

In addition, as Ar in the general formula (III) ₅Concrete structure, the Ar shown in the said structure group 1 in the time of can enumerating k=0 ₁～Ar ₄The structure of m=1 and the Ar shown in the said structure group 1 during k=1 ₁～Ar ₄The structure of m=0.

As the concrete example of the compound shown in the general formula (III), can enumerate the compound (III-1)～(III-61) of expression in the following table 1, but the compound of representing with general formula (III) used in the present invention is not limited only to these compounds.

[Ar in the table 1 ₁]～[Ar ₅] in the structural formula shown in the hurdle, be bonded in " S " group on the phenyl ring ' mean that 1 valency group shown in [S] hurdle in the table 1 (is equivalent in the general formula (I)-D-Si (R ²) _(3-a)Q _aThe group of the structure of expression).

Table 1

As the concrete example of general formula (II), can enumerate the compound shown in following (II)-1～(II)-26.But the invention is not restricted to these compounds.

Chemical formula 9

Chemical formula 10

Chemical formula 11

In addition, in order to control various rerum naturas such as intensity, membrane impedance, also can add compound with following general formula (IV) expression.

Si(R ²) _(4-c)Q _c (IV)

In general formula (IV), R ²Expression hydrogen, alkyl, replacement or unsubstituted aryl, Q represents water-disintegrable group, c represents 1～4 integer.

As the concrete example of the compound of representing with general formula (IV), can enumerate as following silane coupling agent.

Can enumerate the alkoxy silane (c=4) of 4 functionalities such as tetramethoxy-silicane, tetraethoxysilane; Methyltrimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, methyl trimethoxy oxygen base oxethyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-An Jibingjisanyiyangjiguiwan, the gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyl dimethoxysilane, N-β (amino-ethyl) γ-An Jibingjisanyiyangjiguiwan, (13 fluoro-1,1,2,2-tetrahydrochysene octyl group) triethoxysilane, (3,3,3,-three fluoro propyl group) trimethoxy silane, 3-(seven fluorine isopropoxies) propyl-triethoxysilicane, 1H, 1H, 2H, 2H-perfluoroalkyl triethoxysilane, 1H, 1H, 2H, 2H-perfluor decyl triethoxysilane, 1H, 1H, 2H, the alkoxy silane (c=3) of 3 functionalities such as 2H-perfluoro capryl triethoxysilane; The alkoxy silane (c=2) of 2 functionalities such as dimethyldimethoxysil,ne, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane; The alkoxy silane (c=1) of 1 functionality such as trimethyl methoxy silane etc.In order to improve film strength, preferred 3 and the alkoxy silane of 4 functionalities, in order to improve pliability, film forming, preferred 2 and the alkoxy silane of 1 functionality.

In addition, also can use the silicon of these coupling made of main usefulness is hard coating agent.As commercially available hard coating agent, can use KP-85, X-40-9740, X-40-2239 (more than be SILICONE company of SHIN-ETSU HANTOTAI make) and AY42-440, AY42-441, AY49-208 (more than be Toray Dow Corning company make) etc.

In addition, in order to improve intensity, also preferred use as general formula (V) in represent have a compound more than or equal to 2 silicon atoms.

B-(Si(R ²) _(3-a)Q _a) ₂ (V)

In general formula (V), B represents divalent organic group, R ²Expression hydrogen, alkyl, replacement or unsubstituted aryl, Q represents water-disintegrable group, a represents 1～3 integer.

Particularly, the material that can enumerate expression in following table 2 is as preferred material, but the present invention is not limited to this.

Table 2

And then, for controlling diaphragm characteristic, prolongation solution life-span etc., can be added on soluble resin in alcohol system, the ketone series solvent.As such resin, the part that can enumerate polyvinyl butyral resin, vinyl-formal resin, butyral by with modifications such as dimethoxym ethane or acetals polyvinyl acetal resins such as part polyvinyl alcohol of acetalization acetal resin (for example ponding chemical company make Eslek B, K etc.); Polyamide; Celluosic resin; Phenol resin etc.Preferably polyethylene acetal resin aspect electrical characteristics especially.

In addition, for the purpose of discharge gas patience, physical strength, scoring resistance, particle dispersiveness, viscosity control, torque reduction, abrasion value control, prolongation useful life etc., can add various resins.Particularly under the situation of siloxane-based resin, preferably be added in the resin that dissolves in the alcohol.

As soluble resin in pure series solvent, the part that can enumerate polyvinyl butyral resin, vinyl-formal resin, butyral by with modifications such as dimethoxym ethane or acetals polyvinyl acetal resins such as part polyvinyl alcohol of acetalization acetal resin (for example ponding chemical company make Eslek B, K etc.); Polyamide; Celluosic resin; Phenol resin etc.Preferably polyethylene acetal resin aspect electrical characteristics particularly.

The molecular weight of above-mentioned resin preferred 2000～100000, further preferred 5000～50000.If molecular weight just can not obtain desirable effect less than 2000, if will reduce greater than 100000 solubleness, thereby or limited addition, perhaps when coating, become the reason of bad film forming.The preferred 1 weight % of the addition of above-mentioned resin～40 weight %, further preferred 1 weight %～30 weight %, most preferably 5 weight %～20 weight %.When addition is less than 1 weight %, be difficult to obtain desirable effect,, then probably can be easy to take place image blurring under hot and humid if more than 40 weight %.In addition, these resins can be used alone, but also also mix together.

In addition, for the ring compound that prolongs useful life, controlling diaphragm characteristic, can contain constitutional repeating unit or the derivant of this compound with following general formula (VI) expression.

Chemical formula 12

In chemical formula (VI), A ¹, A ²The organic group of representing monovalence respectively independently.

As ring compound, can enumerate commercially available annular siloxane with constitutional repeating unit of expression in the chemical formula (VI).Particularly, can enumerate hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ring-type dimethyl cyclosiloxane classes such as ten diformazan basic rings, six siloxane, 1,3,5-trimethyl-1,3,5-triphenyl cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7, ring-type methyl phenyl ring siloxane classes such as 9-pentaphene basic ring five siloxane, ring-type phenyl ring siloxane classes such as hexaphenyl cyclotrisiloxane, 3-(3,3,3-three fluoro propyl group) methyl cyclotrisiloxane etc. contains the cyclosiloxane class of fluorine, the hydrogenated methyl mixture of siloxanes, the pentamethyl D5, phenyl hydrogenation cyclosiloxane etc. contains the cyclosiloxane class of hydrogenation silicyl, and five vinyl pentamethyl D5s etc. contain annular siloxane of cyclosiloxane class of vinyl etc. etc.These cyclic siloxane compounds can be used alone, but also also mix together.

And then, in order to improve anti-pollution thing tack, the lubricity of photosensitive surface, also can add various particulates.These particulates can use separately, also can and use.As an example of particulate, can enumerate the particulate that contains silicon.The particulate that what is called contains silicon is meant the particulate that contains silicon in component, particularly, can enumerate cataloid and silicone particulate etc.The cataloid that uses as the particulate that contains silicon, mean grain size is 1nm～100nm, preferred mean grain size be 10nm～30nm and be selected from the aqueous dispersions that is distributed to acidity or alkalescence or organic solvents such as alcohol, ketone, ester in material, generally can use commercially available material.Though there is no particular limitation, but consider from film forming, electrical characteristics, intensity aspect, the solid component content of cataloid accounts for the scope of the 0.1 weight %～50 weight % in the superficial layer all solids composition in the superficial layer, preferably uses in the scope of 0.1 weight %～30 weight %.

As the employed silicone particulate of the particulate that contains silicon is spherical, mean grain size is 1nm～500nm, preferred mean grain size is 10nm～100nm and is selected from silicone resin particle, silicone rubber particle, silicone surface processing silicon dioxide granule, generally can use commercially available material.The silicone particulate be chemically inert, to the dispersed superior path particle of resin, and then, reduce necessary content in order to obtain sufficient characteristic, therefore can not hinder cross-linking reaction and can improve the surface texture of photoreceptor.That is, under the state of in firm cross-linked structure, being enclosed equably, improved lubricity, the water proofing property of photosensitive surface, through also keeping good abrasion performance, anti-pollution thing tack for a long time.In the photoreceptor of the present invention, the content of the silicone particulate in the superficial layer is the 0.1 weight %～30 weight % that account for superficial layer all solids composition, the scope of preferred 0.5 weight %～10 weight %.

In addition, as other particulates, can enumerate fluorine such as tetrafluoroethene, trifluoro-ethylene, hexafluoropropylene, fluorothene, vinylidene is particulate, or such shown in " the 8th polymeric material forum give a lecture pre-original text collection the 89th page ", contain the particulate that makes the resin that monomer copolymerization with above-mentioned fluororesin and hydroxyl obtains, ZnO-Al ₂O ₃, SnO ₂-Sb ₂O ₃, In ₂O ₃-SnO ₂, ZnO-TiO ₂, ZnO-TiO ₂, MgO-Al ₂O ₃, FeO-TiO ₂, TiO ₂, SnO ₂, In ₂O ₃, semiconductions such as ZnO, MgO metal oxide.

In addition, under identical purpose, also can add silicone wet goods oil.As silicone oil, for example can enumerate silicone oils such as dimethyl polysiloxane, diphenyl polysiloxane, phenyl methyl siloxane, the silicone oil of amino modified polysiloxane, epoxy radicals modified polyorganosiloxane, carbonyl modified polyorganosiloxane, methyl alcohol modified polyorganosiloxane, isobutenyl modified polyorganosiloxane, sulfhydryl modified polysiloxane, phenol modified polyorganosiloxane isoreactivity.

In addition, the rate of exposing to the protective seam surface of above-mentioned particulate is preferably smaller or equal to 40%.If exceed aforementioned range, the influence of particle monomer will increase, and takes place easily to flow based on the image of Low ESRization.The further preferable range of aforementioned range is smaller or equal to 30%, the particle that exposes the from the teeth outwards portion's material that is cleaned is regenerated effectively, through the toner components filming that also can suppress photosensitive surface for a long time, remove discharge product, the abrasion of keeping the cleaning section material that reduces based on torque reduce.

In addition, also can use adjuvants such as plastifier, surface modifier, antioxidant, anti-light aging agent.As plastifier, for example can enumerate various fluorinated hydrocarbons such as phenylbenzene, chlorination phenylbenzene, terphenyl, dibutyl phthalate, diglycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene.

Can add the antioxidant with hindered phenol, hindered amine, thioether or phosphite ester part-structure in protective seam, the potential stability image quality during to the raising environmental change is effective.As antioxidant, can enumerate following compound, for example be as hindered phenol, can enumerate " Sumilizer BHT-R " that sumitomo chemical company is made, " Sumilizer MDP-R ", " Sumilizer BBM-S ", " Sumilizer WX-R ", " Sumilizer NW ", " Sumilizer BP-76 ", " SumilizerBP-101 ", " Sumilizer GA-80 ", " Sumilizer GM ", " Sumilizer GS ", " Sumilizer ", the vapour Bart plants " IRGANOX1010 " that chemical company is made, " IRGANOX1035 ", " IRGANOX1076 ", " IRGANOX1098 ", " IRGANOX1135 ", " IRGANOX1141 ", " IRGANOX1222 ", " IRGANOX1330 ", " IRGANOX1425WL ", " IRGANOX1520L ", " IRGANOX245 ", " IRGANOX259 ", " IRGANOX3114 ", " IRGANOX3790 ", " IRGANOX5057 ", " IRGANOX565 ", " the ADK STAB AO-20 " that rising sun electrification is made, " ADK STAB AO-30 ", " ADK STAB AO-40 ", " ADK STAB AO-50 ", " ADK STAB AO-60 ", " ADK STAB AO-70 ", " ADK STAB AO-80 ", " ADK STAB AO-330 "; As hindered amine system, can enumerate " SANOL LS 2626 ", " SANOL LS 765 ", " SANOL LS 770 ", " SANOL LS744 ", " TINUVIN 144 ", " TINUVIN 622LD ", " MARK LA 57 ", " MARKLA 67 ", " MARK LA 62 ", " MARK LA 68 ", " MARK LA 63 ", " SumilizerTPS "; As thioether system, can enumerate " Sumilizer TP-D "; As phosphite ester system, can enumerate " MARK 2112 ", " MARK PEP8 ", " MARK PEP24G ", " MARKPEP36 ", " MARK 329K ", " MARK HP10 ".And, these materials also can with can with the material generation cross-linking reaction that forms cross linking membrane, substituting group such as for example alkoxysilyl carries out modification.

For the coating fluid that is used to form protective seam, preferably when making this coating fluid, add or the use catalyzer.As employed catalyzer, can use mineral acids such as hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, base catalysts such as potassium hydroxide, NaOH, calcium hydroxide, ammonia, triethylamine can also use insoluble solid catalyst in system shown below.

For example can enumerate ambrite 15, ambrite 200C, ambrite 15E (more than be Rohm and Haas company make); Dowex MWC-1-H, Dowex 88, DowexHCR-W2 (more than be DOWCHEMICAL company make); Lewatit SPC-108, Lewatit SPC-118 (more than be Beyer Co., Ltd make); Diaion RCP-150H (Mitsubishi changes into company and makes); Sumika Ion KC-470, Duolite C-26-C, Duolite C-433, Duolite-464 (more than be Sumitomo Chemical Co. Ltd. make); Nafion-H Zeo-karbs such as (manufacturings of DUPONT company); Anion exchange resins such as AMBERLITE IRA-400, AMBERLITE IRA-45 (more than be Rohm and Haas company make); Be combined with from the teeth outwards and contain Zr (O ₃PCH ₂CH ₂SO ₃H) ₂, Th (O ₃PCH ₂CH ₂COOH) ₂Inoganic solids Deng the group of proton acidic group; Have sulfonic polysiloxane etc. and contain the polysiloxane of proton acidic group; Different polyacid such as cobalt wolframic acid, phosphomolybdic acid; Isopolyacids such as niobic acid, tantalic acid, molybdic acid; Elemental metals oxides such as silica gel, aluminium oxide, chromium oxide, zirconia, calcium oxide, magnesium oxide; Composite metal oxides such as silica-alumina, monox-magnesium oxide, monox-zirconia, zeolite; Clay minerals such as Emathlite, atlapulgite, smectite, smalite; Metal sulfate such as lithium sulfate, magnesium sulphate; Metal phosphate such as basic zirconium phosphate, lanthanum orthophosphate; Metal nitrate such as lithium nitrate, manganese nitrate; The solid that aminopropyltriethoxywerene werene is reacted and obtain etc. is combined with the inoganic solids that contains amino group from the teeth outwards; Ammonia modified silicone resin etc. contains amino polysiloxane etc.

In addition, when making coating fluid,, then have the trend that improves application liquid stability if in exhibiting optical function compound, resultant of reaction, water, solvent etc., use insoluble solid catalyst, thus preferred.So-called in system insoluble solid catalyst, as long as catalyst component is the compound represented among general formula (I), (II), (III), (V) and insoluble in other adjuvant, water, solvent etc., there is no particular limitation.The use amount of these solid catalysts has no particular limits, but with respect to the compound with hydrolization group that adds up to 100 weight portions, it is preferably 0.1 weight portion～100 weight portions.And as mentioned above, these solid catalysts are because insoluble in starting compound, resultant of reaction, solvent etc., and therefore the reaction back can easily be removed according to well-established law.Temperature of reaction and reaction time are suitably selected according to the kind and the use amount of starting compound, solid catalyst, and temperature of reaction is generally 0 ℃～100 ℃, and preferred 10 ℃～70 ℃, more preferably 15 ℃～50 ℃, preferred 10 minutes～100 hours of reaction time.If the reaction time surpasses above-mentioned higher limit, just have the trend that is easy to cause gelation.

In the coating fluid production process in the use system during insoluble catalyzer, in order to improve intensity and to improve solution storage stability etc., further in the preferred system and use soluble catalyzer.As such catalyzer, except above-mentioned substance, can also use organo-aluminum compounds such as three aluminium ethylates, aluminum isopropylate, three aluminium secondary butylates, single sec-butoxy diethyl aluminium propoxide, diisopropoxy (ethyl acetoacetate) aluminium, tri ethylacetoacetate aluminium, ethyl diacetoacetate single acetyl pyruvic acid aluminium, praseodynium acid aluminium, diisopropoxy (acetopyruvic acid) aluminium, isopropoxy two (acetopyruvic acid) aluminium, three (three fluoro acetopyruvic acids) aluminium, three (hexafluoro acetopyruvic acid) aluminium.

Except that organo-aluminum compound, also can use organo-tin compounds such as dibutyltin dilaurate, dibutyl tin dicaprylate, dibutyl tin diacetate esters; Organic titanic compounds such as four (acetopyruvic acid) titanium, two (butoxy) two (acetopyruvic acid) titaniums, two (isobutoxy) two (acetopyruvic acid) titaniums; Organic zirconates such as four (acetopyruvic acid) zirconium, two (butoxy) two (acetopyruvic acid) zirconiums, two (isobutoxy) two (acetopyruvic acid) zirconiums etc., but viewpoint from security, low cost, useful life length, preferred organo-aluminum compound, the more preferably aluminium chelate compound of using.The use amount of these catalyzer is not limited especially, but preferably with respect to the total amount of the compound with hydrolization group of 100 weight portions, the use amount of catalyzer is 0.1 weight portion～20 weight portions, is preferably 0.3 weight portion～10 weight portions especially.

In the occasion of using organometallics as catalyzer, consider from the aspect of useful life, curing efficiency, preferably add multidentate ligand simultaneously.As such multidentate ligand, the material that can enumerate material as follows and derive by these materials, but the invention is not restricted to these materials.

Specifically can enumerate beta-diketon classes such as pentanedione, trifluoroacetyl benzylacetone, hexafluoro pentanedione, two valeryl methyl acetones; Acetoacetic ester such as methyl acetoacetate, ethyl acetoacetate; Pyridine and derivant thereof; Glycocoll and derivant thereof; 1,2-ethylenediamine and derivant thereof; Oxine and derivant thereof; Salicylide and derivant thereof; Catechol and derivant thereof; 2 tooth parts such as 2-hydroxyl azo-compound; Diethyl triamine and derivant thereof; 3 tooth parts such as itrile group triacetic acid and derivant thereof; 6 tooth parts such as ethylenediamine tetraacetic acid (EDTA) and derivant thereof etc.And then, except that organic system part as described above, can enumerate the part of inorganic systems such as pyrophosphoric acid, triphosphoric acid.As multidentate ligand, preferred 2 tooth parts, concrete example can be enumerated 2 tooth parts with following general formula (VII) expression except that above-mentioned.Wherein more preferably use 2 tooth parts of following general formula (VII) expression, the R in the preferred especially following general formula (VII) ⁵And R ⁶2 identical tooth parts.By making R ⁵And R ⁶Identical, near the coordination power of the part the room temperature strengthens, the further stabilization that can seek coating fluid.

Chemical formula 13

In the general formula (VII), R ⁵And R ⁶Respectively independently expression have 1～10 carbon atom alkyl or fluoro-alkyl, have the alkoxy of 1～10 carbon atom.

The blending amount of multidentate ligand can be set arbitrarily, but preferably with respect to 1 mole of employed organometallics, and the blending amount is more than or equal to 0.01 mole, be preferably greater than or equal 0.1 mole, more preferably greater than or equal 1 mole.

The manufacturing of coating fluid also can be carried out under solvent-free condition, but can use alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols as required; Ketone such as acetone, MEK; Tetrahydrofuran; Ethers such as Anaesthetie Ether, diox etc. also can use other all kinds of solvents.As such solvent, preferred boiling point is less than or equal to 100 ℃, can mix use arbitrarily.Quantity of solvent can be set arbitrarily, if but quantity of solvent is crossed at least that organo-silicon compound are easy to separate out, so preferably with respect to 1 weight portion organo-silicon compound, solvent is 0.5 weight portion～30 weight portions, be preferably 1 weight portion～20 weight portions.

Temperature of reaction and reaction time when coating fluid is solidified do not have particular determination, but from the physical strength of the silicones that obtains and the angle of chemical stability, temperature of reaction preferably is greater than or equal to 60 ℃, and more preferably 80 ℃～200 ℃, the reaction time is preferably 10 minutes～and 5 hours.In addition, coating fluid is solidified the protective seam that obtains remain on the high humility state, this is being effective aspect stabilization of seeking the protective seam characteristic.And then, also can use hexamethyldisilazane and trimethyl chlorosilane etc. that protective seam is implemented surface treatment and make its hydrophobization according to purposes.

It is also abundant that the resin bed that comprises the resin that has charge transport properties and have cross-linked structure has excellent physical strength and photoelectric characteristic, so it directly can be used as the charge transport layer of lamination type photoreceptor.In this case, can use knife coating, Mel rod to be coated with usual ways such as method, spraying process, dip coating, Tu Bianfa, airblade coating method, curtain coating method.Wherein, by once being coated with under the situation that can not obtain necessary thickness, can obtain necessary thickness by repeatedly being coated with repeatedly.Under situation about repeatedly being coated with repeatedly, heat treated can be coated with all at every turn carries out, and also can repeatedly carry out after the coating repeatedly again.

Under the situation of single-layer type photographic layer, contain the charge generating material addressed previously and adhesive resin and form photographic layer.As adhesive resin, can use and aforementioned charge generation layer and the identical resin of the employed adhesive resin of electric charge transport layer.The content of the charge generating material in the single-layer type photographic layer is the degree of 10 weight %～85 weight %, is preferably 20～50 weight %.In order to improve purposes such as photoelectric characteristic, also can in the single-layer type photographic layer, add charge transport materials and polymer charge transferring material.Its addition is preferably 5 weight %～50 weight %.In addition, also can add the compound of representing with general formula (I).Be coated with used solvent and coating process and can use as hereinbefore solvent and method.Thickness is preferably the degree of 5 μ m～50 μ m, more preferably 10 μ m～40 μ m.

-toner-

Comprise the imaging device of handle box of the present invention and cleaning device or the toner of imaging device of the present invention as being used to, can use usually known toner and, but this toner preferably has and is lower than 140 shape coefficient SF without any special restriction.If shape coefficient SF more than or equal to 140, may be difficult to obtain good transfer printing performance sometimes, and the image that is difficult to obtain having high image quality.

Described shape coefficient SF is the value of following (13) definition that establishes an equation.

Formula (13): SF=ML ²/ (4A/ π)

Wherein ML represents the maximum length (μ m) of this toner; A represents projected area (the μ m of this toner ²).

Can use LUZEX image dissector (FT is made by NIRECOCorp.) to measure shape coefficient SF according to method as described below.

At first, take the optical microscopic image that is sprayed on the toner on the microslide, and, measure 50 toner-particles maximum length (ML) and projected area (A) separately this image input LUZEX image dissector with video camera.Then, calculate (maximum length value square)/(4 * projected area/π), i.e. ML respectively at each toner-particle ²/ (4A/ π), and the mean value of each value is defined as shape coefficient SF.

On the other hand, be used for the volume average particle size that toner of the present invention preferably has 2 μ m～8 μ m, to obtain high quality images.

Used toner comprises adhesive resin and the colorant as neccessary composition among the present invention, can comprise release agent and other adjuvant in case of necessity.As adhesive resin, can use the adhesive resin that is generally used for toner and without any special restriction.

The instantiation of adhesive resin is: the homopolymer of following monomer, and described monomer is for styrene for example, to chlorostyrene and α-Jia Jibenyixi; Acrylic monomer, for example methyl acrylate, ethyl acrylate, acrylic acid n-propyl, lauryl acrylate and acrylic acid-2-ethyl caproite; Methacrylic monomer, for example methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, lauryl methacrylate and methacrylic acid-2-Octyl Nitrite; Ethylenic unsaturated acid monomer, for example acrylic acid, methacrylic acid and Sodium styrene sulfonate; Vinyl nitrile, for example vinyl cyanide and methacrylonitrile; Vinyl ether, for example vinyl methyl ether and vinyl isobutyl ether; Vinyl ketone, for example vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; And alkene, for example ethene, propylene and butadiene; In these monomers two kinds or more than the multipolymer of two kinds monomer; And the potpourri of described homopolymer and described multipolymer.

In addition, can enumerate potpourri: non-vinyl condensed type resin, for example epoxy resin, vibrin, urethane resin, polyamide, celluosic resin and polyether resin by these homopolymer, multipolymer and potpourri and following mixed with resin; Or with the potpourri of above-mentioned vinyl-type mixed with resin; And under the coexistence of these polymkeric substance and potpourri the graft polymer by the vinyl-type monomer polymerization is obtained.

As colorant, can use usually known colorant and without any special restriction.Can enumerate: various pigment, for example carbon black, chrome yellow, hansa yellow, benzidine yellow, intellectual circle's Huang (ThreneYellow), quinoline yellow, permanent orange GTR, pyrazolone orange, Vulcan orange, C lake red CAN'T (WatchungRed), permanent red, bright carmine 3B, brilliant carmine 6B, Du Pont (Du-pont) oil red, pyrazolone red, lithol red, rhodamine B lake, lake red C, rose-red, aniline blue, ultramarine blue, copper oil blue (Chalco Oil Blue), protochloride methyl indigo plant, phthalocyanine blue, phthalocyanine green and peacock green oxalate; With various dyestuffs, the for example blue or green, dioxazine of acridine, xanthene, azo, benzoquinones, azine, anthraquinone, thioindigo, thiazine, azomethine, indigo-blue, phthalocyanine, nigrosine, polymethine, triphenylmethane, diphenyl-methane and thiazole (thioazole) type, these pigment and dyestuff can use separately or two or more is used in combination.

The example that adds as required in the used toner of the present invention as the material of release agent is a low-molecular-weight polyolefin, for example tygon, polypropylene and polybutylene; Silicone oil; Fatty acid amide, for example oleamide, mustard seed acid amides, castor-oil plant acid amides and stearmide; Vegetable wax, for example Brazil wax, rice wax, candelila wax, turbid wax (haze wax) and jojoba oil; Animal wax, for example beeswax; Mineral wax or pertroleum wax, for example montan wax, ceresine, ceresin, paraffin, microcrystalline wax and f-t synthetic wax and their modified product.Can be with at least a adding toner-particle in these waxes.

In order to control various performances, the various compositions except that mentioned component can be added toner.For example, as under the situation of magnetic color tuner, can add Magnaglo (for example ferrite and magnetic iron ore) at described toner; As metals such as reduced iron, cobalt, nickel and manganese; Compound with alloy that comprises described metal and described metal.In addition, as required, can suitably select the charge control agent used always for example quaternary ammonium salt, nigrosine type compound and triphenyl methane type pigment, and it is added toner.

Method to the used toner of production the present invention is not particularly limited, can use known toner production process, for example produce the method for toner in the following manner: conventional comminuting method, be used for known polymerization usually such as the wet type fusion-nodularization method of producing and for example suspension polymerization, dispersin polymerization, emulsion polymerization agglutination at dispersion medium.

The toner that uses among the present invention can an amount of fine inorganic particles of additional mixing, and for example mean grain size is silica and titania, the lapping compound of about 0.2 μ m～3 μ m and the lubricant of about 3 μ m～15 μ m of 10nm～300nm.The carriers such as ferrite pearl that can be 35 μ m with the toner that so obtains and for example mean grain size mix, to obtain two-component developer.

The instantiation of-cleaning balde, imaging device and cleaning device-

Then, will describe cleaning balde of the present invention in detail, use the imaging device of this cleaning balde and the instantiation of cleaning device together with accompanying drawing.

Fig. 1 shows that the example of imaging device of the present invention is the synoptic diagram of so-called tandem type imaging device.

Among Fig. 1, the 21st, body shell; 22,22a～22d is an imaging engine; The 23rd, the band assembly; The 24th, the recording materials supply box; The 25th, the recording materials drive access; The 30th, each photoreceptor unit; The 31st, photoconductor drum; The 33rd, each developing cell; The 34th, cleaning device; 35,35a～35d is a toner Cartridge; The 40th, exposing unit; The 41st, cell enclosure; The 42nd, polygon prism; The 51st, the primary transfer device; The 52nd, the secondary transfer printing device; The 53rd, the band cleaning device; The 61st, paper-feed roll; The 62nd, get paper bowl; The 63rd, alignment rolls (resist roll); The 66th, fixing device; The 67th, exit roller; The 68th, the paper delivery pallet; The 71st, the manual paper feeding device; The 72nd, paper-feed roll, the 73rd, double-sided recording modes unit; The 74th, guide roller; The 76th, drive access; The 77th, transfer roller; The 230th, intermediate transfer belt; 231 and 232 is a frame roller (over-striding roll); The 521st, secondary transfer roller; The 531st, cleaning balde.

Tandem type imaging device shown in Fig. 1 comprises: four looks of landscape configuration in body shell 21 (being black, yellow, magenta and cyan in this embodiment) imaging engine 22 (is specially 22a～22d); Place the band assembly 23 of described engine top, this band assembly 23 comprises along the intermediate transfer belt 230 of the configuration direction cyclic transfer of each imaging engine 22; Recording materials supply box 24, this supply box is positioned at the bottom of body shell 21, and for example paper of recording materials (not shown) is housed; With the recording materials drive access 25 of arranged perpendicular, this path is the path that sends from writing down the recording materials of material supplies box 24.

In this embodiment, (22a～22d) is used for forming toner image successively from the upstream side of the loop direction of middle transfer belt 230 each imaging engine 22, black, yellow, magenta and cyan (described configuration is not necessarily according to this order) toner image for example, each engine comprises each photoreceptor unit 30, each developing cell 33 and shared exposing unit 40 respectively.

By will be for example following component-assembled be integral and sub-box type made in photoreceptor unit 30: photoconductor drum 31, be used for photoconductor drum 31 is carried out precharge charging device (Fig. 1 is not shown, hereinafter will be described the charging roller shown in Fig. 2 32) and is used to remove the cleaning device 34 of the remaining toner on the photoconductor drum 31.

Developing cell 33 is used for making the color toner corresponding with electrostatic latent image (this embodiment is a negative polarity) to develop, described electrostatic latent image is exposed on charged photoconductor drum 31 by exposing unit 40, described developing cell 33 with comprise that for example the sub-box of photoreceptor unit 30 (sub cartridge) is integrated, thereby constitute handle box (so-called CRU:Customer Replaceable Unit (client's replaceable units)).

Photoreceptor unit 30 can be arranged with developing cell and form CRU into independent in 33 minutes.Among Fig. 1, (35a～35d) expression is used for each colour content toner is supplied to the toner Cartridge (the toner feed path is not shown) of corresponding developing cell 33 to Reference numeral 35.

On the other hand, exposing unit 40 is equipped with for example four semiconductor lasers (not shown) of being positioned at unit housings 41, polygon prism 42, imaging len (not shown) and corresponding to each reflective mirror (not shown) of each photoreceptor unit 30, this constitute to make can be by polygon prism 42 deflections and scanning from the light corresponding to the semiconductor laser of each colour content, and light image is directed at corresponding exposure station on the photoconductor drum 31 via imaging len and mirror.

In this embodiment, band assembly 23 is by constituting intermediate transfer belt 230 horizontal hanging between a pair of the frame roller (one of them is a driven roller) 231 and 232, primary transfer device (in this example for primary transfer roller) 51 is arranged on the back side of the intermediate transfer belt 230 corresponding with the photoconductor drum 31 of each photoreceptor unit 30, and by polarity and the opposite polarity voltage of toner charge are applied to primary transfer device 51, thereby under electrostatic interaction, the toner image on the photoconductor drum 31 is transferred to intermediate transfer belt 230 sides.Corresponding to the position of opening frame roller 232 secondary transfer printing device 52 is being set, so that with the described primary transfer image secondary transfer printing (transfer printing in the lump) on the intermediate transfer belt 230 to recording materials, described frame roller 232 is positioned at the downstream of imaging engine 22d, and described imaging engine 22d is positioned at the downstream of intermediate transfer belt 230.

In this embodiment, secondary transfer printing device 52 comprises with undertake the printing of secondary transfer roller 521 that the mode of face is provided with and be configured in intermediate transfer belt 230 rear side, form the backing roll (in this example shared open frame roller 232) of the counter electrode of secondary transfer roller 521 of the toner image of crimping intermediate transfer belt 230.With described secondary transfer roller 521 ground connection, and the bias voltage that polarity is identical with the polarity of toner charge is applied to backing roll (opening frame roller 232).

In addition, at the upstream side of the imaging engine 22a of the upstream side that is positioned at intermediate transfer belt 230 band cleaning device 53 is set, to remove the remaining toner on the intermediate transfer belt 230.

In addition, in recording materials supply box 24, be provided for picking up the intake roller 61 of recording materials, and after being right after intake roller 61, be provided for sending recording materials get paper bowl 62, and the position before being right after the secondary transfer printing position on the recording materials drive access 25, be provided for recording materials being supplied to the alignment rolls (registration roll) 63 at secondary transfer printing position by predetermined timing (timing).On the other hand, fixing device 66 is set in place on the recording materials drive access 25 of the position, downstream at secondary transfer printing position, the exit roller 67 that will be used to discharge recording materials is arranged on the downstream of fixing device 66, and the recording materials of discharge will be packed in the paper delivery pallet 68 that forms in the top of body shell 21.

In this embodiment manually feeding mechanism (MSI) 71 be arranged on the side of body shell 21, by intake roller 72 with get paper bowl 62 recording materials on the manual feeding mechanism 71 are sent to recording materials drive access 25.

In addition, double-sided recording modes unit 73 is attached on the body shell 21, when the duplexmode of document image on the two sides that is chosen in recording materials, double-sided recording modes unit 73 is by reverse rotation exit roller 67, and uses guide roller 74 importing inside through the recording materials of single face record before inlet; Transfer roller 77 with right quantity transmits these recording materials along recording materials echo-plex path 76; And once more these recording materials are supplied to alignment rolls 63.

Then, detailed description is configured in the cleaning device 34 of tandem type imaging device inside shown in Figure 1.

Fig. 2 is the synoptic diagram that shows the example of cleaning device of the present invention, with the cleaning device shown in Fig. 1 34, has also shown sub-box type photoconductor drum 31, charging roller 32 and developing cell 33 simultaneously.

Among Fig. 2, the 32nd, charging roller (charging device), the 331st, unit housings, the 332nd, developer roll, the 333rd, transmit spiral, the 334th, transmit blade, the 335th, arrangement parts (trimming member), the 341st, cleaning housing, the 342nd, cleaning balde, the 344th, membrane seal, the 345th, transmit spiral.

Cleaning device 34 comprises and is used for putting remaining toner therein and has cleaning housing 341 with photoconductor drum 31 opening opposing, cleaning balde 342 is attached to the lower edge of the opening of the cleaning housing 341 that contacts photoconductor drum 31 with carriage not shown in the accompanying drawing, on the other hand, will be used to keep and photoconductor drum 31 between bubble-tight membrane seal 344 be attached to the top edge of the opening of cleaning housing 341.Reference numeral 345 expressions are used for importing the transmission spiral of having used toner container with toner with what cleaning housing 341 was equipped with.

Then, will describe the cleaning balde that is configured in the cleaning device 34 in detail together with accompanying drawing.

Fig. 3 is the synoptic diagram that shows an example of cleaning balde of the present invention, and this figure explains cleaning balde shown in Figure 2 342 and the photoconductor drum 31 that contacts with this cleaning balde have been described.Among Fig. 3,342a is the layer of cleaning edge side, and 342b is the layer of rear side.The cleaning balde 342 that Fig. 3 shows is to be made of two-layer: with the layer 342a of photoreceptor 31 contacted cleaning edge sides and the layer 342b of rear side; And make by the urethane rubber elastomeric material.

The polyurethane material that constitutes the layer 342b of rear side can be ester type polyurethane and ether-based polyurethane, preferably the ester type polyurethane.

When producing ester type polyurethane rubber, can use the pure and mild polyisocyanates of polyester polyols.

As polyisocyanates, can enumerate 2,6-toluene diisocyanate (TDI), 4,4 '-'-diphenylmethane diisocyanate (MDI), PPDI (PPDI), 1,5-naphthalene diisocyanate (NDT), 3,3-dimethyl diphenyl-4,4 '-diisocyanate (TODI).Consider performance and cost, preferred especially MDI.

When using above-mentioned polyester polyol to produce urethane rubber, the pure and mild short chain polyvalent alcohol as chain extender of polyester polyols is mixed and react with polyisocyanates.For example prepolymer method and single-step process etc. are carried out this reaction to conventional method that can be by producing polyurethane.

Except be used to form the back side the layer 342b material, can also use the soft chain segment material that satisfies above-mentioned (1)～condition that (4) are limited to make the layer 342a of cleaning edge side, described soft chain segment material is for for example having the acrylic resin of two or more hydroxyls, the epoxy resin that has the polybutadiene of two or more hydroxyls or have two or more epoxy radicals.

With the cleaning edge side the layer 342a THICKNESS CONTROL at 0.5mm, with rear side the layer 342b THICKNESS CONTROL at 1.5mm.The layer 342a of cleaning edge side that can be by production sheet in advance and the layer 342b of rear side, and adopt sticker, double sticky tape etc. that the material of each layer is sticked together to make cleaning balde 342.In addition, under the situation of producing by centrifugal casting, when make-up machine injects the raw material of each layer, inject described material successively to form cleaning balde by the regular hour difference.

In addition, the contact pressure of 342 pairs of photoconductor drums 31 of cleaning balde is set to about 2.0～6.0gf/mm (=2.0 * 10 ^-3* 9.8N/mm to 6.0 * 10 ^-3* 9.8N/mm).

In this embodiment, in all cleaning devices 34 of each imaging engine 22 (22a to 22d), use cleaning balde of the present invention as cleaning balde 342, in addition, the cleaning balde 531 that is used for described band cleaning device 53 also can be a cleaning balde of the present invention.

As shown in Figure 2, the developing cell (developing apparatus) 33 that is used for this embodiment of the present invention comprises and is storing developer and having unit housings 331 with photoconductor drum 31 opening opposing.Developer roll 332 is arranged on towards the position of the opening of unit housings 331, in unit housings 331, is provided for stirring and transmitting the transmission spiral 333 of developer.In addition, as required, transmit blade 334 and can be arranged between developer roll 332 and the transmission spiral 333.

During development, developer feeding to developer roll 332, under the condition with the layer thickness of arrangement parts 335 control developers, is sent to the developing regional relative with photoconductor drum 31 with developer.

In this embodiment,, use to comprise the two-component developer of toner and carrier, but also can use the developing cell of the one-pack type developer that is used for only comprising toner as developing cell 33.

Under the situation of using two-component developing agent, after BCO took place, the carrier fragment may be imbedded and anchor in the surface of image carrier 30.Yet, even in this case, because cleaning device 34 is equipped with cleaning balde of the present invention, thus generation that still can the long term inhibition gap, and can keep favourable cleaning performance continuously.

Can use above-mentioned toner as being used for the toner of this embodiment, and consider that transfer printing performance and image quality, described toner preferably have and be lower than 140 shape coefficient SF.

Then, the operation of the related imaging device of this embodiment will be described in detail.At first, when (when 22a～22d) formed corresponding to the monochromatic toner image of each color, overlapping successively and primary transfer and made it and initially original copy information is consistent to the surface of intermediate transfer belt 230 with monochromatic toner image of all kinds with each imaging engine 22.Subsequently, to be transferred to the surface that intermediate transfer belt 230 lip-deep color toner images are transferred to recording materials with secondary transfer printing device 52, and carry out photographic fixing with the recording materials of 66 pairs of transfer printing chromatic colours of fixing device toner image and handle, then it is expelled to paper delivery pallet 68.

On the other hand, each imaging engine 22 (among the 22a～22d), the remaining toner of removing on the photoconductor drums 31 with cleaning device 34, and with the remaining toner on the band cleaning device 53 removing intermediate transfer belts 230.

In this formation method, remove remaining toner by cleaning device 34 (or band cleaning device 53).

In addition, as shown in Figure 2, cleaning balde 342 can directly not be fixed on the frame parts in the cleaning device 34, and fixes by spring material.

Fig. 4 is the synoptic diagram of an example of the fixing means of expression cleaning balde of the present invention, among the figure, and 342 expression cleaning baldes, 342c represents spring material, 342d represents support.As shown in Figure 4, a face (not contacting the face on sensitization side) of cleaning balde 342 engages and to be fixed on the tabular spring material 342c, and this spring material 342c is equipped with support 342d, and described support is installed in and the fixing opposite side of cleaning balde side.As spring material 342c, can utilize the low metal parts such as SUS of temperature dependency that are difficult to produce plastic yield, Young modulus.

As shown in Figure 4, for the situation that cleaning balde is fixed in the frame parts of cleaning device by spring material and support, because spring material supports the pressurization of cleaning balde, therefore compare with the situation that cleaning balde is fixed on the frame parts of cleaning device, can suppress the fatigure failure of cleaning balde, reduce to contact the environment interdependence of pressure simultaneously.Thereby through long-time, cleaning balde is pressed stable to the contact of photoreceptor, can keep excellent clean-up performance.

Embodiment

Hereinafter, will the present invention be described with preferred embodiment, but this and mean that the present invention only limits to the embodiment of being set forth.Under the situation that does not break away from main idea of the present invention and scope, can make amendment and replace specific process conditions and structure.

The production of-cleaning balde-

＜cleaning balde A1 〉

At first, hard segment materials and soft chain segment material are mixed with 8: 2 (by weight), wherein hard segment materials comprises polycaprolactone polyol as polyol component (by Daicel ChemicalIndustries, Ltd. the Placcel 205 of Sheng Chaning, mean molecular weight is 529, hydroxyl value is 212mgKOH/g) and polycaprolactone polyol (by Daicel Chemical Industries, Ltd. the Placcel 240 of Sheng Chaning, mean molecular weight is 4155, hydroxyl value is 27mgKOH/g), described soft chain segment material comprises the acrylic resin (grinding the Actflow UMB-2005B that chemical society produces by combining) that contains two or more hydroxyls.

Then, potpourri that 100 weight portions are made up of hard segment materials and soft chain segment material and 6.26 weight portions 4 as isocyanate compound, 4 '-'-diphenylmethane diisocyanate is (by NipponPolyurethane Industry Co., Ltd. the Millionate MT of Sheng Chaning, MDI hereinafter referred to as) mix, and under nitrogen atmosphere in 70 ℃ of reactions 3 hours.

Selection is used for the amount of the isocyanate compound of this reaction, is 0.5 to regulate isocyanate group contained in this reaction system to the ratio (isocyanate group/hydroxyl) of hydroxyl.

Then, further the above-mentioned isocyanate compound with 34.3 weight portions adds wherein, reacts 3 hours to obtain prepolymer in 70 ℃ under nitrogen atmosphere.

The total amount of employed isocyanate compound is 40.56 weight portions when using this prepolymer.

Then, this prepolymer is heated to 100 ℃, and under reduced pressure froth breaking 1 hour, then, with respect to the prepolymer of 100 weight portions, with this prepolymer and 7.14 weight portions by 1, the potpourri that 4-butylene glycol and trimethylolpropane (weight ratio=60/40) are formed mixes, fully mixed 3 minutes so that entrained foam not wherein, be adjusted to 140 ℃ centrifugal shaper with mold temperature then and be cured to obtain flat board.Make this flat board at 110 ℃ after crosslinked 24 hours, with its cooling, and to be cut into preliminary dimension be the cleaning balde A1 of 2mm to obtain thickness.

＜cleaning balde A2 〉

As hard segment materials, use used same hard segment materials when producing cleaning balde A1, and as the soft chain segment material, the weight ratio of described hard segment materials and soft chain segment material is 8: 2 to use the polybutadiene (by the R-45HT of the emerging product of bright dipping society production) with two or more hydroxyls.

Except using described potpourri, produce cleaning balde A2 in the mode identical with embodiment 1.

＜cleaning balde A3 〉

As hard segment materials, use used same hard segment materials when producing cleaning balde A1, and as the soft chain segment material, the weight ratio of described hard segment materials and soft chain segment material is 8: 2 to use epoxy resin with two or more epoxy radicals (the EPICLON EXA-4850-150 that is produced by big Japanese ink chemical industry society).

Except using described potpourri, produce cleaning balde A3 in the mode identical with embodiment 1.

＜cleaning balde A4 〉

In the preparation of cleaning balde A1, the blending ratio of hard segment materials and soft chain segment material was changed to 9: 1, in addition,, obtain cleaning balde A4 to be prepared with the same mode of cleaning balde A1.

＜cleaning balde A5 〉

In the preparation of cleaning balde A1, the blending ratio of hard segment materials and soft chain segment material was changed to 96: 4, in addition,, obtain cleaning balde A5 to be prepared with the same mode of cleaning balde A1.

＜cleaning balde A6 〉

In the preparation of cleaning balde A1, the blending ratio of hard segment materials and soft chain segment material was changed to 98: 2, in addition,, obtain cleaning balde A6 to be prepared with the same mode of cleaning balde A1.

＜cleaning balde B1 〉

Produce cleaning balde B1 in the mode identical with embodiment 1, difference is only to use polyol component to replace the potpourri of being made up of hard segment materials and soft chain segment material, and with the Nippollan 4038 of 6.8 weight portions (by Nippon Polyurethane Industry Co., Ltd. production) Coronate 4086 as polyol component (by NipponPolyurethane Industry Co., Ltd. produces) as isocyanate compound and 100 weight portions is used in combination.

＜cleaning balde B2 〉

Produce cleaning balde B2 in the mode identical with embodiment 1, difference is only to use polyol component to replace the potpourri of being made up of hard segment materials and soft chain segment material, and with the Nippollan 4379 of 75 weight portions (by Nippon Polyurethane Industry Co., Ltd. production) Coronate 4370 as polyol component (by NipponPolyurethane Industry Co., Ltd. produces) as isocyanate compound and 100 weight portions is used in combination.

＜cleaning balde B3 〉

Produce cleaning balde B3 in the mode identical with embodiment 1, difference is only to use polyol component to replace the potpourri of being made up of hard segment materials and soft chain segment material, and with the Nippollan 4379 of 85 weight portions (by Nippon Polyurethane Industry Co., Ltd. production) Coronate 4370 as polyol component (by NipponPolyurethane Industry Co., Ltd. produces) as isocyanate compound and 100 weight portions is used in combination.

The production of-photoreceptor-

＜photoreceptor A 〉

Acquisition is used to form the coating fluid of bottom by the following method: the organic zirconate (diacetone butyric acid zirconium) of 30 weight portions and the organic silane compound (gamma-amino propyl trimethoxy silicane) of 3 weight portions are added the normal butyl alcohol of 170 weight portions and mixing with it, wherein be dissolved with the polyvinyl butyral resin (by the S-Lec BM-S of ponding chemistry society production) of 4 weight portions in this normal butyl alcohol.

This coating fluid is coated in the mode of dipping that the external diameter of surface roughening is the aluminum support of 40mm by the honing processing, and at room temperature air-dry 5 minutes, with 10 minutes the support that obtains is heated to 50 ℃ then, after this support being placed 50 ℃, the constant temperature and humidity of 85%RH (47 ℃ of dew points) indoor, it is added moisture curing promote to handle 20 minutes.Afterwards, this support is put into air drier 170 ℃ of dryings 10 minutes to form bottom.

As charge generating material, use gallium chloride-phthalocyanine complex, and the potpourri that uses sand mill will comprise the normal butyl alcohol of the described complex compound of 15 weight portions, the vinyl chloride-vinyl acetate copolymer resin of 10 weight portions (by the VMCH of Nippon Unicar Co.Ltd. production) and 300 weight portions disperses 4 hours to obtain dispersion liquid.By dipping this dispersion liquid is coated on described bottom, and dry formation film thickness is the charge generation layer of 0.2 μ m.

Then, N with 40 weight portions, N '-two (3-aminomethyl phenyl)-N, bisphenol Z-the polycarbonate resin of N '-diphenylbenzidine and 60 weight portions (molecular weight is 40000) fully is dissolved in the monochloro-benzene of the tetrahydrofuran of 235 weight portions and 100 weight portions and mixes with it, thereby obtain coating fluid, by dipping this coating fluid is applied to the aluminum support that is coated with charge generation layer, be the charge transport layer of 24 μ m to form film thickness in 40 minutes 120 ℃ of dryings then, thereby obtain photoreceptor A.

＜photoreceptor B 〉

N with 40 weight portions, N '-two (3-aminomethyl phenyl)-N, bisphenol Z-the polycarbonate resin of N '-diphenylbenzidine and 60 weight portions (molecular weight 40000) fully is dissolved in 280 weight portion tetrahydrofurans and 120 parts by weight of toluene and mixes with it, again to the tetrafluoroethylene resin particle that wherein adds 10 weight portions and further mix.

At this moment, room temperature is set at 25 ℃, and the fluid temperature will mix the time remains on 25 ℃.Then, by the sand mill that uses beaded glass this potpourri is dispersed into the tetrafluoroethylene resin particle dispersion.At this moment, make 24 ℃ the container of water by sand mill remain on 50 ℃ with temperature with this dispersion liquid.

In the same manner as described above, thus obtained coating fluid is applied to the surface of the cylindrical substrate that is coated with charge generation layer in the mode of dipping, and was the charge transport layer of 25 μ m to form film thickness in 40 minutes, thereby obtain photoreceptor B 120 ℃ of dryings.

＜photoreceptor C 〉

The following compound 1 of 2 weight portions and the Resitop PL 4852 of 2 weight portions (by the flourish chemical production of group) are dissolved in the isopropyl alcohol of 10 weight portions to obtain being used to form the coating fluid of protective seam.The coating fluid that is used to form protective seam is applied to the charge transport layer of the photoreceptor of under the condition identical, producing with the working condition of photoreceptor A in the mode of dipping; difference is the film thickness of charge transport layer is become 22 μ m; at room temperature air-dry then 30 minutes; be the protective seam of 4 μ m to form film thickness in 60 minutes further then, thereby obtain photoreceptor C 140 ℃ of following dryings.

Compound 1

Above-described cleaning balde A1～A3 and B1～B3 and photoreceptor A～C are made up by the described mode of table 3, and be installed in the imaging device (by the DocuCentre Color 400CP of Fuji Xerox Co., Ltd's manufacturing), carry out various assessments test, the composition of result and the cleaning balde that is used to test and physical property are combined be shown in table 3.

The expression be used for embodiment 1～3 and Comparative Examples 1～3 cleaning balde the mutual relationship of answering variation and stress chart as shown in Figure 5.

The appraisal procedure and the evaluation criteria that are used to assess edge abrasion, edge gap, photoreceptor scratch and photoreceptor rate of wear are as follows.

-edge abrasion-

When the assessment edge abrasion, use the paper (210 * 297mm of A4 size, P paper by the production of society of Fuji-Xerox) carries out imaging, up under high temperature, high humidity environment (28 ℃, 85%RH) the accumulative total number of revolutions of photoreceptor reaches 100,000 circles (k-cycle), assesses the wearing and tearing and the cleaning condition of poor of the edge termination of each cleaning balde afterwards together.

In when test, in order under harsh conditions, to assess, the image density of the image that form is set at 1%, described harsh conditions are meant the condition that the lubricant effect of the contact portion between photoreceptor and the cleaning balde is little.

Then, use the wearing depth of the laser microscope VK-8510 that produces by the Keyence Corp edge termination after the sectional side observation test of each cleaning balde, and measure the depth capacity of each cleaning balde in the edge of photosensitive surface side gap part.

After finishing above-mentioned test; clean bad assessment; by will be formed with not transfer printing on the spot image (paper of the A3 size of picture size: 400mm * 290mm) is sent between photoreceptor and each cleaning balde with normal process speed on the spot; and after the rearmost end of this uncertain image on direction of transfer partly passed contact portion between photoreceptor and the cleaning balde; this device is shut down, and the hangover of the toner that detects by an unaided eye (passing through).Observing under the situation of obvious hangover, can think to clean bad.

Cause stopping up the part that stops toner and produce under the situation of gap wearing and tearing taking place owing to edge termination and produce gap, along with the wearing depth and the gap degree of depth at edge deepens, often easier generation cleaning is bad in the above-mentioned test, makes this test very useful for the wearing and tearing and the gap of qualitative evaluation edge termination like this.The evaluation criteria of edge abrasion is shown in table 2.The scope that allows is G0-G2.

Table 4

The edge abrasion evaluation grade	The wearing depth at edge	Clean bad
			G0	Be less than or equal to 3 μ m and do not have wear print	Do not take place
G1	Be less than or equal to 3 μ m	Do not take place
			G2	Greater than 3 μ m and be less than or equal to 5 μ m	Do not take place
G3	Greater than 3 μ m and be less than or equal to 5 μ m	Take place
			G4	Greater than 5 μ m and be less than or equal to 10 μ m	Take place
G5	Greater than 10 μ m	Take place

-edge gap-

The edge gap is owing to be attached to the contact portion of foreign matter between photoreceptor and cleaning balde of photosensitive surface repeatedly by causing.Therefore, under low temperature, low humidity (10 ℃ and 15%RH) environment, the elasticity of each cleaning balde all reduces, it is big that stress becomes when cleaning balde strikes foreign matter, per 5,000 circles form the toner band with 5mm width, after photoconductor drum moves 100,000 circles, measure the degree of depth and the quantity of edge gap.

When using the laser microscope VK-8510 that is produced by Keyence Corp to observe the sectional side of cleaning balde, the degree of depth of the edge gap part of the photosensitive surface side by measuring cleaning balde is measured the degree of depth of edge gap.In this case, the assessment width is the quantity of 5 μ m or wideer gap.The evaluation criteria of edge gap is shown in table 5.The scope that allows is G0-G2.

Table 5

Edge gap evaluation grade	The quantity of 5 μ m or wideer gap
		G0
	0
		G1	1～5
G2	6～10
		G3	11～20
G4	21～30
		G5	31 or more

The scratch of-photoreceptor-

Print half tone image behind running 100000 circles, the white stripes because of due to the photoreceptor scratch that occurs when printing is assessed the scratch of each photoreceptor.The evaluation criteria of photoreceptor scratch is as follows.The grade that allows is G1.

G1: do not form white stripes during printing.

G2: form white stripes during printing.

The rate of wear of-photoreceptor-

Use the vortex patern thin-film thickness meter to measure photoreceptor before described test and film thickness afterwards and calculate this difference, calculate the photoreceptor rate of wear of every operation 1000 circles of this photoreceptor with this.

The assessment of-edge local deformation-

Except that above-mentioned assessment,, also assessed edge local deformation for cleaning balde A1, A4, A5, A6.

Cleaning balde A1, A4, A5, A6 and photoreceptor A are made up shown in following table 6, be installed as imaging device (company of Fuji-Xerox produces, DocuCenter Color 400CP), to assess.Composition, the rerum natura of used cleaning balde are together listed in the following table 6 in assessment result and the experiment.

[table 6]

The appraisal procedure and the evaluation criteria of the edge local deformation shown in the table 6 are as described below.

The appraisal procedure of＜edge local deformation 〉

When assessment edge local deformation, use A4 paper (210 * 297mm, P paper by the production of company of Fuji-Xerox) carry out imaging, up to (10 ℃ of the low temperature and low humidity environment of caoutchouc elasticity reduction, adhesion and slip behavior dull, 15RH%) the accumulative total number of revolutions of photoreceptor reaches 100,000 circles down, assesses the distortion and the cleaning condition of poor of the edge termination of cleaning balde then together.

In when test, in order under harsh conditions, to assess, the image density of formation image is set at 1%, described harsh conditions are meant the condition that the lubricant effect of the contact portion between photoreceptor and the cleaning balde is little.

Then, use laser microscope VK-8510 comes the distortion of the edge termination after the observation test, and the length of the part of local deformation takes place the Width that is determined at edge termination this moment.

After finishing above-mentioned test; clean bad assessment; by will be formed with not transfer printing on the spot image (paper of the A3 size of picture size: 400mm * 290mm) is sent between photoreceptor and each cleaning balde with common process speed on the spot; and after the rearmost end of this uncertain image on direction of transfer partly passed contact portion between photoreceptor and the cleaning balde; this device is shut down, and the hangover of the toner that detects by an unaided eye.Correspondingly occur to think to clean bad under the situation of obviously hangover at the position of observing generation local deformation.

Evaluation criteria in the table 6 is as described below.

G0: do not observe edge local deformation fully, also do not produce because the cleaning that edge local deformation causes is bad.

G1: observe edge local deformation, but do not produce because the cleaning that edge local deformation causes is bad.

G2: observe edge local deformation, and produce because the cleaning that edge local deformation causes is bad.

Claims (29)

1. cleaning balde, this cleaning balde by with the surface that is used to clean the described parts that are cleaned that contacts on the surface of the parts that are cleaned, wherein, the material of the part that contacts with the surface of the described parts that are cleaned at least on the described cleaning balde is for satisfying the elastomeric material that comprises hard segment and soft chain segment of following inequality (1)～(3), and in the general assembly (TW) of material that constitutes described hard segment and the material that constitutes described soft chain segment, the weight ratio that constitutes the material of described hard segment is the 46 weight %～96 weight % of described general assembly (TW), and described inequality (1)～(3) are respectively:

Inequality (1) 3.92≤M≤29.42;

Inequality (2) 0＜α≤0.294; With

Inequality (3) S 〉=250,

In inequality (1)～(3), M represents 100% modulus, and unit is MPa; α is illustrated in the stress-strain curve, answer in the variation scope 100%～200%, STRESS VARIATION is that Δ stress is the ratio of Δ strain for strain variation, and calculate according to following formula: Δ stress/Δ answers that variation=(answering stress under the variation-at 100% stress of answering under the variation 200%)/(200-100), wherein the unit of α is MPa/%; And S represents breaking elongation, and unit is %.

2. cleaning balde as claimed in claim 1, wherein, described breaking elongation S is less than or equal to 500.

3. cleaning balde as claimed in claim 1, wherein, the glass transition temperature of the part that contacts with the surface of the described parts that are cleaned is less than or equal to 10 ℃.

4. cleaning balde as claimed in claim 1 wherein, is greater than or equal in temperature under 10 ℃ the environment, and the rebound resilience of the material of the part that contacts with the surface of the described parts that are cleaned is more than or equal to 10%.

5. cleaning balde as claimed in claim 1, wherein, described hard segment comprises urethane resin.

6. cleaning balde as claimed in claim 1, wherein, described soft chain segment comprises a kind of resin, this resin comprises isocyanate group is had reactive functional group, glass transition temperature is for being less than or equal to 0 ℃, viscosity in the time of 25 ℃ is 600mPas～35000mPas, and weight-average molecular weight is 700～3000.

7. cleaning balde as claimed in claim 6, wherein, described resin comprises acryl resin with two or more hydroxyls or the polybutadiene with two or more hydroxyls.

8. cleaning balde as claimed in claim 6, wherein, described resin comprises the epoxy resin with two or more epoxy radicals.

9. cleaning balde as claimed in claim 1, described cleaning balde is by two-layer or constitute more than two-layer layer, described two-layer or more than comprise in the two-layer layer contact with the surface of the described parts that are cleaned layer, wherein, the surfaces described and parts that are cleaned contact the layer make by the material that satisfies inequality (1)～(3).

10. cleaning device that comprises the described cleaning balde of claim 1.

11. cleaning device as claimed in claim 10, wherein, described breaking elongation S is less than or equal to 500.

12. cleaning device as claimed in claim 10, wherein, the glass transition temperature of the part that contacts with the surface of the described parts that are cleaned is less than or equal to 10 ℃.

13. cleaning device as claimed in claim 10 wherein, is greater than or equal in temperature under 10 ℃ the environment, the rebound resilience of the material of the part that contacts with the surface of the described parts that are cleaned is more than or equal to 10%.

14. handle box, described handle box comprises image carrier and cleaning device, described cleaning device has the cleaning balde that contacts with the surface of described image carrier with the surface that is used to clean described image carrier, and this handle box is made the form that can load and unload on imaging device, wherein, described cleaning balde is the described cleaning balde of claim 1.

15. handle box as claimed in claim 14, wherein, described breaking elongation S is less than or equal to 500.

16. handle box as claimed in claim 14, wherein, the glass transition temperature of the part that contacts with the surface of the described parts that are cleaned is less than or equal to 10 ℃.

17. handle box as claimed in claim 14 wherein, is greater than or equal in temperature under 10 ℃ the environment, the rebound resilience of the material of the part that contacts with the surface of the described parts that are cleaned is more than or equal to 10%.

18. handle box as claimed in claim 14, wherein, the surface of described image carrier is the layer that contains fluororesin.

19. handle box as claimed in claim 14, wherein, the surface of described image carrier is the layer that comprises resin, and described resin comprises the structural unit with charge transport ability and has cross-linked structure.

20. handle box as claimed in claim 19, wherein, described resin is the resin that is selected from the group of being made up of phenol resin, urethane resin and silicone resin.

21. imaging device, described imaging device comprises at least one be cleaned parts and one or more cleaning device, described cleaning device has the cleaning balde that contacts with the surface of the described parts that are cleaned with the surface that is used to clean these parts that are cleaned, wherein, at least one cleaning device has the described cleaning balde of claim 1.

22. imaging device as claimed in claim 21, wherein, described breaking elongation S is less than or equal to 500.

23. imaging device as claimed in claim 21, wherein, the glass transition temperature of the part that contacts with the surface of the described parts that are cleaned is less than or equal to 10 ℃.

24. imaging device as claimed in claim 21 wherein, is greater than or equal in temperature under 10 ℃ the environment, the rebound resilience of the material of the part that contacts with the surface of the described parts that are cleaned is more than or equal to 10%.

25. imaging device as claimed in claim 21, wherein, described hard segment comprises urethane resin.

26. imaging device as claimed in claim 21, wherein, described soft chain segment comprises a kind of resin, this resin comprises isocyanate group is had reactive functional group, glass transition temperature is for being less than or equal to 0 ℃, viscosity in the time of 25 ℃ is 600mPas～35000mPas, and weight-average molecular weight is 700～3000.

27. imaging device as claimed in claim 26, wherein, described resin comprises acryl resin with two or more hydroxyls or the polybutadiene with two or more hydroxyls.

28. imaging device as claimed in claim 26, wherein, described resin comprises the epoxy resin with two or more epoxy radicals.

29. imaging device as claimed in claim 21, wherein, described cleaning balde is by two-layer or constitute more than two-layer layer, described two-layer or more than comprise in the two-layer layer contact with the surface of the described parts that are cleaned layer, wherein, the surfaces described and parts that are cleaned contact the layer make by the material that satisfies inequality (1)～(3).

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