JP5429609B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to a toner and a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and an image forming apparatus.

In recent years, market demands for energy saving and high speed are increasing for image forming apparatuses such as printers, copiers, and facsimiles. As a result, toners for electrophotography (hereinafter sometimes simply referred to as “toners”) are also required to have excellent low-temperature fixability, while being resistant to offset and heat-resistant storage (blocking resistance). There is a need for a toner having characteristics that are contrary to low-temperature fixability, such as contamination resistance to a developing roller.
In response to such demands, a toner containing a linear polyester resin with specified physical properties such as molecular weight (Patent Document 1), a toner containing a non-linear cross-linked polyester resin using rosins as an acid component (Patent Document 1) 2) Toner with improved fixability using rosin modified with maleic acid (Patent Document 3), polyester composed of alcohol component and carboxylic acid component containing (meth) acrylic acid modified rosin as binder resin The toner used (Patent Documents 4 and 5) has been proposed. Further, a method of blending a low molecular weight resin and a high molecular weight resin has been proposed (Patent Document 6).

On the other hand, in recent years, the field of print on demand (POD) has grown, and the demand for toner from the printing market has become even higher. POD utilizing the electrophotographic method is good at printing a small number of copies and variable printing, and is expected as an alternative to light printing. However, because there is a need for an ultra-high-speed system that is faster than the printing speed of conventional high-speed copiers and a wide range of paper types, toner with less fouling on developing rollers, etc. Was newly demanded.

In the field of print on demand (POD) utilizing the electrophotographic method, ultra-high-speed systems that are faster than the printing speed of conventional high-speed copying machines and a wide range of paper types are required. A toner having poor pulverizability and low productivity, such as a toner containing a linear polyester resin that defines physical properties such as molecular weight in Document 1, is not preferable. The rosins used in Patent Documents 2 and 3 are effective in improving the low-temperature fixability, but have a drawback that odor is likely to be generated depending on the type of rosins. Furthermore, the toner using the alcohol component of Patent Documents 4 and 5 and the polyester comprising the carboxylic acid component carboxylic acid component containing the (meth) acrylic acid-modified rosin as the binder resin has a wide range of images from conventional low speed machines to high speed machines. Excellent fixing performance can be demonstrated for forming devices, but in ultra-high-speed systems, compatibility between low-temperature fixability and contamination of carriers, developing rollers, etc. is a problem, as in the print on demand (POD) field described above. It could not meet new demands.

Conventional dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are those obtained by melt-kneading a toner binder such as a styrene resin and a polyester resin together with a colorant and finely pulverizing them, so-called pulverized toner. Is widely used. The pulverized toner not only consumes a lot of energy for melt-kneading and pulverization, but also has a process of selecting particles with an appropriate particle size, such as classification, because the particle size distribution after pulverization is wide. It will decrease. In addition, due to the recent demand for low-temperature fixability due to higher speed and energy saving, lowering the softening point of the resin and lowering productivity due to over-pulverization in the pulverization process has become an issue.

In the pulverized toner, internal additives such as a colorant, a charge control agent, and a release agent are melt-kneaded and dispersed in a binder resin (Patent Documents 7 and 8). However, in such a pulverization method, it is easy to pulverize at the interface between the internal additive and the binder resin at the time of pulverization, and it is difficult to obtain uniformity between individual toner particles and one toner particle surface. But it has the disadvantage of being prone to problems. Further, even if classification is performed, the toner particle size distribution is wide, so that the image quality is changed by repeated development. This is because there is a toner particle size that is easy to develop in the development process. In two-component development using a carrier, a large toner is easily developed. Therefore, when development is repeated, the toner in the developer becomes small and the image density decreases. It becomes a trend. In one-component development, a small toner is easily developed. Therefore, when the development is repeated, the toner in the developer becomes large and the dot reproducibility and gradation tend to be lowered.
Along with the improvement of these drawbacks, in recent years, there has been a demand for a production method that has a narrow toner particle size distribution, uniform toner particle surface, energy saving, and less environmental pollution, due to the recent demand for reducing environmental load.

In recent years, so-called polymerized toners such as a suspension polymerization method, an emulsion polymerization aggregation method, and a polymer dissolution suspension polymerization method have been studied.
Although these polymerized toners have the advantages that the uniformity of the toner particle surface can be easily obtained and the particle size distribution can be narrowed compared with the pulverized toner, the toner is used in order to use the dispersant in the aqueous medium. Dispersant that impairs the charging characteristics of the toner remains on the toner surface and the environmental stability of the charge amount is liable to occur, and a very large amount of washing water is required to remove this dispersant as much as possible. Is known and is not necessarily a satisfactory production method in terms of environmental impact.

As an alternative toner manufacturing method, a so-called spray-drying method in which a toner composition liquid is formed into droplets in a gas phase without using water and then solidified has been proposed, but has a drawback of wide particle size distribution.
As an attempt to make the toner composition liquid droplets in the gas phase and narrow the particle size distribution, a method has been proposed in which fine droplets are formed using piezoelectric pulses, which are then dried and solidified to become toner (patent) Reference 9). Furthermore, a method has also been proposed in which fine droplets are formed by using thermal expansion in the nozzle, and this is dried and solidified into a toner (Patent Document 10). Furthermore, a method of performing the same processing using an acoustic lens has been proposed (Patent Document 11). However, in these methods, ejection is performed due to the change in the volume of the nozzle composition or the volume of the toner composition liquid in the nozzle. It is difficult, and since the pressure pulse concentrates locally in the toner composition liquid storage part, there are problems that a plurality of nozzles cannot be provided, the number of droplets that can be ejected per unit time is small, and productivity is poor. At the same time, the spread of the particle size distribution due to coalescence of the droplets is unavoidable, and it is not satisfactory in terms of monodispersibility.

Further, the toner obtained by this method becomes spherical due to the surface tension of the toner composition liquid, and it is very difficult to clean the toner that has not been transferred from the electrostatic latent image carrier with a blade. There are challenges.

Further, the present applicant has proposed a toner manufacturing method in which the entire toner composition liquid reservoir is vibrated and the toner composition liquid is discharged from the through hole of the reservoir (Patent Document 12). However, in this method, since the toner composition liquid discharged from the through hole forms a liquid column, the particle size distribution cannot be sufficiently narrowed, and a method of discharging from a nozzle oscillated at a constant frequency is proposed (Patent Document) 13 and 14).

An object of the present invention is to solve various problems in the prior art and achieve the following objects. In other words, the present invention achieves both low-temperature fixability, offset resistance, and heat-resistant storage stability at a level that can be applied to ultra-high speed systems, and is much more stable in charge rise and environmental fluctuation than conventional toners. An object of the present invention is to provide a toner, a developer, and an image forming apparatus that are excellent, have a uniform charge on the surface of toner particles, can stably obtain a high-quality image, and have excellent blade cleaning properties. . Furthermore, these effects can be further improved by making the particle size distribution of the toner very sharp.

The present invention is solved by the following (1) to ( 7 ).
(1) From a plurality of nozzles having the same opening diameter formed in a thin film provided in a storage portion for storing the toner composition liquid, the toner composition liquid is periodically discharged into the gas phase by mechanical vibration means to form droplets. A method for producing a toner , comprising: a periodic droplet forming step, and a particle forming step for solidifying the dropletized toner composition liquid ,
The toner composition liquid is obtained by dissolving and / or dispersing a toner composition containing at least a binder resin, a colorant, and a release agent in an organic solvent, and the binder resin is modified with an alcohol component. A polyester resin obtained by condensation polymerization with a carboxylic acid component containing a purified rosin,
The mechanical vibration means is a vibration means having a vibration surface parallel to the thin film, and the vibration surface vibrates vertically in the vertical direction, and the periodic droplet forming step is performed by the mechanical vibration means. A method for producing a toner, wherein the toner composition liquid is periodically discharged into a gas phase from a plurality of nozzles having the same opening diameter formed in the thin film by utilizing a liquid resonance phenomenon. .
( 2 ) The toner manufacturing method as described in (1) above, wherein the mechanical vibration means is a horn type vibrator.
(3) The toner production method according to (1) or (2), wherein the toner composition liquid contains a polycondensate obtained by a polycondensation reaction of phenols and aldehydes.
(4) The polyester resin is obtained by polycondensation of an alcohol component containing 65 mol% or more of 1,2-propanediol in a divalent alcohol component and a carboxylic acid component containing a modified purified rosin. The method for producing a toner according to any one of (1) to (3).
(5) The toner according to any one of (1) to (4), wherein the modified purified rosin is modified with at least one of acrylic acid, fumaric acid, and maleic acid.
(6) The method for producing a toner according to (5), wherein the toner composition liquid has a solid content of 5% by mass to 15% by mass.
(7) The method for producing a toner according to any one of (1) to (6), wherein the circularity is in a range of 0.94 to 0.98 .

The present invention achieves both low-temperature fixability, offset resistance, and heat-resistant storage stability at a level that can be applied to ultra-high speed systems. It is possible to provide a toner, a developer, and an image forming apparatus in which charging is uniform and a high-quality image can be stably obtained, and excellent blade cleaning properties can be obtained.

FIG. 3 is a schematic configuration diagram illustrating an example of a toner manufacturing apparatus according to the present invention. FIG. 6 is an enlarged explanatory diagram for explaining a droplet ejecting unit of the toner manufacturing apparatus. It is bottom explanatory drawing which looked at FIG. 2 from the lower side. It is a typical explanatory view showing an example of a step type horn type vibrator constituting the vibration generating means of the liquid droplet ejecting unit. It is a typical explanatory view showing an example of an exponential horn type vibrator constituting the vibration generating means of the liquid droplet ejecting unit. It is a typical explanatory view showing an example of a conical horn type vibrator constituting the vibration generating means of the liquid droplet ejecting unit. FIG. 6 is an enlarged explanatory diagram for explaining another example of the droplet ejecting unit of the toner manufacturing apparatus. FIG. 10 is an enlarged explanatory view for explaining still another example of the droplet ejecting unit of the toner manufacturing apparatus. FIG. 10 is an enlarged explanatory view for explaining still another example of the droplet ejecting unit of the toner manufacturing apparatus. FIG. 10 is an explanatory diagram for explaining an example in which a plurality of droplet ejecting units of FIG. 9 are arranged. 1 is a schematic configuration diagram illustrating an embodiment of a toner manufacturing apparatus according to the present invention. FIG. 6 is an enlarged explanatory diagram for explaining a droplet ejecting unit of the toner manufacturing apparatus. It is bottom face explanatory drawing which looked at FIG. 13 from the lower side. It is expansion sectional explanatory drawing of the droplet formation means of the droplet ejection unit. It is expansion sectional explanatory drawing of the droplet formation means which concerns on a comparative example structure. FIG. 3 is a main part explanatory diagram for explaining a specific application of the toner manufacturing apparatus. It is a typical explanatory view of a thin film used for explanation of an operation principle of droplet formation by the droplet ejection unit. It is explanatory drawing similarly used for description of a fundamental vibration mode. It is explanatory drawing similarly used for description of secondary vibration mode. It is explanatory drawing similarly used for description of a tertiary vibration mode. It is explanatory drawing at the time of forming a convex part in the center part of a thin film similarly. 1 is a schematic configuration diagram showing an embodiment of an image forming apparatus of the present invention. It is a schematic block diagram which shows embodiment of the other example of the image forming apparatus of this invention. It is a schematic block diagram which shows embodiment of the other example of the image forming apparatus of this invention. FIG. 26 is a schematic configuration diagram illustrating an image forming unit of the image forming apparatus in FIG. 25. It is a schematic block diagram which shows one Embodiment of the process cartridge of this invention. 1 is a schematic configuration diagram illustrating an example of a liquid resonance type toner manufacturing apparatus according to the present invention. FIG. 28 is an enlarged explanatory diagram for explaining a droplet ejecting unit of the toner manufacturing apparatus of FIG. 27. It is explanatory drawing of the method of making the cross-sectional shape of the nozzle in the manufacturing apparatus of the liquid resonance type toner which concerns on this invention into a two-stage type.

Hereinafter, the present invention will be described in more detail.

(toner)
The toner of the present invention contains at least a binder resin, a release agent, and a colorant, and further contains a charge control agent, an external additive, and, if necessary, other components.

(Binder resin)
The binder resin is a polyester resin obtained by polycondensation of an alcohol component and a carboxylic acid component, preferably in the presence of an esterification catalyst.

-Carboxylic acid component-
It has a great feature in that a purified rosin modified in the carboxylic acid component is contained. By using a modified purified rosin, fixing can be performed at an extremely low temperature, and storage stability is improved. The modified purified rosin is preferably acrylic acid, fumaric acid, and maleic acid.
Since acrylic acid-modified rosin is a rosin having two functional groups, it can extend the molecular chain as part of the main chain of the polyester and increase the molecular weight. On the other hand, a low molecular weight component having a molecular weight of 500 or less, that is, a residual monomer Since the components and oligomer components are reduced, it is presumed that there is a surprising effect that it is possible to achieve both contradictory properties such as low-temperature fixability, offset resistance and storage stability.
Fumaric acid-modified rosin has extremely high glass transition temperature (Tg) compared to conventional rosin, so low molecular weight components are reduced, and conflicting properties such as low-temperature fixability, offset resistance and storage stability. It is presumed that there is an unexpected and surprising effect that it is possible to achieve both.
The maleic acid-modified rosin modified with maleic acid functions as a cross-linking agent because it has three functional groups. It is estimated that there is an effect.

-Alcohol component-
A branched-chain alcohol having 3 carbon atoms used for the aliphatic alcohol component is preferred. In particular, 1,2-propanediol, which is a branched chain alcohol having 3 carbon atoms, is effective for improving low-temperature fixability while maintaining offset resistance as compared with alcohol having 2 carbon atoms or less. Compared with branched chain alcohols with 4 or more carbon atoms, it is effective in preventing deterioration of storage stability due to a decrease in glass transition temperature, and can be fixed at an extremely low temperature. Can be compatible. In particular, when the content of 1,2-propanediol is 65 mol% or more in the divalent alcohol component, excellent low-temperature fixability and offset resistance are exhibited.
As the alcohol component, an alcohol other than 1,2-propanediol may be contained as long as the object and the effect of the present invention are not impaired, but the content of 1,2-propanediol is 2 It is 65 mol% or more in the valence alcohol component, 70 mol% or more is preferable, 80 mol% or more is more preferable, and 90 mol% or more is still more preferable.
Examples of the divalent alcohol component other than 1,2-propanediol include 1,3-propanediol, ethylene glycol having a different carbon number, hydrogenated bisphenol A, bisphenol F, or alkylene thereof (2 to 4 carbon atoms). Aliphatic dialcohols such as oxide (average added mole number 1 to 16) adducts and the like can be mentioned. The content of the divalent alcohol component is preferably 60 mol% to 95 mol%, more preferably 65 mol% to 90 mol% in the alcohol component.

From the viewpoint of offset resistance, it is preferable that 1,3-propanediol is contained. The molar ratio of 1,2-propanediol to 1,3-propanediol (1,2-propanediol / 1,3-propanediol) in the alcohol component of the polyester resin is preferably 99/1 to 65/35. 95/3 to 70/30 is more preferable, and 95/3 to 75/25 is still more preferable.
Further, when a trivalent or higher valent alcohol component is contained in the alcohol component, the effect of improving the hot offset resistance is improved. The content of the trihydric or higher alcohol component is preferably 20 mol% or less, more preferably 5 mol% to 30 mol% in the total amount of alcohol components. Examples of the trihydric or higher polyhydric alcohol component include glycerin, pentaerythritol, trimethylolpropane, sorbitol, or an alkylene (2 to 4 carbon) oxide (average added mole number 1 to 16) adduct thereof. In particular, glycerin is preferable because it does not inhibit low-temperature fixability.
Examples of the alcohol component include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane. Aromatic alcohols such as alkylene oxide adducts of bisphenol A may be contained, but those consisting only of aliphatic alcohols are preferred. Here, in the present invention, the “alcohol component consisting essentially of an aliphatic alcohol” means that the content of the aliphatic alcohol is 90 mol% or more in the alcohol component.

-Esterification catalyst-
The polycondensation of the alcohol component and the carboxylic acid component of the polyester resin is preferably performed in the presence of an esterification catalyst.
Examples of the esterification catalyst include Lewis acids such as p-toluenesulfonic acid, titanium compounds, tin (II) compounds having no Sn-C bond, and these are used alone or in combination. Used. In the present invention, a titanium compound and / or a tin (II) compound having no Sn—C bond is preferable.
As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group, or an acyloxy group is more preferable.
As the titanium compounds such as titanium diisopropylate bistriethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 3 H 7 O) 2 ], titanium diisopropylate bis diethanol aminate [Ti _(C 4 H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diethylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₁ (C ₃ H ₇ O) ₃ ], titanium monopropylate tris (triethanolaminate) [ Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ O) ₁ ] and the like, among these, titanium diisopropylate bistriethanolamate, titanium diisopropylate bisdiethanolamate and titanium dipentylate Bistriethanolamate is preferred, and these are also available as, for example, commercial products of Matsumoto Kosho Co., Ltd.
Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H _{37 O) 4],} tetra myristyl titanate _{[Ti (C 14 H 29 O)} 4 ], tetraoctyl titanate _{[Ti (C 8 H 17 O)} 4 ], dioctyl-dihydroxy-octyl titanate _[Ti (C _{8 H 17} O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate and dioctyl dihydroxyoctyl titanate are preferable. These can be obtained, for example, by reacting a titanium halide with a corresponding alcohol, or can be obtained as a commercial product such as Nisso.
The abundance of the titanium compound is preferably 0.01 parts by mass to 1.0 part by mass and more preferably 0.1 parts by mass to 0.7 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. preferable.
Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Is preferable, and a tin (II) compound having a Sn-O bond is more preferable.
Examples of the tin (II) compound having a Sn-O bond include tin (II) oxalate, tin (II) diacetate, tin (II) dioctanoate, tin (II) dilaurate, and tin (II) distearate. Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms, such as tin (II) dioleate; dioctyloxytin (II), dilauroxytin (II), distearoxytin (II), dioleoxytin (II) Dialkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms, such as tin (II) oxide, tin (II) sulfate, etc., tin (II) Examples of the compound include tin (II) halides such as tin (II) chloride and tin (II) bromide, and among these, (R ₁ COO) from the standpoint of charge rising effect and catalytic ability. ₂ Sn (wherein _{R 1} is alkyl or alkenyl of 5-19 carbon atoms Fatty acid tin represented by indicating the Le group) _(II), (R _{2 O)} dialkoxy tin represented by 2 Sn (wherein _{R 2} represents an alkyl or alkenyl group having 6 to 20 carbon atoms) ( II) and tin oxide (II) represented by SnO are preferred, fatty acid tin (II) and tin oxide (II) represented by (R ₁ COO) ₂ Sn are more preferred, tin (II) dioctanoate, distearin Even more preferred are tin (II) acid and tin (II) oxide.
The abundance of the tin (II) compound is preferably 0.01 parts by mass to 1.0 part by mass, and 0.1 parts by mass to 0.00 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 7 parts by mass is more preferable.
When the titanium compound and the tin (II) compound are used in combination, the total amount of the titanium compound and the tin (II) compound is 0.01 parts by mass to 1. 0 mass part is preferable and 0.1 mass part-0.7 mass part are more preferable.
The condensation polymerization of the alcohol component and the carboxylic acid component can be performed, for example, at a temperature of 180 ° C. to 250 ° C. in an inert gas atmosphere in the presence of the esterification catalyst.

(Release agent)
In the present invention, waxes can be included as a release agent for the purpose of preventing offset during fixing.
The waxes are not particularly limited and can be appropriately selected and used as those usually used as a toner release agent. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, Aliphatic hydrocarbon waxes such as paraffin wax and sazol wax, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof, candelilla wax, carnauba wax, wood wax, jojoba wax, etc. Plant waxes, animal waxes such as beeswax, lanolin and spermaceti, mineral waxes such as ozokerite, ceresin and petrolatum, and waxes based on fatty acid esters such as montanic ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.
Examples of the waxes further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, and linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinaline. Unsaturated fatty acids such as acids, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, saturated alcohols such as long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefins Fatty acid amides such as acid amides, lauric acid amides, methylene biscapric acid amides, ethylene bis lauric acid amides, saturated fatty acid bisamides such as hexamethylene bis stearic acid amides, ethylene bis oleic acid amides, hexamethylene vinyl Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted onto aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid. Examples thereof include waxes, partial ester compounds of polyhydric alcohols such as behenic acid monoglycerides, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.
More preferable examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and hydrocarbons having functional groups Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.
In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.
The melting point of the wax is preferably 60 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance blocking resistance and offset resistance. If it is less than 60 degreeC, blocking resistance may fall, and if it exceeds 140 degreeC, an offset-resistant effect may become difficult to express.
In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax.
The wax or toner DSC measuring device is preferably measured with a high-precision internal heat input compensation type differential scanning calorimeter. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after raising and lowering the temperature once and taking a previous history.
In the present invention, the addition amount of the release agent is preferably 1 to 30% by mass, and more preferably 2 to 20% by mass with respect to the toner.

(Coloring agent)
There is no restriction | limiting in particular as said coloring agent, Although the coloring agent used normally can be selected suitably and can be used, For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu , Permanent red 4R, para red, Yisei Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lakes, malachite green lakes, phthalocyanine greens, anthraquinone greens, titanium oxides, zinc whites, litbons, and mixtures thereof.
The content of the colorant is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass with respect to the toner.
The colorant used in the present invention can also be used as a master batch combined with a resin. The binder resin kneaded with the master batch includes polyester resin, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and substituted polymers thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate Copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, Styrene-vinyl Styrene copolymers such as tilketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Combined; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin Aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant with a high shear force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 2-30 mass parts is preferable with respect to 100 mass parts of binder resin.
The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100 mgKOH / g, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less, the amine value Is more preferably 10 to 50 mg KOH / g, and the colorant is dispersed and used. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. Further, when the amine value is less than 1 mgKOH / g and when the amine value exceeds 100 mgKOH / g, the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.
The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). , “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.
The mass average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene in gel permeation chromatography, and is preferably 500 to 100,000, and from the viewpoint of pigment dispersibility, 3,000 to 100 1,000 is more preferable. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.
The addition amount of the dispersant is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 50 parts by mass, the chargeability may be lowered.

(Charge control agent)
The toner of the present invention uses a negatively chargeable charge control agent containing a polycondensate obtained by a polycondensation reaction of phenols and aldehydes as a charge control agent.
The phenols are a group consisting of p-alkylphenol, p-aralkylphenol, p-phenylphenol, and p-hydroxybenzoic acid ester having one phenolic hydroxyl group and hydrogen bonded to the ortho position of the hydroxyl group. It contains at least one selected phenol compound, and as the aldehydes, aldehydes such as paraformaldehyde, formaldehyde, paraaldehyde, and furfural can be appropriately used.
Examples of the charge control agent that is commercially available include a charge control agent (Fujikura Kasei Co., Ltd.) containing an FCA-N type condensation polymer.
As a reaction method, for example, phenols and aldehydes are added in an organic solvent such as xylene, and in the presence of a strong base such as a hydroxide of an alkali metal or an alkaline earth metal, the boiling point of the solvent, Preferably, a polycondensation reaction is performed for 3 to 20 hours while distilling off water at a temperature from 100 ° C. to the boiling point of the solvent, followed by recrystallization using a poor solvent such as alcohol, or after drying the organic solvent under reduced pressure. And a method of washing with an alcohol such as methanol, ethanol, or isopropanol. As the strong base, sodium hydroxide, rubidium hydroxide, potassium hydroxide and the like can be preferably used.
The polycondensate obtained by the polycondensation reaction of phenols and aldehydes is obtained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner composition to obtain excellent chargeability and non-sphericalization. Can do. If the content is more than 5 parts by mass, the fixability may be lowered.
In addition, you may use a conventionally well-known charge control agent together as needed.
For example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt, alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, Fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, and the like. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E- of salicylic acid metal complex 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

(Toner composition liquid and solvent)
A toner composition liquid can be obtained by dissolving or dispersing a toner composition such as a binder resin, a colorant, and a charge control agent in an organic solvent. An organic solvent is selected that is used when a toner composition liquid is formed into droplets in a gas phase and dried to produce a toner, dissolves the binder resin, allows the dispersion to be stably dispersed, and can be easily dried.
As the organic solvent, for example, ethers, ketones, esters, hydrocarbons, and alcohols are preferably used, and tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), ethyl acetate, and toluene are particularly preferably used. These may be used alone or in combination.
In preparing the toner composition liquid, it is important to use a homomixer or a bead mill to make the dispersion such as the colorant and the release agent sufficiently fine with respect to the nozzle opening diameter in order to prevent clogging of the nozzle. Become.
The solid content of the toner composition liquid is preferably 5 to 40% by mass. When the solid content is less than 5% by mass, not only the productivity is lowered, but also the dispersion such as the colorant, the release agent fine particles, and the magnetic material is liable to cause sedimentation and aggregation, so that the composition of each toner particle is not uniform. The toner quality is likely to deteriorate. If the solid content exceeds 40% by mass, a toner having a small particle size may not be obtained.

(External additive)
The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include silica fine particles, hydrophobic silica, and fatty acid metal salts (for example, zinc stearate, aluminum stearate). Metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, and the like. Among these, hydrophobized silica fine particles, hydrophobized titania fine particles, hydrophobized titanium oxide fine particles, and hydrophobized alumina fine particles are preferable.
Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Japan) Aerosil Co., Ltd.). Further, as the titania fine particles, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), Examples include MT-150W, MT-500B, MT-600B, and MT-150A (all manufactured by Teika Corporation). Among these, as hydrophobized titanium oxide fine particles, T-805 (made by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both made by Titanium Industry Co., Ltd.); TAF-500T, TAF -1500T (all manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

In order to obtain the hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles, the hydrophilic fine particles are methyltrimethoxysilane, methyltriethoxysilane. It can be obtained by treatment with a silane coupling agent such as octyltrimethoxysilane. Further, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
The amount of the external additive added is preferably 0.1% by mass to 5% by mass and more preferably 0.3% by mass to 3% by mass with respect to the toner. The average particle size of the primary particles of the inorganic fine particles is preferably 100 nm or less, and more preferably 3 nm to 70 nm. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. If it is larger than this range, the surface of the electrostatic latent image carrier is undesirably damaged. As the external additive, inorganic fine particles and hydrophobized inorganic particles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, particularly at least 5 nm to 70 nm inorganic fine particles. It is more preferable to include two types. Further, it is more preferable that at least two types of inorganic fine particles having an average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment and at least one type of inorganic fine particles of 30 nm or more are included. In addition, the specific surface area by BET method ^is preferably 20m ² / g~500m 2 / g.

Examples of the surface treatment agent for the external additive containing the fine oxide particles include silane coupling agents such as dialkyl dihalogenated silane, trialkyl halogenated silane, alkyl trihalogenated silane, and hexaalkyldisilazane, silylating agents, and fluorine. Examples thereof include silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and silicone varnishes.
Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin It is done. By using in combination with such resin fine particles, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01% by mass to 5% by mass, and more preferably 0.1% by mass to 2% by mass with respect to the toner.

(Other ingredients)
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, etc. are mentioned.
The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having an alkyl fluoride group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner to remove the developer after transfer remaining on the electrostatic latent image carrier or the intermediate transfer member. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as metal salts, polymethyl methacrylate fine particles, and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a mass average particle size of 0.01 μm to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

In the particle forming step in which the vibration plane parallel to the thin film in the present invention is longitudinally vibrated in the vertical direction, the solid content of the toner composition liquid containing the toner composition can be reduced, and the solid content is reduced to a droplet. Since the organic solvent is removed from the dry film, the toner composition liquid is not deformed and becomes spherical, and the particle size distribution becomes sharp. Therefore, the solid content of the toner composition liquid is 5 mass% or more and 15 mass%. The following is preferable.

<Toner particle size and particle size distribution>
The smaller the toner particle size, the better the reproducibility of dots and fine lines, and a sharp and high-quality image can be obtained without roughness. However, if the toner particle size is too small, the apparent adhesion increases and developability and transfer are improved. In order to reduce the property, the weight average particle size is preferably 1 to 15 μm, more preferably 2 to 10 μm, and further preferably 3 to 8 μm.
The particle size distribution is represented by the ratio D4 / Dn between the weight average particle size (D4) and the number average particle size (Dn). D4 / Dn of the pulverized toner is about 1.2 to 1.4 in consideration of a decrease in productivity due to classification. Electrophotographic development methods are roughly classified into a one-component development method and a two-component development method, but since there is a particle size that is easy to develop in any of the development methods, the toner remaining in the developing device by repeated development Therefore, it is desirable that the particle size distribution is as narrow as possible. In order to obtain a very stable image even after repeated development, D4 / Dn is preferably 1.00 to 1.15, more preferably 1.00 to 1.10.

[Developer]
The toner of the present invention can be mixed with a carrier and used as a two-component developer. As the carrier, ordinary carriers such as ferrite and magnetite and resin-coated carriers can be used.
The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.
Examples of the resin used in the coating material include styrene-acrylic ester copolymers, styrene-acrylic resins such as styrene-methacrylic ester copolymers, acrylic ester copolymers, methacrylic ester copolymers, and the like. Preferable examples include fluorine-containing resins such as acrylic resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins. In addition to these, resins that can be used as a coating material for a carrier such as an ionomer resin and a polyphenylene sulfide resin can be used. These resins may be used alone or in combination of two or more.

A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.
In the resin-coated carrier, as a method for coating the surface of the carrier core with at least a resin coating agent, a method in which the resin is dissolved or suspended in a solvent and adhered to the applied carrier core, or a method in which the resin core is simply mixed in a powder state Is applicable.
The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass and more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.
Examples of use in which a magnetic material is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. Those treated with 12 parts by mass of the mixture, and (2) those treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.
Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable.
Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-2-ethylhexyl acrylate copolymer (copolymer mass ratio 10:90 to 90:10) and styrene A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50) is mentioned.
Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.

Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof.
The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.
The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the unevenness of the surface of the carrier and the amount of resin to be coated.
The carrier having a particle size of 4 to 200 μm can be used, preferably 10 to 150 μm, more preferably 20 to 100 μm. In particular, the resin-coated carrier preferably has a 50% particle size of 20 to 70 μm.
In the two-component developer, it is preferable to use 1 to 100 parts by mass of the toner of the present invention with respect to 100 parts by mass of the carrier, and 2 to 50 parts by mass of toner with respect to 100 parts by mass of the carrier. More preferred.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier, or a non-magnetic toner.

(Toner production method)
The conventional pulverization method and spraying method, which are toner manufacturing methods, and the vibration jetting method, which is the manufacturing method of the present invention, will be described.
<Crushing method>
This is a conventional method for producing toner, and the toner composition is melt-kneaded with a two-roll or twin-screw extruder, etc., and after cooling, coarsely pulverized, finely pulverized and classified, and if necessary In this method, external additives such as a fluidizing agent are mixed using a Henschel mixer. A known production apparatus such as a rotoplex or pulverizer can be used for coarse pulverization, a jet mill or a turbo mill can be used for fine pulverization, and an elbow jet or various air classifiers can be used for classification.

<Spraying method>
Single fluid nozzle (pressurized nozzle) sprayer that continuously pressurizes liquid and sprays from nozzle, multi-fluid spray nozzle sprayer that mixes and sprays liquid and compressed gas, centrifugal force of liquid using rotating disk In this method, the toner composition liquid is formed into droplets in a gas phase by using a rotating disk type sprayer or the like that forms droplets by the above method. Commercially available equipment can be used as a spray-drying system that performs spraying and drying at the same time, but if sufficient drying is not possible, secondary drying such as fluidized bed drying is performed, and if necessary, fluidizing agent etc. with a Henschel mixer etc. The external additive is mixed.

<Vibration injection method>
A method of granulating a thin film having a plurality of nozzles with the same opening diameter by mechanical vibration. The raw material is produced by a spray method (spray method) in which pressure is continuously applied, or by changing the volume of the raw material reservoir or the volume of the raw material. This is different from the method of extruding from the nozzle. Due to the vertical vibration of the thin film, the liquid protruding from the nozzle is forcibly separated and droplets are discharged. The thin film oscillates periodically (at equal intervals), so that droplets with a uniform particle size can be generated and the timing of droplet discharge is aligned, so that adhesion between droplets can be prevented, In this method, the droplets are dried to obtain toner particles. The mechanical vibration means may be arranged in any way as long as it vibrates in the direction perpendicular to the film having the nozzle. In the present invention, the following two systems are preferably used.
One is a mechanical means (mechanical longitudinal vibration means) having a vibration surface parallel to a thin film having a plurality of nozzles and longitudinally vibrating (vertically moving) in the vertical direction, via the toner composition liquid. The other is a method of vibrating the thin film, and the other is a thin film formed by a mechanical vibration means (annular mechanical vibration means) formed in an annular shape around a region where a thin film nozzle having a plurality of nozzles is provided. This is a method of vibrating.
Hereinafter, each method will be described.

(Mechanical longitudinal vibration means)
First, an example of a toner manufacturing apparatus provided with mechanical longitudinal vibration means will be described with reference to the schematic configuration diagram of FIG.
The toner manufacturing apparatus 1 periodically discharges a toner composition liquid from a plurality of nozzles having the same opening diameter, and a droplet ejecting unit 2 as a droplet forming unit in a periodic droplet forming process for forming droplets in a gas phase. The droplet jetting unit 2 is disposed above, and the droplets of the toner composition liquid droplets discharged from the droplet jetting unit 2 are solidified to form toner particles T in the particle forming step. A particle forming unit 3 as a means, a toner collecting unit 4 that collects toner particles T formed by the particle forming unit 3, and a toner particle T collected by the toner collecting unit 4 are passed through the tube 5. The toner storage unit 6 serving as a toner storage unit that stores the transferred toner particles T, the raw material storage unit 7 that stores the toner composition liquid 10, and the droplet ejection unit 2 from the raw material storage unit 7. Then, the toner composition liquid 10 is fed. A pipe (liquid feed pipe) 8, and a pump 9 for pumping supplying toner composition liquid 10, such as during operation.
In addition, the toner composition liquid 10 from the raw material container 7 is supplied to the droplet ejection unit 2 in a self-sufficient manner due to the droplet formation phenomenon by the droplet ejection unit 2. In particular, the pump 9 is used to supply the liquid.

Next, the droplet ejecting unit 2 will be described with reference to FIGS.
FIG. 2 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit 2, and FIG.
The droplet ejection unit 2 includes a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, mechanical vibration means (hereinafter referred to as “vibration means”) 13 that vibrates the thin film 12, and the thin film 12 and vibration means 13. And a flow path member 15 that forms a reservoir (liquid flow path) 14 for supplying the toner composition liquid 10 therebetween.
The thin film 12 having the plurality of nozzles 11 is disposed in parallel to the vibration surface 13a of the vibration means 13, and a flow path is formed by a resin binder material in which a part of the thin film 12 does not dissolve in the solder or the toner composition liquid. It is bonded and fixed to the member 15 and has a substantially vertical positional relationship with the vibration direction of the vibration means 13. A communication means 24 is provided so that a voltage signal is applied to the upper and lower surfaces of the vibration generating means 21 of the vibration means 13, and the signal from the drive signal generating source 23 can be converted into mechanical vibration. As a communication means for providing an electrical signal, a lead wire whose surface is insulated is suitable. In addition, it is suitable for efficient and stable toner production that the vibration means 13 uses elements having a large vibration amplitude such as various horn type vibrators and bolted Langevin type vibrators described later.

The vibration unit 13 includes a vibration generation unit 21 that generates vibrations and a vibration amplification unit 22 that amplifies the vibrations generated by the vibration generation unit 21. The drive unit (drive signal generation source) 23 drives a required frequency. When a voltage (drive signal) is applied between the electrodes 21 a and 21 b of the vibration generating means 21, vibration is excited in the vibration generating means 21, and this vibration is amplified by the vibration amplifying means 22 and arranged in parallel with the thin film 12. The vibrating surface 13a is periodically vibrated, and the thin film 12 is vibrated at a required frequency by the periodic pressure caused by the vibration of the vibrating surface 13a.
The vibrating means 13 is not particularly limited as long as it can give a certain longitudinal vibration (vertical movement) to the thin film 12 at a constant frequency, and can be appropriately selected and used. Therefore, the vibration generating means 21 is preferably a piezoelectric body 21A in which bimorph type flexural vibration is excited. The piezoelectric body 21A has a function of converting electrical energy into mechanical energy. Specifically, by applying a voltage, flexural vibration is excited and the thin film 12 can be vibrated.

Examples of the piezoelectric body 21A constituting the vibration generating means 21 include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, they are often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.
The vibration means 13 may be arranged in any way as long as it gives vibration in the vertical direction to the thin film 12 having the nozzle 11, but the vibration surface 13 a and the thin film 12 are arranged in parallel.
In the illustrated example, a horn type vibrator is used as the vibration means 13 composed of the vibration generation means 21 and the vibration amplification means 22, and this horn type vibration amplifies the amplitude of the vibration generation means 21 such as a piezoelectric element. Since it can be amplified by the horn 22A as the means 22, the vibration generating means 21 itself for generating mechanical vibration may be a small vibration, and the mechanical load is reduced, leading to a long life as a production apparatus.
As the horn type vibrator, a known typical horn shape may be used, and examples thereof include a step type as shown in FIG. 4, an exponential type as shown in FIG. 5, a conical type as shown in FIG. Can do. In these horn-type vibrators, a piezoelectric body 21A is arranged on the surface of the horn 22A having a large area, and the piezoelectric body 21A uses longitudinal vibration (vertical movement) to induce efficient vibration of the horn 22A. A surface having a small area is used as the vibration surface 13a, and the vibration surface 13a is designed to be the maximum vibration surface. Lead wires 24 are arranged above and below the piezoelectric body 21, and an AC voltage signal is given from the drive circuit 23. The maximum vibration surface of these horn vibrators is designed to have a shape of 13a.
Further, as the vibration means 13, a particularly high-strength bolted Langevin type vibrator can be used. This bolted Langevin type vibrator is mechanically coupled with piezoelectric ceramics and will not be damaged during high amplitude excitation.
The configuration of the reservoir, the mechanical vibration means, and the thin film will be described in detail with reference to the schematic diagram of FIG. The storage unit 14 is provided with at least one liquid supply tube 18, and as shown in a partial cross-sectional view, the liquid is introduced into the liquid storage unit through the flow path. Moreover, it is also possible to provide the bubble discharge tube 19 as needed. The droplet ejection unit 2 is installed and held on the top surface portion of the particle forming unit 3 by a support member (not shown) attached to the flow path member 15. In addition, although the example which has arrange | positioned the droplet injection unit 2 in the top | upper surface part of the particle formation part 3 is demonstrated here, the droplet injection unit 2 is provided in the drying part side wall used as the particle formation part 3, or a bottom part. It can also be set as the structure to install.

The size of the vibration means 13 that generates mechanical vibration is generally increased as the oscillation frequency decreases, and according to the necessary frequency, the vibration means is directly drilled to provide a reservoir. be able to. It is also possible to vibrate the entire storage part efficiently.
In this case, the vibration surface is defined as a surface parallel to the thin film having the plurality of nozzles or a surface on which the thin film is bonded.
Since the vibration surface is wider than the thin film, the vibration is not concentrated locally in the toner composition liquid storage portion, and a plurality of nozzles can be provided.

Different examples of the droplet jetting unit 2 having such a configuration will be described with reference to FIGS.
The example shown in FIG. 7 uses a horn-type vibrator 80 composed of a piezoelectric body 81 as a vibration generating unit and a horn 82 as a vibration amplifying unit as the vibration unit 80 (13). A reservoir (flow path) 14 is formed. The droplet jetting unit 2 is preferably fixed to the wall surface of the particle forming unit 3 (drying means) by a fixing unit (flange unit) 83 integrally formed with the horn 82 of the horn-type vibrator 80. Loss of vibration From the viewpoint of preventing this, it may be fixed using an elastic body (not shown).

  The example shown in FIG. 8 is a bolt-clamped Langevin type vibrator configured by mechanically firmly fixing piezoelectric bodies 91A and 91B and horns 92A and 92B as vibration generating parts as bolts as vibration means 90 (13). 90 is used to form a reservoir (flow path 14) in the horn 92A. Depending on the frequency condition, the element may be large, and as shown in the drawing, the fluid introduction / discharge path and the reservoir can be processed in a part of the vibrator, and a metal thin film having a plurality of thin films can be attached.

  FIG. 1 shows an example in which only one droplet ejecting unit 2 is attached to the particle forming unit 3, but a plurality of droplet ejecting units 2 are arranged above the particle forming unit 3 (drying tower). Paralleling is preferable from the viewpoint of improving productivity, and the number thereof is preferably in the range of 100 to 1000 from the viewpoint of controllability. In this case, the toner composition liquid 10 is supplied to each storage section 14 of the droplet ejection unit 2 through the pipe 8 to the raw material storage section (common liquid reservoir) 7. The toner composition liquid 10 may be configured to be supplied in a self-contained manner as droplets are formed, or may be configured to supply the liquid supplementarily using the pump 9 during operation of the apparatus. it can.

Another example of the droplet ejecting unit will be described with reference to FIG. FIG. 9 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit.
As in the above-described example, the liquid droplet ejecting unit 2 uses a horn-type vibrator as the vibration means 13 and has a flow path member 15 that surrounds the vibration generation means 13 and supplies the toner composition liquid 10. The reservoir 14 is formed on the horn 22 of the vibration generating means 13 at the portion facing the thin film 12. Further, an air flow path forming member 36 that forms an air flow path 37 through which the air flow 35 flows is disposed around the flow path member 15 at a required interval. In order to simplify the illustration, the number of the nozzles 11 of the thin film 12 is one, but a plurality of nozzles 11 are provided as described above.
As shown in FIG. 10, from the viewpoint of controllability, a plurality of, for example, 100 to 1,000 droplet ejecting units 2 are arranged side by side on the top of the drying tower constituting the particle forming unit 3. Thereby, productivity can be further improved.

(Annular mechanical vibration means)
FIG. 11 shows the apparatus shown in FIG. 1 in which the droplet ejection unit is replaced with a ring type.
The ring type droplet ejecting unit 2 will be described with reference to FIGS. 12 is a cross-sectional explanatory view of the liquid droplet ejecting unit 2, FIG. 13 is an explanatory bottom view of the main part when FIG. 12 is viewed from the lower side, and FIG.
The droplet ejecting unit 2 includes at least a droplet forming unit 16 that discharges the toner composition liquid 10 into droplets, and a storage unit (liquid channel) 14 that supplies the toner composition liquid 10 to the droplet forming unit 16. The formed flow path member 15 is provided.

  The droplet forming means 16 includes a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, and an annular vibration generating means (electromechanical conversion means) 17 that vibrates the thin film 12. Here, the thin film 12 is bonded and fixed to the flow path member 15 with a resin binding material that does not dissolve in the solder or the toner composition liquid at the outermost peripheral portion (region shown by hatching in FIG. 14). The vibration generating means 17 is arranged around a region provided with a nozzle in the deformable region 16A (region not fixed to the flow path member 15) of the thin film 12. As shown in FIG. 2, the vibration generating means 17 is applied with a driving voltage (driving signal) having a required frequency from a driving circuit (driving signal generating source) 23 through a lead wire 24, thereby generating, for example, flexural vibration. .

  The droplet forming means 16 has an annular vibration generating means 17 arranged around the area where the nozzles are provided in the deformable area 16A of the thin film 12 having the plurality of nozzles 11 facing the storage section 14. For example, as compared with the configuration in which the vibration generating means 17A holds the periphery of the thin film 12 as in the comparative example configuration shown in FIG. 15, the displacement amount of the thin film 12 is relatively large, and this large displacement amount is obtained. A plurality of nozzles 11 can be arranged in a region having a large area (φ1 mm or more), and more liquid droplets can be stably formed and discharged at a time than the plurality of nozzles 11.

  In FIG. 11, an example in which one droplet ejecting unit 2 is arranged is illustrated, but preferably, as shown in FIG. 16, a plurality of, for example, 100 to 1,000 (for example, from the viewpoint of controllability) In FIG. 16, only four liquid droplet ejecting units 2 are arranged side by side on the top surface portion 3A of the particle forming unit 3, and a pipe 8 is provided in each liquid droplet ejecting unit 2 in the raw material container 7 (common liquid reservoir). Then, the toner composition liquid 10 is supplied. As a result, more droplets can be discharged at a time, and the production efficiency can be improved.

(Droplet formation mechanism)
Next, the mechanism of droplet formation by the droplet ejecting unit 2 as the droplet forming means will be described.
As described above, the droplet ejecting unit 2 causes the thin film 12 having the plurality of nozzles 11 facing the storage unit 14 to propagate the vibration generated by the vibration means 13 that is a mechanical vibration means, thereby periodically causing the thin film 12 to move. By vibrating, a plurality of nozzles 11 are arranged in a relatively large area (φ1 mm or more), and droplets can be periodically and stably formed and discharged from the plurality of nozzles 11.
When the peripheral portion 12A of the simple circular membrane 12 as shown in FIG. 17 is fixed, the basic vibration has a node around the periphery, and as shown in FIG. It becomes a shape and vibrates vertically in the vibration direction.
Further, it is known that higher order modes as shown in FIGS. 19 and 20 exist. These modes have one or more concentric nodes in a circular membrane, and are substantially axisymmetric deformation shapes. In addition, as shown in FIG. 21, the central portion has a convex shape 12c, so that the traveling direction of the droplet can be controlled and the vibration amplitude can be adjusted.

Due to the vibration of the circular thin film, a sound pressure P _ac proportional to the vibration speed V _{m of the} film is generated in the liquid in the vicinity of the nozzles provided in the circular film. Sound pressure, medium are known to occur as a reaction of the radiation impedance Z _r of (toner constituent liquid), sound pressure, using the following equation (1) by the product of the radiation impedance and film vibration velocity Vm expressed.
P _ac (r, t) = Z _r · V _m (r, t) (1)
Is a function of time (t) since the vibration speed V _m of the film fluctuates periodically with time, for example a sine wave, such as a rectangular waveform, it is possible to form various periodic variations. Further, as described above, the vibration displacement in the vibration direction is different in each part of the film, and V _m is also a function of the position coordinates on the film. The vibration mode of the film used in the present invention is an axial object as described above. Therefore, it is substantially a function of the radius (r) coordinate.
As described above, a sound pressure proportional to the vibration displacement speed of the distributed film is generated, and the toner composition liquid is discharged into the gas phase in response to the periodic change of the sound pressure.
Since the toner composition liquid periodically discharged to the gas phase forms a sphere due to a difference in surface tension between the liquid phase and the gas phase, droplet formation occurs periodically.

As the vibration frequency of the film that enables droplet formation, a region of 20 kHz to 2.0 MHz is used, and a range of 50 kHz to 500 kHz is more preferably used. If the vibration period is 20 kHz or more, the dispersion of fine particles such as pigment and wax in the toner composition liquid is promoted by the excitation of the liquid.
Furthermore, when the displacement amount of the sound pressure is 10 kPa or more, the above-described fine particle dispersion promoting action is more preferably generated.
Here, the diameter of the formed droplet tends to increase as the vibration displacement in the vicinity of the nozzle of the film increases, and when the vibration displacement is small, a small droplet is formed or is not formed into a droplet. In order to reduce such a variation in droplet size at each nozzle site, it is necessary to define the nozzle arrangement at an optimum position of the membrane vibration displacement.
In the present invention, as explained in FIGS. 18 to 20, the ratio R (= ΔLmax / ΔLmin) of the maximum value ΔLmax and the minimum value ΔLmin of the vibration direction displacement ΔL of the film in the vicinity of the nozzle generated by the mechanical vibration means. However, it has been found that by arranging the nozzle in a portion within 2.0, the variation in the droplet size can be maintained in a necessary region as toner fine particles capable of providing a high-quality image.

  The conditions of the toner composition liquid were changed, and since the satellite generation start region was the same in the region of the viscosity of 20 mPa · s or less and the surface tension of 20 to 75 mN / m, the displacement amount of the sound pressure was 500 kPa or less. More preferably, it is 100 kPa or less.

(Thin film with multiple nozzles)
As described above, the thin film having the nozzle is a member that discharges a solution or dispersion of the toner composition into droplets.
The material of the thin film 12 and the shape of the nozzle 11 are not particularly limited and may be appropriately selected. For example, the thin film 12 is formed of a metal plate having a thickness of 5 to 500 μm and An opening diameter of 3 to 30 μm is preferable from the viewpoint of generating fine liquid droplets having a very uniform particle diameter when the liquid droplets of the toner composition liquid 10 are ejected from the nozzle 11. The opening diameter of the nozzle 11 means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse. The number of the plurality of nozzles 11 is preferably 2 to 3000.

(Liquid resonance method)
An example of a liquid resonance type toner manufacturing apparatus is shown in FIG. 27, and an example of a droplet ejection unit is shown in FIG. Its basic configuration is almost the same as the mechanical longitudinal vibration method, but the mechanical longitudinal vibration method oscillates a thin film with a nozzle by means of vibration generation to form droplets, whereas in the liquid resonance method The difference is that droplets are formed not by the vibration of the thin film having the nozzle but by the dense wave traveling in the nozzle direction due to the resonance of the liquid.
Therefore, the strength of the thin film is increased to the extent that it does not vibrate. As the material, silicon, silicon oxide, or the like is used, and it is desirable to use a silicon substrate, particularly an SOI (Silicon on Insulator) substrate in terms of nozzle formation. In addition, when the film thickness is very large with respect to the opening diameter of the nozzle, the discharge performance is improved by making the cross-sectional shape of the nozzle two-stage.

FIG. 28B is a schematic cross-sectional explanatory view of the droplet ejecting unit 2, FIG. 28A is an assembly view for explaining in more detail, and FIG. It is explanatory drawing of the droplet formation by the droplet ejection unit shown to b).
This droplet jetting unit 2 includes a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, a vibration unit 13, and at least a resin, a colorant, and a specific phenol type between the thin film 12 and the vibration unit 13. And a reservoir constituting member 15 that forms a reservoir (liquid channel) 14 for supplying the toner composition liquid 10 containing a resin. A configuration in which the position is fixed by a vibration separating member 26 so as not to transmit vibration between the vibration means and the reservoir wall is desirable, but the vibration means has a node portion 27 having a small vibration amplitude. It may be in the form of being fixed directly to the wall. The toner composition liquid 10 is supplied to the liquid storage unit 14 through a pipe 18 used for liquid supply and liquid circulation.
As the vibration means 13 and the vibration amplification means 22, those described in the description of the membrane vibration method using the mechanical longitudinal vibration means described above can be similarly used.
The members constituting the partition of the liquid storage part are made of a common material such as metal, ceramics, and plastic that does not dissolve in the spray liquid and does not cause modification of the spray liquid. In addition, the liquid storage unit 14 is divided into a plurality of liquid storage regions 29 by a plurality of partition walls. By dividing the partition wall in this way, the vibration pressure distribution in the liquid chamber becomes uniform in the drive of several tens of kHz, so that uniform discharge can be performed and the effect of increasing the resonance frequency can be expected.

  Next, the mechanism of droplet formation by the droplet ejecting unit 2 as the droplet forming means will be described with reference to FIG. The vibration generated on the vibration surface 13a by the vibration means is transmitted to the liquid in the reservoir, and the liquid in the reservoir causes a liquid resonance phenomenon. In a plurality of nozzles provided in the thin film 12, the liquid is discharged to the gas side in a state of being uniformly pressurized. By the action of resonance of the entire liquid, the liquid is uniformly ejected from all the nozzles, and further, the dispersed fine particles contained in the toner composition liquid are suspended in the storage part without being deposited on the storage part surface of the thin film. Therefore, the liquid can be stably ejected stably.

  Next, a method of making the cross-sectional shape of the nozzle into a two-stage type will be described with reference to FIG. A resist 111 is coated on both surfaces of the silicon substrate (11a), covered with a photomask on which a nozzle pattern is formed, exposed to ultraviolet rays, and the resist 111 is formed as a nozzle pattern (11b). Anisotropic dry etching using ICP discharge is performed from the surface side of the support layer 112 to form the first nozzle hole 115, and the same anisotropic dry etching is performed on the surface side of the active layer 114 to perform the second nozzle 116. (11c), and finally, the dielectric layer 113 is removed with a hydrofluoric acid-based etching solution to obtain a two-stage through hole (11d), which is most preferable for uniformly forming the deep nozzle shape. Although not shown, the nozzle can be formed by a similar method even when the silicon substrate is not an SOI substrate but a single layer silicon substrate. In that case, the depth of the first nozzle hole and the depth of the second nozzle hole can be adjusted by adjusting the etching time.

There is no restriction | limiting in particular as a shape of the nozzle 11, Although it can be set as the shape selected suitably, for example, the thin film 12 is 30-1000 micrometers in thickness, and the opening diameter of the nozzle 11 is 4-15 micrometers. 11 is preferable from the viewpoint of generating fine droplets having a uniform particle diameter when the droplets of toner composition liquid 10 are ejected from No. 11. The opening diameter of the nozzle 11 means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.
Any vibration means 13 can be used as long as it can apply mechanical ultrasonic vibration to the liquid at a high amplitude, such as a laminated PZT or a combination of an ultrasonic vibrator and an ultrasonic horn described later. It doesn't matter.

The vibration generated by the vibration means is transmitted to the liquid in the reservoir, and the liquid in the reservoir causes a liquid resonance phenomenon. In a plurality of nozzles provided in the thin film, the liquid is discharged to the gas side in a state of being uniformly pressurized. By the action of resonance of the entire liquid, the liquid is uniformly ejected from all the nozzles, and further, the dispersed fine particles contained in the toner composition liquid are suspended in the storage part without being deposited on the storage part surface of the thin film. Therefore, the liquid can be stably ejected stably.
When a thin film provided with a plurality of nozzles is vibrated mechanically, there is an advantage that nozzle clogging is difficult to occur. However, if the thin film area is large, uniform vibrations may not be obtained and the droplet size distribution may be obtained. On the other hand, in the liquid resonance method, a substantially equal vibration pressure is applied to each nozzle, so that droplets with a narrow particle size distribution are easily obtained even with a wide thin film.

(Dry)
The drying process (particle forming process) for removing the solvent from the droplets is performed by discharging the droplets into a gas such as heated dry nitrogen. If necessary, secondary drying such as fluidized bed drying or vacuum drying is further performed.
Among the toner production methods described above, toner obtained by spraying or vibration jetting, in which the toner composition liquid employed in the present invention is formed into droplets in the gas phase and then dried, has excellent charging characteristics. A non-spherical shape with excellent blade cleaning properties can be obtained. The surface of the toner particles dried after forming the toner composition liquid into droplets was analyzed by TOF-SIMS, and the polycondensation obtained by the polycondensation reaction between phenols and aldehydes was performed. As the amount of toner added increases, the strength of the binder resin inherent component decreases rapidly, and the polycondensate obtained by the polycondensation reaction of phenols and aldehydes is unevenly distributed on the toner surface. The result which suggests was obtained.
As described above, since there are many charge control agents containing a polycondensate obtained by polycondensation reaction of phenols and aldehydes on the toner surface, good chargeability can be obtained as compared with the pulverized toner. It is thought that there is.

Also, the reason why the charge control agent is unevenly distributed on the toner surface is not clear, but the charge control agent is unevenly distributed on the toner surface, so that the charge control agent existing on the surface during drying is dried first. However, it is considered that a dent is generated due to the later removal of the solvent in the internal binder resin and the toner becomes non-spherical (deformed).
In addition, the vibration jet method provides a very sharp particle size distribution compared to the spray method, which is thought to result in less variation in the charge amount between the toner particles, but is superior in image stability during actual use. It was.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image using the toner or developer of the present invention. A development process for forming a visible image, a transfer process for transferring the visible image to a recording medium, and a transfer image transferred to the recording medium is heated and pressed using a roller-shaped or belt-shaped fixing member to fix the image. And a fixing step, and further includes, for example, a static elimination step, a cleaning step, and a recycling step as necessary.

  Further, the image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. Developing means for developing a toner or developer using the developer to form a visible image, transferring means for transferring the visible image to a recording medium, and a roller-shaped or belt-shaped fixing member for transferring the transferred image to the recording medium And at least fixing means for fixing by heating and pressurizing, and further having other means appropriately selected as necessary, for example, static elimination means, cleaning means, recycling means, control means, etc. .

-Electrostatic latent image forming process and means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier are not particularly limited, and can be appropriately selected from known ones. The shape is preferably a drum shape. Examples of the material include organic photoreceptors, inorganic photoreceptors such as amorphous silicon and selenium, and the like.
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developer capable of bringing the toner or the developer into contact or non-contact with the electrostatic latent image is provided. Etc. are more preferable.
The developing device may be a single color developing device or a multi-color developing device. For example, a stirrer for charging the toner or the developer by frictional stirring, and a rotatable magnet. The thing which has a roller etc. are mentioned suitably.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).
The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the intermediate transfer member or the recording medium using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

-Fixing process and means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 120 to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

-Other processes and means-
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.
The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.
The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

-Embodiment of image forming apparatus-
One mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. An image forming apparatus 800 shown in FIG. 23 includes a photosensitive drum 810 (hereinafter referred to as “photosensitive body 810”) as the electrostatic latent image carrier, a charging roller 820 as the charging unit, and exposure as the exposure unit. The apparatus 830 includes a developing device 840 as the developing means, an intermediate transfer member 850, a cleaning device 860 as the cleaning means having a cleaning blade, and a static elimination lamp 870 as the static elimination means.
The intermediate transfer member 850 is an endless belt, and is designed to be movable in the direction of an arrow in the figure by three rollers 851 that are arranged on the inner side and stretch the belt. Part of the three rollers 851 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 850. An intermediate transfer body cleaning blade 890 is disposed in the vicinity of the intermediate transfer body 850, and a transfer bias for transferring (secondary transfer) a visible image (toner image) to the recording medium 895 is applied. Possible transfer rollers 880 as the transfer means are arranged to face each other. Around the intermediate transfer member 850, a corona charger 858 for applying a charge to the visible image on the intermediate transfer member 850 is arranged with the electrostatic latent image carrier 810 in the rotation direction of the intermediate transfer member 850. It is disposed between a contact portion with the intermediate transfer member 850 and a contact portion between the intermediate transfer member 850 and the recording medium 895.

  The developing device 840 includes a developing belt 841 as a developer carrier, and a black developing unit 845K, a yellow developing unit 845Y, a magenta developing unit 845M, and a cyan developing unit 845C provided around the developing belt 841. Yes. The black developing unit 845K includes a developer containing portion 842K, a developer supply roller 843K, and a developing roller 844K. The yellow developing unit 845Y includes a developer accommodating portion 842Y, a developer supply roller 843Y, and a developing roller 844Y. The magenta developing unit 845M includes a developer accommodating portion 842M, a developer supply roller 843M, and a developing roller 844M. The cyan developing unit 845C includes a developer accommodating portion 842C, a developer supply roller 843C, and a developing roller 844C. Further, the developing belt 841 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 810.

  In the image forming apparatus 800 illustrated in FIG. 22, for example, the charging roller 820 uniformly charges the photosensitive drum 810. The exposure device 830 performs imagewise exposure on the photosensitive drum 810 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 810 is supplied with toner from the developing device 840 and developed to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer body 850 by the voltage applied from the roller 851, and further transferred onto the transfer paper 895 (secondary transfer). As a result, a transfer image is formed on the transfer paper 895. The residual toner on the photoconductor 810 is removed by the cleaning device 860, and the charge on the photoconductor 810 is temporarily removed by the charge eliminating lamp 870.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus 900 shown in FIG. 23 is different from the image forming apparatus 800 shown in FIG. 22 in that the developing belt 841 is not provided, and a black developing unit 845K, a yellow developing unit 845Y, a magenta developing unit 845M, and Except for the fact that the cyan developing unit 845C is directly opposed, it has the same configuration as the image forming apparatus 800 shown in FIG. In FIG. 23, the same components as those in FIG. 22 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 24 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying machine main body 150 is provided with an endless belt-shaped intermediate transfer member 1050 at the center. The intermediate transfer member 1050 is stretched around the support rollers 1014, 1015, and 1016, and can rotate clockwise in FIG. An intermediate transfer body cleaning device 1017 for removing residual toner on the intermediate transfer body 1050 is disposed in the vicinity of the support roller 1015. The intermediate transfer member 1050 stretched by the support roller 1014 and the support roller 1015 has a tandem type in which four image forming units 1018 of yellow, cyan, magenta, and black face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 1021 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 1022 is disposed on the side of the intermediate transfer body 1050 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 1022, a secondary transfer belt 1024, which is an endless belt, is stretched around a pair of rollers 1023, and the transfer sheet conveyed on the secondary transfer belt 1024 and the intermediate transfer body 1050 are in contact with each other. Is possible. A fixing device 1025 is disposed in the vicinity of the secondary transfer device 1022. The fixing device 1025 includes a fixing belt 1026 that is an endless belt, and a pressure roller 1027 that is pressed against the fixing belt 1026.
In the tandem image forming apparatus, a sheet reversing device 1028 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 1022 and the fixing device 1025. .

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 1032 of the scanner 300. 400 is closed.
When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 1032 and then the document is set on the contact glass 1032. Immediately after that, the scanner 300 is driven, and the first traveling body 1033 and the second traveling body 1034 travel. At this time, the light from the light source is emitted from the first traveling body 1033 and the reflected light from the document surface is reflected by the mirror in the second traveling body 1034 and is received by the reading sensor 1036 through the imaging lens 1035 to be color. A document (color image) is read and used as black, yellow, magenta, and cyan image information.

Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 1018 (black image forming unit, yellow image forming unit, magenta image forming unit, cyan image) in the tandem developing unit 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 1018 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing means 120 is a static image as shown in FIG. An electrostatic latent image carrier 1110 (an electrostatic latent image carrier for black 1010K, an electrostatic latent image carrier for yellow 1010Y, an electrostatic latent image carrier for magenta 1010M, and an electrostatic latent image carrier for cyan 1010C); The electrostatic latent image carrier 1110 is uniformly charged, and the electrostatic latent image carrier is exposed for each color image corresponding image based on each color image information (L in FIG. 25). An exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner). And a cyan toner) to form a toner image with each color toner, a transfer charger 1062 for transferring the toner image onto the intermediate transfer body 1050, a cleaning device 63, And a single-color image (a black image, a yellow image, a magenta image, and a cyan image) based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to an electrostatic latent image carrier 1010K for black on an intermediate transfer member 1050 that is rotated by support rollers 1014, 1015, and 1016. The black image formed above, the yellow image formed on the yellow electrostatic latent image carrier 1010Y, the magenta image formed on the magenta electrostatic latent image carrier 1010M, and the electrostatic latent image carrier for cyan The cyan image formed on 1010C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 1050 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one and sent to the sheet feeding path 146, conveyed by the conveying roller 147, guided to the sheet feeding path 148 in the copying machine main body 150, and abutted against the registration roller 1049 to stop. Alternatively, the sheet feeding roller 142 is rotated to feed out the sheets (recording paper) on the manual feed tray 1054, separated one by one by the separation roller 1058, put into the manual feed path 1053, and abutted against the registration roller 1049 and stopped. . The registration roller 1049 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 1049 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 1050, and a sheet (recording paper) is interposed between the intermediate transfer member 1050 and the secondary transfer device 1022. And transferring the composite color image (color transfer image) onto the sheet (recording paper) by the secondary transfer device 1022, thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 1050 after the image transfer is cleaned by the intermediate transfer member cleaning device 1017.

The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 1022 and sent to the fixing device 1025, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 1055 and discharged by the discharge roller 1056 and stacked on the paper discharge tray 1057 or switched by the switching claw 1055 and reversed by the sheet reversing device 1028 and transferred again. After being guided to the position and recording an image on the back side, it is discharged by the discharge roller 1056 and stacked on the discharge tray 1057.
In the image forming method and the image forming apparatus of the present invention, the toner of the present invention having a sharp particle size distribution and good toner characteristics such as chargeability, environmental properties, and stability over time is used. A quality image can be formed.

FIG. 26 shows a schematic configuration of a process cartridge using the toner of the present invention. The process cartridge includes a photoreceptor (701), and at least one of a charging unit (702), a developing unit (704), a transfer unit (708), a cleaning unit (707), and a charge eliminating unit (not shown). And an apparatus (part) that can be attached to and detached from the main body of the image forming apparatus. Referring to the image forming process by the apparatus illustrated in FIG. 7, the surface of the photoreceptor (701) is exposed by charging by the charging means (702) and exposure by the exposure means (703) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed, and this electrostatic latent image is developed with toner by a developing means (704). The toner development is transferred to a transfer body (705) by a transfer means (708), and printed. Be out. Next, the surface of the photoconductor after the image transfer is cleaned by a cleaning unit (707), and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following Examples and Comparative Examples, “softening point of polyester resin”, “glass transition temperature (Tg) of polyester resin”, “softening point of rosin”, “acid value of polyester resin and rosin”, “hydroxyl group of polyester resin” The value was measured as follows.

<Measurement of softening point of polyester resin>
Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), as a sample, 1 g of each polyester-based binder resin was heated at a heating rate of 6 ° C./min. Extrusion was performed from a nozzle having a length of 1 mm and a length of 1 mm, and the amount of plunger drop of the flow tester was plotted against the temperature. The temperature at which half of the sample flowed out was taken as the softening point.

<Measurement of glass transition temperature (Tg) of polyester resin>
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), 0.01 to 0.02 g of each polyester-based binder resin was weighed into an aluminum pan as a sample, heated to 200 ° C., and the temperature The sample was cooled to 0 ° C at a rate of temperature decrease of 10 ° C / min, and the temperature was increased at a rate of temperature increase of 10 ° C / min, extending from the baseline extension line below the endothermic peak temperature and from the peak rise to the peak apex. The temperature at the intersection with the tangent showing the maximum inclination was defined as the glass transition temperature.

<Measurement of softening point of rosin>
(1) Preparation of sample 10 g of rosin was melted on a hot plate at 170 ° C. for 2 hours. Thereafter, the sample was naturally cooled for 1 hour in an open state at a temperature of 25 ° C. and a relative humidity of 50%, and pulverized for 10 seconds with a coffee mill (National MK-61M) to prepare a sample.
(2) Measurement Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C./min. The sample was extruded from a nozzle having a thickness of 1 mm, and the plunger drop amount of the flow tester was plotted against the temperature. The temperature at which half of the sample flowed out was defined as the softening point.

<Acid value of polyester resin and rosin>
It measured based on the method of JISK0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

<Hydroxyl value of polyester resin>
It measured based on the method of JISK0070.

<Particle size distribution>
The weight average particle diameter (D4) and number average particle diameter (Dn) of the toner of the present invention were measured with an aperture diameter of 100 μm using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.), and analysis software ( The analysis was performed with a Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, 0.5 g of each toner is added, and the mixture is stirred with a micropartel. 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size. As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted. After measuring the volume and number of toner particles or toner, the volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained. As an index of the particle size distribution, D4 / Dn obtained by dividing the weight average particle size (D4) of the toner by the number average particle size (Dn) is used. If it is completely monodisperse, it becomes 1, and the larger the value, the wider the distribution.

<Circularity>
The average circularity can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. . If it is a true sphere, the circularity is 1.

<Measurement of charging characteristics>
(Measurement of charge amount of normal temperature normal products)
After exposing 96 parts by mass of a magnetic carrier to 4 parts by mass of the toner base particles in an environment of 20 ° C./50% RH for 24 hours, the toner and the carrier are put in a ball mill in the environment, and then for 30 seconds, 10 minutes. The mixture was mixed with a ball mill for 30 minutes to prepare a two-component developer at normal temperature and humidity for 30 seconds, a 10-minute stirred product, and a 30-minute stirred product, and the charge amount was measured by a blow-off method described later.
It can be said that as the charge amount of the 30-second stir product is closer to the charge amount of the 10-minute stir product, the charging stability is better as the charge amount of the 30-second stir product is closer to the charge amount of the 10-minute stir product. It's good.

(Measurement of charge amount of high temperature and high humidity product)
Further, after 4 parts by weight of toner base particles and 96 parts by weight of magnetic carrier were exposed to an environment of 30 ° C./90% RH for 24 hours, the toner and carrier were put into the ball mill in that environment, and the ball mill was used for 10 minutes. A two-component developer high-temperature and high-humidity product was prepared by mixing, and the charge amount was measured by a blow-off method.
It can be said that the smaller the difference between the charge amount of the high-temperature and high-humidity product and the charge amount of the product stirred at room temperature and normal humidity for 10 minutes, the better the environmental stability.

<Charge amount: Blow-off method>
6 g of developer is put into a metal cylindrical container provided with a stainless steel mesh with openings of 20 μm on both bottoms, and only the toner is removed by blowing nitrogen gas, the charge q of the remaining carrier is measured, and the removed toner The charge amount was determined as q / m divided by the mass m.

-Performance evaluation-
Next, the toners of Examples and Comparative Examples were evaluated for image stability, cleaning properties, heat resistant storage stability, cold offset resistance, hot offset resistance, developing roller contamination resistance, and odor as follows. The results are shown in Tables 3 and 4.

<Image stability evaluation>
The developer is put into a copying machine (Imagio Neo C285) manufactured by Ricoh, and the area ratio of the image in an environment of 30 ° C./90% RH and 10 ° C./30% RH using Ricoh type 6000 paper. Table 1 shows the results of evaluating 100 images each of 2%, 10%, and 50% images that were output continuously. In any environment and image area ratio, the 100th image is better than the initial image when the 100th image is as good as the initial image. The 100th image is clearer than the initial image in any environment and image area ratio. When a change occurred, it was indicated by “x”.

<Cleanability>
Each developer is put in a commercially available copier (Imagioneo C325, manufactured by Ricoh Co., Ltd.), developed an image with an image area ratio of 30%, transferred to transfer paper, and then the residual toner remaining on the photoreceptor is cleaned with a cleaning blade The copier is stopped during cleaning, and the transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M Co., Ltd.). Ten points were measured, and the difference between the average value and the measurement result when the tape was simply pasted on a white paper was determined and evaluated according to the following criteria. A cleaning blade after cleaning 20,000 sheets was used.
〔Evaluation criteria〕
◎ (very good): difference is 0.01 or less ○ (good): difference is 0.015 or less × (defect): difference exceeds 0.015

<Heat resistant storage stability>
The heat-resistant storage stability was measured using a penetration tester (manufactured by Nikka Engineering Co., Ltd.). Specifically, 10 g of each toner was weighed and placed in a 30 ml glass container (screw vial) in an environment of 20 to 25 ° C. and 40 to 60% RH, and the lid was closed. After tapping the glass container containing the toner 200 times, leaving it in a thermostat set at 50 ° C. for 48 hours, measuring the penetration with a penetration tester, and heat-resistant storage stability according to the following evaluation criteria Evaluated. The greater the penetration value, the better the heat resistant storage stability.
〔Evaluation criteria〕
◎: Needle penetration is 30 mm or more ○: Needle penetration is 20 mm to 29 mm
Δ: penetration is 15 mm to 19 mm (equivalent to conventional toner)
X: The penetration is 8 mm to 14 mm
XX: Needle penetration is 7mm or less

<Cold offset resistance>
Each developer is loaded into an ultra-high speed digital laser printer IPSiO SP9500Pro remodeling machine, and the toner adhesion amount is 0.20 ± 0.1 mg / cm 2 on a thick paper transfer paper (manufactured by NBS Ricoh Co., Ltd., copy printing paper <135>). Create a 1cm square solid image, attach Scotch Mending Tape 810 (width 24mm, manufactured by 3M) on the solid image, and apply a metal roller (φ50, manufactured by SUS) weighing 1kg from the tape at a speed of 10mm / s. 10 reciprocations while rolling. The tape was peeled in a fixed direction at a speed of 10 mm / s, the image afterimage rate was determined from the image density before and after the tape peeling using the following formula (ii), and the cold offset resistance was evaluated according to the following evaluation criteria.
[Formula (ii)]
Image residual ratio (%) = (image density after peeling / image density before peeling) × 100
〔Evaluation criteria〕
A: Image remaining rate is 97% or more. B: Image remaining rate is 92% or more and less than 97%. Δ: Image remaining rate is 85% or more and less than 92%. X: Image remaining rate is 80% or more and less than 85%. )
XX: Image remaining rate is less than 80%

<Hot offset resistance>
Each developer is loaded into an ultra-high speed digital laser printer IPSiO SP9500Pro remodeling machine, and the toner adhesion amount is 0.40 ± 0.1 mg / cm 2 on a thin paper transfer paper (manufactured by NBS Ricoh Co., Ltd., copy printing paper <55>). Create a 1cm square solid image, fix by changing the fixing roller temperature, visually evaluate the presence or absence of hot offset, set the upper limit temperature at which hot offset does not occur as the upper limit temperature for fixing, and evaluate hot offset resistance according to the following criteria did.
〔Evaluation criteria〕
A: The upper limit temperature of fixing is 240 ° C. or higher. ○: The upper limit temperature of fixing is 220 ° C. or higher and lower than 240 ° C. Δ: The upper limit temperature of fixing is 200 ° C. or higher and lower than 220 ° C. x: The upper limit temperature of fixing is 180 ° C. or higher and lower than 200 ° C. )
XX: Fixing upper limit temperature is less than 180 ° C.

<Development roller contamination resistance>
Each developer is loaded into an ultra-high-speed digital laser printer IPSiO SP9500Pro remodeling machine. After printing 100,000 sheets on a 5% image area chart, the developer and toner on the developing roller are removed, and the developing roller in the blank paper passing section The soil was visually evaluated to evaluate the stain resistance of the developing roller.
〔Evaluation criteria〕
◎: The developing roller is not soiled at all ○: Soil that is almost indistinguishable visually is observed △: Slightly worried is generated ×: Slightly problematic soil is generated (same as conventional toner)
XX: Dirt that is obviously problematic and difficult to use

<Toner Odor Evaluation Method>
20 g of each toner was weighed into an aluminum cup and allowed to stand on a hot plate heated to 150 ° C. for 30 minutes, and the odor generated from the toner was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◎: Odor is not felt at all ○: Odor is hardly felt △: Odor is felt slightly, but there is no practical problem ×: Odor is felt strongly

(Synthesis example)
-Purification example of rosin-
1,000 g of tall rosin is added to a 2,000 mL distillation flask equipped with a fractionation tube, a reflux condenser, and a receiver, and distilled under a reduced pressure of 1 kPa to distill at 195 ° C. to 250 ° C. Collected as the main fraction. Hereinafter, tall rosin subjected to purification is referred to as unpurified rosin, and rosin collected as a main fraction is referred to as purified rosin.
20 g of unpurified rosin and purified rosin were each pulverized with a coffee mill (National MK-61M) for 5 seconds, and passed through a sieve with an opening of 1 mm, and 0.5 g was measured in a headspace vial (20 mL). The headspace gas was sampled, and impurities in the unpurified rosin and the purified rosin were analyzed by the headspace GC-MS method as follows. The results are shown in Table 1.

[Measurement conditions for headspace GC-MS method]
A. Headspace sampler (Agilent, HP7694)
Sample temperature: 200 ℃
Loop temperature: 200 ° C
Transfer line temperature: 200 ° C
Sample heating equilibration time: 30min
Bayal pressurized gas: Helium (He)
Bayal pressurization time: 0.3min
Loop filling time: 0.03min
Loop equilibration time: 0.3min
Injection time: 1min

B. GC (Gas Chromatography) (Agilent, HP6890)
Analytical column: DB-1 (60m-320μm-5μm)
Carrier: Helium (He)
Flow rate condition: 1ml / min
Inlet temperature: 210 ° C
Column head pressure: 34.2kPa
Injection mode: split
Split ratio: 10: 1
Oven temperature condition: 45 ℃ (3min) -10 ℃ / min-280 ℃ (15min)

C. MS (mass spectrometry) (Agilent, HP5973)
Ionization method: EI (electron impact) method
Interface temperature: 280 ℃
Ion source temperature: 230 ° C
Quadrupole temperature: 150 ° C
Detection mode: Scan 29-350m / s

-Synthesis of acrylic acid-modified rosin-
The purified rosin (6,084 g, 18 mol) and acrylic acid (907.9 g, 12.6 mol) were added to a 10 L flask equipped with a fractionation tube, a reflux condenser, and a receiver. After raising the temperature to 220 ° C. over 8 hours and reacting at 220 ° C. for 2 hours, distillation was further performed under reduced pressure of 5.3 kPa to obtain acrylic acid-modified rosin.

-Synthesis of fumaric acid-modified rosin-
Purified rosin 5,408 g (16 mol), fumaric acid 928 g (8 mol), and t-butylcatechol 0.4 g were added to a 10 L flask equipped with a fractionation tube, a reflux condenser, and a receiver. The temperature was raised from 160 ° C. to 200 ° C. over 2 hours and reacted at 200 ° C. for 2 hours, followed by distillation under reduced pressure of 5.3 kPa to obtain a fumaric acid-modified rosin.

-Synthesis of maleic acid-modified rosin-
Purified rosin 6,084 g (18 mol) and maleic anhydride 1,323 g (13.5 mol) were added to a 10 L flask equipped with a fractionation tube, reflux condenser and receiver, and the temperature was increased from 160 ° C. to 220 ° C. over 8 hours. The temperature was raised and reacted at 220 ° C. for 2 hours, and further distilled under reduced pressure at 220 ° C. and 5.3 kPa to obtain a maleic acid-modified rosin.

(Synthesis Examples 1-7)
The alcohol component, carboxylic acid component excluding trimellitic anhydride and esterification catalyst shown in Table 2 were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, and a nitrogen atmosphere The polycondensation reaction was carried out at 230 ° C. for 10 hours, and then the reaction was carried out at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 220 ° C., trimellitic anhydride was added and reacted at normal pressure for 1 hour, and then reacted at 220 ° C. and 20 kPa until a desired softening point was reached to obtain a polyester.

＊未精製ロジン：未変性ロジン
＊ＢＰＡ−ＰＯ：ビスフェノールＡプロピレンオキシド付加物、ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン
［参考例１］

* Unpurified rosin: unmodified rosin * BPA-PO: bisphenol A propylene oxide adduct, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane [ Reference Example 1]

-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400; manufactured by Cabot) 20 parts by mass and pigment dispersant 2 parts by mass were primarily dispersed in 78 parts by mass of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Furthermore, a liquid having a pore size of 1 μm (made of PTFE) and passing through a submicron region was prepared.

-Preparation of wax dispersion-
In a container in which a stirring blade and a thermometer are set, 30 parts by mass of the polyester resin of Synthesis Example 1 as a binder resin, 10 parts by mass of carnauba wax, and 160 parts by mass of ethyl acetate are charged, heated to 85 ° C., and stirred for 20 minutes. The polyester resin and carnauba wax were dissolved, and then rapidly cooled to precipitate carnauba wax fine particles. This wax dispersion is further finely dispersed by a strong shearing force using a star mill LMZ06 (manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconia beads of 0.1 μmφ, and the average particle size of the wax is 0.3 μm and the largest particle The diameter was adjusted to 0.8 μm or less. The particle size of the wax was measured using NPA150 manufactured by Microtrac.

-Preparation of toner composition liquid-
50 parts by weight of the carbon black dispersion 100 parts by weight of the wax dispersion A 20% by weight solid solution of the polyester resin of Synthesis Example 1 is obtained by a polycondensation reaction of 337.5 parts by weight of phenols and aldehydes. The resulting polycondensate (FCA-2508N manufactured by Fujikura Kasei Co., Ltd.) was stirred and mixed for 10 minutes using a mixer having a stirring blade of 102.5 parts by weight of ethyl acetate and 102.5 parts by weight of ethyl acetate. [Toner Composition Liquid 1] having a solid content of 10% by mass was prepared.

-Preparation of toner-
The obtained [Toner Composition Liquid 1] is supplied to a ring-type vibrator head in which the vibration generating means (piezoelectric member) shown in FIG. 11 is formed in an annular shape, and in nitrogen at 45 ° C. under the following toner preparation conditions. After the droplets were discharged to the solid, the droplets were dried and solidified, collected with a cyclone, and then air-dried at 40 ° C./90% RH for 1 day and at 40 ° C./50% RH for 3 days, and the weight average Obtained by polycondensation reaction of phenols and aldehydes having a particle size of 5.2 μm, a weight average particle size / number average particle size (D4 / Dn) of 1.13 and a sharp particle size distribution of 0.96 circularity. [Toner base particle a1] containing 1.5% by mass of the polycondensate was prepared.
The used nozzle plate was produced by electroforming a perfect circular discharge hole having a diameter of 8 μm on a nickel plate having an outer diameter of 8.0 mm and a thickness of 20 μm. The discharge holes were provided in a staggered pattern so that the distance between the discharge holes was 100 μm, and only in the range of about 5 mmφ at the center of the nozzle plate. In this case, the number of effective ejection holes is about 1000.

[Toner preparation conditions]
Dry air flow rate: Dispersing nitrogen gas 2.0 L / min,
Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 38 to 40 ° C
Nozzle frequency: 98 kHz
Piezoelectric applied voltage: 10V

-Fabrication of carrier-
Silicone resin (organostraight silicone) 100 parts by mass Toluene 100 parts by mass γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts by mass Carbon black 10 parts by mass The above mixture is dispersed with a homomixer for 20 minutes, and a coating layer is formed. A forming solution was prepared. This coating layer forming liquid was coated on the surface of 1000 parts of spherical magnetite having a particle diameter of 50 μm using a fluidized bed coating apparatus to obtain a magnetic carrier.
[Toner base particles a1] and a magnetic carrier were used to prepare a two-component developer at room temperature and humidity for 30 seconds, a product for 10 minutes, and a product for 30 minutes, and the charge amount was measured by a blow-off method.
Further, a two-component developer high-temperature and high-humidity product was prepared using [toner base particle a1] and a magnetic carrier, and the charge amount was measured by a blow-off method. The evaluation results are shown in Tables 3 and 4.

-Production of developer-
[Toner base particle a1] To 99.0 parts by mass, 1.0 part by mass of hydrophobic silica (HDK H2000, manufactured by Clariant Japan) as an external additive is added and mixed with a Henschel mixer to obtain [Toner A1]. Produced.
With respect to 4 parts by mass of the obtained [Toner A1], 96 parts by mass of the magnetic carrier were exposed to an environment of 20 ° C./50% RH for 24 hours, and then the toner and carrier were put into the ball mill in the environment. A two-component developer was prepared by mixing with a ball mill for 10 minutes.
Tables 3 and 4 show the results shown in the section of the evaluation method using the obtained developer.
[ Reference Example 2]

Using [Toner Composition Liquid 1] obtained in Reference Example 1, the toner is supplied to nozzle 1 of the toner production apparatus shown in FIG. Thereafter, the droplets were dried and solidified, collected by a cyclone, and then air-dried at 40 ° C./90% RH for 1 day and at 40 ° C./50% RH for 3 days, and the weight average particle size was 4.9 μm. The polycondensation obtained by the polycondensation reaction of phenols and aldehydes having a weight average particle size / number average particle size (D4 / Dn) of 1.08 and a very sharp particle size distribution with a circularity of 0.97. [Toner base particle b1] containing 1.5% by mass of toner was prepared.
The used nozzle plate was produced by electroforming a perfect circular discharge hole having a diameter of 8 μm on a nickel plate having an outer diameter of 8.0 mm and a thickness of 20 μm. The discharge holes were provided in a staggered pattern so that the distance between the discharge holes was 100 μm, and only in the range of about 5 mmφ at the center of the nozzle plate. In this case, the number of effective discharge holes in calculation is 1000.

[Toner preparation conditions]
Dry air flow rate: Dispersing nitrogen gas 2.0 L / min,
Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 38 to 40 ° C
Nozzle frequency: 180 kHz
Piezoelectric applied voltage: 10V
Tables 3 and 4 show the results of evaluation using this [toner base particle b1] in the same manner as in Reference Example 1.
[Example 1 ]

[Toner Composition Liquid 1] obtained in Reference Example 1 is supplied to the droplet jetting unit of the toner manufacturing apparatus shown in FIG. 27, and after the droplets are ejected into nitrogen at 45 ° C., the droplets are discharged. The toner was dried and solidified and collected with a cyclone to prepare a toner.
The thin film (nozzle plate) uses a 500 μm thick SOI substrate, and the nozzle is formed as a two-stage shape (convex shape) having a 115 opening diameter of 100 μm and a 116 opening diameter of 8.5 μm as shown in FIG. Was used as the side from which the liquid was released. It was provided in a staggered pattern so that the distance between each discharge hole was 100 μm. The liquid storage part used what was comprised by the liquid storage area | region divided | segmented equally. The excitation frequency used in this example and the configuration of the liquid reservoir are shown below.

<Liquid reservoir configuration and drive frequency>
Excitation frequency: 32.7 kHz (resonance frequency)
Number of liquid storage part divisions (number of liquid storage areas): 6
Liquid reservoir longitudinal direction dimension A: 8 mm
Liquid reservoir short side dimension B: 8mm
Number of nozzles per liquid storage area: 480

As secondary drying, air drying was performed at 40 ° C./90% RH for 1 day and at 40 ° C./50% RH for 3 days. Dn) is 1.06 and contains 1.5% by mass of a polycondensate obtained by a polycondensation reaction between phenols and aldehydes having a circularity of 0.97 and a very sharp particle size distribution [toner base particles c1].
[Example 2 ]

-Preparation of toner composition liquid-
50 parts by mass of a carbon black dispersion prepared as in Reference Example 1
The polyester resin of Synthesis Example 1 used in Reference Example 1 was changed to the polyester resin of Synthesis Example 2, and the wax dispersion prepared in the same manner as in Reference Example 1 was 100 parts by mass of the solid content of the polyester resin of Synthesis Example 2 20% by mass. 337.5 parts by mass of an ethyl acetate solution 10 parts by mass of a 15% by mass ethyl acetate solution of a polycondensate (FCA-2508N manufactured by Fujikura Kasei Co., Ltd.) obtained by polycondensation reaction of phenols and aldehydes 502.5 parts by mass of ethyl acetate was mixed with stirring for 10 minutes using a mixer having stirring blades to prepare [Toner Composition Liquid 2] having a solid content of 10% by mass.

-Preparation of toner-
Using the obtained [Toner Composition Liquid 2], in the same manner as in Example 1 , the weight average particle diameter was 4.9 μm, and the weight average particle diameter / number average particle diameter (D4 / Dn) was 1.05. [Toner base particle c2] containing 1.5% by mass of a polycondensate obtained by a polycondensation reaction between phenols and aldehydes having a sharp particle size distribution and a circularity of 0.97.
Tables 3 and 4 show the results of evaluation using this [toner base particle c2] in the same manner as in Reference Example 1.
[Example 3 ]

-Preparation of toner composition liquid-
50 parts by mass of a carbon black dispersion prepared as in Reference Example 1
The polyester resin of Synthesis Example 1 used in Reference Example 1 was changed to the polyester resin of Synthesis Example 3, and 100 parts by mass of the wax dispersion prepared in the same manner as in Reference Example 1 was 20% by mass of the polyester resin of Synthesis Example 3 337.5 parts by mass of an ethyl acetate solution 10 parts by mass of a 15% by mass ethyl acetate solution of a polycondensate (FCA-2508N manufactured by Fujikura Kasei Co., Ltd.) obtained by polycondensation reaction of phenols and aldehydes 502.5 parts by mass of ethyl acetate was mixed with stirring for 10 minutes using a mixer having stirring blades to prepare [Toner Composition Liquid 3] having a solid content of 10% by mass.

-Preparation of toner-
Using the obtained [Toner Composition Liquid 3], in the same manner as in Example 1 , the weight average particle diameter was 5.0 μm, and the weight average particle diameter / number average particle diameter (D4 / Dn) was 1.08. [Toner base particle c3] containing 1.5% by mass of a polycondensate obtained by a polycondensation reaction of phenols and aldehydes having a sharp particle size distribution and a circularity of 0.97.
Tables 3 and 4 show the results of evaluation using this [toner base particle c3] in the same manner as in Reference Example 1.
[Example 4 ]

-Preparation of toner composition liquid-
50 parts by mass of a carbon black dispersion prepared as in Reference Example 1
The polyester resin of Synthesis Example 1 used in Reference Example 1 was changed to the polyester resin of Synthesis Example 4, and 100 parts by mass of the wax dispersion prepared in the same manner as in Reference Example 1 was 20% by mass of the polyester resin of Synthesis Example 4 337.5 parts by mass of an ethyl acetate solution 10 parts by mass of a 15% by mass ethyl acetate solution of a polycondensate (FCA-2508N manufactured by Fujikura Kasei Co., Ltd.) obtained by polycondensation reaction of phenols and aldehydes 502.5 parts by mass of ethyl acetate was mixed with stirring for 10 minutes using a mixer having stirring blades to prepare [Toner Composition Liquid 4] having a solid content of 10% by mass.

-Preparation of toner-
Using the obtained [Toner Composition Liquid 4], in the same manner as in Example 1 , the weight average particle diameter was 4.9 μm and the weight average particle diameter / number average particle diameter (D4 / Dn) was 1.08. [Toner base particles c4] containing 1.5% by mass of a polycondensate obtained by a polycondensation reaction between phenols and aldehydes having a sharp particle size distribution and a circularity of 0.97.
Tables 3 and 4 show the results of evaluation using this [toner base particle c4] in the same manner as in Reference Example 1.
[Example 5 ]

-Preparation of toner composition liquid-
50 parts by mass of a carbon black dispersion prepared as in Reference Example 1
The polyester resin of Synthesis Example 1 used in Reference Example 1 was changed to the polyester resin of Synthesis Example 5, and 100 parts by mass of the wax dispersion prepared in the same manner as in Reference Example 1 was 20% by mass of the polyester resin of Synthesis Example 5 337.5 parts by mass of an ethyl acetate solution 10 parts by mass of a 15% by mass ethyl acetate solution of a polycondensate (FCA-2508N manufactured by Fujikura Kasei Co., Ltd.) obtained by polycondensation reaction of phenols and aldehydes 502.5 parts by mass of ethyl acetate was mixed with stirring for 10 minutes using a mixer having stirring blades to prepare [Toner Composition Liquid 5] having a solid content of 10% by mass.

-Preparation of toner-
Using the obtained [Toner Composition Liquid 5], in the same manner as in Example 1 , the weight average particle diameter was 4.8 μm, and the weight average particle diameter / number average particle diameter (D4 / Dn) was 1.09. [Toner base particle a5] containing 1.5% by mass of a polycondensate obtained by a polycondensation reaction between phenols and aldehydes having a sharp particle size distribution and a circularity of 0.97.
Tables 3 and 4 show the results of evaluation using this [toner base particle c5] in the same manner as in Reference Example 1.
[Example 6 ]

-Preparation of toner composition liquid-
50 parts by mass of a carbon black dispersion prepared as in Reference Example 1
The polyester resin of Synthesis Example 1 used in Reference Example 1 was changed to the polyester resin of Synthesis Example 2, and the wax dispersion prepared in the same manner as in Reference Example 1 was 100 parts by mass of the solid content of the polyester resin of Synthesis Example 6 20% by mass. 337.5 parts by mass of an ethyl acetate solution 10 parts by mass of a 15% by mass ethyl acetate solution of a polycondensate (FCA-2508N manufactured by Fujikura Kasei Co., Ltd.) obtained by polycondensation reaction of phenols and aldehydes 502.5 parts by mass of ethyl acetate was mixed with stirring for 10 minutes using a mixer having stirring blades to prepare [Toner Composition Liquid 6] having a solid content of 10% by mass.

-Preparation of toner-
Using the obtained [Toner Composition Liquid 6], in the same manner as in Example 1 , the weight average particle diameter was 5.1 μm, and the weight average particle diameter / number average particle diameter (D4 / Dn) was 1.07. [Toner base particles c6] containing 1.5% by mass of a polycondensate obtained by a polycondensation reaction of phenols and aldehydes having a sharp particle size distribution and a circularity of 0.96.
Tables 3 and 4 show the results of evaluation using this [toner base particle c6] in the same manner as in Reference Example 1.

[Comparative Example 1]
-Preparation of toner composition liquid-
50 parts by mass of a carbon black dispersion prepared as in Reference Example 1
The polyester resin of Synthesis Example 1 used in Reference Example 1 was changed to the polyester resin of Synthesis Example 7, and 100 parts by mass of the wax dispersion prepared in the same manner as in Reference Example 1 was 20% by mass of the polyester resin of Synthesis Example 7 337.5 parts by mass of an ethyl acetate solution 10 parts by mass of a 15% by mass ethyl acetate solution of a polycondensate (FCA-2508N manufactured by Fujikura Kasei Co., Ltd.) obtained by polycondensation reaction of phenols and aldehydes 502.5 parts by mass of ethyl acetate was mixed with stirring for 10 minutes using a mixer having stirring blades to prepare [Toner Composition Liquid 7] having a solid content of 10% by mass.

-Preparation of toner-
Using the obtained [Toner Composition Liquid c7], in the same manner as in Example 1 , the weight average particle diameter was 5.0 μm, and the weight average particle diameter / number average particle diameter (D4 / Dn) was 1.07. [Toner base particle c7] containing 1.5% by mass of a polycondensate obtained by a polycondensation reaction between phenols and aldehydes having a sharp particle size distribution and a circularity of 0.96 was obtained.
Tables 3 and 4 show the results of evaluation using this [toner base particle c7] in the same manner as in Reference Example 1.

[Comparative Example 2]
-Preparation of toner-
The [Toner Composition Liquid 1] was sprayed into nitrogen at 45 ° C. at a pneumatic pressure of 0.15 MPa using a two-fluid nozzle (spray dry method) having a nozzle diameter of 250 μm, collected by a cyclone, and then 40 ° C./90%. Blow drying was performed at RH for 1 day and at 40 ° C./50% RH for 3 days to obtain black fine particles.
Further, the black fine particles are adjusted in particle size distribution by air classification, and the weight average particle diameter is 6.9 μm, the weight average particle diameter / number average particle diameter (D4 / Dn) is 1.24, and the degree of circularity is 0.96. [Toner base particle d1] containing 1.5% by mass of a polycondensate obtained by a polycondensation reaction with aldehydes was produced.
Tables 3 and 4 show the results of evaluation using this [toner base particle d1] in the same manner as in Reference Example 1.

[Comparative Example 3]
Binder resin: Polyester resin of Synthesis Example 1 83.5 parts by mass Colorant: Carbon black ("MOGUL L", manufactured by Cabot Corporation) 10 parts by mass Charge control agent: Obtained by polycondensation reaction of phenols and aldehydes Polycondensate 1.5 parts by weight Release agent: Carnauba wax 5 parts by weight were charged into a Henschel mixer (“MF20C / I type”, manufactured by Mitsui Miike Processing Co., Ltd.) The mixture was kneaded with a machine (manufactured by Toshiba Machine Co., Ltd.), rolled with a cooled two roll, and then cooled on a steel belt. Here, the kneading was performed such that the temperature of the kneaded product at the exit of the twin-screw extruder was about 120 ° C. Next, coarsely pulverized with a rotoplex, finely pulverized with a jet mill, and the particle size distribution is adjusted by air classification, the weight average particle size is 7.0 μm, the weight average particle size / number average particle size (D4 / Dn) Was a pulverization method [toner base particle e] containing 1.5% by mass of a polycondensate obtained by a polycondensation reaction of phenols having a circularity of 0.94 and an aldehyde of 0.94.
Tables 3 and 4 show the results of evaluation using this [toner base particle e] in the same manner as in Reference Example 1.

(About FIGS. 1 to 21)
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 3 Particle formation part (solvent removal part)
DESCRIPTION OF SYMBOLS 4 Toner collection part 5 Tube 6 Toner collection part 7 Raw material accommodating part 8 Piping 9 Pump 10 Toner composition liquid 11 Nozzle 12 Thin film 13 Vibrating means 13a Vibrating surface 14 Storage part 15 Flow path member 16 Droplet forming means 17 Vibration generating means (Electromechanical conversion means)
18 liquid supply tube 19 bubble discharge tube 20 support member 21 vibration generating means 21A piezoelectric body 22 vibration amplifying means 22A horn 23 drive circuit (drive signal generation source)
24 communication means 31 droplet 35 airflow 41 taper surface 42 eddy current (airflow)
43 Static elimination means 43A Soft X-ray irradiation device 80 Horn type vibrator 81 Piezoelectric body 82 Horn 83 Fixing part 90 Langevin type vibrator 91 Piezoelectric body 92 Horn T Toner particles (about FIGS. 22 to 26)
61 Developing device 63 Cleaning device 64 Static eliminator 120 Tandem type developing device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146, 148 Paper feed path 147 Conveyance roller 150 Copying device main body 160 Charging device 200 Paper feed Table 300 Scanner 400 Automatic document feeder 701 Electrostatic latent image carrier 702 Charging means 703 Exposure 704 Developing means 705 Recording medium 707 Cleaning means 708 Transfer means 800, 900 Image forming apparatus 810 Photosensitive body 820 Charging roller 830 Exposure apparatus 840 Developing apparatus 841 Developing belt 842K, 842Y, 842M, 842C Developer container 843K, 843Y, 843M, 843C Developer supply roller 844K, 844Y, 844M, 844C Developing low 845K Black development unit 845Y Yellow development unit 845M Magenta development unit 845C Cyan development unit 850 Intermediate transfer body 851 Roller 858 Corona charger 860 Cleaning device 870 Static elimination lamp 880 Transfer roller 890 Intermediate transfer body cleaning blade 895 Recording medium 1010 Electrostatic latent image Supporting body 1014, 1015, 1016 Support roller 1017 Intermediate transfer body cleaning device 1018 Image forming means 1021 Exposure device 1022 Secondary transfer device 1023 Roller 1024 Secondary transfer belt 1025 Fixing device 1026 Fixing belt 1027 Pressure roller 1028 Sheet reversing device 1032 Contact Glass 1033 First traveling body 1034 Second traveling body 1035 Imaging lens 1036 Reading sensor 1049 Resist Over La 1050 intermediate transfer member 1055 a switching claw 1056 discharge roller 1057 discharge tray 1062 transfer charger (about 27 to 29)
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 3 Particle formation part (solvent removal part)
DESCRIPTION OF SYMBOLS 4 Toner collection part 5 Tube 6 Toner storage part 7 Raw material storage part 8 Piping 9 Pump 10 Toner composition liquid 11 Nozzle 12 Thin film 13 Vibration means 13a Vibrating surface 14 Storage part 15 Storage part component 16 Droplet formation means 16A Deformable area 17 Vibration generating means (electromechanical conversion means)
18 liquid supply tube 19 bubble discharge tube 20 support member 21 vibration generating means 21A piezoelectric body 21a, 21b electrode 22 vibration amplifying means 22A horn 23 drive circuit (drive signal generation source)
24 communication means 26 vibration separating member 27 node portion of vibration means having small vibration amplitude 29 liquid storage area 31 droplet 35 air flow 41 taper surface 42 vortex flow (air flow)
80 Horn type vibrator 81 Piezoelectric body 82 Horn 83 Fixed portion 90 Langevin type vibrator 91 Piezoelectric body 92 Horn 111 Resist 112 Support layer 113 Dielectric layer 114 Active layer 115 First nozzle hole 116 Second nozzle hole T Toner particle

JP 2004-245854 A JP-A-4-70765 JP-A-4-307557 JP 2007-292860 A JP 2007-292869 A Japanese Patent Laid-Open No. 2-82267 Japanese Patent No. 2851895 Japanese Patent No. 3772910 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 2007-199463 A JP 2006-293320 A JP 2008-276146 A

Claims (7)

Periodically, the toner composition liquid is periodically discharged into the gas phase by mechanical vibration means from a plurality of nozzles having the same opening diameter formed in a thin film provided in a storage portion for storing the toner composition liquid. A method for producing a toner , comprising: a droplet forming step; and a particle forming step for solidifying the dropletized toner composition liquid ,
The toner composition liquid is obtained by dissolving and / or dispersing a toner composition containing at least a binder resin, a colorant, and a release agent in an organic solvent, and the binder resin is modified with an alcohol component. A polyester resin obtained by condensation polymerization with a carboxylic acid component containing a purified rosin,
The mechanical vibration means is a vibration means having a vibration surface parallel to the thin film, and the vibration surface vibrates vertically in the vertical direction, and the periodic droplet forming step is performed by the mechanical vibration means. A method for producing a toner, wherein the toner composition liquid is periodically discharged into a gas phase from a plurality of nozzles having the same opening diameter formed in the thin film by utilizing a liquid resonance phenomenon. . The toner manufacturing method according to claim 1, wherein the mechanical vibration unit is a horn-type vibrator. The toner production method according to claim 1, wherein the toner composition liquid contains a polycondensate obtained by a polycondensation reaction of phenols and aldehydes. The polyester resin is obtained by polycondensing an alcohol component containing 65 mol% or more of 1,2-propanediol in a divalent alcohol component and a carboxylic acid component containing a modified purified rosin. 4. The method for producing a toner according to any one of items 1 to 3. The method for producing a toner according to claim 1, wherein the modified purified rosin is modified with at least one of acrylic acid, fumaric acid, and maleic acid. 6. The method for producing a toner according to claim 1, wherein the toner composition liquid has a solid content of 5% by mass to 15% by mass. The method for producing a toner according to claim 1, wherein the circularity is in a range of 0.94 to 0.98.

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