JP2012185219A - Toner, developer and method for producing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner, a developer and a method for producing a toner, by which a toner having a small particle diameter and mono-dispersibility can be efficiently produced without clogging in a discharge hole caused by a releasing agent, and the toner shows excellent hot offset resistance and can form high-definition and high-quality images free of contamination of a base for a long period of time.SOLUTION: A method for producing a toner includes: a toner composition liquid preparation step of preparing a toner composition liquid by dissolving or dispersing a binder resin, a colorant and a releasing agent in an organic solvent and dissolving the binder resin and the releasing agent; a droplet formation step of forming standing waves in the toner composition liquid in a liquid column resonance chamber having a plurality of discharge holes by liquid column resonance using vibrating means, and discharging the toner composition liquid from the discharge holes that are formed in a region corresponding to an antinode of the standing wave to form droplets; and a toner particle formation step of removing the organic solvent from the droplets to form toner particles in which the binder resin and the releasing agent cause a phase separation.

Description

  The present invention relates to a toner for developing an electrostatic charge image in a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, a developer containing the toner, and a method for producing the toner.

In the developing process, toner used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as an electrostatic latent image carrier on which an electrostatic charge image is formed. After being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. As a fixing method, a method of fixing by contact heating and melting using a heated roll or belt is generally performed because of high thermal efficiency.
However, the contact heating fixing method has a problem that hot offset is likely to occur in which toner is fused to a heat roll or belt.

  In order to prevent this hot offset, conventionally, release oil such as silicone oil has been applied to a heat roll and a belt. However, the method of applying the release oil to the hot roll requires an oil tank and an oil application device, which is problematic in that the device is complicated and large. In addition, it is unavoidable that oil adheres to copy paper, OHP (overhead projector) film, etc., and there are problems such as writing properties with water-based ink and deterioration of color tone due to attached oil in OHP.

  Therefore, several methods for adding a releasing agent such as wax to the toner itself have been proposed as a method for preventing toner fusion without applying oil to the heating roller or belt. As an example, a toner containing a wax having an endothermic peak with a specific differential scanning calorimetry (DSC) has been proposed (see Patent Document 1). As other examples, it has been proposed to use candelilla wax, higher fatty acid wax, higher alcohol wax, plant natural wax (carnauba wax, rice wax), montan ester wax and the like as a release agent. (See Patent Document 2).

On the other hand, as a dry toner manufacturing method used for electrophotography, electrostatic recording, electrostatic printing, etc., a toner binder such as a styrene resin or a polyester resin is melt-kneaded with a colorant or the like and finely pulverized, so-called A pulverized toner is widely used.
However, in recent years, there has been a tendency for the toner to have a small particle size in order to obtain a high-quality image. In the above pulverization method, when the particle size is 8 μm or less, the pulverization efficiency decreases and the loss due to classification increases, resulting in increased productivity. This is a problem in that the cost is low and the cost is increased.

  Recently, a so-called polymerization type toner such as a suspension polymerization method and an emulsion polymerization aggregation method and a method involving volume shrinkage called a polymer dissolution suspension method have been proposed and put into practical use. Although these toners are excellent in terms of producing a toner having a small particle diameter, since it is premised on the use of a dispersant in an aqueous medium, a dispersant that impairs the charging characteristics of the toner remains on the toner surface. As a result, it is known that problems such as loss of environmental stability occur, and that a very large amount of washing water is required to remove the problem, which is problematic in terms of environmental load.

As an alternative method for producing a toner, a liquid obtained by dissolving or dispersing a raw material component of a toner in an organic solvent (hereinafter sometimes referred to as “toner composition liquid”) is finely divided using various atomizers. There is known a spray granulation method in which powdered toner is obtained by drying (see, for example, Patent Documents 3 to 5). According to this method, it is not necessary to use water, and steps such as washing and drying can be greatly reduced, so that the disadvantages of the polymerization method can be avoided.
However, in this toner manufacturing method, droplets corresponding to the nozzle diameter must be discharged from a nozzle (also referred to as “ejection hole” or “through hole”), and this method has a wide toner particle size distribution. Therefore, a classification process for removing fine powder and coarse powder is required, which is a problem in that productivity is lowered.

With respect to such problems, the toner production method by jet granulation proposed by the applicant of the present application does not require a large amount of cleaning liquid, solvent and particle separation, and is extremely efficient in production and energy saving. A toner having a narrow diameter distribution can be manufactured (see Patent Document 6).
However, in the case of the method of forming toner particles by discharging the toner composition from such minute discharge holes, the discharge holes are easily clogged due to pigments and release agents contained as particles in the toner composition. There was a problem. Pigment is relatively easy to miniaturize, and it is more convenient to make it finer from the viewpoint of color reproducibility. However, in the case of a release agent, it is difficult to make finer and at the same time, refining makes it easy to release. This is a problem because it tends to cause the discharge hole to be clogged.
In particular, carnauba wax and paraffin wax are particularly difficult to miniaturize, and there is a problem that discharge holes are frequently clogged with large-sized wax particles.

Further, pressurizing a storage part for storing the toner composition liquid, discharging the toner composition liquid from the discharge hole of the storage part to form a liquid column, and applying a fine vibration to the liquid column by a vibrating means, A method of forming a droplet by inducing Rayleigh splitting in the liquid column is also known (see Patent Document 7).
However, since this Rayleigh splitting method requires pressure resistance in the storage part in which the discharge hole is formed, the film thickness of the storage part must be increased, and it is difficult to form a small-diameter discharge hole. There has been a problem that variation in toner particle size becomes large.

  Therefore, it is possible to efficiently produce a toner having a small particle size and monodispersibility, no clogging of discharge holes due to the release agent, excellent hot offset resistance, and no background stains. However, the present situation is that it is desired to provide a toner, a developer, and a toner manufacturing method capable of providing a high-definition and high-quality image over a long period of time.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention can efficiently produce a toner having a small particle size and monodispersibility, does not cause clogging of discharge holes due to a release agent, has excellent hot offset resistance, An object of the present invention is to provide a toner, a developer, and a toner manufacturing method capable of providing a high-definition and high-quality image over a long period of time without any background contamination.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in an organic solvent, and the binder resin and the release agent are dissolved so as not to phase-separate. A toner composition liquid preparation step for preparing a toner composition liquid, and vibrations are applied to the toner composition liquid in a liquid column resonance liquid chamber in which a plurality of ejection holes are formed to form a standing wave by liquid column resonance. A droplet forming step of forming droplets by periodically discharging the toner composition liquid to the outside of the discharge holes from the plurality of discharge holes formed in an antinode of the standing wave; A toner particle forming step of removing the organic solvent from the droplet formed in the droplet forming step to form toner particles in which the binder resin and the release agent are phase-separated. Use toner with small particle size and monodispersibility It can be produced, and it does not cause clogging of discharge holes due to the mold release agent, has excellent hot offset resistance, and has no background stain, and can provide high-definition and high-quality images over a long period of time. As a result, the present invention has been completed.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in an organic solvent, and the binder resin and the release agent are dissolved so as not to phase-separate. A toner composition liquid preparation step for preparing the toner composition liquid;
A vibration is applied to the toner composition liquid in the liquid column resonance liquid chamber in which a plurality of ejection holes are formed to form a standing wave by liquid column resonance, and is formed in a region that becomes an antinode of the standing wave. A droplet forming step of forming droplets by periodically discharging the toner composition liquid from the plurality of discharge holes to the outside of the discharge holes;
A toner particle forming step of removing the organic solvent from the droplet formed in the droplet forming step to form toner particles in which the binder resin and the release agent are phase-separated;
A method for producing a toner, comprising:
<2> The method for producing a toner according to <1>, wherein a plurality of ejection holes are formed in at least one of the regions that are antinodes of the standing wave.
<3> The method for producing a toner according to any one of <1> to <2>, wherein the temperature of the toner composition liquid in the droplet forming step satisfies the following formula (I).
Temperature of toner composition liquid (° C.) <[Boiling point of organic solvent (° C.) − 20 (° C.)] Formula (I)
<4> The method for producing a toner according to any one of <1> to <3>, wherein the release agent includes at least one of a synthetic ester wax, a synthetic amide wax, and a microcrystalline wax.
<5> The method for producing a toner according to any one of <1> to <4>, wherein the addition amount of the release agent is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the binder resin. .
<6> The toner according to any one of <1> to <5>, wherein the binder resin includes at least one of a polyester resin having a weight average molecular weight of 5,000 to 300,000 and a styrene acrylic acid copolymer. It is a manufacturing method.
<7> The method for producing a toner according to any one of <1> to <6>, wherein an opening diameter of an ejection hole formed in the liquid column resonance liquid chamber is 3 μm to 30 μm.
<8> The vibration means has a vibration surface parallel to a surface in which the plurality of discharge holes of the liquid column resonance liquid chamber are formed, and the vibration surface forms a plurality of discharge holes in the liquid column resonance liquid chamber. The method for producing a toner according to any one of <1> to <7>, wherein the toner is vibration means that vibrates longitudinally in a direction perpendicular to the surface.
<9> The toner production according to any one of <3> to <8>, further including a temperature control step of controlling the temperature of the toner composition liquid and the temperature of the member in contact with the toner composition liquid at a predetermined temperature in the droplet forming process. Is the method.
<10> Obtained by the method for producing a toner according to any one of <1> to <9>, having a volume average particle diameter of 1 μm to 8 μm and a particle size distribution (volume average particle diameter / number average particle diameter). The toner is in the range of 1.00 to 1.15.
<11> A developer containing at least the toner according to <10> and a carrier.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and a toner having a small particle size and monodispersibility can be efficiently produced, resulting from a release agent. Provided are a toner, a developer, and a toner manufacturing method capable of providing high-definition and high-quality images over a long period of time without causing clogging of discharge holes, excellent hot offset resistance, and free from background stains. can do.

FIG. 1 is a schematic cross-sectional view showing an example of a liquid column resonance droplet forming unit. FIG. 2 is a schematic diagram illustrating an example of a liquid column resonance droplet unit, and is a bottom view of FIG. 1 viewed from the ejection surface. FIG. 3A is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is a fixed end on one side and N = 1. FIG. 3B is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is fixed on both sides and N = 2. FIG. 3C is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is open at both sides and N = 2. FIG. 3D is a schematic explanatory diagram showing a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is one side fixed end and N = 3. FIG. 4A is a schematic explanatory diagram showing a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is fixed at both sides and N = 4. FIG. 4B is a schematic explanatory diagram showing a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is open at both sides and N = 4. FIG. 4C is a schematic explanatory diagram showing a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is one side fixed end and N = 5. FIG. 5A is a schematic diagram showing the state of a liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber of the liquid column resonance droplet forming means. FIG. 5B is a schematic diagram showing the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber of the liquid column resonance droplet forming means. FIG. 5C is a schematic diagram showing the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber of the liquid column resonance droplet forming means. FIG. 5D is a schematic diagram illustrating a liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber of the liquid column resonance droplet forming unit. FIG. 5E is a schematic diagram showing the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber of the liquid column resonance droplet forming means. FIG. 6 is a diagram showing a state of actual droplet discharge by the liquid column resonance droplet forming means. FIG. 7 is a characteristic diagram showing an example of frequency characteristics of the driving frequency and the droplet discharge speed. Vertical axis: discharge speed (m / s), horizontal axis: drive frequency (kHz) FIG. 8A is a schematic diagram illustrating an example of the shape of the ejection hole as viewed from the cross section of the liquid column resonance liquid chamber. FIG. 8B is a schematic diagram illustrating an example of the shape of the ejection hole as viewed from the cross section of the liquid column resonance liquid chamber. FIG. 8C is a schematic diagram illustrating an example of the shape of the ejection hole as viewed from the cross section of the liquid column resonance liquid chamber. FIG. 8D is a schematic view showing an example of the shape of the discharge hole as seen from the cross section of the liquid column resonance liquid chamber. FIG. 9 is a schematic cross-sectional view showing an example of a toner manufacturing apparatus used in the toner manufacturing method of the present invention. FIG. 10 is a schematic view showing another example of the airflow passage. FIG. 11 is a schematic view showing still another example of the airflow passage. FIG. 12 is a schematic diagram illustrating an example of a coalescence prevention process using an auxiliary airflow. FIG. 13 is a graph showing an example of a toner particle size distribution obtained by the toner manufacturing method of the present invention. FIG. 14 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Example 1 with a transmission electron microscope (TEM). FIG. 15 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Example 2 with a transmission electron microscope (TEM). FIG. 16 is a transmission electron microscope (TEM) observation image (magnification: 15,000 times) of the toner base particles prepared in Example 3. FIG. 17 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Example 4 using a transmission electron microscope (TEM). FIG. 18 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Example 5 with a transmission electron microscope (TEM). FIG. 19 is a transmission electron microscope (TEM) observation image (magnification: 15,000 times) of the toner base particles prepared in Example 6. FIG. 20 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Example 7 using a transmission electron microscope (TEM). FIG. 21 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Comparative Example 2 with a transmission electron microscope (TEM). FIG. 22 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Comparative Example 3 with a transmission electron microscope (TEM). FIG. 23 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Comparative Example 4 with a transmission electron microscope (TEM). 24 is a view showing an observation image (magnification: 15,000 times) of the toner base particles prepared in Comparative Example 5 with a transmission electron microscope (TEM).

(Toner production method)
The toner production method of the present invention includes at least a toner composition liquid preparation step, a droplet formation step, and a toner particle formation step. Process.

<Toner composition liquid preparation process>
The toner composition liquid preparation step is a step of preparing a toner composition liquid in which a toner composition is dissolved or dispersed in an organic solvent.
The toner composition contains at least a binder resin, a colorant, and a release agent, and further contains other components as necessary.

<< Toner Composition Liquid >>
The toner composition liquid contains at least a binder resin, a colorant, a release agent, and an organic solvent, and further contains other components as necessary.

  In the toner composition liquid, it is essential that the binder resin and the release agent are dissolved without phase separation. In the toner composition liquid, the binder resin and the release agent are dissolved without phase separation so that the temperature is lower than the temperature of 20 ° C. lower than the boiling point of the organic solvent in the toner composition liquid. What is necessary is just to be transparent when it pinches | interposes with the heated slide glass and cover glass, and it observes with a transmission optical microscope (magnification 1,000 times). As a specific example of the observation method for observing dissolution, when ethyl acetate (boiling point 77 ° C.) is used as an organic solvent, the toner composition liquid is sandwiched between a slide glass and a cover glass heated to a temperature of less than 57 ° C. and transmitted. This can be confirmed by observing with a scanning optical microscope.

-Binder resin-
The binder resin is not particularly limited as long as it is soluble in the organic solvent, and can be appropriately selected from known resins according to the purpose. Monomers, vinyl monomers such as methacrylic monomers, copolymers comprising two or more of these monomers, polyester resins, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, Examples thereof include epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, and petroleum resins. These may be used alone or in combination of two or more.

--Vinyl monomer or copolymer-
There is no restriction | limiting in particular as said styrene monomer, According to the objective, it can select suitably, For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p- Ethyl styrene, 2,4-dimethyl styrene, pn-amyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn- Styrene such as decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof. Can be mentioned.
There is no restriction | limiting in particular as said derivative | guide_body, According to the objective, it can select suitably.

There is no restriction | limiting in particular as said acrylic acid monomer, According to the objective, it can select suitably, For example, acrylic acid, esters of acrylic acid, etc. are mentioned.
The esters of acrylic acid are not particularly limited and may be appropriately selected depending on the intended purpose. For example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic Examples include n-octyl acid, n-dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate.

There is no restriction | limiting in particular as said methacryl monomer, According to the objective, it can select suitably, For example, methacrylic acid, esters of methacrylic acid, etc. are mentioned.
The esters of methacrylic acid are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid. Examples include n-octyl acid, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

There is no restriction | limiting in particular as another monomer, According to the objective, it can select suitably, For example, the following (1)-(18) etc. are mentioned.
(1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8) vinyl naphthalenes; (9) acrylonitrile, methacrylate. Ronitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic acid anhydride and alkenyl succinic acid anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid Unsaturated (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; (16) Monomers having a carboxyl group such as anhydrides of α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides and monoesters thereof; (17) 2- Acrylic acid or methacrylic acid hydroxyalkyl esters such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy- Monomers having a hydroxy group such as 1-methylhexyl) styrene.

  Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic acid copolymer is preferable.

The vinyl monomer or vinyl copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and an alkyl chain such as those obtained by replacing the acrylate of these compounds with methacrylate Diacrylate compounds; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 Acrylate, dipropylene glycol diacrylate, and diacrylate compounds connected with an alkyl chain containing an ether bond, such as those of acrylates of these compounds is replaced with methacrylate and the like. Other examples include diacrylate compounds and dimethacrylate compounds connected by a chain containing an aromatic group and an ether bond. Moreover, as said crosslinking agent, polyester type diacrylates, such as brand name: MANDA (made by Nippon Kayaku Co., Ltd.), etc. can be used, for example.

  Further, as the cross-linking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate, triallyl cyanurate And polyfunctional crosslinking agents such as triallyl trimellitate.

These crosslinking agents may be used individually by 1 type, and may use 2 or more types together.
Among these cross-linking agents, aromatic divinyl compounds (particularly divinylbenzene), diacrylate compounds linked by a bond chain containing one aromatic group and an ether bond from the viewpoint of toner fixing properties and hot offset resistance. Is preferred.
The amount of the crosslinking agent added is not particularly limited as long as the binder resin can be dissolved in the organic solvent, and can be appropriately selected according to the purpose.

  There is no restriction | limiting in particular as a polymerization initiator used for manufacture of the said vinyl copolymer, According to the objective, it can select suitably, For example, 2,2'- azobisisobutyronitrile, 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl-2 , 2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4 -Trimethylpentane), 2-phenylazo-2 ', 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide , Ketone peroxides such as acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3 3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxide Bonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3 -Methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaur Tert-butyl-oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylpa To-2-ethyl hexanoate, di -tert- butyl peroxy the hexa hydro terephthalate, and the like are tert- butylperoxy azelate. These may be used alone or in combination of two or more.

When the binder resin is a styrene-acrylic resin, the weight average molecular weight is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable from the viewpoint of toner fixability and hot offset resistance.
The molecular weight distribution of the binder resin can be measured by gel permeation chromatography (GPC) using THF as a solvent.

--- Polyester resin--
There is no restriction | limiting in particular as a monomer which comprises the said polyester resin (polymer), Although it can select suitably according to the objective, It is preferable to consist of an alcohol component and an acid component.

  The alcohol component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. , Diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or bisphenol A with ethylene oxide, propylene Examples thereof include divalent alcohol components such as diols obtained by polymerizing cyclic ethers such as oxides. These may be used alone or in combination of two or more.

Moreover, the polyester resin can be crosslinked by using a trihydric or higher polyhydric alcohol together.
The trihydric or higher polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, penta Erythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, tri Examples include methylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene and the like. These may be used alone or in combination of two or more.
The content of the trihydric or higher polyhydric alcohol is not particularly limited as long as the binder resin can be dissolved in the organic solvent, and can be appropriately selected according to the purpose.

  The acid component forming the polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof, and succinic acid. Alkyl dicarboxylic acids such as acid, adipic acid, sebacic acid, azelaic acid or anhydrides thereof, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride , Unsaturated dibasic acid anhydrides such as citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride, and the like. These may be used alone or in combination of two or more.

Moreover, the said polyester resin can be bridge | crosslinked by using trivalent or more acid together.
The trivalent or higher acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimetic acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzene. Tricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy- Multivalents such as 2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, or anhydrides thereof, partially lower alkyl esters, etc. Examples include carboxylic acid components. These may be used alone or in combination of two or more.
The content of the trivalent or higher acid is not particularly limited as long as the binder resin can be dissolved in the organic solvent without phase separation, and can be appropriately selected according to the purpose.

When the binder resin is a polyester resin, the weight average molecular weight is not particularly limited and may be appropriately selected depending on the intended purpose. However, at least one peak exists in the region of 25,000 to 100,000. It is preferable that at least one peak exists in the region of 5,000 to 300,000. When the weight average molecular weight is within the preferred range, it is advantageous in that the toner has excellent fixability and hot offset resistance.
Further, a binder resin in which a component having a weight average molecular weight of 50,000 or less in a tetrahydrofuran (THF) -soluble component is 70% to 100% is preferable from the viewpoint of dischargeability.

  The binder resin can be appropriately selected depending on the organic solvent and release agent used, but when a release agent having excellent solubility in the organic solvent is used, the softening point of the toner may be lowered. is there. In such a case, increasing the weight average molecular weight of the binder resin to increase the softening point of the binder resin is an effective means for maintaining good hot offset resistance.

  When the binder resin is a polyester resin, the acid value is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 mgKOH / g to 100 mgKOH / g, preferably 0.1 mgKOH / g. -70 mgKOH / g is more preferable, and 0.1 mgKOH / g-50 mgKOH / g is particularly preferable.

In the present invention, the acid value of the binder resin component in the toner composition liquid is measured by the following method according to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are used. Find in advance. A sample to be measured is precisely weighed from 0.5 g to 2.0 g, and the weight of the polymer component is defined as Wg. For example, when the acid value of the binder resin is measured from toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) Put the sample to be measured into a 300 mL beaker, and add 150 mL of a mixed solution of toluene / ethanol (4/1 (volume ratio)) to dissolve.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / L potassium hydroxide (KOH).
(4) The amount of KOH ethanol solution used at this time is S (mL), and a blank is measured at the same time. The amount of KOH ethanol solution used at this time is B (mL) and is calculated by the following formula (C). To do. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W Formula (C)

The glass transition temperature (Tg) of the binder resin and the toner composition liquid containing the binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. -80 ° C is preferable, and 40 ° C-70 ° C is more preferable. If the glass transition temperature (Tg) is less than 35 ° C., the toner may be easily deteriorated in a high temperature atmosphere, and if it exceeds 80 ° C., the fixability may be lowered.
The glass transition temperature can be measured, for example, according to JIS K7121, using a differential scanning calorimeter (for example, “DSC-60”, manufactured by Shimadzu Corporation) at a heating rate of 10 ° C./min.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known colorants according to the purpose. 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 Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimony 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 Examples include lakes, malachite green lakes, phthalocyanine greens, anthraquinone greens, titanium oxides, zinc whites, and litbons. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as content of the said colorant, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable with respect to a toner, and 3 mass%-10 mass% are more preferable. .

The colorant can also be used as a master batch combined with a resin.
The masterbatch resin kneaded with the masterbatch is not particularly limited and can be appropriately selected according to the purpose. For example, a modified polyester resin obtained by modifying a polyester resin with an isocyanate group or an epoxy, a polyester resin A non-modified polyester resin composed of styrene and polycarboxylic acid, a polymer of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and the like; a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, Styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Coalescence, styrene-meta Methyl acrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer Styrene copolymers such as polymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; Methyl 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 or kneading the masterbatch resin and the colorant under high shear.
At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin for the masterbatch. Also, the so-called flushing method, which is an aqueous paste containing water of the colorant, is mixed or kneaded together with the resin for the masterbatch and an organic solvent, and the colorant is transferred to the resin side for the masterbatch, The method of removing moisture and the organic solvent component is also preferably used because the wet cake of the colorant can be used as it is, and does not need to be dried.
In order to mix or knead the resin for the master batch and the colorant, a high shear dispersion device such as a three-roll mill can be suitably used.

  There is no restriction | limiting in particular as the usage-amount of the said masterbatch, Although it can select suitably according to the objective, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of said binder resins.

The resin for the master batch has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and preferably used by dispersing the colorant. The acid value is 20 mgKOH / g or less and the amine value is 10 to 10. 50, it is more preferable to use the colorant dispersed.
When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered and the pigment dispersibility may be insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient.
The acid value can be measured, for example, by the method described in JIS K0070, and the amine value can be measured, for example, by the method described in JIS K7237.

--- Pigment dispersion-
The colorant can also be used as a colorant dispersion dispersed in a pigment dispersion.
The pigment dispersant is not particularly limited and may be appropriately selected according to the purpose. However, in terms of pigment dispersibility, the compatibility with the binder resin is preferably high, Examples of such commercially available products include Ajisper PB821, Azisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk-2001 (manufactured by BYK Chemie), EFKA-4010 (manufactured by EFKA), and the like. . These may be used alone or in combination of two or more.

  The weight average molecular weight of the pigment dispersant is preferably 500 to 100,000 as the maximum molecular weight of the main peak in terms of styrene equivalent weight in gel permeation chromatography, and from the viewpoint of pigment dispersibility, 3,000. To 100,000 is more preferable, 5,000 to 50,000 is more preferable, and 5,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 500, the polarity becomes high and the dispersibility of the colorant may be lowered. When the weight average molecular weight exceeds 100,000, the affinity with a solvent increases. The dispersibility of the colorant may decrease.

  There is no restriction | limiting in particular as addition amount of the said pigment dispersant, Although it can select suitably according to the objective, 1 mass part-200 mass parts are preferable with respect to 100 mass parts of coloring agents, and 5 mass parts- 80 parts by mass is more preferable. When the addition amount is less than 1 part by mass, the dispersibility may be lowered, and when it exceeds 200 parts by mass, the chargeability may be lowered.

-Release agent-
The release agent is not particularly limited as long as it is soluble in the organic solvent, and can be appropriately selected from known release agents according to the purpose, but waxes are preferable.
It is possible to dissolve the release agent by heating the organic solvent and the toner composition liquid. However, in this case, heating at a temperature satisfying the following formula (I ′) for stable continuous ejection. Is important. When heating is performed at a temperature satisfying the following formula (I ′), bubbles are generated in the toner composition liquid chamber due to evaporation of the organic solvent, or the toner composition liquid is dried in the vicinity of the discharge holes to narrow the discharge holes. There is a case where stable ejection is hindered.
Heating temperature of release agent (° C.) <[Boiling point of organic solvent (° C.) − 20 (° C.)] Formula (I ′)

  The release agent needs to be dissolved in the toner composition liquid in order to prevent clogging of the discharge holes, but does not phase separate from the binder resin dissolved in the toner composition liquid. It is important to obtain a uniform toner particle that it is dissolved in the toner. Further, in order to exhibit releasability during fixing and prevent hot offset resistance, it is important that the binder resin and the release agent are phase separated in the toner particles from which the organic solvent has been removed. It is. If the release agent is not phase-separated from the binder resin, not only the release property cannot be exhibited, but also the viscosity and elasticity at the time of melting of the binder resin are lowered, resulting in more hot offset. It becomes easy. Accordingly, an optimum release agent is selected depending on the organic solvent and binder resin used.

Examples of such a release agent include aliphatic hydrocarbon waxes such as low molecular weight polyethylene wax, low molecular weight polypropylene wax, polyolefin wax, microcrystalline wax, paraffin wax and sazol wax; aliphatic such as polyethylene oxide wax Oxide of hydrocarbon wax or block copolymer thereof; plant wax such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal wax such as beeswax, lanolin, whale wax; ozokerite, ceresin, petrolatum Mineral waxes such as; waxes mainly composed of fatty acid esters such as montanic acid ester wax and caster wax; various synthetic ester waxes and synthetic amide waxes. These may be used alone or in combination of two or more.
Among these, the mold release agent contains at least one of synthetic ester wax, synthetic amide wax, and microcrystalline wax, and ensures the solubility of the wax in order to stably discharge droplets. It is preferable in that it can be performed.

There is no restriction | limiting in particular as said synthetic ester wax, According to the objective, it can select suitably, For example, what is obtained from a bivalent or more alcohol component and a fatty acid is mentioned.
There is no restriction | limiting in particular as said bivalent or more alcohol component, According to the objective, it can select suitably, For example, the component etc. which were mentioned by the said polyester resin are mentioned.
There is no restriction | limiting in particular as said fatty acid, Although it can select suitably according to the objective, The fatty acid etc. which have a C12-C28 linear or branched chain are mentioned.
Specific examples of the synthetic ester wax include WAX-42 and WEP-2 (manufactured by NOF CORPORATION) as trade names.

The synthetic amide wax is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those obtained from aliphatic amines and fatty acids.
Examples of such a synthetic amide wax include lauric acid amide, palmitic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, N-stearyl stearic acid amide, N-stearyl erucic acid amide, methylol stearic acid amide, Methylol behenic acid amide, dimethylol oil amide, dimethyl lauric acid amide, dimethyl stearic acid amide, ethylene bis oleic acid amide, ethylene bis stearic acid amide, ethylene biscaproic acid amide, methylene bis stearic acid amide, ethylene bis lauric acid amide Hexamethylene bis oleic acid amide, hexamethylene bis stearic acid amide, butylene bis stearic acid amide, m-xylylene bis stearic acid amide, m-xylylene bis-12 hydroxy Stearic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl isophthalic acid amide, N, N′-distearyl terephthalic acid amide, N— Examples include butyl-N'stearyl urea, N-propyl-N'stearyl urea, N-allyl-N'stearyl urea, N-stearyl-N'stearyl urea.
Specific examples of the synthetic amide wax include WAX-3, WAX-4, and WA-8 (manufactured by NOF CORPORATION) as trade names.

There is no restriction | limiting in particular as said microcrystalline wax, According to the objective, it can select suitably, For example, a C30-C60 hydrocarbon and the thing of a weight average molecular weight 500-800 are mentioned.
Specific examples of the microcrystalline wax include BSQ-180W (manufactured by Toyo Adre Co., Ltd.) under the trade name.

  The release agent may be other than wax. Examples of the release agent other than wax include palmitic acid, stearic acid, montanic acid, and other linear alkyl carboxylic acids having a linear alkyl group. Saturated straight-chain fatty acids; Unsaturated fatty acids such as prandidic acid, eleostearic acid, valinalic acid; stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, and other long-chain alkyl alcohols Saturated alcohols such as sorbitol; polyhydric alcohols such as sorbitol; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate; and vinyl hydrocarbon monomers such as styrene and acrylic acid in aliphatic hydrocarbon waxes Grafted Waxes; partial ester compound of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride; like methyl ester compounds having hydroxyl groups obtained by the vegetable oil is hydrogenated. These may be used alone or in combination of two or more.

  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 removed are preferably used as the release agent.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, From a viewpoint of balancing a fixing property and hot offset resistance, 50 to 140 degreeC is preferable, and 55 degreeC is preferable. ˜120 ° C. is more preferable. When the melting point is less than 50 ° C., the blocking resistance may be lowered, and when it exceeds 140 ° C., the hot offset resistance effect may be hardly exhibited.

In the present invention, the melting point of the release agent means the temperature at the peak top of the maximum endothermic peak of the release agent measured by differential scanning calorimetry (DSC).
As the DSC measuring instrument for measuring the melting points of the release agent and the toner, a highly accurate internal heat input compensation type differential scanning calorimeter is preferable. 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 once raising and lowering the temperature and taking a previous history.

  There is no restriction | limiting in particular as content of a mold release agent, Although it can select suitably according to the melt viscoelasticity, the fixing system, etc. of the said binder resin, it is 1 mass with respect to 100 mass parts of said binder resins. Part-50 mass parts is preferable, and 5 mass part-10 mass parts is more preferable. If the content of the release agent is less than 1 part by mass, the releasability at the time of fixing may be insufficient, and if it exceeds 50 parts by mass, the color developability may be impaired, Life may be reduced.

-Organic solvent-
The organic solvent is a volatile solvent that can dissolve or disperse the toner composition in the toner composition liquid, and does not cause phase separation of the binder resin and the release agent in the toner composition liquid. If it can be dissolved, there will be no restriction | limiting in particular, According to the objective, it can select suitably.

  The boiling point of the organic solvent is not particularly limited and may be appropriately selected depending on the kind of the binder resin and the release agent in the toner composition liquid, and is preferably 50 ° C to 120 ° C. 70 to 100 degreeC is more preferable. When the boiling point is less than 50 ° C., the volatility is too high and it may be difficult to handle the toner composition liquid. When the boiling point exceeds 120 ° C., the drying is slow and the energy required for drying becomes enormous. Since the droplets are difficult to dry, coalescence may occur where the discharged droplets are combined before drying.

Examples of such an organic solvent include ethers such as tetrahydrofuran (THF) (boiling point: 66 ° C.); acetone (boiling point: 57 ° C.), methyl ethyl ketone (MEK) (boiling point: 80 ° C.), methyl isobutyl ketone (boiling point). : Ketones such as 116 ° C; esters such as ethyl acetate (boiling point: 77 ° C) and butyl acetate (boiling point: 126 ° C); hydrocarbons such as toluene (boiling point: 110.6 ° C); 2-propanol ( Alcohols such as boiling point: 82 ° C.). These may be used alone or in combination of two or more.
Among these, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, and toluene are particularly preferable.

  There is no restriction | limiting in particular as content of the said organic solvent in the said toner composition liquid, Although it can select suitably according to the objective, 50 mass%-95 mass% are preferable, and 80 mass%-90 mass% are preferable. More preferred. When the content of the organic solvent is less than 50% by mass, the toner composition liquid exhibits a high viscosity, so that the ejection of droplets may become unstable. When the content exceeds 95% by mass, the recoverable toner weight And the drying energy at the time of forming the toner particles is increased, so that productivity may be lowered.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected from known materials used for conventional electrophotographic toners according to the purpose. For example, a charge control agent, various metal soaps, fluorine And surfactants such as surfactants. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as content of the said other component, In the range which does not impair the effect of this invention, it can select suitably according to the objective.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, and molybdate chelate pigments. , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, salicylic acid derivatives And metal salts thereof. These may be used alone or in combination of two or more.

Specific examples of the charge control agent include trade names such as “Bontron 03” as a nigrosine dye, “Bontron P-51” as a quaternary ammonium salt, “Bontron S-34” as a metal-containing azo dye, and Oxynaphtho. "E-82" of acid metal complex, "E-84" of salicylic acid metal complex, "E-89" of phenol condensate (above, manufactured by Orient Chemical Industry Co., Ltd.); quaternary ammonium salt molybdenum complex “TP-302”, “TP-415” (manufactured by Hodogaya Chemical Co., Ltd.); quaternary ammonium salt “copy charge PSY VP2038”, triphenylmethane derivative “copy blue PR”, fourth “Copy Charge NEG VP2036”, “Copy Charge NX VP434” (above, manufactured by Hoechst), “LRA-901” (Manufactured by Japan Carlit Co., Ltd.); boron complex "LR-147" (Japan Carlit Co., Ltd.), and the like.
Also usable are copper phthalocyanine, perylene, quinacridone, azo pigments, other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, quaternary ammonium salts, phenolic resins, fluorine compounds, and the like. .

The amount of the charge control agent used is not particularly limited and may be appropriately selected depending on the type of the binder resin, the presence or absence of additives used as necessary, the toner production method including the dispersion method, and the like. However, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of said binder resin, and 0.2 mass part-5 mass parts are more preferable. When the amount of the charge control agent used exceeds 10 parts by mass, toner fixability may be hindered.
These charge control agents are preferably dissolved in an organic solvent from the viewpoint of ejection stability, but may be finely dispersed in the organic solvent using a bead mill or the like.

<< Method for Preparing Toner Composition Liquid >>
The method for preparing the toner composition liquid is not particularly limited as long as the binder resin and the release agent can be dissolved in the toner composition liquid without phase separation, and may be appropriately selected depending on the purpose. Can do.
For the preparation of the toner composition liquid, it is important to use a homomixer or a bead mill to make the dispersion such as the colorant sufficiently fine with respect to the nozzle opening diameter in order to prevent clogging of the discharge holes. Become.

  There is no restriction | limiting in particular as solid content of the said toner composition liquid, Although it can select suitably according to the objective, It is preferable that it is 3 mass%-40 mass%. When the solid content is less than 3% by mass, not only the productivity of toner particles is decreased, but also the dispersion of the colorant and the like tends to cause sedimentation and aggregation, so that the composition of the toner particles is not uniform. The toner quality is likely to deteriorate. When the solid content exceeds 40% by mass, a toner having a small particle size may not be obtained.

<Droplet formation process>
In the droplet forming step, vibration is applied to the toner composition liquid in the liquid column resonance liquid chamber in which a plurality of ejection holes are formed to form a standing wave by liquid column resonance, and the standing wave In this step, the toner composition liquid is periodically ejected outside the ejection holes from the plurality of ejection holes formed in an antinode region to form droplets. By using this liquid column resonance method, a toner having a small particle size and monodispersibility can be efficiently produced.

In the droplet forming step, the temperature of the toner composition liquid is not particularly limited, and can be appropriately selected according to the deposition temperature of the dissolved matter, the freezing point of the organic solvent, the droplet discharge limit by the device, and the like. However, satisfying the following formula (I) enables the binder resin and the release agent to be dissolved in the toner composition liquid without phase separation, and stable continuous ejection can be performed. It is preferable at a point, It is more preferable to satisfy | fill following formula (II), It is especially preferable to satisfy | fill following formula (III).
Temperature of toner composition liquid (° C.) <[Boiling point of organic solvent (° C.) − 20 (° C.)] Formula (I)
Temperature (° C.) of toner composition liquid <[boiling point of organic solvent (° C.) − 30 (° C.)] Formula (II)
Temperature (° C.) of toner composition liquid <[boiling point of organic solvent (° C.) − 40 (° C.)] Formula (III)

Further, at this time, the temperature of a member (for example, a liquid column resonance liquid chamber) in contact with the toner composition liquid is preferably equal to or higher than the temperature of the toner composition liquid satisfying the formula (I). More preferably, it is about the same as the temperature. When the temperature of the member is lower than the temperature of the toner composition liquid satisfying the formula (I), the solubility of the binder resin and the release agent in the toner composition liquid may be reduced and may precipitate. The discharge hole may be clogged.
The temperature of the toner composition liquid and the member in contact with the toner composition liquid can be controlled to a desired temperature in a temperature control process described later.

  The liquid column resonance method is preferably performed by a liquid column resonance droplet forming unit, and the liquid column resonance droplet forming unit includes at least a liquid column resonance liquid chamber having the plurality of ejection holes, and a vibration unit. And have other means as needed.

<< Liquid column resonance liquid chamber >>
The liquid column resonance liquid chamber is a liquid chamber capable of forming a pressure standing wave by vibration applied by the vibrating means in accordance with the principle of the liquid column resonance phenomenon described later. A discharge hole is formed in the region, and a communication port for supplying the toner composition liquid is provided. If necessary, at least a part of one end or both ends in the longitudinal direction of the liquid column resonance liquid chamber is a reflection wall surface. Have
The communication port for supplying the toner composition liquid is preferably provided at an end portion in the longitudinal direction of the liquid column resonance liquid chamber, and the reflection wall surface is perpendicular to the longitudinal axis of the liquid column resonance liquid chamber. It is preferable to be provided on the surface.
Further, the liquid column resonance liquid chamber preferably has a vibration means disposed on one of the walls parallel to the longitudinal direction of the liquid column resonance liquid chamber, and the wall facing the wall on which the vibration means is disposed. It is preferable that a discharge hole is formed on the surface.

  The shape of the liquid column resonance liquid chamber is not particularly limited as long as a pressure standing wave can be formed by the vibration, and can be selected as appropriate. For example, a square column (rectangular body), a cylinder, a truncated cone Etc.

  It is preferable that the reflection wall surface is provided on at least a part of both ends in the longitudinal direction of the liquid column resonance liquid chamber. Here, the “reflective wall surface” refers to a wall surface formed by a member that is hard enough to reflect the sound wave of the liquid, for example, a metal member such as aluminum or stainless steel, a member such as silicone, or the like.

The length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber shown in FIG. 1 is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably determined based on the column resonance principle.
Further, the width W of the liquid column resonance liquid chamber shown in FIG. 2 is not particularly limited and can be appropriately selected according to the purpose. It is preferable that the length is less than one half of the length L of the liquid column resonance liquid chamber.

  Further, when the distance between the end portion on the liquid common supply path side and the center portion of the discharge hole 19 closest to the end portion is Le, the distance ratio (Le / L) between L and Le is as follows: There is no restriction | limiting in particular, Although it can select suitably according to the objective, It is preferable that it is larger than 0.6.

  Further, the liquid column resonance liquid chamber is formed by joining frames formed of a material having high rigidity that does not affect the resonance frequency of the toner composition liquid at the vibration drive frequency. Preferably, examples of such a material include metal, ceramics, and silicone.

  The thickness of the surface on which the plurality of ejection holes are formed in the liquid column resonance liquid chamber is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 μm to 200 μm, more preferably 5 μm to 100 μm. 10 μm to 60 μm is particularly preferable. When the thickness is less than 5 μm, the rigidity of the film is insufficient and the discharge of droplets may become unstable. When the thickness exceeds 100 μm, it is difficult to form a discharge hole having a small diameter (small opening diameter). The variation in the toner particle size may become large.

In the liquid column resonance liquid chamber, an insulating liquid repellent film, which will be described later, may be formed on the entire exposed surface.
The material used for the liquid repellent film is not particularly limited as long as it is an insulator, and can be appropriately selected according to the purpose. For example, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether Examples thereof include fluorine resins such as copolymers (PFA), fluorinated ethylene propylene (FEP), and polyvinylidene fluoride; epoxy resins such as bisphenol A and bisphenol F; and SiO ₂ . These may be used alone or in combination of two or more. Further, described in JP-A-2010-107904, it has a perfluoroalkyl group on the SiO ₂ film, and liquid-repellent film made of a compound having a siloxane bond group at the terminal can also be suitably used.

  It is preferable that a plurality of the liquid column resonance liquid chambers are arranged with respect to one droplet forming unit in order to dramatically improve the productivity of the toner. The number of liquid column resonance liquid chambers installed for one droplet forming means is not particularly limited and can be appropriately selected according to the purpose. However, in terms of achieving both operability and productivity, 100 to 2,000 are preferable, 100 to 1,000 are more preferable, and 100 to 400 are particularly preferable. If the number of liquid column resonance liquid chambers is one droplet forming unit provided in the above preferred range, it is advantageous in that both operability and productivity can be achieved.

-Discharge hole-
The discharge holes (sometimes referred to as “nozzles” or “through holes”) are formed on one surface (wall) of the liquid column resonance liquid chamber.
The discharge hole is not particularly limited as long as it is formed in a region that becomes the antinode of the pressure standing wave, and can be appropriately selected according to the purpose. It is preferable that a plurality of regions be formed for at least one of the regions.

The “region that becomes the antinode of the pressure standing wave” is a region where the amplitude in the pressure wave of the liquid column resonance standing wave is large and the pressure fluctuation is large, and is large enough to eject a droplet. This is a region having pressure fluctuation. There is no particular limitation on the region that becomes the antinode of such a pressure standing wave, and it can be appropriately selected according to the purpose. However, the position where the amplitude of the pressure standing wave becomes a maximum (as a velocity standing wave) ± 1/3 wavelength is preferable from the section of (1) to the position where it becomes the minimum, and ± 1/4 wavelength is more preferable.
When the discharge hole is formed in a region that becomes the antinode of the pressure standing wave, even if a plurality of discharge holes are opened, a substantially uniform droplet can be formed from each discharge hole. Furthermore, it is preferable in that the droplets can be efficiently discharged and the discharge holes are not easily clogged.

  The number (number of openings) of the discharge holes formed for at least one of the regions that become the antinodes of the pressure standing wave is not particularly limited and can be appropriately selected according to the purpose. The number is preferably 20 to 20, more preferably 4 to 15, and particularly preferably 4 to 10. The productivity increases as the number of the ejection holes increases, but when the number exceeds 20, the ejection holes become too dense and the ejected droplets may coalesce into coarse particles, which may adversely affect image quality. .

  In one liquid column resonance liquid chamber, a plurality of discharge holes are arranged, preferably 2 to 100, more preferably 4 to 60, and particularly preferably 4 to 20. If the number of ejection holes exceeds 100, it is necessary to set a high voltage to the vibration means when forming droplets of a desired toner composition liquid from the 100 ejection holes. May become unstable. In addition, when 4 to 20 discharge holes are arranged in one liquid column resonance liquid chamber, the standing wave is stable and productivity is maintained.

The plurality of discharge holes may all have the same opening diameter, or two or more discharge holes may have different opening diameters, but all preferably have the same opening diameter.
Here, the opening diameter of the discharge hole means the opening diameter of the discharge opening (the end of the discharge hole in the discharge direction) of the discharge hole. The opening diameter of the discharge hole means a diameter if it is a perfect circle, and an average diameter if it is a polygon such as an ellipse, a rectangle, a hexagon, an octagon, or a regular polygon. Further, “the same opening diameter” means that the average opening diameter is within a range of ± 10%.

  The opening diameter of the discharge hole is not particularly limited and may be appropriately selected depending on the intended purpose. 1 μm to 30 μm is a very uniform particle when a toner composition liquid droplet is discharged from the discharge hole. It is preferable at the point which generates the micro droplet which has a diameter, 3 micrometers-30 micrometers are more preferable, 3 micrometers-20 micrometers are still more preferable, and 5 micrometers-15 micrometers are especially preferable. If the opening diameter is less than 1 μm, the formed droplets are very small, and toner may not be obtained. Further, when solid fine particles such as a pigment are contained as a component of the toner composition liquid, there is a possibility that the ejection holes are frequently blocked and the productivity is lowered. Further, when the opening diameter exceeds 30 μm, the diameter of the toner droplet is large, and when this is dried and solidified to obtain a desired toner particle diameter of 1 μm to 8 μm, the toner composition is made very dilute with an organic solvent. In some cases, it is necessary to dilute, and a large amount of drying energy is required to obtain a certain amount of toner, which is inconvenient.

There is no restriction | limiting in particular as the pitch between the said discharge holes (shortest space | interval between the center part of an adjacent discharge hole), Although it can select suitably according to the objective, As a lower limit, 20 micrometers or more are preferable. Further, the upper limit value can be appropriately selected according to the length in the longitudinal direction of the liquid column resonance liquid chamber described later. The pitch is more preferably 20 μm to 200 μm, further preferably 40 μm to 135 μm, and particularly preferably 40 μm to 80 μm. When the pitch between the ejection holes is less than 20 μm, there is a high probability that droplets discharged from adjacent ejection holes collide with each other to form large droplets, which may lead to deterioration in toner particle size distribution. .
The pitch between the discharge holes may be all at equal intervals between the plurality of discharge holes, or at least one pitch may be different. It is preferable in that it can be obtained.

There is no restriction | limiting in particular as a cross-sectional shape of the said discharge hole in the thickness direction of the said liquid column resonance liquid chamber, According to the objective, it can select suitably, For example, cross-sectional shape as shown to FIG. It is done.
FIG. 8A shows a shape in which the opening diameter becomes narrow while having a round shape from the liquid contact surface 69 of the discharge hole 19 toward the discharge direction, and near the outlet of the discharge hole 19 when vibration occurs. Since the pressure applied to the toner composition liquid is maximized, it is the most preferable shape for stabilizing the ejection.
FIG. 8B has a shape in which the opening diameter becomes narrow at a certain angle from the liquid contact surface 69 of the discharge hole 19 toward the discharge direction, and the liquid contact surface in the section of the discharge hole is directed to the discharge port. The angle (hereinafter sometimes referred to as “the angle of the discharge hole”) 44 can be changed as appropriate. As in FIG. 8A, the pressure applied to the liquid can be increased near the outlet of the discharge hole 19 when vibration is generated by the angle 44 of the discharge hole. There is no restriction | limiting in particular as an angle of the said discharge hole, Although it can select suitably according to the objective, 60 degrees-90 degrees are preferable. When the angle is less than 60 °, it is difficult to apply pressure to the toner composition liquid, and it is difficult to process the toner composition liquid.
When the angle of the discharge hole is 90 °, FIG. 8C corresponds, but since it is difficult to apply pressure to the outlet of the discharge hole 19, 90 ° is the maximum value. When the angle exceeds 90 °, no pressure is applied to the outlet of the discharge hole 19, so that the droplet discharge becomes very unstable.
FIG. 8D is a shape that combines FIG. 8A and FIG. 8B. In this way, the shape may be changed step by step.

  A method for forming the discharge hole in the liquid column resonance liquid chamber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method for processing by electroforming and a method for processing by electric discharge. It is done. Moreover, there is no restriction | limiting in particular as a method of processing an ejection hole in arbitrary shapes, According to the objective, it can select suitably, For example, when processing by electroforming, when processing by a LIGA process and electric discharge And a method of controlling with an electrode.

<< Vibration means >>
The vibration means is not particularly limited as long as vibration can be generated, and can be appropriately selected according to the purpose. As a result, the toner composition liquid in the plurality of ejection holes in the liquid column resonance liquid chamber is ejected in droplets.
The vibrating means has a vibrating surface parallel to a surface on which the plurality of discharge holes of the liquid column resonance liquid chamber are formed, and the vibration surface is formed with a plurality of discharge holes of the liquid column resonance liquid chamber. It is preferable that it vibrates longitudinally in a direction perpendicular to the surface.

Specific examples of the vibration generator include an ultrasonic generator that generates mechanical vibration by a piezoelectric effect or a magnetostriction effect. Among these, those capable of converting electricity into mechanical vibration by the piezoelectric effect are preferable in that vibration can be efficiently generated at a higher frequency, and examples thereof include a piezoelectric body.
The material of the piezoelectric body is not particularly limited and may be appropriately selected depending on the purpose. Since the piezoelectric ceramics generally have a small displacement, they are often used by being laminated. Other examples include piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , and KNbO ₃ . Among these, the vibration means is preferably lead zirconate titanate (PZT) in terms of vibration controllability.

It is preferable that the vibration means is bonded to an elastic plate, and the elastic plate preferably forms part of the wall of the liquid column resonance liquid chamber so that the vibration means does not come into contact with the liquid.
Furthermore, it is preferable that the vibration means is arranged so that it can be individually controlled for each liquid column resonance liquid chamber. In addition, it is preferable to arrange vibration means such as a block-like piezoelectric body via an elastic plate in accordance with the arrangement of the liquid column resonance liquid chambers, from the viewpoint that each liquid column resonance liquid chamber can be individually controlled.

<< Mechanism of droplet formation >>
Next, the mechanism of droplet formation according to the present embodiment will be described.
FIG. 1 is a cross-sectional view showing an example of a liquid column resonance droplet forming unit. The liquid column resonance droplet forming unit 11 shown in FIG. 1 has a liquid column resonance liquid chamber 18 and a common liquid supply path 17 for storing the toner composition liquid 14 therein. The liquid column resonance liquid chamber 18 communicates with a liquid common supply path 17 provided on one of the wall surfaces at both ends in the longitudinal direction. Further, the liquid column resonance liquid chamber 18 is provided on a wall surface facing the discharge hole 19 and a discharge hole 19 for discharging the droplet 21 to one wall surface of the wall surfaces connected to both ends. Vibration generating means 20 for generating high-frequency vibrations to form a standing wave. The vibration generating means 20 is connected to a high frequency power source (not shown).

First, the principle of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 18 in the liquid column resonance droplet forming means 11 of FIG. 1 will be described. When the sound velocity of the toner composition liquid in the liquid column resonance liquid chamber is c and the drive frequency applied from the vibrating means 20 to the toner composition liquid 14 as a medium is f, the wavelength λ at which the liquid resonance occurs is There is a relationship of Formula 1).
λ = c / f (Formula 1)

Further, in the liquid column resonance liquid chamber 18 of FIG. 1, the length from the end of the frame on the fixed end side to the end on the common liquid supply path 17 side is L, and further, the end of the frame on the common liquid supply path 17 side And the height of the communication port is h2.
In the case of a both-side fixed end that is assumed to be equivalent to a closed fixed end on the liquid common supply path 17 side, resonance occurs when the length L matches an even multiple of a quarter of the wavelength λ. Most efficiently formed. That is, it is expressed by the following (Formula 2).
L = (N / 4) λ (Expression 2)
(However, N represents an even number.)

The case where it is equivalent to the fixed end is a case where it can be considered that there is no pressure relief portion at a certain end. For example, the height of the reflection wall surface at a certain end is the communication for supplying the toner composition liquid. This refers to the case where the height of the mouth is twice or more, and the case where the area of the reflection wall surface at a certain end is twice or more the area of the opening of the communication port for supplying the toner composition liquid.
In FIG. 1, the length from the end of the frame on the fixed end side of the liquid column resonance liquid chamber 18 to the end on the liquid common supply path 17 side corresponds to the length L. Further, the height h1 (= about 80 μm) of the end of the frame on the liquid common supply path 17 side is about twice the height h2 (= about 40 μm) of the communication port, and the both ends are fixed. Can be considered equivalent to.

Further, the above (Formula 2) is also established in the case of a double-sided open end where both ends are completely open or equivalent to a double-sided open end.
Similarly, when one side is equivalent to an open end with a pressure relief portion and the other side is closed (fixed end), that is, one side fixed end or one side open end, the length L is the wavelength λ. Resonance is most efficiently formed when it matches an odd multiple of a quarter. That is, N in (Expression 2) is expressed as an odd number. In the case of the open ends on both sides, L corresponds to an even multiple of a quarter of the wavelength, and in the case of one side fixed end, L corresponds to an odd multiple of a quarter of the wavelength.

For the drive frequency f with the highest efficiency, the following (Expression 3) is derived from (Expression 1) and (Expression 2).
f = N × c / (4L) (Formula 3)
(However, L represents the length of the liquid column resonance liquid chamber in the longitudinal direction, c represents the velocity of the sound wave of the toner composition liquid, and N represents an integer.)
Therefore, in the toner manufacturing method of the present invention, it is preferable to apply a vibration having a frequency f at which (Equation 1) holds to the toner composition liquid. However, in reality, since the liquid has a viscosity that attenuates resonance, the vibration is not amplified infinitely, and has a Q value. As shown in (Expression 4) and (Expression 5) described later, Resonance also occurs at a frequency in the vicinity of the drive frequency f with the highest efficiency shown in Equation 3).

3A to 3D show the shape of the standing wave of the velocity and pressure fluctuation (resonance mode) when N = 1, 2, and 3. FIGS. 4A to 4C show the velocity and pressure when N = 4 and 5 The shape of the fluctuation standing wave (resonance mode) is shown.
Although it is originally a sparse / dense wave (longitudinal wave), it is generally expressed as in FIGS. 3A to 3D and 4A to 4C. In FIGS. 3A to 3D and FIGS. 4A to 4C, the solid line is the velocity standing wave, and the dotted line is the pressure standing wave.
For example, as can be seen from FIG. 3A showing the case of the one-side fixed end with N = 1, in the case of the speed distribution, the amplitude of the speed distribution becomes zero at the closed end, and the amplitude becomes maximum at the open end.
When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, the wavelength at which the liquid resonates is λ, and the standing wave is most efficiently generated when the integer N is 1 to 5. . In addition, since the standing wave pattern varies depending on the open / closed state of both ends, they are also shown. As will be described later, the condition of the end is determined by the state of the opening of the discharge hole and the opening of the supply side.
In acoustics, the open end is an end at which the moving speed of the medium (liquid) in the longitudinal direction becomes zero, and conversely, the pressure becomes maximum. Conversely, the closed end is defined as an end where the moving speed of the medium becomes zero. The closed end is considered as an acoustically hard wall and wave reflection occurs. When ideally completely closed or open, resonance standing waves having the forms shown in FIGS. 3A to 3D and FIGS. 4A to C are generated by superposition of waves, but the number of discharge holes and the opening positions of the discharge holes The standing wave pattern also fluctuates, and the resonance frequency appears at a position deviated from the position obtained from the above (Equation 3). However, a stable ejection condition can be created by appropriately adjusting the driving frequency.

For example, the sound velocity c of the liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, wall surfaces exist at both ends, and N = 2 resonance that is completely equivalent to the fixed ends on both sides. When the mode is used, the most efficient resonance frequency is derived as 324 kHz from (Equation 2).
In another example, the sound velocity c of the liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, and the same conditions as described above are used. When the equivalent N = 4 resonance mode is used, the most efficient resonance frequency is derived from (Formula 2) as 648 kHz, and even in a liquid column resonance liquid chamber having the same structure, a higher order resonance frequency is obtained. Resonance can be used.

  The liquid column resonance liquid chamber 18 in the liquid column resonance droplet forming unit 11 shown in FIG. 1 is described as an acoustically soft wall because both ends are equivalent to the closed end state or due to the opening of the discharge hole 19. Although it is preferable for the frequency to be high that it can be an end, the end is not limited to this, and may be an open end. The influence of the opening of the discharge hole 19 here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. Therefore, forming wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 as shown in FIG. 3B and FIG. 4A means that the resonance mode of the both-side fixed ends and all resonances of the one-side open ends considered to be openings on the discharge hole side. The mode is preferred because it is available.

Further, the numerical aperture of the discharge holes 19, the opening arrangement position, and the cross-sectional shape of the discharge holes are factors that determine the drive frequency, and the drive frequency can be appropriately determined according to this.
For example, when the number of the discharge holes 19 (numerical aperture) is increased, the restriction at the tip of the liquid column resonance liquid chamber 18 which has been a fixed end gradually becomes loose, and a resonance standing wave almost close to the open end is generated and driven. The frequency increases. Furthermore, the opening position of the discharge hole 19 existing closest to the liquid common supply path 17 is a starting point, and a loose constraint condition is established. The cross-sectional shape of the discharge hole 19 is round or the volume of the discharge hole due to the thickness of the frame is large. The actual standing wave fluctuates or has a short wavelength, which is higher than the driving frequency. When a voltage is applied to the vibration means at the drive frequency determined in this way, the vibration means 20 is deformed, and a resonant standing wave is generated most efficiently at the drive frequency. Further, the liquid column resonance standing wave is generated even at a frequency in the vicinity of the drive frequency at which the resonance standing wave is generated most efficiently. That is, when the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, and the distance to the discharge hole 19 closest to the end on the liquid common supply path 17 side is Le, the length of both L and Le The vibration means is vibrated using a driving waveform having a driving frequency f in the range determined by the following (Equation 4) and (Equation 5) as a main component, and liquid droplet resonance is induced to eject a droplet. It is possible to discharge from the hole.

N × c / (4L) ≦ f ≦ N × c / (4Le) (Formula 4)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (Formula 5)
(However, L represents the length of the liquid column resonance liquid chamber in the longitudinal direction, Le represents the distance to the discharge hole closest to the end on the liquid supply path side, c represents the velocity of the sound wave of the toner composition liquid, N represents an integer.)

  A liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 18 of FIG. 1 using the principle of the liquid column resonance phenomenon described above, and the discharge holes 19 arranged in a part of the liquid column resonance liquid chamber 18. In this case, droplet discharge occurs continuously. Note that it is preferable to dispose the discharge hole 19 at a position where the pressure of the standing wave fluctuates the most, since the discharge efficiency is increased and the driving can be performed with a low voltage.

Next, the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber in the liquid column resonance droplet forming means will be described with reference to FIGS.
5A to 5E, the solid line written in the liquid column resonance liquid chamber is a velocity obtained by plotting the velocity at each arbitrary measurement position from the fixed end side to the end on the liquid common supply path side in the liquid column resonance liquid chamber. The distribution is shown, and the direction from the common liquid supply path to the liquid column resonance liquid chamber is “+”, and the opposite direction is “−”.
In addition, the dotted line marked in the liquid column resonance liquid chamber indicates a pressure distribution in which the pressure value at each arbitrary measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted. The positive pressure is “+” with respect to the atmospheric pressure, and the negative pressure is “−”. Moreover, if it is a positive pressure, a pressure will be applied to the downward direction in the figure, and if it is a negative pressure, a pressure will be applied to the upward direction in the figure.
5A to 5E, the liquid common supply path side is opened as described above, but the height of the opening where the liquid common supply path 17 and the liquid column resonance liquid chamber 18 communicate with each other (height h2 shown in FIG. 1). 1), the height of the frame serving as the fixed end (height h1 shown in FIG. 1) is preferably about twice or more, so that the liquid column resonance liquid chamber 18 is approximately the fixed end on both sides. Each change over time of the velocity distribution and the pressure distribution under the condition is shown.

  FIG. 5A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 at the time of droplet discharge. In FIG. 5B, the meniscus pressure increases again after the liquid is drawn immediately after the droplet is discharged. As shown in FIGS. 5A and 5B, the pressure in the flow path provided with the discharge hole 19 in the liquid column resonance liquid chamber 18 is maximum. Thereafter, as shown in FIG. 5C, the positive pressure in the vicinity of the discharge hole 19 decreases, and the liquid droplet 21 is discharged in a negative pressure direction.

  And as shown to FIG. 5D, the pressure of the discharge hole 19 vicinity becomes the minimum. From this time, the filling of the toner composition liquid 14 into the liquid column resonance liquid chamber 18 starts. Thereafter, as shown in FIG. 5E, the negative pressure in the vicinity of the discharge hole 19 decreases, and shifts to the positive pressure direction. At this time, the filling of the toner composition liquid 14 is completed. Then, as shown in FIG. 5A again, the positive pressure in the droplet discharge region of the liquid column resonance liquid chamber 18 becomes maximum, and the droplet 21 is discharged from the discharge hole 19. As described above, a standing wave due to liquid column resonance is generated in the liquid column resonance liquid chamber by high-frequency driving of the vibration means, and corresponds to an antinode of standing wave due to liquid column resonance at a position where the pressure fluctuates most. Since the discharge hole 19 is disposed in the droplet discharge region, the toner droplet 21 is continuously discharged from the discharge hole 19 in accordance with the antinode period.

Next, an example where droplets are actually ejected by the liquid column resonance method will be described. An example of this is the resonance mode (fixed on both sides) in which the length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 in FIG. 1 is 1.85 mm and N = 2, and the first to fourth discharges. FIG. 6 shows a state in which ejection holes are arranged at the antinodes of the resonance mode pressure standing wave with N = 2 and the ejection performed with a sine wave with a driving frequency of 340 kHz is photographed by the laser shadowgraphy method. As can be seen from FIG. 6, the discharge of the liquid droplets having very uniform diameters and substantially uniform discharge speeds is realized.
Further, in FIG. 7, the first to fourth discharge holes are arranged at the antinodes of the resonance mode pressure standing wave with N = 1, and driven by the same amplitude sine wave with a drive frequency of 85 kHz to 165 kHz. Droplet velocity frequency characteristics, and the first to fourth discharge holes are arranged at the antinode of the resonance mode pressure standing wave with N = 2, and the same amplitude sine wave with a drive frequency of 290 kHz to 395 kHz It is a characteristic view which shows the droplet velocity frequency characteristic at the time of driving by. As can be seen from FIG. 7, in the first to fourth discharge holes, when the drive frequency is around 340 kHz, the discharge speed from each discharge hole is uniform and the maximum discharge speed. From this characteristic result, it can be seen that uniform ejection is realized at the antinode position of the liquid column resonance standing wave in the resonance mode of N = 2 of the liquid column resonance frequency and the drive frequency of 340 kHz. Further, from the characteristic results of FIG. 7, the droplet is between the droplet discharge speed peak at 130 kHz which is the resonance mode of N = 1 and the droplet discharge speed peak at 340 kHz which is the resonance mode of N = 2. It can be seen that the characteristic frequency characteristic of the liquid column resonance standing wave of the liquid column resonance that does not discharge is generated in the liquid column resonance liquid chamber.

  Hereinafter, an embodiment of a droplet forming step using the liquid column resonance method of the toner manufacturing method of the present invention will be described in detail with reference to the drawings. The droplet forming step in the toner manufacturing method of the present invention includes: It is not limited to this.

FIG. 9 is an example of a cross-sectional view showing the entire toner manufacturing apparatus for carrying out the toner manufacturing method of the present invention, and mainly includes the droplet forming means 2 and the toner particle forming means 60.
In the liquid column resonance method, the droplet forming means 2 (droplet discharge unit) is a liquid column resonance liquid chamber having a liquid discharge region communicating with the outside through the discharge hole 19 shown in FIGS. A droplet forming unit in which a plurality of droplet forming means 2 for discharging the toner composition liquid 14 in the liquid column resonance liquid chamber 18 in which the liquid column resonance standing wave is generated by the mechanism as droplets 21 from the discharge holes 19 is arranged. .

First, with reference to FIG. 9, an example of a form of feeding the toner composition liquid 14 to the droplet forming unit 2 will be described.
The toner manufacturing apparatus 1 pumps the toner composition liquid 14 stored in the raw material container 13 by the liquid circulation pump 15 through the liquid supply pipe 16 and supplies it to the droplet forming means 2. Further, the toner composition liquid 14 returns from the droplet forming means 2 to the raw material container 13 through the liquid return pipe 22.

  As shown in FIG. 1, the droplet forming unit is a liquid column resonance droplet forming unit 11 having a liquid common supply path 17 and a liquid column resonance liquid chamber 18. The liquid column resonance liquid chamber 18 communicates with a liquid common supply path 17 provided on one of the wall surfaces at both ends in the longitudinal direction. The liquid column resonance liquid chamber 18 is provided on a wall surface facing the discharge hole 19 and a discharge hole 19 that discharges the toner droplet 21 to one wall surface of the wall surfaces connected to both ends. And vibration means 20 for generating high-frequency vibration to form a standing wave. Note that a high-frequency power source (not shown) is connected to the vibration means 20.

FIG. 2 is a view of the liquid column resonance droplet forming unit 11 of FIG. 1 as viewed from below (a surface parallel to the opening surface of the discharge hole). For each liquid column resonance liquid chamber, a flow path for supplying liquid is connected in communication from the liquid common supply path 17, and the liquid common supply path 17 communicates with a plurality of liquid column resonance liquid chambers 18.
A plurality of discharge holes 19 are formed in the liquid column resonance liquid chamber 18. As shown in FIG. 2, it is preferable to provide the plurality of discharge holes 19 in the width W direction in the liquid column resonance liquid chamber 18 because a large number of openings of the discharge holes 19 can be provided. . In addition, since the liquid column resonance frequency varies depending on the arrangement of the discharge holes 19, it is desirable that the liquid column resonance frequency is appropriately determined by confirming the discharge of the droplet.

  The vibrating means 20 in the liquid column resonant droplet forming means 11 is not particularly limited as long as it can be driven at a predetermined frequency, and can be appropriately selected according to the purpose. A form bonded to a plate is preferable. The elastic plate forms a part of the wall of the liquid column resonance liquid chamber so that the piezoelectric body does not come into contact with the elastic body.

  In addition, although the cross-sectional shape of the discharge hole 19 is described as a shape in which the opening diameter becomes narrow at a certain angle toward the discharge direction in FIG. 1, the cross-sectional shape can be changed as appropriate.

Next, an outline of droplet formation by the liquid column resonance method will be described.
The toner composition liquid 14 accommodated in the raw material container 13 shown in FIG. 9 is passed through the liquid supply pipe 16 by the liquid circulation pump 15 for circulating the toner composition liquid 14, and the droplet forming unit shown in FIG. The liquid common supply path 17 is supplied to the liquid column resonance liquid chamber 18 of the liquid column resonance droplet forming means 11 shown in FIG.
In the liquid column resonance liquid chamber 18 filled with the toner composition liquid 14, a pressure distribution is formed by the liquid column resonance standing wave generated by the vibration unit 20. Then, the toner droplet 21 is ejected from the ejection hole 19 arranged in a region where the amplitude of the liquid column resonance standing wave has a large amplitude and the pressure fluctuation is large and becomes the antinode of the standing wave.

  The liquid feeding pressure to the droplet forming means 2 and the pressure in the chamber 61 are managed by the liquid pressure gauge P1 and the in-chamber pressure gauge P2. At this time, if P1> P2, the toner composition liquid 14 may ooze out from the discharge hole, and if P1 <P2, gas may enter the droplet forming means 2 and discharge may stop. Therefore, it is desirable that P1≈P2.

  The toner composition liquid 14 that has passed through the common liquid supply path 17 flows through the liquid return pipe 22 shown in FIG. 9 and is returned to the raw material container 13. When the amount of the toner composition liquid 14 in the liquid column resonance liquid chamber 18 decreases due to the ejection of the toner droplets 21, a suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 18 acts, and the liquid common The flow rate of the toner composition liquid 14 supplied from the supply path 17 increases, and the toner composition liquid 14 is replenished into the liquid column resonance liquid chamber 18. Then, when the toner composition liquid 14 is replenished in the liquid column resonance liquid chamber 18, the flow rate of the toner composition liquid 14 passing through the liquid common supply path 17 is restored to the original, and the liquid supply pipe 16 and the liquid return pipe 22 are supplied. The flow of the toner composition liquid 14 circulating in the apparatus is again formed.

<Temperature control process>
The temperature control step is a step of controlling the temperature of the toner composition liquid and the members in the toner manufacturing apparatus with which the toner composition liquid contacts. The temperature control step is preferably performed by temperature control means.
There is no restriction | limiting in particular as said temperature control means, According to the objective, it can select suitably, For example, an indirect heating type heater, a contact heating type heater, etc. are mentioned. Further, it is possible to circulate a liquid at a constant temperature in a tank equipped with a heater and a temperature regulator to immerse the means, or to form a circulation path so that the liquid at a constant temperature is in close contact with the means.
The member in contact with the toner composition liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a raw material container, a liquid supply pipe, and a droplet forming unit (droplet forming unit). .

<Toner particle forming step>
The toner particle forming step is a step of forming toner particles by removing the organic solvent from the droplets formed in the droplet forming step and drying and solidifying the liquid. The toner particle forming step is preferably performed by toner particle forming means.
In the toner particles, it is essential that the binder resin and the release agent are phase-separated. In the toner particles, wherein the binder resin and the releasing agent are phase separation, were embedded toner particles of a known material such as an epoxy resin, and sectioned at Ultrasonic microtome, RuO ₄ This can be confirmed by observation with a transmission electron microscope (TEM).

  Hereinafter, an embodiment of a toner particle forming step of the toner manufacturing method of the present invention will be described in detail with reference to the drawings. However, the toner particle forming step in the toner manufacturing method of the present invention is not limited to this. .

As shown in FIGS. 1 and 2, the droplet 21 of the toner composition liquid 14 discharged from the liquid column resonance droplet forming means 11 in the droplet forming step is generated in the airflow passage 12 by a conveying airflow (not shown). When the conveying air flow 101 generated by the means passes, it flows out to the toner particle forming means 60 side shown in FIG.
In FIG. 1, the direction of the airflow passage 12 is the same as the direction in which the droplets 21 are discharged, but this is not always necessary, and the direction of the airflow passage 12 can be selected as appropriate.

  FIG. 10 is a diagram illustrating another example of the airflow passage 12. The airflow passage 12 includes a first airflow passage 12-1, a second airflow passage 12-2 that communicates with the first airflow passage 12-1, and that leads to the gas phase of the chamber 61 in the toner particle forming means 60. Consists of. The direction of the first airflow passage 12-1 is substantially perpendicular to the droplet discharge direction, and the second airflow passage 12-1 is substantially orthogonal to the direction of the first airflow passage 12-1. And the same direction as the droplet discharge direction.

  FIG. 11 is a view showing still another example of the airflow passage 12. The direction of the air flow passage 12 is a direction substantially orthogonal to the droplet discharge direction, and this direction is the direction to the gas phase of the chamber 61 in the toner particle forming means 60.

The toner particle forming unit 60 shown in FIG. 9 includes a chamber 61, a toner collecting unit 62, and a toner storage unit 63. In the chamber 61, the carrier airflow 102 flows from the carrier airflow inlet 64 to form a descending airflow. Since the droplet 21 ejected from the droplet forming means 2 is transported downward not only by gravity but also by the transport air flow 102, the ejected toner droplet 21 is decelerated by air resistance. Can be suppressed. Accordingly, when the toner droplets 21 are continuously ejected, the toner droplets 21 ejected before are decelerated by air resistance before drying, and the toner droplets 21 ejected later are ejected before. By catching up with the toner droplets 21, it is possible to suppress the toner droplets 21 from being joined and integrated to increase the particle size of the toner droplets 21. The droplet 21 composed of the toner composition liquid 14 is in a liquid state immediately after being ejected from the droplet forming means 2, but the volatile solvent contained in the toner composition liquid is not conveyed while being transported in the chamber 61. Drying progresses by volatilization and changes from liquid to solid. In FIG. 9, the droplet forming means 2 ejects the droplet 21 in the direction of gravity, but this is not always necessary, and the angle at which the droplet 21 is ejected can be selected as appropriate.
In addition, as a conveyance airflow generation means for generating the conveyance airflow 102, either a method of providing a blower at the conveyance airflow inlet 64 at the upper portion of the chamber 61 and pressurizing it, or a method of suctioning from the conveyance airflow outlet 65 can be adopted. .

As the toner collecting means 62, a known collecting device can be used, and a cyclone collecting machine, a back filter, or the like can be used.
The carrier airflow (101, 102) is not particularly limited as long as the coalescence of the droplets 21 can be suppressed, and can be appropriately selected according to the purpose, and is a laminar flow, a swirl flow, or a turbulent flow. It doesn't matter. There are no particular limitations on the type of gas that makes up the carrier airflow (101, 102), and it may be air or an incombustible gas such as nitrogen, but the droplet 21 will not coalesce when dried. Therefore, it is preferable to have conditions that can promote drying of the droplets 21.
For this reason, it is preferable that the transport airflow (101, 102) does not contain the vapor of the organic solvent contained in the toner composition liquid. Further, the temperature of the conveying airflow (101, 102) can be adjusted as appropriate, and it is desirable that there is no fluctuation during production.
Further, a means for changing the airflow state of the carrier airflow (101, 102) in the chamber 61 may be taken. The carrier airflow (101, 102) is used not only to prevent the adhesion of the droplets 21 but also to prevent adhesion to the chamber 61 and the airflow passages (12, 12-1, 12-2). Also good.

  When the droplets are in a solid state after being dried and solidified, no coalescence occurs even if the particles come into contact with each other, and can be recovered as toner particles (powder) by the toner collecting means 62. Examples of the toner collecting unit 62 include a rotating airflow generator that generates a rotating airflow that rotates around an axis parallel to the vertical direction. The toner collected by the toner collecting means 62 can be stored in the toner storage unit 63 via a collecting tube connected to the chamber 61.

The toner stored in the toner storage unit 63 may be secondarily dried in a separate process as necessary. There is no restriction | limiting in particular as a method of performing the said secondary drying, According to the objective, it can select suitably, For example, a fluid bed drying method, a vacuum drying method, a ventilation drying method etc. are mentioned.
If the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage stability, fixability, and charging characteristics will change over time, but the organic solvent will volatilize during fixing by heating, which will adversely affect users and peripheral devices. Therefore, it is necessary to carry out sufficient drying. Therefore, secondary drying is advantageous in that the organic solvent in the toner composition liquid can be sufficiently dried.

<Fixing prevention process>
In the toner particle forming step, the coalescence of the particles can be suppressed by the air flow, but if this is still insufficient, the toner production method of the present invention may include a further adhesion prevention step. . The said adhesion prevention process is suitably performed by an adhesion prevention means.
The adhesion preventing means is not particularly limited and may be appropriately selected depending on the purpose. For example, means for introducing an auxiliary transport airflow in the vicinity of the droplet forming means, and charging with the same polarity to the droplets The means to do is mentioned.

FIG. 12 is a diagram showing an example in which an auxiliary transport airflow is used as the adhesion preventing means.
A shroud 66 is disposed around the droplet forming means 2, and an auxiliary transport airflow inlet 67 is disposed in a part thereof. The gas introduced from the auxiliary conveyance airflow inlet 67 passes through the auxiliary conveyance airflow passage 12-3 formed by the shroud 66, and an auxiliary conveyance airflow 68 is created around the discharge hole 19 of the droplet forming means 2. The droplets 21 ejected from the droplet forming means 2 are moved by the auxiliary transport airflow 68 in the vicinity of the droplet forming means 2 without decreasing the speed, so that the frequency of coalescence of the droplets is extremely low. Can be suppressed. The speed of the auxiliary transport air flow 68 is desirably the same or faster than the droplet speed immediately after being ejected from the droplet forming means 2, and if it is slower, the effect may be counterproductive.

  As shown in FIG. 12, the direction of the auxiliary transport air flow 68 is not particularly limited as long as it can prevent coalescence, and can be appropriately selected according to the purpose, but is the same as the traveling direction of the droplet 21. It is preferable that

The shape of the shroud 66 is not particularly limited and can be appropriately selected according to the purpose. For example, as shown in FIG. 12, there is a shape in which the opening is narrowed in the vicinity of the discharge hole 19 of the droplet forming unit 2. Can be mentioned. This makes it possible to control the flow velocity, but it is not necessary to have a restriction.
There is no restriction | limiting in particular as a kind of gas which comprises the said auxiliary | assistant conveyance airflow 68, According to the objective, it can select suitably, For example, nonflammable gas, such as air and nitrogen, etc. are mentioned. These may be used alone or in combination of two or more.

(toner)
The toner of the present invention is a toner obtained by the toner production method of the present invention, and its volume average particle size is 1 μm to 8 μm, preferably 3 μm to 6 μm. When the volume average particle diameter of the toner is in the range of 1 μm to 8 μm, a high-resolution, high-definition and high-quality image can be formed.

The particle size distribution of the toner can be compared by the ratio of the volume average particle diameter (Dv) and the number average particle diameter (Dn), and can be expressed as Dv / Dn. The smallest Dv / Dn value is 1.0, indicating that all particle sizes are the same. A larger Dv / Dn indicates a wider particle size distribution.
The particle size distribution (Dv / Dn) of the toner is 1.00 to 1.15, preferably 1.00 to 1.10, and particularly preferably 1.00 to 1.05. When Dv / Dn is in the range of 1.00 to 1.15, a stable image can be maintained over a long period of time.
A general pulverized toner has a Dv / Dn of about 1.15 to 1.25. The polymerized toner has a Dv / Dn of about 1.10 to 1.15.
According to the method for producing a toner of the present invention, it is advantageous in that a toner having Dv / Dn of 1.00 to 1.15 as well as 1.00 to 1.10 can be easily obtained.
An example of the particle size distribution of the toner obtained by the toner manufacturing method of the present invention is shown in FIG. This is an example of the collected toner, but it can be seen that there are almost only toner particles having a single particle size. This is obtained when the droplet 21 is obtained by drying without coalescence in the toner particle forming step.
The particle size distribution of the toner can be measured using a particle size measuring device (trade name: Multisizer III, manufactured by Beckman Coulter, Inc.).

  In the toner of the present invention, a fluidity improver, a cleaning property improver and the like may be added to the surface as necessary.

-Fluidity improver-
The fluidity improver improves the fluidity of the toner (makes it easier to flow) when added to the toner surface.
The fluidity improver is not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal such as fine powder silica such as wet process silica and dry process silica, fine powder unoxidized titanium, fine powder unalumina and the like. Oxide fine powder, and treated silica, titanium oxide, treated alumina, surface treated with silane coupling agent, titanium coupling agent, silicone oil, etc .; vinylidene fluoride fine powder, polytetrafluoroethylene fine powder And fluorine resin powders. These may be used alone or in combination of two or more.
Among these, the fluidity improver is preferably fine powdered silica, finely powdered titanium oxide, or finely powdered non-alumina, and more preferably treated silica obtained by subjecting these to surface treatment with a silane coupling agent or silicone oil.
There is no restriction | limiting in particular as an average primary particle size of the said fluid improvement agent, Although it can select suitably according to the objective, 0.001 micrometer-2 micrometers are preferable, and 0.002 micrometer-0.2 micrometer are more preferable.

The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.
Specific examples of commercially available silica fine powders produced by vapor phase oxidation of the silicon halogen compound include trade names of AEROSIL-130, AEROSIL-300, AEROSIL-380, AEROSIL-TT600, AEROSIL-MOX170, AEROSIL-MOX80. AEROSIL-COK84 (Nippon Aerosil Co., Ltd.); Ca-O-SiL-M-5, Ca-O-SiL-MS-7, Ca-O-SiL-MS-75, Ca-O-SiL-HS -5, Ca-O-SiL-EH-5 (above, manufactured by CABOT); Wacker HDK-N20 V15, Wacker HDK-N20E, Wacker HDK-T30, Wacker HDK-T40 (above, manufactured by ACKER-CHEMIE); D-CFineSi1ica (Da Corning); Franso1 (manufactured Fransi1 companies), and the like.

  Further, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halogen compound is more preferable. The treated silica fine powder is preferably obtained by treating the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is 30% to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. A method of treating fine silica powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferred.

  There is no restriction | limiting in particular as said organosilicon compound, According to the objective, it can select suitably, For example, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane , Vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, Allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane , Β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltri Methoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule Silyl such as dimethylpolysiloxane, dimethylsilicone oil or the like containing 0 to 1 hydroxyl group bonded to Si in the unit located at the end. N'oiru and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

There is no restriction | limiting in particular as a number average particle diameter of the said fluid improvement agent, Although it can select suitably according to the objective, 5 nm-100 nm are preferable, and 5 nm-50 nm are more preferable. The number average diameter can be determined by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.
As the specific surface area of the flowability improving agent according to the measured nitrogen adsorption by the BET method is not particularly limited, suitably it can be selected, preferably at least ^{30 m} 2 / g according to the ^purpose, 60m 2 / ^{g~400m 2} / g is more preferable.
The specific surface area of the surface-treated fine powder is not particularly limited and may be appropriately selected depending on the intended purpose, is preferably at least ^{20m 2 / g, 40m 2 /} g~300m 2 / g and more preferably . The specific surface area of the fine powder can be determined by a BET specific surface area measuring device.

  There is no restriction | limiting in particular as the addition amount with respect to the toner particle of the said fluid improvement agent, Although it can select suitably according to the objective, 0.03 mass%-8 mass% are preferable.

-Cleaning improver-
The cleaning property improving agent is for improving the removability of the toner remaining on the electrostatic latent image carrier or the primary transfer medium after the toner is transferred to a recording paper or the like.
The cleaning improver is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a soap such as zinc stearate, calcium stearate, fatty acid metal salt such as stearic acid, polymethyl methacrylate fine particles, polystyrene fine particles Examples thereof include fine polymer particles produced by free emulsion polymerization. These may be used alone or in combination of two or more.
The polymer fine particles preferably have a relatively narrow particle size distribution and a weight average particle size of 0.01 μm to 1 μm.

  The fluidity improving agent and the cleaning property improving agent are also referred to as external additives because they are used by adhering or fixing to the toner surface. A method for externally adding such an external additive to the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, various powder mixers are used. Examples of the powder mixer include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. As a powder mixer used for immobilization, a hybridizer is used. , Mechanofusion, Q mixer and the like.

(Developer)
The developer of the present invention contains at least the toner of the present invention and a carrier, and further contains other components as necessary.

<Career>
There is no restriction | limiting in particular as said carrier, According to the objective, it can select suitably, For example, carriers, such as a ferrite and a magnetite, a resin coat carrier, etc. can be mentioned.
The resin-coated carrier includes carrier core particles and a resin coating material that is a resin for coating (coating) the surfaces of the carrier core particles.

-Carrier core particles-
The magnetic material of the carrier core is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include ferrite, iron-rich ferrite, magnetite, and γ-iron oxide oxide, iron, cobalt, nickel Or a metal thereof, or an alloy 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, vanadium, etc. Can be mentioned.
These magnetic materials may be used alone or in combination of two or more. Among these magnetic materials, 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 particularly preferable.
Further, as the carrier core particles, a binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

-Resin coating material-
There is no restriction | limiting in particular as resin (resin coating material) used for the said coating | cover, According to the objective, it can select suitably, For example, a styrene-acrylic acid ester copolymer, a styrene-methacrylic acid ester copolymer, etc. Styrene-acrylic resins of the above; acrylic resins such as acrylic ester copolymers and methacrylic ester copolymers; fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymers and polyvinylidene fluoride; silicone resins; Preferred examples include polyester resins, polyamide resins, polyvinyl butyral, amino acrylate resins, and the like. In addition to these, resins that can be used as coating materials for carriers such as ionomer resins and polyphenylene sulfide resins can be used. These may be used alone or in combination of two or more.
Among these, as the resin coating material, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, a silicone resin, and the like are preferable, and a silicone resin is particularly preferable.

  The mixture of the fluororesin and the styrene copolymer is not particularly limited and may be appropriately selected depending on the purpose. For example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, Mixture of polytetrafluoroethylene and styrene-methyl methacrylate copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:10 (copolymer mass ratio)) and styrene-2-ethylhexyl acrylate Copolymer (10: 90-90: 10 (copolymer mass ratio)) and styrene-2-ethylhexyl acrylate-methyl methacrylate copolymer (20-60: 5-30: 10: 50 (copolymer) And a mixture thereof with a mass ratio)).

  The silicone resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a modified resin produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with the silicone resin. Examples include silicone resins.

  Examples of use in which the carrier core particles (magnetic material) are coated with the resin coating material of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethyl silicone oil (1 : 5 (mass ratio)) treated with 12 parts by mass of the mixture, (2) 20 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (1: 5 (mass ratio)) with respect to 100 parts by mass of the silica fine powder. The one processed in the department.

  In the resin-coated carrier, the method for coating at least the surface of the carrier core particles with the resin coating agent is not particularly limited and can be appropriately selected depending on the purpose. For example, the resin is dissolved in a solvent. Alternatively, a method of suspending and adhering to a coated carrier core, or a method of simply mixing in a powder state may be used.

  There is no restriction | limiting in particular as a usage-ratio of the said resin coating material with respect to the said resin coat carrier, Although it can select suitably according to the objective, 0.01 mass%-5 mass with respect to 100 mass parts of resin coat carriers % Is preferable, and 0.1% by mass to 1% by mass is more preferable.

The volume resistivity of the carrier is not particularly limited, the degree of irregularity surface of the carrier, can be set by adjusting appropriately depending on the amount of resin to be coated, ^{10 6} Ω · cm~10 10 Ω · cm is preferred.

  There is no restriction | limiting in particular as an average particle diameter of the said carrier, Although it can select suitably according to the objective, 4 micrometers-200 micrometers are preferable, 10 micrometers-150 micrometers are more preferable, 20 micrometers-100 micrometers are especially preferable. Among these, as the particle diameter of the resin-coated carrier, the 50% particle diameter is most preferably 20 μm to 70 μm.

  There is no restriction | limiting in particular as the usage-amount of the said carrier in the said developer, Although it can select suitably according to the objective, The toner of this invention is 1 mass part-200 mass parts with respect to 100 mass parts of carriers. Is preferable, and 2-50 mass parts is more preferable.

<Application>
As the developer using the toner of the present invention, all electrostatic latent image carriers used in conventional electrophotography can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, a selenium electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

  EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.

(Synthesis Example 1: Synthesis of polyester resin A)
Polyester resin A was synthesized by reacting 50 parts of terephthalic acid and 50 parts of isophthalic acid, 50 parts of neopentyl glycol and 50 parts of ethylene glycol.
The obtained polyester resin A had a weight average molecular weight of 65,000, a glass transition temperature (Tg) of 60 ° C., and an acid value of 10 mg / KOH.

-Measurement of weight average molecular weight-
The weight average molecular weight (Mw) of the polyester resin A was determined by measuring the THF dissolved content of the polyester resin A with a GPC (gel permeation chromatography) measuring device (trade name: GPC-150C, manufactured by Waters). KF801-807 (manufactured by Shodex) was used for the column, and RI (refractive index) detector was used for the detector.

-Measurement of glass transition temperature-
The glass transition temperature (Tg) of the polyester resin A was measured at a temperature increase rate of 10 ° C./min using a differential scanning calorimeter (for example, “DSC-60” manufactured by Shimadzu Corporation) in accordance with JIS K7121.

-Measurement of acid value-
The acid value of the polyester resin A was determined by the following method in accordance with JIS K-0070.
(1) 0.5 to 2.0 g of polyester resin A was precisely weighed, and the weight of the polyester resin A was set to Wg.
(2) Polyester resin A was placed in a 300 mL beaker, and 150 mL of a mixed solution of toluene / ethanol (4/1 (volume ratio)) was added and dissolved.
(3) Titration was performed using a potentiometric titrator using an ethanol solution of 0.1 mol / L KOH.
(4) The amount of KOH ethanol solution used at this time is S (mL), and a blank is measured at the same time. The amount of KOH ethanol solution used at this time is B (mL) and is calculated by the following formula (C). did. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W Formula (C)

(Synthesis Example 2: Synthesis of polyester resin B)
Polyester resin B was synthesized by reacting 50 parts of terephthalic acid, 45 parts of isophthalic acid, 5 parts of adipic acid, 50 parts of neopentyl glycol and 50 parts of ethylene glycol.
When the weight average molecular weight, glass transition temperature, and acid value of the obtained polyester resin B were measured in the same manner as in Synthesis Example 1, the weight average molecular weight was 61,000, the glass transition temperature (Tg) was 50 ° C., and the acid value was 10 mg. / KOH.

(Synthesis Example 3: Synthesis of styrene-methyl acrylate copolymer)
A styrene-methyl acrylate copolymer was synthesized by reacting 55 mol of styrene with 45 mol of methyl acrylate.
When the weight average molecular weight, glass transition temperature, and acid value of the obtained styrene-methyl acrylate copolymer were measured in the same manner as in Synthesis Example 1, the weight average molecular weight was 68,000 and the glass transition temperature (Tg) was 60. ° C. The copolymerization ratio of styrene and methyl acrylate was styrene: methyl acrylate = 55: 45 (molar ratio).

Example 1
<Preparation of colorant dispersion>
Using a mixer having a stirring blade, 20 parts by mass of carbon black (trade name: Regal 400, manufactured by Cabot) and 2 parts by mass of a pigment dispersant (trade name: Ajisper PB821, manufactured by Ajinomoto Fine Techno Co., Ltd.) Primary dispersion was performed in 78 parts by mass. The obtained primary dispersion was finely dispersed by a strong shearing force using a bead mill (trade name: LMZ manufactured by Ashizawa Finetech Co., Ltd., zirconia beads 0.3 mmφ) to obtain a secondary dispersion from which aggregates were completely removed. Prepared. Furthermore, a polytetrafluoroethylene (PTFE) filter (trade name: Fluorinert Membrane Filter FHLP09050, Nihon Millipore Corporation) having 0.45 μm pores was passed through to prepare a carbon black dispersion liquid dispersed to the submicron region. .

<Preparation of toner composition liquid>
To 676.7 parts by mass of ethyl acetate, 10 parts by mass of release agent (trade name: WAX-42, manufactured by NOF Corporation), and 263.3 parts by mass of binder resin (polyester resin A synthesized in Synthesis Example 1) Were mixed and dissolved at 25 ° C. using a mixer having stirring blades.
A toner composition liquid was prepared by further mixing 50 parts by mass of the carbon black dispersion with this solution and stirring for 10 minutes.
Note that WAX-42 is a synthetic ester wax, and its melting point measured by the method described later was 55.2 ° C., and 11 mass% could be dissolved in ethyl acetate at 25 ° C. The boiling point of ethyl acetate was 76.8 ° C.

  When the separation of the release agent and the binder resin in the solution before adding the carbon black dispersion was analyzed by the method described below, the release agent and the binder resin were both transparent to ethyl acetate without phase separation. It was dissolved (compatible).

<Preparation of toner>
After the obtained toner composition liquid was discharged under the following conditions using the toner production apparatus of FIG. 9 having the liquid column resonance droplet forming means 11 shown in FIG. 1 as the droplet forming means, The droplets are dried and solidified by droplet solidification means using dry nitrogen, and collected by a cyclone, and then further for 48 hours at a temperature of 35 ° C. and a relative humidity of 90%, for 24 hours at a temperature of 40 ° C. and a relative humidity of 50%. The toner base particles of Example 1 were prepared by air drying.
At this time, the toner composition liquid and the member of the toner manufacturing apparatus that comes into contact with the toner composition liquid are charged in a water tank in which all the devices are circulated at 25 ° C. with the electrical wiring wired in a sealed system. The temperature was controlled at 25 ± 1 ° C.
[Droplet discharge conditions]
Length L in the longitudinal direction of the liquid column resonance liquid chamber 18: 1.85 mm
Wall thickness of the liquid column resonance liquid chamber 18 on the surface where the discharge holes 19 are formed: 130 μm
Cross-sectional shape of the discharge hole: shape with the discharge hole angle of 90 ° shown in FIG. 8C shape of the opening of the discharge hole: perfect circle opening diameter of the discharge hole opening: 8.0 μm
Discharge hole pitch: 135 μm
Drying temperature (nitrogen): 40 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The separation of the release agent and the binder resin in the prepared toner base particles was analyzed by the method described later.
The results are shown in FIG. In FIG. 14, the black part is the release agent (WAX-42), the white part is the place where the release agent has fallen off during measurement (the part that is originally the release agent), and the other parts are bound. Resin (polyester resin A). From this, it was confirmed that the binder resin and the release agent were phase-separated.

  Next, 2.0 parts by mass of hydrophobic silica (trade name: H2000, manufactured by Clariant Japan Co.) is added to 100.0 parts by mass of the toner base particles using a Henschel mixer (manufactured by Nihon Coke Kogyo Co., Ltd.). Addition treatment was performed to prepare a black toner.

  As a result of measuring the particle size and particle size distribution of the obtained black toner by the method described later, the volume average particle size (Dv) is 4.8 μm, and Dv / Dn is 1.05, which is very sharp. It was a particle size distribution. In addition, the toner was continuously prepared for 6 hours, and the obstruction of the discharge holes was evaluated by the method described below. As a result, the discharge holes were not clogged and good results were obtained. These results are shown in Table 2 below.

<Preparation of carrier>
A mixture of the following materials was dispersed with a homomixer for 20 minutes to prepare a coating layer forming solution. This coating layer forming liquid was coated on the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus to obtain a magnetic carrier.
-Material of coating layer forming liquid-
100 parts by mass of silicone resin (trade name: Organo straight silicone, manufactured by Toray Dow Corning Silicone Co., Ltd.)
Toluene 100 parts by mass γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts by mass Carbon black 10 parts by mass

<Preparation of developer>
A developer was prepared by mixing 4 parts by mass of toner and 96.0 parts by mass of the magnetic carrier with a ball mill.
As a result of evaluating the hot offset resistance and image stability of the obtained developer by the methods described later, both the hot offset resistance and the image stability were good. The results are shown in Table 2 below.

<Analysis method and evaluation method>
<< Analysis of Separation of Release Agent and Binder Resin in Toner Composition Liquid >>
A solution obtained by dissolving a release agent and a binder resin in an organic solvent (a solution before adding the carbon black dispersion) is the same temperature as the solution at the time of preparing the solution (25 ° C. in Example 1). Was observed with a transmission optical microscope (magnification 1,000 times). As a result of the observation, it was judged that the transparent one was dissolved in the organic solvent with the release agent and the binder resin.

<< Analysis of Separation of Release Agent and Binder Resin in Toner Particles >>
The toner base particles were embedded in an epoxy resin, sections were prepared with an ultrasonic microtome, stained with RuO ₄ , and observed with a transmission electron microscope (TEM).

<< Evaluation of blockage of discharge hole >>
After the toner was continuously prepared for 6 hours, the presence or absence of blocking of the discharge holes and the decrease in the amount of discharged liquid was evaluated based on the following evaluation criteria.
[Evaluation criteria]
○: The discharge hole was not clogged and the initial discharge amount was maintained. Δ: The decrease in the discharge liquid amount was less than 20%, and a blockage was observed in a part of the discharge hole. The amount of reduction was 20% or more, and a blockage was observed in a part of the discharge hole.

<< Measurement of Particle Size and Particle Size Distribution of Toner >>
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner were measured using a particle size measuring device (trade name: Multisizer III, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 50 μm. That is, after measuring the volume and number of toner particles or toner, the volume distribution and number distribution were calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner were determined. As an index of the particle size distribution, Dv / Dn obtained by dividing the volume average particle diameter (Dv) of the toner by the number average particle diameter (Dn) was used. If it is completely monodisperse, it becomes 1, and the larger the value, the wider the distribution.

<< Evaluation of hot offset resistance >>
The developer is put in a commercially available copying machine (trade name: Imagiono 455, manufactured by Ricoh Co., Ltd.), and the fixing temperature is changed from a low temperature to a high temperature using a recording medium (trade name: type 6000 paper, manufactured by Ricoh Co., Ltd.). While outputting the image. The temperature at which the glossiness of the image decreased or the case where an offset image was seen in the image was defined as the offset generation temperature. This offset generation temperature was evaluated based on the following evaluation criteria.
[Evaluation criteria]
○: Offset generation temperature is 200 ° C or more ×: Offset generation temperature is less than 200 ° C

<< Evaluation of image stability >>
The developer is put in a commercially available copying machine (trade name: Imagiono 455, manufactured by Ricoh Co., Ltd.), and a recording medium (trade name: type 6000 paper, manufactured by Ricoh Co., Ltd.) is used with an image occupancy rate of 7%. A continuous running test of 50,000 sheets was performed, and the image quality (image density, fine line reproducibility, and background contamination) of the 50,000th sheet was evaluated based on the following evaluation criteria.
[Evaluation criteria]
○: Even the 50,000th image is a good image equivalent to the initial image. Δ: A change occurred from the initial image in any of the evaluation items of image density, fine line reproducibility, and background stain, but the allowable range was changed. ×: The image density, the fine line reproducibility, and the background contamination are not acceptable levels due to obvious changes from the initial image.

(Example 2)
In Example 1, the toner composition liquid, toner, carrier, and development of Example 2 were the same as Example 1 except that the toner composition liquid preparation method and toner preparation method were changed to the following methods. An agent was prepared.

<Preparation of toner composition liquid>
In the preparation of the toner composition liquid of Example 1, WA-4 (manufactured by NOF Corporation) was used as a release agent in place of WAX-42, and the dissolution temperature was changed to 25 ° C. to 30 ° C. A toner composition liquid of Example 2 was prepared in the same manner as in Example 1.
WA-4 is a synthetic amide wax, the melting point measured by the method described in Example 1 is 62.6 ° C., and 2.9% by mass can be dissolved in ethyl acetate at 30 ° C. .

<Preparation of toner>
In the preparation of the toner of Example 1, the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were changed to temperature control at 25 ± 1 ° C., except that the temperature was controlled at 30 ± 1 ° C. The toner of Example 2 was prepared in the same manner as in Example 1.

For the toner composition liquid, toner, and developer of Example 2, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the release agent and the binder resin in the toner composition liquid were both transparently dissolved (compatible) in ethyl acetate without phase separation.
In addition, there is no clogging of the ejection holes in toner preparation, and the toner has a very sharp particle size distribution with a volume average particle diameter (Dv) of 4.9 μm and Dv / Dn of 1.05. The hot offset resistance and image stability were also good. The results are shown in Table 2 below.
Further, the result of observation of the toner base particles prepared in Example 2 with a transmission electron microscope (TEM) in the same manner as in Example 1 is shown in FIG. In FIG. 15, the black part is the release agent (WAX-4), the white part is the place where the release agent has fallen off during measurement (the part that is originally the release agent), and the other parts are bound. Resin (polyester resin A). From this, it was confirmed that the binder resin and the release agent were phase-separated.

(Example 3)
In Example 1, the toner composition liquid, toner, carrier, and development of Example 3 were the same as in Example 1 except that the toner composition liquid preparation method and toner preparation method were changed to the following methods. An agent was prepared.

<Preparation of toner composition liquid>
In the preparation of the toner composition liquid of Example 1, WA-3 (manufactured by NOF Corporation) was used instead of WAX-42 as a release agent, and synthesis was performed in Synthesis Example 2 instead of polyester resin A as a binder resin. A toner composition liquid of Example 3 was prepared in the same manner as in Example 1 except that the polyester resin B was used and the melting temperature was changed to 25 ° C. to 35 ° C.
WA-3 is a synthetic amide wax, the melting point measured by the method described in Example 1 is 61.0 ° C., and 3.3% by mass was soluble in ethyl acetate at 35 ° C. .

<Preparation of toner>
In the preparation of the toner of Example 1, the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were changed to temperature control at 25 ± 1 ° C., except that the temperature was controlled at 35 ± 1 ° C. The toner of Example 3 was prepared in the same manner as in Example 1.

For the toner composition liquid, toner, and developer of Example 3, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the release agent and the binder resin in the toner composition liquid were both transparently dissolved (compatible) in ethyl acetate without phase separation.
In addition, there is no clogging of the ejection holes in toner preparation, the toner has a very sharp particle size distribution with a volume average particle diameter (Dv) of 5.1 μm, and Dv / Dn of 1.06, and a good image The hot offset resistance and image stability were also good. The results are shown in Table 2 below.
Further, the result of observation of the toner base particles prepared in Example 3 with a transmission electron microscope (TE is shown in FIG. 16 in the same way as in Example 1. In FIG. WA-3), the white part is where the release agent has fallen off during the measurement (the part that is originally the release agent), and the other part is the binder resin (polyester resin B). It was confirmed that the binder resin and the release agent were phase-separated.

Example 4
In Example 1, the toner composition liquid, toner, carrier, and development of Example 4 were the same as Example 1 except that the toner composition liquid preparation method and toner preparation method were changed to the following methods. An agent was prepared.

<Preparation of toner composition liquid>
In the preparation of the toner composition liquid of Example 1, WEP-2 (manufactured by NOF Corporation) was used instead of WAX-42 as a release agent, and synthesis was performed in Synthesis Example 2 instead of polyester resin A as a binder resin. A toner composition liquid of Example 4 was prepared in the same manner as in Example 1 except that polyester resin B was used and the melting temperature was changed to 25 ° C. to 40 ° C.
In addition, WEP-2 is a synthetic ester wax, the melting point measured by the method described in Example 1 is 75.2 ° C., and 4.4 mass% was soluble in ethyl acetate at 40 ° C. .

<Preparation of toner>
In the preparation of the toner of Example 1, the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were changed to temperature control at 25 ± 1 ° C., except that the temperature was controlled at 40 ± 1 ° C. The toner of Example 4 was prepared in the same manner as in Example 1.

With respect to the toner composition liquid, toner, and developer of Example 4, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the release agent and the binder resin in the toner composition liquid were both transparently dissolved (compatible) in ethyl acetate without phase separation.
In addition, there is no clogging of the ejection holes in toner preparation, the toner has a very sharp particle size distribution with a volume average particle diameter (Dv) of 5.1 μm, and Dv / Dn of 1.06, and a good image The hot offset resistance and image stability were also good. The results are shown in Table 2 below.
In addition, the toner base particles prepared in Example 4 were observed with a transmission electron microscope (TE) as in Example 1. The result of observation with TE is shown in FIG. 17. In FIG. The white part is where the release agent has fallen off during the measurement (the part that is originally the release agent), and the other part is the binder resin (polyester resin B). It was confirmed that and the release agent were phase-separated.

(Example 5)
In Example 1, the toner composition liquid, toner, carrier, and development of Example 5 were the same as Example 1 except that the toner composition liquid preparation method and the toner preparation method were changed to the following methods. An agent was prepared.

<Preparation of toner composition liquid>
In the preparation of the toner composition liquid of Example 1, WA-8 (manufactured by NOF Corporation) is used instead of WAX-42 as a release agent, and polyester resin B is used instead of polyester resin A as a binder resin. A toner composition liquid of Example 5 was prepared in the same manner as in Example 1 except that the melting temperature was changed to 25 ° C. to 50 ° C.
Note that WA-8 is a synthetic amide wax, the melting point measured by the method described in Example 1 is 67.4 ° C., and 9.5% by mass can be dissolved in ethyl acetate at 50 ° C. .

<Preparation of toner>
In the preparation of the toner of Example 1, except that the temperature of the toner composition liquid and the toner manufacturing apparatus member in contact with the toner composition liquid is controlled at 50 ± 1 ° C. instead of the temperature control at 25 ± 1 ° C. The toner of Example 5 was prepared in the same manner as in Example 1.

For the toner composition liquid, toner, and developer of Example 5, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the release agent and the binder resin in the toner composition liquid were both transparently dissolved (compatible) in ethyl acetate without phase separation.
In addition, there is no clogging of the ejection holes in toner preparation, and the toner has a very sharp particle size distribution with a volume average particle diameter (Dv) of 5.2 μm and Dv / Dn of 1.07. The hot offset resistance and image stability were also good. The results are shown in Table 2 below.
Further, the result of observation of the toner base particles prepared in Example 5 with a transmission electron microscope (TE is shown in FIG. 18 in the same manner as in Example 1. In FIG. 18, the black and elongated portions are the release agent (WA-8). The white part is where the release agent has fallen off during the measurement (the part that is originally the release agent), and the other part is the binder resin (polyester resin B). It was confirmed that the resin and the release agent were phase separated.

(Example 6)
In Example 5, the toner composition liquid, toner, carrier, and development of Example 6 were performed in the same manner as in Example 5 except that the toner composition liquid preparation method and toner preparation method were changed to the following methods. An agent was prepared.

<Preparation of toner composition liquid>
A toner composition liquid of Example 6 was prepared in the same manner as in Example 5 except that in the preparation of the toner composition liquid of Example 5, the melting temperature was changed to 50 ° C. to 55 ° C.

<Preparation of toner>
The toner of Example 5 was prepared except that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid contacts were controlled at 55 ± 1 ° C. instead of being controlled at 50 ± 1 ° C. In the same manner as in Example 5, the toner of Example 6 was prepared.

For the toner composition liquid, toner, and developer of Example 6, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles was performed in the same manner as in Example 1. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the release agent and the binder resin in the toner composition liquid were both transparently dissolved (compatible) in ethyl acetate without phase separation.
Further, in the toner preparation, a part of the discharge hole was clogged, and the discharge amount after 6 hours from the start of the toner preparation decreased by 4% compared to the initial stage.
Although the volume average particle diameter (Dv) of the toner was 5.1 μm and Dv / Dn was 1.11, a slight increase in the amount of fine powder was observed, but the hot offset resistance and the image stability were good. The results are shown in Table 2 below.
Further, the result of observation of the toner base particles prepared in Example 6 with a transmission electron microscope (TE is shown in FIG. 19 in the same manner as in Example 1. In FIG. 19, the black elongated portion is the release agent (WA-8). The white part is where the release agent has fallen off during the measurement (the part that is originally the release agent), and the other part is the binder resin (polyester resin B). It was confirmed that the resin and the release agent were phase separated.

(Example 7)
In Example 1, the toner composition liquid, toner, carrier and development of Example 7 were the same as Example 1 except that the toner composition liquid preparation method and the toner preparation method were changed to the following methods. An agent was prepared.

<Preparation of toner composition liquid>
Styrene-methyl acrylate copolymer 263 synthesized in Synthesis Example 3 as a release resin (trade name: BSQ-180W, manufactured by Toyo Adre Co., Ltd.) and 106.7 parts by mass of toluene, 676.7 parts by mass .3 parts by mass were mixed and dissolved at 70 ° C. using a mixer having stirring blades. A toner composition liquid was prepared by further mixing 50 parts by mass of the carbon black dispersion with the solution and stirring for 10 minutes.
BSQ-180W is a microcrystalline wax, the melting point measured by the method described in Example 1 was 86.4 ° C., and 6 mass% could be dissolved in toluene at 70 ° C. Moreover, the boiling point of toluene was 110.6 degreeC.

<Preparation of toner>
In the preparation of the toner of Example 1, except that the temperature of the toner composition liquid and the toner manufacturing apparatus member in contact with the toner composition liquid is controlled at 70 ± 1 ° C. instead of the temperature control at 25 ± 1 ° C. In the same manner as in Example 1, the toner of Example 7 was prepared.

For the toner composition liquid, toner, and developer of Example 7, in the same manner as in Example 1, analysis of separation of release agent and binder resin in toner composition liquid, release agent and binder in toner particles Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the release agent and the binder resin in the toner composition liquid were both transparently dissolved (compatible) in ethyl acetate without phase separation.
In addition, there is no clogging of the ejection holes in toner preparation, the toner has a very sharp particle size distribution with a volume average particle diameter (Dv) of 4.9 μm and Dv / Dn of 1.07, and a good image The resulting hot offset resistance and image stability were also good. The results are shown in Table 2 below.
Further, the result of observation of the toner base particles prepared in Example 7 with a transmission electron microscope (TE as in Example 1 is shown in FIG. 20. In FIG. 20, the black elongated portion indicates a release agent (BSQ-180W). The white part is where the release agent has fallen off during the measurement (the part that is originally the release agent), and the other part is the binder resin (styrene-methyl acrylate copolymer). From this, it was confirmed that the binder resin and the release agent were phase-separated.

(Comparative Example 1)
In Example 1, the toner composition liquid, toner, carrier and developer of Comparative Example 1 were prepared in the same manner as in Example 1 except that the method for preparing the toner composition liquid was changed to the following method.

<Preparation of toner composition liquid>
In the preparation of the toner composition liquid of Example 1, the release agent was not added, the amount of ethyl acetate added was changed to 676.7 parts by mass to 653.3 parts by mass, and the amount of polyester resin A added was 263.3. A toner composition liquid of Comparative Example 1 was prepared in the same manner as in Example 1 except that the amount was changed to 296.7 parts by mass.

For the toner composition liquid, toner, and developer of Comparative Example 1, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the ejection holes were not clogged during toner preparation, and the toner had a very sharp particle size distribution with a volume average particle diameter (Dv) of 4.8 μm and Dv / Dn of 1.05. However, a hot offset occurred even when fixing at a low temperature, and an image stability test could not be performed.

(Comparative Example 2)
In Example 1, the toner composition liquid, toner, carrier and developer of Comparative Example 2 were prepared in the same manner as in Example 1 except that the method for preparing the toner composition liquid was changed to the following method.

<Preparation of toner composition liquid>
The toner of Comparative Example 2 was prepared in the same manner as in Example 1 except that Irganox 245 (manufactured by Ciba Japan Co., Ltd.) was used instead of WAX-42 as a release agent in the preparation of the toner composition liquid of Example 1. A composition solution was prepared.
Irganox 245 is a hindered phenol ester, the melting point measured by the method described in Example 1 is 76 ° C., and 30 mass% or more was soluble in ethyl acetate at 25 ° C.

With respect to the toner composition liquid, toner, and developer of Comparative Example 2, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the release agent and the binder resin in the toner composition liquid were both transparently dissolved (compatible) in toluene without phase separation.
In addition, there was no clogging of the ejection holes during toner preparation, and the toner had a very sharp particle size distribution with a volume average particle diameter (Dv) of 4.8 μm and Dv / Dn of 1.05. Even in the fixing at 1, hot offset occurred, and the image stability test could not be carried out. The results are shown in Table 2 below.
FIG. 21 shows the result of observation of the toner base particles prepared in Comparative Example 2 with a transmission electron microscope (TEM) in the same manner as in Example 1. In FIG. 21, the release agent (Irganox 245) could not be confirmed, and it was confirmed that the binder resin and the release agent were not phase separated.

(Comparative Example 3)
In Example 3, the toner composition liquid, toner, carrier and developer of Comparative Example 3 were prepared in the same manner as in Example 3 except that the toner preparation method was changed to the following method.

<Preparation of toner>
The toner composition liquid is produced using the toner production apparatus shown in FIG. 9 having a two-fluid spray nozzle (6552-1 / 8 JAC, manufactured by Spraying Systems Japan Co., Ltd., nozzle opening diameter: 250 μm) as a droplet forming means. After spraying into dry nitrogen at 15 MPa and collecting the cyclone, it was further blown and dried at a temperature of 35 ° C. and a relative humidity of 90% for 48 hours, and at a temperature of 40 ° C. and a relative humidity of 50% for 24 hours. Toner base particles were prepared.
At this time, the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact was controlled at 35 ° C. ± 1 ° C.

With respect to the toner composition liquid, toner and developer of Comparative Example 3, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, the release agent and the binder resin in the toner composition liquid were both transparently dissolved (compatible) in ethyl acetate without phase separation.
Further, although clogging of the ejection holes did not occur in the toner preparation, the toner has a very wide particle size distribution with a volume average particle diameter (Dv) of 5.3 μm and Dv / Dn of 1.47. The image of the 50,000th run test clearly changed, and the image density was decreased, the fine line was thickened, and an increase in background staining was observed. The results are shown in Table 2 below.
Further, the results of observation of the toner base particles prepared in Comparative Example 3 with a transmission electron microscope (TEM) in the same manner as in Example 1 are shown in FIG. In FIG. 22, the black part is the release agent (WA-3), the white part is the place where the release agent has fallen off during measurement (the part that is originally the release agent), and the other part is the binder resin. (Polyester resin A). From this, it was confirmed that the binder resin and the release agent were phase-separated.

(Comparative Example 4)
In Example 5, the toner composition liquid, toner, carrier and developer of Comparative Example 4 were prepared in the same manner as in Example 5 except that the method for preparing the toner composition liquid was changed to the following method.

<Preparation of toner composition liquid>
-Preparation of wax dispersion-
In a container in which a stirring blade and a thermometer are set, 20 parts by weight of WA-8 and 80 parts by weight of ethyl acetate are charged, stirred for 20 minutes while heating to 60 ° C., dissolved in WA-8, and then rapidly cooled. Then, WA-8 fine particles were precipitated. This WA-8 dispersion was further finely dispersed at 1,800 rpm with a star mill (trade name: LMZ06, manufactured by Ashizawa Finetech Co., Ltd.) filled with 0.3 μmφ zirconia beads. A WA-8 dispersion having an average particle size of 0.3 μm and a maximum particle size of 0.8 μm was prepared. The particle size of the wax was measured with a particle size distribution meter (trade name: NPA150, manufactured by Microtrac).

  After 263.3 parts by mass of polyester resin B as a binder resin was dissolved in 676.7 parts by mass of ethyl acetate, 50 parts by mass of the above WA-8 dispersion was obtained using a mixer having stirring blades at 25 ° C. Part of the carbon black dispersion prepared in Example 1 was mixed to prepare a toner composition liquid.

For the toner composition liquid, toner, and developer of Comparative Example 4, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, it was confirmed that the release agent and the binder resin in the toner composition liquid were phase separated.
Further, some of the ejection holes were clogged, and the ejection amount after 6 hours from the start of toner preparation was reduced by 38% compared to the initial stage. The volume average particle diameter (Dv) of the toner was 5.0 μm, and Dv / Dn was 1.28, and an increase in the amount of fine powder was observed. Although the hot offset resistance was good, the image of the 50,000th running test showed a slight thickening of fine lines and a slight increase of background stains. The results are shown in Table 2 below.
Further, the result of observation of the toner base particles prepared in Comparative Example 4 with a transmission electron microscope (TE is shown in FIG. 23 in the same manner as in Example 1. In FIG. 23, the black elongated portion indicates the release agent (WA-8). The white part is where the release agent has fallen off during the measurement (the part that is originally the release agent), and the other part is the binder resin (polyester resin B). It was confirmed that the resin and the release agent were phase separated.

(Comparative Example 5)
In Example 5, the toner composition liquid, toner, carrier and development of Comparative Example 5 were the same as Example 5 except that the toner composition liquid preparation method and the toner preparation method were changed to the following methods. An agent was prepared.

<Preparation of toner composition liquid>
A toner composition liquid of Comparative Example 5 was prepared in the same manner as in Example 5 except that in the preparation of the toner composition liquid of Example 5, the dissolution temperature was changed to 50 ° C. to 60 ° C.

<Preparation of toner>
The toner of Example 5 was prepared except that the temperature of the toner composition liquid and the toner manufacturing apparatus member in contact with the toner composition liquid was controlled at 60 ± 1 ° C. instead of the temperature control at 50 ± 1 ° C. In the same manner as in Example 5, a toner of Comparative Example 5 was prepared.

With respect to the toner composition liquid, toner and developer of Comparative Example 5, in the same manner as in Example 1, analysis of separation of the release agent and binder resin in the toner composition liquid, release agent and binder in the toner particles were performed. Analysis of separation of the adhesion resin, evaluation of ejection hole clogging, measurement of toner particle size and particle size distribution, evaluation of hot offset resistance, and evaluation of image stability were performed.
As a result, it was confirmed that the release agent and the binder resin in the toner composition liquid were phase separated.
Further, some of the ejection holes were clogged, and the ejection amount after 6 hours from the start of toner preparation decreased by 29% compared to the initial stage. The volume average particle diameter (Dv) of the toner was 5.4 μm, and Dv / Dn was 1.22, and an increase in the amount of fine powder was observed. Although the hot offset resistance was good, a slight increase in background stain was observed in the 50,000th image of the running test. The results are shown in Table 2 below.
In addition, the toner base particles prepared in Comparative Example 5 were observed with a transmission electron microscope (TE) as in Example 1, and the results are shown in FIG. 24. In FIG. 24, the black part is the release agent (WA-8). The white part is where the release agent has fallen off during the measurement (the part that is originally the release agent), and the other part is the binder resin (polyester resin B). It was confirmed that and the release agent were phase-separated.

  Table 1 below summarizes the toner composition solution preparation conditions and toner preparation conditions of Examples 1 to 7 and Comparative Examples 1 to 5. Moreover, the result of Examples 1-7 and Comparative Examples 1-5 is put together in the following Table 2, and is shown.

  The toner production method of the present invention can efficiently produce a toner having a small particle size and monodispersibility, and does not cause clogging of discharge holes due to a release agent, and is resistant to hot offset. It is excellent and can provide a high-definition and high-quality image over a long period of time without any background contamination. Therefore, the toner and developer produced by the toner production method of the present invention can be suitably used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like.

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet formation means 6 Toner composition liquid supply port 11 Liquid column resonance droplet formation means 12 Airflow path 12-1 1st airflow path 12-2 2nd airflow path 12-3 Auxiliary conveyance airflow path 13 Raw material container 14 Toner composition liquid 15 Liquid circulation pump 16 Liquid supply pipe 17 Liquid common supply path 18 Liquid column resonance liquid chamber 19 Discharge hole 20 Vibration generating means 21 Droplet 22 Liquid return pipe 44 Angle of discharge hole 60 Toner particle forming means 61 Chamber 62 Toner Collecting Means 63 Toner Storage Portion 64 Transport Airflow Inlet 65 Transport Airflow Outlet 66 Shroud 67 Auxiliary Transport Airflow Inlet 68 Auxiliary Transport Airflow 69 Liquid Contact Surface 101, 102 Transport Airflow P1 Liquid Pressure Gauge P2 Chamber Pressure Total

JP-A-7-84401 Japanese Patent Application Laid-Open No. 5-341579 Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP-A-57-201248 JP 2006-293320 A JP 2008-64979A

Claims (11)

A toner composition in which a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in an organic solvent, and the binder resin and the release agent are dissolved so as not to phase-separate. A toner composition liquid preparation step for preparing the liquid;
A vibration is applied to the toner composition liquid in the liquid column resonance liquid chamber in which a plurality of ejection holes are formed to form a standing wave by liquid column resonance, and is formed in a region that becomes an antinode of the standing wave. A droplet forming step of forming droplets by periodically discharging the toner composition liquid from the plurality of discharge holes to the outside of the discharge holes;
A toner particle forming step of removing the organic solvent from the droplet formed in the droplet forming step to form toner particles in which the binder resin and the release agent are phase-separated;
A method for producing a toner, comprising:   The toner manufacturing method according to claim 1, wherein a plurality of ejection holes are formed in at least one of the regions that become antinodes of the standing wave. The method for producing a toner according to claim 1, wherein the temperature of the toner composition liquid in the droplet forming step satisfies the following formula (I).
Temperature of toner composition liquid (° C.) <[Boiling point of organic solvent (° C.) − 20 (° C.)] Formula (I)   The method for producing a toner according to claim 1, wherein the release agent contains at least one of a synthetic ester wax, a synthetic amide wax, and a microcrystalline wax.   The method for producing a toner according to claim 1, wherein the addition amount of the release agent is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the binder resin.   The method for producing a toner according to claim 1, wherein the binder resin contains at least one of a polyester resin having a weight average molecular weight of 5,000 to 300,000 and a styrene acrylic acid copolymer.   The method for producing a toner according to claim 1, wherein the opening diameter of the discharge hole formed in the liquid column resonance liquid chamber is 3 μm to 30 μm.   The vibration means has a vibration surface parallel to a surface of the liquid column resonance liquid chamber in which the plurality of discharge holes are formed, and the vibration surface is a surface in which the plurality of discharge holes of the liquid column resonance liquid chamber is formed. The toner manufacturing method according to claim 1, wherein the toner is a vibration unit that vibrates longitudinally in a vertical direction.   9. The toner manufacturing method according to claim 3, further comprising a temperature control step of controlling the temperature of the toner composition liquid and the temperature of the member in contact with the toner composition liquid at a predetermined temperature in the droplet forming step.   A volume average particle diameter of 1 to 8 μm obtained by the toner production method according to claim 1, and a particle size distribution (volume average particle diameter / number average particle diameter) of 1.00 to 1 .. A toner in the range of .15.   A developer comprising at least the toner according to claim 10 and a carrier.