JPS62238581A - Black liquid developing agent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention generally relates to liquid developers, methods of making the same, and electrostatographic imaging methods using the same.

In particular, the present invention relates to special black liquid developer compositions comprising a mixture of specific dyes absorbed into the same particles. Therefore,
In one aspect of the present invention, a black liquid developer composition is provided in which each particle has a particular mixture of black, cyan, magenta, and yellow dyes absorbed therein. The composition has acceptable fusing properties, excellent shelf life stability, and a preselected black color. The black liquid developer of the present invention is particularly effective for forming black images in electrostatic imaging systems and in a variety of known printing systems, including commercially available persatic printing devices. .

For example, the development of electrostatic latent images with liquid developer compositions comprising pigments dispersed in liquid hydrocarbons is known. In these methods, an electrostatic latent image, usually formed on a single sheet of photoconductive paper such as zinc oxide, is passed through a bath of the liquid developer. Contact with the liquid developer causes the band 'ItpJ material particles present in the liquid developer to be transferred from the liquid to the zinc oxide sheet in the structure of a charged image. after that,
The sheet is withdrawn from the liquid developer with the charged pigment particles adhering to the electrostatic latent image with microstructure. The thin film of residual developer left on the surface of the sheet is then evaporated of the solvent in a relatively short period of time, typically less than 5 seconds. Also,
The microstructured marking pigment particles may be fixed to the sheet, for example by heat.

US%! 'F No. 5.554.946 describes a carrier liquid consisting of a hydrocarbon, electrostatically negatively charged toner particles dispersed in the carrier liquid, carton black, aniline black, etc. Electrophotographic liquid developers have been disclosed which are comprised of pigments such as, zol cyan sol, phthalocyanine red, and cadmium diro. According to this teaching, the surfaces of pigment particles are coated with a comonomer for the purpose of imparting a negative electrostatic charge to these particles. Other patents disclosing similar liquid developer compositions include U.S. Pat. No. 3,623,986; i3.
No. 625.897; No. g3.900.412; No. 5.
No. 976.583: No. 4,081,391; No. 3,9
No. 00,412, etc. In particular, the '1412 patent includes:
A stable developer is disclosed that is comprised of a polymer core with a steric barrier attached to the surface of the selected polymer. Column 15 of this patent specifies that the pigment or dye is selected;
Colored liquid developers made by physically dispersing them by ball milling or high shear mixing are disclosed. In an attempt to obtain color liquid developer compositions by the described ball milling process, it has been found, for example, that the desired size of the latex particles is between 0.2 and 0.2 in diameter.
0.3μ is particularly successful in obtaining developers with acceptable optical densities; this ball milling technique produces dispersions of carbon black and other pigment particles much smaller in size than about 0.7 to about 0.8μ. It is very difficult to provide things. Consequently, the addition of carbon black pigment particles to latex particles of, for example, 0.2-0.3 microns in diameter by mail milling results in relatively small latex particles deposited on the surface of the pigment particles.

Further, U.S. Pat. No. 4,476,210 (the disclosure of which is incorporated herein by reference in its entirety) discloses a method for dispersing heat in an insulating liquid medium that is substantially insoluble in the dispersion medium. a plastic core; an amphiphilic block or graft copolymer steric stabilizer irreversibly chemically or physically affixed to the thermoplastic core; and a steric stabilizer soluble in the thermoplastic core and in the dispersion medium. A stable colored liquid developer is shown comprised of an insoluble colored dye absorbed into a thermoplastic resin core.

Many of the dyes disclosed in the above patents are useful in the liquid developer compositions of the present invention. And, although the liquid developer of the present application is similar to the developer described and engineered in the '210 patent, a special combination of dyes, particularly a special combination of dyes, which allows for a preselected black color liquid developer, is used. The selection of black dye is not disclosed in US Pat. No. 4,476.210.

Additionally, in the '210 patent, a black liquid developer is obtained by intermixing latex particles, each individually dyed with a cyan, magenta, or yellow pigment. Therefore, the obtained liquid developer has a density of 500 to 550
nm and 600-700 um, which imparts an undesirable greenish hue to black developers, which is aesthetically unacceptable in some cases. In contrast, when the liquid developer of the invention is used, it exhibits strong absorption properties in the above nm range: moreover, the black developer of the invention has an ideal optical density of 1.3. Additionally, when three separate colored latexes are mixed together, as shown in the '1210 patent, the resulting composition has disparate potentials, i.e., the charge of the individual colors/ The mass ratio is different (for example, the 4th, 4th
Table 1 of the 76.210 patent). Thus, development consumes each color at different rates, resulting in a new composition of black developer, eg, having a different tone than the stored toner after developer particles are consumed. The ink compositions of the present invention are formulated by mixing proportions of dyes in suitable solvents as described below. The above problem is solved by providing an ink with black intensity that allows FM. Furthermore, in the liquid developer of the present invention, this dye solution is absorbed by each particle, making it possible to impart a similar black color to the particles, so that when the resulting black latex is charged, Each particle carries a substantially identical charge/mass ratio which allows for the color stability necessary for acceptable development over long periods of time. Furthermore, mixtures of dyes, as conventionally selected, often precipitate because, for example, the dyes are usually ionic and therefore incompatible in common solvents. The problem is overcome by the liquid developer of the invention, since the mixture of dyes of the invention provides a higher compatibility.

While the liquid developers described above are suitable for their intended purposes (particularly those disclosed in U.S. Pat. No. 4,476,210), there remains a need for improved developing compositions. In particular, there is a need for black liquid toner compositions in preselected colors. There is also a need for a special black hue stable liquid developer composition in which each particle of toner has absorbed a suitable, specified mixture of dyes.

There is also a need for a black liquid developer that enables images to have excellent optical densities, such as from about 1.0 to about 1.5, and exhibit excellent adhesion to paper. Additionally, there is a particular need for a liquid developer that has an aesthetically pleasing black color and is particularly effective in printing processes such as persatic printing and plotting equipment.

It also contains a special Orasol (0raao1) black dye mixed with magenta, yellow and cyan dyes, which pre-black with improved stability where the dyes are absorbed into each particle of the toner. There is a need for a hue selective liquid developer. There are also many different types of printing methods, such as xerography, electrographic recording, electrostatic printing, facsimile printing, and other printing methods, especially commercially available persatic printers and plotters. There is a need for a black liquid developer that can be used in reproduction processes. The liquid developer composition of the present invention satisfies all of the above requirements.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a special black liquid developer composition which overcomes many of the above sixteen disadvantages.

Another object of the present invention is to provide a preselected black liquid developer in which each particle of toner has a specific mixture of dyes absorbed therein.

It is a further object of the present invention to provide a special black liquid developer having excellent shelf life stability and acceptable fusing properties.

Furthermore, another object of the present invention is to use special Orasol Black RL, Neodevon (Neogapon) as one of the dyes.
) ° Black x5-7, or Sabinyl (5aVi
An object of the present invention is to provide an improved black liquid developer composition containing a black R1,E1 composition.

Another object of the present invention is to provide a black liquid developer composition which makes it possible to substantially reduce the level of background deposits in the final developed image.

Yet another object of the present invention is to provide a black liquid developer composition with improved dispersion stability of marking particles.

Yet another object of the present invention is to provide a special black liquid developer composition consisting of an absorbing dye mixture present on the core of thermoplastic marking particles.

Yet another object of the present invention is to provide a special black liquid developer composition with improved fusing properties to paper or transparency film.

Furthermore, an important object of the present invention is to provide an electrostatic imaging system;
electrographic recording, electrostatic) printing, coaximil) printing, and other methods (e.g., commercially available persatonic)
The present invention provides a special black liquid developer composition that is useful in a variety of reproduction processes, such as those included in printers and plotters.

It is also an object of the present invention to provide a liquid developer which, when selected for development in various commercially available printing methods such as persatic printers, enables matte or glossy black images. Our goal is to provide the following. Moreover, the resulting image has acceptable fusing properties. These and other objects of the present invention are achieved by providing a stable black liquid developer composition and method for making the same. In particular, one aspect of the invention includes a thermoplastic resin core that is substantially insoluble in the insulating liquid medium and a thermoplastic resin core that is soluble in the dispersion medium and that is chemically or physically injected into the resin core. an amphiphilic block or graft copolymer steric stabilizer that is molecularly dispersible, soluble in the thermoplastic core, and insoluble in the dispersion medium; A stable black liquid developer is provided comprising a dispersion of black marking particles comprised of an adsorbed specific dye mixture.

Therefore, according to a specific embodiment of the present invention, a thermoplastic resin core of a homopolymer or copolymer of vinyl acetate, N-vinyl-2-pyrrolidone, or ethyl acetate in an aliphatic hydrocarbon dispersion medium; Poly(2-pyrrolidone) or ethyl acrylate grafted poly(2-
Ethylhexyl methacrylate) is also poly(2-
Amphiphilic stabilizer consisting of a graft copolymer of ethylhexyl acrylate) solution: '! or poly(isozotylene--isoprene) copolymer grafted with vinyl acetate, N-vinyl-2-pyrrolidone, or ethyl acrylate (available as Karen 800 from Hardman Company, New Jersey) as a stabilizer in solution. selected Orasol Black RL, Orasol Sol-20IJN, Orasol Red G, Orasol Yellow 20LN, Sabinyl Black RLEi, Sabinil Red 3 BLIII, absorbed in its thermoplastic core;
Sabinyl Yellow 2m, Sun, Neo Devon Black X5
Orasol Black RL, Orasol Sol-2, absorbed into its thermoplastic core;
GLN, Orasol Red G1 Orasol Yellow 2 C
A stable black liquid developer composition is provided comprising black marking particles comprised of a mixture of dyes comprising k'LH.

A key feature of the invention lies in the selection of specific dye mixtures. This mixture (typically present in an amount of about 5-30 mft%) may be mixed with any or a combination of red or magenta, blue or cyan, and yellow dyes, such as Orasol Black RL (Ciba's ear dyes). (commercially available from Sandox); Savinyl Black RLS (commercially available from Sandox);
Special black dyes such as Black
5 parts by weight). In the above mixture, the magenta or red dye is about 10% by weight to about 40f
the yellow dye is present in an amount of about 10% to about 35% by weight; and the cyan or blue dye is present in an amount of about 10% to about 35% by weight.
It is present in an amount of about 50% by weight, preferably about 20% by weight. A preferred neodebon mixture is X57
Zoratsuk approx. 75 i - Yu ~ approx. 95! It consists of about 5 x red dye to about 20 x weight. These mixtures make it possible to create a liquid developer with a preselected special silk color.

Concerning the dye mixture further, it can be prepared by punching precise amounts of each dye and then dissolving them in methanol or other suitable solvent. The dye mixture usually has a weight of 2 to about 30 couls, preferably about 7 to about 14 g.
Exists at Ik. The solution may be heated to help dissolve the dye. Then, the solution was washed with Whatman# before adding it to the latex dispersion in the dyeing process.
It may be filtered using filter paper No. 4. -=yt, the proportion of petroleum, e.g., Isopar, in the final developer is usually 98-99.8% by weight.

A specific example of a dye other than black dye selected for the liquid developer composition of the present invention is Oranlu Blue tJ.

Orasol Red 2BL, Orasol Del-GL■, Orasol Yellow 2RLN, Orasol Red 2B.

Oranlu Sol-20LN, Orasol Erow 20LN
.

Orasol Red O (all available from Chipagayer, Ontario, Canada); Molfast Blue 100, Molfast Red ioi, Molfast Red 104, Molfast Yellow 102
(Available from Morton Chemicals, Inc., Ontario, Canada); Sabinyl Yellow RLS, Sabinyl Pink 6BL8° Sabinyl Red 5BLS, Sabinyl Red () L5 (Available from Ndo's, Inc., Mississauga, Ontario, Canada) etc. Other dyes can also be selected as long as they are coupled with the object of the present invention. Furthermore, the dye selected must be insoluble in the carrier medium. The insolubility of the dye in the carrier medium allows the dye mixture to be absorbed into the resin core and inhibited subsequent diffusion into the carrier medium. Moreover, the dispersion medium insolubility of the dyes ensures a reduction in background build-up, and the water insolubility of these dyes ensures the permanence of the resulting black image.

Various suitable materials may be selected as the dispersion medium, but preferably have a resistivity greater than 109 Ω/CM and a fermentation rate less than 6.5, so that the dispersion of the electrostatic latent image 'IJf,'
t- It is something that protects the skin. Additionally, these materials generally have a viscosity of less than about 2.5 centipoise to permit easy movement of marking particles therethrough. Furthermore, a dispersion should be selected that has a rapid evaporation rate such that a thin film appears in about 2-3 seconds. Specific examples of dispersion media include aliphatic hydrocarbons such as petroleum, such as Isopar G1, Einvar H1 and Isopar 1 Isopar L, all of which are available from Exxon. Other similar colorless, odorless, non-flammable dispersion media that can be selected are Amsco 460m agent and Amsco MS
(Available from Mineral Spirits)
, Deirituzos Petroleum Tsurtrol, Mobil Oils Pagasol, Shelsol (which is commercially available from Char Oil). The dispersion medium is generally a final black liquid of 1M! Approximately 99.91% of the agent composition
to about 98% by weight, preferably about 99.8% to about 99% by weight
i total %.

Marking particles (i.e., marking particles that enable a special black intensity image) are dispersed in the petroleum distillate, as shown here. A synthetic resin core that is non-molecular and has a solvated steric stabilizer irreversibly fixed (i.e., the steric stabilizer is physically or (chemically bonded) to absorb the specific dye mixture previously described. Further, in a preferred embodiment of the present invention, the marking particles contain a charge control agent present on the surface of the particles. In addition, it is important that the marking particles are preferably essentially monodisperse, ie, they are generally of the same size and shape; and have a relatively narrow size distribution.

Typically, the size of these particles is on the order of about 0.1 micron to about 1.0 micron in diameter. Substantially uniform charge on each particle or substantially uniform charge/mass ratio of the developer thereby ensuring a more accurate response of the charge marking particles to electrostatic imaging. Essentially 1!
Monodisperse particles of 71-diameter are preferred.

A wide variety of suitable thermoplastic resins can be selected as the core for the marking particles, including many known resins that have been selected for dry toner compositions.

Specific examples of the core resin include materials that are capable of non-aqueous dispersion polymerization and that are suitable for dispersion media, such as poly(methyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), and poly(hydroxyethyl). methacrylate), poly(2-ethoxyethyl methacrylate), poly(butoxyethoxyethyl methacrylate),
Poly(dimethylaminoethyl methacrylate), poly(
acrylic acid), poly(methyl acrylic acid), poly(acrylamide), poly(methacrylamide), poly(acrylonitrile), poly(vinyl chloride), poly(ureido-ethyl vinyl ether), similar equivalent resins, and the like. Preferred resins include homopolymers of 6114♂yl, K-vinyl-2-pyrrolidone, and ethyl acrylate monomers, and copolymers of any of the above polymers.

The mechanical properties of the final particles depend in some cases on the choice of resin. Thus, for example, if the core polymer is Te+f? vinegar(
N-vinyl-2-pyrrolidone) is used,
Hard particles are produced which maintain their spherical shape upon drying; on the other hand,
In the case of poly(ethyl acrylate), coalescence can occur during drying to form a film. This allows for the formation of matte or glossy developed images by controlling the thermal and mechanical dynamics that are essential to both transfer and direct liquid development of the resulting developer.

These resins are present in the final ink formulation in an amount of from about 0.1% to about 2%, preferably from about 0.3% to about 1% by weight.

The amphiphilic stabilizer that is irreversibly fixed to the resin core can be comprised of a variety of suitable materials.

Generally, these stabilizers consist of grafted housings or block copolymers containing a moiety that has an affinity for the dispersion medium and a moiety that has an affinity for the synthetic core.

Therefore, for -1 book type, this stable MIJ is about 10
．． 000 to about I CJ 13,000, and is comprised of a normally centripetal rigid containment chain grafted onto a circular polymeric backbone. Alternatively, the steric stabilizer may consist of an AB or ABA block copolymer composition. Typical block copolymers are poly(vinyl acetate-b-dimethylsiloxane), poly(styrene-b-dimethylsiloxane), poly(methacrylic methyl-b-dimethylsiloxane X poly(vinyl acetate-b-inbutylene), Poly(vinyl acetate-b-2-ethylhexyl methacrylate), poly(styrene-b-methacrylic fR2-ethylhexyl), poly(ethyl methacrylate-b-2-ethylhexyl methacrylate), poly(dimethylsiloxane-
styrene-dimethylsiloxane), etc.

Typical polymers for use as the soluble backbone portion of the graft copolymer (to which the second polymer is grafted) include polyisobutylene; polydimethylsiloxane; poly(
(vinyltoluene): f(12-hydroxystearic acid); poly(isobornyl methacrylate); long chain esters of acrylic and methacrylic acids (e.g. stearyl,
lauryl, octyl, hexyl, 2-ethylhexyl)
acrylic and methacrylic polymers; polymers of long chain surface vinyl esters (e.g. vinyl sterate, vinyl laurin, vinyl palmitate); polymerized vinyl alkyl ethers, e.g. poly(vinylethyl ether), poly( vinyl in zolobyl ether), poly(vinyl inbutyl ether), poly(vinyl n-butyl ether)
: and copolymers thereof.

Preferred main chain polymers are polyisobutylene, botadimethylsiloxane, poly(2-ethylhexyl acrylate),
These include poly(2-ethylhexyl methacrylate), poly(inbutylene-CO-inzolene), and the like.

Representative JI effective as immature moiety of graft copolymer
Lit forms are vinyl acetate, methyl acrylate, ethyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid and droxyethyl, hydroxyethyl methacrylate, acrylonitrile, acrylamide, methacrylonitrile, methacrylamide, acrylic acid, methacrylic acid, maleic acid. monoethyl acid, monoethyl fumarate, styrene, maleic anhydride, maleic acid, a-vinyl-2-
Pyrrolide ν etc. The preferred material is vinyl acetate, N
- Vinyl-2-pyrrolidone, ethyl acrylate.

First, they are non-toxic, inexpensive, and can be easily grafted onto a variety of compatible primary fiJ4 polymers;
This is because it makes friends with all the layers. As mentioned above, the synthetic resin core must be insoluble in the dispersion liquid, whereas the backbone portion of the amphiphilic stabilizer must be soluble in the dispersion liquid, imparting colloidal stability to the particles.

These stabilizers are present in the final liquid developer composition at approximately 0.1 weight f.
It is present in an amount from about 1.0 weight percent to about 1.0 weight percent, preferably from about 0.1 weight percent to about 3.0 weight percent.

may be selected for the liquid imager compositions of the present invention, about 0
．． 01% by weight to about 0.1% by weight, preferably about 0.01% by weight.
．． The charge control agents present at a concentration of from 0.2 to about 0.06% by weight include the lithium, cadmium, calcium, manganese, magnesium, and zinc salts of hebutanoate; barium, aluminum, cobalt, and 2-ethylhexanoate; Manganese, zinc, cerium, and zirconium salts (these are known as octanoic acid); barium, aluminum, zinc, copper, lead, and iron salts of stearate; calcium, body, manganese, and naphthenate; nickel,
Zinc, and iron salts; ammonium lauryl sulfate, zohexyl sulfochloride/acid +) 9 rum, sodium dioctyl sulfosuccinate, aluminum diinzolopyrsalicylate, aluminum dorezate, 3.5-di-t-
These include aluminum salts of decyl r-resorcylic acid. Mixtures of these materials can also be used. A preferred charge control agent is zirconium octoate, which is soluble in the preferred dispersion liquid and imparts a positive charge to the synthetic resin particles.

The liquid developer of the present invention can be manufactured by a variety of suitable techniques. The procedure for one method is to first prepare an amphiphilic stabilizer in a dispersion medium for a liquid developer, and add to it an excess of single reed or mixed single reed to form a synthetic resin core. The monomers are then added in the presence of a radical initiator and the monomers are then polymerized, and then to this fraction, a solution of the fermented dye mixture in the mixed solvent is added. It is added to cause the dye to be absorbed into the core of the marking particle.

During polymerization, the amphiphilic stabilizer becomes tightly bound to the synthetic resin core. The XIW bond involves chemical and physical interactions that irreversibly fix the amphiphilic stabilizer so that it cannot be removed from the particle under normal operating conditions.

Once the stabilized resin core is formed, the dye is adsorbed into the resin core according to the procedure described below, and then to the dispersion is added tg, 1ulJ. preparation of a medium-based stabilizer, b) non-aqueous dispersion polymerization of the core monocarboxylic group in the presence of an amphiphilic stabilizer to obtain stabilized particles, C) dyeing of the non-aqueous dispersed particles, and d) After preparing the stabilizer in the 5° dispersion medium with charging of the particles, a synthetic resin core is obtained by non-aqueous dispersion polymerization. This is done by adding an excess of the monomer to be polymerized to a solution containing an amphiphilic stabilizer which acts as a steric stabilizer during the growth of the polymer particles.

Growth is approximately 60°C to 9°C at atmospheric pressure in the presence of a radical initiator.
It is carried out at a high temperature of 0°C. Over several hours, i.e., 2 to 20 hours, the polymeric core of the marking particle grows in the presence of the steric stabilizer, resulting in a relatively uniform diameter size ranging from about 0.1 to about 1.0 microns. Most of the particles are 0.3 to 0.
A dispersion containing up to about 50 weight particles of particles in the 4μ size range is produced.

During growth of the polymer core, the amphiphilic polymer acts as a steric stabilizer to keep the individual growing particles apart in the dispersion. For example, if the dispersion polymerization of core particles is carried out without stabilizers, the polymer formed from the monomers will phase separate to form the core of the particle; It coagulates and precipitates as a main body. On the other hand, when polymerization is carried out in the presence of a stabilizer, the stabilizer becomes tightly bound to the resulting polymer core in a thermodynamically irreversible manner. provides stable particles.

The resulting marking particles are then dyed with stable fractions to enable the core particles to form a toner image having an acceptable optical density and a special black color. In particular, a dye mixture consisting of Orasol Plaque RL, red or magenta, 1K or cyan, and yellow is molecularly introduced into the core particles by the dye impivition absorption method. This method is described in U.S. Pat. No. 4,476.
No. 210, the disclosure of which is incorporated herein by reference in its entirety, which involves dissolving a dye mixture in a polar solvent that is essentially insoluble in the dispersion medium; It involves absorbing into the core particles. Examples of these bath media are methanol, glacial acetic acid, ethylene glycol,
Dimethyl sulfoxide, N.

N'-dimethylformamide and a mixture thereof. Approximately 5% to approximately 50M1 preferably approximately 10M to approximately 20
The rlLlcv solver is selected. However, the above-mentioned in-vision method is performed at high temperatures (i.e., from about 0°C to about 60°C) to achieve an acceptable fit of the dye mixture <i.e., about 5 iL-chills of about 3
0]fJi%) for a sufficient time to absorb into the core particles,
It will be done.

To further explain the nature of each component selected for the solid developer of the present invention, various suitable proportions may be used.

Accordingly, the liquid developer of the present invention is present in the dispersion medium at about 0.1 to about 2.0 mol% (preferably from about 0.2 to about i,
oxt%). Each particle has about 50 to about 98 weight polymer cores and about 50 to about 2 m
% amphipathic stabilizer. In addition, the polymeric core typically contains from about 5% to about 30% by weight of the dye mixture, and the charge control agent has a charge/mass ratio of 10 to >2,000 micron/g. It is present in about 19% to about 5% by weight of the particles to give .

Next, the present invention will be explained by specific preferred embodiments, but these examples are merely illustrative. The present invention is not limited to the cleaning materials, conditions, and process parameters recited therein. Parts and percentages not otherwise specified 11! ! Due to heavy packing.

Examples 1-4 relate to the production of amphipathic stabilizers; Example 5
-8 relate to non-aqueous dispersions of particle cores: and Example 9
-18 relate to latex dyeing.

Example 1 Addition of Isopar 0500 m to 200 rats of poly(2-ethylhexyl methacrylate) prepared as described in Example 4. The solution was heated to 75° C. and purged with nitrogen for 30 minutes, after which 0.3 y of peroxide was added to the solution. 2 more
After heating for an hour, 2.0 - of vinylpyrrolidone was added to the solution and the polymerization was continued at 70°C for an additional 16 hours.

Next, a clear vinegar solution is obtained.

Example 2 125 ml of 2-ethylhexyl acrylate was dissolved in Isopar 05[][]m. The solution was heated to 75°C and purged with nitrogen for approximately 30 minutes. 1.6y of benzoyl peroxide was then added to this solution and the polymerization was continued at 75° C. for about 16 hours under continuous stirring. An m-liquid of poly(acrylic acid 2-ethylhexyl alcohol) was obtained. Then, this polymer m-liquid 280 mK Ainpar G 5 Q Q
txl and the resulting mixture was heated to 75 °C and purged with nitrogen for 30 min. Then, add 1 azobis-isobutyronitrile (AIBN) to this solution.
．． 211 was added.

After heating for an additional 2 hours, this solution was added with 12 ethyl acrylate.
m1 was added and the polymerization was allowed to stand at 75° C. for 16 hours. A clear graft copolymer solution was obtained.

Example 3 Poly(isodetylene-Yin!ren) (available as Karen 800 from Hardman, New Jersey)5. @'e Dissolved in Isopar 050g. ``Heat the solution to 75° C. and purge with nitrogen for about 30 minutes.'' Add 0.5 g of ethyl acrylate to the resulting constant stirring solution.
azobis-inbutyronitrile (A to FJ) 0.1
It was added with g. Polymerization was continued for 4 hours, resulting in a clear solution of amphiphilic copolymer.

Example 4 Isovar A 240 was added to 75mj of poly(2-ethylhexyl acrylate) prepared as in Example B. The solution was heated to 75°G and purged with nitrogen for 30 minutes. Then, add 0 benzoyl peroxide to this solution.
．． 4g was added. After heating for a further 2 hours, 8 rata of vinyl acetate was added to the solution and the polymerization was allowed to wait for a further 16 hours at 75°C.

A clear liquid of the graft polymer was served.

Example 5 A 700M graft copolymer solution prepared in Example 1 was heated to 70°C and purged with nitrogen for 60 minutes. Next, AIEIJ 1.01 was added to this I@ solution, and after another 1 hour, N-vinyl-2-pyrrolidone 230 I
1 liter was added. The reaction was allowed to proceed for an additional 16 hours at 70° C. under continuous stirring. A latex with a particle diameter of 0.4μ was obtained as evidenced by electron microscopy. The solids content of this latex was adjusted to 4% (weight/volume) by addition of approximately 4.52 kg of Isopar G.

Example 6) Polymer stabilized by amphiphilic copolymer The graft copolymer fluid prepared in Example 4 was mixed with 300 at.
Heat to 0°C and purge with nitrogen for 30 minutes. Then, 2.0 g of benzoyl peroxide was cooled to this liquid, and after 1 hour, 5 Qml of ethyl acrylate was added. The reaction was allowed to proceed for 16 hours at 70° C. under continuous sweeping. ′
A latex with a particle diameter of 0.4 microns was obtained as indicated by a 1-round scale. The solids content of this latex was adjusted to 4% (weight/volume) by adding about 1.21% of Isopar G.

Example 7 Poly(ethyl acrylate-co-N-vinyl-2)
- Pyrrolidone) Latex Preparation The graft copolymer solution 800 produced in Example 2 was heated to 70°C and purged with nitrogen for 30 minutes. Next, 14 g of A was added to this continuously stirred/8 solution, and 1 hour later, 11 Qm of ethyl acrylate was further added. The reaction was allowed to proceed for 16 hours at 70°C. Then, 2.5 g of AlBN was added to this dispersion, and 40 dt of N-vinyl-2-pyrrolidone was further cooled one hour later. The reaction was allowed to proceed for an additional 16 hours at 70° C. with constant stirring.
A latex with a particle diameter of 4μ was obtained. The solids content of this latex was adjusted to 4% (weight ik/volume) by addition of approximately 32 kg of Isopar G.

Example 8 800 m of the graft copolymer solution prepared in Example 3
1 was heated to 70° C. and purged with nitrogen for 60 minutes.

AIBIJ was then added to this constantly stirred solution.
511 was added, and after 1 hour, 11 more ethyl acetate was added.
Add 0 and mix. The reaction was allowed to wait for 16 hours at 70°C. Then, AINB 2.5.9 was added to this dispersion and after 1 hour, monovinyl-2-pyrrolidone 40M
t-cooled. 1 more time at 70°C with constant stirring.
The reaction was allowed to proceed for 6 hours. A latex of 0.4 micron particle diameter was obtained as evidenced by electron microscopy. The solids content of this latex was adjusted to 4% (weight/volume) by addition of Isopar G form 3.

Example 9 Dyeing of latex The solids content of each latex particle in the table below was adjusted to about 4% (yield/volume) by the addition of Isopar(). The dyes used are listed in the table. They were dissolved in anhydrous methanol in the specified amounts and filtered through Whattman A64 filter paper. In each example, the dye methanol solution was added dropwise to the latex with constant stirring. This absorption process takes place at 60℃
The methanol was then removed by distillation under a pressure of 2 torr, and the dyed latex obtained was filtered through glass wool to remove any undesirable substances. However, its components are described in US Pat. No. 4,476,210, the disclosure of which is incorporated by reference in its entirety.

h sa, 0 0 mouth 0
0 to 1” (be/F/ size ℃ ＼ c
o II I+=”-”
−” ?+1:I11′ Example 10 Production of liquid toner Isopar 0280Mt− was added to each 40− of the dyed latex produced in Example 9 to give a solid content of 0.5% (Vv).
A dispersion was obtained. This latex was then treated with a 6% solution of zirconium octoate (Nuodex, available from Nuodex Canada, Toronto, Canada).
．． A positively charged developer was obtained by adding 5M. Other charge control agents, such as cobalt neodecanoate (obtained as Cobalt Temuchem 6% M solution from Mooney Chemicals, Leapland, Ohio), iron naphthenate (from Mooney Chemicals, Leapland, Ohio); iron naradiol (obtained as a 6% solution),
Nickel octoate (obtained from Mooney Chemicals, Leapland, Ohio, as a nickel-hemuke solution), calcium naphthenate (obtained from Mooney Chemicals, Leapland, Ohio, 6% cobalt naphthenate). (obtained as a liquid) was also selected in the same proportion as zirconium octoate.

These dispersions were then used as liquid developers to print various UT papers (Jams River Graphics Co., Parlin, Hampshire, California) on a Persattic Saw 80 electrostatic printer/plotter. The electrostatic latent image is developed using a commercially available electrostatic latent image. All images obtained had optical densities ranging from 1.1 to 1.5 as measured with a Macbeth TR927 densitometer. The degree of image fixation on paper was quantified using a Teledyne taper abrasion tester (Model 503) and compared.

These materials have excellent water resistance and fastness of 80 to 90%.
(excellent) and was not removed after 48 hours of soaking in a water bath. The image obtained is the core of the particle! 11! Depending on the polymer selected for construction, it can be formed with a glossy or matte surface finish. For example, if the glass transition temperature Tg of the core particles is less than about 20° C., the developer will aggregate to form a film during image formation, giving a gloss gR with significant fixation to the paper. When the Tg of the core particles is greater than about 20° C., the developer particles maintain their spherical shape during image formation and provide a matte image.

Typical results are listed in Table 1 below. It was determined by crushing the mound in a water bath at 45°C for 48 hours and measuring the optical density of the mound before and after the test. A rating of "Excellent" means that there is no change in optical density after testing.

3. This is 1 kg before the test and with the taper abrasion tester.
Determined by measuring the optical density of the image after abrasion testing the image with a ring for 20 cycles. A rating of "Excellent" means that there is no change in the optical density of the image after testing. "
"Good" means that the optical density does not decrease by more than 25ts in the test, and "fair" means that the optical density does not decrease by more than 25ts in the test.
This means a decrease of ~50 inches.

4. This is based on visual observation.

Example 11 A conventional ink composition was prepared having the ingredients of Example B10 of U.S. Pat. No. 4,476,210. In detail, poly(ethyl acrylate-co-N-vinyl-12-pyrrolidone) latex 1 colored with 2nd Vine Blue 20LN
Along with 2go, the same latex 1Qm/colored with Oracle Red G and latex 1011 colored with Oracle Yellow 20LN! J' (rm was added. Then, this ink was used in the persatic printer Km described here.
Upon scanning, a black image with an undesirable greenish hue was obtained.

Although the present invention has been described above with specific examples of preferred embodiments, the present invention is not limited to these. It should be recognized that many transformations are possible.

Claims (23)

[Claims] (1) In an insulating liquid medium, a thermoplastic resin core that is substantially insoluble in the liquid medium and a thermoplastic resin core that is soluble in the liquid medium and irreversibly chemically or physically applied to the thermoplastic resin core. an affixed amphiphilic block or graft copolymer steric stabilizer and an orasol black soluble in the thermoplastic core and insoluble in the dispersion medium and absorbed in the thermoplastic core; RL, Neozapon Black X57, and Sabinyl Black RL
a black dye present in an amount from about 5 to about 25% by weight selected from the group consisting of S; a red dye present in an amount from about 10 to about 40% by weight; and a red dye present in an amount from about 10 to about 35% by weight. A stable black liquid developer composition comprising dispersed therein marking particles comprised of a dye mixture comprising a yellow dye present and a blue dye present in an amount from about 10 to about 50% by weight. . 2. The developer composition of claim 1, wherein the liquid dispersion medium comprises an aliphatic hydrocarbon having a resistivity greater than about 10^9 ohms/cm. (3) The composition according to claim 2, wherein the aliphatic hydrocarbon is a petroleum distillate. (4) The thermoplastic resin core is made of a homopolymer of N-vinyl-2-pyrrolidone, vinyl acetate, or ethyl acrylate monomer, or a copolymer of vinyl acetate or ethyl acrylate. The developer composition according to item 1. (5) Claim 1, wherein the steric stabilizer consists of a graft copolymer having a main chain portion that is soluble in the dispersion medium and a second portion that is insoluble in the dispersion medium and has an affinity for the thermoplastic resin core. The developer composition described in . (6) The soluble backbone is poly(alkyl acrylate), poly(alkyl methacrylate), or poly(isobutylene-co-isoprene), with the proviso that the alkyl group has at least 3 carbon atoms. 6. The developer composition according to item 5. (7) Poly(2-ethylhexyl methacrylate) or poly(2
- ethylhexyl acrylate) solution). (8) Orasol Black RL, Neozapon Black X5 in which the black dye is present in an amount of about 15% to about 25% by weight;
7 or Savinyl Black RLS. (9) selected from the group consisting of Orasol Red G, Sabinyl Red 3GLS, and Sabinyl Pink 6BOS, wherein the red dye is present in an amount from about 25% to about 35% by weight;
The blue dye is selected from the group consisting of Orasol Blue GN and Orasol Blue 2GLN, wherein the blue dye is present in an amount of about 25% to about 35% by weight, and the yellow dye is present in an amount of about 25% to about 35% by weight.
selected from the group consisting of Orasol Yellow 2GLN and Savinyl Yellow RLS present in an amount of about 30% by weight;
A developer composition according to claim 1. (10) The developer composition according to claim 1, further comprising a charge control agent soluble in the liquid dispersion medium. (11) The liquid developer according to claim 10, wherein the charge control agent is zirconium octoate, cobalt neodecanoate, nickel octoate, or calcium naphthenate. (12) Thermoplastic resin core has a diameter of about 0.1μ to about 1.0μ
The improved composition of claim 1, wherein the composition is substantially monodisperse particles of μ. (13) After forming an image with a printing device, the image is developed using the developer composition according to claim 1,
and a method of developing the image, consisting of transferring the resulting image to a suitable substrate. 14. The method of claim 13, wherein the liquid medium comprises an aliphatic hydrocarbon having a resistivity greater than about 10^9 ohms/cm. (15) The image forming method according to claim 13, wherein the aliphatic hydrocarbon is a petroleum distillate. (16) The thermoplastic resin core is made of a homopolymer of N-vinyl-2-pyrrolidone, vinyl acetate, or ethyl acrylate monomer, or a copolymer of vinyl acetate or ethyl acrylate. The image forming method according to item 13. (17) a main chain portion in which the steric stabilizer is soluble in the dispersion medium;
14. The method of forming an image according to claim 13, comprising a graft copolymer having a second portion that is insoluble in the dispersion medium and has an affinity for the thermoplastic resin core. (18) the soluble main chain is poly(alkyl acrylate);
18. The method of claim 17, wherein the alkyl group is poly(alkyl methacrylate) or poly(isobutylene-co-isoprene), with the proviso that the alkyl group has at least 3 carbon atoms. (19) Poly(2-ethylhexyl methacrylate) or poly(
18. The image forming method according to claim 17, wherein the graft copolymer is a graft copolymer of a 2-ethylhexyl acrylate solution. (20) Orasol Black RL, Neozapon Black
17. The image forming method according to claim 16, wherein the image forming method is RLS. (21) Orasol Red G, Savinyl Red 3 GLS in which the red dye is present in an amount of about 25% to about 35% by weight)
and Sabinyl Pink 6BOS, the blue dye is selected from the group consisting of Orasol Blue GN and Orasol Blue 2GLN, wherein the blue dye is present in an amount of about 25% to about 35% by weight, and the yellow dye is about 25% by weight.
Orasol Yellow 2GLN present in an amount of ~30% by weight
and Sabinyl Yellow RLS. (22) The image forming method according to claim 13, wherein the liquid dispersion medium further contains a soluble charge control agent. (23) The image forming method according to claim 22, wherein the charge control agent is zirconium octoate, cobalt neodecanoate, nickel octoate, or calcium naphthenate.