CN103852981A - Laminated type electronic photographing photoreceptor, manufacturing method thereof and image forming device - Google Patents

Laminated type electronic photographing photoreceptor, manufacturing method thereof and image forming device Download PDF

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CN103852981A
CN103852981A CN201310618545.4A CN201310618545A CN103852981A CN 103852981 A CN103852981 A CN 103852981A CN 201310618545 A CN201310618545 A CN 201310618545A CN 103852981 A CN103852981 A CN 103852981A
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charge transport
general formula
transport layer
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resin
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CN103852981B (en
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东润
大坪淳一朗
井上孝行
冈田英树
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Kyocera Document Solutions Inc
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Abstract

The invention provides a laminated type electronic photographing photoreceptor, a manufacturing method thereof and an image forming device. According to the invention, the laminated photosensitive layer on which an electric charge generating layer and an electric charge transport layer are successively laminated is formed on a electrically conductive base body; the electric charge generating layer contains electric charge generating materials; the electric transport layer contains electric charge transport materials and cohesive resin; the electric charge transport materials contain tri-arylated amine ramification which is expressed by the following general formula (1) and used as hole transport materials; and the content of the electric charge transport material in the electric charge transport layer is lower than 55 parts by mass relative to 100 parts by mass of the adhesive resin.

Description

Laminated electronic photosensitive body, its manufacture method and image processing system
Technical field
The present invention relates to laminated electronic photosensitive body, its manufacture method and image processing system.
Background technology
The image processing system of electrofax mode possesses Electrophtography photosensor.Electrophtography photosensor has inorganic photoreceptor and Organophotoreceptor.Inorganic photoreceptor possesses the photographic layer of being made up of the inorganic material such as selenium, amorphous silicon.Organophotoreceptor possesses the photographic layer of being mainly made up of organic materials such as binding resin, charge generating material or charge transport materials.Compared with inorganic photoreceptor, Organophotoreceptor is easily manufactured.In addition, Organophotoreceptor owing to can selecting the material of photographic layer from the material of relative broad range, and the degree of freedom of design is high.Therefore, Organophotoreceptor is used widely.Such Organophotoreceptor is roughly divided into single-layer type Organophotoreceptor and cascade type Organophotoreceptor the structure of layer.Particularly cascade type Organophotoreceptor, because the function of each layer separates, aspect ease of design and function control, performance excellence, is commonly used in recent years.
Such laminated electronic photosensitive body, mostly is on conductive base, has stacked gradually charge generation layer and charge transport layer.Charge generation layer contains charge generating material.Charge transport layer contains charge transport material.
The charge transport material containing as charge transport layer, uses electron transport materials and hole transporting material.For hole transporting material, due to charge delivery capability excellence, propose to use the scheme of various three arylamine (triarylamine) derivant.In addition,, as the concrete example of the preferred triarylamine derivative of hole transporting material, can enumerate following compound (HTM-A and HTM-B).
[Chemical formula 1]
Figure BDA0000424430350000011
Summary of the invention
But while using above-mentioned triarylamine derivative (HTM-A and HTM-B) to form photographic layer, the photoreceptor obtaining is difficult to obtain excellent light sensitivity characteristic and mar proof simultaneously.In addition, above-mentioned triarylamine derivative and binding resin are used in combination.According to the kind of binding resin, triarylamine derivative is very easy to crystallization in photographic layer.If produce the crystallization problem of triarylamine derivative in photographic layer, the electrical characteristics (light sensitivity characteristic) of Electrophtography photosensor can be subject to obvious damage.
The present invention makes in view of the above problems, and its object is, the laminated electronic photosensitive body of mar proof and light sensitivity excellent is provided.Further, the invention provides and possess the manufacture method of this laminated electronic photosensitive body as image processing system and this laminated electronic photosensitive body of image carrier.
More particularly, the invention provides following technical scheme.
In the laminated electronic photosensitive body relating in the first scheme of the present invention, on conductive base, be formed with the cascade type photographic layer that stacks gradually charge generation layer and charge transport layer, described charge generation layer contains charge generating material, and described charge transport layer contains charge transport material and binding resin.Described charge transport material contains the triarylamine derivative representing using following general formula (1) as hole transporting material.The content of the described charge transport material in described charge transport layer is, with respect to the described binding resin of 100 mass parts, to contain below 55 mass parts.
[Chemical formula 2]
Figure BDA0000424430350000021
In general formula (1), Ar 1for aryl or there is the heterocyclic radical of conjugated double bond, Ar 2for aryl.Ar 1and Ar 2can selected free carbon atom number more than one group in the group that forms of the alkyl that is 1～6, alkoxy that carbon number is 1～6 and phenoxy group replace.
The image processing system that alternative plan of the present invention relates to, thus possess image carrier, make the electro-mechanical part of the surface charging of described image carrier, exposed in the surface of charged described the image carrier development section that forms the exposure portion of electrostatic latent image on the surface of described image carrier, develops described electrostatic latent image as toner image, the transfer section that described toner image is transferred to transfer printing body from described image carrier.Described image carrier is the laminated electronic photosensitive body that the first scheme of the present invention relates to.
According to the present invention, can provide mar proof and light sensitivity excellent laminated electronic photosensitive body, possess the manufacture method of this laminated electronic photosensitive body as image processing system and this laminated electronic photosensitive body of image carrier.
Brief description of the drawings
Fig. 1 is the figure that represents the structure of cascade type photoreceptor.
Fig. 2 is the structural representation that represents an example of image processing system of the present invention.
Fig. 3 represents triarylamine derivative of the present invention (HTM-1) 1the figure of H-NMR (300MHz) collection of illustrative plates.
Fig. 4 represents triarylamine derivative of the present invention (HTM-3) 1the figure of H-NMR (300MHz) collection of illustrative plates.
Fig. 5 represents triarylamine derivative of the present invention (HTM-4) 1the figure of H-NMR (300MHz) collection of illustrative plates.
Fig. 6 represents triarylamine derivative of the present invention (HTM-8) 1the figure of H-NMR (300MHz) collection of illustrative plates.
Fig. 7 represents triarylamine derivative of the present invention (HTM-10) 1the figure of H-NMR (300MHz) collection of illustrative plates.
Embodiment
Below embodiments of the present invention are specifically described, but the present invention do not limit by following embodiment, can carry out suitably changing and implementing to the present invention within the scope of the invention.In addition, repeat part for explanation, exist and omit the suitably situation of explanation, but therefore do not limit invention.
[embodiment one]
The laminated electronic photosensitive body (below also referred to as " cascade type photoreceptor ") of embodiments of the present invention one, on conductive base, possesses the cascade type photographic layer that stacks gradually charge generation layer and charge transport layer, this charge generation layer contains charge generating material, and this charge transport layer contains charge transport material and binding resin.Charge transport material contains the triarylamine derivative representing using following general formula (1) as electron transport materials.In addition, the content of the charge transport material in charge transport layer is, with respect to the binding resin of 100 mass parts, to contain below 55 mass parts.
[chemical formula 3]
Figure BDA0000424430350000041
In general formula (1), Ar 1for aryl or there is the heterocyclic radical of conjugated double bond, Ar 2for aryl.Ar 1and Ar 2more than one the group that can be selected from alkoxy and the phenoxy group that carbon number is 1～6 alkyl, carbon number is 1～6 replaces.
In the application's instructions and the scope of claims, the resin containing in the charge transport layer of cascade type photoreceptor is called to " binding resin ".In addition, when the charge generation layer of cascade type photoreceptor contains resin, the resin containing in charge generation layer is called to " matrix resin (base resin) ".Below, the laminated electronic photosensitive body of embodiments of the present invention one is described.
" laminated electronic photosensitive body "
As shown in Fig. 1 (a), laminated electronic photosensitive body 10 can be made as follows., on conductive base 11, form the charge generation layer 12 that contains charge generating material by the method such as evaporation or coating.Then,, after the coating fluid that coating contains charge transport material and binding resin on charge generation layer 12, be dried and form charge transport layer 13.
The Electrophtography photosensor of cascade type is by suitably selecting the kind of charge transport material, in positively charged and electronegative any one charged mode.
In addition,, as shown in Fig. 1 (b), before forming photographic layer, preferably on conductive base 11, be pre-formed bottom 14.This is due to by charge injection that bottom 14 can prevent conductive base 11 sides being set to photographic layer.And, by bottom 14 is set, can make photographic layer be glued fast on conductive base 11, and cover the lip-deep defect of conductive base 11 and make the surface smoothing of conductive base 11.
Below, about cascade type photoreceptor, the method for making of conductive base, photographic layer and photographic layer is illustrated successively.
(conductive base)
Conductive base, as long as can, as the conductive base of Electrophtography photosensor, not be particularly limited.Specifically, the material that can enumerate to have electric conductivity at least forms the conductive base of surface element.For example, conductive base can be the conductive base being formed by the material with electric conductivity, or the conductive base being formed by the surface with material plastic covering material of electric conductivity etc.In addition as the material with electric conductivity, for example can enumerate: aluminium, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel or brass.In addition, as the material with electric conductivity, can use separately a kind of material with electric conductivity, also can combine the two or more materials with electric conductivity and use, for example, use alloy.In addition, as conductive base, in above-mentioned material, the conductive base preferably being formed by aluminum or aluminum alloy.By using the conductive base being formed by aluminum or aluminum alloy, can provide the photoreceptor that can form better image.This is owing to considering that the migration of electric charge from photographic layer to conductive base is good.
The shape of conductive base can coordinate the structure of used image processing system suitably to select.As conductive base, can preferably use the matrix for example with the shape such as sheet or drum type.In addition, the thickness of conductive base can suitably be selected according to above-mentioned shape.
(photographic layer)
Cascade type photoreceptor, is made up of the charge generation layer that at least contains charge generating material forming on conductive base and the charge transport layer that at least contains charge transport material and binding resin.Charge generation layer can also contain matrix resin.Below, binding resin, charge transport material, charge generating material and matrix resin are illustrated successively.
(binding resin)
The binding resin using in charge transport layer is not particularly limited in the scope that does not hinder the object of the invention.Can use the binding resin conventionally using in the charge transport layer of cascade type photoreceptor.As the concrete example of preferred binding resin, can enumerate: polycarbonate resin, polyarylate resin, Styrene-Butadiene, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-propene acid copolymer, polyvinyl resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene resin, Corvic, acrylic resin, ionomer resin, vinyl chloride-vinyl acetate copolymer, alkyd resin, polyamide, urethane resin, polysulfone resin, diallyl phthalate ester resin, ketone resin, polyvinyl acetal resin, polyvinyl butyral resin, polyether resin, silicone resin, epoxy resin, phenolics, carbamide resin, melamine resin, Epocryl or urethanes-acrylate resin.These binding resins can use separately a kind of binding resin, or also with two or more binding resins.In order to suppress the wear extent of photographic layer, in above-mentioned binding resin, preferably use polycarbonate resin.As the concrete example of polycarbonate resin, can enumerate: bisphenol Z type polycarbonate resin, bisphenol Z C type polycarbonate resin, bisphenol-c type polycarbonate resin or bisphenol A polycarbonate resin.In addition, in polycarbonate resin, the polycarbonate resin more preferably representing with following general formula (2).
[chemical formula 4]
Figure BDA0000424430350000061
In general formula (2), p+q=1,0.35≤p < 0.7.Ar 4for being selected from a biradical of following general formula (2-1)～(2-4), R 1～R 4be hydrogen atom, alkyl or aryl independently respectively.R 3and R 4bonding forms ring alkylidene (cyclo alkylidene group) mutually.
[chemical formula 5]
Figure BDA0000424430350000071
There is the substituent R of the polycarbonate of general formula (2) 1～R 4during for alkyl, as substituent R 1～R 4be preferably carbon number and be 1～12 alkyl, the alkyl that more preferably carbon number is 1～8, is particularly preferably carbon number and is 1～6 alkyl.
With R 1～R 4when the substituting group representing is alkyl, as the concrete example of alkyl, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, isohesyl, n-heptyl, n-octyl, 2-ethylhexyl, tertiary octyl group, n-nonyl, positive decyl, n-undecane base or dodecyl.
In addition, in general formula (2), R 3and R 4bonding forms ring alkylidene mutually.R 3and R 4when bonding forms ring alkylidene mutually, the ring that forms ring alkylidene is preferably four-membered ring～octatomic ring, more preferably five-membered ring～hexatomic ring.
Substituent R in general formula (2) 1～R 4during for aryl, be preferably phenyl as aryl.In addition, be preferably as aryl the group that 2～6 phenyl ring condensations form or are connected to form by singly-bound.The phenyl ring number that aryl comprises is preferably 1～6, and more preferably 1～3, be particularly preferably 1 or 2.
As with R 1～R 4the concrete example of the substituting group representing while being aryl, can enumerate: phenyl, naphthyl, xenyl, fear base, phenanthryl or pyrenyl.
Ar in general formula (2) 4for being selected from the biradical of following general formula (2-1)～(2-4).
[chemical formula 6]
Figure BDA0000424430350000081
The preparation method of the polycarbonate resin representing with general formula (2) is not particularly limited.The polycarbonate resin representing with general formula (2), for example, can use the bisphenol compound corresponding with repetitive general formula (2) Suo Shu, is prepared according to the preparation method of known polycarbonate resin.
In the polycarbonate resin representing with general formula (2), can enumerate as the concrete example of preferred resin the Resin2-1～Resin2-5 representing with following general formula.P and q and general formula (2) synonym in the general formula of expression Resin2-1～Resin2-5.
[chemical formula 7]
Figure BDA0000424430350000091
The polycarbonate resin representing with general formula (2) is not particularly limited in the scope that does not hinder the object of the invention, can be any in random copolymers and segmented copolymer.The viscosity average molecular weigh of the polycarbonate resin representing with general formula (2), is preferably 5,000～200,000, and more preferably 20,000～60,000.By making the viscosity average molecular weigh of binding resin 5,000～200, in 000 scope, binding resin can form suitable hardness.Therefore,, by charge transport material is dispersed in binding resin well, can obtain the photoreceptor of electrical characteristics and excellent in wear resistance.
While measuring the viscosity average molecular weigh [M] of polycarbonate resin, use Ostwald viscosimeter, obtain limiting viscosity (1imiting viscosity) [η].Then, according to Schnell formula, by [η]=1.23 × 10 -4m 0.83calculate the viscosity average molecular weigh [M] of polycarbonate resin.And [η] can use polycarbonate resin solution to measure.Polycarbonate resin solution is at 20 DEG C, and using methylene chloride as solvent, dissolved polycarbonate resin is so that its concentration is 6.0g/dm 3obtain.
The content of the polycarbonate resin representing with general formula (2) with respect to binding resin total amount in charge transport layer is not particularly limited in the scope that does not hinder the object of the invention.But, more than the content of the polycarbonate resin representing with general formula (2) is preferably 70 quality %, more preferably more than 90 quality %, be particularly preferably 100 quality %.
(charge transport material)
As charge transport material, for example, can enumerate hole transporting material and electron transport materials.In the laminated electronic photosensitive body relating in embodiments of the present invention one, charge transport layer contains the triarylamine derivative representing using following general formula (1) as hole transporting material.
[chemical formula 8]
Figure BDA0000424430350000101
In general formula (1), Ar 1for aryl or there is the heterocyclic radical of conjugated double bond, Ar 2for aryl, Ar 1and Ar 2the more than one group that can be selected from alkoxy and the phenoxy group that carbon number is 1～6 alkyl, carbon number is 1～6 replaces.
Ar in general formula (1) 1and Ar 2during for aryl, be preferably phenyl as aryl.In addition, be preferably as aryl the group that 2～3 phenyl ring condensations form or are connected to form by singly-bound.The phenyl ring number that aryl comprises is 1～3, is preferably 1 or 2.As Ar 1and Ar 2concrete example during for aryl, can enumerate: phenyl, naphthyl, xenyl, fear base or phenanthryl.
In general formula (1), Ar 1during for " having the heterocyclic radical of conjugated double bond ", this heterocyclic radical is five yuan or the hexa-atomic monocycle that contains more than one N, S or O.Or, this heterocyclic radical be above-mentioned monocycle each other or the heterocyclic radical that forms of above-mentioned monocycle and phenyl ring condensation.In addition, this heterocyclic radical and Ar 1the ring of the nitrogen-atoms phase bonding of institute's bonding has conjugated double bond.Ar 1during for heterocyclic radical as condensed ring, form in the monocycle of condensed ring, with Ar 1the monocycle of the nitrogen-atoms phase bonding of institute's bonding has conjugated double bond.When heterocyclic radical is condensed ring, number of rings mostly is 3 most.
Ar 1when thering is the heterocyclic radical of conjugated double bond, form the example of the preferred heterocycle of heterocyclic radical, can enumerate: thiophene, furans, pyrroles, imidazoles, pyrazoles, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, triazole, tetrazolium, indoles, 1H-indazole, purine, 4H-quinolizine, isoquinoline, quinoline, phthalazines, naphthyridines, quinoxaline, quinazoline, cinnolines, pteridine, coumarone, 1,3-Ben Bing bis-Evil luxuriant (Benzodioxole), benzoxazoles, benzothiazole, benzimidazole, benzimidazolone or phthalimide.
Ar 1and Ar 2the more than one group that can be selected from alkoxy and the phenoxy group that carbon number is 1～6 alkyl, carbon number is 1～6 replaces.The concrete example of the alkyl that is 1～6 as carbon number, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl or isohesyl.In addition, the concrete example of the alkoxy that is 1～6 as carbon number, can enumerate: methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy, neopentyl oxygen, just own oxygen base or dissident's oxygen base.
In addition Ar, 1and Ar 2respectively at Ar 1and Ar 2on ortho position while thering is substituting group, multiple substituting groups mutually bonding form condensed ring.When the substituting group of adjacency forms condensed ring, condensed ring is preferably five-membered ring or hexatomic ring.
In general formula (1), two Ar 2can be identical or different.The compound representing with general formula (1), preferably two Ar 2there is identical group.In this case, can simplify the preparation section of triarylamine derivative, and can prepare triarylamine derivative with low cost.
In general formula (1), Ar 1preferably there are one or more substituting groups.Ar 1while having one or more substituting group, the oxygen atomicity and the carbon number that in preferred one or more substituting groups, contain add up to more than 2.As the compound representing with general formula (1), use Ar 1when the compound of such group, be easy to suppress the crystallization of the charge transport material in charge transport.
In the triarylamine derivative representing at general formula (1), as the concrete example of preferred compound, can enumerate following HTM-1～HTM-11.
[chemical formula 9]
Figure BDA0000424430350000121
(preparation method of triarylamine derivative)
The preparation method of the triarylamine derivative representing with general formula (1) is not particularly limited.As the preferred preparation method of the triarylamine derivative representing with general formula (1), can enumerate the method for operation (a)～operation (c) that for example comprises following explanation.
(operation (a))
Operation (a) is to make the compound of general formula (3) expression react the operation of the compound of preparing general formula (4) expression with triethyl phosphite.Operation (a) represents with following reaction equation.And, the compd A r that general formula (3) represents 2compd A r with general formula (1) expression 2identical.X 1for halogen atom.As X 1, from the viewpoint of excellent with the reactivity of triethyl phosphite, preferably chlorine or bromine.
[Chemical formula 1 0]
Figure BDA0000424430350000131
In the reaction of operation (a), the consumption of the compound that triethyl phosphite represents with respect to general formula (3), as long as can carry out well the reaction of operation (a), is not particularly limited.The consumption of triethyl phosphite, the compound representing with respect to general formula (3), is preferably etc. mole～2.5 times moles.If the consumption of triethyl phosphite is very few, in the compound representing at general formula (4), easily sneak into the compound that unreacted general formula (3) represents, refining load increases.If the consumption of triethyl phosphite is too much, the preparation cost of the compound that general formula (4) represents increases.
Temperature of reaction in operation (a), as long as can carry out well the reaction of operation (a), is not particularly limited.Temperature of reaction in operation (a) is preferably 160 DEG C～200 DEG C.In addition, the reaction time of operation (a) is for example 2～6 hours.
(operation (b))
Operation (b) is to make the compound of general formula (4) expression being obtained by operation (a) and 3-(4-halogenophenyl) acrolein reaction that general formula (5) represents, prepares the operation of the compound of general formula (6) expression.Operation (b) represents with following reaction equation.And, the X of general formula (5) 2for halogen atom.As X 2, aspect the reactivity following operation (c) is excellent, consider, preferably chlorine or bromine.
[Chemical formula 1 1]
Figure BDA0000424430350000141
In the reaction of operation (b), the consumption of the compound that the Compound Phase that general formula (5) represents represents for general formula (4), as long as can carry out well the reaction of operation (b), is not particularly limited.The consumption of the compound representing with general formula (5), with respect to the compound representing with general formula (4), is preferably etc. mole～2.5 times moles.
Temperature of reaction in operation (b), as long as can carry out well the reaction of operation (b), is not particularly limited.Temperature of reaction in operation (b) is preferably-20 DEG C～30 DEG C.In addition, the reaction time of operation (b) is 5～30 hours.
The reaction of operation (b) is carried out under the existence of alkali.As the preferred alkali using in operation (b), can enumerate: the alkali metal alcoholates of sodium methoxide or caustic alcohol and so on; The alkali metal hydride of sodium hydride or hydrofining and so on; The lithium alkyl of n-BuLi and so on.These alkali can combine two or more use.
The consumption of the alkali in operation (b), the compound representing with respect to general formula (5), is preferably 1 times～1.5 times moles.If when 1 times mole of use the quantity not sufficient of the alkali of the compound representing with respect to general formula (5), likely significantly reduction of the reactivity of operation (b) reaction.If when the consumption of the alkali of the compound representing with respect to general formula (5) exceedes 1.5 times moles, be likely difficult to control the reaction of operation (b).
The solvent using in operation (b), if be nonactive concerning the reaction of operation (b), is not particularly limited.As the concrete example of the preferred solvent using in operation (b), can enumerate: the ethers of diethyl ether, tetrahydrofuran or Isosorbide-5-Nitrae-dioxan and so on; The halogenated hydrocarbon of methylene chloride, chloroform or ethylene dichloride and so on; The aromatic hydrocarbon of benzene,toluene,xylene or ethylbenzene and so on; Dimethyl formamide.
(operation (c))
Operation (c) is that the amine that the general formula (7) of 1 mole represents is reacted with the compound that the general formula (6) of 2 moles represents, prepares the operation of the triarylamine derivative of general formula (1) expression.Operation (c) represents with following reaction equation.And, the Ar in general formula (7) 1the Ar of compound representing with general formula (1) 1identical.
[Chemical formula 1 2]
Figure BDA0000424430350000151
In the reaction of operation (c), the Compound Phase representing with general formula (7), for the consumption of the compound representing with general formula (6), as long as can carry out well the reaction of operation (c), is not particularly limited.The consumption of the compound representing with general formula (6), with respect to the compound representing with general formula (7), is preferably 2 times～5 times moles.
Temperature of reaction in operation (c), as long as can carry out well the reaction of operation (c), is not particularly limited.Temperature of reaction in operation (c) is preferably 80 DEG C～140 DEG C.In addition, the reaction time of operation (c) is for example 2～10 hours.
The reaction of operation (c) is preferably carried out under the existence of palladium catalyst and alkali.In the reaction of carrying out under such condition, the hydrogen halides producing in reactant liquor is promptly neutralized, and therefore catalyst activity improves.Consequently, utilize palladium catalyst can reduce well the energy of activation of the reaction of operation (c).Therefore,, by using palladium catalyst and alkali, can obtain the triarylamine derivative representing with general formula (1) with good especially yield.
As the concrete example of palladium compound that can be preferably used as palladium catalyst, can enumerate: the tetravalence palladium compound of the sour sodium tetrahydrate of chlordene palladium (IV) or the sour potassium tetrahydrate of chlordene palladium (IV) and so on; The divalence palladium compound of palladium bichloride (II), palladium bromide (II), acid chloride (II), acetoacetate palladium (II), two (cyanobenzene) palladium chloride (II), two (triphenylphosphine) palladium chloride (II), dichloro four ammonia palladiums (II) or (ring octyl group-1,5-diene) palladium chloride (II) and so on; The palladium compound of three (dibenzalacetone) two palladiums (0), three (dibenzalacetone) two palladium chloroform complex compounds (0) or tetrakis triphenylphosphine palladium (0) and so on.Palladium catalyst can combine two or more use.
The consumption of palladium catalyst, as long as can carry out well the reaction of operation (c), is not particularly limited.The consumption of palladium catalyst, the amine of the general formula (7) with respect to 1 mole, is preferably 0.00025～20 mole, more preferably 0.0005～10 mole.
The alkali using in the reaction of operation (c), as long as can react well, is not particularly limited.In the reaction of operation (c), can use any one in inorganic base and organic base.As the concrete example of the alkali preferably using in the reaction of operation (c), can enumerate: the alkali metal alcoholates of sodium methoxide, caustic alcohol, potassium methoxide, potassium ethoxide, tert-butyl alcohol lithium, sodium tert-butoxide or potassium tert-butoxide and so on.In alkali metal alcoholates, be particularly preferably sodium tert-butoxide.In addition can also preferably use, the inorganic base of tripotassium phosphate or cesium fluoride and so on.
The consumption of the alkali in the reaction of operation (c), considers that the consumption of palladium catalyst decides.For example, the amine of the general formula (7) with respect to 1 mole, adds in the situation of palladium compound of 0.005 mole, and the consumption of the alkali in the reaction of operation (c) is preferably 0.995～5 mole, more preferably 1～5 mole.
The solvent using in operation (c), if be nonactive concerning the reaction of operation (c), is not particularly limited.As the concrete example of preferred solvent, can enumerate: the aromatic hydrocarbon of benzene,toluene,xylene or ethylbenzene and so on.
In addition, two Ar in general formula (1) 2while being two kinds of different groups, the triarylamine derivative representing with general formula (1) can become asymmetric triarylamine derivative.Asymmetric triarylamine derivative like this, can be divided into two stages by reacting of compound that the amine of the general formula (7) in operation (c) and general formula (6) are represented and prepare.Specifically, in the first stage, reacting of the compound representing with general formula (6) by the amine of general formula (7), prepares Diaromatic amine derivatives.Then in subordinate phase, the Diaromatic amine derivatives obtaining in the first stage is reacted with the compound that the general formula (6) that is different from the first stage represents, thus, can prepare asymmetric triarylamine derivative.
Charge transport layer, not hindering in the scope of object of the present invention, beyond the triarylamine derivative representing divided by general formula (1), can also contain the various hole transporting materials and the electron transport materials that in Electrophtography photosensor, are used as charge transport material all the time.
As the hole transporting material that can use together with the triarylamine derivative of general formula (1) expression, can enumerate following material: benzidine derivative, 2,5-bis-(4-methylamino phenyl)-1,3, the furodiazole compound of 4-oxadiazoles and so on; The styrene compound that 9-(4-lignocaine styryl) fears and so on; The carbazole compound of Polyvinyl carbazole and so on; Organopolysilane compound; The pyrazoline compounds of 1-phenyl-3-(to dimethylaminophenyl) pyrazoline and so on; Hydrazone compounds; Triphenylamine compound outside the compound that general formula (1) represents; Benzazole compounds; Oxazole compounds; Isoxazole class compound; Thiazole compound; Thiadiazole compound; Glyoxaline compound; Pyrazole compound; Nitrogenous ring type compound or the condensation polycyclic compound of triazole class compounds and so on.These hole transporting materials, may be used singly or in combination of two or more to use.
In hole transporting material, contain can with general formula (1) represent triarylamine derivative together with contain, general formula (1) represent triarylamine derivative beyond compound time, more than the quality ratio of the gross mass with respect to hole transporting material of the triarylamine derivative representing with general formula (1) is preferably 80 quality %, more preferably more than 90 quality %, be particularly preferably 100 quality %.
For the electron transport materials that can use together with the triarylamine derivative of general formula (1) expression, not hindering in the scope of the object of the invention, be not particularly limited, can from the electron transport materials using the photographic layer of Electrophtography photosensor, suitably select.As the concrete example of the preferred electron transport materials that use together with the triarylamine derivative that can represent with general formula (1), can enumerate: naphthoquinone derivatives, diphenoquinone, fear quinone derivative, azo quinone derivative (Azo Quinone), nitro and fear quinone derivative or dinitro and fear the quinone derivative of quinone derivative and so on.Or, as the concrete example of the preferred electron transport materials that can use together with the triarylamine derivative of general formula (1) expression, can also enumerate: malononitrile derivant, thiapyran derivant, trinitro-thioxanthone derivates, 3,4,5,7-tetranitro-9-Fluorenone derivant, dinitro are feared derivant, dinitro acridine derivatives, tetracyanoethylene, 2,4,8-trinitro-thioxanthones, dinitro benzene, dinitro are feared, dinitro acridine, succinic anhydride, maleic anhydride or dibromomaleic acid acid anhydride.Among them, more preferably quinone derivative.
(charge generating material)
Charge generating material, not hindering in the scope of the object of the invention, is not particularly limited, and can from the charge generating material using the photographic layer of Electrophtography photosensor, suitably select.As charge generating material, can enumerate: the X-type metal-free phthalocyanine (x-H that following general formula (I) represents 2pc), α type or Y-shaped oxygen titanium phthalocyanines (Y-TiOPc) that following general formula (II) represents, perylene pigment, disazo pigment, dithione pyrrolopyrrole (dithioketo pyrrolo pyrrole) pigment, without metal naphthalene phthalocyanine pigment, metal naphthalene phthalocyanine pigment, side's acid color, trisazo pigment, indigo pigment, azulene pigment (azulenium pigment), phthalocyanine pigments, inorganic light conductive material (for example: selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide or amorphous silicon) powder, pyralium salt, fear embedding and fear quinones pigment, triphenylmethane pigment, intellectual circle's class pigment, toluene amine pigment, pyrazolines pigment or quinacridine ketone pigment.In these charge generating materials, preferably use the titanyl phthalocyanine of X-type metal-free phthalocyanine and α type or Y type etc.
[Chemical formula 1 3]
[Chemical formula 1 4]
Figure BDA0000424430350000182
In order to improve light sensitivity, preferably following titanyl phthalocyanine is as charge generating material.
In (A) CuK α characteristic X-ray diffraction spectrum, in Bragg angle 2 θ+0.2 °=27.2 ° located peak signal peak, in the calorimetric analysis of (B) differential scanning, except the signal peak producing due to the gasification of planar water, in the scope of 50～270 DEG C, there is the titanyl phthalocyanine of a signal peak.
Except the feature of (A), and, in the calorimetric analysis of (C) differential scanning, except the signal peak producing due to the gasification of planar water, in the scope of 50～400 DEG C, there is no the titanyl phthalocyanine of signal peak.
Except the feature of (A), and, in the calorimetric analysis of (D) differential scanning, except the signal peak producing due to the gasification of planar water, in the scope of 50～270 DEG C, there is no signal peak, in the scope of 270～400 DEG C, have the titanyl phthalocyanine of a signal peak.
In addition, in desired region, have the charge generating material of absorbing wavelength can be separately with or combine two or more use.Further, in above-mentioned charge generating material, particularly, on the image processing system of digit optical system, preferably the wavelength region may of use more than 700nm has the Electrophtography photosensor of light sensitivity.As the image processing system of digit optical system, can enumerate the laser beam printer or the facsimile recorder that use the light sources such as semiconductor laser.And, as charge generating material, preferably use the phthalocyanine pigment of for example metal-free phthalocyanine or titanyl phthalocyanine and so on.In addition, the crystal formation of above-mentioned phthalocyanine pigment is not particularly limited, can uses the phthalocyanine pigment of various crystal formations.In addition,, for the image processing system of simulated optical system that uses electrostatic duplicating machine of the white light sources such as such as halide lamp and so on, preferably use the Electrophtography photosensor in visibility region with light sensitivity.For this reason, as the Electrophtography photosensor of such image processing system, preferably use perylene pigment or disazo pigment.
(matrix resin)
When the solution that coating contains charge generating material on conductive base forms charge generation layer, can use matrix resin together with charge generating material.In the present embodiment, as the matrix resin for charge generation layer, can use the resin same with the binding resin using at charge transport layer, but, because cascade type photoreceptor is coated with charge generation layer conventionally successively, charge transport layer forms photographic layer, be therefore chosen in the matrix resin in the coating solvent that charge generation layer in the coating of charge transport layer is not dissolved into charge transport layer.
(method for making of photographic layer)
Photographic layer in cascade type photoreceptor is by conductive base or be formed on and stack gradually charge generation layer on the bottom on conductive base and charge transport layer forms.
The thickness of the charge generation layer in cascade type photoreceptor is preferably 0.1 μ m～5 μ m, more preferably 0.1 μ m～3 μ m.In addition, the thickness of charge transport layer is preferably 2 μ m～100 μ m, more preferably 5 μ m～50 μ m.
The content of the charge generating material in charge generation layer, not hindering in the scope of the object of the invention, is not particularly limited.While forming charge generation layer by coating coating fluid, the content of charge generating material, with respect to the matrix resin of 100 mass parts, is preferably 10～500 mass parts, more preferably 30～300 mass parts.
The content of the charge transport material in charge transport layer, with respect to the binding resin of 100 mass parts, is below 55 mass parts, is preferably 5～55 mass parts, more preferably 10～55 mass parts.In addition, the content of charge transport material is the total amount of the content of the hole transporting material in charge transport layer and the content of electron transport materials.By the content of charge transport material is contained below 55 mass parts with respect to the binding resin of 100 mass parts, the cascade type photoreceptor of the excellent in wear resistance that is easy to get.
In charge transport layer, contain charge transport material.In charge transport material, contain the triarylamine derivative representing using general formula (1) as hole transporting material.The content of the triarylamine derivative representing with general formula (1) in charge transport layer, with respect to the binding resin of 100 mass parts, is preferably 10～55 mass parts, more preferably 20～55 mass parts.Contain 10～55 mass parts by the content that makes the triarylamine derivative representing with general formula (1) with respect to the binding resin of 100 mass parts, be difficult to occur the crystallization of charge transport material, thereby easily form the high cascade type photoreceptor of permanance of electrical characteristics excellence.
As the formation method of charge generation layer, can enumerate the vacuum evaporation of charge generating material or the method for coating coating fluid.As the formation method of charge generation layer, be preferably coated with the method for coating fluid.Coating fluid at least contains charge generating material, matrix resin and solvent.If use the method, without expensive evaporation coating device, and masking processing ease.In addition,, as the formation method of charge transport layer, can enumerate the method that coating at least contains the coating fluid of charge transport material, binding resin and solvent.
As the solvent for preparing the coating fluid forming as photographic layer, the various organic solvents that can use the coating fluid forming as photographic layer to use.Specifically, can enumerate: the alcohols of methyl alcohol, ethanol, isopropyl alcohol or butanols and so on; The aliphatic hydrocarbon of normal hexane, octane or cyclohexane and so on; The aromatic hydrocarbon of benzene, toluene or dimethylbenzene and so on; The halogenated hydrocarbon of methylene chloride, ethylene dichloride, chloroform, phenixin or chlorobenzene and so on; The ethers of dimethyl ether, diethyl ether, tetrahydrofuran, dioxan, dioxolanes, glycol dimethyl ether or diethylene glycol dimethyl ether and so on; The ketone of acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone and so on; The ester class of ethyl acetate or methyl acetate and so on; N, the non-proton property polar organic solvent of N-dimethylformaldehyde, DMF or dimethyl sulfoxide (DMSO) and so on.The solvent that the coating fluid forming as photographic layer uses, can use separately one, or and with two or more.
In the solvent that the coating fluid forming as photographic layer at these uses, preferably use and contain more than one the solvent of solvent that selects group that free toluene, dioxolanes and o-xylene form.Toluene, dioxolanes and o-xylene are preferably respectively with together with the tetrahydrofuran of the good solvent as polycarbonate (binding resin) and use.As the coating fluid forming as photographic layer, with containing while selecting group's that free toluene, dioxolanes and o-xylene form more than one the solvent of solvent to form photographic layer, can suppress the blushing on photographic layer surface, thus the photoreceptor of the light sensitivity excellence that is easy to get.This is due to the group's who selects free toluene, dioxolanes and o-xylene to form solvent, can delay the volatilization of the solvent of coating fluid, thereby prevent that solvent from volatilizing rapidly from the coated film on conductive base surface.
In the coating fluid as charge generation layer or charge transport layer, not bringing electrofax characteristic in dysgenic scope, can mix existing known various adjuvants.As the preferred adjuvant being mixed in coating fluid, for example, can enumerate: the anti-deterioration agent of antioxidant, radical scavenger, singlet quencher (singlet quencher), ultraviolet light absorber and so on; Softening agent, plastifier, surface modifier, extender, thickening agent, dispersion stabilizer, wax, acceptor or donor.In addition,, in order to improve the dispersiveness of charge transport material or charge generating material or the flatness on photographic layer surface, also can use for example surfactant or levelling agent to be used as adjuvant.
Be not particularly limited as charge generation layer or as the coating process of the coating fluid of charge transport layer, can enumerate and for example use rotary coating machine, apply the method for smearing machine, flush coater, metering bar coater, dip coaterd or scraper.
Be coated with coating fluid by said method, can form the film of coating fluid.Then, by using high-temperature drier or pressure Reduction Dryer dry coating, remove the solvent in film, thereby form charge generation layer and charge transport layer.Baking temperature is preferably 40～150 DEG C.By the temperature range inner drying film at 40～150 DEG C, can remove rapidly desolventizing, more effectively form charge generation layer and the charge transport layer of even thickness.When baking temperature is too high, likely there is thermal decomposition in the composition containing in photographic layer.
In addition, the bottom on conductive base can form as follows.,, by the inorganic particles such as resin, zinc paste or titanium dioxide, solvent preparation coating fluid, be dried after this coating fluid is coated on conductive base, thereby form bottom.
The laminated electronic photosensitive body that embodiment one described above relates to, due to mar proof and light sensitivity excellent, is adapted at using on various image processing systems.
[embodiment two]
The image processing system that embodiments of the present invention two relate to, thus possess image carrier, make the electro-mechanical part of the surface charging of image carrier, exposed in the surface of charged the image carrier development section that forms the exposure portion of electrostatic latent image on the surface of image carrier, develops electrostatic latent image as toner image, the transfer section that toner image is transferred to transfer printing body from image carrier.In embodiment two, the laminated electronic photosensitive body that image carrier uses embodiment one to relate to.
In the image processing system relating at embodiment two, the parts beyond the image carriers such as electro-mechanical part, exposure portion, development section and transfer section, suitably select in the parts that can use from common image processing system.
The image processing system relating to as embodiment two, preferably monochrome image forms the color image forming device of device or series connection (tandem) mode.More specifically, can enumerate the color image forming device of the series system of routine use multiple color correctives described as follows.At this, the color image forming device of series system is described.
In addition, possess the color image forming device of the series system of the laminated electronic photosensitive body that embodiment one relates to, possess multiple image carriers and multiple development section.Multiple image carriers, in order to form the toner image being formed by the toner of different colours respectively on each surface, are arranged side by side in prescribed direction.Multiple development sections have the developer roll with the configuration of image carrier subtend.Developer roll carries and carries toner in its surface, and the toner of carrying is supplied with respectively to each image carrier surface.In embodiment two, as each image carrier, the laminated electronic photosensitive body that uses respectively embodiment one to relate to.
Fig. 2 is the schematic diagram that represents the structure of the image processing system that possesses laminated electronic photosensitive body.Here, as image processing system, describe as an example of color printer 1 example.
As shown in Figure 2, color copy machine 1 has the equipment body 1a of box.In this equipment body 1a, be provided with sheet feed section 2, image forming part 3 and photographic fixing portion 4.Sheet feed section 2 is supplied with paper P.Image forming part 3 is carried the paper P being supplied with by sheet feed section 2 and the toner image based on view data etc. is transferred on paper P.Photographic fixing portion 4 is to being transferred to the toner image of the not photographic fixing on paper P by image forming part 3, impose photographic fixing to the photographic fixing processing on paper P.In addition, be provided with paper delivery portion 5 at the upper surface of equipment body 1a.The paper P that imposes photographic fixing processing in photographic fixing portion 4 is discharged to paper delivery portion 5.
Sheet feed section 2 possesses paper feeding cassette 121, gets paper bowl 122, paper feed roller 123,124 and 125 and alignment rolls 126.Paper feeding cassette 121 is arranged to from equipment body 1a dismounting, to store the paper P of various sizes.Get paper bowl 122 and be arranged on the position, upper left side of the paper feeding cassette 121 shown in Fig. 2, by be stored in paper P in paper feeding cassette 121 a sheet by a sheet take out.Paper feed roller 123,124 and 125 will pass out to paper transport passage for transporting by getting the paper P that paper bowl 122 takes out.Alignment rolls 126 makes to pass out to after temporary transient wait of paper P of paper transport passage for transporting by paper feed roller 123,124 and 125, in the timing of regulation, paper P is supplied to image forming part 3.
In addition, sheet feed section 2 further possess the equipment body 1a being arranged on shown in Fig. 2 left surface not shown manual pallet and get paper bowl 127.This is got paper bowl 127 and takes out the paper P being placed on manual pallet.Pass out to paper transport passage for transporting by getting the paper P that paper bowl 127 takes out by paper feed roller 123 and 125, be supplied to image forming part 3 by alignment rolls 126 in the timing of regulation.
Image forming part 3 possesses image formation unit 7, intermediate transfer belt 31 and secondary transfer roller 32.By image formation unit 7, the surface (with the surface of contact of secondary transfer roller 32) by the toner image primary transfer of the view data based on from electric transmission such as computing machines to intermediate transfer belt 31.Secondary transfer roller 32, by the toner image secondary transfer printing on intermediate transfer belt 31 to the paper P sending into from paper feeding cassette 121.
Image formation unit 7 possesses the unit 7K, yellow with unit 7Y, cyan unit 7C and magenta unit 7M for black arranging successively towards downstream from upstream side (being right side in Fig. 2).At each unit 7K, 7Y, 7C and 7M middle position separately, can dispose rotationally the laminated electronic photosensitive body 37 (following, to be called photoreceptor 37) as image carrier along arrow (clockwise) direction.And, around each photoreceptor 37, dispose respectively successively electro-mechanical part 39, exposure portion 38, development section 71, not shown cleaning section and not shown except electric portion as required from rotation direction upstream side.In addition, as photoreceptor 37, the laminated electronic photosensitive body that uses embodiment one to relate to.
Electro-mechanical part 39 makes the side face of the photoreceptor 37 rotating along the direction of arrow charged equably.Electro-mechanical part 39, as long as can make the side face of photoreceptor 37 charged equably, is not particularly limited, and can be cordless or the way of contact.As the concrete example of electro-mechanical part 39, can enumerate corona charging device, charged roller or band brush.As electro-mechanical part 39, be preferably charged roller or the Charging system with ways of contact such as brushes, more preferably charged roller.By using the electro-mechanical part 39 of the way of contact, can suppress the ozone that produced by electro-mechanical part 39 or the discharge of oxides of nitrogen isoreactivity gas.Thus, can prevent photographic layer deteriorated of the photoreceptor causing because of active gases, further can consider that working environment etc. designs.
When electro-mechanical part 39 possesses the charged roller of the way of contact, charged roller makes the side face (surface) of photoreceptor 37 charged under the state contacting with photoreceptor 37.As this charged roller, for example can enumerate under the state contacting with photoreceptor 37, follow the rotation of photoreceptor 37 and the charged roller of rotating.In addition,, as charged roller, for example can enumerate the roller that at least surface element is made up of resin.More specifically, can enumerate and for example possess the cored bar that supported by axle rotationally, be formed on the resin bed on cored bar and cored bar executed to the roller of alive voltage application portion.Possess the electro-mechanical part of this charged roller, by voltage application portion, cored bar being applied to voltage, can make the surface charging via the photoreceptor 37 of resin bed contact.
The voltage that is imposed on charged roller by voltage application portion is not particularly limited.But, compared with charged roller being applied to the structure of alternating voltage or overlapping voltage (the overlapping voltage that has alternating voltage in DC voltage), preferably charged roller is only applied the structure of DC voltage.Charged roller is only applied to the structure of DC voltage, because the wear extent of photographic layer easily reduces, therefore easily form suitable image.The DC voltage that imposes on charged roller, is preferably 100V～2000V, and more preferably 1200V～1800V, is particularly preferably 1400V～1600V.
In addition, form the resin of the resin bed of charged roller, as long as can make the side face of photoreceptor 37 charged well, be not particularly limited.As the concrete example of the resin using in resin bed, can enumerate silicones, urethane resin or silicon modified resin etc.In addition, in resin bed, also can contain inorganic filling material.
Exposure portion 38 is so-called laser scan unit.The view data of personal computer (PC) input of exposure portion 38 based on from as upstream device, all surface irradiation lasers of the photoreceptor 37 of uniform charged to passing through electro-mechanical part 39, thus, on photoreceptor 37, form the electrostatic latent image based on view data.Development section 71 is supplied with toner by the side face of the photoreceptor 37 to being formed with electrostatic latent image, forms the toner image based on view data, and then, this toner image is arrived intermediate transfer belt 31 by primary transfer.Cleaning section, after toner image finishes to the primary transfer of intermediate transfer belt 31, cleans the toner of the side face that remains in photoreceptor 37.Except electric portion is after primary transfer finishes, the side face of photoreceptor 37 is removed to electricity.Clean the side face of the photoreceptor 37 of processing by cleaning section with except electric portion, in order to carry out new band electric treatment, carry out new band electric treatment towards electro-mechanical part.In addition, cleaning section and except electric portion not shown.
The banded rotor that intermediate transfer belt 31 is ring-type.It is upper that intermediate transfer belt 31 is erected at multiple rollers (driven roller 33, driven voller 34, backing roll 35 and primary transfer roller 36), the surface (surface of contact) of intermediate transfer belt 31 and the side face butt of each photoreceptor 37.In addition, intermediate transfer belt 31 is by being forced into photoreceptor 37 with the primary transfer roller 36 of each photoreceptor 37 subtend configurations.Be forced under the state of photoreceptor 37 at intermediate transfer belt 31, rotating along with the rotation of multiple rollers.Driven roller 33 for example, carries out rotating drive by drive source (, stepping motor), and intermediate transfer belt 31 is rotated.Driven voller 34, backing roll 35 and primary transfer roller 36 are rotated freely and arrange, the driven rotation along with the rotation of the intermediate transfer belt 31 being driven by driven roller 33.The active rotation of these roller 34,35 and 36 response driven rollers 33 is carried out driven rotation via intermediate transfer belt 31, intermediate transfer belt 31 is supported simultaneously.
Intermediate transfer belt 31, between each photoreceptor 37 and primary transfer roller 36, drives along arrow (counterclockwise) direction rotation by driven roller 33.In addition, primary transfer bias voltage (with the charged opposite polarity polarity of toner) is imposed on intermediate transfer belt 31 by primary transfer roller 36, thus, be formed on toner image on each photoreceptor 37 with overlapping coating state transfer printing successively (primary transfer) to intermediate transfer belt 31.Then, as required, by removing electricity by the electric portion (not shown) that removes that electricity is removed in the surface of each photoreceptor 37 except electric light.Then, each photoreceptor 37 further rotates, and enters into next processing.
Secondary transfer roller 32 will be applied to paper P with the secondary transfer printing bias voltage of toner image opposite polarity.By such processing, primary transfer is transferred to paper P to the toner image on intermediate transfer belt 31 between secondary transfer roller 32 and backing roll 35.Thus, colored transferred image (the not toner image of photographic fixing) is transferred to paper P.
Photographic fixing portion 4 imposes photographic fixing processing to the transferred image that is transferred to paper P at image forming part 3.Photographic fixing portion 4 possess the warm-up mill 41 that heats by heating power body, with these warm-up mill 41 subtends configuration and compacted backer rolls 42 that abut to warm-up mill 41 side faces of side face.
Then, be transferred to the transferred image of paper P at image forming part 3 by secondary transfer roller 32, the heat fixer processing while passing through between warm-up mill 41 and backer roll 42 by this paper P, is arrived paper P by photographic fixing.Then, the paper P that has imposed photographic fixing processing is discharged to paper delivery portion 5.In addition,, in the color printer 1 of present embodiment, the suitable position between photographic fixing portion 4 and paper delivery portion 5 is equipped with carrying roller 6.
Paper delivery portion 5 forms by the top depression of the equipment body 1a of color printer 1.Be formed with the paper delivery pallet 51 of the paper P that receives discharge in the bottom of the recess of this depression.
Color printer 1 forms operation by above-mentioned image, on paper P, forms image.And the image processing system of above-mentioned series system, possesses Electrophtography photosensor that the embodiment one of mar proof and light sensitivity excellent relates to as image carrier.Therefore, such image processing system, can form high-quality image for a long time.
[embodiment]
In embodiment and comparative example, as hole transporting material (HTM), use following HTM-1～HTM-13.In addition,, as electron transport materials (ETM), use following ETM-1.In addition,, as binding resin, use the Resin-1～Resin-6 being formed by repetitive representing with following formula.
< hole transporting material >
[Chemical formula 1 5]
Figure BDA0000424430350000271
< electron transport materials >
[Chemical formula 1 6]
Figure BDA0000424430350000281
< binding resin >
[Chemical formula 1 7]
Figure BDA0000424430350000291
(synthesis example 1)
(preparation of HTM-1)
< operation (a) >
In the eggplant type flask that is 200mL at capacity, inject the compound (1-a) of 20.0g (0.13 mole) and the triethyl phosphite of 25.0g (0.15 mole), at 180 DEG C, react 5 hours.After cooling, under reduced pressure add thermal distillation and remove remaining triethyl phosphite, obtain the compound (1-b) of the white liquid of 29.8g with 90% yield.
[Chemical formula 1 8]
Figure BDA0000424430350000301
< operation (b) >
Two mouthfuls of flasks that are 500mL by the capacity by argon replaces are cooled to 0 DEG C.Then, temperature is remained on to 0 DEG C, and the methanol solution of sodium methylate that is 28 quality % by the concentration of the dry tetrahydrofuran of the compound (1-b) of 20.0g (0.08 mole), 100mL and 16.7g (0.09 mole) injects two mouthfuls of flasks.At 0 DEG C, in flask, stir 30 minutes.Then, add the compound (1-c) of 13.1g (0.08 mole) and the dry tetrahydrofuran of 100mL, at room temperature stir the reaction of carrying out 12 hours.After reaction finishes, reactant liquor is injected to the ion exchange water of 300mL, at room temperature, extract compound (1-d) with the toluene of 100mL.Organic layer (toluene layer) after extracting for 5 times with the ion exchange water cleaning of 100mL.With the organic layer after anhydrous sodium sulfate drying washing, filter after sodium sulphate, make the dry sclerosis of organic layer.Use the mixed solvent being formed by the toluene of 20mL and the methyl alcohol of 100mL to make residue recrystallization, obtain the compound (1-d) of the white crystals of 16.8g with 80% yield.
[Chemical formula 1 9]
< operation (c) >
In two mouthfuls of flasks that are 300mL at the capacity by argon replaces, the o-xylene of 100mL after compound (1-e) and the distillation of three (dibenzalacetone) two palladiums (0) of the compound (1-d) of injection 12.5g (0.0469 mole), 2-(dicyclohexylphosphontetrafluoroborate) biphenyl of 0.082g (0.002 mole), 0.108g (0.0001 mole), the sodium tert-butoxide of 4.87g (0.0507 mole), 3.20g (0.0234 mole) stirs the reaction of carrying out 5 hours at 120 DEG C.By after the reactant liquor cool to room temperature obtaining, with atlapulgite processing reaction liquid.From reactant liquor after treatment, distillation, except after desolventizing, with column chromatography (eluent: methenyl choloride/hexane) refining residue, obtains the golden yellow crystallization of the HTM-1 of 12.0g with 86% yield.By the triarylamine derivative obtaining 1the collection of illustrative plates of H-NMR (300MHz) is illustrated in (solvent: CDCl in Fig. 3 3, standard substance: TMS).
[Chemical formula 2 0]
(synthesis example 2)
(preparation of HTM-2)
Except compound (1-e) is become 4-aminoanisole, similarly obtain the HTM-2 of 11.3g with synthesis example 1.Yield in operation (c) is 83%.
(synthesis example 3)
(preparation of HTM-3)
Except compound (1-e) is become n-butyl aniline, similarly obtain the HTM-3 of 12.2g with synthesis example 1.Yield in operation (c) is 86%.By the triarylamine derivative obtaining 1the collection of illustrative plates of H-NMR (300MHz) is illustrated in (solvent: CDCl in Fig. 4 3, standard substance: TMS).
(synthesis example 4)
(preparation of HTM-4)
Except compound (1-e) is become 5-amino tetrahydronaphthalenand, similarly obtain the HTM-4 of 11.8g with synthesis example 1.Yield in operation (c) is 83%.By the triarylamine derivative obtaining 1the collection of illustrative plates of H-NMR (300MHz) is illustrated in (solvent: CDCl in Fig. 5 3, standard substance: TMS).
(synthesis example 5)
(preparation of HTM-5)
Except compound (1-e) is become cumidine, similarly obtain the HTM-5 of 12.1g with synthesis example 1.Yield in operation (c) is 87%.
(synthesis example 6)
(preparation of HTM-6)
Except compound (1-e) is become 2-aminobphenyl, similarly obtain the HTM-6 of 12.1g with synthesis example 1.Yield in operation (c) is 82%.
(synthesis example 7)
(preparation of HTM-7)
Except compound (1-e) is become beyond 3,4-methylene dioxo group aniline, similarly obtain the HTM-7 of 11.1g with synthesis example 1.Yield in operation (c) is 80%.
(synthesis example 8)
(preparation of HTM-8)
Except compound (1-e) being become 2-ethyl-6-methylaniline, similarly obtain the HTM-8 of 11.5g with synthesis example 1.Yield in operation (c) is 83%.By the triarylamine derivative obtaining 1the collection of illustrative plates of H-NMR (300MHz) is illustrated in (solvent: CDCl in Fig. 6 3, standard substance: TMS).
(synthesis example 9)
(preparation of HTM-9)
Except compound (1-e) being become to the chloro-1-propylene of 1-(4-aminomethyl phenyl)-3-, similarly obtain the HTM-9 of 11.5g with synthesis example 8.Yield in operation (c) is 79%.
(synthesis example 10)
(preparation of HTM-10)
Except compound (1-e) is become ortho-aminotoluene, similarly obtain the HTM-10 of 11.7g with synthesis example 1.Yield in operation (c) is 88%.By the triarylamine derivative obtaining 1the collection of illustrative plates of H-NMR (300MHz) is illustrated in (solvent: CDCl in Fig. 7 3, standard substance: TMS).
(synthesis example 11)
(preparation of HTM-11)
Except compound (1-e) is become para-aminotoluene, similarly obtain the HTM-11 of 11.3g with synthesis example 1.Yield in operation (c) is 85%.
[embodiment 1～25 and comparative example 1～4]
In embodiment 1～25 and comparative example 1～4, according to following method, thereby on conductive base, form bottom successively and photographic layer has formed photoreceptor.
(formation of bottom)
By carrying out after surface treatment with aluminium oxide and silicon dioxide of 2 mass parts, (Chemical Co., Ltd of kingdom manufactures to disperse to utilize hydrogenated methyl polysiloxane to carry out surface-treated titanium dioxide by wet type, SMT-A (preproduction), number equal primary particle sizes be 10nm) and 1 mass parts 6, 12, 66, (Dongli Ltd. manufactures 610 quarternary copolymerized polyamides, Amilan CM8000), the methyl alcohol that use contains 10 mass parts, the solvent of the toluene of the butanols of 1 mass parts and 1 mass parts, utilize ball mill to carry out the dispersion treatment of 5 hours, make the coating fluid as bottom.
After the filtrator as the coating fluid of bottom opening 5 μ m obtaining is filtered, the coating fluid as bottom is coated on the conductive base being formed by the drum (diameter 30mm, overall length 246mm) of aluminum with dip coating.Be coated with after this coating fluid, at 130 DEG C, process 30 minutes, on conductive base, form the bottom of thickness 2 μ m.
(formation of photographic layer)
(formation of charge generation layer)
By the polyvinyl acetal of the Y-shaped oxygen titanium phthalocyanines of 1.5 mass parts (Y-TiOPc, charge generating material), 1 mass parts (matrix resin, Sekisui Chemical Co., Ltd's manufacture, S-LEC BX-5), mix with the dispersion solvent of the tetrahydrofuran of the propylene glycol monomethyl ether that contains 40 mass parts and 40 mass parts, carry out 2 hours dispersion treatment with ball mill, make the coating fluid as charge generation layer.After the filtrator as the coating fluid of charge generation layer opening 3 μ m obtaining is filtered, the coating fluid as charge generation layer is coated on bottom with dip coating.Be coated with after this coating fluid, at 50 DEG C, process 5 minutes, form the charge generation layer of thickness 0.3 μ m.
(formation of charge transport layer)
By the binding resin of the kind described in table 1 and the table 2 of the electron transport materials (ETM-1) of the adjuvant of the hole transporting material of the kind described in table 1 and table 2 and consumption, 0.5 mass parts (IRGANOX1010, Ciba Amada Co., Ltd. manufacture), 1 mass parts, 100 mass parts, be dissolved in the solvent of kind described in table 1 and table 2 and consumption, make the coating fluid as charge transport layer.Use the method same with being coated with charge generation layer to be coated on charge generation layer the coating fluid as charge transport layer obtaining.Be coated with after this coating fluid, at 120 DEG C, process 40 minutes, form the charge transport layer of thickness 20 μ m.
" evaluation of the electrical characteristics to photoreceptor and the cosmetic variation of photographic layer "
To the laminated electronic photosensitive body in embodiment and comparative example, evaluate by the following method electrical characteristics, the cosmetic variation of photosensitive surface and the wear extent of photographic layer of photoreceptor.
< electrical characteristics measuring method >
Utilize drum sensitivity test machine (manufacture of GENTEC company), charged to the state of-600V (V0) at the surface potential that makes laminated electronic photosensitive body, by monochromatic light (half amplitude 20nm, the light intensity 1.5 μ j/m of the wavelength 780nm that utilizes bandpass filter to take out from the white light of halide lamp 2) irradiate 1.5 seconds at photosensitive surface.To from exposure starts, be V through photosensitive surface current potential moment of 0.05 second, when blank sheet of paper image printing 0, surface potential when solid 100% image printing is V l, measure the light sensitivity of photoreceptor.The electrical characteristics of the photoreceptor of embodiment 1～25 and comparative example 1～4 are recorded in table 1 or table 2.
< cosmetic variation evaluation method >
The state of visualization photosensitive surface and whether have foreign matter.Judge with optical microscope whether the foreign matter being visually observed is crystallinity.In the foreign matter of observing, find that crystallization is when more than 1, being judged as this foreign matter is crystallinity foreign matter, measures the diameter of crystallinity foreign matter with diameter gauge.In addition, judge cosmetic variation according to following standard.In addition, not the cosmetic variation of expecting although turn white with slight crystallization, do not have to allow in great dysgenic scope in the light sensitivity characteristic to photoreceptor and mar proof.
Good (zero): do not find crystallinity foreign matter and albinism.
Turn white: observing photosensitive surface has blushing.
Slight crystallization: the diameter of crystallinity foreign matter is more than 0.5mm and not enough 2mm.
Severe crystallization: the diameter of crystallinity foreign matter is more than 2mm.
(being used as the formation of the charge transport layer of abrasion amount measuring)
In embodiment 1～9, embodiment 11, embodiment 14, embodiment 16～25 and comparative example 1～4, make in accordance with the following methods the charge transport layer as abrasion amount measuring.In addition, for embodiment 10 and embodiment 12, because the hole transporting material (HTM), electron transport materials (ETM) and the binding resin that form for photographic layer are all identical with embodiment 11, also carried out abrasion amount measuring.In addition,, for embodiment 13 and embodiment 15, because the hole transporting material (HTM), electron transport materials (ETM) and the binding resin that form for photographic layer are all identical with embodiment 14, also carried out abrasion amount measuring.
By the coating fluid as charge transport layer using in embodiment 1～9, embodiment 11, embodiment 14, embodiment 16～25 and comparative example 1～4, be coated on dip coating on the PP sheet material (thickness 0.3mm) on the aluminum tube that is wound on diameter 78mm.Be coated with after this coating fluid, at 120 DEG C, process 40 minutes, become the charge transport layer of thickness 30 μ m at PP sheet shaped.Then, peel off charge transport layer from PP sheet material, obtain the charge transport layer as abrasion amount measuring.
" the abrasion amount measuring method of charge transport layer "
By being arranged on as the charge transport layer of abrasion amount measuring, sample installation paster (manufacture of Taber company, " S-36 ") is upper, is made into the sheet material as abrasion amount measuring.Utilize Taber abrasion tester (manufacture of Toyo Co., Ltd. essence machine, " rotary abrasion tester (ROTARY ABRASION TESTER) ") and wear ring (manufacture of Taber company, " C-10 "), at loading 500g, rotational speed 60rpm, be rotated the Taber wear test of 1000 times.Measure the variable quantity of the sheet material as abrasion amount measuring before and after wear test as wear extent.The measurement result of wear extent is recorded in table 1 and table 2.
[table 1]
Figure BDA0000424430350000361
[table 2]
Figure BDA0000424430350000362
Figure BDA0000424430350000371
In the Electrophtography photosensor relating at embodiment 1～25, HTM-1～HTM-11 that use contains the triarylamine derivative representing using general formula (1) is as the charge transport material of hole transporting material.In addition, the content of the charge transport material in charge transport layer is to contain below 55 mass parts with respect to the binding resin of 100 mass parts.Known according to embodiment 1～25, such Electrophtography photosensor, V lthe low electrical characteristics excellence of value, and wear extent is few.
In the Electrophtography photosensor relating at embodiment 1～19 and 21～25, in binding resin, contain the Resin-1～Resin-5 as polycarbonate resin representing using general formula (2).The Electrophtography photosensor known, such according to embodiment 1～19 and 21～25, mar proof is excellent especially.
In the Electrophtography photosensor relating at embodiment 1～11,13,14 and 16～25, charge transport layer uses as the coating fluid of charge transport layer and forms, and should be to use to contain that to be selected from more than one solvent of toluene, dioxolanes, o-xylene formulated as the coating fluid of charge transport layer.The Electrophtography photosensor known, such according to embodiment 1～11,13,14 and 16～25, can suppress the blushing on photographic layer surface.
In the Electrophtography photosensor relating at comparative example 1 and 2, charge transport layer is to use to contain the triarylamine derivative that do not comprise in general formula (1) and form as the charge transport material of hole transporting material.The Electrophtography photosensor known, such according to comparative example 1 and 2, can produce the crystallization of charge transport material, and the light sensitivity characteristic of photoreceptor obviously suffers damage.
In the Electrophtography photosensor relating at comparative example 3 and 4, exceed 55 mass parts with respect to the consumption of the charge transport material of the binding resin of 100 mass parts.The Electrophtography photosensor known, such according to comparative example 3 and 4, mar proof obviously suffers damage.

Claims (9)

1. a laminated electronic photosensitive body, it is characterized in that, on conductive base, be formed with the cascade type photographic layer that stacks gradually charge generation layer and charge transport layer on conductive base, described charge generation layer contains charge generating material, described charge transport layer contains charge transport material and binding resin
Described charge transport material contains the triarylamine derivative representing using following general formula (1) as hole transporting material,
The content of the described charge transport material in described charge transport layer is, with respect to the described binding resin of 100 mass parts, contains below 55 mass parts,
[Chemical formula 1]
Figure FDA0000424430340000011
In general formula (1), Ar 1for aryl or there is the heterocyclic radical of conjugated double bond, Ar 2for aryl, Ar 1and Ar 2can selected free carbon atom number more than one group in the group that forms of the alkyl that is 1～6, alkoxy that carbon number is 1～6 and phenoxy group replace.
2. laminated electronic photosensitive body according to claim 1, is characterized in that described Ar 1there is substituting group.
3. laminated electronic photosensitive body according to claim 2, is characterized in that described Ar 1adding up to more than 2 of the oxygen atomicity containing in the one or more substituting groups that have and carbon number.
4. according to the laminated electronic photosensitive body described in any one in claim 1～3, it is characterized in that, described binding resin contains the polycarbonate resin representing with following general formula (2),
[Chemical formula 2]
Figure FDA0000424430340000021
In general formula (2), p+q=1,0.35≤p < 0.7, Ar 4for being selected from the biradical of following general formula (2-1)～(2-4), R 1～R 4be hydrogen atom, alkyl or aryl independently respectively, R 3and R 4bonding forms ring alkylidene mutually.
[chemical formula 3]
5. according to the laminated electronic photosensitive body described in any one in claim 1～3, it is characterized in that, described charge transport layer is that coating forms as the coating fluid of charge transport layer on described charge generation layer, the described coating fluid as charge transport layer is containing in more than one the solvent of solvent that selects group that free toluene, dioxolanes and o-xylene form, be at least dissolved with described charge transport material and described binding resin.
6. according to the laminated electronic photosensitive body described in any one in claim 1～3, it is characterized in that, the content of the described charge transport material in described charge transport layer is, with respect to the described binding resin of 100 mass parts, to contain 5～55 mass parts.
7. according to the laminated electronic photosensitive body described in any one in claim 1～3, it is characterized in that, in the described triarylamine derivative representing with general formula (1), two Ar 2for identical each other group.
8. an image processing system, is characterized in that, possesses:
Image carrier;
Electro-mechanical part, this electro-mechanical part makes the surface charging of described image carrier;
Exposure portion, this exposure portion exposes to the surface of charged described image carrier, thereby forms electrostatic latent image on the surface of described image carrier;
Development section, this development section is toner image by described latent electrostatic image developing; And
Transfer section, this transfer section is transferred to transfer printing body by described toner image from described image carrier,
Described image carrier is the laminated electronic photosensitive body described in any one in claim 1～3.
9. a manufacture method for the laminated electronic photosensitive body described in any one in claim 1～3, is characterized in that, comprising:
On described conductive base, form the operation of described charge generation layer, described charge generation layer contains described charge generating material;
Thereby coating forms the operation of described charge transport layer as the coating fluid of charge transport layer on described charge generation layer, the described coating fluid as charge transport layer at least contains described charge transport material and described binding resin;
In the solvent that the described coating fluid as charge transport layer contains, contain more than one the solvent that selects group that free toluene, dioxolanes and o-xylene form.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384647A (en) * 2014-08-28 2016-03-09 京瓷办公信息***株式会社 Triphenylamine derivative, electrophotographic photosensitive member, and image forming apparatus
CN107098818A (en) * 2016-02-19 2017-08-29 郑建鸿 Aromatic compound and the Organic Light Emitting Diode comprising it
CN108121180A (en) * 2014-06-30 2018-06-05 京瓷办公信息***株式会社 Electrophtography photosensor
CN111108443A (en) * 2018-01-19 2020-05-05 富士电机株式会社 Electrophotographic photoreceptor, method for producing electrophotographic photoreceptor, and electrophotographic apparatus

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6443273B2 (en) * 2015-09-04 2018-12-26 京セラドキュメントソリューションズ株式会社 Multilayer electrophotographic photoreceptor and method for producing multilayer electrophotographic photoreceptor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101273305A (en) * 2005-09-28 2008-09-24 三菱化学株式会社 Electrophotographic photosensitive body, image-forming device using same and cartridge
CN102262363A (en) * 2010-05-28 2011-11-30 京瓷美达株式会社 Image forming device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4276959B2 (en) * 2004-01-22 2009-06-10 シャープ株式会社 Novel amine-bisdiene and -bistriene compounds, and electrophotographic photoreceptors and image forming apparatuses using the same
JP5417378B2 (en) * 2011-05-31 2014-02-12 京セラドキュメントソリューションズ株式会社 Triarylamine derivative, electrophotographic photosensitive member, and image forming apparatus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101273305A (en) * 2005-09-28 2008-09-24 三菱化学株式会社 Electrophotographic photosensitive body, image-forming device using same and cartridge
CN102262363A (en) * 2010-05-28 2011-11-30 京瓷美达株式会社 Image forming device

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* Cited by examiner, † Cited by third party
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CN108121180B (en) * 2014-06-30 2021-06-15 京瓷办公信息***株式会社 Electrophotographic photoreceptor
CN105384647A (en) * 2014-08-28 2016-03-09 京瓷办公信息***株式会社 Triphenylamine derivative, electrophotographic photosensitive member, and image forming apparatus
CN107098818A (en) * 2016-02-19 2017-08-29 郑建鸿 Aromatic compound and the Organic Light Emitting Diode comprising it
CN107098818B (en) * 2016-02-19 2020-05-12 郑建鸿 Aromatic compound and organic light emitting diode comprising same
CN111108443A (en) * 2018-01-19 2020-05-05 富士电机株式会社 Electrophotographic photoreceptor, method for producing electrophotographic photoreceptor, and electrophotographic apparatus
CN111108443B (en) * 2018-01-19 2024-01-02 富士电机株式会社 Electrophotographic photoreceptor, method for producing the same, and electrophotographic apparatus

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