阅读说明：本技术 静电图像显影用双组分显影剂 (Electrostatic image development two-component developing agent ) 是由 小原慎也 柴田幸治 上田隼也 高桥拓也 内野哲 于 2019-05-17 设计创作，主要内容包括：本发明涉及静电图像显影用双组分显影剂。本发明提供一种静电图像显影用双组分显影剂,其即使在连续印刷具有高印字率的图像时,可以保持高图像质量并且抑制灰雾的发生。静电图像显影用双组分显影剂,其具有：调色剂粒子和载体粒子,所述调色剂粒子包含调色剂母体粒子及设置在所述调色剂母体粒子表面上的外部添加剂；所述载体粒子包含芯材粒子及设置在所述芯材粒子表面上的包覆部,其中,所述外部添加剂含有氧化铝粒子,所述芯材粒子的露出面积比率为4.0％以上且15.0％以下。(The present invention relates to electrostatic image development two-component developing agents.The present invention provides a kind of electrostatic image development two-component developing agent, even if can keep high image quality when continuous printing has the image of high lettering rate and inhibit the generation of photographic fog.Electrostatic image development two-component developing agent, includes toner particle and carrier particle, and the toner particle includes toner mother particle and the external additive being arranged on the toner mother particle surface；The carrier particle includes core material particle and the covering portion being arranged on the core material particle surface, wherein the external additive contains aluminium oxide particles, and the exposing area ratio of the core material particle is 4.0% or more and 15.0% or less.)

1. a kind of electrostatic image development two-component developing agent includes toner particle and carrier particle, the toner grain Attached bag particle containing toner mother and the external additive being arranged on the toner mother particle surface；The carrier particle Include core material particle and the covering portion being arranged on the core material particle surface, wherein

The external additive contains aluminium oxide particles,

The exposing area ratio of the core material particle is 4.0% or more and 15.0% or less.

2. a kind of electrostatic image development two-component developing agent includes toner particle and carrier particle, the toner grain Attached bag particle containing toner mother and the external additive being arranged on the toner mother particle surface；The carrier particle Include core material particle and the covering portion being arranged on the core material particle surface, wherein

The external additive contains aluminium oxide particles,

The form factor of the core material particle is 115~150.

3. electrostatic image development two-component developing agent according to claim 1 or 2, wherein

The dynamic electric resistor rate of the carrier particle is 1.0 × 10⁸Ω cm or more and 1.0 × 10¹¹Ω cm or less.

4. electrostatic image development two-component developing agent described in any one of claim 1 to 3, wherein

The volume resistivity of the aluminium oxide particles is higher than the dynamic electric resistor rate of the carrier particle.

5. electrostatic image development two-component developing agent according to any one of claims 1 to 4, wherein

The equal primary particle size of the number of the aluminium oxide particles is 10nm or more and 40nm or less.

6. electrostatic image development two-component developing agent according to any one of claims 1 to 5, wherein

The covering portion includes the resin with naphthenic base.

Technical field

The present invention relates to electrostatic image development two-component developing agents.

Background technique

It is universal with duplicator and printing machine, higher performance is required for toner used in printing.In recent years, Referred to as " on-demand printing (the print on demand for not having plate-making process and being directly printed；POD digital printing skill) " Art is concerned.It is excellent since POD can correspond to small lot printing and change the variable printed of each print content In traditional lithographic printing.

When by traditional image forming method by electrofax be applied to POD when, in addition to the high speed of print speed printing speed, It reduces except operating cost, important also resides in: can be exported with a variety of printing rates, and can be in a variety of environment Steadily export image high-definition.In particular, in the high graphic art of lettering rate, when continuous output has high lettering rate Image when, external additive is easy to be transferred to carrier from toner, and the chargeability of carrier reduces, and thus leads to toner Carried charge reduces.Therefore, when POD will be applied to by the image forming method of electrofax mode, it may occur that background portion The dusting etc. of toner when photographic fog and transfer, it is believed that it is difficult to steadily export image high-definition.

In order to solve this problem, following technologies are disclosed: by using with partial size difference, shape difference, work function difference Different a variety of external additives prevent external additive from dissociating from toner mother particle, so that charging property stabilization (for example, Referring to patent document 1).Patent document 1 is disclosed comprising the toner particle with toner mother particle and external additive Toner.External additive includes with different average primary particle diameters, hydrophobic negative charging silica and hydrophobic Rutile-anatase titanium dioxide (TiO 2 particles) of property.

In toner documented by patent document 1, although the free of TiO 2 particles is received with large-sized negative The inhibition of charging property silica, but since TiO 2 particles have low resistance, when a small amount of electric charge transfer is to carrier particle, The electric charge transfer to carrier particle is promoted, so that the carried charge of toner reduces.Furthermore, it is possible to think: with a large amount of surface Modifying agent carries out surface to TiO 2 particles and is modified, and makes it have resistance level identical with carrier particle.

It is also known that there is the method for the resistance for adjusting carrier particle itself (for example, with reference to patent document 2).In general, packet Core material particle used in type carrier particle is covered with low-resistance value, and the material for covering portion has high resistance, therefore can The resistance value of the carrier particle is adjusted with the covering portion by carrier particle surface.Patent document 2 discloses, in covering portion Metal oxides such as disperse black carbon, tin oxide, titanium oxide, zinc oxide etc. adjust the technology of the resistance value of covering portion.

Summary of the invention

Invent the technical issues of solved

In the technology described in patent document 1, TiO 2 particles occur to agglomerate and be easy to from toner mother each other Dissociate in particle, the surface of carrier particle may be polluted.If carrier particle surface is contaminated due to external additive, adjust The flow behavior of toner is unstable, influences the conveying characteristic of toner, and causes the fluctuation of picture quality.In addition, in patent In technology documented by document 2, when adding a large amount of resistivity modifier, the charge maintenance capability of covering portion substantially drops sometimes It is low.In addition, when covering portion abrasion, it may occur however that resistivity modifier is attached to the problems such as on toner.In addition, ought add on a small quantity When resistivity modifier, initial carrier too high in resistance is easy to remain the charge opposite with toner on carrier particle, causes to connect Image color in continuous printing reduces.As described above, the side for taking into account the high image qualityization to form image and photographic fog being inhibited to occur Face, there are still improved spaces.

The technical problem to be solved in the present invention is to provide a kind of electrostatic image development two-component developing agents, even if even When continuous printing has the image of high lettering rate, high image quality can also be kept and inhibit the generation of photographic fog.

Technical means to solve problem

As the technological means to solve the above problems, the present invention provides a kind of electrostatic image development two-component developing agent, It includes toner particle and carrier particle, and the toner particle includes toner mother particle and is arranged in the toning External additive on agent parent particle surface；The carrier particle includes core material particle and is arranged on the core material particle surface On covering portion, wherein the external additive contains aluminium oxide particles, and the exposing area ratio of the core material particle is 4.0% or more and 15.0% or less.

As the technological means to solve the above problems, the present invention provides a kind of electrostatic image development two-component developing agent, It includes toner particle and carrier particle, and the toner particle includes toner mother particle and is arranged in the toning External additive on agent parent particle surface；The carrier particle includes core material particle and is arranged on the core material particle surface On covering portion, wherein the external additive contains aluminium oxide particles, the form factor of the core material particle is 115~ 150。

The effect of invention

According to the present invention, a kind of electrostatic image development two-component developing agent is provided, even if there is height in continuous printing When the image of lettering rate, high image quality can also be kept and inhibit the generation of photographic fog.

Specific embodiment

<composition of electrostatic image development two-component developing agent>

Electrostatic image development has carrier particle and toner particle with two-component developing agent.

The example of carrier particle includes: comprising the metals shape such as the metals such as iron, ferrite, magnetic iron ore, these metals and aluminium, lead At the conventional known material such as alloy magnetic particle.Include in the example of carrier particle: cladded type carrier particle has Core material particle and covering portion, the core material particle include magnetic substance, and the covering portion, which has, coats core material particle surface Covering material；Resin dispersion type carrier particle, is dispersed in resin by the micro mist of magnetic substance and is formed.From inhibition carrier grain For son to from the perspective of the attachment of photoreceptor, carrier particle is preferably cladded type carrier particle.

Core material particle is magnetic substance obtained from for example being magnetized strongly in this direction as magnetic field.Magnetic substance can be independent Using one kind, can also be applied in combination two or more.The example of magnetic substance includes: that iron, nickel, cobalt etc. show ferromagnetic gold Belong to, the alloy containing these metals or compound and ferromagnetic alloy shown by heat treatment.

The example for showing ferromagnetic metal or the compound containing the metal includes: iron, by the iron of following formula (a) expression Oxysome, the magnetic iron ore indicated by following formula (b).M in formula (a) and (b) indicates to be selected from Mn, Fe, Ni, Co, Cu, Mg, Zn, Cd and Li One or more of monovalence or divalent metal.

MO·Fe₂O₃Formula (a)

MFe₂O₄Formula (b)

The example for showing ferromagnetic alloy includes: Heusler alloy and the dioxies such as manganese-copper-aluminium, manganese-copper-tin Change chromium.

Core material particle is preferably various ferrites.The specific gravity of cladded type carrier particle is less than the metal for constituting core material particle Specific gravity.Therefore, various ferrites can further decrease the impact force stirred in developing apparatus.

Covering portion is arranged on the surface of core material particle.Covering portion has covering material.Covering material can be used alone One kind can also be applied in combination two or more.Covering material can be used to be used in the cladding of core material particle in carrier particle Well known resin.The example of resin as covering material includes: the polyolefin resins such as polyethylene, polypropylene；Polyphenyl second Olefine resin；Polymethyl methacrylate etc. (methyl) acrylic resin, polyvinyl acetate, polyvinyl alcohol, gathers polyacrylonitrile The polyvinyl resins such as vinyl butyral, polyvinyl chloride and polyvinylidene resin；Vinyl chloride vinyl acetate copolymer and benzene The copolymer resins such as ethylene-acrylic acid copolymer；The polyorganosiloxane resin or its modified resin that organosiloxane key is constituted；Poly- fluorine The fluororesin such as ethylene；Polyamide；Polyester resin；Polyurethane resin；Polycarbonate resin；The amino such as urea-formaldehyde resin Resin；Epoxy resin.The example of modified resin includes the modification by alkyd resin, polyester resin, epoxy resin, polyurethane etc. Resin.

From the viewpoint of the adaptation of the core material particle in the viewpoint for the water absorption for reducing carrier particle, raising and covering portion It sets out, the resin as covering material is preferably the resin with naphthenic base.The example of naphthenic base include: cyclohexyl, cyclopenta, Cyclopropyl, cyclobutyl, suberyl, cyclooctyl, cyclononyl and cyclodecyl.The sight of adaptation between covering portion and core material particle Point sets out, and naphthenic base is preferably cyclohexyl or cyclopenta, more preferably cyclohexyl.

The weight average molecular weight (Mw) of resin with naphthenic base is preferably 10000~800000, more preferably 100000~ 750000.The content of Component units in the resin containing naphthenic base is, for example, 10~90 mass %.Naphthenic base in the resin Content for example can by P-GC/MS or¹Instrumental method well known to H-NMR etc. and acquire.

The exposing area ratio of core material particle on initial carrier particle surface is 4.0% or more and 15.0% or less. Here " initial " refers to that toner particle and carrier particle are mixed to manufacture the rank of electrostatic image development two-component developing agent Section.When exposing area ratio less than 4.0%, the resistance value of carrier particle is excessively high, between carrier particle and toner particle Electrostatic adhesion strength increases, the replaceability deterioration of toner particle, and photographic fog and picture quality is caused to reduce.On the other hand, when When exposing area ratio greater than 15.0%, the resistance value of carrier particle itself is reduced, therefore the carried charge of toner particle reduces, Picture quality is caused to deteriorate.

The exposing area ratio of core material particle on carrier particle surface can be for example measured by the following method.Make With XPS sensing equipment (K-Alpha；Manufactured by Thermo Fisher Scientific), use Al homogeneous X-ray to penetrate as X Acceleration voltage is set as 7kV and emission current is set as 6mV by line source.Then, to as the main member for constituting clad The carbon of element is measured, and is measured to the iron as the essential element for constituting core material particle.Also, by the measurement result of iron With the ratio between, Carbon analysis result and the measurement result of iron as exposing area ratio.

In terms of the median particle diameter of volume reference, the average grain diameter of carrier particle is preferably 20~100 μm, more preferably 25~ 80μm.The median particle diameter of the volume reference of carrier particle can for example pass through the laser diffraction type granularity equipped with wet type disperser Distribution measurement device (HELOS；SYMPATEC company) it is measured.

The form factor (SF-1) of core material particle is 115 or more and 150 or less.When form factor is less than 115, measurement The shape of particle is close to proper sphere, and therefore, the bulk density (g/cc) of carrier increases, electrostatic image development two-component developing agent quilt It is excessively transported in development nip portion, dispersing for photographic fog or toner occurs.On the other hand, when form factor is greater than 150, Concave-convex rise and fall on core material particle surface becomes acutely, hole to be generated inside core material particle.Therefore, the magnetization of each core material particle The defects of reduction, carrier particle itself develop on the photoreceptor at developer roll gap portion, and the scratch on photosensitive surface occurs.It is logical It crosses and the firing temperature in ablating work procedure is set as 1300~1500 DEG C higher than the prior art, can obtain form factor is about 115~150 core material particle.

For form factor, with scanning electron microscope with the photo of 150 times random shooting 100 or more particles, The photograph image captured by scanner is measured using image processing and analyzing device LUZEX AP (Nireko Co., Ltd.).Core material grain The form factor (SF-1) of son is acquired by following formula (1).

SF-1=(maximum length of particle)²/ (projected area of particle) × (π/4) × 100 formula (1)

Form factor indicates the concave-convex degree of core material particle to be determined, should when the concave-convex fluctuating when surface becomes violent Coefficient value becomes larger.

The dynamic electric resistor rate of carrier particle is preferably 1.0 × 10⁸Ω cm or more and 1.0 × 10¹¹Ω cm or less.Carrier The dynamic electric resistor rate of particle is less than 1.0 × 10⁸When Ω cm, the charge maintenance capability of carrier particle itself is reduced, and is difficult to sometimes Keep the carried charge of toner particle.On the other hand, when the dynamic electric resistor rate of carrier particle is greater than 1.0 × 10¹¹When Ω cm, with The opposite charge accumulation of toner particle on carrier particle, leads to the electrostatic adhesion strength between toner particle and carrier particle It increases, the replaceability deterioration of toner particle.Therefore, photographic fog and picture quality is caused to deteriorate sometimes.

For the dynamic electric resistor rate of carrier particle, the aluminum electrode of size identical as photoconductor drum is replaced with photoconductor drum Drum, carrier particle is supplied to form magnetic brush on development sleeve, electrode drum is wiped using the magnetic brush, in sleeve and photoconductor drum Between apply voltage (500V) to measure the electric current that flows between the two, asked as a result, by following formula (2) crystalline polyester resin c1 Obtain the dynamic electric resistor rate of carrier particle.

DVR (Ω cm)=(V/I) × (N × L/Dsd) formula (2)

DVR: carrier resistance (Ω cm)

V: the voltage (V) between development sleeve and drum

I: measurement current value (A)

N: width (cm) between developer roll

L: development sleeve length (cm)

Dsd: the distance between development sleeve and photoconductor drum (cm)

In the later-described embodiments, V=500V, N=1cm, L=6cm, Dsd=0.6mm are measured as.

The example of the manufacturing method of cladded type carrier particle with core material particle and covering portion include: wet coating method and Dry coating method.The example of wet coating includes: fluidized bed type spray coating method, impregnated rubbing method, polymerization.

" fluidized bed type spray coating method " refers to, is dissolved in obtained in solvent using the resin that fluidized bed will act as covering material Coating fluid is sprayed on the surface of magnetic substance particle, is then dried, the method for forming covering portion." impregnated rubbing method " is Refer to, magnetic substance particle is immersed in the resin as covering material is dissolved in coating fluid obtained in solvent and be coated place Reason, is dried, the method for preparing covering portion." polymerization " refers to, magnetic substance particle is immersed in reactive compounds dissolution It is coated processing in the coating fluid obtained in a solvent, polymerization reaction is then carried out to prepare the side of covering portion by heating etc. Method.

" dry coating method " refers to, the resin that will act as covering material is attached on the surface of core material particle, then applies Mechanicalness impact force makes the resin melting being attached on core material particle surface or softening, solidifies it to prepare the side of covering portion Method.Specifically, to core material particle, being used as covering material using the high-speed stirring mixer that can apply mechanicalness impact force Resin, low resistance particle high-speed stirred is carried out under the conditions of non-heated, impact force is applied repeatedly to the mixture so that magnetic The surface of body particle is dissolved or softening, makes its solidification to prepare carrier.As the condition of cladding, in case of heating, preferably 80~130 DEG C, for causing the wind speed of impact, preferably 10m/s or more, mutual from inhibition carrier particle coagulate when heated From the perspective of poly-, preferably 5m/s or less while cooling.The time for applying impact force is preferably 20~60 minutes.

By mixing electrostatic image developing toner and carrier particle of the invention, two-component developing agent can be obtained. The mixing arrangement used when as mixing, is not particularly limited.The example of mixing arrangement includes Nauta mixer, W taper, V-type Mixer.The content (toner concentration) of toner particle of the electrostatic image development in two-component developing agent does not limit especially System, preferably 4.0~8.0 mass %.

Toner particle includes toner mother particle and external additive.Toner mother particle includes crystalline resin As binder resin.

(crystalline resin)

Crystalline resin is with crystalline resin." crystallinity " refers to, in differential scanning calorimetry (DSC), tool There is specific endothermic peak rather than interim change of heat absorption." specific endothermic peak " specifically refers to, in DSC, with 10 DEG C/ When the rate of heat addition of min is measured, peak of the half breadth of endothermic peak in 15 DEG C.

As long as crystalline resin its with above-mentioned characteristic, be not particularly limited.As crystalline resin, can be used Crystalline resin well known in the art.The example of crystalline resin include: crystalline polyester resin, crystalline polyurethane resin, Crystallinity carbamide resin, crystalline polyamide resin, crystallinity polyether resin.Crystalline resin can be used alone, It can be applied in combination two or more.

From the viewpoint of making toner image good for the low-temperature fixability of recording medium, crystalline resin is preferred For crystalline polyester resin." crystalline polyester resin " refers to, passes through carboxylic acid (polybasic carboxylic acid) and its derivative more than divalent With it is more than divalent alcohol (polyalcohol) and its polycondensation reaction of derivative obtained from well known polyester resin, have it is above-mentioned The resin of endothermic character.The fusing point of crystalline polyester resin is not particularly limited.The fusing point of crystalline polyester resin is preferably 55 ~90 DEG C, more preferably 60~85 DEG C.When the fusing point of crystalline polyester resin within the above range when, when toner fixing is being remembered When on recording medium and during melting, charge is sufficiently discharged.The fusing point of crystalline polyester resin can pass through resin Composition is controlled.

The fusing point of crystalline resin can for example measure by the following method.For the fusing point of crystalline resin, use Differential scanning calorimetry device (Diamond DSC；Manufactured by Perkin Elmer), 3.0mg sample is enclosed in aluminium dish and placed In the bracket, use empty aluminium dish as compareing, and successively carrying out determination condition (heating/cooling condition) of following processes DSC curve: the 1st temperature-rise period is obtained, is warming up to 200 DEG C from 0 DEG C with the heating rate of 10 DEG C/min；Cooling procedure, with 10 DEG C/ The cooling rate of min is cooled to 0 DEG C from 200 DEG C；2nd temperature-rise period is warming up to 200 from 0 DEG C with the heating rate of 10 DEG C/min ℃.Also, it is based on the DSC curve, the maximum temperature of the endothermic peak from crystalline resin in the 1st temperature-rise period is set as molten Point.

The chemical valence of the polybasic carboxylic acid and polyalcohol that constitute crystalline polyester resin is respectively preferably 2~3, more preferably 2. Here, the dicarboxylic acid component that chemical valence is 2 and the diol component that chemical valence is 2 will be described.

The dicarboxylic acid component that chemical valence is 2 is preferably aliphatic dicarboxylic acid, and aromatic series can also be applied in combination as needed Dicarboxylic acids.From the viewpoint of improving crystallinity, aliphatic dicarboxylic acid is preferably straight-chain.Dicarboxylic acid component can individually make With can also be applied in combination two or more.

The example of aliphatic dicarboxylic acid includes: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pungent two Acid, azelaic acid, decanedioic acid, 1,9- nonyl dicarboxylic acids, 1,10- last of the ten Heavenly stems dicarboxylic acids (dodecanedioic acid), 1,11- heneicosane dicarboxylic acid, 1, 12- dodecanedicarboxylic acid (tetracosandioic acid), 1,13- astrotone, 1,14- tetradecane dicarboxylic acid, 1,16- hexadecane two Carboxylic acid, 1,18- octadecane dicarboxylic acids.

Dicarboxylic acid component is preferably the aliphatic dicarboxylic acid that carbon atom number is 6~14, and more preferably carbon atom number is 8~14 Aliphatic dicarboxylic acid.

The example for the aromatic dicarboxylic acid that can be applied in combination with aliphatic dicarboxylic acid includes: phthalic acid, terephthaldehyde Acid, M-phthalic acid, phthalic acid, tert-butyl isophthalic acid, 2,6- naphthalenedicarboxylic acid, 4,4 '-biphenyl dicarboxylic acids.As can It is preferably right from the viewpoint of availability and easy emulsibility with the aromatic dicarboxylic acid being applied in combination with aliphatic dicarboxylic acid Phthalic acid, M-phthalic acid, tert-butyl isophthalic acid.

In addition, can be used as polybasic carboxylic acid: more than the ternarys such as trimellitic acid, Pyromellitic Acid polybasic carboxylic acid, on Acid anhydrides or the carbon atom number of carboxylic acid compound are stated as 1~3 Arrcostab.

When the dicarboxylic acid component for being used to form crystalline polyester resin is set as 100 moles of %, aliphatic dicarboxylic acid Content is preferably 50 moles of % or more, more preferably 70 moles of % or more, further preferably 80 moles of % or more, particularly preferably For 100 moles of %.If above-mentioned content is 50 moles of % or more, the crystallinity of crystalline polyester resin can be substantially ensured.

The diol component that chemical valence is 2 is preferably aliphatic diol, and aliphatic diol can also be applied in combination as needed Glycol in addition.From the viewpoint of improving crystallinity, aliphatic diol is preferably straight-chain.Diol component can be used alone One kind can also be applied in combination two or more.

The example of aliphatic diol includes: ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,5- penta 2 Alcohol, 1,6-HD, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 1,11- undecane, 1, 12- dodecanediol, 1,13- tridecane diols, 1,14- tetradecane diols, 1,18- octacosanol, 1,20- icosane diols Neopentyl glycol.

The aliphatic diol that the preferred carbon atom number of diol component is 2~12, the aliphatic that more preferable carbon atom number is 3~10 Glycol.

The glycol that can be applied in combination with aliphatic diol includes the glycol with double bond.The example packet of glycol with double bond It includes: 1,4- butylene glycol, 2- butylene-1,4-diol, 3- butene-1,6- glycol, 4- butene-1,8- glycol.

When the diol component for being used to form crystalline polyester resin is set as 100 moles of %, the content of aliphatic diol Preferably 50 moles of % or more, more preferably 70 moles of % or more, further preferably 80 moles of % or more, particularly preferably 100 moles of %.If the content of aliphatic diol is 50 moles of % or more in diol component, crystalline polyester tree may insure The crystallinity of rouge.

The example of polyalcohol includes the glycerol that chemical valence is 3 or more, pentaerythrite, trimethylolpropane, D-sorbite.

From the viewpoint of reliably realizing sufficient low-temperature fixability and long-term resistance to hot storage stability simultaneously, crystallization The weight average molecular weight (Mw) of property polyester resin is preferably 3000~100000, and more preferably 4000~50000, particularly preferably 5000~20000.For the use ratio of above-mentioned diol component and dicarboxylic acid component, the equivalent [OH] of the hydroxyl of diol component With ratio [OH]/[COOH] of the equivalent [COOH] of the carboxyl of dicarboxylic acid component be 1.5/1~1/1.5, more preferably 1.2/1~ 1/1.2。

The synthetic method of crystalline polyester resin is not particularly limited, and well known esterification catalyst can be used, by more The polycondensation (esterification) of first carboxylic acid and polyalcohol is synthesized.

The example for the catalyst that can be used in the synthesis of crystalline polyester resin includes: the alkali metal compounds such as sodium, lithium； Compound containing the 2nd race's element such as magnesium, calcium；The compound of the metals such as aluminium, zinc, manganese, antimony, titanium, tin, zirconium, germanium；Phosphorous acid chemical combination Object；Phosphate cpd；And amine compounds.The example of tin compound include: Dibutyltin oxide, tin octoate, two tin octoates and Their salt.The example of titanium compound includes: tetra-n-butyl titanate, tetraisopropyl titanate, tetramethoxy titanate ester, four stearyl ester of metatitanic acid Etc. titanium alkoxides；The acylated titaniums such as multi-hydroxy stearic acid titanium；The titanium chelates such as four titanium acetylacetones, lactic acid titanium, triethanolamine titanium.Germanium The example for closing object includes: germanium dioxide.The example of aluminium compound includes: the oxides such as poly- aluminium hydroxide, aluminium alkoxide, three fourth of aluminic acid Ester.These compounds can be used alone, and can also be applied in combination two or more.

Crystalline resin is preferably 5.0 matter in toner mother particle relative to the content for the binder resin total amount for including Measure % or more and 15.0 mass % or less.When the content of crystalline resin in the range when, electric removing effect is excellent, crystallinity tree Rouge is not exposed to the surface of toner mother particle, and the stabilisation of carried charge is excellent.

(non-crystalline resin)

In addition to crystalline resin, binder resin may include non-crystalline resin.

Non-crystalline resin does not have crystallinity actually, such as includes amorphism part in its resin.It is noncrystalline The example of property resin includes: vinyl group resin, polyurethane based resin, urea resinoid, unbodied polyester resin, partially changes The modified polyester resin of property.Non-crystalline resin preferably comprises vinyl group resin.Non-crystalline resin can for example pass through public affairs The method known is synthesized.Non-crystalline resin can be used alone, and can also be applied in combination two or more.

Vinyl group resin is the tree comprising having the monomer of compound of vinyl or derivatives thereof to be polymerized Rouge.Vinylite can be used alone, and can also be applied in combination two or more.

The example of vinylite includes styrene-(methyl) acrylic resin.Styrene-(methyl) acrylic compounds tree Rouge contains the molecular structure of the free radical polyalcohol of the compound with free-radical polymerised unsaturated bond.Styrene-(methyl) Acrylic resin can for example be closed by the free radical polymerization of the compound with free-radical polymerised unsaturated bond At.Compound with free-radical polymerised unsaturated bond can be used alone, and can also be applied in combination two or more.Tool The example for having the compound of free-radical polymerised unsaturated bond includes: Styrene and its derivatives, (methyl) acrylic acid and its spreads out Biology.

The example of Styrene and its derivatives include: styrene, o-methyl styrene, m-methyl styrene, to methylbenzene Ethylene, to methoxy styrene, to styryl phenyl, p-chlorostyrene, p -ethyl-styrene, to n-butylstyrene, to uncle Butylstyrene, to positive hexyl phenenyl ethylene, to n-octyl ethylene, to n-nonyl styrene, to positive decyl styrene, to positive ten Dialkylstyrene, 2,4- dimethyl styrene, 3,4- dichlorostyrene.

The example of (methyl) acrylic acid and its derivative includes: methyl acrylate, ethyl acrylate, butyl acrylate, third Olefin(e) acid 2- ethylhexyl, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, metering system Acid butyl ester, hexyl methacrylate, 2-Ethylhexyl Methacrylate, beta-hydroxy ethyl acrylate, gamma-amino acrylic acid third Ester, octadecyl methacrylate, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate.

The content of vinylite in amorphous resin is preferably 50 mass % or more, more preferably 60 mass % with On, further preferably 70 mass % or more.

Non-crystalline resin is preferably 50 matter in toner mother particle relative to the content for the binder resin total amount for including Measure % or more and 80 mass % or less.When the content of non-crystalline resin within the above range when, binder resin have high rigidity, Therefore the crush resistance etc. mixed with carrier particle etc. is improved.

Crystalline resin can be mixed crystallization polyester resin.Mixed crystallization polyester resin has crystalline polyester tree Structure made of rouge unit and non-crystalline resin unit chemical bonding.

" crystalline polyester resin unit " indicates, the portion of the crystalline polyester resin in mixed crystal crystalline polyester resin Point." non-crystalline resin unit " indicates, does not have crystalline resin (amorphism in mixed crystal crystalline polyester resin Resin) part.

As crystalline polyester resin, above-mentioned crystalline polyester resin can be used.In addition, as non-crystalline resin, Above-mentioned non-crystalline resin can be used.

In mixed crystallization polyester resin, for crystalline polyester resin unit and non-crystalline resin unit, In Crystalline polyester resin unit each other, non-crystalline resin unit each other or the model that is chemically bonded each other of these resins In enclosing, continuous or random arrangement can be carried out.In addition, two units can connect as chain, can also with a unit with it is another A unit carries out grafting bonding.

It should be noted that chemical bond is, for example, ester bond, or obtained by the addition reaction by unsaturated group covalently Key.Mixed crystallization polyester resin can be obtained by following methods: make crystalline polyester resin unit and non-by chemical bond The well known method of crystalline resin unit bonding.For example, mixed crystallization polyester resin can be synthesized by following methods: using In constituting the monomer of resin unit and the process of double reactive monomer polymerization and in obtained backbone precursor in main chain In the presence of, it is used in the work of the polymerization of one or both of the monomer for constituting the resin unit in side chain and nucleating agent or reaction Sequence.

Further, it is also possible to which the substituent groups such as sulfonic group, carboxyl, carbamate groups are imported mixed crystallization polyester resin In.The introduction site of substituent group can be crystalline polyester resin unit, be also possible to non-crystalline resin unit.

For the structure and amount of main chain and side chain in obtained resin, for example, can by nuclear magnetic resonance (NMR) or Instrumental method well known to LC-MS spectrometry (ESI-MS) etc. being determined to binder resin or its hydrolysate or Presumption.

In addition, can further contain in the raw materials such as monomer of above-mentioned resin unit in the synthesis of above-mentioned resin unit For adjusting the chain-transferring agent of the molecular weight of obtained resin.Chain-transferring agent can be used alone, and can also be applied in combination It is two or more.The example of chain-transferring agent includes: the sulphur such as ethylene chlorhydrin, octyl mercaptan, lauryl mercaptan, tert-dodecylmercaotan Alcohol and styrene dimer.

Here " grafting bonding " refer to, the polymer as main chain with as branch different types of polymer (or Monomer) between chemical bond.From the viewpoint of the comprehensive desired characteristic for improving toner, mixed crystallization polyester resin There can be the grafting of crystalline polyester resin unit to be bonded to structure obtained from non-crystalline resin unit.

The content of crystalline polyester resin unit and non-crystalline resin unit in mixed crystallization polyester resin can be with It is suitably determined in the range of can obtain the effect of present embodiment.For example, when non-in mixed crystallization polyester resin When the content of crystalline resin unit is too low, dispersibility of the mixed crystallization polyester resin in toner mother particle may not Sufficiently, and when the content of non-crystalline resin unit is excessive, low-temperature stability may be insufficient.From such a viewpoint, The content is preferably 5~30 mass %, and from the viewpoint of improving high temperature dwell sustainability and charging uniformity, which is more preferably 5~20 mass %.

From the same viewpoint, the content of the crystalline polyester resin unit in mixed crystallization polyester resin is preferably 65~95 mass %, more preferably 70~90 mass %.In addition, mixed crystallization polyester resin can obtain this implementation Further containing the other components in addition to Unit two in the effect of mode.The example of other components includes: other resin units With the various additives that should be added in toner mother particle.

Toner mother particle may include the other components such as colorant, release agent (wax), charge control agent.

(colorant)

The example of colorant includes: carbon black, magnetic substance, dyestuff, pigment.The example of carbon black includes: channel black, furnace black, acetylene Black, thermal crack black, lampblack.The example of magnetic substance include: the ferromagnetisms such as iron, nickel, cobalt metal, the alloy containing these metals, The compound of the ferromagnetisms metal such as ferrite or magnetic iron ore.The example of dyestuff include: C.I. solvent red 1, C.I. solvent red 49, C.I. solvent red 52, C.I. solvent red 58, C.I. solvent red 63, C.I. solvent red 111, C.I. solvent red 122, C.I. solvent yellow 19, C.I. solvent yellow 44, C.I. solvent yellow 77, C.I. solvent yellow 79, C.I. solvent yellow 81, C.I. solvent yellow 82, C.I. solvent Huang 93, C.I. solvent yellow 98, C.I. solvent yellow 103, C.I. solvent yellow 104, C.I. solvent yellow 112, C.I. solvent yellow 16 2, C.I. solvent blue 25, C.I. solvent blue 36, C.I. solvent blue 60, C.I. solvent blue 70, C.I. solvent blue 93, C.I. solvent blue 95 And their mixture.The example of pigment includes: C.I. paratonere 5, C.I. pigment red 4 8:1, C.I. pigment red 4 8:3, C.I. Paratonere 53:1, C.I. paratonere 57:1, C.I. pigment red 81: 4, C.I. pigment red 122, C.I. paratonere 139, C.I. pigment Red 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 222, C.I. pigment orange 31, C.I. pigment orange 43, C.I. pigment Yellow 14, 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 155, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. Pigment Green 7, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 60 or their mixture.

(release agent)

As release agent, various known waxes can be used.The example of wax includes: the polyenes such as polyethylene wax, polypropylene wax Chloroflo, microwax etc. are branched chloroflo；The long chain hydrocarbons waxes such as paraffin, husky rope wax；The dialkyl group ketone wax such as distearyl ketone；Cohune Palmitic acid wax, lignite wax, behenic acid behenyl ester, trimethylolpropane tris behenate, four behenyl ester of pentaerythrite, pentaerythrite diethyl Two behenate of acid esters, glycerol tri-docosanoic acid ester, 1,18- octacosanol distearate, three stearyl trimellitates, two The amide-based wax such as the ester wax such as stearyl maleate, ethylenediamine behenyl amide, tri trimellitate stearmide.Relative to bonding 100 mass parts of resin, the content of release agent are preferably 0.1~30 mass parts, more preferably 1~10 mass parts.Release agent can be with One kind is used alone, can also be applied in combination two or more.From the viewpoint of the low-temperature fixability of toner and release property, take off The fusing point of mould agent is preferably 50~95 DEG C.

(charge control agent)

As charge control agent, the well known substance of dispersion in an aqueous medium can be used.The example of charge control agent It include: metal salt, alkoxylated amines, quarternary ammonium salt compound, the azo metal network of aniline black byestuffs, aphthenic acids or higher fatty acids Close object, salicylic acid metal salt or its metal complex.

(external additive)

External additive includes aluminium oxide particles.Aluminium oxide is by Al₂O₃The aluminium oxide of expression.Aluminium oxide has α type, γ The forms such as type, σ type or their mixture.The shape of aluminium oxide can be selected by control crystallizing system, including vertical Cube shape and spherical.Aluminium oxide can be prepared by well known method.For the example of the preparation method of aluminium oxide, lead to It is often used Bayer process, but in order to obtain the aluminium oxide of high-purity and nano-scale, is also suitable Hydrolyze method, gas phase synthesis method, flame Spark-discharge method in Hydrolyze method, water.

Aluminium atom existence rate on surfaces of toner particles is 0.80atom% or more and 5.00atom% hereinafter, preferably 1.50atom% or more and 4.0atom% or less.When aluminium atom there are ratio in the range when, electrostatic image development adjust The carried charge of toner can be kept constant, and can release charge in fixing.When aluminium atom existence rate is less than When 0.80atom%, in the fixing of electrostatic image developing toner, charge cannot be released sufficiently.On the other hand, when aluminium original When sub- existence rate is more than 5.0atom%, the carried charge holding capacity of electrostatic image developing toner is reduced.

Here " aluminium atom existence rate " refer to, on surfaces of toner particles aluminium atom there are ratios.Aluminium atom exists Rate is the value obtained as follows: use x-ray photoelectron spectroscopy device, all elements on quantitative analysis surfaces of toner particles, And each atomic concentration on surfaces of toner particles is calculated using relative sensitivity coefficient according to each atom peak area.Here " surfaces of toner particles " refers to, toner under the conditions of aftermentioned, when being measured using x-ray photoelectron spectroscopy device The outmost surface of particle and since outmost surface depth be 3nm in the range of.

The equal primary particle size of the number of aluminium oxide particles be preferably 10nm or more and 40nm hereinafter, more preferably 15nm or more and 30nm or less.When the equal primary particle size of the number of aluminium oxide particles is less than 10nm, it is easy to be embedded in due to the collision with carrier particle On the surface of toner mother particle, charge when cannot steadily carry out the stabilisation and fixing of carried charge is released.Another party Face, when the equal primary particle size of the number of aluminium oxide particles is greater than 40nm, it is difficult to which they are fixed on to the surface of toner mother particle On, this may cause the pollution on carrier particle surface and the reduction of picture quality.

For the equal primary particle size of the number of aluminium oxide particles, scanning electron microscope (SEM) (JSM-7401F is used；By day The manufacture of this Electronics Co., Ltd), the photograph image of shooting is read out by scanner, uses image processing and analyzing device (LUZEX AP；Manufactured by Nireco) binary conversion treatment is carried out to the aluminium oxide particles of the shooting image.Then, 100 are calculated The horizontal direction Feret diameter of a aluminium oxide particles, and using its average value as the equal primary particle size of number.

It is modified surface can be carried out to aluminium oxide particles with surface modifier.Have by the modified aluminium oxide particles in surface The surface modifier residue of aluminium oxide particles and setting on the surface thereof.Surface modifier includes: on aluminium oxide particles surface The reacting part of hydroxyl reaction, hydroxyl reaction on He Buyu aluminium oxide particles surface non-reacting part.By modified with surface Agent carries out surface to aluminium oxide particles and is modified, and surface modifier residue is arranged on the surface of aluminium oxide particles.Surface is modified Agent residue is usually organic group.The structure of surface modifier residue can be selected according to selected surface modifier.Table The example of face modifying residues includes alkyl, aryl, alkoxy.

The example of surface modifier includes: to indicate silane coupled by following formula (A) silazane indicated and by following formula (B) Agent.

(R₁、R₂、R₃)-Si-NH-Si-(R₁、R₂、R₃) formula (A)

(R₄)_4-n-Si-(OR₅)_nFormula (B)

R₁~R₅It is each independently hydrogen, alkyl, aryl or alkoxy, can have substituent group, R₁~R₅Can it is identical or It is different.

As silazane, well known silazane can be used, as long as not damaging the effect of present embodiment.From inhibition Viewpoint that external additive particle aggregates with one another and with from the perspective of the reactivity of external additive particle surface, silazane Preferably hexamethyldisilazane (in above formula (A), R₁、R₂And R₃Respectively indicate methyl) or hexaethyl disilazine it is (above-mentioned logical In formula (A), R₁、R₂And R₃Respectively indicate ethyl), particularly preferably hexamethyldisilazane.

As silane coupling agent, well known silane coupling agent can be used, as long as not damaging the effect of present embodiment i.e. It can.It is the straight chained alkyl in the range of 1~12 that silane coupling agent, which preferably comprises carbon atom number,.Straight chained alkyl can have substitution Base.In above formula (B), work as R₄When being the alkyl that carbon atom number is 1~12, external additive particle is each other due between alkyl It interacts and there is molecular separating force appropriate, can inhibit to agglomerate.R₄Carbon atom number be more preferably 4~8.Work as R₄Carbon it is former When subnumber is more than 12, coherency is improved without showing sufficient effect.R in above-mentioned formula (B)₅It is not particularly limited, only Want can to obtain the effect of present embodiment.R₅Example include methyl or ethyl.Work as R₅Functional group on space structure compared with When big, it is difficult to the surface for carrying out aluminium oxide particles is modified, therefore, and from the viewpoint of reactivity, R₅More preferably methyl.Separately Outside, in R₅In the case where being hydrogen atom, above formula (B) is the compound with hydroxyl, therefore is increased with the chemical affinity of water, As a result, becoming the point that carried charge leaks under hot and humid environment, it is not preferable.

It, can be by being taken off between the hydroxyl on aluminium oxide particles surface when silazane is used as surface modifier Amino reaction is generated with flowering structure.

(Al_*-O)₁-Si(-R₁、R₂、R₃)

[Al_*: aoxidize the atom of aluminium surface]

When alkoxy silane (silane coupling agent) is used as surface modifier, can be generated by hydrolysis and dehydration With flowering structure.

(Al_*-O)_n-Si(R₁)(OR₂)_3-n

The modified method in surface can be carried out as by aluminium oxide particles using well known method.The modified method in surface Example includes dry and wet.

In dry method, aluminium oxide particles and surface modifier are stirred or are mixed in a fluidized bed reactor.Wet In method, firstly, aluminium oxide particles are dispersed the slurry to form aluminium oxide particles in a solvent.Then, by surface modifier plus Enter into the slurry, (hydrophobization) is modified to the surface of aluminium oxide particles.

At this point, aluminium oxide particles and surface modifier heat 0.5~5 hour preferably at 100~200 DEG C.At this heat Reason can effectively be modified the hydroxyl in oxidation aluminium surface.In addition, the amount of surface modifier is not particularly limited, relatively In 100 mass parts of aluminium oxide particles, preferably 5~30 mass parts, more preferably 8~20 mass parts.

It is measured by the volume resistivity of the modified aluminium oxide particles in surface by following manner: by what is be modified by surface Aluminium oxide particles are in 200kg/cm²Pressure under be press-formed, the particle shape of diameter 20mm, thickness 3.0mm is made, use Digital LCR analyzer (4261A；Manufactured by Nippon Hewlett Packard company) electricity is measured in 20 DEG C 50% of environment Resistance.

Volume resistivity by the modified aluminium oxide particles in surface is preferably 1.0 × 10⁸Ω cm or more and 1.0 × 10¹³Ω cm is hereinafter, more preferably 1.0 × 10⁹Ω cm or more and 1.0 × 10¹¹Ω cm or less.When volume resistivity is less than 1.0×10⁸When Ω cm, charge holding be may be decreased, and the carried charge of toner may be decreased.In addition, if volume is electric Resistance rate is more than 1.0 × 10¹³Ω cm is then likely difficult to release charge in fixing.

The volume resistivity of aluminium oxide particles is preferably higher than the dynamic electric resistor rate of aftermentioned carrier particle.If aoxidizing aluminum shot The volume resistivity of son is lower than the dynamic electric resistor rate of aftermentioned carrier particle, then electric charge transfer to carrier particle when can cause to charge The reduction of amount.

The equal primary particle size of number by the modified aluminium oxide particles in surface can be considered as being substantially equal to without surface The equal primary particle size of the number of modified aluminium oxide particles, therefore the description thereof will be omitted.

Other than aluminium oxide particles, external additive also may include silicon dioxide granule.Silicon dioxide granule can pass through Well known method enumerates preparation, such as: sol-gal process, vapor phase method (gas combustion method), fusion method.From the viewpoint of control shape It sets out, preferred sols gel method is as the method for preparing silicon dioxide granule.Silicon dioxide granule is prepared by sol-gal process Method it is as described below: in the presence of the alcohol containing base catalyst, be supplied respectively to tetraalkoxysilane and base catalyst, and make Tetraalkoxysilane reaction, the method generated.Vapor phase method refers to, silicon chloride is made to gasify and pass through in the hydrogen flame of high temperature The method that gas phase reaction carrys out synthetic silica particle.In addition, fusion method refers to, it include by smashed silicate silica And the reducing agents such as silicon metal powder or carbon dust or be used to form pulp-like water mixed raw material, height in a reducing atmosphere It is heat-treated under temperature, to form SiO gas, method that it is quickly cooled down under an oxygen-containing atmosphere.

The equal primary particle size of the number of silicon dioxide granule is preferably 70nm or more and 150nm or less.When silicon dioxide granule When the equal primary particle size of number is less than 70nm, need to reinforce the transfer electricity for being transferred to electrostatic image developing toner on paper , and image itself is easy to charge by transfer electric field, it may occur that the adherency of recording medium to each other.Another party Face, when the equal primary particle size of the number of silicon dioxide granule is greater than 150nm, the amount for being transferred to carrier particle surface increases, can energy loss The stabilisation of the flow behavior of the stabilisation and toner of evil carried charge.

The method for preparing electrostatic image developing toner is not particularly limited.Prepare electrostatic image developing toner The example of method includes: to be kneaded comminuting method, suspension polymerization, emulsion coagulation method, dissolution suspension method, polyester elongation method, disperse to gather It is legal.From the viewpoint of the controllability of the uniformity of partial size and shape, preferably using emulsion coagulation method as preparing electrostatic image The method of developing toner.

Emulsion coagulation method refers to that the adhesive resin particles for dispersing surfactant or dispersion stabilizer are (hereinafter, also referred to as For " adhesive resin particles ") dispersion liquid, as needed and with the particle of colorant (hereinafter, also referred to as " colorant particle ") Dispersion liquid mixing, be condensed into desired toner particle diameters, and carry out it is fusible between adhesive resin particles, carry out shape Shape control, thus the method for manufacturing toner particle.Here, the particle of binder resin can optionally contain release agent, Charge controlled Agent etc..Using emulsion coagulation method, the example for the case where obtaining toner particle with a core-shell structure is as follows.

(1) process of colorant particle dispersion liquid obtained by the dispersion in an aqueous medium of preparation colorant particle

(2) preparation is as needed and obtained from the dispersion in an aqueous medium of the adhesive resin particles containing internal additives The process of resin particle dispersion liquid (core use/shell resin particle dispersion liquid)

(3) colorant particle dispersion liquid and core are mixed with resin particle dispersion liquid, to obtain cohesion resin particle Sub- dispersion liquid agglomerates colorant particle and adhesive resin particles in the presence of flocculating agent, melting, is formed as core particle The process (cohesion/melting process) of aggregated particle

(4) shell of the adhesive resin particles comprising shell is added to point comprising core particle with resin particle dispersion liquid In dispersion liquid, make the particle coacervation of shell, be melted on core particle surface, to form the toner mother particle of core-shell structure Process (cohesion/melting process)

(5) toner mother grain is filtered out from the dispersion liquid of toner mother particle (toner mother particle dispersion) Son removes the process (washing procedure) of surfactant etc.

(6) process (drying process) that toner parent particle is dried

(7) process (external additive treatment process) of external additive is added into toner mother particle.

For toner particle with a core-shell structure, firstly, making the adhesive resin particles and colorant of core particle Particle coacervation, melting are to prepare core particle.Next, the adhesive resin particles of shell to be added to the dispersion liquid of core particle In, so that the adhesive resin particles of shell agglomerated, be melted on core particle surface, to form the shell on cladding core particle surface. However, the toner particle formed by single layer particle can be manufactured in an identical manner for example in above-mentioned operation (4), without Add shell resin particle dispersion liquid.

In said external additive treating process, mechanical mixing apparatus can be used.The example of mechanical mixing apparatus It include: Henschel mixer, Nauta mixer, Turbula mixer.In external additive treatment process, picture can be used Henschel mixer is such, can apply the mixing arrangement of shearing force to particle to be processed, such as carries out extension mixing The mixed processing of the rotation circular velocity of time or raising stirring blade etc..In addition, when using a variety of external additives, it is all External additive can disposably carry out mixed processing with toner particle, can also be divided into according to external additive repeatedly Carry out mixed processing.For the mixed method of external additive, using above-mentioned mechanical mixing apparatus, by mixing intensity I.e. the circular velocity, incorporation time of stirring blade, mixing temperature etc. are controlled, to control the degree of crushing of external additive or glue Close intensity.

It in the present embodiment, is 0.8atom% or more there are ratio due to aluminium atom on surfaces of toner particles And therefore 5.0atom% is hereinafter, can also keep high image quality even if in the continuous printing under high lettering rate, and can To inhibit the adherency between recording medium.