JPH11160918A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high image density, resolution and gradation by using a liquid toner prepared by using a copolymer of a coloring agent and a reactive silicone compd. to form an image. SOLUTION: In the process to develop an electrostatic latent image with a liquid toner, the liquid toner consists of a copolymer of a coloring agent and a reactive silicone compd., and a nonwater dispersion medium. The reactive silicone compd. is an amino-modified silicone compd., epoxy-modified silicone compd., carboxyl-modified silicone compd. or the like. As for the monomer to copolymerize with the reactive silicone compd., a copolymer of an oleophilic methacrylate and a hydrophilic polar monomer is used. The polar monomer is, for example, a monomer having carboxyl groups such as methacrylic acid, itaconic acid and maleic acid anhydride and its metal salt. The nonwater solvent is an aliphatic hydrocarbon, silicone oil, fatty acid ester, low mol.wt. polyolefin or low mol.wt. copolymer containing olefins as a monomer component, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a liquid developer used in the fields of electrophotography, electrostatic printing, electrostatic recording and the like.

[0002]

2. Description of the Related Art A liquid developer used in the field of electrophotography and the like comprises an aliphatic hydrocarbon solvent, a colorant, a fixing agent, a dispersant, and various additives which are added as required. It is manufactured by finely pulverizing the mixture with a ball mill, an attritor, or the like. That is, in the conventional liquid developer manufacturing method, since the dispersant, the fixing agent, and the like are separately manufactured, and then the raw materials are mixed and finely pulverized, there is a problem that the number of processes is increased and the manufacturing cost is increased. .

On the other hand, JP-A-63-174070 discloses that a polymer latex obtained by polymerizing styrene, an acrylic monomer or the like in a non-aqueous solvent is dyed with a dye.
A colored liquid developer using this as a coloring agent is disclosed.
However, in this method, it is difficult to produce a black liquid developer, and there is also a problem in fixability to copy paper. In addition, Tokiko 56
JP-A-1010619 discloses an electrophotographic liquid developer in which resin particles obtained by polymerizing an acrylic monomer in an aliphatic hydrocarbon-based solvent are dyed with a dye such as Victoria Blue, and this is used as a colorant. ing. However, a copy image obtained by using this liquid developer has a low density and is easily discolored, and offset fixing in which toner adheres to the heat roller when fixing with the heat roller is apt to occur. As described above, when a colorant obtained by dyeing the resin particles with a dye is used in a dye, a printing ink, an ink for ink jet, or the like, there are problems in adhesiveness, fading property, fixing property, image density, and the like. or,
Japanese Patent Application Laid-Open Nos. 9-183859 and 179354 disclose polymerized toners, but have problems such as low fixability and low resolution.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a liquid toner in which a pigment, a dye and a resin are integrated as a colorant in an electrophotographic liquid developer, various inks, various paints, and the like. It is an object of the present invention to provide an image forming method capable of forming an image having good tonality, resolution and fixability, and having excellent dispersibility and cleaning properties.

[0005]

SUMMARY OF THE INVENTION The present invention is as follows. (1) In a process of developing an electrostatic latent image with a liquid toner applied on a belt or a roller member, the liquid toner is composed of a colorant, at least a copolymer of a reactive silicone compound, and a non-aqueous dispersion medium. An image forming method comprising:

(2) The non-aqueous dispersion medium according to the above (1), wherein the non-aqueous dispersion medium is one or a mixture of two or more selected from the group consisting of aliphatic hydrocarbons, silicone oils, fatty acid esters, polyolefins, and liquid paraffins. Image forming method. (3) The above (1) or (2) using colorant particles obtained by reacting a reactive silicone compound with an isocyanate compound.
The image forming method as described in the above.

(4) The image forming method according to any one of the above (1) to (3), wherein the colorant has an active hydrogen group. (5) The process of developing an electrostatic latent image is a method of forming a toner layer on a roller or a belt, performing a corona discharge on the toner layer, and then developing the electrostatic latent image. The image forming method according to any one of 4).

(6) The image forming method according to (1) or (5), wherein the electrostatic latent image is developed after being wetted with a pre-wet liquid. (7) The image forming method according to the above (1), (5) or (6), wherein the electrostatic latent image is developed with liquid toner, the toner image is transferred to an intermediate transfer member, and an image is formed on a transfer member.

(8) The photoconductor which forms an electrostatic latent image has a water-repellent and oil-repellent surface (θ = 30 ° or more).
The image forming method according to (5), (6) or (7). Next, an image forming process using the liquid toner of the present invention will be specifically described with reference to the drawings.

FIG. 1 shows that a photoconductor L, for example, an organic semiconductor, selenium, amorphous silicone, or another inorganic photoconductor rotating in the direction of the arrow is charged by corona charging E while rotating. When pre-wetting the carrier liquid, the F roller applies the insulating liquid with the F roller. Do not apply if prewetting is not required.

G is a writing exposure unit. K may be a toner developing roller and may be applied by an electrodeposition method in which the toner is uniformly applied to the developing roller K from the toner container I by the toner roller J. A voltage is applied to the toner layer on the developing roller by the corona discharge unit H or not, and then the latent image on the photoconductor L is developed by the developing roller K and visualized. Each roller may be made of rubber, metal, plastics, or the like and has elasticity or a sponge-like roller.

The transfer material B transfers the toner image on the photoconductor L onto the transfer material B by the transfer roller A. A good image can be formed on the transfer material by a transfer method such as pressure, corona discharge, heating, or a combination of heating and pressure, corona and pressure, or a combination of corona and heating. Further, in order to clean the surface of the photoconductor, the remaining toner is removed by a cleaning roller C and a cleaning blade D, and the next copy is performed.

FIG. 2 differs from FIG. 1 in that it includes a step F of coating the pre-wet liquid with a felt F from a roller. The pre-wet liquid is applied with felt as needed, but need not always be applied. The toner is applied to the developing roller K from the toner container I through the rollers J ₁ and J ₂ , and a DC voltage is applied to the applied toner layer from the corona discharge unit H. The developing roller K in FIG.
The width of contact with the photoconductor L is made longer so that the latent image can be sufficiently developed with toner. The toner image developed on the photoconductor is transferred to the transfer member B by the corona discharge section A to form an image. If necessary, the toner image is further fixed on the transfer member in the drying section.

FIG. 3 shows an example of a developing process when a color copy is output. Yellow, magenta, cyan and black toner containers I and J on photoconductor
The latent image on the photoreceptor L is developed for each color, transferred to the intermediate transfer member M, and then transferred to the transfer member B by the transfer roller A using pressure, corona, heat, a combination of pressure and heat, and color copy. Create FIG. 4 shows an image forming process for color copying.

As in FIG. 3, yellow, magenta, cyan,
The latent image on the photoconductor L is developed by the belt N for applying the toner layer to the toner containers J and I for storing the black toner, and the toner image is transferred to the transfer member B. For the belt N for applying the toner layer, a cleaning roller O and a cleaning blade P are used for cleaning C and the belt is reused. Belt N is PET, EVA, VC
L, rubber, metal belt and the like. The belt can be used with its elasticity, surface roughness, surface energy, etc. degraded. The liquid toner used in the present invention comprises a copolymer of a colorant and a reactive silicone compound and a non-aqueous dispersion medium.

The above-mentioned reactive silicone compound is a compound manufactured and sold by Shin-Etsu Chemical Co., Ltd., and the compound is shown below under the trade name of Shin-Etsu Chemical Co., Ltd. The indication of amino modification or epoxy modification shown below means that the compound has an amino group or an epoxy group as a reactive substituent having active hydrogen.

Amino-modified silicone compound: X-22-
161A, KF-861, KF-865, etc .; Epoxy-modified silicone compound: X-22-163B, KF-10
1, X-22-169B, KF-103, KF-102
Etc .; carboxyl-modified silicone compound: X-22-1
62A, X-22-162C, X-22-3710 and the like;
Carbinol-modified silicone compound: X-22-160
AS, KF-6001, KF-6002, KF-600
3 etc .; mercapto-modified silicone compound: X-22-1
67B, X-22-980, etc .; Phenol-modified silicone compound: X-22-165B, etc .; One-terminal reactive silicone compound: X-22-170B, X-22-173
B, X-22-174D, X-22-174DX, X-
22-176B and the like; Heterofunctional group-modified silicone compound:
Amino and alkoxy group-modified KF-857, KF-8
62, KF-8001 etc .: X-22-3939A etc. modified with an amino group and a polyether group: The methacryl-modified silicone compound: X-22-5002, Silaprene FM0711, FM0721, FM07 manufactured by Nitrogen Co., Ltd.
25, TM0701, etc. Next, the monomers to be copolymerized with the reactive silicone compound are shown below.

A copolymer of a lipophilic long-chain (meth) acrylate and a hydrophilic polar monomer may be used. Specific examples of lipophilic long-chain (meth) acrylates include hexyl (meth) acrylate and cyclohexyl (meth)
Examples include acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.

Specific examples of polar monomers include (meth) acrylic acid, itaconic acid, maleic anhydride,
Monomers having a carboxyl group such as maleic acid, vinyl acetic acid, vinyl chlicogenic acid, vinyl acrylic acid, vinyl benzoic acid, and metal salts thereof (Li, Na, K, C
a, a metal salt such as Mg, Al, etc.), a monomer having a sulfone group such as vinyl sulfonic acid, vinyl benzene sulfonic acid, vinyl benzyl sulfonic acid, and vinyl benzene sulfinic acid, a sulfin group, a metal salt thereof, and a monomer having a phosphate group And metal salts thereof, shown in the following (A) to (F). Examples include a nitrogen-containing monomer.

(A) N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-hydroxyethylaminoethyl ( (Meth) acrylates having an aliphatic amino such as (meth) acrylate, N-benzyl, N-ethylaminoethyl (meth) acrylate; (B) N-vinylimidazole, N-vinylindazole, 2-vinylpyridine, Nitrogen-containing heterocyclic vinyl monomers such as -vinylpyridine, 2-vinylquinoline, 4-vinylquinoline and 2-vinyloxazole; (C) N-vinyl-substituted cyclic amide monomers such as N-vinylpyrrolidone and N-vinylpiperidone; (D) N-methylacrylamide, N-octylacrylia De, N- phenylmethyl acrylamide, N- cyclohexyl acrylamide, acrylic piperidine, such as an acrylic mono-Folin (meth) acrylamides;
(E) aromatic-substituted ethylene monomers having a nitrogen-containing group such as dimethylaminostyrene, diethylaminostyrene, dioctylaminostyrene, etc .; (F) vinyl-N-ethyl-N-phenylaminoethyl ether, vinyl-N-butyl-N -Nitrogen-containing vinyl ether monomers such as phenylaminoethyl ether, triethanolamine divinyl ether and vinyl pyrrolidyl amino ether.

Other monomers include fluorine-containing monomers such as fluoroethyl methacrylate and pentadecafluorooctyl acrylate. The monomer copolymerizable with the reactive silicone compound is 1-90 / 10-
99 parts by weight are polymerized in a non-aqueous solvent in the presence of a polymerization initiator. If necessary, it is necessary to carry out the polymerization with a monomer constitution which gives the fixing property and the dispersibility and the polarity controllability.

Binary, ternary copolymers, graft copolymers,
A crosslinked polymer block copolymer can be used as needed. As a polymerization solvent, isoparaffin, normal paraffin, silicone oil, fatty acid ester,
As a polymerization initiator such as food oil, it is possible to use a usual polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, di-t-butyl peroxide and lauryl peroxide.

The non-aqueous solvent used in producing the colorant in the present invention includes aliphatic hydrocarbons, silicone oils, fatty acid esters, low molecular weight polyolefins, low molecular weight copolymers containing olefins as monomer components, halogenated Aliphatic hydrocarbons and the like, the former five being preferred.

As the aliphatic hydrocarbon, hexane, pentane, octane, nonane, decane, undecane, dodecane and the like are used. Further, various electrically insulating aliphatic hydrocarbon mixed liquids having a boiling point range of 68 to 250 ° C., an electric resistance of 10 ⁹ Ω · cm or more in volume resistance, and a dielectric constant of 3 or less can be used. Such a liquid mixture is a liquid mixture used as a carrier liquid of an electrophotographic liquid developer, and when the liquid mixture is used as a non-aqueous solvent when the colorant production method of the present invention is carried out, the liquid mixture is produced in the present invention. An electrophotographic liquid developer or ink-jet ink using the colored particles to be produced as a colorant can be produced in one step. As such a mixture,
There are "Isopar G", "Isopar H", "Isopar L", "Isopar M", "Isopar V" and the like manufactured and sold by Exxon, and a mixed solution having a boiling point range of 150 to 250C is particularly preferable.

As the silicone oil used for the non-aqueous solvent, a commercially available product may be used. For example, Shin-Etsu Chemical Co., Ltd.
KF-995, KF-994, KF-86, KF-
85, KF-96-300cs, KF96-1000c
s, KF96-5000cs, KF-96-1.5cs
Etc. should be used. Fatty acid esters used for non-aqueous solvents include isopropyl maleate, isopropyl myristate, isopropyl laurate, ethyl oleate,
Butyl myristate and the like.

The colorant of the present invention contains, as raw materials, at least a reactive silicone compound having a pigment and / or dye, active hydrogen and an isocyanate compound, and heats a dispersion in which these raw materials are dispersed in a non-aqueous solvent. Provided by reacting.

That is, after the pigment and / or dye is sufficiently uniformly dispersed in the active hydrogen-containing reactive silicone compound, the isocyanate compound is reacted, whereby the coloring agent in which the urethane-crosslinked colored resin particles are highly dispersed is removed. It is characterized by being manufactured. When the raw material pigment or dye has an active hydrogen-containing group, it undergoes a urethanation reaction with an isocyanate compound, whereby the integration of the resin particles with the pigment or dye is strengthened, and the colorant properties can be improved. . Further, these urethanization reactions are carried out in a non-aqueous solvent. If a carrier liquid used for an electrophotographic liquid developer is used for the non-aqueous solvent, an electrophotographic liquid developer can be produced in one step. . Similarly, if a non-aqueous solvent is appropriately selected according to the purpose, a solvent or an additive can be added to the colorant dispersion liquid after production to obtain various inks and paints. Next, the raw materials used in the production of the colorant of the present invention will be described in detail.

(1) Reactive Silicone Compound The reactive silicone compound is represented by the following general formula (1)
One or two selected from the group of compounds represented by (4)
Mixtures of more than one species are used.

[0029]

Embedded image

In the general formulas (1) to (4), R _{1 to} R
_{Although 29} may be the same or different, they represent a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or a phenyl group. X _{1 to} X ₇ may be the same or different, but these are substituents having an active hydrogen which reacts with the isocyanate compound, and specifically represent the following substituents. And n and m represent an integer of 1 or more.

[0031]

Embedded image

Of the compounds of the above general formulas (1) to (4), particularly preferred compounds as the colorant raw material of the present invention are specifically shown in Tables 1 to 4. )
Table 2 illustrates the compound of the general formula (2), Table 3 illustrates the compound of the general formula (3), and Table 4 illustrates the compound of the general formula (4).

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

(2) Isocyanate Compound The isocyanate compound used as a colorant material in the present invention is a polyvalent isocyanate compound such as a diisocyanate compound or a triisocyanate compound. That is, paraphenylene diisocyanate, 2-chloro-
1,4-phenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, 4,4′-diphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate, Isophorone diisocyanate, trimethylhexamethylene diisocyanate and the like. Further, a urethane resin in which isocyanate groups remain can be used as an isocyanate compound. For example, a product obtained by reacting 1 mol of trimethylhexamethylene diisocyanate, 1.1 mol of decanediol and 0.4 mol of glycerin at 100 ° C. for 6 hours, wherein isocyanate is 0.2% by weight
The remaining mixture can be used as the isocyanate compound.

(3) Pigments and Dyes The pigments and dyes used in the present invention as colorant raw materials are not limited, and include carbon black, spirit black, aniline black, oil black, nigrosine, wool black, blue black E, alkali blue, Phthalocyanine blue, oil blue, acid blue, dianidin blue, Victoria blue, methylene blue, chrysoidin, sutan violet, crystal violet, oil violet, methyl violet, phthalocyanine green, acid black green, malachite green, safranin, brilliant carmine 6
B, Rhodamine 6G Lake, Fast Red, Oil Red, Congo Red, Auramine, Rhodamine B Lake, Barium Red 2B, Calcium Red 2B, Strontium Red, Manganese Red 2B, Barium Sole Red, Calcium Red 52, Lake Red C,
Formaloon L-58, Brilliant Carmine 3B, Brilliant Scarlet G, Quinacridone Magenta, Bismarck Brown, Benzidine Yellow, Hansa Yellow, First Yellow G, First Yellow 10
G, Disazo Yellow AAA, Disazo Yellow AAM
X, disazo yellow AAOT, disazo yellow AA
OA: Kayaset Yellow AG, Kayaset Red B, Kayaset Blue FR, Kayaseron Yellow E-5
G, Kayaseron Yellow E-3GL, Kayaseron Yellow E-HGL, Kayaseron Red E-GL, Kayaseron Red E-BF, Kayaseron Red E-2BL, Kayaseron Blue E-2BL, Kayaseron Blue E-BR , Kayaceron Blue E-BG, Kayaceron Blue E-5G,
Kayaceron Torquay's Blue E-GL, Kayaceron Navy Blue E-EX, Kayaceron Black E-EX (all manufactured by Nippon Kayaku); Sumicaron Brilliant Flavin S
-10G, Sumicaron Yellow SE-5G, Sumicaron Yellow SE-3GLConc. Sumicaron Yellow SE-RPD, Sumicaron Yellow E-RPD, Sumicaron Yellow SR, Sumicaron Yellow S-RPD,
Sumicaron Orange SE-RPD, Sumicaron Orange SR, Sumicaron Red E-3BR, Sumicaron Red S-BDF, Sumicaron Red E-RPD, Sumicaron Red E-FBL, Sumicaron Red S-BLF, Sumi Karon Red S-RPD, Sumikaron Red SB
F, Sumicaron Blue S-3RF, Sumicaron Blue E
-GRL, Sumicaron Blue SE-RF, Sumicaron Blue ER, Sumicaron Blue E-BL, Sumicaron Blue E-FBL, Sumicaron Blue E (all manufactured by Sumitomo Chemical Co., Ltd.) and the like can be used. . Table 5 shows a coloring material having active hydrogen which is particularly preferable as the coloring material in the present invention.

[0039]

[Table 5]

The low molecular weight polyolefin used for the non-aqueous solvent is a polyolefin having a molecular weight of 3000 or less.
Low molecular weight copolymers containing olefins used in non-aqueous solvents include ethylene-methacrylic acid copolymers and propylene-
It may be a lauryl methacrylate-acrylic acid copolymer or the like, and may be a low molecular weight copolymer that maintains a liquid state under the reaction conditions. As the halogenated aliphatic hydrocarbon used for the non-aqueous solvent, perchlorethylene, pentachloroethane and the like are used.

When a colorant is produced in the method of the present invention,
Polymerizable monomers such as lauryl methacrylate, acrylic acid, styrene, methyl methacrylate, and acrylonitrile and a polymerization initiator such as benzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN) may be added to the reaction system. In some cases, the physical properties of the resin constituting the colored particles may be improved by adding the compound.
For the purpose of controlling the particle size of the obtained resin particles and improving the dispersibility, it is also possible to add a surfactant that does not hinder the urethanization reaction. In addition, known additives which are added at the time of crosslinking reaction or emulsion formation can be added as necessary.

The colorant raw materials described in detail above include the non-aqueous solvent 1
1 to 50 parts by weight of pigment and / or dye per 100 parts by weight,
Preferably 5 to 20 parts by weight; 0.1 to 80 parts by weight of the reactive silicone compound, preferably 5 to 50 parts by weight; 0.05 to 50 parts by weight, preferably 1 to 20 parts by weight of the isocyanate compound. And heat-react it after mixing well. In this case, if the amount of the dye / pigment as the coloring raw material is less than 1 part by weight, the coloring power is weak, and if it exceeds 50 parts by weight, the particle size increases and the dispersibility decreases. When the amount of the reactive silicone compound is less than 0.1 part by weight, the water and oil repellency of the obtained colored particles is reduced, and when it exceeds 80 parts by weight, the dispersibility of the colored particles is reduced. If the amount of the isocyanate compound is less than 0.05 part by weight, the reactivity and the binding property between the resin particles and the coloring material of the coloring material are reduced, and
If the amount exceeds part by weight, the particle size increases and the dispersibility decreases.

The colorant raw material having the above composition is dispersed and mixed for 1 to 5 hours, preferably 2 to 4 hours by a powerful dispersing mixer such as a ball mill or an attritor, and then the reaction temperature is adjusted to 60 to 15 hours.
A desired colorant can be obtained by reacting at 0 ° C., preferably 80 to 100 ° C., for 2 to 24 hours, preferably 3 to 15 hours.

The colored particles obtained here can be used in liquid developers, various inks, paints and the like without being separated from the non-aqueous solvent. For example, by simply diluting the colorant obtained as described above with a solvent, or with a solvent dilution, a charge control agent,
An electrophotographic liquid developer can be obtained by adding a viscosity modifier, a surfactant for improving the dispersibility of the colored particles, a non-aqueous solvent, and the like as necessary. As the charge controlling agent, an electron-donating dye such as a nigrosine dye or a metal soap for positive charging is used, and an electron-accepting organic complex such as a chromium-containing dye or a metal salt of dodecylbenzenesulfonic acid for negative charging is used. used. In addition, viscosity modifiers such as ethylene glycol, propylene glycol, diethylene glycol,
Dipropylene glycol, triethylene glycol, tripropylene glycol and the like are used, and as the surfactant, sodium dodecylbenzenesulfonate and sorbitan monooleate are used.

[0045]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Parts described below are parts by weight. Example 1 100 parts of Isopar M, 10 parts of carbon black (# 44, manufactured by Mitsubishi Chemical Corporation), and 50 parts of a reactive silicone compound No. 150 shown in Table 1 were dispersed with an attritor for 2 hours, and the resulting dispersion was dispersed. 15 parts of paraphenylene diisocyanate was added while stirring at 80 ° C. in a flask,
This was reacted at 90 ° C. with good stirring for 10 hours.
After the completion of the reaction, a liquid toner A containing black resin particles having an average particle size of 1.5 μm was obtained. The image density was 1.20, the gradation was 6 steps, and the resolution was 6.3 lines / mm when a copy was made using the liquid toner A by the image forming process of FIG.

Example 2 A liquid toner B was obtained in the same manner as in Example 1 except that linseed oil was used instead of Isopar M as the non-aqueous solvent. When a copy experiment was attempted in exactly the same manner as in Example 1, an image density of 1.2
1. A copied image having a resolution of 6.3 lines / mm and a gradation of 7.0 steps was obtained, and the image fixing rate was 72%.

(Fixing rate is measured by a clock meter method) Example 3 100 parts of silicone oil KF96-300CS, 15 parts of phthalocyanine blue, and 30 parts of a methacryl-modified silicone compound (X-22-5002 manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts of 2,4-tolylene diisocyanate and BPO
A flask was charged with 3 parts of acrylic acid and 2 parts of acrylic acid, and reacted at 90 ° C. for 12 hours with good stirring to produce a liquid toner C containing cyan resin particles. When a copying experiment was conducted in exactly the same manner as in Example 1, the image density was 1.28, the resolution was 6.3 lines / mm, the gradation was 7 steps, and the fixing rate was 74%.

Example 4 A liquid toner D was prepared in the same manner as in Example 3 except that the reactive silicone compound No. 4 shown in Table 2 was used instead of the methacryl-modified silicone compound used in Example 3. Produced. When the same evaluation experiment as in Example 3 was performed using this toner, a high-quality copy image having an image density of 1.44, a resolution of 7.2 lines / mm, and a gradation of 7.0 steps was obtained. . The liquid toner D produced in this example is a toner that gives a water-repellent and oil-repellent copy image, and could be fixed by a heat roller. The image fixing rate was as high as 81%.

Example 5 A liquid toner E was prepared in exactly the same manner as in Example 4 except that Acid Red 154 shown in Table 5 was used instead of phthalocyanine blue. An evaluation test was attempted. As a result, the image density was 1.32,
An extremely excellent copied image having a resolution of 7.3 lines / mm and a gradation of 8.0 steps was obtained, and the image fixing rate was as high as 83%, and no offset occurred even when the image was fixed with a heat roller. Further, the liquid toner remaining on the photoconductor, the developing roller, and the belt could be easily cleaned by the cleaning roller and the blade.

Example 6 After stirring, 300 g of isooctane was placed in a 2.0-liter four-necked flask equipped with a thermometer and a reflux condenser, and charged with
Heated to ° C. In this, dodecyl methacrylate 190
g, methacrylic acid 10 g, reactive silicone compound X-
A solution consisting of 22-500250 g and 6 g of azobisisobutyronitrile was added dropwise over 3 hours, followed by stirring at the above temperature for another 4 hours to carry out a polymerization reaction, and a conversion of 90%
To obtain a dispersion A having a viscosity of 560 cp. The particle size of the resin was 0.3 to 2 μm.

Carmine 6B was added to 100 parts by weight of the dispersion A.
15 parts by weight were added and dispersed by an attritor for 2 hours to obtain a liquid toner F. When this toner F was evaluated by the image forming process shown in FIG. 3, the image density was 1.38 and the resolution was 7.3 lines /
mm. Further, the transferability from the intermediate transfer roller to the transfer paper was good, and the toner remaining on the intermediate transfer roller had good cleaning performance.

Example 7 Silicon oil KF96-3 was placed in the same flask as in Example 6.
500 g of 000 cs was taken and heated to 90 ° C. Next, 50 g of lauryl methacrylate, 5 g of N-vinylpyridine, and a reactive silicone compound X-22-163B were added thereto.
A solution consisting of 300 g and 3 g of benzoyl peroxide was added to 1.
After dropping over 5 hours, the mixture was stirred at the above temperature for 4 hours to carry out a polymerization reaction, a polymerization rate of 91%, a viscosity of 2600 cp and a particle size of 2
~ 5μ of resin dispersion B was obtained.

To 100 parts by weight of this dispersion B, 10 parts by weight of carbon black and 50 parts by weight of KF96-1000 cst silicone oil were added and dispersed by an attritor for 4 hours to obtain a liquid toner G. When this toner was evaluated by the image forming process in FIG. 4, the image density was 1.40 and the resolution was 7.3 lines /
mm, and the cleaning property of the residual toner on the developing belt N was good.

Example 8 Silicon oil KF58 2 was placed in the same flask as in Example 1.
00 g, 100 g of Isopar L and 60 g of polyethylene (AC-6 manufactured by Allied Chemical Co., Ltd.) were added and heated to 95 ° C. Next, in this, stearyl methacrylate 50 g,
A solution consisting of 40 g of lauryl methacrylate, 3 g of fumaric acid, 100 g of reactive silicone compound KF857 and 4 g of lauryl peroxide was added dropwise over 3 hours, and the mixture was further stirred at the above temperature for 3 hours to carry out a polymerization reaction. A resin dispersion C having a viscosity of 1800 cp and a particle size of 2 to 4 μ was obtained.

A liquid toner H was prepared by adding 50 parts by weight of Microlith Black CT to 100 parts by weight of the resin dispersion C and dispersing it for 2 hours with an attritor. When this liquid toner was evaluated using the image forming process shown in FIG. 2, high image quality was obtained with an image density of 1.44, a resolution of 7.6 lines / mm, and a gradation of 8 steps. The liquid toner of the present invention had good toner supply to the developing roller.

Example 9 In Example 8, when the electrostatic latent image on the photoconductor was pre-wet with silicone oil KF58, the gradation was 9 steps.
The image density was 1.44, the resolution was 7.6 lines / mm, and the gradation was improved.

Example 10 In Example 8, 6 k of toner was applied to the toner surface on the developing roller K.
When a corona discharge of V was performed by the roller H, the image density was 1.42, the gradation was 8 steps, and the resolution was 8.6 lines / mm. In particular, the resolution was improved.

Example 11 A test was conducted in the same manner as in Example 10 except that the surface of the photoconductor was subjected to water and oil repellency treatment with a fluorine acrylic block copolymer. θ is 60 °, the image density is 1.46,
The transfer ratio was 100% at 9 gradations.

[0059]

According to the image forming method of the present invention, an image is formed with a liquid toner using a copolymer of a colorant and a reactive silicone compound. , Resolution and gradation are high. Example 6 by using the dispersion medium of claim 2
As shown in FIGS. 7 and 8, since the coating property of the liquid toner on the developing roller and the belt becomes uniform, high-quality image development becomes possible.

In the liquid toner using the reaction product of the reactive silicone compound, the isocyanate compound and the colorant according to the third and fourth aspects, the image quality and the copy quality can be simultaneously improved as described in Examples 1, 2, 3, 4, and 5. An improvement in fixability is observed. By performing corona discharge on the toner layer on the developing roller according to claim 5, improvement in resolution is recognized as shown in Example 10. In claims 6, 7, and 8, the embodiments 1, 2,
3,4,5,6,7,8,9,10,11, improvement of image quality and improvement of photoconductor, intermediate transfer belt, roller, developing belt, cleaning property on roller, transfer property, etc. The liquid toner of the present invention was found to be effective.

[Brief description of the drawings]

FIG. 1 shows an example of an image forming process to which the present invention is applied.

FIG. 2 shows another example of an image forming process to which the present invention is applied.

FIG. 3 shows another example of an image forming process to which the present invention is applied.

FIG. 4 shows another example of an image forming process to which the present invention is applied.

Claims (8)

[Claims] In a process of developing an electrostatic latent image with a liquid toner applied on a belt or a roller member, the liquid toner is formed by a copolymer of a colorant and at least a reactive silicone compound and a non-aqueous dispersion medium. An image forming method comprising: 2. The image forming method according to claim 1, wherein the non-aqueous dispersion medium is at least one selected from the group consisting of aliphatic hydrocarbons, silicone oils, fatty acid esters, polyolefins, and liquid paraffins. Method. 3. The image forming method according to claim 1, wherein colorant particles obtained by reacting a reactive silicone compound with an isocyanate compound are used. 4. The image forming method according to claim 1, wherein the colorant has an active hydrogen group. 5. The method for developing an electrostatic latent image according to claim 1, wherein the process of developing the electrostatic latent image is a method of forming a toner layer on a roller or a belt, performing corona discharge on the toner layer, and then developing the electrostatic latent image. 5. The image forming method according to any one of 4. 6. The image forming method according to claim 1, wherein the electrostatic latent image is developed after being wetted with a pre-wet liquid. 7. The image forming method according to claim 1, wherein the electrostatic latent image is developed with a liquid toner, the toner image is transferred to an intermediate transfer member, and an image is formed on a transfer member. 8. The photoconductor which forms an electrostatic latent image has a water-repellent and oil-repellent surface (θ = 30 ° or more).
Or the image forming method according to 7.