CN101339374B - Toner, method of manufacturing the toner, developing device, and image forming apparatus - Google Patents

Toner, method of manufacturing the toner, developing device, and image forming apparatus Download PDF

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CN101339374B
CN101339374B CN2008101356022A CN200810135602A CN101339374B CN 101339374 B CN101339374 B CN 101339374B CN 2008101356022 A CN2008101356022 A CN 2008101356022A CN 200810135602 A CN200810135602 A CN 200810135602A CN 101339374 B CN101339374 B CN 101339374B
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toner
resin
particle
biomass
slurries
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CN101339374A (en
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芝井康博
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Sharp Corp
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Sharp Corp
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Abstract

The invention provides a toner that allows prevention of environmental contamination and is nevertheless free from toner durability degradation, wherein a sufficiently wide color reproduction range can be secured even when it is applied to color toner, and variation in characteristics among toner particles can be suppressed, as well as a method of manufacturing a toner, a developing device, and an image forming apparatus. In the toner particle (1) is formed the biomass resin-containing domain (2).

Description

Toner and manufacture method thereof, developing apparatus and image processing system
Technical field
The present invention relates to toner and manufacture method thereof, developing apparatus and image processing system.
In the image processing system that uses the electrofax mode, make latent electrostatic image developing form the toner picture by supplying with toner to the electrostatic latent image that is formed at photosensitive surface, and by making this toner form image as photographic fixing in recording medium.The following manufacturing of the toner that uses in this image processing system: raw materials such as mixed colorant, release agent and charge control agent in binder resin, granulate and make its particle diameter that reaches defined, thereby make.
Used toner is imbedded in the soil or is calcined and discard, but under the situation of discarding calcining, not only can be in atmosphere emission greenhouse effect atmospheric carbon dioxide, and contained metals such as colorant or charge control agent might become environomental pollution source.Therefore, a plurality of toners of discarding have been proposed with can suppressing environmental pollution.
For example, Japanese kokai publication hei 4-218063 communique discloses the toner that contains binder resin, colorant, charge control agent and biodegradable resin at least, and the toner that further contains the photodissociation agent.The disclosed toner of this Japanese kokai publication hei 4-218063 communique is owing to contain biodegradable resin, and therefore when toner being imbedded when discarding in the soil, toner is decomposed, and can suppress environmental pollution.But biodegradable resin comminuted poor is difficult to carry out micronize.Therefore, be difficult to make the small particle size toner that is used to carry out high-quality and high-resolution image formation.
In order to address this is that, TOHKEMY 2004-177554 communique discloses biodegradable resin and colorant be dissolved or dispersed in makes coloring liquid in the organic solvent, generate the manufacture method of the toner of pigmentary resin particle by mixing this coloring liquid and aqueous medium.By utilizing the disclosed method of TOHKEMY 2004-177554 communique to make toner, even if the biodegradable resin of comminuted difference, also micronize easily can be made the toner of small particle diameter.
Fig. 8 is the sectional view of the toner particle 51 of prior art.The disclosed toner of Japanese kokai publication hei 4-218063 communique is owing to making the temporary transient fusion of binder resin and biodegradable resin or cooling off after softening the mixing, so the biodegradable resin crystallization, is scattered in the toner particle with the island state.Promptly, in the disclosed toner of Japanese kokai publication hei 4-218063 communique, as shown in Figure 8, in the toner particle 51 as sea component, the island component that is made of the biodegradable resins 52 of different sizes disperses respectively to exist with unsetting state that can not given shape.
In this toner, the toner fracture takes place in the interface of binder resin and biodegradable resin easily, thereby can not be to contain biodegradable resin at high proportion in toner particle.In addition, because the different sizes of the crystalline portion of biodegradable resin, and be dispersed into very complicated shape, therefore cause the transparency of toner to reduce.As a result, when being applied to color toner, color reproducible range narrows down.In addition, biodegradable resin disperses equably, and the toner composition becomes inhomogeneous, so the characteristic of each toner particle produces inequality, toner rerum naturas such as uncontrollable charged characteristic.
In the manufacture method of the disclosed toner of TOHKEMY 2004-177554 communique, in organic solvent,, in aqueous medium, carry out Phase inversion emulsification with biodegradable resin fusion or softening, obtain toner.In this toner, owing to biodegradable resin contains as binder resin, therefore since photographic fixing when recording medium heat and crystallization causes the transparency to reduce, when being applied to color toner, color reproducible range narrows down.In addition, permanance is also low.
Summary of the invention
The present invention is in order to solve above-mentioned problem, and purpose is to provide the toner that can suppress environmental pollution.In addition, the objective of the invention is to when suppressing environmental pollution, guarantee fully the permanance of toner.And, the present invention also aims to provide the toner that also can guarantee sufficient color reproducible range as color toner.
In addition, the object of the present invention is to provide toner, the manufacture method that is used to obtain this toner, the developer that uses this toner that are used to reach above-mentioned purpose, use developing apparatus that this developer develops and the image processing system that possesses this developing apparatus.
The present invention is a kind of toner, it is characterized in that, contains the toner particle that contains binder resin at least, forms to contain biomass resin zone in toner particle.
According to the present invention, contain biomass resin zone and be scattered in the toner particle owing to form, thereby can prevent that the biomass resin is scattered in the toner particle with the island state.Therefore, can not reduce the permanance of toner, can suppress environmental pollution to contain the biomass resin at high proportion in toner particle.In addition,, therefore can not reduce the transparency of toner,, can guarantee sufficient color reproducible range yet, can suppress the characteristic inequality between toner particle even if when being applied to color toner owing to can prevent to follow the gonorrhoeaization of biomass resin crystallization.
In addition, in the present invention, preferably contain biomass resin zone and be almost spherical or its combination shape.
According to the present invention, contain biomass resin zone and be almost spherical or its combination shape.By making the shape that contains biomass resin zone roughly certain, can reduce the property difference between toner particle.
In addition, in the present invention, preferred biomass resin is a crystalline resin.
According to the present invention, the biomass resin is a crystalline resin.Usually, crystalline resin is compared with unsetting resin has tangible meltbility, and the toner that therefore contains crystalline resin can improve storage stability keeping under the state of fixing temperature.
In addition, among the present invention, with respect to 100 weight fraction toners, the content of biomass resin is preferably more than 20 weight portions, below 60 weight portions.
According to the present invention, with respect to 100 weight fraction toners, the content of biomass resin is preferably more than 20 weight portions, below 60 weight portions.Thus, can bring into play the effect of the inhibition environmental pollution that the biomass resin produced fully.In addition, be below 60 weight portions by the content that makes the biomass resin, can obtain sufficient toner permanance.
In addition, in the present invention, preferably in containing biomass resin zone, do not contain colorant.
According to the present invention, in containing biomass resin zone, do not contain colorant.When containing colorant in the biomass resin, because the filling effect of colorant, the biomass resin is reinforced, hardness improves, and softening temperature improves simultaneously.Do not contain colorant by making to contain in the biomass resin zone, can prevent that the softening temperature of biomass resin from improving,, can prevent the toner fixing reduction when adjusting toner heating, pressurization and photographic fixing on recording medium the time.
In addition, among the present invention, the regional diameter that preferably contains biomass resin zone is below the 1 μ m.
According to the present invention, the regional diameter that contains biomass resin zone is below the 1 μ m.By making regional diameter is below the 1 μ m, can prevent that the become particle diameter of excessive, toner particle of regional diameter from increasing.Therefore, can make the little toner of particle diameter of toner particle.In addition, be below the 1 μ m by making regional diameter, can obtain the good toner of the transparency.And, because the biomass resin can be exposed the ratio of toner surface suppresses lowlyer, therefore the storage stability of toner can be maintained under the high state, simultaneously can prevent that the ratio that the biomass resin contacts with recording medium when photographic fixing from increasing, thereby prevent the reduction of toner fixing.
In addition, in the present invention, the regional diameter that preferably contains biomass resin zone is more than the 0.5 μ m, below the 1 μ m.
According to the present invention, the regional diameter that contains biomass resin zone is more than the 0.5 μ m, below the 1 μ m.By making regional diameter is more than the 0.5 μ m, can prevent that regional diameter from becoming too small, can prevent owing to forming binder resin and the biomass resin compatible (compatible to each other) that heating when containing biomass resin zone etc. causes.Therefore, can prevent that the glass transition temperature (Tg) of binder resin from reducing, thereby the storage stability that can prevent toner reduces.
In addition, preferred binder resin is a vibrin among the present invention.
According to the present invention, binder resin is a vibrin.Thus, can obtain the toner that the transparency is good and permanance is good.
In addition, in the present invention, preferably coat the surface of toner particle with resin molding.
According to the present invention, coat the surface of toner particle with resin molding.Thus, can further improve the permanance of toner.
In addition, in the present invention, resin molding is preferably formed by the styrene-acrylonitrile copolymer acid resin that utilizes emulsion polymerization to make.
According to the present invention, resin molding is formed by the styrene-acrylonitrile copolymer acid resin that utilizes emulsion polymerization to make.Utilize styrene-acrylonitrile copolymer acid resin that emulsion polymerization makes because the particle diameter of its resin particle is little and even, so surfaces of toner particles is when being coated, can be formed evenly, the resin molding of film like.In addition, the styrene-acrylonitrile copolymer acid resin is because the content of ester bond isopolarity group is few, so hydroscopicity is little, even if also can improve the charged stability of toner under high humidity environment.
In addition, the present invention is a kind of method for preparing toner, it is characterized in that, comprises following operation: be dispersed in the liquid medium to major general's binder resin and obtain the adhesive resin particles dispersion step of adhesive resin particles slurries; To major general's biomass resin dispersion in liquid medium and obtain the biomass resin particle dispersion step of biomass resin particle slurries; And hybrid bonding resin particle slurries and biomass resin particle slurries and make the cohesion process of adhesive resin particles and the cohesion of biomass resin particle.
According to the present invention, hybrid bonding resin particle slurries and biomass resin particle slurries make the cohesion of adhesive resin particles and biomass resin particle.Therefore, can not have under the compatible state the biomass resin dispersion in toner particle at binder resin and biomass resin.As a result, can be under the situation that can not reduce the toner permanance in toner particle to contain the biomass resin at high proportion, can suppress environmental pollution.In addition, when the biomass resin cools off, produce gonorrhoea sometimes after by temporary transient fusion.Contain biomass resin zone owing to the cohesion of adhesive resin particles and biomass resin particle is formed, therefore can suppress the fusion of biomass resin.Thereby, can suppress the gonorrhoea of biomass resin, can prevent that the transparency of toner from reducing.As a result, the raw material that also can be effective as the color toner of the special requirement toner transparency uses.
In addition, among the present invention, contain colorant in the preferred adhesive resin particles.
According to the present invention, contain colorant in the adhesive resin particles.Therefore, the dispersion of colorant in the toner particle can be improved, color emissivity and chroma can be improved.
In addition, the present invention preferably also comprises and is scattered in the liquid medium to major general's colorant and obtains the colorant particle dispersion step of colorant particle slurries, in cohesion process, hybrid bonding resin particle slurries, biomass resin particle slurries and colorant particle slurries make adhesive resin particles, biomass resin particle and colorant particle cohesion.
According to the present invention, also comprise and be scattered in the liquid medium to major general's colorant and obtain the colorant particle dispersion step of colorant particle slurries, in cohesion process, hybrid bonding resin particle slurries, biomass resin particle slurries and colorant particle slurries make adhesive resin particles, biomass resin particle and colorant particle cohesion.Therefore, the control of the shape of toner particle becomes easy.In addition, owing to do not need in advance the operation of colorant melting mixing in binder resin, therefore can simplified manufacturing technique.
In addition, in the present invention, the particle diameter of preferred adhesive resin particles is more than 1/4, below 1/2 with respect to the particle diameter of biomass resin particle.
According to the present invention, the particle diameter of adhesive resin particles is more than 1/4, below 1/2 with respect to the particle diameter of biomass resin particle.Thus, the particle diameter that can prevent to have the adhesive resin particles of the effect of keeping the toner permanance becomes too small.Therefore, the permanance that can prevent toner reduces.In addition, can prevent that regional diameter from becoming excessive, being scattered in and contacting between the biomass resin zone in the toner particle and engage.Therefore, the permanance that can prevent toner reduces.
In addition, the particle diameter by making adhesive resin particles is more than 1/4 with respect to the particle diameter of biomass resin particle, can prevent binder resin and biomass resin compatible.Therefore, the glass transition temperature (Tg) that can prevent binder resin reduces, prevents that the storage stability of toner from reducing.And, particle diameter by making adhesive resin particles is below 1/2 with respect to the particle diameter of biomass resin particle, the ratio that the biomass resin exposes toner surface in the time of long-term operation can being used suppresses lowlyer, therefore the permanance of toner can be maintained under the high state, biomass resin and the contacted ratio of recording medium increase in the time of simultaneously can preventing photographic fixing, thereby the fixation performance that prevents toner reduces.
In addition; among the present invention, preferred biomass resin particle dispersion step comprises following operation: under heating and pressurizing, make biomass resin particle slurries the grain refined operation, will be in the heating and pressurizing state the decompression of biomass resin particle slurries the decompression operation and with the refrigerating work procedure of the biomass resin particle slurries cooling of decompression.
According to the present invention, when making biomass resin particle slurries, at first under the heating and pressurizing condition, the biomass resin is pulverized, it is dispersed in the liquid medium, obtain dispersion liquid.Then, will be in dispersion liquid decompression, cooling under the heating and pressurizing condition, make biomass resin particle slurries.Owing under the heating and pressurizing condition, pulverize the biomass resin, therefore can pulverize the biomass resin efficiently.The situation that produces gonorrhoea is arranged when in addition, the biomass resin cools off after heating for a long time.Because the dispersion liquid that contains the biomass resin that is under the heating and pressurizing condition is pressurizeed forcibly, cools off, therefore can suppress the biomass resin and produce gonorrhoea, can prevent that the transparency of toner from reducing.
In addition, among the present invention, preferred biomass resin particle dispersion step is undertaken by high pressure homogenization method.
According to the present invention, the biomass resin particle disperses to make by high pressure homogenization method.Thus, the biomass resin can be pulverized is the state that particle diameter is little and particle size distribution range is little.
In addition, the present invention is a kind of toner, it is characterized in that, by the manufacture method manufacturing of above-mentioned toner.
According to the present invention, owing to the manufacture method of toner by above-mentioned toner obtains, therefore contain biomass resin zone and have the interior particle diameter of certain limit, be scattered in the toner particle substantially equably.Therefore, can be under the situation that does not reduce the toner permanance in toner particle to contain the biomass resin at high proportion, can suppress environmental pollution.In addition, owing to the gonorrhoeaization that can prevent to follow the crystallization of biomass resin to produce, therefore can not reduce the transparency of toner,, can suppress the characteristic inequality between toner particle even if be applied to can to guarantee sufficient color reproducible range under the situation of color toner yet.
In addition, as developer, also can use the two-component developing agent that contains above-mentioned toner and carrier.
Two-component developing agent contains above-mentioned toner and carrier.Therefore, can obtain under the situation that does not reduce the toner permanance, suppressing the two-component developing agent of environmental pollution.And, because two-component developing agent contains above-mentioned toner, promptly also can be applied to the transparent high toner of color toner, therefore can obtain forming the two-component developing agent of transparent high high resolution image.
In addition, the present invention is a kind of developing apparatus, it is characterized in that, uses the developer that contains above-mentioned toner to develop.
According to the present invention, developing apparatus uses the developer that contains above-mentioned toner to develop.Therefore, not only can on photoreceptor, form the toner picture of high image quality, and can suppress environmental pollution.
In addition, the present invention is a kind of image processing system, it is characterized in that, possesses above-mentioned developing apparatus.
According to the present invention, image processing system possesses above-mentioned developing apparatus.Therefore, can form the high high resolution image of the transparency.In addition, though when image forms unwanted toner be recovered, discarded, can suppress the environmental pollution that this waste toner causes.
Purpose of the present invention, characteristic and advantage will be more readily apparent from by following detailed explanation and accompanying drawing.
Description of drawings
Fig. 1 is the figure in cross section of the toner particle of expression one embodiment of the present invention.
Fig. 2 A～Fig. 2 E is the figure that expression contains the cross sectional shape in biomass resin zone.
Fig. 3 is the process flow diagram of expression toner particle manufacture method the 1st example.
Fig. 4 is the process flow diagram of expression toner particle manufacture method the 2nd example.
Fig. 5 is the process flow diagram of expression toner particle manufacture method the 3rd example.
Fig. 6 is the sectional view that the image processing system of one embodiment of the present invention constitutes.
Fig. 7 is the figure that expression developing apparatus of the present invention constitutes.
Fig. 8 is the figure in cross section of the toner particle of expression prior art.
Embodiment
Explain preferred implementation of the present invention below with reference to accompanying drawing.
Fig. 1 is the figure in the cross section of the toner particle 1 of expression one embodiment of the present invention.In addition, Fig. 2 A～Fig. 2 E contains the figure of the cross sectional shape in biomass resin zone 2 for expression.Toner of the present invention contains the toner particle 1 that contains biomass resin, binder resin at least, forms to contain biomass resin zone 2 in toner particle 1.
Among the present invention, preferably contain biomass resin zone 2 and be almost spherical or its combination shape.This shape can't obtain by making temporary transient fusion of binder resin and biodegradable resin or the softening method of making the toner particle that contains biodegradable resin as prior art, can obtain by manufacture method of the present invention described later.
At this, almost spherical or its combination shape can enumerate cross sectional shape for spheroid circular shown in Fig. 2 A, cross sectional shape for oval-shaped ellipsoid shown in Fig. 2 B, cross sectional shape for the cross sectional shape of ovoid avette shown in Fig. 2 C, 2 spheroid be combined intos for the cross sectional shape of silk cocoon shape combination shape shown in Fig. 2 D, 3 spheroid be combined intos for the combination shape of shape shown in Fig. 2 E etc.In addition, though the combination shape is represented the example of a plurality of spheroid combinations, also can be the form of ellipsoid combination for example, can also be the form that spheroid combines with ellipsoid in addition.And the above-mentioned conceptual shape that is shaped as that contains biomass resin zone 2 also comprises the spheroid or the approaching ellipsoidal form that approach these shapes, for example misalignment.By making the shape that contains biomass resin zone 2 roughly certain, can reduce the property difference of 1 of toner particle.And, as the regional diameter that contains biomass resin zone 2 of almost spherical or its combination shape, be converted into to have and try to achieve with regional sectional area diameter of a circle of the same area.
Among the present invention, the biomass resin is meant that containing with plant is the resin of the compound of skeleton as raw material by photosynthesis fixing carbon atom from Atmospheric Carbon Dioxide.Therefore, even if burning biomass resin produces carbon dioxide, the actual increase that also can suppress carbon dioxide in the atmosphere.Therefore, the toner that contains the biomass resin can be called the toner of discarding with can suppressing environmental pollution.
The biomass resin roughly is divided into the natural goods resinoid that itself can be used as polymkeric substance and use, the polymkeric substance that makes the biomass source or the chemosynthesis resinoid of monomer chemical polymerization, the microorganisms resinoid of polymerization in microbial body.The natural goods resinoid for example can be enumerated cellulose acetate, esterification starch, chitosan, fibroin, collagen, gelatin, natural rubber etc.The chemosynthesis resinoid can be enumerated PLA, polyglycol, poly terephthalic acid methylene glycol ester (Poly (methylene terephthalate)), poly butylene succinate etc.The microorganisms resinoid can be enumerated poly butyric ester, PHA, bacteria cellulose, polyglutamic acid etc.There is no particular restriction for the biomass resin, for example can use PLA, poly terephthalic acid methylene glycol ester, poly butylene succinate, poly butyric ester, PHA and with succinic acid, 1, ammediol or itaconic acid are the synthetic polyester of monomer etc., can use a kind or and with more than 2 kinds separately.
Have crystalline resin that noncrystalline resin is also arranged in the biomass resin, can use any, but preferred crystalline resin.Usually, crystalline resin is compared with unsetting resin has tangible meltbility, and the toner that therefore contains crystalline resin can improve storage stability keeping under the state of fixing temperature.As crystal material, for example can enumerate PLA, poly terephthalic acid methylene glycol ester, poly butylene succinate, poly(hydrobutyl ester), PHA etc., by in the synthetic polyester of monomer crystal material being arranged also.
Degradative resin in distress and biodegradable resin in the biomass resin can use any.As the biomass resin of difficult degradation, for example can enumerate soybean polyvalent alcohol as the polyvalent alcohol in soybean oil source, with obtain by fermentation method 1, the terephthalic acid (TPA) that ammediol and fossil resource are originated is the polyester of raw material etc.As biodegradable biomass resin, can enumerate the multipolymer etc. of multipolymer, PLA, PLA and aliphatic polyester of multipolymer, aliphatic polyester and the polyamide of poly-butyric acid class, aliphatic polyester, aromatic polyester and aliphatic polyester.Object lesson as biodegradable resin, can enumerate following material: poly-(3-hydroxybutyric acid), the multipolymer of 3-hydroxybutyric acid and 3-hydroxypentanoic acid, the poly-butyric acid classes such as multipolymer of 3-hydroxybutyric acid and 4 hydroxybutyric acid, as lactide, glycolide, beta-propiolactone, gamma-valerolactone, the aliphatic polyester compound of ring-opening polymerization polymers such as 6-caprolactone, hexane diacid and 1, the polyester that the 4-butylene glycol forms, succinic acid and 1, the polyester that the 4-butylene glycol forms, the polyester of aliphatic dibasic acid such as the polyester that succinic acid and 1,6-hexanediol form and aliphatic dihydroxy alcohol formation.
In addition, multipolymer as aliphatic polyester and aromatic polyester, above-mentioned aliphatic polyester compound be can enumerate, the aromatic dicarboxylic acid such as terephthalic acid (TPA), m-phthalic acid, naphthalene dicarboxylic acids of 1～50 weight % or P-hydroxybenzoic acid perhaps when synthetic these compounds, made, to hydroxyethylbenzene formic acid, to the resin of aromatic hydroxy-carboxylics such as hydroxyphenyl acetate reaction.In addition, multipolymer as PLA and aliphatic polyester, can enumerate PLA with by ethylene glycol, 1,2-butylene glycol, 1, the multipolymer of the aliphatic polyester that polybasic carboxylic acid such as polyalcohols such as 6-hexanediol, neopentyl glycol, cyclohexanedimethanol, triethylene glycol, dipropylene glycol, dibutylene glycol, polytetramethylene glycol and succinic acid, methylglutaric acid, hexane diacid, azelaic acid, decanedioic acid, tridecandioic acid, tetracosandioic acid, cyclohexyl dicarboxylic acid, maleic anhydride, fumaric acid obtains.Biodegradable resin is the preferred multipolymer that uses poly-butyric acid class, PLA, PLA and aliphatic polyester in above-mentioned resin.
As binder resin, then do not have special restriction so long as can under molten condition, granulate, for example can enumerate Polyvinylchloride, polyvinyl acetate (PVA), tygon, polypropylene, polyester, polyamide, styrenic polymer, (methyl) acryl resin, polyvinyl butyral, organic siliconresin, polyurethane, epoxy resin, phenolics, xylene resin, modified rosin resin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, fragrant same clan petroleum resin etc.Synthetic resin can use separately a kind or and with more than 2 kinds.In these materials, preferably the wet granulation by aqueous systems obtains having polyester, styrenic polymer, (methyl) acrylic polymers, polyurethane, epoxy resin of the particle of high surface smoothing etc. easily.
Known material can be used as polyester, the condensed polymer of polyprotonic acid and polyvalent alcohol etc. can be enumerated.Polyprotonic acid can use as polyester monomer known substances, aromatic carboxylic acid classes such as terephthalic acid (TPA), m-phthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalene dicarboxylic acids for example, aliphatic carboxylic acid classes such as maleic anhydride, fumaric acid, succinic acid, alkylene succinic anhydride, hexane diacid, the esterification thing of these polyprotonic acids etc.Polyprotonic acid can use separately a kind or and with more than 2 kinds.Polyvalent alcohol also can use as polyester monomer known substances, for example can enumerate aliphatic polyol classes such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, neopentyl glycol, glycerine, ester ring type polyalcohols such as cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, aromatic diol classes such as the ethylene oxide adduct of bisphenol-A, the propylene oxide adduct of bisphenol-A etc.Polyvalent alcohol can use separately a kind or and with more than 2 kinds.The polycondensation reaction of polyprotonic acid and polyvalent alcohol can be implemented according to well-established law, for example organic solvent exist or not in the presence of and polycondensation catalyst in the presence of, undertaken by polyprotonic acid is contacted with polyvalent alcohol, the acid value of the polyester that is produced, softening temperature etc. stop when reaching setting.Thus, can obtain polyester.When the part of polyprotonic acid is used the esterification thing of polyprotonic acid, carry out the separating methanol polycondensation reaction.In this polycondensation reaction, the mixing ratio by appropriate change polyprotonic acid and polyvalent alcohol, reaction rate etc. for example can be adjusted the carboxyl-content of polyester end, and then can be with the characteristic modification of gained polyester.In addition, when using trimellitic anhydride,, also can obtain modified poly ester by easily carboxyl being imported in the main chain of polyester as polyprotonic acid.And, can also use hydrophilic radicals such as carboxyl, sulfonic group be combined on the main chain of polyester and/or the side chain, in water from dispersed polyester.
As styrenic polymer, can enumerate styrene monomer homopolymer, styrene monomer and can with multipolymer of the monomer of styrene monomer copolymerization etc.Styrene monomer for example can enumerate styrene, o-methyl styrene, ethyl styrene, to methoxy styrene, to styryl phenyl, 2, the 4-dimethyl styrene, to n-octyl styrene, align decyl styrene, align dodecyl styrene etc.As can with the monomer of styrene monomer copolymerization, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid n-octyl, (methyl) dodecylacrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) stearyl acrylate acid esters, (methyl) phenyl acrylate, (methyl) esters of acrylic acids such as (methyl) acrylic acid dimethylamino ethyl ester, vinyl cyanide, Methacrylamide, glycidyl methacrylate, N hydroxymethyl acrylamide, the N-methylol methacrylamide, acrylic acid-(methyl) acrylic monomer classes such as 2-hydroxyethyl ester, vinyl methyl ether, EVE, vinyl ethers such as vinyl isobutyl ether, ethenyl methyl ketone, the vinyl hexyl ketone, vinyl ketones such as methyl isopropenyl ketone, the N-vinyl pyrrolidone, the N-vinylcarbazole, N-vinyl compounds such as N-vinyl indoles etc.Styrene monomer and can using respectively more than a kind or 2 kinds with the monomer of phenylethylene list copolymerization.
As (methyl) acryl resin, the homopolymer, (methyl) esters of acrylic acid that can enumerate (methyl) esters of acrylic acid with can be with the multipolymer of the monomer of (methyl) acrylic ester copolymerization etc.(methyl) esters of acrylic acid for example can be enumerated material same as described above.As can with the monomer of (methyl) acrylic ester copolymerization, can enumerate (methyl) acrylic monomer class, vinyl ethers, vinyl ketones, N-vinyl compound etc.These materials can use material same as described above.As (methyl) acryl resin, can also use the acroleic acid resin that contains acidic-group.The acryl resin that contains acidic groups for example can be when making acryl resin monomer or acryl resin monomer and vinyl monomer copolymerization, and with the acryl resin monomer that contains acidic-group or hydrophilic radical and/or have acidic-group or the vinyl monomer of hydrophilic radical and making.Can use known material as the acryl resin monomer, for example can enumerate and have substituent acrylic acid sometimes, have substituent methacrylic acid sometimes, have substituent acrylate sometimes and have substituent methacrylate etc. sometimes.The acryl resin monomer can use separately a kind or and with more than 2 kinds.Known material be can also use as vinyl monomer, styrene, α-Jia Jibenyixi, bromine ethene, vinyl chloride, vinyl acetate, vinyl cyanide and methacrylonitrile etc. for example can be enumerated.Vinyl monomer can use separately a kind or and with more than 2 kinds.Styrenic polymer can use general radical initiator to be undertaken by solution polymerization, outstanding turbid polymerization, emulsion polymerization etc. with the polymerization of (methyl) acryl resin.
There is no particular restriction as polyurethane, for example can preferably use the polyurethane that contains acidic-group or basic group.The polyurethane that contains acidic-group or basic group can be by the known method manufacturing.For example, can make glycol, polyvalent alcohol and the polyisocyanate polyaddition that contains acidic-group or basic group.For example can enumerate dihydromethyl propionic acid and N methyldiethanol amine etc. as the glycol that contains acidic-group or basic group.For example can enumerate polyether polyol, polyester polyol, propylene acid polyol, the many alcohol of polybutadiene etc. such as polyglycol as polyvalent alcohol.For example can enumerate toluene diisocyanate, hexamethylene diisocyanate, isofoer diisocyanate etc. as polyisocyanates.These each compositions can distinguish use separately a kind or and with more than 2 kinds.There is no particular restriction for epoxy resin, can preferably use the epikote that contains acidic-group or basic group.The epoxy resin that contains acidic-group or basic group for example can be made on the epoxy resin that becomes the basis by making amine addition such as polyprotonic acid such as hexane diacid, trimellitic anhydride or dibutylamine, ethylenediamine or addition polymerization.
In these binder resins, preferred polyester.Polyester can obtain transparent good, the good toner of while permanance.In addition, can also be with polyester and acryl resin grafting and use.Binder resin can use a kind or and with different more than 2 kinds separately.And, even if identical resin also can use any differences or all different such as various molecular weights, monomer composition.
Among the present invention, binder resin also can use the self-dispersion type resin.The self-dispersion type resin is meant possess hydrophilic property group in its molecule, has dispersed resin with respect to liquid such as water.As hydrophilic radical for example can enumerate-the COO-group ,-SO 3-group ,-the CO-group ,-the OH group ,-OSO 3-group ,-PO 3H 2Group ,-PO 4-group, their salt etc.In these groups, especially preferably-the COO-group ,-SO 3Anionic property hydrophilic radicals such as-group.The self-dispersion type resin more than a kind or 2 kinds with this hydrophilic radical does not use spreading agent or only uses the spreading agent of minute quantity to be scattered in the water.There is no particular restriction for the contained hydrophilic radical amount of self-dispersion type resin, is 0.001～0.050 mole, more preferably 0.005～0.030 mole with respect to 100g self-dispersion type resin preferably.The self-dispersion type resin for example can be by making possess hydrophilic property group and unsaturated double-bond compound (below be called " compound that contains hydrophilic radical ") be incorporated on the resin and make.The compound that contains hydrophilic radical can be implemented by methods such as graft polymerization, block polymerizations the combination of resin.In addition, by the compound that makes the compound that contains hydrophilic radical or contain hydrophilic radical with can with the compound polymerization of its copolymerization, also can make the self-dispersion type resin.
As the resin that makes the compound combination that contains hydrophilic radical, for example can enumerate polystyrene, poly alpha methylstyrene, the chloro polystyrene, styrene-chloro-styrene copolymer, the styrene-propene multipolymer, Styrene-Butadiene, styrene-vinyl chloride copolymer, styrene-vinyl acetate co-polymer, styrene-maleic acid copolymer, copolymer in cinnamic acrylic ester, styrene-methacrylate copolymer, cinnamic acrylic ester-methacrylate copolymer, styrene-α-Lv Bingxisuanjiazhi multipolymer, styrene-acrylonitrile-acrylate copolymer, styrene resins such as styrene-ethylene ylmethyl ether copolymer, (methyl) acryl resin, polycarbonate, polyester, tygon, polypropylene, Polyvinylchloride, epoxy resin, urethane-modified epoxy resin, modifying epoxy resin by organosilicon, Abietyl modified maleic acid resin, ionomer resin, polyurethane, organic siliconresin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral, terpene resin, phenolics, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin etc.
Contain in the compound of hydrophilic radical and for example can enumerate unsaturated carboxylic acid compounds, unsaturated sulfonic acid compound etc.Unsaturated carboxylic acid compounds for example can be enumerated unsaturated carboxylic acids such as (methyl) acrylic acid, crotonic acid, iso-crotonic acid, unsaturated dicarboxylics such as maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, acid anhydrides such as maleic anhydride, citraconic anhydride, their Arrcostab, dialkyl, metal alkyl salt, alkali metal salt,, alkali salt, ammonium salt etc.The unsaturated sulfonic acid compound for example can be enumerated styrene sulfonic acid class, (methyl) acrylic acid sulfo group alkyl esters, their slaine, ammonium salt etc.The compound that contains hydrophilic radical can use a kind separately, perhaps also with more than 2 kinds.In addition, for example can use sulfoacid compound etc. as the monomeric compound beyond the compound that contains hydrophilic radical.For example can enumerate sulfoisophthalic acid, sulfo group terephthalic acid (TPA), sulfosalicylic phthalate, sulfosuccinic acid, sulfosalicylic acid, sulfosalicylic acid, their slaine, ammonium salt etc. as sulfoacid compound.
The binder resin that uses among the present invention can also contain general synthetic resin adjuvant more than a kind or 2 kinds.For example can enumerate inorganic filler, colorant, antioxidant, release agent, antistatic agent, charge control agent, lubricant, thermal stabilizer, fire retardant, dripping inhibitor, ultraviolet light absorber, light stabilizer, opacifier, metal inerting agent, antiaging agent, smoothing preparation, plastifier, impact strength modifying agent, bulking agent of different shape (particle shape, fibrous, flakey) etc. with the object lesson of adjuvant as this synthetic resin.
Toner of the present invention can also contain colorant except biomass resin, binder resin.There is no particular restriction for colorant, for example can enumerate organic class dyestuff, organic class pigment, mineral-type dyestuff, mineral-type pigment etc.
Black colorant for example can be enumerated carbon black, cupric oxide, manganese dioxide, nigrosine, activated charcoal, non magnetic ferrite, magnetic ferrite and magnetic iron ore etc.
Yellow colorants for example can be enumerated chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, the mineral fast yellow, nickel titanium yellow, navel Huang (navel yellow), naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow G R, quinoline yellow lake, permanent yellow NGG, tartrazine lake, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 17, C.I. pigment yellow 74, C.I. pigment yellow 93, C.I. pigment yellow 94, C.I. pigment yellow 13 8, C.I. pigment yellow 180, C.I. pigment yellow 185 etc.
Orange colorant for example can be enumerated chrome orange, molybdate orange, solid orange GTR, pyrazolone orange, the orange of anti-sulfuration the, indanthrene brilliant orange RK, Benzidine orange G, indanthrene brilliant orange GK, C.I. pigment orange 31, C.I. pigment orange 43 etc. forever.
Red stain for example can be enumerated colcother, cadmium red, the red lead, mercuric sulphide, cadmium, permanent bordeaux 4R, lithol red, pyrazolone red, Hua Qionghong (watching red), calcium salt, lake red C, C lake red CAN'T D, brilliant carmine 6B, eosine lake, rhodamine color lake B, alizarine lake, bright carmine 3B, C.I. paratonere 2, C.I. pigment red 3, C.I. paratonere 5, C.I. paratonere 6, C.I. paratonere 7, C.I. paratonere 15, C.I. paratonere 16, C.I. pigment red 4 8:1, C.I. paratonere 53:1, C.I. paratonere 57:1, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 139, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 222 etc.
Violet colorant for example can be enumerated manganese violet, Fast violet B, methyl violet color lake etc.
That blue colorant for example can be enumerated is dark blue, cobalt blue, alkali blue lake, Victoria blue color lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue part chloride, fast sky blue, indanthrene blue BC, C.I. pigment blue 15, C.I. pigment blue 15: 2, C.I. pigment blue 15: 3, C.I. pigment blue 16, C.I. pigment blue 60 etc.
Green colourant for example can be enumerated chrome green, chromium oxide, pigment green B, peacock green color lake, ultimate yellowish green G, C.I. pigment Green 7 etc.
White color agents for example can be enumerated compounds such as zinc white, titania, stibium trioxide, zinc sulphide.
Colorant can use a kind or and with the colorant of different colours more than 2 kinds separately.In addition, even if identical color, also two or more kinds may be used.
Be formed with the toner particle 1 that contains biomass resin zone 2 and describe in detail, for example can make the adhesive resin particles slurries that disperse binder resin at least and make and disperse the biomass resin and the biomass resin particle slurries cohesion made and obtaining in the back.
Fig. 3 is the process flow diagram of manufacture method the 1st example of expression toner particle 1.
[adhesive resin particles dispersion step]
The adhesive resin particles dispersion step of step a1 is to be scattered in the liquid medium and the operation of making the adhesive resin particles slurries to major general's binder resin.In the adhesive resin particles slurries, for example can contain other toner components such as release agent, charge control agent.Release agent is in order to give the toner release property with toner fixing on recording medium the time and to add.Therefore, compare, can improve the stained beginning temperature of high temperature, improve high temperature resistant stained property with the situation of not using release agent.In addition, the heating during by fusing toner makes the release agent fusion, can reduce photographic fixing and begin temperature, improves low-temperature fixing.There is no particular restriction for release agent, for example can enumerate paraffin and derivant thereof, petroleum-type such as microcrystalline wax and derivant thereof wax, Fischer-Tropsch synthetic wax and derivant thereof, polyolefin-wax and derivant thereof, low-molecular-weight polypropylene wax and derivant thereof, hydro carbons synthetic waxs such as polyolefin polymers wax (low molecular weight polyethylene wax etc.) and derivant thereof, Brazil wax and derivant thereof, rice wax and derivant thereof, candelila wax and derivant thereof, plant class waxes such as haze tallow, beeswax, animal waxs such as spermaceti, fatty acid amide, grease class synthetic waxs such as phenol fatty acid ester, long-chain carboxylic acid and derivant thereof, long-chain alcohol and derivant thereof, silicone based polymkeric substance, higher fatty acid etc.Derivant comprises the graft modification thing etc. of segmented copolymer, vinyl monomer and the wax of oxide, vinyl monomer and wax.Release agent can use separately a kind or and with more than 2 kinds.
Charge control agent is used to give the preferred charging property of toner and adds.There is no particular restriction as charge control agent, can use the material that is used to control positive charge and is used to control negative charge.As the charge control agent that is used to control positive charge, for example can enumerate basic-dyeable fibre, quaternary ammonium salt, quaternary alkylphosphonium salt, aminopyrine, pyrimidine compound, multinuclear polyamino compounds, amino silane, aniline black byestuffs and derivant thereof, triphenylmethane derivative, guanidinesalt, amidine salt etc.Can enumerate the metal complex of hydrocarbon black, ス ピ ロ Application Block ラ Star Network oil-soluble dyes such as (SpironBlack), containing metal azo-compound, azo complex compound dyestuff, metal naphthenate, salicylic acid and derivant thereof and slaine (metal is chromium, zinc, zirconium etc.), fatty acid soaps, chain alkyl carboxylate, resin acid soaps etc. as the charge control agent that is used to control negative charge.Charge control agent can use a kind separately, perhaps as required also with more than 2 kinds.
There is no particular restriction in the dispersion of adhesive resin particles in liquid medium; can be undertaken by known method, but preferably the high pressure homogenization method of the refrigerating work procedure of the decompression operation of the grain refined operation by comprising step a1-(a), step a1-(b), step a1-(c) carries out.Thus, binder resin can be pulverized is the state that particle diameter is little and particle size distribution is little.In the present embodiment, the adhesive resin particles dispersion step is undertaken by high pressure homogenizer.
High pressure homogenizer comprises that jar, presser unit, well heater, pulverizing constitute with nozzle, pressure relief assembly and cooler.Jar for having the container-like member of inner space, store that binder resin is scattered in the liquid flux and the dispersion liquid that obtains.Presser unit is pressurizeed to the dispersion liquid of binder resin.Well heater heats the dispersion liquid of the binder resin by presser unit pressurization.Pulverizing is flowed through by the dispersion liquid that makes the binder resin that is in the heating and pressurizing state with nozzle and is formed at its inner stream and binder resin is ground into adhesive resin particles, makes the adhesive resin particles slurries.Pressure relief assembly reduces pressure not cause the mode that causes bubble to produce because of bumping to the adhesive resin particles slurries that are in the heating and pressurizing state.Cooler will be in the adhesive resin particles slurries cooling of heated condition.High pressure homogenizer market is on sale.Its object lesson for example can be enumerated NANO3000 (trade name, the U.S. grain system of Co., Ltd.) etc.
(grain refined operation)
The grain refined operation of step a-1 (a) is binder resin is pulverized and to be scattered in the liquid medium and to obtain the operation of adhesive resin particles slurries.At first, in the jar that high pressure homogenizer had, store the dispersion liquid that contains binder resin.Hydrophilic media such as liquid medium preferred water of mixing with binder resin or alcohol can suitably be added dispersion stabilizer, tackifier, surfactant etc.Be stored in the dispersion liquid that contains binder resin in the jar by presser unit pressurization, by heater heats, flow through and pulverize with the stream that forms in the nozzle, thereby with the binder resin coarse crushing.There is no particular restriction for the pressurized, heated condition of binder resin dispersion liquid of this moment, preferably be forced into 15MPa above, below the 120MPa, and more than 10 ℃ and less than the glass transition temperature (Tg) of binder resin.The dispersion liquid of binder resin after coarse crushing further flowed through and pulverized with the stream that forms in the nozzle, thereby with the binder resin grain refined, obtains the adhesive resin particles slurries.There is no particular restriction for the pressurized, heated condition of this moment, preferably is forced into more than the 50MPa, below the 250MPa, and is heated to more than 50 ℃.Owing to pulverizing binder resin under the pressurized, heated condition like this, therefore can pulverize binder resin efficiently.
(decompression operation)
The decompression operation of step a1-(b) is the operation that the adhesive resin particles slurries that are in the pressurized, heated state are reduced pressure.Be decompressed to atmospheric pressure or the pressure approaching with pressure relief assembly not cause the adhesive resin particles slurries that cause the mode of bubble generation will be in the heating and pressurizing state because of bumping with it.
(refrigerating work procedure)
The refrigerating work procedure of step a1-(c) is to be in the operation of the adhesive resin particles slurries cooling of heated condition.The adhesive resin particles slurries that will be in heated condition with cooler are cooled to about 20 ℃～about 40 ℃ within a short period of time.
Like this, can obtain the adhesive resin particles slurries.In this manufacture method, by suitable adjustment flow through applied pressure when pulverizing with nozzle and (or) solid component concentration in the temperature, adhesive resin particles slurries, pulverize number of times etc., can control the particle diameter of gained adhesive resin particles.Preferred each condition of adjusting makes that the volume average particle size of adhesive resin particles preferably reaches below the 1 μ m, more preferably reaches 0.01～1 μ m.When volume average particle size surpassed 1 μ m, it is wide that the size distribution of the toner particle that finally obtains becomes, and produces free particle, causes the reduction of toner performance, reliability easily.
[biomass resin particle dispersion step]
The biomass resin particle dispersion step of step a2 be with the biomass resin dispersion in liquid medium and make operation as the biomass resin particle slurries of the slurries of biomass resin particle.There is no particular restriction in the dispersion of biomass resin particle in liquid medium; can be undertaken by known method, but preferably the high pressure homogenization method of the refrigerating work procedure of the decompression operation of the grain refined operation by comprising step a2-(a), step a2-(b), step a2-(c) carries out.Thus, the biomass resin can be pulverized is the state that particle diameter is little and particle size distribution is little.In the present embodiment, biomass resin particle dispersion step is undertaken by the high pressure homogenizer that uses in the above-mentioned adhesive resin particles dispersion step.
(grain refined operation)
The grain refined operation of step a-2 (a) is the biomass resin is pulverized and to be scattered in the liquid medium and to obtain the operation of biomass resin particle slurries.The same with the liquid medium that uses in the liquid medium of biomass mixed with resin and the adhesive resin particles dispersion step, hydrophilic media such as preferred water or alcohol can suitably be added dispersion stabilizer, tackifier, surfactant etc.At this moment, preferably do not add colorant.When containing colorant in the biomass resin, because the filling effect of colorant, the biomass resin is reinforced, hardness improves, and softening temperature also improves.Do not contain colorant by making in the biomass resin particle slurries, can prevent that the softening temperature of biomass resin from improving, when with toner heating, pressurization and photographic fixing on recording medium the time can prevent that the fixation performance of toner from reducing.In addition, the dispersion liquid that contains the biomass resin is the same with the adhesive resin particles dispersion step, flows through to pulverize under the pressurized, heated condition and uses nozzle, and the biomass resin is pulverized, grain refined, obtains biomass resin particle slurries.Owing under the pressurized, heated condition, pulverize the biomass resin like this, therefore can pulverize the biomass resin efficiently.
(decompression operation)
The decompression operation of step a2-(b) is the operation that the biomass resin particle slurries that are in the pressurized, heated state are reduced pressure.Be decompressed to atmospheric pressure or the pressure approaching with pressure relief assembly not cause the biomass resin particle slurries that cause the mode of bubble generation will be in the heating and pressurizing state because of bumping with it.
(refrigerating work procedure)
The refrigerating work procedure of step a2-(c) is to be in the operation of the biomass resin particle slurries cooling of heated condition.The biomass resin particle slurries that will be in heated condition with cooler are cooled to about 20 ℃～about 40 ℃ within a short period of time.Like this, owing to cool off biomass resin particle slurries within a short period of time forcibly, the crystallization that therefore can suppress the biomass resin particle is promoted, can prevent that the transparency of toner from reducing.
Like this, can obtain biomass resin particle slurries.In this manufacture method, by suitable adjustment flow through applied pressure when pulverizing with nozzle and (or) solid component concentration in the temperature, biomass resin particle slurries, pulverize number of times etc., can control the particle diameter of gained biomass resin particle.Among the present invention, preferably adjust each condition and make the volume average particle size of biomass resin particle preferably reach more than the 0.5 μ m, below the 1 μ m.Thus, can preferably be controlled at the toner particle 1 contained regional diameter that contains biomass resin zone 2 below the 1 μ m, more preferably be controlled at more than the 0.5 μ m, below the 1 μ m, details be in the back narration.
[cohesion process]
The cohesion process of step a3 is to add polycoagulant in the mixed serum that is mixed with adhesive resin particles slurries and biomass resin particle slurries, make the cohesion of adhesive resin particles and biomass resin particle, make the operation of the slurries (below be called " toner particle slurries ") of toner particle 1.In the cohesion process, use the stirred vessel that possesses the mixed serum that stores adhesive resin particles slurries and biomass resin particle slurries and be arranged at the granulation device that stirs the mixing part of slurries in the stirred vessel, mix slurries.
Polycoagulant as being used to make adhesive resin particles and the cohesion of biomass resin particle can use the salt of 1 valency, the salt of divalent, the salt of 3 valencys etc.As the salt of 1 valency, for example can enumerate cationic spreading agents such as alkyl trimethyl ammonium chloride, inorganic salts such as sodium chloride, potassium chloride, ammonium chloride etc.As the salt of divalent, for example can enumerate magnesium chloride, lime chloride, zinc chloride, cupric chloride (II), magnesium sulphate, manganese sulfate etc.As the salt of 3 valencys, for example can enumerate ammonium chloride, iron chloride (III) etc.In the above-mentioned illustrative polycoagulant, the preferred alkyl trimethyl ammonium chloride.As the object lesson of alkyl trimethyl ammonium chloride, for example can enumerate OTAC, three (polyoxyethylene) octadecyl ammonium chloride, DTAC etc.Polycoagulant can use separately a kind or and with more than 2 kinds.There is no particular restriction for the addition of polycoagulant, can suitably select in very wide scope, preferably contains in mixed serum with the ratio more than the 0.1 weight %, below the 5 weight % with respect to the mixed serum total amount.
In the present embodiment, polycoagulant is added into mixed serum after, utilize granulation device to stir while heat mixed serum.There is no particular restriction for the heating-up temperature of mixed serum, according to suitably decision such as the particle diameter of the toner particle of wanting to obtain 1, the solid component concentration in the mixed serum, used polycoagulant.The heating-up temperature of mixed serum is preferred more than 65 ℃ and less than 90 ℃.During less than 65 ℃, does not merge with adhesive resin particles sometimes in the formed biomass resin zone 2 that contains, and the situation of the permanance reduction of toner is arranged.In addition, be more than 90 ℃ the time, formed to contain biomass resin zone 2 compatible with adhesive resin particles sometimes, the situation that has the permanance of toner to reduce.The heating-up temperature of mixed serum can be according to cohesion carry out the degree appropriate change.
In addition, utilize the mixing time of granulation device and stirring rate also not to have special restriction, according to suitably decision such as the particle diameter of the toner particle of wanting to obtain 1, the solid component concentration in the mixed serum, used polycoagulant.The mixing time of mixed serum and stirring rate can be according to cohesion carry out the degree appropriate change.
Like this, can obtain being formed with the slurries of the toner particle 1 that contains biomass resin zone 2.Contain biomass resin zone 2 and have the interior particle diameter of certain limit, be evenly dispersed in substantially in the toner particle 1, therefore can prevent that the biomass resin is scattered in the toner particle 1 with the island state.Therefore, can be under the situation that does not reduce the toner permanance a kind of toner particle to contain the biomass resin at high proportion, can suppress environmental pollution.In addition,, therefore the toner transparency can be do not reduced,, the characteristic inequality between toner particle can be suppressed even if also can guarantee sufficient color reproducible range when being applied to color toner owing to can prevent to follow the gonorrhoeaization of biomass resin crystallization.
In this manufacture method,, the particle diameter of gained toner particle 1 can be controlled, the regional diameter that contains biomass resin zone 2 that is formed in the toner particle 1 can be controlled simultaneously by heating-up temperature, mixing time and the stirring rate etc. of suitable adjustment mixed serum.Among the present invention, toner particle 1 preferably carries out granularity control so that its volume average particle size is that 4 μ m are above, makes below the 8 μ m.Volume average particle size is 4 μ m are above, 8 μ m are a following toner particle 1 when using as toner, can stably make charged excellent in stability, high concentration and high meticulous, image repetition well, do not have a high quality image of image problem.
In addition, contain that biomass resin zone 2 is preferably controlled so that its regional diameter is that 1 μ m is following, preferred 0.5 μ m is above, 1 μ m is following makes.By such control area diameter, can prevent regional diameter become too small, binder resin and the biomass resin because the heating of cohesion process etc. and compatible.Therefore, the glass transition temperature (Tg) that can prevent binder resin reduces, prevents that the storage stability of toner from reducing.In addition, can prevent that regional diameter from becoming excessive, thereby the particle diameter that prevents toner particle 1 increases.Therefore, can make the little toner of particle diameter of toner particle 1.In addition, be below the 1 μ m by making regional diameter, can obtain the good toner of the transparency.And owing to the ratio that the biomass resin can be exposed toner surface suppresses lowlyer, therefore the storage stability of toner can be maintained under the high state, the contacted ratio of biomass resin and recording medium increases when preventing photographic fixing simultaneously, prevents the toner fixing reduction.
[washing procedure]
The washing procedure of step a4 is the operation with toner particle 1 contained in the toner particle slurries cooling back washing toner particle slurries.The washing of toner particle 1 is in order to remove surfactant contained in the toner particle slurries, spreading agent, tackifier etc. and to come from the impurity etc. of these materials and implement.Washing methods for example adds entry and stirs in the toner particle slurries, remove the supernatant by separation such as centrifugings.The washing that preferably repeats toner particle 1 reaches below the 10 μ S/cm, preferably reaches below the 5 μ S/cm until the conductivity of the supernatant of mensuration such as use conductivity meter.
[separation circuit]
The separation circuit of step a5 is the operation of separating toner particle 1 and reclaiming from the potpourri of the liquid medium that contains washing back toner particle 1.There is no particular restriction from the separation of liquid medium for toner particle 1, for example can be undertaken by filtration, suction filtration, centrifuging etc.
[drying process]
Toner particle 1 drying after the drying process of step a6 will wash, separate.There is no particular restriction for the drying of toner particle 1, can pass through enforcements such as freeze-drying, air-flowing type seasoning.During with toner particle 1 drying, the manufacturing of toner particle 1 finishes.
Fig. 4 is the process flow diagram of manufacture method the 2nd example of expression toner particle 1.
[pigmentary resin melting mixing operation]
The pigmentary resin melting mixing operation of step s1 is that to make with binder resin and colorant be must composition and then contain the operation of the melting mixing thing of release agent, charge control agent etc.Release agent adds in order to give the toner release property when making toner fixing in recording medium.Therefore, compare, can improve the stained beginning temperature of high temperature, improve high temperature resistant stained property with the situation of not using release agent.In addition, the heating during by fusing toner makes the release agent fusion, can reduce photographic fixing and begin temperature, improves low-temperature fixing.There is no particular restriction for release agent, for example can enumerate paraffin and derivant thereof, petroleum-type such as microcrystalline wax and derivant thereof wax, Fischer-Tropsch synthetic wax and derivant thereof, polyolefin-wax and derivant thereof, low-molecular-weight polypropylene wax and derivant thereof, hydro carbons synthetic waxs such as polyolefin polymers wax (low molecular weight polyethylene wax etc.) and derivant thereof, Brazil wax and derivant thereof, rice wax and derivant thereof, candelila wax and derivant thereof, plant class waxes such as haze tallow, beeswax, animal waxs such as spermaceti, fatty acid amide, grease class synthetic waxs such as phenol fatty acid ester, long-chain carboxylic acid and derivant thereof, long-chain alcohol and derivant thereof, silicone based polymkeric substance, higher fatty acid etc.Derivant comprises the graft modification thing etc. of segmented copolymer, vinyl monomer and the wax of oxide, vinyl monomer and wax.Release agent can use separately a kind or and with more than 2 kinds.
Charge control agent is used to give the preferred charging property of toner and adds.There is no particular restriction as charge control agent, can use the material that is used to control positive charge and is used to control negative charge.As the charge control agent that is used to control positive charge, for example can enumerate basic-dyeable fibre, quaternary ammonium salt, quaternary alkylphosphonium salt, aminopyrine, pyrimidine compound, multinuclear polyamino compounds, amino silane, aniline black byestuffs and derivant thereof, triphenylmethane derivative, guanidinesalt, amidine salt etc.Can enumerate the metal complex of hydrocarbon black, ス ピ ロ Application Block ラ Star Network oil-soluble dyes such as (SpironBlack), containing metal azo-compound, azo complex compound dyestuff, metal naphthenate, salicylic acid and derivant thereof and slaine (metal is chromium, zinc, zirconium etc.), fatty acid soaps, chain alkyl carboxylate, resin acid soaps etc. as the charge control agent that is used to control negative charge.Charge control agent can use a kind separately, perhaps as required also with more than 2 kinds.
The melting mixing thing for example can be made gained powder mixture melting mixing with mixing roll by after with mixer dry types such as binder resin, colorant and release agent as required, charge control agent being mixed.Melting temperature is the above temperature of the melt temperature of binder resin (being generally about 80 ℃～about 200 ℃, preferred about 100 ℃～about 150 ℃).Mixer can use known device, for example can enumerate Henschel mixer (trade name, Mitsui Mining Co Ltd. BJ Offc's system), ス one パ one ミ キ サ (trade name, the カ ワ タ of Co., Ltd. system), メ カ ノ ミ Le Henschel type mixing arrangements such as (trade name, field, ridge Jinggong Co., Ltd systems), オ Application グ ミ Le (trade name, ホ ソ カ ワ ミ Network ロ Application Co., Ltd. system), Ha イ Block リ ダ イ ゼ one シ ョ Application シ ス テ system (trade name, Nara Machinery Co., Ltd.'s system), コ ス モ シ ス テ system (trade name, Kawasaki Heavy Industries Ltd's system) etc.
Mixing roll can use known device, for example can use kneader, double screw extrusion machine, two roller mills, three-roll grinder, ラ ボ プ ラ ス ト ミ Le general mixing rolls such as (laboplast mill).More particularly, for example can enumerate the mixing roll of single screw rods such as TEM-100B (trade name, Toshiba Machinery Co., Ltd.'s system), PCM-65/87, PCM-30 (more than be trade name, Co., Ltd.'s pond shellfish system) or double screw extruder, ニ one デ Star Network ス open roll shapes such as (trade name, Mitsui Mining Co Ltd. BJ Offc's systems).Melting mixing can also use a plurality of mixing rolls to carry out.
[pigmentary resin particle dispersion step]
The pigmentary resin particle dispersion step of step s2 is that the melting mixing thing that will make in the pigmentary resin melting mixing operation is scattered in the liquid medium and makes operation as the pigmentary resin particle slurries of the slurries of pigmentary resin particle.There is no particular restriction in the dispersion of pigmentary resin particle in liquid medium; can be undertaken by known method, preferably the high pressure homogenization method of the refrigerating work procedure of the decompression operation of the grain refined operation by comprising step a2-(a), step a2-(b), step a2-(c) carries out.Thus, the melting mixing thing can be pulverized is the state that particle diameter is little and particle size distribution is little.In the present embodiment, pigmentary resin particle dispersion step is undertaken by the high pressure homogenizer that uses in the above-mentioned adhesive resin particles dispersion step.
(grain refined operation)
The grain refined operation of step a-2 (a) be with melting mixing thing grinding dispersion in liquid medium and obtain the operation of pigmentary resin particle slurries.At first, the dispersion liquid that will contain the melting mixing thing is stored in the jar that high pressure homogenizer has.The liquid medium that mixes with the melting mixing thing is not so long as dissolve the melting mixing thing and can make its homodisperse liquid material then not have special restriction, but consider the easiness of process management, all the liquid waste processing after the operation, handle easiness etc., hydrophilic media such as preferred water or alcohol more preferably contains the hydrophilic media of dispersion stabilizer.Dispersion stabilizer preferably made an addition in the hydrophilic media before making an addition to the melting mixing thing in the hydrophilic media in advance.
Dispersion stabilizer can use material commonly used in this field.Wherein, preferred hydrophilic macromolecular dispersion stabilizer.The hydrophilic macromolecule dispersion stabilizer for example can be enumerated (methyl) acrylic polymers, polyoxyethylene base polymer, cellulosic polymer, polyoxyalkylene alkyl aryl ether sulfate, polyoxyalkylene alkyl sulfate etc.
(methyl) acrylic polymers comprises and is selected from (methyl) acrylic acid, alpha-cyanoacrylate, the alpha-cyano methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, acrylic monomers such as maleic anhydride, senecioate-hydroxy methacrylate, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxy propyl ester, methacrylic acid-beta-hydroxy propyl ester, acrylic acid-γ-hydroxy propyl ester, methacrylic acid-γ-hydroxy propyl ester, acrylic acid-3-chloro-2-hydroxy propyl ester, methacrylic acid-3-chloro-2-hydroxy propyl ester etc. contains the acrylic monomer of hydroxyl, diethylene glycol monoacrylate, the diethylene glycol monomethacrylates, the glycerine mono acrylic ester, esters monomers such as glycerin monomethyl acrylic ester, N hydroxymethyl acrylamide, vinyl alcohol monomers such as N-methylol methacrylamide, vinyl methyl ether, EVE, vinyl alkyl ethers class monomers such as vinyl propyl ether, vinyl acetate, propionate, vinyl alkyl class monomers such as vinyl butyrate, styrene, α-Jia Jibenyixi, aromatic vinyl base class monomers such as vinyltoluene, acrylamide, Methacrylamide, diacetone acrylamide, their amide-type monomers such as methylol compound, vinyl cyanide, nitrile monomers such as methacrylonitrile, acryloyl chloride, acyl chloride monomers such as methacrylic chloride, vinylpyridine, vinyl pyrrolidone, vinyl imidazole, vinyl imines vinyl nitrogen heterocyclic ring class monomers such as (ethyleneimine), Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate, allyl methacrylate, 1 kind or 2 kinds hydrophilic monomer of cross-linkable monomers such as divinylbenzene etc.
The example of polyoxyethylene base polymer comprises polyoxyethylene, polyoxypropylene, polyoxyethylene alkyl amine, polyoxypropylene alkyl amine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylplenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene octadecyl phenylester, polyoxyethylene nonyl phenylester.
The example of cellulosic polymer comprises methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose.
The example of polyoxyalkylene alkyl aryl ether sulfate comprises polyoxyethylene lauryl phenyl ether sodium sulphate, polyoxyethylene lauryl phenyl ether glazier's salt, polyoxyethylene nonylplenyl ether sodium sulphate, polyoxyethylene oil base phenyl ether sodium sulphate, polyoxyethylene cetyl base phenyl ether sodium sulphate, polyoxyethylene lauryl phenyl ether ammonium sulfate, polyoxyethylene nonylplenyl ether ammonium sulfate, polyoxyethylene oil base phenyl ether ammonium sulfate.
The example of polyoxyalkylene alkyl sulfate comprises polyoxyethylene lauryl ether sodium sulphate, polyoxyethylene lauryl ether glazier's salt, polyoxyethylene oleyl ether sodium sulphate, polyoxyethylene cetyl base ether sodium sulfate, polyoxyethylene lauryl ether ammonium sulfate, polyoxyethylene oleyl ether ammonium sulfate.Dispersion stabilizer can use separately a kind or and with more than 2 kinds.There is no particular restriction for the addition of dispersion stabilizer, and the 0.05 weight % that is preferably pigmentary resin particle slurries is above, below the 10 weight %, more preferably 0.1 weight % above, below the 3 weight %.
In the dispersion liquid of melting mixing thing, also can add tackifier, surfactant etc. with dispersion stabilizer.The tackifier for example further micronize for the pigmentary resin particle are effective.Surfactant for example further improves the dispersiveness of pigmentary resin particle in hydrophilic media.Tackifier are preferably selected from the polysaccharide tackifier of synthetic high polymer polysaccharide and natural macromolecule amylose class.The synthetic high polymer polysaccharide can use known material, for example block polymer of cationized cellulose, hydroxyethyl cellulose, starch, ionization starch derivative, starch and synthetic high polymer etc.The natural macromolecule amylose class for example can be enumerated hyaluronic acid, carragheen, locust bean gum, xanthans, guar gum, gellan gum etc.Tackifier can use separately a kind or and with more than 2 kinds.There is no particular restriction for the addition of tackifier, and the 0.01 weight % that is preferably pigmentary resin particle slurries total amount is above, below the 2 weight %.
Surfactant for example can be enumerated sulfosuccinic acid lauryl disodium, polyoxyethylene sulfosuccinic acid lauryl disodium, the polyxyethylated (sulfosuccinate ester salts such as disodium sulfosuccinate, sulfosuccinic acid polyoxyethylene lauroyl glycollic amide disodium, Sodium docusate of C12～C14).Surfactant can use separately a kind or and with more than 2 kinds.There is no particular restriction for the addition of surfactant, and the 0.05 weight % that is preferably pigmentary resin particle slurries total amount is above, below the 0.2 weight %.
The dispersion liquid that is stored in the melting mixing thing in the jar that high pressure homogenizer has through presser unit pressurization, heater heats, the stream of flowing through and forming in pulverizing with nozzle, with the coarse crushing of melting mixing thing.There is no particular restriction for the pressurized, heated condition of dispersion liquid of the melting mixing thing of this moment, preferably be forced into 15MPa above, below the 120MPa, and more than 10 ℃ and less than the glass transition temperature (Tg) of binder resin.The dispersion liquid of melting mixing thing after coarse crushing further flowed through and pulverized with the stream that forms in the nozzle, with melting mixing thing grain refined, obtains pigmentary resin particle slurries.There is no particular restriction for the pressurized, heated condition of this moment, preferably is forced into more than the 50MPa, below the 250MPa, and is heated to more than 50 ℃.Owing to, therefore can pulverize efficiently pulverizing the melting mixing thing under the pressurized, heated condition like this.
(decompression operation)
The decompression operation of step s2-(b) is the operation that the pigmentary resin particle slurries that are in the pressurized, heated state are reduced pressure.Be decompressed to atmospheric pressure or the pressure approaching with pressure relief assembly not cause the pigmentary resin particle slurries that cause the mode of bubble generation will be in the heating and pressurizing state because of bumping with it.
(refrigerating work procedure)
The refrigerating work procedure of step s2-(c) is to be in the operation of the pigmentary resin particle slurries cooling of heated condition.The pigmentary resin particle slurries that will be in heated condition with cooler are cooled to about 20 ℃～about 40 ℃ within a short period of time.
Like this, can obtain containing the pigmentary resin particle slurries of binder resin and the necessary composition of colorant conduct.In this manufacture method, by suitable adjustment flow through applied pressure when pulverizing with nozzle and (or) solid component concentration in the temperature, pigmentary resin particle slurries, pulverize number of times etc., can control the particle diameter of gained pigmentary resin particle.Among the present invention, preferred each condition of adjusting, make the volume average particle size of pigmentary resin particle preferably reach 0.2 μ m above, below the 0.5 μ m, and controlling it, to reach the volume average particle size that forms the biomass resin particle that contains biomass resin zone 2 with respect to aftermentioned be more than 1/4, below 1/2.Thus, the particle diameter that can prevent to have the pigmentary resin particle of keeping toner permanance effect becomes too small.Therefore, the permanance that can prevent toner reduces.In addition, can prevent that regional diameter from becoming excessive, being scattered in and contacting between the biomass resin zone 2 containing in the toner particle 1 and engage.Therefore, the permanance that can prevent toner reduces.
In addition, the volume average particle size by making the pigmentary resin particle is more than 1/4 with respect to the volume average particle size of biomass resin particle, can prevent pigmentary resin and biomass resin compatible.Therefore, can prevent that the glass transition temperature (Tg) of the binder resin that pigmentary resin is contained from reducing, thereby the storage stability that prevents toner reduces.And then, volume average particle size by making the pigmentary resin particle is below 1/2 with respect to the volume average particle size of biomass resin particle, the ratio that the biomass resin exposes toner surface in the time of long-term operation can being used suppresses lowlyer, therefore the permanance of toner can be maintained under the high state, biomass resin and the contacted ratio of recording medium increase in the time of simultaneously can preventing photographic fixing, thereby the fixation performance that prevents toner reduces.
[biomass resin particle dispersion step]
The biomass resin particle dispersion step of step s3 can similarly be carried out with the biomass resin particle dispersion step of step a2 in above-mentioned manufacture method the 1st example in manufacture method the 2nd example.That is, the biomass resin particle dispersion step of step s3 comprises the grain refined operation of step s3-(a), the decompression operation of step s3-(b), the refrigerating work procedure of step s3-(c).The grain refined operation of step s3-(a) is identical with the grain refined operation of step a2-(a) in above-mentioned manufacture method the 1st example, omits its explanation.The decompression operation of step s3-(b) is identical with the decompression operation of step a2-(b) in above-mentioned manufacture method the 1st example, omits its explanation.The refrigerating work procedure of step s3-(c) is identical with the refrigerating work procedure of step a2-(c) in above-mentioned manufacture method the 1st example, omits its explanation.
[cohesion process]
The cohesion process of step s4 is to add polycoagulant and make pigmentary resin particle and the cohesion of biomass resin particle in the mixed serum that is mixed with pigmentary resin particle slurries and biomass resin particle slurries, makes the operation of the slurries (below be called " toner particle slurries ") of toner particle 1.In the cohesion process, use the stirred vessel that possesses the mixed serum that stores pigmentary resin particle slurries and biomass resin particle slurries and be arranged at the granulation device that stirs the mixing part of slurries in the stirred vessel, mix slurries.
Polycoagulant as being used to make pigmentary resin particle and the cohesion of biomass resin particle can use the salt of 1 valency, the salt of divalent, the salt of 3 valencys etc.As the salt of 1 valency, for example can enumerate cationic spreading agents such as alkyl trimethyl ammonium chloride, inorganic salts such as sodium chloride, potassium chloride, ammonium chloride etc.As the salt of divalent, for example can enumerate magnesium chloride, lime chloride, zinc chloride, cupric chloride (II), magnesium sulphate, manganese sulfate etc.As the salt of 3 valencys, for example can enumerate ammonium chloride, iron chloride (III) etc.In the above-mentioned illustrative polycoagulant, the preferred alkyl trimethyl ammonium chloride.As the object lesson of alkyl trimethyl ammonium chloride, for example can enumerate OTAC, three (polyoxyethylene) octadecyl ammonium chloride, DTAC etc.Polycoagulant can use separately a kind or and with more than 2 kinds.There is no particular restriction for the addition of polycoagulant, can suitably select in very wide scope, preferably contains in mixed serum with the ratio more than the 0.1 weight %, below the 5 weight % with respect to the mixed serum total amount.
In the present embodiment, polycoagulant is added into mixed serum after, utilize granulation device to stir while heat mixed serum.There is no particular restriction for the heating-up temperature of mixed serum, according to suitably decision such as the particle diameter of the toner particle of wanting to obtain 1, the solid component concentration in the mixed serum, used polycoagulant.The heating-up temperature of mixed serum is preferred more than 65 ℃ and less than 90 ℃.During less than 65 ℃, does not merge with adhesive resin particles sometimes in the formed biomass resin zone 2 that contains, and the situation of the permanance reduction of toner is arranged.In addition, be more than 90 ℃ the time, formed to contain biomass resin zone 2 compatible with adhesive resin particles sometimes, the situation that has the permanance of toner to reduce.The heating-up temperature of mixed serum can be according to cohesion carry out the degree appropriate change.
In addition, utilize the mixing time of granulation device and stirring rate also not to have special restriction, according to suitably decision such as the particle diameter of the toner particle of wanting to obtain 1, the solid component concentration in the mixed serum, used polycoagulant.The mixing time of mixed serum and stirring rate can be according to cohesion carry out the degree appropriate change.
Like this, can obtain being formed with the slurries of the toner particle 1 that contains biomass resin zone 2.Contain biomass resin zone 2 and have the interior particle diameter of certain limit, be evenly dispersed in substantially in the toner particle 1, therefore can prevent that the biomass resin is scattered in the toner particle 1 with the island state.Therefore, can be under the situation that does not reduce the toner permanance a kind of toner particle to contain the biomass resin at high proportion, can suppress environmental pollution.In addition,, therefore the toner transparency can be do not reduced,, the characteristic inequality between toner particle can be suppressed even if also can guarantee sufficient color reproducible range when being applied to color toner owing to can prevent to follow the gonorrhoeaization of biomass resin crystallization.
In this manufacture method,, the particle diameter of gained toner particle 1 can be controlled, the regional diameter that contains biomass resin zone 2 that is formed in the toner particle 1 can be controlled simultaneously by heating-up temperature, mixing time and the stirring rate etc. of suitable adjustment mixed serum.Among the present invention, toner particle 1 preferably carries out granularity control so that its volume average particle size is that 4 μ m are above, makes below the 8 μ m.Volume average particle size is 4 μ m are above, 8 μ m are a following toner particle 1 when using as toner, can be manufactured on stably that storage stability under the heating of developing trough etc. is good, high concentration and high meticulous, image repetition well, do not have a high quality image of image problem.
In addition, contain that biomass resin zone 2 is preferably controlled so that its regional diameter is that 1 μ m is following, preferred 0.5 μ m is above, 1 μ m is following makes.By such control area diameter, can prevent regional diameter become too small, binder resin and the biomass resin because the heating of cohesion process etc. and compatible.Therefore, the permanance that can prevent toner reduces.In addition, can prevent that regional diameter from becoming excessive, thereby the particle diameter that prevents toner particle 1 increases.Therefore, can make the little toner of particle diameter of toner particle 1.
In addition, be below the 1 μ m by making regional diameter, can obtain the good toner of the transparency.And owing to the ratio that the biomass resin can be exposed toner surface suppresses lowlyer, therefore the storage stability of toner can be maintained under the high state, the contacted ratio of biomass resin and recording medium increases when preventing photographic fixing simultaneously, thereby prevents the toner fixing reduction.
[washing procedure]
The washing procedure of step a5 is the operation with toner particle 1 contained in the toner particle slurries cooling back washing toner particle slurries.The washing of toner particle 1 is in order to remove surfactant contained in the toner particle slurries, spreading agent, tackifier etc. and to come from the impurity etc. of these materials and implement.Washing methods for example adds entry and stirs in the toner particle slurries, remove the supernatant by separation such as centrifugings.The washing that preferably repeats toner particle 1 reaches below the 10 μ S/cm, preferably reaches below the 5 μ S/cm until the conductivity of the supernatant of mensuration such as use conductivity meter.
[separation circuit]
The separation circuit of step a6 is the operation of separating toner particle 1 and reclaiming from the potpourri of the liquid medium that contains washing back toner particle 1.There is no particular restriction from the separation of liquid medium for toner particle 1, for example can be undertaken by filtration, suction filtration, centrifuging etc.
[drying process]
Toner particle 1 drying after the drying process of step a7 will wash, separate.There is no particular restriction for the drying of toner particle 1, can pass through enforcements such as freeze-drying, air-flowing type seasoning.During with toner particle 1 drying, the manufacturing of toner particle 1 finishes.
Fig. 5 is the process flow diagram of manufacture method the 3rd example of expression toner particle 1.
[adhesive resin particles dispersion step]
The adhesive resin particles dispersion step of step b1 can similarly be carried out with the adhesive resin particles dispersion step of step a1 in above-mentioned manufacture method the 1st example in manufacture method the 3rd example.That is, the adhesive resin particles dispersion step of step b1 comprises the grain refined operation of step b1-(a), the decompression operation of step b1-(b), the refrigerating work procedure of step b1-(c).The grain refined operation of step b1-(a) is identical with the grain refined operation of step a1-(a) in above-mentioned manufacture method the 1st example, omits its explanation.The decompression operation of step b1-(b) is identical with the decompression operation of step a1-(b) in above-mentioned manufacture method the 1st example, omits its explanation.The refrigerating work procedure of step b1-(c) is identical with the refrigerating work procedure of step a1-(c) in above-mentioned manufacture method the 1st example, omits its explanation.
[biomass resin particle dispersion step]
The biomass resin particle dispersion step of step b2 can similarly be carried out with the biomass resin particle dispersion step of step s3 in step a2 in above-mentioned manufacture method the 1st example and manufacture method the 2nd example in manufacture method the 3rd example.That is, the biomass resin particle dispersion step of step b2 comprises the grain refined operation of step b2-(a), the decompression operation of step b2-(b), the refrigerating work procedure of step b2-(c).In the grain refined operation of step b2-(a) and above-mentioned manufacture method the 1st example in step a2-(a) and manufacture method the 2nd example grain refined operation of step s3-(a) identical, omit its explanation.In the decompression operation of step b2-(b) and above-mentioned manufacture method the 1st example in step a2-(b) and manufacture method the 2nd example decompression operation of step s3-(b) identical, omit its explanation.In the refrigerating work procedure of step b2-(c) and above-mentioned manufacture method the 1st example in step a2-(c) and manufacture method the 2nd example refrigerating work procedure of step s3-(c) identical, omit its explanation.
[colorant particle dispersion step]
The colorant particle dispersion step of step b3 is for being scattered in colorant the operation that obtains in the liquid medium as the colorant particle slurries of the slurries of colorant particle.The liquid medium that uses in liquid medium and the adhesive resin particles dispersion step is the same, and hydrophilic media such as preferred water or alcohol can suitably be added dispersion stabilizer, tackifier, surfactant etc.Colorant preferably to be the ratio use more than 5 weight portions, below 50 weight portions with respect to 100 weight portion liquid mediums, more preferably uses with the ratio more than 20 weight portions, below 40 weight portions.The usage ratio of colorant is during less than 5 weight portions, because colorant is very few with respect to the amount of liquid medium, so dispersing uniformity reduces.When the usage ratio of colorant surpasses 50 weight portions, because colorant is too much with respect to the amount of liquid medium, the viscosity of colorant particle slurries becomes too high, and dispersiveness also reduces thus.
As stable dispersant, can use inorganic or organic spreading agent, as the inorganic dispersant of inorganic spreading agent preferred hydrophilic.By using hydrophilic inorganic dispersant, can make the grain size of micropowder of the colorant in the liquid medium more even.For example can enumerate silicon dioxide, aluminium oxide, titania, lime carbonate, magnesium carbonate, calcium phosphate, clay, zeyssatite, bentonitic clay etc. as hydrophilic inorganic dispersant.In these materials, preferred lime carbonate.
The number average particle diameter of preferred its 1 particle of above-mentioned inorganic dispersant be 1nm above, below the 1000nm, more preferably 5nm above, below the 500nm, more preferably 10nm above, below the 300nm.The number average particle diameter of 1 particle of inorganic dispersant is difficult to make inorganic dispersant to be scattered in the liquid medium during less than 1nm.When the number average particle diameter of 1 particle of inorganic dispersant surpassed 1000nm, the difference of the particle diameter of the meal of colorant and the particle diameter of inorganic dispersant reduced, and was difficult to make the meal of colorant stably to disperse and was maintained in the liquid medium.
Inorganic dispersant preferably to be the scope use more than 1 weight portion, below 300 weight portions with respect to 100 weight portion colorants, more preferably uses with the scope more than 4 weight portions, below 100 weight portions.The use amount of inorganic dispersant is difficult to make inorganic dispersant to be scattered in the liquid medium during less than 1 weight portion.When the use amount of inorganic dispersant surpassed 30 weight portions, the viscosity of colorant particle slurries was too high, and dispersiveness reduces sometimes.
In addition, in liquid medium, can also add macromolecule dispersing agent with inorganic dispersant.Macromolecule dispersing agent for example preferably uses hydroaropic substance, more preferably uses the material with carboxyl, does not especially preferably contain the material of lipophilic groups such as propoxyl, methoxyl.This macromolecule dispersing agent for example can be enumerated water-soluble cellulose ethers such as carboxymethyl cellulose, carboxyethyl cellulose etc.In these materials, special preferably carboxymethyl cellulose.Macromolecule dispersing agent is preferably with respect to 100 weight portion colorants to be the ratio use more than 0.1 weight portion, below 5.0 weight portions.
Organic spreading agent preferred anionic class spreading agent.The ability that the anionic species spreading agent improves the dispersiveness of colorant particle in water is good.As the anionic species spreading agent, for example can enumerate sulfonic acid type anionic species spreading agent, sulfuric acid ester type anionic species spreading agent, polyoxyethylene ether type anionic species spreading agent, phosphate type anionic species spreading agent, polyacrylate etc.The object lesson of anionic species spreading agent for example can preferably use neopelex, sodium polyacrylate, polyoxyethylene phenyl ether etc.The anionic species spreading agent can use separately a kind or and with more than 2 kinds.
In addition, organically spreading agent is not to be defined in the anionic species spreading agent, can also be the cationic spreading agent.The cationic spreading agent is preferred alkyl trimethyl ammonium type cationic spreading agent, alkylamide amine-type cationic class spreading agent, alkyl dimethyl benzyl ammonium type cationic spreading agent, cationization glycan cationic spreading agent, alkyl betaine-type cationic spreading agent, alkyl amido betaine type cationic spreading agent, sulfobetaines type cationic spreading agent, amine oxide type cationic spreading agent, slaine etc. for example.Slaine for example can be enumerated chloride, sulfate of sodium, potassium, calcium, magnesium etc. etc.
In these, more preferably alkyl trimethyl ammonium type cationic spreading agent.The object lesson of alkyl trimethyl ammonium type cationic spreading agent for example can be enumerated OTAC, three (polyoxyethylene) octadecyl ammonium chloride, DTAC etc.The cationic spreading agent can use separately a kind or and with more than 2 kinds.
There is no particular restriction for the addition of organic dispersing agent, can select in very wide scope, but be more than 0.1 weight portion, below 5 weight portions with respect to 100 weight portion colorants preferably.Addition utilizes the colorant dispersion effect of spreading agent to become insufficient, might condense during less than 0.1 weight portion.Surpass 5 weight portions even if organic dispersing agent adds, dispersion effect can not improve yet again, because the viscosity of colorant slurries increases, the dispersiveness of colorant reduces on the contrary.The result might cause cohesion.
Can also use commercially available product as dispersion stabilizer.For example can enumerate BYK-182, BYK-161, BYK-116, BYK-111, BYK-2000 (above PVC Star Network ケ ミ one ジ ヤ パ Application Co., Ltd. system), Solsperse-2000, Solsperse-38500 (above ア PVC シ ア Co., Ltd. system), EFKA-4046, EFKA-4047 (above エ Off カ one ケ ミ カ Le ズ society system), サ one Off イ ノ one Le GA (エ ア one プ ロ ダ Network Star society system) etc. as commercially available spreading agent.These commercially available spreading agents can use a kind or be mixed with two or more separately.
This commercially available spreading agent more preferably uses with the ratio more than 20 weight portions, below 50 weight portions preferably to be the ratio use more than 10 weight portions, below 100 weight portions with respect to 100 weight portion colorants.The usage ratio of commercial dispersants utilizes the colorant dispersion effect of spreading agent to become insufficient, might condense during less than 10 weight portions.When the usage ratio of commercial dispersants surpassed 100 weight portions, because the viscosity of colorant particle slurries increases, the dispersiveness of colorant reduced.The result might cause cohesion.
There is no particular restriction in the mixing of liquid medium and dispersion stabilizer, can use known method to carry out.When mixing inorganic dispersant and liquid medium, the dispersion machine, high pressure dispersion machine, ultrasonic dispersing machine etc. that can use bowl mill, sand mill etc. to have medium are scattered in inorganic dispersant in the water of liquid medium.When mixing organic dispersing agent and liquid medium,, then can add by any method, disperse so long as spreading agent can be dissolved in equably method in the liquid medium.The colored particles dispersion step is preferably undertaken by the high pressure homogenization method that comprises grain refined operation, decompression operation, refrigerating work procedure.Thus, colorant can be pulverized is the state that particle diameter is little and particle size distribution is little.In the present embodiment, the colorant particle dispersion step is undertaken by the high pressure homogenizer that uses in above-mentioned adhesive resin particles dispersion step.
(grain refined operation)
The grain refined operation of step b-3 (a) is colorant is pulverized and to be scattered in the liquid medium and to obtain the operation of colorant particle slurries.The liquid medium that uses in liquid medium that mixes with colorant and the adhesive resin particles dispersion step is the same, and hydrophilic media such as preferred water or alcohol can suitably be added dispersion stabilizer, tackifier, surfactant etc.In addition, the dispersion liquid that contains colorant is the same with the adhesive resin particles dispersion step, flows through to pulverize under the pressurized, heated condition and uses nozzle, and colorant is by pulverizing and grain refined obtains the colorant particle slurries.Owing to pulverizing colorant under the pressurized, heated condition like this, therefore can pulverize colorant efficiently.
(decompression operation)
The decompression operation of step b3-(b) is the operation that the colorant particle slurries that are in the pressurized, heated state are reduced pressure.Be decompressed to atmospheric pressure or the pressure approaching with pressure relief assembly not cause the colorant particle slurries that cause the mode of bubble generation will be in the heating and pressurizing state because of bumping with it.
(refrigerating work procedure)
The refrigerating work procedure of step b3-(c) is to be in the operation of the colorant particle slurries cooling of heated condition.Be cooled to about 20 ℃～about 40 ℃ with the colorant particle slurries that cooler will be in heated condition within a short period of time.
Like this, can obtain the colorant particle slurries.In this manufacture method, by suitable adjustment flow through applied pressure when pulverizing with nozzle and (or) solid component concentration in the temperature, colorant particle slurries, pulverize number of times etc., can control the particle diameter of gained colorant particle.Among the present invention, preferably adjust each condition, make the volume average particle size of colorant particle preferably reach more than the 50nm, below the 200nm.The mean grain size of colorant utilize the high pressure homogenizer grain refined to need for a long time, and the colorant particle that might take place after the grain refined is condensed once more during less than 50nm.When the mean grain size of colorant particle surpassed 200nm, the dispersiveness of colorant in toner particle might reduce.The mean grain size of colorant particle for example can be utilized the microscope (trade name: DLS-700, Otsuka Electronics Co., Ltd. system) measure of laser light scattering mode.
[cohesion process]
The cohesion process of step b4 is to add polycoagulant and make adhesive resin particles, biomass resin particle and colorant particle cohesion in the mixed serum that is mixed with adhesive resin particles slurries, biomass resin particle slurries and colorant particle slurries, makes the operation of the slurries (below be called " toner particle slurries ") of toner particle 1.In the cohesion process, use the stirred vessel that possesses the mixed serum that stores adhesive resin particles slurries, biomass resin particle slurries and colorant particle slurries and be arranged at the granulation device that stirs the mixing part of slurries in the stirred vessel, mix slurries.
Polycoagulant as being used to make adhesive resin particles, biomass resin particle and colorant particle cohesion can use the salt of 1 valency, the salt of divalent, the salt of 3 valencys etc.As the salt of 1 valency, for example can enumerate cationic spreading agents such as alkyl trimethyl ammonium chloride, inorganic salts such as sodium chloride, potassium chloride, ammonium chloride etc.As the salt of divalent, for example can enumerate magnesium chloride, lime chloride, zinc chloride, cupric chloride (II), magnesium sulphate, manganese sulfate etc.As the salt of 3 valencys, for example can enumerate ammonium chloride, iron chloride (III) etc.In the above-mentioned illustrative polycoagulant, the preferred alkyl trimethyl ammonium chloride.As the object lesson of alkyl trimethyl ammonium chloride, for example can enumerate OTAC, three (polyoxyethylene) octadecyl ammonium chloride, DTAC etc.Polycoagulant can use separately a kind or and with more than 2 kinds.There is no particular restriction for the addition of polycoagulant, can suitably select in very wide scope, preferably contains in mixed serum with the ratio more than the 0.1 weight %, below the 5 weight % with respect to the mixed serum total amount.
In the present embodiment, polycoagulant is added into mixed serum after, utilize granulation device to stir while heat mixed serum.There is no particular restriction for the heating-up temperature of mixed serum, according to suitably decision such as the particle diameter of the toner particle of wanting to obtain 1, the solid component concentration in the mixed serum, used polycoagulant.The heating-up temperature of mixed serum is preferred more than 65 ℃ and less than 90 ℃.During less than 65 ℃, does not merge with adhesive resin particles sometimes in the formed biomass resin zone 2 that contains, and the situation of the permanance reduction of toner is arranged.In addition, be more than 90 ℃ the time, formed to contain biomass resin zone 2 compatible with adhesive resin particles sometimes, the situation that has the permanance of toner to reduce.The heating-up temperature of mixed serum can be according to cohesion carry out the degree appropriate change.
In addition, utilize the mixing time of granulation device and stirring rate also not to have special restriction, according to suitably decision such as the particle diameter of the toner particle of wanting to obtain 1, the solid component concentration in the mixed serum, used polycoagulant.The mixing time of mixed serum and stirring rate can be according to cohesion carry out the degree appropriate change.
Like this, can obtain being formed with the slurries of the toner particle 1 that contains biomass resin zone 2.Contain biomass resin zone 2 and have the interior particle diameter of certain limit, be evenly dispersed in substantially in the toner particle 1, therefore can prevent that the biomass resin is scattered in the toner particle 1 with the island state.Therefore, can be under the situation that does not reduce the toner permanance a kind of toner particle to contain the biomass resin at high proportion, can suppress environmental pollution.In addition,, therefore the toner transparency can be do not reduced,, the characteristic inequality between toner particle can be suppressed even if also can guarantee sufficient color reproducible range when being applied to color toner owing to can prevent to follow the gonorrhoeaization of biomass resin crystallization.
In this manufacture method,, the particle diameter of gained toner particle 1 can be controlled, the regional diameter that contains biomass resin zone 2 that is formed in the toner particle 1 can be controlled simultaneously by heating-up temperature, mixing time and the stirring rate etc. of suitable adjustment mixed serum.Among the present invention, toner particle 1 preferably carries out granularity control so that its volume average particle size is that 4 μ m are above, makes below the 8 μ m.Volume average particle size is 4 μ m are above, 8 μ m are a following toner particle 1 when using as toner, can be manufactured on stably that storage stability under the heating of developing trough etc. is good, high concentration and high meticulous, image repetition well, do not have a high quality image of image problem.
In addition, contain that biomass resin zone 2 is preferably controlled so that its regional diameter is that 1 μ m is following, preferred 0.5 μ m is above, 1 μ m is following makes.By such control area diameter, can prevent regional diameter become too small, binder resin and the biomass resin because the heating of cohesion process etc. and compatible.Therefore, the permanance that can prevent toner reduces.In addition, can prevent that regional diameter from becoming excessive, thereby the particle diameter that can prevent toner particle 1 increases, and prevent that size distribution, distribution of shapes from broadening.Therefore, can make the little toner of particle diameter of toner particle 1.
In addition, be below the 1 μ m by making regional diameter, can obtain the good toner of the transparency.And owing to the ratio that the biomass resin can be exposed toner surface suppresses lowlyer, therefore the storage stability of toner can be maintained under the high state, the contacted ratio of biomass resin and recording medium increases when preventing photographic fixing simultaneously, thereby prevents the toner fixing reduction.
[washing procedure]
The washing procedure of step b5 is the operation with toner particle 1 contained in the toner particle slurries cooling back washing toner particle slurries.The washing of toner particle 1 is in order to remove surfactant contained in the toner particle slurries, spreading agent, tackifier etc. and to come from the impurity etc. of these materials and implement.Washing methods for example adds entry and stirs in the toner particle slurries, remove the supernatant by separation such as centrifugings.The washing that preferably repeats toner particle 1 reaches below the 10 μ S/cm, preferably reaches below the 5 μ S/cm until the conductivity of the supernatant of mensuration such as use conductivity meter.
[separation circuit]
The separation circuit of step b6 is the operation of separating toner particle 1 and reclaiming from the potpourri of the liquid medium that contains washing back toner particle 1.There is no particular restriction from the separation of liquid medium for toner particle 1, for example can be undertaken by filtration, suction filtration, centrifuging etc.
[drying process]
Toner particle 1 drying after the drying process of step b7 will wash, separate.There is no particular restriction for the drying of toner particle 1, can pass through enforcements such as freeze-drying, air-flowing type seasoning.During with toner particle 1 drying, the manufacturing of toner particle 1 finishes.
Like this, can be manufactured on and be formed with the toner particle 1 that contains biomass resin zone 2 in the toner particle 1.At this moment, with respect to 100 weight portion toners, the content of biomass resin is preferably set to 20 weight portions～60 weight portions.Thus, in the effect of giving full play to the inhibition environmental pollution that utilizes the biomass resin, also can obtain the permanance of toner fully.
In addition, the surface of preferred toner is coated by resin molding.Thus, can further improve the permanance of toner.The resin that constitutes resin molding can be enumerated polyacrylate, polymethacrylate, polystyrene and their derivant, styrene-acrylonitrile copolymer acid resin etc.As the method for the surperficial resin-coated film of toner, for example can enumerate dissolving or the solution that is dispersed with above-mentioned resin is sprayed onto on the toner and form resin molding spray-on process, dissolving or be dispersed with dipping toner in the solution of above-mentioned resin and form resin molding infusion process, make utilize particulate that emulsion polymerization obtains by saltouing at the coacervation that toner surface is separated out, make emulsion polymerization between the monomer that constitutes above-mentioned resin form the in-situ method etc. of resin molding in toner surface.In these, preferably make emulsion polymerization particulate that the styrene-acrylonitrile copolymer acid resin constitutes separate out and form resin molding in toner surface.
Therefore the styrene-acrylonitrile copolymer acid resin of making of emulsion polymerization when being coated on toner surface, can be formed uniformly the resin molding of film because the particle diameter of its resin particle is little, even.In addition, the styrene-acrylonitrile copolymer acid resin is because the content of ester bond isopolarity group is few, so hydroscopicity is little, also can improve the charged stability of toner under high humidity environment.When making the emulsion polymerization particulate separate out, form the resin molding of styrene-acrylonitrile copolymer acid resin formation in toner surface, at first will join by the particulate that emulsion polymerization obtains in the toner dispersion liquid.Then, under heating, stir, add polycoagulant such as lime chloride simultaneously, the emulsion polymerization particulate is separated out in toner surface.The styrene-acrylonitrile copolymer acid resin can be coated on toner surface like this.
As above in the toner particle of Zhi Zaoing, for example can also mix and play the external additive that improves powder fluidity, improves frictional electrification, improves thermotolerance and long preservation, improves sanitary characteristics and control functions such as photosensitive surface wearing character.External additive can be enumerated fine silica powder end, fine titanium dioxide powder end and alumina powder end etc.External additive can use separately a kind or and with more than 2 kinds.The addition of external additive is considered the necessary carried charge of toner, is added external additive to the influence of the wearing and tearing of photoreceptor and the environmental characteristics of toner etc., is more than 0.1 weight portion, below 10 weight portions with respect to 100 weight portion toner particles preferably.
The toner of the present invention of Zhi Zaoing can be used to utilize the development of xerography, the electrostatic charge image when electrostatic recording forms image like this, the development of the magnetic sub-image when perhaps being used to utilize magnetography to form image etc.In addition, can be used as monocomponent toner or two-component developing agent uses.
When using as monocomponent toner, in development sleeve, use blade to make its frictional electrification, toner is sticked on the sleeve, carry toner thus, carrying out image forms, but monocomponent toner of the present invention is owing to contain the high toner of permanance that the percent crystallization in massecuite that will contain biomass resin zone 2 suppresses lowlyer, therefore is not easy to occur in fusion on the blade etc. or photoreceptor film forming etc.
Two-component developing agent of the present invention contains above-mentioned toner and carrier.Therefore, can obtain under the situation of the permanance that does not reduce toner, suppressing the two-component developing agent of environmental pollution.And therefore two-component developing agent can obtain forming the two-component developing agent of the high high resolution image of the transparency owing to contain as the above-mentioned toner that also can be applied to the transparent high toner of color toner.
Carrier can use the particle with magnetic.Object lesson with particle of magnetic for example can be enumerated alloy of metals such as iron, ferrite and magnetic iron ore, these metals and metals such as aluminium or lead etc.In these materials, preferred ferrite.In addition, can also use at the resin dispersion type carrier etc. that has resin-coated carrier resin-coated on the particle of magnetic or in resin, be dispersed with particle as carrier with magnetic.Have the resin of particle of magnetic there is no particular restriction as coating, for example can enumerate olefine kind resin, styrene resin, styrene/acrylic resinoid, silicone based resin, esters resin and fluoropolymer resinoid etc.In addition, there is no particular restriction as the used resin of resin dispersion type carrier, for example can enumerate styrene acrylic resin, vibrin, fluorine-type resin and phenolics etc.
Preferred sphere of the shape of carrier or flat pattern.In addition, there is no particular restriction for the volume average particle size of carrier, but consider high image qualityization, be preferably 10 μ m above, below the 100 μ m, more preferably 20 μ m above, below the 50 μ m.And the resistivity of carrier is preferably 10 8Ω cm is above, more preferably 10 12More than the Ω cm.The resistivity of carrier has 0.50cm for carrier is put into 2After rapping in the container of sectional area, the particle in being contained in container applies 1kg/cm 2Load, between load and bottom-side electrodes, apply the voltage that produces the 1000V/cm electric field, read the current value of this moment and the value that obtains.When resistivity is hanged down, be injected into carrier at electric charge when development sleeve applies bias voltage, carrier particle is easily attached on the photoreceptor.The puncture of bias voltage takes place in addition, easily.
The magnetization of carrier (maximal magnetization) be preferably 10emu/g above, below the 60emu/g, more preferably 15emu/g above, below the 40emu/g.Though the magnetization depends on the magnetic flux density of developer roll, under the general magnetic flux density condition of developer roll, when less than 10emu/g, the magnetic binding force is inoperative, might become the reason that carrier disperses.In addition, when the magnetization surpasses 60emu/g, in the noncontact that the projection (fringe found Chi) of carrier becomes too high is developed, be difficult to support body maintenance contactless state with image.In addition, in contact is developed, in the toner picture trace might appear easily sweeping.
There is no particular restriction for the usage ratio of toner and carrier in the two-component developing agent, can suitably select according to the kind of toner and carrier, with the ferrite carrier is example, uses toner according to containing in the developer more than the 2 weight % that toner reaches the developer total amount, below the 30 weight %, more than the preferred 2 weight %, below the 20 weight %.In addition, in the two-component developing agent, that the clad ratio of the carrier of toner is preferably 40 weight % is above～below the 80 weight %.
Fig. 6 is the sectional view of the formation of the image processing system 100 of expression one embodiment of the present invention.Image processing system 100 possesses the developing apparatus 14 that uses above-mentioned two-component developing agent to develop.Therefore, not only can suppress environmental pollution, and can on photosensitive drum body 11, form the toner picture of high image quality, can form the high high resolution image of the transparency by developing apparatus 14.
Image processing system 100 according to the image information of being transmitted, forms full color or monochromatic image for having the compounding machine of copy function, printing function and facsimile function concurrently on recording medium.Promptly, image processing system 100 has copy mode, printing model and FAX mode 3 kind printing mode, according to operation input from not shown operating portion, from PC, mobile terminal device, information recording medium storage, use the acceptance etc. of presswork of the external unit of memory storage, select printing mode by not shown control part.Image processing system 100 comprises toner picture formation portion 7, transfer printing portion 3, photographic fixing portion 4, recording medium supply unit 5 and discharge portion 6.For corresponding color image information contained black (b), blue or green (c), fuchsin (m) and yellow (y) image information of all kinds, each member and the transfer printing portion 3 contained partial component that constitute toner picture formation portion 7 are provided with 4 respectively.Here, corresponding to of all kinds and each member of 4 respectively is set has expression letter of all kinds at the end of reference label and distinguish, only use during general designation and represent with reference to label.
Toner picture formation portion 7 comprises photosensitive drum body 11, electro-mechanical part 12, exposing unit 13, developing apparatus 14, cleaning unit 15.Electro-mechanical part 12, developing apparatus 14 and cleaning unit 15 are configured in around the sense of rotation of photosensitive drum body 11 in order.Electro-mechanical part 12 is configured in the vertical direction below of developing apparatus 14 and cleaning unit 15.
Photosensitive drum body 11 passes through not shown drive division to be supported, and makes it possible to drive around the axis rotation, comprises not shown conductive base and the photographic layer that is formed at the conductive base surface.Conductive base can adopt different shape, for example can enumerate cylindric, cylindric, film sheet etc.Preferably drum shape in these.Conductive base is formed by conductive material.Conductive material can use this field material commonly used, metals such as aluminium, copper, brass, zinc, nickel, stainless steel, chromium, molybdenum, vanadium, indium, titanium, gold, platinum for example, the alloy more than 2 kinds of these metals, on film like matrixes such as film of synthetic resin, metallic film, paper, form the conductive membrane of the conductive layer that constitutes more than a kind or 2 kinds by aluminium, aluminium alloy, tin oxide, gold, indium oxide etc., contain the resin combination of electroconductive particle and/or electric conductive polymer etc.And, as the employed film like matrix of conductive membrane, preferred film of synthetic resin, special preferred polyester film.In addition, as the formation method of the conductive layer of conductive membrane, preferred evaporation, coating etc.
The charge transport layer that photographic layer for example contains the charge generation layer of charge generation material and contains the charge transport material by lamination forms.At this moment, inter coat (undercoat layer) preferably is set between conductive base and charge generation layer or the charge transport layer.By inter coat is set, have the following advantages: cover the scar be present in the conductive base surface and concavo-convex, make the photographic layer smoothing; The charging property variation of photographic layer when preventing to use repeatedly; Improve the charged characteristic of the photographic layer under low temperature and/or the low wet environment.In addition, can also be the big three-decker laminated photosensitive body of permanance that is provided with the photosensitive surface protective seam in the superiors.
Charge generation layer is a major component with the charge generation material that produces electric charge by rayed, contains known binder resin, plastifier, sensitizer etc. as required.The charge generation material can use material commonly used in this field, for example can Ju Chu perylene diimide perylene acid anhydrides perylene class pigment, quinacridone, polycyclic quinone pigment such as anthraquinone, metal and metal-free phthalocyanine, phthalocyanine pigments such as halogenation metal-free phthalocyanine, side's sour cyanines (Squarylium) pigment, azulene (Azulenium) pigment, the thiapyran pigment has the carbazole skeleton, styryl talan skeleton, the triphenylamine skeleton, dibenzothiophene skeleton oxadiazole skeleton, the Fluorenone skeleton, two Stilbene (bisstilbene) skeleton, the AZO pigments of Er Ben Yi Xi oxadiazole skeleton or diphenylethyllene carbazole skeleton etc.
In these materials, metal-free phthalocyanine, titanyl phthalocyanine pigment, contain the disazo pigment of fluorenes ring and/or Fluorenone ring, disazo pigment of being made of aromatic amine, trisazo pigment etc. have high charge generation ability, is suitable for obtaining highly sensitive photographic layer.The charge generation material can use separately a kind or and with more than 2 kinds.There is no particular restriction for the content of charge generation material, but with respect to the binder resin in the 100 weight portion charge generation layers, be preferably 5 weight portions above, below 500 weight portions, more preferably 10 weight portions above, below 200 weight portions.The binder resin of using as charge generation layer also can use material commonly used in this field, for example can enumerate melamine resin, epoxy resin, organic siliconresin, polyurethane, acryl resin, vinyl chloride-vinyl acetate copolymer resins, polycarbonate, phenoxy resin, polyvinyl butyral, polyacrylate, polyamide, polyester etc.Binder resin can use a kind or as required and with more than 2 kinds separately.
Charge generation layer can followingly form: with dissolving such as an amount of charge generation material and binder resin and plastifier as required, sensitizer or be dispersed in the suitable organic solvent that can dissolve or disperse these compositions, preparation charge generation layer masking liquid is coated in this charge generation layer masking liquid on the conductive base surface and carries out drying.There is no particular restriction for the thickness of the charge generation layer that obtains like this, be preferably 0.05 μ m above, below the 5 μ m, more preferably 0.1 μ m above, below the 2.5 μ m.
The charge transport layer that is laminated on the charge generation layer is essential composition to have acceptance, to carry the charge transport material and the charge transport layer binder resin of the ability of the electric charge that is produced by the charge generation material, contains known antioxidant, plastifier, sensitizer, lubricant etc. as required.The charge transport material can use this field material commonly used, for example can enumerate poly-N-vinyl carbazole and derivant thereof, poly--γ-carbazyl ethyl glutamate and derivant thereof, pyrene-formaldehyde condensation products and derivant thereof, the polyvinyl pyrene, the luxuriant and rich with fragrance oxazole of polyvinyl derivant oxadiazole derivant, imdazole derivatives, 9-(to the diethylamino styryl) anthracene, 1, two (the 4-dibenzyl amino phenyl) propane of 1-, the styryl anthracene, the styryl pyrazoline, pyrazoline derivative, the phenyl hydrazones class, hydazone derivative, the triphenylamine compounds, the tetraphenyl diamine compounds, the triphenyl methane compounds, stilbenes compound, the sub-property materials of power supply such as azines with 3-methyl-2-[4-morpholinodithio quinoline ring, fluorenone derivatives, dibenzothiophene derivatives, the indeno thiophene derivant, the phenanthrenequione derivant, the indenopyridine derivant, thioxanthone derivates, benzo [c] cinnoline derivatives, the azophenlyene oxide derivative, TCNE, tetracyano-p-quinodimethane, tetrabromoquinone, tetrachloro is for 1,4-benzoquinone, benzoquinones etc. are subjected to electronics material etc.
The charge transport material can use separately a kind or and with more than 2 kinds.There is no particular restriction for the content of charge transport material, with respect to the binder resin in the 100 weight portion charge transport materials, be preferably 10 weight portions above, below 300 weight portions, more preferably 30 weight portions above, below 150 weight portions.Charge transport layer can use in this field commonly used and material that the charge transport material can be disperseed equably with binder resin, for example can enumerate polycarbonate, polyacrylate, Polyvinyl butyral, polyamide, polyester, polyketone, epoxy resin, polyurethane, tygon ketone, polystyrene, polyacrylamide, phenolics, phenoxy resin, polysulfone resin, their copolymer resins etc.In these materials, when considering the mar proof, electrical characteristics etc. of film forming, gained charge transport layer, preferably contain bisphenol Z as potpourri of polycarbonate (being called " bisphenol Z type polycarbonate " later on), bisphenol Z type polycarbonate and other polycarbonate of monomer component etc.Binder resin can use separately a kind or and with more than 2 kinds.
In charge transport layer, preferably contain antioxidant with binder resin with charge transport material and charge transport layer.Antioxidant also can use material commonly used in this field, for example can enumerate vitamin E, quinhydrones, hindered amine, hindered phenol, p-phenylenediamine (PPD), aryl alkane and their derivant, organosulfur compound, organic phosphorus compound etc.Antioxidant can use separately a kind or and with more than 2 kinds.There is no particular restriction for the content of antioxidant, more than the 0.01 weight % for the composition total amount that constitutes charge transport layer, below the 10 weight %, be preferably 0.05 weight % above, below the 5 weight %.Charge transport layer can followingly form: with dissolving such as an amount of charge transport material and binder resin and antioxidant as required, plastifier, sensitizer or be dispersed in the suitable organic solvent that can dissolve or disperse these compositions, preparation charge transport layer masking liquid, this charge transport layer is coated in the charge generation laminar surface with masking liquid, and carries out drying.
There is no particular restriction for the thickness of the charge generation layer that obtains like this, be preferably 10 μ m above, below the 50 μ m, more preferably 15 μ m above, below the 40 μ m.And, can also in a layer, form the photographic layer that has charge generation material and charge transport material.At this moment, the kind of the kind of charge generation material and charge transport material, content, binder resin, other adjuvant etc. can be same when forming charge generation layer and charge transport layer respectively.
Use above-mentioned formation to use the photosensitive drum body of the organic photosensitive layer of charge generation material and charge transport material in the present embodiment, but can use the photosensitive drum body that forms the inorganic photographic layer that uses silicon etc. to replace.
Electro-mechanical part 12 makes photosensitive drum body 11 surfaces with going up required polarity and current potential according to having the gap and configuration dividually in the face of photosensitive drum body 11, along photosensitive drum body 11 length directions and with photosensitive drum body 11 surfaces.Electro-mechanical part 12 can use the charged device of charged brush type, the charged device of charge type, the charged device of sawtooth pattern, ion generating apparatus etc.In the present embodiment, electro-mechanical part 12 is according to being provided with away from photosensitive drum body 11 surface, but not limited thereto.For example can use charged roller as electro-mechanical part 12, with charged roller and photosensitive drum body mutually the mode of crimping dispose charged roller, can also use the charged device of contact electrification modes such as charged brush, magnetic brush.
Exposing unit 13 disposes as follows: and the corresponding light of information of all kinds that is penetrated by exposing unit 13 is by being radiated at the surface of photosensitive drum body 11 between electro-mechanical part 12 and the developing apparatus 14.Exposing unit 13 is transformed into image information the light of corresponding b, c, m, y information of all kinds in this unit, the light that utilizes corresponding information of all kinds forms electrostatic latent image in its surface to exposing with photosensitive drum body 11 surfaces of going up same current potential by electro-mechanical part 12.Exposing unit 13 for example can use the laser scan unit with laser irradiating part and a plurality of catoptrons.In addition, can also use appropriate combination that the unit of LED (Light Emitting Diode) array, liquid crystal shutter and light source is arranged.
Fig. 7 is the figure of the formation of expression developing apparatus 14.Developing apparatus 14 comprises developing trough 20 and toner feeding funnel 21.Developing trough 20 is following container-like members: this container-like member disposes in the mode towards photosensitive drum body 11 surfaces, and toner supply is developed to the electrostatic latent image that is formed at photosensitive drum body 11 surfaces, forms the toner picture as visible image.Developing trough 20 is accommodated toner in the portion space within it, and accommodates and support with rotating freely roller component or spiral components such as developer roll 22, donor rollers 23, agitating roller 24.Developing trough 20 in the face of forming peristome on the side of photosensitive drum body 11, across this peristome at the rotatable developer roll 22 that is provided with drivingly on the position of photosensitive drum body 11.
Developer roll 22 is with the pressure contact portion of photosensitive drum body 11 or the roller shape member of toner is provided to the electrostatic latent image on photoreceptor 11 surfaces near the portion place.When supplying with toner, will be that the current potential of opposite polarity is applied on developer roll 22 surfaces as the development bias voltage with the charged current potential of toner.Thus, the toner on developer roll 22 surfaces is supplied with electrostatic latent image swimmingly.And, by changing the development bias value, can control the toning dosage (toner adhesion amount) of supplying with electrostatic latent image.
Donor rollers 23 is in the face of developer roll 22 and the rotatable roller shape member that is provided with drivingly, with toner supply around developer roll 22.Agitating roller 24 is in the face of donor rollers 23 and the rotatable roller shape member that is provided with drivingly, will newly supply to toners in the developing trough 20 from toner feeding funnel 21 and deliver to around the donor rollers 23.The toner that toner feeding funnel 21 is arranged on its vertical direction bottom according to connection replenish mouthful (not shown) and be arranged on developing trough 20 vertical direction tops toner receiving port (not shown) mode and be provided with, according to the additional toner of the toner consumption situation of developing trough 20.In addition, also can not use toner feeding funnel 21, constitute according to the mode of directly replenishing toner from toner Cartridge of all kinds.
Cleaning unit 15 is removed the toner that remains in photosensitive drum body 11 surfaces after toner being looked like to be needed on the recording medium, the surface of cleaning photosensitive drum body 11.In the cleaning unit 15, for example use tabular components such as cleaning blade.And, in the image processing system 100 of the present invention, mainly use the Organophotoreceptor cylinder, because the surface of Organophotoreceptor cylinder is based on resinous principle as photosensitive drum body 11, therefore because by the chemical action of the ozone that corona discharge produced of Charging system, the surface is variation easily.Yet, variation surface portion be subjected to the rubbing action of cleaning unit 15 and wear and tear, though positively be removed very slowly.Therefore, in fact eliminate the problem of the surperficial variation that ozone etc. caused, can keep the charged current potential that produces by charged action long-term and stably.Cleaning unit 15 is set in the present embodiment, but not limited thereto, also cleaning unit 15 can be set.
By toner picture formation portion 7, to the surface that is in the photosensitive drum body 11 of uniform charged state by electro-mechanical part 12, flashlight from exposing unit 13 irradiation correspondence image information, form electrostatic latent image, supply with toner by developing apparatus 14 to it, form the toner picture, look like to be transferred to this toner on the intermediate transfer belt 25 after, remove with cleaning unit 15 and to remain in photosensitive drum body 11 lip-deep toners.Implement the operation that this a series of toner picture forms repeatedly.
Transfer printing portion 3 is configured in the top of photosensitive drum body 11, comprises intermediate transfer belt 25, driven roller 26, driven voller 27, intermediate transfer rollers 28 (b, c, m, y), transfer belt cleaning unit 29, transfer roll 30.Intermediate transfer belt 25 is formed the ring-band shape member of ring-type mobile route by driven roller 26 and driven voller 27 tensioners, rotation drives on the direction of arrow B.Contacting with photosensitive drum body 11 and when the photosensitive drum body 11 at intermediate transfer belt 25, from the charged polarity that applies across the intermediate transfer belt 25 and the intermediate transfer rollers 28 of photosensitive drum body 11 relative configurations with the toner on photosensitive drum body 11 surfaces is the transfer bias of opposite polarity, and the toner that is formed at photosensitive drum body 11 surfaces is looked like to be transferred on the intermediate transfer belt 25.
During for full-color image, the toner image of all kinds that forms by each photosensitive drum body 11 transfer printing and overlapping on the intermediate transfer belt 25 successively, thus form full color toner picture.Driven roller 26, drives by this rotation around the rotatable setting drivingly of its axis by not shown drive division, and intermediate transfer belt 25 is driven to the rotation of arrow B direction.Driven voller 27 is driven according to driving with the rotation of driven roller 26 to be provided with rotatably, gives intermediate transfer belt 25 certain force of strain so that intermediate transfer belt 25 is not lax.Intermediate transfer rollers 28 is crimped on the photosensitive drum body 11 and is provided with drivingly around its axis is rotatable by not shown drive division across intermediate transfer belt 25.Intermediate transfer rollers 28 is connected with the not shown power supply that applies transfer bias as mentioned above, has toner with photosensitive drum body 11 surfaces and looks like to be transferred to function on the intermediate transfer belt 25.
Transfer belt cleaning unit 29 is to be provided with in the face of driven voller 27 and the mode that contacts the outer peripheral face of intermediate transfer belt 25 across intermediate transfer belt 25.By becoming the reason of polluting the recording medium back side with contacting of photosensitive drum body 11 attached to the toner on the intermediate transfer belt 25, so remove the toner on intermediate transfer belt 25 surfaces, reclaim transfer belt cleaning unit 29.Transfer roll 30 is crimped on driven roller 26 across intermediate transfer belt 25, is provided with drivingly around its axis is rotatable by not shown drive division.Pressure contact portion (transfer nip) at transfer roll 30 and driven roller 26 is located, and the toner that is supported, transports by intermediate transfer belt 25 looks like to be transferred on the recording medium of being sent here by aftermentioned recording medium supply unit 5.The recording medium that supports the toner picture is sent to photographic fixing portion 4.By transfer printing portion 3, pressure contact portion place in photosensitive drum body 11 and intermediate transfer rollers 28, be transferred to toner picture on the intermediate transfer belt 25 by photosensitive drum body 11 and drive by rotation and be transported to transfer nip, therefore be transferred on the recording medium to the arrow B direction of intermediate transfer belt 25.
Photographic fixing portion 4 compares the conveyance direction downstream side that is arranged on more close recording medium with transfer printing portion 3, comprises fixing roller 31 and backer roll 32.Fixing roller 31 is provided with drivingly by not shown drive division is rotatable, and heating constitutes the toner of the unfixing toner picture that supports on the recording medium and makes its fusion, photographic fixing on recording medium.The inside of fixing roller 31 is provided with not shown heating part.The heating part reaches set point of temperature (heating-up temperature) heat fixing roll 31 according to fixing roller 31 surfaces.Well heater, halogen lamp etc. for example can be used in the heating part.The heating part is controlled by fixing conditions control part described later.The back that is controlled at for the heating-up temperature of utilizing the fixing conditions control part is described in detail.
At fixing roller 31 near surfaces temperature detection sensor is set, detects the surface temperature of fixing roller 31.The testing result of temperature detection sensor is written into the storage part of aftermentioned control part.Warm-up mill 32 is provided with according to being crimped on fixing roller 31, can be driven supported rotatably with the rotation driving of backer roll 32.Backer roll 32 by fixing roller 31 when toner fusion and photographic fixing are on recording medium, by extruding toner and recording medium, the auxiliary photographic fixing of toner picture on recording medium.The pressure contact portion of fixing roller 31 and backer roll 32 is the photographic fixing clamping part.By photographic fixing portion 4, the recording medium that is printed on the toner picture in 3 transfers of transfer printing portion is by fixing roller 31 and backer roll 32 clampings, by the photographic fixing clamping part time, the toner picture is pressed on the recording medium under heating, thus, toner on recording medium, forms image as photographic fixing.
Recording medium supply unit 5 comprises automatic paper feeding box 35, pick-up roller 36, conveying roller 37, alignment roller 38, manual feed box 39.Automatic paper feeding box 35 is arranged on the vertical direction bottom of image processing system 100, is the container-like member of store recording medium.Recording medium has common paper, color photocopying paper, overhead projector's sheet material, postcard etc.More than ground of recording medium that pick-up roller 36 will be stored in the automatic paper feeding box 35 take out, and deliver to paper transport path S1.The pair of rolls member that conveying roller 37 is provided with for the mode with mutual crimping is to alignment roller 38 conveying recording mediums.
Alignment roller 38 when the toner that intermediate transfer belt 25 supports looks like to be transported to transfer nip, will be delivered to transfer nip for the pair of rolls member that the mode with mutual crimping is provided with by the recording medium that conveying roller 37 is sent here.Manual feed box 39 is devices of store recording medium for recording medium being put into image processing system 100, be stored in recording medium in the manual feed box 39 and be be stored in automatic paper feeding box 35 in the different arbitrary dimension recording medium of recording medium.The recording medium that takes out from manual feed box 39 passes through with in the paper transport path S2 by conveying roller 37, is sent to alignment roller 38.By recording medium supply unit 5, when the toner that intermediate transfer belt 25 supports looks like to be transported to transfer nip, will more than deliver to transfer nip from the recording medium of automatic paper feeding box 35 or 39 supplies of manual feed box.
Discharge portion 6 comprises conveying roller 37, distributing roller 40 and delivery cassette 41.Conveying roller 37 is provided with than ground, the more close downstream of photographic fixing clamping part on the paper throughput direction, will have the record images medium to carry to distributing roller 40 by 4 photographic fixing of photographic fixing portion.Distributing roller 40 has the record images medium to be expelled to delivery cassette 41 above the vertical direction of being located at image processing system 100 photographic fixing.Delivery cassette 41 has the record images medium to store photographic fixing.
Image processing system 100 comprises not shown control module.Control module for example is arranged on the top of the inner space of image processing system 100, comprises storage part, operational part and control part.To the various setting values of the storage part of control module input by being configured in the not shown guidance panel above the image processing system 100, from the testing result that is disposed at image processing system 100 inside not shown sensor everywhere etc., from the image information of external unit etc.In addition, write the program of carrying out various functional imperative.Various functional imperative are meant for example recording medium detection unit, adhesion amount control part, fixing conditions control part etc.Storage part can use memory storage commonly used in this field, for example can enumerate read-only memory bank (ROM), random access memory body (RAM), hard disk drive (HDD) etc.
External unit can use electric, the electronic equipment that can form or obtain image information and can be electrically connected on image processing system 100, for example can enumerate computing machine, digital camera, television receiver, video recorder, DVD (Digital Versatile Disc) video recorder, HDDVD (High-Definition Digital Versatile Disc), Blu-ray Disc video recorder, facsimile unit, mobile terminal device etc.Operational part will write the various data (image forms order, testing result, image information etc.) of storage part and the program of various functional imperative is taken out, and carry out various judgements.Control part is delivered to related device according to the result of determination of operational part with control signal, moves control.Control part and operational part comprise the treatment circuit that the possess central processing unit microcomputer, microprocessor etc. of (CPU, CentralProcessing Unit) are realized.Control module comprises above-mentioned treatment circuit and primary power, power supply not only to control module, also to each unit feeding electric power of image processing system 100 inside.
The toner of the application of the invention, two-component developing agent, developing apparatus, image processing system carry out image and form, and not only can suppress environmental pollution, but also can form the high high resolution image of the transparency.
(embodiment)
Below enumerate embodiment and comparative example, specifically describe the present invention.And, as the following mensuration of fusing point of the glass transition temperature (Tg) of the binder resin of raw material for toner and softening temperature (Tm), release agent.
[glass transition temperature of binder resin]
Use differential scanning calorimeter (trade name: DSC220, セ イ コ one electronics industry Co., Ltd. system),,, measure the DSC curve with the programming rate heating sample 1g of 10 ℃ of per minutes according to JIS (JIS) K7121-1987.To be equivalent to straight line that the baseline of high temperature side of endothermic peak of the glass transition of gained DSC curve extends to low temperature side, try to achieve as glass transition temperature (Tg) with temperature at the intersection point of the tangent line of drawing with respect to peak rising part to the point of the rate of curve maximum on summit.
[softening temperature of binder resin]
In flow characteristics evaluating apparatus (trade name: Off ロ one テ ス タ one CFT-100C, Shimadzu Scisakusho Ltd's system), according to imposed load 10kgf/cm 2(9.8 * 10 5Pa) mode that sample 1g is extruded from mould (nozzle diameter 1mm, length 1mm) is set, and with 6 ℃ of heating of programming rate per minute, tries to achieve sample flows out half when amount from mould temperature, as softening temperature.
[fusing point of release agent]
Use differential scanning calorimeter (trade name: DSC220, セ イ コ one electronics industry Co., Ltd. system), with the programming rate of 10 ℃ of per minutes with sample 1g from 10 ℃ be warming up to 200 ℃, then from 200 ℃ of quenchings to 20 ℃, repeat aforesaid operations 2 times, measure the DSC curve.The temperature on the endothermic peak summit that is equivalent to melt of the DSC curve that will measure in the 2nd operation is tried to achieve as the fusing point of release agent.
(embodiment 1)
[manufacturings of pigmentary resin particle slurries]
After using Henschel mixer that vibrin (glass transition temperature (Tg): 58 ℃, softening temperature (Tm): 110 ℃) 82 weight portions, phthalocyanine blue (trade name: copper phthalocyanine 15:3, Network ラ イ ア Application ト society system) 8 weight portions, paraffin (85 ℃ of fusing points) 8 weight portions, charge control agent (trade name: TRH, the native ケ paddy chemical industry of guarantor Co., Ltd. system) 2 weight portions are mixed 10 minutes, use twin-screw to extrude mixing roll (trade name: PCM65, Co., Ltd.'s pond shellfish system) melting mixing.Mix this melting mixing thing 100g (10 weight portion), anionic species surfactant sodium polyacrylate (trade name: D-H14-N L-7403KN, Japanese emulsifying agent Co., Ltd. system) 3g (0.3 weight portion) and water (20 ℃ of temperature, conductivity 0.5 μ S/cm) 897g (89.7 weight %), the gained potpourri is dropped in the jar of high pressure homogenizer (trade name: NANO3000, the U.S. grain system of Co., Ltd.), under 25 ℃, the condition of 100MPa, carry out coarse crushing.Then, circulation is carried out micronize 3 times under 150 ℃, the condition of 160MPa, makes pigmentary resin particle slurries.The volume average particle size of gained pigmentary resin particle is the 0.35 μ m (coefficient of variation (CV value): 30).
[manufacturings of biomass resin particle slurries]
L-lactide 3kg, DL-lactide 2kg, tin octoate 1.2g are put into polymerization reaction trough, after nitrogen environment, 195 ℃ of following heating made its ring-opening polymerization in 1 hour, further add 1, ammediol 100g, terephthalic acid (TPA) 50g, 190 ℃ of following polymerizations 2 hours, obtaining molecular weight was that matter average molecular weight Mw:10500, number-average molecular weight Mn:3900, softening temperature are the copolymer of poly lactic acid (CE-1) of 135 ℃ acid value 8.8.The sodium polyacrylate (trade name: D-H14-NL-7403KN, Japanese emulsifying agent Co., Ltd. system) 5g (0.5 weight portion), water (20 ℃ of temperature, the conductivity 0.5 μ S/cm) 895g (89.5 weight %) that mix this copolymer of poly lactic acid (CE-1) 100g (10 weight portion), anionic species surfactant, the gained potpourri is dropped in the jar of high pressure homogenizer (trade name: NANO3000, the U.S. grain system of Co., Ltd.), under 25 ℃, the condition of 100MPa, carry out coarse crushing.Then, under 160 ℃, the condition of 180MPa, carry out micronize, make biomass resin particle slurries.The volume average particle size of gained biomass resin particle is the 0.85 μ m (coefficient of variation (CV value): 32).
[manufacturing of toner particle]
In gained pigmentary resin particle slurries 50 weight portions, biomass resin particle slurries 50 weight portions, add polycoagulant sodium chloride (trade name: superfine sodium chloride, キ シ ダ KCC system) 3.0 weight portions, the mulser (trade name: Network レ ア ミ Star Network ス, エ system テ Network ニ Star Network Co., Ltd. system) that uses single mode of motion stir process 10 minutes under 80 ℃ of condensation temperatures, rotary speed of rotator 8000rpm, stirred 5 minutes down at 85 ℃ more afterwards, make the aggregated particle slurries that cohesion has resin particle thus.With the washing of gained aggregated particle slurries, separation, drying, obtain the volume average particle size 5.8 μ m (coefficient of variation (CV value): toner particle 22) (aggregated particle).Mix these toner powder 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 1.
(embodiment 2)
[manufacturings of pigmentary resin particle slurries]
After using Henschel mixer that vibrin (glass transition temperature (Tg): 58 ℃, softening temperature (Tm): 110 ℃) 86 weight portions, phthalocyanine blue (trade name: copper phthalocyanine 15:3, Network ラ イ ア Application ト society system) 4 weight portions, paraffin (85 ℃ of fusing points) 8 weight portions, charge control agent (trade name: TRH, the native ケ paddy chemical industry of guarantor Co., Ltd. system) 2 weight portions are mixed 10 minutes, use twin-screw to extrude mixing roll (trade name: PCM65, Co., Ltd.'s pond shellfish system) melting mixing.Mix this melting mixing thing 100g (10 weight portion), anionic species surfactant sodium polyacrylate (trade name: D-H14-N L-7403KN, Japanese emulsifying agent Co., Ltd. system) 3g (0.3 weight portion) and water (20 ℃ of temperature, conductivity 0.5 μ S/cm) 897g (89.7 weight %), the gained potpourri is dropped in the jar of high pressure homogenizer (trade name: NANO3000, the U.S. grain system of Co., Ltd.), under 25 ℃, the condition of 100MPa, carry out coarse crushing.Then, circulation is carried out micronize 3 times under 160 ℃, the condition of 160MPa, makes pigmentary resin particle slurries.The volume average particle size of gained pigmentary resin particle is the 0.52 μ m (coefficient of variation (CV value): 29).
[manufacturings of biomass resin particle slurries]
After using Henschel mixer that PLA (CE-1) 96 weight portions, phthalocyanine blue (trade name: copper phthalocyanine 15:3, Network ラ イ ア Application ト society system) 4 weight portions are mixed 10 minutes, use twin-screw to extrude mixing roll (trade name: PCM65, Co., Ltd.'s pond shellfish system) melting mixing.Mix this melting mixing thing 100g (10 weight portion), anionic species surfactant sodium polyacrylate (trade name: D-H14-N L-7403KN, Japanese emulsifying agent Co., Ltd. system) 5g (0.5 weight portion) and water (20 ℃ of temperature, conductivity 0.5 μ S/cm) 895g (89.5 weight %), the gained potpourri is dropped in the jar of high pressure homogenizer (trade name: NANO3000, the U.S. grain system of Co., Ltd.), under 25 ℃, the condition of 100MPa, carry out coarse crushing.Then, under 170 ℃, the condition of 200MPa, carry out micronize, make biomass resin particle slurries.The volume average particle size of gained biomass resin particle is the 0.75 μ m (coefficient of variation (CV value): 35).
[manufacturing of toner particle]
Use gained pigmentary resin particle slurries and biomass resin particle slurries, by method similarly to Example 1, obtaining volume average particle size is the 5.6 μ m (coefficient of variation (CV value): toner particle 23).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 2.
(embodiment 3)
In the manufacturing of biomass resin particle slurries; except the temperature conditions of micronize operation and pressure condition being become 180 ℃, 250MPa, making volume average particle size respectively is the 0.60 μ m (coefficient of variation (CV value): the biomass resin particle slurries 40); by method similarly to Example 1, obtaining volume average particle size is the 5.4 μ m (coefficient of variation (CV value): toner particle 22).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 3.
(embodiment 4)
In the manufacturing of biomass resin particle slurries; except the temperature conditions of micronize operation and pressure condition being become 160 ℃, 160MPa, making volume average particle size respectively is the 1.15 μ m (coefficient of variation (CV value): the biomass resin particle slurries 40); by method similarly to Example 1, obtain the volume average particle size 6.4 μ m (coefficient of variation (CV value): toner particle 25).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 4.
(embodiment 5)
The particulate of the styrene-acrylonitrile copolymer acid resin by 0.1 μ m (glass transition temperature (Tg): 64 ℃, softening temperature (Tm): the 122 ℃) formation that obtains by emulsion polymerization is separated out in toner surface, form the resin molding of thickness 0.15 μ m on the surface of the toner of embodiment 1, obtaining volume average particle size is the 5.8 μ m (coefficient of variation (CV value): toner particle 22).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 5.
(embodiment 6)
In the manufacturing of pigmentary resin particle slurries; except the temperature conditions of micronize operation and pressure condition being become 150 ℃, 200MPa, making volume average particle size respectively is the 0.24 μ m (coefficient of variation (CV value): the pigmentary resin particle slurries 28); by method similarly to Example 1, obtain the volume average particle size 5.7 μ m (coefficient of variation (CV value): toner particle 20).Mix these toner powder 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 6.
(embodiment 7)
Except the pigmentary resin particle slurries that use embodiment 6 manufacturings,, obtain the volume average particle size 6.1 μ m (coefficient of variation (CV value): toner particle 21) by method similarly to Example 3.Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 7.
(embodiment 8)
In the manufacturing of pigmentary resin particle slurries; except temperature conditions and pressure condition with the micronize operation become 150 ℃, 140MPa, the making volume average particle size 0.40 μ m (coefficient of variation (CV value): the pigmentary resin particle slurries 32) respectively; by method similarly to Example 1, obtain the volume average particle size 6.5 μ m (coefficient of variation (CV value): toner particle 26).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 8.
(embodiment 9)
Except the biomass resin particle slurries of the pigmentary resin particle slurries that use embodiment 8 manufacturings and embodiment 2 manufacturings, by method similarly to Example 3, obtaining volume average particle size is the 5.5 μ m (coefficient of variation (CV value): toner particle 22).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 9.
(embodiment 10)
In the manufacturing of pigmentary resin particle slurries; except temperature conditions and the pressure condition that makes the micronize operation becomes 150 ℃, 230MPa, the making volume average particle size 0.12 μ m (coefficient of variation (CV value): the pigmentary resin particle slurries 28) respectively; by method similarly to Example 3, obtaining volume average particle size is the 5.5 μ m (coefficient of variation (CV value): toner particle 22).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 10.
(embodiment 11)
In the manufacturing of biomass resin particle slurries; except the temperature conditions of micronize operation and pressure condition being become 185 ℃, 260MPa, making volume average particle size respectively is the 0.50 μ m (coefficient of variation (CV value): the biomass resin particle slurries 35); by method similarly to Example 6, obtaining volume average particle size is the 5.5 μ m (coefficient of variation (CV value): toner particle 22).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 11.
(embodiment 12)
In the manufacturing of toner particle, except the combined amount with pigmentary resin particle slurries and biomass resin particle slurries becomes respectively 35 weight portions, 65 weight portions, by method similarly to Example 1, obtaining volume average particle size is the 5.6 μ m (coefficient of variation (CV value): toner particle 22).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 12.
(embodiment 13)
In the manufacturing of biomass resin particle slurries; be respectively 175 ℃ at temperature conditions that makes the micronize operation and pressure condition; 190MPa and the volume average particle size 0.75 μ m (coefficient of variation (CV value): biomass resin particle slurries 40 weight portions 38) that obtains; (the glass transition temperature (Tg): 58 ℃ of the styrene-acrylonitrile copolymer acid resin by 0.25 μ m that obtains by emulsion polymerization; softening temperature (Tm): 112 ℃) resin particle slurries 47 weight portions of Gou Chenging; be separated into the phthalocyanine blue slurries (trade name: copper phthalocyanine 15:3 of 0.08 μ m; Network ラ イ ア Application ト society system) 5 weight portions; be separated into the sodium chloride (trade name: superfine sodium chloride that adds in paraffin (85 ℃ of fusing points) 8 weight portions of 0.4 μ m as polycoagulant; キ シ ダ KCC system) 2.5 weight portions; use the mulser (trade name: Network レ ア ミ Star Network ス of single mode of motion; エ system テ Network ニ Star Network Co., Ltd. system) 80 ℃ of condensation temperature; stir process is 10 minutes under the rotary speed of rotator 8000rpm; stirred 5 minutes down at 85 ℃ more afterwards, make the aggregated particle slurries that cohesion has resin particle thus.With the washing of gained aggregated particle slurries, separation, drying, obtaining volume average particle size is the 5.3 μ m (coefficient of variation (CV value): toner particle 20) (cohesion resin particle).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 13.
(embodiment 14)
(the glass transition temperature (Tg): 58 ℃ of the styrene-acrylonitrile copolymer acid resin by 0.25 μ m that is obtaining by emulsion polymerization, softening temperature (Tm): 112 ℃) resin particle slurries 87 weight portions of Gou Chenging, be separated into the phthalocyanine blue slurries (trade name: copper phthalocyanine 15:3 of 0.08 μ m, Network ラ イ ア Application ト society system) 5 weight portions, be separated into the sodium chloride (trade name: superfine sodium chloride that adds in paraffin (85 ℃ of fusing points) 8 weight portions of 0.4 μ m as polycoagulant, キ シ ダ KCC system) 2.5 weight portions, use the mulser (trade name: Network レ ア ミ Star Network ス of single mode of motion, エ system テ Network ニ Star Network Co., Ltd. system) 80 ℃ of condensation temperature, stir process is 10 minutes under the rotary speed of rotator 8000rpm, stirred 5 minutes down at 85 ℃ afterwards, make the aggregated particle slurries that cohesion has resin particle thus.With the washing of gained aggregated particle slurries, separation, drying, obtaining volume average particle size is the 5.5 μ m (coefficient of variation (CV value): toner particle 18) (aggregated particle).Mix these toner powder 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 14.
(embodiment 15)
Except not using the phthalocyanine blue slurries, by method similarly to Example 14, obtaining volume average particle size is the 5.4 μ m (coefficient of variation (CV value): toner particle 18).Mix these toner powder 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 15.
(embodiment 16)
The particulate by 0.1 μ m styrene-acrylonitrile copolymer acid resin (glass transition temperature (Tg): 64 ℃, softening temperature (Tm): 122 ℃) formation that obtains by emulsion polymerization is separated out in toner surface, form the resin molding of thickness 0.15 μ m on the surface of the toner of embodiment 14, obtaining volume average particle size is the 5.6 μ m (coefficient of variation (CV value): toner particle 20).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of embodiment 16.
(comparative example 1)
In the manufacture method of comparative example 1, obtain toner particle as the PLA of biomass resin with as the potpourri of the manufacturings such as vibrin of binder resin by melting mixing.Therefore, the biomass resin is scattered in the toner particle under the state compatible with binder resin.Below put down in writing the manufacture method of the toner particle of comparative example 1.
After using Henschel mixer that PLA (CE-1) 40.5 weight portions, vibrin (glass transition temperature (Tg): 60 ℃, softening temperature (Tm): 110 ℃) 40.5 weight portions, phthalocyanine blue (trade name: copper phthalocyanine 15:3, Network ラ イ ア Application ト society system) 4 weight portions, paraffin (85 ℃ of fusing points) 4 weight portions, charge control agent (trade name: TRH, the native ケ paddy chemical industry of guarantor Co., Ltd. system) 1 weight portion are mixed 10 minutes, use twin-screw to extrude mixing roll (trade name: PCM65, Co., Ltd.'s pond shellfish system) melting mixing.Mix this melting mixing thing 100g (10 weight portion), anionic species surfactant sodium polyacrylate (trade name: D-H14-N L-7403KN, Japanese emulsifying agent Co., Ltd. system) 5g (0.5 weight portion) and water (20 ℃ of temperature, conductivity 0.5 μ S/cm) 895g (89.5 weight %), the gained potpourri is dropped in the jar of high pressure homogenizer (trade name: NANO3000, the U.S. grain system of Co., Ltd.), under 25 ℃, the condition of 100MPa, carry out coarse crushing.Then, under 160 ℃, the condition of 185MPa, carry out micronize, make the resin particle slurries.The volume average particle size of gained resin particle is the 0.82 μ m (coefficient of variation (CV value): 29).
Then, in gained resin particle slurries 100 weight portions, add polycoagulant sodium chloride (trade name: superfine sodium chloride, キ シ ダ KCC system) 3.2 weight portions, the mulser (trade name: Network レ ア ミ Star Network ス, エ system テ Network ニ Star Network Co., Ltd. system) that uses single mode of motion stir process 10 minutes under 80 ℃ of condensation temperatures, rotary speed of rotator 8000rpm, stirred 5 minutes down at 85 ℃ more afterwards, make the cohesion resin particle slurries that cohesion has resin particle thus.Gained is condensed the washing of resin particle slurries, separation, drying, and obtaining volume average particle size is the 5.8 μ m (coefficient of variation (CV value): toner particle 22).Mix these toner particle 200 weight portions and hydrophobic silica powder body (trade name: RX-200, Japanese ア エ ロ ジ Le Co., Ltd. system) 2.5 weight portions, obtain the toner of comparative example 1.
For the toner of embodiment and comparative example, evaluation region diameter, volume average particle size, the coefficient of variation, fixation performance, permanance and the transparency.Evaluation method is as described below.
＜regional diameter 〉
The regional diameter that contains biomass resin zone in the toner particle is for being scaled regional cross section the diameter of bowlder.The disperse state that contains biomass resin zone in the toner particle can followingly be confirmed: toner particle is embedded in the epoxy resin of normal temperature cure, obtain solidfied material, use has the microtome of adamas blade with the thickness of gained solidfied material ultra-thin section to about 100 μ m, utilize transmission electron microscope (TEM, trade name: H-8100, society of Hitachi Co., Ltd system) to observe, thereby confirm with 20000 times of cross sections to toner particle.The regional diameter that contains biomass resin zone of Que Rening is for being scaled the cross section in zone the diameter of bowlder like this.
＜the volume average particle size and the coefficient of variation (CV value) 〉
In electrolytic solution (trade name: ISOTON-II, ベ Star Network マ Application コ one Le タ one society's system) 50ml, add sample 20mg and alkyl ether sulphate sodium 1ml, by ultrasonic disperser (trade name: UH-50, STM corporate system) dispersion treatment 3 minutes under ultrasonic frequency 20kHz, formation determination sample.Measure sample for this, use particle size distribution device (trade name: Multisizer3, ベ Star Network マ Application コ one Le タ one society's system), in the aperture is that 20 μ m, mensuration population are to measure under 50000 conditions of counting, and tries to achieve volume average particle size by the volume particle size distribution of sample particle.In addition, according to volume average particle size and standard deviation thereof, calculate the coefficient of variation of toner by following formula.And the volume average particle size and the coefficient of variation of above-mentioned pigmentary resin particle and biomass resin particle are also measured by the present invention.
Coefficient of variation CV (%)=(standard deviation/volume average particle size of volume particle size distribution) * 100
＜fixation performance 〉
The developer that will contain the toner of embodiment and comparative example is filled among the ARC-150 of image processing system Sharp Corp system.Image processing system is worked, at paper used for recording (grammes per square metre 52g/m in the mode that processing speed reaches 88mm/ second 2) the last uncertain image of drawing along the figure of regulation that forms.Use the outside photographic fixing machine of no oil type photographic fixing mode, make the uncertain image photographic fixing that is formed on the paper used for recording on paper used for recording when changing temperature, the rotation of visual valuation fixing roller has or not set-off to paper used for recording later 2 times.Evaluation criterion is as follows.
◎: very good.During photographic fixing in temperature is 120～200 ℃ scope set-off does not take place.
Zero: good.During photographic fixing in temperature is 130～190 ℃ scope set-off does not take place.
△: it is no problem that actual use is gone up.
*: can not actually use.
＜permanance 〉
The developer that will contain the toner of embodiment and comparative example is filled among the ARC-150 of image processing system Sharp Corp system.Image processing system is worked, at paper used for recording (the grammes per square metre 75g/m of A4 size in the mode that processing speed reaches 88mm/ second 2) the last image of drawing along the figure of regulation that forms.At this moment, on 10000 paper used for recording, form image, by the blank sheet of paper part after 10000 processing of visual valuation.Evaluation criterion is as follows.
◎: very good.
Zero: good.
△: it is no problem that actual use is gone up.
*: can not actually use.
And, for the toner of embodiment 14, utilize Coulter-counter to measure the size-grade distribution of the toner after 10000 processing, size-grade distribution not have to change substantially before and after handling, and confirms as well.
＜the transparency 〉
The developer that will contain the toner of embodiment and comparative example is filled among the ARC-150 of image processing system Sharp Corp system.Image processing system is worked in the mode that processing speed reaches 88mm/ second.Under colourity, the optimized development of chroma and fixing conditions, in OHP sheet material (シ ヤ one プ De キ コ メ Application ト シ ス テ system system: IJ188OHP) go up formation, estimate actual usability by visual judgement along the image that the figure that stipulates draws.Evaluation criterion is as follows.
◎: very good.
Zero: good.
△: it is no problem that actual use is gone up.
*: can not actually use.
＜keeping quality 〉
In the toner bottle of special use, put into the toner 300g of embodiment and comparative example, in 50 ℃ calibration cell, place after 2 days, survey the rate that exists of condensation product with 400 purpose sieve mesh inspections.Evaluation criterion is as described below.
◎: very good.
Zero: good.
△: it is no problem that actual use is gone up.
*: can not actually use.
And comprehensive evaluation is estimated according to following standard.
◎: all items is the situation more than zero.
Zero: △ is in the situation more than 1.
*: * in the situation more than 1.
To be shown in table 1 to the evaluation result of regional diameter, volume average particle size, the coefficient of variation, fixation performance, permanance, the transparency, keeping quality and the comprehensive evaluation of the toner of embodiment and comparative example.
As shown in Table 1, the fixation performance of toner of the present invention is good, and permanance, the transparency and keeping quality are good.Particularly, the regional diameter that contains biomass resin zone is more than the 0.5 μ m, below the 1 μ m, the particle diameter of adhesive resin particles is more than 1/4, below 1/2 with the ratio (a/c) of the particle diameter of biomass resin particle, and the biomass resin is below 60 weight portions with respect to the content of 100 weight portion toners, the various toner qualities of the toner of embodiment 1,5～7,13～16 are comprehensive higher, and comprehensive evaluation is " ◎ ".
Figure S2008101356022D00661
The present invention can implement with other variety of way under the situation that does not break away from its spirit or principal character.Therefore, above-mentioned embodiment only is example in all respects, and scope of the present invention is the scope shown in claims, is not subjected to instructions any qualification in full.And, belong to the claim scope distortion or the change also all within the scope of the invention.

Claims (19)

1. toner, it is characterized in that, contain the toner particle that contains binder resin at least, in toner particle, form and contain biomass resin zone, contain biomass resin zone and be almost spherical or its combination shape, described biomass resin is meant that containing with plant is the resin of the compound of skeleton as raw material by photosynthesis fixing carbon atom from Atmospheric Carbon Dioxide.
2. toner as claimed in claim 1, wherein, the biomass resin is a crystalline resin.
3. toner as claimed in claim 1, wherein, with respect to toner 100 weight portions, the content of biomass resin is more than 20 weight portions, below 60 weight portions.
4. toner as claimed in claim 1 wherein, does not contain colorant in containing biomass resin zone.
5. toner as claimed in claim 1, wherein, the regional diameter that contains biomass resin zone is below the 1 μ m, described regional diameter has diameter of a circle of the same area with regional sectional area and obtains by being converted into.
6. toner as claimed in claim 5, wherein, the regional diameter that contains biomass resin zone is more than the 0.5 μ m, below the 1 μ m.
7. toner as claimed in claim 1, wherein, binder resin is a vibrin.
8. toner as claimed in claim 1 wherein, coats the surface of toner particle with resin molding.
9. toner as claimed in claim 8, wherein, resin molding is formed by the styrene-acrylonitrile copolymer acid resin of making of emulsion polymerization.
10. a method for preparing toner is characterized in that, comprises following operation:
Be dispersed in the liquid medium to major general's binder resin and obtain the adhesive resin particles dispersion step of adhesive resin particles slurries;
To major general's biomass resin dispersion in liquid medium and obtain the biomass resin particle dispersion step of biomass resin particle slurries; And
Hybrid bonding resin particle slurries and biomass resin particle slurries, the cohesion process that adhesive resin particles and biomass resin particle are condensed,
Wherein, the particle diameter of adhesive resin particles is more than 1/4, below 1/2 with respect to the particle diameter of biomass resin particle,
Described biomass resin is meant that containing with plant is the resin of the compound of skeleton as raw material by photosynthesis fixing carbon atom from Atmospheric Carbon Dioxide.
11. the manufacture method of toner as claimed in claim 10 wherein, contains colorant in the adhesive resin particles.
12. the manufacture method of toner as claimed in claim 10 wherein, also comprises being scattered in the liquid medium to major general's colorant and obtaining the colorant particle dispersion step of colorant particle slurries,
In cohesion process, hybrid bonding resin particle slurries, biomass resin particle slurries and colorant particle slurries make adhesive resin particles, biomass resin particle and colorant particle cohesion.
13. the manufacture method of toner as claimed in claim 10, wherein, biomass resin particle dispersion step comprises following operation: the grain refined operation of making biomass resin particle slurries under heating and pressurizing; To be in the decompression operation of the biomass resin particle slurries decompression of heating and pressurizing state; Refrigerating work procedure with the biomass resin particle slurries cooling of will reduce pressure.
14. the manufacture method of toner as claimed in claim 10, wherein, biomass resin particle dispersion step is undertaken by high pressure homogenization method.
15. a toner is characterized in that, by the manufacture method manufacturing of the described toner of claim 10.
16. a developing apparatus is characterized in that, uses the developer that contains the described toner of claim 1 to develop.
17. an image processing system is characterized in that, possesses the described developing apparatus of claim 16.
18. a developing apparatus is characterized in that, uses the developer that contains the described toner of claim 15 to develop.
19. an image processing system is characterized in that, possesses the described developing apparatus of claim 18.
CN2008101356022A 2007-07-06 2008-07-07 Toner, method of manufacturing the toner, developing device, and image forming apparatus Expired - Fee Related CN101339374B (en)

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