CN100535787C - Developing member and electrophotographic image forming apparatus - Google Patents
Developing member and electrophotographic image forming apparatus Download PDFInfo
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- CN100535787C CN100535787C CNB2007101525149A CN200710152514A CN100535787C CN 100535787 C CN100535787 C CN 100535787C CN B2007101525149 A CNB2007101525149 A CN B2007101525149A CN 200710152514 A CN200710152514 A CN 200710152514A CN 100535787 C CN100535787 C CN 100535787C
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Abstract
A developing member is provided which is capable of forming a high-quality image by simultaneously solving the problem of fogging in a high temperature and high humidity environment and the problem of ghosts in a low temperature and low humidity environment. The developing member includes a mandrel and a resin layer formed on the periphery of the mandrel, and has an outermost surface layer containing a non-reactive silicone compound. The non-reactive silicone compound satisfies the following requirements: (A) a copolymer of silicone and polyoxyethylene; (B) a specific gravity (25 DEG C) d of 0.99 d 1.03; and (C) a solubility in water (25 DEG C) of less than 0.1% by mass.
Description
Technical field
The present invention relates to be used for the developing member such as the developer roll of electrophotographic image forming such as duplicating machine or laser printer, and relate to the electrophotographic image forming that uses this developing member.
Background technology
Traditionally, the pressure develoment method is one of developing method that uses such as the electronic photographing device of duplicating machine, printer and facsimile receiver.The pressure develoment method is used the developer of nonmagnetic toner composition, and this developer is sticked on the sub-image on the photosensitive drums, so that this sub-image is visual.
The pressure develoment method is widely used, because its advantage that has for example: do not need magnetic material; Can make this simplified equipment or miniaturization easily; And can utilize color toner to constitute developer easily.
On the electrophotographic image forming of working pressure developing method, utilize the photosensitive drums uniform charging of charging member to rotation, then, utilize laser that it is carried out irradiation, to form electrostatic latent image.Subsequently, developing apparatus is applied to developer on this electrostatic latent image, to obtain toner image, then, this toner image is transferred on the transfer materials (recording materials) from photosensitive drums.At last, by heating etc., the toner image on the photographic fixing transfer materials thereon.
Transfer printing behind this toner image, make the surface-discharge of photosensitive drums, to remove residual developer.Thereby enter the waiting status that is ready to new imaging.
Above-mentioned developing apparatus comprises: hold-up vessel is used for receiving photographic developer; Developing member is representative with the developer roll, arranges this developer roll, so that its opening part at the container of closing partly exposes; And developer supply roller, be used to provide developer roll lip-deep developer.
Can developing blade further be set to this developing apparatus, so that utilize developer supply roller on developing roller surface, evenly to form the laminagraphy agent.When developer roll rotates, the film developer can be transferred on the expose portion of developer roll.
The film developer is sticked on the electrostatic latent image on the photosensitive drums that relative developer roll expose portion is provided with,, thereby on this photosensitive drums, form toner image so that this electrostatic latent image is visual.
In many cases, for the developing roller surface of using in this developing apparatus, utilize urethane resin to improve the static characteristic of toner.Yet urethane resin has high water absorption character.Therefore, on this developing member, in some cases, under high temperature and high humility, the electrostatic charge quantity of toner reduces.In order to address the above problem, the Jap.P. spy opens No.H11-212354 (U.S. Patent No. 6,360,069) the electrostatic charge quantity that discloses the inhibition toner is under high temperature and high humility situation, specifically in 35 ℃ temperature and the following technology that reduces of the humidity of 85%RH (relative humidity).Promptly, proposed a kind of structure, in this structure, the key component of this superficial layer is polyvalent alcohol and isocyanate compound or the urethane resin that reacts and obtain with isocyanate compound and cahin extension agent, and wherein one of polyvalent alcohol and cahin extension agent or the two comprise the polysiloxane skeleton.
Further, open among the No.2003-167398 (US patent application publication No.US-2003-0118372) the Jap.P. spy, propose to use conductive member as outermost resin layer, in this outermost resin layer, conductive member is made of the resin material that contains urethane resin and polysiloxane composition.Purpose is,, prevents to haze after starting stage and extension operation with when satisfying the long requirement of high image quality, high speed and permanance at the stable photosensitive material that adheres to.
The idea that urethane resin and polysiloxane are combined may be in realizing high performance charging member effectively as mentioned above.Yet, along with growth of requirement to the high reliability developer roll, under opposite extreme environmental conditions, for example, hot and humid (30 ℃/85%RH) under the environment and (15 ℃/10%RH) under the environment, may be difficult to make characteristics of image consistent mutually of low temperature and low humidities.Specifically, in hot and humid environment, because developer frictional electrification ability significantly worsens, so may haze.In order to address this is that,, then obtain the effect that inhibition is hazed if strengthen the frictional electrification ability.Yet, in this case, when using this developer roll in the low temperature and low humidity environment, obvious ghost image may appear, because because high frictional electrification ability causes developer charging (charge-up).Because this relation is an inverse correlation, so be difficult to be implemented in the hot and humid environment and the developing member that all has more stable chargeability under the low temperature environment.
Summary of the invention
Therefore, the purpose of this invention is to provide the developing member with height reliability, it can prevent to haze in hot and humid environment and in the low temperature and low humidity environment ghost image takes place simultaneously.Another object of the present invention provides the electrophotographic image forming that uses this developing member.
Developing member according to the present invention comprises mandrel and is formed on the resin bed that this mandrel is placed outward, and have the outermost layer that contains non-reacted silicone compounds, wherein this non-reacted silicone compounds satisfies following requirements (A) to (C): (A) silicone and polyoxyethylated multipolymer; (B) proportion of 0.99≤d≤1.03 (25 ℃) d; And (C) solubleness in water (25 ℃) less than 0.1 quality %.
To achieve these goals, the present inventor has carried out intensive research.Particularly, in order to solve the problem that hazes in the hot and humid environment, the present inventor is primarily focused on the frictional electrification ability of developing member to toner that strengthen.In addition, in order to solve the ghost image problem under the low temperature and low humidity environment, the present inventor is primarily focused on the surface interface state of developing member and the influence of water.
Ether has high frictional electrification ability for toner, and this is because its dense electron cloud in the highest occupied molecular orbital with electronics releasing properties (electron-releasing property).Therefore, the present inventor is primarily focused on the multipolymer of polyoxyethylene and silicone, and it has high relatively ether concentration in polyethers, and the present inventor studies hazing in the hot and humid environment.As a result, the molecular weight of polyoxyethylene part is too big, and proportion (25 ℃) d may reach toner triboelectric charge leakage point greater than 1.03 the strong water wettability of multipolymer demonstration.Therefore, in some cases, can not fully avoid hazing in the hot and humid environment.On the other hand, d is lower than at 0.99 o'clock at proportion (25 ℃), and the molecular weight of polyoxyethylene part is relatively little.Therefore, can not obtain sufficiently high frictional electrification ability, therefore, be easy to haze.
The present inventor is that the silicone and the polyoxyethylated multipolymer of 0.99≤d≤1.03 studied to having proportion (25 ℃) d, and they provide the toner with good charged ability in hot and humid environment.Yet it is insufficient that some demonstrations in them are suppressed at the effect that ghost image takes place in the low temperature and low humidity environment.Therefore, the present inventor finds to have the multipolymer that solubleness in water (25 ℃) is lower than 0.1 quality % and can not produce ghost image in the low temperature and low humidity environment.Above-mentioned detailed mechanism is also unknowable.Yet, can imagine, reduce, not produce charged toner even under low-humidity environment, be present in the effect of the water on the surface interface of the superficial layer that contains this multipolymer on a small quantity, the ghost image problem is resolved, and this is because this multipolymer is extremely low to the compatibility of water.
In addition, have silicone and polyoxyethylated multipolymer more than the solubleness 0.1 quality % in water (25 ℃), that is, those with surfactant function produce ghost image easily in the low temperature and low humidity environment, and produce in hot and humid environment and haze.Amphipathic making with multipolymer of surfactant function is difficult to change the developing roller surface characteristic, and think: in hot and humid environment, the generation of triboelectric charge leakage point can not be prevented, and in the low temperature and low humidity environment, the influence of the low amounts of water on the developing roller surface interface can not be prevented.Therefore, based on acquired these the multiple discoveries of the present inventor, finished the present invention.
Electrophotographic image forming according to the present invention comprises: the image-carrier that is used to carry electrostatic latent image; Be used for charging device that image-carrier is once charged; Exposure device is used for forming electrostatic latent image on the image-carrier of once charging; Be used to make latent electrostatic image developing, thereby form the developing apparatus of toner image; And be used for toner image is transferred to transfer device on the transfer materials, wherein this developing apparatus comprises developing member.
According to the description of following typical embodiments and with reference to the accompanying drawings, other features of the present invention will become apparent.
Description of drawings
Fig. 1 is the axial cut-open view of developer roll according to embodiments of the present invention.
Fig. 2 is the axial cut-open view of developer roll according to another embodiment of the invention.
Fig. 3 is to use the cut-open view of the electronic photographing device of developing apparatus of the present invention.
Embodiment
Below, will further describe the present invention.
(developer roll)
Fig. 1 is the schematic cross sectional views as the developer roll of the embodiment of developing member of the present invention.
Because resin bed 2 contains the non-reacted silicone compounds that satisfies above-mentioned requirements (A) to (C), so can control the influence of frictional electrification ability, developing roller surface-interfacial state (surface-boundary state) and the water of developer.As a result, can be suppressed at simultaneously and haze in the hot and humid environment and in the low temperature and low humidity environment, ghost image takes place.
Preferred non-reacted silicone compounds does not have cloud point.When not having cloud point, just do not have the function of surfactant.Therefore, can prevent because any trouble of above-mentioned amphipathic generation.
This non-reacted silicone compounds does not have hydrogen such as the reactive hydrogen (hydrogen of hydroxyl or amino hydrogen) with the isocyanates radical reaction; Reactive double bond such as vinyl; Epoxy radicals; And carboxyl.The existence of reactive functional groups may cause the reduction greatly of molecular migration rate, this be because non-reacted silicone compounds as the part of base material (resin) and chemistry is introduced.Therefore, be difficult to realize effect of the present invention with ad hoc fashion.
The form of copolymerization can be to have silicone part and polyoxyethylene straight chain block polymer type, side chain block polymer type or graft polymer type partly between the silicone of this compound part and polyoxyethylene part.Ad hoc structure can be described below as general formula (A) to (D):
Wherein m and n are positive integer independently of one another.
In addition, the structure that can more effectively realize the non-reacted silicone compounds of effect of the present invention is the structure by following structural molecule formula (1) expression:
Wherein m, n and x are the integer more than 1 independently of one another, and R represents alkyl.
In addition, above-mentioned non-reacted silicone compounds can preferably have weight-average molecular weight (Mw) 6,000≤Mw≤11,000.As long as the weight-average molecular weight of non-reacted silicone compounds is in above-mentioned scope, this non-reacted silicone compounds is easier being present on the developing roller surface just, therefore, and easier realization effect of the present invention.
, in 95/5 to 70/30 scope, can meet the demands (B) and (C) by the silicone in the non-reacted silicone compounds of suitable adjusting part and polyoxyethylene components by weight (silicone part/polyoxyethylene part) partly.
Preferably above-mentioned non-reacted silicone compounds is added in the resin (base material) that forms the outmost surface layer with amount with respect to 100 mass parts resins, 0.1 to 20 mass parts, thereby can suitably control the influence of frictional electrification ability, developing roller surface interfacial state and the water of developer, thereby can strengthen effect of the present invention.More preferably add non-reacted silicone compounds with the amount of 0.5 mass parts to 10 mass parts.
By utilizing suitable means that non-reacted silicone compounds is carried out any classic method such as pyrolysis GC/MS, NMR, IR or ultimate analysis from the superficial layer separation and with institute's isolated compound, can discern the molecular structure of non-reacted silicone compounds and the structure of silicone and polyoxyethylene part.In addition, the addition of this compound can be with reference to quantitatively recently determining when it extracts from superficial layer.
In the present invention, can utilize the measurement mechanism of the vibrating densimeter method (determining the density of chemical products and the method for proportion) of using JIS K 0061 definition to determine the proportion (25 ℃) of non-reacted silicone compounds.Specifically, utilize density proportion instrument (trade name: DA-520, by Kyoto Electronics Manufacturing Co., Ltd. makes) to measure.
In the present invention, the following method of determining the solubleness of compound in water (25 ℃): prepare 0.1 quality % above-mentioned non-reacted silicone compounds aqueous solution (for example, weighing 100g distilled water (25 ℃) and the non-reacted silicone compounds of 0.1g mix them in glass beaker); When this non-reacted silicone compounds being dissolved fully in 24 hours by with magnetic stirring apparatus this aqueous solution being stirred, thereby when forming clear water solution, solubleness in the water of non-reacted silicone compounds (25 ℃) is confirmed as more than the 0.1 quality %.On the other hand, residual or when becoming muddy suspended matter, the solubleness of this compound is confirmed as being lower than 0.1 quality % when insoluble matter.
In the present invention, the following measurement of carrying out cloud point: the aqueous solution (for example, the non-reacted silicone compounds of weighing 100g distilled water and 1.0g, and in test tube, being blended together) for preparing the above-mentioned non-reacted silicone compounds of 1.0 quality %; And in hot water this aqueous solution of heating, and the temperature when this clear solution become muddiness is defined as cloud point.Even, then this solution is confirmed as not having the solution of cloud point if this solution is still constant limpid and keep muddy after being cooled to 1.0 ℃.
In the present invention, utilize general gel permeation chromatography (GPC) to use the method for molecular weight distribution to carry out the measurement of weight-average molecular weight.
(Mw) can measure under the following conditions by the weight-average molecular weight in the chromatogram of GPC: make post stable in 40 ℃ heating chamber; Make as the toluene of solvent and flow into this post with the flow velocity of 1ml/min; The about 100 μ l of toluene sample solution that non-reacted silicone compounds wherein is adjusted to as 0.3 quality % of sample concentration inject in this post.In order to determine the molecular weight of this sample,, calculate the molecular weight distribution in this sample according to the logarithm value of the analytic curve of several monodisperse polystyrene standard models and the relation between the count value (retention time).In order to make this analytic curve, at least 10 different polystyrene standard samples of preferred use.Specifically, for example, use to have molecular weight 6 * 10
2, 2.1 * 10
3, 4 * 10
3, 1.75 * 10
4, 5.1 * 10
4, 1.1 * 10
5, 3.9 * 10
5, 8.6 * 10
5, 2 * 10
6, and 4.48 * 10
6Those.For example, the polystyrene standard sample can be commercially available those of Tosoh Corporation or Pressure Chemicals Ltd..In addition, as detecting device, can use differential refraction detector.
As post, can preferably use the combination of commercially available polystyrene-gel column.Can enumerate following: for example, Showa Denko Co., the Shodex GPCKF-801,802,803,804,805 that Ltd. makes, 806 and 807 combination; And Waters Co., μ-styragel 500,103,104 that Ltd. makes and 105 combination.
(mandrel)
Axle 1 as the mandrel setting can be any materials with satisfactory electrical conductivity.Usually, use external diameter 4 to the 10mm round metal bobbins of making by aluminium, iron or SUS.
The example of basic material of placing the resin bed 2 of formation at axle 1 outer comprises: polyamide, urethane resin, Lauxite, imide resin, melamine resin, fluororesin, phenolics, alkyd resin, vibrin, polyether resin, acryl resin, natural rubber, butyl rubber, nitrile rubber, polyisoprene rubber, polybutadiene rubber, silicon rubber, styrene-butadiene rubber, EP rubbers, ethylene-propylene-diene rubber, neoprene and their potpourri.
Wherein, urethane resin is preferably used as the basic material of resin bed 2, and this is because it has the higher friction of passing through and makes the charged ability of developer and show abrasion performance.Specifically, the starting material of urethane resin comprise polyvalent alcohol and isocyanates and chain extender in case of necessity.To comprise as the raw-material polyvalent alcohol of urethane resin: polyether glycol, polyester polyol, polycarbonate polyol, polyolefin polyhydric alcohol, acrylic compounds polyvalent alcohol and their potpourri.To comprise as the raw-material isocyanates of urethane resin: toluene diisocyanate (TDI), methyl diphenylene diisocyanate (MDI), naphthalene diisocyanate (NDI), dimethyl diphenyl diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), phenylene vulcabond (PPDI), XDI (XDI), tetramethylxylylene diisocyanate (TMXDI), cyclohexane diisocyanate and their potpourri.Comprise as the raw-material chain extender of urethane resin: difunctionality low-molecular-weight diol, ethylene glycol, 1 for example, 4-butylene glycol and 3-methyl pentanediol; Trifunctional hangs down the molecule trihydroxy alcohol, for example, and trimethylolpropane; And their potpourri.
Especially, in urethane resin, the preferred polyether-polyurethane resin that uses polyether glycol.In this case, the compatibility of the polyoxyethylene of resin material and non-reacted silicone compounds part prevents that above-mentioned non-reacted silicone compounds from oozing out and move to another member, reduces from characteristic simultaneously and the low temperature and low humidity environment ghost image takes place from this resin.
By basic material and electric conductivity imparting agent such as electron conduction material or ionic conductivity material are mixed, be preferably 10 by having proper resistor rate scope (specific insulation)
3Ω cm to 10
11The material of Ω cm forms resin bed 2.The specific insulation of resin bed 2 is more preferably 10
4Ω cm to 10
10In the Ω cm scope.In addition, the thickness of resin bed 2 is preferably in the scope of 0.3mm to 10.0mm, more preferably in the scope of 1.0mm to 5.0mm.
The electron conduction examples of substances of giving resin bed 2 electric conductivity comprises: conductive carbon such as Ketjen black (Ketjen Black) EC (LION Corporation manufacturing) and acetylene black; The carbon such as SAF, ISAF, HAF, FEF, GPF, SRF, FT and the MT that are used for rubber; Carried out the carbon that is used for colorant (China ink) of oxidation processes; Metal such as copper, silver and germanium; And metal oxide.
Wherein, preferred carbon black (conductive carbon, the carbon that is used for the carbon of rubber and is used for colorant (China ink)), this is because can be easily with a small amount of control conductivity.
The ionic conductivity examples of substances of giving resin bed 2 electric conductivity comprises: inorganic ions conductive material such as sodium perchlorate, lithium perchlorate, Calcium perchlorate and lithium chloride; And organic ion conductive material such as sex change aliphatic series dimethyl disulfide acetoacetic ester ammonium (dimethylammonium ethosulfate) and stearyl ammonium acetate (stearyl ammoniumacetate).
Use these electric conductivity imparting agents resin bed is provided the required amount of above-mentioned proper volume resistivity.Usually, preferably with respect to 100 mass parts base materials to be the scope use electric conductivity imparting agent of 1 mass parts to 50 mass parts.
By EU resin-shaped resin layer 2 time, the weight-average molecular weight of above-mentioned non-reacted silicone compounds (Mw) and satisfy Mw＜N as the relation between the weight-average molecular weight (N) of the raw-material polyether glycol of above-mentioned EU.By the relation of design Mw and N, to satisfy Mw＜N, the interaction of molecules between the polyether chain of EU and the polyoxyethylene of the non-reacted silicone compounds part becomes very strong.Therefore, non-reacted silicone compounds can firmly remain on the surperficial urethane resin layer, keeps its molecular migration rate simultaneously.Therefore, can significantly prevent to haze in the hot and humid environment and in the low temperature and low humidity environment, ghost image takes place.
Fig. 2 is the schematic cross sectional views of developer roll according to another embodiment of the invention.In Fig. 2, developer roll 200 is made of the resin bed of mandrel 1 and this mandrel 1 periphery of two-layer covering.This two layers of resin layer is made of the resin bed 202 that is formed on this mandrel 1 lip-deep resin bed 201 and be formed on this resin bed 201 as the developer roll superficial layer.
The good resin of resin preferred elastomeric that uses in the resin bed 201 can guarantee to have stable roll-gap width with photosensitive drums so that constitute the resin bed 201 of lower floor, thereby keeps the homogeneity of image and continous-stable output image for a long time.The preferred example of this resin comprises: natural rubber, butyl rubber, nitrile rubber, polyisoprene rubber, polybutadiene rubber, silicon rubber, styrene-butadiene rubber, EP rubbers, ethylene-propylene-diene rubber, neoprene and their potpourri.Wherein, preferred especially silicon rubber and ethylene-propylene-diene rubber.
In addition, preferably conductive material is introduced resin bed 201, so that its electrical resistivity range (specific insulation) is adjusted to proper range.That is, the specific insulation of this resin preferably 10
3Ω cm to 10
10Ω cm is more preferably 10
4Ω cm to 10
8Ω cm.
Above-mentioned conductive material can with add above-mentioned resin bed 2 in identical.What in addition, the addition of conductive material can be with in above-mentioned resin bed 2 is identical.
In addition, resin bed 201 can have 25 ° to 70 ° of ASKER-C hardness, preferred 35 ° to 50 °.
And resin bed 201 preferably has the thickness of 0.3mm to 10mm usually, more preferably has the thickness of 1.0mm to 5.0mm.On the other hand, in order to prevent lower-layer resin layer forfeiture elasticity, resin bed 202 preferably has the thickness of 0.5 μ m to 100 μ m.
The developer roll that resin bed is formed thereon is cut into 9, utilizes its xsect of kind of calliper, determines the thickness of its mean value as each resin bed.If the thickness of this resin bed little (1.0mm is following) then utilizes videomicroscopy (5 times to 3,000 times enlargement ratios) to measure 9 cross sections, and its mean value is defined as the thickness of each resin bed.
Can following production developer roll formed according to the present invention as depicted in figs. 1 and 2.
Composition by the non-reacted silicone compounds preparation that will will add when mediating above-mentioned resin (base material), electric conductivity imparting agent and forming the outmost surface layer at least injects in the cavity of the mould of wherein placing mandrel in advance produces developer roll.The predetermined tubular structure that can also have preliminary dimension from the flat board (slab) that forms respectively by above-mentioned composition or piece (block) cutting.Then, mandrel is pressed into this tubular structure, on this mandrel, forming resin bed, thereby forms developer roll as the outmost surface layer.If desired, can further cut or polish, and it is adjusted to predetermined outer diameter the developer roll that obtains.
The developer roll that is shown in Fig. 2 can be produced in the following manner: thus by spraying or dip coating above-mentioned composition is applied in advance on the outer surface of the peripheral resin bed 201 that forms of mandrel to form resin bed 202, and this coating more in time is heating and curing.
Profit is (1) or (2) in the following method, can form resin bed 201:(1) comprise that the above-mentioned composition that will form this resin bed injects in the cavity of the mould of wherein placing mandrel in advance, follows the method for the step of thermmohardening; And (2) comprise and form flat board or piece by the composition that is used to form this resin bed in advance to have the predetermined tubular structure of preliminary dimension from flat board or piece cutting, and this mandrel is pressed into the method for the step of this tubular structure.
In method (1) and (2), outside mandrel, place formed resin bed 201 after, if desired, can further cut or polish, and it is adjusted to predetermined outer diameter.
When forming resin bed 202, the non-reacted silicone compounds of mediating above-mentioned resin (base material), electric conductivity imparting agent and when forming the outmost surface layer, will adding at least.Can utilize equipment such as bowl mill to mediate, and the roughening particle that will be used to regulate the developer roll surfaceness when needing adds and disperse, then rigidizer or hardening catalyst are added this potpourri and stir.Thus obtained composition can apply as spraying or dip coating by using rubbing method.The example of the roughening particle that adds comprises: rubber grain such as EPDM, NBR, SBR, CR and silicone rubber particles; Elastomer particles such as polystyrene, polyolefin, Polyvinylchloride, polyurethane, polyester and based on the thermoplastic elastomer (TPE) of polyamide; And resin particle such as PMMA, urethane resin, fluororesin, silicone resin, phenolics, naphthalene resin, furane resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer and polyacrylonitrile resin.Can be separately or can two kinds or more ofly be used in combination the particle of these types.In this case, usually developing roller surface roughness Rz is adjusted to 1 μ m to 15 μ m.The developing roller surface roughness is defined as the Rz according to JIS B0601:2001.
(electrophotographic image forming)
Electrophotographic image forming according to the present invention comprises following structural detail: (1) is used to carry the image-carrier of electrostatic latent image.(2) be used for charging device that image-carrier is once charged.(3) be used on the image-carrier of once charging, forming the exposure device of electrostatic latent image.(4) be used for making latent electrostatic image developing to form the developing apparatus of toner image by developer.(5) be used for toner image is transferred to transfer device on the transfer materials.
Subsequently, the developing apparatus of above-mentioned (4) comprises according to developing member of the present invention.
Fig. 3 illustrates the schematic cross sectional views of electrophotographic image forming of the present invention.
About developing, carry out on exposed portion, forming the discharged-area development processing of toner image.By the toner image on the photosensitive drums 21 being transferred on a piece of paper 33 as transfer materials as the transfer roll 29 of transfer member.Then, with thereon the paper 33 of transfer printing toner image carry out photographic fixing by fixing device 32 and handle, then from this equipment, arrange paper.Therefore, finish printing.
On the other hand, will after transfer printing, not be transferred the residual developer that remains on the photosensitive drums 21 by cleaning balde 30 and strike off, and it will be contained in the waste developer container 31 as the cleaning element that is used to remove photosensitive drum surface.The imaging process that the photosensitive drums 21 of cleaning is used for wherein repeating aforesaid operations.
Developing apparatus 24 is provided with: wherein store as the developer container 34 of the non magnetic developer 28 of monocomponent toner with as the developer roll 25 of developer carrier, this developer roll is placed on along the longitudinal extension of developer container 34 and towards the peristome of photosensitive drums 21.Design developing apparatus 24 is so that the latent electrostatic image developing on the development photosensitive drums 21 and visual.In addition, electronic photography process cartridge have in developing apparatus and image-carrier, charging member, cleaning element and the transfer member one of at least, their integrated maintenances also are removably mounted on the imaging device.
In addition, developer roll 25 is with butt joint width contact photosensitive drums 21.In developing apparatus 24, with respect to the contact site that wherein contacts with the surface of developer roll 25 as the developing blade 27 of developer adjustment means, developer supply roller 26 contacts at the upstream side along the sense of rotation of developer roll 25 in the developer container 34 with developer roll 25.In addition, supporting developer supply roller 26 is so that can rotate.
According to the present invention, can obtain to be suppressed in the hot and humid environment and haze on the electrophotographic image and in the low temperature and low humidity environment, ghost image is taking place with high level.
(embodiment)
To utilize embodiment and comparative example to describe the present invention in detail below.Yet embodiment does not limit the present invention in any way.
(non-reacted silicone compounds)
As non-reacted silicone compounds, the non-reacted silicone compounds No.1 to 9 that preparation is following.
No.1: using weight-average molecular weight Mw is 11,000, and proportion (25 ℃) d is 1.02 non-reacted silicone compounds (trade name: TSF4446, by GE ToshibaSilicone Co., Ltd. makes).Its solubleness that has in the water (25 ℃) is lower than 0.1 quality %, and does not have cloud point.
No.2: using weight-average molecular weight Mw is that 9,200 proportions (25 ℃) d is 1.03 non-reacted silicone compounds (trade name: TSF4445, by GE Toshiba SiliconeCo., Ltd. makes).Solubleness in its water (25 ℃) is lower than 0.1 quality %, and does not have cloud point.
No.3: at first add the concentrated sulphuric acid of 0.022mol to 2ml and contain in the aqueous solution of 0.014mol chromium oxide (VI),, add 4ml water then simultaneously in cooled on ice, thus the preparation Jones reagent.
Subsequently, under 20 ℃, (by Aldrich Co., Ltd. makes, and Mn=550) reaction is 24 hours, thereby obtains the starting material of polyether moiety to make Jones reagent and 10g poly glycol monomethyl ether.Then, under 40 ℃, these starting material of 5.0g and 0.014mol oxalyl chloride (by Aldrich Co., Ltd. makes) were reacted 5 hours in benzene, thereby obtain acid chloride.
At room temperature, the acid chloride (2.5g) of acquisition was reacted 24 hours in the presence of a small amount of pyridine in diethyl ether with 16g polysiloxane compound (trade name: X22-170BX, by Shin-EtsuChemical Co., Ltd. makes).As a result, obtaining to have weight-average molecular weight Mw is 3,850 non-reacted silicone compounds (No.3).
Proportion (25 ℃) d of the non-reacted silicone compounds that obtains is 1.03, and its solubleness in water (25 ℃) is less than 0.1 quality %, and does not have cloud point.
No.4: under 20 ℃, (by Aldrich Co., Ltd. makes, and Mn=750) reaction is 24 hours, thereby obtains the starting material of polyether moiety with the 10g poly glycol monomethyl ether in acetone to make above-mentioned Jones reagent.Then, under 40 ℃, these starting material of 5.0g and 0.010mol oxalyl chloride (by Aldrich Co., Ltd. makes) were reacted 5 hours in benzene, thereby obtain acid chloride.Then, at room temperature, the 2.5g acid chloride of acquisition was reacted 24 hours in the presence of a small amount of pyridine in diethyl ether with 6.6g polysiloxane compound (trade name: KF 6002, by Shin-Etsu Chemical Co., Ltd. makes).As a result, obtaining to have weight-average molecular weight Mw is 7,000 non-reacted silicone compounds (No.4).
Proportion (25 ℃) d of the non-reacted silicone compounds that obtains is 1.01, and the solubleness in water (25 ℃) is less than 0.1 quality %, and does not have cloud point.
No.5: under 20 ℃, (by Aldrich Co., the Ltd. manufacturing Mn=550) was reacted 24 hours in acetone, thereby obtained the starting material of polyether moiety to make above-mentioned Jones reagent and 10g polyglycol monomethyl ether.Then, under 40 ℃, these starting material of 5.0g and 0.014mol oxalyl chloride (by Aldrich Co., Ltd. makes) were reacted 5 hours in benzene, thereby obtain acid chloride.Then, at room temperature, the 2.5g acid chloride of acquisition was reacted 24 hours in the presence of a small amount of pyridine in diethyl ether with 27.5g polysiloxane compound (Ltd. makes for trade name: X22-170DX, Shin-Etsu Chemical Co.).As a result, obtaining to have weight-average molecular weight Mw is 6,000 non-reacted silicone compounds (No.5).
Proportion (25 ℃) d of the non-reacted silicone compounds that obtains is 0.99, and the solubleness in water (25 ℃) is less than 0.1 quality %, and does not have cloud point.
No.6: under 20 ℃, above-mentioned Jones reagent and 10g polyglycol (by Aldrich Co., Ltd. makes, Mn=1,000) were reacted 24 hours in acetone, thereby obtain the starting material of polyether moiety.Then, under 40 ℃, these starting material of 5.0g and 0.014mol oxalyl chloride (by Aldrich Co., Ltd. makes) were reacted 5 hours in benzene, thereby obtain acid chloride.Then, at room temperature, the 2.5g acid chloride of acquisition was reacted 24 hours in the presence of a small amount of pyridine in diethyl ether with 41.2g polysiloxane compound (trade name: X22-170DX, by Shin-Etsu Chemical Co., Ltd. makes).As a result, obtaining to have weight-average molecular weight Mw is 12,000 non-reacted silicone compounds (No.6).
Proportion (25 ℃) d of the non-reacted silicone compounds that obtains is 1.00, and the solubleness in water (25 ℃) is less than 0.1 quality %, and does not have cloud point.
No.7: use have weight-average molecular weight Mw be 3,000 and proportion (25 ℃) d be 1.05 non-reacted silicone compounds (trade name: SILWET L8600, by GEToshiba Silicone Co., Ltd. makes).The solubleness of this non-reacted silicone compounds in water (25 ℃) is more than the 0.1 quality %, and its cloud point is 76 ℃.
No.8: use have weight-average molecular weight Mw be 3,200 and proportion (25 ℃) d be 0.96 non-reacted silicone compounds (trade name: TSF451-50, by GE ToshibaSilicone Co., Ltd. makes).The solubleness of this non-reacted silicone compounds in water (25 ℃) is less than 0.1 quality %, and do not have cloud point.
No.9: under 20 ℃, above-mentioned Jones reagent and 10g diethylene glycol monoethyl ether (by Aldrich Co., Ltd. makes) were reacted 24 hours in acetone, thereby obtain the starting material of polyether moiety.Then, under 40 ℃, these starting material of 5.0g and 0.052mol oxalyl chloride (by Aldrich Co., Ltd. makes) were reacted 5 hours in benzene, thereby obtain acid chloride.Then, at room temperature, the 2.5g acid chloride of acquisition was reacted 24 hours in the presence of a small amount of pyridine in diethyl ether with 123g polysiloxane compound (trade name: X22-170DX, by Shin-Etsu Chemical Co., Ltd. makes).As a result, obtaining to have weight-average molecular weight Mw is 5,700 non-reacted silicone compounds (No.9).
Proportion (25 ℃) d of the non-reacted silicone compounds that obtains is 0.98, and the solubleness in water (25 ℃) is less than 0.1 quality %, and does not have cloud point.
Show the basic structure of the non-reacted silicone compounds of aforesaid No.1 to No.9 below.In every kind of structural formula, m, n and x are respectively 1 or greater than 1 integer independently.In addition, R, R
1And R
2Represent alkyl respectively.
No.1
(in the said structure formula, m, n and x are respectively 1 or greater than 1 integer, and R represents alkyl).
No.2
(in the said structure formula, m, n and x are respectively 1 or greater than 1 integer, and R represents alkyl).
No.3
*[-C
2H
4O]n-CH
3
No.4
No.5
*[-C
2H
4O]n-CH
3
No.6
No.7
*[-C
2H
4O]x-R
2
No.8
No.9
*-CH
2CH
2-O-CH
2CH
3
(manufacturing of developer roll)
(embodiment 1)
In internal diameter is the cylindric mould of 16mm external diameter being installed is the plug (mandrel) of 8mm, makes itself and mould arranged concentric.Then, (by DowCorning Toray Silicone Co., Ltd. makes, and ASKER-C hardness is 40 °, and specific insulation is 1 * 10 with liquid conductivity silicon rubber
7Ω cm) injects cylindric mould as the material that is used to form elastic layer.After this, it is placed in 130 ℃ the baking oven, heating and moulding are 20 minutes then.After unloading shaped article from this mould, in 200 ℃ baking oven, it was carried out post-cure 4 hours, thereby form the thick elastic layer of 4mm outer the placing of plug.
Then, the material below in methyl ethyl ketone solvent, progressively mixing, and make it under blanket of nitrogen, react to each other 3 hours at 80 ℃.As a result, obtain weight-average molecular weight Mw be 12,000 and hydroxyl value be 17.2 polyether glycol prepolymer (1).
Polytetramethylene glycol (Ltd. makes for trade name: PTG1000SN, Hodogaya Chemical Co.): 100 mass parts.
Isocyanates (trade name: Millionate MT, by Nippon PolyurethaneIndustry Co., Ltd. makes): 18.7 mass parts.
Then, mix following starting material, add MEK then so that solids content is 28 quality %.The product that obtains is used to form the starting material liquid of resin bed.
Above-mentioned polyether glycol prepolymer (1): 100 mass parts.
Isocyanates (trade name: C2521, by Nippon Polyurethane IndustryCo., Ltd. makes): 85 mass parts.
The non-reacted silicone compounds of above-mentioned No.1: 1 mass parts.
(trade name: MX-1000 is by Soken Chemical ﹠amp with 20 mass parts carbon blacks (trade name: KA100, by Mitsubishi ChemicalCorporation make) and 30 mass parts acrylic resin particles; Engineering Co., Ltd. makes) add in the solid constituent of starting material liquid, utilize bowl mill to stir again and dispersion.By dipping, on the elastic layer that the coating fluid paint that obtains is formed in advance, be the film of 15 μ m to form thickness, then, in baking oven 80 ℃ dry 15 minutes down.Further, in baking oven, hardened 4 hours down, to form resin bed as the outmost surface layer at 140 ℃.Thereby obtain the developer roll of embodiment 1.
(embodiment 2)
To prepare the plug that covers with elastic layer with mode identical in embodiment 1.
The coating fluid that is used to form resin bed is prepared as follows.
At first, following material is progressively mixed in methyl ethyl ketone solvent and make it under blanket of nitrogen, react to each other 3 hours at 80 ℃.As a result, obtaining weight-average molecular weight Mw is 6,800, and hydroxyl value is 43 polyether glycol prepolymer (2).
Polytetramethylene glycol (trade name: PTG650SN, by Hodogaya Chemical Co., Ltd. makes): 100 mass parts.
Trimethylolpropane (by Mitsubishi Gas Chemical Company, INC makes): 3 mass parts.
Isophorone diisocyanate (by AldrichCo., Ltd. makes): 30 mass parts.
Then, mix following starting material, then, add MEK, so that solids content is 28 quality %.The product that obtains is used to form the starting material liquid of resin bed.
Above-mentioned polyether glycol prepolymer (2): 100 mass parts.
Isocyanates (trade name: C2521, by Nippon Polyurethane IndustryCo., Ltd. makes): 152 mass parts.
The non-reacted silicone compounds of above-mentioned No.2: 3 mass parts.
(trade name: MX-1000 is by Soken Chemical ﹠amp with 20 mass parts carbon blacks (trade name: KA100, by Mitsubishi ChemicalCorporation make) and 30 mass parts acrylic resin particles; Engineering Co., Ltd. makes) add in the solid constituent of starting material liquid, utilize bowl mill to stir again and dispersion, thereby obtain to be used to form the coating fluid of resin bed.
By dipping, the coating fluid paint that obtains is covered on the elastic layer of mandrel of prepared beforehand, be the film of 15 μ m to form thickness, then, in baking oven 80 ℃ dry 15 minutes down.Further, in baking oven, hardened 4 hours down, to form resin bed as the outmost surface layer at 140 ℃.Thereby obtain the developer roll of embodiment 2.
(embodiment 3)
Except utilizing non-reacted silicone compounds No.3 to replace to be used to prepare the non-reacted silicone compounds No.2 that is used to form as the coating fluid of the resin bed of outmost surface layer; And its combined amount becomes beyond 0.5 mass parts, with embodiment 2 in the developer roll of identical mode production example 3.
(embodiment 4)
Except utilizing non-reacted silicone compounds No.4 to replace to be used to prepare the non-reacted silicone compounds No.2 that is used to form as the coating fluid of the resin bed of outmost surface layer, with embodiment 2 in the developer roll of identical mode production example 4.
(embodiment 5)
Except utilizing non-reacted silicone compounds No.5 to replace to be used to prepare the non-reacted silicone compounds No.1 that is used to form as the coating fluid of the resin bed of outmost surface layer; And its combined amount becomes beyond 10 mass parts, with embodiment 1 in the developer roll of identical mode production example 5.
(embodiment 6)
Except utilizing non-reacted silicone compounds No.6 to replace to be used to prepare the non-reacted silicone compounds No.1 that is used to form as the coating fluid of the resin bed of outmost surface layer; And its combined amount becomes beyond 3 mass parts, with embodiment 1 in the developer roll of identical mode production example 6.
(comparative example 1)
Except not having to be used to prepare the non-reacted silicone compounds No.1 that is used to form as the resin bed of outmost surface layer, with embodiment 1 in identical mode produce the developer roll of comparative example 1.
(comparative example 2)
Except utilizing non-reacted silicone compounds No.7 to replace to be used to prepare the non-reacted silicone compounds No.1 that is used to form as the coating fluid of the resin bed of outmost surface layer; And its combined amount becomes beyond 3 mass parts, with embodiment 1 in identical mode produce the developer roll of comparative example 2.
(comparative example 3)
Except utilizing non-reacted silicone compounds No.8 to replace to be used to prepare the non-reacted silicone compounds No.1 that is used to form as the coating fluid of the resin bed of outmost surface layer, with embodiment 1 in identical mode produce the developer roll of comparative example 3.
(comparative example 4)
Except utilizing non-reacted silicone compounds No.9 to replace to be used to prepare the non-reacted silicone compounds No.2 that is used to form as the starting material liquid of the resin bed of outmost surface layer, with embodiment 2 in identical mode produce the developer roll of comparative example 4.
(picture appraisal)
(" evaluation of hazing " in the hot and humid environment under (30 ℃/humidity 85%RH of temperature))
In the electronic photography process cartridge of following color laser printer, each of developer roll of the foregoing description and above-mentioned comparative example is set.Utilize color laser printer (Ltd. makes for trade name: Color LaserJet 4700, Hewlett-PackardCo.), estimate.
As developer, use the blue developer on the cyan print cartridge that is installed in Color LaserJet 4700.
In evaluation procedure, in hot and humid environment, on 15,000 paper, print 2% print image.After this, this color laser printer was placed 24 hours.Subsequently, in hot and humid environment, go up the white solid image of output at a glossy paper (HP glossy paper).In this case, every bit in 10 o'clock is measured the printing reflection density in white background zone afterwards, and its mean value is defined as Ds (%), the every bit in 10 o'clock is measured the printing reflection density of white glossy paper before, and its mean value is defined as Dr (%).In this case, the level of hazing is defined as Ds-Dr.
Utilize reflection densitometer (trade name: REFLECTOMETER MODELTC-6DS/A, by Tokyodenshoku, Co., Ltd. makes) to measure reflection density.
The level of hazing is lower than 0.5% situation and is confirmed as extremely excellent images.
The level of hazing is the good image that is confirmed as not hazing basically more than 0.5% and less than 1.5% situation.
The degree of hazing is that the situation more than 1.5% is confirmed as having the image of not knowing that significantly hazes.
(in the ambient temperature and moisture environment " evaluation of hazing " of (23 ℃/humidity 55%RH of temperature))
In the ambient temperature and moisture environment, to estimate " hazing " with " evaluation of hazing " identical mode in hot and humid environment.
(in the environment of low temperature and low humidity (15 ℃/humidity 10%RH of temperature) " ghost image evaluation ")
In the electronic photography process cartridge of following color laser printer, each of the developer roll of placement the foregoing description and above-mentioned comparative example.Utilize color laser printer (trade name: Color LaserJet 4700, by Hewlett-PackardCo., Ltd. makes), estimate.
As developer, former state is used the blue developer on the cyan print cartridge that is installed in Color LaserJet 4700.
In evaluation procedure, in the low temperature and low humidity environment, this color laser printer was placed 48 hours, the output ghost image is measured image on a piece of paper, utilizes this image of visual assessment then.By after just having printed 15mm * 15mm square chart picture, printing the 60h half tone image, obtain ghost image and measure image.In this case, based on following standard, estimate the density difference printed the half tone image that developer roll rotates a circle behind the square solid image of 15mm * 15mm.
A: do not find density difference.
B: see extremely slight density difference, but do not have difference basically.
C: see slight density difference, but in fact can accept.
(" ghost image evaluation " in ambient temperature and moisture (23 ℃/humidity 55%RH of temperature) environment)
With with " ghost image evaluation " identical mode in the low temperature and low humidity environment, under the ambient temperature and moisture environment, estimate ghost image.
The evaluation result of embodiment and comparative example is shown in following table 1.
Table 1
Shown in top table 1, in embodiment 1 to 6, by overcome simultaneously in the hot and humid environment haze and the low temperature and low humidity environment under ghost image, can obtain high quality graphic.
Although described the present invention with reference to typical embodiment, be to be understood that the present invention is not limited to disclosed typical embodiments.Give the wideest explanation with the scope of following claim, to comprise all these type of modifications and equivalent structure and function.
Claims (7)
1. developing member, it comprises mandrel and is formed on the resin bed that this mandrel is placed outward, and has and contain non-reacted outermost surface layer, wherein
This non-reacted silicone compounds satisfies following requirements (A) to (C):
(A) silicone and polyoxyethylated multipolymer;
(B) 25 ℃ proportion d:0.99≤d≤1.03; And
(C) solubleness in 25 ℃ water is less than 0.1 quality %.
2. developing member according to claim 2, wherein this resin bed has 2 layers at least.
3. developing member according to claim 1, wherein this non-reacted silicone compounds has the weight-average molecular weight Mw of 6,000≤Mw≤11,000.
4. developing member according to claim 1, wherein this non-reacted silicone compounds has the structure by formula (1) expression:
Wherein m, n and x are to be respectively integer more than 1 independently; R represents alkyl.
5. developing member according to claim 1, wherein this resin bed contains the polyether-polyurethane by polyether glycol and isocyanate reaction are obtained.
6. developing member according to claim 5, wherein this non-reacted silicone compounds has the weight-average molecular weight Mw that satisfies Mw＜N, and wherein the weight-average molecular weight of polyether glycol is defined as N.
7. electrophotographic image forming, it comprises:
Be used to carry the image-carrier of electrostatic latent image;
Be used to charging device that image-carrier is once charged;
Be used on the image-carrier of once charging, forming the exposure device of electrostatic latent image;
Be used for latent electrostatic image developing to form the developing apparatus of toner image; And
Be used for toner image is transferred to transfer device on the transfer materials, wherein
This developing apparatus comprises developing member according to claim 1.
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|---|---|---|---|
| JP2006269657 | 2006-09-29 | ||
| JP2006269657 | 2006-09-29 | ||
| JP2007199230 | 2007-07-31 |
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| US8182405B2 (en) * | 2008-09-30 | 2012-05-22 | Canon Kabushiki Kaisha | Developing roller, developing roller production method, process cartridge, and electrophotographic apparatus |
| JP4455671B1 (en) * | 2008-11-18 | 2010-04-21 | キヤノン株式会社 | Developing roller and manufacturing method thereof, process cartridge, and electrophotographic image forming apparatus |
| EP3130963B1 (en) * | 2014-04-08 | 2020-03-25 | NOK Corporation | Rubber member for developing roll, and method for manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165562C (en) * | 1997-11-11 | 2004-09-08 | 东海橡胶工业株式会社 | Conductive roller |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165562C (en) * | 1997-11-11 | 2004-09-08 | 东海橡胶工业株式会社 | Conductive roller |
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