WO1993019400A1

WO1993019400A1 - Wet toner and production thereof

Info

Publication number: WO1993019400A1
Application number: PCT/JP1993/000344
Authority: WO
Inventors: Yoichi Higuchi; Takashi Miyama; Satoru Kuramochi; Fumiyasu Takekawa
Original assignee: Dai Nippon Printing Co., Ltd.
Priority date: 1992-03-26
Filing date: 1993-03-24
Publication date: 1993-09-30
Also published as: DE4391162T1

Abstract

A process for producing a wet toner readily without the necessity for ball milling or the like, comprising the granulating step wherein a molten olefinic carboxylic acid or ester resin is put into a liquid aliphatic hydrocarbon and cooled to deposit the resin particles in the presence of a tri- to decamer of a hydroxy carboxylic acid ester by using a charge control agent comprising lecithin or a salt of a dialkyl sulfosuccinate with a transition metal selected from among cobalt, manganese, zirconium, yttrium and nickel. The oligomer of a hydroxy carboxylic acid ester has not only the function of controlling the granulation but also that of dispersing stably the resin particles in an electrical insulating liquid in virtue of the affinity for the particles, and hence the resin particles can be stably dispersed in the toner for long, thus giving a wet toner which does not deteriorate and can form stable colored images.

Description

TECHNICAL FIELD 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. In addition, 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. In this method, 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.

Conventionally, 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.

In addition, a charge control agent is added to charge the toner particles. However, 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.

Further, 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. In 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

Further, 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. 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. In the presence of 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. Further, in 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.

In addition, 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. After mixing, 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. In the manufacturing process, a hydroxycarboxylic ester of 3- to 10-mer containing a hydroxycarboxylic ester as a monomer, and a liquid fat. This is a method for producing a wet toner in which a negative charge regulator compatible with an aromatic hydrocarbon is present.

In addition, 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. In 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. In the presence of a 3- to 10-mer polycarboxylic acid carboxylate having a hydroxycarboxylic acid ester as a monomer, 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.

In addition, 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.

In addition, 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.

Further, 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.

Further, 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. In forming the toner particles, 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.

Particle size 10 to 100 nm as carbon black, specific surface area by BET method 30 to 260 m ² / 8Γ Γ DBP oil absorption 45 to 200 ml This is a wet toner using carbon black with physical properties of / 100 gr and a surface PH of 3.0 to 8.0.

In addition, the charge control agent is selected from cobalt, manganese, zirconia, ittrium, and nickel. It is a wet toner that is a transition metal salt.

In addition, 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. This is a method for producing a wet toner for depositing toner particles. BRIEF DESCRIPTION OF THE DRAWING Fig. 1 shows the marking using a wet toner with the addition of cyan pigment. 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. 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. and Mitsui DuPont Polychemical Co., Ltd. Flex series, for example 45 X, Y-W, 150, 210, 220, 250, 260, 310, 360, 41 0, 20, 450, 460, 550, 560, etc., Nippon Gosei Co., Ltd. Soaprene Series, such as BH, CH, CI, DH, etc. The Solex series, for example, RBH, RCH, RDH, etc., Dumilan series of Takeda Pharmaceutical Co., Ltd., for example, Dumilan D-219, D- 2 2 9, D—2 5 1 S, C 2 2 8 0, C 1 2 7 0, C 1 5 9 0, C 1 1 570, C 1

550 and the like. Also, Yukalon Eva manufactured by Mitsubishi Yuka Co., Ltd., Elpack manufactured by DuPont, etc. can be used.

In addition, N-Polymer manufactured by Nippon Petrochemical Co., Ltd., and Tonen Petrochemical Co., Ltd. Tonen CMP—HA Series, Mitsubishi Yuka Co., Ltd., MODIC, Sumitomo Seika Co., Ltd., Zyxen, Mitsui Toatsu Chemicals, Ltd. Chemistry

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.

In addition, 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. When using an ethylene-vinyl acetate copolymer resin, 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

If 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. In other words, if 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. . On the other hand, if 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. For example, Mitsui and Evaflex 45X (MI = 95, manufactured by Dupont Polychemical Co., Ltd., 46% by weight of a butyl acetate component). 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. 5, 6), 515 F (2.5, 6), 530 (75, 6), 537 (8.5, 6), 537 L (8.5, 6) ), 537S (8.5, 6), 525 (20, 7), 52F (2, 8), 540 (3, 10), 540F (3) , 10), 5 4 1 (9, 10) , 541 (9, 10), 625 (14, 15), 630 (1.5, 15), 630F (1.8, 15) , 682 (1550, 15), 627 (0.8, 20), 631 (1.5, 20), 633 (20, 20) ), 680 (1650, 20), 681 (350, 20), 635 (2.4, 25), 634 (4, 26) , 710 (18, 28), 720 (150, 28), 722 (400, 28), 725 (100, 28), 7 51 (6, 28), 750 (30, 32), 760 (70, 42), etc., and a Sumitomo Chemical Co., Ltd. DB—10 (70, 10), HA—20 (20, 70), the same HC—10 (150, 20), the same HE—10 (300, 20), the same KA—20 (3, 25), the same KA—31 (7 , 28), same KC 10 (150, 28), same KE— 1

0 (300, 28), MB-11 (60, 32), and RB11 (60, 41).

In addition, Nippon Gosei Kogyo Co., Ltd. Soaprene BH (150-200, 55), CH (50-100, 60), CI (50-100) 011 (40-50, 70), Dumiran D-219 (Takeda Pharmaceutical Co., Ltd.) (MI = 170> The same applies to Ml values below), D — 2 2 9 (7 2), D- 2 5 1 S (1 4), C 1 2 2 0 (9 3), C 1 2 2 0 (85), C 1 5 9 9 ( 1 0), same C 1 5 7 0 (2 0), same C 1

1550 (15), E-222 (65), G22-22A (75), G3632A (1), C579-1 (50). This series is obtained by partially saponifying vinyl acetate and further adding a partial modification such as introduction of a carboxy group. As a result of resin analysis using FT-IR, etc., the IR chart is used. carbonic - Le group stretching vibration range ^{1 7 0 0 cm- 1 ~ 1} 8 0 0 cm "1 and around the primary OH group stretching vibration range 3 2 0 0 cm ¹ near denaturation rate from a rate of about 3 0 to 40% belongs to.

Next, the solvent for the olefin resin will be described. 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. Such 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.

Next, the liquid aliphatic hydrocarbon will be described. 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.

Examples of the liquid aliphatic hydrocarbon include n-paraffinic hydrocarbon, isoparaffinic hydrocarbon, or a mixture thereof, and halogenated aliphatic hydrocarbon. Is mentioned. Particularly preferred are 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. 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. As a wet toner at the time of development, it is preferable to use it after diluting it with a liquid aliphatic hydrocarbon so that the solid content concentration becomes 0.5 to 2% by weight. Is obtained.

Further, 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. By using the liquid aliphatic hydrocarbon as the solvent, 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.

When mixing and dispersing an olefin resin in a liquid aliphatic hydrocarbon under a heating condition, 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. In the present invention, the expression “resin solution” also means a dispersion in which a resin is fluidized in a solvent.

In addition, as a method of performing dispersion treatment by grinding using a grinding medium, 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.

In the process of grinding resin in liquid aliphatic hydrocarbons, it is possible to use pole mills, atomizers, fits mills, fez mills, vic trim mills, Fine Victor, No., Leveler, Fine Parrizer, Device Integral, Micron No. Mills, on-mills, high-speed dispersers, homogenizers and the like are used. In addition, such crushers as feed hoppers, feeders, crushed product collectors, classifiers, tanks, transport systems, etc. A grinding system is configured. In addition, by using a mechanical stirrer and a mixer together, a ribbon blender, a Nauta mixer (reactor), and a turbulizer are used. However, it is also possible to achieve dispersion achievement in a short time. Generally required for grinding Mechanical external forces are dispersed using compressive, shear, impact, and frictional forces, and are more efficiently dispersed by acting in combination. And classification is performed.

As 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.

Next, a known organic or inorganic colorant can be used as a colorant that can be used as required in the present invention.

Examples of the black colorant include inorganic carbon black, triiron tetroxide, and organic cyan black.

Examples of the yellow colorant include inorganic yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, and orange. As an 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 (Pigment Yellow 3), Hansa Yellow RN (Pig nent Yellow 65), Nonza Briliant Yellow 5GX (Pigment Yellow 7 4) , Non The Brilliant Yellow 10 GX (Pigaent Yellow 98), No. 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). Further, as the penzimidazolone monoazo pigments, 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). Further, as the isodolin non-pigmented pigments, there may be mentioned Irgazine Yellow 3 RLTN (Pigment Yellow 110), Irgazine Yellow 2 RLT, and Gazin Yellow 2 GLT (Ρ igient Yellow 109), Fast Gensono. One yellow GR 0 H (Pigment Yellow 13 7), fast geneno. (1) Yellow GR 0 (Pigment Yellow 110) and 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).

In addition, examples of the magenta-based coloring agent 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. , 'Mounted Red F5R (Pigent Red 48), Resource Red (Pignent Red49), Persian Orange (Pigment Orange 17), Cryorange (Pignent Orange 18), Heliorange TD (Pignent Orange 19), Pigment Scarlet (PigBent Red 60: 1), Brilliant scarlet G (Pigment 64: 1), Helio RMT (Pigient Red 51), Bold 10B (Pigment Red 63), Heli Opoldo BL (Pigient Red 54); and insoluble azo systems (monoazo, disazo systems, and condensed azo systems) include parared (Pignent Red 54). 1), Rakelet 4 R (Pigment Re d 3), Permanent Orange (Pignent Orange 5), No. 1 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. Orange 3 8), Non- * Palm Red HF 4 B (Pigment Red 18 7), Novaberm Orange H L.HL-1 70 (Pigment Orange 3 6) , PV Carmine HF 4 C (Pig Ment Red 18 5), Hosta Balm Brown HFR (Pigment B rown 25), No, * Lucane Orange (Pigment Orange 16), pyrazolone orange (Pigment Orange 13) and pyrazolone red (Pigment Red 38). Further, chromophore as a condensed azo pigment is exemplified. Tar Orange 4 R (Pigment Orange 3 1), Chromo Scan mosquito one les Tsu preparative R (Pignent R ed 1 6 6), click B motor full data Lumpur les star de BR (Pigment Red 1 4 4) is that mentioned o

In addition, as 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 Perignon 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). .

Examples of 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

3) and indultone blue (PB-60P, PB-22, PB-21, PB-6

4), and basic dye lake pigments such as methylbiolettoline << molybdenic acid lake (PV-3). In addition, colorants called so-called processed pigments, which coat a resin on the surface of the colorant, can also be used.o

Considering the storage stability as a wet toner, or the transparency and color mixing of an image when a color image is formed using the obtained wet toner, among the above colorants, Carbon black for black system, mixture of benzene yellow and Hansa yellow for yellow system, priori for magenta system It is preferable to use Phthalocyanin Blue for non-Carmin 6B and Cyan.

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. In order to reproduce the continuous gradation of toner, it is necessary that 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. In order to obtain an optical reflection density of 0.7 or more for each color, 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.

In particular, 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 It is preferable to use a carbon black having a surface physical property of 200 ml Z 1.008T and a surface PH of 3.0 to 8.0.

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. Alternatively, 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. In order to reproduce a continuous tone equivalent to that described above, it is necessary that the optical reflection density after transfer to the transfer target is 0.7 or more, and preferably 1.0 or more. In order to make the optical reflection density 0.7 or more, it becomes 10 to 150% by weight on the same weight basis as above. Outside of the above range, after development, the optical reflection density of the formed image is reduced and background contamination is likely to occur. Next, 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

Formula H O-X-C O O H

Wherein 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. Preferred as such hydroxycarboxylic acid derivatives are, for example, 12-hydroxymethyl stearate methyl ester, 12-hydroxy Hydroxy carboxylic acid esters such as hydroxy styrene ester, 1

2 — 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. In the present invention, 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.

In the wet toner of the present invention, metal dialkyl sulfosuccinate, manganese naphthenate, calcium naphthenate, and naphthenate are used as charge control agents. Zirconium, sodium naphthenate, iron naphthenate, lead naphthenate, nickel naphthenate, chromium naphthenate, naphthenate Zinc zincate, magnesium naphthenate, manganese octylate, calcium octylate, dimethyl octylate, occ Iron titanate, lead octoate, octyl octoate, chromium octoate, zinc octoate, magnesium octoate, dodecyl Acid manganese, calcium dodecylate, zirconium dodecylate, iron dodecylate, lead dodecylate, cobalt dodecylate, dodecylate De Metallic tests such as nickel silicate, chromium dodecylate, zinc dodecylate, magnesium dodecylate, dodecyl Benzensulfonate calcium, dodecylbenzene sodium sulfonate, dodecylbenzene sodium sulfonate Alkenylbenzenesulfonate, such as calcium, phospholipids, such as sehalin, and organic amines, such as n-decylamine, are preferably added. You. In particular, use 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. For example, 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. However, according to the production method of the present invention, 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.

In addition, 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. In this case, 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.

In particular, the metal dialkyl sulfo succinate is a metal dialkyl sulfo succinate having an alkyl group of 5 to 17 carbon atoms. From the scandium at atomic number 21 to the zinc at 30 in the table, from the 39th trimester to the cadmium at 48 in the table, 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. Also, 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.

In addition, 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. Resin, synthetic rubber, polyalkylene oxide, polyvinyl acetate (including petital), and vinyl acetate resin.

In addition, many anionic, cation, amphoteric, or nonionic surfactants can be added to the wet toner obtained in the present invention as a dispersant. An aliphatic acid salt used as a charge adjusting agent, a synthetic resin used as the fixing agent, and the like can be used as a dispersant. The method for producing a wet toner of the present invention also has a special feature in the granulation step. That is, 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

De la Lee Ai scan for the cooling rate, quenched with liquid nitrogen and the like was charged natural cooling or during cooling with liquid aliphatic hydrocarbons, 5:. 1 5 is cooled to ^e C resin particles From the colorant-dispersed resin solution. When the colorant-dispersed resin solution is introduced into the liquid aliphatic hydrocarbon, 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.

In this granulation process, 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 μm, 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.

Next, when the liquid aliphatic hydrocarbon is not used as a solvent after the resin particles are precipitated, it is desirable to replace the solvent with the liquid aliphatic hydrocarbon. As the method, 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. Okisid, Polivi -Polyvinyl acetate, such as ruptilaral, and butyl acetate resin can be added.

Further, many 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

When 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. This is considered to be due to the presence of the carbonyl group in the galboxyl group or the ester group contained in the resin particles in the toner, thereby improving the adhesiveness to paper, plastic, metal, and the like. It is considered that the appropriate flexibility provided by the resin particles absorbs the impact during printing.

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.

Hereinafter, examples of the present invention will be described. In the examples, a method for preparing a dialkyl sulfosuccinate used as a charge control agent is as follows. It is right.

(1) Preparation of cobalt dialkyl sulfosuccinate

Mix 25 parts by weight of sodium alkyl sodium sulfo succinate (Aerosol 0T, manufactured by Wako Pure Chemical Industries, Ltd.) with 100 parts by weight of tetrahydrofuran. , 5 0 ^{after e} C-heating and stirring to dissolve, the dissolved nitrate cobalt 1 3 parts by weight in a mixed solvent consisting of Te preparative La inhibit mud off run-3 0 parts by weight METHANOL 5 parts The solution was added, and the mixture was heated and stirred at 50 for 30 minutes to precipitate a white salt. 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.

(2) Preparation of dialkyl sulfosuccinate citrate

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.

(3) Preparation of nickel-sulfo-nickel succinate

In the above method of preparing dialkyl sulfosuccinate cobalt, nickel nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) was used instead of cobalt nitrate. Was used for the reaction to obtain nickel dialkylsulfosuccinate in a yield of 82%. Partially deposited green The crystals were removed by filtration under heating. 25 against Vaisoper G (exxon). The solubility in C is 0.1 lg / ml solvent ο

Example 1

200 m 1 Partially modified polyethylene-vinyl acetate copolymer (Takeda Pharmaceutical Co., Ltd., Dumilan 2)

2.70, degree of saponification 70%) 2.58Γν Diisooctylsulfosuccinate Concentrate 260 mg and tetrahydrofuran 50 ml are mixed. The mixture was heated and stirred at 50 ° C for 1 hour to dissolve the resin, thereby preparing a resin solution.

In another container, Monastral blue FBR (metal phthalocyanine pigment, manufactured by ICI) 2.58: as a colorant, dispersant (solsperse 17,000, manufactured by ICI) 40 mg 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. Ter (manufactured by Ito Oil Co., Ltd., trimer, acid: 40.8 to 42.8, chelation value: 16.9 to 19.7, weight average molecular weight: 1200, hue ( Gardner-Herge 1) 6-7, light gray-brown wax) 20 mg and 60-80 using an ultrasonic homogenizer. The resulting mixture was mixed and dispersed with C to prepare a coloring agent-dispersed resin solution.

A colorant-dispersed resin solution this, 5 § cooled to ^e C b Sopa G (Manufactured by Exxon Co., Ltd.) The resin particles were put into 15 m 1 and mixed for 1 hour using an ultrasonic homogenizer to precipitate 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.

Next, after separating the resin particles using a centrifuge (Model 90-4, manufactured by Sakuma Seisakusho Co., Ltd.), the resin particles are washed with Vispar G (manufactured by Exxon), and further separated. It was dispersed in Isobar G (manufactured by Xeon).

The resin particles after the solvent substitution, this filtrate and the particle size analyzed similarly, resin particles, 0. 4 2~ 0. 9 6 m particle size range, the average particle diameter D _5. Had a sharp, single-peak distribution spectrum of 0.60 μm.

In addition, infrared absorption spectrum measurement was carried out to confirm that the polyester particles adhered to the resin particles. Quantification of 0H group stretching vibration region of 380 to 3200 cm- ¹ and 176 to 177 of the carboxylic group in carboxylate ester 0 cm one ¹ of the check the options by the peak position change.

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).

In order to evaluate the electrophoretic properties of the toner, a microammeter (manufactured by Advantech Co., Ltd.) and HIGH V0LTAG ESOURCE MEASURE UNIT C KEITHLEY (237) were used. Fill the wet toner between metal electrode plates with electrode spacing lcm and electrode area 2.5 cm x 3 cm, apply a voltage of 100 V between rain electrodes, initial current value and current value after 60 seconds Along with the measurement, the quantity of electricity (Q Zm, unit fi / g ¹⁾ per toner weight attached to the electrode was measured. The difference between the initial current value and the current value after 60 seconds was measured. The larger the QZm value and the higher the QZm value, the better the electrophoretic properties of the toner.

In addition, regarding printability, visual evaluation was performed on the image quality, whether or not there was any roughness, the flow of images, whether or not there was blur, and the degree of fog.

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.

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.

Example 3

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.

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.

Example 4

200 ml Partially modified styrene-vinyl acetate copolymer in round-bottomed flask (Takeda Pharmaceutical Co., Ltd., Dumilane 270, 2.5 g, cobalt (2,6 mg) of diisooctyl sulfoconoate, and 50 ml of tetrahydrofuran (50 ml) are mixed. Heat and stir at 0 ~ 80 ° C for 1 hour to dissolve the resin To prepare a resin solution.

On the other hand, in a separate container, Monastral blue RFN (metal phthalocyanine pigment, manufactured by ICI) as a colorant 2.5 gr and poly 12-hydroxystearic acid Ultrasonic homogenizer (US-300T, manufactured by Nippon Seiki Seisaku-sho, Ltd.) containing 90 mg of methyl ester (trimer) in 50% of tetrahydrofuran. Was used for dispersion to prepare a pigment dispersion.

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.

When 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.

Next, using a centrifuge (Model 90-4, manufactured by Sakuma Seisakusho Co., Ltd.), the resin particles are separated, and the resin particles are washed using a Biospar G (manufactured by Xeon). After that, the resultant was further dispersed in Isoper G (manufactured by Exon).

This and have One resin particles after the solvent substitution, similarly this filtrate and the particle size analysis, resin particles 0. 42~:. L 2 m of particle size range, the average particle diameter of 0 _5. 0.8 m, sharp, single peak distribution spectrum Had a toll.

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 5

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.

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 6

Instead of the resin of Example 4, an ethylene monoacetate copolymer (Mitsui DuPont Polychemical Co., Ltd., Enoflex 250, a cellulose acetate component of 28 % By weight, MI = 150) and using magnesium naphthenate instead of disooctyl sulphonic succinic acid. A wet toner was produced in the same manner as in Example 4.

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.

The evaluation as a wet toner was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 7

Instead of the resin of Example 4, an ethylene-vinyl acetate copolymer (Mitsui • DuPont Polychemical Co., Ltd.), Evaflex 450, a vinyl acetate component containing 19% by weight, A wet toner was prepared in the same manner as in Example 6, except that MI = 150) was used.

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.

Comparative Example 1

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.

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. In addition, 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.

Comparative Example 2

Instead of poly (12-hydroxystearate) methyl ester (trimer) in Example 4, poly (12-hydroxystearin) was used. Acid methyl ester (manufactured by Ito Oil Co., Ltd., 10-mer or more, weight average molecular weight 420, molecular weight distribution width (= number average molecular weight Z weight average molecular weight) 1.63, hue (gar donor) A wet toner was prepared in the same manner as in Example 4 except that 5-6, a light gray-brown solid) was used.

For 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., And the current value is 115 nA, and 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.

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. In the table, ◎ means excellent, 〇 means good, △ means slightly bad, and X means bad. OD value Current value Q / m Image quality Flow Fog

1) 2) Example 1 L1 or more 1050-480 128 ◎ ◎ 〇 Example 2 Nono 1661-715 201 ◎ ◎ 〇 Example 3 "1294-637 71 o

o ◎ ◎

1

650-8O0 106 ◎ o 〇 Example 5 Nono 222-50 105 〇〇〇 Example 6 Zono 220-134 420 〇〇例 Example 7 Nono 70.2 〇 o Δ Comparative Example 1 0. Below 51.4 XXX Comparative Example 2 0.5 or less 140-115 30 XXX

^{1} The} initial current value (left) and the current value after 60 seconds are indicated by n A,

2) Unit is zC / s

Example 8

20 O ml EVA (Ethylene monoacetate vinyl copolymer, Mitsui DuPont Polychemical Co., Ltd.), Evaflex 2 50, 28% by weight of acetate acetate component, MI = 150) 2.5 g, tetraethyl 2-ethylsulfonoconoate, * lute 2556 mg, and eye 100 g of Soper G (manufactured by Exon) was mixed, and the mixture was heated and stirred at 150'C for 1 hour in an oil bath.

On the other hand, in a separate container, as 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. Next, a mixture of this was allowed to stand at room temperature, after which the temperature was lowered to about 7 0 ^e C, then poured into a 5 'C § Lee Seo bar G 1 0 0 double 1, ultrasonic Ho mode Jinai Heather ( Dispersion and mixing were performed using a US-300T manufactured by Nippon Seiki Seisakusho to obtain a wet toner.

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 μm.

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.

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.

In addition, 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.

Furthermore, regarding printability, the image quality (whether there is The squid, flow (whether or not blurred), and the degree of fogging were visually evaluated.

Table 2 shows the results of each evaluation. In the evaluation items in the table, 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. In the flow, 〇 indicates that there is no “bleeding”, X indicates that there is “bleeding”, and ◎ indicates that it is particularly excellent. In "Fogging", O indicates no fogging and X indicates that there is fogging.

Example 9

Instead of 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 ッ) was used in the same manner.

When the particle size of the resin particles was analyzed in the same manner as in Example 8, the distribution of a single single peak having a particle size width of 0.17 to 5.27 m and an average particle size of 1.12 was obtained. Had the spectrum. The developing characteristics are positively chargeable, and the electrostatic latent image of the negatively chargeable pattern can be developed.

Further, 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 10

Poly 12-Hydroxy Stearate in Example 8 Instead of the ester (trimer), 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.

When the particle size analysis of the resin particles was performed in the same manner as in Example 8, the distribution of a single peak in a sharp shape having a particle size width of 0.17 to 6.53 m and an average particle size of 1.25 was obtained. Had a spectrum. The developing characteristic is positively chargeable, and enables the electrostatic latent image of the negatively chargeable pattern to be developed.

Example 1 1

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.

Example 1 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. In addition, 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.

Example 13 In place of the resin of Example 8, EVA (ethylene butyl acetate copolymer, Mitsui Dupont Chemical Co., Ltd.), Evaflex 460, and a vinyl acetate component were used. 19% by weight, MI = 2.5) 2. Ogr and EVA 1 — WAX (Ethylene vinyl acetate copolymer, containing wax components, BASF, 10 weight percent vinyl acetate component) %) A wet toner was prepared in the same manner except that 0.5 g was mixed and used.

When the particle size of the resin particles was analyzed in the same manner as in Example 8, it was found that 0.35 to L: a particle size width of 0.6 m and an average particle size of 0. Had a vector. The development characteristics were negative charging.

Example 14

Instead of the resin of Example 8, EVA (ethylene monoacetate vinyl copolymer, Mitsui Dupont Chemical Co., Ltd.), Eva Frettus 410, acetic acid A wet toner was prepared in the same manner except that the bull component was 19% by weight and MI = 400).

When 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.

In addition, 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 15 EVA (Ethylene monoacetate vinyl copolymer, Mitsui Dupont Chemical Co., Ltd.), Enoflex 410, acetic acid in place of the resin of Example 8 The same procedure was carried out except that the bul component was 19% by weight, MI-400), and the resin solution adjusting step and the mixed liquid dispersing step before the cooling step were performed under heating conditions of 7 O'C. Thus, a wet toner was prepared.

When 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.

Example 16

EVA (X-ethylene monoacetate copolymer), Mitsui-Dupont Chemical Co., Ltd., Evaflex 220, acetic acid in place of the resin of Example 8. Except that the resin component used was 28% by weight and MI = 150), and the mixed solution dispersion step before the resin solution preparation step and the cooling step was performed under a heating condition of 70'C. Prepared a wet toner in the same manner.

When the particle size of the resin particles was analyzed in the same manner as in Example 8, it was found that the resin particles had a particle size range of 0.12 to 15 It had a single distribution peak. The development characteristics were positive charging.

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

In place of the resin of Example 8, EVA (ethylene monoacetate copolymer, Sumitomo Chemical Co., Ltd., Smit DB-10, 10% by weight of vinyl acetate component, Ml = 7 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.

When the particle size analysis of the resin particles was performed in the same manner as in Example 8, 0.1

It had a sharp, single peak distribution spectrum with a particle size width of 2-1.3 m and an average particle size of 0. The development characteristics were positive charging.

Further, evaluation as a wet toner was performed in the same manner as in Example 8, and the results are also shown in Table 2.

Example 18

EVA (Ethylene Monoacetate Copolymer, Sumitomo Chemical Co., Ltd., Smitate MB—11, 32% by weight of vinyl acetate component, MI = 6) in place of the resin of Example 8. 0) was used, and 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.

When the particle size analysis of the resin particles was performed in the same manner as in Example 8, 0.2

It had a sharp, single peak distribution spectrum with a particle size range of 3-2 1. and an average particle size of 1.58 m. The development characteristics were positive charging.

Further, 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 19

200 m 1 Partially modified styrene-butyl acetate copolymer in round-bottomed flask (Takeda Pharmaceutical Co., Ltd., Dumilan 22)

70, 70% saponification, 28% by weight butyl acetate, MI = 85) 2.5 g, cobalt diisooctyl sulfoconoate 2.56 mg Was mixed with 50 ml of tetrahydrofuran, and heated and stirred at 60-80 ° C for 1 hour to dissolve the resin.

On the other hand, in a separate container, Monastral blue FBR (metal phthalocyanine pigment manufactured by ICI) is used as a colorant. 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.

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.

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 μm 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).

When 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.

In addition, the infrared absorption spectrum measurement of the adhesion of the polyhydroxycarboxylic acid ester to the resin particles showed that the 0H group of ^{380 to 320} cm ^_1 was Quantification of stretching vibration region and force 176

It could be confirmed by the change in the peak position of O cm- ¹ .

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.

Example 20

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.

Figure 1 shows.

Example 2 1 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.

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.

/ o

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.

Example 22

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.

Example 23

200 ml EVA (Ethylene monoacetate copolymer, Sumitomo Chemical Co., Ltd., Smitate DB—10, 10% by weight of vinyl acetate component) %, MI = 70) 2.5 g, diisooctyl sulfo succinate corn 25 56 m8Γ, 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.

On the other hand, in 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.

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.

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.

Next, the resin particles were separated using a centrifugal separator (Model 90-4, manufactured by Sakuma Seisakusho Co., Ltd.), and the resin particles were washed with Visoper G (manufactured by Exxon). It was dispersed in Isoper G (exxon).

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.

After cooling the above pigment-dispersed resin solution to about 6 O'C while leaving it at room temperature, put it in Isopar G (manufactured by Exon) as described above, and disperse and mix the resin particles. Similar results were obtained when the precipitate was deposited.

Example 2 4

Instead of the cyan pigment of Example 8, magenta pigment brilliant, carmine 68 #? 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.

When 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 μm 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.

Further, 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. When the particle size analysis of the resin particles was performed in the same manner as in Example 8, 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 2 5

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.

When the particle size analysis of the resin particles was performed in the same manner as in Example 8, the distribution of a single peak in a shape with a particle size width of 0.34 to 21 # m and an average particle size of 4.30 m was obtained. It had a spectrum.

Example 26

In place of the tetra-2-sulfo succinate of Example 8, * lute 2 56 m 8 Γ, 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.

Example 2 7

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.

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.

Comparative Example 3

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).

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.

Comparative Example 4

Instead of the resin in Example 8, ethylene-butyl acetate Except for using a copolymer (Ultracene 725, manufactured by Tosoh Corporation, degree of saponification: 0%, butyl acetate component: 28% by weight, MI = 100000) A wet toner was produced in the same manner as in Example 1.

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.

Further, 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.

Comparative Example 5

In place of the methyl 12-hydroxystearate (trimer) in Example 8, 12-hydroxystearic acid (manufactured by Kanto Chemical Co., Ltd.) A wet toner was prepared in the same manner except that) was used. The development characteristics were positively chargeable.

When the particle size analysis of the resin particles was performed in the same manner as in Example 8, the particle size range was 0.17 to 60 m, and the average particle size was 7.53 zm. Value 23 8 η A, current value after 13 seconds is 60 nsec, electrophoretic force is small, and solid image formed after corona charging on electrostatic recording paper is sharp and clean Nabeta The image was not obtained, and there was a problem that the flow on the electrode plate and the fixation were poor.

In addition, the evaluation as a wet toner was performed as in Example 8, and the results are shown in Table 3.

Comparative Example 6

Poly 1 in Example 1 12—Hydroxystearate In place of methyl stearate (trimer), poly 1 2—Hydroxy Methyl stearate ester (manufactured by Ito Oil Co., Ltd., 10-mer or more, weight average molecular weight 420, molecular weight distribution width (= number average molecular weight / weight average molecular weight) 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.

When the particle size analysis of the resin particles was performed in the same manner as in Example 8, 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 η 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.

The evaluation as a wet toner was performed in the same manner as in Example 8, and the results are also shown in Table 3.

Comparative Example 7

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. Was prepared. When 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.

Further, evaluation as a wet toner was performed in the same manner as in Example 8, and the results are also shown in Table 3.

Comparative Example 8

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

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. When 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 η Α, 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. In addition, evaluation as a wet toner was performed in the same manner as in Example 8, and the results are shown in Table 3.

Comparative Example 10

Instead of poly (12-hydroxymethyl stearate) (trimer) in Example 19, methyl (poly) 12-hydroxystearate was used. Estel (manufactured by Ito Oil Co., Ltd., 10-mer or more, weight average molecular weight 420, molecular weight distribution width (= number average molecular weight Z weight average molecular weight) 1.63, hue (gardner, to Wet toner was prepared in the same manner, except that lige 1), 5-6, and a light gray-brown solid) were used.

When the particle size analysis of the resin particles was performed in the same manner as in Example 8, the particle size range was 0.36 to 60 ^ m, and the average particle size was 15.9 m. Current value 1 17 nA, current value 86 nA after 60 seconds, electrophoretic force is small, and solid images formed after corona charging on electrostatic recording paper are very bulky Thus, a clean solid image could not be obtained, and the flow on the electrode plate and the fixing were poor.

In addition, the evaluation as a wet toner was performed in the same manner as in Example 8, and the results are also shown in Table 3.

Comparative Example 1 1

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.

When 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 η 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.

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 1 2

A wet toner was prepared in the same manner as in Example 19 except that the negative charge regulator was omitted. In addition, 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

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.

Comparative Example 1 4

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.

The evaluation as a wet toner was performed in the same manner as in Example 8, and the results are similarly shown in Table 3.

Table 2

¹ 'mm. (The separation value between male and 60 fine is n A c 2 ^> Unit is / iCZsr

3 ^> πι ² / νsec Table 3

B A job value (left side) and 60 job positions are n A, 2 ^{) The} unit is 〃 CZg

m ² ZV * sec Example 2 8

20 O ml EVA (Ethylene monoacetate vinyl copolymer, Mitsui Dupont Chemical Co., Ltd.), Evaflex 25 in a round bottom flask 0, 28% by weight of vinyl acetate component, MI = 150) 2.5 gr, lecithin (trade name: Lecitine Fro, Soy Beans, manufactured by Junsei Chemical Co., Ltd.) 500 m8: , And Isobar G (manufactured by Exon) (100 ml) were mixed, and the mixture was heated and stirred in an oil bath at 120 · <1 hour.

On the other hand, in a separate container, Monastral blue FBR (metal phthalocyanine pigment, manufactured by ICI) as a cyan pigment 2.58Γ 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. Next, 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.

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. After forming various electrostatic patterns up to the above, development printing was performed by a roller developing machine using the wet toner prepared above. The developing machine speed was 2.6 m / min and 10.0 mZ min. Evaluation of the image deletion was performed by visually observing the image obtained by development.

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. Fill the wet toner between the electrodes of Shinyo made of Japan, apply a voltage of 100 V between both electrodes, measure the initial current value, and measure the current value after 60 seconds. 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 2 9

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 Ϊ was used in the same manner.

When the particle size of the resin particles was analyzed in the same manner as in Example 27, the distribution of a single sharp beak having a particle size width of 0.35 to 2.42 m and an average particle size of 0.94 m was obtained. Had a vector.

In addition, evaluation as a wet toner was performed in the same manner as in Example 28, and the results are shown in Table 4 in the same manner.

Example 30

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.

When the particle size of the resin particles was analyzed in the same manner as in Example 28, a particle size width of 0.1 to 2.60 m and an average particle size of 1.01 It had a distribution spectrum.

The evaluation as a wet toner was performed in the same manner as in Example 28, and the results are similarly shown in Table 4.

Example 3 1

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) 2.5 sr, lecithin (trade name: Lecitine Froa Soy Beans, manufactured by Junsei Chemical Co., Ltd.) 350 mg ", 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.

On the other hand, Monastral blue FBR (metal phthalocyanine pigment, manufactured by ICI) as a colorant in a separate container 2.58: Chil ester (manufactured by Ito Oil Co., Ltd., trimer, acid value 40.8-42.8, chelation value 196.9-199.7, weight average molecular weight 1 200, Hue (Gardner Helige) 6-7, Light-grey-brown wax) 90 mg: 50 mL of tetrahydrofuran and an ultrasonic homogenizer Dispersion was carried out for 10 minutes using a Jinizer (US-300T, manufactured by Nippon Seiki Seisakusho Co., Ltd.) to prepare a pigment dispersion.

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) Pour into 300 ml and disperse for 2 minutes with an ultrasonic homogenizer.

Further, 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.

In addition, it was confirmed by infrared absorption spectrum measurement that the polycarboxylic acid ester was attached to the resin particles. Was. 3 8 0 0~ 3 2 0 0 c m- 1 1 7 6 shed-mosquito Ruponiru group that put the quantitative and mosquito Rubo Nsan'e scan ether of OH groups stretching vibration region

It was confirmed by the peak position change of 1770 cm- ¹ .

Example 3 2

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 μm and an average particle size of 0.39 ^ m. Had a sharp, single-beak distribution spectrum.

Example 3 3

A wet toner was prepared in the same manner as in Example 31 except that the amount of lecithin added in Example 31 was 1.58Γ, 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 3 4

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.

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 μm in particle size width and average particle size of 0.36. ^ m had a sharp, single-beak distribution spectrum.

Example 3 5

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 3 6

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 3 7

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. As a result, 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.

Comparative Example 15

The resin in Example 28 was changed to an ethylene vinyl acetate copolymer (EVA Flex 260, manufactured by Mitsui DuPont Polychemical Co., Ltd.). 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.

Comparative Example 16

The resin in Example 31 was replaced with an ethylene-butyl acetate copolymer (EVA Flex 260, manufactured by Mitsui Dupont Chemical Co., Ltd.). 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.

Comparative Example 1 8

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.

Comparative Example 1 9

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.

In Table 4, ◎ means excellent, O means good, Δ means somewhat bad, and X means bad.

Table 4 Initial current value Current value after 60 seconds Q / m Image flow (nA) (nA)

Example 28 1250 460 130 O Example 29 1345 10 162 〇 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 Δ Comparative example 17 4258 4129 Unmeasurable X Comparative example 18 3559 2425 1 1 〇 Comparative example 19 5642 51 15 Not measurable X Example 3 8

EVA (Ethylene monoacetate vinyl copolymer, Mitsui • DuPont Polike) was added to a stainless steel constant temperature circulating dispersion port (GETZMAN N) for 500 m1. 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.

Next, 2.5 g of Monastral blue FBR (a metal phthalocyanine pigment manufactured by ICI), which is a cyan pigment, was added to the dispersion, followed by addition of a poly 12-hydroxy stear. Methyl phosphate ester (manufactured by Ito Oil Co., Ltd., trimer, acid value 40.8 to 42.8, chelation value 196.9 to 197.7, Weight average molecular weight: 1200, Hue (Gas donor helage) 6-7, Light gray brown wax) 90m8: and Isobar G (manufactured by Xeon) 100 m1 was further added, and 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. ) manufactured by Sodafu Li beads, diameter 0. 2 mm - 0. 8 mm mixed product) using a 6 hours circulating the hot water ^{9 0 e C, 3 5 0} 0 revolutions, preparative Torque peripheral speed 2 Dispersion treatment using grinding media at 0 to 25 m / min It was.

After cooling the dispersion of this up to 6 0 ^e C under standing at room temperature, 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. ff O

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.

Evaluation of development characteristics and the like was performed in the same manner as in Example 8. Table 5 shows the obtained results. Further, mobility 2. 4 X 1 0 - met ¹ ⁰ cm ² / sec · V.

In addition, 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 the evaluation items in the table, ◎ in `` Image quality '' is excellent, 〇 indicates no roughness, X indicates crispness, O in `` Flow '' indicates no bleeding, X indicates bleeding Is shown.

Example 3 9

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. When 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 μm and a distribution vector with an average particle size of 0.89 ^ m. I was

The evaluation as a wet toner was performed in the same manner as in Example 38, and the results are shown in Table 5 in the same manner.

Example 40

In place of the 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.

When the particle size analysis of the resin particles was carried out in the same manner as in Example 38, a distribution spectrum having a particle size width of 0.17 to 2.6 ^ m and a uniform particle size of 0.94 zm was obtained. Was.

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 4 1

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.

When the particle size analysis of the resin particles was performed in the same manner as in Example 1, a distribution vector having a particle size range of 0.17 to 0.42> m and an average particle size of 0.24 m was obtained. Was. Further, evaluation as a wet toner was performed in the same manner as in Example 38, and the results are similarly shown in Table 5.

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 μm in average particle size. The development characteristics were negatively chargeable.

Example 42

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. A wet toner was prepared in the same manner as in Example 38 except that 2.5 g of 19% by weight, MI = 4 6 2 • 5) was used. The development characteristics were positively chargeable.

When the particle size of the resin particles was analyzed in the same manner as in Example 1, the particle size distribution was 0.48 to 2, and the average particle size was 1.37 m.

Further, 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 4 3

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 4 4

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.

Comparative Example 20

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.

When the particle size analysis of the resin particles was performed in the same manner as in Example 38, 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 η. 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.

Comparative Example 2 1 In place of the methyl ester of poly (hydroxystearate) (trimer) in Example 38, methyl ester of poly (hydroxyl) stearate was used. (Manufactured by Ito Oil Co., Ltd., 10-mer or more, weight-average molecular weight 4200, molecular weight distribution width (= number-average molecular weight Z-weight-average molecular weight) 1.63, hue (Gardner-Herige 1) 5 , A light gray-brown solid) was used in the same manner as in Example 38 to prepare a wet toner.

When the particle size analysis of the resin particles was performed in the same manner as in Example 38, 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 η 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.

O was o

Comparative Example 2 2

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.

The evaluation as a wet toner was performed in the same manner as in Example 38. Table 5 also shows the results.

Comparative Example 2 3

Example 3 In place of 25 g mΓ 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. The solubility of calcium sodium disooctylsulfonate (produced by Wako Pure Chemical Industries, Ltd.) in bisop G (produced by Xeon Corporation) at 25X; is 0.28. : Ml / solvent.

Comparative Example 2 4

A wet toner was prepared in the same manner as in Example 38, except that poly (12-hydroxymethyl stearate) (trimer) was not used.

When the particle size analysis of the resin particles was performed in the same manner as in Example 38, 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.

Comparative Example 2 5

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.

When the particle size analysis of the resin particles was performed in the same manner as in Example 38, it was found that the particle size width was 1.32 m, and the average particle size was 11. In the high-speed solid print image test described above, white spots were generated.

Comparative Example 2 6

A wet toner was produced in the same manner as in Example 38 except that the negative charge regulator was not used.

In addition, an evaluation as a wet toner was performed in the same manner as in Example 38, and the results are also shown in Table 5.

Table 5

^} Initial current value (left) and current value after 60 seconds (nA) Example 45

20 O ml EVA (Ethylene-vinyl acetate copolymer, EVA Flex manufactured by Mitsui Dupont Chemical Co., Ltd.) 0) 3 sr, tetrabutyl 2-ethylsulfosuccinate cobalt as a charge control agent 200 mgr, ISOBER G (manufactured by Exon) as a solvent 1 Then, the mixture was heated and stirred at 70 for 1 hour to dissolve the resin, thereby preparing a resin solution.

Meanwhile, in a separate container, mosquitoes over Bonn Bed rack pigment # 5 0 (Mitsubishi Kasei Co. particle size 2 8 ^ m, a specific surface area of ^{1 0 3 m 2 / sr,} DBP oil absorption amount 6 5 ml Z 100gr, surface pH 6.0) was treated with 2ST and poly 12-methylester methyl ester (manufactured by Izumi Oil Co., Ltd., 3 volume) Body, acid 偭 40.8-42.8, ketone value 196.9-19.7.7, weight average molecular weight 1200, hue (gas donor / helicide) 6 ~ 7 The light gray-brown wax) 95 m8Γ was mixed and dispersed in 60 ml of tetrahydrofuran using an ultrasonic homogenizer. 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.

After granulation, 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.

When the particle size of the resin particles was analyzed using a microtrack-ESRA type (manufactured by Nikkiso Co., Ltd.), 5. granularity width of 2 7 zm, average particle diameter D _5. However, it had a spectral distribution of a single peak with a sharpness of 1.12 m. Figure 4 shows the logarithm of the particle size on the horizontal axis and the histogram and cumulative particle size distribution of the frequency on the vertical axis.

In addition, 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 ηA, 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.

Example 4 6

200 ml EVA (Ethylene Monophosphate Copolymer, Evaflex manufactured by Mitsui DuPont Polychemicals, Inc.) in a round bottom flask 450 ) 3 gr, tetrabutyl 2-ethyl sulphoconodic acid cobalt 200 mg as a charge adjusting agent, Isopar G (manufactured by Xeon) as a solvent The mixture was mixed with 100 ml and heated and stirred at 70 ° C. for 1 hour to dissolve the resin, thereby preparing a resin solution.

On the other hand, in a separate container, 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). 40.8 to 42.8, saponification 偭 19.6.9 to: 19.7.7, weight-average molecular weight 1,200, hue (Gardner-Herige 1) 6 to 7, pale 95 m sr was mixed and dispersed in 60 ml of tetrahydrofuran using an ultrasonic homogenizer.

Next, resin particles were precipitated in the same manner as in Example 45. The particle size of the precipitated resin particles was analyzed. Child, Yes at 0.1 from 7 to 3.7 3 granularity width of m, the average particle diameter D ₅₀ of 1.3 4〃 m, a scan Bae click preparative Le distribution of a single peak in sheet catcher-loop Was. In Fig. 5, the horizontal axis represents the logarithm of the particle size in logarithm, and the vertical axis represents the histogram showing the frequency and the cumulative particle size distribution by a polygonal line.

The evaluation as a wet toner was performed in the same manner as in Example 1.

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. Has a charge value (QZm, unit ^ Cg) of 300, and has a large difference between the initial current value and the current value after 60 seconds and a large Q / m value, resulting in excellent toner electrophoresis. It is. 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.

Example 47

EVA (Ethylene monoacetate butyl copolymer, Evaflex 4500, manufactured by Mitsui DuPont Polychemicals, Inc.) in 200 ml round bottom flask 8Γ> Tetra 2-ethyl sulfoconoconic acid salt 200 mg as a charge control agent, AISONO as a solvent, 'I-G (EXON Was mixed and heated and stirred at 70 for 1 hour to dissolve the resin to prepare a resin solution.

In a separate container, add carbon black pigment 220 B (manufactured by Mitsubishi Chemical Co., Ltd., particle size: 18 nm, BET specific surface area: 210 m ² gr, DBP oil absorption) 45 ml Z 100 g, pH 3.0) and 2 g of poly 12-hydroxystearic acid methyl ester (manufactured by Ito Oil Co., Ltd.) , Trimer, acid value of 40.8 to 42.8, chemical value of 19.6. To 19.7.7, weight average molecular weight of 1200, Using an ultrasonic homogenizer, add 6 to 7 hues (Gardner Helige) and 95 mg of light gray-brown wax to 60 ml of tetrahydrofuran using an ultrasonic homogenizer. It was mixed and dispersed.

Next, resin particles were precipitated in the same manner as in Example 45. The precipitated resin particles, and rollers were granulometric, resin particles child 0.6 6: 1 at the granularity width of 4, the average particle diameter D ₅₀ of a single peak in sheet Sharp 4. 4 0 m The particle size distribution was slightly larger depending on the particle size distribution. In Fig. 6, the horizontal axis represents the logarithm of the particle size, and the vertical axis represents the histogram showing the frequency and the cumulative particle size distribution by a polygonal line.

Further, evaluation as a wet toner was performed in the same manner as in Example 45. 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.

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.

Example 4 8

Car Bonn Bed rack and to carbon emissions 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.

Further, 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 ηA after applying electricity for 60 seconds, and the weight of toner attached to the electrode. The charge value per unit time (QZm, unit ^ C / 8Γ) 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.

Further, with regard to printability, a good printed matter was obtained without image deletion or crushing, and the solid surface was uniform.

Example 4 9

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 / 8Γ Resin particles were produced in the same manner as in Example 45 except that 2 g of the DBP oil absorption lOOml / 100 0 (Ρ3.5) was used.

Then, the precipitated resin particles, this filtrate to have a particle size analysis, 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.

Also, as in 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.

Comparative Example 2 7

Resin particles were produced in the same manner as in Example 45 except that polyhydroxymethyl stearate ester was not used.

Next, resin particles were precipitated in the same manner as in Example 45. Particle size analysis of the precipitated resin particles showed that the resin particles had a particle size width of 0.17 to 60.0 um and an average particle size D _s . However, the resin particles had a wide particle size distribution of 7.37111. In Fig. 9, the horizontal axis represents the logarithm of the particle size, and the vertical axis represents the histogram and cumulative particle size distribution of the frequency by a line.

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.

Furthermore, regarding printability, although image formation was possible, image deletion occurred. In addition, the printed surface is uneven printed matter.o

Comparative Example 2 8

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.

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, and 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.

Furthermore, with regard to printability, although image formation was possible, image deletion and crushed prints occurred. Furthermore, the solid surface was uneven printed matter.

Comparative Example 2 9

Example: Except that the resin used is a Sumitomo Chemical Co., Ltd. Sumitomo Chemical Co., Ltd. Sumitomo Chemical Co., Ltd. Sumitomo DB-10, which has high crystallinity and a high Ml value. Under the same conditions as 45 Thus, resin particles were produced.

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.

Further, with respect to printability, image deletion occurred, and a printed matter having an uneven solid surface was obtained.

Comparative Example 30

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 ηA 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.

Furthermore, regarding printability, although image formation was possible, image deletion occurred. Further, the solid surface was an uneven printed matter. Comparative 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 μl of DBP oil absorption of 65 ml / 100 g, pH 3.5) was used.

From the wet toner containing the obtained resin particles, a developing solution was prepared in the same manner as in Example 45, and the developing characteristics were evaluated in the same manner.

Developing characteristics show negative polarity, OD value 0.5, initial current value 1410 nA, current value after energizing for 60 seconds at 1328 nA, weight of toner attached to electrode Charge value (Q / m, unit // C / 8 /) is 120, the difference between the initial current value and the current value after 60 seconds and the Q Zm value are small, and the toner The electrophoresis was also poor.

Furthermore, with regard to printability, images could be formed, but image deletion occurred. Further, the solid surface was an uneven printed matter. Comparative Example 3 2

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. .

The developing characteristics show negative polarity, the OD value is 0.5, the initial current value is 1 η η η 電流, 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.

Furthermore, regarding printability, although image formation was possible, image deletion occurred. Furthermore, the solid surface was a non-uniform printed matter. Comparative Example 3 3

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 (ΓΛ2.5) were used.

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 ηA 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.

Furthermore, regarding printability, although image formation was possible, image deletion occurred. Further, the solid surface was an uneven printed matter. Comparative Example 34

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. 1 2 ^ m The resin particles had a wide particle size distribution. In Fig. 10, 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.

Developing characteristics show negative polarity, 0 D value 0.4, initial current value 2 Ι η η 電流, current value after passing for 60 seconds at 180 nA, weight of toner adhering to electrode The charge value (QZm, unit: CZ sr) was 40, and the difference between the initial current value and the current value after 60 seconds, the Q Zm value was small, and the electrophoretic property of the toner was poor.

Furthermore, with regard to printability, images could be formed, but image deletion occurred. Further, the solid surface was an uneven printed matter. Comparative Example 3 5

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.

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 η 電流, 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.

Further, with regard to printability, although image formation was possible, image deletion occurred. Further, the solid surface was a uniform printed matter. Comparative Example 3 6

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.

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.

Furthermore, with regard to printability, images could be formed, but image deletion occurred. Further, the solid surface was an uneven printed matter. Comparative Example 3 7

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.

Developing characteristics show negative polarity, OD value 0.4, initial current value 107 nA, current value after passing electricity for 60 seconds at 93 nA, charge per unit weight of toner attached to electrode The quantity value (QZm, unit CZsr) was 23, 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.

Furthermore, with regard to printability, although image formation was possible, image deletion occurred. Further, the solid surface was an uneven printed matter. Comparative Example 3 8

Car Bo assembler Uz click the car Bonn bra 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 Β} Ρ 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 μm, ρ 7.0) was used.

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.

Further, with regard to printability, an image flow occurred, which was possible to form an image. Further, the solid surface was an uneven printed matter. Comparative Example 39

As a charge controlling agent, 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.) in 200 ml round bottom flask ) 3 g, Y—0 T (hexyl 2-ethyl sulfoconodic acid yttrium) as a charge control agent 200 m 8, 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.

- How, in separate containers, 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 ヽ pH 3.0) and 1-hydroxymethyl stearate methyl ester (manufactured by Ito Oil Co., Ltd., 3 volumes) Body, acid 偭 40.8-42.8, saponification 偭 19.6.-: 1.97.7, weight-average molecular weight 1,200, hue (gardner-hedge) 6-7, pale Using an ultrasonic homogenizer, 95 mg of a gray-brown wax) was mixed and dispersed in 100 ml of Isoper G (manufactured by Exon).

Next, 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 ηA, 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.

In the case of C a and N a, the initial current value is almost the same, and the current value after passing the current for 60 seconds at 102 nA is 654 nA. showed that. However, those having higher OD values as image densities are in the order of Co> Y> Ni> Na. In the case of Na, the 0 D value was 0.9.

Comparative Example 40

Instead of the 12-hydroxymethyl stearate methyl ester of Example 45, a 12-hydroxymethyl stearate methyl ester was used. After granulation in the same manner as in Example 1 except that Ter (monomer) (special grade reagent manufactured by Junsei Chemical Co., Ltd.) was used, 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. In Fig. 11, 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 8Γ) 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.

Industrial applicability By using olefin resin particles having a carboxyl group or an ester group as the resin particles in a wet toner, 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.

Further, 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. In addition to the presence of 3- to 10-mer polyhydroxycarboxylic acid esters having a monomer of siloxane ester as a monomer, 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.

In addition, 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.

Claims

The scope of the claims

(1) An olefin resin particle having a carboxyl 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. And 3- to 10-mer poly (hydroxy carboxylate) ester containing hydroxy carboxylic acid ester as monomer in wet toner consisting of Wet toner characterized by the presence of

(2) The wet process according to (1), wherein a charge control agent compatible with the liquid aliphatic hydrocarbon is present together with the polyhydroxycarboxylic acid ester. Toner.

(3) The charge control agent is selected from lecithin, cobalt, manganese, zirconia, yttrium, and nickel. A wet toner characterized by being a transition metal salt of an acid.

(4) A resin having a carboxyl group or an ester group is an ethylene resin having a melt flow index of 2.5 to 9550. 2. The wet toner according to claim 1, comprising a vinyl acetate copolymer.

(5) The structure is characterized in that the structure has a large carbon black as a colorant together with a charge control agent compatible with the liquid aliphatic hydrocarbon. The wet toner according to claim 1.

(6) months over Bonn Bed rack particle size 1 0~ 1 0 0 nm, BET specific surface area is ^{3 0~ 2 6 0 m 2 Z} gr, DBP oil absorption 6. The wet toner according to claim 5, wherein the toner has a physical property of 45 to 200 ml / 100 g and a surface pH of 3.0 to 8.0.

(7) A resin having a carboxyl group or an ester group alone or a resin having a carboxyl group or an ester group to which a coloring agent is added. The fin-based resin is heated and dissolved in a solvent having high temperature dependency in solubility to the resin to form a resin solution, and then the resin solution is treated with a hydroxycarboxylic ester. In the presence of a 3- to 10-mer polyhydroxycarboxylic acid ester as a monomer, it is poured into a liquid aliphatic hydrocarbon and cooled to precipitate resin particles, and a solvent is added to the fatty acid. A method for producing a wet toner, comprising replacing with a group hydrocarbon.

(8) The method according to claim 7, wherein a charge controlling agent compatible with the liquid aliphatic hydrocarbon is present together with the polyester ester of polycarboxylic acid. Manufacturing method of wet toner.

(9) The charge control agent is lecithin or cobalt, manganese, zirconium, yttrium, nickel, or a dialkyl sulfosuccinic acid. 9. The method for producing a wet toner according to claim 8, wherein the method is a transition metal salt.

(10) The resin having a carboxyl group or an ester group is an ethylene resin having a melt flow index of 2.5 to 950. 10. The method for producing a wet toner according to any one of claims 7 to 9, which is a vinyl acetate copolymer resin.

(11) A claim characterized in that the structure includes a large carbon black as well as a polycarboxylic ester. Manufacture of wet toner as described in any of 7 to 9 Method.

(12) After dispersing an olefin resin having a carboxyl group or an ester group in a liquid aliphatic hydrocarbon using a pulverizing medium while heating, the dispersion liquid Is cooled to form toner particles, a 3- to 10-mer poly (hydroxycarboxylic acid ester) containing a hydroxycarboxylic acid ester as a monomer, and a coloring agent. A method for producing a wet toner, further comprising forming a toner particle in the presence of a charge control agent compatible with a liquid aliphatic hydrocarbon.