JP2015175933A - toner and developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner capable of inhibiting filming and base contamination.SOLUTION: The toner comprises at least a binder resin, a release agent, and a pigment, in which an abundance ratio of the pigment in a region from the outermost surface of the toner to 100 nm inside, obtained by the following method, is more than 0% and 10% or less. An abundance ratio is obtained by measuring a cut face image of the toner with a transmission electron microscope (TEM), and by dividing an area of the pigment in a region from the outermost surface of the toner to 100 nm depth in the cut face image by an area of the pigment in the whole cut face image so to obtain an area ratio that is regarded as an abundance ratio.

Description

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

Conventionally, as a method for producing an electrostatic charge image developing toner used in a copying machine, a printer, a fax machine, and a composite machine based on an electrophotographic recording method, only a pulverization method has been used in recent years. The method of forming toner particles in an aqueous medium has been widely used, and is surpassing the pulverization method. The toner produced by the polymerization method is called “polymerized toner” or “chemical toner” in some countries.
The polymerization method is referred to as such because it involves the polymerization reaction of the toner raw material at the time of toner particle formation or in the process. Various polymerization methods have been put into practical use and include suspension polymerization, emulsion polymerization, polymer suspension (polymer aggregation), ester elongation reaction, and the like.

  According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limit to the selection of the toner material. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be sufficiently brittle. For this reason, when the toner composition is actually pulverized into particles, a wide range of particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size The fine powder of 5 μm or less, particularly 3 μm or less and the coarse powder of 20 μm or more must be removed by classification, which has the disadvantage that the yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. In addition, since the colorant added to the toner is exposed on the surface of the obtained toner, there is a problem that the toner surface is not uniformly charged, the charge distribution of the toner is expanded, and the development characteristics are deteriorated. Therefore, due to these problems, the pulverization method cannot sufficiently meet the demand for high performance.

  In recent years, in order to overcome these problems in the pulverization method, a toner production method by the suspension polymerization method has been proposed and implemented. However, the toner particles obtained by the suspension polymerization method are spherical and have a drawback of poor cleaning properties. In development and transfer with a low image area ratio, there is little transfer residual toner, and cleaning defects do not become a problem. However, untransferred images were formed due to high image area ratios such as photographic images, as well as poor paper feed. In some cases, toner is generated as a transfer residual toner on the photosensitive member, and when the toner is accumulated, background smearing of the image occurs.

  In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. Furthermore, since the resin is polymerized at the same time as the preparation of the toner, the materials used in conventional toners cannot be used in many cases. Even if polymerization can be performed using conventional materials, the particle size may not be sufficiently controlled due to the influence of additives such as resins and colorants. There is a problem that is small. Particularly problematic is that the polyester resin that has developed excellent fixing performance and color suitability by the conventional pulverization method cannot be used basically, so that it can sufficiently cope with downsizing, high speed, colorization, etc. This is not possible.

On the other hand, there is disclosed a method for obtaining irregularly shaped toner particles by associating resin fine particles obtained by the emulsion polymerization method (see Patent Document 1).
However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, resulting in poor soiling of the obtained image. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, etc. (filming occurs), and the original charging ability cannot be exhibited. In addition, since the colorant is likely to aggregate, it is difficult to add and disperse the colorant uniformly in the toner, and the way in which the colorant enters varies depending on the toner. There is also a problem that the stability when used is lowered. In the case of color output, a slight deterioration in developability and transferability causes a problem in color balance and gradation. Furthermore, since the colorant in the toner is generally hydrophilic and incompatible with the resin, there is also a problem that the transmitted light is irregularly reflected at the interface and the image density and saturation are deteriorated.

Patent Document 2 discloses a step of preparing a pigment dispersion by dissolving and / or dispersing a pigment and a pigment dispersant surface-treated with a fatty acid in a first organic solvent solubilizing a binder resin; A step of preparing an oil component by mixing the binder resin and the pigment dispersion in a second organic solvent solubilizing the binder resin, and a step of suspending the oil component in an aqueous medium and atomizing the mixture. A toner obtained by removing the solvent from the resulting suspension is disclosed.
However, fatty acids do not have amino groups that control the chargeability of the toner. Furthermore, in particular, in color output machines, an oil-less toner is generally used in which an oil supply device for the fixing device is not required and a release agent that replaces the oil is added to the toner. Since it cannot be atomized as much as a colorant, it is difficult to add and disperse more uniformly, and there is also a problem that charging properties, developability and storage stability are hindered if the release agent is poorly dispersed.

In addition, with recent full-color printers, the demand for image quality is increasing year by year. In Patent Documents 3 and 4, a pigment is a synergist (pigment derivative) and a polymer dispersant, and the pigment is highly dispersed in the toner to achieve high saturation, coloring power, and transparency.
However, since the synergist and the polymer dispersant disperse the pigment using the characteristics of acid-base, a highly polar salt is formed on the pigment surface. Therefore, underwater granulation, which is a normal chemical toner manufacturing method, causes pigmentation to be unevenly distributed on the toner surface, which causes filming that contaminates the carrier, photoconductor, charging roller, developing roller, etc. Or the surface state changes, and the original charging ability cannot be exhibited.

  Further, in Patent Document 5, by using a pigment dispersant having an aromatic skeleton, a π electron cloud expressing an aromatic contained in an organic pigment and a π electron cloud having an aromatic skeleton of the pigment dispersant are π. It forms a bond due to -π interaction, can be adsorbed on the pigment surface without generating polarity, and retains the dispersibility of the pigment due to steric hindrance due to the polyester skeleton serving as the base skeleton. Thereby, although the surface uneven distribution of the pigment is improved, the pigment distributed near the surface is also seen.

  Accordingly, the present situation is that a toner and a developer capable of sufficiently suppressing filming and background contamination that can sufficiently meet the demand for higher performance have not yet been provided.

  SUMMARY An advantage of some aspects of the invention is that it provides a toner capable of suppressing filming and background contamination.

In order to solve the above-described problems, the present invention provides a toner containing at least a binder resin, a release agent, and a pigment, and a pigment in a region within a depth of 100 nm from the outermost surface of the toner obtained by the following method. The existence ratio is greater than 0% and 10% or less.
(How to find the existence ratio)
A section image of the toner was measured with a transmission electron microscope (TEM). In this section image, the area of the pigment in a region within a depth of 100 nm from the outermost surface of the toner was divided by the pigment area of the entire section section image. The area ratio at the time is the existence ratio.

  According to the present invention, it is possible to provide a toner capable of suppressing filming and background contamination.

It is sectional drawing which shows an example of a structure of a liquid column resonance droplet formation means. It is sectional drawing which shows an example of a structure of a liquid column resonance droplet unit. It is sectional drawing which shows an example of a discharge outlet. It is the schematic which shows an example of the standing wave of the speed and pressure fluctuation in the case of N = 1, 2, 3. It is the schematic which shows an example of the standing wave of the speed and pressure fluctuation in the case of N = 4 and 5. It is the schematic which shows an example of the mode of the liquid column resonance phenomenon which arises in the liquid column resonance flow path of a liquid column resonance droplet formation means. FIG. 2 is a schematic diagram illustrating an example of a toner manufacturing apparatus. It is sectional drawing which shows another structure of a liquid column resonance droplet formation means. It is a figure which shows an example of the transmission electron microscope (TEM) photograph which shows the particle | grain structure of a toner. It is a figure which shows the other example of the transmission electron microscope (TEM) photograph which shows the particle | grain structure of a toner.

  The toner and developer according to the present invention will be described below with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

(toner)
The toner of the present invention contains at least a binder resin, a release agent, and a pigment, and if necessary, other components such as a pigment derivative, a dispersant, a charge control agent, an organic solvent, and an additive. Further, the ratio of the pigment present in a region within a depth of 100 nm from the outermost surface of the toner determined by the following method is larger than 0% and not larger than 10%.
(How to find the existence ratio)
A section image of the toner was measured with a transmission electron microscope (TEM). In this section image, the area of the pigment in a region within a depth of 100 nm from the outermost surface of the toner was divided by the pigment area of the entire section section image. The area ratio at the time is the existence ratio.

<Pigment abundance>
In the present invention, the abundance ratio of the pigment in the region within a depth of 100 nm from the outermost surface of the toner is required to be larger than 0% and not larger than 10%. The abundance ratio of the pigment is preferably 3 to 10%.
Underwater granulation, which is a normal chemical toner manufacturing method, pigments are unevenly distributed on the toner surface, which can cause contamination (filming) of the carrier, photoconductor, charging roller, developing roller, etc. The state changes and soiling occurs, and the original charging ability cannot be exhibited.
In the present invention, by suppressing the distribution of the pigment near the toner surface and satisfying the above requirements, it is possible to prevent the original charging ability of the toner from being impaired due to the pigment distributed on the toner surface.

  In the present invention, “toner” in “the pigment abundance ratio in a region within a depth of 100 nm from the outermost surface of the toner” means toner base particles, and the toner base particles satisfying a predetermined range of the pigment abundance ratio. Treatment with an external additive treatment or resin particles may be performed.

  As a method for determining the abundance ratio of the pigment in a region within a depth of 100 nm from the outermost surface of the toner, a split cross-sectional image of the toner base particle by a transmission electron microscope (TEM) is analyzed, and the pigment distributed near the toner particle surface The area ratio is calculated. Details are shown below.

First, the toner base particles are embedded in an epoxy resin, a section is prepared with an ultrasonic microtome, dyed with RuO ₄ , and then observed with a transmission electron microscope (TEM). A transmission electron microscope (TEM) uses H7000 manufactured by Hitachi High-Tech.
FIG. 9 shows a TEM photograph as a specific example in the case where the abundance ratio of the pigment in the region within 100 nm depth from the outermost surface of the toner is 10% or less. FIG. 10 shows a TEM photograph as a specific example when the abundance ratio does not satisfy 10% or less. 9 and 10, black portions indicate pigments, white portions indicate release agents, and other portions indicate binder resins. From FIG. 9, it can be seen that the pigment is hardly present in a region within a depth of 100 nm from the outermost surface of the toner. On the other hand, in FIG. 10, it can be seen that pigments (black portions in the figure) are unevenly distributed near the outermost surface of the toner.

  Next, image analysis of the TEM photograph is performed. In the image analysis, the area ratio is obtained by obtaining the area of the pigment in a region within a depth of 100 nm from the outermost surface of the toner particle in the split cross-sectional image and dividing by the area of the entire pigment of the split cross-sectional image. The existence ratio is obtained by obtaining one area ratio for one toner and obtaining an average value for about 30 toners.

In order to make the abundance ratio of the pigment in a region within a depth of 100 nm from the outermost surface of the toner greater than 0% and 10% or less, a toner material, a toner production method (toner method), and the like are appropriately selected. It is possible to control by.
If the abundance ratio exceeds 10%, the pigment is unevenly distributed on the toner surface, which may contaminate the carrier, the photosensitive member, the charging roller, the developing roller, etc. Will occur.

<Binder resin>
The binder resin is not particularly limited, and vinyl polymers such as styrene monomers, acrylic monomers, and methacrylic monomers, copolymers of these monomers or two or more types, polyesters Use binder resin such as polymer, polyol resin, phenol resin, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, petroleum resin Can do. These may be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

When the binder resin is a styrene-acrylic resin, the weight average molecular weight is not particularly limited and may be appropriately selected depending on the intended purpose. However, at least one peak is in the region of 5,000 to 300,000. It is preferable from the viewpoint of toner fixability and hot offset resistance.
The molecular weight distribution of the binder resin can be measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

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

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

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

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

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

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

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

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

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

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

<Release agent>
There is no restriction | limiting in particular as said mold release agent, Although it can select suitably according to the objective, Waxes are preferable.
The waxes are not particularly limited, and those that are usually used can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax Aliphatic hydrocarbon waxes such as: Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; Animal waxes such as lanolin, whale wax, etc .; mineral waxes such as ozokerite, ceresin, and petrolatum; waxes based on fatty acid esters such as montanate ester wax and castor wax; fatty acids such as deoxidized carnauba wax ester Such as those deoxidizing a part or the whole thereof.

  Examples of the waxes further include saturated straight chain fatty acids such as palmitic acid, stearic acid, montanic acid, or straight chain alkyl carboxylic acids having a straight chain alkyl group; prundic acid, eleostearic acid, valinaline Unsaturated fatty acids such as acids; stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesilyl alcohol, or long-chain alkyl alcohols; saturated alcohols such as sorbitol; linoleic acid amides, olefins Fatty acid amides such as acid amides and lauric acid amides; Saturated fatty acid bisamides such as methylene biscapric acid amides, ethylene bislauric acid amides and hexamethylene bisstearic acid amides; Ethylene bisoleic acid amides and hexamethylene vinyls Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasic acid amide; m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Aromatic bisamides such as amides; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid Wax; partial ester compound of fatty acid such as behenic acid monoglyceride and polyhydric alcohol; methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like.

  More preferable examples of the waxes include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and catalysts such as Ziegler catalysts and metallocene catalysts under low pressures. Polymerized polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by pyrolyzing high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, Synthetic hydrocarbon waxes synthesized by the Age method, synthetic waxes using a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and functional groups Mixture of hydrocarbon wax having a styrene these waxes as a matrix, maleic acid esters, acrylates, methacrylates, and graft modified wax with vinyl monomers such as maleic anhydride.

Further, those waxes having a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method are also included. Also, low molecular weight solid fatty acids, low molecular weight solid alcohols, low molecular weight solid compounds, and other impurities are preferably used.
These release agents may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 140 degreeC is preferable at the point which balances fixing property and offset resistance, and 60 to 120 ° C. is more preferable. When the melting point of the mold release agent is less than 50 ° C., the blocking resistance may be lowered, and when it exceeds 140 ° C., the anti-offset effect may be hardly exhibited.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, It contains 3 mass%-20 mass% in the toner solidified in the drying process mentioned later. Preferably, 4 to 15% by mass is contained. When the content of the release agent is less than 3% by mass, the toner becomes difficult to be released from the fixing roller at the time of fixing, and offset is likely to occur. When the content exceeds 20% by mass, The toner strength may be weakened and durability may be lost.

<Pigment>
The pigment is generally added to a toner and used for color development on paper or an image carrier. The toner of the present invention preferably further contains a pigment derivative.
The pigment is not particularly limited. For example, carbon black, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, Polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol F 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, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B , Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B , Thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chromeba Million, 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, Bituminous Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthra Examples thereof include quinone green, titanium oxide, zinc white, litbon, and mixtures thereof.
These may be used alone or in combination of two or more.

  Examples of black pigments include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And aniline black (CI Pigment Black 1).

  Examples of magenta pigments 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, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of cyan pigments 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 yellow pigments 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, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The pigment is preferably contained in the toner in an amount of 4 to 8 parts by weight. When it is out of this range, the image density and the haze degree are inferior. The haze degree is also referred to as haze and is measured as a measure of the transparency (pigment dispersibility) of the toner. The lower this value, the higher the transparency and the better the color developability.

The pigment derivative preferably has a common skeleton with the pigment, and is preferably a pigment derivative having a polarity capable of having a strong interaction with the pigment. Moreover, what has a strong interaction with the pigment dispersant mentioned later is more preferable. By using the pigment derivative, particularly when the pigment derivative is a polar pigment, the pigment tends to move closer to the inside of the toner in the air granulation (details will be described later) as in the present invention. As a result, filming and background contamination can be suppressed, and damage to the original charging ability of the toner can be suppressed.
In addition, although demonstrated also about the location of a pigment dispersant, when a pigment dispersant is a basic high molecular compound, it is preferable that a pigment derivative has an acidic functional group.

  The pigment derivative is not particularly limited. For example, the pigment is C.I. I. In the case of CI Pigment Blue 15: 3 (cyan pigment), SOLPERSE 5000 manufactured by Lubrizol Corporation or the like can be used. Moreover, EFKA-6746 etc. by EFKA company are mentioned.

In order to have the said polarity, it is mentioned that a pigment derivative has an acidic or basic functional group.
The acidic group is not particularly limited, and examples thereof include a carboxy group and a sulfonic acid group.
The basic group is not particularly limited, and examples thereof include an amino group.

  Moreover, it is preferable that content of a pigment derivative is 3 to 10 weight% with respect to a pigment. If it is less than 3% by weight, the image density and the haze degree are inferior. If it is more than 10% by weight, the color tone is affected.

<Dispersant>
There is no restriction | limiting in particular as said dispersing agent, Although it can select suitably according to the objective, It is preferable that compatibility with binder resin is high at the point of pigment dispersibility.
Specific examples of the dispersant include trade names of “Ajisper PB821”, “Ajisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “Disperbyk-2001” (manufactured by BYK Chemie Co., Ltd.), and “EFKA-4010”. (Manufactured by EFKA). These may be used alone or in combination of two or more.

  The weight average molecular weight of the dispersant is not particularly limited and may be appropriately selected depending on the intended purpose, but is the maximum molecular weight of the main peak in terms of styrene equivalent weight in gel permeation chromatography, 100,000 is preferable, and from the viewpoint of pigment dispersibility, 3,000 to 100,000 is more preferable, 5,000 to 50,000 is further preferable, and 5,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the weight average molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant increases. May decrease.

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

The toner of the present invention preferably contains a pigment dispersant. By containing a pigment dispersant, image density, haze degree, and filming can be improved.
Moreover, it is preferable that content of a pigment dispersant is 5 to 50 weight% with respect to a pigment. If it is less than 5% by weight, the effect of the pigment dispersant cannot be obtained, and the image density, haze degree, and filming cannot be improved. When it is larger than 50% by weight, the image density and the haze degree are inferior.

In the present invention, it is preferable to use both a pigment derivative and a pigment dispersant, and the pigment derivative and the pigment dispersant preferably have a strong interaction with each other. Therefore, it is preferable that the pigment dispersant is a basic polymer compound and the pigment derivative is a compound having an acidic functional group.
The basic polymer compound is not particularly limited, and examples thereof include a polyester dispersant. Moreover, as a commercial item, Ajisper PB822 (made by Ajinomoto Fine Techno Co.), EFKA PX4701 (made by BASF) etc. are mentioned, for example.
Although it does not necessarily restrict | limit as an acidic functional group in a pigment derivative, The above-mentioned acidic functional group is mentioned.

When the pigment dispersant is a basic polymer compound and the pigment derivative is a compound having an acidic functional group, image density, haze degree, and filming can be improved.
The content ratio of the pigment dispersant to the pigment derivative is preferably 1: 2 to 20: 1.

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

  Specific examples of the charge control agent include trade names such as Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, and oxynaphthoic acid metal complex E. -82, E-84 of salicylic acid metal complex, E-89 of phenol condensate (above, manufactured by Orient Chemical Industries, Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, retained) Tsuchiya Chemical Industry 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 (above, manufactured by Hoechst) , LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.) Manufactured by a chemical company), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

  The amount of the charge control agent used is not particularly limited and can be appropriately selected according to the type of the binder resin, the presence or absence of additives used as necessary, the toner production method including the dispersion method, and the like. However, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of said binder resin, and 0.2 mass part-5 mass parts are more preferable. If the amount of the charge control agent used exceeds 10 parts by mass, the chargeability of the toner may be too high, leading to a decrease in image density.

<Organic solvent>
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. However, an organic solvent capable of dissolving the binder resin, stably dispersing the dispersion, and easily drying is preferably selected. .
Examples of such organic solvents include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), methoxyethanol, dimethoxyethane, dioxane, dioxolane, and anisole; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and the like. Ketones; esters such as ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate; hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, toluene; methanol , Alcohols such as ethanol, n-propanol, i-propanol, and butanol. These may be used alone or in combination of two or more.
Among these, the organic solvent is preferably tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), ethyl acetate, toluene or the like because the solubility of the crystalline polyester is high.

<Method for preparing toner composition liquid>
A method for preparing the toner composition liquid is not particularly limited as long as the composition containing the binder resin, the release agent, and the pigment (sometimes referred to as toner composition) can be dissolved or dispersed in the organic solvent. It can be appropriately selected depending on the purpose. The toner composition preferably contains the pigment derivative. Thereby, it can suppress more that a pigment is unevenly distributed in the toner surface.

  The method of mixing the toner composition and the organic solvent using a homomixer or a bead mill can make the components in the toner composition sufficiently fine with respect to the opening diameter of the discharge holes. This is preferable because clogging of the discharge holes can be prevented.

  The release agent and other components as necessary in the toner composition may be melt-kneaded together with the binder resin, or may be added when dissolved or dispersed in an organic solvent. The toner composition and the organic solvent may be hot melt kneaded, and a solution obtained by dissolving or dispersing the obtained kneaded material once in various solvents may be used as the toner composition liquid.

  The temperature of the toner composition liquid is not particularly limited and may be appropriately selected depending on the type of the organic solvent. The temperature is preferably from the freezing point to the boiling point of the organic solvent. When the temperature of the toner composition liquid is high, the toner composition liquid is easily dried and the discharge holes of the toner composition liquid are easily clogged. For this reason, it is necessary to prevent drying by applying an organic solvent vapor in the vicinity of the discharge hole of the toner composition liquid. On the other hand, when the temperature of the toner composition liquid is low, the crystalline polyester may not dissolve.

  There is no restriction | limiting in particular as solid content of the said toner composition liquid, Although it can select suitably according to the objective, 5 mass%-40 mass% are preferable. When the solid content is less than 5% by mass, the productivity is lowered, and the dispersion of the release agent, pigment, and other components is liable to cause sedimentation and aggregation. It tends to be non-uniform and toner quality may be reduced. If the solid content exceeds 40% by mass, a toner having a small particle size may not be obtained.

<Developer>
The developer of the present invention contains at least a toner and a carrier, and further contains other components as necessary. The two-component developer is advantageous in that it can improve the service life when used in a high-speed printer or the like that can improve the information processing speed. Since the toner contained in the developer is the toner of the present invention described above, detailed description thereof is omitted.

-Career-
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose. However, a resin-coated carrier having carrier core particles and a coating layer obtained by coating (coating) the carrier core particles with a coating material is preferable.

--Carrier core particles--
There is no restriction | limiting in particular as a material of the said carrier core particle, According to the objective, it can select suitably from well-known things. Examples thereof include oxides such as ferrite, iron-rich ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, and magnetic materials such as alloys thereof.
There is no restriction | limiting in particular as an element contained in the said magnetic material, According to the objective, it can select suitably. For example, iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, vanadium, and the like can be given. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components; manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are particularly preferable.

--- Coating layer--
The material for the coating layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers. Acrylic resins such as acrylic acid ester copolymers and methacrylic acid ester copolymers; fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer and polyvinylidene fluoride; silicone resins, polyester resins, polyamide resins, Preferable examples include polyvinyl butyral and aminoacrylate resin. In addition, an ionomer resin, a polyphenylene sulfide resin, etc. are also mentioned. These may be used alone or in combination of two or more.
A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

  In the resin-coated carrier, the method for coating the surface of the carrier core with at least a resin coating material is not particularly limited and can be appropriately selected according to the purpose. For example, the resin is dissolved or suspended in a solvent. And a method of adhering to the coated carrier core, or a method of simply mixing in a powder state.

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

  There is no restriction | limiting in particular as a usage example which coat | covers carrier core particle | grains (magnetic body) with the coating | coated (coat) material of 2 or more types of mixtures, According to the objective, it can select suitably. For example, (1) 100 parts by mass of titanium oxide fine powder treated with 12 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5), (2) with respect to 100 parts by mass of silica fine powder And those treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5). Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable.

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

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

The volume resistance value of the carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 ⁶ Ω · cm to 10 ¹⁰ Ω · cm. Examples of the method for adjusting the volume resistance value include a method for adjusting the degree of unevenness on the surface of the carrier and the amount of resin to be coated.

  There is no restriction | limiting in particular as a particle size of the said carrier, Although it can select suitably according to the objective, 4 micrometers-200 micrometers are preferable, 10 micrometers-150 micrometers are more preferable, 20 micrometers-100 micrometers are still more preferable. Among these, it is particularly preferable that the carrier has a 50% particle size of 20 μm to 70 μm.

  The mixing ratio of the toner and the carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 part by mass to 200 parts by mass of the toner with respect to 100 parts by mass of the carrier. The toner is more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the carrier.

  In the developing method using the toner of the present invention, any electrostatic latent image carrier used in the conventional electrophotographic method can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, a selenium electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

(Toner production method)
An example of a method for producing the toner of the present invention is a jet granulation method having a droplet forming step and a droplet solidifying step. Hereinafter, a description will be given with reference to FIGS.
The toner component liquid used in the present invention may be in a liquid state in which the toner component is dissolved or dispersed in a solvent, or may be free from a solvent as long as it is liquid under the conditions of discharge. All are mixed in a molten state and present a liquid state. Further, as the toner material, the same material as the conventional electrophotographic toner can be used as long as the toner component liquid can be adjusted. This can be made into fine droplets from the droplet forming step described later, and the target toner particles can be produced by the droplet solidifying step.

<Droplet formation process>
In the droplet forming step, droplets are formed by discharging a mixed solution in which the composition containing the binder resin, the release agent and the pigment is dissolved or dispersed in an organic solvent. The binder resin, pigment, and release agent contained in the composition may be those described above. Moreover, the other material may contain as needed. The composition preferably includes the pigment derivative, and more preferably includes the pigment dispersant. The content of each material is described above.

-Droplet ejection means-
The droplet discharge means used in the present invention is not particularly limited as long as the particle size distribution of the discharged droplets is narrow, and a known one can be used. Examples of the droplet discharge means include a one-fluid nozzle, a two-fluid nozzle, a membrane vibration type discharge means, a Rayleigh split type discharge means, a liquid vibration type discharge means, and a liquid column resonance type discharge means. As the membrane vibration type, for example, those described in Japanese Patent Application Laid-Open No. 2008-292976, Rayleigh splitting type as described in Japanese Patent No. 4647506, and liquid vibration type as described in Japanese Patent Application Laid-Open No. 2010-102195 can be used.
In order to ensure the productivity of the toner with a narrow droplet size distribution, vibration is imparted to the liquid in the liquid column resonance liquid chamber in which a plurality of ejection holes are formed to form a standing wave by liquid column resonance. In addition, liquid droplet resonance that ejects liquid from the ejection hole formed in the region that becomes the antinode of the standing wave is effective. In the present invention, any of these is preferably used.

-Liquid column resonance ejection means-
The liquid column resonance type discharge means that discharges using the resonance of the liquid column will be described.
FIG. 1 shows a liquid column resonance droplet discharge means 11. The liquid common supply path 17 and the liquid column resonance liquid chamber 18 are included. The liquid column resonance liquid chamber 18 communicates with a liquid common supply path 17 provided on one of the wall surfaces at both ends in the longitudinal direction. Further, the liquid column resonance liquid chamber 18 is provided on a wall surface facing the discharge hole 19 and a discharge hole 19 for discharging the droplet 21 to one wall surface of the wall surfaces connected to both ends. Vibration generating means 20 for generating high-frequency vibrations to form standing waves. The vibration generating means 20 is connected to a high frequency power source (not shown).

  The liquid discharged from the discharge means in the present invention is a “particulate component-containing liquid” in which the component of the fine particles to be obtained is dissolved or dispersed, or a solvent if it is liquid under the conditions of discharge. “Particulate component melt” that does not need to be contained and is in a state where the fine particle component is melted is mentioned. Hereinafter, in order to describe the case of manufacturing the toner, these will be described as “toner component liquid”.

  The toner component liquid 14 passes through a liquid supply pipe by a liquid circulation pump (not shown) and flows into the liquid common supply path 17 of the liquid column resonance droplet forming unit 10 shown in FIG. 2, and the liquid column resonance droplet shown in FIG. It is supplied to the liquid column resonance liquid chamber 18 of the discharge means 11. A pressure distribution is formed in the liquid column resonance liquid chamber 18 filled with the toner component liquid 14 by the liquid column resonance standing wave generated by the vibration generating means 20. Then, the droplet 21 is ejected from the ejection hole 19 arranged in a region where the amplitude of the liquid column resonance standing wave is large and the pressure fluctuation is large and which is an antinode of the standing wave.

  The region that becomes the antinode of the standing wave due to the liquid column resonance means a region other than the node of the standing wave. Preferably, it is a region where the pressure fluctuation of the standing wave has an amplitude large enough to discharge the liquid, and more preferably a position where the amplitude of the pressure standing wave becomes a maximum (a section as a velocity standing wave). ) To a minimum position in a range of ± 1/4 wavelength. If the region is an antinode of a standing wave, even if there are a plurality of discharge holes, substantially uniform droplets can be formed from each, and moreover, the droplets can be discharged efficiently. And clogging of the discharge holes is less likely to occur.

  The toner component liquid 14 that has passed through the liquid common supply path 17 flows through a liquid return pipe (not shown) and is returned to the raw material container. When the amount of the toner component liquid 14 in the liquid column resonance liquid chamber 18 decreases due to the discharge of the liquid droplets 21, a suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 18 acts, and the liquid common supply The flow rate of the toner component liquid 14 supplied from the path 17 increases, and the toner component liquid 14 is replenished into the liquid column resonance liquid chamber 18. When the toner component liquid 14 is replenished in the liquid column resonance liquid chamber 18, the flow rate of the toner component liquid 14 passing through the liquid common supply path 17 is restored.

  Each of the liquid column resonance liquid chambers 18 in the liquid column resonance droplet discharge means 11 has a frame formed of a material having such a high rigidity that does not affect the resonance frequency of the liquid at a driving frequency such as metal, ceramics, or silicon. It is formed by bonding. Further, as shown in FIG. 1, the length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 is determined based on the liquid column resonance principle as described later.

  Further, the width W of the liquid column resonance liquid chamber 18 shown in FIG. 2 is desirably smaller than one half of the length L of the liquid column resonance liquid chamber 18 so as not to give an extra frequency to the liquid column resonance. . Furthermore, it is preferable that a plurality of liquid column resonance liquid chambers 18 are arranged for one droplet forming unit 10 in order to dramatically improve productivity. The range is not limited, but one droplet forming unit provided with 100 to 2000 liquid column resonance liquid chambers 18 is more preferable because both operability and productivity can be achieved. In addition, for each liquid column resonance liquid chamber, a flow path for supplying liquid is connected from the common liquid supply path 17, and the common liquid supply path 17 communicates with a plurality of liquid column resonance liquid chambers 18. .

Further, the vibration generating means 20 in the liquid column resonance droplet discharging means 11 is not particularly limited as long as it can be driven at a predetermined frequency, but a form in which a piezoelectric body is bonded to the elastic plate 9 is desirable. The elastic plate constitutes a part of the wall of the liquid column resonance liquid chamber so that the piezoelectric body does not come into contact with the liquid. Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, the piezoelectric body is 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. Furthermore, it is desirable that the vibration generating means 20 is arranged so that it can be individually controlled for each liquid column resonance liquid chamber. In addition, a configuration in which the block-shaped vibrating member made of one material described above is partially cut in accordance with the arrangement of the liquid column resonance liquid chambers, and each liquid column resonance liquid chamber can be individually controlled via an elastic plate. desirable.

  Moreover, it is preferable that the diameter of the opening part of the discharge hole 19 is the range of 1 micrometer-40 micrometers. If the particle size is smaller than 1 μm, the formed droplets may become very small, and thus the toner may not be obtained. In the case where the solid component such as a pigment is contained as a component of the toner, the discharge hole 19 is blocked. May occur frequently and productivity may decrease. When the particle diameter is larger than 40 μm, the diameter of the droplet is large, and when this is dried and solidified to obtain a desired toner particle diameter of 3 to 6 μm, it is necessary to dilute the toner composition with an organic solvent to a very dilute liquid. There is a case. Therefore, a large amount of drying energy is required to obtain a certain amount of toner, which is inconvenient. Further, as can be seen from FIG. 2, adopting a configuration in which the discharge holes 19 are provided in the width direction in the liquid column resonance liquid chamber 18 can provide a large number of openings of the discharge holes 19, thereby increasing the production efficiency. Therefore, it is preferable. Further, since the liquid column resonance frequency varies depending on the arrangement of the discharge holes 19, it is desirable to appropriately determine the liquid column resonance frequency after confirming the discharge of the droplet.

The sectional shape of the discharge hole 19 is described as a tapered shape in which the diameter of the opening is reduced in FIG. 1 and the like, but the sectional shape can be appropriately selected.
FIG. 3 shows a cross-sectional shape that the discharge hole 19 can take. (A) has such a shape that the opening diameter becomes narrow while having a round shape from the liquid contact surface of the discharge hole 19 toward the discharge port, and near the outlet of the discharge hole 19 when the thin film 41 vibrates. Since the pressure applied to the liquid is maximized, it is the most preferable shape for stabilizing the discharge.
(B) has a shape in which the opening diameter becomes narrower from the liquid contact surface of the discharge hole 19 toward the discharge port, and the nozzle angle 24 can be appropriately changed. Although the pressure applied to the liquid can be increased near the outlet of the discharge hole 19 when the thin film 41 vibrates by this nozzle angle similar to (a), the range is greater than 60 and preferably less than 90 °. If it is 60 ° or less, it is difficult to apply pressure to the liquid, and it is difficult to process the thin film 41, which is not preferable.
When the nozzle angle 24 is 90 °, (c) corresponds, but it is difficult to apply pressure to the outlet, and 90 ° is the maximum value. If the angle is 90 ° or more, no pressure is applied to the outlet of the discharge hole 19, so that the droplet discharge becomes very unstable.
(D) is a shape combining (a) and (b). In this way, the shape may be changed step by step.

Next, the mechanism of droplet formation by the droplet formation unit in liquid column resonance will be described.
First, the principle of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 18 in the liquid column resonance droplet discharge means 11 of FIG. 1 will be described. When the sound velocity of the toner component liquid in the liquid column resonance liquid chamber is c and the drive frequency applied to the toner component liquid as a medium from the vibration generating means 20 is f, the wavelength λ at which the liquid resonance occurs is
λ = c / f (Formula 1)
Are in a relationship.

Further, in the liquid column resonance liquid chamber 18 of FIG. 1, when the length from the end of the frame on the fixed end side to the end on the liquid common supply path 17 side is L, the end of the frame on the liquid common supply path 17 side The height h1 (= about 80 μm) is preferably about twice the height h2 (= about 40 μm) of the communication port. In the configuration example shown in FIG. 1, h1 and h2 are about 80 μm and 40 μm, respectively.
Also, in the case of the fixed ends on both sides that are equivalent to the closed fixed ends, the resonance is most efficient when the length L coincides with an even multiple of a quarter of the wavelength λ. It is formed. That is, it is expressed by the following formula 2.
L = (N / 4) λ (Expression 2)
(However, N represents an even number.)

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

The most efficient drive frequency f is obtained from the above formula 1 and the above formula 2.
f = N × c / (4L) (Formula 3)
(L: length of liquid column resonance liquid chamber in longitudinal direction, c: velocity of sound wave of toner composition liquid, N: integer)
It is guided. However, in reality, since the liquid has a viscosity that attenuates the resonance, the vibration is not amplified infinitely, and has a Q value. As shown in equations 4 and 5, which will be described later, Resonance also occurs at frequencies near the highly efficient drive frequency f.

  FIG. 4 shows the shape of the standing wave of velocity and pressure fluctuation (resonance mode) when N = 1, 2, and 3. FIG. 5 shows the standing wave of velocity and pressure fluctuation when N = 4, 5. The shape (resonance mode) is shown. Originally, it is a dense wave (longitudinal wave), but it is generally expressed as shown in FIG. 4 or FIG. In these figures, the solid line indicates the velocity standing wave, and the dotted line indicates the pressure standing wave. For example, as can be seen from FIG. 3A showing the case of a fixed end with N = 1, in the case of velocity distribution, the amplitude of the velocity distribution is zero at the closed end, and the amplitude is maximum at the open end. Easy to understand.

  When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, the wavelength at which the liquid resonates is λ, and the standing wave is most efficiently generated when the integer N is 1 to 5. . In addition, since the standing wave pattern varies depending on the open / closed state of both ends, they are also shown. As will be described later, the condition of the end is determined by the state of the opening of the discharge hole and the opening of the supply side.

  In acoustics, the open end is the end where the moving speed of the medium (liquid) in the longitudinal direction is maximized, and conversely, the pressure is zero. Conversely, the closed end is defined as an end where the moving speed of the medium becomes zero. The closed end is considered as an acoustically hard wall and wave reflection occurs. When ideally completely closed or open, a resonant standing wave of the form shown in FIGS. 4 and 5 is generated by superposition of waves, but it is also determined by the number of discharge holes and the position of the discharge holes. The standing wave pattern fluctuates, and the resonance frequency appears at a position deviated from the position obtained from the above equation 3. However, stable ejection conditions can be created by appropriately adjusting the driving frequency.

For example, the sound velocity c of the liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, wall surfaces exist at both ends, and N = 2 resonance that is completely equivalent to the fixed ends on both sides. When the mode is used, the most efficient resonance frequency is derived as 324 kHz from the above equation (3).
As another example, the sound speed c of the liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, and the same conditions as described above are used. A case where an equivalent N = 4 resonance mode is used. In this case, from the above formula (3), the most efficient resonance frequency is derived as 648 kHz, and higher-order resonance can be used even in the liquid column resonance liquid chamber having the same configuration.

  The liquid column resonance liquid chamber in the liquid column resonance droplet discharge means 11 shown in FIG. 1 is an end that can be described as an acoustically soft wall due to the influence of the opening of the discharge hole or whether both ends are equivalent to the closed end state. Although it is preferable to increase the frequency, it is not limited to this and may be an open end. The influence of the opening of the discharge hole here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. Therefore, the configuration in which the wall surfaces are formed at both ends in the longitudinal direction of the liquid column resonance liquid chamber as shown in FIG. 4B and FIG. 5A is the resonance mode of both fixed ends, and the discharge hole side is opened. This is a preferable configuration because all the resonance modes of the one-side open end to be considered can be used.

  In addition, the numerical aperture of the discharge holes, the opening arrangement position, and the cross-sectional shape of the discharge holes are factors that determine the drive frequency, and the drive frequency can be appropriately determined accordingly. For example, when the number of ejection holes is increased, the restriction at the tip of the liquid column resonance liquid chamber, which has been the fixed end, gradually loosens, a resonance standing wave that is almost close to the open end is generated, and the drive frequency increases. In addition, the opening position of the discharge hole that is closest to the liquid supply path is the starting point, and it becomes a loose constraint condition. The cross-sectional shape of the discharge hole is round, or the volume of the discharge hole varies depending on the thickness of the frame. The upper standing wave has a short wavelength and is higher than the driving frequency. When a voltage is applied to the vibration generating means at the drive frequency determined in this way, the vibration generating means is deformed, and a resonant standing wave is generated most efficiently at the drive frequency.

  Further, the liquid column resonance standing wave is generated even at a frequency in the vicinity of the drive frequency at which the resonance standing wave is generated most efficiently. That is, when the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, and the distance to the discharge hole closest to the end on the liquid supply side is Le, the following formulas 4 and 5 hold. Thereby, the vibration generating means is vibrated using the drive waveform mainly composed of the drive frequency f in the range determined by the following formulas 4 and 5 using the lengths of both L and Le, and the liquid column resonance is performed. It is possible to induce and discharge a droplet from the discharge hole.

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

  The ratio of the length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber to the distance Le to the discharge hole closest to the end on the liquid supply side is preferably Le / L> 0.6.

A liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 18 of FIG. 1 using the principle of the liquid column resonance phenomenon described above, and the discharge holes 19 arranged in a part of the liquid column resonance liquid chamber 18. In this case, droplet discharge occurs continuously.
Note that it is preferable to dispose the discharge hole 19 at a position where the pressure of the standing wave fluctuates the most, since the discharge efficiency is increased and the driving can be performed with a low voltage. Further, one discharge hole 19 may be provided for one liquid column resonance liquid chamber 18, but it is preferable to arrange a plurality of discharge holes 19 from the viewpoint of productivity. Specifically, it is preferably between 2 and 100. When the number exceeds 100, if a desired droplet is to be formed from the 100 ejection holes 19, it is necessary to set a high voltage to the vibration generating means 20, and the behavior of the piezoelectric body as the vibration generating means 20 is increased. Becomes unstable. Further, when the plurality of discharge holes 19 are opened, the pitch between the discharge holes is preferably 20 μm or more and not more than the length of the liquid column resonance liquid chamber. When the pitch between the ejection holes is smaller than 20 μm, there is a high probability that the droplets discharged from the adjacent ejection holes collide with each other to form large droplets, leading to deterioration in the toner particle size distribution.

Next, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge head in the droplet forming unit will be described with reference to FIG.
In FIG. 6, the solid line drawn in the liquid column resonance liquid chamber represents a velocity distribution plotting the velocity at each arbitrary measurement position from the fixed end side to the liquid common supply path side end in the liquid column resonance liquid chamber. The direction from the common liquid supply path to the liquid column resonance liquid chamber is +, and the opposite direction is −. In addition, the dotted line marked in the liquid column resonance liquid chamber indicates a pressure distribution in which the pressure value at each arbitrary measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted. The positive pressure is + with respect to the atmospheric pressure, and the negative pressure is-. Moreover, if it is a positive pressure, a pressure will be applied to the downward direction in the figure, and if it is a negative pressure, a pressure will be applied to the upward direction in the figure.

  Further, in FIG. 6, the liquid common supply path side is opened as described above, but the height of the opening (the height h2 shown in FIG. 1) where the liquid common supply path 17 and the liquid column resonance liquid chamber 18 communicate with each other. In comparison, the height of the frame serving as the fixed end (height h1 shown in FIG. 1) is preferably about twice or more. The liquid column resonance liquid chamber 18 shows respective changes in the velocity distribution and the pressure distribution over time under an approximate condition that the liquid column resonance liquid chamber 18 is substantially fixed on both sides.

  FIG. 6A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 when droplets are discharged. FIG. 6B shows a velocity waveform in the case where the meniscus pressure is increased again after the liquid is drawn immediately after the droplet is discharged. As shown in FIGS. 6A and 6B, the pressure in the flow path in the liquid column resonance liquid chamber 18 provided with the discharge hole 19 is maximum. Thereafter, as shown in FIG. 6C, the positive pressure in the vicinity of the ejection hole 19 decreases, and the liquid droplet 21 is ejected in a negative pressure direction.

Then, as shown in FIG. 6D, the pressure in the vicinity of the discharge hole 19 is minimized. From this time, filling of the liquid component resonance liquid chamber 18 with the toner component liquid 14 starts. Thereafter, as shown in FIG. 6E, the negative pressure in the vicinity of the discharge hole 19 becomes smaller and shifts to the positive pressure direction. At this time, the filling of the toner component liquid 14 is completed. Then, as shown in FIG. 6A again, the positive pressure in the droplet discharge region of the liquid column resonance liquid chamber 18 becomes maximum, and the droplet 21 is discharged from the discharge hole 19. As described above, a standing wave due to liquid column resonance is generated in the liquid column resonance liquid chamber by high-frequency driving of the vibration generating means, and corresponds to an antinode of standing wave due to liquid column resonance at a position where the pressure fluctuates the most. Since the discharge holes 19 are arranged in the droplet discharge region to be discharged, the droplets 21 are continuously discharged from the discharge holes 19 in accordance with the antinode period.

<Droplet solidification process>
Next, the droplet solidifying step will be described. The droplet solidification step is a step of solidifying the droplets formed by the droplet formation step to form fine particles. The toner of the present invention can be obtained by solidifying the liquid droplets of the toner component liquid and then collecting the liquid.

-Droplet solidification means-
In order to solidify, although the way of thinking is different depending on the properties of the toner component liquid, basically any means can be used as long as the toner component liquid can be in a solid state.
For example, if the toner component liquid is obtained by dissolving or dispersing a solid raw material in a solvent capable of volatilization, it can be achieved by drying the droplets in the conveying airflow after the droplets are jetted, that is, volatilizing the solvent. In drying the solvent, the drying state can be adjusted by appropriately selecting the temperature, vapor pressure, gas type, and the like of the gas to be injected. Further, even if the particles are not completely dried, they may be additionally dried in a separate step after the collection as long as the collected particles maintain a solid state. Even if it does not follow the said example, you may achieve by application of a temperature change, a chemical reaction, etc.

-Means for collecting solidified particles-
The solidified particles can be recovered from the air by a known powder collecting means such as a cyclone collecting or a back filter.
FIG. 7 is a cross-sectional view showing an example of an apparatus for carrying out the toner manufacturing method of the present invention. The toner manufacturing apparatus 1 mainly includes a droplet discharge means 2 and a dry collection unit 60.
In the droplet discharge means 2, a raw material container 13 for storing the toner component liquid 14 and a mechanism in which the toner component liquid 14 stored in the raw material container 13 is supplied to the droplet discharge means 2 through the liquid supply pipe 16. have. Further, a liquid circulation pump 15 for pumping the toner component liquid 14 in the liquid supply pipe 16 to return to the raw material container 13 through the liquid return pipe 22 and the liquid supply pipe 16 are connected. It can be supplied to the droplet discharge means 2 at any time. The liquid supply pipe 16 is provided with a pressure measuring device P1 and the dry collecting unit P2 is provided. The liquid feeding pressure to the droplet discharge means 2 and the pressure in the dry collecting unit are measured by pressure gauges P1 and P2. Managed. At this time, if the relationship of P1> P2, the toner component liquid 14 may ooze out. If P1 <P2, there is a possibility that gas enters the discharge means and the discharge stops, so P1≈P2. It is desirable that there is.

  In the chamber 61, a descending airflow 101 created from the carrier airflow inlet 64 is formed. The droplets 21 discharged from the droplet discharge means 2 are transported downward not only by gravity but also by the transport airflow 101 and are collected by the solidified particle collecting means 62.

-Conveyance airflow-
When the ejected droplets come into contact with each other before drying, the droplets coalesce and become one particle (hereinafter, this phenomenon is called coalescence). Therefore, in order to obtain solidified particles having a uniform particle size distribution, it is necessary to maintain the distance between the ejected droplets. However, the ejected droplets have a constant initial velocity, but eventually become stalled due to air resistance. The jetted droplets catch up with the stalled particles and coalesce as a result. Since this phenomenon occurs constantly, the particle size distribution is greatly deteriorated when the particles are collected. In order to prevent coalescence, it is necessary to transport the liquid droplets while solidifying the droplets while preventing the liquid droplets from decreasing in speed and preventing the liquid droplets from coming into contact with each other while preventing the coalescence. It is necessary to carry the solidified particles to the collecting means.

  For example, as shown in FIG. 7, a part of the transport airflow 101 is arranged as a first airflow in the vicinity of the droplet discharge means in the same direction as the droplet discharge direction, thereby reducing the droplet velocity immediately after the droplet discharge. Can be prevented and coalescence can be prevented. Alternatively, as shown in FIG. 8, the direction may be transverse to the ejection direction. Alternatively, although not shown, it may have an angle, and it is desirable to have an angle at which the droplets are separated from the droplet discharge means. As shown in FIG. 8, when the anti-adhesion airflow is applied from the lateral direction to the droplet discharge, it is desirable that the trajectories do not overlap when the droplets are conveyed by the anti-adhesion airflow from the discharge port. .

After preventing coalescence by the first air stream as described above, the solidified particles may be carried to the solidified particle collecting means by the second air stream.
It is desirable that the velocity of the first air flow is equal to or higher than the droplet jet velocity. If the speed of the anti-adhesion airflow is lower than the droplet ejection speed, it is difficult to exert the function of preventing the droplet particles, which is the original purpose of the anti-adhesion airflow, from contacting.
The property of the first air stream can be added with a condition such that the droplets do not coalesce with each other, and may not necessarily be the same as the second air stream. In addition, a chemical substance that promotes solidification of the particle surface may be mixed in the anti-adhesion airflow, or may be imparted in anticipation of a physical action.

  The carrier airflow 101 is not particularly limited as a state of the airflow, and may be a laminar flow, a swirl flow, or a turbulent flow. There is no particular limitation on the type of gas constituting the carrier airflow 101, and air or a nonflammable gas such as nitrogen may be used. Moreover, the temperature of the conveyance airflow 101 can be adjusted as appropriate, and it is desirable that there is no fluctuation during production. Further, a means for changing the airflow state of the carrier airflow 101 in the chamber 61 may be taken. The carrier airflow 101 may be used not only to prevent the droplets 21 from being attached to each other but also to prevent the droplets 21 from adhering to the chamber 61.

-Secondary drying-
When the amount of residual solvent contained in the toner particles obtained by the dry collecting means shown in FIG. 7 is large, secondary drying is performed as necessary to reduce this. As the secondary drying, general known drying means such as fluidized bed drying or vacuum drying can be used. If the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage stability, fixing properties, and charging characteristics will change over time. Since the organic solvent volatilizes at the time of fixing by heating and increases the possibility of adversely affecting the user and peripheral devices, it is necessary to perform sufficient drying.

In underwater granulation, which is a normal chemical toner manufacturing method, pigments are unevenly distributed on the toner surface, which can cause contamination of the carrier, photoconductor, charging roller, developing roller, etc., or change the surface condition. As a result, the original charging ability cannot be exhibited.
On the other hand, since the toner produced by the so-called jet granulation method described above is granulated in the air, particularly a pigment having a polarity subjected to a derivative treatment tends to approach the inside of the toner. Thereby, it is possible to suppress the pigment from being distributed on the toner surface, and it is possible to prevent the original charging ability of the toner from being impaired due to the pigment distributed on the toner surface.

  EXAMPLES Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited by these examples, and these examples are appropriately modified without departing from the gist of the present invention. Is also within the scope of the present invention. Hereinafter, “part” means “part by mass”.

Example 1
<Preparation of cyan pigment dispersion>
Cyan pigment C.I. I. PB15: 3 (manufactured by Dainichi Seika Kogyo Co., Ltd.) 17 parts by weight, pigment derivative 3 to pigment weight% (indicating the content with respect to the pigment, the same shall apply hereinafter), 82.5 parts by weight of ethyl acetate, Used and primarily dispersed. As the pigment derivative, SOLPERSE 5000 (manufactured by Lubrizol) was used (hereinafter referred to as derivative A). The obtained primary dispersion is finely dispersed by a strong shearing force using a bead mill (LMZ type manufactured by Ashizawa Finetech Co., Ltd., zirconia bead diameter 0.3 mm), and the secondary dispersion in which aggregates of 5 μm or more are completely removed. A liquid was prepared.

<Preparation of toner composition liquid>
Next, each dispersion or solution is stirred for 10 minutes using a mixer having stirring blades so that the binder resin, the pigment, the release agent, and the charge control agent have the composition shown in Table 1, and uniform. To obtain a toner composition liquid. The releasing agent was once dissolved in ethyl acetate having a liquid temperature of 60 ° C., and the liquid temperature was adjusted to 45 ° C. during and after the liquid preparation in order to prevent precipitation. In addition, the pigment and the release agent particles did not aggregate due to shock due to solvent dilution.

In Table 1, a polyester resin manufactured by DIC was used as the binder resin.
As a mold release agent, an ester wax manufactured by NOF Corporation was used.
As the charge control agent, FCA-2508N manufactured by Fujikura Kasei Co., Ltd. was used.

<Production of toner>
Using the toner production apparatus shown in FIGS. 1 to 3, the toner composition liquid was ejected under the following conditions by a liquid droplet ejection head using the liquid column resonance principle shown in FIG. 3. Thereafter, the liquid droplets were dried and solidified, collected by a cyclone, and then secondarily dried at 38 ° C. for 48 hours to produce [Toner Base Particles 1].

-Liquid column resonance condition-
Resonance mode: N = 2
Length between both ends in the longitudinal direction of the liquid column resonance liquid chamber: L = 1.8 mm
Height of end of frame on liquid common supply path side of liquid column resonance liquid chamber: h1 = 80 μm
The height of the communication port of the liquid column resonance liquid chamber: h2 = 40 μm

-Preparation conditions of toner base particles-
Dispersion specific gravity: ρ = 1.1 g / cm ³
Discharge port shape: perfect circle Discharge port diameter: 7.5μm
Number of discharge ports: 4 per liquid column resonance liquid chamber Minimum distance between adjacent discharge ports: 130 μm (all at equal intervals)
Dry air temperature: 40 ° C
Applied voltage: 10.0V
Drive frequency: 395 kHz

(Example 2)
[Toner base particle 2] was produced in the same manner as in Example 1, except that the pigment content in the toner composition liquid was changed to 10 parts by weight.

(Example 3)
[Toner base particle 3] was prepared in the same manner as in Example 1, except that the pigment content in the toner composition liquid was changed to 3.8 parts by weight.

Example 4
[Toner base particle 4] was prepared in the same manner as in Example 1 except that the amount of the pigment derivative added to the cyan pigment dispersion was changed to 1% by weight.

(Example 5)
[Toner] in the same manner as in Example 1 except that 10% by weight of the pigment dispersant Ajisper PB822 (Ajinomoto Fine Techno Co., Ltd., basic polymer compound) was added to the cyan pigment dispersion. Base particles 5] were prepared.

(Example 6)
[Toner base particles 6] were prepared in the same manner as in Example 5, except that the amount of the pigment dispersant added to the cyan pigment dispersion was changed to 3% by weight.

(Example 7)
[Toner base particle 7] was prepared in the same manner as in Example 5, except that the amount of the pigment dispersant added to the cyan pigment dispersion was changed to 60% by weight.

(Example 8)
[Toner base particle 8] in Example 5 except that the pigment dispersant in the cyan pigment dispersion was changed to Florene G-900 (manufactured by Kyoeisha Chemical Co., Ltd., modified carboxyl group-containing polymer). ] Was produced.

Example 9
[Toner base particle 9] in the same manner as in Example 8, except that the pigment derivative in the cyan pigment dispersion was changed to derivative B having a basic functional group (Astra Blue 6GLL, manufactured by Sigma Aldrich). Was made.

(Comparative Example 1)
With respect to the toner granulated with the aqueous solvent, [Emulsified toner base particle 10] was prepared. Details will be described below.
<Preparation of fine particle emulsion>
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts by mass of styrene Part, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to copolymerize a vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). ) Aqueous dispersion [fine particle dispersion].
The volume average particle size of the obtained [fine particle dispersion] measured with a particle size distribution analyzer (LA-920, manufactured by Horiba Seisakusho) was 105 nm. A part of the [fine particle dispersion] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the weight average molecular weight (Mw) was 150,000.

<Synthesis of polyester resin>
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propylene oxide 3-mole adduct, 208 parts by mass of terephthalic acid, adipic acid 46 parts by mass and 2 parts by mass of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at 5 to 10 mm under reduced pressure of 10 to 15 mmHg. The polyester resin was obtained by putting a part and making it react at 180 degreeC under a normal pressure for 2 hours. The polyester resin had a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 20 mgKOH / g.

<Preparation of aqueous phase>
990 parts by mass of water, 183 parts by mass of the fine particle dispersion, 37 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7” manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by mass of ethyl acetate The parts were mixed and stirred to obtain a milky white liquid (aqueous phase).

<Synthesis of low molecular weight polyester>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, A low molecular weight polyester was synthesized by charging 22 parts by weight of merit acid and 2 parts by weight of dibutyltin oxide and reacting at 230 ° C. for 5 hours under normal pressure.
The obtained low molecular weight polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., and an acid value of 0.5 mgKOH / g. The hydroxyl value was 51 mgKOH / g.

<Synthesis of Modified Polyester Having Reactive Substituent>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts by mass of the low molecular weight polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were charged and reacted at 100 ° C. for 5 hours. Then, a modified polyester having a reactive substituent (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained modified polyester having a reactive substituent was 1.53% by mass.

<Preparation of cyan master batch>
1200 parts by weight of water and C.I. I. 270 parts by mass of PB15: 3 (manufactured by Dainichi Seika Kogyo Co., Ltd.), 8 parts by mass of pigment derivative SOLSPERSE5000 (manufactured by Lubrizol), and 1200 parts by mass of the polyester resin were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

<Preparation of organic solvent phase>
In a reaction vessel equipped with a stirring rod and a thermometer, 378 parts by mass of the polyester resin, 110 parts by mass of carnauba wax, and 947 parts by mass of ethyl acetate are charged, and the temperature is raised to 80 ° C. with stirring, and remains at 80 ° C. After maintaining for 30 hours, the mixture was cooled to 30 ° C. over 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia. The carnauba wax was dispersed by dispersing for 9 hours under the condition of 80% by volume of beads.
Next, 1324 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion, and 500 parts by mass of the master batch and 500 parts by mass of ethyl acetate were charged and mixed for 1 hour. Next, the mixed liquid was kept at 25 ° C., and an organic solvent phase (pigment / wax dispersion) was prepared by passing 4 passes at a flow rate of 1 kg / min with an Ebara milder (combination of G, M, and S from the inlet side).
The solid content concentration of the obtained organic solvent phase (130 ° C., 30 minutes) was 50% by mass.

<Emulsification and dispersion>
Into a reaction vessel, 749 parts by mass of the organic solvent phase, 115 parts by mass of the modified polyester having a reactive substituent, and 2.9 parts by mass of isophoronediamine (manufactured by Wako Pure Chemical Industries, Ltd.) compound are charged, and a homomixer is prepared. After mixing for 1 minute at 5,000 rpm using TK Homomixer MKII (made by Tokushu Kika Kogyo Co., Ltd.), 1200 parts by mass of the aqueous phase was added to the reaction vessel, and the rotation speed was 9 with the homomixer. 3 minutes at 1,000 rpm. Thereafter, the mixture was stirred with a stirrer for 20 minutes to prepare an emulsified slurry.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 25 ° C. After removing the organic solvent, aging was performed at 45 ° C. for 15 hours to obtain a dispersed slurry.

<Washing process>
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a homomixer (rotation speed: 8,000 rpm for 10 minutes), and then filtered.
100 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a homomixer (10 minutes at a rotation speed of 8,000 rpm), and then filtered under reduced pressure.
100 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the filter cake obtained here, it mixed with the homomixer (10 minutes at the rotation speed of 8,000 rpm), and then filtered.
100 mass parts of 10 mass% hydrochloric acid was added to the filter cake obtained here, it mixed with the homomixer (10 minutes at the rotation speed of 8,000 rpm), and then filtered.
300 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a homomixer (10 minutes at a rotation speed of 8,000 rpm), and then filtered twice to obtain a final filter cake.
The final filter cake obtained here was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain [Emulsified toner base particles 10].

(Comparative Example 2)
[Emulsified toner base particles 11] were produced in the same manner as in Comparative Example 1 except that the amount of the pigment derivative added to the cyan master batch was changed to 2.7 parts by mass in Comparative Example 1.

(Comparative Example 3)
[Comparative Example 1] [Emulsion toner] In the same manner as in Comparative Example 1 except that 27 parts by mass of the pigment dispersant Ajisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd., basic polymer compound) was newly added to the cyan masterbatch. Base particles 12] were prepared.

(Comparative Example 4)
For the toner produced by the pulverization method, [Crushing toner base particles 13] were prepared. Details will be described below.
<Synthesis of polyester resin>
443 parts of PO adduct of bisphenol A (propylene oxide adduct of bisphenol A: hydroxyl value 320), 135 parts of diethylene glycol, 211 parts of terephthalic acid, fumarate in a reaction vessel equipped with a thermometer, stirrer, cooler and nitrogen introduction tube 211 parts of acid and 2.5 parts of dibutyltin oxide were added and reacted at 150 ° C. to 230 ° C. to obtain a polyester resin.

<Master batch adjustment>
A master batch for use in toner formulation was prepared as follows. The materials shown in the following masterbatch formulation were mixed for 3 minutes at 1500 rpm using a Henschel mixer (Henschel 20B, Mitsui Mining Co., Ltd.), and the resulting mixture was kneaded for 45 minutes at 120 ° C. using two rolls. After that, it was cooled by rolling and pulverized with a pulverizer to obtain a master batch.

-Formulation of cyan masterbatch-
Water 25 parts C.I. I. PB15: 3 (manufactured by Dainichi Seika Kogyo Co., Ltd.) 50 parts Pigment derivative (manufactured by Lubrizol Corporation, SOLPERSE 5000) 1.5 parts Polyester resin 50 parts

<Preparation of crosslinking agent>
75 parts of diglyceryl monostearate (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) as a pigment dispersant, 25 parts of benzoyl peroxide (manufactured by Merck) as a crosslinking initiator, and Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.) are used. Mix at 1000 rpm for 3 minutes, and knead in a single screw kneader (Small Bus Co Kneader, Buss) under the conditions of set temperature: inlet 60 ° C, outlet 40 ° C, feed rate: 10 kg / Hr. [Crosslinking agent] was obtained.
Set temperature: inlet portion 60 ° C., outlet portion 40 ° C., feed amount: 10 kg / Hr

<Manufacture of pulverized toner base particles 13>
[Toner Base Particle 13] was produced by the following formulation using the polyester resin, masterbatch, cross-linking agent obtained above, and paraffin wax (HNP-11, manufactured by Nippon Seiki Co., Ltd.).
Polyester resin 51 parts Paraffin wax 5 parts Masterbatch 8 parts Crosslinker 2 parts

  The material shown in the prescription of the above [toner base particle 13] was mixed at 1500 rpm for 3 minutes using a Henschel mixer (Henschel 20B: manufactured by Mitsui Mining Co., Ltd.), and a single-screw kneader (compact bus co-kneader: manufactured by Buss). ), Kneading was performed under the conditions of set temperature: inlet part 90 ° C., outlet part 60 ° C., feed amount: 10 kg / Hr.

  Next, after kneading, rolling and cooling, pulverizing with a pulverizer, and using a flat impingement plate with an I-type mill (manufactured by Nippon Pneumatic Co., Ltd .: IDS-2 type), air pressure: 6.0 atm / cm 2 Then, fine pulverization was performed under the condition of feed amount: 0.5 kg / hr, and classification was further performed (132MP, manufactured by Alpine Co., Ltd.) to obtain [Crushing toner base particles 13].

(Comparative Example 5)
In Comparative Example 4, [Crushing toner base particles 14] were produced in the same manner as in Comparative Example 4, except that the master batch formulation was changed as follows.

-Formulation of cyan masterbatch-
Water 25 parts C.I. I. PB15: 3 (manufactured by Dainichi Seika Kogyo Co., Ltd.) 50 parts Pigment derivative (manufactured by Lubrizol, SOLPERSE5000) 1.5 parts Pigment dispersant (manufactured by Ajinomoto Fine Techno Co., Ajisper PB822) 5 parts Polyester resin 50 parts

(Evaluation)
<Measurement of pigment content>
The split cross-sectional images of the toner base particles of Examples 1 to 9 and Comparative Examples 1 to 5 were analyzed using a transmission electron microscope (TEM), and the area ratio of the pigment distributed near the toner particle surface was calculated. Details are shown below.

The toner base particles of Examples and Comparative Examples were embedded in an epoxy resin, sections were prepared with an ultrasonic microtome, stained with RuO ₄ , and then observed with a transmission electron microscope (TEM). . The transmission electron microscope (TEM) used was H7000 manufactured by Hitachi High-Tech.
As a specific example, the TEM photograph of Example 5 is shown in FIG. 9, and the TEM photograph of Comparative Example 1 is shown in FIG. In FIG. 9, the black part is a pigment (cyan pigment), the white part is a release agent, and the other part is a binder resin. From FIG. 9, it can be seen that the pigment is hardly present in a region within a depth of 100 nm from the outermost surface of the toner. On the other hand, in FIG. 10, it can be seen that pigments (black portions in the figure) are unevenly distributed near the outermost surface of the toner.
Next, the image analysis of the TEM photograph obtained by the Example and the comparative example was performed. In the image analysis, the area ratio is obtained by obtaining the area of the pigment in a region within a depth of 100 nm from the outermost surface of the toner particle in the split cross-sectional image and dividing by the area of the entire pigment of the split cross-sectional image. In each of the examples and comparative examples, one area ratio was obtained for one toner, and an average value obtained for 30 toners was obtained.
The results are shown in Table 2, respectively.

As can be seen from Table 2, in Examples 1 to 9, the proportion of the pigment distributed near the outermost surface of the toner is relatively small. Further, from the TEM photograph of the cyan toner of Example 5 shown in FIG. 9, it can be confirmed that the pigment is hardly distributed on the outermost surface of the toner.
On the other hand, in Comparative Examples 1 to 3, which are toners based on the emulsification method, it can be said from Table 2 that the ratio of the pigment distributed near the surface is large and the pigment is unevenly distributed on the toner surface. Further, it can be confirmed from the TEM photograph of the cyan toner of Comparative Example 1 shown in FIG. 10 that the pigment is unevenly distributed on the toner surface.
Further, in Comparative Examples 4 and 5 which are toners by the pulverization method, although there are few pigments distributed near the outermost surface of the toner as compared with the emulsification method toner, they were relatively large compared with the jet granulation method of the example.

<External additive treatment>
To 100 parts by mass of the obtained toner base particles of Examples 1 to 9 and Comparative Examples 1 to 5, 1.0 part by mass of hydrophobic silica (“H2000”; manufactured by Clariant Japan) as an external additive was added to Henschel. Using a mixer (manufactured by Mitsui Mining Co., Ltd.), a process of mixing at a peripheral speed of 30 m / s for 30 seconds and resting for 1 minute is performed for 5 cycles, sieved with a mesh of 35 μm, and toners of Examples 1-9 and Comparative Examples 1-5 Manufactured.

Next, a carrier was produced as follows.
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (“organostraight silicone”, 5 parts by mass of r- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black were added, and the mixture was mixed with a homomixer for 20 minutes. A magnetic layer was prepared by coating the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluidized bed type coating apparatus.

  5 parts by mass of each of the toners of Examples 1 to 9 and Comparative Examples 1 to 5 that have been subjected to external additive treatment and 95 parts by mass of the carrier are ball mill mixed, and each of the two components of Examples 1 to 9 and Comparative Examples 1 to 5 is mixed. A developer was produced.

  Hereinafter, image density, saturation, haze degree, filming and background stain were evaluated using the two-component developers of Examples 1 to 9 and Comparative Examples 1 to 5. The results are shown in Table 3, respectively.

<Image density>
Using a tandem color image forming apparatus, the surface temperature of the fixing roller is set to 150 ° C., and the toner adhesion amount is 0.40 mg / cm ² on the copy paper TYPE 6000 <70 W> (manufactured by Ricoh Co., Ltd.). I made an image. About the formed solid image, the image density of five arbitrary places was measured using the chromaticity meter (X-Rite company make: X-Rite939), image density (average value) was calculated | required, and the following reference | standard evaluated.

〔Evaluation criteria〕
◎: Image density is 1.50 or more ○: Image density is 1.40 or more and less than 1.50 Δ: Image density is 1.30 or more and less than 1.40 ×: Image density is less than 1.30

<Saturation>
Similar to the image density evaluation, only the paper is imaged on the POD gloss coated paper so as to have an adhesion amount of 0.40 mg / cm ^2, and the fixing member temperature is always controlled to be 190 ° C., and the image is fixed for evaluation. A sample was used.
About the formed solid image, the chromaticness index a ^* and b ^* in the L ^* a ^* b ^* color system (CIE: 1976) was measured using a chromaticity meter (X-Rite, manufactured by X-Rite). Then, the value of C ^{* represented} by the following formula (I) was determined, and the saturation of each toner was evaluated.
C ^* = [(a ^* ) ² + (b ^* ) ² ] ^1/2 ... Formula (I)

<Haze degree>
The haze degree is also referred to as haze and is measured as a measure of the transparency (pigment dispersibility) of the toner. The lower this value, the higher the transparency and the better the color developability when using an OHP sheet. .
As a fixing color evaluation image sample, a single color image sample was developed on an OHP sheet type PPC-DX (manufactured by Ricoh Co., Ltd.) with a fixing belt temperature of 160 ° C., and a direct reading haze degree computer (HGM) -2DP type, manufactured by Suga Test Instruments Co., Ltd.).

〔Evaluation criteria〕
◎: Haze degree is less than 20% ○: Haze degree is 20% or more and less than 30% △: Haze degree is 30% or more and less than 40% ×: Haze degree is 40% or more

<Filming>
When the toner is filmed on the electrophotographic carrier, the composition of the outermost surface of the electrophotographic carrier is changed and the charge amount is reduced. It is determined that the smaller the change in the charge amount before and after the run, the less the filming of the toner onto the electrophotographic carrier.
Using the tandem type color image forming apparatus (image Neo Neo450, manufactured by Ricoh Co., Ltd.), control the toner density so that the image density of the developer is 20% and the image density becomes 1.4 ± 0.2. However, the amount of change (μc / g) in the charge amount (μc / g) of the developer for electrophotography after outputting 200,000 sheets (the amount of decrease in charge amount after 200,000 sheet run / charge amount at the initial stage of run) The following criteria were evaluated in comparison with the values. The charge amount was measured by a blow-off method.

〔Evaluation criteria〕
◎: Less than 15% ○: 15% or more and less than 30% △: 30% or more and less than 50% ×: 50% or more

<Soil dirt>
Background stains on the background of an image when 200,000 charts with an image area ratio of 5% are continuously output using a tandem color image forming apparatus (image Neo Neo 450, manufactured by Ricoh Co., Ltd.) using each developer. The degree of was visually evaluated according to the following criteria.

〔Evaluation criteria〕
○: No background stain on the image background. △: Slight background stain on the image background, but no problem in actual use. ×: Background stain in the image background, which is a problem in actual use. Is

As can be seen from Table 3, the injection granulated toner of the present invention obtained in Examples 1 to 9 showed no serious problems in any evaluation, and was stable with high coloring power and saturation. It can be seen that it has charging characteristics. In particular, Example 5 in which a pigment derivative and a pigment dispersant were appropriately selected exhibited excellent characteristics.
On the other hand, although the emulsification type toner and the pulverized toner of the comparative example showed high characteristics in terms of coloring power and saturation due to the introduction of the pigment derivative, the original charging ability of the toner decreased due to the pigment distributed on the outermost surface. , Leading to a reduction in filming and dirt.

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet discharge means 6 Toner component liquid supply port 7 Toner component liquid flow path 8 Toner component liquid discharge port 9 Elastic plate 10 Liquid column resonance droplet discharge unit 11 Liquid column resonance droplet discharge means 12 Airflow path 13 Raw material container 14 Toner component liquid 15 Liquid circulation pump 16 Liquid supply pipe 17 Liquid common supply path 18 Liquid column resonance flow path 19 Discharge hole 20 Vibration generating means 21 Liquid droplet 22 Liquid return pipe 23 Merged liquid droplet 24 Nozzle angle 60 Drying Collection means 61 Chamber 62 Toner collection means 63 Toner storage part 64 Conveyance airflow inlet 65 Conveyance airflow outlet 101 Conveyance airflow P1 Liquid pressure gauge P2 In-chamber pressure gauge

Japanese Patent No. 2537503 JP 2001-66827 A Japanese Patent Laid-Open No. 11-231572 JP 2002-131986 JP 2010-152208 A

Claims (10)

A toner containing at least a binder resin, a release agent, and a pigment, wherein the abundance ratio of the pigment in a region within a depth of 100 nm from the outermost surface of the toner determined by the following method is greater than 0% and 10% Toner characterized by:
(How to find the existence ratio)
A section image of the toner was measured with a transmission electron microscope (TEM). In this section image, the area of the pigment in a region within a depth of 100 nm from the outermost surface of the toner was divided by the pigment area of the entire section section image. The area ratio at the time is the existence ratio.   The toner according to claim 1, further comprising a derivative of the pigment.   The toner according to claim 2, wherein a content of the pigment derivative is 3% by weight or more and 10% by weight or less based on the pigment.   The toner according to claim 1, wherein the content of the pigment is 4 to 8 parts by weight with respect to the toner.   The toner according to claim 1, further comprising a pigment dispersant.   The toner according to claim 5, wherein the content of the pigment dispersant is 5% by weight or more and 50% by weight or less based on the pigment.   The toner according to claim 5, wherein the pigment dispersant is a basic polymer compound, and the pigment derivative is a compound having an acidic functional group. A droplet forming step of forming droplets by discharging a mixed solution in which a composition containing the binder resin, a release agent and a pigment is dissolved or dispersed in an organic solvent;
The toner according to claim 1, wherein the toner is obtained by a method including a droplet solidifying step of solidifying the droplets to form fine particles.   The toner according to claim 8, wherein the composition further contains the pigment derivative. A developer comprising at least the toner according to claim 1 and a carrier.