CN1873553A - Image forming apparatus - Google Patents

Image forming apparatus Download PDF

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Publication number
CN1873553A
CN1873553A CN 200610092307 CN200610092307A CN1873553A CN 1873553 A CN1873553 A CN 1873553A CN 200610092307 CN200610092307 CN 200610092307 CN 200610092307 A CN200610092307 A CN 200610092307A CN 1873553 A CN1873553 A CN 1873553A
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toner
image
colour toners
particle
transparent toner
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CN 200610092307
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CN100517099C (en
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小俣晴彦
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Canon Inc
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Canon Inc
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Abstract

An image forming apparatus including: colored toner image forming devices each developing an electrostatic image with colored toner to form a colored toner image; a transparent toner image forming device developing an electrostatic image with transparent toner to form a transparent toner image; a transfer device superimposing and transferring the colored toner images and the transparent toner image on a transfer medium; and a fixing device fixing the superimposed toner images on the transfer medium. An image forming operation by the transparent toner image forming device is controlled in such a manner that the heights of the superimposed toner images fixed by the fixing device are substantially constant. The transparent toner has an absolute value for a charge amount per unit weight smaller than an absolute value for the charge amount of each of the colored toners per unit weight.

Description

Imaging device
Technical field
The present invention relates to a kind of imaging device, this equipment is by for example electrophotographic printer method or electrostatic recording method, forms electrostatic image according to the view data of original copy on image bearing member; With including developer developing electrostatic image colour toners and that be charged to predetermined polarity, so that toner image to be provided; Transfer printing toner image on recording materials; And the photographic fixing image is to provide the coloured image with gloss.The present invention relates to the imaging device such as printer, duplicating machine or fax.
Background technology
Fig. 1 has shown an example according to the color-image forming apparatus of electrophotographic printer method.Below the imaging device of this example will be described briefly according to Fig. 1.
The color electrophotographic image forming apparatus 100 of this example has five imaging moiety P (Pa, Pb, Pc, Pd and Pe), and they are set parallel to each other in the horizontal direction.Each imaging moiety P (Pa, Pb, Pc, Pd and Pe) has a corresponding cydariform electrophotographic photosensitive member (being designated hereinafter simply as " photosensitive drums ") 1 (1a, 1b, 1c, 1d, and 1e) as image bearing member.
Each photosensitive drums 1 (1a, 1b, 1c, 1d and 1e) is all rotated by the drive unit clockwise direction among Fig. 1.In addition, each photosensitive drums 1 (1a, 1b, 1c, 1d, and 1e) is provided with at its periphery: a corresponding charging device 2 (2a, 2b, 2c, 2d and 2e), be used for being charged in the surface of photosensitive drums 1 equably, a corresponding exposure device 3 (3a, 3b, 3c, 3d and 3e), a corresponding developing apparatus 4 (4a, 4b, 4c, 4d and 4e), and a corresponding cleaning device 5 (5a, 5b, 5c, 5d and 5e).
In addition, also provide the conveying belt 7 that serves as the recording materials conveying device, be used for carrying recording materials S to each imaging moiety P (Pa, Pb, Pc, Pd and Pe).Conveying belt 7 tensioning between driver roller 81 and backing roll 82 and 83, and rotating by the arrow indicated direction.
In each imaging moiety P (Pa, Pb, Pc, Pd and Pe), charged equably by a charging device 2 (2a, 2b, 2c, 2d and 2e) of correspondence in the surface of any one photosensitive drums 1 (1a, 1b, 1c, 1d and 1e), then, exposure device 3 (3a, 3b, 3c, a 3d by correspondence, and 3e), thereby forms electrostatic latent image with the light image irradiation.
The electrostatic latent image of each photosensitive drums 1 (1a, 1b, 1c, 1d and 1e) is developed by a developing apparatus 4 (4a, 4b, 4c, 4d and 4e) of correspondence and is visual picture, that is, and and toner image.
That is, each developing apparatus 4 (4a, 4b, 4c, 4d and 4e) is filled with cyan, magenta, yellow, black or the transparent toner of scheduled volume by the feeding mechanism (not shown), as developer.Developing apparatus 4 (4a, 4b, 4c, 4d and 4e) is gone up the development sub-image in photosensitive drums 1 (1a, 1b, 1c, 1d and 1e), image visual being turned to cyan toner image, magenta toner image, yellow toner image, black toner image, and the transparent toner image.
Recording materials S is stored in the recording materials box 10, and is provided to conveying belt 7 by a plurality of conveying rollers 11 and alignment roller 12 from this box.Recording materials S is transferred and is with 7 to carry, and is fed to continuously and the relative transfer section of photosensitive drums 1 (1a, 1b, 1c, 1d and 1e).The transfer printing blade 6 (6a, 6b, 6c, 6d and 6e) that toner image is provided as transfer device for transfer section is transferred on the material.
Next, above it transfer printing the recording materials S of toner image separate with conveying belt 7, separated recording materials S is transferred part 13 and is transported to fixing device 9.
To transfer printing above it four kinds of coloured toner images and transparent toner record images material S carry out photographic fixing and handle so that mix toner image, and with image fixing in recording materials S.So, form panchromatic duplicate pictures, and it is discharged into page or leaf discharging pallet 14.
Fig. 2 has shown the example of each developing apparatus 4 (4a, 4b, 4c, 4d and 4e) of the imaging device that is used to have said structure.All developing apparatus 4a, 4b, 4c, 4d and 4e have identical structure.Below developing apparatus 4 will be described.
In this example, for each developing apparatus 4 all provides development sleeve 40 as developer bearing part, magnetic roller 41, regulates parts 42, developer conveying screw rod 43 and 44 or the like.
Development sleeve 40 has magnetic roller 41, and is wherein fixing and comprised a plurality of magnetic poles (S1, N1, S2, N2 and N3), and the rotation development sleeve simultaneously, keeps predetermined developments interval therein between the sleeve of a photosensitive drums 1 and the peripheral surface.Regulate parts 42 and have rigidity and magnetic, and can arrange in every way.For example, these parts can be arranged so that between these parts and development sleeve 40 and to keep predetermined interval, and perhaps it can carry out pressure with development sleeve 40 and contacts under predetermined load, does not wherein insert developer between these parts and sleeve.
Can use any developing method.Specifically, preferable methods relates to: apply alternating voltage to development sleeve 40, to form AC field at developing regional A (in this zone, development sleeve 40 and photosensitive drums 1 are toward each other); Under magnetic brush and photosensitive drums 1 state of contact, develop.
Wish that the distance (S-D distance) between development sleeve 40 and the photosensitive drums 1 is 100 to 1,000 μ m, be used to prevent that carrier from adhering to, and be used for improving the some reproducibility.When this distance during less than 100 μ m, developer is easy to be provided deficiently, and therefore, image density reduces.When this distance surpasses 1,000 μ m, come the magnetic line of force expansion of autography magnetic pole S1.As a result, the density of magnetic brush reduces, some reproducibility variation, and perhaps, carrier so, takes place and adheres in constraining force reduction on the carrier easily.
The P-to-P voltage of AC field is preferably 300 to 3,000V, and the frequency of AC field is 500 to 10,000Hz.Can correspondingly select and use in P-to-P voltage and the frequency each according to process.In the case, the example of waveform that is used to form the AC bias of AC field comprises triangular wave, square wave, sine wave, and by changing the waveform that duty ratio obtains.Preferably carry out development, so that the variation in the speed of reply formation toner image by apply development bias voltage (intermittently exchanging superimposed voltage) to development sleeve with discontinuous AC bias.When the voltage that applies is lower than 300V, almost can not obtain enough image densities, also can successfully collect the vaporific toner (fog toner) of non-image part.When voltage surpasses 3, during 000V, sub-image is by the magnetic brush multilated, and picture quality may reduce thus.
In addition, use tow-component developer can reduce demist voltage (Vback), so, can reduce the once charging (primary charging) of each photosensitive drums 1 with the toner that successfully charges.As a result, can prolong the life-span of each photosensitive drums 1.The value of Vback is preferably 200V or littler, is more preferably, and is 150V or littler, though preferred range is different and different along with toning system.Use 100 to 400V development contrast, so that can obtain enough image densities.Development contrast is preferably high as much as possible, and is preferably 300V or higher, so that the level (gradation) of shadow tone that can stabilized image.
When frequency is lower than 500Hz, when returning, the toner that contacts with each photosensitive drums 1 do not apply enough vibrations to development sleeve, so, photographic fog (fog) takes place easily, though the photographic fog degree is relevant with processing speed.When frequency surpasses 10, during 000Hz, toner can not be followed electric field, and therefore, picture quality also reduces easily.
In aforesaid such conventional imaging equipment, the white portion in the document image that is produced does not use toner.Directly determined the visual properties such as color and gloss of document image as the optical characteristics of the paper of recording materials.On the other hand, wherein superpose and most of visual properties of having write down the part of a large amount of black toners or C, M, Y and K colour toners (as concentrating the brown toner) are to be determined by the optical characteristics of toner.
As for the gloss by the document image of exporting such as imaging device as described above, under the situation as described above of white and black, black generally has higher gloss than white.This is because as mentioned above, the gloss of the toner generally gloss than paper is higher.
As a result, produced a problem: picture quality is output that the gloss difference between the pixel damages significantly in the image.
In addition, be approximately 5 to 10 μ m at the height with highdensity part toner, so, produced a problem: the unevenness of toner image is remarkable especially, and this causes picture quality to reduce.
Imaging device as the gloss of having considered aforesaid toner and unevenness, for example, describe as JP 07-266614 A, proposed such method: the height that calculates the image section place toner that will on the surface of recording materials, form by toner high computational part according to view data; Calculate the amount that will be printed on the transparent toner on each part by transparent toner printing amount calculating section according to the difference between the maximal value of the toner height of image section and toner height with gloss; By the needed amount print transpatent of the unevenness toner of eliminating the toner on the toner image so that the article of record to be provided; Gloss is provided for the article of record; And eliminate surface heterogeneity so that glossiness image to be provided.
Yet the method by transparent toner smoothing surface relates to uses the transparent toner of the amount identical with the amount of the maximum toning dosage that colour toners is arranged to form image.
In other words, must use the transparent toner of the amount identical to form image in the part that forms image by transparent toner with the maximum toning dosage that produces by the four kinds of colors (cyan, magenta, yellow and black) that suitably superpose.
For example, relating to stack two or more have under the situation of Flame Image Process of colour toners having used, is 0.5mg/cm when each has the maximum toning dosage of colour toners 2The time, for imaging, must once use 1.0mg/cm 2Or more transparent toner.
Be similar to and adopt the formation method have colour toners to carry out imaging, when the transparent toner of an imaging moiety by the amount bigger than the amount that colour toners is arranged forms image, have difficulties.
Provide detailed description below with reference to Fig. 3.
To be described as example with the electromotive force of each photosensitive drums 1 in the common imaging and the electromotive force of development sleeve 40 below.When environment (23 ℃, 50%Rh) in the quantity of electric charge that colour toners is arranged (being designated hereinafter simply as " triboelectricity ") of per unit weight when being approximately-30 μ C/g, apply high voltage to each charging device 2, so that the surface potential of photosensitive drums 1 is controlled as-650V.
Simultaneously ,-the DC component of 500V and the AC compounent of 1.2kV p-p are superposeed each other and the AC bias that obtains is applied to development sleeve 40.When each photosensitive drums 1 during to laser explosure, photosensitive drums demonstrates in the position that has formed the electrostatic latent image that serves as the image with maximal density to be had-the photoelectricity gesture of 100V.
Therefore, has 0.5mg/cm when development 2Maximum bearing capacity colour toners is arranged the time, development contrast is set to about 400V.
When using under the situation of transparent toner in such structure, if the triboelectricity of hypothesis transparent toner is about-30uC/g, identical with the situation of the triboelectricity that colour toners is arranged, 1.0mg/cm then develops 2The needed electric potential difference of transparent toner be about 800V.In the case, on each photosensitive drums 1, must form the sub-image electromotive force of about 900V.It is unpractical providing high like this electromotive force to common photosensitive drum 1, because owing to the performance of photosensitive drums causes the charging performance instability.
For example, also have following control available: the development contrast according to the maximum electrical potential of the quantity of electric charge of each photosensitive drums 1 is 400V, this value is defined as the value for the transparent toner setting, and the maximum toning dosage according to colour toners is arranged has the development contrast of colour toners to be set to 200V.Yet in the case, produced such problem: the level that the shadow tone of colour toners is arranged is unsettled.
Summary of the invention
According to the present invention, under stable image-forming condition, can obtain the maximum bearing capacity of transparent toner.
To achieve these goals, imaging device of the present invention comprises:
Some have a colour toners imaging device, and each device all forms electrostatic image, and with this electrostatic image of coloured toner development, to be formed with the colour toners image; This has the colour toners imaging device to form toner image by the colour toners that has that differs from one another,
The transparent toner imaging device, this device forms electrostatic image, and with transparent toner this electrostatic image that develops, to form the transparent toner image; The quantity of electric charge of the per unit weight of transparent toner has the quantity of electric charge of the per unit weight of colour toners less than each,
Transfer device, this device is with coloured toner image and transparent toner image overlay and be transferred to pumped (conveying) medium.
Description of drawings
Fig. 1 is the view that has shown according to the schematic construction of imaging device of the present invention;
Fig. 2 is the view of schematic construction that has shown an example of developing apparatus;
Fig. 3 is the view that developing method has been described;
Fig. 4 has illustrated by the view of transparent toner elimination to an example of the influence of the difference of height (step) of image;
Fig. 5 is the view that an example of the imaging control operation of carrying out by transparent toner has been described;
Fig. 6 is the schematic views that the method for the triboelectricity that is used to measure toner has been described and has been used to measure the equipment of triboelectricity; And
Fig. 7 is the view that has shown according to the schematic construction of another example of imaging device of the present invention.
Embodiment
Below with reference to the accompanying drawings than describing in greater detail according to imaging device of the present invention.
(total of imaging device)
Employed imaging device and earlier in respect of figures 1 described conventional imaging equipment have same structure and function in this example.Therefore, quote the description of front, and omitted the detailed description that repeats.
In other words, as shown in Figure 1, the imaging device 100 of this example has five imaging moiety P (Pa, Pb, Pc, Pd and Pe), and they are set parallel to each other in the horizontal direction.Each imaging moiety P (Pa, Pb, Pc, Pd and Pe) has a corresponding cydariform electronic photographic photosensitive component, that is, photosensitive drums 1 (1a, 1b, 1c, 1d and 1e) is as image bearing member, and these photosensitive drums can be rotated.
In addition, each photosensitive drums 1 (1a, 1b, 1c, 1d and 1e) all is provided with at its periphery: a corresponding charging device 2 (2a, 2b, 2c, 2d and 2e), be used for being charged in the surface of photosensitive drums 1 equably, a corresponding exposure device 3 (3a, 3b, 3c, 3d and 3e), a corresponding developing apparatus 4 (4a, 4b, 4c, 4d and 4e), and a corresponding cleaning device 5 (5a, 5b, 5c, 5d and 5e).
In each imaging moiety P (Pa, Pb, Pc, Pd and Pe), the surface of any one photosensitive drums 1 (1a, 1b, 1c, 1d and 1e) that the charging device 2 (2a, 2b, 2c, 2d and 2e) that quilt is corresponding charges is equably shone with light image by an exposure device 3 (3a, 3b, 3c, 3d and 3e) of correspondence, thereby forms electrostatic latent image.Imaging moiety Pa, Pb, Pc and Pd have the colour toners imaging device, and imaging part Pe is the transparent toner imaging device.
The electrostatic latent image of each photosensitive drums 1 (1a, 1b, 1c, 1d and 1e) is developed by a developing apparatus 4 (4a, 4b, 4c, 4d and 4e) of correspondence and is visual picture, that is, and and toner image.
Each developing apparatus 4 (4a, 4b, 4c, 4d and 4e) is filled with cyan, magenta, yellow, black or the transparent toner of scheduled volume by the feeding mechanism (not shown), as developer.Corresponding developing apparatus 4a, 4b, 4c, 4d and the 4e sub-image that develops on photosensitive drums 1a, 1b, 1c, 1d and 1e is to turn to image visual cyan toner image, magenta toner image, yellow toner image, black toner image and transparent toner image.
Below, the toner of respective color is abbreviated as follows: cyan toner is abbreviated as the C toner, and magenta toner is abbreviated as the M toner, and Yellow toner is abbreviated as the Y toner, black toner is abbreviated as the K toner, and transparent toner is abbreviated as the T toner.
Toner image on the corresponding photosensitive drums 1 (1a, 1b, 1c, 1d and 1e) is transferred on the recording materials S that is carried by conveying belt 7.In addition, above it transfer printing the recording materials S of toner image of respective color, be equipped with the fixing device 9 of fixing roller 91 and pressure roll 92 under heat and pressure, toner image to be carried out photographic fixing.Then, the recording materials image that is used as record is discharged into the outside of equipment.
Imaging device has wherein by cyan, magenta, yellow, and the colour toners that has of black carries out the pattern of imaging and the pattern by carrying out imaging at the image-region stack transparent toner that has formed these coloured toner images wherein.
Also can use any outside cyan, magenta, yellow or the black toner that colour toners is arranged.For example, can adopt following process: a kind of toner in use and those toners has same hue and has low-density toner, use has highdensity toner and has two kinds of toners of low-density toner and form image, so that improve reproducibility.
(forming the transparent toner image)
To form the method for transparent toner image as feature description of the present invention below, and wherein use transparent toner to make height (that is, the height of the toner that on recording materials S, the forms) homogenising of the image of record, so that eliminate unevenness.
Fig. 4 shown recording materials S, formed the part of the image R of record thereon, that is, and the article SR of record.
Recording materials S is paper, ohp film or the like.In addition, in this example, the article SR of record has been meant as forming of the result of the imaging operation of electrophotographic image forming 100 the recording materials S of the image R of record thereon.
As shown in Figure 4, according to this example, information based on the height (h) of the document image R on the recording materials S that has write down record images article SR thereon, carry out addition record by transparent toner T by this way, promptly, make that the height of entire image is mutually the same in the maximal value (H) of height (h) of the image R that writes down in the image-region and this zone, thereby make the surface of article SR of record level and smooth basically the height substantial constant of toner image (make).So, can provide uniform gloss, and the image recording of the picture quality of improvement can be provided.Here employed term " basically level and smooth (substantial constant) " is meant in short transverse, and toner image is changed to 3 μ m or littler state after the photographic fixing.
The information of the height of the image of relevant record (toner image) R for example can be determined by following method: relate to according to picture signal method of reading information from the table of storage in advance, relate to by using and determine the method for information, or relate to method with contact or non-contact mode measuring height by calculating from the essential information of table.
Here employed term " essential information " is meant the needed information of height that recording materials S goes up toner image of calculating, such as the bearing capacity of toner image with respect to the level (level of electrostatic image) of record, the flowability of toner image, and the structured value of recording materials S.
Wish whole height basically with the height of the image R of record (h1, h2, h3, h4 ...) maximal value (H) identical.
By means of determining the color reproduction scope, define the maximum bearing capacity of colour toners by the appropriate combination of cyan, magenta, yellow and black.Generally speaking, designed image by this way promptly, makes maximum bearing capacity be approximately the twice that solid color wherein provides the toning dosage of maximal density.When the color reproduction scope of design broad, can design maximum bearing capacity, be about 2.5 times of maximum bearing capacity of toning dosage.
Therefore, for the height that makes integral body can be identical with maximal value, transparent toner, promptly, the T toner must be printed on so-called " white portion " to be approximately each twice that colour toners (C, M, Y and K toner) is arranged or higher amount, in this part, in image-region, be not provided with color image (by C, M, Y and K toner).The amount of the T toner that use in the case, and the printing amount of toner increase in normal image sharp.Therefore, highly not necessarily must be identical with maximal value.The amount of T toner can reduce to the picture quality degree of variation indistinctively that makes.
Can use basically the method identical to determine to be provided with the position and the toning dosage of transparent toner (T toner) with method described in the JP 07-266614 A.
The method of the amount of the position of determining to be provided with the T toner and toner is described below with reference to Fig. 5.
Rgb signal corresponding to each pixel of image all is recorded in from the view data 102 of view data reading section 101 inputs by 256 gray levels.The rgb signal of each pixel all is converted to four kinds of printing amounts that the minimum printing unit of colour toners is arranged by RGB-CMYK conversion portion 103.
RGB-CMYK conversion portion 103 for example can use and relate to the method for using 3 * 4 masking matrixs, or such method: by 3 * 3 matrixes rgb signal is converted to the CMY signal; Carry out so-called ink-jet by 3 * 4 matrixes, to produce Chinese ink (Chinese ink) K.In addition, in this conversion, can also use so-called " pseudo-halftone representation ".Each pixel of R, G and B can not printed unit with the minimum of C, M, Y and K toner and become relation one to one.In this case, calculate the printing amount of each toner of C, the M, Y and the K toner that are used for minimum printing unit.
CMYK toner printing portion 104 at the described above-mentioned imaging device of reference Fig. 1 and 2, promptly, imaging moiety P (Pa, Pb, Pc, Pd), according to the printing amount of each toner in C, M, Y and the K toner, form the toner image of corresponding four kinds of colors by the electrophotographic printer method.
The printing amount that toner high computational part 105 is used for each toner of minimum C, M, Y and the K toner of printing unit by calculating be identified for minimum print unit the colour toners height arranged.
Toner maximum height calculating section 106 is determined the maximum height of the toner of the printing in the specify image zone according to being used for the minimum colour toners height that has of printing unit.
According to the present invention, for height (that is the height of the toner image that, on recording materials, the forms) homogenising of the image that makes record, to eliminate unevenness, use transparent toner, promptly the T toner comes the inhomogeneous part of coloured toner image is filled.
In this example, In view of the foregoing, T toner printing amount calculating section 107 is determined the toner maximum heights and is used for each minimum poor between the colour toners height of having of printing unit.This difference is defined as printing with minimum the T toner height of unit.Next, calculate the T toner printing amount that is used to obtain this height for least unit.
T toner printing portion 108, that is, the imaging moiety Pe of imaging device 100 prints the T toner printing amount that is used for minimum printing unit that is calculated by T toner printing amount calculating section 107.
From the article output 109 of record, that is, and imaging device 100, the article of the record that output is printed as carrying out the result of said process by control device 200.The article of record have section shape shown in Figure 4 as described above, and have the preferable image quality.The imaging operation of 200 couples of imaging moiety Pe of control device is controlled.Here employed term " imaging operation " is meant the operation at imaging moiety formation or developing electrostatic image.
(developer)
Next, employed developer in this example will be described.
In this example, developer comprises as magnetic coated carrier (coat carrier) and toner described in the JP 2004-271660 A.
The surface-coated of employed carrier particle resin and/or coupling agent in this example.
The coated carrier of this example is the lower carrier of magnetization degree, and having the magnetization (σ 1,000) under 1,000/4 π kA/m (79.58kA/m) is 25 to 60Am 2/ kg, or preferably 25 arrive 50Am 2/ kg.
Can be by for example Riken Denshi Co., the magnetic characteristic self-recording unit BHV-35 of the oscillating magnetic field type that Ltd. makes measures the magnetic characteristic of coated carrier.Measuring condition when using this device will be described below.Generate the external magnetic field of 1,000/4 π (kA/m).Simultaneously, by this way coated carrier is packaged in the cylindrical plastic container fully thick and fast, that is, makes carrier particle not move.Under this state, measure magnetic moment.Measure the actual weight when placing sample.Then, determine the magnetization (Am 2/ kg).
The coated carrier of this example preferably has the volume average particle size of 25 to 60 μ m, or is more preferably the volume average particle size with 30 to 50 μ m.When the volume average particle size of carrier particle during, may not prevent successfully that the carrier that the particle owing to the particulate side in the size-grade distribution of carrier particle causes from adhering to non-image part less than 25 μ m.
In addition, the size-grade distribution of wishing coated carrier is such, promptly, wherein the particle diameter of being measured by MEANS OF NODAL METHOD (mesh method) of each particle is that the content of 20 μ m or littler carrier particle is 0.01 to 3 quality %, and wherein the particle diameter of measuring by MEANS OF NODAL METHOD of each particle be 75 μ m or higher carrier particle content be 0.01 to 3 quality %.When the particle diameter of each particle wherein be the content of 20 μ m or littler carrier particle for less than 0.01 quality % the time, developer is easy to block densely, and is easy to deterioration, therefore, the situation that toner is distributed to machine intimate takes place easily.When the particle diameter of each particle wherein is the content of 20 μ m or littler carrier particle when surpassing 3 quality %, take place easily because the carrier adhesion that the carrier particle fine powder causes.Similarly, when the particle diameter of each particle wherein is the content of 75 μ m or higher carrier particle during less than 0.01 quality %, developer is owing to high density is easy to deterioration.When this content surpassed 3 quality %, can not obtain fully provided the suitable required surface area of the quantity of electric charge to toner, therefore, similarly, is easy to take place the situation that toner is distributed to machine intimate.
In addition, when 1,000/4 π, wherein the particle diameter of being measured by MEANS OF NODAL METHOD of each particle is each magnetic characteristic σ 1,000 of 20 μ m or littler carrier particle, adheres to and from developer bearing part (promptly with regard to carrier, development sleeve 40) removes developer effectively, be preferably 30 to 50Am 2/ kg.
For example can according to the condition that produces carrier particle, by any sieve and various sorting device to the classification of carrier particle and to the mixing of the product of classifying, adjust the volume average particle size and the size-grade distribution of coated carrier.
The volume average particle size of coated carrier is meant 50% mean grain size based on the volume of being measured by laser diffraction type size-grade distribution meter (by HORIBA, Ltd. makes).
In addition, the particle diameter of measuring by MEANS OF NODAL METHOD is the amount of 20 μ m or littler fine powder and is the amount of 75 μ m or higher meal by the particle diameter that MEANS OF NODAL METHOD is measured, mesh that can be by preparing each aperture and by for example using electromagnetism experiment ro-tap testing sieve shaker (by FritschJapan Co., the Analysette 3 that Ltd. makes) to measure.When using ro-tap testing sieve shaker, carry out according to following method and to measure: timer=5 minute, oscillator intensity=2, the amount of the sample that use is 500g.
The carrier magnetic core (promptly, magnetic core) example comprises: magnetic particle, the rare earth (each rare earth all has oxidation or unoxidized surface) selected from comprise the group such as the magnetic metal of iron, nickel, copper, zinc, cobalt, manganese, chromium, magnetic alloy, magnetic oxide, and their magnetic ferrites; And, by magnetic powder being distributed to the magnetic material dispersion resin carrier that obtains in the resin.
The content of the metallic compound particle in the carrier particle of magnetic material dispersion resin carrier is preferably 80 to 95 quality %.
The adhesive resin of magnetic material dispersion resin carrier is preferably thermoset resin, is more preferably partially or even wholly by crosslinked three-dimensionally resin, as comprises the thermoset resin of phenolics.Use this resin can retrain the metallic compound particle of dispersion forcefully, therefore, can improve the intensity of magnetic material dispersion resin carrier.In addition, even under the situation of duplicating many pages or leaves, the situation of metallic compound particle desorption can take place hardly also, therefore, the situation that toner is diffused into machine intimate can not take place.As a result, can obtain the image of its improved stability.
In addition, the surface of the carrier of this example applied with coating resin and/or coupling agent before using.Use thermoset resin to cause forming the coating of improvement as adhesive resin, this coating is beat the Dutch aspect tack and homogeneity.
The method that produces magnetic material dispersion resin carrier is not particularly limited.In this example, suitably use production method based on polymerization, this method relates to monomer polymerization to produce particle, each monomer all serves as the adhesive resin in the solution (monomer, metallic compound particle and solvent disperse or dissolve in this solution equably), especially, use such method, the metallic compound particle that this method relates to being distributed in the carrier particle carries out the lipophilicity processing, to produce magnetic material dispersion resin carrier, this carrier has sharp-pointed size-grade distribution, and does not comprise fine powder.
Can use the monomer of monomer-polymerisable monomer (free radical polymerizable monomer) as the adhesive resin that will be used for magnetic material dispersion resin carrier.The example of monomer-polymerisable monomer comprises, styrene; Styrene derivative, as o-methyl styrene, a methyl styrene, to methoxy styrene, to ethyl styrene, and to t-butyl styrene; Esters of acrylic acid, as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid n-propyl, isopropyl acrylate, 2-ethyl hexyl acrylate, dodecylacrylate, 2-EHA, stearyl acrylate base ester, acrylic acid 2-chloroethene ester, and phenyl acrylate; Methyl acrylic ester, as methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, the positive butyl ester of metering system ester, isobutyl methacrylate, n octyl methacrylate, lauryl methacrylate, methacrylic acid 2-Octyl Nitrite, methacrylic acid stearyl, methacrylic acid phenylester, dimethylaminoethyl acrylate methyl base amino methyl, diethyl aminoethyl methacrylate, and benzyl methacrylate; Acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester; Vinyl cyanide, methacrylonitrile, and acrylamide; Vinyl ether, as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl ether, isobutyl ether, β-chloroethyl vinyl ether, Vinyl phenyl ether, p-methylphenyl ether, rubigan ether, to bromophenyl ether, p-nitrophenyl vinyl ether, and the p-methoxyphenyl vinyl ether; And diolefin compound, as butadiene.
Can use each monomer separately, maybe can use two or more as potpourri.Can select to provide the suitable polymkeric substance complex of preferred characteristics.
As mentioned above, the adhesive resin of magnetic material dispersion resin carrier is preferably crosslinked three-dimensionally, and preferably uses the so crosslinked crosslinking chemical of formation.Preferably use each molecule to have the crosslinking chemical of two or more polymerisable double bonds as this crosslinking chemical.
The example of crosslinking chemical comprises: aromatic divinyl compound, as divinylbenzene and divinyl naphthalene; Ethylene glycol diacrylate, Ethylene glycol dimethacrylate, the dimethacrylate triethyleneglycol ester, dimethacrylate tetraethylene glycol ester, dimethacrylate 1, the 3-butanediol ester, trimethyol propane triacrylate, trihydroxy methyl propane trimethyl acrylate, diacrylate 1, the 4-butanediol ester, diacrylic acid pentyl diol ester, two propylene esters 1,6-hexylene glycol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, the dimethacrylate pentaerythritol ester, pentaerythritol tetramethacrylate, dimethacrylate sweet three oily acryloxy esters, N, N-divinyl aniline (anilene), divinyl ether, vinyl thioether, and divinylsulfone.
Can suitably mix and use two or more in those crosslinking chemicals.Can in advance crosslinking chemical be mixed mutually with polymerizable mixture, perhaps also can in polymerization process, suitably add as required.
The example of other monomers of the adhesive resin that will use in magnetic material dispersion resin carrier comprises: the bis-phenol and the chloropropylene oxide that serve as the raw material of epoxy resin; The phenols and the aldehydes that serve as the raw material of phenolics; The urea and the aldehydes that serve as the raw material of Lauxite; The melamine and the aldehydes that serve as the raw material of melamine resin.
Most preferred adhesive resin is a phenolics.The example of the raw material of phenolics comprises: phenolic compounds, as phenol,, 3,5-xylenols, to alkylphenol, resorcinol (resorcinol), and p-t-butyl phenol; Aldehyde compound, as formalin, paraformaldehyde, and furfural.The combination of preferred especially phenol and formalin.
During any in using these phenolics and melamine resin, can use base catalyst as curing catalysts.Can use and be used for any of various catalyzer that common resol produces as base catalyst.The concrete example of base catalyst comprises amine, as ammoniacal liquor, urotropine, diethyl triamine, and polyvinylamine.
The example of the metallic compound particle that will use in magnetic material dispersion resin carrier comprises magnetic iron ore and ferrite, and wherein each all demonstrates magnetic, and each can be by formula MOFe 2O 3Or MFe 2O 4Represent.In each formula, M represents trivalent, divalence or valent metal ion.
The example of M comprises Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Nb, Mo, Cd, Sn, Ba, Pb, Li, or the like.
For each metallic compound particle, can use its M is the compound of single-element, or uses the compound that comprises multiple M.The example of metallic compound particle for example comprises, such as the oxide based on iron of magnetic iron ore, based on the ferrite of Zn-Fe, based on the ferrite of Mn-Zn-Fe, based on the ferrite of Ni-Zn-Fe, based on the ferrite of Mn-Mg-Fe, based on the ferrite of Ca-Mn-Fe, based on the ferrite of Ca-Mg-Fe, based on the ferrite of Li-Fe, and based on the ferrite of Cu-Zn-Fe.
Carrier preferably comprises the ferromagnetic metal compound particles of magnetic iron ore as described above, ferrite etc., and the magnetic that comprises each metal oxide particle wherein metal oxide particle more weak than the magnetic of each metallic compound particle (following can abbreviate " metal oxide particle " as), as the metallic compound particle.As long as the magnetic of each metal oxide particle must be weaker than the magnetic of each metallic compound particle, and metal oxide particle can be non magnetic.The example of such metal oxide particle comprises Al 2O 3, SiO 2, CaO, TiO 2, V 2O 5, CrO, MnO 2, α-Fe 2O 3, CoO, NiO, CuO, ZnO, SrO, Y 2O 3And ZrO 2
When mixing like that as mentioned above and use at least two kinds of metallic compound particles, be more preferably, use has the similar proportion and the similar metallic compound particle of shape, so that improve the tack with adhesive resin, and improves the intensity of each carrier particle.The example of the such combination that can preferably use comprises: the combination of magnetic iron ore and haematite; Magnetic iron ore and γ Fe 2O 3Combination; Magnetic iron ore and SiO 2Combination; Magnetic iron ore and Al 2O 3Combination; And magnetic iron ore and TiO 2Combination.In these combinations, can particularly preferably use the combination of magnetic iron ore and haematite.
When using aforesaid such metallic compound particle, the number average bead diameter of metallic compound particle (each all demonstrates ferromagnetism) is preferably 0.02 to 2 μ m, though preferred range is along with the particle diameter of each carrier particle is different and different.When using two or more metallic compound particles, the number average bead diameter of metallic compound particle (each all demonstrates ferromagnetism) is 0.02 to 2 μ m, and the number average bead diameter of metal oxide particle is 0.05 to 5 μ m.
In the case, the particle diameter ratio rb/ra of the number average bead diameter (mean grain size ra) of the number average bead diameter of metal oxide particle (mean grain size rb) metallizing thing particle (each all demonstrates ferromagnetism) was preferably in for 1.0 (not comprising 1.0) within the scope of 5.0 (comprising 5.0), was more preferably in 1.2 to 4.5 (the two ends point value all comprises).When this ratio is 1.0 or more hour, resistance coefficient is low, metallic compound particle (each all demonstrates ferromagnetism) is easy to occur from the teeth outwards.As a result, the resistivity of each carrier particle improves hardly, can obtain the preventive effect that carrier adheres to hardly.When this ratio surpassed 5, the intensity of each carrier particle was easy to reduce, and the breakage of carrier particle takes place easily, and the result causes toner to be distributed to machine intimate.
Can be by for example Hitachi, the transmission electron microscope H-800 that Ltd. makes measures the number average bead diameter of metallic compound particle.Desirable method relates to when using microscope: prepare photographs by microscope with 5,000 to 20,000 magnification; 300 of stochastic samplings or multiparticle more, each particle all has 0.01 μ m or higher particle diameter; The Flame Image Process and the analytical equipment Luzex 3 that make by for example Nireco Corporation measure particle Feret diameter in a horizontal direction, as the particle diameter of metallic compound particle; The particle diameter of measuring is asked on average, to calculate number average bead diameter.
Wherein each all demonstrates ferromagnetic metallic compound particle and is preferably in 70 quality % (not comprising this value) in the 95 quality % scope of (comprising this value) with respect to the content of the integral body of the metallic compound particle in the magnetic material dispersion resin that has wherein disperseed two or more metallic compound particles.When this content is 70 quality % or more hour, the resistance of magnetic material dispersion resin carrier can successfully improve, still, therefore carrier, may take place and adhere in the reduction of the magnetic force of carrier particle.When this content surpasses 95 quality %, the resistance of magnetic material dispersion resin carrier can not more successfully increase, and carrier may take place similarly adhere to, though the degree that carrier adheres to changes along with the resistivity of each metallic compound particle (each all demonstrates ferromagnetism).
Metallic compound particle in the magnetic material dispersion resin carrier of this example of this embodiment preferably is carried out lipophilicity and handles, so that the size-grade distribution of sharpening magnetic carrier particle, and prevention metallic compound particle is from the carrier particle desorption.Especially, when the polymerization that uses under by preferable case is produced carrier particle, side by side in this solution, produce insoluble particle with the process of polyreaction in the solution (in this solution, monomer and solvent are homogenized).At this moment, expection is carried out lipophilicity and is handled, and is absorbed operation in the particle with high density equably to take metal oxide wherein, and takes wherein to prevent particle coalescent, so that the operation of sharpening size-grade distribution.
In addition, use and carried out the metallic compound particle that lipophilicity is handled, just can use the suspension stabilizer such as calcium fluoride.The result, can prevent to remain in the inhibition of the charge characteristic that causes on the surface of carrier particle owing to suspension stabilizer, the unevenness of coating resin when preventing to apply, and prevent when carrier coated during such as at least a reactive material in organic siliconresin and the coupling agent to the inhibition of reaction.
The lipophilicity processing is preferably undertaken by organic compound, this organic compound has the one or two or more functional groups of selecting from epoxy radicals, amino, sulfydryl, or carries out lipophilicity by the lipophilicity treating agent as the potpourri of this organic compound and handle.Especially, when this polymerization that uses under by preferable case produces carrier particle, the processing of being undertaken by the treating agent with aforesaid base averages out between lipophilicity, hydrophobicity and water wettability, this provides highly lasting carrier particle, and each particle all has stable electric charge provides (charge imparting) performance and high particle intensity.Particularly preferably use epoxy radicals.
The lipophilicity treating agent of 100 parts metallic compound particle the most handy 0.1 to 10 part by mass (being more preferably 0.2 to 6 part by mass) is handled by mass, so that improve the lipophilicity and the hydrophobicity of each metallic compound particle.
Example with amino lipophilic reagent comprises: γ-aminopropyl-trimethoxy silane, γ-aminopropyl-methoxyl-diethoxy silane, gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl-trimethoxy silane, N-β (aminoethyl)-γ-aminopropyl-methyl dimethoxysilane, N-phenyl-γ-aminopropyl-trimethoxy silane, ethylenediamine, ethylidene triamine (ethylenetriamine), styrene-() dimethylaminoethyl acrylate copolymer, isopropyl three (N-aminoethyl) titanate esters, or the like.
Example with lipophilic reagent of sulfydryl comprises: mercaptoethanol, mercaptopropionic acid, γ-Qiu Jibingjisanjiayangjiguiwan, or the like.
Example with lipophilic reagent of epoxy radicals comprises: γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxypropyltrime,hoxysilane, β-(3,4-epoxy cyclohexyl) trimethoxy silane, chloropropylene oxide, epoxypropane, styrene-(methyl) glycidyl acrylate copolymer, or the like.
As mentioned above, from improving the viewpoint that electric charge provides characteristic and improves inefficacy resistance (spentresistance), before using, the surface of carrier particle preferably is coated with coating resin and/or coupling agent; Suppose to be not particularly limited to being used for the resin of coating surface.
The example of such surface treatment resin comprises, acrylic resin, as polystyrene and copolymer in cinnamic acrylic ester, vinyl chloride, vinyl acetate, polyvinylidene fluoride resin, fluorocarbon resin, the perfluorocarbon resin, dissolve in the perfluorocarbon resin of solvent, polyvinyl alcohol (PVA), polyvinyl acetal, polyvinylpyrrolidone, petroleum resin, cellulose, cellulose derivative, novolac resin, low molecular weight polyethylene, the saturated alkyl vibrin, aromatic polyester resin, polyamide, polyacetal resin, polycarbonate resin, polyethersulfone resin, polysulfone resin, polyphenylene sulfide, polyether ketone resin, phenol resin, the phenol resin of modification, maleic resin, alkyd resin, epoxy resin, acrylic resin, pass through maleic anhydride, the unsaturated polyester (UP) that terephthalic acid (TPA) and polyvalent alcohol polycondensation obtain, Lauxite, melamine resin, urea-melamine resin, xylene resin, toluene resin, guanamine resin, melamine-guanamine resin, the acetylguanamine resin, glyptal resin, furane resin, organic siliconresin, polyimide resin, polyamide-imide resin, polyetherimide resin, urethane resin, fluororesin, or the like.
Wherein, for example, preferably use organic siliconresin and fluororesin, can use in them each separately from the tack of magnetic core with prevent the viewpoint that lost efficacy; Suppose, preferably use each in them so that improve the coating film strength, thereby charging is controlled to preferred situation with coupling agent.
In addition, the part of above-mentioned coupling agent preferably is used as with the resin spraying and covers so-called " bottoming agent " that is used to handle before the magnetic core surface.Use coupling agent can cause forming resin bed after a while, because covalent bond strengthens tack as bottoming agent.
As mentioned above, in this example of this embodiment, can use any of various silane compounds as coupling agent; Suppose to wish to use amino silicon alkane as having amino silane compound.As a result, the amino with the chargeable property of positive charge can be introduced in carrier surface, thereby can provide the preferred quantity of electric charge for toner.In addition, An Ji existence can activate lipophilicity treating agent and the organic siliconresin that preferably is used for handling metallic compound.As a result, the tack between organic siliconresin and the carrier particle can further be improved, and simultaneously, has promoted the curing of resin, thereby can form its strengthened coating.
The nonmagnetic toner that uses in this example of this embodiment can produce by breaking method.Yet the example of the method for optimizing of the production nonmagnetic toner in this example of this embodiment comprises: in medium, directly produce the method (polymerization) of toner, and as suspension polymerization, interfacial polymerization method, and dispersion polymerization processes.Each polymerization all relates to: dissolving or disperse is served as the polymerisable monomer of adhesive resin composition and colorant (and polymerization initiator, crosslinking chemical, charge control agent, other adjuvants as required, or the like) with preparation monomer complex equably; The monomer complex is distributed in the successive layers (as water) that comprises dispersion stabilizer by suitable stirrer; And when stirring, carry out polyreaction, have the toner of desirable particle diameter with generation.
Nonmagnetic toner preferably comprises release agent.Add an amount of wax and can prevent that as release agent toner from fusing in any one photosensitive drums 1 as image bearing member, realizes the compatibility between high resolving power and the offset resistance simultaneously.
The example of the wax that can use in nonmagnetic toner comprises: oil type wax, and as paraffin, microcrystalline wax and vaseline, and their derivant; Ceresine and derivant thereof; Hydro carbons paraffin and derivant thereof based on Fischer-Tropsch method (Fischer-Tropsch process); With polypropylene and tygon is the polyolefin-wax of representative, and their derivant; And the natural wax such as Brazil wax and candelila wax, and their derivant.The example of derivant comprise oxide, with the segmented copolymer of vinyl-type monomer, and grafting-sex change product.Can also use higher aliphatic alcohols, aliphatic acids (as stearic acid and palmitic acid) or these sour compounds, amino acid wax, ester type waxes, ketone, hardened castor oil and derivant thereof, vegetable wax, animal wax, or the like.
Any with respect to 100 parts adhesive resin by mass in those waxes in the nonmagnetic toner is preferably in by mass in 0.5 to 25 part scope.
In this example of this embodiment that produces by polishing under the situation of related nonmagnetic toner particle, the example of adhesive resin comprises styrene and such as the single polymer of its substitute of polystyrene and tygon toluene; The styrene type multipolymer, as the styrene-propene multipolymer, styrene-ethylene base toluene multipolymer, styrene-ethylene base naphthalenedicarboxylate copolymer, styrene-propene acid methyl terpolymer, styrene-propene acetoacetic ester multipolymer, the styrene-propene butyl acrylate copolymer, the misery ester copolymer of styrene-propene, styrene-propene acid diformazan ammonia ethyl ester multipolymer, styrene-methylmethacrylate copolymer, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl acrylate methyl ammonia ethyl ester multipolymer, styrene-ethylene ylmethyl ether copolymer, styrene-ethoxyethyl group ether copolymer, styrene-ethylene ylmethyl ketone copolymers, Styrene-Butadiene, styrene-pentadiene copolymer, styrene maleic acid ester copolymer, and styrene-ester maleate copolymer; Polymethylmethacrylate, poly-n-butyl methacrylate, polyvinyl acetate, tygon, polypropylene, polyvinyl butyral, organic siliconresin, vibrin, polyamide, epoxy resin, and polyacrylamide resin.Can use these separately, also can use with being mixed with each other.Specifically, with regard to development feature and photographic fixing feature, optimization styrene type multipolymer and vibrin.
When the nonmagnetic toner that produces by polymerization according to this example of this embodiment, the polymerisable monomer that has constituted the adhesive resin composition comprises following monomer.
Here the example of operable monomer comprises styrene type monomer, as styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, to methoxy styrene, and to ethyl styrene; Acrylate is as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid n-propyl, acrylic acid n-octyl, dodecylacrylate, 2-EHA, stearyl acrylate base ester, acrylic acid 2-chloroethene ester and phenyl acrylate; Methacrylate, 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, methacrylic acid phenylester, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, and methacrylic acid diethyl amino ethyl ester; Other vinyl cyanide, methacrylonitrile, and acrylamide.Can use these monomers separately, also can use with being mixed with each other.In these monomers, with regard to development feature and photographic fixing feature, use styrene or styrene derivative separately, it is preferred perhaps using styrene or styrene derivative with other monomers with mixing.
In this example of this embodiment, under the preferable case, nonmagnetic toner comprises vibrin.
According to the investigation that the present inventor carries out, add vibrin and can improve the intensity on the surface of toner.When adding from the outside such as the adjuvant of inorganic particles and being used in combination, prevent because the effect that the inorganic particles that causes for a long time is embedded in the surfaces of toner particles in the toner particle becomes big, thereby charging is stablized with coloured toner particle.As a result, can prevent to be diffused into the situation of machine intimate owing to the toner that causes for a long time.
Vibrin preferably has 6,000 to 100,000 weight-average molecular weight (Mw).When Mw less than 6,000 o'clock, prevent that the effect that external adjuvant is embedded in the toner particle is little, therefore, do not observe the effect that the quantity of electric charge that prevents to cause owing to the duration reduces.On the other hand, when Mw surpasses at 100,000 o'clock, condensation resin is distributed to the situation variation of toner particle, the result, and the size-grade distribution of the toner of Huo Deing broadens at last.
In each method in polymerization and breaking method, the glass transition temperature of adhesive resin (Tg) is preferably within 40 to 70 ℃ the scope, perhaps is more preferably within 45 to 65 ℃ of scopes.Can use monomer separately with the glass transition temperature in the above-mentioned scope.Perhaps, generally speaking, mix monomer suitably, and using by this way promptly, makes publication Polymer Handbook (second edition III, p 139-192, JohnWiley ﹠amp; The Sons publication) it is 40 to 70 ℃ that the theoretical glass transition temperature (Tg) described in demonstrates.
Coloured nonmagnetic toner in this example of this embodiment, that is, C, M and Y toner all comprise colorant, so that give colorability for each toner.Be preferably in the organic pigment that uses in this example of this embodiment or the example of dyestuff and comprise following pigment and dyestuff.
Comprise based on the painted organic pigment of cyan or the example of organic dyestuff as operable here: copper phthalocyanine compound and derivant thereof, the color lake compound of anthraquinone compounds and basic-dyeable fibre (lake compound).Specifically, can comprise C.I. pigment blueness 1, C.I. pigment blueness 7, C.I. pigment blueness 15, the blue 15:1 of C.I. pigment, the blue 15:2 of C.I. pigment, the blue 15:3 of C.I. pigment, the blue 15:4 of C.I. pigment, C.I. pigment blueness 60, C.I. pigment blueness 62, and C.I. pigment blueness 66.
As operable painted organic pigment or the example of the organic dyestuff color lake compound, naphthol compound, benzimidazolone compound, sulfuration indigo compound and the perylene compound that comprise azo condensation product, Diketopyrrolo-pyrrole compounds, anthraquinone compounds, quinoline a word used for translation dione compounds, basic-dyeable fibre based on magenta here.Specifically, can comprise C.I. pigment redness 2, C.I. the pigment redness 3, C.I. the pigment redness 5, C.I. the pigment redness 6, C.I. the pigment redness 7, C.I. the pigment violet rowland 19, C.I. the pigment redness 23, C.I. the red 48:2 of pigment, C.I. the red 48:3 of pigment, C.I. the red 48:4 of pigment, C.I. the red 57:1 of pigment, C.I. the red 81:1 of pigment, C.I. the pigment redness 122, C.I. the pigment redness 144, C.I. the pigment redness 146, C.I. the pigment redness 166, C.I. the pigment redness 169, C.I. the pigment redness 177, C.I. the pigment redness 184, C.I. the pigment redness 185, C.I. the pigment redness 202, C.I. the pigment redness 206, C.I. the pigment redness 220, C.I. the pigment redness 221, and C.I. pigment redness 254.
As operable based on the painted organic pigment of yellow or the example of organic dyestuff here, by azo condensation product, iron oxide yellow (isoindolinone) compound, anthraquinone compounds, blue sheet (azometal) complex compound, methylidyne compound, and the acrylamide compound representative.Specifically, can comprise the C.I. pigment Yellow 12, C.I. the pigment yellow 13, C.I. the pigment yellow 14, C.I. the pigment yellow 15, C.I. the pigment yellow 17, C.I. the pigment yellow 62, C.I. the pigment yellow 74, C.I. the pigment yellow 83, C.I. the pigment yellow 93, and C.I. pigment yellow 94, C.I. the pigment yellow 95, C.I. the pigment yellow 97, C.I. the pigment yellow 109, C.I. the pigment yellow 110, C.I. the pigment yellow 111, C.I. the pigment yellow 120, C.I. pigment Yellow 12 7, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. the pigment yellow 147, C.I. the pigment yellow 151, C.I. the pigment yellow 154, C.I. the pigment yellow 168, C.I. the pigment yellow 174, C.I. the pigment yellow 175, C.I. the pigment yellow 176, C.I. the pigment yellow 180, C.I. the pigment yellow 181, C.I. the pigment yellow 191, and C.I. pigment yellow 194.
Can use each colorant separately, maybe can use two or more as potpourri.In addition, can under the solid solution state, use each colorant.With regard to hue angle, colourity, brightness, photostability, OHP transparency, and the dispersiveness in the toner, the colorant that uses in the colour toners that has in this example selected.
The amount of each colorant that adds is 1 to 20 part by mass with respect to 100 parts adhesive resin by mass.
Nonmagnetic toner in this example can mix with the charge control agent that is used for the constant charge characteristic.
Can use known charge control agent, particularly preferably be the charge control agent that has high charge speed and stably keep the ability of constant charge amount.In addition, has the charge control agent that oligomerization is forbidden characteristic and do not comprised the material that dissolves in the water-based dispersion medium substantially when producing by polymerization when colour toners is arranged, particularly preferably being.The concrete example of the charge control agent that can charge negatively comprises: such as salicylic acid, alkyl salicylate, dialkyl salicylic acid, naphthoic acid, and the aromatic carboxylic acid's of dicarboxylic acid and so on metallic compound; The slaine of azo dyes or AZO pigments or metal complex; Polymkeric substance, boron compound, carbamide compound, silicon compound, and calixarenes all have sulfo group or carboxyl at its side chain.The concrete example of the charge control agent that can charge comprises positively: quaternary ammonium salt; And polymkeric substance, guanidine compound, Buddhist nun's lattice type compound, and imidazolium compounds, all have quaternary ammonium salt at its side chain.
Preferably by using charge control agent for 0.5 to 10 part amount by mass with respect to 100 parts resin by mass.
Producing by polymerization under the situation of the nonmagnetic toner particle in the example, the polymerization initiator that preferably uses in the generation of nonmagnetic toner particle is: in polyreaction, the half life period of this polymerization initiator is 0.5 to 30 hour, and to use polymerization initiator with respect to 100 parts polymerization single polymerization monomer by mass for 0.5 to 20 part ratio by mass.Such polymerization initiator can provide desirable intensity and suitable solubility feature.Here the example of operable polymerization initiator comprises: azo-type or diazonium-type polymerization initiator, as: 2,2 '-azo-(2, the 4-methyl pentane nitrile), 2,2 '-azobis isobutyronitrile, 1,1 '-azo (cyclohexane-1-nitrile), 2,2 '-azo-4-methoxyl-2,4-methyl pentane nitrile, and azobis isobutyronitrile; The peroxide type polymerization initiator, as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxocarbonate, cumene hydroperoxide, peroxidating 2,4-dichloro-benzoyl, lauroyl peroxide, and t-butyl peroxy-2 ethyl hexanoic acid ester.
When the nonmagnetic toner particle that produces by polymerization in this example, can add crosslinking chemical.The amount of the crosslinking chemical that adds is 0.001 to 15 quality % of polymerisable monomer complex preferably.
Basically, used crosslinking chemical here with two or more polymerisable double bonds.The example of operable crosslinking chemical comprises aromatic divinyl compound, as divinylbenzene and divinyl naphthalene; Carboxylate with two two keys, as ethylene glycol diacrylate, Ethylene glycol dimethacrylate, and the acid of methacrylic acid 1,3 butylene glycol; Divinyl compound, as divinyl aniline, divinyl ether, vinyl thioether, and divinylsulfone; And compound with three or more vinyl groups.Can use these materials separately, also can use with being mixed with each other.
When the nonmagnetic toner particle that produces by polymerization in this example, generally speaking, above-mentioned have a colour toners complex, it is polymerisable monomer, suitably added each required composition of toner, as colorant, release agent, plastifier, charge control agent, and crosslinking chemical, and other adjuvants.Dissolve equably or dispersed mixture by the dispersing apparatus such as homogenizer, bowl mill, colloid mill or ultrasonic dispersing equipment, with preparation polymerisable monomer system.System is suspended in the aqueous medium that comprises dispersion stabilizer.At this moment, the high-speed dispersion equipment such as high speed agitator or ultrasonic dispersing equipment is used in suggestion, so that desirable toner particle size to be provided in one stroke (stroke), because the size-grade distribution of the toner particle of gained is sharpened.Polymerization initiator can side by side add in polymerisable monomer with other adjuvants of interpolation, or mixed immediately before in being suspended to aqueous medium.In addition, follow closely after granulating, before the startup of polyreaction, can add the polymerization initiator that is dissolved in polymerisable monomer or the solvent.
After granulating, only will stir and carry out so far with general mixer, that is, make and keep particle state, and can prevent floating and precipitation of particle.
When the nonmagnetic toner that produces by polymerization in this example, can use known surfactant or known organic or inorganic spreading agent as dispersion stabilizer.In these materials, preferably use inorganic dispersant.Below the reason of doing like this will be described.Inorganic dispersant can produce harmful superfines hardly.Even under the situation that temperature of reaction changes, the stability of inorganic dispersant also can fail hardly, because spreading agent is owing to the steric hindrance characteristic has dispersion stabilization.Can wash inorganic dispersant like a cork, very little to the negative effect of toner.The example of such inorganic dispersant comprises: such as calcium phosphate, magnesium phosphate, aluminum phosphate, and the polyvalent metal phosphate of trbasic zinc phosphate; Carbonate such as lime carbonate and magnesium carbonate; Such as calcium metasilicate, calcium sulphate, and the inorganic salts of barium sulphate; And such as calcium hydroxide, magnesium hydroxide, aluminium hydroxide, silica, bentonitic clay, and the inorganic oxide of alumina.
Hope with respect to 100 parts polymerisable monomer by mass for being that 0.2 to 20 part amount is used each in these inorganic dispersants separately by quality.Yet, use in these inorganic dispersants each all can not be enough to reduce the particle diameter of toner separately, though this use can generate ultra-fine particle hardly.Correspondingly, can use inorganic dispersant with 0.001 to 0.1 part combinations-of surfactants ground by mass.The example of surfactant comprises neopelex, sodium tetradecyl sulfate, pentadecyl sodium sulphate, sodium octyl sulfate, Sodium Caprylate, sodium laurate, odium stearate, and potassium stearate.
Can use each inorganic dispersant same as before.Can in aqueous medium, produce the particle of inorganic dispersant, so that obtain the particle that each particle wherein all has the particle diameter that dwindles.For example, under the situation of calcium phosphate, under high-speed stirred, the aqueous solution of mixed phosphate sodium and the aqueous solution of lime chloride, thus can produce water-fast calcium phosphate.As a result, in the time of can disperseing, wherein homogeneity is improved, and fineness is also improved.At this moment, as secondary product, produce water-soluble sodium chloride salt simultaneously.Water-soluble salt existing in aqueous medium is more convenient, is dissolved in the water because polymerisable monomer is restrained in this existence, therefore, can produce hardly because the ultra-fine toner that emulsion polymerization causes.Wish the exchange aqueous medium, perhaps, wish to desalt by ion exchange resin because the latter stage of removing polyreaction during remaining polymerisable monomer salt become barrier.After finishing polymerization, being dissolved into by inorganic dispersant in acid or the alkali, can be almost completely with its removal.
In polymerization procedure, be preferably under 40 ℃ or the higher polymerization temperature, perhaps generally speaking under 50 to 90 ℃, carry out polymerization.In the latter stage of polyreaction, temperature of reaction can be brought up to 90 to 150 ℃, so that consume remaining polymerisable monomer.
After finishing polymerization, filter, wash and dry the toner particle of polymerization by known method, will be such as the external adjuvant and the mix particles of inorganic particles, so that external additive adhesion is to the surface of each particle.As a result, can obtain toner.Under the desirable pattern of another kind, classification step is joined in the production stage, so that filter out meal and fine powder.
When producing the nonmagnetic toner particle, can utilize known method by breaking method.An example of this method relates to: by the mixer such as Henschel Mixer or bowl mill, fully be mixed with needed each composition of colour toners particle, such as adhesive resin, release agent, charge control agent, and colorant, other adjuvants, or the like; Melt and the potpourri of kneading by heating kneading machine, so that each resin is compatible each other such as warm-up mill, kneading machine or extruder; Cooling and curing gains; Pulverize gains; The classification gains; As required gains are carried out surface treatment, to produce toner particle.Can before surface treatment, classify, or vice versa.With regard to production efficiency, in classification step, preferably use many parts sorter.
The method of known comminutor that can be by relating to use such as physical shock type comminutor or ejection-type comminutor is carried out pulverising step.In order to obtain the colour toners that has with specific circularity, be preferably under the situation of other heating and pulverize, or the processing of assisting, to apply physical shock.Also can carry out the coloured toner particle that relates to meticulous pulverizing (and classification) as requested and be distributed to water-bath method in the hot water, and carry out and relate to the method for transmitting particle by thermal current or the like.
The example that is used to apply the device of mechanical impact force comprises and being used for by means of force of compression, friction force or the like, by the blade that at full speed rotates, Mechanofusion System and NARAMACHINERY CO. such as the HOSOKAWAMICRONCORPORATION manufacturing, LTD. the Hybridization System of Zhi Zaoing pushes toner particle applies device from mechanical impact force to the nonmagnetic toner particle to enclosure interior.
In addition, the nonmagnetic toner particle of Shi Yonging can also produce by any method that produces toner particle in this example, such as following method: described in JP 56-13945 B or the like, relate to by use dish or multithread body shower nozzle molten mixture atomized in air to produce the method for spherical toner particle; And the polymerization outside the suspension polymerization, comprise: (1) relates to that (monomer is dissolvable in water wherein by using aqueous organic solvent, and polymkeric substance to be obtained can not be dissolved in wherein) directly produce the dispersion polymerization processes of toner particle, and (2) emulsion polymerisation process, its exemplary process has: have in existence under the situation of polymerization initiator of water-soluble polarity and directly carry out polymerization, to produce the soap-free polymerization method of toner particle.
In this example, nonmagnetic toner comprises inorganic particles, and each particulate all serves as external adjuvant, and the main mean grain size of inorganic particles preferably 4 arrives 80nm.
Preferably inorganic particles is carried out hydrophobic and handles so that even under high humidity environment, also the quantity of electric charge of each toner particle can be maintained high level, and can prevent the toner diffusion.
For example, a kind of method relates to: carry out Silanization reaction by using silane coupling agent etc. to react as the first order; Eliminate silanol group by chemical bond, perhaps, another kind of method relates to by using silicone oil to form hydrophobic membrane from the teeth outwards, handles applicable to inorganic particles being carried out hydrophobic one of in these methods.
In this example, according to following process, the average main particle diameter of inorganic particles is confirmed as number average bead diameter.By scanning electron microscope nonmagnetic toner is carried out macrophotography.Photo with the element map nonmagnetic toner in each inorganic particles.And photo check analysis device, such as the XMA that is connected to scanning electron microscope, measure the surface adhere to nonmagnetic toner or 100 of the inorganic particles that discharges from the surface of nonmagnetic toner or how main particle the particle diameter of each particle.
Can use silica, alumina, titania or the like particulate as the inorganic particles in this example.
For example, abbreviate the aerosil that so-called " the dry silica " of dry method silica or the vapour-phase oxidation by silicon halide produce as, and, all can be used as silica microparticle from so-called " wet silica " that water glass etc. produces.In these particulates, have the minor amount of silicon alkanol from the teeth outwards, and generate the produced in small quantities waste residue (such as Na in inside 2O or SO 3 2-) dry silica be preferred.In the production stage of dry silica, for example, can use metal halide in combination such as aluminum chloride or titanium chloride, and silicon halide, to produce the composite fine powders of silica and other metal oxides, this composite fine powders is also included within the scope of dry silica.
The amount of the inorganic particles that adds preferably is 0.1 to 3.0 part by mass with respect to 100 parts nonmagnetic toner particle by mass.When this measures by mass less than 0.1 part, the effect deficiency of interpolation.When this amount surpassed 3.0 parts by mass, the release of inorganic particles became significantly, and the charge amount distribution of toner enlarges, thereby the situation that toner is diffused into machine intimate may take place.
Can use a spot of other adjuvants by following degree in the nonmagnetic toner of Shi Yonging in this example, that is, and the feasible negative effect that can not produce essence to toner.The example of other adjuvants comprises: lubricant powder, and as tygon fluoride powder, zinc stearate powder, and the polyvinylidene fluoride powder; Lapping compound, as cerium oxide powder, carborundum powder, and strontium titanate powder; Inorganic or organic fine particles, each particulate all almost has sphere, and and in to big particle diameter (main particle diameter surpasses 30nm), such as spherical silica microparticle and spherical resin grain, for example be used to improve sanitary characteristics; Other polarity organic and inorganic particulate respect to one another, each particle all serves as development property improver.Before using, can carry out hydrophobic to the surface of each adjuvant and handle.
The nonmagnetic toner particle in this example in the developer and the T/C ratio of carrier particle generally are set to 3.0 to 12.0 quality %, or are preferably 5.0 to 9.0 quality %, so that can obtain good result.When toner concentration during less than 3.0 quality %, image density is too low, is difficult to drop into practical application, and the deterioration of carrier accelerates, the result, and shorten the serviceable life of developer.When toner concentration surpassed 12.0 quality %, photographic fog or the frequency that is diffused in the machine improved, and therefore, also can shorten the serviceable life of developer.
(measuring the method for the triboelectricity of toner)
Below, the method for the triboelectricity (quantity of electric charge of per unit weight) of measuring the toner in the tow-component developer will be described with reference to the drawings.
Fig. 6 is the explanatory of the equipment of the quantity of electric charge that is used to measure the per unit weight of toner (below abbreviate " triboelectricity " as).
At first, it is in 50 to 100ml the tygon bottle that the tow-component developer that will measure its triboelectricity is placed on volume, and with hand moving about 10 to 40 seconds.Then, in the bottom has the metal measuring vessel 112 of 500-purpose sieve 113, fill about 0.5 to 1.5g developer, and cover this container with metal lid 114.
Measure the total quality of measuring vessel 112 this moment, and represent (kg) this quality with W1.Next, suck resin by inhalation device 111 (its at least a portion that contacts with measuring vessel 112 is an insulator) from inlet hole 117, by adjusting control damper 116, the pressure of being indicated by vacuum meter 115 is set to 250mmAq.Under this state, carry out fully and suck operation, perhaps continue to carry out 2 minutes, so that suck and remove resin.This moment, the electromotive force of pot 119 indications was represented by V (volt).Here, the electric capacity of capacitor 118 is C (F).In addition, measure the total quality of measuring vessel 112 after sucking, and represent (kg) this quality with W2.Can calculate the triboelectricity of toner according to following expression formula.
The quantity of electric charge of the per unit mass of toner (C/kg)=(C * V * 10 -3)/(W1-W2)
(generation carrier)
Carrier produces example 1
Carbolic acid: 3.6 parts by mass
Formalin solution (comprise about 40% formaldehyde, about 10% methyl alcohol, all the other are water): 5.4 parts by mass
γ-glycidoxypropyltrime,hoxysilane (mean grain size and 4 * 10 with 1.0 quality % with 0.23 μ m 5The resistivity of Ω cm) carried out the magnetic iron ore particulate that lipophilicity is handled: 62.0 parts by mass
γ-glycidoxypropyltrime,hoxysilane (mean grain size and 2.2 * 10 with 1.0 quality % with 0.57 μ m 9The resistivity of Ω cm) carried out α-Fe that lipophilicity is handled 2O 3Particulate: 26.0 parts by mass
To inject the slurries of flask as the ammoniacal liquor of base catalyst and water.In 40 minutes, the temperature of potpourri is brought up to 85 ℃, and remain on this temperature, stir simultaneously and mix this potpourri, reacted then 3 hours.Produce also phenolic resin cured.Then, the cooling gains are removed supernatant liquor after adding water.Water flushing sediment, and under the pressure that reduces with its oven dry.So, obtained to comprise the spherical magnetic carrier magnetic core particle of magnetic iron ore particulate, they all use phenolics as adhesive resin separately.
The surface of each of gained carrier magnetic core particle all uses the gamma-amino propyl trimethoxy silicane (diluting as bottoming agent with toluene solvant) of 0.3 quality % to handle.Subsequently, particle applies with the potpourri of the gamma-amino propyl trimethoxy silicane of straight chain (straight) organic siliconresin (its all substituting groups are methyl) of 0.65 quality % and 0.02 quality % (with toluene as solvent).Here, coating agent is the organic siliconresin of straight chain, and coupling agent is the gamma-amino propyl trimethoxy silicane.In addition, magnetic coated carrier cures under 140 ℃, filters out coalescent corase particles by 100 purposes sieve.Next, remove fine powder and meal by using many parts air classifier, so that adjust size-grade distribution.So, obtain coated carrier No.1.The size of the mesh by changing sieve can change the particle diameter of carrier.
Carrier produces example 2
Produce coated carrier No.2 to produce the identical mode of example 1 with carrier, but removed the bottoming agent of coating, the amount of coating agent changes into 0.4%, and the amount of coupling agent changes into 0.01%.Table 1 has shown the coated carrier No.1 that obtained and the production method of coated carrier No.2.
Table 1
NO. Adhesive resin The magnetic core particle Coating
Magnetic material Nonmagnetic substance Magnetic material/nonmagnetic substance Bottoming agent Addition (wt%) Coating agent Addition (wt%) Coupling agent Addition (wt%)
1 Phenolics Magnetic iron ore Haematite 70/30 Amino silane 0.3 Methyl-monosilane 0.65 Amodimethicone 0.02
2 Phenolics Magnetic iron ore Haematite 70/30 Amino silane 0 Methyl-monosilane 0.4 Amodimethicone 0.01
(generation of nonmagnetic toner)
Nonmagnetic toner produces example 1
(A) colour toners (C, Y, M and K toner) is arranged
The Na of 250 parts 0.1M by mass 3PO 4Aqueous solution is loaded into by mass in 405 parts the water of ion-exchange, and the temperature of potpourri increases to 60 ℃.Then, with 40.0 parts the CaCl of 1.07M by mass 2Aqueous solution is little by little added in the gains, thereby obtains to comprise the aqueous medium of synthos.
Simultaneously, disperse and mix following prescription equably by masher (MITSUI MIIKE MACHINERY CO., LTD. makes).
Styrene: 80 parts by mass
N-butyl acrylate: 20 parts by mass
Divinylbenzene: 0.2 part by mass
Saturated polyester resin (Mw=41,000):
4.0 parts by mass
The charge control agent that can charge negatively (the salicylic aluminium compound of di-tert-butyl):
1 part by mass
C.I. the blue 15:3 of pigment is 6.0 parts by mass
The temperature of monomer complex is brought up to 60 ℃, 12 parts the ester type waxes by mass that mainly comprises behenic acid mountain Yu ester is (when adding thermal measurement in DSC, in the time of 72 ℃, have the highest endothermic peak) be added in this complex, mix with it, and be dissolved in this complex.With by mass 3 parts 2,2 '-azo two (2, the 4-methyl pentane nitrile) [t1/2=140 60 ℃ the time] is dissolved in the gains as polymerization initiator.
Above-mentioned polymerisable monomer system is packed in the aqueous medium, at N 2Atmosphere, under 60.5 ℃, with 10,000rpm stirred whole 15 minutes, carried out granulating afterwards with TK homogenizer (being made by Tokushu Kika Kogyo).Then, under 60.5 ℃, gains were reacted 6 hours, simultaneously, stir gains with oar shape stirring vane.Then, continue again to stir 4 hours, wherein make fluid temperature remain on 80 ℃.After finishing reaction, distilled 3 hours down at 80 ℃.Then, suspending liquid is cooled, and is added hydrochloric acid then, so that the dissolving phosphoric acid calcium salt.Gains are filtered, and wash with water.So, obtained wet colored particle.
Next, under 40 ℃,, thereby obtain colored particle (toner particle) with dry 12 hours of particle.
Handle with silicone oil, wherein each particle all has 130m 2The BET value of/g and the main particle diameter of 12nm divide 100 parts toner particle and 1.2 parts hydrophobic silica microparticle by mass by mass, used Henschel mixer (MITSUI MIIKEMACHINERY CO., LTD. make) mix, thus obtain nonmagnetic toner (cyan toner) 1.
Producing nonmagnetic toner (pinkish red toner) 1, but be to use 8.0 parts C.I. pigment redness 122 by mass, to replace 6.0 parts the blue 15:3 of C.I. pigment by mass with the same mode of the generation example of cyan toner.
Similarly, producing nonmagnetic toner (Yellow toner) 1, but be to use 8.0 parts C.I. pigment yellow 17 by mass, to replace 6.0 parts the blue 15:3 of C.I. pigment by mass with the same mode of the generation example of cyan toner.
Similarly, producing nonmagnetic toner (black toner) 1, but be to use 5 parts carbon black by mass, to replace 6.0 parts the blue 15:3 of C.I. pigment by mass with the same mode of the generation example of cyan toner.
(B) transparent toner (T toner)
Producing nonmagnetic toner (transparent toner) 1, but there not be the colorant of use such as C.I. pigment blueness with the same mode of the generation example of cyan toner.
The Na of 250 parts 0.1M by mass 3PO 4Aqueous solution is loaded into by mass in 405 parts the ion exchange water, and the temperature of potpourri is increased to 60 ℃.Then, with 40.0 parts the CaCl of 1.07M by mass 2Aqueous solution is little by little added in the gains, thereby can obtain to comprise the aqueous medium of synthos.
Simultaneously, disperse and mix following prescription equably by masher (MITSUI MIIKE MACHINERY CO., LTD. makes).
Styrene: 80 parts by mass
N-butyl acrylate: 20 parts by mass
Divinylbenzene: by 0.2 part of quality
Saturated polyester resin (Mw=41,000):
4.0 parts by mass
The charge control agent that can charge negatively (aluminium compound of di-tert-butyl salicylic acid):
1 part by mass
The temperature of monomer complex is brought up to 60 ℃, 12 parts the ester type waxes by mass that mainly comprises behenic acid mountain Yu ester is (when adding thermal measurement in DSC, in the time of 72 ℃, have the highest endothermic peak) be added in this complex, mix with it, and be dissolved in this complex.With by mass 3 parts 2,2 '-two (2, the 4-methyl pentane nitrile) [at the 60 o'clock t1/2=140] of azo are dissolved in the gains as polymerization initiator.
Above-mentioned polymerisable monomer system is packed in the aqueous medium, at N 2Atmosphere, under 60.5 ℃, with 10,000rpm stirred whole 15 minutes, afterwards, carried out granulating with TK homogenizer (being made by Tokushu Kikthe Kogyo).Then, under 60.5 ℃, complex was reacted 6 hours, simultaneously, stir gains with oar shape stirring vane.Then, continue again to stir 4 hours, wherein make fluid temperature remain on 80 ℃.After finishing reaction, distilled 3 hours down at 80 ℃.After this, cooling suspension adds hydrochloric acid then, so that the dissolving phosphoric acid calcium salt.Gains are filtered, and wash with water.So, obtained wet colored particle.
Next, under 40 ℃,, thereby obtain transparent particles (transparent toner particle) with dry 12 hours of particle.
Handle with silicone oil, wherein each particle all has 130m 2100 parts the toner particle and 1.2 parts the hydrophobic silica microparticle by mass by mass of the BET value of/g and the main particle diameter of 12nm, used Henschel mixer (MITSUI MIIKEMACHINERY CO., LTD. make) mix, thus obtain nonmagnetic toner (cyan toner) 1.
Nonmagnetic toner produces example 2
Produce nonmagnetic toner 2 to produce mode identical in the example 1, that is, colour toners (C, M, Y and K toner) and transparent toner (T toner) are arranged, be changed but nonmagnetic toner produces the adjuvant of the toner of example 1 with nonmagnetic toner.
In other words, in nonmagnetic toner produces example 2, with hexamethyldisilazane handle handle with silicone oil then, wherein each particle all has 130m 2100 part toner particle and 0.6 part the hydrophobic silica microparticle by mass by mass of the BET value of/g and the main particle diameter of 12nm, used Henschel mixer (MITSUI MIIKEMACHINERY CO., LTD. make) mix, and be used as the external adjuvant of toner, thereby obtain nonmagnetic toner (coloured and transparent toner) 2.
(two assembly developing apparatus)
In this example, used the developing apparatus that has above with reference to figure 2 described structures.
In this example, the aluminum coating sleeve is used as development sleeve 40, and this sleeve is a developer bearing part, and the distance between development sleeve 40 and each photosensitive drums 1 is set to 450 μ m.For the Dc bias of using of developing be-500V to what development sleeve 40 applied, AC bias is set to 1, the P-to-P voltage of 200Vpp, and frequency is 2,000Hz.
In addition,, used the corona charging method of contactless, controlled by this way, that is, made the surface of each photosensitive drums will be charged to-650V for each charging device 2.
Each photosensitive drums all is suitable in the position that the irradiation by light image has formation an electrostatic latent image of maximum image density having-the photoelectricity gesture of 100V.That is, development contrast is set to 400V.
Example 1
In this example, designed image promptly, makes that the maximum bearing capacity when forming image by the stack that colour toners (that is, C, M, Y and K toner) is arranged will be corresponding to two kinds of colors by this way, that is, maximum bearing capacity will be 1.0mg/cm 2It is at this moment, single that the maximum toner bearing capacity of colour toners is arranged is 0.5mg/cm 2Nonmagnetic toner No.1 is used as colour toners, and nonmagnetic toner No.2 is used as transparent toner (T toner).That is, adding each with 1.2 parts silica by mass to as external adjuvant has in the colour toners, adds in the transparent toner as external adjuvant with 0.6 part silica by mass.Coloured and transparent toner differs from one another aspect the weight rate of toner at external adjuvant.In other words, reduce the quantity of electric charge by the amount that reduces the external adjuvant that will be added to transparent toner.Being mixed by vee-blender is each toner of 8 parts by mass, and 92 parts coated carrier No.1 by mass, and this potpourri is defined as the developer A that is used to begin.
Resulting developer is loaded into each developing apparatus 4 (4a, 4b, 4c, 4d and 4e) corresponding to the imaging moiety of the toner color of the imaging device 100 with five stations shown in Figure 1.
At this moment, each has the triboelectricity of colour toners all is-32 μ C/g, and the triboelectricity of transparent toner is-16 μ C/g.That is, each has the absolute value of the quantity of electric charge of the per unit weight of colour toners is 32 μ C/g, and the absolute value of the quantity of electric charge of the per unit weight of transparent toner is 16 μ C/g.The absolute value of transparent toner has the absolute value of colour toners less than each.
Utilize such structure to carry out imaging.As a result, development contrast is almost 400V, and can realize the 0.5mg/cm that each has colour toners 2Development, and the 1.0mg/cm of transparent toner 2Development, wherein each value all is the maximum toning dosage on the photosensitive drums.
According to this example, utilize said structure, to have the triboelectricity of colour toners to compare fully little with each for the triboelectricity that makes transparent toner, thereby, can be by being substantially equal to the develop required toning dosage of transparent toner of each contrast that the development contrast of colour toners is arranged.In addition, the needed electromotive force of transparent toner that can obtain to develop, and can form image by the needed toning dosage of the unevenness that is used for removal of images.
In other words, as mentioned above, the triboelectricity of transparent toner is lowered to than each has the triboelectricity of colour toners low, and transparent toner is added to the part corresponding to image.As a result, imaging device can: the unevenness and the lustre lacking uniformity that prevent toner; Realization is carried out imaging by the transparent toner by the amount that equals each maximum bearing capacity that colour toners is arranged, and wherein for each toner in coloured and the transparent toner, formation method does not almost change.
Example 2
In this example, nonmagnetic toner No.1 is used as colour toners (that is, C, M, Y and K toner) and transparent toner (T toner).Weighing also uses by mass each of 8 parts that colour toners and 92 parts coated carrier No.1 are by mass arranged.Weighing is 8 parts transparent toner and 92 parts coated carrier No.2 by mass by mass.Each combination all mixes by vee-blender, and potpourri is defined as the developer B that is used to begin.Then, each developer B is loaded in the station corresponding to the toner color of imaging device.
In example 1, designed image promptly, makes that the maximum bearing capacity when the colour toners stack is arranged will be corresponding to two kinds of colors by this way, that is, maximum bearing capacity will be 1.0mg/cm 2In example 2, designed image promptly, makes that the maximum bearing capacity when the colour toners stack is arranged will be corresponding to 2.4 kinds of colors by this way, that is, maximum bearing capacity will be 1.2mg/cm 2Therefore, change according to this, each triboelectricity that colour toners is arranged is-32 μ C/g, and the triboelectricity of transparent toner be by with (32 μ C/g) divided by 2.4 values that obtained (that is μ C/g ,-13).For this reason, wherein each particulate all serves as the amount of hydrophobic silica microparticle that will be added to the external adjuvant of nonmagnetic toner No.1 and is adjusted to amount in the situation about being lower than in the example 1.
In addition, the appropriate value of can method as described below determining the triboelectricity of the transparent toner in this example.That is, multiply by single maximum bearing capacity (for example, the 0.5mg/cm that colour toners is arranged by the triboelectricity (for example, 32 μ C/g) that each is had colour toners 2) maximum bearing capacity (for example, 1.2mg/cm when being superimposed with the colour toners image 2) between ratio (0.5/1.2=0.42), can determine this value (32 * 0.42=13 μ C/g).
Form image by toner with coated carrier No.1.As a result, development contrast is almost 400V, can realize the 0.5mg/cm that each has colour toners 2Development, and the 1.2mg/cm of transparent toner 2Development, wherein each value all is the maximum toning dosage on the photosensitive drums.
Can adjust the triboelectricity of nonmagnetic toner according to the amount of the external adjuvant that will add, also can change any other material into from the hydrophobic silica microparticle and adjust by material with toner.This is because different materials is differing from one another aspect the electrification by friction characteristic.Can suitably select and use any in the external adjuvant in the above-mentioned example.Here employed term " electrification by friction characteristic " is meant charging polarity and the charge volume when rubbing between same type of material.
In this example, by adjusting for example type or the amount of external adjuvant, reduce the triboelectricity of transparent toner pro rata with each number of colors that colour toners is arranged that all has a maximum bearing capacity.So, form image by transparent toner with the amount that equals each maximum bearing capacity that colour toners is arranged, transparent toner is added to the part corresponding to image, the unevenness and the lustre lacking uniformity of toner have been prevented, wherein for each toner in coloured and the transparent toner, formation method does not almost change.
Example 3
In this example, identical with the situation of example 1, designed image promptly, makes that the maximum bearing capacity when the colour toners stack is arranged will be 1.0mg/cm by this way 2
Nonmagnetic toner No.1 is used as colour toners (C, M, Y and K toner) and transparent toner (T toner).By sieving coated carrier No.2 with screen cloth to have the mean grain size of 25 μ m, obtaining each has the carrier that will use in the colour toners.By the mean grain size of coated carrier No.2 being changed into 35 μ m, obtain the carrier that will use in the transparent toner.Weighing is 8 parts each toner and 92 parts the coated carrier of correspondence by mass by mass, and with vee-blender they is mixed, and potpourri is defined as the developer C that is used to begin.This developer is loaded in the station corresponding to the toner color of imaging device.
At this moment, each has the triboelectricity of colour toners all is-34 μ C/g, and the triboelectricity of transparent toner is-15 μ C/g.
Utilize such structure to carry out imaging.As a result, development contrast is almost 400V, obtains the 0.5mg/cm that each has colour toners 2Development, and the 1.0mg/cm of transparent toner 2Development, wherein each value all is the maximum toning dosage on the photosensitive drums.
Along with the mean grain size of carrier reduces, for identical weight, the quantity of particle increases, and surface area also increases.Correspondingly, the charging ability of expection toner improves, and the triboelectricity of expection toner also improves.
Another aspect except its particle diameter of carrier also influences the triboelectricity of toner.
Shown in above-mentioned table 1,, can adjust carrier, so that it is suitable for desirable toner triboelectricity by changing each the amount in bottoming agent, coating reagent and the coupling agent.
For example, can use any resin in the treated resin in various surface as described above, as bottoming agent, coating reagent, and in the coupling agent each.Wish to adjust type of material and addition,,, can obtain different electrification by friction characteristics because depend on the charging order of selected material so that obtain desirable electrification by friction characteristic.
As mentioned above, in this example, by changing the particle diameter of carrier, the triboelectricity of transparent toner is lowered to than each has the triboelectricity of colour toners low.So, the amount that equals each maximum bearing capacity that colour toners is arranged by transparent toner forms image, transparent toner is added to the part corresponding to image, and the unevenness and the lustre lacking uniformity of toner have been prevented, wherein for each toner in coloured and the transparent toner, formation method does not almost change.
Example 4
Fig. 7 has shown the schematic construction according to coloured imaging device of intermediate transfer method as another example of the present invention.
In this example, except more following, imaging device 100 has same structure with panchromatic (four looks) electrophotographic image forming of on line method described in each example in example 1 to 3.In the imaging device 100 in each example in example 1 to 3, directly and continuously be transferred on the recording materials S at the toner image that forms on the surface of photosensitive drums 1, these recording materials be transported to respective imaging part P (Pa, Pb, Pc, Pd and Pe) with record color image by conveying belt 7.Yet, in this example, provide belt like intermediate transfer body 7T to replace conveying belt 7.
Therefore, same reference numerals be given with example 1 to 3 in the imaging device of each example parts with same structure and function, quoted the description of each example in the example 1 to 3, and omitted and be repeated in this description.
As mentioned above, different with example 1 to 3, in this example, at first, be transferred to continuously on the intermediate conveyor belt 7 to form coloured image at the toner image that forms on the surface of corresponding photosensitive drums 1.Next, by applying voltage to transfer roll 60 as the secondary transfer printing device, the coloured image on the intermediate conveyor belt 7 be transferred to from recording materials box 10 separate and the recording materials S that presents on.
Next, recording materials S is transported to fixing device 9, and to recording materials S heating and pressurizing, thereby the toner image of photographic fixing transfer printing.Then, recording materials S is discharged into discharge unit 14.
Even in color-image forming apparatus according to the intermediate transfer method of this example, with the same way as of example 1, make the triboelectricity of transparent toner have the triboelectricity of colour toners to compare fully little with each.As a result, can be by being substantially equal to the develop necessary toning dosage of transparent toner of each contrast that the development contrast of colour toners is arranged.In addition, the needed electromotive force of transparent toner that can obtain to develop, and can form image by the needed toning dosage of the unevenness of removal of images.
In addition, in the mode identical, by adjusting for example type or the amount of external adjuvant, reduce the triboelectricity of transparent toner pro rata with each number of colors that colour toners is arranged that has colour toners all to have maximum bearing capacity wherein with example 2.So, form image by transparent toner with the amount that equals each maximum bearing capacity that colour toners is arranged, transparent toner is added to the part corresponding to image, and can prevent the unevenness and the lustre lacking uniformity of toner, wherein for each toner in coloured and the transparent toner, formation method does not almost change.
In addition, in the mode identical, by changing: the particle diameter of the magnetic core of carrier with example 3; The material of the coating of magnetic core (that is, coating resin and/or coupling agent); Or the addition of material, the triboelectricity of transparent toner is reduced to than each has the triboelectricity of colour toners low.So, form image by transparent toner with the amount that equals each maximum bearing capacity that colour toners is arranged, transparent toner is added to the part corresponding to image, and can prevent the unevenness and the lustre lacking uniformity of toner, wherein for each toner in coloured and the transparent toner, formation method does not almost change.

Claims (9)

1, a kind of imaging device comprises:
Some have a colour toners imaging device, each device all forms electrostatic image, and with this electrostatic image of coloured toner development being formed with the colour toners image, this has the colour toners imaging device to be used for forming toner image by the colour toners that has that differs from one another;
The transparent toner imaging device, this device forms electrostatic image, and showing this shadow electrostatic image to form the transparent toner image with transparent toner, the quantity of electric charge of the per unit weight of this transparent toner has the quantity of electric charge of the per unit weight of colour toners less than each;
Transfer device, this device is with coloured toner image and transparent toner image overlay and be transferred on the offset medium.
2, imaging device according to claim 1, wherein, when differ from one another have colour toners to be superimposed upon on the offset medium time unit area maximum toner bearing capacity be 2 to 2.5 times of a kind of maximum toner bearing capacity that the colour toners unit area arranged.
3, imaging device according to claim 1, wherein, the described colour toners that has that differs from one another differs from one another aspect color.
4, imaging device according to claim 1, wherein, adding each to from the outside has the external adjuvant the colour toners and the external adjuvant that adds to the transparent toner from the outside is differing from one another aspect the electrification by friction characteristic.
5, imaging device according to claim 1, wherein, adding each to from the outside has the external adjuvant the colour toners and the external adjuvant that adds to the transparent toner from the outside is differing from one another aspect the weight ratio of toner.
6, imaging device according to claim 1, wherein:
There is each toner in colour toners and the transparent toner all to comprise nonmagnetic toner, and mixes mutually with the magnetic carrier that is used as tow-component developer; And
There are magnetic carrier that colour toners mixes and the magnetic carrier that mixes with transparent toner differing from one another aspect the electrification by friction characteristic with each.
7, imaging device according to claim 6, wherein:
Obtain each magnetic carrier by on the surface of magnetic core, forming coat; And
The magnetic core of the magnetic carrier that with each magnetic core of the magnetic carrier that colour toners mixes is arranged and mix with transparent toner differs from one another aspect the particle diameter.
8, imaging device according to claim 6, wherein:
Obtain each magnetic carrier by on the surface of magnetic core, forming coat; And
The coat of the magnetic carrier that with each coat of the magnetic carrier that colour toners mixes is arranged and mix with transparent toner is differing from one another aspect the electrification by friction characteristic.
9, imaging device according to claim 1 also comprises:
Fixing device, this device will the stack toner image to offset medium; And
Control device, this device come the imaging operation that the transparent toner imaging device is carried out is controlled in such a way,, make by the height of the toner image of the stack of fixing device photographic fixing it is constant basically that is.
CNB2006100923074A 2005-06-01 2006-06-01 Image forming apparatus Expired - Fee Related CN100517099C (en)

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CN101364065B (en) * 2007-08-03 2011-05-25 佳能株式会社 Image forming system
CN102163023A (en) * 2010-02-24 2011-08-24 佳能株式会社 Image forming apparatus and control method thereof
CN101598913B (en) * 2008-06-03 2011-12-14 佳能株式会社 Image processing apparatus, and control method therefor
CN102937781A (en) * 2012-10-17 2013-02-20 河北科技大学 Preparation method for toner adopting polyester and styrene-acrylate copolymer as binding resins
CN103002185A (en) * 2011-09-14 2013-03-27 株式会社理光 Imaging device, image reading device and image processing system
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