JP5407439B2 - Toner and developer - Google Patents

Description

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

Developers used in electrophotography, electrostatic recording, electrostatic printing, and the like are once attached to an electrostatic latent image carrier on which an electrostatic charge image is formed, for example, in the development process, and then in a transfer process. After being transferred from the electrostatic latent image carrier onto a transfer medium such as transfer paper, it is fixed on the paper surface in a fixing step. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners are known.
Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like, a binder resin such as a styrene resin or a polyester resin (also referred to as a toner binder) is melt-kneaded together with a colorant or the like to obtain a fine toner. A pulverized toner, so-called pulverized toner, is widely used.
Recently, a toner production method using a suspension polymerization method, an emulsion polymerization aggregation method, or the like, a so-called chemical toner has been studied. As one of chemical toner production methods, a method called volumetric shrinkage called a polymer dissolution suspension method has been studied (see Patent Document 1). In this method, the toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile organic solvent is removed. . Unlike suspension polymerization and emulsion polymerization agglomeration methods, this method is a versatile resin that can be applied, and is particularly useful for full-color processes that require transparency and smoothness of the image area after fixing. It is excellent in that it can be used.

However, since the chemical toner method as described above is based on the premise that the dispersant is used in the aqueous medium, the dispersant remains on the surface of the toner, and the environmental stability of the charging characteristics of the toner is impaired. There were drawbacks such as requiring a large amount of washing water to remove the dispersant.
Therefore, as an alternative method for producing toner, a method has been proposed in which fine droplets are formed using piezoelectric pulses, and further dried and solidified to form a toner (see Patent Document 2). In addition, a method has been proposed in which fine droplets are formed using thermal expansion in the nozzle, and then solidified by drying and solidifying (see Patent Document 3). Furthermore, a method of forming fine droplets using an acoustic lens and drying and solidifying has been proposed (see Patent Document 4). In addition, a toner material containing a thermosetting resin or UV curable resin is used as a dispersoid, and a dispersion finely dispersed in a dispersion medium is intermittently discharged as droplets from a nozzle, and then the droplets are aggregated. There is also proposed a method of stabilizing the particle formation by curing a thermosetting resin or a UV curable resin (see Patent Documents 5 and 6).

  However, these methods have a problem that productivity is poor because the number of droplets that can be ejected from a single nozzle per unit time is small. Moreover, the spread of the particle size distribution due to the coalescence of the droplets is unavoidable, and it is not satisfactory in terms of monodispersibility.

On the other hand, with the development of electrophotographic technology, toners with excellent low-temperature fixability are required, while toners with characteristics that are contrary to low-temperature fixability such as offset resistance and heat-resistant storage stability (blocking resistance). Is needed.
Many toners using an aromatic polyester resin have been proposed in response to such demands, but have the disadvantage of being inferior in grindability at the time of toner production. Thus, a method of blending a low molecular weight polyester and a high molecular weight polyester using an aliphatic alcohol excellent in grindability as a monomer has been proposed (see Patent Document 7). However, low molecular weight polyesters using aliphatic alcohols have a low glass transition temperature due to their structure, which deteriorates the heat-resistant storage stability of the toner and achieves both low-temperature fixability, offset resistance, and heat-resistant storage stability at a high level. It is difficult to do.

On the other hand, a toner using an alcohol component composed of a branched aliphatic alcohol such as 1,2-propanediol and a polyester composed of a carboxylic acid component as a binder resin has been proposed (Patent Document 8). And 9). The toner described above is excellent in that it has excellent low-temperature fixability for a wide range of conventional image forming apparatuses ranging from low speed machines to high speed machines, and is capable of achieving both offset resistance and heat resistant storage stability at a high level. Further, since the pulverization property is excellent, the pulverization toner has an advantage in productivity.
However, these toners are excellent in pulverization properties, but are easily crushed by agitation stress inside the developing device. In particular, the pulverized toner tends to generate fine powder due to its irregular shape. For this reason, there is a problem that the fine powder contaminates the carrier in the developer, the charging member and the like, and adversely affects the image quality. Further, although the dispersibility of the fatty acid ester and the aliphatic hydrocarbon release agent (wax) is excellent, there is a problem that it is difficult to obtain the image releasability at the time of fixing.

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention is a particle having a single particle dispersibility with a small particle size and an unprecedented particle size. There is no or very little variation in the particle size observed in the manufacturing method, and it has excellent offset resistance, low-temperature fixability, heat-resistant storage stability, stain resistance, and fixing releasability. An object of the present invention is to provide a toner and a developer capable of forming a high-definition and high-quality image with resolution and having no image deterioration over a long period of time.

Means for solving the problems are as follows. That is,
<1> A plurality of the same opening diameters formed in a thin film provided in a storage portion for storing a toner composition liquid in which a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in a solvent A periodic droplet forming step in which the toner composition liquid is periodically discharged into the gas phase by mechanical vibration means from the nozzle of
A toner produced by a toner production method comprising solidifying the dropletized toner composition liquid to form toner particles,
The mechanical vibration means is a vibration means having a parallel vibration surface with respect to the thin film, and the vibration surface vibrates longitudinally in a vertical direction;
The binder resin contains at least one polyester resin, and the one polyester resin or at least one of the two or more polyester resins contains 1,2-propanediol in a divalent alcohol component. A toner comprising a polyester resin obtained by condensation polymerization of an alcohol component containing 65 mol% or more and a carboxylic acid component.
<2> Using the liquid resonance phenomenon caused by the mechanical vibration means, the toner composition liquid is periodically discharged into a gas phase from a plurality of nozzles having the same opening diameter formed in a thin film, and the liquid is formed into droplets <1 >.
<3> The toner according to any one of <1> to <2>, wherein the mechanical vibration unit is a horn-type vibrator.
<4> The binder resin comprises a polyester resin (A) having a softening point Tm (A) of 120 ° C. or higher and 160 ° C. or lower and a polyester resin (B) having a softening point Tm (B) of 80 ° C. or higher and lower than 120 ° C. And at least one of the polyester resins (A) and (B) is obtained by condensing an alcohol component containing 65 mol% or more of 1,2-propanediol in a divalent alcohol component and a carboxylic acid component. The toner according to any one of <1> to <3>, wherein the toner is a polyester resin obtained by polymerization.
<5> The toner according to <4>, wherein the alcohol component of the polyester resin (A) further contains 1,3-propanediol.
<6> The toner according to any one of <1> to <5>, wherein the release agent is carnauba wax.
<7> Any one of <1> to <6>, wherein a ratio (D ₄ / Dn) of the mass average particle diameter (D ₄ ) to the number average particle diameter (Dn) in the toner is 1.00 to 1.10. The toner according to claim 1.
<8> A developer containing the toner according to any one of <1> to <7>.

The toner of the present invention is the same as that formed on a thin film provided in a storage portion for storing a toner composition liquid 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. A periodic droplet forming step of periodically discharging the toner composition liquid into a gas phase by a mechanical vibration means from a plurality of nozzles having an opening diameter;
A toner produced by a toner production method comprising solidifying the dropletized toner composition liquid to form toner particles,
The mechanical vibration means is a vibration means having a parallel vibration surface with respect to the thin film, and the vibration surface vibrates longitudinally in a vertical direction;
The binder resin contains at least one polyester resin, and the one polyester resin or at least one of the two or more polyester resins contains 1,2-propanediol in a divalent alcohol component. It contains a polyester resin obtained by condensation polymerization of an alcohol component containing 65 mol% or more and a carboxylic acid component.
In the toner of the present invention, the binder resin of the toner is excellent in compatibility between low-temperature fixability, hot offset resistance and heat-resistant storage stability. In addition, when the binder resin is used in the toner manufacturing method of the present invention, when the toner composition liquid is formed into droplets, the release agent moves into the droplets. It does not exist when the release agent is almost exposed. Further, the release agent exists in a slightly aggregated state in the droplet, and maintains an appropriate dispersion diameter to exhibit sufficient fixing release properties. Furthermore, since it is possible to produce particles having a single particle dispersibility with a small particle size and an unprecedented particle size, many of the characteristic values required for toners such as fluidity and charging characteristics are found in the conventional production methods. A toner with little or no variation due to the particles is obtained. In addition, since a particle shape close to a spherical shape is obtained, the generation of fine powder due to toner crushing in the developing device is eliminated, and the release agent is not exposed on the outermost surface of the toner. Significantly improved.

  According to the present invention, conventional problems can be solved, and particles having a single particle dispersibility with a small particle size and an unprecedented particle size are required for toners such as fluidity and charging characteristics. There is no or very little variation in the characteristic values of the particles in the conventional toner production methods, and offset resistance, low-temperature fixability, heat-resistant storage stability, stain resistance, fixing separation It is possible to provide a toner and a developer that have excellent moldability, can form high-definition, high-definition and high-quality images, and have no image deterioration over a long period of time.

FIG. 1 is a schematic view showing an example of the toner production apparatus of the present invention. FIG. 2 is an enlarged explanatory view for explaining the droplet jetting unit of the toner manufacturing apparatus of the present invention. FIG. 3 is an explanatory bottom view of FIG. 2 as viewed from below. FIG. 4 is a schematic explanatory view showing an example of a step-type horn type vibrator constituting the vibration generating means of the droplet jetting unit of the toner manufacturing apparatus of the present invention. FIG. 5 is a schematic explanatory view showing an example of an exponential horn type vibrator constituting the vibration generating means of the droplet jetting unit of the toner manufacturing apparatus of the present invention. FIG. 6 is a schematic explanatory view showing an example of a conical horn type vibrator constituting the vibration generating means of the droplet jetting unit of the toner manufacturing apparatus of the present invention. FIG. 7 is an enlarged explanatory view for explaining another example of the droplet ejecting unit of the toner manufacturing apparatus of the present invention. FIG. 8 is an enlarged explanatory view for explaining still another example of the droplet ejecting unit of the toner manufacturing apparatus of the present invention. FIG. 9 is an enlarged explanatory view for explaining still another example of the droplet ejecting unit of the toner manufacturing apparatus of the present invention. FIG. 10 is an explanatory diagram for explaining an example in which a plurality of liquid droplet ejecting units in FIG. 9 are arranged. FIG. 11A is a schematic explanatory diagram of a thin film for explaining the principle of droplet formation by the droplet ejection unit. FIG. 11B is a schematic explanatory diagram of a thin film for explaining the principle of droplet formation by the droplet ejection unit. FIG. 12 is an explanatory diagram for explaining the fundamental vibration mode. FIG. 13 is an explanatory diagram for explaining the secondary vibration mode. FIG. 14 is an explanatory diagram for explaining the tertiary vibration mode. FIG. 15 is an explanatory diagram when a convex portion is formed at the center of the thin film. FIG. 16 is a schematic configuration diagram illustrating an example of a liquid resonance type toner manufacturing apparatus according to the present invention. FIG. 17A is an enlarged explanatory view for explaining a droplet ejecting unit of the toner manufacturing apparatus of FIG. FIG. 17B is an enlarged explanatory view for explaining a droplet ejecting unit of the toner manufacturing apparatus of FIG. 16. FIG. 17C is an enlarged explanatory view for explaining a droplet ejecting unit of the toner manufacturing apparatus of FIG. 16. FIG. 18 is an explanatory diagram of a method of making the cross-sectional shape of the nozzle two-stage in the liquid resonance type toner manufacturing apparatus according to the present invention.

(toner)
The toner of the present invention uses a toner composition liquid in which a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in a solvent, and a periodic droplet forming process and a toner particle forming process It is manufactured by the manufacturing method of the toner containing these.

<Toner composition liquid>
In the toner composition liquid, a binder resin is dissolved in various solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. A solution obtained by dissolving or dispersing the kneaded material once in various solvents may be used. Further, the toner composition liquid contains other components as necessary.

-Binder resin-
The binder resin contains at least one polyester resin.
When the polyester resin is one kind, the one kind of polyester resin polycondenses the alcohol component containing 65 mol% or more of 1,2-propanediol in the divalent alcohol component and the carboxylic acid component. The polyester resin obtained is contained.
When there are two or more polyester resins, at least one of the two or more polyester resins contains an alcohol component containing 65 mol% or more of 1,2-propanediol in a divalent alcohol component, and a carboxylic acid. Contains a polyester resin obtained by condensation polymerization of the components.

--- Alcohol component--
1,2-propanediol, which is a branched-chain alcohol having 3 carbon atoms used for the alcohol component, improves low-temperature fixability while maintaining offset resistance as compared with alcohol having 2 or less carbon atoms. It is effective and effective in preventing deterioration of storage stability due to a decrease in glass transition temperature compared with branched chain alcohols having 4 or more carbon atoms, and can be fixed at an extremely low temperature. Both hot offset properties can be achieved. In particular, when the content of 1,2-propanediol is 65 mol% or more in the divalent alcohol component, excellent low-temperature fixability and offset resistance are exhibited.

In the present invention, it is preferable to use two types of polyester resins having different softening points as the binder resin from the viewpoints of low-temperature fixability, hot offset resistance, and heat-resistant storage stability. In the present invention, two kinds of polyester resins having different softening points are respectively referred to as polyester resin (A) and polyester resin (B), and the respective softening points are referred to as softening point Tm (A) and softening point Tm (B). The polyester resin (A) has a softening point Tm (A) of 120 ° C. or higher and 160 ° C. or lower, preferably 130 ° C. or higher and 155 ° C. or lower, and more preferably 135 ° C. or higher and 155 ° C. or lower. The polyester resin (B) has a softening point Tm (B) of 80 ° C. or higher and lower than 120 ° C., preferably 85 ° C. or higher and 115 ° C. or lower, and more preferably 90 ° C. or higher and 110 ° C. or lower.
By setting the softening points Tm (A) and Tm (B) within the above ranges, it is possible to achieve both a low-temperature fixability, a hot offset resistance, and a heat-resistant storage stability, and to obtain extremely good fixing quality. Further, as a preferable condition for obtaining better fixing quality, the difference [ΔTm; Tm (A) −Tm (B)] between Tm (A) and Tm (B) is preferably 10 ° C. or more. 15 to 55 degreeC is more preferable, and 20 to 50 degreeC is still more preferable.

Further, as a more preferable condition for achieving both low temperature fixability, hot offset resistance, and heat resistant storage stability, the polyester resin (A) and the polyester resin (B) and the mass ratio [((A) / (B )) Is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, and still more preferably 30/70 to 70/30.
The high softening point polyester resin (A) having such characteristics contributes to improvement in hot offset resistance, and the low softening point polyester resin (B) contributes to improvement in low-temperature fixability. The combined use of the polyester resin (A) and the polyester resin (B) is effective in achieving both low temperature fixability and hot offset resistance.

  As an alcohol component of the said polyester resin (A) and the said polyester resin (B), content of 1, 2- propanediol is 65 mol% or more in a bivalent alcohol component, 70 mol% or more is preferable, 80 Mole% or more is more preferable, and 90 mol% or more is still more preferable. Examples of the divalent alcohol component other than 1,2-propanediol include 1,3-propanediol, ethylene glycol having a different carbon number, hydrogenated bisphenol A, bisphenol F, or alkylene thereof (2 to 4 carbon atoms). Aliphatic dialcohols such as oxide (average added mole number 1 to 16) adducts and the like can be mentioned. The content of the divalent alcohol component is preferably 60 mol% or more, more preferably 60 mol% to 95 mol%, still more preferably 65 mol% to 90 mol% in the alcohol component.

The alcohol component of the polyester resin (A) preferably contains 1,3-propanediol from the viewpoint of low-temperature fixability. The molar ratio of 1,2-propanediol to 1,3-propanediol in the alcohol component of the polyester resin (A) (1,2-propanediol / 1,3-propanediol) is 99/1 to 65 / 35 is preferable, 95/3 to 70/30 is more preferable, and 95/3 to 75/25 is still more preferable.
Moreover, when the alcohol component contains a trivalent or higher valent alcohol component, the effect of improving the hot offset resistance is improved. The content of the trihydric or higher alcohol component is preferably 0 mol% to 20 mol%, more preferably 5 mol% to 30 mol%, in the total amount of the alcohol component. Examples of the trihydric or higher polyhydric alcohol component include glycerin, pentaerythritol, trimethylolpropane, sorbitol, or an alkylene (2 to 4 carbon) oxide (average added mole number 1 to 16) adduct thereof. In particular, glycerin is preferable because it does not inhibit low-temperature fixability.

  Examples of the alcohol component of the polyester resin (A) and the polyester resin (B) include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2)- Aromatic alcohols such as alkylene oxide adducts of bisphenol A such as 2,2-bis (4-hydroxyphenyl) propane may be contained.

--Carboxylic acid component--
There is no restriction | limiting in particular as a carboxylic acid component of the said polyester resin (A) and the said polyester resin (B), According to the objective, it can select suitably. For example, benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof, maleic acid, citraconic acid, itaconic acid Unsaturated dibasic acids such as alkenyl succinic acid, fumaric acid, mesaconic acid, unsaturated dibasic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Can be mentioned. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.
Among these, it is preferable that an aromatic polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or the like is contained from the viewpoint of heat-resistant storage stability and mechanical strength of the resin. The resin content of the aromatic polyvalent carboxylic acid compound is preferably 40 mol% to 95 mol%, more preferably 50 mol% to 90 mol%, still more preferably 60 mol% to 80 mol% in the carboxylic acid component. .

  Further, among the carboxylic acid compounds described above, when an aliphatic dicarboxylic acid compound having 2 to 5 carbon atoms is contained, a toner having particularly excellent grindability, low-temperature fixability, and antifouling properties can be obtained. Examples of the aliphatic dicarboxylic acid compound having 2 to 5 carbon atoms include succinic acid, maleic acid, citraconic acid, itaconic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, etc. In particular, itaconic acid and itaconic anhydride are preferably used. The content of the aliphatic dicarboxylic acid compound having 2 to 5 carbon atoms is preferably 5 mol% to 60 mol%, more preferably 10 mol% to 50 mol%, and more preferably 20 mol% to 40 mol% in the carboxylic acid component. Further preferred.

  The carboxylic acid component may contain rosin. The rosin having a polycyclic aromatic ring reduces the water absorption that the conventional aliphatic alcohol polyesters have, and further enhances the effect of reducing the charge amount under high temperature and high humidity. The rosin is a natural resin obtained from pine, and the main component thereof is a resin acid such as abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, or the like. It is a mixture of these. The rosin is roughly divided into tall rosin obtained from tall oil obtained as a by-product in the process of producing pulp, gum rosin obtained from raw pine ani, wood rosin obtained from pine stumps, etc. From the viewpoint of low-temperature fixability, tall rosin is preferable. In addition, a modified rosin such as a disproportionated rosin or a hydrogenated rosin may be used, but in the present invention, from the viewpoint of low-temperature fixability and storage stability, a so-called raw rosin that is not modified may be used. preferable. The rosin is preferably a purified rosin from the viewpoint of improving storage stability and odor.

--Esterification catalyst--
The condensation polymerization of the alcohol component and the carboxylic acid component is preferably performed in the presence of an esterification catalyst. Examples of the esterification catalyst include Lewis acids such as p-toluenesulfonic acid, titanium compounds, and tin (II) compounds having no Sn-C bond, and these are used alone or in combination. . Among these, a titanium compound and a tin (II) compound having no Sn—C bond are particularly preferable.
As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group, or an acyloxy group is more preferable.

Examples of the titanium compound include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diethylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) _2], titanium distearate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 18 H 37 O) 2 ], Chitanto Isopropylate triethanolaminate _{[Ti (C 6 H 14 O 3} N) 1 (C 3 H 7 O) 3 ], titanium monopropylate tris (triethanolaminate) _{[Ti (C 6 H 14 O 3} N) ₃ (C ₃ H ₇ O) ₁ ] and the like. Among these, titanium diisopropylate bistriethanolaminate, titanium diisopropylate bisdiethanolamate, and titanium dipentylate bistriethanolamate are particularly preferred, and these are also available as, for example, commercial products manufactured by Matsumoto Kosho Co., Ltd. It is.

Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H ₃₇ O) _4], tetra myristyl titanate _{[Ti (C 14 H 29 O)} 4 ], tetraoctyl titanate _{[Ti (C 8 H 17 O)} 4 ], dioctyl-dihydroxy-octyl titanate [Ti _(C 8 _{H 17} O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate, and dioctyl dihydroxy octyl titanate are preferable. These can be obtained by reacting, for example, titanium halide with a corresponding alcohol. It is also available as a commercial product.

  The abundance of the titanium compound is preferably 0.01 parts by mass to 1.0 part by mass, and 0.1 parts by mass to 0.7 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Is more preferable.

Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, and a tin (II) having a Sn—X bond (where X represents a halogen atom). A compound etc. are preferable and the tin (II) compound which has a Sn-O bond is more preferable.
Examples of the tin (II) compound having a Sn-O bond include tin (II) oxalate, tin (II) diacetate, tin (II) dioctanoate, tin (II) dilaurate, and tin (II) distearate. Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms, such as tin (II) dioleate; dioctyloxytin (II), dilauroxytin (II), distearoxytin (II), dioleoxytin (II) Dialkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as tin oxide (II) and tin sulfate (II).

Examples of the compound having the Sn-X (wherein X represents a halogen atom) bond include tin (II) halides such as tin (II) chloride and tin (II) bromide, among these. And fatty acid tin (II) represented by (R ₁ COO) ₂ Sn (wherein R ₁ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R 1 ₂ O) ₂ Sn (provided that, _{R 2} is dialkoxy tin represented by an alkyl group or alkenyl group having 6 to 20 carbon atoms) (II), tin oxide represented by SnO (II) are preferred, ( Fatty acid tin (II) and tin (II) oxide represented by R ₁ COO) ₂ Sn are more preferable, and tin (II) dioctanoate, tin (II) distearate, and tin (II) oxide are more preferable.
The abundance of the tin (II) compound having no Sn—C bond is preferably 0.01 parts by mass to 1.0 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.1 parts by mass to 0.7 parts by mass is more preferable.
When the titanium compound and the tin (II) compound having no Sn-C bond are used in combination, the total amount of the titanium compound and the tin (II) compound is 100% of the total amount of the alcohol component and the carboxylic acid component. 0.01-1.0 mass part is preferable with respect to mass part, and 0.1-0.7 mass part is more preferable.

The condensation polymerization of the alcohol component and the carboxylic acid component can be performed, for example, at a temperature of 180 ° C. to 250 ° C. in an inert gas atmosphere in the presence of the esterification catalyst. The softening point of the polyester resin can be adjusted by the reaction time.
The glass transition temperatures of the polyester resins (A) and (B) are preferably 45 ° C. to 75 ° C., more preferably 50 ° C. to 70 ° C., and 50 ° C. to 65 ° C. from the viewpoints of fixability, storage stability and durability. Is more preferable. The acid value is preferably from 1 to 80 mgKOH / g, more preferably from 10 to 50 mgKOH / g, from the viewpoints of chargeability and environmental stability.

In the present invention, the polyester resins (A) and (B) are preferably amorphous polyesters different from crystallinity. In this specification, “amorphous polyester” refers to a polyester having a difference between the softening point and the glass transition temperature (Tg) of 30 ° C. or more.
The polyester resins (A) and (B) may be modified polyester resins. The modified polyester resin refers to a polyester resin grafted or blocked with phenol, urethane or the like.
The binder resin is used in combination with a known binder resin, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, or the like, as long as the effects of the present invention are not impaired. However, the total content of the polyester resin (A) and the polyester resin (B) is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the binder resin. It is particularly preferable that the content is substantially 100% by mass.

-Release agent-
The release agent (wax) is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax , Aliphatic hydrocarbon waxes such as sazol wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; plants such as candelilla wax, carnauba wax, wood wax, jojoba wax Waxes; animal waxes such as beeswax, lanolin, spermaceti; mineral waxes such as ozokerite, ceresin, and petrolatum; waxes based on fatty acid esters such as montanate ester wax and castor wax; deacidified carnauba wax Fatty acids such as Those deoxidizing a part or the whole of the ester, and the like.

  Examples of the mold release agent include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, and linear alkyl carboxylic acids having a linear alkyl group, prundic acid, eleostearic acid, and valinal acid. Unsaturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnupyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amides, lauric acid amides, saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide, ethylene bis oleic acid amide, hexamethylene bis olei Unsaturated fatty acid amides such as acid amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid amide Such as aromatic bisamides such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate and other fatty acid metal salts, and aliphatic hydrocarbon waxes grafted with vinyl monomers such as styrene and acrylic acid. And a partial ester compound of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol, a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils, and the like.

  Further, polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, polyolefins polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressure, radiation, electromagnetic waves Or synthesized using light-polymerized polyolefin, low-molecular-weight polyolefin obtained by pyrolyzing high-molecular-weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. A hydrocarbon wax, a synthetic wax using a compound having one carbon atom as a monomer, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, a hydrocarbon wax and a hydrocarbon wax having a functional group Compounds, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.

In addition, these release agents may be obtained by using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a liquid crystal deposition method to sharpen the molecular weight distribution, or a low molecular weight solid fatty acid. , Low molecular weight solid alcohol, low molecular weight solid compound, and other impurities are preferably used.
In particular, in the case of a toner manufactured by a pulverization method, since it is easily pulverized at the interface between the binder resin and the release agent, the release agent is exposed on the surface of the toner, causing filming on the photosensitive member or carrier. Although there is a problem, the binder resin in the present invention has very good dispersibility of the release agent, and the release agent is hardly detached from the toner due to the compatible action of the binder resin and the release agent. For this reason, the occurrence of filming is extremely small as compared with the conventional toner. Especially for the binder resin used in the present invention, among the above release agents, carnauba wax is more preferable because it exhibits the best dispersibility. Among the carnauba waxes, those from which free fatty acids have been eliminated are particularly preferred.

The melting point of the release agent is preferably 60 to 120 ° C. and more preferably 70 to 110 ° C. in order to balance the fixability and the offset resistance. When the melting point is less than 60 ° C., the blocking resistance may be lowered, and when it exceeds 120 ° C., the anti-offset effect may be hardly exhibited.
Further, by using two or more different types of release agents in combination, the plasticizing action and the release action, which are the actions of the release agent, can be expressed simultaneously. Examples of the type of release agent having a plasticizing action include a release agent having a low melting point, a branch having a molecular structure, and a structure having a polar group. Examples of the mold release agent having a mold release action include a mold release agent having a high melting point, and examples of the molecular structure include a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different release agents having a melting point difference of 10 to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
When selecting two types of release agents, in the case of a release agent having the same structure, a release agent having a relatively low melting point exerts a plasticizing action, and a release agent having a high melting point is released. Demonstrate the effect. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the release agents is preferably 60 to 120 ° C, more preferably 70 to 110 ° C because it tends to easily exhibit the function separation effect.

As the release agent, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and have a more linear structure, Nonpolar or non-denatured straight ones that do not have a functional group exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, carnauba wax, can Delila wax, rice wax or montan wax and hydrocarbon wax The combination of the scan and the like.
In any case, since it becomes easy to balance the toner storage stability and the fixing property, there is a peak top temperature of the maximum peak in the region of 60 to 120 ° C. in the endothermic peak observed in the DSC measurement of the toner. Preferably, it has a maximum peak in the region of 70 to 110 ° C. In the present invention, the temperature at the peak top of the maximum endothermic peak of the release agent (wax) measured by DSC is defined as the melting point of the release agent.
Here, a differential scanning calorimeter (manufactured by Shimadzu Corp., TA-60WS and DSC-60) was used as a DSC measuring instrument for the release agent or toner, and the DSC curve was measured. As a measuring method, it was performed according to ASTM D3418-82. The DSC curve used in the present invention was one that was measured when the temperature was raised at a temperature rate of 10 ° C./min after raising and lowering the temperature once and taking a previous history.
As the total content of the release agent in the toner of the present invention, a preferable dispersion state is obtained by being 0.2 to 30% by mass with respect to the binder resin. 3 to 15 parts by mass is particularly preferable.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments 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, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise 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, Pogment 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, Oh Lured, 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 Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include degreen lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a color of the said coloring agent, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black material include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and titanium oxide. And organic pigments such as aniline black (CI Pigment Black 1).
Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, the coloring power decreases, and the electrical characteristics of the toner. May be reduced.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin, rosin, modified rosin, terpene Examples thereof include resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffins. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the styrene or substituted polymer thereof include polyester resin, polystyrene resin, poly p-chlorostyrene resin, and polyvinyl toluene resin. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - like maleic acid ester copolymer.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and the organic solvent component. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

-Charge control agent-
In the present invention, a charge control agent for controlling the charge amount of the toner may be used. The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone Or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (all manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (all manufactured by Hodogaya Chemical Co., Ltd.), Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron complex LR-147 (made by Nippon Carlit Co., Ltd.); quinacridone, azo pigment; Examples thereof include polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or the toner. You may fix to the toner surface after particle manufacture.
The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1 mass part-10 mass parts are preferable, and 0.2 mass part-5 mass parts are more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

-Solvent-
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, water; Alcohols, such as methanol, ethanol, isopropanol, n-butanol, methyl isocarbinol; Acetone, 2-butanone, ethyl Ketones such as amyl ketone, diacetone alcohol, isophorone and cyclohexanone; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4 -Ethers such as dihydro-2H-pyran; glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate Glycol ether acetates such as tate and 2-butoxyethyl acetate; esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate and ethylene carbonate; aromatic hydrocarbons such as benzene, toluene and xylene; hexane Aliphatic hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene; sulfoxides such as dimethyl sulfoxide; N-methyl-2 Pyrrolidones such as pyrrolidone and N-octyl-2-pyrrolidone. These may be used individually by 1 type and may use 2 or more types together.

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

<Toner production method>
Hereinafter, a pulverization method that is a conventional toner production method and a vibration injection method that is a production method of the present invention will be described.

  The pulverization method is a general toner production method that has been conventionally performed. A toner composition containing at least a binder resin, a colorant, and a release agent is removed by a two-roll or a twin-screw extruder. In this method, after melt-kneading, cooling, coarse pulverization, fine pulverization, and classification are performed, and external additives such as a fluidizing agent are mixed with a Henschel mixer as necessary. A known production apparatus such as a rotoplex or pulverizer can be used for coarse pulverization, a jet mill or a turbo mill can be used for fine pulverization, and an elbow jet or various air classifiers can be used for classification.

  The vibration jet method mechanically vibrates a thin film having a plurality of nozzles having the same opening diameter, thereby periodically discharging a toner composition liquid from the nozzles to generate droplets having a uniform particle size and drying. Thus, toner particles are obtained. The mechanical vibration means may be arranged in any direction as long as it vibrates in the vertical direction with respect to the film having nozzles. However, in the present invention, the mechanical vibration means has a parallel vibration surface with respect to the thin film having a plurality of nozzles, and is perpendicular to the film. A system using mechanical means that vibrates longitudinally (mechanical longitudinal vibration means) is preferably used.

First, an example of a toner manufacturing apparatus provided with mechanical longitudinal vibration means will be described with reference to the schematic configuration diagram of FIG.
The toner manufacturing apparatus 1 periodically discharges a toner composition solution in which a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in a solvent from a plurality of nozzles having the same opening diameter. The droplet ejecting unit 2 as droplet forming means in the periodic droplet forming step for forming droplets in the gas phase, and the droplet ejecting unit 2 are disposed above and discharged from the droplet ejecting unit 2 In the particle forming step of solidifying the droplets of the toner composition liquid thus formed to form toner particles T, the particle forming unit 3 as a particle forming means and the toner particles T formed by the particle forming unit 3 are collected. A toner collecting unit 4 to which the toner particles T collected by the toner collecting unit 4 are transferred via the tube 5 and a toner storing unit 6 as a toner storing unit for storing the transferred toner particles T; Contains toner composition liquid 10. The material container 7, the pipe (liquid feed pipe) 8 for feeding the toner composition liquid 10 from the raw material container 7 to the droplet ejection unit 2, and the toner composition liquid 10 are supplied by pressure during operation. And a pump 9 for the purpose.
In addition, the toner composition liquid 10 from the raw material container 7 is supplied to the droplet ejection unit 2 in a self-sufficient manner due to the droplet formation phenomenon by the droplet ejection unit 2. In particular, the pump 9 is used to supply the liquid.

Next, the droplet ejecting unit 2 will be described.
FIG. 2 is a schematic cross-sectional explanatory view of the droplet ejecting unit 2, and FIG. 3 is an explanatory bottom view of the main part of FIG.
The droplet ejection unit 2 includes a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, mechanical vibration means (hereinafter referred to as “vibration means”) 13 that vibrates the thin film 12, and the thin film 12 and vibration means 13. And a flow path member 15 that forms a reservoir (liquid flow path) 14 for supplying the toner composition liquid 10 therebetween.
The thin film 12 having the plurality of nozzles 11 is disposed in parallel to the vibration surface 13a of the vibration means 13, and a flow path is formed by a resin binder material in which a part of the thin film 12 is not dissolved in solder or a toner composition liquid. It is bonded and fixed to the member 15 and has a substantially vertical positional relationship with the vibration direction of the vibration means 13. A communication means 24 is provided so that a voltage signal is applied to the upper and lower surfaces of the vibration generating means 21 of the vibration means 13, and the signal from the drive signal generating source 23 can be converted into mechanical vibration. As a communication means for providing an electrical signal, a lead wire whose surface is insulated is suitable. In addition, it is suitable for efficient and stable toner production that the vibration means 13 uses elements having a large vibration amplitude such as various horn type vibrators and bolted Langevin type vibrators described later.

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

Examples of the piezoelectric body 21A constituting the vibration generating means 21 include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, they are often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.
The vibration means 13 may be arranged in any way as long as it gives vibration in the vertical direction to the thin film 12 having the nozzle 11, but the vibration surface 13 a and the thin film 12 are arranged in parallel.
In the illustrated example, a horn type vibrator is used as the vibration means 13 composed of the vibration generation means 21 and the vibration amplification means 22, and this horn type vibration amplifies the amplitude of the vibration generation means 21 such as a piezoelectric element. Since it can be amplified by the horn 22A as the means 22, the vibration generating means 21 itself for generating mechanical vibration may be a small vibration, and the mechanical load is reduced, leading to a long life as a production apparatus.

As the horn type vibrator, a known typical horn shape may be used, and examples thereof include a step type as shown in FIG. 4, an exponential type as shown in FIG. 5, a conical type as shown in FIG. Can do. In these horn-type vibrators, the piezoelectric body 21A is disposed on the surface of the horn 22A having a large area. The piezoelectric body 21A uses longitudinal vibration to induce efficient vibration of the horn 22A, and the horn 22A has a small area. The surface is a vibration surface 13a, and the vibration surface 13a is designed to be the maximum vibration surface. Lead wires 24 are arranged above and below the piezoelectric body 21, and an AC voltage signal is given from the drive circuit 23. The maximum vibration surface of these horn vibrators is designed to have a shape of 13a.
Further, as the vibration means 13, a particularly high-strength bolted Langevin type vibrator can be used. This bolted Langevin type vibrator is mechanically coupled with piezoelectric ceramics and will not be damaged during high amplitude excitation.

The configuration of the reservoir, the mechanical vibration means, and the thin film will be described in detail with reference to the schematic diagram of FIG. The storage unit 14 is provided with at least one liquid supply tube 18, and as shown in a partial cross-sectional view, the liquid is introduced into the liquid storage unit through the flow path. Moreover, it is also possible to provide the bubble discharge tube 19 as needed. The droplet ejection unit 2 is installed and held on the top surface portion of the particle forming unit 3 by a support member (not shown) attached to the flow path member 15. In addition, although the example which has arrange | positioned the droplet injection unit 2 in the top | upper surface part of the particle formation part 3 is demonstrated here, the droplet injection unit 2 is provided in the drying part side wall used as the particle formation part 3, or a bottom part. It can also be set as the structure to install.
The size of the vibration means 13 that generates mechanical vibration is generally increased as the oscillation frequency decreases, and according to the necessary frequency, the vibration means is directly drilled to provide a reservoir. be able to. It is also possible to vibrate the entire storage part efficiently.
In this case, the vibration surface is defined as a surface on which the thin films having the plurality of nozzles are bonded.

Different examples of the droplet jetting unit 2 having such a configuration will be described with reference to FIGS.
The example shown in FIG. 7 uses a horn-type vibrator 80 composed of a piezoelectric body 81 as a vibration generating unit and a horn 82 as a vibration amplifying unit as the vibration unit 80 (13). A reservoir (flow path) 14 is formed. The droplet jetting unit 2 is preferably fixed to the wall surface of the particle forming unit 3 (drying means) by a fixing unit (flange unit) 83 integrally formed with the horn 82 of the horn-type vibrator 80. Loss of vibration From the viewpoint of preventing this, it may be fixed using an elastic body (not shown).
The example shown in FIG. 8 is a bolt-clamped Langevin type vibrator configured by mechanically firmly fixing piezoelectric bodies 91A and 91B and horns 92A and 92B as vibration generating parts as bolts as vibration means 90 (13). 90 is used to form a reservoir (flow path 14) in the horn 92A. Depending on the frequency condition, the element may be large, and as shown in the drawing, the fluid introduction / discharge path and the reservoir can be processed in a part of the vibrator, and a metal thin film having a plurality of thin films can be attached.
FIG. 1 shows an example in which only one droplet ejecting unit 2 is attached to the particle forming unit 3, but a plurality of droplet ejecting units 2 are arranged above the particle forming unit 3 (drying tower). Paralleling is preferable from the viewpoint of improving productivity, and the number thereof is preferably in the range of 100 to 1000 from the viewpoint of controllability. In this case, the toner composition liquid 10 is supplied to each storage section 14 of the droplet ejection unit 2 through the pipe 8 to the raw material storage section (common liquid reservoir) 7. The toner composition liquid 10 may be configured to be supplied in a self-contained manner as droplets are formed, or may be configured to supply the liquid supplementarily using the pump 9 during operation of the apparatus. it can.

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

Next, the mechanism of droplet formation by the droplet ejecting unit 2 as the droplet forming means will be described.
As described above, the droplet ejecting unit 2 causes the thin film 12 having the plurality of nozzles 11 facing the storage unit 14 to propagate the vibration generated by the vibration means 13 that is a mechanical vibration means, thereby periodically causing the thin film 12 to move. By vibrating, a plurality of nozzles 11 are arranged in a relatively large area (diameter of 1 mm or more), and droplets can be periodically and stably formed and discharged from the plurality of nozzles 11.
When the peripheral portion 12A of the simple circular film 12 as shown in FIGS. 11A and 11B is fixed, the periphery of the basic vibration is a node, and the displacement ΔL is maximum (ΔLmax) at the center O of the thin film as shown in FIG. The cross-sectional shape becomes a vertical vibration in the vibration direction.
Further, it is known that higher order modes as shown in FIGS. 13 and 14 exist. These modes have one or more concentric nodes in a circular membrane, and are substantially axisymmetric deformation shapes. Further, as shown in FIG. 15, by making the central portion have a convex shape 12c, it is possible to control the traveling direction of the droplet and adjust the vibration amplitude.

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

As described above, a sound pressure proportional to the vibration displacement speed of the distributed film is generated, and the toner composition liquid is discharged into the gas phase in response to the periodic change of the sound pressure.
Since the toner composition liquid periodically discharged to the gas phase forms a sphere due to a difference in surface tension between the liquid phase and the gas phase, droplet formation occurs periodically.
As the vibration frequency of the film that enables droplet formation, a region of 20 kHz to 2.0 MHz is used, and a range of 50 kHz to 500 kHz is more preferably used. If the vibration period is 20 kHz or more, the dispersion of fine particles such as pigment and wax in the toner composition liquid is promoted by the excitation of the liquid.
Furthermore, when the displacement amount of the sound pressure is 10 kPa or more, the above-described fine particle dispersion promoting action is more preferably generated.
Here, the diameter of the formed droplet tends to increase as the vibration displacement in the vicinity of the nozzle of the film increases, and when the vibration displacement is small, a droplet is formed or is not formed into a droplet. In order to reduce such a variation in droplet size at each nozzle site, it is necessary to define the nozzle arrangement at an optimum position of the membrane vibration displacement.

In the present invention, as will be described with reference to FIGS. 12 to 14, the ratio R (= ΔLmax / ΔLmin) of the maximum value ΔLmax and the minimum value ΔLmin of the vibration direction displacement ΔL of the film in the vicinity of the nozzle generated by the mechanical vibration means. However, it has been found that by arranging the nozzle in a portion within 2.0, the variation in the droplet size can be maintained in a necessary region as toner fine particles capable of providing a high-quality image.
The conditions of the toner composition liquid were changed, and the satellite generation start region was the same in the region having a viscosity of 20 mPa · s or less and a surface tension of 20 mN / m to 75 mN / m. Therefore, the displacement of the sound pressure was 500 kPa or less. More preferably, it is 100 kPa or less.

As described above, the thin film having the nozzle is a member that discharges a solution or dispersion of the toner composition into droplets.
The material of the thin film 12 and the shape of the nozzle 11 are not particularly limited and may be appropriately selected. For example, the thin film 12 is formed of a metal plate having a thickness of 5 μm to 500 μm, and An opening diameter of 3 to 30 μm is preferable from the viewpoint of generating fine liquid droplets having a very uniform particle diameter when the liquid droplets of the toner composition liquid 10 are ejected from the nozzle 11. The opening diameter of the nozzle 11 means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse. Further, the number of the plurality of nozzles 11 is preferably 2 to 3,000, and the opening diameters of the plurality of nozzles are the same.

An example of a liquid resonance type toner manufacturing apparatus is shown in FIG. 16, and examples of droplet ejection units are shown in FIGS. 17A to 17C. Its basic configuration is almost the same as the mechanical longitudinal vibration method, but the mechanical longitudinal vibration method oscillates a thin film with a nozzle by means of vibration generation to form droplets, whereas in the liquid resonance method The difference is that the droplets are not formed by the vibration of the thin film having the nozzles but by the resonance of the liquid.
Therefore, the strength of the thin film is increased to the extent that it does not vibrate. As the material, silicon, silicon oxide, or the like is used, and it is desirable to use a silicon substrate, particularly an SOI (Silicon on Insulator) substrate in terms of nozzle formation. In addition, when the film thickness is very large with respect to the opening diameter of the nozzle, the discharge performance is improved by making the cross-sectional shape of the nozzle two-stage.
17B is a schematic cross-sectional explanatory view of the droplet ejecting unit 2, FIG. 17A is an assembly diagram for explaining in more detail, and FIG. 17C is a droplet formation by the droplet ejecting unit shown in FIGS. 17A and 17B. It is explanatory drawing of.
This droplet jetting unit 2 includes a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, a vibration unit 13, and at least a resin, a colorant, and a specific phenol type between the thin film 12 and the vibration unit 13. And a reservoir constituting member 15 that forms a reservoir (liquid channel) 14 for supplying the toner composition liquid 10 containing a resin. A configuration in which the position is fixed by a vibration separating member 26 so as not to transmit vibration between the vibration means and the reservoir wall is desirable, but the vibration means has a node portion 27 having a small vibration amplitude. It may be in the form of being fixed directly to the wall. The toner composition liquid 10 is supplied to the liquid storage unit 14 through a pipe 18 used for liquid supply and liquid circulation.
As the vibration means 13 and the vibration amplification means 22, those described in the description of the membrane vibration method using the mechanical longitudinal vibration means described above can be similarly used.
The members constituting the partition of the liquid storage part are made of a common material such as metal, ceramics, and plastic that does not dissolve in the spray liquid and does not cause modification of the spray liquid. In addition, the liquid storage unit 14 is divided into a plurality of liquid storage regions 29 by a plurality of partition walls. By dividing the partition wall in this way, the vibration pressure distribution in the liquid chamber becomes uniform in the drive of several tens of kHz, so that uniform discharge can be performed and the effect of increasing the resonance frequency can be expected.

  Next, the mechanism of droplet formation by the droplet ejecting unit 2 as the droplet forming means will be described with reference to FIG. 17C. The vibration generated on the vibration surface 13a by the vibration means is transmitted to the liquid in the reservoir, and the liquid in the reservoir causes a liquid resonance phenomenon. In a plurality of nozzles provided in the thin film 12, the liquid is discharged to the gas side in a state of being uniformly pressurized. By the action of resonance of the entire liquid, the liquid is uniformly ejected from all the nozzles, and further, the dispersed fine particles contained in the toner composition liquid are suspended in the storage part without being deposited on the storage part surface of the thin film. Therefore, the liquid can be stably ejected stably.

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

There is no restriction | limiting in particular as a shape of the nozzle 11, Although it can be set as the shape selected suitably, for example, the thin film 12 is 30-1000 micrometers in thickness, and the opening diameter of the nozzle 11 is 4-15 micrometers. 11 is preferable from the viewpoint of generating fine droplets having a uniform particle diameter when the droplets of toner composition liquid 10 are ejected from No. 11. The opening diameter of the nozzle 11 means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse. The number of nozzles 11 is preferably 2 to 3,000, and the opening diameters of the plurality of nozzles are the same.
Any vibration means 13 can be used as long as it can apply mechanical ultrasonic vibration to the liquid at a high amplitude, such as a laminated PZT or a combination of an ultrasonic vibrator and an ultrasonic horn described later. It doesn't matter.
The vibration generated by the vibration means is transmitted to the liquid in the reservoir, and the liquid in the reservoir causes a liquid resonance phenomenon. In a plurality of nozzles provided in the thin film, the liquid is discharged to the gas side in a state of being uniformly pressurized. By the action of resonance of the entire liquid, the liquid is uniformly ejected from all the nozzles, and further, the dispersed fine particles contained in the toner composition liquid are suspended in the storage part without being deposited on the storage part surface of the thin film. Therefore, the liquid can be stably ejected stably.
When a thin film provided with a plurality of nozzles is vibrated mechanically, there is an advantage that nozzle clogging is difficult to occur. However, if the thin film area is large, uniform vibrations may not be obtained and the droplet size distribution may be obtained. On the other hand, in the liquid resonance method, a substantially equal vibration pressure is applied to each nozzle, so that droplets with a narrow particle size distribution are easily obtained even with a wide thin film.
The drying process (particle forming process) for removing the solvent from the droplets is performed by discharging the droplets into a gas such as heated dry nitrogen. If necessary, secondary drying such as fluidized bed drying or vacuum drying is performed to obtain a toner.

  In the present invention, an external additive may be added to the toner surface in order to impart functions such as fluidity and chargeability to the toner. The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, And aluminum oxide stearate); metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.

In order to obtain the hydrophobized silica fine particles, the hydrophobized titania fine particles, and the hydrophobized alumina fine particles, the hydrophilic fine particles are made of silane cups such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. It can be obtained by treating with a ring agent.
Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

Further, silicone oil-treated inorganic fine particles obtained by treating the inorganic fine particles with silicone oil if necessary are also suitable.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Examples thereof include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

The average particle size of primary particles of the inorganic fine particles is preferably 1 nm to 100 nm, and more preferably 3 nm to 70 nm. If the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. If the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. May end up. As the external additive, inorganic fine particles and hydrophobized inorganic particles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, and more preferably 5 nm to 70 nm. More preferably, the primary particles subjected to the hydrophobization treatment include at least two types of inorganic fine particles having an average particle diameter of 20 nm or less and at least one type of inorganic fine particles of 30 nm or more. Moreover, it is preferable that the specific surface area by the BET method of the said inorganic fine particle is 20-500 m < ² > / g.
The amount of the external additive added is preferably 0.1% by mass to 5% by mass and more preferably 0.3% by mass to 3% by mass with respect to the toner.

  Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the toner.

The toner according to the present invention is a toner manufactured by a toner manufacturing method using the above-described toner manufacturing apparatus, and thus a toner having a very monodispersed particle size distribution can be obtained.
Specifically, the particle size distribution (mass average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.10, more preferably 1.00 to 1.05. . The mass average particle diameter is preferably in the range of 1 μm to 20 μm, and more preferably 3 μm to 10 μm from the viewpoint of high image quality.
Here, the mass average particle diameter and the number average particle diameter of the toner can be obtained as follows.
・ Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
・ Aperture diameter: 100μm
・ Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter)
・ Electrolyte: Isoton II (Beckman Coulter)
-Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte-Dispersion condition: 10 mg of a measurement sample is added to 5 ml of the dispersion, and 1 with an ultrasonic disperser. Disperse for 25 minutes, then add 25 ml of electrolyte and further disperse for 1 minute with an ultrasonic disperser.
Measurement conditions: 100 ml of electrolyte solution and dispersion were added to a beaker, and 30,000 particles were measured at a concentration capable of measuring the particle size of 30,000 particles in 20 seconds. Determine the number average particle size.

(Developer)
The developer of the present invention contains at least the toner and contains other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, the filming of the toner on the developing roller as the developer carrying member, and the thinning of the toner are performed. There is no fusion of toner to a layer thickness regulating member such as a blade for layering, and good and stable developability and images can be obtained even when the developing means is used for a long time (stirring). Further, in the case of the two-component developer using the toner, even if the toner balance is maintained over a long period of time, the toner particle diameter in the developer is small, and even if it is stirred for a long time in the developing means, it is good and stable. Developability is obtained.

There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 μm to 200 μm, and more preferably 40 μm to 100 μm. When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyesters Resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and Copolymers with vinyl fluoride, fluoroterpolymers (triple fluoride (multiple) copolymer) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. . These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin, Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.
The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, for example, 90 to 98 mass. % Is preferable, and 93 to 97% by mass is more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

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

<Measurement of softening point of resin>
Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), 1 g of resin as a sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger, Extrusion from the nozzle, the plunger drop amount of the flow tester against the temperature was plotted, and the temperature at which half of the sample flowed out was taken as the softening point.

<Measurement of glass transition temperature (Tg) of resin>
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), 0.01 to 0.02 g of sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature was lowered at a rate of 10 ° C./min. The sample cooled to 0 ° C is heated at a heating rate of 10 ° C / min, and the intersection of the baseline extension line below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rise to the peak apex Was defined as the glass transition temperature.

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

(Synthesis Example 1)
-Synthesis of polyester resin 1-
The alcohol components, terephthalic acid, and esterification catalyst of resins A1, A6, A8, A10, and B1 to B7 shown in Table 1 and Table 2, a nitrogen introduction tube, a dehydration tube, a rectification column, a stirrer, and a thermocouple Was placed in a 5 liter four-necked flask equipped with the above, and subjected to a condensation polymerization reaction at 230 ° C. for 15 hours under a nitrogen atmosphere, and then reacted at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 180 ° C., itaconic acid is added, the temperature is raised to 210 ° C. over 2 hours, the reaction is carried out at 210 ° C. and 10 kPa to the desired softening point, and polyester resins (resins A1, A6, A8) are obtained. , A10, B1-B7) were synthesized.

(Synthesis Example 2)
-Synthesis of polyester resin 2-
5 liters equipped with the alcohol components, terephthalic acid, and esterification catalyst of resins A2 to A5, A7, and A9 shown in Tables 1 and 2 and equipped with a nitrogen introduction tube, a dehydration tube, a rectifying column, a stirrer, and a thermocouple In a 4-necked flask and subjected to a condensation polymerization reaction at 230 ° C. for 15 hours under a nitrogen atmosphere, and then reacted at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 180 ° C., itaconic acid was added and reacted at 200 ° C. for 8 hours. After cooling to 180 ° C., trimellitic anhydride is added, the temperature is raised to 210 ° C. over 2 hours, the reaction is carried out at 210 ° C. and 10 kPa to the desired softening point, and polyester resins (resins A2 to A5) are obtained. , A7, A9) were synthesized.

* The values in parentheses in the amounts of alcohol component and carboxylic acid component used are molar ratios.
* The amount of the esterification catalyst used is 0.5 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.
* BPA-EO indicates a bisphenol A ethylene oxide adduct.

* The values in parentheses in the amounts of alcohol component and carboxylic acid component used are molar ratios.
* The amount of the esterification catalyst used is 0.5 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.
* BPA-EO indicates a bisphenol A ethylene oxide adduct.

(Production Example 1)
-Carrier manufacturing-
A carrier used for a two-component developer was produced as follows.
A coating material having the following composition is dispersed with a stirrer for 10 minutes to prepare a coating solution, and 5,000 parts by mass of this coating solution and a core material (Mn ferrite particles, mass average particle size = 35 μm) are rotated in a fluidized bed. The coating liquid was applied to the core material by applying it to a coating apparatus for coating while forming a swirling flow provided with a bottom plate disk and stirring blades. The obtained coated product was baked in an electric furnace at 250 ° C. for 2 hours to produce a carrier.
[Composition of coating material]
-Toluene: 450 parts by mass-Silicone resin (SR2400, manufactured by Toray Dow Corning Silicone Co., Ltd., nonvolatile content 50 mass%): 450 parts by mass-Aminosilane (SH6020, manufactured by Toray Dow Corning Silicone Co., Ltd.) ) ... 10 parts by mass Carbon black ... 10 parts by mass

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

-Preparation of wax dispersion-
In a container in which a stirring blade and a thermometer are set, 30 parts by mass of a polyester resin (A) as a binder resin described in Table 3, 10 parts by mass of a wax described in Table 3, and 160 parts by mass of ethyl acetate are charged. The mixture was heated to 85 ° C. and stirred for 20 minutes to dissolve the polyester resin and wax, and then rapidly cooled to precipitate wax fine particles. This wax dispersion was further finely dispersed by a strong shearing force using a dyno mill, and the maximum particle size of the wax was adjusted to 1 μm or less.

-Preparation of toner composition liquid-
50 parts by mass of the carbon black dispersion (10 parts by mass of inner carbon black), 100 parts by mass of the wax dispersion (5 parts by mass of inner wax, 15 parts by mass of the polyester resin (A)), and the polyester resin shown in Table 3 Add 425 parts by mass of (A) 20% by mass ethyl acetate solution (85 parts by mass of the inner polyester resin (A)), and then add ethyl acetate so that the solids concentration is 15% by mass. The toner composition liquid was prepared by stirring and mixing for 10 minutes using the mixer which has.

-Preparation of toner-
The obtained toner composition liquid is supplied to the nozzle 1 of the toner manufacturing apparatus shown in FIG. 1, and after droplets are discharged into nitrogen at 45 ° C. under the following toner production conditions, the droplets are dried and solidified. After being collected by a cyclone, it was blown and dried at 40 ° C. for 3 days to obtain black fine particles.
The used nozzle plate was produced by electroforming a perfect circular discharge hole having a diameter of 8 μm on a nickel plate having an outer diameter of 8.0 mm and a thickness of 20 μm. The discharge holes were provided in a staggered pattern so that the distance between the discharge holes was 100 μm and only in the range of 5 mm in diameter at the center of the nozzle plate. In this case, the number of effective discharge holes in calculation is 1,000, and the diameters (opening diameters) of these discharge holes are all the same.
[Toner preparation conditions]
Dry air flow rate: Dispersing nitrogen gas 2.0 L / min,
: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 38 to 40 ° C
Nozzle frequency: 180 kHz
Piezoelectric applied voltage: 10V

Next, the toner particles 1 were prepared by adjusting the particle size distribution of the black fine particles by air classification.
Next, 1.0 part by mass of additive (HDK-2000, manufactured by Clariant Co., Ltd.) and 0.5 part by mass of titanium oxide (JMT-150IB, manufactured by Teica Co., Ltd.) are added to 100 parts by mass of toner base particles using a Henschel mixer. Toner 1 was prepared by stirring and mixing.

<Manufacture of two-component developer>
The carrier used for the two-component developer is obtained with respect to the carrier produced above (ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin at an average thickness of 0.5 μm) and 100 parts by mass of the carrier. 7 parts by weight of the toner was added to the container, and the mixture was uniformly mixed and charged at 48 rpm for 3 minutes using a tumbler mixer (manufactured by Willy et Bacchofen (WAB)) where the container was rolled and stirred. Component developer 1 was prepared.

(Examples 2 to 11)
The toner composition liquid of Example 1 was prepared by adding 50 parts by mass of the carbon black dispersion (10 parts by mass of inner carbon black) and 100 parts by mass of the wax dispersion (5 parts by mass of inner wax, polyester resin (A) 15 175 parts by mass (inner polyester resin (A) 35 parts by mass) of the polyester resin (A) solid content 20% by mass of the polyester resin (A) shown in Table 3 and the polyester resin (B) shown in Table 3 Add 250 parts by mass of an ethyl acetate solution with a solid content of 20% by mass (50 parts by mass of the inner polyester resin (B)), add ethyl acetate so that the solid content concentration becomes 15% by mass, and add a mixer having stirring blades. Toners 2 to 11 and developers 2 to 11 were prepared in the same manner as in Example 1 except that the toner composition liquid was prepared by stirring and mixing for 10 minutes.

(Example 12)
The toner composition liquid obtained in Example 2 is supplied to the droplet jetting unit of the toner manufacturing apparatus shown in FIG. 16, and after the droplets are discharged into nitrogen at 45 ° C., the droplets are dried and solidified. After being collected by a cyclone, it was blown and dried at 40 ° C. for 3 days to produce toner base particles 12.
The thin film (nozzle plate) uses a 500 μm thick SOI substrate, and the nozzle is formed in a two-stage shape (convex shape) in which the diameter of the opening 115 shown in FIG. 18 is 100 μm and the diameter of the opening 116 is 8.5 μm. Part 116 was used as the side from which the liquid was released. The number of the openings 116 is 1,000, and the diameters of these openings 116 are all the same, and the openings 116 are provided in a staggered pattern so that the distance between the discharge holes is 100 μm. The liquid storage part used what was comprised by the liquid storage area | region divided | segmented equally. The excitation frequency used in this example and the configuration of the liquid reservoir are shown below.
<Liquid reservoir configuration and drive frequency>
・ Excitation frequency: 32.7 kHz (resonance frequency)
-Number of liquid storage part divisions (number of liquid storage areas): 6
・ Liquid reservoir longitudinal dimension A: 8mm
-Liquid storage part short side dimension B: 8mm
-Number of nozzles per liquid storage area: 480

Next, the black fine particles were adjusted in particle size distribution by air classification to produce toner base particles.
Next, 1.0 part by mass of additive (HDK-2000, manufactured by Clariant Co., Ltd.) and 0.5 part by mass of titanium oxide (JMT-150IB, manufactured by Teica Co., Ltd.) are added to 100 parts by mass of toner base particles using a Henschel mixer. The toner 12 was prepared by stirring and mixing.
The carrier used for the two-component developer is obtained with respect to the carrier produced above (ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin at an average thickness of 0.5 μm) and 100 parts by mass of the carrier. 7 parts by weight of the toner was added to the container, and the mixture was uniformly mixed and charged at 48 rpm for 3 minutes using a tumbler mixer (manufactured by Willy et Bacchofen (WAB)) in which the container was rolled and stirred. Component developer 12 was produced.

(Comparative Example 1)
In Example 1, a toner 13 and a two-component developer 13 were produced in the same manner as in Example 1 except that the polyester resin (A) described in Toner 13 in Table 3 was used.

(Comparative Example 2 and Reference Examples 1 to 4)
The toner composition liquid of Example 1 was prepared by mixing 50 parts by mass of carbon black dispersion (10 parts by mass of inner carbon black) and 100 parts by mass of the wax dispersion (5 parts by mass of inner wax, 15 parts by mass of polyester resin (A)). Part), a solid content 20% by mass ethyl acetate solution of the polyester resin (A) described in Table 3 (175 parts by mass (inner polyester resin (A) 35 parts by mass)), and a solid resin of the polyester resin (B) described in Table 3 Add 250 parts by weight of 20% by weight ethyl acetate solution (50 parts by weight of the inner polyester resin (B)), add ethyl acetate so that the solids concentration is 15% by weight, and use a mixer with stirring blades. Then, toners 14 to 18 and two-component developers 14 to 18 were produced in the same manner as in Example 1 except that the toner composition liquid was changed by stirring and mixing for 10 minutes.

[Comparative Example 3]
Polyester resin (A) (resin A2) 50 parts by mass, polyester resin (B) (resin B1) 50 parts by mass, paraffin wax (HNP-9PD, manufactured by Nippon Seiwa Co., Ltd.), which are resins used for toner 19 shown in Table 3 , Melting point 76.1 ° C.) 5 parts by mass and carbon black (Regal 400, manufactured by Cabot Corp.) 10 parts by mass using a Henschel mixer (manufactured by Mitsui Miike Chemical Industries, Ltd., FM10B) The mixture was melted and kneaded at a temperature of 100 to 130 ° C. with a shaft kneader (manufactured by Ikegai Co., Ltd., PCM-30). The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 to 300 μm with a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer, Labojet (manufactured by Nippon Pneumatic Industry Co., Ltd.), adjusting the pulverization air pressure appropriately so that the mass average particle diameter becomes 4.2 ± 0.3 μm. The louver opening is adjusted so that the mass average particle size is 5.0 ± 0.3 μm, and the fine powder amount of 4 μm or less is 50% by number or less with an airflow classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Classification was carried out with appropriate adjustment to obtain toner base particles.
Next, 1.0 part by mass of silica (HDK-2000, manufactured by Clariant Co., Ltd.) and 0.5 part by mass of titanium oxide (JMT-150IB, manufactured by Teika Co., Ltd.) are used as additives with respect to 100 parts by mass of toner base particles. Toner 19 was produced by stirring and mixing with a Henschel mixer.
The carrier used for the two-component developer is obtained with respect to the carrier produced above (ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin at an average thickness of 0.5 μm) and 100 parts by mass of the carrier. 7 parts by weight of the toner was added to the container, and the mixture was uniformly mixed and charged at 48 rpm for 3 minutes using a tumbler mixer (manufactured by Willy et Bacchofen (WAB)) in which the container was rolled and stirred. Component developer 19 was prepared.

HNP-9PD (manufactured by Nippon Seiwa Co., Ltd., melting point: 76.1 ° C.) is used as the release agent paraffin wax described in Table 3, and WA-03 (Toago Kasei Co., Ltd.) is used as the free fatty acid carnauba wax. Company, melting point 82.8 ° C) was used.

Next, for each of the obtained toners, the mass average particle diameter (D ₄ ), the ratio (D ₄ / Dn), and the heat resistant storage stability were evaluated as follows. The results are shown in Table 4.

<Mass average particle diameter (D ₄ ) and ratio (D ₄ / Dn)>
The mass average particle diameter and the ratio (D ₄ / Dn) of the toner were determined as follows.
・ Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
・ Aperture diameter: 100μm
・ Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter)
・ Electrolyte: Isoton II (Beckman Coulter)
-Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte-Dispersion condition: 10 mg of a measurement sample is added to 5 ml of the dispersion, and 1 with an ultrasonic disperser. Then, 25 ml of the electrolytic solution was added, and further dispersed for 1 minute with an ultrasonic disperser.
Measurement conditions: Add 100 ml of electrolyte and dispersion into a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the mass average particle size ( D ₄ ), number average particle diameter (Dn), and D ₄ / Dn were determined.

<Heat resistant storage stability of toner>
The heat-resistant storage stability was measured using a penetration tester (manufactured by Nikka Engineering Co., Ltd.). Specifically, 10 g of each toner was weighed and placed in a 30 ml glass container (screw vial) in an environment of 20 to 25 ° C. and 40 to 60% RH, and the lid was closed. After tapping the glass container containing the toner 100 times, leaving it in a thermostatic bath set at 50 ° C. for 24 hours, measuring the penetration with a penetration tester and heat-resistant storage stability according to the following evaluation criteria Evaluated. The greater the penetration value, the better the heat resistant storage stability.
〔Evaluation criteria〕
◎: Needle penetration is 30 mm or more ○: Needle penetration is 20 mm to 29 mm
Δ: penetration is 15 mm to 19 mm
X: The penetration is 8 mm to 14 mm
XX: Needle penetration is 7mm or less

  Next, each two-component developer was loaded into an image forming apparatus to form an image, and various performance evaluations were performed as follows. The image forming apparatus includes a non-contact charging system, a two-component developing system, a direct transfer system, a blade cleaning system, and an external heating roller fixing system, an image forming apparatus digital multi-function apparatus imagio MP 7500 (copy speed 75 sheets / A4). Next to size, Ricoh Co., Ltd.) was used. The results are shown in Table 4.

<Low temperature fixability>
Using the image forming apparatus, a single-color solid image having a toner adhesion amount of 0.80 ± 0.02 mg / cm ² is formed on a thick transfer paper (manufactured by NBS Ricoh Co., Ltd., copy printing paper <135>), and a fixing roller The surface of the fixed image thus obtained was fixed using a drawing tester (AD-401, manufactured by Ueshima Seisakusho), a ruby needle (tip radius 260 to 320 μmR, tip angle 60 degrees), load 50 g. Then, the surface of the drawing was strongly rubbed 5 times with fibers (Hanicot # 440, manufactured by Hanilon Co., Ltd.), and the fixing belt temperature at which image shaving was almost eliminated was defined as the minimum fixing temperature. The solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction.
〔Evaluation criteria〕
A: Fixing lower limit temperature is 140 ° C. or less ○: Fixing lower limit temperature is 141 ° C. or more and 150 ° C. or less Δ: Fixing lower limit temperature is 151 ° C. or more and 160 ° C. or less X: Fixing lower limit temperature is 161 ° C. or more and 170 ° C. or less XX: Fixing lower limit temperature Temperature is over 171 ° C

<Hot offset resistance>
Using the image forming apparatus, a monochrome solid image with a toner adhesion amount of 0.60 ± 0.02 mg / cm ² is created on a plain paper transfer paper (Type 6200, manufactured by Ricoh Co., Ltd.), and the temperature of the fixing roller is changed. Then, a fixing test was performed, and the presence or absence of hot offset was visually evaluated. The upper limit temperature at which hot offset did not occur was defined as the upper limit fixing temperature, and hot offset resistance was evaluated according to the following criteria. The solid image was created on the transfer paper at a position 3 mm from the front end in the paper passing direction.
〔Evaluation criteria〕
A: Fixing upper limit temperature is 230 ° C. or higher. ○: Fixing upper limit temperature is 210 ° C. or higher and lower than 230 ° C. Δ: Fixing upper limit temperature is 190 ° C. or higher and lower than 210 ° C. ×: Fixing upper limit temperature is 180 ° C. or higher and lower than 190 ° C. Temperature is less than 180 ° C

<Fixing releasability>
Using the image forming apparatus, a solid image with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² is created on a plain paper transfer paper (Ricoh Co., Ltd., type 6200 (horizontal)), and the fixing roller or roller This occurs when a fixing test is performed by changing the temperature, and a fixed image discharged in the A4 size lateral direction comes into contact with a separation claw arranged to separate the fixing paper and the fixing belt near the exit of the fixing nip. The degree of scars on the fixed image was visually evaluated. The extent of the scar was evaluated in five stages using a rank sample, and an upper limit temperature at which no scar or jam was generated was used as an index for fixing releasability. The solid image was created on the transfer paper at a position 1 mm from the front end in the paper passing direction.
〔Evaluation criteria〕
A: Fixing upper limit temperature is 230 ° C. or higher. ○: Fixing upper limit temperature is 210 ° C. or higher and lower than 230 ° C. Δ: Fixing upper limit temperature is 190 ° C. or higher and lower than 210 ° C. ×: Fixing upper limit temperature is 180 ° C. or higher and lower than 190 ° C. Temperature is less than 180 ° C

<Initial image quality>
The initial image quality was evaluated by using the image forming apparatus, outputting an image evaluation chart, and determining the presence or absence of fog, image density, and blurring. The presence / absence of abnormality and the rank evaluation of the image quality were visually evaluated and judged in the following five stages.
〔Evaluation criteria〕
A: Image abnormality is not observed at all and is good.
○: Compared with the original image, a slight difference in color tone, image density, background stain, etc. is observed, but it is satisfactory in practical use.
Δ: A slight change is felt in the color tone (tone), image density, background stain, and the like.
X: Change in color tone, change in density, dirt on the background are obvious and cause problems.
XX: Color tone change, density change, background stain, etc. are severe, and a normal image cannot be obtained.

<Stability over time>
With respect to the image quality over time, after running 400,000 image charts having a 12% image area using the image forming apparatus, an image evaluation chart is output, and an evaluation similar to the initial image quality evaluation is performed. Comparison with images was performed and evaluation was performed according to the following criteria.
〔Evaluation criteria〕
A: Image abnormality is not observed at all and is good.
◯: Compared to the initial image, a slight difference in hue, image density, background stain, etc. is observed, but it is at a level that does not cause a problem in a normal temperature and humidity environment.
Δ: Compared with the initial image, a slight change is felt in the color tone (hue), image density, background stain, and the like.
×: Compared with the initial image, color tone change, density change, background stain, etc. are obvious and cause problems.
XX: Compared with the initial image, the color change, density change, background stain, etc. are severe, and a normal image cannot be obtained.

<Development roller contamination>
Using the image forming apparatus, after running 100,000 image charts having a 50% image area, the toner adhesion state on the developing roller in the developing machine was visually evaluated. Considering the presence or absence of abnormality in the output image, the determination was made in the following five stages.
〔Evaluation criteria〕
(Double-circle): There is no image abnormality at all and there is no toner adhesion on a roller.
◯: There is no image abnormality at all, but a slight toner fixation is observed on the roller.
Δ: Some abnormal image is seen, and clear toner fixation is seen on the roller.
×: Obvious image abnormality is observed, toner adhesion on the roller is severe, and there is a problem level.
XX: A clear image abnormality is observed, toner adhesion on the roller is severe, and a normal image cannot be obtained.

<Carrier contamination>
Using the image forming apparatus, the developer after running an image chart with a 50% image area of 100,000 sheets is extracted, and the developer is put in a gauge with a mesh having a mesh size of 32 μm and air blown. The toner and carrier were separated. 1.0 g of the obtained carrier was put in a 50 ml glass bottle, 10 ml of chloroform was added, and the mixture was shaken 50 times and allowed to stand for 10 minutes. Thereafter, the supernatant chloroform solution was placed in a glass cell, and the transmittance of the chloroform solution was measured using a turbidimeter, and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Transmittance is 95% or more ○: Transmittance is 90% or more and 94% or less △: Transmittance is 80% or more and 89% or less ×: Transmittance is 70% or more and 79% or less XX: Transmittance is 69% or less

  Since the toner of the present invention is a particle having a single particle dispersibility having a small particle size and an unprecedented particle size, the toner of the past can be used in many characteristic values required for the toner such as fluidity and charging property. There is no or very little variation in the particle size observed in the manufacturing method, and it has excellent offset resistance, low-temperature fixability, heat-resistant storage stability, stain resistance, and fixing releasability. High-resolution, high-quality images with high resolution and no image deterioration over a long period of time. For example, laser printers, direct digital platemakers, full-color copiers using direct or indirect electrophotographic multicolor image development systems, full-color It can be widely used for laser printers and full-color plain paper fax machines.

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 3 Particle formation part (solvent removal part)
DESCRIPTION OF SYMBOLS 4 Toner collection part 5 Tube 6 Toner collection part 7 Raw material accommodating part 8 Piping 9 Pump 10 Toner composition liquid 11 Nozzle 12 Thin film 13 Vibrating means 13a Vibrating surface 14 Reserving part 15 Flow path member 18 Liquid supply tube 21 Vibration generating means 21A Piezoelectric body 22 Vibration amplification means 22A Horn 23 Drive circuit (drive signal generation source)
24 communication means 31 droplet 35 air flow 36 air flow path forming member 37 air flow path 80 horn type vibrator 81 piezoelectric body 82 horn 83 fixing portion 90 Langevin type vibrator 91 piezoelectric body 92 horn 111 resist 112 support layer 113 dielectric layer 114 active Layer 115 first nozzle hole 116 second nozzle hole T toner particles

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 2006-28432 A JP 2006-28433 A JP 2002-287427 A JP 2007-155978 A JP 2008-129411 A

Claims (7)

From a plurality of nozzles having the same opening diameter formed in a thin film provided in a storage portion for storing a toner composition liquid in which a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in a solvent A periodic droplet forming step in which the toner composition liquid is periodically discharged into a gas phase by mechanical vibration means to form droplets;
A toner produced by a toner production method comprising solidifying the dropletized toner composition liquid to form toner particles,
The mechanical vibration means is a vibration means having a parallel vibration surface with respect to the thin film, and the vibration surface vibrates longitudinally in a vertical direction;
The binder resin contains a polyester resin (A) having a softening point Tm (A) of 120 ° C. or higher and 160 ° C. or lower and a polyester resin (B) having a softening point Tm (B) of 80 ° C. or higher and lower than 120 ° C. And at least one of the polyester resins (A) and (B) is obtained by polycondensing an alcohol component containing 65 mol% or more of 1,2-propanediol in a divalent alcohol component and a carboxylic acid component. A toner obtained by using a polyester resin .   2. The liquid composition according to claim 1, wherein the toner composition liquid is periodically discharged into a gas phase from a plurality of nozzles having the same opening diameter formed in a thin film by utilizing a liquid resonance phenomenon caused by mechanical vibration means. toner.   The toner according to claim 1, wherein the mechanical vibration means is a horn type vibrator. The toner according to claim 1, wherein the alcohol component of the polyester resin (A) further contains 1,3-propanediol. The toner according to claim 1, wherein the release agent is carnauba wax. Mass average particle diameter (D ₄ ) And the number average particle diameter (Dn) (D ₄ The toner according to claim 1, wherein / Dn) is 1.00 to 1.10. A developer comprising the toner according to claim 1.