CN100498553C - Curable resin composition, electrophotographic photoreceptor, process cartridge, and image-forming apparatus - Google Patents
Curable resin composition, electrophotographic photoreceptor, process cartridge, and image-forming apparatus Download PDFInfo
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- CN100498553C CN100498553C CNB2006100935090A CN200610093509A CN100498553C CN 100498553 C CN100498553 C CN 100498553C CN B2006100935090 A CNB2006100935090 A CN B2006100935090A CN 200610093509 A CN200610093509 A CN 200610093509A CN 100498553 C CN100498553 C CN 100498553C
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Abstract
A curable resin composition for use as a constituting material of an electrophotographic photoreceptor, comprises: a phenolic resin; a charge transportable material having a reactive functional group; and at least one of an organic sulfonic acid and its derivative.
Description
Technical field
The present invention relates to hardening resin composition, Electrophtography photosensor, handle box and image forming apparatus.
Background technology
In recent years, by the technical progress and the development of each parts and system, realize having charged elements, the high speed and the long lifetime of the image forming apparatus of the so-called xerographic printing system of exposing unit, developing cell and transfer printing unit.Be accompanied by this trend, more and more higher for the demand of the high-speed response of subsystem and height reliability.Particularly, at the Electrophtography photosensor (according to circumstances being called " photoreceptor " hereinafter) that uses aspect the writing of image be used to clean the further high-speed response of cleaning unit needs and the height reliability of photoreceptor.In addition, the slip each other of photoreceptor and cleaning unit has applied very big stress to photoreceptor and cleaning unit.Therefore, photoreceptor is subject to the influence of scratch, wearing and tearing and gap, and this is the reason that causes image deflects.
On the other hand, also very strong for the demand of high image quality, and make great efforts to make toner-particle to become more meticulous, even particle size distributionization and spheroidization.As the manufacture method of the toner that satisfies this quality, developing the toner made from main moisture solvent widely, promptly so-called chemical toner.Therefore, in recent years even can obtain the quality of photographic image.
For prolonging the Electrophtography photosensor life-span, it is highly important that, improve the physical strength of the photographic layer that constitutes photoreceptor.Therefore; disclose by the method that the protective seam that uses phenolics improves the physical strength of photographic layer is set in Electrophtography photosensor, for example opened that 2002-82466 communique, spy are opened the 2002-82469 communique, the spy opens in 2003-186215 communique and the Te Kai 2003-186234 communique TOHKEMY 2002-6527 communique, spy.
Yet; though opening 2002-82466 communique, spy TOHKEMY 2002-6527 communique, spy opens 2002-82469 communique, spy and opens the physical strength of the photographic layer of disclosed Electrophtography photosensor in 2003-186215 communique and the Te Kai 2003-186234 communique and be improved by using phenolics; but must adopt electrically conductive microparticle or charge-transporting material so that photoreceptor obtains gratifying electrical characteristics; yet the use of these materials causes the reduction of physical strength; therefore, it is very difficult reaching physical strength and electrical characteristics simultaneously.
Summary of the invention
In view of the problem of correlation technique and finished the present invention.Therefore, the objective of the invention is, a kind of hardening resin composition is provided, described hardening resin composition is under the situation that forms the functional layer that contains phenolics that constitutes Electrophtography photosensor, physical strength and electrical characteristics both sides are reached an agreement on high level, and the present invention also provides Electrophtography photosensor, handle box and the image forming apparatus that uses described hardening resin composition.
The invention provides a kind of hardening resin composition, described hardening resin composition comprises: phenolics; The charge-transporting material that contains reactive functional groups; Organic sulfonic acid and/or its derivant.
According to described hardening resin composition, when forming the functional layer of Electrophtography photosensor by the charge-transporting material that is used in combination phenolics and contains reactive functional groups, the charge-transporting material that contains reactive functional groups can be mixed in the firm cross-linked structure that forms by this phenolics, make like this and can realize excellent physical strength and excellent electrical characteristics simultaneously.In addition, the organic sulfonic acid that is contained in this hardening resin composition and/or its derivant demonstrate as the excellent function that is used for phenolic resin cured catalyzer, and can quicken the curing reaction of phenolics fully, thus, the physical strength of the functional layer that is obtained can further improve.In addition, described organic sulfonic acid and/or its derivant have shown as the excellent function to the adulterant of the charge-transporting material that contains reactive functional groups, so the electrical characteristics of the functional layer that is obtained can further improve.Therefore, according to hardening resin composition of the present invention, when forming the functional layer of Electrophtography photosensor, can on high level, reach physical strength and electrical characteristics simultaneously.
In addition, also find,, can obtain to have the Electrophtography photosensor of excellent filming performance according to hardening resin composition of the present invention.The reason that can obtain excellent filming performance why is not necessarily clear, but, be due to the fact that by inference by in hardening resin composition, containing organic sulfonic acid and/or organic sulfonic acid derivant, can make in the phenolics or phenolics and the polyreaction that contains between the charge-transporting material of reactive functional groups advance expeditiously.
In hardening resin composition of the present invention, in the total solids content of hardening resin composition, the content of organic sulfonic acid and/or organic sulfonic acid derivant is preferably about 0.01 weight % to about 5 weight %.
When the content of organic sulfonic acid and/or organic sulfonic acid derivant during less than about 0.01 weight %, can not obtain enough catalytic effects, thereby make when forming the functional layer of Electrophtography photosensor, physical strength may be not enough.When content surpasses about 5 weight %, too high as the ability of adulterant, might increase dark current.
In hardening resin composition of the present invention, phenolics is preferably resol type phenol resin.By using hardening resin composition, when forming the functional layer of Electrophtography photosensor, physical strength can be further improved.
In hardening resin composition of the present invention, preferably, the charge-transporting material that contains reactive functional groups contains with following general formula (I), (II), (III), (IV) or (XVIII) one or more compounds of expression:
F[-(X
1)
n1R
1-Z
1H]
m1 (I)
Wherein F represents the organic group by the compound deriving with cavity conveying characteristic, R
1The expression alkylidene, Z
1Expression oxygen atom, sulphur atom, NH or COO, X
1Expression oxygen atom or sulphur atom, m1 represents integer 1～4, and n1 represents 0 or 1;
F[-(X
2)
n2-(R
2)
n3-(Z
2)
n4G]
n5 (II)
Wherein F represents the organic group by the compound deriving with cavity conveying characteristic, X
2Expression oxygen atom or sulphur atom, R
2The expression alkylidene, Z
2Expression oxygen atom, sulphur atom, NH or COO, G represents epoxy radicals, n2, n3 and n4 all represent 0 or 1, and n5 represents integer 1～4;
Wherein F represents that T represents divalent group by the organic group of the compound deriving with cavity conveying characteristic, and Y represents oxygen atom or sulphur atom, R
3, R
4And R
5Represent hydrogen atom or unit price organic group separately, R
6Expression unit price organic group, m2 represents 0 or 1, and n6 represents integer 1～4, and R
5And R
6Bonding and forming with Y mutually as heteroatomic heterocycle,
Wherein F represents that T represents divalent group by the organic group of the compound deriving with cavity conveying characteristic, R
7Expression unit price organic group, m3 represents 0 or 1, and n7 represents integer 1～4,
Wherein F represents the organic group by the compound deriving with cavity conveying characteristic; R
8Expression unit price organic group; L represents alkylidene; And n8 represents integer 1～4.
By in hardening resin composition, use by general formula (I), (II), (III), (IV) or (XVIII) one or more compounds of expression as the charge-transporting material that contains reactive functional groups, when forming the functional layer of Electrophtography photosensor, excellent mechanical hardness and excellent electrical characteristics are reached an agreement on higher level.
Here, at the group that is preferably by the F in the compound of above-mentioned general formula (I)～(IV) and (XVIII) expression by following general formula (V) expression:
Ar wherein
1, Ar
2, Ar
3And Ar
4Expression has substituent or does not have substituent aryl separately; Ar
5Expression has substituent or does not have substituent aryl or arlydene; And Ar
1～Ar
5Among 1～4 group and following position bonding: by the position in the compound of general formula (I) expression by following general formula (VI) expression, by the position in the compound of general formula (II) expression by following general formula (VII) expression, by the position in the compound of general formula (III) expression by following general formula (VIII) expression, by in the compound of general formula (IV) expression by the position of following general formula (IX) expression or by the position in the compound of general formula (XVIII) expression by following general formula (XIX) expression:
-(X
1)
n1R
1-Z
1H (VI)
-(X
2)
n2-(R
2)
n3-(Z
2)
n4G (VII)
—L—O—R
8 (XIX)
When in hardening resin composition, containing the charge-transporting material, under the situation of the functional layer that forms Electrophtography photosensor, can obtain electrical characteristics steady in a long-term.
The present invention also provides a kind of Electrophtography photosensor, and described photoreceptor contains electric conductivity support and the photographic layer that is arranged on this electric conductivity support, and wherein, described photographic layer has the functional layer of the cured product that comprises described hardening resin composition.
According to described Electrophtography photosensor,, can obtain excellent physical strength and excellent electrical characteristics simultaneously by having the functional layer of the cured product that contains hardening resin composition of the present invention.Therefore, when in image forming apparatus, using Electrophtography photosensor of the present invention, can form the image of better quality chronically.
In Electrophtography photosensor of the present invention, described functional layer preferably is arranged in the outermost surfaces layer from electric conductivity support position farthest.
According to described Electrophtography photosensor, because physical strength on the outermost surfaces layer and electrical characteristics can realize with high level, so can prevent chronically when Electrophtography photosensor uses in image forming apparatus, scratch, wearing and tearing and gap appear on photosensitive surface owing to the slip of photoreceptor and cleaning unit, can guarantee simultaneously the light sensitivity, charged characteristic of photoreceptor etc. chronically, like this, can form image for a long time with better quality.
The present invention further provides a kind of handle box, described handle box comprises Electrophtography photosensor of the present invention and being selected from at least one unit in the lower unit: make the electrophotographic photoreceptor belt electricity charged elements, form the developing cell of toner image and the cleaning unit of removing the lip-deep remaining toner of Electrophtography photosensor by make the latent electrostatic image developing that is formed on the Electrophtography photosensor with toner.
The present invention further provides a kind of image forming apparatus, and described image forming apparatus comprises Electrophtography photosensor of the present invention, makes the charged elements of electrophotographic photoreceptor belt electricity, forms the exposing unit of electrostatic latent image on charged described Electrophtography photosensor, by make latent electrostatic image developing with developing cell that forms toner image and the transfer printing unit that toner image is transferred to body to be transferred from described Electrophtography photosensor with toner.
The handle box and the image forming apparatus that dispose Electrophtography photosensor of the present invention can form the image with better quality chronically.
Preferably, image forming apparatus of the present invention further disposes the cleaning unit that cleans the surface of described Electrophtography photosensor after the image transfer printing, and this cleaning unit has blade member and/or fibrous member.
According to the image forming apparatus of the cleaning unit that disposes described structure, can obtain excellent clean-up performance chronically.
In image forming apparatus, preferably, Electrophtography photosensor is fixed on the main body of image forming apparatus, and this cleaning unit be can with the main body of image forming apparatus on connect and therefrom dismounting.
In image forming apparatus of the present invention, further preferably, transfer printing unit has the formation that adopts the intermediate transfer mode, that is, the lip-deep toner image of Electrophtography photosensor is transferred on the body to be transferred via the intermediate transfer body.
Image forming apparatus of the present invention can have following formation: contain a plurality of diameters and be less than or equal to 30mm
Electrophtography photosensor, and be transferred to body to be transferred and form coloured image by being formed on toner image on the Electrophtography photosensor.
In addition, in image forming apparatus of the present invention, further preferably, exposing unit is to dispose the multiple beam formula exposing unit of surface-emission laser array as exposure light source, perhaps disposes the exposing unit of LED (light emitting diode) as exposure light source.
When in image forming apparatus of the present invention, using the surface-emission laser array as exposing unit, can realize the raising of image quality and the increase that image forms speed, using under the situation of LED as exposing unit, can prevent from interference fringe to occur between the electric conductivity support of Electrophtography photosensor and the photographic layer.
In image forming apparatus of the present invention, the average shape factor of toner is preferably 100～150, and volume average particle size is preferably 3～12 microns.
Has high quality images by in image forming apparatus of the present invention, using above-mentioned toner, can forming.
In addition, preferably, image forming apparatus of the present invention disposes the lubricant feed unit, lubricant is supplied to the surface of Electrophtography photosensor.
According to described image forming apparatus, the lubricity on Electrophtography photosensor surface is improved because of the lubricant of being supplied with, thereby can contain the wearing and tearing of photographic layer.
In order to form the functional layer that contains phenolics that constitutes Electrophtography photosensor, the present invention can provide the hardening resin composition that can realize physical strength and electrical characteristics with high level simultaneously.
In addition, when the Electrophtography photosensor that will have the functional layer that is formed by hardening resin composition of the present invention is used for image forming apparatus, can obtain to have the image of better quality for a long time.
In addition, by being equipped with this Electrophtography photosensor, the present invention can provide and can form treatment of picture box and the image forming apparatus with better quality for a long time.
Description of drawings
To describe each embodiment in detail according to following accompanying drawing, wherein:
Fig. 1 is the typical section figure of an exemplary embodiment of expression Electrophtography photosensor of the present invention;
Fig. 2 is the typical section figure of another exemplary embodiment of expression Electrophtography photosensor of the present invention;
Fig. 3 is the typical section figure of another exemplary embodiment of expression Electrophtography photosensor of the present invention;
Fig. 4 is the typical section figure of another exemplary embodiment of expression Electrophtography photosensor of the present invention;
Fig. 5 is the typical section figure of another exemplary embodiment of expression Electrophtography photosensor of the present invention;
Fig. 6 is typical case's diagram of an exemplary embodiment of expression image forming apparatus of the present invention;
Fig. 7 is typical case's diagram of another exemplary embodiment of expression image forming apparatus of the present invention;
Fig. 8 is typical case's diagram of another exemplary embodiment of expression image forming apparatus of the present invention;
Fig. 9 is typical case's diagram of another exemplary embodiment of expression image forming apparatus of the present invention; And
Figure 10 is that the synoptic diagram as an example of the exposure device (light scanning apparatus) of the surface-emission laser array of exposure light source is disposed in expression.
Embodiment
Be described in detail exemplary embodiment of the present invention below with reference to the accompanying drawings.In the following description, identical or suitable parts are had identical symbol, and omit the narration of repetition.
Electrophtography photosensor and hardening resin composition:
Fig. 1 is the typical section figure of an exemplary embodiment of expression Electrophtography photosensor of the present invention.Electrophtography photosensor 1 shown in Fig. 1 has laminar structure, and described laminar structure comprises electric conductivity support 2, has undercoat 4, charge generation layer 5, charge transport layer 6 and protective seam 7 on this electric conductivity support 2 successively.In Electrophtography photosensor shown in Figure 11; protective seam 7 as the outermost surfaces layer is by the formed functional layer of the cured product of hardening resin composition, and described hardening resin composition comprises phenolics, contains the charge-transporting material of reactive functional groups and the derivant of organic sulfonic acid and/or organic sulfonic acid.
Fig. 2～5th, the typical section figure of other exemplary embodiment of expression Electrophtography photosensor of the present invention.Similar to Electrophtography photosensor shown in Figure 1, represented Electrophtography photosensor disposes photographic layer 3 among Fig. 2 and Fig. 3, and this photographic layer 3 is divided into charge generation layer 5 and charge transport layer 6 on function.In Fig. 4 and Fig. 5, charge generating material and charge transport material are included in same one deck (single-layer type photographic layer 8).
As mentioned above, the photographic layer of Electrophtography photosensor of the present invention can be that charge generating material and charge transport material are included in the single-layer type photographic layer in one deck, perhaps can be function divergence type photographic layer, described function divergence type photographic layer comprises layer that contains charge generating material (charge generation layer) that separates separately and the layer (charge transport layer) that contains charge transport material.Under the situation of function divergence type photographic layer, can be with the arbitrary layer in charge generation layer or the charge transport layer as the upper strata.Under the situation of function divergence type photographic layer, can realize higher function, because function is separated, each layer can satisfy function separately fully.
As representational example,, each key element is described based on Electrophtography photosensor shown in Figure 11.
As electric conductivity support 2, can enumerate the sheet metal formed by following metal or alloy, metal drum, metal tape etc.: for example, aluminium, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, platinum etc.As electric conductivity support 2, also can use coating, deposition or lamination paper, plastic foil and band with conductive compound or metal or alloy, described conductive compound for example is electric conductive polymer, indium oxide etc., and described metal is for example aluminium, palladium, gold etc.
For the interference fringe that prevents to occur in the laser beam irradiation, preferably, surface roughening is carried out on the surface of electric conductivity support 2 handle, be 0.04～0.5 micron so that make center line average surface roughness (Ra).When the Ra value on the surface of electric conductivity support 2 during less than 0.04 micron because should the surface near minute surface, so prevent that the effect of interference fringe is often not enough.On the other hand, when the Ra value surpassed 0.5 micron, even form film, image quality was also often not enough.When using incoherent light as described light source, the surface roughening processing that prevents interference fringe is not necessary especially, and this is suitable for life-saving, produces defective because can prevent like this owing to the surface heterogeneity of electric conductivity support 2.
Handle as surface roughening, preferably: will be suspended in lapping compound in the water be sprayed onto wet type honing on the support, by carrying out the centreless grinding and the anodization of continuously grinding processing on the grinding stone that support is pressed onto rotation.
As another kind of surface roughening disposal route, can also preferably make with the following method, promptly, roughening is not carried out on the surface of electric conductivity support 2, but in resin dispersed electro-conductive or semiconduction powder, on the support surface, form the described dispersion of one deck, make this surface roughening by the particulate that is dispersed in this layer then.
Anodization is to carry out anodization with aluminium as anode in electrolyte solution, so that form oxide film on the aluminium surface.Example as electrolyte solution has sulfuric acid solution, ethane diacid solution etc.Yet the chemical property of the porous anodic oxide film in the reality is active, vulnerable to pollution, and the resistance fluctuation that is caused by environment is bigger.Therefore, carrying out sealing of hole by following step handles: (can add slaine in pressurized vapor or boiling water, nickel salt etc. for example) utilizes the volumetric expansion due to the aquation in, described surface is become more stable hydrous oxid, handle thereby the micropore of antianode oxide film carries out sealing of hole.
The thickness of anode oxide film is preferably 0.3～15 micron.When thickness during less than 0.3 micron, too low to the shielding properties of injecting, therefore, the effect of processing is tended to deficiency.On the other hand, when thickness surpasses 15 microns, tend to increase because of reusing the residual electromotive force that produces.
In addition, can carry out acidic aqueous solution processing or boehmite processing to electric conductivity support 2.Undertaken by following with the processing that the acidic treatment liquid that contains phosphoric acid, chromic acid and hydrofluorite carries out.At first, preparation acidic treatment liquid.The blending ratio of phosphoric acid, chromic acid and hydrofluorite is in acidic treatment liquid: phosphoric acid is about 10 weight %～about 11 weight %, chromic acid is about 3 weight %～about 5 weight %, hydrofluorite is about 0.5 weight %～about 2 weight %, and these sour total concentrations are preferably about 13.5 weight %～about 18 weight %.Treatment temperature is preferably 42～48 ℃, but by keeping the high processing temperature, can accelerate processing procedure and can form thicker film.Film thickness is preferably 0.3～15 micron.When thickness during less than 0.3 micron, too low to the shielding properties of injecting, therefore, the effect of processing is tended to deficiency.On the other hand, when thickness surpasses 15 microns, tend to increase because of reusing the residual electromotive force that produces.
Can by in 90～100 ℃ pure water with support impregnation 5 minutes～60 minutes, or in 90～120 ℃ vapours, handle and carried out boehmite in 5 minutes～60 minutes and handle.Film thickness is preferably 0.1～5 micron.Can further carry out anodization to the support of having handled, for example hexane diacid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate or citrate with the lower electrolyte solution of film dissolubility.
On electric conductivity support 2, form undercoat 4.Undercoat 4 is made up of organometallics and/or adhesive resin.
As organometallics, have for example: organic zirconate, for example zirconium chelate, zirconium alcoholates and zirconium coupling agent; Organic titanic compound, for example titanium chelate, titanium alcoholates and titanium coupling agent; Organo-aluminum compound, for example aluminium chelate compound and aluminum coupling agent; In addition, also have antimony alcoholates, germanium alcoholates, indium alcoholates, indium chelate, manganese alcoholates, manganic chelates, tin alcoholates, tin chelate, sial alcoholates, titanium aluminum alcoholate and zirconium aluminum alcoholate.
As organometallics, because their the low-residual electromotive force and the good electronics photographic property of demonstration, thereby especially preferably adopt organic zirconate, organic titanium oxygen compound and organo-aluminum compound.
As adhesive resin, have for example: well-known resin, for example polyvinyl alcohol (PVA), polyvinyl methyl ether, poly-N-vinyl imidazoles, polyethylene oxide, ethyl cellulose, methylcellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, tygon, polyester, phenolics, vinyl chloride vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinylpyridine, polyurethane, polyglutamic acid and polyacrylic acid.As required, two or more of these adhesive resins can be used in combination with any blending ratio.
Consider low-residual electromotive force and environmental stability, also can mix/disperse use electron transport pigment in the undercoat 4.The example of electron transport pigment is included in disclosed organic pigment among the Japanese kokai publication sho 47-30330, Li such as perylene dye, bisbenzimidazole-perylene dyes, encircles quinone pigments, indigo pigment and quinacridone pigment more; For example contain organic pigments such as the disazo pigment of electron-withdrawing substituent or phthalocyanine color, described electron-withdrawing substituent is for example cyano group, nitro, nitroso-or halogen atom; And inorganic pigment, for example zinc paste and titanium dioxide.
In these pigment, because their high electron mobility, preferred Cai Yong perylene dye, bisbenzimidazole-perylene dyes, encircle quinone pigments, zinc paste and titanium dioxide more.
For the purpose of control dispersiveness and charge-transporting, can carry out surface treatment to the surface of these pigment with above-mentioned coupling agent and adhesive resin.
If the amount of electron transport pigment is too many, then can reduce the intensity of undercoat 4, cause the film defective, therefore, based on the total amount of solids in the undercoat 4, this amount is preferably and is less than or equal to about 95 weight %, more preferably is less than or equal to about 90 weight %.
For improving the purpose of electrical characteristics and light diffuse reflection performance, preferably multiple fine powder organic and mineral compound is added undercoat 4.Particularly, can adopt Chinese white effectively, for example titanium dioxide, zinc paste, the flowers of zinc (zinc flower), zinc sulphide, white lead and lithopone; As the inorganic pigment of extender pigment, for example aluminium oxide, lime carbonate and barium sulphate; And polyflon particle, benzoguanamine resin particle and styrene resin particle.
The volume average particle size of the fine powder that is added is preferably 0.01 micron～2 microns.Add fine powder as required, based on the total amount of solids in the undercoat 4, this addition is preferably about 10 weight %～about 90 weight %, more preferably about 30 weight %～about 80 weight %.
Can use the undercoats 4 that contain these formation components to form and form undercoat 4 with coating fluid.Form without limits being used for this undercoat,, and when electron transport pigment being mixed and/or disperse, can not cause that gelation and aggegation get final product as long as they can dissolve described organometallics and adhesive resin with the organic solvent of coating fluid.
As organic solvent, can adopt the solvent of general use, for example methyl alcohol, ethanol, n-propanol, normal butyl alcohol, phenmethylol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, diox, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene and toluene.Can use these solvents separately, perhaps can mix and use two kinds or more than two kinds solvent.
Can mix and/or disperse according to for example using bowl mill, roller mill, sand mill, masher, vibromill, colloid mill, pigment stirrer or hyperacoustic commonsense method will constitute component.Described mixing and/or dispersion can be carried out in organic solvent.
As the coating process of undercoat 4, can use general coating process, for example scraper coating, coiling rod coating (wire bar coating), spraying coating, dip-coating, bead coating, airblade coating and curtain coating method.
Dry generally can evaporating solvent and form under the temperature of film and carry out.Through easy especially not enough, therefore be preferably formed undercoat 4 in existence aspect the ability of covering up the base material defective with the electric conductivity support 2 that acidic aqueous solution is handled or boehmite is handled.
The thickness of undercoat 4 is preferably 0.01 micron～30 microns, is preferably 0.05 micron～25 microns especially.
As charge generating material, can use well-known material, organic pigment for example is such as AZO pigments, as bisdiazo and trisazo-; Condensed ring aromatic pigment is as dibromo anthrone (dibromoanthoanthrone); He perylene dye, pyrrolo-pyrrole pigments, phthalocyanine color etc.; Inorganic pigment, for example tripartite selenium and zinc paste.Among these, what especially preferably use is that the disclosed hydroxy gallium phthalocyanine of the flat 5-279591 communique of Japanese kokai publication hei 5-263007 communique and Te Kai, spy open the disclosed gallium chlorine phthalocyaninate of flat 5-98181 communique, the spy opens flat 5-140472 communique and the flat 5-140473 communique disclosed dichloro tin phthalocyanine of Te Kai and spy and opens flat 4-189873 and the disclosed titanyl phthalocyanine of the flat 5-43813 of Te Kai.
Among described hydroxy gallium phthalocyanine, particularly preferably be, dividing the absorption maximum in the optical absorption spectra is 810 nanometers～839 nanometers, primary particle diameter is less than or equal to 0.10 micron, and BET method specific surface area value is more than or equal to 45m
2The hydroxy gallium phthalocyanine of/g.
When used exposure light source wavelength is 380 nanometers～500 nanometers, preferably use metal or nonmetallic phthalocyanine color, tripartite selenium and dibromo anthrone as charge generating material.
Adhesive resin can be selected from far-ranging insulative resin.Adhesive resin also can be selected from the organic photoconductive polymkeric substance, for example poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene and polysilane.As the preferred adhesive resin, have for example: insulative resin, for example polyvinyl butyral resin, polyarylate resin (condensed polymer of bisphenol-A and phthalic acid etc.), polycarbonate resin, vibrin, phenoxy resin, vinyl chloride vinyl acetate copolymer, polyamide, acrylic resin, polyacrylamide resin, polyvinylpyridine resin, celluosic resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin and polyvinyl pyrrolidone resin, but the present invention used be not limited to these.Can use these adhesive resins separately, perhaps two or more adhesive resin can be mixed and use.
Produce material or form by deposited charge and form charge generation layer 5 with coating fluid by the charge generation layer that coating contains charge generating material and adhesive resin.When using charge generation layer formation to form charge generation layer 5 with coating fluid, the proportioning of charge generating material and adhesive resin (by weight) is preferably 10/1 to 1/10.
Form with in the coating fluid for constituent material being dispersed in charge generation layer, can adopt general process for dispersing, for example bowl mill process for dispersing, masher process for dispersing and sand mill process for dispersing.At this moment, the condition of requirement is that the crystal formation of pigment can not change because of dispersion.In addition, be effectively by disperseing to make particle diameter preferably be less than or equal to 0.5 micron, more preferably be less than or equal to 0.3 micron, be more preferably and be less than or equal to 0.15 micron.
As the organic solvent that in dispersion, uses, can use organic solvent commonly used, for example methyl alcohol, ethanol, n-propanol, normal butyl alcohol, phenmethylol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, diox, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene and toluene.Can use these solvents separately, perhaps can mix the solvent that uses two or more.
Form charge generation layer 5 in order to use charge generation layer to form with coating fluid, can adopt general coating process, for example scraper coating, the coating of coiling rod, spraying coating, dip-coating, bead coating, airblade coating and curtain coating method.
The thickness of charge generation layer 5 is preferably 0.1 micron～5 microns, more preferably 0.2 micron～2.0 microns.
As charge transport material, have for example: the electron transport compound, quinones for example, as 1,4-benzoquinone, tetrachloro for 1,4-benzoquinone, tetrabromoquinone and anthraquinone; Four cyano 1,4-benzoquinone bismethane compound; The Fluorenone compound, as 2,4, the 7-trinitro-fluorenone; The xanthone compound; The benzophenone compound; The cyano group vinyl compound; And vinyl compound; The cavity conveying compound, the vinyl compound, stilbene compounds, anthracene compound and the hydrazone compound that replace of triarylamine compound, benzidine compound, aromatic yl paraffin compound, aryl for example, but the present invention has more than and is limited to these compounds.Can use these charge transport materials separately, perhaps two or more material can be used as potpourri.
In view of mobility, preferred use with following general formula (a-1), (a-2) or (a-3) compound of expression as charge transport material.
In general formula (a-1), R
34Expression hydrogen atom or methyl, k10 represents 1 or 2, Ar
6And Ar
7Separately the expression have substituent or do not have substituent aryl ,-C
6H
4-C (R
38)=C (R
39) (R
40) or-C
6H
4-CH=CH-CH=C (Ar)
2As substituting group, halogen atom is arranged for example, contain 1～5 carbon atom alkyl, contain the alkoxy of 1～5 carbon atom and with the alkyl that contains 1～3 carbon atom as substituent substituted-amino.R
38, R
39And R
40Represent hydrogen atom separately, have substituent or do not have substituent alkyl or have substituent or do not have substituent aryl that Ar represents to have substituent or do not have substituent aryl.
In above-mentioned general formula (a-2), R
35And R
35 'Represent hydrogen atom, halogen atom separately, contain the alkyl of 1～5 carbon atom or contain the alkoxy of 1～5 carbon atom, R
36, R
36 ', R
37And R
37 'Represent halogen atom separately, contain 1～5 carbon atom alkyl, contain 1～5 carbon atom alkoxy, with the alkyl that contains 1 or 2 carbon atom as substituent amino, have substituent or do not have substituent aryl ,-C (R
38)=C (R
39) (R
40) or-CH=CH-CH=C (Ar)
2, R
38, R
39And R
40Represent hydrogen atom separately, have substituent or do not have substituent alkyl or have substituent or do not have substituent aryl that Ar represents to have substituent or do not have substituent aryl, m4 and m5 represent from 0 to 2 integer separately.
In above-mentioned general formula (a-3), R
41The expression hydrogen atom, contain 1～5 carbon atom alkyl, contain 1～5 carbon atom alkoxy, have substituent or do not have substituent aryl or-CH=CH-CH=C (Ar)
2, Ar represents to have substituent or does not have substituent aryl, R
42, R
42 ', R
43And R
43 'Represent hydrogen atom, halogen atom separately, contain 1～5 carbon atom alkyl, contain 1～5 carbon atom alkoxy, with the alkyl that contains 1 or 2 carbon atom as substituent amino, have substituent or do not have substituent aryl.
Adhesive resin as using in charge transport layer 6 has: polycarbonate resin, vibrin, methacrylic resin, acryl resin, Corvic, polyvinylidene chloride resin, polystyrene resin, vinylite, Styrene-Butadiene, vinylidene chloride-acrylonitrile copolymer, vinyl chloride vinyl acetate copolymer, vinyl chloride-vinyl acetate-copolymer-maleic anhydride, silicone resin, silicone-alkyd resin, phenolics and styrene-alkyd resin for example.Can use these adhesive resins separately, perhaps two or more adhesive resin can be used as potpourri.The proportion scale of charge transport material and adhesive resin (by weight) is preferably 10/1 to 1/5.
Carry material as polymer charge, can adopt well-known macromolecular material, for example poly-N-vinyl carbazole and polysilane with charge delivery capability.Disclosed polyesters polymer charge carries material to have high charge delivery capability in Japanese kokai publication hei 8-176293 communique and the flat 8-208820 communique of Te Kai, thereby is particularly preferred.
Polymer charge can be carried material to be used alone as the component of charge transport layer 6, also they can be mixed with adhesive resin to form film.
Can use the charge transport layer that contains above-mentioned constituent material to form and form charge transport layer 6 with coating fluid.
Form solvent as being used for charge transport layer, have for example with coating fluid: organic solvent commonly used, aromatic hydrocarbons for example is as benzene,toluene,xylene and chlorobenzene; Ketone is as acetone and 2-butanone; Halogenated aliphatic hydrocarbon is as methylene chloride, chloroform and ethylene dichloride; Ring type or linear are as tetrahydrofuran and ether.Can use these solvents separately, perhaps can mix and use two or more solvent.
Form the coating process of using coating fluid as charge transport layer, can adopt general coating process, for example scraper coating, the coating of coiling rod, spray coating, dip-coating, bead coating, airblade coating and curtain coating method.
The thickness of charge transport layer 6 is preferably 5 microns～50 microns, more preferably 10 microns～30 microns.
Purpose for the ozone that prevents to produce in image forming apparatus and oxidizing gas or light and heat damage photoreceptor can join for example adjuvants such as antioxidant, light stabilizer and thermal stabilizer in the photographic layer 3.
As antioxidant, have for example: the derivant of hindered phenol, hindered amine, p-phenylenediamine (PPD), aromatic yl paraffin, quinhydrones, spiral shell chroman, spiral shell indone and these compounds; Organosulfur compound and organic phosphorus compound.As light stabilizer, have for example: the derivant of benzophenone, benzotriazole, dithiocarbamate and tetramethyl piperidine etc.
In addition,, reduce residual electromotive force, and reduce, at least a electronics acceptance material can be joined photographic layer 3 owing to reuse the fatigue that causes in order to improve light sensitivity.
As electronics acceptance material, adducible have: for example, succinic anhydride, maleic anhydride, dibromomaleic acid acid anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, four cyano 1,4-benzoquinone bismethane, o-dinitrobenzene, meta-dinitro-benzent, tetrachloro are for 1,4-benzoquinone, dinitroanthraquinone, trinitro-fluorenone, picric acid, o-nitrobenzoic acid, paranitrobenzoic acid and phthalic acid.In these compounds, particularly preferably be Fluorenone class and quinones and have for example Cl, CN, NO
2Benzene derivative Deng electron-withdrawing substituent.
In Electrophtography photosensor of the present invention; protective seam 7 is outermost surfaces layers that the cured product by hardening resin composition forms, and described hardening resin composition comprises phenolics, contains the charge-transporting material of reactive functional groups and the derivant of organic sulfonic acid and/or organic sulfonic acid.Each composition that constitutes this hardening resin composition is described as follows.
As described phenolics, in the presence of acidic catalyst or base catalyst, with following compound and formaldehyde or the paraformaldehyde reaction that contains the phenol structure, to make monomethylol phenols, dihydroxymethyl phenols or the monomer of trihydroxy methyl phenols, the potpourri of these compounds, the oligomerization product of these compounds and the potpourri of this monomer and this oligomer, the described compound that contains the phenol structure is for example resorcinol and bis-phenol; The substituted phenol that contains a hydroxyl, for example phenol, cresols, xylenols, to alkyl phenol and p-phenyl phenol; The substituted phenol that contains two hydroxyls, for example catechol, resorcinol and quinhydrones; Bisphenols, for example bisphenol-A and bisphenol Z; Perhaps xenol.In prepared these compounds, having about 2～20 bigger molecules that constitute repetitives is oligomer, and lower than these is monomer.
Acidic catalyst as this moment can use sulfuric acid, p-toluenesulfonic acid, phenolsulfonic acid and phosphoric acid.As base catalyst, can use the oxyhydroxide and the oxide of alkaline metal and earth alkali metal, for example NaOH, KOH, Ca (OH)
2, Mg (OH)
2, Ba (OH)
2, CaO and MgO; Amines catalyst; And acetate salt, for example zinc acetate and sodium acetate.
As amines catalyst, have for example: ammonia, hexamethylene tetramine, trimethylamine, triethylamine and triethanolamine, but the present invention is not limited to this.
When using base catalyst, exist carrier to be caught and damage the situation of electrofax characteristic significantly by residual catalyst.In this case described, preferably, residual catalyst is under reduced pressure steamed, with acid neutralization, make it inactivation by contacting with adsorbent such as for example silica gel or ion exchange resin, perhaps remove residual catalyst.Also can in curing reaction, adopt curing catalysts.Curing catalysts is not particularly limited, as long as they do not have adverse effect to electrical characteristics.
Be necessary in hardening resin composition, to use at least the derivant of organic sulfonic acid and/or organic sulfonic acid as acidic catalyst.
Derivant as organic sulfonic acid and/or organic sulfonic acid has for example: p-toluenesulfonic acid, dinonylnaphthalene sulfonic acid (DNNSA), dinonylnaphthalene disulfonic acid (DNNDSA), dodecylbenzene sulfonic acid and phenolsulfonic acid.In these compounds, from catalyst function and film forming characteristics, preferably p-toluenesulfonic acid and dodecylbenzene sulfonic acid.In addition, if organic sulfonate takes place by dissociating to a certain degree, also can use organic sulfonate in hardening resin composition.
Based on the total amount of the solid of hardening resin composition, the content of the phenolics in the hardening resin composition is preferably about 20 weight %～about 90 weight %, is preferably about 30 weight %～about 70 weight % especially.When the content of phenolics during less than about 20 weight %, the physical strength of protective seam 7 is often not enough, and when content surpasses about 90 weight %, is difficult to carry out the smooth delivery of power of electric charge, thereby electrical characteristics deficiency often.
Total amount based on the solid of hardening resin composition, the content of organic sulfonic acid in the hardening resin composition and/or organic sulfonic acid derivant is preferably about 0.01 weight % to about 5 weight %, more preferably about 0.05 weight % is preferably about 0.1 weight % to about 1 weight % especially to about 3 weight %.When content during less than about 0.01 weight %, can not obtain the effect of catalyzer fully, like this, the physical strength of protective seam 7 is often not enough, and when content during above about 5 weight %, too high as the ability of adulterant, might increase dark current.
As the charge-transporting material that contains reactive functional groups, preferably good with used phenolics compatibility material more preferably forms the material of chemical bond with used phenolics.
As the charge-transporting material that contains reactive functional groups, for make film forming characteristics, physical strength and stable aspect excellent performance, the preferably compound represented of general formula arbitrarily by general formula (I), (II), (III), (IV) or (XVIII).
F[-(X
1)
n1R
1-Z
1H]
m1 (I)
Wherein F represents the organic group by the compound deriving with cavity conveying characteristic, R
1The expression alkylidene, Z
1Expression oxygen atom, sulphur atom, NH or COO, X
1Expression oxygen atom or sulphur atom, m1 represents integer 1～4, and n1 represents 0 or 1;
F[-(X
2)
n2-(R
2)
n3-(Z
2)
n4G]
n5 (II)
Wherein F represents the organic group by the compound deriving with cavity conveying characteristic, X
2Expression oxygen atom or sulphur atom, R
2The expression alkylidene, Z
2Expression oxygen atom, sulphur atom, NH or COO, G represents epoxy radicals, n2, n3 and n4 represent 0 or 1 separately, and n5 represents integer 1～4;
Wherein F represents that T represents divalent group by the organic group of the compound deriving with cavity conveying characteristic, and Y represents oxygen atom or sulphur atom, R
3, R
4And R
5Represent hydrogen atom or unit price organic group separately, R
6Expression unit price organic group, m2 represents 0 or 1, and n6 represents integer 1～4, and R5 and R6 bonding and forming with Y as heteroatomic heterocycle mutually,
Wherein F represents that T represents divalent group by the organic group of the compound deriving with cavity conveying characteristic, R
7Expression unit price organic group, m3 represents 0 or 1, and n7 represents integer 1～4,
Wherein F represents the organic group by the compound deriving with cavity conveying characteristic; R
8Expression unit price organic group; L represents alkylidene; And n8 represents integer 1～4.
In addition, the F in the compound of being represented by above-mentioned general formula (I)～(IV) and any general formula (XVIII) is preferably the group by following general formula (V) expression:
Ar wherein
1, Ar
2, Ar
3And Ar
4Expression has substituent or does not have substituent aryl separately; Ar
5Expression has substituent or does not have substituent aryl or arlydene; And Ar
1～Ar
5Among 1～4 group and following position bonding: by the position in the compound of general formula (I) expression by following general formula (VI) expression, by the position in the compound of general formula (II) expression by following general formula (VII) expression, by the position in the compound of general formula (III) expression by following general formula (VIII) expression, by in the compound of general formula (IV) expression by the position of following general formula (IX) expression or by the position in the compound of general formula (XVIII) expression by following general formula (XIX) expression:
-(X
1)
n1R
1-Z
1H (VI)
-(X
2)
n2-(R
2)
n3—(Z
2)
n4G (VII)
—L—O—R8 (XIX)
As in above-mentioned general formula (V) by Ar
1～Ar
4The having substituent or do not have substituent aryl of expression is especially preferably by the aryl of following general formula (1)～(7) expression.
—Ar(Z’)s—Ar—(D)c (7)
In general formula (1)～(7), R
9The expression hydrogen atom, contain 1～4 carbon atom alkyl, contain 1～4 carbon atom alkoxy, with these groups as substituent phenyl, do not have substituent phenyl or contain the aralkyl of 7～10 carbon atoms; R
10, R
11And R
12Represent hydrogen atom separately, contain 1～4 carbon atom alkyl, contain 1～4 carbon atom alkoxy, with these groups as substituent phenyl, do not have substituent phenyl, contain the aralkyl or the halogen atom of 7～10 carbon atoms; Ar represents to have substituent or does not have substituent arlydene; D represents by general formula (VI), (VII), (VIII) or (IX) arbitrary structure of expression; C and s represent 0 or 1 separately; T represents 1 to 3 integer.
As by the Ar in the aryl of above-mentioned general formula (7) expression, be preferably arlydene by following general formula (8) or (9) expression.
In general formula (8) and (9), R
13And R
14Represent hydrogen atom separately, contain 1～4 carbon atom alkyl, contain 1～4 carbon atom alkoxy, with the alkoxy that contains 1～4 carbon atom as substituent phenyl, do not have substituent phenyl, contain the aralkyl or the halogen atom of 7～10 carbon atoms; T represents 1 to 3 integer.
As by the Z ' in the aryl of above-mentioned general formula (7) expression, be preferably divalent group by following general formula (10) or (17) expression.
—(CH
2)
q— (10)
—(CH
2CH
2O)
r— (11)
In general formula (10)～(17), R
16And R
16Represent hydrogen atom separately, contain 1～4 carbon atom alkyl, contain 1～4 carbon atom alkoxy, with the alkoxy that contains 1～4 carbon atom as substituent phenyl, do not have substituent phenyl, contain the aralkyl or the halogen atom of 7～10 carbon atoms; W represents divalent group; Q and r represent 1 to 10 integer separately; T represents 1 to 3 integer.
In above-mentioned general formula (16) or (17), W represents the divalent group with any expression of following general formula (18)～(26).In general formula (25), u represents 0 to 3 integer.
—CH
2— (18)
—C(CH
3)
2— (19)
—O— (20)
—S— (21)
—C(CF
3)
2— (22)
—Si(CH
3)
2— (23)
As Ar in the above-mentioned general formula (V)
5Ad hoc structure, have for example: when k represents 0, at Ar
1～Ar
4Ad hoc structure in the structure of c=1; When k represents 1, at Ar
1～Ar
4Ad hoc structure in the structure of c=0.
As examples for compounds, more particularly, can enumerate following compound (I-1)～(I-37) with general formula (I) expression.In following form, do not show substituent compound for demonstrating chemical bond, its substituting group is a methyl.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
As examples for compounds, more particularly, can enumerate following compound (II-1)～(II-47) with general formula (II) expression.In following form, for demonstrating Me and chemical bond but do not show substituent compound, its substituting group is a methyl, and Et is meant ethyl.
Table 10
Table 11
Table 12
Table 13
Table 14
Table 15
Table 16
Table 17
Table 18
Table 19
Table 20
Table 21
Table 22
Table 23
As examples for compounds, more particularly, can enumerate following compound (III-1)～(III-40) with general formula (III) expression.In following form, for demonstrating Me and chemical bond but do not show substituent compound, its substituting group is a methyl, and Et is meant ethyl.
Table 24
Table 25
Table 26
Table 27
Table 28
Table 29
Table 30
Table 31
Table 32
Table 33
As examples for compounds, more particularly, can enumerate following compound (IV-1)～(IV-55) with general formula (IV) expression.In following form, for demonstrating Me and chemical bond but do not show substituent compound, its substituting group is a methyl.
Table 34
Table 35
Table 36
Table 37
Table 38
Table 39
Table 40
Table 41
Table 42
Table 43
In addition, in above-mentioned general formula (XVIII), R
8Be preferably the unit price organic group that contains 1～18 carbon atom; More preferably can have halogen atom as the substituent univalence hydrocarbyl that contains 1～18 carbon atom, or by-(CH
2)
f-O-R
24The group of expression; Further be preferably the alkyl that contains 1～4 carbon atom or by-(CH
2)
f-O-R
24The group of expression is preferably methyl especially.R
24For containing the alkyl of 1～6 carbon atom, it can form ring, is preferably aliphatic hydrocarbyl, for example methyl, ethyl, propyl group or butyl.F is 1～12 integer, and is preferably 1～4 integer.In general formula (XVIII), L is preferably the alkylidene that contains 1～18 carbon atom of branching or non-branching, more preferably methylene.In general formula (XVIII), as a plurality of R
8Or L is when existing, and they can be identical or different.
As the instantiation by the compound of general formula (XVIII) expression, the compound (XVIII-1) shown in below can enumerating is to (XVIII-59).Compound by general formula (XVIII) expression never only limits to this.In following form, shown chemical bond but do not shown under the substituent situation that this substituting group is a methyl.
Table 44
Table 45
Table 46
Table 47
Table 48
Table 49
Table 50
Table 51
Above-mentioned compound self by general formula (XVIII) expression can solidify separately, and has the character that can show stable electric characteristics.Therefore, when the derivant of these compounds and phenolics and organic sulfonic acid and/or organic sulfonic acid is used in combination, can improve the physical strength and the electrical characteristics of protective seam 7 significantly simultaneously.The mechanism why organic sulfonic acid and/or its derivant demonstrate above-mentioned effect is not necessarily clear, but, it is believed that, organic sulfonic acid and/or its derivant have been brought into play the function of catalyzer in the reaction of compound of being represented by general formula (XVIII) and phenolics, thereby can form point-device cross-linked structure, simultaneously, also given play to the function of adulterant, made like this and can further improve electrical characteristics.In addition, according to the Electrophtography photosensor with described protective seam 7, the fluctuation of charged electromotive force in the time of can suppressing fully to use for a long time can form the image with better quality steadily in the long term.
Can suppress the fluctuation of charged electromotive force fully during from long-term use Electrophtography photosensor and fully improve the angle of physical strength, be preferably compound especially by following general formula (XX) expression by the compound of general formula (XVIII) expression.
X wherein
11, X
12And X
13Represent halogen atom separately, contain 1～10 carbon atom alkyl, contain 1～10 carbon atom alkoxy, have substituent or do not have substituent aryl, contain 7～10 carbon atoms aralkyl, have substituent or do not have substituent styryl, have substituent or do not have substituent butadienyl or have substituent or do not have substituent hydrazone group; R
21, R
22And R
23Representative contains the unit price organic group of 1～18 carbon atom separately; L
1, L
2And L
3Represent alkylidene separately; P1, p2 and p3 represent 0 to 2 integer separately; Q1, q2 and q3 represent 0 or 1 separately, and satisfy q1+q2+q3
1.
In general formula (XX), R
21, R
22And R
23Be preferably separately and can have halogen atom as the substituent univalence hydrocarbyl that contains 1～18 carbon atom, or by-(CH
2)
f-O-R
24The group of expression; More preferably contain the alkyl of 1～4 carbon atom or by-(CH
2)
f-O-R
24The group of expression is preferably methyl especially.R
24Expression contains the alkyl of 1～6 carbon atom, and it can form ring, and is preferably aliphatic hydrocarbyl, for example methyl, ethyl, propyl group or butyl.F is 1～12 integer, and is preferably 1～4 integer.
In general formula (XX), L
1, L
2And L
3Be preferably the alkylidene that contains 1～18 carbon atom branching or non-branching separately, more preferably methylene.In general formula (XX), X
11, X
12And X
13Be preferably the alkyl that contains 1～10 carbon atom separately, more preferably contain the alkyl of 1～4 carbon atom.
As the instantiation by the charge-transporting compound of general formula (XX) expression, the compound (1) shown in below can enumerating is to (125).Following compound (1) to (125) is by the X in the compound of general formula (XX) expression
11, X
12, X
13, R
21, R
22, R
23, L
1, L
2, L
3, p1, p2, p3, q1, q2 and the q3 compound that makes up as shown in the table.
In the table, " 3-p " refers to the 3-position below, and " 4-p " refers to the 4-position, and " 3,4-p " refer to 3, the 4-position, and " 3,5-p " refer to 3, the 5-position.
Compound by general formula (XVIII) expression can be synthetic according to for example following method at an easy rate: will have the triphenyl amine compound of hydroxyalkyl and dialkylsulfates or alkiodide and react with the described hydroxyalkyl of etherificate.In this case, agents useful for same can be selected from dimethyl suflfate, dithyl sulfate, iodomethane, iodic ether etc. arbitrarily, and 1～3 equivalent that its consumption is equivalent to hydroxyalkyl gets final product, and is preferably 1～2 equivalent.As base catalyst, can use the base catalyst that is selected from NaOH, potassium hydroxide, sodium methoxide, caustic alcohol, sodium butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, sodium metal etc. arbitrarily, 1～3 equivalent that its consumption is equivalent to hydroxyalkyl gets final product, and is preferably 1～2 equivalent.This reaction can be carried out under the temperature of the boiling point from 0 ℃ to the solvent that uses.
Solvent as used in reaction has for example: benzene, toluene, methylene chloride, tetrahydrofuran, N, N '-dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidinone etc.Can use these solvents separately, perhaps can mix the solvent that uses two or more.According to the type of reaction, can use quaternary ammonium salt (for example tetrabutylammonium iodide) as the interlayer moving catalyst.
For the hardening resin composition that is used to form protective seam 7,, also can in said composition, add compound by following general formula (X) expression in order to control the multiple physical property such as for example intensity and film resistance etc. of protective seam 7.
Si(R
50)
(4-c)Q
c (X)
R wherein
50Represent hydrogen atom, alkyl or have substituent or do not have substituent aryl, Q represents hydrolyzable groups, and c represents 1～4 integer.
Instantiation by the compound of general formula (X) expression comprises silane coupling agent shown below.As silane coupling agent, have for example: four functional alkoxysilanes (c=4), for example tetramethoxy-silicane and tetraethoxysilane; Trifunctional alkoxy silane (c=3), methyltrimethoxy silane for example, methyl triethoxysilane, ethyl trimethoxy silane, methyl trimethoxy oxygen base oxethyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyltrimewasxysilane, γ-An Jibingjisanyiyangjiguiwan, the gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyl dimethoxysilane, N-β-(aminoethyl)-γ-An Jibingjisanyiyangjiguiwan, (13 fluoro-1,1,2,2-tetrahydrochysene octyl group) triethoxysilane, (3,3, the 3-trifluoro propyl) trimethoxy silane, 3-(seven fluorine isopropoxies) propyl-triethoxysilicane, 1H, 1H, 2H, 2H-perfluoroalkyl triethoxysilane, 1H, 1H, 2H, 2H-perfluor decyl triethoxysilane and 1H, 1H, 2H, 2H-perfluoro capryl triethoxysilane; Difunctionality alkoxy silane (c=2), for example dimethyldimethoxysil,ne, dimethoxydiphenylsilane and aminomethyl phenyl dimethoxy silane; And simple function alkoxy silane (c=1), for example trimethyl methoxy silane.In order to improve film strength, preferred three or four functional alkoxysilanes are in order to improve flexibility and filming performance, preferred list or difunctionality alkoxy silane.
In addition, also can use the hard smears of mainly making of silicon class by these coupling agents.As commercially available hard smears, can use KP-85, X-40-9740 and X-40-2239 (by chemistry society of SHIN-ETSU HANTOTAI, Silicone Division makes), and AY42-440, AY42-441 and AY49-208 (by TorayDow-Coming Silicone Co., Ltd. makes).
In order to improve the intensity of protective seam 7, in the hardening resin composition that forms protective seam 7, also can preferably use the compound that contains two or more silicon atoms by following general formula (XI) expression.
B-[Si(R
51)
(3-d)Q
d]
2 (XI)
Wherein B represents divalent organic group, R
51Refer to hydrogen atom, alkyl or have substituent or do not have substituent aryl that Q represents hydrolyzable group, d represents integer 1～3.
As examples for compounds, more particularly, can enumerate following compound (XI-1)～(XI-16) by general formula (XI) expression.
Table 61
In addition, in the serviceable life for controlling diaphragm characteristic and prolongation liquid, can add the resin that dissolves in alcohols and ketones solvent.As described resin, have for example: polyvinyl butyral resin, vinyl-formal resin, polyvinyl acetal resin, for example, the polyvinyl acetal resin of part acetalation, wherein with a part of butyral with dimethoxym ethane or the modification of acetyl acetal (for example S-LEC B, K etc., ponding chemistry society makes); Polyamide; Celluosic resin; And phenolics.From improving the viewpoint of electrical characteristics, special preferably polyethylene alcohol acetate resin.
In addition, in order to improve tolerance, physical strength, resistance to scraping, particle dispersion, viscosity control, minimizing torque, control wear extent and life-saving, can in described hardening resin composition, add various kinds of resin to discharge gas.In the present invention, preferably further comprise the resin that dissolves in alcohol.As the resin that dissolves in alcohols solvent, have for example: polyvinyl butyral resin, vinyl-formal resin, polyvinyl acetal resin, for example, the polyvinyl acetal resin of part acetalation, wherein with a part of butyral with dimethoxym ethane or the modification of acetyl acetal (for example S-LEC B, K etc., ponding chemistry society makes); Polyamide; And celluosic resin.From improving the viewpoint of electrical characteristics, special preferably polyethylene alcohol acetate resin.
The weight-average molecular weight of these resins is preferably 2000～100000, and more preferably 5000～50000.When weight-average molecular weight less than 2000 the time, often can not obtain desired effect, but when weight-average molecular weight greater than 100000 the time, solubleness reduces, addition is limited and often causes the film defective in coating.The addition of resin is preferably about 1 weight %～about 40 weight %, and more preferably 1 weight %～30 weight % most preferably are about 5 weight %～about 20 weight %.When addition during less than about 1 weight %, be difficult to obtain desired effect, when addition during greater than about 40 weight %, under hot and humid degree condition image blur might take place.Described resin can use separately or can two or more use as potpourri.
For life-saving and controlling diaphragm characteristic, preferably comprise and have by the ring compound of the constitutional repeating unit of following general formula (XII) expression or the derivant of described compound.
A wherein
1And A
2Represent the unit price organic group separately.
As the ring compound that has by the constitutional repeating unit of general formula (XII) expression, can enumerate commercially available annular siloxane.Specifically, can enumerate: annular siloxane, ring-type dimethyl cyclosiloxane for example is as hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane and ten diformazan basic rings, six siloxane; The ring-type methyl phenyl ring siloxane, as 1,3,5-trimethyl-1,3,5-triphenyl cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl cyclotetrasiloxane and 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphene basic ring five siloxane; The ring-type phenyl ring siloxane is as the hexaphenyl cyclotrisiloxane; Fluorine-containing cyclosiloxane is as 3-(3,3, the 3-trifluoro propyl) methyl cyclotrisiloxane; The cyclosiloxane that contains the hydrogenation silicyl is as hydrogenated methyl mixture of siloxanes, pentamethyl D5 and phenyl hydrogenation cyclosiloxane; With the cyclosiloxane that contains vinyl, as five vinyl pentamethyl D5s.Described cyclic siloxane compound can use separately, perhaps two or more compound can be used as potpourri.
In addition, in order to control the lip-deep anti-pollution thing of Electrophtography photosensor tack, lubricity and hardness, various particulates can be added the hardening resin composition that is used to form protective seam 7.
As the example of particulate, can enumerate siliceous particulate.Described siliceous particulate is to contain silicon atom as the particulate that constitutes element, specifically, can enumerate colloidal silica and silicone particulate.The volume average particle size of the colloidal silica that uses as siliceous particulate is preferably 1～100 nanometer, 10～30 nanometers more preferably, it is selected from the aqueous dispersions and for example dispersion liquid of organic solvents such as alcohols, ketone and ethers of acidity or alkalescence, and can use the commercially available prod.Solids content to the colloidal silica in the hardening resin composition is not particularly limited, but in view of filming performance, electrical characteristics and intensity, based on the total solids content in the hardening resin composition, described content is preferably about 0.1 weight %～about 50 weight %, more preferably about 0.1 weight %～about 30 weight %.
Preferably spherical as the silicone particulate of siliceous particulate, its volume average particle size is preferably 1～500 nanometer, 10～100 nanometers more preferably, it is selected from the silica dioxide granule that silicon resin particle, silicone rubber particles and surface are crossed with silicone-treated, and can use the commercially available prod.
The silicone particulate is to be chemical inertness and the small size particle of excellent dispersion in resin.In addition, just can obtain enough characteristics, therefore, can improve the surface property of Electrophtography photosensor and can not hinder cross-linking reaction with little addition.That is to say that under the state that enters stable cross-linked structure equably, this particulate can improve the lubricity and the repellency on Electrophtography photosensor surface, and can keep advantages of good abrasion and anti-pollution thing tack for a long time.Based on the total solids content in the hardening resin composition, the content of silicone particulate is preferably about 0.1 weight %～about 30 weight % in this hardening resin composition, more preferably about 0.5 weight %～about 10 weight %.
As the example of other particulate, can enumerate: fluorine particulate, for example tetrafluoroethene, trifluoro-ethylene, hexafluoropropylene, vinyl fluoride and vinylidene fluoride; As
Eighth Forum of Polymer Materials (No. the 8th polymeric material forum)The 89th page of collection of thesis described in, comprise by fluororesin and contain the particulate of the resin that the copolyreaction of the monomer of hydroxyl obtains; And semiconduction metal oxide, for example ZnO-Al
2O
3, SnO
2-Sb
2O
3, In
2O
3-SnO
2, ZnO-TiO
2, MgO-Al
2O
3, FeO-TiO
2, TiO
2, SnO
2, In
2O
3, ZnO and MgO.
As particulate, preferably in the hardening resin composition that is used to form protective seam 7, add electrically conductive microparticle, for example metal, metal oxide and carbon black.As metal, the plastic grain that aluminium, zinc, copper, chromium, nickel, silver and stainless steel is arranged for example and surface deposition is had described metal.As metal oxide, the tin oxide of indium oxide, antimony dopant or tantalum of zinc paste, titanium dioxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, doped tin and the zirconia of antimony dopant are arranged for example.Described metal and metal oxide can use separately or two or more is used in combination.When with two or more metal and oxide-metal combinations use, the form of combination can only be to mix, and perhaps they can be solid solution or molten state.
Consider the transparency of protective seam 7, the volume average particle size of electrically conductive microparticle is preferably and is less than or equal to 0.3 micron, more preferably is less than or equal to 0.1 micron.In above-mentioned electrically conductive microparticle, with regard to the transparency, especially preferably use metal oxide.In order to control dispersiveness, preferably this particulate is carried out surface treatment.As surface conditioning agent, silane coupling agent, silicone oil, silicone compounds and surfactant are arranged for example.The preferred surface conditioning agent that contains fluorine atom that uses.
By the interpolation of described electrically conductive microparticle, often can improve the charge-transporting and the electrical characteristics of protective seam 7.
In order to control the lip-deep anti-pollution thing of Electrophtography photosensor tack, lubricity and hardness, also can add such as oil such as silicone oil.As silicone oil, can enumerate: silicone oil, for example dimethyl polysiloxane, diphenyl polysiloxane and phenyl methyl siloxane; Reactive silicone oil, the ester modified polysiloxane of the polysiloxane of for example amino modified polysiloxane, epoxy radicals modification, carboxy-modified polysiloxane, the polysiloxane of methyl alcohol modification, methacrylic acid, sulfhydryl modified polysiloxane and phenol-modified polysiloxane.Silicone oil can be added the hardening resin composition that is used to form protective seam 7 in advance, perhaps can be after making photoreceptor carry out dip treating reducing pressure or add to depress.
The hardening resin composition that is used to form protective seam 7 also can contain adjuvant, for example plastifier, surface modifier, antioxidant and anti-photodegradable aid.As plastifier, biphenyl, chlorinated biphenyl, terphenyl, dibutyl phthalate, diethylene glycol phthalate ester, dioctyl phthalate, triphenyl phosphate, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene and various fluorhydrocarbon are arranged for example.
The hardening resin composition that is used to form protective seam 7 can contain antioxidant; for example hindered phenol, hindered amine and have thioether or the antioxidant of phosphite ester part-structure, these compounds be the electromotive force during the stable environment fluctuation and improve image quality effectively.
As antioxidant, can enumerate following compound.For example:, SumilizerBHT-R, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer WX-R, SumilizerNW, Sumilizer BP-76, Sumilizer BP-101, Sumilizer GA-80, Sumilizer GM and Sumilizer GS (being made by Sumitomo Chemical society) are arranged as hindered phenol; IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1141, IRGANOX 1222, IRGANOX 1330, IRGANOX 1425WL, IRGANOX1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX3790, IRGANOX 5057 and IRGANOX 565 (making) by Ciba Specialty Chemicals Inc.; Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, AdekastabAO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80 and Adekastab AO-330 (making) by rising sun electrification; As hindered amine, Sanol LS2626, SanolLS765, Sanol LS770 and Sanol LS744 (by Sankyo Lifetech Co., Ltd. makes) are arranged; Tinuvin 144 and Tinuvin 622LD (making) by Ciba Specialty Chemicals Inc.; MarkLA57, Mark LA67, Mark LA62, Mark LA68 and Mark LA63 (making) by rising sun electrification; Sumilizer TPS (making) by Sumitomo Chemical society; As the thioether class, Sumilizer TP-D (being made by Sumitomo Chemical society) is arranged; As phosphorous acid esters, Mark 2112, Mark PEP8, MarkPEP24G, Mark PEP36, Mark 329K and Mark HP10 (being made by rising sun electrification) are arranged, particularly preferably be hindered phenol and hindered amines antioxidant.Can be further with material that forms cross linking membrane and the substituting group (for example alkoxysilyl) that can carry out cross-linking reaction, with described antioxidant modification.
The hardening resin composition that is used to form protective seam 7 can contain insulative resin, for example: polyvinyl butyral resin, polyarylate resin (polycondensation product of bisphenol-A and phthalic acid etc.), polycarbonate resin, vibrin, phenoxy resin, vinyl chloride vinyl acetate copolymer, polyamide, acrylic resin, polyacrylamide resin, polyvinylpyridine resin, celluosic resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin and polyvinyl pyrrolidone resin.Described insulative resin can be added with arbitrary proportion, can control stickability, thermal shrinkage and because the coated film defective that repellency causes of protective seam 7 and charge transport layer 6 by the adding of insulative resin.
Catalyzer can be joined the hardening resin composition that is used to form protective seam 7, or when preparation protective seam 7, add described catalyzer.As catalyzer, have for example: mineral acid, for example hydrochloric acid, acetate and sulfuric acid; Organic acid, for example formic acid, propionic acid, ethane diacid, benzoic acid, phthalic acid and maleic acid; Base catalyst, for example potassium hydroxide, NaOH, calcium hydroxide, ammonia and triethylamine, and the solid catalyst that is insoluble to reaction system shown in following.
Solid catalyst as being insoluble to reaction system has for example: Zeo-karb, and for example Amberlite 15, Amberlite 200C and Amberlite 15E are (by Rohm ﹠amp; Haas makes); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (making) by Dow Chemical Company, Lebachit SPC-108 and Lebachit SPC-118 (making) by Bayer Yakuhin Ltd.; DiaionRCP-150H (changing into society by Mitsubishi makes); Sumikaion KC-470, Duolite C26-C, DuoliteC-433 and Duolite 464 (making) by Sumitomo Chemical society; And Nafion H (making) by E.I.Du Pontde Nemours; Anion exchange resins, for example Amberlite IRA-400 and AmberliteIRA-45 are (by Rohm ﹠amp; Haas makes); Surface bond has the inoganic solids of the group that contains the proton acid group, for example Zr (O
3PCH
2CH
2SO
3H)
2, Th (O
3PCH
2CH
2COOH); The polysiloxane that contains the proton acid group for example contains the polysiloxane of sulfate group; Heteropoly acid, for example cobalt wolframic acid and phosphomolybdic acid; Isopolyacid, for example niobic acid, tantalic acid and molybdic acid; Single element metal oxide, for example silica gel, aluminium oxide, chromium oxide, zirconia, CaO and MgO; Composite metal oxide, for example silica-alumina, silica-magnesia, silicon dioxide-zirconia and zeolite; Clay mineral, for example acid clay, activated clay, smectite and smalite; Metal sulfate, for example LiSO
4And MgSO
4Metal phosphate, for example basic zirconium phosphate and lanthanum orthophosphate; Metal nitrate, for example LiNO
3And Mn (NO
3)
2Surface bond has the inoganic solids that contains amino group, for example the solid that obtains of the reaction by the aminopropyl triethoxysilane on silica gel; And the polysiloxane that contains amino, for example amino modified silicone resin.
When use in the preparation at hardening resin composition was insoluble to the solid catalyst of light functionality compound, reaction product, water and solvent, the stability of coating fluid trended towards improving, and is preferred therefore.The solid catalyst that is insoluble to this reaction system is not particularly limited, as long as catalyst component is insoluble to charge-transporting material, other adjuvant, water and the solvent with reactive functional groups.
The described use amount that is insoluble to the solid catalyst of this reaction system is not particularly limited, and still, with respect to the charge-transporting material that contains reactive functional groups of per 100 weight portions, this consumption is preferably 0.1～100 weight portion.In addition, as mentioned above,, therefore after using the usual method reaction, can at an easy rate they be removed because described solid catalyst is insoluble to starting compound, reaction product and solvent.
Kind and consumption according to starting compound and solid catalyst come at random choice reaction temperature and reaction time, but temperature of reaction is generally 0～100 ℃, is preferably 10～70 ℃, and more preferably 15～50 ℃, the reaction time is preferably 10 minutes to 100 hours.When the reaction time exceeded above-mentioned higher limit, gelation often took place.
In preparation during hardening resin composition, be insoluble in use under the situation of catalyzer of reaction system, in order to improve the storage stability of intensity and solution, preferably further be used in combination the catalyzer that dissolves in reaction system.As the catalyzer that dissolves in reaction system, except that the above, can use organo-aluminum compound, for example three aluminium ethylates, aluminum isopropylate, three aluminium secondary butylates, Mono-sec-butoxyaluminium diisopropylate, diisopropoxy aluminium (ethyl acetoacetate), three (ethyl acetoacetate) aluminium, two (ethyl acetoacetate) single acetyl acetone aluminium, praseodynium aluminium, diisopropoxy (diacetone) aluminium, isopropoxy-two (diacetone) aluminium, three (trifluoroacetylacetone (TFA)) aluminium and three (hexafluoroacetylacetone) aluminium.
Except organo-aluminum compound, can also use: organo-tin compound, for example dibutyl tin laurate, two sad dibutyl tin and dibutyltin diacetates; Organic titanic compound, for example four (diacetone) titanium, two (butoxy) two (diacetone) titanium and two (isopropoxy) two (diacetone) titanium; Zirconium compounds, for example four (diacetone) zirconium, two (butoxy) two (diacetone) zirconium and two (isopropoxy) two (diacetone) zirconiums, but the safety of considering, low cost and long-life are preferably used organo-aluminum compound, and aluminium chelate compound more preferably.
The described use amount that dissolves in the catalyzer of reaction system is not particularly limited, and still, with respect to the charge-transporting material that contains reactive functional groups of per 100 weight portions, this consumption is preferably 0.1～20 weight portion, is preferably 0.3～10 weight portion especially.
When with the catalyzer of organometallics when forming protective seam 7, the viewpoint from life-span and curing efficiency preferably adds said composition with multidentate ligand.As multidentate ligand, can enumerate compound shown below and by the compound of described compound deriving, but the present invention is not limited to this.
Specifically, multidentate ligand comprises the beta-diketon class, for example diacetone, trifluoroacetylacetone (TFA), hexafluoroacetylacetone and two uncle's valeryl methyl acetones; Acetoacetic ester, for example methyl acetoacetate and ethyl acetoacetate; Dipyridine and derivant thereof; Glycocoll and derivant thereof; Ethylenediamine and derivant thereof; Oxine and derivant thereof; Salicylide and derivant thereof; Catechol and derivant thereof; Bidentate ligand, 2-hydroxyl azo-compound for example; Diethyl triamine and derivant thereof; Terdentate ligand, for example nitrilotriacetic acid(NTA) and derivant thereof; Sexidentate ligand, for example ethylenediamine tetraacetic acid (EDTA) and derivant thereof.In addition, except above-mentioned organic ligand, can enumerate inorganic ligand, for example pyrophosphoric acid and triphosphoric acid.As multidentate ligand, preferred especially bidentate ligand, and, except above-mentioned ligand, can enumerate bidentate ligand by general formula (XIII) expression as instantiation.
R wherein
51And R
52Expression contains alkyl, the fluorinated alkyl of 1～10 carbon atom or contains the alkoxy of 1～10 carbon atom separately.
As multidentate ligand, the preferred bidentate ligand that uses by above-mentioned general formula (XIII) expression, especially preferably R wherein
51And R
52The general formula (XIII) of representing same group.By making R
51And R
52Identical, near the coordination intensity grow of this ligand room temperature, therefore, hardening resin composition can obtain further stabilization.
The proportioning of multidentate ligand can be set arbitrarily, but used organometallics with respect to every mole, and this amount is preferably more than or equals about 0.01 mole, more preferably more than or equal to about 0.1 mole, is preferably more than especially or equals about 1 mole.
Form protective seam 7 with protective seam formation with coating fluid, described coating fluid comprises the hardening resin composition that contains the above constituent material.
The hardening resin composition that contains above constituent can prepare not using solvent or use under the situation of solvent, and described solvent is, alcohols for example is as methyl alcohol, ethanol, propyl alcohol, butanols etc.; Ketone is as acetone, methyl ethyl ketone etc.; And ethers, as tetrahydrofuran, diethyl ether, diox etc.Can use these solvents separately, perhaps can mix the solvent that uses two or more, preferably boiling point is less than or equal to 100 ℃ solvent.The use amount of solvent can be set arbitrarily, but the too little meeting of consumption causes containing the precipitation of the charge-transporting material of reactive functional groups, therefore, the charge-transporting material that contains reactive functional groups with respect to 1 weight portion, this consumption is preferably 0.5～30 weight portion, more preferably 1～20 weight portion.
Temperature of reaction and reaction time when hardening resin composition is solidified are not particularly limited; but consider the physical strength and the chemical stability of formed protective seam 7; temperature of reaction is preferably and is greater than or equal to 60 ℃; more preferably 80～200 ℃, and the reaction time is preferably 10 minutes to 5 hours.To remain on the condition of high temperature by making hardening resin composition solidify the protective seam 7 that obtains, effectively the characteristic of stabilized protection course 7.In addition, according to purposes, can come that protective seam 7 is carried out hydrophobization by the surface treatment of using hexamethyldisilazane and trimethyl chlorosilane and handle.
When coating hardening resin composition on charge transport layer 6, can adopt general coating process, for example scraper coating, the coating of coiling rod, spraying coating, dip-coating, the coating of ring-like meniscus (ring-type meniscus coating), bead coating, airblade coating and curtain coating method.
If can not obtain required layer thickness, can obtain required layer thickness by being coated with again several times by once being coated with.When repeatedly being coated with again, when each coating, can carry out heat treated, perhaps can carry out heat treated after the coating more several times.
The thickness of protective seam 7 is preferably 0.5 micron～15 microns, is preferably 1 micron～10 microns again, is more preferably 1 micron～5 microns.
Have excellent charge-transporting and the physical strength of excellence and enough photoelectric characteristics by the protective seam 7 that hardening resin composition is solidified to form, therefore, protective seam 7 directly can be used as the charge transport layer of laminated-type photoreceptor.
As shown in Figure 4 and Figure 5, have under the situation of single-layer type photographic layer 8 as Electrophtography photosensor at photographic layer 3, single-layer type photographic layer 8 is formed by charge generating material and adhesive resin.As charge generating material, can use the charge generation layer 5 employed same materials in function separation property photographic layer, as adhesive resin, can use charge generation layer 5 and charge transport layer 6 employed same binder resins in function separation property photographic layer.In single-layer type photographic layer 8, based on the total solids content of single-layer type photographic layer 8, the content of charge generating material is preferably about 10 weight %～about 85 weight %, more preferably about 20 weight %～about 50 weight %.In order to improve photoelectric characteristic, can carry material to add single-layer type photographic layer 8 charge transport material and polymer charge.Based on the total solids content of single-layer type photographic layer 8, the addition of described material is preferably about 5 weight %～about 50 weight %.In coating employed solvent and coating process can with each layer of narrating above in employed identical.The layer thickness of single-layer type photographic layer 8 is preferably 5～50 microns, more preferably 10～40 microns.
In the Electrophtography photosensor shown in Fig. 1～5 1, be the functional layer that comprises the cured product of hardening resin composition of the present invention as the protective seam 7 of outermost surfaces layer, but described functional layer outermost surfaces layer not necessarily.For example, undercoat 4 can be the functional layer that comprises the cured product of hardening resin composition of the present invention.
Image forming apparatus and handle box:
Fig. 6 is the exemplary drawings of an exemplary embodiment of expression image forming apparatus of the present invention.Image forming apparatus 100 shown in Figure 6 comprises the main body (not shown) of image forming apparatus, and described image forming apparatus 100 has handle box 20, exposure device 30, transfer device 40 and the intermediate transfer body 50 that has disposed Electrophtography photosensor 1.In image forming apparatus 100, exposure device 30 is arranged in the position that can expose to Electrophtography photosensor 1 by the opening of handle box 20, transfer device 40 is arranged in across the relative position of intermediate transfer body 50 and Electrophtography photosensor 1, and arrange intermediate transfer body 50, it is partly contacted with Electrophtography photosensor 1.
Charging system 21 is to be used for making the charged charged device of Electrophtography photosensor 1 with the way of contact.Developing apparatus 25 is to form the unit of toner image by the electrostatic latent image on the Electrophtography photosensor 1 is developed.
The toner that uses in developing apparatus 25 is as described below.Average shape factor (the ML of toner
2/ A) be preferably 100～150, more preferably 100～140, volume average particle size is preferably 2 microns～12 microns, more preferably 3 microns～9 microns.By the toner that use has above-mentioned average shape factor and volume average particle size, can obtain to have the image of high development, transfer printing and image quality.
Average shape factor ML
2/ A calculates according to following formula (1).
(ML
2/ A)=((maximum length)
2/ projected area) * (π/4) * 100 (1)
As the concrete grammar that is used to calculate average shape factor, toner image got from optical microscope be input to image dissector (LUZEX (III), by NIRECO company produce) so that measure 100 toner-particles equivalent circle diameter separately arbitrarily.Then,, obtain the shape coefficient value shown in the formula, and average institute value is to obtain average shape factor according to their maximum length and area.
Though toner is not subjected to the special restriction of manufacture method, as long as but satisfy the above-mentioned scope of average shape factor and volume average particle size, can use the toner of making by following method, for example: the comminuting method of kneading, promptly, with adhesive resin, colorant and release agent, add charge control agent in case of necessity and knead, and pulverize and classification; By using mechanical impact force or heat energy to change the method for the form of the particle that obtains by the comminuting method of kneading; The emulsion polymerization agglutination promptly, with the polymerisable monomer emulsion polymerization of adhesive resin, mixes the dispersion liquid of gained and colorant and release agent and the dispersion liquid that adds charge control agent in case of necessity, and aggegation is also merged by heating, thereby obtains toner-particle; Suspension polymerization promptly, will be used for obtaining polymerisable monomer, colorant and the release agent of adhesive resin and the solution of charge control agent in case of necessity and be suspended in aqueous solvent, carry out polyreaction; The dissolving suspension method promptly, is suspended in adhesive resin, colorant and release agent and charge control agent in case of necessity in the aqueous solvent, thereby obtains particle.
In addition, can use well-known method, for example: as nuclear, make it to merge the manufacture method that makes core/shell structure by heating again by further adhering to agglutinating particle with the toner-particle of above-mentioned acquisition.As the method for making of toner, from the viewpoint of control shape and size-grade distribution, preferably use suspension polymerization, emulsion polymerization agglutination and the dissolving suspension method of aqueous solvent, particularly preferably be the emulsion polymerization agglutination.
The toner master batch contains adhesive resin, colorant and release agent and silicon dioxide in case of necessity and charge control agent.
As the adhesive resin that in the toner master batch, uses, can enumerate the homopolymer and the multipolymer of following monomer: phenylethylene for example, as styrene and chlorostyrene; Mono-olefin is as ethene, propylene, butylene and isoprene; Vinyl esters is as vinyl acetate, propionate, benzoic acid vinyl esters and vinyl butyrate; Alpha-methylene aliphatic monocarboxylic acid ester is as methyl acrylate, ethyl acrylate, butyl acrylate, dodecylacrylate, 2-ethyl hexyl acrylate, phenyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate and lauryl methacrylate; Vinyl ether, for example vinyl methyl ether, EVE and vinyl butyl ether; Vinyl ketone, for example ethenyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone, and the vibrin that produces by the copolyreaction of dicarboxylic acid and glycol.
As representational adhesive resin, can enumerate: polystyrene, styrene-propene acid alkyl ester multipolymer, styrene-alkyl methacrylate multipolymer, styrene-acrylonitrile copolymer, Styrene-Butadiene, styrene-maleic anhydride copolymer, tygon, polypropylene and vibrin.In addition, can also enumerate polyurethane, epoxy resin, silicone resin, polyamide, modified rosin and paraffin.
As representational colorant, have for example: Magnaglo, for example magnetic iron ore and ferrite; Carbon black, aniline blue, calyl indigo plant, chrome yellow, ultramarine blue, Du Pont's oil red, quinoline yellow, methylene chloride indigo plant, phthalocyanine blue, peacock green oxalates, dim, rose-red, C.I. pigment red 4 8:1, C.I. pigment red 122, C.I. paratonere 57:1, C.I. pigment yellow 97, C.I. pigment yellow 17, C.I. pigment blue 15: 1 and the C.I. pigment blue 15: 3.
As release agent, representative example has: low molecular weight polyethylene, low-molecular-weight polypropylene, f-t synthetic wax, montan wax, Brazil wax, rice bran wax, candelila wax etc.
As charge control agent, can use the compound of knowing, for example azo metal coordination compound, salicylic acid metal coordination compound, and can use resin type charge control agent with polar group.When making toner,, preferably use almost water-fast material according to the viewpoint of control ionic strength and minimizing waste water environmental pollution with wet method.Toner can be to contain the magnetic color tuner of magnetic material and do not contain any toner in the nonmagnetic toner of magnetic material.
Employed toner can make by the adjuvant that uses Henschel mixer or V-mixer to mix above-mentioned toner master batch and to add in developing apparatus 25.When making the toner master batch, can use wet method to add adjuvant from the outside according to wet method.
Employed toner can contain the lubricity particle in developing apparatus 25.As the example of lubricity particle, can use for example kollag, as graphite, molybdenum disulfide, talcum, fatty acid metal salts etc.; Low-molecular-weight polyolefin is as polypropylene, tygon, polybutylene etc.; Silicone with thermoplastic point; Fatty acid amide is as oleamide, mustard seed acid amides, castor-oil plant acid amides, stearmide etc.; Vegetable wax is as Brazil wax, rice bran wax, candelila wax, Japan tallow, Jojoba wet goods; Animal wax is as beeswax; Mineral, pertroleum wax, as montan wax, ceresine (ozokerite), ceresin (ceresin), paraffin, microcrystalline wax, f-t synthetic wax, and the modified product of these compounds.These compounds can use separately or two or more compound is used in combination.Yet the volume average particle size of these compounds is preferably 0.1 micron～10 microns, makes all particles have uniform-dimension thereby the particle with above-mentioned chemical constitution can be pulverized.Addition to toner is preferably about 0.05 weight %～about 2.0 weight %, more preferably about 0.1 weight %～about 1.5 weight %.
For lip-deep attachment of Electrophtography photosensor and degradation product are removed, can be attached to organic fine particles with inorganic particles, organic fine particles and with inorganic particles and the composite particles that obtains joins employed toner in the developing apparatus 25.
As inorganic particles, preferred various inorganic oxides, nitride and boride, for example silicon dioxide, aluminium oxide, titanium dioxide, zirconia, barium titanate, aluminium titanates, strontium titanates, magnesium titanate, zinc paste, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, manganese oxide, boron oxide, silit, boron carbide, titanium carbide, silicon nitride, titanium nitride, the boron nitride etc. of using.
Can carry out surface treatment to described inorganic particles with following material: titanium coupling agent, for example butyl titanate, metatitanic acid four monooctyl esters, isopropyl triisostearoyltitanate, three decyl benzenesulfonyl isopropyl titanates, two (dioctylphyrophosphoric acid ester) oxo acetic acid esters titanate esters etc.; Silane coupling agent, for example γ-(2-amino-ethyl) aminopropyl-trimethoxy silane, γ-(2-amino-ethyl) aminopropyl methyl-dimethoxy silane, γ-methacryloxypropyl trimethoxy silane, N-β-(N-vinyl benzyl aminoethyl)-gamma-amino propyl trimethoxy silicane hydrochloride, hexamethyldisilazane, methyltrimethoxy silane, butyl trimethoxy silane, the isobutyl trimethoxy silane, the hexyl trimethoxy silane, the octyl group trimethoxy silane, the decyl trimethoxy silane, the decyl trimethoxy silane, the dodecyl trimethoxy silane, phenyltrimethoxysila,e, the o-methyl-phenyl-trimethoxy silane, p-methylphenyl trimethoxy silane etc.In addition, the also preferred inorganic particles of handling with silicone oil and higher fatty acid slaine (for example aluminium stearate, zinc stearate, calcium stearate etc.) hydrophobization that uses.
As organic fine particles, that can give an example has: styrene resin particle, styrene-acrylonitrile copolymer acid resin particle, polyester resin particle and urethane resin particles.
The particle diameter of described particulate is preferably 5～1 in volume average particle size, 000 nanometer, and more preferably 5～800 nanometers are preferably 5～700 nanometers again.When volume average particle size during less than lowest limit, particle often lacks wearing quality.On the other hand, when its during greater than the maximum value, scratch takes place on the Electrophtography photosensor surface easily.Equally preferably, the addition summation of the above particle and lubricity particle is more than or equal to about 0.6 weight %.
As other inorganic oxide that joins in the toner, for flowability and the charging property of controlling particulate, the preferred small particle diameter inorganic oxide that uses primary particle diameter to be less than or equal to 40 nanometers, and, further, charged in order to reduce adhesion with control, preferably use the inorganic oxide of particle diameter greater than aforementioned inorganic oxide.Although can use the inorganic oxide particle of knowing, in order to carry out accurate charged control, preferred compositions is used silicon dioxide and titanium dioxide.In addition, by the surface treatment of particulate, the dispersed raising, the effect that improves the particulate flowability uprises.Equally, in order to remove discharging product, preferably in toner, add inorganic minerals such as carbonate such as lime carbonate and magnesium carbonate and hydrotalcite.
The electrophotography color toner can be mixed together use with carrier.As carrier, can use iron powder, beaded glass, ferrite powder, nickel powder and through these resin-coated powder.Can set arbitrarily with the blending ratio of carrier.
For example, when adopting roller shape parts, preferably the lubricity composition is supplied to the Electrophtography photosensor surface by it is contacted with lubricity compositions such as metallic soap for example and waxes as fibrous member 27a.As cleaning balde 27b, use rubber flap commonly used.When using rubber flap as cleaning balde 27b, it is effective especially to the gap and the wearing and tearing that suppress scraper plate that the lubricity composition is supplied to the Electrophtography photosensor surface.
Described handle box 20 can freely be connected with the main body of image forming apparatus and therefrom dismounting, and with the main body composing images forming device of image forming apparatus.
Thereby, exposure device 30 forms electrostatic latent image as long as can exposing to charged Electrophtography photosensor 1.As the light source of exposure device 30, preferably use multiple beam formula surface-emission laser.
As long as transfer device 40 can be transferred to the toner image on the Electrophtography photosensor 1 body to be transferred (intermediate transfer body 50), and can use general roller shape transfer device.
As intermediate transfer body 50, can use shoestring (intermediate transfer belt) such as for example polyimide, polyamidoimide, polycarbonate, polyarylate, polyester or rubber with semiconduction.As the shape of intermediate transfer body 50, except shoestring, also can adopt cydariform.Also have the direct transfer-type image forming apparatus that does not dispose the intermediate transfer body, Electrophtography photosensor of the present invention is applicable to described image forming apparatus.Its reason is, because the paper powder and the talcum that produce from printing paper are attached to Electrophtography photosensor easily, often take place by the image deflects due to the attachment, but Electrophtography photosensor of the present invention is excellence aspect clean-up performance, like this, paper powder and talcum are easy to remove, even use direct transfer-type image forming apparatus also can obtain stable image.
Medium to be transferred of the present invention is not particularly limited, so long as the toner image transfer printing medium thereon that is formed on the Electrophtography photosensor 1 can be got final product.For example, when with image directly when Electrophtography photosensor 1 for example is transferred to paper, this paper is medium to be transferred, when using intermediate transfer body 50, this intermediate transfer body is a medium to be transferred.
Fig. 7 is the exemplary drawings of another exemplary embodiment of expression image forming apparatus of the present invention.In image forming apparatus shown in Figure 7 110, Electrophtography photosensor 1 is fixed on the image forming apparatus main body, Charging system 22, developing apparatus 25 and cleaning device 27 handle box separately of being packed into respectively is independently as charged box, Delevoping cartridge and clean box.Charging system 22 has in the corona discharge mode makes the charged Charging system of photoreceptor.
In image forming apparatus 110, Electrophtography photosensor 1 separates with miscellaneous equipment, Charging system 22, developing apparatus 25 and cleaning device 27 are not to be fixed on the main body of image forming apparatus with modes such as mechanical bolt, riveted joint, bonding and welding, they can be connected with this main body and therefrom dismounting by the operation of pulling out or advancing.
Because Electrophtography photosensor of the present invention excellent performance aspect wear-resistant might install each in the box of all packing into.Therefore, because Charging system 22, developing apparatus 25 can be connected with the main body of image forming apparatus by the operation of pulling out or advancing with cleaning device 27 and therefrom dismantle, rather than be fixed on this main body by modes such as mechanical bolt, riveted joint, bonding and welding, so, by such formation, can reduce the component costs of per 1 printing.In addition, two or more in these can being installed are packed into and can be connected the handle box of dismounting accordingly, and thus, the component costs of per 1 printing can further reduce.
Except corresponding process cartridge that Charging system 22, developing apparatus 25 and cleaning device 27 are packed into, image forming apparatus 110 has the formation identical with image forming apparatus 100.
Fig. 8 is the exemplary drawings of another exemplary embodiment of expression image forming apparatus of the present invention.Image forming apparatus 120 is the tandem full-colour image forming devices that dispose four handle boxes 20.In image forming apparatus 120, four handle boxes 20 are arranged in formation one row on the intermediate transfer body 50, wherein each color can be used an Electrophtography photosensor.Except image forming apparatus 120 is to adopt the series system, image forming apparatus 120 has the formation identical with image forming apparatus 100.
In tandem type image forming device 120, the wear extent of each Electrophtography photosensor is different because of the usage ratio of every kind of color, and therefore, there is the trend that differs from one another in the electrical characteristics of each Electrophtography photosensor.According to this trend, the development of toner gradually changes from original state, and the tone of printed images changes, and often is difficult to obtain stable image.Particularly, in order to make the image forming apparatus miniaturization, have the trend of using miniature electric photosensitive body, this trend is less than or equal to 30mm in employing
The situation of Electrophtography photosensor under more remarkable.When Electrophtography photosensor of the present invention is configured for Electrophtography photosensor, even the diameter of this Electrophtography photosensor is less than or equal to 30mm
, also can suppress the wearing and tearing on Electrophtography photosensor surface fully.Therefore, the Electrophtography photosensor among the present invention is effective especially for the tandem type image forming device.
Fig. 9 is the exemplary drawings of another exemplary embodiment of expression image forming apparatus of the present invention.Image forming apparatus 130 shown in Figure 9 is the what is called four circulating image forming apparatus that form the multi-color toner image with an Electrophtography photosensor.Image forming apparatus 130 disposes photosensitive drums 1, and described photosensitive drums 1 is driven with the rotating speed rotation in accordance with regulations of arrow A direction in scheming by the driver element (not shown), will be used to make the charged Charging system 22 of photosensitive drums 1 outer peripheral face to be arranged on the top of photosensitive drums 1.
Dispose the surface-emission laser array and be arranged in the top of Charging system 22 as the exposure device 30 of exposure light source.Exposure device 30 is modulated the multiple laser Shu Jinhang from light emitted according to formed image, make laser beam polarization on the direction of scanning, and on the outer peripheral face of photosensitive drums 1, scan along the direction parallel with the axle of photosensitive drums 1, thus, on the charged outer peripheral face of photosensitive drums 1, form electrostatic latent image.
Developing apparatus 25 is arranged in the side of photosensitive drums 1.Developing apparatus 25 disposes the roller shape host body that can rotate freely through arranging.Be formed with four in the inside of host body and accommodate part, accommodate in the part at each developing cell 25Y, 25M, 25C or 25K are set.Each developing cell 25Y, 25M, 25C or 25K dispose developer roll 26, and the toner of Y, M, C or K color is stored in each developing cell.
In the process of photosensitive drums 1 rotation four times, in image forming apparatus 130, form full-colour image.That is to say, carry out in the process of four rotations in photosensitive drums 1, Charging system 22 makes outer peripheral face charged of photosensitive drums 1, exposure device 30 scanning laser beam repeatedly on the outer peripheral face of photosensitive drums 1, this laser beam forms according to Y, the M of the coloured image of representing to form, any view data modulation of C, K, and photosensitive drums 1 whenever rotates a circle, and changes the view data that is used for modulating lasering beam.Under any developer roll 26 of developing cell 25Y, 25M, 25C and 25K state corresponding with the outer peripheral face of photosensitive drums 1, this developing cell that developing apparatus 25 starts corresponding to the outer peripheral face of photosensitive drums 1, make the latent electrostatic image developing on the outer peripheral face that is formed on photosensitive drums 1 with specific color, on the outer peripheral face of photosensitive drums 1, form the toner image of particular color thus, repeat this program, and photosensitive drums 1 whenever rotates a circle, rotate host body, be used to make the developing cell of latent electrostatic image developing with conversion.By such operation, photosensitive drums 1 whenever rotates a circle, and can form Y, M, C and K toner image in succession on the outer peripheral face of photosensitive drums 1 with overlapping each other, when photosensitive drums 1 rotates four circles, can form full-color toner image on the outer peripheral face of photosensitive drums 1.
Ring-type intermediate transfer belt 50 is arranged in position near the below of photosensitive drums 1.Intermediate transfer belt 50 is centered on roller 51,53 and 55 tensionings, and be arranged to the form that its outer peripheral face contacts with the outer peripheral face of photosensitive drums 1. Roller 51,53 and 55 is rotated by the transmission of the driving force of motor (not shown), and intermediate transfer belt 50 is pressed the rotation of direction shown in the arrow B among Fig. 9 thus.
Across the relative side of photosensitive drums 1 and developing apparatus 25, feeding lubricating device 29 and cleaning device 27 are arranged in the outer peripheral face of photosensitive drums 1.When the toner image on the outer peripheral face that will be formed on photosensitive drums 1 is transferred to intermediate transfer belt 50, by feeding lubricating device 2 lubricant is supplied to the outer peripheral face of photosensitive drums 1, the zone of carrying the toner image of transfer printing to some extent on the outer peripheral face by 27 pairs of photosensitive drums 1 of cleaning device is cleaned.
Then, be described as the exemplary embodiment of the exposure device 30 of exposure light source disposing the surface-emission laser array with reference to Figure 10.Exposure device 30 disposes the surface-emission laser array 70 of emission m (m is more than or equal to 3) bundle laser beam.In Figure 10, for simplicity, only shown 3 bundle laser beam, but the surface-emission laser array 70 that comprises the surface-emission laser of lining up array can comprise the surface-emission laser array of launching tens bundle laser beam.About the array of surface-emission laser bundle (array of the laser beam that penetrates from surface-emission laser array 70), except the single-column type array, can also be two-dimensional array (for example matrix-like array).
Because the opposition side of the laser emitting side of surface-emitting laser is emission of lasering beam (under the situation of end face emitting laser from the two ends emission of lasering beam) not, so be necessary part exposure is separated with laser beam, and detect its light quantity as mentioned above, so that detect and the control light quantity.
The transmission of the driving force by the motor (not shown) makes the direction rotation of rotation polygon prism 86 by the arrow C of Figure 10, makes laser beam by 84 reflections of upset mirror and incident along main scanning direction generation polarization, and with its reflection.On the laser beam emitting side of rotation polygon prism 86, arrange the F θ lens 88,90 that only on main scanning direction, have magnification, by rotation polygon prism 86 polarizations and laser light reflected bundle, move on the outer peripheral face of Electrophtography photosensor 1 with almost equal speed, and by F θ lens 88,90 with its refraction consistent so that the image on the main scanning direction forms the position with the outer peripheral face of Electrophtography photosensor 1.
Arranged in sequence only has the cylindricality mirror 92,94 of magnification on sub scanning direction on the laser beam emitting side of F θ lens 88,90, so that the image of sub scanning direction forms the position mode consistent with the outer peripheral face of Electrophtography photosensor 1, to reflect through the laser beam of F θ lens 88,90 transmissions by cylindricality mirror 92,94, and be radiated on the outer peripheral face of Electrophtography photosensor 1. Cylindricality mirror 92,94 also has the compensate function that the surface subsides, thereby makes rotation polygon prism 86 and Electrophtography photosensor 1 outer peripheral face form conjugation on sub scanning direction.
On the laser beam emitting side of cylindricality mirror 92, with pick-up mirror (pickup mirror)) 96 be arranged in the corresponding position, end (SOS:Start of Scan) with the scanning origination side of laser beam flying scope, light-beam position detects inductor 98 and is arranged on the laser beam emitting side of pick-up mirror 96.When the face of reflection lasering beam of each reflecting surface of rotation polygon prism 86 change and towards with the corresponding direction of SOS on during the direction of emitting incident light bundle,, and make it to inject light-beam position and detect inductor 98 (also can with reference to the imaginary line among Figure 10) by pick-up mirror 96 reflection from surface-emission laser array 70 emitted laser bundles.
With the rotation of rotation polygon prism 86 when coming the laser beam of modulated scanning Electrophtography photosensor 1 outer peripheral face to form electrostatic latent image with this, the initial timing of modulation in the time of will being used to make each main sweep from the signal that light-beam position detects inductor 98 outputs is carried out synchronously.
In exposure device 30, arrange collimation lens 72, cylindrical lens 82 and two cylindricality mirrors 92,94 respectively, so that be the non-focusing state on each comfortable sub scanning direction.Its reason is, suppress the difference between the scanning line bending of multiple laser bundle and the sweep trace that produces by the multiple laser bundle between the last change of distance.
Embodiment
Be described more specifically the present invention with reference to embodiment and comparative example, but the present invention is not limited to this.
With the centreless grinding device grinding cylindric aluminium base is ground, so that surfaceness (10 mean roughness: Rz) reach 0.6 micron.Carry out ungrease treatment successively, carry out 1 minute etch processing, neutralisation treatment and pure water washing, cleaning through the aluminium base of centreless grinding with the sodium hydroxide solution of 2 weight %.Then, the sulfuric acid solution with 10 weight % forms anode oxide film (current density: 1.0A/dm on the aluminium base surface
2).After washing with water, handle by in 1 weight % nickel acetate solution, the aluminium base dipping being carried out sealing of hole in 25 minutes at 80 ℃.Further, with the pure water washing, carry out dried then.So, obtain being formed with on the surface aluminium base of the about 7.5 microns anode oxide films of thickness.
Next step, with the gallium chlorine phthalocyaninate of 1 weight portion (in the X-ray diffraction spectrum that uses CuK α characteristic X ray to obtain, described gallium chlorine phthalocyaninate locates to show strong diffraction peak at the Bragg angle of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° (2 θ ± 0.2 °)), 1 weight account polyethylene butyral (S-LEC BM-S, make by the ponding chemistry) and the mixing of 100 weight portion n-butyl acetates, afterwards by in the pigment stirrer, making it in 1 hour to disperse, to obtain charge generation layer formation coating fluid with the beaded glass processing.Coating fluid is coated on the aluminium base with dip coating,, obtains the about 0.15 micron charge generation layer of layer thickness with this by coming drying coated layer in 10 minutes 100 ℃ of heating.
Then, 2 weight portions are contained macromolecular compound with the structural unit of general formula (XV) expression shown in following (viscosity-average molecular weight: 39000) dissolve in 25 weight portion chlorobenzenes, obtain charge transport layer with this and form and use coating fluid with the benzidine compound of the expression of general formula (XIV) shown in following and 2.5 weight portions.
Coating fluid is coated on the charge generation layer with dip coating, by coming drying coated layer in 40 minutes, with the charge transport layer of 20 microns of this cambium layer thickness 130 ℃ of heating.
With the exemplary compounds (I-25) of 4.5 weight portions and the resol type phenol resin (PL-4852 of 5.5 weight portions; make by group Rong Huaxue society) dissolve in the 20 weight portion butanols; then 0.045 weight portion p-toluenesulfonic acid is added above-mentioned solution, obtain protective seam formation coating fluid with this.The coating fluid that obtains is coated on the charge transport layer with dip coating,, obtains the protective seam (outermost surfaces layer) of 2.5 microns of layer thicknesses with this by coming drying coated layer in 40 minutes 150 ℃ of heating.So, finished the making of Electrophtography photosensor.
At first, prepare the cylindric aluminium base that the process honing is handled.Then, with 100 weight portion zirconium compounds (Orgatix ZC540, by Matsumoto Chemical Industry Co., Ltd. manufacturing), 10 weight portion silane compound (A1100, by Nippon Unicar Co., Ltd. manufacturing), 3 weight account polyethylene butyrals (S-LEC BM-S, society makes by the ponding chemistry), 380 weight portion isopropyl alcohols and the mixing of 200 weight portion butanols form with the preparation undercoat and use coating fluid.Coating fluid is coated on the aluminium base with dip coating,, obtains the about 0.17 micron undercoat of layer thickness with this by coming drying coated layer in 10 minutes 150 ℃ of heating.
Secondly, with 1 weight portion hydroxy gallium phthalocyanine (in the X-ray diffraction spectrum that uses CuK α characteristic X ray, described hydroxy gallium phthalocyanine locates to show strong diffraction peak at the Bragg angle of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° (2 θ ± 0.2 °)), 1 weight account polyethylene butyral (S-LEC BM-S, by the manufacturing of ponding chemistry society) and the mixing of 100 weight portion n-butyl acetates, afterwards by in the pigment stirrer, making it in 2 hours to disperse to obtain charge generation layer formation coating fluid with the beaded glass processing.Coating fluid is coated on the undercoat with dip coating,, obtains the about 0.15 micron charge generation layer of layer thickness with this by coming drying coated layer in 10 minutes 100 ℃ of heating.
Then, 2 weight portions are contained macromolecular compound with the structural unit of general formula (XVII) expression shown in following (viscosity-average molecular weight: 50000) dissolve in 20 weight portion chlorobenzenes, obtain charge transport layer with this and form and use coating fluid with the compound of the expression of general formula (XVI) shown in following and 3 weight portions.
The coating fluid that obtains is coated on the charge generation layer with dip coating, by coming drying coated layer in 45 minutes, with the charge transport layer of 20 microns of this cambium layer thickness 120 ℃ of heating.
Then; exemplary compounds (II-16) and 5.5 weight portion resol type phenol resin (PR-53123 with 4.5 weight portions; changing into society by the Sumitomo makes) dissolve in the 20 weight portion butanols; then 0.04 weight portion dodecylbenzene sulfonic acid is added above-mentioned solution, obtain protective seam formation coating fluid with this.The coating fluid that obtains is coated on the charge transport layer with dip coating,, obtains the protective seam (outermost surfaces layer) of 3 microns of layer thicknesses with this by coming drying coated layer in 40 minutes 150 ℃ of heating.So, finish the making of Electrophtography photosensor.
According to embodiment 2 in identical program on aluminium base, form the about 0.17 micron undercoat of thickness.
Then, (described titanyl phthalocyanine is in the X-ray diffraction spectrum that uses CuK α characteristic X ray with 1 weight portion titanyl phthalocyanine, locate to demonstrate strong diffraction peak at 27.2 ° Bragg angles (2 θ ± 0.2 °)), 1 weight account polyethylene butyral (S-LEC BM-S, by the manufacturing of ponding chemistry society) and the mixing of 100 weight portion n-butyl acetates, afterwards by in the pigment stirrer, making it in 1 hour to disperse to obtain charge generation layer formation coating fluid with the beaded glass processing.Coating fluid is coated on the undercoat with dip coating,, obtains the about 0.15 micron charge generation layer of layer thickness with this by coming drying coated layer in 10 minutes 100 ℃ of heating.
Subsequently, 2 weight portions are contained macromolecular compound with the structural unit of general formula (XV) expression shown in top (viscosity-average molecular weight: 79000) dissolve in 25 weight portion chlorobenzenes, obtain charge transport layer with this and form and use coating fluid with the benzidine compound of the expression of general formula (XIV) shown in top and 2.5 weight portions.Coating fluid is coated on the charge generation layer with dip coating, by coming drying coated layer in 40 minutes, with the charge transport layer of 20 microns of this cambium layer thickness 130 ℃ of heating.
Next step; (Phenolite 5010 with the exemplary compounds (III-6) of 3 weight portions and 3 weight portion resol type phenol resins; chemical society makes by big Japanese ink) dissolve in the 20 weight portion butanols; then that 0.1 weight portion is polyether-modified silicone oil (KF615 (A); make by SHIN-ETSU HANTOTAI chemistry society) and 0.02 weight portion phenolsulfonic acid add above-mentioned solution, obtain protective seam formation coating fluid with this.The coating fluid that obtains is coated on the charge transport layer with ring-like meniscus rubbing method; at room temperature with air-dry 3 minutes of coating layer; then by being cured in 1 hour, with the protective seam (outermost surfaces layer) of 3 microns of this cambium layer thickness 130 ℃ of heat treated.Thereby, finish the making of Electrophtography photosensor.
100 part by weight of zinc oxide (SMZ-017N is made by TAYCA CORPORATION) are mixed with 500 parts by weight of toluene, afterwards 2 weight portion silane coupling agents (A1100, by Nippon Unicar Co., Ltd. makes) are added, stirred the mixture 5 hours.Under reduced pressure toluene is steamed then, reaction system is placed 120 ℃ of bakings 2 hours.As the x-ray fluorescence analysis result of the surface treated zinc paste of gained, element silicon intensity is 1.8 * 10 with respect to the ratio of zinc element-intensities
-4
With the above-mentioned surface treated zinc paste of 35 weight portions, 15 weight portions blocked isocyanate (Sumidule3175 as hardening agent, make by Sumitomo Bayer Urethane Co.), 6 weight portion butyral resin (BM-1, society makes by the ponding chemistry) and the mixing of 44 weight portion methyl ethyl ketones, potpourri is used 1mm in sand mill
(diameter) beaded glass disperses 2 hours to obtain dispersion liquid.In the dispersion liquid that is obtained, add 0.005 weight portion, two lauric acid dioctyl tins and 17 weight portion Tospear130 (making) and form with the preparation undercoat and use coating fluid by GE Toshiba Silicones.Coating fluid is coated on the aluminium base,, forms the undercoat of 20 microns of thickness with this by being cured in 100 minutes 160 ℃ of dryings.
Then, with 1 weight portion hydroxy gallium phthalocyanine (in the X-ray diffraction spectrum that uses CuK α characteristic X ray, described hydroxy gallium phthalocyanine locates to demonstrate strong diffraction peak at the Bragg angle of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° (2 θ ± 0.2 °)), 1 weight account polyethylene butyral (S-LEC BM-S, by the manufacturing of ponding chemistry society) and the mixing of 100 weight portion n-butyl acetates, afterwards by in the pigment stirrer, making it in 1 hour to disperse to obtain charge generation layer formation coating fluid with the beaded glass processing.Coating fluid is coated on the undercoat with dip coating, by coming drying coated layer in 10 minutes, with the about 0.15 micron charge generation layer of this cambium layer thickness 100 ℃ of heating.
Subsequently, 2 weight portions are contained macromolecular compound with the structural unit of general formula (XV) expression shown in top (viscosity-average molecular weight: 79000) dissolve in 25 weight portion chlorobenzenes, obtain charge transport layer with this and form and use coating fluid with the benzidine compound of the expression of general formula (XIV) shown in top and 2.5 weight portions.The coating fluid that is obtained is coated on the charge generation layer with dip coating, by coming drying coated layer in 40 minutes, with the charge transport layer of 20 microns of this cambium layer thickness 110 ℃ of heating.
Next step; exemplary compounds (IV-6) and 3 weight portion resol type phenol resin (PL-2211 with 3 weight portions; make by group Rong Huaxue society) dissolve in the 20 weight portion butanols, then 0.02 weight portion p-toluenesulfonic acid is added above-mentioned solution, obtain protective seam formation coating fluid with this.The coating fluid that obtains is coated on the charge transport layer with ring-like meniscus rubbing method, then by solidifying coating layer in 1 hour, with the protective seam (outermost surfaces layer) of 3 microns of this cambium layer thickness 130 ℃ of heat treated.Thereby, finish the making of Electrophtography photosensor.
According to embodiment 4 in identical program on aluminium base, form the undercoat of 20 microns of thickness.Then, on undercoat, form the about 0.15 micron charge generation layer of thickness, further on charge generation layer, form the about 20 microns charge transport layer of thickness.
Next step; exemplary compounds (IV-11) and 3 weight portion resol type phenol resin (PL-4852 with 3 weight portions; make by group Rong Huaxue society) dissolve in the 20 weight portion butanols, then 0.02 weight portion dodecylbenzene sulfonic acid is added above-mentioned solution, obtain protective seam formation coating fluid with this.The coating fluid that obtains is coated on the charge transport layer with ring-like meniscus rubbing method, then by solidifying coating layer in 1 hour, with the protective seam (outermost surfaces layer) of 3 microns of this cambium layer thickness 130 ℃ of heat treated.Thereby, finish the making of Electrophtography photosensor.
According to embodiment 4 in identical program on aluminium base, form the undercoat of 20 microns of thickness.Then, on undercoat, form the about 0.15 micron charge generation layer of thickness, further on charge generation layer, form the about 20 microns charge transport layer of thickness.
Next step; exemplary compounds (XVIII-10) and 2.2 weight portion resol type phenol resin (PL-4852 with 2 weight portions; make by group Rong Huaxue society) dissolve in the 10 weight portion normal butyl alcohols; then with 0.4 weight portion 3; 5-di-t-butyl-4-hydroxy-methylbenzene (BHT) and 0.3 weight portion p-toluenesulfonic acid add above-mentioned solution and at room temperature stirred 30 minutes; be that 0.5 micron filtrator filters solution by the aperture then, obtain protective seam with this and form and use coating fluid.The coating fluid that obtains is coated on the charge transport layer with ring-like meniscus rubbing method; with at room temperature air-dry 30 minutes of coating layer; by solidifying coating layer in 1 hour, form the protective seam (outermost surfaces layer) of 3 microns of thickness then with this 140 ℃ of heat treated.Thereby, finish the making of Electrophtography photosensor.
Compound (XVIII-10) synthetic as follows.That is, 100 grams, 4,4 '-two methylol triphenylamines are dissolved in 600 milliliters of tetrahydrofurans, add 120 gram potassium tert-butoxides afterwards, then with solution stirring 1 hour.To slowly be added drop-wise to above-mentioned solution by the solution that the 160 gram methyl iodides of dissolving in 80 milliliters of tetrahydrofurans obtain with two hours.After dripping termination, solution was stirred 2 hours fully, pour separatory funnel into, add 500 milliliters of toluene, then, with 500 ml distilled waters washing four hours.The dry toluene layer steams solvent, with silica gel column chromatography purified reaction product, obtains 102 with this and digests compound (XVIII-10).
According to embodiment 4 in identical program on aluminium base, form the undercoat of 20 microns of thickness.Then, on undercoat, form the about 0.15 micron charge generation layer of thickness, further on charge generation layer, form the about 20 microns charge transport layer of thickness.
Next step, exemplary compounds (XVIII-50) and 2.3 weight portion resol type phenol resin (PL-4852 with 2 weight portions, make by group Rong Huaxue society) dissolve in the 10 weight portion normal butyl alcohols, with 0.4 weight portion 3,5-di-t-butyl-4-hydroxy-methylbenzene (BHT) adds above-mentioned solution and at room temperature stirred 30 minutes then.Add 0.5 weight portion tin oxide particulate (S-1 is made by JEMCO) in the solution that is obtained, described tin oxide particulate carried out surface treatment (treatment capacity: 5 weight %) with fluorine coupling agent (KBM7103 is made by chemistry society of SHIN-ETSU HANTOTAI); By means of the pigment stirrer with beaded glass with this solution dispersion treatment 1 hour.Remove after the beaded glass, further 0.3 weight portion dodecylbenzene sulfonic acid is joined in the reaction solution, obtain protective seam formation coating fluid with this.The coating fluid that obtains is coated on the charge transport layer with ring-like dip coating,, by solidifying coating layer in 1 hour, forms the protective seam (outermost surfaces layer) of 3 microns of thickness then with this 150 ℃ of heat treated with at room temperature air-dry 30 minutes of coating layer.Thereby, finish the making of Electrophtography photosensor.
Comparative example 1
Adopt the method identical with embodiment 3 to make the Electrophtography photosensor of comparative example 1, difference is phenolsulfonic acid not to be joined protective seam and forms in the usefulness coating fluid.
Comparative example 2
Adopt the method identical to make the Electrophtography photosensor of comparative example 2 with embodiment 3; difference is; form with in the coating fluid at protective seam; replace the exemplary compounds (III-6) of 3 weight portions with 3 weight portion triphenylamines, and replace 20 weight portion butanols with 10 weight portion butanols and 10 weight portion cyclohexanone.
Comparative example 3
Adopt the method identical with embodiment 3 to make the Electrophtography photosensor of comparative example 3, difference is, forms in the usefulness coating fluid at protective seam, replaces 0.02 weight portion phenolsulfonic acid with 0.02 weight portion hexamethylene tetramine.
Film forming evaluation test 1:
Surface (surface of protective seam) with the Electrophtography photosensor of optics observation by microscope embodiment 1～7 and comparative example 1～3 preparation; by the quantity of statistics overshooting shape fault (breadth extreme is more than or equal to about 50 microns projection) from the teeth outwards, estimate the film forming of each sample according to following evaluation criterion.What obtain the results are shown in the following table 62.
A: on the surface of Electrophtography photosensor, do not observe the overshooting shape fault.
B: on the surface of Electrophtography photosensor, observe and be less than or equal 50 overshooting shape faults (available).
C: observing 50～100 overshooting shape faults (spot being required when reality is used in the harsh color machines problem can take place) on the surface of Electrophtography photosensor.
D: on the surface of Electrophtography photosensor, observe above 100 overshooting shape faults (meeting generation problem in actual the use).
Charged and exposure is tested:
The Electrophtography photosensor that makes 1～3 preparation of embodiment 1～7 and comparative example hot and humid degree (27 ℃, 75%RH) experience following process (A) under the condition, (B) and (C).
(A) apply voltage makes the electrophotographic photoreceptor belt electricity for-700 volts the charged device of scorotron charged process with grid
(B), shine 10.0 ergs/cm with the semiconductor laser of wavelength 780 nanometers in process (A) 1 second afterwards
2The exposure process of light
(C) in process (A) 3 seconds afterwards, shine 50.0 ergs/cm
2Red LED (wavelength 780 nanometers) remove electric process
In these processes, the scanner (XP-15 that is made by Fuji Xerox Co., Ltd is transformed) that uses laser printer to transform.With process (A) and (B) repeat 100,000 circulations (kcycle), the electromotive force (V when carrying out 1,000 round-robin processes (C)
RP) and the electromotive force (V when carrying out 100,000 round-robin processes (C)
RP) acquisition potential change amount Δ V
RP(absolute value).With potential change amount Δ V
RP(absolute value) is the basis, estimates the repetition stability of each Electrophtography photosensor according to following evaluation criterion.What obtain the results are shown in the following table 62.
A: Δ V
RPFor being less than or equal to 10 volts (problem can not take place).
B: Δ V
RPFor being less than or equal to 20 volts (problem can not take place in actual use).
C: Δ V
RPFor being less than or equal to 30 volts (between the long-term operating period, problem might take place).
D: Δ V
RPFor more than or equal to 30 volts (in actual use problem can take place).
Machine run test 1:
To be installed in printing machine DocuCentre Color 500 (being made by Fuji Xerox Co., Ltd) with each Electrophtography photosensor of embodiment 1～7 and comparative example 1～3 preparation and go up to make image forming apparatus, described printing machine disposes intermediate transfer body, blade member, fibrous member and lubricity material supply part.Use above-mentioned image forming apparatus, (28 ℃ of hot and humid degree, 80%RH) carry out quantity with no paper matrix formula under the condition and be equivalent to 5, the image of 000 paper forms test (image color: about 5%), then (10 ℃ of low temperature and low humidity degree, 20%RH) carry out quantity under the condition and be equivalent to 5, the image of 000 paper forms test (image color: about 5%), after above-mentioned test (28 ℃ of hot and humid degree, 80%RH) under the condition, estimate image quality (45 ° of line reproducibility in 1 dot line diagonal angle and 20% shadow tone repeatability) according to following evaluation criterion.When having defective (for example overshooting shape fault and striated peel off fault) on Electrophtography photosensor, the image quality evaluation is carried out in flawless place.What obtain the results are shown in the following table 62.
A: no problem.
B: observe concentration and reduce (no problem in actual the use) slightly.
C: observe concentration and reduce (becoming problem in actual the use).
Machine run test 2:
Each Electrophtography photosensor of embodiment 1～7 and comparative example 1～3 preparation is installed on the printing machine DocuColor 1256GA (being made by Fuji Xerox Co., Ltd) that disposes multiple beam formula surface-emitting laser, to make image forming apparatus.Use above-mentioned image forming apparatus, (28 ℃ of hot and humid degree, 80%RH) carry out quantity with general modfel under the condition and be equivalent to 5, the image of 000 paper forms test (image color: about 5%) afterwards, (10 ℃ of low temperature and low humidity degree, 20%RH) carry out quantity under the condition and be equivalent to 5, the image of 000 paper forms test (image color: about 5%), according to above-mentioned evaluation criterion (machine run test 1) estimate hot and humid degree (28 ℃, the 80%RH) image quality under the condition (45 ° of line reproducibility in 1 dot line diagonal angle and 20% shadow tone repeatability).What obtain the results are shown in the following table 62.
Machine run test 3:
Each Electrophtography photosensor of embodiment 1～7 and comparative example 1～3 preparation is installed on the printing machine DocuCentre Color 400CP (being made by Fuji Xerox Co., Ltd), to make image forming apparatus.Use above-mentioned image forming apparatus, (28 ℃ of hot and humid degree, 80%RH) carry out quantity with general modfel under the condition and be equivalent to 5, the image of 000 paper forms test (image color: about 5%) afterwards, (10 ℃ of low temperature and low humidity degree, 20%RH) carry out quantity under the condition and be equivalent to 5, the image of 000 paper forms test (image color: about 5%), according to above-mentioned evaluation criterion (machine run test 1) estimate hot and humid degree (28 ℃, the 80%RH) image quality under the condition (45 ° of line reproducibility in 1dot line diagonal angle and 20% shadow tone repeatability).What obtain the results are shown in the following table 62.
Film forming evaluation test 2:
The surface (surface of protective seam) of Electrophtography photosensor after machine run test 2 with observation by light microscope embodiment 1～7 and comparative example 1～3 preparation; statistics striated from the teeth outwards peels off the quantity of fault, estimates according to following evaluation criterion.What obtain the results are shown in the following table 62.
A: do not find that striated peels off fault.
B: confirm to exist on the photoreceptor to be less than or to equal five striated and peel off fault (upwards be 1 millimeter, width for more than or equal to 0.5 millimeter) (problem can not take place in actual use) the operator.
C: confirm on photoreceptor, to exist more than 5 and be less than or equal 20 striated and peel off fault (upwards be 1 millimeter, width for more than or equal to 0.5 millimeter) (when spot being required in the harsh color machines actual the use, problem can take place) the operator.
D: confirm on photoreceptor, to exist striated to peel off fault (upwards be 1 millimeter the operator, width is more than or equal to 0.5 millimeter) (in actual use problem can take place) more than 20.
From the result shown in the table 62 as can be seen, can confirm, compare with the Electrophtography photosensor of comparative example 1～3, exemplary embodiment of the present invention (embodiment 1～7) though Electrophtography photosensor also be stable aspect electrical characteristics when using for a long time, hardly image deterioration can take place, therefore can realize high image quality and long-life.In addition, the handle box of exemplary embodiment of the present invention and image forming apparatus can suppress image deflects fully and realize high image quality and long-life.Can confirm further that from The above results the hardening resin composition of exemplary embodiment according to the present invention can be formed on the functional layer that realizes the Electrophtography photosensor of physical strength and electrical characteristics on the high level simultaneously.
Claims (7)
1. hardening resin composition, described hardening resin composition comprises:
Resol type phenol resin, based on the total solids content of described hardening resin composition, the content of described resol type phenol resin is 20 weight %～90 weight %;
The charge-transporting material that contains reactive functional groups; With
Organic sulfonic acid and/or its derivant, total solids content based on described hardening resin composition, the content of described organic sulfonic acid and/or its derivant is 0.01 weight %～5 weight %, and described organic sulfonic acid and/or its derivant are at least a organic sulfonic acids that is selected from p-toluenesulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid and the phenolsulfonic acid
The described charge-transporting material that contains reactive functional groups is any in the following material:
Or
2. Electrophtography photosensor, described Electrophtography photosensor comprises:
The electric conductivity support; With
Be arranged on the photographic layer on the described electric conductivity support, described photographic layer comprises functional layer,
Wherein, described functional layer comprises the cured product of curable resin, and described curable resin comprises: resol type phenol resin; The charge-transporting material that contains reactive functional groups; With organic sulfonic acid and/or its derivant,
And based on the total solids content of described hardening resin composition, the content of described resol type phenol resin is 20 weight %～90 weight %,
Total solids content based on described hardening resin composition, the content of described organic sulfonic acid and/or its derivant is 0.01 weight %～5 weight %, and described organic sulfonic acid and/or its derivant are at least a organic sulfonic acids that is selected from p-toluenesulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid and the phenolsulfonic acid
The described charge-transporting material that contains reactive functional groups is any in the following material:
Or
3. Electrophtography photosensor as claimed in claim 2, wherein, described functional layer is the outermost surfaces layer that is arranged in from described electric conductivity support position farthest.
4. handle box, described handle box comprises:
(i) Electrophtography photosensor, this Electrophtography photosensor comprises:
The electric conductivity support; With
Be arranged on the photographic layer on the described electric conductivity support, described photographic layer comprises functional layer, and wherein, described functional layer contains the cured product of curable resin, and described curable resin comprises: resol type phenol resin; The charge-transporting material that contains reactive functional groups; With organic sulfonic acid and/or its derivant; With
(ii) be selected from at least one unit in the lower unit: make the charged elements of described electrophotographic photoreceptor belt electricity, cleaning unit by making the latent electrostatic image developing that is formed on the described Electrophtography photosensor form the developing cell of toner image and remove the lip-deep remaining toner of described Electrophtography photosensor with toner
And based on the total solids content of described hardening resin composition, the content of described resol type phenol resin is 20 weight %～90 weight %,
Total solids content based on described hardening resin composition, the content of described organic sulfonic acid and/or its derivant is 0.01 weight %～5 weight %, and described organic sulfonic acid and/or its derivant to be selected from be at least a organic sulfonic acid that is selected from p-toluenesulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid and the phenolsulfonic acid
In the described following material of charge-transporting material that contains reactive functional groups any:
Or
5. image forming apparatus, described image forming apparatus comprises:
(i) Electrophtography photosensor, it comprises:
The electric conductivity support; With
Be arranged on the photographic layer on the described electric conductivity support, described photographic layer comprises functional layer, and wherein, described functional layer contains the cured product of curable resin, and described curable resin comprises: resol type phenol resin; The charge-transporting material that contains reactive functional groups; With organic sulfonic acid and/or its derivant; With
(ii) make the charged elements of described electrophotographic photoreceptor belt electricity;
(iii) exposing unit, described exposing unit forms electrostatic latent image on charged described Electrophtography photosensor;
(iv) developing cell, described developing cell is by making described latent electrostatic image developing to form toner image with toner; With
(v) transfer printing unit, described transfer printing unit is transferred to body to be transferred with described toner image from described Electrophtography photosensor,
And based on the total solids content of described hardening resin composition, the content of described resol type phenol resin is 20 weight %～90 weight %,
Total solids content based on described hardening resin composition, the content of described organic sulfonic acid and/or its derivant is 0.01 weight %～5 weight %, and described organic sulfonic acid and/or its derivant are at least a organic sulfonic acids that is selected from p-toluenesulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid and the phenolsulfonic acid
The described charge-transporting material that contains reactive functional groups is any in the following material:
Or
6. image forming apparatus as claimed in claim 5, described image forming apparatus also comprises cleaning unit, described cleaning unit cleans the surface of described Electrophtography photosensor after the image transfer printing, and described cleaning unit comprises at least a parts in blade member and the fibrous member.
7. image forming apparatus as claimed in claim 5, wherein, described transfer printing unit is transferred to the lip-deep toner image of described Electrophtography photosensor on the described body to be transferred via the intermediate transfer body.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005185378 | 2005-06-24 | ||
| JP2005185378 | 2005-06-24 | ||
| JP2005373310 | 2005-12-26 |
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| CN1885175A CN1885175A (en) | 2006-12-27 |
| CN100498553C true CN100498553C (en) | 2009-06-10 |
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| JP4442641B2 (en) * | 2007-06-04 | 2010-03-31 | 富士ゼロックス株式会社 | Electrophotographic photosensitive member manufacturing method, electrophotographic photosensitive member, image forming apparatus, and process cartridge |
| CN103180048B (en) | 2010-11-01 | 2015-07-29 | 英派尔科技开发有限公司 | Air cleaning system and the method for clean air |
| JP6630754B2 (en) * | 2017-02-16 | 2020-01-15 | 住友化学株式会社 | Curable resin composition, cured film and display device |
| CN112534356A (en) * | 2019-07-17 | 2021-03-19 | 富士电机株式会社 | Electrophotographic photoreceptor, method for producing the same, and electrophotographic apparatus |
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