JPH06138717A - Toner for wet processing and its production - Google Patents

Abstract

PURPOSE:To improve the dispersion stability of resin particles and the mobility of the resin particle and to form images having good brightness by allowing spiculisporic acid or its deriv. to exist in a developer dispersed with the resin particles. CONSTITUTION:This toner consists of olefinic resin particles alone having a carboxyl group or ester group or the olefinic resin particles having the carboxyl group or ester group added with coloring agents and the greater part of a liquid aliphat. hydrocarbon. The spiculisporic acid or its deriv. is made to exist together with polyhyroxycarboxylate of 3 to 10-mers, the monomer of which is hyroxycarboxylate. The spiculisporic acid or its deriv. is made to exist in the resin particles or the dispersion of the resin particles. Further, the toner is so formed as to have the metallic salt of dialkylsulfosuccinic acid as a charge control agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wet toner for developing an electrostatic latent image with a toner dispersed in an insulating liquid and a method for producing the wet toner, for electrophotography, electrostatic printing and information recording. A suitable wet toner and its manufacturing method.

[0002]

2. Description of the Related Art An electrostatic latent image formed by exposing an electrostatically charged optical semiconductor to light is developed by toner particles made of a colorant or the like dispersed in an electrically insulating liquid. A method of forming an image using a wet toner for transferring the image is well known. Conventionally, a wet toner used in this type of image forming method comprises an electrically insulating liquid and colorant particles having a particle size of 0.1 to 1 μm dispersed therein, and the colorant particles are dispersed in the electrically insulative liquid. A resin in which a resin is dissolved for the purpose of fixing, charge control, and the like is used.

In the wet type developer, the charge polarity of the surface of the colored particles in the liquid aliphatic hydrocarbon is determined by the chemical structure of the material constituting the liquid developer, the physical work function and the electronic level such as the Fermi level. Was said. Further, various additives such as charge control agents are added to the wet toner, and the charge polarity on the surface of the colored particles is also affected by these additives, and the characteristics and latent properties of the photoconductor that form an electrostatic latent image are also affected. The charging characteristics are affected by the image forming method, and the charging characteristics of the developer have been selected according to each latent image.

Further, a surfactant is added to the wet developer to utilize the hydrophilic group and hydrophobic group of the surfactant,
It has been used to stabilize the dispersion and lower the surface tension to change the wetting characteristics of the solution and the dispersion.

Further, as to the improvement and stability of the image at the time of high-speed development, since it depends on the difference in the charge polarity between the latent image for development and the wet developer as described above, the resin which is a component of the developer has a high content. It is preferable to add a charge control agent to the developer consisting of an insulating solvent and a colorant, but such a wet developer gives a good resolved image quality,
It is also recognized that charging and image quality are highly dependent on raw materials.

For example, when a colorant is present in the resin used in the present invention in the formulation, particularly good image quality can be obtained, but when the pigment is removed, the electrification is insufficient and the image quality may be poor. . Therefore, it can be improved by using oxide fine particles such as silica, titanium oxide, and alumina sol in such a developing solution. However, when a coloring agent such as magenta or yellow is contained, addition of silica is performed. It was also found that the above did not show appropriate charging characteristics.

[0007]

SUMMARY OF THE INVENTION According to the present invention, the electric charge of wet toner particles produced by a method of granulating a resin utilizing the difference in solubility depending on the solvent and temperature is maintained stable for a long time, and the initial development during high-speed development is performed. It is an object to obtain a wet type toner capable of recovering and maintaining the characteristics, and particularly to obtain a good charging property regardless of the type of the coloring pigment present in the resin particles. Is.

[0008]

In order to solve the above-mentioned problems, the present invention provides 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 colorant is added. And a majority of liquid aliphatic hydrocarbons, a wet toner in which spiculisporic acid or a derivative thereof is present together with a polyhydroxycarboxylic acid ester of a 3- to 10-mer having a hydroxycarboxylic acid ester as a monomer. .

Further, the present invention is a wet toner in which spiculisporic acid or a derivative thereof in the wet toner is present in the resin particles or the dispersion liquid of the resin particles. Further, the present invention is a wet toner having a dialkyl sulfosuccinic acid metal salt as a charge control agent.

In the present invention, a resin solution containing spiculisporic acid or a derivative thereof in an olefin resin having a carboxyl group or an ester group alone or in an olefin resin having a carboxyl group or an ester group to which a colorant is added is treated with a hydroxy group. In the presence of a 3- to 10-mer polyhydroxycarboxylic acid ester having a carboxylic acid as a monomer and a charge control agent, the liquid aliphatic hydrocarbon is charged and cooled to precipitate resin particles, and the solvent is used as a liquid aliphatic hydrocarbon. It is a method of manufacturing a wet toner in which hydrocarbon is substituted. Further, the present invention relates to a olefin resin resin solution having a carboxyl group or an ester group, or an olefin resin resin solution having a carboxyl group or an ester group, to which a colorant is added. In the presence of the polyhydroxycarboxylic acid ester and the charge control agent, the liquid aliphatic hydrocarbon is charged and cooled to precipitate the resin particles, and after replacing the solvent with the liquid aliphatic hydrocarbon, spiculisporic acid or A method for producing a wet toner in which the derivative is present in a liquid aliphatic hydrocarbon. First, the constituent components of the wet toner of the present invention will be described. The liquid aliphatic hydrocarbon, which is an electrically insulating liquid, has a volume resistance of 10 ¹⁰ Ω · cm or more, and is used for the purpose of enhancing the electrical insulating property in a wet toner. It is required that the dissolving power of the resin is relatively small, which prevents deterioration as a wet toner.

Liquid aliphatic hydrocarbons include liquid n
-Paraffinic hydrocarbons, iso-paraffinic hydrocarbons, or mixtures thereof, halogenated aliphatic hydrocarbons and the like. Branched-chain aliphatic hydrocarbons are particularly preferable, and for example, Isopar G, Isopar H, Isopar K, Isopar L, Isopar M, Isopar V manufactured by Exxon Co. are preferably used. These have almost no solubility in ethylene-vinyl acetate copolymer resins. For example, the solubility of the resin in Isopar H is 0.001 g / ml of solvent at 25 ° C and 65 ° C. is there. During storage of the wet toner, the liquid aliphatic hydrocarbon may be present in an amount of 0.01 to 80% by weight, preferably 0.1 to 50% by weight, based on the total weight of the wet toner, and concentrated to this solid content concentration. It is preferable to store in the state as it does not change with time. It should be noted that the wet toner at the time of development may be diluted with a liquid aliphatic hydrocarbon so as to have a solid content concentration of 0.5 to 2% by weight, and a preferable printed matter can be obtained.

The olefin resin is preferably an ethylene-vinyl acetate copolymer. The ethylene-vinyl acetate copolymer is, for example, an Ultrasen series manufactured by Tosoh Corporation, such as 510X, 515F, 530,537,537
L, 537S, 525,520F, 540,540F, 541,541L, 625,630,630F, 68
2,627,631,633,680,681,635,634,710,720,722,725,751,
750,760 etc., Sumitomo Chemical Co., Ltd.'s Sumitate series, eg DD-10, HA-20, HC-10, HE-10, KA-10, KA-20, KA-3
1, KC-10, KE-10, MB-11, RB-11, etc.Evaflex series manufactured by Mitsui DuPont Polychemicals Co., Ltd., eg 45X,
YW, 150,210,220,250,260,310,360,410,420,450,460,55
0,560 etc., Soagoren series of Nippon Gohsei Co., Ltd.,
For example, BH, CH, CI, DH, etc., Soarex series, for example, RBH, RCH, RDH, etc., Takeda Pharmaceutical Co., Ltd. Dumiran series, for example, Dumiran D-219, D-229, D-251S, C-
2280, C-2270, C-1590, C-1570, C-1550 and the like can be mentioned. Also, Yucaron-Eva manufactured by Mitsubishi Petrochemical Co., Ltd., Elpax manufactured by DuPont, USA and the like can be used.

In addition, a product obtained by modifying a polyolefin resin to introduce a carboxyl group, an example of which is a product name,
N-Polymer made by Nippon Petrochemical Co., Ltd., Tonen Petrochemical Co., Ltd.
Tonen CMP-HA series manufactured by Mitsubishi Yuka Co., Ltd. MOD
IC, Sumitomo Seika Co., Ltd. Saixen, Mitsui Toatsu Chemical
Ronply Co., Ltd., Mitsui Petrochemical Co., Ltd. Admer, etc., and copolymers of ethylene and acrylic acid, Dow EAA copolymers manufactured by Dow Chemical Co.
Mitsubishi Yuka Co., Ltd., Yucaron EAA, Mitsui DuPont Polychemical Co., Ltd., Nucrel, Sumitomo Chemical Co., Ltd., Acryft, etc., and a copolymer of ethylene and acrylic acid or methacrylic acid, or a cross-linked product thereof. So-called ionomers, Surname made by DuPont of the United States, Himilan made by Mitsui DuPont Polychemical Co., Ltd.
Asahi Kasei's corborene latex, etc., BASF's EVA1 wax added, partially saponified copolymer of ethylene and vinyl acetate, trade name: Takeda Chemical Industries' dumilan, etc., ethylene Copolymer of acrylic acid ester and acrylic acid, Nippon Unicar
Examples include DPD-6169 manufactured by Co., Ltd., and a polyolefin resin containing a carboxylic carbonyl group. These resins may be used alone or in combination of two or more.

Next, the polyhydroxycarboxylic acid ester will be described. The polyhydroxycarboxylic acid ester has a granulation adjusting function when it is present in the resin particle forming step, and resin particles having a uniform particle size distribution can be obtained. Further, it has affinity with the resin particles due to its structure, and also functions as a dispersant.

The hydroxycarboxylic acid ester, which is a raw material for polymerizing the polyhydroxycarboxylic acid ester, is a hydroxycarboxylic acid represented by the following formula in which the carboxylic acid is alkylated or aralkyl esterified, amidated, or a metal. It is salted. Formula HO-X-COOH, where X is at least 12
A divalent saturated or unsaturated aliphatic hydrocarbon containing carbon atoms, or a divalent aromatic hydrocarbon containing at least 6 carbon atoms, and at least 4 groups between the hydroxy group and the carboxyl group. There are carbon atoms of. ) Examples of such hydroxycarboxylic acids include ricinoleic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, hydrogenated castor oil fatty acid (containing a small amount of stearic acid and palmitic acid in 12-hydroxystearic acid). , 16-hydroxyhexadecanoic acid, 15
-Hydroxypentadecanoic acid, 12-hydroxydodecanoic acid, 4-hydroxybenzoic acid, 2-hydroxy-1-
Naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 4-hydroxyphenylacetic acid, and 3- (4-hydroxyphenyl) -propion Such as acids.

Examples of hydroxycarboxylic acid derivatives include hydroxycarboxylic alkyl esters such as 12-hydroxystearic acid methyl ester and 12-hydroxystearic acid ethyl ester, lithium 12-hydroxycarboxylic acid, and aluminum 12-hydroxycarboxylic acid. Examples thereof include hydroxycarboxylic acid metal salts, hydroxycarboxylic acid amides, hydrogenated castor oil, and the like.

The polyhydroxycarboxylic acid ester is obtained by polymerizing the above-mentioned hydroxycarboxylic acid ester by partially saponifying it in the presence of a small amount of amines or a catalyst, and its polymerization form is intermolecular esterification. And various forms such as those by intramolecular esterification. The degree of polymerization of the polyhydroxycarboxylic acid ester in the present invention is preferably a 3- to 10-mer, and is a light gray brown wax-like substance. If the degree of polymerization is less than 3 or more than 10, it is not compatible with the liquid aliphatic hydrocarbon and the resin particles have a wide particle size distribution even when used in the granulation step, and the desired product is obtained. Absent. The addition amount of the polyhydroxycarboxylic acid ester is not particularly limited, but it is used in a ratio of 0.01% by weight to 200% by weight based on the weight of the resin.

In the wet toner of the present invention, as a charge control agent, a metal salt of dialkyl sulfosuccinate, manganese naphthenate, calcium naphthenate, zirconium naphthenate, cobalt naphthenate, iron naphthenate, lead naphthenate, naphthenic acid. Nickel, chromium naphthenate, zinc naphthenate, magnesium naphthenate, manganese octylate, calcium octylate, zirconium octylate,
Cobalt octylate, iron octylate, lead octylate, nickel octylate, chromium octylate, zinc octylate, magnesium octylate, manganese dodecylate, calcium dodecylate, zirconium dodecylate, cobalt dodecylate, iron dodecylate, dodecylate Metallic soap such as lead, nickel dodecylate, chromium dodecylate, zinc dodecylate, magnesium dodecylate, etc., alkyl dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, barium dodecylbenzenesulfonate, etc. Metal salts, phospholipids such as lecithin and sehalin, organic amines such as n-decylamine and the like can be added. In particular, dialkyl sulfosuccinic acid cobalt, manganese,
It is desirable to use transition metal salts such as zirconium, yttrium, nickel and the like. The addition amount may be the minimum amount showing the charge adjusting effect, but it is generally preferably 0.01 to 50% by weight in the liquid aliphatic hydrocarbon.

Next, as the colorant, a known organic or inorganic colorant can be used. Examples of the black colorant include inorganic carbon black, ferric tetroxide, and organic cyanine black. Examples of the yellow colorant include inorganic yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, ocher and the like.
Further, as an acetoacetic acid anilide monoazo pigment of a poorly soluble metal salt (azo lake), Hansa Yellow G (CIN
o. pigment Yellow 1, hereafter, the same), Hansa Yellow 10G (pigment Yellow 3), Hansa Yellow RN
(Pigment Yellow 65), Hansa Brilliant Yellow 5GX (pigment Yellow 74), Hansa Brilliant Yellow 10GX (pigment Yellow 98), Permanent Yellow FGL (pigment Yellow 97), Shimura Lake Fast Yellow 6G (pigment Yellow 13)
3), Lionol Yellow K-2R (pigment Yellow
169), and as acetoacetic acid anilide disazo pigments, disazo yellow G (pigment Yellow 12), disazo yellow GR (pigment Yellow 13), disazo yellow 5G (pigment Yellow 14), disazo yellow 8G (pigment Yellow 17), disazo yellow R (pigment Yellow 55) and permanent yellow HR (pigment Yellow 83).

Examples of condensed azo pigments include chromophthal yellow 3G (pigment Yellow 93), chromophthal yellow 6G (pigment Yellow 94), and chromophthal yellow GR (pigment Yellow 95). Further, as the benzimidazolone monoazo pigment, Hosta Palm Yellow H3G (pigment Yellow 154),
Hosta Palm Yellow H4G (pigment Yellow 15
1), Hosta Palm Yellow H2G (pigment Yellow
120), Hosta Palm Yellow H6G (pigmentYell
ow 175), Hosta Palm Yellow HLR (pigment
Yellow 156). Further, as an isoindolinone-based pigment, Irgadine Yellow 3RLTN (p
igment Yellow 110), Irgadine Yellow 2RL
T, Irgadine Yellow 2GLT (pigment Yellow 1
09), Fastgen Super Yellow GROH (pig
ment Yellow 137), Fastgen Super Yellow GRO (pigment Yellow 110), Sandrin Yellow 6GL (pigment Yellow 173), and flantron (pigment Yel) which is a slene-based pigment.
low 24), anthramyrimidine (pigment Yellow 1
08), phthaloylamide type anthraquinone (pigment
Yellow 123), Heliofast Yellow E3R (p
igment Yellow 99), an azo nickel complex pigment (pigment Green 10) which is a metal complex pigment, a nitroso nickel complex pigment (pigment Yellow 153), an azomethine copper complex pigment (pigment Yellow 117), and a phthalimido quinophthalone pigment which is a quinophthalone pigment. (Pig
ment Yellow 138) and the like.

Examples of magenta colorants include inorganic cadmium red, red iron oxide, silver vermilion, red lead and antimony vermilion. As an azo lake type azo pigment, Brilliant Carmine 6B (pigment Red 57:
1), lake red (pigment Red53: 1), permanent red F5R (pigment Red48), resole red (pigment Red49), persia orange (pigme
nt Orange17), Kurosei Orange (pigment Orange
18), Helio Orange TD (pigment Orange1
9), pigment scarlet (pigment Red60:
1), Brilliant Scarlet G (pigment 64:
1), Helio Red RMT (pigment Red51), Bordeaux 10B (pigment Red63), Helio Bordeaux BL
(Pigment Red 54), and as the insoluble azo type (monoazo, disazo type, condensed azo type), Para Red (pigment Red 1), Lake Red 4R (pigme
nt Red3), Permanent Orange (pigment Orange)
5), Permanent Red FR2 (pigment Red2),
Permanent Red FRLL (pigment Red9), Permanent Red FGR (pigment Red112), Brilliant Carmine BS (pigment Red114), Permanent Carmine FB (pigment Red5), P.I. V. Carmine HR (pigment Red150), Permanent Carmine FBB (pigmentRed146), Nova Palm Red F3
RK-F5RK (pigment Red170), Nova Palm Red HFG (pigment Orange38), Nova Palm Red HF4B (pigment Red187), Nova Palm Orange HL. HL-70 (pigment Orange36), P.I.
V. Carmine HF4C (pigment Red185), Hostabum Brown HFR (pigment Brown25), Vulcan Orange (pigment Orange16), Pyrazolone Orange (pigment Orange13), Pyrazolone Red (pi
gment Red38), and as a condensed azo pigment, Chromophtal orange 4R (pigment Orange3)
1), Chromophtal Scarlet R (pigment Red1
66), chromophthal red BR (pigment Red14
4) is mentioned.

Further, pyranthrone orange (pigment Orange) is used as an anthraquinone pigment which is a condensed polycyclic pigment.
40), Antoanthrone Orange (pigment Orange
168), dianthraquinonyl red (pigment Red1
77), thioindigo magenta (pigment Violet38), thioindigo violet (pigment Violet36), thioindigo red (pigment Red88), and perinone orange (pigment Orange43). In addition, as perylene pigments, perylene red (pigment Red190), perylene vermillion (pig
ment Red123), Perylene Maroon (pigment Red1)
79), perilence scarlet (pigment Red14
9) and perylene red (pigment Red 178), and as a quinacridone-based pigment, quinacridone red (p
igment Violet19), quinacridone magenta (pigme
nt Red122), quinacridone maroon (pigment Red
206), quinacridone scarlet (pigment Red2
07), and other condensed polycyclic pigments include pyrocholine pigments, red fluorbin pigments, and dyed lake pigments (water-soluble dye + precipitating agent → lake fixing).

As the cyan colorant, an inorganic ultramarine blue,
Navy blue, cobalt blue, cerulean blue, etc. are mentioned, and as the phthalocyanine type, Fast Gemble-BB (pigment Blue 15), Sumiton cyanine.
Blue HB (pigment Blue 15), cyanine blue 5
020 (pigment Blue 15: 1), Sumika print
Cyanine Blue GN-O (pigment Blue 15), Fast Sky Blue A-612 (pigment Blue 1
7), cyanine green GB (pigment Green7),
Cyanine Green S537-2Y (pigment green3
6), Sumiton Fast Violet RL (pigment
Violet 23), and indanthrone blue (PB-60P, PB-22, P) which is a slene-based pigment.
B-21, PB-64), a basic dye lake pigment, methyl violet / phosphorus / molybdic acid lake (PV
-3) and the like. In addition, a colorant called a so-called processed pigment in which the surface of the colorant is coated with a resin can be similarly used.

Considering the storage stability as a wet toner, or the transparency and color mixture of an image when a color image is formed using the obtained wet toner, among the above colorants, the black-based toner is It is preferable to use a mixture of benzidine yellow and Hansa yellow as the bonblack and yellow type, brilliant carmine 6B for the magenta type, and phthalocyanine blue for the cyan type.

The colorant has a particle size of 30 to 15 in the secondary aggregation state.
It is advisable to use a powder of 0 μm, and the amount used is 0.0001 to 2000% by weight based on the weight of the resin.
However, in order to reproduce the multi-color continuous gradation equivalent to that of offset printing, it is necessary that the optical reflection density after transfer of each color toner to the transfer target be 0.7 or more. And 1.0 especially for cyan and black
It is desirable to have more than one. In order to make the optical reflection density of 0.7 or more for each color, in the case of black and cyan, it is 10 to 150% by weight based on the same weight as above, in the case of magenta 40 to 150% by weight, and in the case of yellow 10 to 10.
It is advisable to set it to 100% by weight. If any of the colors exceeds the above range, the background stain is likely to occur after development.

The spiculisporic acid used in the present invention will be described. It has been conventionally known that microorganisms produce a surfactant depending on culture conditions. As is the case with spiculisporic acid in this case, the surfactants produced by microorganisms are biometabolizable and highly biodegradable and have low toxicity. Further, it is possible to produce a chemical structure such as an asymmetric optical activity peculiar to microorganisms, and it is found out that the produced surfactant has many performances superior to those obtained by conventional chemical synthesis.

The spiculisporic acid used here is one of them (reported by University of Tsukuba, Tabuchi et al., Eg, T. Tabuch).
i. J. Ferment. Technol. , 55,
37 (1977)). The spiculisporic acid obtained from filamentous fungus is a polybasic acid having a long-chain alkyl group and having the chemical structure shown below.

[0028]

[Chemical 1]

Further, the activity of the alkali salt of spiculisporic acid is superior to that of other surfactants and shows high surface activity. In the present case, further, by applying not only spiculisporic acid simple substance but also its derivative alkali salt to a wet developer, the charge polarity on or near the insoluble colored particle surface in the liquid aliphatic hydrocarbon is ionized or micelle. This is a wet type developer which, when incorporated, makes it possible to stably maintain the chargeability of electric charges, to stabilize the dispersion for a long period of time, and to recover and maintain the initial development characteristics during high-speed development. Further, the charge polarity generated by the resin used alone, by the charge of the opposite polarity formed by the electric double layer of the micelle, to form a charge polarity of the opposite polarity to the original colored particle surface on the outer periphery of the resin-surfactant micelle, The polarity of the wet type developer can be easily reversed.

It is possible to use various derivatives obtained from spiculisporic acid. For example, a dibasic acid salt obtained by the neutralization reaction of spiculisporic acid or a saponified tribasic acid salt, an ethylene oxide and polyethylene glycol adduct by esterification, a diol and a polyester, an alcohol and a mono (di,
Amines such as tri) esters, acid anhydrides and imides by dehydration, derivatives from acid chlorides with thionyl chloride,
Examples thereof include acid amination products obtained by reacting an amine acid with an acid halide and nitrites obtained by an amidation reaction. Furthermore, among these, particularly preferable are:
Preferred are spiculisporic acid ester derivatives and acid anhydrides and their derivatives, and spiculisporic acid metal salts. You may use these individually or in mixture of 2 or more types.

The micelle formation in the present invention does not occur by ionization of the surfactant alone by the hydrophilic group or the hydrophobic group, and further utilizes the ability of a special structure which is also a surfactant, such as polyethers, to take up ions. It does not utilize the polarity of ions. These things
In the case of the present invention, the interaction between the coloring component excluding the synthetic resin and the surfactant alone is weak, and it is shown that the polarity change of the developer cannot be obtained by the ionization by the surfactant. That is, the micelle formation of the present invention is strongly influenced by the interaction with the synthetic resin, and the addition concentration has an influence on the ionic polarity generated on the micelle surface.

Therefore, those in which the substituent or chemical structure of the surfactant interacts electrostatically with the resin used in the present invention are used. In particular, the present invention uses an olefin resin having a carboxyl group or an ester group, and exerts a great effect by using spiculisporic acid ester derivative and acid anhydride type and its derivative, and spiculisporic acid metal salt as a surfactant. To do.

Although the detailed reason for these action mechanisms and the like is not clear, it is presumed that the thickness of the electric double layer increases due to the formation of the surface-active micelles, so that static electricity can exist more stably in a dispersed manner on the outer periphery of the coloring component. To be done.

The spiculisporic acid and its derivative used in the wet developer of the present invention may be added to a resin liquid containing an olefin resin having a carboxyl group or an ester group for granulation. In addition to the granulated liquid aliphatic hydrocarbon dispersion, it may be present during wet development.

When mixed with resin particles, spiculisporic acid and its derivative added to the wet toner of the present invention is 0.001 to 300% by weight, preferably 0.001 to 50% by weight based on the amount of resin used. % By weight. Also,
When mixed in the dispersion liquid of the wet toner, the content of the insoluble particles is 50% by weight or less, preferably 0.001 to 10
% By weight.

When it is mixed with the resin particles in an amount of more than 300% by weight, a remarkable granulation effect due to spiculisporic acid can be obtained, but it is difficult to make the granulation particle size distribution uniform. If it is less than 0.001% by weight, the effect of stabilizing charge and dispersion of spiculisporic acid does not appear remarkably.

When mixed in the dispersion liquid, 50% by weight
If it is more than 0.001% by weight, the electric resistance of the dispersion liquid is lowered, and it becomes difficult to perform highly efficient charging, and if it is less than 0.001% by weight, sufficient micelle formation is not carried out. I can't keep it.

[0038]

The wet toner of the present invention comprises a olefin resin particle having a carboxyl group or an ester group alone, or a olefin resin particle having a carboxyl group or an ester group having a colorant added, and a liquid aliphatic hydrocarbon. In the toner, spiculisporic acid and its derivative are present in the resin particles during the granulation process of the resin particles or in the wet developer in which the resin particles are dispersed. By the ability to form micelles, it is to generate a charge of the opposite polarity to the original colored particles on the periphery of the micelle consisting of the resin-surfactant. Occurs,
The polarity of the wet type developer can be easily controlled to be reversed, the mobility of the colored particles can be increased, and the film forming characteristics after development can be improved.

Examples of the present invention will be shown below. The method for preparing cobalt dialkylsulfosuccinate used as a charge control agent in the examples is as follows. Preparation of cobalt dialkyl sulfosuccinate. Sodium dialkyl sulfosuccinate (Wako Pure Chemical Industries, Ltd.)
Manufactured by Aerosol OT) 25 parts by weight of tetrahydrofuran 10
After mixing with 0 part by weight and heating and stirring at 50 ° C. to dissolve, 13 parts by weight of cobalt nitrate was added to 30 parts of tetrahydrofuran.
A solution dissolved in a mixed solvent consisting of parts by weight and 5 parts of methanol was added, and the mixture was heated with stirring at 50 ° C for 30 minutes to precipitate a white salt. This white salt was filtered off, and the light purple filtrate was concentrated using an evaporator to obtain 10.9 parts by weight (yield 81%) of light reddish purple solid cobalt dialkylsulfosuccinate. The solubility at 25 ° C. in Isopar G (manufactured by Exxon) is 0.2 g / ml solvent.

[0040]

【Example】

Example 1 2.5 g of EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Polychemical Co., Ltd. Evaflex 250) in a 200 ml round bottom flask and 256 m of cobalt diisooctylsulfosuccinate as a charge control agent.
g, and 100 ml of tetrahydrofuran was added as a solvent. The mixture was heated and stirred at 80 ° C. for 1 hour in an oil bath. In another container,
Monasutual Blue F as cyan pigment
2.5 g of BR (ICI metal phthalocyanine pigment) and poly-12-hydroxystearic acid methyl ester 3
90 mg of a polymer (made by Ito Oil Co., Ltd.) was dispersed in 100 ml of tetrahydrofuran. This was put into the previously dissolved flask all at once and further stirred and mixed at 100 ° C. for 1 hour to obtain a pigment-dispersed resin solution. The pigment-dispersed resin solution was left at room temperature, lowered to about 65 ° C., and then cooled to −5 ° C. Isop
ER G was dispersed and mixed in 100 ml of an ER G using an ultrasonic homogenizer. After that, the solvent was replaced with tetrahydrofuran for Isoper G using an evaporator. Microtrac Mark II SR for particle size distribution measurement
As a result of measurement with an A type (manufactured by Nikkiso Co., Ltd.), the resin particles have a single particle size distribution width and are sharp, and have a particle size of 0.17 to 5.27.
It had a particle size of μm and had a particle size D ₅₀ = 1.12 μm.
In FIG. 1, the horizontal axis represents 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.

The wet developer was adjusted to a print density of 1% using the same Isoper G. After forming various electrostatic patterns having a surface charge of 150 V to 50 V on the electrostatic recording paper, development printing evaluation was performed with a roller developing machine. The developing machine speed was 2.6 m / min and 10.0 m / min. Furthermore, a micro ammeter (KEITHLEY) is used for initial current value measurement.
237 HIGH VOLTAGE SOURC
E MEASURE UNIT) was used. In the measuring cell filled with the obtained developing solution, the size was 3.8 × 4.
Hold a 5 cm metal electrode plate at a 1 cm interval and
A direct current voltage of 00 V was applied and the initial current value and the charge amount were evaluated.

Further, in order to evaluate the developing characteristics and electrophoretic characteristics of the toner, a zeta potential measuring device (MATEC AP) is used.
Made by PLYED SCIENCE, ESA-8000,
Mobility was measured using an ultrasonic zeta potential analysis system). The photometric and colorimetric evaluation of the printed matter is performed with a spectrocolorimeter system CM-1000 manufactured by MILNOTA Co., Ltd.
The value was measured by Macbeth RD914.

The developing characteristics show that the positive polarity, that is, the negative electrostatic latent image can be developed. OD value of 1.4 or more, initial current value of 1,335 nA, current value of 551 nA after 60 seconds, Q /
m = 481 μC / g, mobility 3.02 × 10 ⁻¹¹ m ²
/ Sec · V, zeta potential 35.1 mV, physical properties of toner were shown.

Even in the developing test at 10 m / min or more, complete solid printing was formed, and neither fog nor image deletion occurred. Next, 50% of spiculisporic acid diethyl ester (manufactured by Iwata Chemical Co., Ltd.) was added to the above-mentioned wet developer.
After adding mg and intermittently irradiating ultrasonic waves with an ultrasonic homogenizer for 3 minutes to disperse, the mixture was developed in the same manner as above, and as a result, the developing property showed a positive polarity. Furthermore, 100 mg of spiculisporic acid diethyl ester was added, and ultrasonic waves were intermittently radiated with an ultrasonic homogenizer for 3 minutes to disperse, and the development was carried out in the same manner as above. As a result, the development characteristics showed a positive polarity. .

Further, 300 mg of spiculisporic acid diethyl ester was added, the mixture was similarly dispersed by an ultrasonic homogenizer, and the same development was carried out. As a result, the developing property showed a positive polarity. In the developing test at 10 m / min or more, perfect solid printing was not formed and image deletion occurred.

Furthermore, when the spiculisporic acid diethyl ester was added to the above-mentioned wet type developer, the change in the mobility with respect to each addition concentration was as follows, and it drastically decreased corresponding to the increase in the addition amount.

[0047]

[Table 1]

Example 2 The charge control agent of Example 1 was replaced by BBP (barium petronate, Wit) which was a mixture of barium alkyl sulfonates.
Co. Chemical Co., Ltd.) Wet developer was prepared in the same manner as in Example 1 except that the amount was changed to 256 mg.

The particle size distribution was measured in the same manner as in Example 1. As a result, the resin particles had a single particle size distribution width and were sharp.
It has a particle size of 0.17 to 2.63 μm and a particle size D ₅₀ = 0.
It was 70 μm. In FIG. 2, the particle size is represented by the logarithm on the horizontal axis, the histogram showing the frequency on the vertical axis, and the cumulative particle size distribution is represented by a broken line, and FIG. 3 shows the particle size distribution after being left for one month. Shows that the particle size distribution is unitary, although it has moved to the larger side.

The printing and other evaluations were the same as in Example 1. The development characteristics show a positive polarity, an OD value of 1.4 or more, an initial current value of 1,235 nA, a current value of 255 nA after 60 seconds,
Q / m = 981 μC / g, mobility is 4.02 × 10 ⁻¹¹
The toner had physical properties of m ² / sec · V and zeta potential of 25.1 mV. Even in the developing test at 10 m / min or more, perfect solid printing was formed, and neither fog nor image deletion occurred.

Next, 50% of spiculisporic acid diethyl ester (manufactured by Iwata Chemical Co., Ltd.) was added to the above wet developer.
After adding mg and intermittently irradiating ultrasonic waves with an ultrasonic homogenizer for 3 minutes to disperse, the mixture was developed in the same manner as above, and as a result, the developing property showed a positive polarity. Furthermore, 100 mg of spiculisporic acid diethyl ester was added, and ultrasonic waves were intermittently radiated with an ultrasonic homogenizer for 3 minutes to disperse, and the development was carried out in the same manner as above. As a result, the development characteristics showed a positive polarity. .

Further, 300 mg of spiculisporic acid diethyl ester was added, the mixture was similarly dispersed with an ultrasonic homogenizer, and the same development was carried out. As a result, the developing property showed a positive polarity. In the developing test at 10 m / min or more, perfect solid printing was not formed and image deletion occurred. Further, when spiculisporic acid diethyl ester was added to the above-mentioned wet developer, the change in the mobility with respect to each addition concentration is as shown in the following table, and it drastically decreased corresponding to the increase in the addition amount.

[0053]

[Table 2]

Example 3 A wet developer was prepared under the same conditions as in Example 1 except that the cyan pigment of Example 2 was changed to 2.5 g of the pigment shown in the table below, and printing and other evaluations were carried out. Same as Example 1.

[0055]

[Table 3]

Example 4 The wet developer of Example 2 was adjusted to a print density of 0.5% with Isoper G.

1% diethyl spiculisporate
After adding and dispersing 50 mg, a wet developer was prepared in the same manner. The printing and other evaluations were the same as in Example 1.

The developing characteristics showed positive polarity. Initial current value is 1,133 nA, current value after 60 seconds is 227 nA, Q /
It was m = 1345 μC / g. A perfect solid print could be formed in the development test at 10 m / min. However, in the development test of 20 m / min, perfect solid printing was not formed and image deletion occurred. Furthermore, when spiculisporic acid diethyl ester was added to the above-mentioned wet developer, the change in mobility with respect to each addition concentration is as shown in the table below, and no abrupt change was observed by the addition.

[0059]

[Table 4]

Example 5 As the wet developing solution, that of Example 2 was used as it was.
The print density was adjusted to 0.5% with per G. 150 mg of spiculisporic anhydride was added and dispersed to prepare a wet developer in the same manner. The particle size distribution was measured in the same manner as in Example 1. As a result, the resin particles had a single particle size distribution width and were sharp, and had a particle size of 0.17 to 1.69 μm.
₅₀ = 0.65 μm. In FIG. 4, the particle size is represented by a logarithm on the horizontal axis, the vertical axis shows a histogram showing the frequency and the cumulative particle size distribution by a polygonal line, and FIG. 5 shows the particle size distribution after being left for one month. Shows that the particle size distribution is unitary, although it has moved to the larger side.

The printing and other evaluations were the same as in Example 1. The development characteristics showed positive polarity. Initial current value 7,704
nA, current value after 60 seconds 4,468 nA, Q / m = 465
It was μC / g. A perfect solid print could be formed in the development test at 10 m / min. Further, even in the high-speed development test of 20 m / min, complete solid printing is formed,
Image deletion did not occur.

Further, when spiculisporic anhydride is added, the change in the mobility with respect to each addition concentration is as shown in the following table, and a rapid change in the mobility is observed with the addition, and high-speed development is observed. It was possible to recover the initial state of the developing solution at the time. Further, the initial zeta potential value of 25.1 mV increased to 43.7 mV after the addition, showing that the dispersion stability was high.

[0063]

[Table 5]

Example 6 The wet developing solution used in Example 2 was used as it was.
The print density was adjusted to 0.5% with super G. 250 mg of monosodium spiculisporate was added and dispersed to prepare a wet developer hereinafter.

The printing and other evaluations were the same as in Example 1. The development characteristics showed positive polarity. Initial current value 1,550
nA, current value 259 nA after 60 seconds, Q / m = 165 μC
/ G. A perfect solid print could be formed in the development test at 10 m / min. However, in the development test of 20 m / min, complete solid printing was not formed and image deletion occurred. Furthermore, when the addition amount of monosodium spiculisporate was increased, the change in mobility with respect to each addition concentration was as shown in the table below, and no abrupt change was observed with respect to the addition.

[0066]

[Table 6]

Example 7 The same wet developer as in Example 2 was used.
The print density was adjusted to 0.5% with super G. 250 mg of disodium spiculisporate was added and dispersed to prepare a wet developer in the same manner.

The printing and other evaluations were the same as in Example 1. The development characteristics showed positive polarity. Initial current value 1550n
A, current value 259 nA after 60 seconds, Q / m = 165 μC /
It was g. A perfect solid print could be formed in the development test at 10 m / min. However, in the development test of 20 m / min, complete solid printing was not formed and image deletion occurred.

Further, when the above-mentioned wet type developer was added with disodium spiculisporate, the change in mobility with respect to each addition concentration is as shown in the following table, and a slight increase change was observed with addition. It was However, the high speed development stability did not change.

[0070]

[Table 7]

Example 8 The wet developing solution used in Example 2 was used as it was.
The print density was adjusted to 0.5% with per G. 250 mg of spiculisporate 1-n-hexylamine was added and dispersed to prepare a wet developer in the same manner.

The particle size distribution was measured in the same manner as in Example 1. As a result, the resin particles had a single particle size distribution width and was sharp.
It has a particle size of 0.17 to 5.27 μm and a particle size D ₅₀ = 1.
It was 35 μm. In FIG. 6, the particle size is represented by the logarithm on the horizontal axis, the vertical axis shows the histogram showing the frequency and the cumulative particle size distribution by a polygonal line, and FIG. 7 shows the particle size distribution after being left for one month. Shows that the particle size distribution is unitary, although it has moved to the larger side. The printing and other evaluations were the same as in Example 1. The development characteristics showed positive polarity. Initial current value of 1,459nA, current value of 284nA after 60 seconds, 284nA, Q
/ M = 1287 μC / g. A perfect solid print could be formed in the development test at 10 m / min. However, in the development test of 20 m / min, complete solid printing was not formed and image deletion occurred.

Further, when the addition amount of spiculisporic acid 1-n-hexylamine was increased, the change in the mobility with respect to each addition concentration is as shown in the following table, and no abrupt change was observed by the addition. It was

[0074]

[Table 8]

Example 9 In a 200 ml round bottom flask, 2.5 g of EVA (ethylene-vinyl acetate copolymer, Mitsui DuPont Chemical Co., Ltd. Evaflex 250) and 250 mg of spiculisporic acid diethyl ester were added and dispersed, BBP (barium petronate, Witco) as charge control agent
Chemical) 256 mg, and tetrahydrofuran 100 ml as a solvent was added. The mixture was heated and stirred in an oil bath at 90 ° C for 1 hour. In a separate container, use Mon as the cyan pigment.
2.5 g of asusual Blue FBR (metal phthalocyanine pigment manufactured by ICI) was added to 10 parts of tetrahydrofuran.
Dispersed in 0 ml. This was put at once into a round-bottomed flask that had been previously dissolved, and further stirred and mixed at 90 ° C. for 1 hour to obtain a pigment-dispersed resin solution. The pigment-dispersed resin solution was allowed to stand at room temperature, lowered to about 60 ° C., and then cooled to −5 ° C. Isope
The mixture was dispersed and mixed in 100 ml of r G using an ultrasonic homogenizer. This wet developer is the same Isope
The print density was adjusted to 1% using r G.

Printing and other evaluations were performed in the same manner as in Example 1. The developing property showed positive polarity. Initial current value 49
1 nA, current value after 60 seconds 262 nA, Q / m = 83.5
It was μC / g. The zeta potential value was 34.1 mV and the dispersion stability was good. In the development test at 10 m / min or more, complete solid printing was formed and image deletion did not occur. Furthermore, the film-forming properties were good and no cracking occurred even after drying. Mobility is 9.31 × 10 ^-11 m ² / sec ・ V
Met. It was possible to increase the mobility more effectively and prevent image deletion than when the same concentration of diethyl spiculisporate was present as an external additive in the dispersion liquid of the developer.

Example 10 A wet developer was prepared in the same manner as in Example 9 except that spiculisporic acid diethyl ester in Example 9 was replaced with spiculisporic acid 1-n-hexylamine. The printing and other evaluations were the same as in Example 1.

The developing characteristics showed positive polarity. Initial current value 2
93 nA, current value 108 nA after 60 seconds, Q / m = 35.
It was 5 μC / g. The zeta potential value was 39.7 mV and the dispersion stability was good. A perfect solid print could be formed in the development test at 10 m / min. However, in the development test of 20 m / min, perfect solid printing was not formed and image deletion occurred. However, in terms of film formation characteristics, cracks occurred after being naturally dried at room temperature.

The mobility is 8.13 × 10 ^-11 m ² /sec.V
Met. It was possible to effectively increase the mobility and prevent image deletion compared with the case where 1-n-hexylamine spiculisporate of the same concentration was added as an external additive to the dispersion liquid of the wet developer.

Example 11 A wet developer was prepared in the same manner as in Example 1 except that 250 mg of spiculisporic anhydride was used instead of spiculisporic acid diethyl ester of Example 9.

The printing and other evaluations were the same as in Example 1. The development characteristics showed positive polarity. Initial current value 293n
A, current value after 60 seconds 108 nA, Q / m = 35.5 μC
/ G. The zeta potential value was 39.7 mV and the dispersion stability was good.

A perfect solid print could be formed in the development test at 10 m / min. However, in the development test of 20 m / min, complete solid printing was not formed and image deletion occurred. The film forming characteristics were good, and no cracks were formed even after drying. The mobility was 0.38 × 10 ^-11 m ² / sec · V.

In this case, the mobility could not be increased more effectively than in the case where spiculisporic anhydride of the same concentration was present as an external additive in the wet developer, but image deletion was prevented. It was possible to obtain an image with high gloss by visual comparison.

However, when this wet type developer was stored at room temperature for a long period of one month, it was presumed that the acid cleavage of the anhydride had an effect, but the particles aggregated and the dispersion stability was poor. In this state, the zeta potential value was measured and found to be 1.5 mV. The rapid decrease in the zeta potential value confirmed the poor dispersion stability.

Example 12 A wet developer was prepared in the same manner as in Example 9 except that 250 mg of monosodium spiculisporate was used in place of the diethyl spiculisporate of Example 9. The printing and other evaluations were the same as in Example 1.

The developing characteristics showed positive polarity. Initial current value 5
19 nA, current value 224 nA after 60 seconds, Q / m = 116
It was μC / g. The zeta potential value was 31.2 mV and the dispersion stability was good. A perfect solid print could be formed in the development test at 10 m / min. But 2
In the development test of 0 m / min, complete solid printing was not formed, and image deletion occurred.

The film forming characteristics were good, and no cracks were formed even after drying. Mobility is 3.38 × 10 ^-11 m ² / sec ・ V
Met. The mobility was almost the same as when the monosodium spiculisporate of the same concentration was added as an external additive to the wet developer, and it was impossible to increase the mobility. However, it was possible to prevent image deletion and obtain an image with high gloss by visual comparison.

Comparative Example 1 2.5 g of EVA (ethylene-vinyl acetate copolymer, Evaflex 250, Mitsui DuPont Polychemical Co., Ltd.) in a 200 ml round bottom flask, and BBP (barium petronate, Witco Ch) as a charge control agent.
256 mg (made by electronic Corp) and 100 ml of tetrahydrofuran as a solvent were added. 150 ° C under oil bath
The mixture was heated and stirred for 1 hour. In a separate container, as a cyan pigment, Monaural Blue FBR (ICI
2.5 g of a metal phthalocyanine pigment manufactured by Co., Ltd. was dispersed in 100 ml of tetrahydrofuran. This was put into the previously dissolved flask at once, and further stirred and mixed at 110 ° C. for 1 hour to obtain a pigment dispersion resin solution. The pigment-dispersed resin solution was allowed to stand at room temperature, lowered to about 60 ° C., and then dispersed and mixed in 100 ml of Isoper G cooled to −5 ° C. while using an ultrasonic homogenizer. The wet developer was adjusted to a print density of 1% with the same Isoper G.

The printing and other evaluations were the same as in Example 1. The development characteristics showed positive polarity. Initial current value 9,080
nA, current value after 60 seconds 5,106 nA, Q / m = 37
It was 5 μC / g. However, in this case, in the development test of 10 m / min, perfect solid printing was not formed and image deletion occurred.

Comparative Example 2 2.5 g of EVA (ethylene-vinyl acetate copolymer, Evaflex 250 manufactured by Mitsui DuPont Polychemical Co., Ltd.) and 100 ml of tetrahydrofuran as a solvent were placed in a 200 ml round bottom flask. 150 ° C under oil bath
The mixture was heated and stirred for 1 hour. In a separate container, as a cyan pigment, Monaural Blue FBR (ICI
2.5 mg of metal phthalocyanine pigment manufactured by Co., Ltd. and poly-
90 mg of 12-hydroxystearic acid methyl ester trimer (made by Ito Oil Co., Ltd.) was added to tetrahydrofuran 1
It was dispersed in 00 ml. This was put into the previously reacted flask all at once and further stirred and mixed at 110 ° C. for 1 hour to obtain a pigment dispersion resin solution.

The temperature of the pigment-dispersed resin solution was lowered to about 60 ° C. at room temperature and then cooled to −5 ° C. to obtain Isoper G 10
The mixture was dispersed and mixed in 0 ml using an ultrasonic homogenizer. The wet developer was adjusted to a print density of 0.5% with the same Isoper G.

The printing and other evaluations were the same as in Example 1. The development characteristics showed positive polarity. Initial current value 450n
A, current value after 60 seconds 138 nA, Q / m = 25 μC /
It was g. A perfect solid print could be formed in the development test at 10 m / min. However, in the development test of 20 m / min, complete solid printing was not formed and image deletion occurred.

Comparative Example 3 A wet type developer was manufactured in the same manner as in Example 9 except that the charge control agent BBP was not used. The printing and other evaluations were the same as in Example 1. The development characteristics showed positive polarity. Initial current value 100nA, current value 58nA after 60 seconds, Q / m
= 25 μC / g. In the development test of 10 m / min, perfect solid printing could not be performed.

[0094]

The olefin resin having a carboxyl group or an ester group alone, or the resin raw material solution of the olefin resin particles having a carboxyl group or an ester group having a colorant added, contains spiculisporic acid or a derivative thereof. , Granulated resin particles, or since spiculisporic acid or a derivative thereof is present in the developer in which the granulated resin particles are dispersed, the dispersion stability of the resin particles and the mobility of the resin particles increase, It is possible to prevent image deletion and form an image with good gloss.

[Brief description of drawings]

FIG. 1 is a diagram illustrating a particle size distribution of resin particles of Example 1.

FIG. 2 is a diagram illustrating a particle size distribution immediately after production of resin particles of Example 2.

FIG. 3 is a diagram illustrating a particle size distribution of the resin particles of Example 2 after being left for one month.

FIG. 4 is a diagram illustrating a particle size distribution immediately after the production of resin particles of Example 5.

FIG. 5 is a diagram illustrating a particle size distribution of the resin particles of Example 5 after being left for one month.

FIG. 6 is a diagram illustrating a particle size distribution of resin particles of Example 8 immediately after production.

FIG. 7 is a diagram illustrating the particle size distribution of the resin particles of Example 8 after being left for one month.

Claims (3)

[Claims] 1. A wet toner comprising an olefin resin 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 colorant is added, and most of liquid aliphatic hydrocarbons, 3-1 with hydroxycarboxylic acid as monomer
A wet toner characterized in that spiculisporic acid or a derivative thereof is present in a resin particle or a dispersion liquid of a resin particle, in addition to the presence of a 0-mer polyhydroxycarboxylic acid ester and a charge control agent. 2. A resin obtained by heating and dissolving an olefin resin particle having a carboxyl group or an ester group alone, or an olefin resin having a carboxyl group or an ester group, to which a colorant is added, in a solvent having a high temperature dependence of solubility. After being made into a solution, the resin solution is charged into a liquid aliphatic hydrocarbon in the presence of a 3- to 10-mer polyhydroxycarboxylic acid ester having a hydroxycarboxylic acid ester as a monomer and a charge control agent, and the resin is cooled. A method for producing a wet toner, which comprises depositing particles and substituting a solvent with an aliphatic hydrocarbon, and then adding spiculisporic acid and its derivative into a liquid hydrocarbon. 3. An olefin resin particle having a carboxyl group or an ester group alone or an olefin resin having a carboxyl group or an ester group, to which a colorant is added, together with spiculisporic acid or a derivative thereof has a high temperature dependence of solubility. In a liquid aliphatic hydrocarbon in the presence of a 3- to 10-mer polyhydroxycarboxylic acid ester having a hydroxycarboxylic acid ester as a monomer and a charge control agent, after the resin solution is dissolved by heating in a solvent. , And cooled to precipitate the resin particles,
A method for producing a wet toner, wherein the solvent is replaced with an aliphatic hydrocarbon.