CN101093368A - Toner - Google Patents

Abstract

In a toner comprising toner particles which comprise toner base particles containing at least a binder resin and a magnetic material, and inorganic fine particles, the toner base particles have been obtained through a pulverization step; and, the toner base particles having a circle-equivalent diameter of from 3 mu m or more to 400 mu m or less as measured with a flow type particle image analyzer have an average circularity of from 0.935 or more to less than 0.970; and the toner base particles have an average surface roughness of from 5.0 nm or more to less than 35.0 nm as measured with a scanning probe microscope. The toner can enjoy less toner consumption per sheet of images, can achieve a long lifetime in a smaller quantity of toner, and has superior developing performance in any environment.

Description

Toner

The application is to be August 2, application number in 2004 the dividing an application for the application of " toner " that be 200410070403.X, denomination of invention the applying date.

Technical field

The present invention relates to a kind ofly be used for the toner that the image forming method of developing electrostatic lotus picture uses in electricity photography etc., and the toner that uses in the ink-vapo(u)r recording.

Background technology

In recent years, the machine that utilizes electric Photographic technique also begins to be used for the printer, facsimile recorder of computing machine output usefulness etc. except being used to duplicate the duplicating machine of original original text.Therefore, the more miniaturization of this device of an urgent demand, more lightweight, more high speed, have higher credibility, begin to constitute the various piece of machinery with more single key element.Its result if can not realize the raising of toner performance, then can't obtain better machinery for further having improved the toner performance demands.

Particularly consider, require further miniaturizations of machinery such as printer from energy savings, saving working space aspect.At this moment, also inevitable requirement will be taken in the container miniaturization of toner, need the toner of low consumption amount, so that can carry out many printouts by enough a spot of toners, promptly the toner with less amount carries out identical image output.

Disclosing manufacture methods such as utilizing spray granulation, solution dissolution method, polymerization makes the shape approximation of toner in the technical scheme of sphere (for example, the spy opens flat 3-84558 communique, spy and opens that flat 3-229268 communique, spy are opened flat 4-1766 communique, the spy opens flat 4-102862 communique).But any above-mentioned technology all must have main equipment when making toner, not only considers it is not preferred from the production efficiency aspect, and can't fully reduce the consumption of toner.

In addition, also disclose by the toner that utilizes the comminuting method manufacturing being applied heat or mechanicalness and impacted and change shape of particle and prima facie technical scheme (for example, the spy opens flat 2-87157 communique, spy and opens that flat 10-97095 communique, spy are opened flat 11-149176 communique, the spy opens flat 11-202557 communique).But, even said method can change the shape of toner, can not say the consumption that has fully reduced toner, in addition, also there is drawbacks such as reducing development sometimes.

In addition, for the good developing property of charging property, flowability, acquisition of adjusting toner, known usually method is for to add the small particle diameter inorganic particles at home and abroad at the toner master batch.

For the toner that has added above-mentioned small particle diameter inorganic particles outward, confirmed when for example using as two-component developer with the pressure of carrier, the pressure that produces by developing blade, development sleeve when using as monocomponent toner or with developer inwall, toner stirring vane, toner between effect such as conflict under, the small particle diameter inorganic particles is in the state that is embedded in toner master batch surface.

In order to reduce the embedding of this small particle diameter inorganic particles, for example open flat 4-204751 communique, spy and open flat 5-346682 communique, spy and open flat 6-313980 communique, spy and open flat 6-332235 communique, spy and open in flat 7-92724 communique etc. disclosed and be effective with the method for big particle diameter inorganic particles the spy.

Because big particle diameter inorganic particles has effect at interval, the toner surface that therefore can prevent to adhere to the small particle diameter inorganic particles directly contacts with carrier, developing blade, development sleeve, developer inwall, toner mixing component, other toners etc., reduces pressure.Thus, suppress the embedding of small particle diameter inorganic particles, prolong the serviceable life of toner.

Open in the flat 4-204751 communique the spy and to disclose a kind of toner, described toner contains hydrophobic silica and hydrophobic titanium oxide or hydrophobicity aluminium oxide, it is characterized by, the primary particle size of hydrophobic titanium oxide or hydrophobicity aluminium oxide has the peak in 10～20nm and 30～60nm.

Open in the flat 5-346682 communique the spy and to disclose a kind of toner, it is characterized by, will be through the not enough 80m of BET specific surface area ²Inorganic micro powder after the silicone oil of/g is handled be 80m through the BET specific surface area ²/ g or 80m ²Inorganic micro powder after the above silane coupling agent of/g is handled mixes.

Open in the flat 6-332235 communique the spy, a kind of electrophotographic toner is disclosed, be by toner master batch and at least two kinds of electrophotographic toners that external additive constitutes, it is characterized by, in the size-grade distribution of toner master batch, the following particle of 5 μ m or 5 μ m exists 1 to 8vol%, the mean grain size of first external additive is counted 0.1 to 0.5 μ m with the number benchmark of primary particle, the mean grain size of second external additive is counted 20nm or below the 20nm, is had hydrophobicity with the number benchmark of primary particle.

Open in the flat 7-104501 communique the spy and to disclose a kind of toner, described toner uses 15 to 20nm hydrophobic silica, 13nm or the hydrophobic silica below the 13nm, aluminium oxide as external additive.

But above-mentioned toner has been owing to added 2 kinds of different hydrophobicity inorganic particles of particle diameter, therefore both Combination or in existing problems aspect the surface dispersion of toner master batch, development permanance or charged stability are insufficient.

Open in the flat 6-313980 communique the spy and to disclose a kind of developer, it is characterized by, in the number primary particle size distribution curve of inorganic particles, (3x≤y≤6x) locates to exist respectively the maximum value of number ratio for primary particle size x (nm) (20≤x≤50) and primary particle size y (nm), and the number ratio that primary particle size (x+y)/2 (nm) is located is 10 number % or below the 10 number %, if having the number ratio of small particle diameter side inorganic particles of the primary particle size of deficiency (x+y)/2 (nm) is X number %, have (x+y)/2 (nm) or when (x+y)/2 the number ratio of the big particle diameter side inorganic particles of (nm) above primary particle size is Y number %, (X/Y) value is in 0.5～2.0 scope, when if the volume average particle size of toner master batch is z (nm), value (z/x) is 150～400.

But, since this inorganic particles in the number primary particle size distributes not only the peak of 1 particle diameter of small particle diameter side big, be 20nm or more than the 20nm, and also has the peak in big particle diameter side, if therefore be converted into weight basis, then with respect to the small particle diameter particle, there are very many big particle diameter particles, existing problems aspect flowability or charging property.

In addition, Te Kaiping 8-36316 communique, spy open the 2000-56595 communique, the spy opens 2002-23414 communique etc. and discloses a kind of contact transfer device, the device that the utilization of described contact transfer device applies bias voltage applies bias voltage on transfer member, the toner master batch that outer interpolation on the sub-image supporting body has been mixed the different external additive of at least 2 kinds of mean grain sizes is transferred to transfer printing body, wherein, stipulated the relation of lax apparent density of toner and transfer member hardness.But because 2 kinds of different external additives of mean grain size that use are handled by hydrophobization respectively herein, therefore, both compendencies or in the differences such as dispersion easiness on toner master batch surface are difficult to make it evenly to disperse on toner master batch surface.

In addition, in order to improve the release property of toner on fixing member, can adopt the method that makes toner contain wax.For example, special public clear 52-3305 communique, spy open clear 58-215659 communique, spy and open clear 62-100775 communique, spy and open flat 4-124676 communique, spy and open flat 4-299357 communique, spy and open flat 4-362953 communique, spy and open flat 5-197192 communique etc. disclose a kind of use for the additive effect that makes wax gives full play to 2 kinds or 2 kinds of toners to wax in the scope from low-temperature region to high-temperature area.But, contain wax in the toner even utilize said method to make, also can't obtain sufficient fixation performance, release property, and take place by the bad image that causes of cleaning bad sometimes.

Summary of the invention

Purpose of the present invention is for providing a kind of toner that has solved above-mentioned prior art problem.

Purpose of the present invention for provide a kind of each open the consumption of toner of image few, can realize the toner in high serviceable life with a spot of toner.

Purpose of the present invention is for providing a kind of toner that all has good development in any environment.

Purpose of the present invention is for providing a kind of toner that the sleeve negative ghost image does not take place, disperse.

Purpose of the present invention is for providing the toner of a kind of absent variable spot (blotch).

The present invention relates to a kind of toner, described toner contains toner master batch and inorganic particles, this toner master batch contains binder resin at least, magnetic, it is characterized by, this toner master batch is to contain the composition melting mixing of binder resin and magnetic at least, the mixing thing that pulverizing obtains is made, the diameter of equivalent circle of measuring with streaming particle image determinator is 3 μ m or more than the 3 μ m, the average circularity of the toner master batch that 400 μ m or 400 μ m are following is more than 0.935 or 0.935, less than 0.970, the average surface roughness that this toner master batch is measured with the sweep type probe microscope are 5.0nm or more than the 5.0nm, not enough 35.0nm.

Description of drawings

Fig. 1 is the concise and to the point sectional view of one of the surface modification device that uses in the surface modification step of the present invention example.

Fig. 2 illustrates the sketch of one of vertical view of dispersion rotor shown in Figure 1 example.

Fig. 3 illustrates methanol concentration-transmittance curve figure of the toner master batch I-1 of embodiment of the invention I-1.

Fig. 4 is the key diagram that is used to estimate the pattern of sleeve ghost image.

Fig. 5 is the concise and to the point outside drawing of the surface processing device system that uses in the comparative example.

Fig. 6 is the concise and to the point sectional view of surface processing device shown in Figure 5.

Embodiment

The inventor etc. found that by the circularity of control toner master batch and the surfaceness of control toner master batch through further investigation, can control the developing property of toner.

By the particle diameter that makes toner master batch of the present invention be 3 μ m or more than the 3 μ m, 400 μ m or below the 400 μ m, average circularity is more than 0.935 or 0.935, less than 0.970, be preferably more than 0.935 or 0.935, less than 0.965, less than 0.960 more preferably more than 0.935 or 0.935,, more preferably more than 0.940 or 0.940, less than 0.955, can reduce the consumption of toner of per unit image area.If the circularity of toner master batch increases, then the flowability owing to toner increases, so each toner moves freely easily.For the toner on being developed in transfer materials such as paper, because the circularity of toner is high more, the accuracy rate of developing in each toner unit is high more, therefore can reduce the picture altitude on the transfer materials, reduces the consumption of toner.At this moment, if the circularity of toner master batch is enough not high, then toner demonstrates the behavior as agglutination body easily, is developed on the transfer materials as agglutination body easily.The picture altitude of such image on transfer materials increases, and when developing image of the same area, a large amount of toners are developed, and causes the consumption of toner to increase.In addition, the toner that is made of the high toner master batch of circularity is in more intensive state easily on the image that is developed.Its result is the coverage rate increase of toner to transfer materials, even less toning dosage also can access enough image colors.

If average circularity less than 0.935, then the height of developed image increases, and the consumption of toner increases.In addition, because the space between toner increases, also can't obtain enough coverage rates on developed image, therefore in order to obtain necessary image concentration, more toning dosage must be arranged, the result causes consumption of toner to increase.If average circularity is more than 0.970 or 0.970, then, cause toner coating unevenly on sleeve owing on development sleeve, supply with excessive toner, spot appears in the result.

In addition, for particle diameter in the toner of the present invention is 3 μ m or more than the 3 μ m, for 400 μ m or the toner particle below the 400 μ m, its average circularity is more than 0.935 or 0.935 by making, less than 0.970, be preferably more than 0.935 or 0.935, less than 0.965, less than 0.960 more preferably more than 0.935 or 0.935,, more preferably more than 0.940 or 0.940, less than 0.955, can further reduce the consumption of toner of per unit area.

Average circularity among the present invention is used following obtaining as showing the short-cut method of shape of particle quantitatively.

I) use the system streaming particle image analytical equipment FPIA-2100 of Sysmex society, in 23 ℃, the environment of 60%RH, be determination object with the particle of diameter of equivalent circle in 0.60 μ m～400 mu m ranges, carry out measuring shape, based on the data that obtain, utilize following formula (1) to obtain the circularity of each particle.

Circularity a=L ₀/ L (1)

(in the formula, L ₀Expression has the girth of the circle of the projected area identical with particle image, and L represents Flame Image Process exploring degree (pixel of the 0.3 μ m * 0.3 μ m) girth of particle projection image when carrying out Flame Image Process with 512 * 512.)

Be 3 μ m or more than the 3 μ m, for 400 μ m or the particle below the 400 μ m ii), obtain average circularity divided by total population with the circularity summation for diameter of equivalent circle.

The circularity of using among the present invention is the index of toner master batch and the concavo-convex degree of toner particle, and toner master batch and toner particle are expressed as 1.000 when spherical completely, and surface configuration is complicated more, and the value of circularity is more little.Need to prove that " FPIA-2100 " as the determinator that uses among the present invention uses following computing method: after calculating the circularity of each particle, when calculating average circularity, according to the circularity that obtains, circularity 0.400～1.000 is divided into 61 parts, promptly more than 0.400 or 0.400, less than 0.410,0.410 or more than 0.410, less than 0.420, ..., 0.980 or more than 0.980, less than 0.990,0.990 or more than 0.990, less than 1.000, and 1.000, thereby, use the central value of cut-point and the calculating that frequency averages circularity with the particle classification.But, the average circularity value of calculating by these computing method is very little with the error of the average circularity of calculating according to the calculating formula of using each particle circularity summation, for ignoring the numerical value of degree in fact, therefore, in the present invention, based on the reason that shortens data processing aspects such as computing time or simplification calculating formula, also can use the notion of utilizing the calculating formula of using each particle circularity summation, carry out the aforementioned calculation method that the part change obtains.And, as " FPIA-2100 " of the determinator that uses among the present invention with use " FPIA-1000 " for the shape of calculating toner master batch and toner particle at present and compare, by improving the multiplying power of handling particle picture, and raising obtains treatment of picture exploring degree (by 256 * 256 → 512 * 512), improved the measuring shape precision of toner master batch and toner particle, realized the seizure more certain thus particulate form.Therefore, as described herein, in the time must more correctly measuring shape and size-grade distribution, the FPIA-2100 that can more correctly obtain the information relevant with shape and size-grade distribution is more useful.

Concrete assay method is as follows: in the water 200～300ml that has removed the impurity in the container in advance, add the surfactant as spreading agent, be preferably alkyl benzene sulfonate 0.1～0.5ml, add the mensuration sample about 0.1～0.5g again.To disperse the suspending liquid of sample to disperse 2 minutes with the ultrasound wave vibration generator, making dispersion liquid concentration be 0.2～1.0 ten thousand/μ l, and the circularity of measuring particle distributes.As the ultrasound wave vibration generator, for example use as lower device, adopt following dispersion condition.

UH-150 (T society of SM Co., Ltd. system)

OUTPUT grade: 5

The constant pattern

The concise and to the point step of measuring is as described below.

Make the stream (streamwise extension) of sample dispersion liquid by level and smooth and flat flow cell (the about 200 μ m of thickness).The configuration of flashlamp (strobe) and CCD camera subtend is installed in the both sides of flow cell, intersects the light path of passing through so that form with the flow cell thickness direction.When the sample dispersion liquid flow through, for the particle picture that obtains to flow in flow cell, with 1/30 second interval illumination flash light, the result photographed the two dimensional image that each particle is parallel with flow cell and have certain limit.Utilize the area of each particle two dimensional image, will have diameter of a circle of the same area and calculate as diameter of equivalent circle.Utilize projected area and projection image's girth of each particle two dimensional image, use above-mentioned circularity calculating formula, calculate the circularity of each particle.

In addition, in the present invention, the diameter of equivalent circle of measuring with streaming particle image determinator is 0.6 μ m or more than the 0.6 μ m, in the number benchmark size distribution of 400 μ m or the toner master batch below the 400 μ m, 0.6 μ m or 0.6 μ m are above, the toner master batch ratio of less than 3 μ m is preferably 0 number % or 0 number % is above, less than 20 number %, above, less than 17 number % of 0 number % or 0 number % more preferably are preferably especially that 1 number % or 1 number % are above, less than 15 number %.0.6 μ m or 0.6 μ m are above, the toner master batch of less than 3 μ m has a significant impact the development of toner, particularly grey mist characteristic.Above-mentioned small toner master batch has too high charged easily, when toner development, causes easily developing superfluously, and produces photographic fog easily on image.But the content by making small toner master batch can reduce photographic fog in above-mentioned scope.

In addition, because the average circularity of toner of the present invention is high to a certain degree, so toner is in more intensive occupied state easily, and more heavy back is toner coated on development sleeve easily.At this moment, the upper strata of toner layer has different carried charges with lower floor on the sleeve, when developing large-area image continuously, compares with the image color of front end, sleeve rotates the image color reduction of image portion later on of the 2nd circle, and so-called " sleeve negative ghost image " takes place sometimes.At this moment, if there is more superfine powder in the toner master batch, then because superfine powder has the carried charge higher than other toner master batches easily, the therefore generation of easier promotion image color difference makes the sleeve negative ghost image worsen easily.But the content by making above-mentioned small toner master batch can suppress the deterioration of sleeve negative ghost image in above-mentioned scope.If 0.6 μ m or 0.6 μ m are above, the particle ratio of less than 3 μ m is 20 number % or more than the 20 number %, then the photographic fog on the image increases sometimes, and then the sleeve negative ghost image takes place worsens.

In addition, in toner master batch of the present invention, the number accumulated value of the toner master batch of circularity less than 0.960 is above, the less than 70 number % of 20 number % or 20 number %, be preferably above, the less than 65 number % of 25 number % or 25 number %, more preferably above, the less than 65 number % of 30 number % or 30 number %, more preferably above, the less than 65 number % of 35 number % or 35 number %.The circularity of toner master batch is different because of the toner master batch.If because the circularity difference, then the characteristic of toner master batch is also different, therefore, consider that from the development aspect that improves the toner master batch preferably making the toner master batch ratio with appropriate circularity is suitable value.In the present invention, the toner master batch has the average circularity of appropriateness, when having the circularity distribution of above-mentioned appropriateness simultaneously, the charged distribution of toner master batch is become evenly, and reduce photographic fog.If toner master batch deterioration then takes place in the number accumulated value less than 20 number % of the toner master batch of circularity less than 0.960 sometimes in durable process.If the number accumulated value of the toner master batch of circularity less than 0.960 is 70 number % or more than the 70 number %, photographic fog then takes place sometimes to be worsened, in the hot and humid environment, image color takes place sometimes reduce.

In addition, in the present invention, the average surface roughness of the toner master batch of measuring with the sweep type probe microscope be 5.0nm or more than the 5.0nm, not enough 35.0nm, be preferably that 8.0nm or 8.0nm are above, not enough 30.0nm, more preferably above, the not enough 25.0nm of 10.0nm or 10.0nm.By making the toner master batch have the surfaceness of appropriateness, can between toner, produce appropriate space, improve the flowability of toner, can obtain better development.Particularly,, can give the toner master batch good flowability by having above-mentioned average surface roughness for having as for the toner master batch of the circularity of feature of the present invention.In addition, in toner master batch of the present invention, the ultramicronized content of less than 3 μ m can give toner better flowability after a little while.That is,, then be trapped in the ultra micron in the recess of toner surface, reduce the space between the toner master batch, hinder sometimes and give toner good flowability if there is more ultra micron in the toner master batch.If the not enough 5.0nm of the average surface roughness of toner master batch then can't give toner enough flowabilities, fade, cause image color to reduce.If the average surface roughness of toner master batch is 35.0nm or more than the 35.0nm, then the space between the toner master batch is too much, toner takes place disperse.

In addition, in the present invention, for the toner that has added external additive, the average circularity of the toner particle of make preferably also that particle diameter is that 3 μ m or 3 μ m are above, 400 μ m or 400 μ m are following is more than 0.935 or 0.935, less than 0.970, average surface roughness is preferably 10.0nm or 10.0nm is above, not enough 26.0nm, more preferably above, the not enough 24.0nm of 12.0nm or 12.0nm.During the average surface roughness of toner particle is not enough 10.0nm, think that the external additive particle is in the state that is embedded in the toner particle recess in a large number, mobile poor, fade, be difficult to obtain preferable image.The average surface roughness of toner particle is 26.0nm or 26.0nm when above, thinks that the external additive particle of surfaces of toner particles is in the state of inhomogeneous coating, since charged bad, disperse easily.Therefore, for above-mentioned toner,, can easily obtain effect of the present invention by having preferred surfaceness and circularity.

In addition, by the maximum height difference that makes the toner master batch of measuring through the sweep type probe microscope be 50nm and more than the 50nm, not enough 250nm, be preferably above, the not enough 220nm of 80nm and 80nm, more preferably above, the not enough 200nm of 100nm and 100nm can give toner better flowability.If the not enough 50nm of the maximum height difference of toner master batch, it is mobile fully then can't to give toner, fades sometimes, causes image color to reduce.If the maximum height difference of toner master batch is 250nm and more than the 250nm, toner then takes place sometimes disperse.

In addition, the surface area when measuring with sweep type probe microscope mensuration toner master batch surface 1 μ m square area is 1.03 μ m ²Or 1.03 μ m ²More than, less than 1.33 μ m ², be preferably 1.05 μ m ²Or 1.05 μ m ²More than, less than 1.30 μ m ², 1.07 μ m more preferably ²Or 1.07 μ m ²More than, less than 1.28 μ m ², can give the toner master batch better flowability.If the surface area deficiency of toner master batch 1.03 μ m ², it is mobile fully then can't to give toner, fades sometimes, causes image color to reduce.If the surface area of toner master batch is 1.33 μ m ²Or 1.33 μ m ²More than, toner then takes place sometimes to disperse.

In the present invention, use the sweep type probe microscope to measure average surface roughness, the maximum height difference of toner master batch, the surface area of toner master batch and toner particle.Below provide the assay method example.

Test platform: SPI3800N (Seiko Instruments (strain) system)

Determination unit: SPA400

Mode determination: DFM (resonance mode) shape picture

Cantilever: SI-DF40P

Exploring degree: X data several 256

Y data several 128

In the present invention, measure 1 μ m square area of toner master batch and surfaces of toner particles.Measuring the zone is with the toner master batch of sweep type probe microscope mensuration and 1 μ m square area of surfaces of toner particles central portion.Toner master batch of measuring and toner particle are from having and the weight average particle diameter (D that utilizes Coulter Counter method to measure ₄) select at random in the toner master batch of the particle diameter that equates and the toner particle, measure this toner master batch and toner particle.Determination data carries out 2 times and proofreaies and correct.Measure toner master batch and toner particle different more than 5 or 5, the mean value of computed information obtains average surface roughness, the maximum height difference of toner master batch, the surface area of this toner master batch and toner particle.

For the toner that has added external additive at the toner master batch at home and abroad, when using the sweep type probe microscope to measure the character of surface of toner master batch, must remove external additive from toner master batch surface,, for example can enumerate following method as concrete grammar.

1) the 45mg toner is put into sample bottle, add 10ml methyl alcohol.

2) with sonic washing machine sample was disperseed 1 minute, separate external additive.

3) carry out suction filtration (10 μ m film filter), the toner master batch is separated with external additive.

Contain at toner under the situation of magnetic, also magnet can be placed at the bottom of the sample bottle, fixedly toner master batch, only separation of supernatant.

4) above-mentioned 2), 3) carry out altogether 3 times, at room temperature, the toner master batch that obtains is fully dry with vacuum drier.

Observe the toner master batch of having removed external additive with scanning electron microscope, after affirmation does not have external additive, can observe the surface of toner master batch with the sweep type probe microscope.Under the situation that external additive is not fully removed, carry out 2 repeatedly), 3) after external additive is fully removed, observe the surface of toner master batch with the sweep type probe microscope.

Instead 2), 3) the additive method of removing external additive, can enumerate the method that external additive is dissolved in alkali.As alkali, preferred sodium hydrate aqueous solution.

Below, each technical terms is described.

Average surface roughness (Ra)

With the three-dimensional amplification of the center line average roughness Ra that defines among the JIS B0601, make it can be applicable to the mensuration face.Average surface roughness averages the value that obtains for the absolute value of deviation that will be from reference field to given side, represents with following formula.

Mathematical expression 1

$R_a=\frac{1}{S_o}{\∫}_{Y_B}^{Y_T}{\∫}_{X_L}^{X_R}|F(X,Y)-Z_o|\mathrm{dXdY}$

F (X, Y): the face of representing total determination data

S ₀: the area when given side is assumed to desirable smooth surface

Z ₀: the mean value of the Z data (with the data of given side vertical direction) in the given side

Given side is meant the square mensuration zone of 1 μ m among the present invention.

Maximum height difference (P-V)

The maximal value of the Z data in the given side and minimum value poor.

Surface area (S)

The surface area of given side.

Next, the method for optimizing as being used to obtain as the toner master batch of feature of the present invention just adopts the toner master batch manufacture method of surface modification step to describe.Below, the limit is with reference to accompanying drawing, and the limit specifies the surface modification device that uses in the surface modification step and utilizes the toner master batch manufacture method of surface modification device.

Need to prove that surface modification of the present invention is the surface smoothing of instigating the toner master batch.

Fig. 1 illustrates one of the surface modification device that can use example in toner master batch of the present invention is made, Fig. 2 illustrates one of the vertical view of Fig. 1 high speed rotor rotated example.

Surface modification device shown in Figure 1 is by constituting as the lower part: shell, can feed sleeve pipe (jacket) (not shown) of chilled water or anti freezing solution, install on the centre rotational axis in the enclosure, have a plurality of angles type dish or cylinder type post 40 above, dispersion rotor (surface modification device) 36 as the rotary body on the disk of high speed rotating, the liner (liner) 34 (need to prove on the pad surfaces and also can not have ditch) that has many ditches on the surface that the periphery of dispersion rotor 36 disposes at certain intervals, as the classification rotor 31 that is used for the raw material through surface modification is classified into the device of regulation particle diameter, be used to import the cold wind introducing port 35 of cold wind, be used to import the raw material supplying mouth 33 of processed raw material, the discharge valve 38 that switchably is provided with in order freely to adjust surperficial modification time, be used to discharge the powder escape hole 32 of the powder after the processing, discharge the micro mist escape hole 32 of the following particle of desirable granularity or this granularity, and as shell being separated into the cylindrical shape guide ring 39 of guide piece that imports first space 41 before the grading plant and be used for utilizing second space 42 of the particle importing surface modification device that grading plant will micro-powder gradedly remove.The gap portion that need to prove dispersion rotor 36 and liner 34 is a surface modified area, and classification rotor 31 and rotor periphery partly are graded region.

Need to prove direction is set constitutes longitudinal type shown in Figure 1 of classification rotor 31, also can constitute lateral type.In addition, the number of classification rotor 31 can be illustrated in figure 1 as 1, also can be for a plurality of.

In the surface modification device that constitutes as mentioned above, close under the state of discharge valve 38, drop into raw material toner master batch by raw material supplying mouth 33, the raw material toner master batch after the input is at first attracted by the fan blower (not shown), classified rotor 31 classifications.

At this moment, the following micro mist of classified regulation particle diameter is expelled to outside the device continuously, and be removed, regulation particle diameter or the above meal of regulation particle diameter, utilize centrifugal force, along the inner peripheral surface (second space 42) of guide ring 39, under the effect of the circular flow that produces by dispersion rotor 36, be imported into surface modified area.The raw material that imports surface modified area carries out surface modification treatment in dispersion rotor 36 and 34 effects that are subjected to mechanical impact force of liner.Surface-modified particles through surface modification treatment, under the effect of the cold wind that feeds machine intimate, outer peripheral face (first space 41) along guide ring 39 is imported into graded region, utilize classification rotor 31, micro mist is discharged machine exterior once more, meal returns surface modified area once more under the effect of circular flow, repeat surface modification.Through behind the certain hour, open discharge valve 38, reclaim surface-modified particles by escape hole 37.

In this surface modification device, in toner master batch surface modification step, can when carrying out toner master batch surface modification, the micro mist composition be removed.Thus, the ultra micron that is present in the toner master batch can not be cemented in toner master batch surface, can obtain to have the toner master batch of desirable circularity, average surface roughness and ultra micron amount effectively.In the time can not removing micro mist simultaneously with surface modification, not only there is ultra micron in a large number in the toner master batch after the surface modification, and in the modifying surfaces of toner particles step, since the influence of mechanicalness, heat, the toner master batch surface that causes the ultra micron composition to be cemented in having suitable particle diameter.The result generates the projection that is formed by fixed micro mist composition on the surface of toner master batch, can't obtain to have the toner master batch of desirable circularity and average surface roughness.

Need to prove that " removing the micro mist composition in surface modification " in the present invention and be meant the surface modification and the micro mist that repeat the toner master batch removes, can use the device that in above-mentioned single device, has different step, also can carry out surface modification and micro mist is removed, repeat step separately with different devices.

(=cycling time surface modification time of this surface modification device, finish to begin to the time of opening till the discharge valve from raw material supplying) be preferably more than 5 seconds or 5 seconds, below 180 seconds or 180 seconds, more preferably more than 15 seconds or 15 seconds, below 120 seconds or 120 seconds.The surface modification deficiency of time because modification time is too short, can't fully obtain surface modification toner master batch in the time of 5 seconds sometimes.In addition, if modification time surpasses 180 seconds,, and reduce processing power then because modification time is long, and the heat that produces in the time of might causing because of surface modification causes machine intimate generation clinkering.

And in toner master batch manufacture method of the present invention, the cold wind temperature T 1 that imports in this surface modification device is preferably below 5 ℃ or 5 ℃.By the cold wind temperature T 1 that imports in this surface modification device is preferably below 5 ℃ or 5 ℃, more preferably below 0 ℃ or 0 ℃, more preferably-5 ℃ or below-5 ℃, be preferably especially below-10 ℃ or-10 ℃, most preferably be below-15 ℃ or-15 ℃, the heat that produces in the time of can preventing because of surface modification causes machine intimate generation clinkering.If the cold wind temperature T 1 that imports in this surface modification device surpasses 5 ℃, the heat that produces in the time of then might be because of surface modification causes machine intimate generation clinkering.

Need to prove from preventing the condensate water aspect consideration of condensing in the locking apparatus, import the cold wind of this surface modification device, preferably cold wind through dehumidifying.Can use known device as dehydrating unit.

The dewpoint temperature of supply gas is preferably below-15 ℃ or-15 ℃, more preferably-20 ℃ or below-20 ℃.

And, for the manufacture method of toner master batch of the present invention, have cooling sleeve pipe in the machine in this surface modification device, preferred limit (is preferably chilled water with refrigerant, anti freezing solution such as ethylene glycol more preferably) feed in this sleeve pipe, surface modification treatment is carried out on the limit.Utilize this sleeve pipe to carry out cooling in the machine, the heat that produces in the time of can preventing because of modifying surfaces of toner particles thus causes taking place in the machine clinkering.

Need to prove that the refrigerant temperature in this sleeve pipe that feeds surface modification device is preferably below 5 ℃ or 5 ℃.Be set at below 5 ℃ or 5 ℃, more preferably below 0 ℃ or 0 ℃, more preferably-5 ℃ or below-5 ℃, the heat that produces in the time of can preventing because of surface modification causes taking place in the machine clinkering by the refrigerant temperature in this sleeve pipe that will feed surface modification device.If the refrigerant temperature that imports in this sleeve pipe surpasses 5 ℃, the heat that produces in the time of then might be because of surface modification causes taking place in the machine clinkering.

And for toner master batch manufacture method of the present invention, preferably the temperature T 2 with this surface modification device internal classification rotor rear is set at below 60 ℃ or 60 ℃.Be set at below 60 ℃ or 60 ℃, be preferably below 50 ℃ or 50 ℃ by the temperature T 2 with this surface modification device internal classification rotor rear, the heat that produces in the time of can preventing because of surface modification causes taking place in the machine clinkering.If the temperature T at this surface modification device internal classification rotor rear 2 surpasses 60 ℃, then in surface modified area, be subjected to the above Temperature Influence of this temperature, the heat that produces in the time of might taking place because of surface modification causes taking place in the machine clinkering.

And for toner master batch manufacture method of the present invention, the minimum interval in the surface modification device between this dispersion rotor and liner is preferably 0.5mm to 15.0mm, more preferably 1.0mm to 10.0mm.In addition, the rotation round speed of this dispersion rotor is preferably 75m/sec to 200m/sec, more preferably 85m/sec to 180m/sec.And, be arranged in the surface modification device this angle type dish or the top of cylindrical shape post and minimum interval between this cylindrical shape guide ring bottom above dispersion rotor and be preferably 2.0mm to 50.0mm, more preferably 5.0mm to 45.0mm.

In the present invention, consider that from toner master batch throughput rate aspect preferably the crushed face to dispersion rotor in this surface modification device and liner carries out wear-resistant processing.Need to prove wear-resistant disposal route be there is no any qualification.In addition, there is not any qualification for the shape of the sword of dispersion rotor in this surface modification device and liner yet.

As toner master batch manufacture method of the present invention; be preferably as follows method: use the airflow classification machine; particulate is in advance turned to micro mist in the raw material toner master batch about desired particle diameter and meal by removing to a certain degree, utilize surface modification device to carry out the surface modification of toner master batch and removing of superfine powder composition then.By removing micro mist in advance, can make the dispersion of toner master batch in the surface modification device become good.Particularly the specific surface area owing to micro mist composition in the toner master batch is big, compare with other bigger toner master batches, carried charge is higher relatively, therefore is difficult to separate from other toner master batches, might be with the classification rotor with the suitably classification of superfine powder composition; By removing the micro mist composition in the toner master batch in advance, each toner master batch dispersion in surface modification device becomes easily, utilizes the classification rotor with the suitably classification of superfine powder composition, can obtain to have the toner master batch of desired size-grade distribution.Removed for the toner of micro mist for utilizing the airflow classification machine, the size-grade distribution result who uses Coulter Counter method to measure is: the accumulated value that the toner master batch number of less than 4 μ m is evenly distributed is more than 10% or 10%, less than 50%, be preferably more than 15% or 15%, less than 45%, more preferably more than 15% or 15%, less than 40%, can utilize surface modification device of the present invention to remove the superfine powder composition effectively.As the airflow classification machine that uses among the present invention, can enumerate Elbow Jet (day ironworker's industry society system) etc.

And, in the present invention, by controlling dispersion rotor in this surface modification device and revolution of classification rotor etc., can be with 0.6 μ m in the circularity of toner master batch and the toner master batch or more than the 0.6 μ m, the particle ratio of less than 3 μ m is controlled to be suitable value.In the present invention, when measuring the toner master batch with respect to the wettability of methanol mixed solvent with the transmitance of 780nm wavelength light, transmitance is that the methanol concentration that 80% o'clock methanol concentration and transmitance are at 50% o'clock is 35～74 volume %, be preferably 40～70 volume %, more preferably 45～65 volume %, more preferably 45～60 volume %.Toner master batch with above-mentioned methanol concentration-light transmission rate can be that suitable treatment conditions obtain by using as the surface modification device of feature of the present invention and with the surface modification treatment condition enactment, each starting material toner master batch surface to expose ratio suitable, can give toner master batch appropriateness and narrow charging property.In addition, the average circularity of toner master batch of the present invention is more than 0.935 or 0.935, less than 0.970, and is when using as toner, mobile good.Distribute for the narrow toner for above-mentioned good fluidity and carried charge, in toner container, toner can have even and high charging property, even long-term the use also can obtain good and stable image color.Particularly under the environment that generation toner aggegation easily, mobile deterioration or carried charges such as hot and humid environment reduce, this toner is effective especially.

Be lower than 35 volume % if the transmitance of toner master batch is the methanol concentration that 80% o'clock methanol concentration and transmitance are at 50% o'clock, then the charging property of toner is insufficient, and the image color variation takes place sometimes.In addition, if the methanol concentration that transmitance is 80% o'clock methanol concentration and transmitance is at 50% o'clock surpasses 75 volume %, then because the compendency of toner uprises, therefore can't obtain sufficient flowability, the development under hot and humid environment is insufficient sometimes.

In addition, the transmitance of toner master batch is that the concentration difference of 80% o'clock methanol concentration and the transmitance methanol concentration that is at 50% o'clock is below 10% or 10%, be preferably below 7% or 7%, more preferably below 5% or 5%, can give toner better development.If concentration difference surpasses 10%, then the surface state of toner particle becomes inhomogeneous, is increased by the toner of undesired development, and photographic fog increases.

In the present invention, the wettability of toner master batch, be that hydrophobic property is used methyl alcohol to drip transmittance curve to measure.Particularly, its determinator for example uses the powder wettability testing machine WET-100P of (strain) Rhesca society system, utilizes the methyl alcohol with following condition and sequential determination to drip transmittance curve.At first, to put into container by the aqueous methanol solution 70ml that methyl alcohol 25～50 volume % and water 50～80 volume % constitute, precision weighing is added in the said vesse as the toner master batch 0.1g of a corpse or other object for laboratory examination and chemical testing, and modulation is used to measure the sample solution of toner master batch hydrophobic property.Then, in this test sample liquid, methyl alcohol is added continuously with the rate of addition of 1.3ml/min in the limit, and the limit makes methyl alcohol shown in Figure 3 and drips transmittance curve with the light measurement transmitance of wavelength 780nm.At this moment, be in order to reduce the influence of strippings such as dyestuff contained in the toner master batch, pigment, charged controlling agent, the surface state of more correctly observing the toner master batch with methyl alcohol as titration solvent.

As the kind of the binder resin that uses among the present invention, can enumerate phenylethylene homopolymer, styrene copolymer, vibrin, polyol resin, Corvic, phenolics, natural modified phenolics, natural resin modification maleic acid resin, acryl resin, methacrylic resin, polyvinyl acetate, organic siliconresin, urethane resin, polyamide, furane resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin or petroleum resinoid.

As the comonomer of styrene monomer in the styrene copolymer, can enumerate styrene derivatives such as vinyltoluene; Acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecylacrylate, 2-ethyl hexyl acrylate, acrylic acid-2-ethyl caproite, acrylate such as phenyl acrylate; Methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylates such as 2-Propenoic acid, 2-methyl-, octyl ester; Maleic acid; Maleic acid butyl ester, maleic acid methyl esters, dimethyl maleate etc. have the dicarboxylic ester of two keys; Acrylamide, vinyl cyanide, methacrylonitrile, butadiene; Vinyl esters such as vinyl chloride, vinyl acetate, benzoic acid vinyl esters; Vinyl alkene such as ethene, propylene, butylene; Vinyl ketones such as ethenyl methyl ketone, vinyl hexyl ketone; Vinyl ether such as vinyl methyl ether, EVE, vinyl isobutyl ether.Above-mentioned vinyl monomer can use separately, also can use more than 2 kinds or 2 kinds.

In the present invention, as binder resin, especially preferably use cinnamic acrylic ester-acrylic copolymer, copolymer in cinnamic acrylic ester, cinnamic acrylic ester-methacrylic acid copolymer as binder resin, thus can be easily the circularity of toner master batch be controlled to be suitable value.

Consider that from the keeping quality aspect glass temperature of the binder resin that uses among the present invention (Tg) is 45～80 ℃, is preferably 50～70 ℃.If Tg is lower than 45 ℃, the reason of skew takes place when then becoming under high-temperature atmosphere toner deterioration or photographic fixing easily.In addition, if Tg surpasses 80 ℃, the tendency that then exists fixation performance to reduce.

The assay method of Tg is for using the system Q-1000 of TA INSTRUMENTS society, carrying out based on ASTM D3418-82.The DSC curve that uses among the present invention be carried out heating up for 1 time, after the pre-treatment of cooling, the DSC curve of measuring when it being heated up with the programming rate of 10 ℃/min.Be defined as follows described.

Glass temperature (Tg): in the DSC curve when heating up, than the line of the baseline mid point before and after the thermal distortion appearance and the temperature of DSC intersections of complex curve.

In addition, the main peak molecular weight of binder resin is preferably 3.0 * 10 ³Or 3.0 * 10 ³More than, less than 3.0 * 10 ⁴, more preferably 5.0 * 10 ³Or 5.0 * 10 ³More than, less than 2.5 * 10 ⁴, be preferably 8.0 * 10 especially ³Or 8.0 * 10 ³More than, 2.0 * 10 ⁴Or 2.0 * 10 ⁴Below, can make the toner master batch have suitable hardness thus, carry out the surface modification of toner master batch easily.

In addition, toner of the present invention is 3.0 * 10 at molecular weight more preferably ³Or 3.0 * 10 ³More than, less than 3.0 * 10 ⁴The zone in have main peak, and be 5.0 * 10 at molecular weight ⁴Or 5.0 * 10 ⁴More than, less than 1.0 * 10 ⁸The zone in have a secondary peak or acromion at least.

Is 3.0 * 10 by making toner at molecular weight ³To less than 3.0 * 10 ⁴The zone in have main peak, can when modifying surfaces of toner particles, obtain the toner particle of high circularity with little load, also improved throughput rate.In addition, can have good fixation performance.Is 5.0 * 10 by making toner at molecular weight ⁴To less than 1.0 * 10 ⁸, be preferably 1.0 * 10 ⁵To less than 3.0 * 10 ⁶The zone in have secondary peak or acromion, can make toner integral body have the appropriateness elasticity, when modifying surfaces of toner particles, make toner have the appropriateness hardness, moderately distribute thus, obtain desirable toner shape easily.In addition, can improve anti-skew.

Have the toner of molecular weight distribution of the present invention and surface modification effect of Combination for can obtain good transfer efficiency.

Because toner balance of the present invention has low molecular weight compositions and high molecular weight components well, toner integral body has the elasticity of appropriateness, therefore, can make magnetic or starting material such as wax, charged controlling agent be evenly distributed in toner surface.Owing to all have uniform composition on the surface, arbitrary place of toner particle, therefore can have same charging property, can make it have narrow charged distribution.If it is inhomogeneous that toner surface is formed, then charged distribution broadens and is inhomogeneous.In addition, by the average surface roughness that makes toner of the present invention have appropriateness, can on surfaces of toner particles, there be the position of the more contact electrification carried out.At this moment, for the toner that balance of the present invention has low molecular weight compositions and high molecular weight components well, can make toner have narrow and high carried charge, improve from photosensitive drums to the transfer printing that is transferred material.And, owing to have the circularity of appropriateness, therefore separate photosensitive drums and toner easily.

If the molecular weight of main peak is less than 3.0 * 10 ³, then the intermiscibility of low molecular weight compositions and high molecular weight components reduces, and the surfaces of toner particles composition becomes inhomogeneous, is difficult to obtain narrow charged distribution the tendency that exists transfer efficiency to reduce.If the molecular weight of main peak 3.0 * 10 ⁴Or 3.0 * 10 ⁴More than, fixation performance variation then, in addition, the load during surface modification treatment increases, and throughput rate also reduces.If the molecular weight of secondary peak or acromion is less than 5.0 * 10 ⁴, then have the tendency of anti-skew deterioration.If the molecular weight of secondary peak or acromion is 1.0 * 10 ⁸Or 1.0 * 10 ⁸More than, then the intermiscibility of low molecular weight compositions and high molecular weight components reduces, and surfaces of toner particles is formed inhomogeneous, is difficult to obtain narrow charged distribution, and transfer efficiency reduces.

In addition, in the present invention, molecular weight is 3.0 * 10 in the toner ³To less than 3.0 * 10 ⁴The content of composition (main peak composition) be preferably 3 0～90 quality %, molecular weight is 5.0 * 10 ⁴To less than 1.0 * 10 ⁸The content of composition (secondary peak or acromion composition) be preferably 10～70 quality %.

In the present invention, have the binder resin of acid number, can further emphasize the charged ability of toner, realize the charged fast of toner, give the high-band electric weight by use.Low molecular weight compositions or high molecular weight components in the binder resin have acid number, and acid number is preferably 0.5～not enough 30mgKOH/g.And, preferably make low molecular weight compositions and high molecular weight components two Fang Jun have acid number, the acid number of low molecular weight compositions is preferably more than the acid number of high molecular weight components especially.

The acid number of solvable composition of the THF of toner and raw material binder resin

In the present invention, the acid number of solvable composition of the THF of toner and raw material binder resin (JIS acid number) utilizes following method to obtain.The acid number that need to prove the raw material binder resin also is meant the acid number of the solvable composition of THF of material resin.

Basic operation is based on JIS K-0070.

(1) remove in advance that the insoluble composition of THF of toner and binder resin re-uses in the sample, or will in the solvable composition measurement of above-mentioned THF, obtain, use as sample with the solvable composition that the THF solvent extraction goes out with soxhlet's extractor.The accurate crushed material of weighing 0.5～2.0 (g) sample is W (g) with the weight of solvable composition.

(2) sample is put into the beaker of 300ml, added the mixed liquor 150 (ml) of toluene/ethanol (4/1), dissolving.

(3) the KOH ethanolic solution of use 0.1mol/l is measured (for example can utilize the potential difference (PD) titration apparatus AT-400 (win workstation) of use capital of a country Electronics Co., Ltd system and the automatic titration device of the electronic dropper of ABP-410) with the potential difference (PD) titration apparatus.

(4) the KOH solution use amount with this moment is S (ml).In addition, do not use the blank test of sample simultaneously, the use amount of KOH solution is B (ml) with this moment.

(5) calculate acid number by following formula.F is the factor of KOH.

Acid number (mgKOH/g)=(S-B) * f * 5.61}/W

In the present invention, by following condition, what measure binder resin is the GPC molecular weight distribution of solvent with THF (tetrahydrofuran).

In 40 ℃ heating chamber, make post stable, make in the post of tetrahydrofuran (THF) as solvent, inject the THF solution of about 100 μ l samples, measure with the flow velocity inflow said temperature of per minute 1ml.When measuring the sample molecule amount, use the logarithm value of the inspection amount line of making according to several monodisperse polystyrene standard samples and the relation of count value, calculate the molecular weight distribution that sample has.As the polystyrene standard sample that is used to draw inspection amount line, for example using Dong Caoshe system or clear and molecular weight electrician society system is 10 ²～10 ⁷About sample, it is more suitable selecting polystyrene standard sample about 10 to chart at least.In addition, detecting device uses RI (refractive index) detecting device.Many commercially available Aquapak A-440 column combinations can be used as post.

For example, can enumerate combination clear and the system Shodex GPC KF-801 of electrician society, 802,803,804,805,806,807,800P, or Dong Caoshe system TSKgel G1000H (H _XL), G2000H (H _XL), G3000H (H _XL), G4000H (H _XL), G5000H (H _XL), G6000H (H _XL), G7000H (H _XL), the combination of TSK guard column.

Following making sample.

Sample is put into THF, place a few hours after, fully concussion makes sample fully mix (until the agglomerate disappearance of sample) with THF, leaves standstill more than 12 hours or 12 hours again.At this moment, the standing time of sample in THF is more than 24 hours or 24 hours.Then, (aperture 0.45～0.5 μ m for example, can use Dong Caoshe system MAISHORIDISK H-25-2 to make it pass through the sample preparation filtrator, Ekichrodisc25CR Gelman SciencesJapan society system etc.), the filtrate that obtains is measured sample as GPC.It is 0.5～5mg/ml that sample solution concentration is adjusted to resinous principle.

In addition, in the present invention, toner utilize the intensification that differential scanning calorimeter (DSC) measures the time the DSC curve in have an endothermic peak at least, the initial temperature of this endothermic peak and the temperature difference of final temperature are more than 20 ℃ or 20 ℃, 80 ℃ of less thaies, be preferably more than 30 ℃ or 30 ℃, 70 ℃ of less thaies, more preferably more than 35 ℃ or 35 ℃, 65 ℃ of less thaies.In the present invention, as making toner have the method for above-mentioned endothermic character, can enumerate the method for in toner, adding wax.Need to prove that the content of closing with wax phase is described below.

Contain the toner that has as the toner master batch of the average circularity of feature of the present invention and average surface roughness and have above-mentioned endothermic character by making, can prevent to result from the bad image deflects of cleaning effectively.Generally speaking, the like that mobile good toner of toner of the present invention is clamp-oned in the gap of cleaning member and photoreceptor in cleaning easily, is difficult to clean, and causes the pollution of parts such as charged roller easily.But, for containing the wax composition so that for the toner that has endothermic character in the above-mentioned wide temperature zone, the wax composition moderately is present in toner surface, described wax composition moderately suppresses the slickness of toner, the toner squeeze-out phenomenon that occurs in the cleaning can be suppressed at effectively, the pollution of parts such as charged roller can be suppressed.

In addition, in the present invention, in the DSC curve when the toner that utilizes DSC to measure heats up, the initial temperature of endothermic peak is more than 50 ℃ or 50 ℃, 110 ℃ of less thaies, be preferably more than 55 ℃ or 55 ℃, 100 ℃ of less thaies, more preferably more than 60 ℃ or 60 ℃, 100 ℃ of less thaies, can give toner good fixation performance.If 50 ℃ of initial temperature less thaies, then the keeping quality of toner worsens sometimes; If initial temperature is more than 110 ℃ or 110 ℃, then the fixation performance of toner becomes insufficient sometimes.

In addition, in the present invention, in the DSC curve when the toner that utilizes DSC to measure heats up, the final temperature of endothermic peak is more than 90 ℃ or 90 ℃, 150 ℃ of less thaies, be preferably more than 95 ℃ or 95 ℃, 145 ℃ of less thaies, more preferably more than 100 ℃ or 100 ℃, 140 ℃ of less thaies, can give toner good anti-skew.If 90 ℃ of final temperature less thaies, the then anti-skew deterioration of toner sometimes; If final temperature is more than 150 ℃ or 150 ℃, then the fixation performance of toner is insufficient sometimes.

In addition, in the present invention, in the DSC curve when the toner that utilizes DSC to measure heats up, 140 ℃ of less thaies more than 60 ℃ or 60 ℃, be preferably 135 ℃ of less thaies more than 65 ℃ or 65 ℃, more preferably 130 ℃ of less thaies more than 70 ℃ or 70 ℃, more preferably have an endothermic peak at least in the zone of 125 ℃ of less thaies more than 70 ℃ or 70 ℃, can give the good photographic fixing of toner, anti-offset characteristic.If 60 ℃ of endotherm peak temperature less thaies, then the keeping quality of toner worsens sometimes; If endotherm peak temperature is more than 140 ℃ or 140 ℃, then the fixation performance of toner is insufficient sometimes.

In the present invention, the DSC of toner can use differential thermal analysis determinator (DSC determinator), DSC Q-1000 (TA INSTRUMENTS JAPAN society system), measures under the following conditions.

Measure based on ASTM D3418.

Sample: 3～15mg, preferred 5～10mg

Assay method: sample is put into the aluminium dish, in contrast, use empty aluminium dish.

Temperature curve: intensification I (20 ℃～180 ℃, programming rate: 10 ℃/min)

Cooling I (180 ℃～10 ℃, cooling rate: 10 ℃/min)

Intensification II (10 ℃～180 ℃, programming rate: 10 ℃/min)

In above-mentioned heating curve, utilize the endothermic curve of measuring in the intensification II process, measure initial temperature, the final temperature of endothermic peak, the endotherm peak temperature of endothermic peak.

The initial temperature of endothermic peak: the differential value at the endothermic peak curve is in the temperature of maximum value, the tangent line of minimum temperature place curve and the temperature of baseline intersection point

The final temperature of endothermic peak: the differential value at the endothermic peak curve is in the minimizing temperature, the tangent line of maximum temperature place curve and the temperature of baseline intersection point

Endotherm peak temperature: in the curve of endothermic peak, be peaked corresponding temperature from the baseline calculated altitude.

Need to prove when having a plurality of endothermic peak, initial temperature with the endothermic peak place that is present in minimum fusing point side in the endothermic peak is the initial temperature of toner, is the final temperature of toner with the final temperature at the endothermic peak place that is present in the peak melting point side in the endothermic peak.In addition, with in the summit of each endothermic peak, having from the baseline calculated altitude is that the endotherm peak temperature of the endothermic peak of peaked summit is the endotherm peak temperature of toner.

As the polymerization of binder resin of the present invention, can enumerate solution polymerization process, emulsion polymerization or suspension polymerization.

The binder resin that uses among the present invention preferred uses following multiple multi-functional polymerization initiator separately or with the simple function polymerization initiator and with generating.

Concrete example as above-mentioned multi-functional polymerization initiator with polyfunctional structure, can enumerate 1,1-di-t-butyl peroxide-3,3, the 5-trimethyl-cyclohexane, 1, two (t-butyl peroxy isopropyl) benzene of 3-, 2,5-dimethyl-2,5-(t-butyl peroxy) hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, three (t-butyl peroxy) triazine, 1,1-two (t-butyl peroxy) cyclohexane, 2,2-two (t-butyl peroxy) butane, 4,4-two (t-butyl peroxy) n-butyl pentanoate, two (t-butyl peroxy) six hydrogen terephthalate, di-t-butyl peroxide azelate, two (t-butyl peroxy) trimethyladipic acid ester, 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) propane, 2, have the multi-functional polymerization initiator that peroxy more than 2 or 2 etc. has the functional group of polymerization initiation in 1 molecule of 2-t-butyl peroxy octane and various oxypolymers; And have peroxy etc. in a part of diallyl peroxide two carbonic esters, t-butyl peroxy maleic acid, t-butyl peroxy allyl carbonate and t-butyl peroxy isopropyl fumarate etc. simultaneously and have the functional group of polymerization initiation and the multi-functional polymerization initiator of polymerism unsaturated group.

Wherein, more preferably 1,1-di-t-butyl peroxide-3,3,5-trimethyl-cyclohexane, 1,1-two (t-butyl peroxy) cyclohexane, di-t-butyl peroxide six hydrogen terephthalate, di-t-butyl peroxide azelate, 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) propane, and t-butyl peroxy allyl carbonate.

In order to satisfy as toner with the desired various performances of bonding agent, preferably with above-mentioned multi-functional polymerization initiator and simple function polymerization initiator and usefulness.Preferred especially and the decomposition temperature that is lower than the 10 hour half life period that is used to obtain this multi-functional polymerization initiator, have the polymerization initiator of 10 hour half life period and use.

Particularly, can enumerate benzoyl peroxide, 1,1-two (t-butyl peroxy)-3,3,5-trimethyl-cyclohexane, normal-butyl-4,4-two (t-butyl peroxy) valerate, peroxidating two cumenes, α, organic peroxides such as α '-two (t-butyl peroxy diisopropyl) benzene, tert-butyl hydroperoxide cumene, di-t-butyl peroxide; Azo and diazo-compoundss such as azoisobutyronitrile, diazoamino azobenzene.

Above-mentioned simple function polymerization initiator can be added in the monomer with above-mentioned multi-functional polymerization initiator simultaneously, but, in order suitably to guarantee the efficient of this multi-functional polymerization initiator, preferably in polymerization procedure, add through after the half life period of this multi-functional polymerization initiator.

Consider that from the efficient aspect above-mentioned polymerization initiator is preferably 0.05～2 mass parts with respect to monomer 100 mass parts.

Binder resin preferably carries out crosslinked with cross-linkable monomer.

As the crosslinking chemical monomer, the main monomer that has more than 2 or 2 two keys that can polymerization that uses.As its concrete example, can enumerate divinyl aromatic compound (for example, divinylbenzene, divinyl naphthalene etc.); The diacrylate compounds that connects with alkyl chain (for example, ethylene glycol diacrylate, diacrylate 1,3-butanediol ester, diacrylate 1,4-butanediol ester, diacrylate 1,5-pentadiol ester, diacrylate 1, the acrylate of 6-hexanediol ester, diacrylic acid pentyl diol ester and above-claimed cpd are replaced the material that forms by methacrylate); Dimethylacrylate compounds (for example, the acrylate of diacrylate diglycol ester, diacrylate triethyleneglycol ester, diacrylate tetraethylene glycol ester, polyglycol #400 diacrylate, polyglycol #600 diacrylate, diacrylate dipropylene glycol ester and above-claimed cpd is replaced the material that forms by methacrylate) with the alkyl chain connection that contains ehter bond; The diacrylate compounds that connects with the chain that contains aromatic group and ehter bond (for example, polyoxyethylene (2)-2,2-two (4-hydroxy phenyl) propane diacrylate, polyoxyethylene (4)-2, the acrylate of 2-two (4-hydroxy phenyl) propane diacrylate and above-claimed cpd are replaced the material that forms by methacrylate); And polyester-type diacrylate compounds (for example, trade name MANDA (Japanese chemical drug).As polyfunctional crosslinking chemical, the acrylate that can enumerate pentaerythritol acrylate, trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, tetra methylol propane triacrylate, tetramethylol methane tetraacrylate, low-polyacrylate and above-claimed cpd is replaced the material that forms by methacrylate; Triallyl cyanurate, triallyl three (mellitic acid) ester etc.

With respect to other monomer component 100 mass parts, above-mentioned crosslinking chemical can use 0.00001～1 mass parts, preferably uses 0.001～0.05 mass parts.

As the method for making adhesive resin composition, can enumerate and utilize solution polymerization process respectively behind synthetic high polymer weight polymers and the low-molecular weight polymer, it is mixed with solution state, then, carry out the solution blending method of desolventizing; Or utilize extruder etc. to carry out the dried fusion method of melting mixing; The low-molecular weight polymer that utilizes solution polymerization process etc. to obtain is dissolved in the monomer that constitutes heavy polymer, carries out suspension polymerization,, obtain the two-stage polymerization of resin combination etc. through washing drying.Wherein, doing the fusion method is demanding urgently improving aspect evenly dispersion mixes.There are many advantages in the two-stage polymerization at aspect such as uniformly dispersed, but, because the solution blending method can increase to low molecular weight compositions more than the high molecular weight components, can the big heavy polymer of synthetic molecular weight, therefore the less problem that the unwanted low-molecular weight polymer of secondary generation occurs is most preferred.In addition, when the acid number with regulation imports the low-molecular weight polymer composition, compare the preferred solution polymerization process of setting acid number easily with the polymerization of using aqueous medium.

Shown in composition when in the present invention, using vibrin as binder resin is for example following.

As glycol component, ethylene glycol, propylene glycol, 1 are for example arranged, 3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, diglycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1, bis-phenol and the derivant thereof shown in 3-hexanediol, hydrogenated bisphenol A or the formula (A)

Chemical formula (1)

(in the formula, R is ethylene group or trimethylene base, and x, y are respectively the integer more than 0 or 0, and the mean value of x+y is 0～10.)

Glycols shown in the formula (B).

(Chemical formula 2)

(in the formula, R ' is-CH ₂CH ₂-,

Or

X ', y ' are respectively the integer more than 0 or 0, and the mean value of x '+y ' is 0～10.)

As dicarboxylic acid component, can enumerate the benzene dicarboxylic acid class of phthalic acid, terephthalic acid (TPA), m-phthalic acid, phthalic anhydride etc. or its acid anhydrides, lower alkyl esters; Alkyl dicarboxylic aid's class or its acid anhydrides or lower alkyl esters such as succinic acid, hexane diacid, decanedioic acid, azelaic acid; Alkenyl succinic or alkyl succinic acid or its acid anhydrides or lower alkyl esters such as positive dodecenyl succinic succinic acid, dodecyl succinic acid; Unsaturated dicarboxylic or omega-dicarboxylic acids and derivants thereof such as its acid anhydrides or lower alkyl esters such as fumaric acid, maleic acid, citraconic acid, itaconic acid.

In addition, preferred and with ternary or the pure composition more than the ternary and ternary or the sour composition more than the ternary as crosslinked composition.

As ternary or the polyol component more than the ternary, can enumerate sorbierite, 1,2,3, the own tetrol of 6-, 1,4-sorbitan, pentaerythrite, dipentaerythritol, tripentaerythritol, 1,2,4-butantriol, 1,2,5-penta triol, glycerine, 2-methyl-prop triol, 2-methyl isophthalic acid, 2,4-butantriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxy benzene etc.

As ternary among the present invention or the polybasic carboxylic acid composition more than the ternary, can enumerate trimellitic acid, Pyromellitic Acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butane tricarboxylic acids, 1,2,5-hexane tricarboxylic acids, 1,3-dicarboxyl-2-methyl-2-methylene carboxyl propane, four (methylene carboxyl) methane, 1,2,7,8-octane tetrabasic carboxylic acid, empol trimer acid (empoltrimer acid) and acid anhydrides thereof, lower alkyl esters; Tetrabasic carboxylic acid shown in the following formula and polybasic carboxylic acid class and derivants thereof such as acid anhydrides or lower alkyl esters.

(chemical formula 3)

(X represents to have the alkylidene or the alkylene group of the carbon number 5～30 of 1 or 1 above carbon number 3 or 3 above side chains in the formula.)

The alcohol composition is preferably 40～60mol%, more preferably 45～55mol%; The acid composition is preferably 60～40mol%, more preferably 55～45mol%.

In addition, the above multi-component of ternary or ternary preferably accounts for 5～60mol% of total composition.This vibrin utilizes general known polycondensation reaction to obtain usually.

Preferably contain charged controlling agent in the toner of the present invention.

The material that toner is controlled to be negative charging can be enumerated following compound.

For example, Organometallic complexes, chelate compound are effectively, and the metal complex of Monoazo metal coordination compound, cetylacetone metallic coordination compound, aromatic hydroxy-carboxylic, aromatic dicarboxylic acid class is arranged.In addition, also have phenol derivatives classes such as aromatic hydroxy-carboxylic, aromatic series monobasic or polybasic carboxylic acid and slaine thereof, acid anhydrides, ester class, bis-phenol etc.

Wherein, the azo metalloid coordination compound of preferred following general formula (1) expression.

(chemical formula 4)

(in the formula, M represents the coordination center metal, can enumerate Sc, Ti, V, Cr, Co, Ni, Mn or Fe.Ar is an aryl, can enumerate phenyl or naphthyl, also substituting group can be arranged.As the substituting group of this moment, can enumerate the alkyl of nitro, halogen group, carboxyl, N-anilide, carbon number 1～18 or the alkoxy of carbon number 1～18.X, X ', Y and Y ' for-O-,-CO-,-NH-or-NR-(R is the alkyl of carbon number 1～4).A ⁺The expression counter ion counterionsl gegenions, expression hydrogen ion, sodion, potassium ion, ammonium ion or aliphatics ammonium ion or their hybrid ionic.)

The preferred especially Fe of central metal, substituting group is preferably halogen, alkyl or N-anilide, and counter ion counterionsl gegenions are preferably hydrogen ion, alkali metal ion, ammonium ion or aliphatics ammonium ion.In addition, the also preferred potpourri that uses with the coordination compound of different counter ion counterionsl gegenions.

Perhaps, the basic organic acid metal complex of preferred following general formula (2) expression is as the charged controlling agent of giving negative charging.

(chemical formula 5)

(in the formula, M represents the coordination center metal, can enumerate Cr, Co, Ni, Mn, Fe, Zn, Al, Si or B.A represents

(also can have substituting groups such as alkyl),

(X represents hydrogen atom, halogen atom, nitro or alkyl) reaches (R is hydrogen atom, C ₁～C ₁₈Alkyl or C ₂～C ₁₈Alkenyl).Y ⁺The expression counter ion counterionsl gegenions, expression hydrogen ion, sodion, potassium ion, ammonium ion or aliphatics ammonium ion or their hybrid ionic.Z is-O-or )

Central metal preferred especially Fe, Cr, Si, Zn or Al, substituting group is preferably alkyl, N-anilide, aryl, halogen atom, and counter ion counterionsl gegenions are preferably hydrogen ion, ammonium ion or aliphatics ammonium ion.

As the material that toner is controlled to be Positively chargeable following compound is arranged.

The modifier that nigrosine and fatty acid metal salts are arranged; Quaternary ammonium salts such as tributyl hexadecyldimethyl benzyl ammonium-1-hydroxyl-4-naphthalene sulfonate, TBuA tetrafluoroborate, and as the slaine of  salt such as the microcosmic salt of its analog and mordant pigment, triphenhlmethane dye and mordant pigment thereof (, phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, the ferricyanide, ferrocyanide etc. being arranged), higher fatty acid as the color lake agent; Oxidation two organic group tin such as dibutyltin oxide, di-n-octyltin oxide, oxidation dicyclohexyl tin; Boric acid two organic group tin such as boric acid dibutyl tin, boric acid dioctyl tin, boric acid dicyclohexyl tin; Guanidine compound, imidazolium compounds.Above-claimed cpd can use separately, also can be used in combination more than 2 kinds or 2 kinds.Wherein, preferably use the triphenyl methane compound, counter ion counterionsl gegenions are not the quaternary ammonium salts of halogen atom.In addition, as the Positively chargeable controlling agent, can use the homopolymer of monomer shown in the following general formula (3) or the multipolymer that forms with polymerizable monomers such as above-mentioned styrene, acrylate, methacrylates.At this moment, above-mentioned charged controlling agent also has (all or part of) effect as binder resin.

(chemical formula 6)

(in the formula, R ₁Expression H or CH ₃, R ₂Or R ₃Expression replacement or unsubstituted alkyl (preferred C1～C4).)

As just charged controlling agent, the compound of preferred especially following general formula (4) expression.

(chemical formula 7)

(R in the formula ¹, R ², R ², R ⁴, R ⁵And R ⁶Can be the same or different, represent hydrogen atom, replacement or unsubstituted alkyl, reach replacement or unsubstituted aryl, R ⁷, R ⁸And R ⁹Can be the same or different expression hydrogen atom, halogen atom, alkyl, alkoxy, A ^-Expression is selected from the negative ion in sulfate ion, nitrate ion, borate ion, phosphate anion, hydroxide ion, organic sulfur acid ion, organic sulfonic acid radical ion, organic phosphoric acid radical ion, carboxylic acid ion, organic boronic radical ion or the tetrafluoroborate.)

As making the method that contains charged controlling agent in the toner, have it is added into the method for toner master batch inside and it is added into the method for toner master batch outside.The use amount of charged controlling agent by the kind of binder resin, have or not other adjuvants, comprise the method for preparing toner decision of process for dispersing, can't unified Definition, with respect to binder resin 100 mass parts, be preferably 0.1～10 mass parts, more preferably 0.1～5 mass parts.

Also can contain wax in the toner of the present invention.The wax that uses among the present invention is as described below.Paraffin and derivant thereof, montan wax and derivant thereof, microcrystalline wax and derivant thereof, Fischer-Tropsch process synthetic wax and derivant, polyolefin-wax and derivant thereof, Brazil wax and derivant thereof etc. are for example arranged.Derivant comprises oxide or the segmented copolymer, the graft modification thing that form with vinyl monomer.

For toner of the present invention, the total content of above-mentioned wax uses 0.1～15 mass parts with respect to binder resin 100 mass parts, and it is effective preferably using 0.5～12 mass parts.

The fusing point that above-mentioned wax uses differential thermal analysis determinator (DSC) to measure is more than 65 ℃ or 65 ℃, 130 ℃ of less thaies, be preferably more than 70 ℃ or 70 ℃, 120 ℃ of less thaies, more preferably more than 70 ℃ or 70 ℃, 110 ℃ of less thaies, more preferably more than 75 ℃ or 75 ℃, 100 ℃ of less thaies.When containing wax in the toner master batch, can have the hardness of appropriateness, in the surface modification step of toner master batch, can obtain desirable circularity, size distribution, average surface roughness effectively with above-mentioned fusing point.If 65 ℃ of the fusing point deficiencies of wax, then the keeping quality of toner worsens sometimes.If the fusing point of wax surpasses 130 ℃, then the toner master batch becomes really up to the mark, makes the throughput rate variation of the toner after the surface modification sometimes.

Need to prove the above-mentioned wax of preferred use, the thermal characteristics in the DSC curve when adjusting the toner intensification that utilizes DSC mensuration as described above.

The fusing point test method of＜wax 〉

In the present invention, the DSC of wax can use differential thermal analysis determinator (DSC determinator), DSC Q-1000 (TA INSTRUMENTS JAPAN society system), measures under the following conditions.

Measure based on ASTM D3418.

Sample: 0.5～2mg, preferred 1mg

Assay method: sample is put into the aluminium dish, in contrast, use empty aluminium dish.

Temperature curve: intensification I (20 ℃～180 ℃, programming rate: 10 ℃/min)

Cooling I (180 ℃～10 ℃, cooling rate: 10 ℃/min)

Intensification II (10 ℃～180 ℃, programming rate: 10 ℃/min)

In above-mentioned heating curve, be fusing point with the endotherm peak temperature of measuring in the intensification II process.

Toner of the present invention contains magnetic.Magnetic also can be brought into play the effect of colorant.As the magnetic that uses in the toner, can enumerate iron oxide such as magnetic iron ore, maghemite, ferrite, alloy that metals such as metal such as iron, cobalt, nickel or above-mentioned metal and aluminium, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium form and composition thereof.

The number average particle diameter of above-mentioned magnetic is preferably 0.05～1.0 μ m, more preferably 0.1～0.5 μ m.Preferred use BET specific surface area is 2～40m ²/ g (4～20m more preferably ²/ g) magnetic.Shape is not particularly limited, can uses arbitrary shape.As magnetic characteristic, when being 795.8kA/m in magnetic field, saturation magnetization is preferably 10～200Am ²/ kg (70～100Am more preferably ²/ kg), the residual magnetization is preferably 1～100Am ²/ kg (2～20Am more preferably ²/ kg), coercive force is preferably 1～30kA/m (more preferably 2～15kA/m).Above-mentioned magnetic is 20～200 mass parts with respect to binder resin 100 mass parts, is preferably 40～150 mass parts.

Number average particle diameter can be by calculating through the photo that bust shots such as transmission electron microscope obtain with mensuration such as digital counters.The magnetic characteristic of magnetic can be used " vibration sample type magnetometer VSM-3S-15 " (the industrial society of eastern English system), measures when externally magnetic field is for 795.8kA/m.Specific surface area can be used specific area measuring device AUTOSOBE1 (the shallow Ionics of soup society system) according to the BET method, makes nitrogen adsorption at specimen surface, utilizes BET multipoint method calculated specific surface area.

As operable other colorants in the toner of the present invention, can enumerate suitable arbitrarily pigment or dyestuff.As pigment, can enumerate carbon black, nigrosine, acetylene black, S naphthol yellow S, hansa yellow, rhodamine color lake, alizarine lake, iron oxide red, phthalocyanine blue, indanthrene blue etc.In order to keep the optical concentration of photographic fixing image, above-mentioned substance must use sufficient quantity, and with respect to binder resin 100 mass parts, addition can be 0.1～20 mass parts, is preferably 0.2～10 mass parts.As dyestuff, can enumerate azo dyes, anthraquinone dye, xanthene dye, methine dyes etc.With respect to binder resin 100 mass parts, the dyestuff addition can be 0.1～20 mass parts, is preferably 0.3～10 mass parts.

In order to give toner charging property or flowability, in toner master batch of the present invention also can beyond add through/the inorganic particles handled without hydrophobization.

As the inorganic particles that uses among the present invention, oxides such as wet method silicon dioxide, dry method silicon dioxide, titanium dioxide, aluminium oxide, zinc paste, tin oxide are arranged; Composite oxides such as strontium titanates or barium titanate, calcium titanate, strontium zirconate or calcium zirconate; Carbonate compound such as lime carbonate and magnesium carbonate etc.; In order to improve development, flowability, the composite oxides of preferred silicon dioxide, titanium dioxide, aluminium oxide or these materials.

As silicon dioxide microparticle, can enumerate the so-called dry method silicon dioxide or pyrolysismethod (fumed) silicon dioxide that utilize the halid vapor phase oxidation of silicon to generate, and utilize wet method silicon dioxide that sodium silicate etc. makes both.Preferred surface and inner few, the few dry method silicon dioxide of manufacturing residue of silanol group.

The micro mist that especially preferably utilizes the halid vapor phase oxidation of silicon to generate, promptly so-called dry method silicon dioxide or pyrogenic silica.For example, the material that utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame to obtain, the fundamental reaction formula is as follows:

SiCl ₄+2H ₂+O ₂→SiO ₂+4HCl

In this manufacturing step, with other metal halides and silicon halogenide and usefulness such as aluminum chloride or titanium chlorides, can access the composite micro-powder of silicon dioxide and other metal oxides thus, this composite micro-powder is also contained in the silicon dioxide that uses among the present invention.

And, preferably silicon dioxide microparticle is carried out hydrophobization and handle.Hydrophobization is handled and can be utilized the organo-silicon compound that react with silicon dioxide microparticle or physisorption takes place to handle hydrophobic property.Method for optimizing for the dry method fine silica powder that generates with the halid vapor phase oxidation of silane compound processing and utilizing silicon after, or when handling with silane compound, the method for handling with organo-silicon compound such as silicone oil.Theing contents are as follows of relevant silane compound, organo-silicon compound is described.

The method that silicone oil is handled is directly mixed the fine silica powder after silane compound is handled with silicone oil for using mixers such as Henschel mixer, also can be the method for injection silicone oil on as the silicon dioxide of matrix.

In appropriate solvent dissolving or disperse silicone oil after, mixes with fine silica powder as matrix, make except that desolvating.

As the preferred process for hydrophobicizing of fine silica powder, can enumerate after hexamethyldisilazane is handled, handle the method for modulating through silicone oil again.

Carrying out the silicone oil processing as described above and can improve the hydrophobization degree effectively after handling fine silica powder with silane compound, is preferred therefore.

Handle and the silicone oil processing with the same hydrophobization of preferably titanium oxide fine powder being implemented that above-mentioned fine silica powder is carried out of silicon dioxide.

In addition, toner and mixing component, toner and development sleeve, toner and developing blade, toner and developer inwall, toner take place to be waited when contacting to each other, in order to bring into play the load that alleviates the small particle diameter inorganic particles, to suppress that the small particle diameter inorganic particles is embedded in the toner master batch surface or from the effect of toner deteriorations such as toner master batch sur-face peeling, except above-mentioned inorganic particles (small particle diameter inorganic oxide particle), also can make it contain big particle diameter inorganic oxide particle.

And, in order highly to prevent toner deterioration, to guarantee not have the high image quality and the high transfer printing of image quality deterioration, adjust small particle diameter inorganic oxide particle and big particle diameter inorganic oxide particle the particle diameter relation, both the amount of coating of toner surface and with toner circularity relation be important.

The number average particle diameter of the primary particle of the first inorganic oxide particle A (small particle diameter) is 7nm or more than the 7nm, not enough 20nm (10nm or more than the 10nm more preferably, 15nm or 15nm are following), and inorganic oxide particle A is 0.5～2.0 with respect to the lining rate A of toner master batch, the number average particle diameter of the primary particle of the second inorganic oxide particle B (big particle diameter) is 20nm or more than the 20nm, following (the 30nm or more than the 30nm more preferably of 50nm or 50nm, not enough 40nm), and inorganic oxide particle B is 0.02～0.15 (more preferably 0.03～0.10) with respect to the lining rate B of toner master batch, and the particle diameter difference of first inorganic oxide particle A and the second inorganic oxide particle B is 10nm or more than the 10nm, 35nm or below the 35nm, the shared ratio X (={ lining rate B/ (lining rate A+ lining rate B) } * 100) of inorganic oxide particle B is preferably 1.0～14.0% (more preferably 5.0～12.0%) in the lining rate of inorganic oxide particle total amount.

If toner deterioration (it is interior to be embedded in the toner parent) though then can improve the flowability of toner, takes place in durable in the number average particle diameter of the primary particle of the inorganic oxide particle A of first small particle diameter not enough 7nm easily; If be 20nm or more than the 20nm, then can't obtain high fluidity, can't realize high image qualityization, high transfer printing.

Inorganic oxide particle A is preferably 0.5～2.0 (more preferably 0.8～1.5) with respect to the lining rate A of toner master batch, if lining rate less than 0.5 then can't obtain high fluidity; If surpass 2.0, the tendency that then exists fixation performance to worsen.

The projected area summation that lining rate of the present invention is an inorganic oxide particle is equivalent to the ratio of toner master batch surface area, represents with following formula.

$=\frac{w_A\×R_T\×{\mathrm{\ρ}}_T}{W_T\×r_{\mathrm{\Λ}}\×{\mathrm{\ρ}}_{\mathrm{\Λ}}\×4}$

(w _A: the addition of inorganic oxide particle, r _A: the number benchmark mean radius of the primary particle of inorganic oxide particle, ρ _A: inorganic oxide particle proportion, W _T: toning dosage, R _T: the mean radius of the number benchmark of toner, ρ _T: toner proportion)

During the number average particle diameter of the primary particle of the second inorganic oxide particle B is not enough 20nm, little with the particle diameter difference of the first small particle diameter inorganic oxide particle A, toner deterioration (being embedded in the toner parent) takes place when durable easily, is difficult to obtain to improve transfer printing, suppress the effect that toner disperses.In addition, surpassing under the situation of 50nm, and it is poor to produce particle diameter between the first small particle diameter inorganic oxide particle A, has the tendency that promotes toner deterioration on the contrary.Infer its former because: if the simultaneously outer material that has the particle diameter difference that adds, then the adhesion to toner produces difference, exists free or make small-particle by the tendency of embedding under the condition of fixed macroparticle from toner.In addition, this tendency in order to satisfy in recent years and under the situation of the widely used toner that contains low melt wax to the requirement of low-temperature fixing (province's energy) relatively significantly.And, when surpassing 50nm, exist because of toner is mobile and worsen the tendency that causes a reappearance to worsen, there is tendency simultaneously, the tendency that exists ghost image to worsen to the supply difference of sleeve (development supporting body).

The preferred scheme of the present invention is: the number average particle diameter difference of the primary particle of the first inorganic oxide particle A and the second inorganic oxide particle B is that 10nm or 10nm are above, 35nm or 35nm following (above, the 30nm of 15nm or 15nm or below the 30nm more preferably, more preferably above, 30nm of 20nm or 20nm or 30nm are following).Under the situation of the not enough 10nm of particle diameter difference, toner deterioration (being embedded in the toner parent in) takes place in toner with flatness of the present invention easily in durable process, the effect that the transfer printing that is difficult to be improved, inhibition toner disperse.On the other hand, surpass under the situation of 35nm, exist, have tendency simultaneously, the tendency that exists ghost image to worsen the supply deterioration of sleeve (development supporting body) because of flowability worsens the tendency that causes a reappearance to worsen in the particle diameter difference.

And, under the outer situation of inorganic oxide particle B with respect to the lining rate B less than 0.02 of toner master batch of adding, toner deterioration (being embedded in the toner parent in) takes place easily when durable, the effect that the transfer printing that is difficult to be improved, inhibition toner disperse.On the other hand, cross with respect to the lining rate B ultrasonic of toner master batch at inorganic oxide particle B under 0.15 the situation, there is the tendency to the supply deterioration of sleeve (toner carrier) in existence simultaneously because of flowability worsens the tendency that causes a reappearance to worsen, the tendency that exists ghost image to worsen.

And, under the situation of inorganic oxide particle B shared ratio X (={ lining rate B/ (lining rate A+ lining rate B) } * 100) less than 1.0% in the lining rate of inorganic oxide total amount, toner deterioration (being embedded in the toner parent in) takes place easily when durable, the effect that the transfer printing that is difficult to be improved, inhibition toner disperse.On the other hand, under 14.0% the situation of surpassing, exist, have tendency simultaneously, have the tendency of ghost image deterioration the supply deterioration of sleeve (toner carrier) because of flowability worsens the tendency that causes a reappearance to worsen.

In the present invention, the average circularity Y of toner master batch and inorganic oxide particle B shared ratio X (={ lining rate B/ (lining rate A+ lining rate B) } * 100) in the lining rate of inorganic oxide total amount satisfies the relation of following formula.

10×10 ^-3×X-0.925≤Y≤3.6×10 ^-3×X+0.915

For toner, use above-mentioned external additive to constitute and to realize purpose of the present invention effectively with above-mentioned circularity.

Owing to reasons such as the flowability of this toner, rubbing machine meeting, toner fillibilities, the degree of toner deterioration depends on the circularity of toner.In contrast, by control silicon dioxide microparticle B shared ratio in the lining rate of inorganic oxide total amount, can prevent toner deterioration to heavens, and keep the flowability of appropriateness, improve transfer efficiency, disperse and the sleeve ghost image.

10 * 10 ^-3During * X-0.925＞Y, toner deterioration (being embedded in the toner parent) takes place easily when durable, transfer printing, the toner that can't improve to heavens as purpose of the present invention disperse.

Y＞3.6 * 10 ^-3During * X+0.915, the mobile deterioration can't be improved reappearance, the transfer printing as purpose of the present invention to heavens and dispersed.

In toner master batch of the present invention, can add other adjuvants outward as required.

The resin particle or the inorganic particles of effect such as the release agent when for example, bringing into play charged assistant, electric conductivity imparting agent, mobility donor, anticaking agent, heat roller fixation, lubricant, lapping compound.

As resin particle, its mean grain size is preferably 0.03～1.0 μ m.As the polymerizable monomer that constitutes this resin, can enumerate styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, to methoxy styrene, to the ethyl styrene derivant; Acrylic acid; Methacrylic acid; Acrylate such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid n-propyl, acrylic acid n-octyl, dodecylacrylate, acrylic acid-2-ethyl caproite, stearyl acrylate base ester, acrylic acid-2-chloroethene ester, phenyl acrylate; Methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, n-BMA, isobutyl methacrylate, n octyl methacrylate, lauryl methacrylate, methacrylic acid-2-Octyl Nitrite, methacrylic acid stearyl, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; Monomers such as vinyl cyanide, methacrylonitrile, acrylamide.

As polymerization, can enumerate suspension polymerization, emulsion polymerization, soap-free polymerization.The particle that more preferably adopts soap-free polymerization to obtain.

As other particulates, can enumerate lubricants such as polyvinyl fluoride, zinc stearate, Kynoar (wherein, preferred Kynoar); Lapping compounds such as cerium oxide, silit, strontium titanates (wherein, preferred strontium titanates); Mobility donor such as titanium dioxide, aluminium oxide (wherein preferred lyophobic dust); Anticaking agent; Electric conductivity imparting agents such as carbon black, zinc paste, antimony oxide, tin oxide.And, also can use on a small quantity with the opposite polarity white particles of toner and black particle as the development improving agent.

Inorganic particles that mixes with toner or resin particle can use 0.01～5 mass parts (being preferably 0.01～3 mass parts) with respect to toner 100 mass parts.

In the present invention, the toner charging property is handled and given easily to hydrophobization or mobile aspect is considered from easily the two evenly being mixed, carrying out, and especially preferably makes small particle diameter inorganic particles, big particle diameter inorganic particles be dry method silicon dioxide.

Inorganic particles of the present invention, the especially preferably particulate of handling through silane compound, silicone oil, the wherein particulate of especially preferably handling through both.Promptly, by carrying out surface treatment with above-mentioned 2 types treating agent, it is consistent with the high hydrophobicity material that the hydrophobization degree is distributed, and handle in heterogeneity, its good flowability, electrical, the moisture-proof of homogeneous band can be given, development and durable stability under toner good development, the particularly super-humid conditions can be given.

As silane compound, can enumerate alkoxyl silicone alkanes such as methoxy silane, Ethoxysilane, propoxyl group silane, halogenated silanes classes such as chlorosilane, bromo-silicane, iodine silane, the silazane class, silane alkanes, alkyl silane class, the aryl-silane class, vinyl silanes class, propenyl silanes, the epoxy silane class, the silyl compound class, type siloxane, silicyl ureas, the silicyl ethanamide, and have the substituent silane compound class different simultaneously with these silane compound classes.By using these silane compounds, can obtain flowability, transfer printing, and charged stabilization.Also can use multiple above-mentioned silane compound.

As concrete example, hexamethyldisilazane is arranged, trimethyl silane, trimethyl chlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, allyl phenyl dichlorosilane, the benzyl dimethyl chlorosilane, the bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, three Organosilyl mercaptan, trimethyl silyl mercaptan, three Organosilyl acrylate, vinyl-dimethyl guanidine-acetic acid base silane, dimethylethoxysilane, dimethyldimethoxysil,ne, diphenyl diethoxy silane, HMDO, 1,3-divinyl tetramethyl disiloxane, 1,3-diphenyl tetramethyl disiloxane, and per molecule has 2～12 siloxane units, be positioned at terminal unit and contain the dimethyl polysiloxane that is combined in the hydroxyl on each Si etc. respectively.Can use a kind in these materials separately, also can use the potpourri more than 2 kinds or 2 kinds.

In the present invention,, preferably use silicone oil, can enumerate amino modified, epoxy radicals modification, carboxy-modified, methyl alcohol modification, methylpropenyl modification, sulfhydryl modified, phenol-modified, xenogenesis functional group modification isoreactivity organosilicon as organo-silicon compound; Non-reactive organic silicones such as polyether-modified, methyl styrene base modification, alkyl-modified, fatty acid modified, alkoxy-modified, fluorine modification; Pure silicons such as dimethyl-silicon, aminomethyl phenyl silicon, diphenyl silicon, hydrogenated methyl silicon.

In these silicone oil, be substituent silicone oil preferably with alkyl, aryl, part or all alkyl that is replaced by fluorine atom of hydrogen atom, hydrogen.Particularly, dimethyl silicon oil is arranged, methyl phenyl silicone oil, hydrogenated methyl silicone oil, fluorine modified silicon oil.

The viscosity of these silicone oil in the time of 25 ℃ is 5～2000mm ²/ s, more preferably 10～1000mm ²/ s most preferably is 30～100mm ²/ s.Not enough 5mm ²During/s, can't obtain sufficient hydrophobicity; Surpass 2000mm ²During/s, inorganic particles is difficult to handle equably when handling, and forms agglutinator easily, can't obtain sufficient flowability.

In addition, hydrophobicity inorganic particles of the present invention can use the particulate of handling through nitrogenous silane compound, is particularly preferred for positive toner.Concrete example as this treating agent has TSL 8330, aminopropyltriethoxywerene werene, the dimethylaminopropyl trimethoxy silane, the diethylamino propyl trimethoxy silicane, the dipropyl TSL 8330, the dibutylamino propyl trimethoxy silicane, the monobutyl TSL 8330, the dioctyl TSL 8330, dibutylamino propyl group dimethoxy silane, dibutylamino propyl group one methoxy silane, the dimethylaminophenyl trimethoxy silane, trimethoxysilyl-γ-propyl group aniline, trimethoxysilyl-γ-propyl group benzyl amine, trimethoxysilyl-γ-propyl group piperidines, trimethoxysilyl-γ-propyl group morpholine, trimethoxysilyl-γ-propyl imidazole etc.Above-mentioned treating agent can be a kind, potpourri more than 2 kinds or 2 kinds, or and with or use after multiple processings.

And, as other organic process, also can handle with the silicone oil that has nitrogen-atoms on the side chain, be particularly preferred for positive toner.As above-mentioned silicone oil, the silicone oil that has section construction shown in following general formula (3), (4) is at least arranged.

And/or

(in the formula, R ₁Expression hydrogen atom, alkyl, aryl or alkoxy, R ₂Expression alkylidene or phenylene, R ₃And R ₄Expression hydrogen atom, alkyl or aryl, R ₅The expression nitrogen heterocyclic ring.)

Need to prove that abovementioned alkyl, aryl, alkylidene, phenylene can contain the organic group with nitrogen-atoms, also can have substituting groups such as halogen atom.

Above-mentioned silicone oil can be a kind, potpourri more than 2 kinds or 2 kinds, or and with or use after multiple processings.In addition, also can handle with silane compound and use.

The silane compound of above-mentioned inorganic particles is handled and can be adopted following known method usually to handle, it is vaporific that means such as i.e. utilization stirring become inorganic particles, make the dry process of the silane compound reaction after the gasification therein, or inorganic particles is dispersed in the solvent, drip silane compound, make its wet method that reacts etc.

For the silane compound of inorganic particles was handled, with respect to inorganic particles substance 100 mass parts, the addition for the treatment of agent was 5～40 mass parts, is preferably 5～35 mass parts, more preferably 10～30 mass parts.

The treatment capacity of oil is when being 3～35 mass parts with respect to inorganic particles 100 mass parts, owing to disperse equably easily in making an addition to toner the time, is not easy also that under hot and humid condition concentration takes place and shoals, and be preferred therefore.

Particularly in the present invention, the preferred use after hexamethyldisilazane carries out the hydrophobization processing, the hydrophobicity inorganic particles of handling through silicone oil again.Though the excellent in uniform that utilizes processing that hexamethyldisilazane carries out to handle can access the toner of good fluidity, when only using hexamethyldisilazane to handle, be difficult to stablize charged in the hot and humid environment.In contrast, the processing that utilizes silicone oil to carry out can keep charged in the hot and humid environment high-levelly, but uniform treatment is difficult, if handle equably, must increase the use amount of silicone oil, and mobile the deterioration taken place easily.If after hexamethyldisilazane was handled, recycle silicon oil was handled, then can handle uniformly with less oil mass, therefore can obtain the charged stability in high fluidity and the hot and humid environment simultaneously.

Hydrophobicity inorganic particles of the present invention for example can followingly carry out hydrophobization to be handled.

With Henschel mixer etc. the substance of small particle diameter inorganic particles with big particle diameter inorganic particles is pre-mixed with any mass ratio; the potpourri that obtains is dropped in the treatment trough; or without mixing; directly drop in the treatment trough respectively with any mass ratio; material in machinery or the jet stir process groove is carried out with stirring vane etc. in the limit; the small particle diameter inorganic particles is mixed with big particle diameter inorganic particles, and the hexamethyldisilazane of limit dropping or spraying ormal weight fully mixes it.At this moment, also hexamethyldisilazane can be handled after with the dilution of pure equal solvent.Contain the inorganic particles substance that mixes the treating agent after disperseing and form powder liquid (powder liquid), in nitrogen atmosphere, this powder liquid is heated to the boiling point of hexamethyldisilazane or the temperature more than the boiling point (being preferably 150 to 250 ℃), in 0.5 to 5 hour, reflux while stirring.Then, can remove superfluous treating agent etc. as required.

The surface-hydrophobicized processing of substance inorganic particles that utilizes silicone oil to carry out; can use technique known; for example; handle similarly with Henschel mixer etc. with hexamethyldisilazane the substance of small particle diameter inorganic particles with big particle diameter inorganic particles is pre-mixed with any mass ratio; the potpourri that obtains is dropped in the treatment trough; or without mixing; directly drop in the treatment trough respectively with any mass ratio; the limit is with the material in machinery such as stirring vane or the jet stir process groove; make the small particle diameter inorganic particles mix limit mixing inorganic particles and silicone oil with big particle diameter inorganic particles.Make its direct mixing with the mixers such as to use Henschel mixer that mixes of silicone oil, also can adopt silicone oil is sprayed at method on the substance inorganic particles.Or, after silicone oil dissolving or being dispersed in the appropriate solvent, mixes with inorganic particles as matrix, be prepared except that desolvating then.

When handling with silane compound and silicone oil, preferably make with the following method: after with silane compound the substance inorganic particles being handled, spraying silicone oil then, is heated to more than 200 ℃ or 200 ℃ and handles.

As the method for optimizing of making the hydrophobicity inorganic particles that uses among the present invention, have the small particle diameter inorganic particles that will be selected from following any combination to handle with silane compound or silicone oil simultaneously in same treatment trough with big particle diameter inorganic particles or handle with silane compound and silicone oil, described combination has untreated small particle diameter inorganic particles and untreated big particle diameter inorganic particles, untreated small particle diameter inorganic particles and the big particle diameter inorganic particles of handling through silane compound, small particle diameter inorganic particles and untreated big particle diameter inorganic particles through the silane compound processing, through silane compound small particle diameter inorganic particles of handling and the big particle diameter inorganic particles of handling through silane compound.

Particularly consider the combination of most preferably untreated small particle diameter inorganic particles and untreated big particle diameter inorganic particles from the small particle diameter inorganic particles and the even Combination aspect of big particle diameter inorganic particles.

Process for hydrophobicizing as hydrophobicity inorganic particles of the present invention, be preferably as follows batch processing method: the batch container of the small particle diameter inorganic particles and the substance of big particle diameter inorganic particles being put into ormal weight, through high-speed stirred the substance of small particle diameter inorganic particles with big particle diameter inorganic particles evenly mixed, mix on the limit, and handle potpourri in the batch container on the limit.The hydrophobicity inorganic particles that utilizes the batch type disposal route to obtain is handled equably, can reappearance be obtained the particulate of stay in grade well.

As preferred process for hydrophobicizing, consider from uniform treatment, evenly dispersion aspect, preferably untreated small particle diameter inorganic particles and untreated big particle diameter inorganic particles are handled with silane compound in the batch type treatment trough, do not take out handled thing, in same treatment trough, carry out the method that silicone oil is handled subsequently again.

In the present invention, above-mentioned in the inorganic particles that hydrophobization is handled, preferably using the methyl alcohol wettability is the particulate that (is preferably more than 70% or 70%, more preferably more than 75% or 75%) more than 60% or 60%.The methyl alcohol wettability is represented the hydrophobization degree of hydrophobicity inorganic particles, and methanol concentration is high more, and the expression hydrophobicity is high more.Therefore if the methyl alcohol wettability less than 60% of hydrophobicity inorganic particles, carried charge in that hot and humid environment is medium-term and long-term when using toner, takes place and reduces the concentration that causes and shoal in the then easy moisture absorption of inorganic particles easily.

In methyl alcohol dropping transmittance curve, do not exist acromion to represent that segregation does not all take place for small particle diameter inorganic particles contained in the hydrophobicity inorganic particles, big particle diameter inorganic particles, mixed equably 1 particle levels, and, hydrophobization is handled the processing difference that the particle diameter by inorganic particles causes is not taken place yet, and each particle is handled equably.If in methyl alcohol dropping transmittance curve, have acromion, then or hydrophobization handle inhomogeneous, perhaps the small particle diameter inorganic particles does not mix equably with big particle diameter inorganic particles, even be added in the toner, also be difficult to disperse in the primary particle level, it is charged perhaps can't to stablize toner, increases photographic fog, perhaps in long-term the use concentration taking place shoals, therefore not preferred.

Above-mentioned hydrophobicity inorganic particles also is applicable to any toners such as color toner, monotone toner, magnetic color tuner, and for visualization way, two components are developed, any visualization way of magnetic single component development all is effective.

Wherein, hydrophobicity inorganic particles of the present invention is particularly preferred for having developer carrier and contact with this developer carrier, be used to limit the image forming method of the toner bed thickness limiting part of toner bed thickness, and, when being added on processing speed and being in the toner that uses in the above image forming method of 300mm/s or 300mm/s, can bring into play good especially effect.If the contact developer carrier limits the toner bed thickness, then because toner powerful pressure under the effect of toner bed thickness limiting part is attached on the developer carrier, therefore the mechanicalness load to toner becomes very big.Be under 300mm/s or the situation more than the 300mm/s particularly in processing speed, because the contact site under friction local heating takes place, so toner also rubbed under the high state of temperature, embedding is attached to the inorganic particles on toner master batch surface easily, deterioration takes place easily, and concentration is shoaled.Hydrophobicity inorganic particles of the present invention disperses equably on toner master batch surface easily, performance prevents the effect of big particle diameter inorganic particles deterioration easily, therefore can adapt to the high speed of the developer with the toner bed thickness limiting part that contacts developer carrier, restriction toner bed thickness.

The weight average particle diameter of toner of the present invention is preferably 2.5～10.0 μ m, 5.0～9.0 μ m more preferably, and 6.0～8.0 μ m more preferably, can bring into play effect of sufficient this moment.

Use Coulter Counter method to measure the weight average particle diameter and the size-grade distribution of toner, for example, can use Coulter Multisizer (Coulter society system).The 1%NaCl aqueous solution of electrolytic solution for using pure sodium chloride to be modulated into.For example, can use ISOTON R-II (CoulterScientific Japan society system).Assay method: in above-mentioned electrolytic aqueous solution 100～150ml, add surfactant (preferred alkyl benzene sulfonate) 0.1～5ml, add again and measure sample 2～20mg as spreading agent.The used for electrolyte ultrasonic disperser of the sample that suspended is carried out about 1～3 minute dispersion treatment, use above-mentioned determinator, with the aperture of 100 μ m, measure volume, the number of the above toner master batch of 2 μ m or 2 μ m, volume calculated distributes and number distributes.Obtain the weight average particle diameter (D of the weight basis of obtaining by volume distributed median of the present invention thus ₄).As the duct, use following 13 ducts: 2.00～less than, 2.52 μ m, 2.52～less than, 3.17 μ m, 3.17～less than 4.00 μ m, 4.00～less than, 5.04 μ m, 5.04～less than, 6.35 μ m, 6.35～less than 8.00 μ m, 8.00～less than 10.08 μ m, 10.08～less than, 12.70 μ m, 12.70～less than, 16.00 μ m, 16.00～less than 20.20 μ m, 20.20～less than 25.40 μ m, 25.40～less than, 32.00 μ m, 32.00～less than, 40.30 μ m.

Toner of the present invention can and be used as two-component developer with carrier and use.The carrier that uses in two component developing methods can use known carrier at present.Particularly, can be that the particle of 20～300 μ m is as carrier particle with the mean grain size that forms by surface oxidation or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth metal and alloy thereof or oxide.

The carrier particle surface preferably adheres to or material such as the styrene resin that is covered, acrylic resin, silicone based resin, fluororesin, vibrin.

The following acquisition of toner master batch among the present invention: will contain binder resin and magnetic, and the composition melting mixing (mixing step) of as required other compositions, and the mixing thing that obtains is pulverized (pulverising step) and obtain.After preferably the constituent material of toner master batch fully being mixed with other mixers such as bowl mill in advance, use the hot milling machine to carry out mixing.In addition, pulverising step can be divided into the coarse crushing step and the micro mist quick short steps are rapid, afterwards, can also carry out classification (classification step).And, in order to satisfy the average circularity and the average surface roughness of toner master batch of the present invention, preferably use above-mentioned surface modification device, particularly preferably in carrying out surface modification after the classification step with toner master batch surface modification.In addition, preferably carrying out micro mist simultaneously with surface modification removes.

As described herein, when making toner, the constituent material of toner master batch evenly and is imperceptibly disperseed in particle through mixing step.In addition, pulverize by the mixing thing that will disperse constituent material well, the distribution of constituent material on the toner master batch surface is become well, and the result can give full play to the effect of the toner master batch of the specific average surface roughness that has as feature of the present invention, average circularity.Without mixing step, when pulverising step is made the toner master batch, be difficult to control the distribution of constituent material on toner master batch surface, even the toner master batch has preferred average surface roughness, average circularity, also can't bring into play effect of sufficient.For example, when employing emulsion agglutination etc. is made the toner master batch, make toner master batch surface have the functional group of too much possess hydrophilic property, be difficult to control charging property, the flowability of toner master batch, be difficult to realize simultaneously the minimizing of consumption of toner and good development.

For example, as mixer, can enumerate Henschel mixer (Mitsui mine society system); Super Mixer (Kawata society system); Conical Ribbon Mixer (society of the former making in great river institute system); Nauta mixer, Turbulizer, Cyclomix (Hosokawa Micron society system); Spiral pin mixer (Spiral Pin Mixer) (Pacific Ocean machine worker society system); Rhedige mixer (Matsubo society system); As mixing roll, for example can enumerate KRC kneader (tremble society of this ironworker institute system); Buss kneader (Buss society system); TEM type extruder (toshiba machine society system); TEX double screw extrusion machine (society of JSW system); PCM mixing roll (society of pond shellfish ironworker institute system); Three-roll mill, Mixing Roll Mill, kneader (aboveground making is made); Kneadex (Mitsui mine society system); MS formula pressurization kneader, Kneader-Ruder (gloomy mountain makes society of institute system); Banbury mixer (Kobe Steel, Ltd society system).As comminutor, for example can enumerate upstream injection mill, Micron Jet, Inomizer (HosokawaMicron society system); IDS type mill, PJM jet mill (the industrial society of Japanese Pneumatic system); Crosswise jet mill (tremble society of this ironworker institute system); Ulmax (day CaoEngineeringShe system); SK jet mill (society of Seishin enterprise system); Criptron (Kawasaki Heavy Industries industry society system); Turbo Mill (Turbo industry society system); Super Rotor (day clear Engineering society system); As grader, airflow classification machine, dry type airflow classification machine, forced vortex flow pattern dry type airflow classification machine (society of Seishin enterprise system) are for example arranged; Turbo grader (day clear Engineering society system); Air classifier, Turboprex (ATP); TSP seperator (Hosokawa Micron society system); Elbow Jet (day iron ore mining industry society system); Disperse seperator (the industrial society of Japanese Pneumatic system); YM Wet-type centrifugal grading plant (peace Chuan Shangshishe system); As the screening plant that is used for screening such as coarse grain, Ultrasonics (shake flourish industry society system) is for example arranged; Rezona screening plant, Gyro screening plant (society of moral longevity work institute); Vibrasonic screening system (Dulton society system); Sonicreen (new eastern industrial society system); Turbo screening plant (Turbo industry society system); Friction noiselessness type grading plant (the wild industry of Maki society system); Circular impact screen etc.

(embodiment)

Below, by specific embodiment explanation the present invention, still, the present invention is not limited thereto.

(example I-1～I-8, Comparative Example I-1～I-7)

Employed binder resin is as shown in table 1, and magnetic is as shown in table 2, and wax is as shown in table 3.

Table 1

	Form	Tg (℃)	The peak molecular weight	Number-average molecular weight Mn	Weight-average molecular weight Mw
						Binder resin 1-1	Styrene-propene acid butyl ester-acrylic copolymer (mass ratio: 78/21/1)	62.1	13500	8500	74000
Binder resin 1-2	Styrene-propene acid butyl ester-maleic acid one butyl ester multipolymer (mass ratio: 70/20/10)	60.3	18000	7900	350000
						Binder resin 1-3	Vibrin (the mol ratio: 31/13/39/17) that bisphenol-A propylene oxide adduct (addition 2mol), bisphenol-A ethylene oxide adduct (addition 2mol), phthalic acid and trimellitic anhydride polycondensation form	58.5	7000	5000	600000

Table 2

	Combination	Si content (quality %)	Number average particle diameter (μ m)	The BET specific surface area	Coercivity H (kA/m)	Saturation magnetization σ s (Am 2/kg)	Residual magnetization σ r (Am 2/kg)
								Magnetic I-1	Magnetic oxide	1.0	0.19	9.2	5.7	85.0	5.5
Magnetic I-2	Magnetic oxide	0.0	0.22	12.3	7.3	88.3	8.7

Table 3

	Kind	Fusing point (℃)	Number-average molecular weight	Weight-average molecular weight
					Wax I-1	Paraffin	76	380	500
Wax I-2	The Fischer-Tropsch process synthetic wax	105	790	1180
					Wax I-3	Tygon	120	2250	3390
Wax I-4	Polypropylene	145	1000	8880

(modulation of toner I-1)

Binder resin I-1 100 mass parts

Magnetic I-1 95 mass parts

Monoazo/iron complex compound (T-77, hodogaya chemical industry society system)

2 mass parts

Wax I-1 4 mass parts

After said mixture carried out premixed with Henschel mixer, carry out melting mixing by the double screw extrusion machine that is heated to 110 ℃, cooled mixing thing is carried out coarse crushing with hammer crusher after, obtain the toner meal and mince.The meal that obtains is minced with mechanical type comminutor Turbo Mill (Turbo industry society system, the coating surface of gyrator and stator contain evanohm (the plating bed thickness 150 μ m of charing chromium, skin hardness HV1050)), condition based on table 4, adjust air themperature, carry out mechanical type and pulverize, it is broken to carry out micro mist, remove with time stage with the micro mist and the meal of grading plant (day iron ore mining industry society system, Elbow Jet grader) during the micro mist that obtains is minced of cutting apart that utilizes attached wall effect more.Weight average particle diameter (the D that toner master batch before the processing that obtains is measured through Coulter Counter method ₄) be 6.6 μ m, the accumulated value that the number of the toner master batch of less than 4 μ m is evenly distributed is 25.2%.

Use surface modification device shown in Figure 1 that toner master batch before this processing is carried out surface modification and micro mist is removed.At this moment, in the present embodiment, dispersion rotor top is provided with 16 angle type dishes, and the interval of type dish in angle on guide ring and the dispersion rotor is set at 60mm, and the interval of dispersion rotor and liner is set at 4mm.In addition, be 140m/sec with the rotation round speed setting of dispersion rotor, the fan blower air quantity is set at 30m ³/ min.In addition, the input amount of the broken product of micro mist is set at 300kg/hr, is set at 45sec cycling time.In addition, the refrigerant temperature that flows in the sleeve pipe is set at-15 ℃, cold wind temperature T 1 is set at-20 ℃.In addition, by the revolution of control classification rotor, can make that 0.6 μ m or 0.6 μ m are above, the particle diameter ratio of less than 3 μ m is desirable value.Through above-mentioned steps, obtain toner master batch I-1, the weight average particle diameter (D that toner master batch I-1 measures through Coulter Counter method ₄) be 6.8 μ m, the accumulated value that the number of the toner master batch of less than 4 μ m is evenly distributed is 18.1%.The rerum natura that toner master batch I-1 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope, methanol concentration-transmittance curve as shown in Figure 3.

With Henschel mixer these toner master batch 100 mass parts and hydrophobic silica micro mist 1.2 mass parts of having carried out the dimethyl-silicon oil processing after hexamethyldisilazane is handled are mixed, be modulated into toner I-1.

The diameter of equivalent circle of measuring through FPIA-2100 among this toner I-1 be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the particle below the 400 μ m is 0.947, is 19.1nm with the average surface roughness of the toner I-1 of sweep type probe microscope mensuration.

(modulation of toner I-2～I-8)

Employed binder resin, magnetic, wax are as shown in table 4, and change the micro mist fringe spare of Turbo Mill as shown in table 4ly, change the classification condition of cutting apart grading plant more, change the condition of surface modification device more as shown in table 4ly, in addition, similarly obtain toner master batch I-1～I-8, toner I-2～I-8 with toner I-1.The rerum natura that toner master batch I-2～I-8 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner I-9)

Employed binder resin, magnetic, wax are as shown in table 4, and change the micro mist fringe spare of Turbo Mill as shown in table 4ly, change the classification condition of cutting apart grading plant more, make toner master batch moment of obtaining hot blast by 300 ℃, handle, in addition, similarly obtain toner master batch I-9, toner I-9 with toner I-1.The rerum natura that toner master batch I-9 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

The diameter of equivalent circle of measuring through FPIA-2100 among this toner I-9 be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the particle below the 400 μ m is 0.973, is 3.7nm with the average surface roughness of the toner I-9 of sweep type probe microscope mensuration.

(modulation of toner I-10)

Employed binder resin, magnetic, wax are as shown in table 4, and change the micro mist fringe spare of Turbo Mill as shown in table 4ly, change the classification condition of cutting apart grading plant more, and do not utilize the surface modification of surface modification device, in addition, similarly obtain toner master batch I-10, toner I-10 with toner I-1.The rerum natura that toner master batch I-10 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner I-11)

Employed binder resin, magnetic, wax are as shown in table 4, do not use the mechanical type comminutor, use jet-stream wind formula comminutor, and change the classification condition of cutting apart grading plant more, make toner master batch moment of obtaining hot blast by 300 ℃, handle, in addition, similarly obtain toner master batch I-11, toner I-11 with toner I-1.The rerum natura that toner master batch I-11 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner I-12)

Employed binder resin, magnetic, wax are as shown in table 4, do not use the mechanical type comminutor, use jet-stream wind formula comminutor, change the classification condition of cutting apart grading plant more, and do not utilize the surface modification of surface modification device, in addition, similarly obtain toner master batch I-12, toner I-12 with toner I-1.The rerum natura that toner master batch I-12 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner I-13)

Employed binder resin, magnetic, wax are as shown in table 4, do not use the mechanical type comminutor, use jet-stream wind formula comminutor, and change the classification condition of cutting apart grading plant more, make toner master batch moment of obtaining hot blast by 300 ℃, handle, in addition, similarly obtain toner master batch I-13, toner I-13 with toner I-1.The rerum natura that toner master batch I-13 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner I-14)

Employed binder resin, magnetic, wax are as shown in table 4, do not use the mechanical type comminutor, use jet-stream wind formula comminutor, change the classification condition of cutting apart grading plant more, and do not utilize the surface modification of surface modification device, in addition, similarly obtain toner master batch I-14, toner I-14 with toner I-1.The rerum natura that toner master batch I-14 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner 1-15)

Binder resin I-1 100 mass parts

Magnetic I-1 95 mass parts

Monoazo/iron complex compound (T-77, hodogaya chemical industry society system)

2 mass parts

Wax I-1 4 mass parts

After said mixture carried out premixed with Henschel mixer, carry out melting mixing by the double screw extrusion machine that is heated to 110 ℃, cooled mixing thing is carried out coarse crushing with hammer crusher after, obtain the toner meal and mince.The meal that obtains is minced with mechanical type comminutor Turbo Mill (Turbo industry society system, the coating surface of gyrator and stator contain evanohm (the plating bed thickness 150 μ m of charing chromium, skin hardness HV1050)), condition based on table 4, adjust air themperature, carry out mechanical type and pulverize, it is broken to carry out micro mist, remove with time stage with the micro mist and the meal of grading plant (day iron ore mining industry society system, Elbow Jet grader) during the micro mist that obtains is minced of cutting apart that utilizes attached wall effect more.At this moment, the weight average particle diameter (D that the toner master batch is measured through Coulter Counter method before the processing that obtains ₄) be 6.8 μ m, the accumulated value that the number of the toner master batch of less than 4 μ m is evenly distributed is 15.2%.

Make the toner master batch that obtains by carrying out surface treatment step in the surface modification device that applies mechanical impact force continuously shown in Figure 5, it is carried out surface treatment.

Use Fig. 5 simple declaration to use the surface treatment of this device.Fig. 5 illustrates the concise and to the point pie graph of the structure of surface modification device system for pattern ground, Fig. 6 be pattern the fragmentary cross-sectional view of structure of the handling part 401 of surface modification device I in Fig. 5 system is shown.This surface modification device utilizes the blade of high speed rotating to make the toner master batch compress inboard at shell under action of centrifugal force, applies the hot mechanicalness impulsive force that is produced by force of compression and friction force at least repeatedly, thus the toner master batch is carried out surface treatment.As shown in Figure 6, handling part 401 is provided with 4 rotor 402a, 402b, 402c and 402d in vertical direction.Rotate under the effect of above-mentioned rotor 402a～402d rotating driveshaft 403 of rotation driven by electro-motor 434, the peripheral speed that makes outer most edge portion for example is 30～60m/s.Make air exhauster 424 runnings again, absorption is equal to or greater than the airshed that makes the scraper plate 409a～409d rotation that is provided with integratedly with each rotor 402a～402d.Toner master batch and air are together attracted and import in the feeding funnel 432 from feeder 415, the toner master batch that is imported into is imported into the central portion of the 1st cylindric process chamber 429a by powder supply pipe 431 and powder supply port 430.In the 1st cylindric process chamber 429a, this toner master batch carries out surface treatment under the effect of scraper plate 409a and sidewall 407, then, toner master batch after the surface treatment is by being arranged on the 1st powder escape hole 410a of guide plate 408a central portion, be imported into the central portion of the 2nd cylindric process chamber 429b, under the effect of scraper plate 409b and sidewall 407, carry out spheroidization again and handle.Surface treated toner master batch is by being arranged on the 2nd powder escape hole 410b of guide plate 408b central portion in the 2nd cylindric process chamber 429b, be imported into the central portion of the 3rd cylindric process chamber 429c, under the effect of scraper plate 409c and sidewall 407, carry out surface treatment again, again by being arranged on the 3rd powder escape hole 410c of guide plate 408c central portion, the toner master batch is imported the central portion of the 4th cylindric process chamber 429d, under the effect of scraper plate 409d and sidewall 407, carry out surface treatment.The air that transports the toner master batch, is excluded outside the apparatus system by vent pipe 417, circulator 420, deep bed filter 422 and air exhauster 424 via the 1st～the 4th cylindric process chamber 429a～429d.The toner master batch that imports in each cylindric process chamber 429a～429d is subjected to mechanicalness strike effect in effect following moment of each scraper plate 409a～409d, impacts sidewall 407 again, is subjected to the effect of mechanicalness impulsive force.Utilization is separately positioned on the rotation of the scraper plate 409a～409d of the given size on rotor 402a～402d, in the superjacent air space on rotor surface from central portion to periphery, from outside circumferentially central portion circulate, produce convection current.The toner master batch is trapped in cylindric process chamber 429a～429d, accepts surface treatment.The heat that utilizes this mechanicalness impulsive force to produce carries out surface treatment to the toner master batch.

The surface-treated concrete grammar is to make each rotor with the rotation of the peripheral speed of 40m/s, at fan blower with 3.0m ²Under the state that air quantity attracts, supply with toner with the speed of 20kg per hour, turned round 1 hour, carry out surface treatment by automatic feeder.At this moment, toner is about 20 seconds by the time in the treating apparatus.In addition, the exhaust outlet gas flow temperature of device is 49 ℃ at this moment.

Through above-mentioned steps, obtain negative charging toner master batch I-15, the weight average particle diameter (D that toner master batch I-15 measures through Coulter Counter method ₄) be 6.8 μ m, the accumulated value that the number of the toner master batch of less than 4 μ m is evenly distributed is 18.0%.The rerum natura that toner master batch I-15 measures through FPIA-2100, and as shown in table 5 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

Handle the back, carried out the hydrophobic silica micro mist 1.2 mass parts mixing of dimethyl-silicon oil processing with these toner master batch 100 mass parts with through hexamethyldisilazane with Henschel mixer, be modulated into toner I-15.

Table 4

	Binder resin	Magnetic	Wax	Mechanical type comminutor air themperature		The size-grade distribution of toner master batch before the surface modification		Surface modification device					The size-grade distribution of toner master batch after the surface modification
															T1 (℃)	T2 (℃)	Weight average particle diameter (μ m)	The number cumulative distribution (%) that 4 μ m or 4 μ m are following	Dispersion rotor peripheral speed (m/sec)	Classification rotor peripheral speed (m/sec)	Cycling time (sec)	Cold wind temperature T 1 (℃)	Classification rotor rear temperature T 2 (℃)	Weight average particle diameter (μ m)	The number cumulative distribution (%) that 4 μ m or 4 μ m are following
				Toner master batch I-1	I-1	I-1	I-1	0	45	6.6	25.2	140	83	45												-20	30	6.8	18.1
Toner master batch I-2	I-1	I-1	I-1												0	45	6.5	26.3	140	90	65	-20	35	6.7	19.5
				Toner master batch I-3	I-1	I-1	I-1	0	45	6.6	23.0	140	87	30												-20	28	6.8	17.8
Toner master batch I-4	I-1	I-1	I-1												0	45	6.7	25.4	145	85	45	-15	37	6.8	18.3
				Toner master batch I-5	I-1	I-1	I-1	0	45	6.7	28.3	135	76	50												-15	31	6.9	17.5
Toner master batch I-6	I-1	I-1	I-2												3	48	6.6	31.2	148	76	50	-15	40	6.8	17.9
				Toner master batch I-7	I-2	I-1	I-3	3	48	6.6	34.4	150	69	50												-12	46	6.8	18.2
Toner master batch I-8	I-3	I-2	I-4												3	48	6.5	38.0	150	69	55	-12	48	6.7	19.6
				Toner master batch I-9	I-1	I-1	I-4	-20	25	6.8	18.4	Hot blast is handled														6.8	18.1
Toner master batch I-10	I-1	I-1	I-4														-20	25	6.7	19.6	(nothing)							6.7	19.6
				Toner master batch I-11	I-1	I-2	I-4	The jet-stream wind formula is pulverized		6.9	17.2	Hot blast is handled														6.9	16.9
Toner master batch I-12	I-1	I-2	I-4														The jet-stream wind formula is pulverized		6.8	18.2	(nothing)							6.8	18.2
				Toner master batch I-13	I-1	I-1	I-1	The jet-stream wind formula is pulverized		6.9	18.6	Hot blast is handled														6.9	18.1
Toner master batch I-14	I-1	I-1	I-1														The jet-stream wind formula is pulverized		6.9	17.9	(nothing)							6.9	17.9
				Toner master batch I-15	I-1	I-1	I-1	0	45	6.8	15.2	Surface modification device shown in Figure 5														6.8	18.0

Table 5

	3 μ m or 3 μ m are above, the average circularity of 400 μ m or the following particle of 400 μ m	0.6 μ m or 0.6 μ m are above, the particle rate (number %) of less than 3 μ m	The number cumulative percentage (number %) of the toner master batch of circularity less than 0.960	Transmitance is 80% o'clock a methanol concentration (volume %)	Transmitance is 50% o'clock a methanol concentration (volume %)	(transmitance is 50% o'clock a methanol concentration)-(transmitance is 80% o'clock a methanol concentration) (volume %)	Average surface roughness (nm)	Maximum height difference (nm)	Surface area (μ m 2)
										Toner master batch I-1	0.947	14.8	48	50	52	2	14.8	132	1.22
Toner master batch I-2	0.950	3.5	37	51	54	3	12.5	111	1.18
										Toner master batch I-3	0.941	6.5	63	48	52	4	20.3	128	1.24
Toner master batch I-4	0.954	10.8	33	59	64	5	11.2	106	1.15
										Toner master batch I-5	0.937	13.5	64	42	47	5	23.0	187	1.27
Toner master batch I-6	0.957	15.2	27	62	68	6	8.7	90	1.06
										Toner master batch I-7	0.963	19.4	23	65	73	8	7.6	72	1.04
Toner master batch I-8	0.969	22.2	18	61	77	16	5.4	49	1.02
										Toner master batch I-9	0.973	27.6	15	64	84	20	4.2	40	1.01
Toner master batch I-10	0.929	31.4	73	32	54	22	43.4	370	1.52
										Toner master batch I-11	0.976	37.3	12	58	76	18	3.3	28	1.01
Toner master batch I-12	0.911	50.8	79	43	67	24	65.1	483	1.71
										Toner master batch I-13	0 974	36.4	13	57	74	17	3.5	32	1.01
Toner master batch I-14	0.912	49.3	78	42	66	24	63.8	474	1.68
										Toner master batch I-15	0.945	23.0	52	47	53	6	41.2	315	1.43

Below, use the toner I-1～I-15 that is modulated into, utilize following method to estimate.Evaluation result is as shown in table 6.

Use the system laser printer Laser Jet 4300n of Hewlett-Packard society to carry out following evaluation.

(1) image color, photographic fog

In ambient temperature and moisture environment (23 ℃, 60%RH), low temperature and low humidity environment (15 ℃, 10%RH), each environment of hot and humid environment (32.5 ℃, 80%RH), with 2/10 seconds print speed, 5% printing ratio, with used in copy machines common paper (A4 size: 75g/m ²) carry out 9000 output tests, placed 1, carry out 18000 output tests of 9000 opening and closing meters again.The result is as shown in table 6.

Image color uses " Macbeth reflection of the concentration " (Macbeth society system), and measuring with original copy concentration is the relative concentration of 0.00 blank parts output image.

The whiteness of relatively using the transfer paper that reflectometer (Tokyo electricity look (strain) system) measures and the whiteness of printing the transfer paper behind the whole white pattern calculate photographic fog.

(2) consumption of toner

Under the ambient temperature and moisture environment (23 ℃, 60%RH), with the image of printing ratio 4%, at used in copy machines common paper (A4 size:75g/m ²) on carry out before 18000 output tests and after the test, measure the toning dosage in the toner container, measure the consumption of toner of every image.

(3) sleeve negative ghost image

Under the low temperature and low humidity environment (15 ℃, 10%RH), with common used in copy machines common paper (A4 size:75g/m ²) export 18000, carry out the evaluation of a sleeve negative ghost image every 4500.When carrying out the picture appraisal relevant with ghost image, sleeve only rotate a circle during in output all black lines, export half tone image then.The sketch of pattern as shown in Figure 4.Evaluation method is: the difference of the reflection density of calculate as described below in a print image, sleeve rotated for the 2nd when week, measuring at the position (black Printing Department) that forms all black image the 1st week and the position (non-image portion) that does not form all black image through Macbeth concentration reflectometer.Negative ghost image is a kind of ghost phenomena, usually in the image of when sleeve rotated for the 2nd week, exporting, sleeve rotates the 1st when week image color as the part of non-image portion when being lower than sleeve and rotating for the 1st week as the image color of the part of black Printing Department, and the pattern form of output reappears out unchangeably when rotating for the 1st week.

Reflection density is poor=reflection density (not forming the position of image when rotating for the 1st week)-reflection density (forming the position of all black image when rotating for the 1st week)

The reflection density difference is more little, more ghost image does not take place, and level is good more.As the comprehensive evaluation of ghost image, to estimate with A, B, 4 stages of C, D, evaluation result the poorest in 4500 evaluation is as shown in table 6.

Reflection density difference A:0.00 or 0.00 above, less than 0.02

B:0.02 or 0.02 above, less than 0.04

C:0.04 or 0.04 above, less than 0.06

More than the D:0.06 or 0.06

(4) disperse

Under ambient temperature and moisture, carry out long duration test, during in the early stage with the 18000th, print the grid pattern (1cm at interval) of 100 μ m (sub-image) lines, use optical microscope, its situation of dispersing of visual assessment.

A: lines are very narrow, almost do not have and disperse

B: have few dispersing, lines are narrow

C: it is more to disperse, and the sensation lines are fuzzy

D: not as good as the level of C

(5) spot

Under the low temperature and low humidity environment, carry out long duration test, carry out the spot evaluation by coating state of the toner on the development sleeve in the image output procedure and print image.

A: almost can not see spot on the development sleeve

B: visible few spot on the development sleeve does not show its influence on the image

C: can see spot on the development sleeve, show few influence on the image

D: can see spot on the development sleeve, significantly show its influence on the image

Table 6

		The low temperature and low humidity environment				The high temperature hot environment		The normal temperature normal temperature environment
											18000 image colors after durable	18000 photographic fogs after durable	Negative sleeve ghost image	Spot	9000 image colors after durable	18000 image colors after durable	18000 image colors after durable	Consumption of toner (mg/ opens)	Disperse
		Example I-1	Toner I-1	1.40	1.5	A	A	1.35	1.38	1.39										42	A
Example I-2	Toner I-2										1.39	1.4	A	A	1.33	1.36	1.38	42	A
		Example I-3	Toner I-3	1.39	1.8	A	A	1.32	1.35	1.37										43	B
Example I-4	Toner I 4										1.38	1.9	A	A	1.32	1.34	1.36	44	A
		Example I-5	Toner I-5	1.39	2.2	A	A	1.33	1.35	1.37										47	B
Example I-6	Toner I-6										1136	2.3	B	A	1.29	1.31	1.33	45	A
		Example I-7	Toner I-7	1.34	2.4	B	B	1.28	1 30	1.32										45	A
Example I-8	Toner I-8										1.32	2.6	B	B	1.26	1.29	1.30	46	B
		Comparative Example I-1	Toner I-9	1.21	3.5	C	D	1.10	1.17	1.19										50	C
Comparative Example I-2	Toner I-10										1.18	3.7	C	C	1.08	1.15	1.17	52	D
		Comparative example 1-3	Toner I-11	1.16	3.8	D	D	1.06	1.12	1.14										53	C
Comparative Example I-4	Toner I-12										1.14	4.0	D	C	1.05	1.09	1.12	55	D
		Comparative Example I-5	Toner I-13	1.17	3.7	D	D	1.07	1.14	1.16										54	C
Comparative Example I-6	Toner I-14										1.15	3.9	D	C	1.06	1.09	1.13	54	D
		Comparative Example I-7	Toner I-15	1.38	2.8	C	A	1.32	1.34	1.35										48	C

(modulation of toner master batch II-1)

Binder resin (the styrene-propene butyl acrylate copolymer (St/BA=83/17, main peak molecular weight=10000, secondary peak molecular weight=650,000, Mn=5500, Mw=35 ten thousand)

100 mass parts

Magnetic (spherical, number average particle diameter=0.2 μ m, magnetic characteristic (the σ r=5.1Am in the 1 kilo-oersted magnetic field ²/ kg, σ s=69.6Am ²/ kg))

90 mass parts

Monoazo/iron complex compound (T-77, hodogaya chemical industry society system)

1 mass parts

Wax (low molecular weight polyethylene, fusing point=102 ℃, Mn=850, Mw=1250)

4 mass parts

After said mixture carried out premixed with Henschel mixer, carry out melting mixing by the double screw extrusion machine that is heated to 100 ℃, cooled mixing thing is carried out coarse crushing with hammer crusher after, obtain the toner meal and mince.The meal that obtains is minced with mechanical type comminutor Turbo Mill (Turbo industry society system, the coating surface of gyrator and stator contain evanohm (the plating bed thickness 150 μ m of charing chromium, skin hardness HV1050)), condition based on table 7, adjust air themperature, carry out mechanical type and pulverize, it is broken to carry out micro mist, remove with time stage with the micro mist and the meal of grading plant (day iron ore mining industry society system, Elbow Jet grader) during the micro mist that obtains is minced of cutting apart that utilizes attached wall effect more.Weight average particle diameter (the D that the raw material toner master batch that obtains is measured through Coulter Counter method ₄) be 6.6 μ m, the accumulated value of the size-grade distribution of the number benchmark of the toner master batch of less than 4 μ m is 24.8 number %.Use surface modification device shown in Figure 1 that this raw material toner master batch is carried out surface modification and micro mist is removed.At this moment, in the present embodiment, dispersion rotor top is provided with 16 angle type dishes, and the interval of type dish in angle on guide ring and the dispersion rotor is set at 60mm, and the interval of dispersion rotor and liner is set at 3.5mm.In addition, be 140m/sec with the rotation round speed setting of dispersion rotor, the fan blower air quantity is set at 30m ³/ min.In addition, the input amount of the broken product of micro mist is set at 300kg/hr, is set at 45sec cycling time.In addition, the refrigerant temperature that flows in the sleeve pipe is set at-15 ℃, cold wind temperature T 1 is set at-20 ℃.In addition, by the revolution of control classification rotor, can make that 0.6 μ m or 0.6 μ m are above, the particle diameter ratio of less than 3.0 μ m is desirable value.Through above-mentioned steps, obtain negative charging toner master batch II-1, the weight average particle diameter (D that toner master batch II-1 measures through Coulter Counter method ₄) be 6.8 μ m, the accumulated value of the number benchmark size-grade distribution of the toner master batch of less than 4 μ m is 18 number %.The rerum natura that toner master batch II-1 measures through FPIA-2100 and the measured value of sweep type probe microscope are as shown in table 8.

(modulation of toner master batch II-2～II-5)

Change the micro mist fringe spare of Turbo Mill, the classification condition of cutting apart grading plant, and the condition of surface modification device more as shown in table 7ly, in addition, similarly obtain toner master batch II-2～II-5 with toner master batch II-1.The rerum natura that toner master batch II-2～II-5 measures through FPIA-2100 and the measured value of sweep type probe microscope are as shown in table 8.

(modulation of toner master batch II-6)

Change the micro mist fringe spare of Turbo Mill as shown in table 7ly, change the classification condition cut apart grading plant more, make the toner master batch moment that obtains pass through 300 ℃ hot blast, handle, in addition, similarly obtain toner master batch II-6 with toner master batch II-1.Toner master batch II-6 is as shown in table 8 through rerum natura and sweep type probe microscope measured value that FPIA-2100 measures.

(modulation of toner master batch II-7)

Do not use the mechanical type comminutor, use jet-stream wind formula comminutor, change and cut apart the classification condition of grading plant more, and do not utilize the surface modification treatment of surface modification device, in addition, similarly obtain toner master batch II-7 with toner master batch II-1.Toner master batch II-7 is as shown in table 8 through rerum natura and sweep type probe microscope measured value that FPIA-2100 measures.

Table 7

	Mechanical type comminutor air themperature		Toner master batch before the surface modification		Surface modification device					Toner master batch after the surface modification
												T1(℃)	T2(℃)	Weight average particle diameter (μ m)	4 μ m or the following number cumulative distribution of 4 μ m (number %)	Dispersion rotor peripheral speed (m/sec)	Classification rotor peripheral speed (m/sec)	Cycling time (sec)	Cold wind temperature T 1 (℃)	Classification rotor rear temperature T 2 (℃)	Weight average particle diameter (μ m)	4 μ m or the following number cumulative distribution of 4 μ m (number %)
	Toner master batch II-1	-5	42	6.6	24.8	140	80	45	-20	30	6.8												18.0
Toner master batch II-2												-5	41	6.5	25.8	145	89	65	-20	35	6.7	20.1
	Toner master batch II-3	-5	40	6.7	25.3	140	83	45	-15	37	6.8												18.2
Toner master batch II-4												-5	40	6.6	27.9	135	77	50	-15	31	6.8	17.5
	Toner master batch II-5	-5	38	6.6	33.8	150	69	50	-12	46	6.8												18.2
Toner master batch II-6												-15	25	6.8	18.1	Hot blast is handled					6.8	18.0
	Toner master batch II-7	The jet-stream wind formula is pulverized		6.7	22.5	(nothing)					6.7												22.5

Table 8

	3 μ m or 3 μ m are above, the average circularity of 400 μ m or the following particle of 400 μ m	0.6 μ m or 0.6 μ m are above, the particle rate (number %) of less than 3 μ m	The number cumulative percentage (number %) of the toner master batch of circularity less than 0.960	Average surface roughness (nm)	Maximum height difference (nm)	Surface area (μ m 2)
							Toner master batch II-1	0.947	14.8	48	30.1	164	1.13
Toner master batch II-2	0.950	3.5	63	24.8	139	1.12
							Toner master batch II-3	0.954	10.8	64	17.2	84	1.11
Toner master batch II-4	0.937	13.5	33	34.5	162	1.14
							Toner master batch II-5	0.963	19.4	27	8.6	46	1.07
Toner master batch II-6	0.973	27.6	72	4.1	20	1.02
							Toner master batch II-7	0.920	50.2	78	88.4	345	1.52

Table 9

	Form	The number average particle diameter of primary particle (nm)	Treating agent
				Inorganic particles A1	Dry method silicon dioxide	14	Hexamethyldisilazane/dimethyl silicon oil
Inorganic particles A2	Dry method silicon dioxide	8	Hexamethyldisilazane/dimethyl silicon oil
				Inorganic particles A3	Dry method silicon dioxide	18	Hexamethyldisilazane/dimethyl silicon oil
Inorganic particles A4	Dry method silicon dioxide	20	Hexamethyldisilazane

Table 10

	Form	The number average particle diameter of primary particle (nm)	Treating agent
				Inorganic particles B1	Dry method silicon dioxide	35	Hexamethyldisilazane/dimethyl silicon oil
Inorganic particles B2	Dry method silicon dioxide	47	Hexamethyldisilazane/dimethyl silicon oil
				Inorganic particles B3	Dry method silicon dioxide	39	Hexamethyldisilazane/dimethyl silicon oil
Inorganic particles B4	Dry method silicon dioxide	47	Hexamethyldisilazane
				Inorganic particles B5	Titanium dioxide		55	Dimethyl silicon oil

Table 11

		Small particle diameter inorganic particles A			Big particle diameter inorganic particles B			Lining rate B * 100/ (lining rate A+ lining rate B)
									Kind	Addition (mass parts)	Lining rate A	Kind	Addition (mass parts)	Lining rate B
		Toner II-1	Toner master batch II-1	A1	1.20	0.91	B1								0.20	0.065	6.7
Toner II-2	Toner master batch II-2							A1	1.20	0.91	B2	0.30	0.070	7.1
		Toner II-3	Toner master batch II-4	A2	1.20	1.72	B1								0.10	0.030	1.7
Toner II-4	Toner master batch II-3							A3	1.20	0.69	B1	0.20	0.060	8.0
		Toner II-5	Toner master batch II-4	A1	1.20	0.91	B3								0.30	0.030	3.2
Toner II-6	Toner master batch II-5							A4	1.35	0.77	B4	0.30	0.070	8.3
		Toner II-7	Toner master batch II-5	A4	1.20	0.70	B2								0.35	0.085	10.8
Toner II-8	Toner master batch II-3							A2	1.50	2.15	B5	0.10	0.020	0.9
		Toner II-9	Toner master batch II-3	A4	1.00	0.57	B4								0.50	0.120	17.4
Toner II-10	Toner master batch II-4							A4	1.20	0.70	-	-	-	-
		Toner II-11	Toner master batch II-6	A4	1.20	0.70	B2								0.35	0.085	10.8
Toner II-12	Toner master batch II-7							A4	1.20	0.70	B2	0.35	0.085	10.8

(example II-1～II-10, Comparative Example I I-1～II-2)

Use toner master batch II-1～II-7,,, add the inorganic particles B shown in inorganic particles A shown in the mixture table 9 and the table 10 outward, obtain toner II-1～II-12 with Henschel mixer with the ratio shown in the table 11 with respect to each toner master batch 100 mass parts.

With toner master batch II-1 be diameter of equivalent circle that the toner II-1 of parent measures through FPIA-2100 be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the toner particle below the 400 μ m is 0.947, the average surface roughness of the toner II-1 that measures through the sweep type probe microscope is 18.0nm.In addition, with toner master batch II-7 be diameter of equivalent circle that the toner II-12 of parent measures through FPIA-2100 be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the toner particle below the 400 μ m is 0.920, the average surface roughness of the toner II-12 that measures through the sweep type probe microscope is 28.5nm.

Below, use the toner that is modulated into, utilize following method to estimate.Evaluation result is as shown in table 12.

The developing blade contact that changes the processing speed of Hewlett-Packard society system laser printer Laser Jet 4300n into 1.1 times of speed, development imaging processing box is pressed and is changed 1.1 times into, uses improved device to carry out following evaluation.Evaluation result is as shown in table 12.

(1) image color, photographic fog

Metewand based on example I-1.

(2) sleeve negative ghost image

Metewand based on example I-1.

(3) disperse

Metewand based on example I-1.

(4) initial stage concentration raises

In the ambient temperature and moisture environment (23 ℃, 50%RH), fill the 80g toner, developing blade is changed to the new product that is not coated with any material, carry out 100 long duration tests with 2/10 seconds speed, estimate its concentration change with the 1st difference with the 100th.

Need to prove that image color uses " Macbeth reflection of the concentration " (Macbeth society system), measuring with respect to original copy concentration is the relative concentration of the output image of 0.00 white portion.

(5) fixation performance

Following evaluation fixation performance: the applying unit area weight is 90g/m ²The used in copy machines common paper, (7.5 ℃ of low temperature and low humidity environment, 10%RH), use the system laser printer Laser Jet 4300n of Hewlett-Packard society transformation apparatus, on the image of just having finished, apply the pressure of 4.9kPa,, measure the rate of descent (%) of wiping front and back image color with soft thin paper wiping photographic fixing image, estimate by following benchmark, need to prove that the toner carrier band amount on the image is 5g/m ²

A: less than 2%

B：2～4％

C：4～8％

D: surpass 8%

Table 12

		The low temperature and low humidity environment			Hot and humid environment		The ambient temperature and moisture environment		Fixation performance
										18000 image colors after durable	18000 photographic fogs after durable	The sleeve negative ghost image	9000 image colors after durable	18000 image colors after durable	Disperse	The initial stage image color
		Example II-1	Toner II-1	1.42	1.1	A	1.40	1.38									A	0.01	A
Example II-2	Toner II-2								1.40	1.2	A	1.39	1.38	A	0.01	B
		Example II-3	Toner II-3	1.38	2.0	A	1.32	1.35									B	0.02	C
Example II-4	Toner II-4								1.38	1.8	A	1.35	1.35	B	0.02	A
		Example II-5	Toner II-5	1.38	1.7	A	1.36	1.34									B	0.03	B
Example II-6	Toner II-6								1.35	2.3	B	1.29	1.31	B	0.03	B
		Example II-7	Toner II-7	1.34	2.4	B	1.28	1.30									B	0.04	A
Example II-8	Toner II-8								1.32	2.6	B	1.25	1.27	B	0.04	C
		Example II-9	Toner II-9	1.20	2.8	C	1.20	1.20									C	0.06	A
Example II-10	Toner II-10								1.35	2.1	B	1.20	1.25	C	0.05	A
		Comparative Example I I-1	Toner II-11	1.17	3.5	D	1.05	1.11									C	0.07	A
Comparative Example I I-2	Toner II-12								1.13	3.9	D	1.04	1.10	D	0.08	A

The Production Example L-1 of＜low molecular weight compositions 〉

In four-hole boiling flask, put into dimethylbenzene 300 mass parts, stir on the limit, fully replace gas in the flask with nitrogen on the limit, heats up to make its backflow, under refluxing, mixed liquor with 4 hours drip styrene 68.8 mass parts, n-butyl acrylate 22 mass parts, maleic acid one butyl ester, 9.2 mass parts and di-t-butyl peroxide 1.8 mass parts, then, kept 2 hours, after the end polymerization, carry out desolventizing, obtain low-molecular weight polymer (L-1).Measure the GPC and the acid number of this polymkeric substance, the result is: the peak molecular weight is 15000, and acid number is 30mgKOH/g.This value is shown in Table 13.

The Production Example L-2 of＜low molecular weight compositions～L-5 〉

Change the amount and the polymerization initiator amount of the styrene among the low molecular weight compositions Production Example L-1, n-butyl acrylate, maleic acid one butyl ester into shown in the table 13 amount, in addition, adopting uses the same method obtains low-molecular weight polymer L-2～L-5.The peak molecular weight of low-molecular weight polymer L-2～L-5, acid number are as shown in table 13.

The Production Example H-1 of＜high molecular weight components 〉

After in four-hole boiling flask, putting into de aerated water 180 mass parts and polyvinyl alcohol (PVA) 2 quality % aqueous solution 20 mass parts, add styrene 75.3 mass parts, n-butyl acrylate 20 mass parts, maleic acid one butyl ester 4.7 mass parts, di-tert-butyl peroxide 0.65 mass parts, divinylbenzene 0.008 mass parts and 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) mixed liquor of propane 0.15 mass parts, stir, obtain suspending liquid.After fully replacing gas in the flask with nitrogen, be warming up to 90 ℃, the beginning polyreaction.Kept 24 hours down synthermal, after the end polymerization, obtain heavy polymer (H-1).Then, this polymkeric substance (H-1) is filtered, after washing, drying, measure GPC and acid number, the result is: the peak molecular weight is 2,300,000, and acid number is 8.7mgKOH/g.This value is shown in Table 13.

The Production Example H-2 of＜high molecular weight components～H-4 〉

With the styrene among the high molecular weight components Production Example H-1, n-butyl acrylate, maleic acid one butyl ester, di-tert-butyl peroxide, divinylbenzene, 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) amount of propane changes the amount shown in the table 13 into, add the divinylbenzene that is more suitable for, in addition, adopt to use the same method and obtain heavy polymer H-2～H-4.The peak molecular weight of heavy polymer H-2～H-4, acid number are as shown in table 13.

Table 13

	Prescription						The peak molecular weight	Acid number (mgKOH/g)
									Styrene	N-butyl acrylate	Maleic acid one butyl ester	Divinylbenzene	Di-tert-butyl peroxide	2,2-two (4,4-di-t-butyl peroxide cyclohexyl) propane
	L-1	68.8	22.0	9.2	-	1.80									-	15000	30.0
L-2							72.0	20.0	8.0	-	1.30	-	28000	27.2
	L-3	70.2	21.0	8.8	-	2.00									-	3100	28.6
L-4							69.5	22.0	8.5	-	1.10	-	35000	28.4
	L-5	85.0	15.0	-	-	1.50									-	24000	0
H-1							75.3	20.0	4.7	0.008	0.65	0.15	2.3×10 6	8.7
	H-2	71.5	21.0	7.5	0.003	0.90									0.22	48000	19.6
H-3							78.7	20.0	1.3	0.050	0.05	0.08	1.1×10 8	3.3
	H-4	83.0	17.0	-	0.006	0.72									0.17	1.9×10 6	0

＜binder resin III-1 〉

Low molecular weight compositions L-1 is mixed in xylene solution with the mass ratio shown in the table 2 with high molecular weight components H-1, obtain binder resin III-1.The rerum natura of the binder resin that obtains is as shown in table 14.

＜binder resin III-2～III-8 〉

Change the type of polymer of mixing among the binder resin Production Example III-1, in addition, III-1 similarly obtains binder resin III-2～III-8 with the binder resin Production Example as shown in table 14ly.

Table 14

	Low-molecular weight polymer	Heavy polymer	Low/heavy polymer is than (L/H)	The main peak molecular weight	Secondary peak or acromion molecular weight	The content of main peak composition (quality %)	Content (the quality % of secondary peak or acromion composition	Acid number (mgKOH/g)	Tg (℃)
										Binder resin III-1	L-1	H-1	75/25	15000	2.3×10 6	73.8	26.2	24.1	60.2
Binder resin III-2	L-2	H-1	70/30	28000	2.3×10 6	69.3	30.7	21.7	61.5
										Binder resin III-3	L-2	H-4	65/35	28000	1.9×10 6	64.4	35.6	17.1	62.2
Binder resin III-4	L-5	H-4	70/30	24000	1.9×10 6	70.6	29.4	0	60.5
										Binder resin III-5	L-4	H-1	80/20	35000	2.3×10 6	78.8	21.2	23.9	62.1
Binder resin III-6	L-4	H-2	50/50	35000	48000	53.2	46.8	23.8	58.6
										Binder resin III-7	L-3	H-1	65/35	2700	2.3×10 6	65.1	34.9	21.6	58.3
Binder resin III-8	L-1	H-3	85/15	15000	1.1×10 8	85.4	14.6	25.3	64.8

＜EXAMPLE III-1 〉

(modulation of toner III-1)

Binder resin III-1 100 mass parts

Spherical magnetic oxide (mean grain size: 0.21 μ m, in the 1 kilo-oersted magnetic field

Magnetic characteristic (σ r:5.1Am ²/ kg, σ s:69.6Am ²/ kg))

95 mass parts

Monoazo/iron complex compound (T-77, hodogaya chemical industry society system)

2 mass parts

Wax (the Fischer-Tropsch process synthetic wax, fusing point=104 ℃, Mn=780, Mw=1060)

4 mass parts

After said mixture carried out premixed with Henschel mixer, carry out melting mixing by the double screw extrusion machine that is heated to 110 ℃, cooled mixing thing is carried out coarse crushing with hammer crusher after, obtain the toner meal and mince.The meal that obtains is minced with mechanical type comminutor Turbo Mill (Turbo industry society system, the coating surface of gyrator and stator contain evanohm (the plating bed thickness 150 μ m of charing chromium, skin hardness HV1050)), condition based on table 15, adjust air themperature, carry out mechanical type and pulverize, it is broken to carry out micro mist, remove with time stage with the micro mist and the meal of grading plant (day iron ore mining industry society system, Elbow Jet grader) during the micro mist that obtains is minced of cutting apart that utilizes attached wall effect more.Weight average particle diameter (the D that the raw material toner master batch that obtains is measured through Coulter Counter method ₄) be 6.6 μ m, the accumulated value of the size-grade distribution of the number benchmark of the toner master batch of less than 4 μ m is 25.3 number %.

Use surface modification device shown in Figure 1 that this raw material toner master batch is carried out surface modification and micro mist is removed.At this moment, in the present embodiment, dispersion rotor top is provided with 16 angle type dishes, and the interval of type dish in angle on guide ring and the dispersion rotor is set at 60mm, and the interval of dispersion rotor and liner is set at 4mm.In addition, be 140m/sec with the rotation round speed setting of dispersion rotor, the fan blower air quantity is set at 30m ³/ min.In addition, the input amount of the broken product of micro mist is set at 300kg, is set at 45sec cycling time.In addition, the refrigerant temperature that flows in the sleeve pipe is set at-15 ℃, cold wind temperature T 1 is set at-20 ℃.In addition, by the revolution of control classification rotor, can make that 0.6 μ m or 0.6 μ m are above, the particle diameter ratio of less than 3.0 μ m is desirable value.Through above-mentioned steps, obtain negative charging toner master batch III-1, the weight average particle diameter (D that toner master batch III-1 measures through Coulter Counter method ₄) be 6.8 μ m, the accumulated value of the number benchmark size distribution of the toner master batch of less than 4 μ m is 18.1 number %.

The rerum natura that toner master batch III-1 measures through FPIA-2100, shown in table 16 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

Handle the back, carried out the hydrophobic silica micro mist 1.2 mass parts mixing of dimethyl-silicon oil processing with these toner master batch 100 mass parts with through hexamethyldisilazane with Henschel mixer, be modulated into toner III-1.

The diameter of equivalent circle that this toner III-1 measures through FPIA-2100 be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the toner particle below the 400 μ m is 0.947, is 16.5nm with the average surface roughness of the toner III-1 of sweep type probe microscope mensuration.

(modulation of toner III-2～III-10)

Employed binder resin is as shown in Table 15, and change the micro mist fringe spare of TurboMill as shown in Table 15ly, change the classification condition of cutting apart grading plant more, change the condition of surface modification device more as shown in Table 15ly, in addition, similarly obtain toner master batch III-2～III-10 and toner III-2～III-10 with toner III-1.The rerum natura that toner master batch III-2～III-10 measures through FPIA-2100, and shown in table 16 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.Wherein, the diameter of equivalent circle that toner III-10 measures through FPIA-2100 be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the particle below the 400 μ m is 0.934, the average surface roughness of the toner II-10 that measures through the sweep type probe microscope is 30.0nm.

(modulation of toner III-11)

Employed binder resin is as shown in Table 15, and change the micro mist fringe spare of TurboMill as shown in Table 15ly, change the classification condition of cutting apart grading plant more, make toner master batch moment of obtaining hot blast by 300 ℃, handle, in addition, similarly obtain toner master batch III-11 and toner III-11 with toner III-1.The rerum natura that toner master batch III-11 measures through FPIA-2100, and shown in table 16 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner III-12)

Employed binder resin is as shown in Table 15, and change the micro mist fringe spare of TurboMill as shown in Table 15ly, change the classification condition of cutting apart grading plant more, and utilize the surface modification of surface modification device, in addition, similarly obtain toner master batch III-12 and toner III-12 with toner III-1.The rerum natura that toner master batch III-12 measures through FPIA-2100, and shown in table 16 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner III-13)

Employed binder resin is as shown in Table 15, do not use the mechanical type comminutor, use jet-stream wind formula comminutor, and change the classification condition of cutting apart grading plant more, make toner master batch moment of obtaining hot blast by 300 ℃, handle, in addition, similarly obtain toner master batch III-13 and toner III-13 with toner III-1.The rerum natura that toner master batch III-13 measures through FPIA-2100, and shown in table 16 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner III-14)

Employed binder resin is as shown in Table 15, do not use the mechanical type comminutor, use jet-stream wind formula comminutor, change the classification condition of cutting apart grading plant more, and do not utilize the surface modification of surface modification device, in addition, similarly obtain toner master batch III-14 and toner III-14 with toner III-1.The rerum natura that toner master batch III-14 measures through FPIA-2100, and shown in table 16 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

Table 15

		Mechanical type comminutor air themperature		The size-grade distribution of toner master batch before the surface modification		Surface modification device					The size-grade distribution of toner master batch after the surface modification
													T1(℃)	T2(℃)	Weight average particle diameter (μ m)	4 μ m or the following number cumulative distribution of 4 μ m (number %)	Dispersion rotor peripheral speed (m/sec)	Classification rotor peripheral speed (m/sec)	Cycling time (sec)	Cold wind temperature T 1 (℃)	Classification rotor rear temperature T 2 (℃)	Weight average particle diameter (μ m)	4 μ m or the following number cumulative distribution of 4 μ m (number %)
		Toner master batch III-1	Binder resin III-1	0	45	6.6	25.3	140	83	45	-20	30												6.8	18.1
Toner master batch III-2	Binder resin III-1												0	45	6.5	26.3	140	90	65	-20	35	6.7	19.6
		Toner master batch III-3	Binder resin III-1	0	45	6.5	22.5	135	87	30	-20	28												6.7	17.2
Toner master batch III-4	Binder resin III-1												3	48	6.5	38.0	135	69	50	-12	39	6.8	20.0
		Toner master batch III-5	Binder resin III-1	3	48	6.8	26.6	140	69	50	-12	42												6.7	18.3
Toner master batch III-6	Binder resin III-2												0	45	6.7	37.5	140	69	50	-15	31	6.9	17.8
		Toner master batch III-7	Binder resin III-2	3	48	6.5	38.5	135	69	50	-12	41												6.9	20.3
Toner master batch III-8	Binder resin III-3												0	45	6.7	36.9	145	69	50	-12	44	6.8	17.8
		Toner master batch III-9	Binder resin III-4	0	45	6.6	37.5	145	69	50	-12	42												6.7	18.1
Toner master batch III-10	Binder resin III-5												3	48	6.7	38.2	140	69	50	-12	43	6.7	18.8
		Toner master batch III-11	Binder resin III-5	-20	25	6.8	18.4	Hot blast is handled																6.8	18.1
Toner master batch III-12	Binder resin III-6												-20	25	6.7	19.6	(nothing)					6.7	19.6
		Toner master batch III-13	Binder resin III-7	The jet-stream wind formula is pulverized		6.9	17.2	Hot blast is handled																6.9	16.9
Toner master batch III-14	Binder resin III-8												The jet-stream wind formula is pulverized		6.8	18.2	(nothing)					6.8	18.2

Table 16

	The toner master batch										Toner
															Toner master batch No.	3 μ m or 3 μ m are above, 400 μ m or the following average circularity of 400 μ m	0.6 μ m or 0.6 μ m are above, less than 3 μ m particle rates (number %)	The number accumulated value (number %) of the toner master batch of circularity less than 0.960	Transmitance is 80% o'clock a methanol concentration (volume %)	Transmitance is 50% o'clock a methanol concentration (volume %)	(transmitance is 50% o'clock a methanol concentration)-(methanol concentration when transmitance is 80 %) (volume %)	Average surface roughness (nm)	Maximum height difference (nm)	Surface area (μ m 2)	The main peak molecular weight	Secondary peak or acromion molecular weight	The content of main peak composition (quality %)	The content of secondary peak or acromion composition (quality %)
	Toner III-1	III-1	0.947	14.0	45	52	50	2	17.3	163	1.19	15000	2,200,000	74.1															25.9
Toner III-2															III-2	0.951	3.5	38	51	54	3	15.7	152	1.06	15000	2,200,000	74.3	25.7
	Toner III-3	III-3	0.942	6.5	64	48	54	6	25.1	198	1.20	15000	2,200,000	73.9															26.1
Toner III-4															III-4	0.937	14.8	67	43	51	8	27.5	192	1.26	15000	2,200,000	74.0	26.0
	Toner III-5	III-5	0.965	16.8	25	61	72	11	11.5	103	1.12	15000	2,200,000	73.8															26.2
Toner III-6															III-6	0.935	18.6	64	40	50	10	28.0	212	1.37	28000	2,100,000	69.1	30.9
	Toner III-7	III-7	0.936	19.2	64	38	49	11	29.3	252	1.35	28000	2,100,000	70.3															29.7
Toner III-8															III-8	0.968	20.4	18	60	78	18	9.8	48	1.04	28000	1,900,000	64.1	35.9
	Toner III-9	III-9	0.969	21.2	17	61	76	15	8.3	40	1.03	24000	1,800,000	70.3															29.7
Toner III-10															III-10	0.934	20.3	71	33	46	13	31.2	260	1.38	35000	2,100,000	78.8	21.2
	Toner III-11	III-11	0.975	26.5	14	65	85	20	4.1	35	1.02	35000	2,300,000	80.5															19.5
Toner III-12															III-12	0.930	31.2	71	30	55	25	42.1	311	1.41	33000	44000	49.8	50.2
	Toner III-13	III-13	0.978	35.0	12	60	77	17	3.1	27	1.03	3500	2,100,000	65.5															34.5
Toner III-14															III-14	0.914	49.6	79	42	66	24	69.4	404	1.48	15000	1,000,000	88.0	12.0

＜EXAMPLE III-1～III-9, Comparative Example I II-1～III-5 〉

Below, use the toner that is modulated into, utilize following method to estimate.Evaluation result is shown in table 17.

Use the system laser printer Laser Jet 4300n of Hewlett-Packard society, carry out following evaluation.

(1) consumption of toner

Metewand based on example I-1.

(2) photographic fixing test

With regard to low-temperature fixing, take out the fixation unit of above-mentioned evaluating apparatus, transform, so that can estimate with 1.1 times of processing speeds to common speed.In heat fixing device, 5 ℃ of ground, interval control heater temperature in 150～240 ℃ temperature range, make the fixing roller surface temperature certain, the recording materials that formed the unfixing toner picture are inserted in the photographic fixing pressure contact portion, with the loading of the 4.9kPa image that obtains of wiping 5 times repeatedly, is that 10% or 10% fixing temperature when following as low-temperature fixing with the concentration reduced rate of image color before and after the wiping with fine sandpaper.This temperature is low more, and the low-temperature fixing of toner is good more.As uncertain image, use common paper (75g/m ²), the toner development amount on the paper is set at 0.6mg/cm ²The all black image fixing.

With regard to high-temperature offset resistance, under fixing conditions same as described above, fully inserted recording materials under the heated state on the fixing roller surface, estimate.Output the first half is that the wide horizontal line pattern of 100 μ m (transverse width 100 μ m, at interval 100 μ m) and all black, the latter half be the image of white, the maximum temperature of not polluting on the mensuration white image.As ph test paper ph, use the used in copy machines common paper (60g/m that skew takes place easily ²).Be evaluated as range estimation and confirm the pollution that takes place because of the elevated temperature excursions phenomenon on the image, and the temperature polluted takes place, with this as high-temperature offset resistance.This temperature is high more, and the high-temperature offset resistance of toner is good more.

(3) transfer efficiency

In the ambient temperature and moisture environment (23 ℃, 60%RH), use used in copy machines common paper (A4size:75g/m ²), proceed to 500 since 100 at initial stage interval.Assay method is: in the process of output all black image, stop body, measure the toning dosage of the unit area of developing on the photoconductor drum and be transferred to the interior toning dosage of unit area that is transferred on the material.Then, with being transferred toning dosage on the material, calculate divided by the toning dosage on the photoconductor drum.The result at per 100 intervals is averaged.

(4) spot

Metewand based on example I-1.

(5) sleeve negative ghost image

Metewand based on example I-1.

(6) disperse

Metewand based on example I-1.

(7) image color, photographic fog

Metewand based on example I-1.

Table 17

	Toner No.	Under the ambient temperature and moisture environment				The low temperature and low humidity environment						Hot and humid environment
														Consumption of toner (mg/ opens)	Low-temperature fixing	Anti-skew	Transfer efficiency (%)	Spot	The sleeve negative ghost image	Disperse	Image color		Photographic fog in the time of 18000	Image color
		Initial stage	18000 Zhang Time	Initial stage	In the time of 18000
						EXAMPLE III-1	III-1	40	140	250	95.3	A	A								A	1.49		1.47	0.3	1.50	1.47
EXAMPLE III-2	III-2	41	140	250	93.1									A	A	A	1.47	1.43	0.5	1.48			1.44
						EXAMPLE III-3	III-3	42	140	250	92.8	A	A								A	1.45		1.40	0.8	1.47	1.42
EXAMPLE III-4	III-4	46	140	250	92.6									A	B	B	1.42	1.37	1.2	1.42			1.39
						EXAMPLE III-5	III-5	43	140	250	91.7	A	A								A	1.43		1.36	1.2	1.44	1.36
EXAMPLE III-6	III-6	44	145	250	88.7									B	B	C	1.39	1.31	1.6	1.40			1.33
						EXAMPLE III-7	III-7	47	145	250	89.5	B	C								C	1.38		1.29	1.7	1.36	1.29
EXAMPLE III-8	III-8	50	145	245	86.0									C	C	B	1.32	1.22	2.3	1.25			1.18
						EXAMPLE III-9	III-9	48	140	245	85.6	C	C								C	1.30		1.21	2.6	1.21	1.17
Comparative Example I II-1	III-10	51	150	250	85.9									B	C	D	1.26	1.20	2.5	1.26			1.19
						Comparative Example I II-2	III-11	51	150	250	83.3	D	D								C	1.27		1.21	2.6	1.19	1.10
Comparative Example I II-3	III-12	53	150	230	82.6									C	D	D	1.11	1.04	2.9	1.20			1.09
						Comparative Example I II-4	III-13	54	135	250	81.5	D	D								C	1.12		1.00	2.6	1.11	1.04
Comparative Example I II-5	III-14	56	140	255	80.3									C	D	D	1.07	0.98	3.5	1.06			0.96

＜EXAMPLE IV-1～IV-8, Comparative Example I V-1～IV-4 〉

The binder resin that uses among the embodiment is shown in table 18, and magnetic is shown in table 19, and wax is shown in table 20.

Table 18

	Form	Tg (℃)	The peak molecular weight	Number-average molecular weight Mn	Weight-average molecular weight Mw
						Binder resin IV-1	Styrene-propene acid butyl ester-acrylic copolymer (mass ratio: 77/22/1)	61.8	13600	8300	73000
Binder resin IV-2	Styrene-propene acid butyl ester-maleic acid one butyl ester multipolymer (mass ratio: 69/21/10)	60.1	17600	7700	320000
						Binder resin IV-3	Vibrin (the mol ratio: 32/13/39/16) that bisphenol-A propylene oxide adduct (2mol addition), bisphenol-A ethylene oxide adduct (2mol addition), phthalic acid and trimellitic anhydride polycondensation form	57.6	6800	4700	560000

Table 19

	Form	Si content (quality %)	Number average particle diameter (μ m)	The BET specific surface area	Coercivity H (kA/m)	Saturation magnetization σ s (Am 2/kg)	Residual magnetization σ r (Am 2/kg)
								Magnetic IV-1	Magnetic oxide	1.1	0.19	8.9	5.6	83.8	5.4
Magnetic IV-2	Magnetic oxide	0.0	0.21	11.2	7.2	88.5	9.3

Table 20

	Kind	Fusing point (℃)	Number-average molecular weight	Weight-average molecular weight
					Wax IV-1	Paraffin	75	370	490
Wax IV-2	Paraffin	64	250	360
					Wax IV-3	The Fischer-Tropsch process synthetic wax	104	780	1060
Wax IV-4	The Fischer-Tropsch process synthetic wax	86	510	830
					Wax IV-5	Tygon	121	2320	3510
Wax IV-6	Polypropylene	144	980	8690

(modulation of toner IV-1)

Binder resin IV-1 100 mass parts

Magnetic IV-1 95 mass parts

Monoazo/iron complex compound (T-77, hodogaya chemical industry society system)

2 mass parts

Wax IV-1 5 mass parts

Wax IV-3 2 mass parts

After said mixture carried out premixed with Henschel mixer, carry out melting mixing by the double screw extrusion machine that is heated to 110 ℃, cooled mixing thing is carried out coarse crushing with hammer crusher after, obtain the toner meal and mince.The meal that obtains is minced with mechanical type comminutor Turbo Mill (Turbo industry society system, the coating surface of gyrator and stator contain evanohm (the plating bed thickness 150 μ m of charing chromium, skin hardness HV1050)), condition based on table 21, adjust air themperature, carry out mechanical type and pulverize, it is broken to carry out micro mist, remove with time stage with the micro mist and the meal of grading plant (day iron ore mining industry society system, Elbow Jet grader) during the micro mist that obtains is minced of cutting apart that utilizes attached wall effect more.Weight average particle diameter (the D that the raw material toner master batch that obtains is measured through Coulter Counter method ₄) be 6.6 μ m, the accumulated value that the number of the toner master batch of less than 4 μ m is evenly distributed is 25.4 number %.

Use surface modification device shown in Figure 1 that this raw material toner master batch is carried out surface modification and micro mist is removed.At this moment, in the present embodiment, dispersion rotor top is provided with 16 angle type dishes, and the interval of type dish in angle on guide ring and the dispersion rotor is set at 60mm, and the interval of dispersion rotor and liner is set at 4mm.In addition, be 138m/sec with the rotation round speed setting of dispersion rotor, the fan blower air quantity is set at 30m ³/ min.In addition, the input amount of the broken product of micro mist is set at 300kg, is set at 47sec cycling time.In addition, the refrigerant temperature that flows in the sleeve pipe is set at-15 ℃, cold wind temperature T 1 is set at-20 ℃.In addition, by the revolution of control classification rotor, can make that 0.6 μ m or 0.6 μ m are above, the particle diameter ratio of less than 3.0 μ m is desirable value.Through above-mentioned steps, obtain negative charging toner master batch IV-1, the weight average particle diameter (D that toner master batch IV-1 measures through Coulter Counter method ₄) be that accumulated value that the number of the toner master batch of 6.8 μ m, less than 4 μ m is evenly distributed is 18.0%.The rerum natura that toner master batch IV-1 measures through FPIA-2100, and shown in table 22 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

Handle the back, carried out the hydrophobic silica micro mist 1.2 mass parts mixing of dimethyl-silicon oil processing with these toner master batch 100 mass parts with through hexamethyldisilazane with Henschel mixer, be modulated into toner IV-1.The diameter of equivalent circle that this negative charging toner IV-1 measures through FPIA-2100 be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the toner particle below the 400 μ m is 0.948, is 18.5nm with the average surface roughness of the toner IV-1 of sweep type probe microscope mensuration.

(modulation of toner IV-2～IV-8)

Employed binder resin, magnetic, wax are shown in table 21, and change the micro mist fringe spare of Turbo Mill shown in table 21ly, change the classification condition of cutting apart grading plant more, change the condition of surface modification device more shown in table 21ly, in addition, similarly obtain toner master batch IV-2～IV-8 and toner IV-2～IV-8 with toner IV-1.The rerum natura that toner master batch IV-2～IV-8 measures through FPIA-2100, and shown in table 22 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner IV-9)

Employed binder resin, magnetic, wax are shown in table 21, and change the micro mist fringe spare of Turbo Mill shown in table 21ly, change the classification condition of cutting apart grading plant more, make toner master batch moment of obtaining hot blast by 300 ℃, handle, in addition, similarly obtain toner master batch IV-9 and toner IV-9 with toner IV-1.The rerum natura that toner master batch IV-9 measures through FPIA-2100, shown in table 22 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.In addition, the diameter of equivalent circle that toner IV-9 measures through FPIA-2100 be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the toner particle below the 400 μ m is 0.974, the average surface roughness of the toner IV-9 that measures through the sweep type probe microscope is 4.1nm.

(modulation of toner IV-10)

Employed binder resin, magnetic, wax are shown in table 21, and change the micro mist fringe spare of Turbo Mill shown in table 21ly, change the classification condition of cutting apart grading plant more, and do not utilize the surface modification of surface modification device, in addition, similarly obtain toner master batch IV-10 and toner IV-10 with toner IV-1.The rerum natura that toner master batch IV-10 measures through FPIA-2100, and shown in table 22 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner IV-11)

Employed binder resin, magnetic, wax are shown in table 21, do not use the mechanical type comminutor, use jet-stream wind formula comminutor, change the classification condition of cutting apart grading plant more, make toner master batch moment of obtaining hot blast by 300 ℃, handle, in addition, similarly obtain toner master batch IV-11 and toner IV-11 with toner IV-1.The rerum natura that toner master batch IV-11 measures through FPIA-2100, and shown in table 22 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

(modulation of toner IV-12)

Employed binder resin, magnetic, wax are shown in table 21, do not use the mechanical type comminutor, use jet-stream wind formula comminutor, change the classification condition of cutting apart grading plant more, and do not utilize the surface modification of surface modification device, in addition, similarly obtain toner master batch IV-12 and toner IV-12 with toner IV-1.The rerum natura that toner master batch IV-12 measures through FPIA-2100, and shown in table 22 corresponding to the measured value of the methanol concentration value of the transmitance of 780nm wavelength light and sweep type probe microscope.

Table 21

	Binder resin (mass parts)	Magnetic (mass parts)	Wax (mass parts)		Mechanical type comminutor air themperature		The size-grade distribution of toner master batch before the surface modification		Surface modification device					The size-grade distribution of toner master batch after the surface modification
																T1 (℃)	T2 (℃)	Weight average particle diameter (μ m)	4 μ m or the following number cumulative distribution of 4 μ m (%)	Dispersion rotor peripheral speed (m/sec)	Classification rotor peripheral speed (m/sec)	Cycling time (sec)	Cold wind temperature T 1 (℃)	Classification rotor rear temperature T 2 (℃)	Weight average particle diameter (μ m)	4 μ m or the following number cumulative distribution of 4 μ m (%)
					Toner master batch IV-1	IV-1 (100)	IV-1 (95)	IV-1 (5)	IV-3 (2)	0	45	6.6	25.4	138	82												47	-20	31	6.8	18.0
Toner master batch IV-2	IV-1 (100)	IV-1 (95)	IV-1 (5)	IV-3 (2)												0	45	6.6	26.2	138	91	67	-20	36	6.7	19.7
					Toner master batch IV-3	IV-1 (100)	IV-1 (95)	IV-1 (5)	IV-5 (2)	0	45	6.7	23.1	138	88												32	-20	27	6.8	17.6
Toner master batch IV-4	IV-1 (100)	IV-1 (95)	IV-4 (3)	IV-3 (4)												0	45	6.6	25.3	143	86	47	-15	36	6.8	18.2
					Toner master batch IV-5	IV-1 (100)	IV-1 (95)	IV-4 (2)	IV-6 (4)	0	45	6.7	28.1	132	75												52	-15	30	6.8	17.3
Toner master batch IV-6	IV-1 (100)	IV-1 (95)	IV-2 (4)	IV-4 (3)												3	48	6.5	31.0	146	75	52	-15	41	6.7	17.8
					Toner master batch IV-7	IV-2 (100)	IV-1 (95)	IV-2 (6)	IV-5 (4)	3	48	6.6	34.6	148	68												52	-12	47	6.8	18.1
Toner master batch IV-8	IV-3 (100)	IV-2 (95)	IV-6 (6)													3	48	6.5	38.2	148	68	57	-12	48	6.7	19.5
					Toner master batch IV-9	IV-1 (100)	IV-1 (95)	IV-2 (2)	IV-5 (5)	-20	25	6.8	18.3	Hot blast is handled													6.8	18.2
Toner master batch IV-10	IV-1 (100)	IV-1 (95)	IV-2 (2)	IV-5 (5)															-20	25	6.8	19.1	(nothing)						6.8	19.5
					Toner master batch IV-11	IV-1 (100)	IV-2 (95)	IV-5 (7)		The jet-stream wind formula is pulverized		6.9	16.8	Hot blast is handled														6.9			16.8
Toner master batch IV-12	IV-1 (100)	IV-2 (95)	IV-5 (7)																The jet-stream wind formula is pulverized		6.8	18.1	(nothing)						6.8	18.1

Table 22

	The toner master batch										Toner
															Toner master batch No.	3 μ m or 3 μ m are above, 400 μ m or the following average circularity of 400 μ m	0.6 μ m or 0.6 μ m are above, the particle rate (number %) of less than 3 μ m	The number accumulated value (number %) of the toner master batch of circularity less than 0.960	Transmitance is 80% o'clock a methanol concentration (volume %)	Transmitance is 50% o'clock a methanol concentration (volume %)	(transmitance is 50% o'clock a methanol concentration)-(transmitance is 80% o'clock a methanol concentration) (volume %)	Average surface roughness (nm)	Maximum height difference (nm)	Surface area (μ m 2)	Initial temperature (℃)	Final temperature (℃)	The difference of initial temperature and final temperature (℃)	Peak temperature (℃)
	Toner IV-1	IV-1	0.948	14.5	47	51	53	2	14.9	133	1.21	67	115	48															81
Toner IV-2															IV-2	0.952	3.6	38	53	56	3	12.3	109	1.17	67	115	48	81
	Toner IV-3	IV-3	0.940	6.4	64	47	50	3	20.2	129	1.25	65	128	63															121
Toner IV-4															IV-4	0.953	10.6	32	60	64	4	11.1	107	1.16	79	116	37	106
	Toner IV-5	IV-5	0.938	13.8	64	41	46	5	23.3	188	1.28	80	148	68															128
Toner IV-6															IV-6	0.958	15.6	26	62	69	7	8.6	89	1.05	58	91	33	68
	Toner IV-7	IV-7	0.964	19.2	21	63	72	9	7.5	70	1.03	52	131	79															64
Toner IV-8															IV-8	0.968	23.0	17	61	78	17	5.3	48	1.01	130	152	22	145
	Toner IV-9	IV-9	0.974	27.8	14	63	83	20	4.0	38	1.01	55	138	83															131
Toner IV-10															IV-10	0.927	31.3	75	31	54	23	44.8	372	1.53	55	138	83	131
	Toner IV-11	IV-11	0.978	37.6	10	58	75	17	3.4	30	1.01	126	141	15															131
Toner IV-12															IV-12	0.910	50.9	80	44	69	25	64.7	495	1.72	126	141	15	131

Below, use the toner IV-1～IV-12 that is modulated into, utilize following method to estimate.Evaluation result is shown in table 23.

Use the system laser printer Laser Jet 4300n of Hewlett-Packard society, carry out following evaluation.

(1) image color, photographic fog

Metewand based on example I-1.

(2) consumption of toner

Metewand based on example I-1.

(3) sleeve negative ghost image

Metewand based on example I-1.

(4) disperse

Metewand based on example I-1.

(5) spot

Metewand based on example I-1.

(6) result from the bad image deflects of cleaning

In the ambient temperature and moisture environment, carry out long duration test, the print image of visual assessment output.

A: do not take place fully

B: small pollution takes place, but no problem in practicality

C: mottled, wire pollution takes place, take place repeatedly, disappear

D: pollute, do not disappear

(7) low-temperature fixing, high-temperature offset resistance

Above-mentioned toner is put into imaging processing box, Hewlett-Packard society system laser printer Laser Jet 4300n is transformed into can be from the outside surface temperature of the warm-up mill of heating and pressurizing roller fuser be changed in 120～250 ℃, the limit is 5 ℃ of change design temperatures at interval, the limit the low temperature and low humidity environment (15 ℃, 10%RH) in the output image sample.The processing speed that need to prove Laser Jet 4300n when carrying out the low-temperature fixing test is 1.2 times of speed, estimates under the condition stricter than low-temperature fixing property.

Low-temperature fixing

Apply the loading of 4.9kPa, with soft thin paper wiping photographic fixing image, with the image color reduced rate (%) before and after the wiping be 10% or 10% minimum temperature when following as minimum fixing temperature, estimate.Ph test paper ph is the stricter used in copy machines common paper (90g/m of fixation performance requirement ²).

High-temperature offset resistance

The sample image of output image area occupation ratio about 5%, the pollution level on the evaluation map picture.Measure the maximum temperature of not polluting on the image.Need to prove that ph test paper ph is the used in copy machines common paper (60g/m that skew takes place easily ²).

Table 23

		The low temperature and low humidity environment				Hot and humid environment		The ambient temperature and moisture environment				Low-temperature fixing	High-temperature offset resistance
														18000 image colors after durable	18000 photographic fogs after durable	Negative sleeve ghost image	Spot	9000 image colors after durable	Long afterwards image color in the time of 18000	18000 image colors after durable	Consumption of toner (mg/ opens)	Disperse	Image contamination
		EXAMPLE IV-1	Toner IV-1	1.41	1.4	A	A	1.36	1.39	1.40	41													A	A	145	245
EXAMPLE IV-2	Toner IV-2											1.40	1.3	A	A	1.34	1.37	1.39	41	A	A	145	245
		EXAMPLE IV-3	Toner IV-3	1.39	1.8	A	A	1.33	1.37	1.37	42													B	A	145	245
EXAMPLE IV-4	Toner IV-4											1.39	1.9	A	A	1.32	1.35	1.36	44	A	A	150	245
		EXAMPLE IV-5	Toner IV-5	1.39	2.2	A	A	1.33	1.35	1.37	46													B	A	150	245
EXAMPLE IV-6	Toner IV-6											1.37	2.2	B	A	1.30	1.32	1.34	44	A	B	140	235
		EXAMPLE IV-7	Toner IV-7	1.35	2.3	B	B	1.29	1.31	1.33	44													A	B	140	240
EXAMPLE IV-8	Toner IV-8											1.33	2.5	B	B	1.26	1.30	1.31	46	B	B	155	245
		Comparative Example I V-1	Toner IV-9	1.22	3.5	C	D	1.11	1.17	1.19	50													C	D	155	235
Comparative Example I V-2	Toner IV-10											1.19	3.6	C	C	1.09	1.16	1.17	51	D	D	155	235
		Comparative Example I V-3	Toner IV-11	1.16	3.8	D	D	1.06	1.13	1.15	52													C	D	160	235
Comparative Example I V-4	Toner IV-12											1.15	3.9	D	C	1.05	1.10	1.13	54	D	D	160	235

Claims (10)

1, a kind of toner, it is the toner that contains toner master batch and inorganic particles, this toner master batch contains binder resin at least, magnetic, it is characterized by, this toner master batch is the composition that contains binder resin and magnetic by melting mixing at least, pulverizing the mixing thing that obtains then makes, with diameter of equivalent circle is 3 μ m or more than the 3 μ m, the following toner master batch of 400 μ m or 400 μ m is a determination object, the average circularity of the toner master batch that records with streaming particle image determinator is more than 0.935 or 0.935, less than 0.970, the average surface roughness that this toner master batch is measured through the sweep type probe microscope is 5.0nm or more than the 5.0nm, not enough 35.0nm, for the wettability of methanol mixed solvent, the transmitance of wavelength 780nm light is that the methanol concentration that 80% o'clock methanol concentration and transmitance are at 50% o'clock is 35～75 volume % for this toner master batch.

2, toner as claimed in claim 1, it is characterized by, this toner master batch is 0.6 μ m or more than the 0.6 μ m, in the number benchmark size distribution of 400 μ m or the toner master batch below the 400 μ m, 0.6 μ m or 0.6 μ m are above, the toner master batch ratio of less than 3 μ m is 0 number % or 0 number % is above, less than 20 number % through the diameter of equivalent circle that streaming particle image determinator is measured.

3, toner as claimed in claim 1 is characterized by, and the number accumulated value of the toner master batch of circularity less than 0.960 is above, the less than 70 number % of 20 number % or 20 number % in this toner master batch.

4, toner as claimed in claim 1 is characterized by, the maximum height difference that this toner master batch is measured through the sweep type probe microscope be 50nm or more than the 50nm, not enough 250nm.

5, toner as claimed in claim 1 is characterized by, and this toner master batch is 1.03 μ m through the surface area of the toner master batch surface 1 μ m square area that the sweep type probe microscope is measured ²Or 1.03 μ m ²More than, less than 1.33 μ m ²

6, toner as claimed in claim 1, it is characterized by, this inorganic particles contains the different inorganic oxide particle more than 2 kinds or 2 kinds of particle diameter, 1. the number average particle diameter of the primary particle of the first inorganic oxide particle A is 7nm or more than the 7nm, not enough 20nm, and inorganic oxide particle A is 0.5～2.0 with respect to the lining rate A of toner master batch, 2. the number average particle diameter of the primary particle of the second inorganic oxide particle B is 20nm or more than the 20nm, 50nm or below the 50nm, and inorganic oxide particle B is 0.02～0.15 with respect to the lining rate B of toner master batch, 3. the particle diameter difference of the first inorganic oxide particle A and the second inorganic oxide particle B is 10nm or more than the 10nm, 35nm or below the 35nm, the shared ratio X of inorganic oxide particle B with respect to the lining rate (A+B) of inorganic oxide total amount is 1.0～14.0%, X={ lining rate B/ (lining rate A+ lining rate B) wherein } * 100

When if the average circularity of this toner master batch is Y, the relation that satisfies following formula with respect to the shared ratio X of the inorganic oxide B of the lining rate of inorganic oxide total amount and Y,

10×10 ^-3×X-0.925≤Y≤3.6×10 ^-3×X+0.915。

7, toner as claimed in claim 1 is characterized by, and in the chromatogram that the gel permeation chromatography of the solvable composition of tetrahydrofuran in utilizing toner obtains, molecular weight is 3.0 * 10 ³Or 3.0 * 10 ³More than, less than 3.0 * 10 ⁴The zone in have main peak, and molecular weight 5.0 * 10 ⁴Or 5.0 * 10 ⁴More than, less than 1.0 * 10 ⁸The zone in have a secondary peak or acromion at least.

8, toner as claimed in claim 1, it is characterized by, toner through differential scanning calorimeter, be DSC measure intensification the time the DSC curve in, have an endothermic peak at least, the initial temperature of this endothermic peak and the temperature difference of final temperature are more than 20 ℃ or 20 ℃, 80 ℃ of less thaies.

9, toner as claimed in claim 1 is characterized by, toner through differential scanning calorimeter, be DSC measure intensification the time the DSC curve in, more than 60 ℃ or 60 ℃, have an endothermic peak at least in the zone of 140 ℃ of less thaies.

10, toner as claimed in claim 1, it is characterized by, the diameter of equivalent circle of measuring through streaming particle image determinator be 3 μ m or more than the 3 μ m, the average circularity of 400 μ m or the toner particle below the 400 μ m is 0.935 or 0.935 or more, less than 0.970, this toner particle through the average surface roughness of sweep type probe microscope mensuration be 10.0nm or more than the 10.0nm, not enough 26.0nm.

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