JPH0769630B2 - Toner composition - Google Patents

Description

Detailed Description of the Invention

[0001]

This invention relates generally to toners, developers,
And an image forming method such as a full color image forming method for forming a multicolor image, and more particularly, the present invention relates to a method for obtaining a multicolor image such as a four color image in which one color is black. In one embodiment, black toner is used in one of the images, which includes charging and developing the imaging member four times. The black toner of the present invention has, for example, from about 15 to about 60 as measured by charge spectroscopy.
Excellent mixing characteristics of seconds, when measured by a known Faraday Cage measurement, for example, desirable triboelectric properties of about + 10 to about 25 microcoulombs / g, having an acceptable and stable A _t like. The black toners of the present invention have substantially no background smearing, acceptable mottle, minimal image graininess, and no unwanted historical image defects, avoiding or minimizing cometing. And provides improved toner flow properties in the developer housing and in the toner dispenser. Furthermore, this toner is substantially inert with respect to each color toner used, for example in that the triboelectric properties of each color toner and the color strength of the developed image are not adversely affected. In each embodiment,
The toner and developer of the present invention can be used in a specific color image forming method such as processing color (process color). Another advantage according to the present invention is that after development a high quality image, i.e. under a wide range of humidity conditions, i.e. 20 to 80% relative humidity, e.g.
About 48.9 ° C), preferably about 60 to about 90 ° F (about 1
Stable positive triboelectric properties that enable the formation of background-free and substantially smear-free images in the effective temperature range of 5.5 to about 32.2 ° C. It is to provide a developer having.

One example of the above-described developing method involves a developer housing having a two magnetic auger transport single magnetic brush design mounted at approximately 6 o'clock. The magnetic brush roll (developer roll) is about 30 mm in diameter, has a grooved surface for developer transport, and preferably operates at about 3.0 times the speed of the photoreceptor or imaging member. The developer roll is about 0.5 mm away from the photoreceptor and is biased by a negative DC bias, for example 200 to about 500 volts. A static magnet is installed internally in the rotating developer roll sleeve, and this magnet contains ferrite having a designed magnetic pole shape, and satisfies the conditions for controlling developer transport and developability. The developer fluidity (amount on the sleeve, or MOS) is controlled by the position of the low permeability trimmer rod in the magnetic field at the time of trimming. Typically about 25 to about 40 mg / cm ^{2 of} MOS
To be sensitive to trim gap, toner concentration (TC) and developer tribo. The two augers in the developer housing holes carry the developer in opposite directions, first through the toner dispenser and then through the developer pickup area of the developer roll. Each auger has slits built into the auger to facilitate mixing of fresh toner added to the developer. Usually, a plurality of latent images of about 4 are formed on the image forming member, and first, with the black toner of the present invention,
Then, the development is sequentially performed with magenta toner, cyan toner, and yellow toner. It is also possible to develop black alone, or black with one or more other colors.

[0003]

As prior art, there are the following U.S. Patents: 4,288,517 and 4,301,228.
Nos. 4,533,616, 4,828,954 and 4,973,540. U.S. Pat. No. 4,94
No. 8,686, some resin particles such as styrene-butadiene, a first pigment such as copper phthalocyanine,
A first toner comprising a charge control additive, colloidal silica as an external additive and a metal salt of a fatty acid;
A terpolymer, a color developer comprising a first carrier comprising a steel core with an overcoating; and a second developing comprising a black toner, a second charge additive and a steel core carrier having a certain polymeric overcoating. A method of forming a two-color image with an agent is disclosed. A two-color image forming method is described in US Pat.
No. 4,186. 1 photosensitive image forming member
A method of charging to one polarity and producing on it an image containing at least three different potential values of the same polarity is disclosed in US Pat. No. 4,078,929. This U.S. patent discloses a charged image on the imaging surface that includes a first charged area as a background area, a second area having a higher voltage than the first area, and a third area having a lower voltage than the first area. A method for forming a two-color image by forming the image is disclosed, and the second and third areas function as image areas. The charged image is developed with positively charged toner particles of the first color in the first step,
In the next development stage, development is performed with negatively charged toner particles of the second color. Further, the charged image may be developed with a dry developer containing toners of two different colors in one developing step.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide toner and developer compositions, and imaging methods using these compositions.

[0005]

The above and other objects of the present invention can be achieved in each embodiment by providing a developer, a toner and an image forming method of the present invention.
In one embodiment of the present invention, resin particles, black pigment particles, magnetite, charge promoting additives, and certain treated colloidal silicas such as UNILIN® available from Petrolite Company. A toner composition is provided that includes a surface additive that includes a mixture with a polymeric hydroxy compound. The developer is a toner such as a carrier such as ferrite, preferably polymethylmethacrylate and KYNAR®.
It can be prepared by mixing with a ferrite carrier coated with a polymer mixture such as (see US Pat. Nos. 4,937,166 and 4,935,326).

Examples of resin particles for use in the toner of the present invention include styrene acrylate, styrene methacrylate, polyester, crosslinked styrene methacrylate, styrene butadiene, especially the commercially available Goodyear Pliolite®,
Some have a high styrene content, such as about 80 to about 95% by weight, such as PLIOTONE®. The resin is present in an effective amount of, for example, about 70 to about 98% by weight. Known toner resins include styrene acrylate and styrene methacrylate (5
8/32); linear and branched polyesters; pliolites, pliotones available from Goodyear Chemical Company; styrene-butadiene polymers, especially in amounts of about 83 to about 93% by weight, preferably about 88% by weight of styrene component. There is a styrene-butadiene copolymer present and having the butadiene component present in an amount of from about 7 to about 17% by weight, preferably about 12% by weight. Also, the styrene-n-butyl methacrylate polymer, especially the styrene segment, is present in an amount of about 50 to about 70% by weight, preferably about 58% by weight, and the n-butylmethacrylate segment is about 30 to about 50% by weight, preferably about 42% by weight. Styrene-n-butyl methacrylate copolymer present in the amount of% may also be suitable. Mixtures of these resins can also be used. Preferred as the toner resin is emulsion polymerized styrene butadiene, preferably present in an amount of about 87 to about 89 weight percent (see US Pat. No. 4,469,770).

Black toner pigments are known and are known as REGAL 330, VULCA.
N), furnace black, etc. The black pigment is present in various effective amounts such as, for example, from about 1 to about 15% by weight of the toner, preferably from about 2 to about 10%. These pigments are called MAPICO BLA
CK) part of a mixture with magnetite.
The mixture is, in each embodiment, preferably about 2 to about 1.
An effective amount of carbon black such as 0% by weight and preferably about 2 to about 10% by weight, more preferably about 2 to about 7% by weight.
It contains magnetite like Mapico Black. 1
One preferred mixture contains 5.5% by weight of Regal 330 carbon black and 4.5% by weight of mapico black.

About 0.5 to about 10% by weight, preferably about 1 to
Examples of charge promoting additives that are present in various effective amounts such as about 2% by weight include known additives such as distearyl dimethyl ammonium methyl sulfate, cetyl pyridinium halides especially chlorides, bisulfides, and mixtures thereof. is there. Examples of specific charge additives include alkyl pyridinium halides, preferably cetyl pyridinium chloride (US Pat. No. 4,29,29).
No. 8,672); organic sulfates and sulfonates (see US Pat. No. 4,338,390); preferred additives, distearyl dimethyl ammonium methyl sulphate (DDAMS) (at 1.2% by weight of toner). U.S. Pat. No. 4,56, which gives excellent mixing properties
0,635)). The black toner of each embodiment typically has a positive charge of from about 5 to about 35 microcoulombs / g, preferably from about 8 to about 25 microcoulombs / g, which charge is the amount of charge promoting additive present; and the toner resin. , Many known factors such as the exact composition of other ingredients such as pigments, carrier cores, and coatings used for carrier cores), and about 15 to about 6
It has a mixing time of 0 seconds, preferably about 15 to about 30 seconds.
In preparing a toner composition, a preparation containing a toner resin, a pigment, magnetite and a charge-accelerating additive can be usually subjected to micronization and classification, which mainly removes fine particles and substantially extremely large particles. And to obtain toner particles having an average volume diameter of, for example, about 8 to about 15 microns, preferably about 8 to about 12 microns. The toner of the present invention in each embodiment can be prepared by a method such as extrusion, in which the resin, black pigment, magnetite, and charge control additive are dry mixed, the materials are placed in an extruder, and the mixture is melt mixed. Then
A continuous process that involves extruding the mixture and attenuating the extruded material to obtain pellets. The pellets are further attenuated by milling or jetting and then classified to particle size. In one embodiment of the invention, toner compositions having an average particle size of about 8 to about 15, preferably about 8 to about 12 microns are preferred. External additives can then be mixed with the above classified toner in a known medium intensity dry powder mixer. Other known toner preparation methods may be used, such as melt mixing the components in a Banbury, followed by cooling, milling and classification.

The toners described above can be used as surface or external component additives in effective amounts such as from about 0.18 to about 1% by weight, and from about 0.8 to about 0.22, preferably about 0.15% by weight. And certain colloidal silicas such as AEROSIL # 76 and UNILIN [Formula: CH ₃ present in an effective amount of about 0.1 to about 0.4, preferably 0.25% by weight. (CH ₂ ) _n CH ₂ OH
A high molecular weight hydroxy compound, wherein n is from about 30 to about 30.
A number of 0, preferably a number of about 30 to about 50]. One preferred hydroxy compound is about 475
To a number average molecular weight of about 1,400, more preferably about 475.
Has a number average molecular weight of about 750. These hydroxy compounds and their toners are described in US Pat. No. 4,883,7.
No. 36. The charge value of the toner can be adjusted by changing the amounts of these two types of external additives. For example, increasing the amount of Erosir # 76 and the high molecular weight hydroxy compound generally adjusts the triboelectric charge in the positive direction to improve mixing time, which is triboelectrically charged after fresh toner contacts the developer. It is a measure of the amount of time it takes.

The carrier for the developer in one embodiment of the present invention is a ferrite, preferably D.I. M. A copper-zinc core having an average volume diameter of about 40 to about 80 microns, preferably about 45 to about 60 microns, available from Steward, and on its surface, such as polyvinylidene fluoride (Kynal) and polymethylmethacrylate. A preferred ratio of 0.15 to 35:65 (however, the first polymer such as kynar is in the range of about 25 to about 45 and the second polymer such as polymethylmethacrylate is in the range of about 55 to about 75). To about 1% by weight, preferably 0.3% by weight of the polymeric coating. A preferred carrier that can be used is a ferrite carrier as disclosed in US Pat. Nos. 4,937,166 and 4,935,326.
These carriers, in one embodiment, comprise a core with two polymer coatings that are not in close proximity in the triboelectric series. These carriers have a particle size of about 40 to about 80 microns, preferably about 45 to about 60 microns in semiconducting ferrite.

Examples of imaging members used in the method of the present invention include xerography such as multilayer organic materials such as those disclosed in US Pat. No. 4,265,990.
There are various dielectric or photoconductive insulating materials that may be suitable in ionography or other electrophotography. In one embodiment, four latent images are formed and one of these images is developed with black toner of the invention as described above. Known color toners are used to develop each of the other latent images. These toners include magenta such as FANAL PINK with about 5% flashing, and PV fast blue (FAST) with about 2% by weight.
BLUE) cyan, about 5% permanent
There is a yellow such as Yellow FGL and the resin is usually emulsion polymerized styrene butadiene, but other toner resins such as those mentioned above may also be used in each embodiment. The developed image is then transferred to any suitable substrate such as paper, transparent material and the like. Transfer is obtained by any suitable means, such as by charging the backside of the substrate with a corotron to the opposite polarity of the toner. The transferred image is then permanently fixed to the substrate by any suitable means. For each toner of the present invention, fixing by heating and pressure is preferable.
On a substrate such as paper, one obtains pictorial colors such as black, green, blue, red, yellow, brown.

Development is generally accomplished by the magnetic brush development method as disclosed in US Pat. No. 2,874,063. The method involves magnetically transporting a developer material containing magnetic toner and magnetic carrier particles. In the method of the present invention, the conductive magnetic brush method is preferred, in which the developer contains conductive carrier particles and is capable of conducting an electric field between the biased magnets through the carrier particles to the photoreceptor. . The developer compositions used in this invention generally contain various effective amounts of carrier and toner. Generally, from about 6 to about 12% by weight, preferably 8.5% by weight of toner, and from about 88 to about 9%.
The developer is prepared by mixing 4% by weight, preferably 91.5% by weight, of the carrier. The toner to carrier ratio may vary depending on, for example, the desired triboelectric charge. The particle size of each color toner is generally about 9 to about 14 microns, preferably about 11 microns by volume average diameter.

Embodiments of the invention include resins, carbon black, magnetite, positive charge promoting additives, and surface additive mixtures of polymeric hydroxy compounds and colloidal silica treated with quaternary ammonium salt compounds. A developer composition comprising toner and carrier particles comprising a ferrite core having a polymer mixture coating on the surface; as well as forming a plurality of individual latent images on the photoconductive imaging member, and then one image. Is developed with a black developer composition, and then the remaining three images are sequentially developed with three different toners containing a resin and a color pigment other than black, and the toner pigment used for the second image is the third one. Unlike the toner pigment used for the image, the toner pigment used for the third image is different from the toner pigment used for the fourth image, and subsequently, each developed image is appropriately processed. There are all colors color image forming method comprising fixing the each image transferred to the substrate to a substrate.

[0014]

【Example】

Example 1 A black developer composition was prepared as follows. 88.8 wt% emulsion polymerized styrene butadiene (89/11), 5.5 wt% Regal 330 carbon black, 4.5 wt% magnetite mapico black, and 1.2 wt% charge additive di Stearyl dimethyl ammonium methyl sulphate is melt mixed in an extruder ZSK53 with the die maintained at a temperature of 130-170 ° C and the airframe temperature in the range of about 70-150 ° C, then cooled, atomized and air classified. To obtain toner particles having a volume average diameter of 9.5 μm. Then, the toner particles are mixed with 0.15
% By weight dimethyloctadecyl-3-trimethoxy (silyl) propyl ammonium chloride treated colloidal silica particles (these particles are POLON MF
It is believed to be EROSIL # 76 treated at -50 and is available from Teika Corporation of Japan] and 0.25
Uniline having a weight percent average molecular weight of 700 (see Example 1 of US Pat. No. 4,883,736, the disclosures of which are all incorporated herein by reference; this uniline was obtained from Petrolite). ). Subsequent carrier particles were prepared by dry powder coating a 50 micron diameter copper zinc ferrite carrier obtained from Steward Chemical Co. at a coating weight of 0.3% with a mixture of 35 wt% Kynal and 65 wt% polymethylmethacrylate. did. Next, 100 parts by weight of the black developer and 10 parts by weight of the above-mentioned coating carrier particles in the Lodige blender for about 15 minutes at 60 RPM in the Lodige blender.
Prepared by obtaining a toner-containing toner having a triboelectric charge of +13 microcoulombs / g as measured in a known Faraday cage apparatus at a toner concentration of about 8.5%. The mixing time for the substantially uncharged additive toner containing the same components as the toner prepared above was about 15 seconds as measured by known charge spectrograms.

Thereafter, the above black magnetic developer was
Includes Zenta toner, Cyan toner and Yellow toner
All Zerox Corporation 5775 All 4 Colors
-Incorporated in an image forming device, it has excellent quality and
Black without background, and red,
With the same developer charged picture pattern of yellow, blue and green
Transfer and add 100,000 copies with text type
Obtained after fixing by heat. Friction of the above magnetic black toner
The charge is about 100,000 developed black images
It remained at 10 to about 15 microcoulombs / g. Use
The imaging member is an aluminum substrate on which a trigonal crystal
Photogenerating layer and 45 wt% macrolone (MAK
ROLLON) dispersed in a polycarbonate binder
Arylamine N, N^,-Diphenyl-N, N^,-Bi
Su (3-methylphenyl) 1,1 ^,-Biphenyl-4,
Four^,-Contains a charge transport top layer of diamine (US
See U.S. Pat. No. 4,265,990.
All are incorporated herein by reference).

[0016]

Example 2 A toner and developer were prepared by repeating the procedure of Example 1, but containing 40% by weight of pigment and 60% by weight of styrene butadiene (obtained as a priolite from Goodyear Chemical Company) as the pigment. Flash-processed Hosta Palm Pink E12.5 wt% without Mapico Black was used. The triboelectric charge of this toner was +15 microcoulombs / g. This toner can be used with the toner of Example 1 and two other color toners in the full color imaging process as described above. Examples of magenta pigments are Hosta Palm Pink E, available from American Hoechst, Hosta Palm Pink EB, B available from American Hoechst.
Farnal Pink D483 available from ASF
0, Ritol Rubin NBD available from BASF
4573, of these, for example, Hosta Palm Pink E
There is an effective mixture such as B or Hostaperm Pink E with Bathonyl Red 560 available from BASF. These magenta pigments are present in the toner in various effective amounts, such as from about 0.1 to about 15% by weight, preferably from about 1 to about 5% by weight. Further, in each embodiment of the magenta toner, 0.1 to 0.3% by weight is used.
About 3.2% by weight containing Busonyl Red 560
Hosta Palm Pink E can be used per 100 parts of toner. Similar toners can be prepared using cyan and yellow pigments instead of Hostaperm Pink.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03G 9/097 9/113 G03G 9/08 361 344 9/10 351 (72) Inventor Julie Sea Picker Ring United States New York 14580 Webster Slashwood Lane 436

Claims (1)

[Claims] 1. A resin, carbon black, magnetite, a charging additive, and a polymeric hydroxy compound and a fourth compound.
A toner composition comprising a surface additive mixture comprising colloidal silica treated with a quaternary ammonium compound; and a developer composition comprising carrier particles comprising a core having a polymer mixture coating on the surface.