CN1963685A - Developing roller and imaging apparatus comprising the same - Google Patents
Developing roller and imaging apparatus comprising the same Download PDFInfo
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- CN1963685A CN1963685A CNA2006101381364A CN200610138136A CN1963685A CN 1963685 A CN1963685 A CN 1963685A CN A2006101381364 A CNA2006101381364 A CN A2006101381364A CN 200610138136 A CN200610138136 A CN 200610138136A CN 1963685 A CN1963685 A CN 1963685A
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Abstract
There is a developing roller having a low compression permanent strain without contaminating a photosensitive drum and deteriorating toners. The developing roller (1) comprises a shaft (2), an elastic layer (3) formed on an outer periphery of the shaft (2) and a surface coating layer (4) formed on an outer peripheral face of the elastic layer (3), in which the surface coating layer (4) comprises a urethane resin formed by crosslinking a lactone-modified polyol with a polyisocyanate. The urethane resin is preferable to be formed by crosslinking the lactone-modified polyol with two or more kinds of polyisocyanates.
Description
Technical field
The present invention relates to developer roll and the imaging device that comprises this developer roll, relate more particularly under high temperature, high humidity environment to have in long-time the use developer roll of low compression set and good anti-toner melting and comprise such developer roll and can form the imaging device of superior images.
Background of invention
For example in the imaging device of duplicating machine, printer etc., the developing method of pressurization is known developing method at electrophotographic system: wherein with toner supply on the photosensitive drums that keeps sub-image with by showing sub-image attached to the toner on the sub-image on the photosensitive drums.In this class pressure development method, for example with photosensitive drum charging to a certain voltage, on photosensitive drums, form electrostatic latent image by the photolithography machine then, the developer roll that after this will be loaded with toner contact with the photosensitive drums that maintains sub-image with toner attached on the sub-image on the photosensitive drums.
In the superincumbent pressure development method, should make developer roll rotation guarantee to keep closure state simultaneously to photosensitive drums, so that it has such structure: the semiconduction elastic layer of being made by semiconductive elastic body or its foaming body are formed at by excellent conductive material outer the placing of the axle made such as metal for example, and this semiconductive elastic body for example obtains in polyurethane, silicon rubber, acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM), the epichlorohydrin rubber (ECO) etc. by carbon black or metal powder are dispersed in elastic body.For the adhesiveness of control charge characteristic or toner, prevent because the purpose of the pollution of the photosensitive drums of elastic layer etc. can also further form surface coating on the surface of elastic layer.
In recent years, use the imaging device of low melt toner to increase gradually along with the look processing in the imaging device, high speed performance, high quality graphic and energy-conservation improvement.When using low melt toner, this class toner is owing to repeatedly carry out compression between the component parts or reunion that friction causes toner, fusing etc. are damaged, so cause that easily bad imaging is for example hazed etc.That is, serviceable life of toner print cartridge at the end, damage toner and make charged characteristic inhomogeneous, so that cause the generation of bad imaging or the problem that shortens serviceable life.Therefore, need to damage hardly the soft developer roll of toner, and knownly wherein that base material (elastic layer) is softening developer roll (JP-A-2003-15404) is arranged and wherein pass through the mixed adipates compound as plastifier and the developer roll (JP-A-2005-128067) that coat film (surface coating) is softening.
On the other hand, when the soft developer roll is used for imaging device, such problem is arranged: the extruding owing to photosensitive drums, scraper plate, feed roller etc. causes vestige on developing roller surface easily.For this reason, need to provide the developer roll that not only has low hardness but also have low compression set in recent years.Yet the material with soft is tending towards increasing compression set, so that be very difficult to hardness and compression set are equilibrated at (referring to JP-A-H08-190263, JP-A-2001-75354 and JP-A-2004-67726) under the enough low degree.Equally, when use is mixed with coat film as the adipate compound of plastifier, this coat film deliquescing, but caused such problem: under high temperature, high humidity environment, caused compression set to become big in long-time the use and cause the toner fusing and in image, produced vertical striped.
Summary of the invention
Therefore, the developer roll that has low especially compression set and good anti-toner melting in the objective of the invention is to solve the problems referred to above of routine techniques and be provided at that high temperature, high humidity environment are long-time down to use.In addition, another object of the present invention provides and comprises this developer roll and can stably form superior images and the imaging device that can not cause that bad imaging is for example hazed etc.
In order to realize above purpose, the inventor has done various researchs and discovery: in having the developer roll of surface coating, in this surface coating, use and pass through the interior ester modified polyvalent alcohol and the urethane resin of multi isocyanate crosslinking acquisition, thereby make that the hardness of developer roll and compression set are sufficiently low and can damage toner hardly, anti-toner melting in long-time the use can also be improved under high temperature, high humidity environment, and excellent images can be stably formed by this developer roll being assembled in the imaging device further.
Promptly, developer roll according to the present invention is such developer roll: it comprises axle, is formed at the elastic layer that this is placed outward, with the surface coating on the peripheral surface that is formed at this elastic layer, wherein this surface coating comprises the urethane resin that forms by with interior ester modified polyvalent alcohol and multi isocyanate crosslinking.
In the preferred embodiment of developer roll of the present invention, interior ester modified polyvalent alcohol has number-average molecular weight (Mn) and is 1000-5000, it is no more than 2.5 for the number-average molecular weight that is converted into polystyrene measured by gel permeation chromatography with by the molecular weight distribution (Mw/Mn) of the weight-average molecular weight of measuring by gel permeation chromatography that is converted into polystyrene (Mw) and the ratio value representation of number-average molecular weight (Mn).
In another preferred embodiment of developer roll of the present invention, by interior ester modified polyvalent alcohol and at least two kinds of multi isocyanate crosslinkings are formed urethane resin.In this case, polyisocyanates preferably contains at least a of isocyanurate-modified hexamethylene diisocyanate or isophorone diisocyanate.
In another preferred embodiment of developer roll of the present invention, the mol ratio ([NCO]/[OH]) that interior ester modified polyvalent alcohol has isocyanate groups (NCO) Yu the hydroxyl (OH) of polyisocyanates is 1.0-2.5.
In another preferred embodiment of developer roll of the present invention, surface coating has storage modulus under 25 ℃ (E ') and is 3-50MPa.
In the further preferred embodiment of developer roll of the present invention, the thickness of surface coating is no more than 30 μ m.
In the further preferred embodiment of developer roll of the present invention, the urethane resin of surface coating has introduces structure in the resin matrix with the silicone with siloxane bond.In this case, urethane resin has such structure: will have siloxane bond and hydroxyl or amino silicone introducing carbamate moiety at its two ends.In addition, the number-average molecular weight that preferably is introduced into the silicone in the resin matrix is 500-10000.
In the further preferred embodiment of developer roll of the present invention, the urethane resin of surface coating is the propenoic methyl carbamate resin (acrylurethane resin) that forms by with interior ester modified polyvalent alcohol and multi isocyanate crosslinking.In this case, this propenoic methyl carbamate resin preferably has such structure: the silicone that has siloxane bond and methacryloxy at the one end is introduced into acrylate moiety.Further, ester modified polyvalent alcohol was introduced into the structure of carbamate moiety in this propenoic methyl carbamate resin preferably had.
In the further preferred embodiment of developer roll of the present invention, surface coating contains ester modified polyvalent alcohol in 5-35 mass parts carbon black/100 mass parts.
In the further preferred embodiment of developer roll of the present invention, surface coating further contains conductive agent.
In the further preferred embodiment of developer roll of the present invention, elastic layer is by making by the isocyanurate foam that adopts mechanical raking that the foaming of carbamate initiation material is obtained.In this case, the isocyanurate foam of composition elastic layer has closed pore.
In the further preferred embodiment of developer roll of the present invention, between as the isocyanurate foam of elastic layer and surface coating, form the inter coat of making by the mixed solution of polymkeric substance and aqueous solvent.
In the further preferred embodiment of developer roll of the present invention, this inter coat is made by acryl resin, urethane resin or rubber latex.
In the further preferred embodiment of developer roll of the present invention, the glass transition temperature of this inter coat is not higher than 10 ℃.
In the further preferred embodiment of developer roll of the present invention, this inter coat is made up of two-layer or multilayer.
In the further preferred embodiment of developer roll of the present invention, this inter coat further contains conductive agent.
In the further preferred embodiment of developer roll of the present invention, the gross thickness of inter coat and surface coating is no more than 100 μ m.
In the further preferred embodiment of developer roll of the present invention, 10 average surface roughness (Rz) of this roller are no more than 10 μ m.
In addition, image-forming apparatus according to the present invention is characterised in that and comprises above-mentioned developer roll.
According to the present invention,, can provide a kind of and under high temperature, high humidity environment, have low compression set and good anti-toner melting in long-time the use and can not pollute the developer roll of photosensitive drums and damage toner as surface coating by the urethane resin that will form by means of polyvalent alcohol ester modified in making and multi isocyanate crosslinking.The imaging device that comprises such developer roll and can stably form superior images can also be provided.
Description of drawings
The present invention is described with reference to the accompanying drawings, wherein:
Fig. 1 is the cross-sectional according to an embodiment of developer roll of the present invention;
Fig. 2 is the cross-sectional according to another embodiment of developer roll of the present invention;
Fig. 3 is the synoptic diagram shown in the part in the section of an embodiment of image-forming apparatus according to the present invention.
Embodiment
＜developer roll 〉
Elaborate with reference to the accompanying drawings according to developer roll of the present invention.Fig. 1 is the cross-sectional according to an embodiment of developer roll of the present invention.Shown developer roll 1 comprises: the surface coating 4 on axle 2, the peripheral surface that is formed at the axle 2 outer elastic layers of placing 3 and is formed at elastic layer 3.In shown embodiment, surface coating 4 is made up of one deck, but the surface coating 4 in developer roll according to the present invention can be made up of two-layer or multilayer.In developer roll according to the present invention, surface coating 4 is arranged in the outer of elastic layer 3 places, so can prevent fully because the polluter that leaches from elastic layer 3 pollutes photosensitive drums.
Axle in the developer roll of the present invention 2 is not particularly limited, but for example can comprise, metal such as iron, stainless steel, aluminium or its analog solid, the hollow cylinder oblique crank Z of metal, axle of good conductive plastics or the like.
Elastic layer 3 in the developer roll of the present invention is made by elastic body, and if necessary, and the component that then can contain other is conductive agent etc. for example.As the elastic body that is used for elastic layer 3, mention polyurethane, silicon rubber, ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber (NBR), natural rubber, styrene butadiene rubbers (SBR), butadiene rubber, isoprene rubber, poly-norbornene rubber, butyl rubber, chloroprene rubber, acrylic rubber, epichlorohydrin rubber (ECO), vinyl-vinyl acetate copolymer (EVA), its potpourri etc.In the middle of them, optimization polyurethane.Can be with elastomeric non-foaming body as elastic layer 3, but preferably by making the elastomer chemical foaming with gas-development agent or by using elastomeric foaming body as in the isocyanurate foam aero-mechanical being blown into etc.When elastic layer 3 was made by foaming body, preferred die swell ratio was in 1.1-30 scope doubly, and density is at 0.05-0.9g/cm
3Scope in.
Especially, preferably in elastic layer 3, use by adopting mechanical raking to make isocyanurate foam that the foaming of carbamate raw material obtains or the isocyanurate foam by the acquisition of mechanical foaming method.By wherein under the condition of not using gas-development agent, carbamate raw material mechanical raking being made isocyanurate foam with the method that bubble is mixed wherein.As the carbamate raw material, what mention is polyvalent alcohol and polyisocyanates or by polyvalent alcohol and the synthetic carbamate prepolymer of polyisocyanates, and can be further chain extender and catalyzer, foaming stabiliser, conductive agent etc. be joined in the carbamate raw material.And the bubble in the isocyanurate foam mainly is a closed pore, and can regulate die swell ratio and density aptly by the method that is blown into air.
As the polyvalent alcohol of the raw material that can be used as isocyanurate foam, mention polybutadiene polyol, polyisoprene polyvalent alcohol of polyester polyol, polyether polyol, polytetramethylene glycol, polybutadiene polyol, epoxypropane (PO) modification etc.In addition, polyester polyol is by polyvalent alcohol for example ethylene glycol, diglycol, 1,4-butylene glycol, 1,6-hexanediol, propylene glycol, trimethylolethane, trimethylolpropane etc. and for example acquisitions such as hexane diacid, glutaric acid, succinic acid, decanedioic acid, heptandioic acid, suberic acid of polybasic carboxylic acid.In addition, by for example oxirane, epoxypropane etc. join polyvalent alcohol and for example obtain polyether glycol in ethylene glycol, propylene glycol, the glycerine etc. with epoxyalkane.
Polyisocyanates as the raw material that can be used as isocyanurate foam, mention toluene diisocyanate (TDI), methyl diphenylene diisocyanate (MDI), rough methyl diphenylene diisocyanate (rough MDI), isophorone diisocyanate (IPDI), the methyl diphenylene diisocyanate of hydrogenation, the toluene diisocyanate, 1 of hydrogenation, hexamethylene-diisocyanate (HDI) and its isocyanurate-modified product, carbodiimide modified product or glycol modification product.The preferred amount of selecting employed polyisocyanates aptly is so that ratio (NCO/OH) scope of isocyanate groups of polyisocyanates (NCO) and hydroxyl groups (OH) is 95/100-110/100.
Can be by single stage method with polyisocyanates and polyol reaction, perhaps can with its in advance with polyol reaction to form carbamate prepolymer, then can be in the presence of catalyzer with reactions such as itself and chain extenders.In addition, the content of the NCO group in the synthetic carbamate prepolymer is preferably in the scope of 3-30 quality %, more preferably in the scope of 5-15 quality %, and preferably be chosen in the synthetic middle polyisocyanates that uses of carbamate prepolymer and the amount of polyvalent alcohol aptly, so that the content of the NCO group in the carbamate prepolymer is in the above scope.In addition, chain extender is the compound that carbamate prepolymer is connected with each other, and comprises ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, ethohexadiol, trimethylolpropane, polyether polyol, polytetramethylene glycol, polybutadiene polyol, polyisoprene polyvalent alcohol etc.The preferred amount of selecting employed chain extender aptly is so that ratio (NCO/OH) scope of the hydroxyl (OH) in isocyanate groups in the carbamate prepolymer (NCO) and the chain extender is 95/100-110/100.
The catalyzer that can be used as the raw material of isocyanurate foam is to be used for carbamate to form catalyst for reaction, and comprising: organo-tin compound is dibutyl tin laurate, dibutyltin diacetate, thiocarboxylic acid dibutyl tin, two maleic acid dibutyl tins, thiocarboxylic acid dioctyl tin, octenoic acid (octentate) tin etc. for example; Organo-lead compound is octene lead plumbate etc. for example; Monoamine is triethylamine, dimethyl cyclohexyl amine etc. for example; Diamines is tetramethylethylenediamine, 4-methyl-diaminopropane, 4-methyl hexamethylene diamine etc. for example; Triamine is five methyl diethylentriamine, pentamethyl dipropylenetriamine, tetramethyl guanidine etc. for example; Cyclammonium is triethylenediamine, lupetazin, Methylethyl piperazine, methyl morpholine, dimethylaminoethyl morpholine, methylimidazole etc. for example; Hydramine is dimethylaminoethanol, dimethylamino ethoxy ethanol, trimethyl amino ethyl ethanolamine, dimethyl hydroxyethyl piperazine, hydroxyethyl morpholine etc. for example; For example two (dimethylaminoethyl) ethers of ether amine, ethylene glycol bis (dimethyl) aminopropyl ether etc., or the like.In the middle of them, preferably have machine tin compound.These catalyzer can be separately or being used in combination with two or more.The amount of employed catalyzer is preferably based on per 100 mass parts polyvalent alcohols or carbamate prepolymer in 0.001-2.0 mass parts scope.
Except for example polyether-modified silicone oil of the foaming stabiliser of silicone base etc., the foaming stabiliser that can be used as the raw material of isocyanurate foam can also comprise anionic surfactant, non-ionic surfactant etc.The amount of employed foaming stabiliser is preferably based on 100 mass parts polyvalent alcohols or carbamate prepolymer in the scope of 0.5-5 mass parts.
The conductive agent that can be used in the elastic layer 3 comprises electronic conduction agent, ionic conductive agent etc.As the electronic conduction agent, mention conductive black, for example Ketjenblack, acetylene black etc.; Rubber black such as SAF, ISAF, HAF, FEF, GPF, SRF, FT, MT; Carry out tin oxide, ITO that the carbon black that is used for painted carbon black, thermal decomposition, native graphite, Delanium, antimony of oxidation processes mix; Metal oxide is tin oxide, titanium dioxide, zinc paste etc. for example; Metal is nickel, copper, silver, germanium etc. for example; Conducting polymer is polyaniline, polypyrrole, polyacetylene etc. for example; Conductive whiskers is carbon whisker, graphite whisker, titanium carbide crystal whisker, conduction potassium titanate crystal whisker, conduction barium titanate whisker, conductive titanium oxide whisker, conductive zinc oxide whisker etc. for example; Or the like.It is the 1-50 mass parts that the amount of the electronic conduction agent that mixes is preferably based on per 100 mass parts elastic bodys, more preferably the 5-40 mass parts.
As ionic conductive agent, what mention is: the perchlorate of the fatty acid dimethyl second ammonium of etamon, tetrabutylammonium, dodecyl trimethylammonium, cetyl trimethylammonium, benzyl trimethylammonium, modification etc., chlorate, hydrochloride, bromate, iodate, borofluoride, sulfate, sulfovinate, carboxylate, sulfonate etc.; Alkaline metal or earth alkali metal be the perchlorate, chlorate, hydrochloride, bromate, iodate, borofluoride, sulfate, trifluoromethyl sulfate, sulfonate etc. of lithium, sodium, potassium, calcium, magnesium etc. for example.It is the 0.01-10 mass parts that the amount of the ionic conductive agent of compounding is preferably based on per 100 mass parts elastic bodys, more preferably the 0.05-5 mass parts.These conductive agents can be separately or with two or more combination, perhaps being used in combination with electronic conduction agent and ionic conductive agent.
By the compounding conductive agent, elastic layer 3 preferably has 10
3-10
10Ω cm, preferred 10
4-10
8The resistance value of Ω cm.When the resistance value of elastic layer 3 less than 10
3During Ω cm, electric charge may leak into that photosensitive drums etc. goes up or developer roll itself may be damaged by voltage, and surpasses 10 when it
10During Ω cm, cause easily and haze.
For the purpose that elastic body is become rubber-like substance, if necessary, elastic layer 3 can contain for example organic peroxide etc. and vulcanizing agent sulphur etc. for example of crosslinking chemical, and can further contain vulcanization aid, vulcanization accelerator, enhancer activator, anti scorching agent etc.Equally, elastic layer 3 can comprise the compounding component that is used for rubber, for example filler, peptizer, frothing agent, plastifier, softening agent, tackifier, detackifier, release agent, swelling agent, colorant etc.
In developer roll according to the present invention, surface coating 4 is characterised in that and comprises the urethane resin that forms by with interior ester modified polyvalent alcohol and multi isocyanate crosslinking.Because surface coating 4 comprises above-mentioned urethane resin, therefore reduced the hardness of developer roll, and can further reduce compression set to form superior images so that can not damage toner.
Developing roller surface coating 4 of the present invention mainly comprises the urethane resin that forms by with interior ester modified polyvalent alcohol and multi isocyanate crosslinking, and if necessary, and the component that then can comprise other is conductive agent etc. for example.In ester modified polyvalent alcohol can by with lactone for example 6-caprolactone etc. the terminal-modified of polyvalent alcohol made, and also can use a commercially available class.In the present invention, interior ester modified polyvalent alcohol preferably has number-average molecular weight (Mn) 1000-5000, it is no more than 2.5 for the number-average molecular weight that is converted into polystyrene measured by gel permeation chromatography with by the molecular weight distribution (Mw/Mn) of the weight-average molecular weight of measuring by gel permeation chromatography that is converted into polystyrene (Mw) and the ratio value representation of number-average molecular weight (Mn).When the number-average molecular weight (Mn) of interior ester modified polyvalent alcohol less than 1000 the time, in under high temperature, high humidity environment, using for a long time, the hardness of developer roll increases and may cause the worry of anti-toner melting deterioration, and when it surpassed 5000, degree of crosslinking reduced and may cause the worry that increases compression set.In addition, when molecular weight distribution (Mw/Mn) surpassed 2.5, compression set increased, anti-toner melting deterioration and causing easily hazes.From setting up the viewpoint of low compression set and good anti-toner melting simultaneously, the number-average molecular weight (Mn) of interior ester modified polyvalent alcohol is preferably 1000-3000, and molecular weight distribution (Mw/Mn) preferably is no more than 2.0.In addition, interior ester modified polyvalent alcohol preferably has and is not less than 500, preferably is not less than 1000 weight-average molecular weight (Mw).
As mentioning with interior ester modified polyvalent alcohol: by the alkylene oxide for example polyether polyol that obtains of the addition polymerization of oxirane, epoxypropane etc. and glycerine etc., polytetramethylene glycol, glycerine, ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, ethohexadiol, polybutadiene polyol, polyisoprene polyvalent alcohol, polyester polyol etc.
As polyisocyanates with interior ester modified polyol crosslink, mention: toluene diisocyanate (TDI), methyl diphenylene diisocyanate (MDI), rough methyl diphenylene diisocyanate (rough MDI), isophorone diisocyanate (IPDI), the methyl diphenylene diisocyanate of hydrogenation, the toluene diisocyanate, 1 of hydrogenation, hexamethylene-diisocyanate (HDI), isocyanurate-modified hexamethylene diisocyanate etc.These polyisocyanates can use separately, but preferably use the combination of two or more polyisocyanates.In addition, from surface coating, setting up the viewpoint of low hardness and low compression set simultaneously, preferably be used for polyisocyanates of the present invention and comprise at least a of isocyanurate-modified hexamethylene diisocyanate and isophorone diisocyanate.
Surface coating 4 can further comprise and be used to promote the interior ester modified polyvalent alcohol and the catalyzer of the cross-linking reaction between the polyisocyanates.As catalyzer, can mention: organo-tin compound is dibutyl tin laurate, dibutyltin diacetate, thiocarboxylic acid dibutyl tin, two maleic acid dibutyl tins, carboxylic acid dioctyl tin, tin octoate etc. for example; Organo-lead compound is lead octoate etc. for example; Monoamine is triethylamine, dimethyl cyclohexyl amine etc. for example; Diamines is tetramethylethylenediamine, 4-methyl-diaminopropane, 4-methyl hexamethylene diamine etc. for example; Triamine is five methyl diethylentriamine, pentamethyl dipropylenetriamine, tetramethyl guanidine etc. for example; Cyclammonium is triethylenediamine, lupetazin, methyl morpholine, dimethylaminoethyl morpholine, methylimidazole etc. for example; Hydramine is dimethylaminoethanol, dimethylamino ethoxy ethanol, trimethyl amino ethyl ethanolamine, dimethyl hydroxyethyl piperazine, hydroxyethyl morpholine etc. for example; For example two (dimethylaminoethyl) ethers of ether amine, ethylene glycol bis (dimethyl) aminopropyl ether etc., or the like.In the middle of these catalyzer, preferably have machine tin compound.These catalyzer can be separately or with two kinds or more of being used in combination.The amount of the catalyzer that uses is preferably based on polyvalent alcohol ester modified in per 100 mass parts in the scope of 0.001-2.0 mass parts.
In the present invention, from the viewpoint that prevents that photoreceptor from avoiding polluting under high temperature and high humidity, preferably the isocyanate groups of isocyanate compound (NCO) is 1.0-2.5, more preferably 1.2-2.0 with the mol ratio ([NCO]/[OH]) of interior ester modified hydroxyl groups (OH).
Purpose for control electric conductivity can cooperate surface coating 4 with conductive agent.As conductive agent, can mention with elastic layer 3 in employed identical conductive agent.Under the situation of ionic conductive agent, the amount that is blended in the conductive agent in the surface coating 4 is preferably based on the urethane resin that 100 mass parts are formed surface coating 4, be no more than 20 mass parts, more preferably 0.01-20 mass parts, further preferred 1-10 mass parts, and the urethane resin that is preferably based on per 100 mass parts composition surface coating 4 under the situation of electronic conduction agent is the 1-70 mass parts, more preferably the 5-50 mass parts.In the present invention, from the viewpoint of the stability of electric conductivity under various environment with carbon black as conductive agent, wherein to be preferably based on the interior ester modified polyvalent alcohol of per 100 mass parts be the 5-35 mass parts to the amount of the carbon black of Hun Heing, more preferably the 10-30 mass parts.In surface coating 4, preferably the volume resistance value is adjusted to 10 by adding conductive agent
3-10
10Ω cm, preferred 10
4-10
8The scope of Ω cm.
In the present invention, from making the hardness of surface coating low to prevent to damage the viewpoint of toner, the storage modulus of surface coating 4 under 25 ℃ is preferably 3-50MPa, more preferably 5-40MPa.
The thickness of surface coating 4 is not particularly limited, but preferably is no more than 30 μ m, more preferably 1-15 μ m.When the thickness of surface coating 4 surpasses 30 μ m, surface coating 4 becomes harder and has destroyed flexibility, permanance is deterioration and cause cracking and such worry arranged also: toner is destroyed and cause toner attached on photosensitive drums or the stratification scraper plate, causes bad imaging thus.
As the urethane resin that is used for surface coating 4, can use the propenoic methyl carbamate resin.In this case, the silicone with siloxane bond can be introduced carbamate moiety and/or acrylate moiety.As the silicone in the carbamate moiety that is introduced in urethane resin and/or propenoic methyl carbamate resin, preferably have siloxane bond and hydroxyl or amino silicone at its two ends, as the silicone in the acrylate moiety that is introduced in the propenoic methyl carbamate resin, preferably has the silicone of siloxane bond and methacryloxy at the one end.Equally, the silicone that is introduced in the resin matrix of urethane resin and/or propenoic methyl carbamate resin preferably has number-average molecular weight (Mn) 500-10,000.In addition, the content preferable range that has the silicone of siloxane bond in urethane resin and propenoic methyl carbamate resin is 5-40 quality %.When the content of silicone during less than 5 quality %, the frictional resistance that reduces surface coating 4 diminishes with the effect of the sliding capability that improves developer roll, and when its during above 40 quality %, it is higher that cost becomes.
The propenoic methyl carbamate resin can have the keyed jointing of block type or graft type between carbamate moiety and acrylate moiety, but preferably acrylate moiety is bonded to as the class on the carbamate moiety of main chain as side chain.Can produce the propenoic methyl carbamate resin in the following manner: hydroxyl is introduced acrylate copolymer polymkeric substance that forms and the carbamate prepolymer reaction that has isocyanate groups in its molecular end by adopting (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester etc., perhaps by in the presence of superoxide, the carbamate prepolymer that will have sulfydryl on its end or side chain carries out free radical polymerization with (methyl) acrylate.Under latter event, sulfydryl generates free radical by superoxide, and (methyl) acrylate carries out free radical polymerization at the free radical place as basic point.In the present invention, have siloxane bond and hydroxyl or the amino synthetic carbamate prepolymer of silicone by using by interior ester modified polyvalent alcohol, polyisocyanates with at its two ends, ester modified polyvalent alcohol and silicone with siloxane bond are introduced into the propenoic methyl carbamate resin of carbamate moiety in having obtained wherein.Equally, by using the silicone that has siloxane bond and methacryloxy at the one end, the silicone that has obtained to have siloxane bond is introduced into the propenoic methyl carbamate resin of acrylate moiety in aforesaid propylene acid polymer synthetic.On the other hand, can be for example have siloxane bond and hydroxyl by interior ester modified polyvalent alcohol, polyisocyanates with at its two ends or amino silicone makes urethane resin.In developer roll according to the present invention, can use the urethane resin and/or the propenoic methyl carbamate resin that obtain by the method except above method.
As the acrylate component of propenoic methyl carbamate resin, mention (methyl) acrylate for example (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) isobutyl acrylate, (methyl) n-butyl acrylate, (methyl) glycidyl acrylate etc.In the propenoic methyl carbamate resin, in this resin the content of acrylate moiety preferably in the scope of 5-80 quality %, the more preferably scope of 10-60 quality %, the scope of further preferred 20-50 quality %.
The method that forms surface coating 4 is not particularly limited, but preferably adopts such method: wherein preparation comprise the coating composition of the surface coating 4 of various ingredients, by dip coating, spraying process or rolling method coating, dry then.
Especially, when elastic layer 3 was made up of isocyanurate foam, if the coating composition coating of raw material that will comprise surface coating 4 is to form surface coating 4, then elastic layer 3 may be by dissolution with solvents in the coating composition or swelling.In order to prevent elastic layer dissolving or swelling, preferably between elastic layer and surface coating, arrange inter coat.Figure 2 illustrates the cross-sectional that is provided with such inter coat according to an embodiment of developer roll of the present invention.Shown developer roll 1 comprises: axle 2, be formed at axle 2 outer elastic layers 3 of placing, be formed at the inter coat 5 on elastic layer 3 peripheral surface and be formed at surface coating 4 on inter coat 5 peripheral surface.In shown embodiment, each of inter coat 5 and surface coating 4 is made up of one deck, but inter coat 5 in developer roll according to the present invention and each of surface coating 4 can be made up of two-layer or multilayer.In developer roll according to the present invention, inter coat 5 and surface coating 4 are arranged in the outer of elastic layer 3 place, so that can prevent fully because the polluter that leaches from elastic layer 3 pollutes photosensitive drums.Equally, never damage the viewpoint of the flexibility of elastic layer 3 and set out, the gross thickness of inter coat 5 and surface coating 4 preferably is no more than 100 μ m.
Inter coat 5 in the developer roll of the present invention is made by the mixed solution of polymkeric substance and aqueous solvent.As polymkeric substance, can use resin and rubber, as long as they can be dissolved or dispersed in the water.In addition, inter coat 5 preferably has glass transition temperature that is not higher than 10 ℃ and the thickness that is no more than 100 μ m.
When the polymkeric substance that is used to form inter coat 5 is resin, can be for example by preparation comprise resin and water mixed solution, by dip coating or spraying process mixed solution is applied on the elastic layer 3, drying forms this inter coat 5 then.As the resin that is used for inter coat 5, preferably aqueous resins.This aqueous resins can be for example water-soluble type of any kind, emulsion type, suspending liquid type etc., and preferably has for example aqueous resins of carboxyl, hydroxyl, amino etc. of reactive hydrogen.As aqueous resins, mention the resin for example acryl resin, urethane resin, vibrin, the polydioxorane etc. that dissolve in warm water.In the middle of them, preferred acrylic resins and urethane resin.Acryl resin is not particularly limited, and is not higher than 10 ℃ glass transition temperature but preferably have.As acryl resin, have thermoplastic-type and crosslink type for example self-crosslinking, that melamine is crosslinked, isocyanate-crosslinked or the like, but can use any kind, as long as they have the glass transition temperature of above-mentioned scope, and in view of the step of formation coated film and hardness and the preferred thermoplastic type.
On the other hand, when the polymkeric substance that is used to form inter coat 5 is rubber, can for example form inter coat in the following manner: rubber latex is coated on the elastic layer 3 by dip coating etc., then with coagulating agent with latex coagulation, perhaps on elastic layer 3, form the layer of coagulating agent by dip coating etc., then the rubber latex coating is solidified thereon and with it, or the like.As the rubber components that is used for inter coat 5, what mention is Styrene-Butadiene rubber, natural rubber etc.In solidifying, preferred use by with coagulating agent for example Kolatex 93 (trade name, by Kawaguchi Kagaku Kogyo Co., Ltd. produces) etc. be dissolved in the acid solution that forms in water or the methyl alcohol.By between alkali latex and acid solution, causing Acid-Base reaction with latex gelation and solidify.In the inter coat 5 that forms by rubber latex, the cleaning step that can be used to remove the drying steps of the water that produces by the Acid-Base reaction aptly or be used to remove the salt that produces by the Acid-Base reaction.
Can be by identical with elastic layer 3 such electric conductivity that conductive agent is regulated inter coat 5 that adds.In this case, add conductive agent so that the specific insulation scope of inter coat 5 is 10
3-10
10Ω cm, preferred 10
4-10
8Ω cm.As the conductive agent that is added to inter coat 5, can exemplify and the identical conduction agent of in the raw material of the isocyanurate foam of forming elastic layer 3, using.It is the 0.1-20 mass parts that the amount of the conductive agent of adding inter coat 5 is preferably based on per 100 mass parts polymkeric substance, more preferably the 1-10 mass parts.
If necessary, can for example thickening agent, thixotropic agent, structural viscosity modifier etc. join in the inter coat 5 with an amount of adjuvant.
The surfaceness that preferably has as 10 mean roughness (Rz) according to developer roll of the present invention is no more than 10 μ m.When 10 mean roughness (Rz) of developer roll surpass 10 μ m, such trend is arranged: the operational throughput of toner increases, but the carried charge deficiency of toner, therefore in image, caused haze or calibration (graduation) bad.
Resistance value according to developer roll of the present invention is not particularly limited, but the resistance that is used to obtain superior images is preferably 10
3-10
10Ω, more preferably 10
4-10
8Ω.When the resistance value of developer roll less than 10
3During Ω, quite be difficult to control calibration, and if in photosensitive drums, have defective, then may cause bias voltage to leak (bias leak).Simultaneously, surpass 10 when resistance value
10During Ω, if toner develops on photosensitive drums, then the high resistance owing to developer roll causes the voltage of development bias voltage to descend, and therefore can not guarantee the development bias voltage that is enough to develop and can not obtain gratifying imaging concentration.In addition, when the peripheral surface with developer roll be pushed to flat or columniform comparative electrode on and when between axle and this comparative electrode, applying the voltage of 100V, can be by the current value measured resistance value.Therefore, by evenly controlling the resistance value of developer roll aptly, can be fully and be kept for electric field intensity that toner is moved equably.
Preferably has the Asker C hardness that is no more than 60 ° according to developer roll of the present invention.In the time will having Asker C hardness and be no more than 60 ° soft developer roll and be assembled in the imaging device, between developer roll, photosensitive drums, scraper plate, toner feed roller etc., prevented the damage of toner, can form enough excellent images thus.
＜imaging device 〉
Image-forming apparatus according to the present invention is characterised in that and comprises above-mentioned developer roll, this developer roll has low compression set and photosensitive drums is polluted and the toner damage, and can stably form superior images and can not cause that bad imaging is for example hazed etc.Except using above-mentioned developer roll, this imaging device is not particularly limited, and can pass through very known method manufacturing.
Describe image-forming apparatus according to the present invention below with reference to accompanying drawings in detail.Fig. 3 is the fragmentary cross-sectional view of an embodiment of image-forming apparatus according to the present invention.Shown imaging device comprises: be used for supplying with toner 6 toner feed roller 7, keep electrostatic latent image photosensitive drums 8, be arranged on above-mentioned developer roll 1 between toner feed roller 7 and the photosensitive drums 8, be arranged near the developer roll 1 stratification scraper plate 9 (top of figure), be arranged near the photosensitive drums 8 charging roller 10 (top of figure), be arranged near the transfer roll 11 (bottom of figure) the photosensitive drums 8 and be arranged near the cleaning section 12 of photosensitive drums 8.In addition, image-forming apparatus according to the present invention can further be provided with the well-known components (not shown) that is generally used for imaging device.
In shown imaging device, by charging roller 10 with photosensitive drum charging to constant voltage, after this on photosensitive drums 8, form electrostatic latent image by the photoprinter (not shown).Then, by making toner feed roller 7, developer roll 1 and photosensitive drums 8 with direction of arrow rotation, the toner 6 that will be present on the toner feed roller 7 is transferred to photosensitive drums 8 by developer roll 1.By stratification scraper plate 9 toner on the developer roll 16 is arranged in uniform thin layer, by 8 rotations of developer roll 1 and photosensitive drums being contacted with each other simultaneously make on toner 6 is attached to electrostatic latent image on the photosensitive drums 8 from developer roll 1, manifests sub-image thus then.To transfer to recording medium for example on the paper etc. attached to the toner on the sub-image 6 by transfer roll 11, after transfer printing, remove simultaneously by the toner 6 that the cleaning balde in the cleaning section 12 13 will be retained on the photosensitive drums 8.In image-forming apparatus according to the present invention, by will according to of the present invention, have low compression set and can not make photosensitive drums is polluted and toner damages developer roll as developer roll 1, can stably form excellent images.
Provide following examples with explanation the present invention, and be not used in restriction the present invention.
(preparation of roll body)
By with 100 mass parts by the synthetic carbamate prepolymer of toluene diisocyanate (TDI) and polyether glycol mix with 2 mass parts acetylene blacks prepare wherein be dispersed with acetylene black carbamate prepolymer as component A.On the other hand, with 30 mass parts polyether glycols and 0.1 mass parts sodium perchlorate (NaClO
4) mix simultaneously 70 ℃ of heating down, and the silicone oil that it is further polyether-modified with 4.5 mass parts (foaming stabiliser) and 0.2 mass parts dibutyl tin laurate (catalyzer) mix with the formation potpourri as B component.Subsequently, with the foaming of component A and B component and be poured in the cylindrical mold of wherein placing core, carry out the RIM moulding then by the mechanical foaming method to make the roll body that comprises the elastic layer of making by isocyanurate foam.
(embodiment 1)
By polyvalent alcohol (PCL205 with 100 mass parts caprolactone modification, by DaicelChemical Industries, Ltd. produce, 500), HDI (the Coronate HX of 35 mass parts carbon blacks and 50 mass parts cyanurate modifications molecular weight:, by NipponPolyurethane Industry Co., Ltd. produces) be distributed in the 300 mass parts MEKs (MEK) and preparation is used for the coating composition of surface coating.Thus obtained coating composition is coated on the outer of roll body with elastic layer of being made by isocyanurate foam places, make developer roll thus to form surface coating.Then, estimate roller resistance, 10 mean roughness (Rz), Asker C hardness and the toner charging performance of thus obtained developer roll by known method.In addition, estimate imaging performance by developer roll being assembled in the laser printer to print.Also be assembled in developer roll in the print cartridge and remain under the environment of 50 ℃ and 90%RH, measure the existence of polluting on the photosensitive drums subsequently or do not exist and on developer roll because the existence of scraper plate extruding vestige or do not exist.The results are shown in the table 1.
(embodiment 2)
By polyvalent alcohol (PCL210N with 100 mass parts caprolactone modification, by DaicelChemical Industries, Ltd. produce, 1000), HDI (the Coronate HX of 35 mass parts carbon blacks and 50 mass parts cyanurate modifications molecular weight:, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using thus obtained coating composition to replace the coating composition of preparation in embodiment 1 to prepare developer roll, estimate then.The results are shown in the table 1.
(embodiment 3)
By polyvalent alcohol (PCL220 with 100 mass parts caprolactone modification, by DaicelChemical Industries, Ltd. produce, 2000), HDI (the Coronate HX of 35 mass parts carbon blacks and 50 mass parts cyanurate modifications molecular weight:, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using thus obtained coating composition to replace the coating composition of preparation in embodiment 1 to prepare developer roll, estimate then.The results are shown in the table 1.
(embodiment 4)
By polyvalent alcohol (PCL312 with 100 mass parts caprolactone modification, by DaicelChemical Industries, Ltd. produce, 1200), HDI (the Coronate HX of 35 mass parts carbon blacks and 50 mass parts cyanurate modifications molecular weight:, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using thus obtained coating composition to replace the coating composition of preparation in embodiment 1 to prepare developer roll, estimate then.The results are shown in the table 1.
(comparative example 1)
By polyurethane paint (N5196 with 100 mass parts PCDL modifications, by Nippon Polyurethane Industry Co., Ltd. production), HDI (the Coronate HX of 35 mass parts carbon blacks and 50 mass parts cyanurate modifications, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using thus obtained coating composition to replace the coating composition of preparation in embodiment 1 to prepare developer roll, estimate then.The results are shown in the table 1.
(comparative example 2)
By polyurethane paint (N3126 with 100 mass parts hexane diacid modifications, by NipponPolyurethane Industry Co., Ltd. production), HDI (the Coronate HX of 35 mass parts carbon blacks and 50 mass parts cyanurate modifications, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using thus obtained coating composition to replace the coating composition of preparation in embodiment 1 to prepare developer roll, estimate then.The results are shown in the table 1.
Table 1
| Embodiment | Comparative example | ||||||
| 1 | 2 | 3 | 4 | 1 | 2 | ||
| Elastic layer | Resin | Polyurethane foam | Polyurethane foam | Polyurethane foam | Polyurethane foam | Polyurethane foam | Polyurethane foam |
| Performance number | Roller resistance (Ω/100V) | 2.5×10 6 | 3.7×10 6 | 4.2×10 6 | 3.5×10 6 | 3.9×10 6 | 2.6×10 6 |
| Rz(μm) | 5.4 | 5.2 | 6.1 | 5.7 | 5.9 | 6.5 | |
| Hardness (Asker C) | 62 | 53 | 55 | 49.2 | 48.6 | 48.8 | |
| The toner chargeding performance | ○ | ○ | ○ | ○ | ○ | ○ | |
| Imaging performance | Imaging concentration | ○ | ○ | ○ | ○ | ○ | ○ |
| Haze | ○ | ○ | ○ | ○ | △ | △ | |
| Shadow tone is inhomogeneous | ○ | ○ | ○ | ○ | Inhomogeneous a little | Inhomogeneous | |
| The stain resistance of photosensitive drums | Under 50 ℃ and 99%RH, kept for 1 week | ○ | ○ | ○ | ○ | △ | ○ |
| Scratch resistance plate extruding vestige | ○ | ○ | ○ | ○ | × | × | |
Zero: good, △: poor slightly, *: poor
As seen from Table 1, because photosensitive drums is not contaminated, compression set is low, do not cause because the extruding vestige of scraper plate and little to the damage of toner, therefore developer roll can stably form superior images according to an embodiment of the invention.
(embodiment 5)
By with polyvalent alcohol (PCL210N ester modified in 100 mass parts, by DaicelChemical Industries, Ltd. produce, Mn=1000, Mw/Mn=1.7), 30 mass parts carbon blacks and 10 mass parts carbamate particle (Artpearl C800, by Negami Kogyo Co., Ltd. produce, mean grain size: 8.8 μ m) be distributed in the 500 mass parts MEKs (MEK), isocyanate curing agent (the Coronate HX that adds 40 mass parts ([NCO]/[OH] mol ratio=1.0), by NipponPolyurethane Industry Co., Ltd. produce, NCO%=21%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.Thus obtained coating composition is coated on the outer of roll body with elastic layer of being made by isocyanurate foam places, make developer roll thus to form surface coating.
(embodiment 6)
By with polyvalent alcohol (PCL230 ester modified in 100 mass parts, by DaicelChemical Industries, Ltd. produce, Mn=3000, Mw/Mn=2.1), (MX 1000 for 30 mass parts carbon blacks and 10 mass parts carbamate particles, by SokenKagaku Kogyo Co., Ltd. produce, mean grain size: 10.0 μ m) be distributed among the 500 mass parts MEK, add 15 mass parts ([NCO]/[OH] mol ratio=1.0) isocyanate curing agent (Coronate HX, by Nippon Polyurethane IndustryCo., Ltd. produces, NCO%=21%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(embodiment 7)
By with polyvalent alcohol ester modified in the 100 mass parts (PCL250B of test, by Daicel Chemical Industries, Ltd. produce, Mn=5000, Mw/Mn=2.3), 30 mass parts carbon blacks and 10 mass parts carbamate particle (Artpearl C800, by Negami Kogyo Co., Ltd. produce, mean grain size: 8.8 μ m) be distributed among the 500 mass parts MEK, isocyanate curing agent (the Coronate HX that adds 8 mass parts ([NCO]/[OH] mol ratio=1.0), by Nippon Polyurethane IndustryCo., Ltd. produce, NCO%=21%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(embodiment 8)
By with polyvalent alcohol ester modified in the 100 mass parts (PCL250B of test, by Daicel Chemical Industries, Ltd. produce, Mn=5000, Mw/Mn=2.3), 30 mass parts carbon blacks and 10 mass parts carbamate particle (VernocCFB101-40, by Dainippon Ink and Chemicals, Inc. produce, mean grain size: 14 μ m) be distributed among the 500 mass parts MEK, isocyanate curing agent (the Coronate HX that adds 20 mass parts ([NCO]/[OH] mol ratio=2.5), by Nippon Polyurethane Industry Co., Ltd. produce, NCO%=21%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(embodiment 9)
By with polyvalent alcohol (PCL210N ester modified in 100 mass parts, by DaicelChemical Industries, Ltd. produce, Mn=1000, Mw/Mn=1.7), 30 mass parts carbon blacks and 10 mass parts carbamate particle (Artpearl C800, by Negami Kogyo Co., Ltd. produce, mean grain size: 8.8 μ m) be distributed among the 500 mass parts MEK, (D-140N is by Mitsui Takeda Chemicals to add the isocyanate curing agent of 80 mass parts ([NCO]/[OH] mol ratio=1.0), Co., Ltd. produce, NCO%=10.5%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(embodiment 10)
By with polyvalent alcohol (PCL230 ester modified in 100 mass parts, by DaicelChemical Industries, Ltd. produce, Mn=3000, Mw/Mn=2.1), 30 mass parts carbon blacks and 10 mass parts carbamate particle (MX1000, by SokenKagaku Kogyo Co., Ltd. produce, mean grain size: 10.0 μ m) be distributed among the 500 mass parts MEK, (D-140N is by Mitsui Takeda Chemicals to add the isocyanate curing agent of 30 mass parts ([NCO]/[OH] mol ratio=1.0), Co., Ltd. produce, NCO%=10.5%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(embodiment 11)
By with polyvalent alcohol ester modified in the 100 mass parts (PCL250B of test, by Daicel Chemical Industries, Ltd. produce, Mn=5000, Mw/Mn=2.3), 30 mass parts carbon blacks and 10 mass parts carbamate particle (Artpearl C800, by Negami Kogyo Co., Ltd. produce, mean grain size: 8.8 μ m) be distributed among the 500 mass parts MEK, (D-140N is by Mitsui Takeda Chemicals to add the isocyanate curing agent of 16 mass parts ([NCO]/[OH] mol ratio=1.0), Co., Ltd. produce, NCO%=10.5%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(embodiment 12)
By with polyvalent alcohol ester modified in the 100 mass parts (PCL250B of test, by Daicel Chemical Industries, Ltd. produce, Mn=5000, Mw/Mn=2.3), 30 mass parts carbon blacks and 10 mass parts carbamate particle (VernocCFB101-40, by Dainippon Ink and Chemicals, Inc. produce, mean grain size: 14 μ m) be distributed among the 500 mass parts MEK, isocyanate curing agent (the D-140N that adds 40 mass parts ([NCO]/[OH] mol ratio=2.5), by Mitsui Takeda Chemicals, Co., Ltd. produce, NCO%=10.5%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(embodiment 13)
By with polyvalent alcohol ester modified in the 100 mass parts (PCL210 of test, by Daicel Chemical Industries, Ltd. produce, Mn=1000, Mw/Mn=1.9), 30 mass parts carbon blacks and 10 mass parts carbamate particle (Artpearl C800, by Negami Kogyo Co., Ltd. produce, mean grain size: 8.8 μ m) be distributed among the 500 mass parts MEK, isocyanate curing agent (the Coronate HX that adds 108 mass parts ([NCO]/[OH] mol ratio=2.5), by Nippon PolyurethaneIndustry Co., Ltd. produce, NCO%=21%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(embodiment 14)
By with the carbamate emulsion coatings (E4000 of test, by Dai-ichiKogyo Seiyaku Co., Ltd. produce) be coated on the outer of roll body as inter coat with the thickness of 70 μ m and place with elastic layer of making by isocyanurate foam, the coating composition coating with embodiment 5 prepares developer roll to form surface coating thereon then.
(comparative example 3)
By with the polyvalent alcohol (P-2010 of 100 mass parts based on adipate, by Kuraray Co., Ltd. produce, Mn=2000, Mw/Mn=2.2), 30 mass parts carbon blacks and 10 mass parts carbamate particle (Artpearl C800, by NegamiKogyo Co., Ltd. produce, mean grain size: 8.8 μ m) be distributed among the 500 mass parts MEK, add 30 mass parts ([NCO]/[OH] mol ratio=1.5) isocyanate curing agent (Coronate HX, by Nippon Polyurethane Industry Co., Ltd. produces, NCO%=21%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(comparative example 4)
By with polyvalent alcohol (PCL205 ester modified in 100 mass parts, by DaicelChemical Industries, Ltd. produce, Mn=500, Mw/Mn=1.6), 30 mass parts carbon blacks and 10 mass parts carbamate particle (Vernoc CFB101-40, by Dainippon Ink and Chemicals, Inc. produce, mean grain size: 14 μ m) be distributed among the 500 mass parts MEK, isocyanate curing agent (the Coronate HX that adds 120 mass parts ([NCO]/[OH] mol ratio=1.5), by Nippon PolyurethaneIndustry Co., Ltd. produce, NCO%=21%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
(comparative example 5)
By with polyvalent alcohol ester modified in the 100 mass parts (PCL220B of test, by Daicel Chemical Industries, Ltd. produce, Mn=2000, Mw/Mn=2.8), 30 mass parts carbon blacks and 10 mass parts carbamate particle (Artpearl C800, by Negami Kogyo Co., Ltd. produce, mean grain size: 8.8 μ m) be distributed among the 500 mass parts MEK, isocyanate curing agent (the Coronate HX that adds 30 mass parts ([NCO]/[OH] mol ratio=1.5), by Nippon Polyurethane IndustryCo., Ltd. produce, NCO%=21%), preparation is used for the coating composition of surface coating with stirring the motor stirring 30 minutes then.By using thus obtained coating composition to replace the coating composition of embodiment 5 to prepare developer roll.
With regard to the developer roll of these embodiment and comparative example, the performance of the performance of surface measurements coating, developer roll and imaging performance by the following method.The evaluation result of these embodiment and comparative example is shown in Table 2.
(1) number-average molecular weight (Mn) and molecular weight distribution
Calculate the number-average molecular weight (Mn) and the molecular weight distribution of the polyvalent alcohol that is used to form each coating composition based on monodispersed polystyrene sample by gel permeation chromatography (GPC).
(2) storage modulus
Making the developing roller surface coating material composition molding of each embodiment and comparative example by rolling process is film, and by heating 1 hour under 100 ℃ after solvent is fully evaporated it is solidify to form the coat film of 0.3mm.After this, by width film is set and forms measuring samples with 6mm.Measure storage modulus in the following manner: at the dynamic viscoelastic device of model DDV-01FP (by A﹠amp; D Corp. makes) in sample be fixed between the chuck apart under the 30mm, and in frequency: 10Hz, strain: heating rate 1%: 5 ℃/min and temperature range: carry out the measurement of stretch mode under-50 ℃ to 80 ℃ the condition.In this case, E ' (25 ℃) is illustrated in the storage modulus under 25 ℃.
(3) roller resistance
Following measuring roller resistance.That is,, between axle and this comparative electrode, apply the voltage of 100V, by its current value measuring roller resistance under the pressure of 1kg the peripheral surface of developer roll being pushed on the columniform comparative electrode.
(4) surfaceness
Estimate arithmetic average roughness (Ra) and 10 mean roughness (Rz) according to JIS B0601.
(5) surfaceness
By adopting miniature durometer MD-1 (by Koubunshi KeikishaCo., Ltd. makes) to measure underproof developing roller surface hardness.
(6) pollution of photosensitive drums
Under the load of 1kg, underproof developer roll is pushed on the photosensitive drums, and under the high temperature of 40 ℃ and 95%RH, high humidity, places.After preset time (1 week) past, developer roll is taken out and is assembled in the actual machine to carry out imaging, and according to the image in the contact site of following standard evaluation between developer roll and photosensitive drums: zero: photosensitive drums is not polluted, △: the photosensitive drums light contamination and *: photosensitive drums is polluted owing to oozing out.
(7) compression set
Carry out as the same test in the pollution of above-mentioned photosensitive drums, with according to the image of following standard evaluation in the contact site between developer roll and the photosensitive drums: zero: do not contact vestige with photosensitive drums, △: with photosensitive drums the slight vestige that contacts is arranged, with *: have with photosensitive drums to contact vestige clearly.
(8) imaging concentration
Underproof developer roll is assembled in the print cartridge, then in the color printer LBP4600 that makes by Hewlett-Packard Co. under the printing rate 2% (15 ℃ of low temperature and low humidity degree (LL) environment, 10%RH), ambient temperature and moisture (NN) environment is (25 ℃, 50%RH) or (30 ℃ of hot and humid (HH) environment, carry out continuous imaging 80%RH), thus in the starting stage with form a kind of image and half tone image of color after printing 5000 paper respectively.With the naked eye estimate the image and the half tone image of these a kind of colors according to following standard: zero: do not exist density unevenness even, △: slightly exist density unevenness even and *: exist density unevenness even.
(9) anti-hazing property
After during forming a kind of white image, stopping the operation of printer by force, compare concentration (by means of the Macbeth densimeter) is measured the toner on photosensitive drums that disperses in white portion quantity by moving based on paper tape.Zero: be less than 0.15, △: 0.15-0.20 and *: surpass 0.20.
(10) anti-toner melting
Underproof developer roll has been spread toner from the teeth outwards and be assembled in the print cartridge, it was placed for 1 week under 40 ℃ and 95%RH, carried out imaging then.Zero: do not have toner attached to developing roller surface, △ from first image: up to the tenth image do not have toner attached to developing roller surface and *: even in the tenth image range, observe toner attached to developing roller surface.
Table 2
| Embodiment | Comparative example | ||||||||||||||
| 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 3 | 4 | 5 | |||
| Performance | Polyvalent alcohol number-average molecular weight (Mn) | 1000 | 3000 | 5000 | 5000 | 1000 | 3000 | 5000 | 5000 | 1000 | 1000 | 2000 | 500 | 2000 | |
| Molecular weight distribution (Mw/Mn) | 1.7 | 2.1 | 2.3 | 2.3 | 1.7 | 2.1 | 2.3 | 2.3 | 1.9 | 1.7 | 2.2 | 1.6 | 2.8 | ||
| The elastic modulus of surface coating (MPa) | 42 | 27 | 18 | 26 | 47 | 36 | 29 | 47 | 53 | 38 | 25 | 55 | 22 | ||
| Roller resistance (Ω/100) | 6.5E+06 | 7.2E+06 | 5.5E+06 | 5.2E+06 | 4.9E+06 | 3.9E+06 | 6.9E+06 | 7.0E+06 | 4.0E+06 | 4.1E+06 | 5.9E+06 | 5.4E+06 | 6.1E+06 | ||
| Surface roughness Ra (μ m) | 0.9 | 1.0 | 1.2 | 1.1 | 1.0 | 0.8 | 0.9 | 0.9 | 1.0 | 1.2 | 1.1 | 1.2 | 0.9 | ||
| Surfaceness Rz (μ m) | 6.1 | 5.7 | 6.4 | 5.5 | 5.4 | 5.1 | 5.9 | 5.9 | 6.0 | 6.2 | 6.3 | 6.5 | 5.9 | ||
| Skin hardness (°) | 43 | 45 | 46 | 29 | 39 | 41 | 40 | 40 | 39 | 34 | 46 | 44 | 43 | ||
| The pollution of photosensitive drums | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ||
| Image property | One color image | Initial stage | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Durable | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | △ | △ | △ | ||
| Half tone image | Initial stage | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Durable | ○ | ○ | ○ | ○ | △ | ○ | △ | △ | △ | ○ | × | △ | △ | ||
| The vestige of compression set | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | △ | × | △ | × | ||
| Anti-hazing property | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | ||
| Anti-toner melting | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | ○ | ○ | × | × | △ | ||
As seen from Table 2, because photosensitive drums is not contaminated, compression set is low, do not cause because the extruding vestige of scraper plate, little and anti-toner melting is good to the damage of toner, therefore developer roll can stably form superior images according to an embodiment of the invention.
(embodiment 15)
By with 5 mass parts carbon black dispersion in 100 mass parts water-containing acrylic acid resins (by Nogawa Chemicals Co., Ltd. produce) and preparation is used for the coating composition of inter coat.Equally, by with the propenoic methyl carbamate of 100 mass parts caprolactone modification (by Azia Kogyo Co., Ltd. produce, silicone is introduced carbamate moiety), 35 mass parts carbon blacks and isocyanurate-modified HDI (the Coronate HX of 50 mass parts, by Nippon Polyurethane Industry Co., Ltd. produces) be distributed in the 300 mass parts MEKs (MEK) and preparation is used for the coating composition of surface coating.The coating composition that will be used for inter coat is coated on the outer of roll body with elastic layer of being made by isocyanurate foam and places to form inter coat, and the coating composition coating that after this will be used for surface coating makes developer roll thus to form surface coating.Roller resistance, 10 mean roughness (Rz), AskerC hardness, friction factor, the toner charging performance of the developer roll that obtains thus by the known method evaluation are estimated image property by this developer roll is assembled in to print in the laser printer simultaneously then.Equally, be assembled in developer roll in the print cartridge and remain in 1 week under the environment of 50 ℃ and 90%RH, measure the existence of polluting on the photosensitive drums subsequently or do not exist and in the lip-deep because existence of the extruding vestige of scraper plate of developer roll or do not exist.The results are shown in the table 3.
(embodiment 16)
By with 5 mass parts carbon black dispersion in 100 mass parts aqueous polyurethane resins (by Dai-ichi Kogyo Seiyaku Co., Ltd. produce) and preparation is used for the coating composition of inter coat.Equally, by with the propenoic methyl carbamate of 100 mass parts caprolactone modification (by Azia Kogyo Co., Ltd. produce, silicone is introduced acrylate moiety), 35 mass parts carbon blacks and isocyanurate-modified HDI (the Coronate HX of 50 mass parts, by Nippon Polyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using the thus obtained coating composition that is used for inter coat and surface coating to replace the coating composition of embodiment 15 to prepare developer roll, and estimate.The results are shown in the table 3.
(embodiment 17)
By with 5 mass parts carbon black dispersion in 100 mass parts aqueous latex (by KouatsuGas Kogyo Co., Ltd. produce) and preparation is used for the coating composition of inter coat.Equally, by with the propenoic methyl carbamate of 100 mass parts caprolactone modification (by AziaKogyo Co., Ltd. produce, silicone is introduced acrylate moiety), 35 mass parts carbon blacks and isocyanurate-modified HDI (the Coronate HX of 50 mass parts, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using the thus obtained coating composition that is used for inter coat and surface coating to replace the coating composition of embodiment 15 to prepare developer roll, and estimate.The results are shown in the table 3.
(embodiment 18)
By with the propenoic methyl carbamate of 100 mass parts caprolactone modification (by AziaKogyo Co., Ltd. produce, silicone is introduced acrylate moiety), HDI (the Coronate HX of 35 mass parts carbon blacks and 50 mass parts cyanurate modifications, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.Do not form inter coat by using the thus obtained coating composition that is used for surface coating to replace the coating composition of embodiment 15 and prepare developer roll, and estimate.The results are shown in the table 3.
(comparative example 6)
By with 5 mass parts carbon black dispersion in 100 mass parts water-containing acrylic acid resins (by Nogawa Chemicals Co., Ltd. produce) and preparation is used for the coating composition of inter coat.Equally, urethane acrylates coating by 100 mass parts not being introduced silicone is (by Azia Kogyo Co., Ltd. production), 35 mass parts carbon blacks and isocyanurate-modified HDI (the Coronate HX of 50 mass parts, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using the thus obtained coating composition that is used for inter coat and surface coating to replace the coating composition of embodiment 15 to prepare developer roll, and estimate.The results are shown in the table 3.
(comparative example 7)
By with 5 mass parts carbon black dispersion in 100 mass parts aqueous polyurethane resins (by Dai-ichi Kogyo Seiyaku Co., Ltd. produce) and preparation is used for the coating composition of inter coat.Equally, urethane acrylates resin by 100 mass parts not being introduced silicone is (by Azia Kogyo Co., Ltd. production), 35 mass parts carbon blacks and isocyanurate-modified HDI (the Coronate HX of 50 mass parts, by NipponPolyurethane Industry Co., Ltd. produces) be distributed among the 300 mass parts MEK and preparation is used for the coating composition of surface coating.By using the thus obtained coating composition that is used for inter coat and surface coating to replace the coating composition of embodiment 15 to prepare developer roll, and estimate.The results are shown in the table 3.
Table 3
| Embodiment | Comparative example | ||||||
| 15 | 16 | 17 | 18 | 6 | 7 | ||
| Elastic layer | Resin | Polyurethane foam | Polyurethane foam | Polyurethane foam | Polyurethane foam | Polyurethane foam | Polyurethane foam |
| Inter coat | Resin | Acryl resin | Polyurethane resin | Latex | - | Acryl resin | Polyurethane resin |
| Surface coating | Resin | ||||||
| The introducing position of silicone | The carbamate part | Acrylate moiety | Acrylate moiety | Acrylate moiety | Do not have | Do not have | |
| Performance | Roller resistance (Ω/100V) | 2.5×10 6 | 3.7×10 6 | 4.2×10 6 | 2.5×10 6 | 3.9×10 6 | 2.6×10 6 |
| Rz(μm) | 5.4 | 5.6 | 6.5 | 5.7 | 5.9 | 6.5 | |
| Hardness (Asker C) | 51 | 46 | 45 | 60 | 48.6 | 48.8 | |
| Friction factor (μ s) | 0.38 | 0.35 | 0.34 | 0.33 | 0.78 | 0.80 | |
| The toner chargeding performance | ○ | ○ | ○ | ○ | ○ | ○ | |
| Image property | Image color | ○ | ○△ | ○ | ○△ | * (generation smear) | * (generation smear) |
| Haze | ○ | ○ | ○ | ○ | △ | △ | |
| The shadow tone unevenness | ○ | ○ | ○ | ○ | Inhomogeneous | Inhomogeneous | |
| The stain resistance of photosensitive drums | After under 50 ℃ and 99%RH, keeping for 1 week | ○ | ○ | ○ | ○ | △ | ○ |
| Because the extruding vestige of scraper plate | ○ | ○ | ○ | ○ | × | × |
Zero: good, zero △: better, and △: poor slightly, *: poor
As seen from Table 3, because photosensitive drums is not contaminated, compression set is low, do not cause because extruding vestige, the lip-deep frictional resistance of scraper plate are low and little to the damage of toner, therefore developer roll can stably form superior images according to an embodiment of the invention.
Claims (25)
1. developer roll, it comprises axle, be formed at this elastic layer of placing outward and be formed at surface coating on the peripheral surface of this elastic layer, wherein this surface coating comprises by will interior ester modified polyvalent alcohol and the urethane resin of multi isocyanate crosslinking formation.
2. developer roll according to claim 1, ester modified polyvalent alcohol has number-average molecular weight (Mn) 1000-5000 wherein, it is no more than 2.5 for the number-average molecular weight that is converted into polystyrene measured by gel permeation chromatography with by the molecular weight distribution (Mw/Mn) of the weight-average molecular weight of measuring by gel permeation chromatography that is converted into polystyrene (Mw) and the ratio value representation of number-average molecular weight (Mn).
3. developer roll according to claim 1 is wherein by forming urethane resin with interior ester modified polyvalent alcohol and at least two kinds of multi isocyanate crosslinkings.
4. developer roll according to claim 3, wherein this polyisocyanates contains at least a of isocyanurate-modified hexamethylene diisocyanate or isophorone diisocyanate.
5. developer roll according to claim 1, the mol ratio ([NCO]/[OH]) that wherein interior ester modified polyvalent alcohol has isocyanate groups (NCO) Yu the hydroxyl (OH) of polyisocyanates is 1.0-2.5.
6. developer roll according to claim 1, wherein this surface coating has storage modulus under 25 ℃ (E ') and is 3-50MPa.
7. developer roll according to claim 1, wherein the thickness of this surface coating is no more than 30 μ m.
8. developer roll according to claim 1, wherein the urethane resin of surface coating has the silicone with siloxane bond is introduced structure in the resin matrix.
9. developer roll according to claim 8, wherein this urethane resin has such structure: will have siloxane bond and hydroxyl or amino silicone introducing carbamate moiety at its two ends.
10. developer roll according to claim 8, the number-average molecular weight that wherein is introduced into the silicone in the resin matrix is 500-10000.
11. developer roll according to claim 1, wherein this urethane resin of this surface coating is the propenoic methyl carbamate resin that forms by with interior ester modified polyvalent alcohol and multi isocyanate crosslinking.
12. developer roll according to claim 11, wherein this propenoic methyl carbamate resin has such structure: will have the silicone introducing acrylate moiety of siloxane bond and methacryloxy at the one end.
13. developer roll according to claim 11, wherein this propenoic methyl carbamate resin has the structure of interior ester modified polyvalent alcohol being introduced carbamate moiety.
14. developer roll according to claim 1, wherein this surface coating contains this interior ester modified polyvalent alcohol of 5-35 mass parts carbon black/100 mass parts.
15. developer roll according to claim 1, wherein this surface coating further contains conductive agent.
16. developer roll according to claim 1, wherein this elastic layer is by making by the isocyanurate foam that adopts mechanical raking that the foaming of carbamate initiation material is obtained.
17. developer roll according to claim 16, this isocyanurate foam of wherein forming this elastic layer has closed pore.
18. developer roll according to claim 16 wherein forms the inter coat of being made by the mixed solution of polymkeric substance and aqueous solvent between this is as the isocyanurate foam of elastic layer and this surface coating.
19. developer roll according to claim 18, wherein this inter coat is made by acryl resin, urethane resin or rubber latex.
20. developer roll according to claim 18, wherein the glass transition temperature of this inter coat is not higher than 10 ℃.
21. developer roll according to claim 18, wherein this inter coat is made up of two-layer or multilayer.
22. developer roll according to claim 18, wherein this inter coat further contains conductive agent.
23. developer roll according to claim 18, wherein the gross thickness of this inter coat and this surface coating is no more than 100 μ m.
24. developer roll according to claim 1, wherein 10 of this roller average surface roughness (Rz) are no more than 10 μ m.
25. an imaging device is characterized in that comprising according to each described developer roll of claim 1 to 24.
Applications Claiming Priority (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005327564A JP5204953B2 (en) | 2005-11-11 | 2005-11-11 | Developing roller and image forming apparatus having the same |
| JP2005-327432 | 2005-11-11 | ||
| JP2005-327564 | 2005-11-11 | ||
| JP2005327439 | 2005-11-11 | ||
| JP2005327432 | 2005-11-11 | ||
| JP2005327512 | 2005-11-11 | ||
| JP2005327439A JP5204952B2 (en) | 2005-11-11 | 2005-11-11 | Developing roller and image forming apparatus having the same |
| JP2005327512A JP2007131770A (en) | 2005-11-11 | 2005-11-11 | Development roller and image-forming apparatus equipped with the same |
| JP2005327564 | 2005-11-11 | ||
| JP2005327432A JP5204951B2 (en) | 2005-11-11 | 2005-11-11 | Developing roller and image forming apparatus having the same |
| JP2005-327512 | 2005-11-11 | ||
| JP2005-327439 | 2005-11-11 | ||
| JP2006112291A JP5025983B2 (en) | 2006-04-14 | 2006-04-14 | Developing roller and image forming apparatus having the same |
| JP2006112291 | 2006-04-14 | ||
| JP2006-112291 | 2006-04-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1963685A true CN1963685A (en) | 2007-05-16 |
| CN1963685B CN1963685B (en) | 2012-05-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2006101381364A Expired - Fee Related CN1963685B (en) | 2005-11-11 | 2006-11-10 | Developing roller and imaging apparatus comprising the same |
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| JP (1) | JP5204951B2 (en) |
| CN (1) | CN1963685B (en) |
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Also Published As
| Publication number | Publication date |
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| JP5204951B2 (en) | 2013-06-05 |
| JP2007133223A (en) | 2007-05-31 |
| CN1963685B (en) | 2012-05-23 |
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