WO1993019400A1 - Toner humide et production de ce toner - Google Patents

Toner humide et production de ce toner Download PDF

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Publication number
WO1993019400A1
WO1993019400A1 PCT/JP1993/000344 JP9300344W WO9319400A1 WO 1993019400 A1 WO1993019400 A1 WO 1993019400A1 JP 9300344 W JP9300344 W JP 9300344W WO 9319400 A1 WO9319400 A1 WO 9319400A1
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WO
WIPO (PCT)
Prior art keywords
resin
same manner
toner
wet toner
particle size
Prior art date
Application number
PCT/JP1993/000344
Other languages
English (en)
Japanese (ja)
Inventor
Yoichi Higuchi
Takashi Miyama
Satoru Kuramochi
Fumiyasu Takekawa
Original Assignee
Dai Nippon Printing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP4068073A external-priority patent/JPH05273792A/ja
Priority claimed from JP09776792A external-priority patent/JP3229646B2/ja
Priority claimed from JP09934192A external-priority patent/JP3229647B2/ja
Priority claimed from JP4134673A external-priority patent/JPH05323680A/ja
Priority claimed from JP4138664A external-priority patent/JPH05333606A/ja
Priority claimed from JP4178519A external-priority patent/JPH0619220A/ja
Application filed by Dai Nippon Printing Co., Ltd. filed Critical Dai Nippon Printing Co., Ltd.
Priority to DE4391162T priority Critical patent/DE4391162T1/de
Publication of WO1993019400A1 publication Critical patent/WO1993019400A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
    • G03G9/131—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/135—Developers with toner particles in liquid developer mixtures characterised by stabiliser or charge-controlling agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/135—Developers with toner particles in liquid developer mixtures characterised by stabiliser or charge-controlling agents
    • G03G9/1355—Ionic, organic compounds

Definitions

  • the present invention relates to a wet toner and a method for producing the same, and particularly relates to an olefin system having a hydroxyl group or an ester group.
  • the present invention relates to a wet toner which is made of resin particles and has excellent particle distribution characteristics, which is suitable for electrophotography, electrostatic printing, and information recording, and a method for producing the same.
  • Background technology An electrostatic latent image formed by exposing an electrostatically charged optical semiconductor to light is developed by toner particles composed of a coloring material or the like dispersed in an electrically insulating liquid, and is necessary.
  • An image forming method by an electrophotographic method using a wet toner for transferring an image obtained in accordance with an image is well known.
  • a method of forming an image portion on a lithographic printing plate by using an electrophotographic method is widely used in the field of light printing by offset printing.
  • a lithographic printing plate precursor prepared by applying a photoconductive zinc oxide powder together with a binder resin to the surface of a conductive treated paper is charged, the image is exposed after charging, and an electrophotographic toner is used.
  • a method of obtaining a lithographic printing plate by developing a latent image, fixing it, and subjecting the non-image area to hydrophilic treatment. is there.
  • a wet toner used as this type of electrophotographic toner comprises an electrically insulating liquid and colorant particles having a particle size of 0.1 to 1 m dispersed therein.
  • a material in which a resin for dispersing, fixing, and controlling the charge of colorant particles is dissolved in an insulating liquid is used.
  • This type of wet toner has the advantage of excellent resolution due to the small particle size of the colorant particles, but because the toner is fixed by drying and fixing of the resin dissolved in the solvent, the wet toner can be used with the plate substrate.
  • the poor adhesion of the printing plate and the small cohesive force of the printing block itself cause the printing block to easily lose the printing block during printing, and thus have the disadvantage of poor printing durability.
  • Japanese Patent Application Laid-Open No. 63-243,966 discloses that in a wet toner in which resin particles are dispersed, hydroxycarboxylic acid is dispersed in the resin particles to improve the physical properties of the toner. Although it is known, the toner properties such as image density, image quality, flow, and fog are not yet sufficient.
  • a charge control agent is added to charge the toner particles.
  • the charge control agent significantly lowers the electric resistance of the electrically insulating liquid, causing image deletion and the like. For this reason, the added amount is limited, and it is difficult to obtain a wet toner having a high specific charge (QZm).
  • the present invention can be prepared only in a single reaction tank, and can be made in submicron units and narrow in particle size distribution without pulverizing resin particles. And improved toner properties such as image density, image quality, flow, fog, etc. And a method for producing the wet toner.
  • Another object of the present invention is to provide a wet toner having an excellent negative charge property and a simple manufacturing method of the wet toner.
  • the present invention provides a wet toner having good chargeability, improved toner properties such as image deletion, and the like, without reducing the electric resistance of the electrically insulating liquid dispersing the wet toner. That is what we do. Disclosure of the invention
  • the present invention relates to an olefin resin particle having a lipoxyl group or an ester group alone, or an olefin resin particle having a carboxyl group or an ester group to which a coloring agent is added.
  • a wet toner composed of fin-based resin particles and most of the liquid aliphatic hydrocarbons, hydroxycarboxylic ester is used as a monomer in the amount of 3 to 10 masses. It is a wet toner in the presence of the body's polycarboxylic acid ester o
  • an olefin resin having a carboxyl group or an ester group alone, or an olefin resin having a carboxyl group or an ester group to which a coloring agent is added may be used.
  • the resin solution After heating and dissolving in a solvent having a high temperature dependency in the solubility of the resin to form a resin solution, the resin solution is used as a hydroxycarboxylic acid ester as a monomer.
  • a 3- to 10-mer polyhydroxycarboxylic acid ester it is poured into a liquid aliphatic hydrocarbon, cooled to precipitate resin particles, and the solvent is removed. This is a method for producing a wet toner which is substituted with the aliphatic hydrocarbon.
  • a wet toner composed of olefin-based resin particles having a coloroxylated or ester group to which a coloring agent is added and most of the liquid aliphatic hydrocarbons, It is compatible with 3- to 10-mer poly (hydroxycarboxylic ester) and liquid aliphatic hydrocarbons, which use a hydroxycarboxylic ester as a monomer. It is a wet toner in which a soluble negative charge regulator is present.
  • an olefin resin having a carboxyl group or an ester group is mixed with a liquid aliphatic hydrocarbon under heating, and a coloring agent is separately added to the liquid aliphatic hydrocarbon.
  • the colorant dispersion is added to the resin dispersion, mixed while heating, and then cooled, and then subjected to a mixing and dispersion step to produce a wet toner.
  • the wet toner of the present invention has an ethylene monoacetate copolymer resin particle having a melt flow index of 2.5 to 950 or a coloring agent.
  • a wet toner comprising an ethylene-vinyl acetate copolymer resin particle having a melt flow index of 2.5 to 950 and most of the liquid aliphatic hydrocarbons, a hysteresis is considered.
  • the presence of a 3- to 10-mer poly (hydroxycarboxylic ester) using a hydroxycarboxylic ester as a monomer and a negative charge regulator It is a thing.
  • Ethylene monoacetate copolymer resin having a melt flow index of 2.5 to 950 is heated to liquid aliphatic hydrocarbons. And, at the same time, a colorant was separately mixed into the liquid aliphatic hydrocarbon, and then the colorant dispersion was added to the resin dispersion, mixed under heating, and then cooled. Then, a 3- to 10-mer poly (hydroxycarboxylic ester) having a hydroxycarboxylic acid ester as a monomer and a negative charge regulator This is a method for producing a wet toner in which resin particles are precipitated in the presence of water.
  • Ethylene vinyl acetate copolymer resin having a melt flow index of 2.5 to 950 alone, or melt flow added with a colorant A resin solution is obtained by heating and dissolving an ethylene monoacetate copolymer resin having a index of 2.5 to 950 in a solvent having high temperature dependency in solubility for the resin.
  • a liquid fatty acid is prepared by using the resin solution as a monomer. This is a method for producing a wet toner in which the resin is deposited into an aromatic hydrocarbon and cooled to precipitate resin particles, and the solvent is replaced with the liquid aliphatic hydrocarbon.
  • an olefin resin particle having a carboxyl group or an ester group alone, or an olefin resin having a coloring agent or an ester group to which a coloring agent is added 3- to 10-mer polyhydroxys containing hydroxycarboxylic ester as the monomer in the resin-based resin particles and most of the liquid aliphatic hydrocarbons It is a wet toner in which a carbonate ester is present, and in which lecithin is present as a charge control agent.
  • an olefin resin having a carboxyl group or an ester group, and a coloring agent are mixed with a liquid aliphatic hydrocarbon while heating. Then, after cooling in a mixing and dispersing step to produce a wet toner, the hydroxycarboxylic acid ester is used as a monomer during the production process. This is a process for producing a wet-type toner in the presence of 010-mer polyhydroxycarboxylic ester and lecithin.
  • a resin in which a colorant is dispersed by heating and dissolving an olefin-based resin having a carboxyl group or an ester group and a colorant in a solvent having high temperature dependency in solubility for the resin After forming the resin solution, the resin solution is obtained by using a hydroxycarboxylic ester as a monomer as a monomer.
  • This is a method for producing a wet toner in which a resin is deposited by cooling into a liquid aliphatic hydrocarbon in the presence of titanium and cooling, and the solvent is replaced with the aliphatic hydrocarbon.
  • an olefin resin having a carboxyl group or an ester group is dispersed in a liquid aliphatic hydrocarbon using a pulverizing medium while being heated, and then the dispersion is cooled and cooled.
  • the hydroxycarboxylic acid ester is used as a monomer, and the 3- to 10-meric polyhydroxycarboxylic acid ester and coloring are used. This is a method for producing a wet toner in which toner particles are formed in the presence of an agent and a charge control agent compatible with a liquid aliphatic hydrocarbon.
  • Polyoxyl resin having olefin-based resin particles having a hydroxyl group or an ester group, a colorant, and a hydroxycarboxylic ester as a monomer In a wet toner composed of a boronic acid ester and a liquid aliphatic hydrocarbon, a 3- to 10-mer polymer in which a hydroxycarboxylic acid ester is used as a monomer. Hydroxy Wet toner having a carbon black with a large structure as a colorant, along with a boronic acid ester, a charge control agent compatible with liquid aliphatic hydrocarbons It is.
  • the charge control agent is selected from cobalt, manganese, zirconia, ittrium, and nickel. It is a wet toner that is a transition metal salt.
  • poly-based resin particles having a carboxyl group or an ester group, a coloring agent, and a polyester containing a hydroxycarboxylic ester as a monomer In a process for producing a wet toner composed of a hydroxycarboxylic acid ester and a liquid aliphatic hydrocarbon, a liquid aliphatic hydrocarbon used as a dispersion medium for a particle component is heated under heating. Dissolve an olefin resin having a carboxyl group or an ester group, and use the hydroxycarboxylic ester as a monomer. After mixing a solvent in which carbon black is dispersed together with a polyester resin of the body and carbon black, the temperature of the solution is lowered.
  • FIG. 4 is a diagram illustrating the relationship between the reflectance and the wavelength of light when printing is performed.
  • FIG. 2 is a diagram illustrating the relationship between the reflectance and the wavelength of light when printing is performed using a wet toner to which a magenta pigment is added.
  • FIG. 3 is a diagram illustrating the relationship between the wavelength of light and the reflectance when printing is performed using a wet toner to which yellow pigment is added.
  • 4 to 8 are diagrams illustrating the particle size distribution of the resin particles of Examples 45 to 49, FIG.
  • FIG. 9 is the particle size distribution of the resin particles of Comparative Example 27, and FIG. 10 is Comparative Example 34.
  • FIGS. 11 to 12 are diagrams illustrating the particle size distribution of the resin particles of Comparative Examples 40 to 41.
  • FIG. BEST MODE FOR CARRYING OUT THE INVENTION As an olefin-based resin that can be used in the liquid toner according to the present invention, an ethylene-vinyl acetate copolymer is preferable.
  • Examples of the ethylene monoacetate copolymer include Ultracene series manufactured by Tosoh Corporation, for example, 5110X, 515F, 53 0, 537, 53 7 L, 53 7 S, 525, 52 0 F, 540, 540 F, 54 1, 54 1 L, 6 25, 6 3 0, 6 3 0 F, 682, 6 27, 6 3 1, 6 3 3, 6 8 0, 6 8 1, 6 3 5, 6 3 4, 7 1 0, 72 0, 72 2, 7 2 5, 7 51, 750, 760, etc., Sumitomo Chemical A series of industries manufactured by Kogyo Co., Ltd., for example, DD-10, HA-20, HC-10, HE-10, KA-10, KA-20, KA-31, KC-10, KE-10, MB-11, RB-11, etc.
  • Adomer Co., Ltd. or a copolymer of ethylene and acrylic acid; Dow Chemical Co., Ltd.'s Dow EAA copolymer and Mitsubishi Yuka Yukaron EAA Co., Ltd., Mitsui Dupont Chemical Chemical Co., Ltd. Nikurel, Sumitomo Chemical Co., Ltd., etc. Copolymers with acrylic acid or meta-acrylic acid, or ionomers obtained by cross-linking them, or DuPont's Saline or Mitsui Dupo BASF's EVA 1 wax, such as Hi-Milan manufactured by Polychemical Chemical Co., Ltd., and Coporate Latex manufactured by Asahi Kasei Co., Ltd. Of acrylonitrile and acrylic acid ester in Japan And other polyolefin resins containing a carboxyl-type hydroxyl group. These resins can be used alone or in combination of two or more.
  • the ethylene-vinyl acetate copolymer resin has a melt flow index (expressed in Ml, which is the value of the minute) of 2.5 to 950, preferably Is preferably in the range of 2.5 to 400.
  • Melt flow index is an index that indicates the flow characteristics and film-forming characteristics of a thermoplastic plastic as defined in ASTM D-1238, and is generally used for polymers. The lower the molecular weight, the larger the melt flow index.
  • the melt flow index value of the resin in forming the resin particles is determined by the image and granulation characteristics of the wet toner. Was found to affect
  • the melt flow index is out of the range of 2.5 to 950, the image characteristics as a wet toner, such as fixing property and fogging property, deteriorate.
  • the ratio is less than 2.5, the resin does not easily melt during the toner fixing process, which impairs the film forming characteristics of the toner image and makes it difficult to produce a print having a constant image quality.
  • it exceeds 950 the solubility, meltability, dispersion stability, etc. of the resin will deteriorate, and problems will occur in the granulation process.
  • the harmful IJ of the vinyl acetate component in the ethylene vinyl acetate copolymer resin is preferably from 19% by weight to 40% by weight, but is not particularly limited.
  • Such an ethylene vinyl acetate copolymer resin is referred to by the trade name.
  • the vinyl component is expressed in terms of% by weight), 40 Y—W (65, 41), 150 (30, 33), 210 (400, 28), 2 20 (15, 28), 25 (15, 28), 26 (6, 28), 31 (40, 25), 36 0 (2, 25), 4 10 (40 0, 19), 4 20 (1 50, 19), 4 5 0 (15, 19), 4 6 0 (2 5, 19), 550 (15, 14), 560 (3.5, 14), and Tosoh's Ultracene 510F (2.
  • the solvent dissolves when the olefin resin dissolves when heated and does not dissolve at room temperature, or dissolves at room temperature and becomes insoluble by cooling. It is sufficient if the solvent gives the dependence, and the difference in solubility between 25'C and 65
  • the solvent may be at least Z solvent ml or more, preferably at least 0.05 g / ml solvent.
  • solvents include, for example, tetrahydrofuran, benzene, toluene, xylene, dimethylformamide (DMF) Dimethyl sulfoxide (DMS0), acetone, methylethylketone (MEK), and the like.
  • the amount of the resin occupying the total amount of the solvent and the olefin-based resin may be arbitrary. Since there is a possibility of forming lumps, the content is preferably in the range of 1 to 80% by weight.
  • the heating conditions for dissolving the resin may be the lowest temperature necessary for dissolving the resin, and it is not preferable to heat more than necessary. During dissolution, it is preferable to stir according to the usual method.
  • Liquid aliphatic hydrocarbons are electrically insulating liquids, have a specific resistance of l OQ ⁇ cm or more, and are used for the purpose of enhancing electrical insulation in wet-type toners. In addition, it is required that the dissolving power for the wet toner component is relatively small, so that the deterioration as the wet toner is prevented.
  • liquid aliphatic hydrocarbon examples include n-paraffinic hydrocarbon, isoparaffinic hydrocarbon, or a mixture thereof, and halogenated aliphatic hydrocarbon.
  • branched-chain aliphatic hydrocarbons such as, for example, Isopar G, Vaisoper H, and Isono, manufactured by Exxon. It is preferable to use K, ISO, M and ISO V. These are olefin systems having a carboxyl or ester group. It has little solubility in resin.For example, the solubility of resin in Isopar H is less than 0.000 lg Z solvent ml at 25'C and 65'C. It is.
  • the liquid aliphatic hydrocarbon is preferably present in an amount of from 0.1 to 80% by weight, preferably from 0.1 to 50% by weight, based on the total weight of the solid component of the wet toner.
  • the liquid aliphatic hydrocarbon is preferably present in an amount of from 0.1 to 80% by weight, preferably from 0.1 to 50% by weight, based on the total weight of the solid component of the wet toner.
  • During storage it is preferable to store in a state where it is concentrated at this solid concentration because there is no change over time.
  • the liquid aliphatic hydrocarbon is used not only for dispersing the toner of the present invention, but also for mixing and dispersing the olefin-based resin under heating or the olefin-based resin.
  • the resin may be used as a fluid in a fluidized state under heating or as a solvent for dissolving.
  • Solvents for olefin-based resins have a temperature dependence in solubility, such as those that dissolve the resin when heated and do not dissolve at room temperature, or that dissolve at room temperature and become insoluble by cooling.
  • the solvent used is a liquid aliphatic hydrocarbon used as a solvent for dispersing the wet toner.
  • the particles precipitated in the wet toner manufacturing process are reduced. There is no need to provide a step for separating the solvent used for dissolving the resin or replacing the solvent used for dissolving the resin with a solvent of a wet toner.
  • the mixing ratio of the olefin resin is such that the olefin resin becomes fluid. Any value within the range is acceptable.
  • the heating conditions for preparing the dispersion of the olefin resin are a temperature that is sufficient for the resin to be plasticized and then turned into a liquid state, and a temperature at which each component is not decomposed. rather I be in a range, typical temperature range is Ru 4 0 ⁇ 1 2 0 e C der. If the temperature is low, the dispersing process takes a long time.
  • the expression “resin solution” also means a dispersion in which a resin is fluidized in a solvent.
  • a liquid aliphatic hydrocarbon and an olefin-based resin are used together with a glass as a grinding medium.
  • examples include a method of mixing and dispersing (media dispersing) in a heated reaction vessel using beads, steel balls, and the like. Finer particle size dispersion is possible by adjusting the bead size of the grinding medium to the particle size attained by dispersion, and by dispersing the media stepwise.
  • a grinding means using a grinding medium besides the use of a dispersion medium such as beads, the use of a cutter such as a disc or the use of a cutter knife In this case, a collision with a high-speed rotating hammer or the like can be used.
  • the grinding means is appropriately combined in accordance with the dispersed material, and the type and dispersing conditions are determined.
  • a known organic or inorganic colorant can be used as a colorant that can be used as required in the present invention.
  • black colorant examples include inorganic carbon black, triiron tetroxide, and organic cyan black.
  • yellow colorant examples include inorganic yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, and orange.
  • acetoacetate anilide-based monoazo pigment of a sparingly soluble metal salt (azo lake) Hanzayello G (C.I. No. Pigment Yellow 1, hereinafter similarly described)
  • Hansa Yellow 10G Patent Yellow 3
  • Hansa Yellow RN Patent Yellow 65
  • Nonza Briliant Yellow 5GX Patent Yellow 7
  • Non The Brilliant Yellow 10 GX Patent Yellow 98
  • One-piece yellow FGL (Pigment Yellow 97), Shimaki Lake Fast Yellow 6G (Pignent Ye 1 low 1 3 3), Lion Yellow K one 2 R (Pigment Yellow 16 9), and as acetoacetate aeride disazo pigments, Disazo Yellow G (Pigment Yellow 12), Disazo Yellow GR (Pigment Yel low 13), Gyazo yellow 5G (Pig gnent Yel low 14), Gyazo yellow 8G (Pigment Yel low 17), Gyazo yellow Low R (Pigment Yellow 55) and permanent yellow HR (Pigment Yellow 83).
  • Condensed azo pigments include Chromophthal Yellow 3G (Pigment Yellow 93), Chromophthal Yellow 6G (Pigment Yellow 94), Lomophthal Yellow GR (Pigment Yellow 95).
  • Hostaperm Yellow H3G (Pigment Yellow 154), Hostaperm Yellow H 4 G (Pigment Yel low 1 5 1), Host balm yellow H 2 G (Pigment Yel low 1 2 0), Host perm yellow H 6 G (Pigment Yel low 1 7) 5) and Hoster Palmierau HLR (Pigment Yellow 150).
  • Irgazine Yellow 3 RLTN Pigment Yellow 110
  • Irgazine Yellow 2 RLT Irgazine Yellow 2 RLT
  • Gazin Yellow 2 GLT ⁇ igient Yellow 109
  • Fast Gensono One yellow GR 0 H (Pigment Yellow 13 7), fast geneno.
  • Yellow GR 0 Pigment Yellow 110
  • Sandrine Yellow 6 GL Pigient Yellow 173
  • Flavantron (Pigment Yellow 24), Antramimidin (Pigment Yellow 108), Phthalylamide-type anthraquinone (Pigment Ye 1 low 123), Heliofast yellow E 3R (Pignent Yel loff 99), Metal complex pigment Azo-based nickel complex pigments (Pigent Green 10), nitroso-based nickel complex pigments (Pigaent Yellow 153), and azomethine-based copper complex pigments (Pignent Yello w 1 17), and a quinophthalone pigment, such as phthalimidinoquinophthalone pigment (PigBent Yellow 138).
  • a quinophthalone pigment such as phthalimidinoquinophthalone pigment
  • magenta-based coloring agent examples include inorganic cadmium mulled red, red iron, silver vermilion, lead red, and antimon vermilion.
  • the azo lakes of azo pigments include brilliant carmine 6B (Pigient Red 57: 1), lake red (Pigment Red 53: 1), and non-aqueous pigments.
  • Mantle Red FR 2 (Pigment Red 2), No., “One Moment Red FRLL (Pignent Red 9), No., One-mount Red FGR (Pigment Red 111), Brilliant Kamin BS (Pigment Red 115), Permanent Kamin FB (Pig «ient Red5), PV Carmin HR (Pigment Red 150) > Permanent carmin FBB (Pigment Red 1 4 6) Novaperm Red F 3 RK-F 5 RK (Pigment Red 1 70), Novaperm Red HFG (P i.g.
  • anthraquinone pigments which are condensed polycyclic pigments, piranthrone orange (Pigment Orange 40) and anthranthrone orange (Pigment orange 168) and dianthraquinonyl red (pigment red 177), and as a thioin digo-based pigment, (Pignent Violet 38), Choi Ngo Goreolet (Pignent Violet 36) ⁇ Choi Ngore Golet (Pignent Red 88), and Perumble orange (Pignent Orange 43) is an example of a perylene pigment, and a perylene pigment is also used as a perylene pigment.
  • Pigment Red 190 Perylene Remillion (Pignent Red 123)> Perylene Mullon (Pigment Red 1979), Perylene Scarlet (Pigment Red 149) and perylene red (Pigment Red 178), and as quinacridone-based pigments, quinata redone (Pigment Violet 19)> quinata Red Magenta (Pigaent Red 122), quinacridone malone (Pignent Red 206), and quinacridone scarlet (Pigment Red 207)
  • Other examples of condensed polycyclic pigments include viricoline pigments, red fluororubin pigments, and dyeing lake pigments (water-soluble dyes + precipitants ⁇ lake fixation). .
  • cyan colorants include inorganic ultramarine blue, navy blue, cobalt blue, and cell humidifiers, and phthalocyanine based Stogen Blue BB (Pigment Blue 15), Smitton Cyanin Blue HB (Pigment Blue 15), Cyanin Blue 500 (Pigaent Blue 15: 1) , Sumika Print Sianin Blue GN-0 (Pignent Blu e 15), Fast Sukai Blue A--61 2 (Pigment Blue 17), Shea Nine Green GB (Pigient Green 7) Cyan Green S5 3 7 — 2 Y (Pigment Green 36), Smitton Fast Payet RL ( Pigment Violet 2
  • the content of the colorant in the resin can be arbitrarily selected within the range of 0.001 to 2000% by weight based on the weight of the resin, but the same multicolor as in offset printing is used.
  • the optical reflection density of each color toner after transfer to the transfer target is 0.7 or more, and in particular, cyan and black. It is desirable that there be more than 1.0 in the market.
  • the black and cyan have a weight of 10 to 150% by weight based on the same weight as above, and the In this case, it is preferable that the weight ratio be 40% or more: I 50% by weight; If any of the colors exceeds the above range, after development, the formed image tends to have optical reflection density and background stain.
  • the coloring agent is used in the form of powder with a secondary coagulation state and a particle diameter of 30 to 150 m.
  • the resin is heated and melted so that the resin and the coloring agent have a predetermined mixing ratio. After mixing the ingredients, disperse in the solvent It may be dissolved, or the resin and the colorant may be separately dissolved in a solvent or dispersed by ultrasonic dispersion or the like, and then mixed, or the powder colorant may be dispersed in the resin solution. You may.
  • the carbon black used as a black colorant is a carbon black having a large structure and a particle size of 30 to 40 in a secondary aggregate state.
  • 1 5 0 / ⁇ powder of even Nodea of m is, the particle diameter 1 0 ⁇ 1 0 0 nm to Ku, BET method specific surface area of 3 0 ⁇ 2 6 0 m 2 / gr or less, DBP oil absorption 45
  • the carbon black may be heated and melted, mixed with a coloring agent, and then dispersed and dissolved in a solvent so that the mixing ratio with the resin is a predetermined ratio.
  • the carbon black may be mixed with the resin.
  • the blacks may be separately dissolved in a solvent or dispersed by ultrasonic dispersion or the like, and then mixed, or the carbon black may be dispersed in a resin solution.
  • the content of carbon black in the resin can be arbitrarily selected within the range of 0.001 to 2000% by weight based on the weight of the resin.
  • the optical reflection density after transfer to the transfer target is 0.7 or more, and preferably 1.0 or more.
  • the polyester ester used in the present invention will be described.
  • Polyhydroxycarboxylic acid esters are soluble in electrically insulating liquids such as liquid aliphatic hydrocarbons, and are resin particles obtained when added to the granulation process.
  • As a dispersing agent it has a granulation control function because it has a uniform particle size distribution, and has an affinity for resin particles in a wet toner. It was found that it also had the function of.
  • Hydroxycarboxylic acid ester which is a raw material for polymerization, is
  • X is a divalent saturated or unsaturated aliphatic hydrocarbon containing at least 12 carbon atoms, or at least It is a divalent aromatic hydrocarbon containing six carbon atoms, and there are at least four carbon atoms between the hydroxy and carboxy groups.
  • hydroxycarboxylic acid derivatives are, for example, 12-hydroxymethyl stearate methyl ester, 12-hydroxy Hydroxy carboxylic acid esters such as hydroxy styrene ester, 1
  • Lithium hydroxycarboxylate 1 2 — Metals of hydroxycarboxylate such as aluminum hydroxycarboxylate Salts, hydroxycarboxylic acid amides, hydrogenated castor oil and the like can be mentioned.
  • the hydroxycarboxylic ester can be used to form a partial carbonyl in the presence of a small amount of an amine or a catalyst. Which is obtained by polymerization, the polymerization It contains various forms such as those formed by esterification between molecules and those formed by esterification within a molecule.
  • the hydroxycarboxylic acid ester is preferably a 3- to 10-mer of a hydroxycarboxylic acid ester, and is a light gray-brown color. It is a wax-like substance. If the degree of polymerization of the polyester is less than 3 or greater than 10, it will not be compatible with the electrically insulating liquid and will be used in the granulation process. However, the desired particle size distribution of the obtained resin particles cannot be obtained.
  • the amount of the polyhydroxycarboxylic acid ester to be added is not particularly limited, but is used in a ratio of 0.01% by weight to 200% by weight per resin weight. You.
  • the hydroxycarboxylic acid ester may be added in the granulation step, but may be added to the resin solution or may be added to the pigment dispersion.
  • metal dialkyl sulfosuccinate, manganese naphthenate, calcium naphthenate, and naphthenate are used as charge control agents.
  • transition metal salts such as diol, manganese, zirconium, yttrium and nickel salts of dialkyl sulfocononic acid. It is desirable to do it.
  • the amount of addition may be a minimum amount that exhibits a charge adjusting effect, but is preferably from 0.1% by weight to 50% by weight in the electrically insulating liquid.
  • the resin particles in the liquid developer thus obtained are charged to a brush or a minus.
  • a positively charged one is one that gives a positive image on an electrophotographic photoreceptor used for negative charging, for example, a zinc oxide Z resin photoreceptor.
  • the charge control agent may be added at any stage in the resin solution, the colorant dispersion liquid, a mixture thereof, or in the granulation step or the final wet toner, but is added to the resin solution. Is preferred.
  • This has the advantage that usable charge control agents are not limited by the electrically insulating liquid. That is, since the charge adjusting agent dissolved in the solvent significantly lowers the electric resistance of the electrically insulating liquid, it is desirable that the amount present in the electrically insulating liquid be as small as possible. In order to ensure that the charge adjusting agent is adsorbed on the particles, it is desirable that the concentration of the charge adjusting agent in the electrically insulating liquid is higher, and both conditions are contradictory.
  • a charge controlling agent is added to the resin solution to sufficiently adsorb the toner particles. This is because the unnecessary charge control agent not involved in the adsorption of toner particles can be removed by solvent replacement after the cleaning, and the above conditions can be satisfied.
  • the resin particles when a negative charge control agent which is compatible with an electrically insulating liquid in which toner is dispersed is mixed as a charge control agent, the resin particles have a high adsorptivity to resin particles and have an excellent property. Shows negative charge, minimizes the amount of use, and has high optical reflection compared to the use of negative charge control agents that are not compatible with liquid aliphatic hydrocarbons A concentration is obtained.
  • having compatibility with the electrically insulating liquid means that the solubility at 25 is not less than 0.005 gr Z solvent mI, and preferably, it is not more than 0. Solvent is more than ml.
  • Examples of such negative charge control agents include metal dialkylsulfosuccinates, metal-containing azo dyes, lecithin, and the like.
  • the metal dialkyl sulfo succinate is a metal dialkyl sulfo succinate having an alkyl group of 5 to 17 carbon atoms.
  • the lanthanum in 57 To 80 mercury to 89 mercury, and more than 89 actinium, preferably cobalt, manganese, zirconium, yttrium, Metal salts such as nickel are preferred.
  • This type of negative charge control agent has a high adsorptivity to pigments and resin particles, and is compatible with an electrically insulating liquid, so that it can achieve its purpose with a minimum amount of use.
  • lecithin can be used as a charge control agent.
  • Lecithin is a phospholipid substance having bipolarity, such as Lecitin From Soy Beans (manufactured by Seikagaku Corporation), Lecitin, Egg) (manufactured by Tokyo Chemical Industry Co., Ltd.), Lecitin (Soya Bean) (manufactured by Tokyo Chemical Industry Co., Ltd.), Lecitin DX manufactured by Nisshin Oil Co., Ltd., the same base LP-20, the same base LP-20E, the same ISIS LP—205,0, ILO LP—207, ILO LG-110E, ILO LG-40, ILO LG— 40 E, same-base LG—40 S, same-base LS—50, same-base LS—60, same-base LS—100, and the like.
  • Lecithin has a high adsorptive capacity for colorants and resin particles, is compatible with liquid aliphatic hydrocarbons, and can achieve its purpose with a minimum amount of use.
  • the amount of lecithin to be added may be the minimum amount that exhibits a charge adjusting effect, but can be from 0.01% to 50% by weight in the liquid aliphatic hydrocarbon.
  • the wet toner obtained in the present invention includes, as other fixing agents, various resins soluble in, for example, an electrically insulating liquid, for example, a modified or unmodified alkyl resin, and an ordinary acrylic resin.
  • an electrically insulating liquid for example, a modified or unmodified alkyl resin, and an ordinary acrylic resin.
  • Resin synthetic rubber, polyalkylene oxide, polyvinyl acetate (including petital), and vinyl acetate resin.
  • a colorant-dispersed resin liquid in which a colorant is dispersed in a resin solution is poured into an electric insulating liquid composed of a liquid aliphatic hydrocarbon, mixed, and then cooled to form particles. It is not necessary to stir the colorant-dispersed resin solution, but preferably, the resin particles to be precipitated are dispersed by at least one kind of dispersing means such as stirring or ultrasonic irradiation. It is desirable to improve
  • the resin particles are precipitated due to a temperature difference, and the resin particles are dispersed due to a difference in solubility between the resin and the liquid aliphatic hydrocarbon which is a poor solvent. Precipitation occurs. It was found that the average particle size of the resin particles was affected by the cooling rate. The slower the cooling rate, the larger the average particle size, and the faster the cooling rate, the smaller the average particle size. Since the temperature at which the resin particles are formed is 24'C to about 30'C, the cooling temperature is increased and the temperature gradient is increased, so that the resin particles quickly pass through the resin particle formation temperature range. By doing so, the average particle size can be reduced.
  • Polyhydroxycarbonate is preferably added to the colorant dispersion, but the resin and the charge control agent may be added to the resin solution.
  • the poly (carboxylic carboxylic acid ester) is compatible with the liquid aliphatic hydrocarbon, while it is strong with the resin particles. It is considered that the resin particles having a high affinity have a submicron unit particle size and a narrow particle size distribution. That is, the particle size of the obtained particles is in the range of 0.1 to 10 ⁇ m, and D 5 represents the average particle size. Shows a single peak of 0.6 to 0.3, and does not require ball milling operation and classification of resin particles, which were required by the conventional method. Speedy disperser, jet mill, -blur, ong mill, ball mill, atomizer, etc., and coloring If only the agent is first milled in a separate process, a sharper wet toner with a further particle size can be obtained.
  • the precipitated resin particles may be separated by means of standing or centrifugation, washed, and the solvent may be removed, thereby increasing the concentration of the electrically insulating liquid.
  • the wet toner according to the present invention is prepared by adding micro silica, fine particle titanium oxide, alumina, or a sol-gel thereof to the wet toner solid component in an amount of 0.01%. It may be added in an amount of up to 10% by weight, so that excess ion in the wet toner is adsorbed, the stability of the toner is increased, and image characteristics such as flow improvement are improved. be able to.
  • Other fixing agents include, for example, various resins soluble in an electrically insulating liquid, such as modified or unmodified alkyl resins, ordinary acrylic resins, synthetic rubbers, and polyalkylenes.
  • modified or unmodified alkyl resins such as modified or unmodified alkyl resins, ordinary acrylic resins, synthetic rubbers, and polyalkylenes.
  • Polivi -Polyvinyl acetate such as ruptilaral, and butyl acetate resin can be added.
  • anionic, cation, amphoteric, or non-ionic surfactants can be added as a dispersant, and the synthetic resin or the like used as the fixing agent can be used as a dispersant. It can also be used as
  • the wet toner according to the present invention is used for electrophotography, it is a matter of course that a normal transfer method, that is, electric field transfer such as corona transfer, is performed on an insulating transfer target such as paper. Although it is possible, it can be efficiently transferred from the surface of the electrophotographic photosensitive member to an electroconductive transfer target such as a metal by a pressure transfer method. Further, by transferring the toner of the present invention to a substrate for a lithographic printing plate, an image portion having high printing durability can be formed on the lithographic printing plate.
  • the Rukoto In addition, when direct printing is performed, it is possible to print at a constant printing pressure to absorb irregularities caused by arrowheads of paper as a printing medium, and to obtain a very smooth printed matter. Since the particles have good adhesiveness to the lithographic printing plate substrate, there are advantages in that sufficient printing durability can be obtained.
  • a method for preparing a dialkyl sulfosuccinate used as a charge control agent is as follows. It is right.
  • the white salt is separated by filtration, and the light purple filtrate is concentrated using an evaporator, and 10.9 parts by weight of dialkyl sulfosuccinic acid cobalt, which is a light red purple solid, is obtained. (81% yield).
  • the solubility at 25 mm in ISOPAR G (manufactured by Exxon) is 0.2 g Z solvent m 1.
  • dialkyl sulfo succinate In the above-mentioned method for preparing dialkyl sulfo succinate, the amount of sodium dialkyl sulfo succinate used was 75 parts by weight. Then, the reaction was carried out using the same amount of potassium nitrate instead of cobalt nitrate, and dialkyl sulfo succinate was obtained in a yield of 45%. .
  • the solubility in Bispar G (manufactured by Exxon) at 25 is 0.2 g / ml solvent.
  • Monastral blue FBR metal phthalocyanine pigment, manufactured by ICI
  • dispersant solsperse 17,000, manufactured by ICI
  • An ultrasonic homogenizer (Nippon Seiki Seisakusho Co., Ltd., US-300T) containing 40 mg gr and a dispersing agent (Solth Perth 5000) and 50 ml of tetrahydrofuran was used.
  • the mixture is mixed and dispersed for 10 minutes to prepare a pigment dispersion.
  • the pigment dispersion, the resin solution previously prepared, and poly (methyl stearate) 12-hydroxystearate are prepared.
  • the resin particles were put into 15 m 1 and mixed for 1 hour using an ultrasonic homogenizer to precipitate resin particles.
  • the resin particles When the particle size of the resin particles was analyzed using a Microcratic II SRA type (manufactured by Nikkiso Co., Ltd.), the resin particles had a particle size width of 0.3 to 1.25 m. The average particle diameter D 5. Had a sharp, single-peak distribution spectrum of 0.60 m.
  • This wet toner was diluted with Vispar G (manufactured by Exon), adjusted to a print density of 1%, and used in the following development process.
  • the development process is carried out on electrostatic recording paper (DS Can Seiko Denshi Co., Ltd., electrostatic plotter, EP-4100 paper) with a surface charge of 150 V to 50 V. After forming various electrostatic patterns up to V, use the wet toner prepared above and apply it to a roller developing machine. More developed and printed. The developing machine speed was 2.6 m / min and 10.0 m / min. For the photometric colorimetric evaluation of the printed matter, the optical reflection density (OD value) was measured using Macbeth RD914 (manufactured by Macbeth Corporation).
  • Table 1 shows the results of each evaluation.
  • Example 2 In place of the poly (1-2) -hydroxystearate ester (trimer) in Example 1, a poly (12-hydroxy) stearate methyl ester (manufactured by Ito Oil Co., Ltd .; 4 Polymer, acid value 35.9 to 37.0, weight average molecular weight 1,560, hue (Gardner-Helige) 6 to 7, light gray-brown wax) A wet toner was prepared in the same manner as in Example 1. The resin particle before Similarly solvent substitution as in Example 1, this filter to have a particle size analysis, 0. 3 to 1. 5 m particle size range, the average particle diameter D 5 0 is 0. 8 9 yw m, It had a sharp single-peak distribution spectrum.
  • Example 2 In place of the poly (1-2) -hydroxyester ester (trimer) in Example 1, the poly (1-2) -hydroxyster Acrylic acid methyl ester (manufactured by Ito Oil Co., Ltd., hexamer, acid value 23.2-25.7, weight average molecular weight 1,890, hue (Gardner-Herri A wet toner was prepared in the same manner as in Example 1 except that g)) 5 to 6 and a light-gray brown wax) were used.
  • the poly (1-2) -hydroxyster Acrylic acid methyl ester manufactured by Ito Oil Co., Ltd., hexamer, acid value 23.2-25.7, weight average molecular weight 1,890, hue (Gardner-Herri A wet toner was prepared in the same manner as in Example 1 except that g)) 5 to 6 and a light-gray brown wax
  • Example 1 About Similarly to the resin particle before solvent replacement, this filtrate to have a particle size analysis, 0.1 7 2. 6 m particle size range, the mean particle diameter D 50 force 0.9 2 111, sheet Sharp Had a single peak distribution spectrum.
  • This pigment dispersion is poured into the previously prepared resin solution at once, and then mixed and dispersed for 1 hour using an ultrasonic homogenizer (as above) at 60 to 80, and the colorant-dispersed resin solution is dispersed. Prepared.
  • This colorant-dispersed resin solution is poured into 150 m1 of Isobar G (manufactured by Exxon) cooled to 5 to 10, and the ultrasonic homogenizer (same as above) is used. , For 0.5 to 1 hour to precipitate resin particles.
  • the particle size of the resin particles was analyzed using Microtrack-1 II SRA type (manufactured by Nikkiso Co., Ltd.), the particle size of the resin particles was 0.17 to 3.0 m. width, the average particle diameter D 5. Had a sharp, single peak distribution spectrum of 0.7 m.
  • This wet toner was diluted with the isopar G, adjusted to a print density of 1%, and evaluated as a wet toner as in Example 1. The results are also shown in Table 1.
  • Example 4 The procedure of Example 4 was repeated, except that the resin of Example 4 was replaced with a partially saponified polyethylene-vinyl acetate copolymer (Dumilan 2280, Takeda Pharmaceutical Co., Ltd., degree of saponification 80%). 4 Similarly, a wet toner was prepared.
  • a partially saponified polyethylene-vinyl acetate copolymer Dumilan 2280, Takeda Pharmaceutical Co., Ltd., degree of saponification 80%. 4
  • a wet toner was prepared.
  • Example 4 Similarly the resin particles before the solvent substitution, this filtrate to have a particle size analysis, 0.1 7 to 0.8 3 ⁇ granularity width of m, the average particle diameter D 5. Had a sharp, single-peak distribution spectrum of 0.
  • Example 4 Similarly the resin particles before the solvent substitution, this filtrate to have a particle size analysis, 0. 1 7 ⁇ 0. 4 2 / m particle size range, the average particle diameter D 5. 0.24 m, sharp, single-peak distribution Had a toll.
  • ethylene-vinyl acetate copolymer Mitsubishi Chemical Co., Ltd.
  • Evaflex 450 a vinyl acetate component containing 19% by weight
  • the particle size of the resin particles before solvent replacement was analyzed in the same manner as in Example 4.
  • the particle size range was 0.12 to 0.42 m, and the average particle size was D s . Had a sharp and single peak distribution spectrum of 0.24 m.
  • Example 4 In place of the methyl 12-hydroxystearate (trimer) in Example 4, 12-hydroxystearic acid (manufactured by Kanto Chemical Co., Ltd.) was used. A wet toner was manufactured in the same manner as in Example 4 except for the above.
  • Example 4 For Example 4 Similarly before solvent replacement resin particles, and rollers were granulometric, 1.5 to 25 // size width of m, the average particle diameter D 50 of 1 2. The even 6 m and particle size wide there were.
  • the initial current value is 11 OnA (current value after 60 seconds is 90 nA), and the electrophoretic force is small, and the solid image formed on the electrostatic recording paper after corona charging is rough. Intense, no clean solid image was obtained, on the electrode plate The problem was that the flow in the country was poorly established.
  • the evaluation as a wet toner was performed in the same manner as in Example 1, and the results are also shown in Table 1.
  • a wet toner was prepared in the same manner as in Example 4 except that 5-6, a light gray-brown solid) was used.
  • Example 4 Similarly before solvent replacement resin particles, this filtrate to have a particle size analysis, 1. 5 ⁇ 3 5 / zm particle size width, the average particle diameter D 50 of 1 5 m and particle size wide Nodea
  • the initial current value is 140 nA
  • the electrophoretic force is small at 60 nsec.
  • the current value is 115 nA
  • the solid image formed after corona charging on the electrostatic recording paper is too small. It had a problem that it was so violent that a clean solid image could not be obtained, that it flowed on the electrode plate, and that the fixation was poor.
  • Unit is zC / s
  • a cyan pigment Monastral blue FBR (metal phthalocyanine pigment, manufactured by ICI) 2.5 sr and poly Are dispersed in 100 ml of Visoper G (manufactured by Exxon), and this pigment dispersion is added at once to the resin solution prepared above, and further added at 150 eC for 1 hour. Stir and mix.
  • Monastral blue FBR metal phthalocyanine pigment, manufactured by ICI
  • Visoper G manufactured by Exxon
  • the resin particles When the particle size of the resin particles was analyzed using Microtrack-Mark II SRA type (manufactured by Nikkiso Co., Ltd.), the resin particles had a particle size range of 0.1 to 1. It had a sharp, single peak distribution spectrum with an average particle size of 0.72 ⁇ m.
  • This wet toner was diluted with Biospar G (manufactured by Exon), adjusted to a print density of 1%, and used in the following development process.
  • the developing characteristic is positively chargeable, and enables development of a negatively charged electrostatic latent image.
  • Example 1 Evaluation of development and the like was performed in the same manner as in Example 1.
  • the photometric colorimetric evaluation of the printed material was performed using a spectrophotometer system CM-1000J manufactured by Minolta Co., Ltd.
  • Fig. 1 shows the relationship between the reflectance and the wavelength of light.
  • a zeta potential measurement device (ESA-800, manufactured by MATEC APPLIED SCIENCES, an ultrasonic zeta potential analysis system) is used to evaluate the development and electrophoretic characteristics of the toner. Then, the mobility (m 2 seconds ⁇ V) was measured. The higher the mobility value, the better the high-speed development characteristics.
  • Table 2 shows the results of each evaluation.
  • a mark in the image quality indicates that there is no “bulk”, an X indicates that there is “bulk”, and ⁇ indicates that the sheet is particularly excellent.
  • ⁇ indicates that there is no “bleeding”
  • X indicates that there is “bleeding”
  • ⁇ indicates that it is particularly excellent.
  • O indicates no fogging and X indicates that there is fogging.
  • poly (12-hydroxystearate ester (trimer) in Example 8 poly (12-hydroxystearate) methyl ester (Ito Manufactured by Oil Refining Co., Ltd., tetramer, acid value 35.9-37.0, weight-average molecular weight 1,560, hue (Gardner-Herige 1) 6-7, light gray-brown wax
  • the toner was prepared in the same manner except that ⁇ ) was used in the same manner.
  • poly-hydroxymethyl stearate ester (manufactured by Ito Oil Co., Ltd., hexamer, acid value 23.2- 25.7, Weight-average molecular weight 1,890, Hue (Gardner-Helige) 5-6, Light-gray-brown wax) Except for using a wet toner in the same manner. did.
  • Nickel of tetral 2-ethyl sulfo succinate was used in place of cobalt 2-tetralsulfo succinate of Example 8. Except for, a wet toner was prepared in the same manner. The development characteristics were bipolar. The evaluation as a wet toner was performed in the same manner as in Example 8, and the results are also shown in Table 2.
  • Tetra 2 -ethyl sulfoconoic acid yttrium instead of tetral 2-ethyl sulfoconoic acid acid salt of Example 1
  • a wet toner was prepared in the same manner except that a rubber was used.
  • the development characteristics were bipolar.
  • the evaluation as a wet toner was performed in the same manner as in Example 8, and the results are similarly shown in Table 2.
  • the particle size of the resin particles was analyzed in the same manner as in Example 8, it was found that the particle size was 0.12 to L; a particle size width of L ⁇ m and an average particle size of 0.88 im were a single sharp type. It had a peak distribution spectrum. The development characteristics were positive charging.
  • Example 15 EVA (Ethylene monoacetate vinyl copolymer, Mitsui Dupont Chemical Co., Ltd.), Enoflex 410, acetic acid in place of the resin of Example 8
  • the bul component was 19% by weight, MI-400
  • the resin solution adjusting step and the mixed liquid dispersing step before the cooling step were performed under heating conditions of 7 O'C.
  • a wet toner was prepared.
  • the particle size of the resin particles was analyzed in the same manner as in Example 8, it was confirmed that the resin particles had a particle size width of 0.12 to 8.9 ⁇ m and an average particle size of 0.83, and had a short and single peak. It had a distribution spectrum. The developing characteristics were positively chargeable.
  • EVA X-ethylene monoacetate copolymer
  • Mitsui-Dupont Chemical Co., Ltd. Evaflex 220
  • Example 17 The evaluation as a wet toner was performed in the same manner as in Example 8, and the results are shown in Table 2 in the same manner.
  • Example 17 The evaluation as a wet toner was performed in the same manner as in Example 8, and the results are shown in Table 2 in the same manner.
  • a wet toner was prepared in the same manner as in Example 1 except that the step of preparing the resin solution and the step of dispersing the mixed solution before the cooling step were performed under the heating condition of 70 ° C.
  • the wet toner was prepared in the same manner except that the resin solution preparation step and the mixed liquid dispersion step before the cooling step were performed under the heating condition of 70 ° C. did.
  • Monastral blue FBR metal phthalocyanine pigment manufactured by ICI
  • 2.5 POLY12-hydroxystearic acid Methyl ester manufactured by Ito Oil Co., Ltd., trimer, acid value 40.8-42.8, chelation value 199.6-199.7, weight average molecular weight 1 200, hue (gardner • hair) 6-7, light gray-brown wax) 90 msr, 50 ml of tetrahydrofuran, and ultrasonic Using a homogenizer (US-300T, manufactured by Nippon Seiki Seisakusho Co., Ltd.), the mixture was mixed and dispersed in an ice bath for 10 minutes to prepare a pigment dispersion.
  • a homogenizer US-300T, manufactured by Nippon Seiki Seisakusho Co., Ltd.
  • This pigment dispersion was put into the previously prepared resin solution and mixed and dispersed at 60 to 80 using an ultrasonic homogenizer to prepare a pigment-dispersed resin solution.
  • This pigment-dispersed resin solution is poured into IOOBI G (manufactured by Exxon Corp.) IOO BI cooled to 5, and mixed for 1 hour using an ultrasonic homogenizer to precipitate resin particles. I let it.
  • the resin particles When the particle size of the resin particles was analyzed in the same manner as in Example 1, the resin particles had a particle size width of 0.1 to 3.0 ⁇ m and an average particle size of 0.7. m, and has a single-peak, distributed spectrum. Next, the resin particles are separated using a centrifuge (Model 90-4, manufactured by Sakuma Seisakusho Co., Ltd.). Then, the resin particles were washed with Isobar G (manufactured by Exxon) and further dispersed in Isoper G (manufactured by Exxon).
  • the resin particles after solvent replacement were subjected to particle size analysis in the same manner, the resin particles were found to have a particle size range of 0.24 to L.56 ⁇ m and an average particle size of 0.80 ⁇ m.
  • the shark had a single peak distribution spectrum.
  • This wet toner was diluted with Visoper G (manufactured by Exon), the print density was adjusted to 1%, and evaluated as a wet toner as in Example 8, and the results were compared. See Table 2. The development characteristics were negatively charged.
  • a wet toner was prepared in the same manner as in Example 19 except that the amount of tetrahydrofuran used was 100 ml, and the evaluation as a wet toner was similarly performed. And the results are shown in the same table.
  • Example 19 In place of the resin of Example 9, a partially saponified vinylene monovinyl acetate copolymer (manufactured by Takeda Pharmaceutical Co., Ltd., Dumilan 2280, a degree of saponification of 70%, and a bulk acetate component) were used. A wet toner was prepared in the same manner except that 28% by weight and Ml value 93) were used.
  • the resin particles When the particle size of the resin particles was analyzed in the same manner as in Example 8, the resin particles had a particle size range of 0.17 to 3.9 / m and an average particle size of 0.96 H. It has a single-peak distribution spectrum.
  • the resin particles When the particle size of the resin particles after solvent replacement was analyzed in the same manner, the resin particles had a particle size range of 0.21 to 10.8 m and an average particle size of 1.54 m. Had a distribution peak of a single peak in the shape.
  • This wet toner was diluted with Isobar G (manufactured by Xeon), adjusted to a print density of 1%, evaluated as a wet toner as in Example 8, and the results were compared. See Table 2.
  • a wet toner was prepared in the same manner as in Example 21 except that the amount of tetrahydrofuran used was 100 ml, and the wet toner was similarly prepared. Table 1 also shows the results.
  • EVA Ethylene monoacetate copolymer, Sumitomo Chemical Co., Ltd., Smitate DB—10, 10% by weight of vinyl acetate component
  • MI 70
  • diisooctyl sulfo succinate corn 25 56 m8 ⁇ , tetrahydrohydr 100 ml of lanthanum was mixed and heated and stirred at 70 ° C. for 1 hour in an oil bath to dissolve the resin, thereby preparing a resin solution.
  • the container (2) 2.5 g of Monastral blue RFR (metal phthalocyanine pigment, manufactured by ICI) was used as a coloring agent, and polyhydroxyl stearic acid was used. 90 mg of methyl ester (trimer) was dispersed in 100 ml of tetrahydrofuran using an ultrasonic homogenizer (US-300T, manufactured by Nippon Seiki Seisaku-sho, Ltd.). Then, a pigment dispersion was prepared.
  • Monastral blue RFR metal phthalocyanine pigment, manufactured by ICI
  • polyhydroxyl stearic acid 90 mg of methyl ester (trimer) was dispersed in 100 ml of tetrahydrofuran using an ultrasonic homogenizer (US-300T, manufactured by Nippon Seiki Seisaku-sho, Ltd.). Then, a pigment dispersion was prepared.
  • the pigment dispersion in a resin solution was adjusted above was introduced at once, further using ultrasound e Mojinai Heather (ibid) at 7 0 e C, was prepared by mixing and dispersing for 1 hour pigment dispersing resin solution.
  • This pigment-dispersed resin solution is put into 150 ml of Isobar G (manufactured by Exxon Corp.), which has been cooled down to 5 ml, and the ultrasonic homogenizer (same as above) is used for 0.5 hour. After mixing, resin particles were precipitated.
  • the resin particles When the particle size of the resin particles was analyzed in the same manner as in Example 8, the resin particles had a particle size width of 0.36 to 12.5 m and an average particle size of 2.13 ⁇ m. It had a single distribution peak.
  • the resin particles When the particle size of the resin particles after the solvent replacement was analyzed in the same manner, the resin particles had a particle size range of 0.36 to 15.7 m and an average particle size of 15.7 m. It had a sharp, single-beak distribution spectrum with a diameter of 2.83 m.
  • This wet toner was diluted with I-Soper G (manufactured by Exon), adjusted to a print density of 1%, evaluated as a wet toner as in Example 8, and the results were the same. Table 2 shows the results.
  • a wet toner was prepared in the same manner as in Example 8, except that the same amount of the partially treated product of I. Pigaent 57: 1 (Rojinichi Seika Co., Ltd.) was used.
  • the particle size analysis of the resin particles was performed in the same manner as in Example 8, the particle size was 0.24 to 1.69 ⁇ m and the average particle size was 0.85 m. It had a peak distribution spectrum.
  • the photometric colorimetric evaluation was performed in the same manner as in Example 8, and FIG. 2 shows the relationship between the wavelength of light and the reflectance.
  • the developing characteristics were positively chargeable.
  • Example 8 In the same manner as in Example 8, except that the cyan pigment of Example 8 was replaced with the same amount of CIPigBent Ye 1 low 17 of Yellow Pigment 240 B (Dainichi Seika Co., Ltd.) Thus, a wet toner was prepared.
  • a single peak was obtained in a sharp shape having a particle size width of 0.83 to 1.1.15 zm and an average particle size of 0.98 m. Distribution spectrum.
  • the development characteristics were positive charging.
  • the photometric colorimetric evaluation was performed in the same manner as in Example 1.
  • FIG. 3 shows the relationship between the wavelength of light and the reflectance.
  • Example 8 In place of the resin of Example 8, EVA (ethylene monoacetate copolymer, Mitsui DuPont Chemical Co., Ltd.), Evaflex 460, and a cellulose acetate component of 1 A wet toner was prepared in the same manner as in Example 8 except that 9 gr% and an Ml value of 462.5) of 2.5 gr were used. The developing characteristics were positively chargeable.
  • EVA ethylene monoacetate copolymer, Mitsui DuPont Chemical Co., Ltd.
  • Evaflex 460 Evaflex 460
  • a cellulose acetate component of 1 was prepared in the same manner as in Example 8 except that 9 gr% and an Ml value of 462.5) of 2.5 gr were used.
  • the developing characteristics were positively chargeable.
  • Example 8 In place of the tetra-2-sulfo succinate of Example 8, * lute 2 56 m 8 ⁇ , the dizoctyl sulpho succinate zirconia 2 A wet toner was prepared in the same manner as in Example 8, except that the toner was used. The development characteristics were bipolar.
  • Tetra 2 of Example 8 Ethyl Sulfoconoic Acid Concentrate 2
  • a wet toner was prepared in the same manner as in Example 8, except that disooctyl rufosuccinate manganese 2 56 mgr was used instead of 56 m8: .
  • the development characteristics were bipolar.
  • Example 8 The resin in Example 8 was prepared by using a polyethylene monoacetate copolymer (EVA Flex 360, manufactured by Mitsui / Dupont Chemical Co., Ltd .; A wet toner was prepared in the same manner as in Example 8, except that the content of the bullet component was 25% by weight and the Ml value was 2.0).
  • EVA Flex 360 manufactured by Mitsui / Dupont Chemical Co., Ltd .
  • a wet toner was prepared in the same manner as in Example 8, except that the content of the bullet component was 25% by weight and the Ml value was 2.0).
  • Example 8 When the wet toner was evaluated in the same manner as in Example 8, the resin coverage of the coloring agent was low, and porous resin particles were obtained. Furthermore, heat melting of the resin during the toner fixing process is unlikely to occur. Also, as in Example 8, in the case of the naturally dried state, there was a problem that the film formation characteristics were poor and a uniform solid image was not obtained for forming the quality of printed matter.
  • a wet toner was prepared in the same manner as in Example 19, except that the resin in Example 19 was replaced with the resin described above.
  • the toner characteristics were evaluated. , under 6 0 ⁇ 8 0 e C there was some minor insolubles. Further, the obtained printed matter had poor film forming characteristics of toner, and the image quality was bulky. For this reason, there was a problem that it was difficult to obtain a uniform and high-concentration solid.
  • Example 2 When the wet toner was evaluated in the same manner as in Example 1, the wettability of the resin with respect to the colorant was poor, and the ability to disperse and maintain in a visper (manufactured by Xeon) was reduced. As a result, a wet toner having low dispersion stability was obtained. Further, the printed matter has a problem that a flow and a swim (smoothness) occur.
  • Example 12 when a wet toner was prepared and evaluated in the same manner as in Example 12 except that the resin in Example 12 was used instead of the above resin, there was a problem with the colorant holding ability during granulation in the same manner as described above. Thus, it was a wet toner that was not uniformly coated with pigment. For this reason, there is a problem that a uniform solid image cannot be obtained for forming a printed matter.
  • a wet toner was prepared in the same manner as in Example 8, except that 1.63, hues (gar donor, helige) 5 to 6, and a light gray-brown solid were used.
  • the particle size range was 0.24 to 60 zm, the average particle size was 8.7, and the particle size was wide.
  • the electrophoretic force was low at 50 ⁇ A, a current value of 95 nA after 60 seconds, and the solid image formed on the electrostatic recording paper after corona charging was very thick. There was a problem that a clean solid image could not be obtained, the flow on the electrode plate, and the fixation was poor.
  • a wet toner was prepared in the same manner as in Example 8 except that poly (12-hydroxystearic acid methyl ester) (trimer) was not used.
  • the particle size of the resin particles was analyzed in the same manner as in Example 8, the particle size range was 1.69 to 60 m, the average particle size was 13.4 zm, and the particle size range was wide. It was not possible to control the particle size in the clone area.
  • the initial current value was 180 nA, and the current value after 60 seconds was 110 nA, and the electrophoretic force was small, and the solid image formed after corona charging on the electrostatic recording paper was too thick. As a result, a clean solid image could not be obtained, and the flow on the electrode plate and the fixing were poor.
  • a wet toner was produced in the same manner as in Example 8, except that the negative charge control agent was not used.
  • the evaluation as a wet toner was performed in the same manner as in Example 8, and the results are shown in Table 3 in the same manner. Comparative Example 9
  • Example 19 Instead of 12-hydroxy stearic acid methyl ester (trimer) in Example 19, 12-hydroxyxstearic acid (manufactured by Kanto Chemical Co., Ltd.) was used. Except for the points, a wet toner was prepared in the same manner.
  • the particle size analysis of the resin particles was performed in the same manner as in Example 8, the particle size range was 1.2 to 60 zm, the average particle size was 8.7 m, and the particle size was wide. 5 ⁇ ⁇ , after 60 seconds, the current value is 90 nA, and the electrophoretic force is small, and the solid image formed after corona charging on the electrostatic recording paper is very sharp and clean. However, there was a problem that the image could not be obtained and the flow on the electrode plate and the fixation were poor.
  • evaluation as a wet toner was performed in the same manner as in Example 8, and the results are shown in Table 3.
  • the particle size range was 0.36 to 60 ⁇ m, and the average particle size was 15.9 m.
  • a wet toner was prepared in the same manner as in Example 19, except that the polyhydroxymethyl stearate methyl ester (trimer) was not used. Was prepared.
  • the particle size of the resin particles was analyzed in the same manner as in Example 8, the particle size range was 0.36 to 60 ⁇ m, and the average particle size was 15.7 ⁇ m.
  • the initial current value is 95 ⁇ A, the current value is 63 nA after 60 seconds, the electrophoretic force is small, and the solid formed after the corona charging on the electrostatic recording paper The image was too bulky to obtain a clean solid image, and had problems such as poor flow on the electrode plate and poor fixation.
  • a wet toner was prepared in the same manner as in Example 19 except that the negative charge regulator was omitted.
  • evaluation as a wet toner was performed in the same manner as in Example 8, and the results are shown in Table 3 in the same manner. Comparative Example 1 3
  • Example 8 instead of using sodium diisooctylsulfoconodate 300 mg "in place of the cobalt diisooctyls rufosuccinate of Example 8 in Example 8, 300 mg" was used. A wet toner was prepared in the same manner as in Example 8. It should be noted that sodium diisooctylsulfosuccinate (Wako Pure Chemical Industries, Ltd., trade name: Aerosol 0T) isoper G ( The solubility at 25 in Exon is about 0.2 g ml solvent Z.
  • a wet process was performed in the same manner as in Example 8 except that 256 mg of calcium diisooctylsulfosuccinate was used instead of 256 mg of diisooctylsulfoconoconate in Example 8. Toner was prepared. The solubility of calcium isoform of diisooctyls rufosuccinate (manufactured by Wako Pure Chemical Industries, Ltd.) in isoper G (manufactured by Exon) at 25 was 0.2. sr Z solvent ml.
  • EVA Ethylene monoacetate vinyl copolymer, Mitsui Dupont Chemical Co., Ltd.
  • lecithin trade name: Lecitine Fro, Soy Beans, manufactured by Junsei Chemical Co., Ltd.
  • Isobar G manufactured by Exon
  • Monastral blue FBR metal phthalocyanine pigment, manufactured by ICI
  • a cyan pigment 2.58 ⁇ Methyl acrylate ester manufactured by Ito Oil Co., Ltd., trimer, acid value 40'.8 ⁇ 42.8, genification value 19.6.9-19-197. 7, weight average molecular weight 1,200, hue (gardner heliger) 6 ⁇ 7, light gray brown wax] 20 m sr and isospar G (manufactured by Xeon)
  • This pigment dispersion was dispersed in 100 ml, and added at once to the resin solution prepared above, and further stirred and mixed at 120'C for 1 hour.
  • the mixed solution was left at room temperature, and the temperature was lowered to about 70. Then, the mixture was poured into 100 m 1 of Isopar G (manufactured by Exon), and the ultrasonic homogenizer was introduced. Dispersion and mixing were performed using a Genizer (US-300T, manufactured by Nippon Seiki Seisaku-sho, Ltd.) to obtain a wet toner.
  • Genizer US-300T, manufactured by Nippon Seiki Seisaku-sho, Ltd.
  • the resin particles When the particle size of the resin particles was analyzed using Microcrack Mark ESRA type (manufactured by Nikkiso Co., Ltd.), the resin particles had a particle size width of 0.44-2.54 m. , an average particle diameter D 5. Is 0.98 m had a sharp, single-peak distribution spectrum.
  • This wet toner was diluted with Vispar G (manufactured by Exon), adjusted to a print density of 1%, and used in the developing process.
  • the development process is carried out on an electrostatic recording paper (DS Can Seiko Denshi Co., Ltd. electrostatic plotter, EP-41010 paper) with a surface charge of 150 V to 20 V.
  • electrostatic recording paper DS Can Seiko Denshi Co., Ltd. electrostatic plotter, EP-41010 paper
  • Example 2 In order to evaluate the electrophoretic properties of the toner, the same high-voltage power supply and measuring device as in Example 1 were used.
  • the electrode spacing was lcm, the electrode area was 5.0 cm X 4.5 cm.
  • the quantity of electricity (Q / m, unit ⁇ CZ gr) per toner weight attached to the sample was measured. The larger the difference between the initial current value and the current value after 60 seconds and the QZm value, the better the electrophoretic property of the toner.
  • Table 4 shows the results of each evaluation.
  • Example 28 Poly- (2-hydroxystearic acid) ester (trimer) was replaced with poly (1- (2-hydroxy) stearate) in Example 8.
  • Methyl ester manufactured by Ito Oil Co., Ltd., tetramer, acid value 35.9-37.0, weight average molecular weight 1560, hue (gar Donor / Herge 1) 6-7, light gray-brown wax:
  • a wet toner was prepared in the same manner except that ⁇ was used in the same manner.
  • Example 28 Poly (12-hydroxystearic acid ester (trimer)) was replaced by poly (12-hydroxymethyl sulphate methyl ester) in Example 28.
  • Teru manufactured by Ito Oil Co., Ltd., hexamer, acid 23.2-25.7, weight-average molecular weight 1,890, hue (Gardner Herige) 5-6, light gray brown
  • a wet toner was prepared in the same manner except that the wax used in Example 1 was used.
  • EVA Ethylene monoacetate vinyl copolymer, Mitsui DuPont Chemical Co., Ltd.
  • Evaflex® 250 ml in round bottom flask , 28% by weight of vinyl acetate component, MI 150
  • lecithin trade name: Lecitine Froa Soy Beans, manufactured by Junsei Chemical Co., Ltd.
  • Tetrahi Drofran 50 ml Were mixed and heated and stirred in a 70 to 80 hot water bath for 1 hour to dissolve the resin, thereby preparing a resin solution.
  • Monastral blue FBR metal phthalocyanine pigment, manufactured by ICI
  • a Jinizer US-300T, manufactured by Nippon Seiki Seisakusho Co., Ltd.
  • the pigment dispersion is poured into the previously prepared resin solution, and the mixture is refluxed for 1 hour in a hot water bath using an ultrasonic homogenizer.
  • Sopar G manufactured by Exon
  • tetrahydrofuran is evaporated and separated from the dispersion by an evaporator, and isobaric G (manufactured by Xeon Corporation) is adjusted to a solid concentration of 1%. Was added.
  • the resin particles after solvent replacement were subjected to particle size analysis in the same manner as in Example 28.
  • the resin particles had a particle size width of 0.18 to 1.34 / zm and an average particle size of 0.36 / m, had a sharp, single-peak distribution spectrum.
  • a wet toner was prepared in the same manner as in Example 31 except that the added amount of lecithin in Example 31 was set to 7500 mg, and the toner characteristics were evaluated in the same manner as in Example 31. Table 4 shows the results.
  • the resin particles after solvent replacement were subjected to particle size analysis in the same manner as in Example 28.
  • the resin particles had a particle size width of 0.18 to 1.38 ⁇ m and an average particle size of 0.39 ⁇ m. Had a sharp, single-beak distribution spectrum.
  • a wet toner was prepared in the same manner as in Example 31 except that the amount of lecithin added in Example 31 was 1.58 ⁇ , and the toner characteristics were evaluated in the same manner as in Example 31. Table 4 shows the results.
  • the resin particles after solvent replacement were subjected to particle size analysis in the same manner as in Example 28.
  • the resin particles had a particle size width of 0.19 to 1.36 zm and an average particle size of 0.40 m.
  • the sharp had a single peak distribution vector.
  • Example 31 The amount of lecithin added in Example 31 was set to 750 mg, and the colorant Mon astral blue FBR was used instead of Sika Fast Yellow 250 B (large). Nissei Chemical Industry Co., Ltd.) Except for that, a wet toner was prepared in the same manner as in Example 31 and the toner characteristics were evaluated in the same manner as in Example 31. Table 4 shows the results.
  • the resin particles When the particle size of the resin particles after solvent replacement was analyzed in the same manner as in Example 28, the resin particles had a particle size of 0.17 to: I.13 ⁇ m in particle size width and average particle size of 0.36. ⁇ m had a sharp, single-beak distribution spectrum.
  • Example 31 The amount of lecithin added in Example 31 was set to 1. O gr, and the colorant was replaced with Monastral blue FBR. Table 4 shows the results of preparing a wet toner in the same manner as in Example 31 except that K.K. Kogyo Co., Ltd. was used, and evaluating the toner characteristics in the same manner as in Example 31.
  • the resin particles after solvent replacement were subjected to particle size analysis in the same manner as in Example 28.
  • the resin particles had a particle size width of 0.30 to 2.51 m and an average particle size of 0.96.
  • the shark had a single peak distribution spectrum.
  • Example 31 The amount of lecithin added in Example 31 was 75 Omgr, and the colorant was replaced with Monastral blue FBR, and MITSUBISI Rikibon Black MA-100 (Mitsubishi Chemical Corporation) A wet toner was prepared in the same manner as in Example 31 except that the above-mentioned was used, and the toner characteristics were evaluated as in Example 31. Table 4 shows the results.
  • the resin particles after solvent replacement were subjected to particle size analysis in the same manner as in Example 28.
  • the resin particles had a particle size range of 0.20 to: I.37 m and an average particle size of 0.49 m. Of a single peak in a sharp It had a cloth stick.
  • Example 31 The amount of lecithin added in Example 31 was set to 750 mg, and the colorant was changed to Sumica phthalocyanine blue GNO-PP (Sumitomo Chemical Co., Ltd.) in place of Monastral blue FBR.
  • a wet toner was prepared in the same manner as in Example 31 except that) was used, and the toner characteristics were evaluated in the same manner as in Example 31. Table 4 shows the results.
  • the resin particles after the solvent replacement were subjected to particle size analysis in the same manner as in Example 28.
  • the resin particles had a particle size width of 0.31 to 1.5 ⁇ m and an average particle diameter of 0.75. It had a sharp, single peak distribution spectrum of ⁇ m.
  • Example 28 The resin in Example 28 was changed to an ethylene vinyl acetate copolymer (EVA Flex 260, manufactured by Mitsui DuPont Polychemical Co., Ltd.).
  • EVA Flex 260 ethylene vinyl acetate copolymer
  • a wet toner was prepared in the same manner as in Example 28, except that 256 mg of cobalt salt of diisosulfosuccinate was used instead of cysteine.
  • Table 4 shows the results of evaluating the toner properties in the same manner as in Example 28.
  • Example 31 The resin in Example 31 was replaced with an ethylene-butyl acetate copolymer (EVA Flex 260, manufactured by Mitsui Dupont Chemical Co., Ltd.).
  • EVA Flex 260 ethylene-butyl acetate copolymer
  • a wet toner was prepared in the same manner as in Example 28, except that 256 mg of cobalt salt of diisosulfosuccinate was used in place of thiophene.
  • Table 4 shows the results of evaluating the toner characteristics in the same manner as in Example 28. Comparative Example 1 7
  • a wet toner was prepared in the same manner as in Example 31 except that cobalt disodium sulfonate (256 mg) was used instead of lecithin in Example 31.
  • Table 4 shows the results of the evaluation of the toner characteristics in the same manner as in Example 31.
  • Example 31 A wet process was performed in the same manner as in Example 31 except that 800 mg of magnesium naphthenate (manufactured by Nippon Chemical Industry Co., Ltd.) was used instead of lecithin in Example 31. Was prepared. Table 4 shows the results of the evaluation of the toner characteristics in the same manner as in Example 31.
  • a wet toner was produced in the same manner as in Example 30 except that magnesium naphthenate (manufactured by Nippon Chemical Industry Co., Ltd.) 6. was used instead of lecithin in Example 31. did.
  • Table 4 shows the results of evaluating the toner characteristics in the same manner as in Example 31.
  • Example 28 1250 460 130 O Example 29 1345 10 162 ⁇ Example 30 1290 154 154 o Example 31 1364 460 757 ⁇ Example 32 4402 1405 2500 ⁇ Example 33 9600 2670 4683 ⁇ Example 34 3240 265 509 ⁇ Example Example 35 4026 2225 1790 ⁇ Example 36 5358 1400 2350 ⁇ Example 37 4458 550 740 ⁇ Comparative example 15 150 95 70 um Comparative example 16 1661 715 201 ⁇ Comparative example 17 4258 4129 Unmeasurable X Comparative example 18 3559 2425 1 1 ⁇ Comparative example 19 5642 51 15 Not measurable X Example 3 8
  • EVA Ethylene monoacetate vinyl copolymer, Mitsui • DuPont Polike
  • GETZMAN N stainless steel constant temperature circulating dispersion port
  • MICAL Co., Ltd., Evaflex 250, vinyl acetate acetate component 28% by weight, MI 150
  • 2.5 sr, tetra 2-ethyl sulfo 25.6 m8 of cobalt oxalate and 100 ml of Vaisova G (manufactured by Exxon) were added, the mixture was circulated with boiling water and heated and stirred at 90 for 1 hour.
  • Monastral blue FBR a metal phthalocyanine pigment manufactured by ICI
  • Monastral blue FBR a metal phthalocyanine pigment manufactured by ICI
  • Methyl phosphate ester manufactured by Ito Oil Co., Ltd., trimer, acid value 40.8 to 42.8, chelation value 196.9 to 197.7
  • a high-speed disperser (DISPERMAT CV type manufactured by VMA-GETZMAN) was used as a dispersing machine, and industrial glass beads (Ashiza Co., Ltd.) was used as a grinding medium.
  • cold eye Seo Par G (manufactured by E click Seo emissions Co.) was added 1 5 0 m 1, pane Sorted chromatography car (Les Tsu Using Dodeville Type 540 (manufactured by Tokyo Denko Corporation), disperse and mix with high-speed shaking, and use a wet toner.
  • the resin particles When the particle size of the resin particles was analyzed using a Microtrac® Mark HS RA type (manufactured by Nikkiso Co., Ltd.), the resin particles had a particle size width of 0.24 to: L. It had a sharp and single peak distribution spectrum with an average particle size D so of 0.78 m.
  • This wet toner was diluted with Visoper G (manufactured by Exon), adjusted to a print density of 1%, and used in the following development process.
  • the printability was evaluated visually with respect to the image quality (whether there is rust), the flow (whether there is bleeding), and the degree of fogging.
  • Table 5 also shows the results of each evaluation.
  • ⁇ in ⁇ Image quality '' is excellent, ⁇ indicates no roughness, X indicates crispness, O in ⁇ Flow '' indicates no bleeding, X indicates bleeding Is shown.
  • poly (12-hydroxystearic acid ester (trimer) in Example 38 instead of poly (12-hydroxystearic acid ester (trimer) in Example 38), poly (12-hydroxycystearate) methyl ester (Ito Oil Co., Ltd.) Co., Ltd., tetramer, acid value 35.9-37.0, weight-average molecular weight 1,560, hue (Gardner Herige) 6-7, light gray brown wax ) was prepared in the same manner as in Example 38 except that was used in the same manner as in Example 38.
  • the particle size of the resin particles was analyzed in the same manner as in Example 38, the resin particles had a particle size width of 0.3 to 1.7 ⁇ m and a distribution vector with an average particle size of 0.89 ⁇ m. I was
  • polyester 12-hydroxystearate ester (trimer) in Example 38, the polyester 12-hydroxystearate was used.
  • Methyl ester manufactured by Ito Oil Co., Ltd., hexamer, acid value 23.2-25.7, weight-average molecular weight 1890, hue (gardner helicopter) 5-6
  • a wet toner was prepared in the same manner as in Example 38 except that a light-gray-brown wax) was used.
  • Example 3 In place of the cyan pigment of 8, the surface pigment of CIPigaent 57: ⁇ of the magenta pigment Puriant Carmin 6B # F (Dainichi Seika Co., Ltd.) A wet toner was prepared in the same manner as in Example 38, except that the same amount of the ester partially treated product was used.
  • Example 38 In addition, in place of using the cyan pigment of Example 38, the same amount of Yellow Pigment Permanent Yellow FGL (manufactured by Dainichi Seika Co., Ltd., CI Pig painting en yellow 97) was used. A wet toner was prepared in the same manner as in Example 38. When the particle size analysis of the resin particles was carried out in the same manner as in Example 38, it was found that the particles had a distribution spectrum of 0.32 to: 0.5 m in particle size width and 0.9 ⁇ m in average particle size. The development characteristics were negatively chargeable.
  • Yellow Pigment Permanent Yellow FGL manufactured by Dainichi Seika Co., Ltd., CI Pig painting en yellow 97
  • Example 38 The resin of Example 8 was replaced with EVA (ethylene monoacetate vinyl copolymer, Mitsui DuPont Polychemical Co., Ltd.), Evaflex 460, and a vinyl acetate component.
  • Example 3 Except that 256 mg of disooctyls rufosuccinate was used in place of 256 mg of tetral-2-ethylsulfosuccinate conform of 8 In the same manner as in Example 38, a wet toner was prepared. The development characteristics were positively chargeable. In addition, the evaluation as a wet toner was performed in the same manner as in Example 38, and the results are similarly shown in Table 5.
  • Example 3 In place of tetrabutyl 2-ethylsulfosuccinate 2556 mg in Example 8, yttrium diisooctylsulfosuccinate 250 mg was used. Except for the above, a wet toner was prepared in the same manner as in Example 38. The development characteristics were bipolar.
  • Example 13 In place of 12-hydroxystearic acid methyl ester (trimer) in Example 8, 12-hydroxystearic acid (trimer) was used. A wet toner was manufactured in the same manner as in Example S8 except that Kanto Chemical Co., Ltd.) was used. The developing characteristics were positively chargeable.
  • the particle size range was 1.6 to 25 zm and the average particle size was 13.8 m, but the initial current value was 12.7 ⁇ . a, 6 Ri Do 0 seconds after the current value 9 8 n a, mobilities is 2. 5 X 1 0 - 11 cm 2 Z s ⁇ [nu and rather small, and et co b na charged electrostatic recording paper The solid image formed afterwards had a problem that the solid image was severe, a clean solid image could not be obtained, and the flow on the electrode plate and the fixation were poor.
  • the particle size width was 1.5 to 35 wm, and the average particle size was 17.2 m, but the initial current value was 13 8 ⁇ A After 60 seconds, the current value was 113 nA, and the electric swimming power was small, and the solid image formed after corona charging on the electrostatic recording paper was sharp and clean. And the flow on the electrode plate and the fixation are poor.
  • Example 3 Except that sodium disooctylsulfoconodate 300 mg was used in place of cobalt 25.6 mgr of disooctylsulfoconodate in Example 8 In the same manner as in Example 38, a wet toner was prepared. Solubility of sodium disooctyl sulfoconoate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: Aerosol 0T) at 25'C in Aisopa-G (manufactured by Xeon) Is about 0.2 grZ solvent m 1.
  • Example 3 In place of 25 g m ⁇ of disooctyls rufosuccinate in Example 8, calcium disooctyls rufosuccinate was used in a proportion of 25 msec. Except for the above, a wet toner was prepared in the same manner as in Example 38.
  • a wet toner was prepared in the same manner as in Example 38, except that poly (12-hydroxymethyl stearate) (trimer) was not used.
  • the particle size width was 2.5 to 64 m and the average particle size was 28 / m, but the initial current value was 96 nA, After 60 seconds, the current value was 27 nA and the electrophoretic force was small, and the solid image formed on the electrostatic recording paper after corona charging was very thick and clean. The image could not be obtained, and there was a problem that the flow on the electrode plate and the fixation were poor.
  • Example 38 In place of the poly (12-hydroxystearate) methyl ester (trimer) in Example 8, the hydrophilic group was replaced with poly (ethylene).
  • Example 38 was prepared in the same manner as in Example 38 except that emalgen 300 (manufactured by Kao Corporation), a nonionic surfactant having a higher alcohol and a higher alcohol group, was used for 70 ms. A wet toner was prepared in the same manner.
  • a wet toner was produced in the same manner as in Example 38 except that the negative charge regulator was not used.
  • the dispersion-mixed liquid was poured into a resin solution flask at once, and further stirred at 70 ° C. for 1 hour to form a coating liquid.
  • the resulting colorant-dispersed resin solution was cooled to 60 ° C while standing at room temperature, and then poured into 100 ml of Cooled G-Spar G (manufactured by Xeon Corporation). Then, an ultrasonic homogenizer was used to precipitate resin particles.
  • the solution was spread on a batch and heated air was blown on the surface to evaporate and remove the tetrahydrofuran used as a solvent.
  • the infrared absorption spectrum measurement of the presence of the polycarboxylic ester attached to the resin particles i.e., 380 to 320 cm - 1 of the OH group stretching vibration area of quantitative and mosquito Le Bonn San'e scan Te le to your only that mosquitoes Le Bo - Ri by the 1 7 6 0-1 7 7 peak position change of the non-cm one 1 Le based on confirmed.
  • This wet toner was diluted with Visoper G (manufactured by Exon), adjusted to a print density of 1%, and used as a developing solution in the following developing process.
  • the development process is performed on electrostatic recording paper (DS Can Seiko Denshi Co., Ltd., electrostatic plotter, EP-4010) for various surface charges of 150 V to 50 V. After the electrostatic pattern was formed, the image was printed by a roller developing machine using the wet toner prepared above. The developing machine speed was 2.6 mZ min and 10 m / min.
  • the toner characteristics were as follows. Using the high-voltage power supply and measuring device used in Example 1, two copper plates 40 mm long and 35 mm wide fixed in the cell at 1 cm intervals were used as electrodes. A developer was filled between the electrodes, and a DC voltage of 100 V was applied between the electrodes. Initial current value and electrophoresis evaluation were performed. As for the OD value of the printed matter, the optical reflection density (OD value) was measured using Macbeth RD914 (manufactured by Macbeth Co., Ltd.).
  • the development characteristics show negative polarity, 0 D value 1.1, initial current value 102 1 nA, current value after passing for 60 seconds at 685 ⁇ A, weight of toner attached to electrode
  • the charge value per unit time (Q / m, unit C / s) is 400, and the difference between the initial current value and the current value after 60 seconds and the Q / m value are large. It has excellent properties. Further, with regard to printability, a good printed matter was obtained without image deletion or crushing, and a printed matter having a uniform solid surface was obtained.
  • carbon black pigment MA 100 (manufactured by Mitsubishi Chemical Co., Ltd., particle size 22 nm, BET specific surface area 13 4 m 2 Zs, DBP oil absorption 10 0 ml Z 100 gr, PH 3.5) was combined with 2 g of poly (methyl styrene) methyl phosphate ester (manufactured by Ito Oil Co., Ltd., trimer, acid).
  • the developing characteristic shows a negative polarity, an OD value of 1.3, an initial current value of 1063 nA, and a current value after passing electricity for 60 seconds at 905 nA, per weight of toner attached to the electrode.
  • EVA Ethylene monoacetate butyl copolymer, Evaflex 4500, manufactured by Mitsui DuPont Polychemicals, Inc.
  • the developing characteristic shows a negative polarity, an OD value of 1.3, an initial current value of 2651 nA, and a current value after passing electricity for 60 seconds at 198 3 nA, per weight of toner attached to the electrode.
  • the charge value (Q / m, unit: CZS) is 300, the difference between the initial current value and the current value after 60 seconds and the Q / m value are large, and the toner electrophoresis is excellent. It is.
  • Bed rack pigment # 9 7 0 (Mitsubishi Chemical Co., Ltd. particle diameter 1 6 nm, a BET specific surface area of 2 5 0 m 2, DBP oil absorption 8 0 Resin particles were precipitated in the same manner as in Example 45, except that ml Z 100 gr and pH 3.5) were used for 2 s. Next, resin particles were precipitated in the same manner as in Example 45. The precipitated resin particles, this filtrate to have a particle size analysis, resin particles child granularity width of 0. 1 7 ⁇ 1. 6 9 m, average particle diameter D 5. Had a single beak spectral distribution with a 0.36 im sharp. In Fig. 7, the horizontal axis represents the logarithm of the particle size in logarithm, and the vertical axis represents the histogram, which shows the frequency, and the cumulative particle size distribution by a line.
  • Example 45 evaluation as a wet toner was performed in the same manner as in Example 45.
  • the development characteristics show a negative polarity, an OD value of 0.66, an initial current value of 72 9 InA, and a current value of 1328 ⁇ A after applying electricity for 60 seconds, and the weight of toner attached to the electrode.
  • the charge value per unit time (QZm, unit ⁇ C / 8 ⁇ ) is 100, and the difference between the initial current value and the current value after 60 seconds and the Q / m value are large. It has excellent properties.
  • Example 4 The carbon black of Example 5 was replaced with a carbon black pigment MA100 (manufactured by Mitsubishi Kasei Co., Ltd., particle size: 22 nm, BET specific surface area: 13 4 m 2 / 8 ⁇ Resin particles were produced in the same manner as in Example 45 except that 2 g of the DBP oil absorption lOOml / 100 0 ( ⁇ 3.5) was used.
  • MA100 manufactured by Mitsubishi Kasei Co., Ltd., particle size: 22 nm, BET specific surface area: 13 4 m 2 / 8 ⁇
  • Resin particles were produced in the same manner as in Example 45 except that 2 g of the DBP oil absorption lOOml / 100 0 ( ⁇ 3.5) was used.
  • the resin particles are 0.1 7 2. 6 3 zm particle size range, the average particle diameter D 5. Had a single-peak spectral distribution with a shape of 0.71 // m.
  • Figure 8 shows the logarithm of the particle size on the horizontal axis and the vertical axis The histogram shows the frequency and the cumulative particle size distribution is shown by a line.
  • Example 45 evaluation as a wet toner was performed.
  • the developing characteristic shows a negative polarity, an OD value of 1.5, an initial current value of 5789 nA, and a current value of 2480 nA after 60 seconds of energization at an initial current value of 5789 nA.
  • the charge value (QZm, unit CZ ff) is 500 or more, and the difference between the initial current value and the current value after 60 seconds and the Q / m value are large and the toner electrophoresis is excellent. is there.
  • Resin particles were produced in the same manner as in Example 45 except that polyhydroxymethyl stearate ester was not used.
  • a developing solution was prepared from the obtained resin particles in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the developing characteristic shows a negative polarity, an OD value of 0.31, an initial current value of 310 nA.
  • the charge value per unit weight of the toner (QZm, unit ⁇ C / g) is 20, and the difference between the initial current value and the current value after 60 seconds and the QZm value are small. Had poor electrophoretic properties.
  • Resin particles were produced under the same conditions as in Example 45, except that tetrabutyl 2-ethylsulfosuccinate cobalt, which was the charge control agent of Example 45, was not used.
  • a developing solution was prepared from the obtained resin particles in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the developing characteristics show bipolarity, and the developing characteristics are better when a negative latent image is developed with a positive polarity.
  • the OD value is 0.51
  • the initial current value is 211
  • the current value after conducting for 60 seconds is 511.
  • the charge amount per toner weight attached to the electrode (Q / m, unit / z CZ sr ) was 40, indicating that the difference between the initial current value and the current value after 60 seconds and the QZm value were small, and the electrophoretic property of the toner was poor.
  • a developing solution was prepared from the obtained resin particles in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the developing characteristic shows a negative polarity, an OD value of 0.41, an initial current value of 750 nA, and a current value of 650 nA after conducting for 60 seconds at an initial current value of 750 nA.
  • Charge per weight of toner attached to the electrode The quantity value (Q / m, unit CZ sr) was 47, and the difference between the initial current value and the current value after 60 seconds and the Q / m value were small, and the toner electrophoresis was inferior.
  • the resin was changed to a partially modified poly (vinyl monoacetate) copolymer (Takeda Pharmaceutical Co., Ltd., Dumilane Series C-1 270, 70% gen.). Resin particles were produced under the same conditions as in Example 45 except for the above.
  • a developer was prepared from the wet toner containing the obtained resin particles in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the development characteristics show a negative polarity, an OD value of 0.54, an initial current value of 41 OnA, and a current value of 288 ⁇ A after applying electricity for 60 seconds, and the weight per toner attached to the electrode.
  • the charge value (QZm, unit C / gr) was 120, and the difference between the initial current value and the current value after 60 seconds, the QZm value was small, and the electrophoretic property of the toner was poor.
  • Example 3 1 The carbon black of Example 45 was replaced with carbon black pigment MA7 (manufactured by Mitsubishi Kasei Corporation, particle diameter: 24 nm, BET specific surface area: 13 m 2 / g) Resin particles were produced in the same manner as in Example 1 except that 28 ⁇ l of DBP oil absorption of 65 ml / 100 g, pH 3.5) was used.
  • a developing solution was prepared in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the carbon black of Example 45 was obtained by combining the carbon black with a low struc- ture and a carbon black pigment legal 33 (Cabbot Corporation, particle size 25 nm, BET Resin particles were produced in the same manner as in Example 1 except that the specific surface area was 94 m 2 gr, the DBP oil absorption was 65 ml / 100 gr, and the pH 2.5) was 2 g. .
  • a developing solution was prepared in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the developing characteristics show negative polarity, the OD value is 0.5, the initial current value is 1 ⁇ ⁇ ⁇ ⁇ , and the current value after energizing for 60 seconds is 88 nA, the weight per toner attached to the electrode.
  • the charge value (Q / m, unit CZ g) is The difference between the initial current value and the current value after 60 seconds, the QZm value was small, and the electrophoresis of the toner was inferior.
  • the carbon black of Example 45 was prepared by reducing the structure of the carbon black to a low force and using a pump black pigment Mogal L (Kyapot Co., Ltd., having a particle diameter of 24 nm and a BET specific surface area). Resin particles were produced in the same manner as in Example 1 except that 2 gr of 13.8 m 2 Zs and DBP oil absorption of 60 m 1/10 0 8 ( ⁇ 2.5) were used.
  • a developer was prepared from the wet toner containing the obtained resin particles in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the development characteristics show a negative polarity, an OD value of 0.4, an initial current value of 90 nA, and a current value of 60 ⁇ A after 60 seconds of energization, and a charge amount per toner weight attached to the electrode.
  • Q Zm, unit C / gr was 70, and the difference between the initial current value and the current value after 60 seconds, the Q / m value was small, and the electrophoresis of the toner was poor.
  • Example 45 The carbon black of Example 45 was replaced with a carbon black pigment mic mouth lith black (Ciba-Gai Gis Co., Ltd., rosin-treated product, particle size 30 nm, BET method ratio) Resin particles were produced in the same manner as in Example 1 except that the surface area was 105 m 2 Z gr, the DBP oil absorption was 35 ml / 100 g, and the pH 3.5) was 2 g. . Then, Resin particles were precipitated in the same manner as in Example 45. The precipitated resin particles, this filtrate to have a particle size analysis, resin particles, 0.2 4 - in 6 0. O ⁇ m and wide particle size range, the mean particle diameter D 50 of 6.
  • the resin particles had a wide particle size distribution.
  • the abscissa represents the particle size in logarithm, and the ordinate represents the histogram showing the frequency and the cumulative particle size distribution in a polygonal line.
  • a developer was prepared from the wet toner containing the obtained resin particles in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • Example 45 The carbon black of Example 45 was replaced with carbon black pigment # 2400B (Mitsubishi Kasei Co., Ltd., particle size: 15 nm, BET method, specific surface area: 260 m 2 / g, DBP oil absorption) Resin particles were produced in the same manner as in Example 45, except that an amount of 45 ml (1000 g of PH, PH 2.0) was used in an amount of 2 gr.
  • carbon black pigment # 2400B Mitsubishi Kasei Co., Ltd., particle size: 15 nm, BET method, specific surface area: 260 m 2 / g, DBP oil absorption
  • a developing solution was prepared in the same manner as in Example 45 from a wet toner containing the obtained resin particles, and the developing characteristics were evaluated in the same manner.
  • the developing characteristic shows negative polarity, 0 D value 1.24, initial current value 5 10 ⁇ ⁇ , current value after passing for 60 seconds at 3 25 nA,
  • the charge amount value per unit weight of the toner (QZm, unit / z CZ gr) is 120, and the difference between the initial current value and the current value after 60 seconds and the QZm value are small. Electrophoresis was also poor.
  • the carbon black of Example 45 was prepared by applying the following method to the carbon black pigment # 850 (manufactured by Mitsubishi Kasei Co., Ltd., having a particle diameter of 18 nm and a BET specific surface area of 2). Resin particles were produced in the same manner as in Example 1 except that 2 gr of 0 m 2 Z gr and DBP oil absorption of 80 m 1 X 100 gr> PH 8.0) were used.
  • a developer was prepared from the wet toner containing the obtained resin particles in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the development characteristics show a negative polarity, an OD value of 0.4, an initial current value of 13011, and a current value after passing for 60 seconds with a current of 6011, and the amount of charge per unit weight of toner attached to the electrode.
  • the value (QZm, unit; zCZsr) was 100, and the difference between the initial current value and the current value after 60 seconds, the Q / m value was small, and the toner electrophoresis was poor.
  • the carbon black of Example 45 was prepared by applying the following formula to the carbon black pigment # 44 (manufactured by Mitsubishi Kasei Corporation, particle diameter 24 nm, BET specific surface area). 1 25 m 2 , DBP oil absorption 76 m I / 100 gr, PH 8.0) Resin particles were produced in the same manner as in Example 1 except for the points used. A developing solution was prepared in the same manner as in Example 45 from a wet toner containing the obtained resin particles, and the developing characteristics were evaluated in the same manner.
  • Example 1 click pigment # 1 0 B Mitsubishi Chemical Co. particle size 8 4 nm, a BET specific surface area 2 8 m 2 8T, D ⁇ ⁇ oil Resin particles were produced in the same manner as in Example 45 except that 2 g of an amount of 83 m 1 (100 ⁇ m, ⁇ 7.0) was used.
  • a developer was prepared from the wet toner containing the obtained resin particles in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.
  • the development characteristics show negative polarity, the OD value is 0.4, the initial current value is 65 nA, and the current value after applying current for 60 seconds is 40 nA, and the amount of charge per toner weight attached to the electrode
  • the value (QZm, unit ⁇ C / g) was 15, and the difference between the initial current value and the current value after 60 seconds, the Q / m value was small, and the toner electrophoresis was poor.
  • a metal-substituted salt (Ca) of sodium alkyl sodium sulfo succinate (Aerosol 0T (metal portion Na) manufactured by Wako Pure Chemical Industries, Ltd.) , Ni, Y) were used.
  • EVA Ethylene monoacetate vinyl copolymer, EVA Flexx manufactured by Mitsui Dupont Chemical Co., Ltd.
  • EVA Flexx manufactured by Mitsui Dupont Chemical Co., Ltd.
  • Y—0 T hexyl 2-ethyl sulfoconodic acid yttrium
  • tetrahydro as a solvent 60 ml of flann was mixed and heated and stirred at 70 in a warm bath for 1 hour to dissolve the resin, thereby preparing a resin solution.
  • car Bonn Bed rack pigment 220 0 B Mitsubishi Kasei KK particle size 1 8 nm, the BET specific surface area of 2 1 0 m 2 Z g, DBP oil absorption 45 2 g of ml Z 100 g ⁇ pH 3.0) and 1-hydroxymethyl stearate methyl ester (manufactured by Ito Oil Co., Ltd., 3 volumes)
  • Example 45 resin particles were produced in the same manner as in Example 45, and a developing solution was prepared from the obtained wet toner containing the resin particles in the same manner as in Example 1, and the development characteristics were evaluated in the same manner.
  • the developing characteristic shows negative polarity, OD value is 1.4, initial current value is 106 nA, current value after conducting for 60 seconds is 704 ⁇ A, weight of toner attached to electrode Charge value (QZm, unit ⁇ C / g) is more than 300 Good toner properties were exhibited. Image formation was possible, and good printed matter was obtained without image deletion or crushing. Further, the solid surface was a uniform printed matter.
  • Example 45 a 12-hydroxymethyl stearate methyl ester was used.
  • Ter (monomer) special grade reagent manufactured by Junsei Chemical Co., Ltd.
  • particle size analysis was performed. It showed a wide distribution of 17 to 60 m.
  • the average particle size D 5. was 5.01 / zm.
  • the horizontal axis is the logarithm of the particle size, and the vertical axis is the histogram, which shows the frequency, and the cumulative particle size distribution is a line.
  • the obtained wet developing solution was diluted with ISOPAR G (manufactured by Exon) to adjust the printing density to 1%. Next, the initial current value was measured and the electrophoretic characteristics were evaluated.
  • the developing characteristics show a negative polarity, an OD value of 0.86, an initial current value of 1291 nA, and a current value of 905 nA after applying electricity for 60 seconds.
  • the charge value (Q / m, unit: CZ 8 ⁇ ) showed toner properties of around 100. Image formation was possible, but there was image deletion. The solid surface was a uniform printed matter.
  • Comparative Example 4 1 Instead of the polyester 12-hydroxyester phosphate of Example 1, the methyl ester polyester 12-hydroxyester stearate was replaced with the methyl ester polyester 12-hydroxyester stearate. The mixture was granulated and subjected to particle size analysis in the same manner as in Example 1 except that it was used (mixed product of 10 monomers or more).
  • the average particle diameter D 50 is 3 6. 26 ⁇ m was Tsu der.
  • Figure 12 shows the logarithm of the particle size on the horizontal axis and the histogram showing the frequency and the cumulative particle size distribution on the vertical axis by a line.
  • the obtained wet developer was diluted with Isopar G (manufactured by Exon) to adjust the printing density to 1%. Next, the initial current value was measured and the electrophoretic properties were evaluated.
  • the developing characteristic shows negative polarity, OD value 0.91, current value 233 nA, current value after passing electricity for 60 seconds at 185 nA, 185 nA, charge per weight of toner attached to electrode
  • the quantitative value (QZm, unit / zC / g) showed a toner property of around 55. Image formation was possible, but there was image deletion. The solid surface was a uniform printed matter.
  • the pressure transferability is excellent, and even at room temperature. It is flexible and does not damage the surface of the photoreceptor during pressure transfer.When it is used as an image portion of a flat plate printing plate, the image portion itself has appropriate elasticity. Will have. Also, if direct printing is performed, It absorbs irregularities due to the transition of the paper, which is a printed body, so it can be printed at a constant printing pressure to obtain a very smooth printed matter, and the adhesiveness of the resin particles to the flat plate printing plate substrate is improved. Since it is good, there are advantages such as obtaining sufficient press life.
  • the present invention provides a method of adding a resin solution using a solvent having solubility to a resin into an electrically insulating liquid, cooling the resin solution, and precipitating the resin particles.
  • a charge control agent By using a type 1 carbon black, the particle size of the precipitated resin particles is in submicron units and the particle size distribution is controlled by the granulation control function. An extremely narrow one can be obtained, and a ball milling operation is not required, and a wet toner can be easily manufactured.
  • the obtained wet toner shows that the poly (carboxylic acid ester) has not only a granulation adjusting function but also an electric insulating liquid due to its affinity with resin particles. It also has the function of dispersing the resin particles stably, so that the dispersed state of the resin particles in the wet toner is kept stable, and a wet toner without deterioration can be obtained.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Liquid Developers In Electrophotography (AREA)

Abstract

Procédé pour produire facilement un toner humide, sans qu'il soit nécessaire d'effectuer un broyage à billes ou autre opération analogue, consistant en une étape de granulation au cours de laquelle un acide carboxylique oléfinique fondu ou une résine d'ester fondue est versé dans un hydrocarbure aliphatique liquide puis refroidi afin que les particules de résine se déposent en présence d'un polymère trimère à décamère d'un ester d'acide carboxylique hydroxy en mettant en ÷uvre un agent de contrôle de charge renfermant de la lécithine ou un sel de dialkyle-sulfosuccinate avec un métal de transition étant le cobalt, le manganèse, le zirconium, l'yttrium ou le nickel. L'oligomère de l'ester d'acide carboxylique hydroxy n'a pas seulement pour fonction de réguler la granulation mais aussi d'assurer une dispersion stable des particules de résine dans un liquide isolant électrique en vertu de son affinité pour les particules, de sorte que ces particules de résine se trouvent dispersées de manière stable et durable dans le toner, donnant ainsi un toner humide qui ne s'altère pas et qui permet de réaliser des images en couleur stables.
PCT/JP1993/000344 1992-03-26 1993-03-24 Toner humide et production de ce toner WO1993019400A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE4391162T DE4391162T1 (de) 1992-03-26 1993-03-24 Flüssiger Toner und seine Herstellung

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP4068073A JPH05273792A (ja) 1992-03-26 1992-03-26 湿式トナー及びその製造方法
JP4/68073 1992-03-26
JP09776792A JP3229646B2 (ja) 1992-04-17 1992-04-17 湿式トナー及びその製造方法
JP4/97767 1992-04-17
JP09934192A JP3229647B2 (ja) 1992-04-20 1992-04-20 湿式トナー及びその製造方法
JP4/99341 1992-04-20
JP4/134673 1992-05-27
JP4134673A JPH05323680A (ja) 1992-05-27 1992-05-27 湿式トナー及びその製造方法
JP4/138664 1992-05-29
JP4138664A JPH05333606A (ja) 1992-05-29 1992-05-29 湿式トナーの製造方法
JP4/178519 1992-07-06
JP4178519A JPH0619220A (ja) 1992-07-06 1992-07-06 湿式トナー及びその製造方法

Publications (1)

Publication Number Publication Date
WO1993019400A1 true WO1993019400A1 (fr) 1993-09-30

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DE (1) DE4391162T1 (fr)
WO (1) WO1993019400A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0754978A1 (fr) * 1995-07-14 1997-01-22 Mitsubishi Chemical Corporation Toner pour le développement d'images électrostatiques
US7300971B2 (en) 2002-06-14 2007-11-27 Canon Kabushiki Kaisha Particle composition, recording method, and recording apparatus using the particle composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6298363A (ja) * 1985-10-25 1987-05-07 Ricoh Co Ltd 静電写真用液体現像剤の製造方法
JPS63243966A (ja) * 1987-03-18 1988-10-11 イー・アイ・デユポン・ド・ネモアース・アンド・コンパニー ヒドロキシカルボン酸を含むネガ型液体静電現像液

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6298363A (ja) * 1985-10-25 1987-05-07 Ricoh Co Ltd 静電写真用液体現像剤の製造方法
JPS63243966A (ja) * 1987-03-18 1988-10-11 イー・アイ・デユポン・ド・ネモアース・アンド・コンパニー ヒドロキシカルボン酸を含むネガ型液体静電現像液

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0754978A1 (fr) * 1995-07-14 1997-01-22 Mitsubishi Chemical Corporation Toner pour le développement d'images électrostatiques
US5851718A (en) * 1995-07-14 1998-12-22 Mitsubishi Chemical Corporation Toner for electrostatic image development by heat
US7300971B2 (en) 2002-06-14 2007-11-27 Canon Kabushiki Kaisha Particle composition, recording method, and recording apparatus using the particle composition

Also Published As

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