JP5239669B2 - Toner and manufacturing method thereof, developer, process cartridge, image forming method, and image forming apparatus - Google Patents

Description

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

In recent years, there has been a demand for higher image quality in the fields of electrophotographic copying machines and printers. In order to satisfy this requirement, a reduction in the particle size of toner has been actively studied.
As a conventional toner production method, there is a pulverization method in which a toner composition containing a binder resin, a colorant, and the like is melt-kneaded, and the obtained kneaded product is pulverized and classified. However, the toner obtained by this pulverization method has a wide particle size distribution, has a technical limit to reducing the toner particle size, and is inferior in productivity such as yield.
Recently, polymerization toners such as suspension polymerization and emulsion polymerization aggregation have been studied. Furthermore, a method involving volume shrinkage called a polymer dissolution suspension method has been studied (see Patent Document 1). In this suspension method, the toner material is dispersed or dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified in an aqueous medium containing a dispersing agent to form droplets and then the volatile solvent is removed. It is. Unlike the suspension polymerization method and the emulsion polymerization aggregation method, the dissolution suspension method has a wide range of versatile resins that can be used, particularly for full color processes that require transparency and smoothness of the image area after fixing. It is excellent in that a useful polyester resin can be used.

However, since the polymerization toner is premised on the use of a dispersant in an aqueous medium, a dispersant that impairs the charging characteristics of the toner may remain on the toner surface, thereby impairing environmental stability. is there. Moreover, in order to remove a dispersing agent, a large amount of washing water is required, resulting in high costs.
Therefore, as a method for producing toner in place of the polymerization type toner, for example, a method of forming fine droplets using a piezoelectric pulse and drying and solidifying the droplets is proposed (see Patent Document 2). In addition, a method has been proposed in which minute droplets are formed by utilizing thermal expansion in the nozzle, and this is dried and solidified to form a toner (see Patent Document 3). In addition, a method has been proposed in which fine droplets are formed using an acoustic lens and dried to solidify into toner (see Patent Document 4).

In the toner manufacturing method in which the fine droplets are ejected to form toner particles, it is energetically preferable to use an organic solvent having a small latent heat as the solution or dispersion to be ejected. However, when such an organic solvent is used, it is extremely difficult to efficiently remove the residual solvent in the obtained toner.
In this case, the residual solvent amount in the toner is preferably 200 ppm or less, more preferably 50 ppm or less from the viewpoint of odor and quality. If the residual solvent amount exceeds 200 ppm, problems such as generation of odor and photoconductor filming will occur if the toner is used in an electrophotographic image forming apparatus. The current situation is rare.

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention is a method for producing toner that forms toner particles by ejecting fine droplets that can efficiently remove the residual solvent at a low cost and in a short time. It is an object of the present invention to provide toner that does not cause problems such as photoconductor filming, a developer using the toner, a process cartridge, an image forming method, and an image forming apparatus.

Means for solving the problems are as follows. That is,
<1> A droplet forming step in which a toner composition liquid containing at least a resin, an organic low molecular compound, and a colorant is discharged from a nozzle to form droplets;
A constant rate drying step of drying the droplets at a constant rate to form toner particles;
A first mixing step of mixing the toner particles and the external additive;
A reduction rate drying step of reducing the toner particles after the first mixing step or simultaneously with the first mixing step;
The first mixing step is a step of mixing an external additive having a primary particle diameter of 50 nm or more in a state where the residual solvent amount of the toner particles after the constant rate drying step is 10,000 ppm or more. This is a toner manufacturing method.
<2> The toner according to <1>, further including a second mixing step of mixing an external additive having a primary particle diameter of 30 nm or less in a state where the residual solvent amount of the toner particles is 200 ppm or less after the reduction rate drying step. It is a manufacturing method.
<3> From the above <1> to <2>, wherein the drying temperature in the decreasing rate drying step is not less than the glass transition temperature (Tg) of the toner particles -20 ° C. and not more than the glass transition temperature (Tg) of the toner particles. The toner production method according to any one of the above.
<4> The toner production method according to any one of <1> to <3>, wherein a stripping method is performed in the reduction rate drying step.
<5> In the droplet forming step, the toner composition liquid is formed into droplets from the plurality of nozzles by vibrating a thin film having a plurality of nozzles provided in a storage portion for storing the toner composition liquid by mechanical vibration generating means. The method for producing a toner according to any one of <1> to <4>, wherein the liquid droplets are periodically ejected in a periodic manner.
<6> The method for producing a toner according to <5>, wherein the mechanical vibration generating unit is a vibration generating unit provided in an annular shape around an area having a plurality of thin film nozzles.
<7> The method for producing a toner according to <5>, wherein the mechanical vibration generating unit is a vibration generating unit having a vibration surface parallel to the thin film, and the vibration surface vibrates in the vertical direction. .
<8> The method for producing a toner according to <7>, wherein the vibration generating unit that vibrates longitudinally is a horn-type vibrator.
<9> A droplet forming step is a step of discharging the toner composition liquid from a through hole provided in a storage portion for storing the toner composition liquid, and the discharged toner composition liquid is constricted from a columnar shape to a liquid The method for producing a toner according to any one of <1> to <4>, including a step of forming droplets.
<10> The method for producing a toner according to <9>, wherein the through hole is a vibration chamber nozzle head.
<11> The droplet forming step uses a thin film in which a plurality of nozzles provided in a storage portion for storing a toner composition liquid is formed, and a single vibration generating unit having a vibration surface parallel to the thin film. The toner manufacturing method according to any one of <1> to <4>, wherein the liquid droplets are formed using a resonance phenomenon of the liquid existing in the composition liquid storage section.
<12> The toner production according to <11>, wherein a resonance frequency of the liquid existing in the storage unit is lower than a resonance frequency of a structure of a member constituting the storage unit including a thin film in which a plurality of nozzles are formed. Is the method.
<13> A toner produced by the method for producing a toner according to any one of <1> to <12>.
<14> A developer comprising the toner according to <13> and a carrier.
<15> an electrostatic latent image carrier, and at least developing means for developing the electrostatic latent image on the electrostatic latent image carrier with the toner according to <13> to form a visible image, A process cartridge is detachable from an image forming apparatus main body.
<16> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to <13> to form a visible image. An image forming method comprising: a developing step for forming; a transferring step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.
<17> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the toner according to <13> And developing means for forming a visible image by development, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus.
<18> A toner-containing container, wherein the toner according to <13> is contained in a container.

  The method for producing a toner of the present invention includes a droplet forming step, a constant rate drying step, a first mixing step, and a reduced rate drying step. In the droplet forming step, a toner composition liquid containing at least a resin, an organic low molecular weight compound, and a colorant is discharged from a nozzle to form droplets. In the constant rate drying step, the droplets are dried at a constant rate to form toner particles. In the first mixing step, the toner particles and the external additive are mixed. In the reduction rate drying step, the toner particles are reduced rate dried after the first mixing step or simultaneously with the first mixing step. The first mixing step is a step of mixing an external additive having a primary particle diameter of 50 nm or more in a state where the residual solvent amount of the toner particles after the constant rate drying step is 10,000 ppm or more. As a result, the residual solvent can be efficiently removed at low cost and in a short time.

  Since the toner of the present invention is produced by the toner production method of the present invention, it is of high quality without causing problems such as odor generation and photoconductor filming.

  According to the present invention, it is possible to solve the conventional problems, and to efficiently remove the residual solvent at a low cost and in a short time. It is possible to provide a toner that has a small amount of solvent and does not cause problems such as generation of odor and photoconductor filming, and a developer, a process cartridge, an image forming method, and an image forming apparatus using the toner.

(Toner and toner production method)
The method for producing a toner of the present invention includes a droplet forming step in which a toner composition liquid containing at least a resin, an organic low molecular weight compound, and a colorant is discharged from a nozzle to form droplets;
A constant rate drying step of drying the droplets at a constant rate to form toner particles;
A first mixing step of mixing the toner particles and the external additive;
After the first mixing step or at the same time as the first mixing step, a reduction rate drying step of drying the toner particles at a reduced rate, preferably including a second mixing step, and if necessary, other Comprising the steps.
The toner of the present invention is manufactured by the toner manufacturing method of the present invention.
Hereinafter, the details of the toner of the present invention will be clarified through the description of the toner production method of the present invention.

<Toner composition liquid>
The toner composition liquid contains at least a resin, an organic low molecular weight compound, and a colorant, and further contains a solvent, an external additive, a charge control agent, and, if necessary, other components.

-Resin-
The resin is not particularly limited and may be appropriately selected from resins usually used as a binder resin for toners, but preferably has a gel component insoluble in a solvent of less than 0.5%. . If the gel component is contained, the spray nozzle may be clogged and production stability may be impaired. Therefore, in the case of using a resin containing a gel component, it is preferable to filter and use the gel component after dissolving the resin.
Examples of the resin include vinyl polymers such as styrene monomers, acrylic monomers, and methacrylic monomers, copolymers of two or more of these monomers, polyester polymers, and polyol resins. Phenol resin, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, petroleum resin, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.
Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid 2 -Acrylic acid such as ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate, or esters thereof.
Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid 2 -Ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacrylic acid such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or esters thereof, and the like.
Examples of other monomers that form the vinyl polymer or copolymer include the following (1) to (18). (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, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic acid anhydride and alkenyl succinic acid anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid Unsaturated (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; (16) Monomers having a carboxyl group such as anhydrides of α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides, or monoesters thereof; (17) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- And monomers having a hydroxy group such as hydroxy-1-methylhexyl) styrene.

The vinyl polymer or copolymer as the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
Examples of the crosslinking agent include aromatic divinyl compounds, diacrylate compounds linked by alkyl chains, diacrylate compounds linked by alkyl chains containing an ether bond, and other compounds. These may be used individually by 1 type and may use 2 or more types together.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.
Examples of the diacrylate compound linked by the alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6- Examples include hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylate of these compounds with methacrylate.
Examples of the diacrylate compound linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.
Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond.
Examples of the polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

In addition, as the polyfunctional crosslinking agent, for example, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, or those obtained by replacing acrylates of these compounds with methacrylates , Triallyl cyanurate, triallyl trimellitate and the like.
These crosslinking agents are preferably used in an amount of 0.01 to 10 parts by mass, and 0.03 to 5 parts by mass with respect to 100 parts by mass of the other monomers forming the vinyl polymer or vinyl copolymer. It is more preferable to use parts by mass. Among these crosslinkable monomers, they are bonded to a toner resin by a bond chain containing at least one of an aromatic divinyl compound (particularly divinylbenzene), an aromatic group, and an ether bond from the viewpoint of fixability and offset resistance. Diacrylate compounds are preferred. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  There is no restriction | limiting in particular as a polymerization initiator used for manufacture of the said vinyl polymer or a 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 and 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 Oxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydica Bonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyi-sopropyl peroxydicarbonate, di (3-methyl -3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylper Oxylaurate, tert-butyl-oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamyl Hexanoate to peroxy-2-ethyl, di -tert- butyl peroxy the hexa hydro terephthalate, tert- butylperoxy azelate, and the like. These may be used individually by 1 type and may use 2 or more types together.

  When the binder resin is a styrene-acrylic resin, the molecular weight distribution is 3,000 to 50 in terms of molecular weight distribution measured by GPC, which is a resin component soluble in tetrahydrofuran (THF) (THF soluble component). A resin having at least one peak in a region of 1,000 (in terms of number average molecular weight) and having at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixability, offset property and storage stability. In addition, in the measurement using THF-soluble component GPC, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and the main peak is in a region having a molecular weight of 5,000 to 30,000. A binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.

  The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 1 mgKOH / g to 50 mgKOH / g is more preferable.

When the binder resin is a polyester resin, examples of the monomer constituting the polyester resin include the following.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.
In order to crosslink the polyester resin, it is preferable to use a trihydric or higher alcohol together.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component constituting the polyester resin include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And the like, and the like. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

  The polyester-based resin preferably has at least one peak in the molecular weight region of 3,000 to 50,000 in the molecular weight distribution of the THF-soluble component of the resin component in terms of toner fixing property and offset resistance. In addition, as a THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60% to 100% is preferable, and the binder resin has at least one peak in a region having a molecular weight of 5,000 to 20,000. Is more preferable.

The acid value of the polyester resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g to 50 mgKOH / g. More preferably, it is g.
The molecular weight distribution is measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

As the binder resin that can be used in the toner of the present invention, a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component can also be used. . Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
Moreover, when using together a polyester polymer, a vinyl polymer, and other binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1 mgKOH / g-50 mgKOH / g. preferable.
The acid value of the binder resin component of the toner composition is determined by the following methods (I) to (IV), and the basic operation is in accordance with JIS K-0070.
(I) 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 obtained in advance. . A sample ground product of 0.5 g to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the 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.
(II) A sample is put into a 300 ml beaker, and 150 ml of a mixed solution of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(III) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / L KOH.
(IV) The amount of KOH solution used at this time is Sml, and a blank is measured at the same time. The amount of KOH solution used at this time is Bml, and the following equation (1) is used for calculation. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (1)

  The binder resin and the toner composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 ° C. to 80 ° C., and more preferably 40 ° C. to 75 ° C., from the viewpoint of toner storage stability. When the glass transition temperature (Tg) is lower than 35 ° C., the toner is likely to be deteriorated in a high temperature atmosphere, and offset is likely to occur during fixing. On the other hand, when the glass transition temperature (Tg) exceeds 80 ° C., fixability may be deteriorated.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from commonly used resins. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fu Issey Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, Nacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt 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 , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.
The content of the colorant is preferably 1% by mass to 15% by mass and more preferably 3% by mass to 10% by mass with respect to the toner.

The method for dispersing the colorant used in the present invention is not particularly limited and may be appropriately selected according to the purpose. At least the resin, the organic low molecular weight compound, and the colorant are mixed with high shearing force and kneaded. And a method of dispersing a dispersing agent and a coloring agent in a solvent in advance. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used. Further, a bead mill is preferably used as an apparatus for dispersing in a solvent.
The particle diameter of the colorant in the dispersion after the colorant is dispersed is preferably 500 nm or less. If it is larger than 500 nm, the discharge nozzle is likely to be clogged. Further, when the toner is formed, the particle size of the colorant is increased, and the image quality is likely to be deteriorated. In particular, the OHP light transmittance is likely to be decreased. More preferably, it is 300 nm or less. Below 300 nm, the light transmission is remarkably improved and the color reproduction range is greatly improved. The particle size of the colorant can be determined, for example, with a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.).

  As binder resin used at the time of dispersion, in addition to the above-mentioned modified polyester resin or unmodified polyester resin, for example, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, etc., or a polymer of its substitution product; styrene-p -Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene- Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylic acid Methyl copolymer, styrene-acrylic Ronitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane A polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

-Organic low molecular weight compounds-
Examples of the organic low molecular weight compounds include esters of aromatic acids such as fatty acid esters and phthalic acids; phosphate esters, maleic acid esters, fumaric acid esters, itaconic acid esters, other esters, benzyl, benzoin compounds, benzoyl compounds, and other ketones. A hindered phenol compound, a benzotriazole compound, an aromatic sulfonamide compound, an aliphatic amide compound, a long chain alcohol, a long chain dialcohol, a long chain carboxylic acid, a long chain dicarboxylic acid, and the like.
Specifically, dimethyl fumarate, monoethyl fumarate, monobutyl fumarate, monomethyl itaconate, monobutyl itaconate, diphenyl adipate, dibenzyl terephthalate, dibenzyl isophthalate, benzyl, benzoin isopropyl ether, 4-benzoylbiphenyl , 4-benzoyldiphenyl ether, 2-benzoylnaphthalene, dibenzoylmethane, 4-biphenylcarboxylic acid, stearyl stearamide, oleyl stearamide, stearoleoleamide, octadecanol, n-octyl alcohol, tetracosanoic acid, eicosane Acid, stearic acid, laurin_, nonadecanoic acid, palmitic acid hydroxyoctanoic acid, docosanoic acid, described in JP-A-2002-105414 And compounds of the general formulas (1) to (17). These may be used individually by 1 type and may use 2 or more types together.

  Also, plant waxes such as carnauba wax, cotton wax, wood wax and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; petroleum waxes such as paraffin, microcrystalline and petrolatum; etc. Natural wax. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of a polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.

The said organic low molecular weight compound may show the following functions by the combination with the said resin.
When the resin used and the crystalline compound are compatible at a temperature equal to or higher than the melting temperature point of the crystalline compound, the crystalline compound functions as a plasticizer. That is, the crystalline compound improves the softening speed of the resin and has low-temperature fixability. The melting temperature of the crystalline compound is preferably 120 ° C. or lower, and more preferably 80 ° C. or lower. If the melting temperature exceeds 120 ° C., the low temperature fixability may be ineffective.

  When the resin used and the crystalline compound are incompatible, the crystalline compound functions as a release agent. In this case, the melting temperature of the crystalline compound having a release function (hereinafter sometimes referred to as a release function crystalline compound) is preferably 100 ° C. or less, and more preferably 80 ° C. or less. When the melting temperature exceeds 100 ° C., a cold offset may easily occur during fixing.

The melt viscosity of the release functional crystalline compound is preferably 5 cps to 1,000 cps, more preferably 10 to 100 cps, as measured at a temperature 20 ° C. higher than the melting temperature of the release functional crystalline compound.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  The organic low molecular weight compound is preferably soluble in a solvent, but an insoluble organic low molecular weight compound can be used as a dispersion. The average particle size of the low molecular weight organic compound in the dispersion after dispersion is preferably 2 μm or less, and more preferably 500 nm or less. When the average particle diameter exceeds 2 μm, the discharge nozzle may be easily clogged. The average particle size of the organic low molecular weight compound can be determined using, for example, a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.).

-Solvent-
The solvent is not particularly limited as long as it is an organic solvent in which the resin and the low molecular weight organic compound can be dissolved, and can be appropriately selected according to the purpose. For example, water; methanol, ethanol, isopropanol, n-butanol Alcohols such as methyl isocarbinol; ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, cyclohexanone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; Ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran; glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether Ters; glycol ether acetates such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate and 2-butoxyethyl acetate; esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate and ethylene carbonate; benzene Aromatic hydrocarbons such as toluene, xylene; aliphatic hydrocarbons such as hexane, heptane, iso-octane, cyclohexane; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene, etc. Sulfoxides such as dimethyl sulfoxide; pyrrolidones such as N-methyl-2-pyrrolidone and N-octyl-2-pyrrolidone; These may be used individually by 1 type and may use 2 or more types together.

  The toner composition liquid is obtained by dissolving or dispersing the toner composition in the solvent. At that time, the toner composition liquid preferably does not contain particles having a particle size of 500 nm or more, more preferably does not contain particles of 300 nm or more, and even more preferably does not contain particles of 200 nm or more.

  In the present invention, the amount of residual solvent in the toner particles is preferably 200 ppm or less, more preferably 50 ppm or less from the viewpoint of odor and quality. When the residual solvent amount exceeds 200 ppm, problems such as odor and photoconductor filming may occur when the toner is used in an electrophotographic image forming apparatus.

-External additive-
As the external additive, inorganic fine particles can be used in order to impart fluidity, heat resistant storage stability, developability, transferability, chargeability and the like to the toner. The content of the inorganic fine particles in the toner is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.01% by mass to 2.0% by mass. If the content is small, the function does not occur. If the content is too large, adverse effects such as an increase in fixing temperature may occur.
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples thereof include silicon, silicon nitride, etc. that have been surface treated to increase hydrophobicity. These may be used individually by 1 type and may use 2 or more types together.
The hydrophobizing treatment includes, for example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, modified silicone oil, etc. Is mentioned.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. As the specific surface area by BET method of the inorganic fine ^particles, 20m ² / ^g~500m 2 / g are preferred.
Here, the primary particle diameter of the inorganic fine particles can be measured by a particle size distribution measuring apparatus using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics. However, since it is difficult to dissociate the secondary aggregation of the particles after the hydrophobization treatment, it is preferable to directly obtain the particle size from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles can be observed, and the average value of the major axis can be obtained.

In the present invention, an external additive having a primary particle diameter of 50 nm or more is mixed in a state where the residual solvent amount of the toner particles after the constant rate drying step is 10,000 ppm or more.
The external additive having a primary particle diameter of 50 nm or more is considered to contribute mainly to improvement in heat-resistant storage stability, developability, and transferability. The external additive having a primary particle diameter of 50 nm or more imparts a spacer effect, but on the other hand, it easily detaches from the toner particles, and the detached external additive adheres to the photoconductor, transfer body, etc. in the image forming apparatus. Cause ming. In the case of effectively using an external additive having a primary particle diameter of 50 nm or more, it is preferable that the primary particles do not leave the toner particles. That is, the removal rate of the external additive is preferably 10% or less, and more preferably 5% or less.
The upper limit of the primary particle diameter is preferably 1,000 nm or less, more preferably 500 nm or less, and still more preferably 300 nm or less. When the primary particle diameter exceeds 1,000 nm, an increase in the degree of toner aggregation, poor toner charging, and image blur may occur.
The upper limit of the residual solvent amount of the toner particles is preferably 50,000 ppm or less, and more preferably 30,000 ppm or less. When the residual solvent amount exceeds 50,000 ppm, the toner particles are fused with each other, and a toner having a target particle size may not be obtained.

Here, for example, the separation rate is determined by measuring the amount A of the external additive mixed with the external additive with fluorescent X-rays, classifying the toner with an elbow jet, and removing the collected toner. The additive mixing amount B is measured in the same manner and can be obtained from the following mathematical formula.
Detachment rate (%) = (external additive mixture amount A-external additive mixture amount B) / external additive mixture amount A

  A part of the external additive having a primary particle diameter of 50 nm or more can be mixed with the toner particle surface being slightly plasticized by mixing the toner particles with a residual solvent amount of 10,000 ppm or more. The embedding / removal rate is greatly reduced, and it is possible to create a state in which the spacer effect is maintained without being completely buried in the toner particles because of the relatively large primary particle diameter of 50 nm or more. . Moreover, when the residual solvent amount of toner particles is 200 ppm or less, it becomes difficult to suppress the rate of separation of the external additive.

In the present invention, it is preferable to mix an external additive having a primary particle diameter of 30 nm or less in a state where the residual solvent amount of the toner particles is 200 ppm or less after the reduction drying step. The external additive having a primary particle diameter of 30 nm or less is considered to contribute mainly to improvement in fluidity and chargeability of toner particles.
The lower limit of the primary particle diameter is preferably 7 nm or more. When the primary particle diameter is less than 7 nm, even if the residual solvent amount of the toner particles is 200 ppm or less, the external additive is easily embedded in the toner particle surface, and the durability of the powder characteristics may be inferior.
The residual solvent amount of the toner particles of 200 ppm or less satisfies the new standard scheduled to be established as the European environmental standard for electrophotographic toners.
It has been confirmed that such external additives are less likely to function when they are embedded in toner particles. In addition, since the primary particle diameter is as small as 30 nm or less, it tends to be buried in toner particles.
If mixing is performed in a state where the residual solvent amount in the toner particles is 10,000 ppm or more, the external additive is completely buried and the effect is not generated. Further, when the residual solvent amount of toner particles is mixed at 200 ppm or less, the toner particles are hardly buried and can be mixed in a state where the effect can be exhibited.

-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 alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, salicylic acid metal salts And metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, and bontron S-34 of a metal-containing azo dye. , E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex, E-89 of a phenol condensate (above, manufactured by Orient Chemical Industry Co., Ltd.); TP- of a quaternary ammonium salt molybdenum complex 302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.); quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (from Hoechst); LRA-901, LR-, which is a boron complex 47 (manufactured by Japan Carlit Co., Ltd.); copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The content of the charge control agent in the toner varies depending on the type of the resin, the presence or absence of an additive, a dispersion method, and the like, and cannot be generally specified. 0.1-10 mass parts is preferable, and 0.2-5 mass parts is more preferable.
When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

  The toner manufacturing method of the present invention includes a droplet forming step, a constant rate drying step, a first mixing step, and a decremental drying step, a second mixing step, and further other steps as necessary. Comprising.

In the first mixing step, an external additive having a primary particle diameter of 50 nm or more is mixed in a state where the residual solvent amount of the toner particles after the constant rate drying step is 10,000 ppm or more.
In the second mixing step, it is preferable that after the reduction rate drying step, an external additive having a primary particle size of 30 nm or less with a residual solvent amount of toner particles of 200 ppm or less is mixed.

A toner manufacturing apparatus for embodying the toner manufacturing method of the present invention will be described below.
The toner production apparatus used in the toner production method of the present invention is not particularly limited as long as it is an apparatus capable of producing toner by a spray drying production method, and can be appropriately selected and used according to the purpose. A droplet forming unit that discharges a toner composition liquid containing at least a resin, a low molecular weight organic compound, and a colorant from a nozzle to form droplets, a constant rate drying unit that dries the droplets, and a residual solvent amount A reduction-rate drying means for reducing the residual solvent amount to 200 ppm or less that can be used as a toner, a first mixing means for mixing with an external additive, and a second mixing means, and further if necessary It has other means.

-Droplet forming means-
Specifically, as the droplet forming means, conventionally, a one-fluid nozzle (pressurizing nozzle) that pressurizes and sprays liquid, a multi-fluid spray nozzle that mixes and sprays liquid and compressed gas, and a rotating disk Rotating disk type sprayers that use liquids to form liquid droplets by centrifugal force are known, and these can be used, but it is difficult to obtain a toner having a small particle diameter, and the obtained toner Since the particle size distribution is wide and classification is required, there is a disadvantage that the yield is lowered and the productivity is lowered.
As a manufacturing method for obtaining a toner having a uniform particle size by improving the above-mentioned drawbacks, the present inventors periodically discharged a toner composition liquid from a thin film having a plurality of nozzles with a uniform diameter by a vibration generating means to form droplets. We have learned how to make liquid droplets.

In the toner production method of the present invention, the toner composition liquid droplets have a uniform particle size by mechanically vibrating a thin film having a plurality of nozzles to continuously discharge the toner composition liquid from the nozzles. Droplets can be generated. The mechanical vibration generating means for vibrating the thin film itself (hereinafter also simply referred to as “membrane vibration system”) may be arranged in any manner as long as it vibrates in the direction perpendicular to the film having the nozzle. The following two methods are preferably used in the method.
One is a method using mechanical means (mechanical longitudinal vibration means) that has a vibration surface parallel to the thin film having a plurality of nozzles and vertically vibrates in the vertical direction (hereinafter also simply referred to as “horn type”) The other is a method of providing mechanical vibration means (annular mechanical vibration means) formed in an annular shape around an area where a thin film nozzle having a plurality of nozzles is provided (hereinafter simply referred to as “ It is also called “ring type”. Hereinafter, each method will be described.

-Membrane vibration method using mechanical longitudinal vibration means-
First, an example of a film manufacturing method toner manufacturing apparatus using mechanical longitudinal vibration means will be described with reference to the schematic configuration diagram of FIG.
The toner manufacturing apparatus 101 has droplets as droplet forming means for discharging a toner composition liquid in which a toner composition containing at least a resin, an organic low molecular weight compound, and a colorant is dissolved or dispersed in a solvent to be discharged. A jet unit 102, and the droplet jet unit 102 is disposed above, and the droplets of the toner composition liquid that has been formed into droplets discharged from the droplet jet unit 102 are solidified to form toner particles T. The particle forming unit 103 as a means, the toner collecting unit 104 that collects the toner particles T formed by the particle forming unit 103, and the toner particles T collected by the toner collecting unit 104 pass through the tube 105. A toner storage unit 106 serving as a toner storage unit that stores the transferred toner particles T, a raw material storage unit 107 that stores the toner composition liquid 110, and this raw material storage unit A pipe (liquid feed pipe) 108 for feeding the toner composition liquid 110 with respect to the droplet jet unit 102 from the inside 07, and a pump 109 for pumping supplying toner composition liquid 110, such as during operation.
Further, the toner composition liquid 110 from the raw material container 107 is supplied to the droplet ejection unit 102 by itself due to the droplet formation phenomenon by the droplet ejection unit 102. Thus, the liquid is supplied using the pump 109. In addition, as the toner composition liquid 110, a toner composition liquid containing at least a resin, an organic low molecular weight compound, and a colorant is used.

Next, the droplet ejecting unit 102 will be described with reference to FIGS.
FIG. 2 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit 102, and FIG.
The droplet ejecting unit 102 includes a thin film 112 in which a plurality of nozzles (discharge ports) 111 are formed, a vibration generating means (hereinafter referred to as “vibrating means”) 113 for vibrating the thin film 112, a thin film 112 and a vibrating means 113. A flow path member that forms a reservoir (liquid flow path) 114 for supplying a toner composition liquid 110 in which a toner composition containing at least a resin, a low molecular weight organic compound, and a colorant is dissolved or dispersed in a solvent. 115.

  The thin film 112 having the plurality of nozzles 111 is installed in parallel to the vibration surface 113a of the vibration means 113, and a flow path is formed by a resin binder material in which a part of the thin film 112 is not dissolved in the solder or the toner composition liquid. It is bonded and fixed to the member 115 and is in a positional relationship substantially perpendicular to the vibration direction of the vibration means 113. A communication means 124 is provided so that a voltage signal is applied to the upper and lower surfaces of the vibration generating means 121 of the vibration means 113, and the signal from the drive signal generating source 123 can be converted into mechanical vibration. As a communication means for providing an electrical signal, a lead wire whose surface is insulated is suitable. For the vibration means 113, it is suitable for efficient and stable toner production to use elements having a large vibration amplitude such as various horn type vibrators and bolted Langevin type vibrators described later.

  The vibration unit 113 includes a vibration generation unit 121 that generates vibration and a vibration amplification unit 122 that amplifies the vibration generated by the vibration generation unit 121, and drives the drive circuit (drive signal generation source) 123 at a required frequency. When a voltage (driving signal) is applied between the electrodes 121 a and 121 b of the vibration generating means 121, vibration is excited in the vibration generating means 121, and this vibration is amplified by the vibration amplifying means 122 and arranged in parallel with the thin film 112. The vibrating surface 113a is periodically vibrated, and the thin film 112 is vibrated at a required frequency by the periodic pressure caused by the vibration of the vibrating surface 113a.

  The vibrating means 113 is not particularly limited as long as it can give a certain longitudinal vibration to the thin film 112 at a constant frequency, and can be appropriately selected and used, but the thin film 112 is vibrated. Therefore, the vibration generating means 121 is preferably a piezoelectric body 121A that is excited by a bimorph type flexural vibration. The piezoelectric body 121A has a function of converting electrical energy into mechanical energy. Specifically, by applying a voltage, flexural vibration is excited and the thin film 112 can be vibrated.

Examples of the piezoelectric body 121A that constitutes the vibration generating means 121 include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, they are often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.
The vibration unit 113 may be arranged in any way as long as it can vibrate in the vertical direction with respect to the thin film 112 having the nozzle 111, but the vibration surface 113a and the thin film 112 are arranged in parallel.
In the illustrated example, a horn type vibrator is used as the vibration means 113 composed of the vibration generation means 121 and the vibration amplification means 122. This horn type vibration amplifies the amplitude of the vibration generation means 121 such as a piezoelectric element. Since it can be amplified by the horn 122A as the means 122, the vibration generating means 121 itself for generating mechanical vibration may be a small vibration, and the mechanical load is reduced, leading to a long life as a production apparatus.

As the horn type vibrator, a known typical horn shape may be used, and examples thereof include a step type as shown in FIG. 4, an exponential type as shown in FIG. 5, a conical type as shown in FIG. Can do. In these horn-type vibrators, a piezoelectric body 121A is disposed on a surface having a large area of the horn 122A. The piezoelectric body 121A uses longitudinal vibration to induce efficient vibration of the horn 122A, and the horn 122A has a small area. The surface is the vibration surface 113a, and the vibration surface 113a is designed to be the maximum vibration surface. Lead wires 124 are arranged above and below the piezoelectric body 121, and an AC voltage signal is given from the drive circuit 123. The maximum vibration surface of these horn vibrators is designed to have a vibration surface 113a.
Further, as the vibration means 113, a particularly high-strength bolted Langevin type vibrator can be used. This bolted Langevin type vibrator is mechanically coupled with piezoelectric ceramics and will not be damaged during high amplitude excitation.

  The configuration of the reservoir, the vibration generating means, and the thin film will be described in detail with reference to the schematic diagram of FIG. The reservoir 114 is provided with at least one liquid supply tube 118, and as shown in a partial cross-sectional view, the liquid is introduced into the liquid reservoir through the flow path. Further, it is possible to provide a bubble discharge tube 119 as necessary. The droplet ejection unit 102 is installed and held on the top surface portion of the particle forming unit 103 by a support member (not shown) attached to the flow path member 115. Here, an example in which the droplet ejecting unit 102 is disposed on the top surface portion of the particle forming unit 103 is described. However, the droplet ejecting unit 102 is disposed on the side wall or the bottom of the drying unit that becomes the particle forming unit 103. It can also be set as the structure to install.

The size of the vibration means 113 that generates mechanical vibration is generally increased as the oscillation frequency decreases, and according to the required frequency, the vibration means is directly drilled and provided with a reservoir. be able to. It is also possible to vibrate the entire storage part efficiently.
In this case, the vibration surface is defined as a surface on which the thin film having the plurality of nozzles is bonded.

Different examples of the droplet ejecting unit 102 having such a configuration will be described with reference to FIGS.
In the example shown in FIG. 7, a horn-type vibrator 180 including a piezoelectric body 181 as a vibration generating unit and a horn 182 as a vibration amplifying unit is used as a vibrating unit 180 (113). A reservoir (flow path) 114 is formed. The droplet ejecting unit 102 is preferably fixed to the wall surface of the particle forming unit 103 (drying unit) by a fixing unit (flange unit) 183 integrally formed with the horn 182 of the horn-type vibrator 180. Loss of vibration From the viewpoint of preventing this, it may be fixed using an elastic body (not shown).

  The example shown in FIG. 8 is a bolt-clamped Langevin type vibrator in which piezoelectric bodies 191A and 191B and horns 192A and 192B as vibration generating parts are mechanically firmly fixed with bolts as vibration means 190 (113). 190 is used to form a reservoir (channel 114) in the horn 192A. Depending on the frequency condition, the element may be large, and as shown in the drawing, the fluid introduction / discharge path and the reservoir can be processed in a part of the vibrator, and a metal thin film having a plurality of thin films can be attached.

  FIG. 1 shows an example in which only one droplet ejecting unit 102 is attached to the particle forming unit 103. However, a plurality of droplet ejecting units 102 are arranged on the particle forming unit 103 (drying tower). Paralleling is preferable from the viewpoint of improving productivity, and the number thereof is preferably in the range of 100 to 1000 from the viewpoint of controllability. In this case, the toner composition liquid 110 is supplied to each storage section 114 of the droplet ejection unit 102 through the pipe 108 to the raw material storage section (common liquid reservoir) 107. The toner composition liquid 110 may be configured to be supplied in a self-contained manner along with droplet formation, or may be configured to supply the liquid supplementarily using the pump 109 when the apparatus is operating. it can.

Another example of the droplet ejecting unit will be described with reference to FIG. FIG. 9 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit.
As in the above-described example, the droplet ejecting unit 102 includes a flow path member 115 that supplies a toner composition liquid 110 by surrounding a periphery of the vibration generating unit 113 using a horn-type vibrator. The reservoir 114 is formed in a portion of the horn 122 of the vibration generating means 113 that is disposed and faces the thin film 112. Further, an air flow path forming member 136 that forms an air flow path 137 through which the air flow 135 flows is provided around the flow path member 115 at a required interval. In order to simplify the illustration, only one nozzle 111 of the thin film 112 is shown, but a plurality of nozzles 111 are provided as described above.
As shown in FIG. 10, a plurality of, for example, 100 to 1,000 droplet ejection units 102 from the viewpoint of controllability are arranged side by side in the drying tower storage unit 103 </ b> A constituting the particle forming unit 103. Thereby, productivity can be further improved.

-Membrane vibration system using annular vibration generating means-
FIG. 11 shows the apparatus shown in FIG. 1 in which the droplet ejection unit is replaced with a ring type.
The ring type droplet ejecting unit 102 will be described with reference to FIGS. 12 is a cross-sectional explanatory view of the liquid droplet ejecting unit 102, FIG. 13 is a main surface bottom explanatory view of FIG. 12 viewed from the lower side, and FIG. 14 is a schematic cross-sectional explanatory view of droplet forming means.
The droplet ejecting unit 102 includes a droplet forming unit 111 that discharges the toner composition liquid 110 containing at least a resin, an organic low-molecular compound, and a colorant into droplets, and the droplet forming unit 111 has a toner composition liquid. And a channel member 115 having a reservoir (liquid channel) 114 for supplying 110.

  The droplet forming unit 116 includes a thin film 112 in which a plurality of nozzles (discharge ports) 111 are formed, and an annular vibration generating unit (electromechanical conversion unit) 117 that vibrates the thin film 112. Here, the thin film 112 is bonded and fixed to the flow path member 115 by the resin that does not dissolve in the solder or the toner composition liquid at the outermost peripheral portion (the region shown by hatching in FIG. 14). The vibration generating means 117 is arranged around the deformable region 116A (region not fixed to the flow path member 115) of the thin film 112. When the driving voltage (driving signal) having a required frequency is applied to the vibration generating means 117 from the driving circuit (driving signal generating source) 123 through the lead wires 121 and 122, for example, bending vibration is generated.

  The droplet forming means 116 has an annular vibration generating means 117 disposed around the deformable region 116A of the thin film 112 having the plurality of nozzles 111 facing the storage portion 114, for example, the comparison shown in FIG. Compared to the configuration in which the vibration generating means 117A holds the periphery of the thin film 112 as in the example configuration, the displacement amount of the thin film 112 is relatively large, and a relatively large area (diameter 1 mm in diameter) from which this large displacement amount can be obtained. The plurality of nozzles 111 can be arranged in the above area, and more liquid droplets can be stably formed and discharged at a time than the plurality of nozzles 111.

  FIG. 11 shows an example in which one droplet ejecting unit 102 is arranged. However, as shown in FIG. 16, a plurality of, for example, 100 to 1,000 (for example, from the viewpoint of controllability) In FIG. 16, only four droplet ejecting units 102 are arranged side by side on the top surface portion 103A of the particle forming unit 103, and each droplet ejecting unit 102 has a pipe 108A in the raw material storage unit 107 (common liquid reservoir). Then, the toner composition liquid 110 is supplied. As a result, more droplets can be discharged at a time, and the production efficiency can be improved.

-Droplet formation mechanism-
Next, the mechanism of droplet formation by the droplet ejecting unit 102 as the droplet forming means will be described.
As described above, the droplet ejecting unit 102 periodically vibrates the thin film 112 by propagating the vibration generated by the vibration means 113 that is the vibration generating means to the thin film 112 having the plurality of nozzles 111 facing the storage portion 114. Thus, a plurality of nozzles 111 are arranged in a relatively large area (diameter of 1 mm or more), and droplets can be stably formed and discharged from the plurality of nozzles 111.

When the peripheral portion 112A of the simple circular film 112 as shown in FIG. 17 is fixed, the basic vibration has a node around the periphery, and the cross section where the displacement ΔL is maximum (ΔLmax) at the center O of the thin film as shown in FIG. It becomes a shape and vibrates up and down periodically in the vibration direction.
Further, it is known that higher order modes as shown in FIGS. 19 and 20 exist. These modes have one or more concentric nodes in a circular membrane, and are substantially axisymmetric deformation shapes. In addition, as shown in FIG. 21, the central portion has a convex shape 112c, so that the traveling direction of the droplet can be controlled and the vibration amplitude can be adjusted.

By the vibration of the circular thin film, the liquid near the nozzle provided in the circular films each place, the sound pressure P _ac proportional to the vibration speed Vm of the film occurs. It is known that the sound pressure is generated as a reaction of the radiation impedance Zr of the medium (toner composition liquid), and the sound pressure is a product of the radiation impedance and the membrane vibration velocity Vm and is expressed by the following equation (1). Is done.
P _ac (r, t) = Z _r · V _m (r, t) (1)
The vibration speed Vm of the film is a function of time because it fluctuates periodically with time. For example, various periodic fluctuations such as a sine waveform and a rectangular waveform can be formed. Further, as described above, the vibration displacement in the vibration direction is different in each part of the film, and Vm is also a function of the position coordinates on the film. The vibration mode of the film used in the present invention is axially symmetric as described above. Therefore, it is substantially a function of the radial coordinate.

As described above, a sound pressure proportional to the vibration displacement speed of the distributed film is generated, and the toner composition liquid is discharged into the gas phase in response to the periodic change of the sound pressure.
Since the toner composition liquid periodically discharged to the gas phase forms a sphere due to a difference in surface tension between the liquid phase and the gas phase, droplet formation occurs periodically.

As the vibration frequency of the film that enables droplet formation, a region of 20 kHz to 2.0 MHz is used, and a range of 50 kHz to 500 kHz is more preferably used. If the vibration period is 20 kHz or more, the dispersion of fine particles such as pigment and wax in the toner composition liquid is promoted by the excitation of the liquid.
Furthermore, when the displacement amount of the sound pressure is 10 kPa or more, the above-described fine particle dispersion promoting action is more preferably generated.

  Here, the diameter of the formed droplet tends to increase as the vibration displacement in the vicinity of the nozzle of the film increases, and when the vibration displacement is small, a small droplet is formed or is not formed into a droplet. In order to reduce such a variation in droplet size at each nozzle site, it is necessary to define the nozzle arrangement at an optimum position of the membrane vibration displacement.

In the present invention, as will be described with reference to FIGS. 18 to 20, the ratio R (= ΔL _max) of the maximum value ΔL _max and the minimum value ΔL _mim of the vibration direction displacement ΔL of the film near the nozzle generated by the vibration generating means. By arranging the nozzle at a site where / ΔL _min ) is within 2.0, the variation in the droplet size can be maintained in a necessary region as toner fine particles capable of providing a high-quality image.
The conditions of the toner composition liquid were changed, and the satellite generation start region was the same in the region where the viscosity was 20 mPa · s or less and the surface tension was 20 to 75 mN / m. Therefore, the displacement of the sound pressure was 500 kPa or less. It is preferably 100 kPa or less.

-Liquid vibration method using mechanical longitudinal vibration means-
Next, a liquid droplet ejecting unit using a liquid vibration system will be described with reference to FIGS. The right figure in FIG. 27 is a schematic cross-sectional explanatory view of the droplet jetting unit, and the left figure in FIG. 27 is an assembly drawing for explaining in more detail. This droplet jetting unit includes at least a resin, an organic low molecular weight compound, and a colorant between a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, a vibration unit 13, and the thin film 12 and the vibration unit 13. And a flow path member that forms a liquid storage portion (liquid flow path) 4 for supplying a toner composition liquid containing the liquid. A configuration in which the position is fixed by the vibration separating member 6 so as not to transmit vibration between the vibration means 13 and the liquid storage portion wall is preferable, but the node portion 7 having a small vibration amplitude of the vibration means is provided. It may be in the form of being directly fixed to the wall. A toner composition liquid is supplied to the liquid storage unit 4 through a pipe 8 used for liquid supply and liquid circulation. The liquid reservoir 4 is divided into liquid reservoir areas 9.
As the vibration means 13 and the vibration amplification means 2, those described in the liquid vibration method using the mechanical longitudinal vibration means can be used.
The member constituting the partition wall of the liquid reservoir is made of a common material such as metal, ceramics, or plastic that does not dissolve in the spray liquid and does not cause modification of the spray liquid. The liquid storage unit 4 is divided into a plurality of liquid storage regions 9 by a plurality of partition walls.

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

-Thin film with multiple nozzles-
As described above, the thin film having the plurality of nozzles is a member that discharges the toner composition liquid to form droplets.
The material of the thin film 112 and the shape of the nozzle 111 are not particularly limited and may be appropriately selected according to the purpose. For example, the thin film 112 is formed of a metal plate having a thickness of 5 μm to 500 μm, and The opening diameter of the nozzle 111 is preferably 3 μm to 30 μm from the viewpoint of generating micro droplets having a very uniform particle size when the droplets of the toner composition liquid 110 are ejected from the nozzle 111. The opening diameter of the nozzle 111 means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.
Further, as a manufacturing method for obtaining a toner having a uniform particle size, a solution or dispersion liquid is quantitatively supplied to the storage unit, and the storage unit is provided with vibration while being vibrated by a vibrating means that contacts a part of the storage unit. Examples include means for discharging the raw material liquid into the granulation space from a plurality of through holes and forming the raw material fluid into droplets from a columnar shape through a constricted state.

Since the storage portion needs to be held at least in a state where the toner composition liquid is pressurized, it is preferably made of a member such as metal such as SUS or aluminum and has a pressure resistance of about 10 MPa. This is not a limitation.
For example, as shown in FIG. 22, a structure provided with a mechanism 139 that holds a plate having a through-hole 143 connected by a pipe 108 that supplies the toner composition liquid to the reservoir 114 is preferable. Further, a vibrating means 113 that vibrates the entire storage unit 114 is in contact with the storage unit 114. The vibration means is connected to the vibration generator 140 and the conductive wire 141 and is preferably controlled. In order to stably form the liquid column, it is preferable to adjust the pressure in the reservoir and to provide an open valve 142 for removing bubbles inside.
The vibration means 113 preferably excites the entire storage part having the through hole 143 by one vibration means.
The vibrating means 113 that vibrates the storage unit 114 is not particularly limited as long as it can provide reliable vibration at a constant frequency, and can be appropriately selected and used. For example, it is preferable that the through hole 143 is vibrated at a constant frequency by expansion and contraction of the piezoelectric body.
The piezoelectric body has a function of converting electrical energy into mechanical energy. Specifically, it is expanded and contracted by applying a voltage, and the through hole can be vibrated by the expansion and contraction.
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.

The fixed frequency is not particularly limited and may be appropriately selected according to the purpose. However, 100 kHz to 10 MHz is preferable, and 200 kHz to 2 MHz is preferable from the viewpoint of generating micro droplets having a very uniform particle size. More preferred.
The vibration means 113 is in contact with the storage portion, and the storage portion holds a plate having a through hole. The vibration means and the plate having the through hole uniformly vibrate the liquid column generated from the through hole. From the viewpoint of giving, it is most preferable that they are arranged in parallel, and even if deformation occurs in the process of vibration, the relationship is preferably maintained within an inclination of 10 °.
Even if only one through hole 143 is provided, particle production is possible. However, from the viewpoint of efficiently generating fine droplets having a very uniform particle diameter, a plurality of through holes 143 are provided and liquid discharged from each through hole is provided. The droplets are preferably dried with one solvent removal facility, in the example shown, the solvent removal facility 105.
From the viewpoint of further improving productivity, it is more preferable to provide a plurality of reservoirs having the vibration means. At this time, the productivity of the toner particles is determined by the product of the number of droplets (frequency) generated per unit time, the number of vibration means, and the number of through-holes acting by one vibration means. From the viewpoint of operability, it is sufficient that the number of through-holes acted by one vibration means as much as possible, that is, the number of through-holes possessed by one reservoir is as large as possible. Not. Therefore, the number of through-holes associated with one reservoir that is vibrated by the one vibrating means is preferably 10 to 10,000 from the viewpoint of productivity and controllability. In order to more reliably generate fine droplets having a very uniform particle size, 10 to 1,000 is preferable.

The support means 144 for fixing and supporting a part of the vibration generating means 113 is provided for fixing the storage section and the vibration generating means to the apparatus, and there is no particular limitation on the material, depending on the purpose. However, any rigid body such as a metal may be used. If necessary, a rubber material, a resin material, or the like as a vibration reducing material may be provided in part so as not to disturb the vibration of the reservoir due to excessive resonance.
As described above, the through hole 143 serving as a droplet forming unit is a member that discharges the toner composition fluid as a liquid column. There is no restriction | limiting in particular as a material and shape of the said through-hole 143, Although it can be set as the shape selected suitably, For example, a discharge hole is formed with a metal plate with a thickness of 5-50 micrometers, and the opening diameter is. 1 μm to 40 μm can generate fine liquid droplets having a very uniform particle size at a vibration frequency of 100 kHz or more without occluding the fine particle dispersion of 1 μm or less contained in the toner composition fluid. From the viewpoint of achieving both. This is because the frequency region in which droplets can be stably obtained by the droplet formation phenomenon decreases substantially as the diameter of the through-hole increases, so that the vibration frequency of 100 kHz or more is considered in consideration of productivity. Is assumed. The opening diameter means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.

The means for supplying the liquid to the common liquid chamber is preferably a metering pump such as a tube pump, a gear pump, a rotary pump, or a syringe pump. Moreover, the pump of the type pressurized and sent with compressed air etc. may be used. With these liquid supply means, the common liquid chamber is filled with the toner composition fluid, and the pressure can be increased to a pressure at which droplets can be formed. The liquid pressure can be measured with a pressure gauge attached to the pump or a dedicated pressure sensor.
By using the above droplet forming means, it is possible to obtain toner particles having a uniform particle size, and it is possible to obtain a highly efficient and low-cost toner manufacturing means that does not require a classification step.

-Constant rate drying means-
The solvent removal equipment 103 which is a constant rate drying means is not particularly limited as long as the solvent of the droplet can be removed, but an air flow is generated by flowing the dry gas A in the same direction as the flying direction of the droplet 131. The toner particles T are preferably formed by transporting the droplets 131 in the solvent removal facility 103 by the air flow and removing the solvent in the droplets 131 during the transport. Here, “dry gas” means a gas having a dew point temperature of −10 ° C. or lower under atmospheric pressure. The dry gas is not particularly limited as long as it is a gas capable of drying the droplets 131, and examples thereof include air and nitrogen gas.

  The temperature of the drying gas is preferably higher in terms of drying efficiency, and even if a drying gas having a boiling point higher than the solvent used is used due to the characteristics of spray drying, the constant rate drying region during drying is used. Thus, the droplet temperature does not rise above the boiling point of the solvent, and the resulting toner is not thermally damaged. However, since the main constituent material of the toner is a thermoplastic resin, if the toner is exposed to a dry gas at a temperature equal to or higher than the glass transition temperature of the resin used after drying, that is, in the reduced-rate drying region, the toners are thermally fused. Or the shape becomes spherical. Therefore, the temperature of the dry gas is preferably optimized in combination with the air volume and the discharge liquid volume so that the product temperature after drying is less than 50 ° C.

-Spray-dried particle collector-
The toner collecting unit 106 is a member provided at the bottom of the toner manufacturing apparatus from the viewpoint of efficiently collecting and transporting toner particles.
The structure of the toner particle collecting unit 106 is not particularly limited as long as the toner particles can be collected, and can be selected as appropriate. From the above viewpoint, as shown in the illustrated example, the taper in which the opening diameter gradually decreases. The toner particles T are formed from the outlet portion having a surface and the opening diameter is smaller than that of the inlet portion, the dry gas A is used to form the flow of the dry gas, and the toner particles are separated by the flow of the dry gas. It is preferably transferred to a toner particle storage container.
As the transfer method, as shown in the illustrated example, the toner particles T may be pumped to the toner particle storage container by a dry gas, or the toner particles T may be sucked from the toner particle storage container side.

There is no restriction | limiting in particular as a flow of the said dry gas, According to the objective, it can select suitably, A vortex | eddy current is preferable from a viewpoint which can generate a centrifugal force and can convey a toner particle reliably.
Further, from the viewpoint of more efficiently transporting the toner particles, the toner particle collecting portion and the toner particle collecting container are formed of a conductive material and are connected to the ground. More preferred. The toner manufacturing apparatus preferably has an exposure specification.

-Reduction rate drying and external additive mixing means-
In the toner manufacturing apparatus, the reduction rate drying unit is provided separately from the constant rate drying unit. If the spray particle temperature during the constant rate drying step is less than the glass transition temperature of the resin that uses the constant rate drying step, 10,000 ppm or more of the solvent remains in the toner particles after the constant rate drying step. It is very difficult to efficiently remove the remaining residual solvent.
Using such residual toner amount of toner particles as a toner causes problems such as odor and safety. Therefore, the residual solvent amount is preferably 200 ppm or less, more preferably 50 ppm or less.
As the rate-decreasing means, a conductive heat transfer type agitation dryer, fluidized bed dryer, moving bed dryer, or the like is used. Usually, the melting temperature point of the organic low molecular weight compound of the toner particles is equal to or higher than the glass transition temperature of the resin used, and therefore the drying temperature at the time of reduced rate drying may be lower than the glass transition temperature (Tg) of the toner particles. A temperature lower by 10 ° C. or more is more preferable. Moreover, in order to raise drying efficiency, it is preferable that it is a drying temperature more than normal temperature. More preferably, the glass transition temperature (Tg) of the toner particles is −20 ° C. or higher.

In the present invention, an external additive having a primary particle diameter of 50 nm or more is mixed in a state where the residual solvent amount of the toner particles after the constant rate drying step is 10,000 ppm or more, and is reduced to 200 ppm or less through the reduction rate drying step. preferable. By mixing an external additive with toner particles having a residual solvent amount of 10,000 ppm or more, it becomes a spacer between the toner particles to prevent the particles from aggregating and binding, and the surface of the toner particles is changed to a dry gas. By being exposed, it is possible to greatly improve the drying efficiency.
The primary particle diameter of the external additive at this time is 50 nm or more, and preferably 100 nm or more. The particles having a primary particle diameter of less than 50 nm are buried in the toner particles immediately after mixing, and the spacer effect is lost immediately.
In addition, an external additive having a primary particle diameter of 50 nm or more imparts a spacer effect and improves developability and transferability. There is a problem that adheres to the body, transfer body, etc. and causes filming. By mixing in a state where the residual solvent amount of the toner particles is 10,000 ppm or more, the toner particles can be mixed in a slightly plasticized state, so that a part of the toner particles are embedded and the separation rate is greatly reduced. Because of the relatively large particle size, the spacer effect can be maintained without being completely buried in the toner particles. In addition, mixing at 10,000 ppm or less makes it difficult to suppress the separation rate.

  The external additive mixing step (the first mixing step and the second mixing step) and the rate-decreasing drying step can be performed simultaneously by using, for example, the rate-decreasing drying of the conductive heat transfer stirring drying method. One example of such a device is a ribocorn manufactured by Okawara Seisakusho. By mixing the external additive and drying at a reduced rate in the same step, it becomes possible to obtain toner particles more efficiently.

It is effective to perform a stripping method in the reduction rate drying process. The stripping method is a method of accelerating drying by exposing to water vapor as a means for removing a residual solvent, reducing the affinity between the resin and the solvent and utilizing the azeotropic phenomenon of the solvent and water. In the granulation method using, it is a method generally used at the time of drying. The residual solvent amount is drastically reduced by removing the residual solvent by stripping and then drying with water.
Even when this stripping method is used, the solvent removal efficiency can be increased by mixing after adding an external additive having a primary particle diameter of 50 nm or more.
For the moisture drying in the stripping method, for example, conductive heat transfer type stirring drying, fluidized bed drying, moving bed drying and the like are used. Further efficient drying is possible by vacuum drying with conductive heat transfer type stirring and drying.

In order to impart fluidity and chargeability to the toner, an external additive having a primary particle diameter of 30 nm or less is used depending on the purpose. It has been confirmed that such external additives are less likely to function when they are embedded in toner particles. Further, since the primary particle diameter is as small as less than 30 nm, it tends to be buried in toner particles.
When the toner particles are mixed in a state where the residual solvent amount is 10,000 ppm or more, the external additive is completely buried and the effect is not generated. Further, when the residual solvent amount of the toner particles is mixed at 200 ppm or less, the toner particles can be mixed in a state of being attached to the toner particles which are hardly buried and produce the effect.

The toner of the present invention is a toner manufactured by a toner manufacturing method using the above-described toner manufacturing apparatus, and thus a toner having a monodispersed particle size distribution can be obtained.
Specifically, the particle size distribution (volume average particle size / number average particle size) of the toner is preferably 1.00 to 1.10, and more preferably 1.00 to 1.05.
Further, the volume average particle diameter (Dv) of the toner is preferably 1 μm to 20 μm, and more preferably 3 μm to 10 μm from the viewpoint of high image quality.

Here, the volume average particle diameter (Dv), the number average particle diameter (Dn), and the ratio (Dv / Dn) of the toner can be determined as follows, for example.
Measuring instrument: Coulter Multisizer II (Beckman Coulter, Inc.)
・ Aperture diameter: 100μm
・ Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter)
・ Electrolyte: Isoton II (Beckman Coulter)
-Dispersion liquid: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% by weight electrolytic solution-Dispersion condition: 10 mg of a measurement sample is added to 5 mL of the dispersion liquid, and an ultrasonic disperser is used. Disperse for 1 minute, then add 25 mL of electrolyte and further disperse for 1 minute with an ultrasonic disperser.
Measurement conditions: Add 100 mL of electrolyte and dispersion into a beaker, measure 30,000 particles at a concentration that allows measurement of the particle size of 30,000 particles in 20 seconds, and determine the volume average particle size from the particle size distribution. The number average particle diameter can be obtained and the ratio (Dv / Dn) can be calculated.

(Developer)
The toner of the present invention is used as a developer, and the developer may contain other appropriately selected components such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, and a blade for thinning the toner The toner is not fused to the layer thickness regulating member such as the like, and good and stable developability and image can be obtained even when the developing means is used (stirred) for a long time. Further, in the case of the two-component developer using the toner, even if the toner balance is maintained over a long period of time, the toner particle diameter in the developer is small, and even if it is stirred for a long time in the developing means, it is good and stable. Developability is obtained.

There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.
The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D ₅₀ )) of 10 to 200 μm, and more preferably 20 to 100 μm. When the average particle size (weight average particle size (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders and lower the magnetization per particle and cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And fluorinated terpolymers (triple fluorinated (multiple) copolymers) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.
The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin, Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.
The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The container containing toner is easy to store and transport, has excellent handling properties, and can be attached to a process cartridge, an image forming apparatus, etc., which will be described later, detachably and can be suitably used for replenishing toner.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (hereinafter, also referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) is particularly limited in terms of material, shape, structure, size, and the like. However, it can be suitably selected from known ones, and the shape thereof is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, polysilane, phthalopolymethine and the like. Organic photoreceptors, and the like. Among these, amorphous silicon or the like is preferable in terms of long life.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developer capable of bringing the toner or the developer into contact or non-contact with the electrostatic latent image is provided. Etc. are more preferable.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoconductor) with the transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Hereinafter, an image forming apparatus using the toner of the present invention will be described in detail with reference to embodiments shown in the drawings.
FIG. 23 shows an example of an internal configuration diagram of a color image forming apparatus which is an embodiment of an electrophotographic image forming apparatus according to the present invention. This specific example is a tandem indirect transfer type electrophotographic copying apparatus, but the image forming apparatus of the present invention is applicable to all electrophotographic systems using a two-component developer, and is limited to this specific example. Not a thing. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus main body 100 is placed, 300 is a scanner (reading optical system) mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) further mounted thereon. ). An endless belt-like intermediate transfer member 10 extending in the lateral direction is provided at the center position of the copying apparatus main body 100. In the illustrated example, the intermediate transfer member is wound around three support rollers 14, 15, and 16 so as to be able to rotate and convey clockwise in the drawing. In this illustrated example, an intermediate transfer body cleaning device 17 that removes residual toner remaining on the intermediate transfer body 10 after image transfer is provided to the left of the second support roller 15 among the three support rollers.

  Further, among the three support rollers, black, yellow, magenta, and cyan are arranged on the intermediate transfer member 10 that is stretched between the first support roller 14 and the second support roller 15 along the conveyance direction. These four image forming means 18 are arranged side by side to constitute a tandem image forming unit 20. An exposure device 21 is further provided immediately above the tandem image forming unit 20 as shown in FIG. On the other hand, a secondary transfer device 22 is provided on the opposite side of the intermediate transfer body 10 from the tandem image forming unit 20. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer body 10. The image on the intermediate transfer body 10 is transferred to a sheet. A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt. The secondary transfer device 22 described above also has a sheet transport function for transporting the image-transferred sheet to the fixing device 25.

In the illustrated example, a sheet reversing device 28 for reversing the sheet to record images on both sides of the sheet in parallel with the above-described tandem image forming unit 20 below the secondary transfer device 22 and the fixing device 25. Is provided. Now, when making a copy using this color electrophotographic apparatus, a document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it. When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. Immediately, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read. When a start switch (not shown) is pressed, one of the support rollers 14, 15 and 16 is rotationally driven by a drive motor (not shown), and the other two support rollers are driven to rotate, so that the intermediate transfer body 10 is moved. Rotate and convey. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10. On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped. Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet. The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image. Are discharged and stacked on the discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56. On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming unit 20 can prepare for another image formation.
In the tandem image forming unit 20 described above, each image forming unit 18 includes a charging device 60, a developing device 61, a primary transfer device 62, and the like around a drum-shaped photoconductor 40. The photoconductor cleaning device 63 has at least a blade cleaning member.

  Further, as shown in FIG. 24, the developing device 61 includes a toner supply side stirring screw 66, a developer carrier side stirring screw 67, a developer carrier (developing roller) as a developer stirring and conveying means in a developer container 65. 68) A doctor blade 77 is provided. A supply port (not shown) is provided on the outer wall of the container of the first developer stirring chamber 86, and toner is supplied from a toner supply device (not shown). The agitation screw 66 on the toner replenishment side agitates and conveys the toner replenished from the toner replenishing device and the developer (two-component developer having magnetic particles and toner) in the developer container 65. The stirring screw 67 in the second developer stirring chamber 87 (developer carrier side) stirs and conveys the developer in the developer container 65 (hereinafter, the second developer stirring chamber is referred to as the development side stirring chamber). Called).

  As shown in FIG. 25, the replenishing side stirring chamber and the developing side stirring chamber are partitioned by a partition plate 80, and there are openings for delivering the developer at both ends. The developer in the developing side agitating chamber is pumped up by the developing sleeve, and the amount thereof is regulated by a doctor blade and supplied to the rubbing portion with the photosensitive member as a latent image carrier. At this time, the developer is given the greatest rubbing force by the doctor blade.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, and is preferably provided detachably in the image forming apparatus of the present invention.

FIG. 26 shows a schematic configuration of a process cartridge using the toner of the present invention. In FIG. 26, 210 indicates the entire process cartridge, 211 is a photosensitive member, 212 is a charging unit, 213 is a developing unit, and 214 is a cleaning unit.
In the present invention, a plurality of components such as the photosensitive member 211, the charging unit 212, the developing unit 213, and the cleaning unit 214 are integrally combined as a process cartridge, and the process cartridge is copied. It is configured to be detachable from an image forming apparatus main body such as a printer or a printer.

As an example of an image forming apparatus having a process cartridge using the toner of the present invention, a photoconductor is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member is uniformly charged at a predetermined positive or negative potential on its peripheral surface by the charging unit, and then receives image exposure light from an image exposing unit such as slit exposure or laser beam scanning exposure. In this way, an electrostatic latent image is sequentially formed on the peripheral surface of the photosensitive member, and the formed electrostatic latent image is developed with toner by the developing unit, and the developed toner image is transferred from the sheet feeding unit to the photosensitive member and the transferring unit. In the meantime, the image is sequentially transferred to a transfer material fed in synchronization with the rotation of the photosensitive member. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy).
The surface of the photoreceptor after the image transfer is cleaned by at least removing the toner remaining after transfer by a cleaning unit having a blade cleaning member, and after being further discharged, it is repeatedly used for image formation.

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

(Production Example 1)
-Preparation of colorant dispersion-
First, a phthalocyanine dispersion as a colorant was prepared.
20 parts by mass of phthalocyanine (CI Pigment Blue 15: 3) and 3 parts by mass of a pigment dispersant (Ajisper PB821, Ajinomoto Fine Techno Co., Ltd.) were added to 57 parts by mass of ethyl acetate, a polyester resin (manufactured by Kao Corporation, RN-289) 20 parts by mass of the resin solution was mixed, and primary dispersion was performed using a mixer having stirring blades.
The obtained primary dispersion was finely dispersed by applying a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Further, a colorant dispersion liquid was prepared by passing through a filter (manufactured by PTFE) having a pore size of 0.5 μm and dispersing to a submicron region.

(Production Example 2)
-Preparation of wax dispersion-
Next, a dispersion having the following composition to which a binder resin and wax were added was prepared.
300 parts by mass of polyester resin (RN-289, manufactured by Kao Corporation) as binder resin, 100 parts by mass of maleic acid-modified paraffin wax (manufactured by Chukyo Yushi Co., Ltd., acid value 20 mgKOH / g), wax dispersant (Sanyo Chemical Industries) Co., Ltd.) 60 parts by mass and 900 parts by mass of ethyl acetate were stirred and dispersed for 10 minutes using a mixer having a stirring blade, and then dispersed using a dyno mill. The mixture was filtered through a filter having a pore size of 0.5 μm (manufactured by PTFE) to prepare a wax dispersion.

(Production Example 3)
-Preparation of resin solution A-
Dissolve 100 parts by mass of a polyester resin as binder resin (RN-289, manufactured by Kao Corporation, glass transition temperature (Tg) = 63.6 ° C., melting point (Tm) = 106.1 ° C.) in 400 parts by mass of ethyl acetate. Then, a resin solution A was prepared.

(Production Example 4)
-Preparation of resin solution B-
100 parts by mass of a styrene-acrylic copolymer (manufactured by Nippon Carbide Corporation, NCI # 52076, glass transition temperature (Tg) = 58.6 ° C., melting point (Tm) = 153.7 ° C.) as a binder resin, A resin solution B was prepared by dissolving in 400 parts by mass of ethyl acetate.

(Production Example 5)
-Preparation of toner composition liquid A-
25 parts by weight of the colorant dispersion, 68 parts by weight of the wax dispersion, 382 parts by weight of the resin solution A, and 275 parts by weight of ethyl acetate were used using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, toner composition liquid A was prepared by mixing at 7.5 m / s for 1 minute.

(Production Example 6)
-Preparation of toner composition liquid B-
25 parts by weight of the colorant dispersion, 68 parts by weight of the wax dispersion, 382 parts by weight of the solution B, and 275 parts by weight of ethyl acetate were added using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The toner composition liquid B was prepared by mixing at 7.5 m / s for 1 minute.

(Production Example 7)
The obtained toner composition liquids A and B are spray-dried at a constant-rate drying air charging temperature of 40 ° C. using the toner production apparatus shown in FIG. 1, and are almost monodispersed with a volume average particle size of 6.0 μm. Spray-dried particles A0 to D0 were produced.

<Preparation of spray-dried particles A0 and B0>
Specifically, the toner composition liquid is periodically discharged from the nozzles of the thin film by vibrating a thin film having a plurality of nozzles provided in a reservoir for storing the toner composition liquid by means of vibration generating means to form droplets. The toner composition liquids A and B are spray-dried under the following conditions using a spraying means using a liquid jet unit (see FIGS. 1 to 10) of a mechanical longitudinal vibration means that periodically forms droplets, and spray-dried particles A0. And B0 were prepared.
-Spray-drying conditions for spray-dried particles A0 and B0-
・ Nozzle diameter: 10μm
・ Dry air flow rate: Nitrogen gas for dispersion 2.0 L / min, Dry nitrogen gas in the apparatus 30.0 L / min ・ Drying inlet temperature: 40 ° C.
・ Drying outlet temperature: 35 ℃
・ Dew point temperature: -20 ℃
・ Drive frequency: 40 kHz

<Preparation of spray-dried particles C0>
The toner composition liquid A was spray-dried under the following conditions using spraying means using a ring-type droplet ejecting unit (see FIGS. 11 to 17) to produce spray-dried particles C0.
-Spray-drying conditions of spray-dried particles C0:
・ Nozzle diameter: 10μm
・ Dry air flow rate: Nitrogen gas for dispersion 2.0 L / min, Dry nitrogen gas in the apparatus 30.0 L / min ・ Drying inlet temperature: 40 ° C.
・ Drying outlet temperature: 35 ℃
・ Dew point temperature: -20 ℃
・ Membrane frequency: 103 kHz

<Preparation of spray-dried particles D0>
The toner composition liquid A is supplied from a plurality of through holes provided in the storage portion while the toner composition liquid A is excited through the storage portion by vibration means that quantitatively supplies the storage portion and contacts a part of the storage portion. Spraying means using a vibrating chamber nozzle head (see FIG. 22) that discharges toner composition liquid A from a columnar shape into droplets through a constricted state and changes the droplets into solid particles in the granulation space. The toner composition liquid A was spray-dried under the following conditions to produce spray-dried particles D0.
-Spraying / drying conditions of spray-dried particles D0-
・ Nozzle diameter: 8μm
・ Dry air flow rate: Nitrogen gas for dispersion 2.0 L / min, Dry nitrogen gas in the apparatus 30.0 L / min ・ Drying inlet temperature: 40 ° C.
・ Drying outlet temperature: 35 ℃
・ Dew point temperature: -20 ℃
・ Membrane frequency: 100 kHz

<Preparation of spray-dried particles E0>
The toner composition liquid A was spray-dried under the following conditions using a spraying means in a droplet jet unit using the liquid vibration system shown in FIG. 27 to produce spray-dried particles E0.
The discharge holes (nozzles) were provided in a staggered pattern so that the distance between the discharge holes was 100 μm. The liquid storage part used what was comprised by the liquid storage area | region divided | segmented equally. The excitation frequency used in this example and the configuration of the liquid reservoir are shown below. All voltage waveforms applied to the vibration means were sine waves.

-Spraying / drying conditions for spray-dried particles E0-
・ Nozzle diameter: 8μm
・ Excitation frequency: 32.7 kHz
-Number of liquid storage part divisions (number of liquid storage areas): 6
・ Liquid reservoir longitudinal dimension A: 8mm
-Liquid storage part short side dimension B: 8mm
-Number of nozzles per liquid storage area: 480
・ Dry air flow rate: Nitrogen gas for dispersion 2.0 L / min, Dry nitrogen gas in the apparatus 30.0 L / min ・ Drying inlet temperature: 40 ° C.
・ Drying outlet temperature: 35 ℃
・ Dew point temperature: -20 ℃

  With respect to the obtained spray-dried particles A0 to E0, the amount of residual solvent and the glass transition temperature (Tg) were measured as follows. The results are shown in Table 1.

<Residual solvent amount>
The residual solvent amount of the toner was measured by the following measuring method.
The toner to be measured was analyzed by gas chromatography (GC-14A, manufactured by Shimadzu Corporation), and the residual solvent concentration was measured by quantifying the solvent in the toner. The measurement conditions at the time of analysis are as follows.
・ Equipment: Shimadzu GC-14A
Column: CBP20-M50-0.25
・ Detector: FID
Carrier gas: He 2.5 kg / cm ²
・ Hydrogen flow rate: 0.6 kg / cm ²
・ Air flow rate: 0.5 kg / cm ²
-Chart speed: 5 mm / min
・ Sensitivity: Range101 × Atten20
-Column temperature: 40 ° C
・ Injection Temp: 150 ℃

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of the toner was measured by the following measuring method. As an apparatus for measuring Tg, TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, 10 mg of a sample was placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. Next, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample is left standing at 150 ° C. for 10 minutes, the sample is cooled to room temperature and left for 10 minutes, and the temperature rising rate is again 10 ° C. up to 150 ° C. in a nitrogen atmosphere. DSC measurement was performed by heating at / min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system. In addition, the base line was drawn automatically and the Tg was output with a TG-DSC system TAS-100 manufactured by Rigaku Corporation.

From the results shown in Table 1, the spray-dried particles A0, C0, D0, and E0 were the same toner composition liquid A, and the results were almost the same in both the residual solvent amount and the glass transition temperature. Considered to be particles.

(Experimental example 1)
-Reduction rate drying process and external additive mixing process-
Out of the spray-dried particles A0 to E0, the spray-dried particles A0 and B0 were mixed with external additives and dried at a reduced rate by the following method.
To 100 parts by mass of spray-dried particles A0 and B0, 1.2 parts by mass of hydrophobized silica (X-24 manufactured by Shin-Etsu Chemical Co., Ltd.) each having a primary particle size of 100 nm are charged and mixed with a Henschel mixer. Spray dried particles A1 and B1 were made.
100 parts by mass of spray-dried particles A0 and B0 are charged with 1.0 part by mass of titanium oxide (manufactured by Teika Co., Ltd., MT-500B) each having a primary particle diameter of 50 nm, mixed with a Henschel mixer, and spray-dried particles A2 and B2 were produced.
To 100 parts by mass of spray-dried particles A0 and B0, 1.5 parts by mass of hydrophobized silica (H-1303, manufactured by Clariant Japan Co., Ltd.) each having a primary particle diameter of 25 nm is added, mixed in a Henschel mixer, and spray-dried. Particles A3 and B3 were produced.
The primary particle size of the inorganic fine particles was obtained directly from a photograph obtained with a scanning electron microscope or a transmission electron microscope. In this case, at least 100 inorganic fine particles were observed, and the average value of the major axis was determined.

Next, for the externally treated spray-dried particles A0, A1, A2, A3, B0, B1, B2, and B3, <Condition 1> is a drying temperature of 50 ° C., <Condition 2> is a drying temperature of 45 ° C., <Conditions 3> was dried at a drying temperature of 35 ° C., and <condition 4> was dried at a drying temperature of 25 ° C. using a fluidized dryer. Based on the following criteria, the drying time until the residual solvent amount of the spray-dried particles became 200 ppm or less and the state of the powder were evaluated. The results are shown in Table 2.
〔Evaluation criteria〕
-The good condition was that the drying time was within 48 hours.
・ The state of the powder is ○ which keeps the state of the powder, △ which is soft agglomerated but is forcibly solved with a Henschel mixer etc. What was not kept was made into x, and only the state of (circle) was made into the quality item.

  Next, when all of the samples that have finished the reduction drying were observed with a scanning electron microscope (SEM), among the samples in which the residual solvent amount satisfied 200 ppm or less, the sample was in the state of powder “◯”, that is, (Spray Dry Particle A1-Decrease Drying Condition 2), (Spray Dry Particle A2-Decrease Dry Condition 3), (Spray Dry Particle B) 1-Decrease Dry Condition 2), (Spray Dry Particle B2-Decrease Dry) In all of the conditions 3), it was possible to observe the external additive on the surface of the toner particles after the reduction drying. This is considered to be because the external additive on the toner particle surface exhibited a spacer effect to prevent aggregation.

-Production of toner particles A0-
Next, 1.0 part by mass of titanium oxide having a primary particle diameter of 50 nm (manufactured by Teika Co., Ltd., MT-500B) is added to 100 parts by mass of the particles (spray-dried particles A0—decreasing drying condition 3), and a Henschel mixer is added. And drying at a reduced rate of 10 hours under reduced rate drying condition 2 to prepare toner particles A0.
The toner particles A0 thus obtained had a residual solvent amount of 150 ppm, and external additives were observed on the toner particle surfaces.

-Production of toner particles B0-
1.2 parts by mass of hydrophobized silica (X-24 manufactured by Shin-Etsu Chemical Co., Ltd.) having a primary particle diameter of 100 nm is added to 100 parts by mass of (spray-dried particles B0—decreasing drying condition 3). The mixture was mixed with a mixer, and dried at a reduced rate of 10 hours under reduced rate drying condition 2 to prepare toner particles B0.
The residual solvent amount of the obtained toner particles B0 was 80 ppm, and external additives were observed on the toner particle surfaces.

-Toner particles A1-
A sample of (spray-dried particles A2—decreasing drying condition 2) was designated as toner particles A1.
-Toner particle B1-
A sample of (spray-dried particle B1—decreasing drying condition 2) was designated as toner particle B1.

<Measurement of external additive removal rate>
The obtained toner particles A0, A1, B0, and B1 were applied to an elbow jet classifier and the external additive removal rate was measured. As a result, the toner particles A0 were 12%, the toner particles A1 were 3%, the toner particles B0 were 15%, and the toner. Particle B1 was 6%.

-Production of toner particles A0 ', A1', A2 ', B0', and B1'-
H1303 (hydrophobized silica, manufactured by Clariant Japan, primary particle diameter of 25 nm) with respect to 100 parts by mass of each toner particle in order to impart appropriate fluidity and chargeability to toner particles A0, A1, B0, and B1. 5 parts by mass and 0.8 part by mass of MA150AI (hydrophobic titania, manufactured by Teika Co., Ltd., primary particle diameter: 14 nm) were mixed with a Henschel mixer to produce toner particles A0 ′, A1 ′, B0 ′, and B1 ′. .
Moreover, H1003 (hydrophobized silica) 1.5 parts by mass and MA150AI (hydrophobized titania) 0.8 parts by mass to a Henschel mixer with respect to 100 parts by mass of (spray-dried particles A2—decreasing drying condition 4). And mixed to prepare toner particles A2 ′.

<Production of developer>
Toner particles A0 ′, A1 ′, A2 ′, B0 ′, and B1 ′ were mixed with the following carriers to prepare two-component developers A0 ′, A1 ′, A2 ′, B0 ′, and B1 ′.
-Career-
A carrier was prepared by coating spherical ferrite particles having a volume average particle diameter of 35 μm as a core material with a mixture of a silicone resin and a melamine resin as a coating material.

(Experimental example 2)
-Actual machine evaluation-
The following evaluation was performed using a tandem type color image forming apparatus (“Imagio Neo C350”, manufactured by Ricoh Co., Ltd.).
Developers A0 ′, A1 ′, A2 ′, B0 ′, and B1 ′ are mounted on the black development unit in the image forming apparatus, respectively, and 6000 paper manufactured by Ricoh Co., Ltd. is used with an image occupancy rate of 5%. After running 10,000 sheets, the photoreceptor filming and odor were evaluated as follows. The results are shown in Table 3. A product that does not generate filming or odor is a good product (◯).

<Photoconductor filming>
When filming occurs on the photosensitive member, streaks occur in the output image during running. Therefore, the presence or absence of the streaks was evaluated in the output image.

<Odor>
The presence or absence of a solvent odor around the running machine (with a radius of about 1.5 m) was confirmed and evaluated.

From the results in Table 3, both odor and filming occurred in developer A2 ′ using toner particles A2 ′ having a residual solvent amount of 200 ppm or more. In addition, the toner particles A0 ′ and B0 ′ using the toner particles A0 ′ and B0 ′ having a removal rate of 10% or more of the external additive caused filming that seems to be caused by the removal of the external additive.

(Experimental example 3)
A stripping method is effective for further improving the rate of drying efficiency.
The spray-dried particles A1, A2, B1, and B2 were stripped and then left to dry for 3 hours at 45 ° C. and 95% RH. Thereafter, reduction drying was performed using a vacuum dryer at a drying temperature of 45 ° C. (Condition 5). Table 4 shows the time course of the residual solvent amount at this time.

From the results shown in Table 4, stripping not only shortened the drying time but also significantly reduced the amount of residual solvent. The external additives of the toner particles that have been reduced and dried under condition 5 can be observed on the surface, and the external additive removal rates are 3%, 6%, 2%, and A1, A2, B1, and B2, respectively. It was 5%.

(Experimental example 4)
Ogawara Seisakusho ribocorn with a humidifying function and a vacuum drying function, a hydrophobized silica with a primary particle size of 100 nm for each 100 parts by mass of spray-dried particles A0 and B0 (Shin-Etsu Chemical Co., Ltd., X- 24) 1.2 parts by mass were charged, stripped with saturated steam at 45 ° C. for 1 hour, mixed with external additives, and further continuously dried in vacuo at 45 ° C. for 4 hours (condition 6).
The residual solvent amount of the toner particles A after drying the spray-dried particles A0 was 38 ppm, and the water content was less than 0.1%. Further, the residual solvent amount of the toner particles B after drying the spray-dried particles B0 was not detected, and the water content was less than 0.1%.
The external additives of toner particles A and B were observable on the surface, and the removal rate of the external additives was less than 1%.
Therefore, the process can be further shortened by simultaneously performing the reduction rate drying process and the external additive mixing process.

  The toner manufactured by the toner manufacturing method of the present invention includes, for example, a laser printer, a direct digital plate making machine, a full color copier using a direct or indirect electrophotographic multicolor image developing system, a full color laser printer, and a full color plain paper fax machine. Can be used widely.

FIG. 1 is a schematic configuration diagram illustrating an example of a toner manufacturing apparatus to which a toner manufacturing method according to the present invention is applied. FIG. 2 is an enlarged explanatory view for explaining a droplet ejecting unit of the toner manufacturing apparatus. FIG. 3 is an explanatory bottom view of FIG. 2 as viewed from below. FIG. 4 is a schematic explanatory view showing an example of a step-type horn type vibrator constituting the vibration generating means of the liquid droplet ejecting unit. FIG. 5 is a schematic explanatory view showing an example of an exponential horn-type vibrator constituting the vibration generating means of the liquid droplet ejecting unit. FIG. 6 is a schematic explanatory view showing an example of a conical horn type vibrator constituting the vibration generating means of the liquid droplet ejecting unit. FIG. 7 is an enlarged explanatory view for explaining another example of the droplet ejecting unit of the toner manufacturing apparatus. FIG. 8 is an enlarged explanatory diagram for explaining still another example of the droplet ejecting unit of the toner manufacturing apparatus. FIG. 9 is an enlarged explanatory view for explaining still another example of the droplet ejecting unit of the toner manufacturing apparatus. FIG. 10 is an explanatory diagram for explaining an example in which a plurality of liquid droplet ejecting units in FIG. 9 are arranged. FIG. 11 is another schematic configuration diagram of a toner manufacturing apparatus to which the toner manufacturing method according to the present invention is applied. FIG. 12 is an enlarged explanatory view for explaining a droplet jetting unit of the toner manufacturing apparatus of FIG. FIG. 13 is an explanatory bottom view of FIG. 12 as viewed from below. FIG. 14 is an enlarged cross-sectional explanatory view of droplet forming means of the droplet jetting unit of FIG. FIG. 15 is an enlarged cross-sectional explanatory view of a droplet forming means according to a comparative configuration. FIG. 16 is an explanatory view of a main part for explaining a specific application of the toner manufacturing apparatus of the present invention. FIG. 17A is a schematic explanatory view of a thin film used for explaining the operation principle of droplet formation by the droplet ejection unit. FIG. 17B is a schematic explanatory diagram of a thin film used for explaining the operation principle of droplet formation by the droplet ejection unit. FIG. 18 is an explanatory diagram for explaining the fundamental vibration mode. FIG. 19 is an explanatory diagram for explaining the secondary vibration mode. FIG. 20 is an explanatory diagram for explaining the tertiary vibration mode. FIG. 21 is an explanatory diagram when a convex portion is formed at the center of the thin film. FIG. 22 is a schematic configuration diagram illustrating another example of a toner manufacturing apparatus to which the toner manufacturing method according to the present invention is applied. FIG. 23 is a schematic configuration diagram showing an example of an electrophotographic image forming apparatus according to the present invention. FIG. 24 is a schematic configuration diagram illustrating an example of an image forming unit in the electrophotographic image forming apparatus according to the present invention. FIG. 25 is a schematic configuration diagram illustrating an example of a developing unit in the electrophotographic image forming apparatus according to the present invention. FIG. 26 is a schematic configuration diagram showing an example of the process cartridge of the present invention. The right figure of FIG. 27 is a schematic sectional view of a droplet jetting unit using a liquid vibration system, and the left figure of FIG. 27 is an assembly drawing of the right figure. FIG. 28 is a diagram for explaining a mechanism of droplet formation by the droplet ejecting unit of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device DESCRIPTION OF SYMBOLS 30 Exposure apparatus 32 Contact glass 33 1st traveling body 34 2nd traveling body 35 Imaging lens 36 Reading sensor 40 Photosensitive body (photosensitive drum)
42 paper feed roller 43 paper bank 44 paper feed cassette 45 separation roller 46 paper feed path 47 transport roller 48 paper feed path 50 intermediate transfer member 51 roller 52 separation roller 53 constant current source 55 switching claw 56 discharge roller 57 discharge tray 100 image formation Apparatus 101 toner production apparatus 102 droplet ejection unit 103 particle forming unit (solvent removing unit)
DESCRIPTION OF SYMBOLS 104 Toner collection part 105 Tube 106 Toner collection part 107 Raw material accommodating part 108 Piping 109 Pump 110 Toner composition liquid 111 Nozzle 112 Thin film 113 Vibrating means 113a Vibrating surface 114 Storage part 115 Channel member 116 Droplet forming means 117 Vibration generating means (Electromechanical conversion means)
118 Liquid supply tube 119 Bubble discharge tube 120 Support member 121 Vibration generation means 121A Piezoelectric body 122 Vibration amplification means 122A Horn 123 Drive circuit (drive signal generation source)
124 communication means 131 droplet 135 air flow 136 air flow path forming member 137 air flow path 150 copying apparatus main body 180 horn type vibrator 181 piezoelectric body 182 horn 183 fixing portion 190 Langevin type vibrator 191 piezoelectric body 192 horn 300 scanner 400 automatic document feeder (ADF)
T toner particles

Claims (18)

A droplet forming step in which a toner composition liquid containing at least a resin, an organic low-molecular compound, and a colorant is discharged from a nozzle to form droplets;
A constant rate drying step of drying the droplets at a constant rate to form toner particles;
A first mixing step of mixing the toner particles and the external additive;
A reduction rate drying step of reducing the toner particles after the first mixing step or simultaneously with the first mixing step;
The first mixing step is a step of mixing an external additive having a primary particle diameter of 50 nm or more in a state where the residual solvent amount of the toner particles after the constant rate drying step is 10,000 ppm or more. Toner manufacturing method.   The toner production method according to claim 1, further comprising a second mixing step of mixing an external additive having a primary particle diameter of 30 nm or less with a residual solvent amount of the toner particles being 200 ppm or less after the reduction rate drying step.   3. The toner according to claim 1, wherein a drying temperature in the decreasing rate drying step is not less than a glass transition temperature (Tg) of the toner particles−20 ° C. and not more than a glass transition temperature (Tg) of the toner particles. Manufacturing method.   The toner manufacturing method according to claim 1, wherein a stripping method is performed in the reduction rate drying step.   In the droplet forming step, a thin film having a plurality of nozzles provided in a storage portion for storing the toner composition liquid is vibrated by a mechanical vibration generating means, and the toner composition liquid is formed into droplets from the plurality of nozzles periodically. The method for producing a toner according to claim 1, wherein the toner is periodically dropped into a droplet.   6. The toner manufacturing method according to claim 5, wherein the mechanical vibration generating means is a vibration generating means provided in an annular shape around a region having a plurality of nozzles of a thin film.   6. The toner manufacturing method according to claim 5, wherein the mechanical vibration generating means is a vibration generating means having a vibration surface parallel to the thin film, and the vibration surface longitudinally vibrates in the vertical direction.   The toner manufacturing method according to claim 7, wherein the vibration generating means for longitudinal vibration is a horn-type vibrator.   In the droplet forming process, the toner composition liquid is discharged from a through hole provided in a storage portion for storing the toner composition liquid, and the discharged toner composition liquid is converted into a droplet from a columnar shape through a constricted state. The method for producing a toner according to claim 1, comprising a step.   The method for producing toner according to claim 9, wherein the through hole is a vibration chamber nozzle head.   The droplet forming process uses a thin film in which a plurality of nozzles provided in a reservoir for storing the toner composition liquid is formed, and one vibration generating means having a vibration surface parallel to the thin film. The method for producing toner according to claim 1, wherein droplets are formed using a resonance phenomenon of a liquid existing in the storage unit.   The toner manufacturing method according to claim 11, wherein a resonance frequency of the liquid existing in the storage portion is lower than a resonance frequency of a structure of a member constituting the storage portion including a thin film in which a plurality of nozzles are formed.   A toner manufactured by the method for manufacturing a toner according to claim 1.   A developer comprising the toner according to claim 13 and a carrier.   An electrostatic latent image carrier and at least developing means for developing a latent image on the electrostatic latent image carrier with the toner according to claim 13 to form a visible image, and an image forming apparatus main body A process cartridge that is detachably attachable.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and a developing step of developing the electrostatic latent image using the toner according to claim 13 to form a visible image. And an image forming method comprising: a transfer step of transferring the visible image onto a recording medium; and a fixing step of fixing the transfer image transferred onto the recording medium.   An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image using the toner according to claim 13. An image forming apparatus, comprising: a developing unit that forms a visible image in the image; a transfer unit that transfers the visible image to a recording medium; and a fixing unit that fixes the transferred image transferred to the recording medium. apparatus.   A toner container, wherein the toner according to claim 13 is contained in a container.