JP2016006474A - Toner, and manufacturing method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having a narrow particle size distribution and a small particle size and having excellent low-temperature fixability, blocking resistance and image stability.
A toner containing at least an amorphous resin and a crystalline substance as a binder resin,
In the split cross-sectional image of the toner in the transmission electron microscope (TEM), the crystalline substance is
The number average particle diameter of the crystalline substance existing in the depth region Aa from the toner surface to 1/6 (1 / 6d) of the toner diameter d is CDa,
The relationship between CDa and CDc when the number average particle diameter of the crystalline material existing in the circular central region Ac having a radius of 1 / 6d and centering on the toner is CDc satisfies the following relationship. Toner.
CDa <CDc
[Selection] Figure 1

Description

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

In recent years, in the market, there is a demand for a toner having a small particle size for improving the quality of an output image and a low-temperature fixing property of the toner for energy saving. Further, from the viewpoint of reducing the environmental load, a toner manufacturing process that saves resources and energy is required.
Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, etc., so-called pulverized toners, in which a toner binder such as a styrene resin or a polyester resin is melt-kneaded together with a colorant and pulverized, are widely used. It is used.
However, in recent years, there has been a tendency for the toner to have a small particle size in order to obtain a high-quality image. In the above pulverization method, if the particle size is 6 μm or less, the pulverization efficiency is reduced and the loss due to classification is increased. Lower costs.

A so-called polymerization type toner such as a suspension polymerization method and an emulsion polymerization aggregation method and a toner production method called volume dissolution called a polymer dissolution suspension method have been proposed (for example, see Patent Document 1). These methods are excellent in that a toner having a small particle diameter can be produced.
However, since it is assumed that the dispersant is used in an aqueous medium, the dispersant that impairs the charging characteristics of the toner remains on the surface of the toner, causing problems such as loss of environmental stability and removal of this. It is known that a very large amount of washing water is required to achieve this, and it is not always satisfactory as a manufacturing method.

As an alternative toner manufacturing method, there has been proposed a toner manufacturing method that uses piezoelectric pulses to form micro droplets from micro nozzles, and further solidifies them by drying and solidifying them (for example, Patent Document 2). reference). In addition, a toner manufacturing method has been proposed in which fine droplets are formed by utilizing thermal expansion in a nozzle, and this is dried and solidified into a toner (for example, see Patent Document 3). Furthermore, a toner manufacturing method has been proposed in which minute droplets are formed using an acoustic lens and dried to solidify into toner (for example, see Patent Document 4).
However, these methods make it easy to reduce the particle size of the toner, but there is a problem that the number of droplets that can be ejected from one nozzle per unit time is small and productivity is low. The spread of the particle size distribution due to coalescence is inevitable, and a toner having a uniform particle diameter cannot be obtained.

On the other hand, in order to save energy, toner that melts at a low temperature is used to reduce energy generated in the fixing process. Therefore, not only an amorphous resin as a binder resin but also a crystalline resin that can be melted at a low temperature is used for the toner. It has been proposed to use (see, for example, Patent Documents 5 to 9).
Toner added with crystalline polyester resin has excellent low-temperature fixability due to its rapid viscosity reduction, but has poor blocking resistance of the toner image after fixing. This causes a problem that the image is likely to be fused and peeled off.
In addition, when such toner is used, an abnormal image is generated when the printed matter is output because the toner component adheres to the carrier over time due to stress in the developing device and the developer deteriorates. (For example, refer to Patent Document 10).

In other words, the conventional technology is insufficient to effectively achieve both offset resistance and toner durability in the apparatus with a small amount of crystalline material, and further improvement is desired at present. is there.
Therefore, there is a demand for providing a toner having a narrow particle size distribution, a small particle size, and excellent in low-temperature fixability, blocking resistance, and image stability.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner having a narrow particle size distribution and a small particle size, and having excellent low-temperature fixability, blocking resistance, and image stability.

Means for solving the problems are as follows. That is, the toner of the present invention is a toner containing at least an amorphous resin and a crystalline substance as a binder resin,
In the split cross-sectional image of the toner in the transmission electron microscope (TEM), the crystalline substance is
The number average particle diameter of the crystalline substance existing in the depth region Aa from the toner surface to 1/6 (1 / 6d) of the toner diameter d is CDa,
The relationship between CDa and CDc when the number average particle diameter of the crystalline substance existing in a circular central region Ac having a radius of 1 / 6d and centering on the toner is CDc satisfies the following relationship. It is characterized by.
CDa <CDc

  According to the present invention, the above-mentioned problems can be solved and the object can be achieved, and the toner has a narrow particle size distribution and a small particle size, and is excellent in low-temperature fixability, blocking resistance, and image stability. Toner can be provided.

FIG. 1 is a cross-sectional view showing an example of the toner of the present invention. FIG. 2A is a diagram in which the contrast of FIG. 1 is adjusted. FIG. 2B is a diagram in which the contrast of FIG. 1 is adjusted. FIG. 3 is a schematic cross-sectional view showing an example of a liquid column resonance droplet forming unit. FIG. 4 is a schematic view showing an example of a liquid column resonance droplet unit, and is a bottom view of FIG. 3 viewed from the ejection surface. FIG. 5A is a schematic diagram illustrating an example of the shape of the discharge hole as viewed from the cross section of the liquid column resonance liquid chamber. FIG. 5B is a schematic diagram illustrating an example of the shape of the ejection hole as viewed from the cross section of the liquid column resonance liquid chamber. FIG. 5C is a schematic diagram illustrating an example of the shape of the ejection hole as viewed from the cross section of the liquid column resonance liquid chamber. FIG. 5D is a schematic diagram illustrating an example of the shape of the ejection hole as viewed from the cross section of the liquid column resonance liquid chamber. FIG. 6A is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is one side fixed end and N = 1. FIG. 6B is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is fixed on both sides and N = 2. FIG. 6C is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is open at both sides and N = 2. FIG. 6D is a schematic explanatory diagram showing a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is a fixed end on one side and N = 3. FIG. 7A is a schematic explanatory diagram showing a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is fixed at both sides and N = 4. FIG. 7B is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is open at both sides and N = 4. FIG. 7C is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is one side fixed end and N = 5. FIG. 8A is a schematic view showing a state of a liquid column resonance phenomenon that occurs in a liquid column resonance liquid chamber of the liquid column resonance droplet forming method. FIG. 8B is a schematic diagram illustrating a liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber of the liquid column resonance droplet forming method. FIG. 8C is a schematic diagram showing a state of a liquid column resonance phenomenon that occurs in a liquid column resonance liquid chamber of the liquid column resonance droplet forming method. FIG. 8D is a schematic diagram illustrating a liquid column resonance phenomenon that occurs in a liquid column resonance liquid chamber of the liquid column resonance droplet forming method. FIG. 8E is a schematic diagram showing the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber of the liquid column resonance droplet forming method. FIG. 9 is a schematic cross-sectional view showing an example of a toner manufacturing apparatus used in the toner manufacturing method of the present invention. FIG. 10 is a schematic view showing another example of the airflow passage. FIG. 11 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. FIG. 12 is a schematic configuration diagram illustrating an example of a process cartridge.

(toner)
The toner of the present invention contains at least an amorphous resin and a crystalline substance as a binder resin, and further contains other components such as a colorant, a pigment dispersant, and a charge control agent as necessary.
In the section image of the toner in a transmission electron microscope (TEM),
The number average particle diameter of the crystalline substance existing in the depth region Aa from the toner surface to 1/6 (1 / 6d) of the toner diameter d is CDa,
The relationship between CDa and CDc, where CDc is the number average particle diameter of the crystalline substance existing in a circular central region Ac having a radius of 1 / 6d centered on the toner center, satisfies the following relationship.
CDa <CDc

  The toner of the present invention in which a crystalline material of a desired size is disposed in a desired region in the toner that satisfies the above requirements maintains the effect of bleeding of the crystalline material during fixing, The toner can be prevented from being exposed to the surface of the toner, the toner can be prevented from being charged down and the occurrence of character smearing, and the toner has excellent low-temperature fixability, blocking resistance, and image stability.

<Binder resin>
The binder resin contains at least an amorphous resin and a crystalline substance.

<< Amorphous resin >>
The amorphous resin is not particularly limited as long as it is soluble in an organic solvent used in the production method described later, and can be appropriately selected from known resins according to the purpose. For example, homopolymers of vinyl monomers such as styrene monomers, acrylic monomers, methacrylic monomers, copolymers comprising two or more of these monomers, polyester resins, polyol resins, phenol resins , 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 alone or in combination of two or more.

-Vinyl monomer-
There is no restriction | limiting in particular as said styrene monomer, According to the objective, it can select suitably. For example, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, 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, p-chloro styrene, 3,4 -Styrene such as dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or a derivative thereof.
There is no restriction | limiting in particular as said acrylic monomer, According to the objective, it can select suitably. Examples thereof include acrylic acid and acrylic acid esters.
The esters of acrylic acid are not particularly limited and may be appropriately selected depending on the intended purpose. For example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic Examples include n-octyl acid, n-dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate.
There is no restriction | limiting in particular as said methacryl monomer, According to the objective, it can select suitably, For example, methacrylic acid, esters of methacrylic acid, etc. are mentioned.
The esters of methacrylic acid are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid. Examples include n-octyl acid, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

There is no restriction | limiting in particular as an example of the other monomer which forms the homopolymer of the said vinyl monomer, or a copolymer, According to the objective, it can select suitably. For example, the following (1) to (18) may be mentioned.
(1) Monoolefins such as ethylene, propylene, butylene and isobutylene (2) Polyenes such as butadiene and isoprene (3) Vinyl halides such as vinyl chloride, vinyl 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, methyl isopropenyl ketone, etc. Vinyl ketones (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone (8) Vinyl naphthalenes (9) Acrylic acid such as acrylonitrile, methacrylonitrile, acrylamide Or (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid (11) maleic anhydride, citraconic anhydride, itaconic anhydride, Unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester Monoesters of unsaturated dibasic acids such as itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester (13) unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid ( 14) Ku Α, β-unsaturated acid such as tonic acid and cinnamic acid (15) α, β-unsaturated acid anhydride such as crotonic anhydride and cinnamic anhydride (16) the α, β-unsaturated acid and lower Monomers having a carboxyl group such as anhydrides with fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides and monoesters thereof (17) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Hydroxy groups such as acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxypropyl methacrylate (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methylhexyl) styrene Monomer with

The binder resin copolymer may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and an alkyl chain such as those obtained by replacing the acrylate of these compounds with methacrylate Diacrylate compounds; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 Acrylate, dipropylene glycol diacrylate, and diacrylate compounds connected with an alkyl chain containing an ether bond, such as those of acrylates of these compounds is replaced with methacrylate and the like.
Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond.

Moreover, as said crosslinking agent, polyester type diacrylates, such as brand name MANDA (made by Nippon Kayaku Co., Ltd.), are mentioned, for example.
Further, as the cross-linking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate, triallyl cyanurate And polyfunctional crosslinking agents such as triallyl trimellitate.
Of these cross-linking agents, aromatic divinyl compounds (particularly divinylbenzene), diacrylate compounds linked by a bond chain containing one aromatic group and an ether bond from the viewpoint of fixing properties and offset resistance in toner resins. Are preferred.
Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used in the production of the vinyl polymer or vinyl copolymer used in the present invention include 2,2′-azobisisobutyronitrile and 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, acetylacetone peroxide Ketone peroxides such as side and cyclohexanone peroxide; 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetra Methyl butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide To oxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethyl Xyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, Acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyl-oxybenzoate Tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexa Benzoate, di -tert- butyl peroxy the hexa hydro terephthalate, and the like tert- butylperoxy azelate.

  When the non-crystalline resin is a styrene-acrylic resin, the molecular weight distribution measured by gel permeation chromatography (GPC) soluble in the resin component tetrahydrofuran (THF) has a molecular weight of 3,000 to 50,000 (number average molecular weight). It is preferable that at least one peak exists in the (converted) region.

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

Examples of the alcohol component 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, diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, and the like Can be mentioned.
The polyester resin can be cross-linked by using a trihydric or higher polyhydric alcohol or a trihydric or higher acid in combination, but it is necessary to make the amount used within a range that does not prevent the resin from dissolving in an organic solvent. .
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-triol Examples thereof include hydroxybenzene.

Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Or its anhydride, unsaturated dibasic acid such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides.
Examples of the trivalent or higher polyvalent carboxylic acid component include, for example, trimetic acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid. Acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (Methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, emporic trimer acid, anhydrides thereof, partial lower alkyl esters, and the like.

Polylactic acid can also be used as the polyester resin.
A generally known method is used in the production of polylactic acid. For example, polylactic acid aqueous solution can be directly dehydrated and condensed while heating under reduced pressure in the presence of an appropriate catalyst, or by heating, or once a low molecular weight polylactic acid is prepared, this is depolymerized and used as a dimer cyclic ester. It can be obtained by a method of ring-opening polymerization of a certain lactide.
Polylactic acid includes optical isomers L-lactic acid and D-lactic acid, but in the present invention, amorphous polylactic acid obtained by combining these into a polymer is preferred. This is because the thermal characteristics required for the toner, that is, for heat melting at an appropriate temperature in the heat fixing system. As the monomer, L-lactide, a combination of D-lactide, or meso-lactide can be used instead of D-lactide.
Polylactic acid is not good in compatibility with other resins because the ester bond site is dominant in the structure. For this reason, for example, when used in combination with a crystalline polyester resin, the interface with the crystalline resin becomes clear, and the crystallization speed after once compatible is increased.

  In the present invention, an embodiment in which the amorphous resin is mainly composed of a polyester resin is preferable.

When the non-crystalline resin is a polyester resin, at least one peak is present 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. This is preferable. In addition, an amorphous resin in which a component having a molecular weight of 100,000 or less in a THF-soluble component is 70% to 100% is preferable from the viewpoint of dischargeability. Furthermore, an amorphous resin in which at least one peak exists in a region having a molecular weight of 5,000 to 20,000 is more preferable.
In the present invention, the molecular weight distribution of the amorphous resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

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

In the present invention, the acid value of the amorphous resin component of the toner composition is determined by the following method in accordance with JIS K-0070 for the basic operation.
(1) The sample is used after removing additives other than the amorphous resin (polymer component) in advance, or the acid value and content of components other than the amorphous resin and the crosslinked amorphous resin are previously determined. I ask for it. The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when the acid value of the amorphous resin is measured from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the amorphous resin is obtained by calculation.
(2) 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.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / L potassium hydroxide (KOH).
(4) The amount of KOH solution used at this time is S (mL), a blank is measured at the same time, and the amount of KOH solution used at this time is B (mL). However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W

The glass transition temperature (Tg) of the non-crystalline resin and the toner composition containing the non-crystalline resin is not particularly limited and may be appropriately selected depending on the intended purpose. 80 degreeC is preferable and 40 to 70 degreeC is more preferable.
If the glass transition temperature (Tg) is lower than 35 ° C., the toner may be easily deteriorated in a high temperature atmosphere. On the other hand, when the glass transition temperature (Tg) exceeds 80 ° C., the fixability may be lowered.

  A non-crystalline resin may be selected more appropriately than the above depending on the organic solvent or crystalline substance to be used. However, when a crystalline substance having excellent solubility in an organic solvent is used, the softening point of the toner is lowered. There is a case. In such a case, increasing the weight average molecular weight of the amorphous resin to increase the softening point of the amorphous resin is an effective means for maintaining good hot offset properties.

<< Crystalline substance >>
The crystalline substance is not particularly limited as long as it is compatible with the amorphous resin, and can be appropriately selected according to the purpose. However, the crystalline substance is improved in terms of improving low-temperature fixability. It is preferable that
Since the crystalline substance is compatible with the amorphous resin at the time of fixing and instantaneously lowers the melt viscosity of the toner, thereby fixing at a low temperature. It is preferable that the non-crystalline resin is compatible in the melting temperature range. These may be used alone or in combination of two or more.

  As such a crystalline substance, it is preferable to use a substance having a certain degree of polarity. In order for the crystalline substance to be polar, the crystalline substance preferably has a polar functional group or binding site. Further, the crystalline substance may have a plurality of functional groups and bonding sites having these polarities. If the crystalline material is a crystalline material having polarity, the mobility of the molecules when melted is high, so that the crystalline material is instantly compatible with the amorphous resin, and the melt viscosity of the entire toner can be quickly reduced.

The functional group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acid groups such as carboxyl group, sulfonyl group and phosphonyl group; bases such as amino group and hydroxyl group; mercapto group and the like. Can be mentioned.
The binding site is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ester bond, ether bond, thioester bond, thioether bond, sulfone bond, amide bond, imide bond, urea bond, urethane bond And isocyanurate bond.
Among these, the crystalline substance includes a straight chain hydrocarbon carboxylic acid or acid amide having 8 to 20 carbon atoms, a straight chain having 8 to 20 per divalent linking group having a total carbon number of ester and amide. A chain hydrocarbon ester, a linear hydrocarbon amide, a linear hydrocarbon ester amide, or the like is easily present stably in the toner, has little influence on the environmental stability of the toner, and is non-crystalline. This is preferable in that the resin is easily compatible when melted.

  The method for analyzing the crystalline substance is not particularly limited and can be appropriately selected according to the purpose. For example, the crystalline substance in the toner can be analyzed using a gas chromatograph / mass spectrometer or a nuclear magnetic resonance apparatus. Examples of the analysis method include a method in which other materials in the toner are dissolved and removed using an organic solvent, and the crystalline substance is separated and then analyzed.

The melting point of the crystalline substance is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a low melting point and more preferably 100 ° C. or less from the viewpoint of realizing low-temperature fixability of the toner. The temperature is more preferably less than 80 ° C., and particularly preferably less than 65 ° C. When the melting point exceeds 100 ° C., the effect on fixability may be hardly exhibited.
The lower limit of the melting point of the crystalline substance is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and particularly preferably 50 ° C. or higher. When the melting point is less than 40 ° C., the heat-resistant storage stability of the toner may be deteriorated.
The combination of the upper limit value and the lower limit value of the melting point is not particularly limited and may be appropriately selected according to the purpose. Among these, the melting point is preferably 40 ° C. to 100 ° C., 45 C. to 80.degree. C. is more preferable, and 50.degree. C. to 65.degree. C. is particularly preferable.
The melting point of the crystalline substance can be measured by, for example, a differential scanning calorimetry (DSC) apparatus (for example, TG-DSC system TAS-100, manufactured by Rigaku Corporation).

The weight average molecular weight (Mw) of the crystalline substance is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2,000 to 100,000, and 5,000 to 60,000. Is more preferable.
The weight average molecular weight (Mw) can be measured, for example, by gel permeation chromatography (GPC).

  The solubility of the crystalline substance is preferably 10 g or more, more preferably 50 g or more, per 100 g of ethyl acetate at 45 ° C. in order to balance the fixability, offset resistance, and sticking resistance. When the solubility is 10 g / (100 g ethyl acetate) or more, the effect of sticking resistance is sufficiently exhibited while having fixability and offset resistance.

  As the crystalline substance, when the amorphous resin is a resin having the polyester skeleton, the crystalline substance is preferably a crystalline polyester resin. When an amorphous polyester resin is used as the non-crystalline resin, if the crystalline substance is a crystalline polyester resin, the structure of the crystalline substance is close to that of the non-crystalline resin, so that the non-crystalline resin is melted. In this case, the crystalline substance is easily compatible with each other, and before heating, it is a polymer and has high mechanical strength, which is advantageous in terms of excellent storage stability.

The crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a saturated aliphatic diol compound having 2 to 12 carbon atoms as an alcohol component, particularly 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol and their derivatives, and at least a double bond (C = Or a dicarboxylic acid having 2 to 12 carbon atoms, or a saturated dicarboxylic acid having 2 to 12 carbon atoms, particularly fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8- A crystalline polyester resin synthesized using octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid and derivatives thereof is preferred.
Among them, the crystalline polyester resin has a small peak half-width and high crystallinity, and in particular, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1 , 10-decanediol, 1,12-dodecanediol alcohol component, fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, It is preferably composed of only one kind of dicarboxylic acid component of 1,10-decanedioic acid and 1,12-dodecanedioic acid.

  In addition, as a method for controlling the crystallinity and softening point of the crystalline polyester resin, a trivalent or higher polyhydric alcohol such as glycerin as an alcohol component or a trivalent or higher valency such as trimellitic anhydride as an acid component at the time of polyester resin synthesis. Examples include a method of designing and using a non-linear polyester resin that has been subjected to condensation polymerization by adding a polyvalent carboxylic acid.

The molecular structure of the crystalline polyester resin in the present invention can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. As an example, a method for detecting, as an example of a crystalline polyester resin, an infrared absorption spectrum having absorption based on δCH (out-of-plane variable vibration) of olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ is given. Can do.

  The solubility of the crystalline polyester resin at 70 ° C. with respect to 100 parts by mass of the organic solvent is preferably 10 parts by mass or more. When the amount is less than 10 parts by mass, the affinity between the organic solvent and the crystalline polyester resin is poor, and it is difficult to uniformly dissolve the amorphous resin and the crystalline polyester resin in the organic solvent.

As for the molecular weight, as a result of earnest examination from the viewpoint that the molecular weight distribution is sharp and the low molecular weight is excellent in low-temperature fixability, and the heat resistant storage stability is deteriorated when there are many components having low molecular weight, the soluble content of o-dichlorobenzene In the molecular weight distribution by GPC, the peak position of the molecular weight distribution diagram in which the horizontal axis is log (M) and the vertical axis is expressed by weight% is in the range of 3.5 to 4.0, and the half width of the peak is 1.5. The weight average molecular weight (Mw) is preferably 3,000 to 30,000, the number average molecular weight (Mn) is 1,000 to 10,000, and Mw / Mn is preferably 1 to 10.
Furthermore, it is preferable that the weight average molecular weight (Mw) is 5,000 to 15,000, the number average molecular weight (Mn) is 2,000 to 10,000, and Mw / Mn is 1 to 5.

The acid value of the crystalline polyester resin is preferably 5 mgKOH / g or more and more preferably 10 mgKOH / g or more in order to achieve the desired low-temperature fixability from the viewpoint of the affinity between paper and resin. On the other hand, 45 mgKOH / g or less is preferable for improving the hot offset property. Further, the hydroxyl value of the crystalline polyester resin is preferably 0 mgKOH / g to 50 mgKOH / g in order to achieve a predetermined low temperature fixability and to achieve good charging characteristics, and is preferably 5 mgKOH / g to 50 mgKOH / g. More preferred.
The acid value can be measured in the same manner as described above, for example, by the method described in JIS K0070.

When the crystalline substance in the present invention is a crystalline polyester resin, the content of the crystalline polyester resin is a value obtained by mass conversion of the endothermic amount of the crystalline polyester resin determined by a DSC (differential scanning calorimeter) method. The content is preferably 1% by mass to 30% by mass based on the total toner.
The ratio measuring method for the amount of the crystalline polyester resin will be described in detail below.
The total amount of the crystalline polyester resin in the toner particles is obtained by a DSC (Differential Scanning Calorimeter) method. Each of the toner sample and the crystalline polyester resin simple substance sample is measured by the following measuring device and conditions, and each is obtained from the ratio of the endothermic amounts of the obtained crystalline polyester resin.
Measurement device: DSC device (DSC60; manufactured by Shimadzu Corporation)
-Sample amount: about 5mg
・ Temperature rise temperature: 10 ℃ / min
・ Measurement range: Room temperature to 150 ℃
Measurement environment: In a nitrogen gas atmosphere The total amount of crystalline polyester resin is calculated using the following formula.
Total amount of crystalline polyester resin (% by mass)
= (Endothermic amount of crystalline polyester resin of toner sample (J / g)) × 100)
/ (Endothermic amount of crystalline polyester resin alone (J / g))
According to this measurement method, even when the crystalline polyester resin flows out during the toner manufacturing process and all of the charged crystalline polyester resin is not contained in the toner, the total amount of the crystalline polyester resin in the toner particles is effectively defined. be able to.
The total amount of the crystalline polyester resin determined by the DSC method is preferably 1% by mass to 30% by mass in the toner particles. When the total amount of the crystalline polyester resin is 1% by mass or more, the amount of the crystalline polyester resin contained in the toner particles is not too small, and sufficient fixing property can be obtained at the time of fixing. The offset property is not lowered. Further, it is preferable that the total amount of the crystalline polyester resin is 30% by mass or less because the filming resistance is not lowered and the glossiness after fixing is not lost in a color image.

<Other ingredients>
The toner of the present invention may contain other components such as a colorant, a pigment dispersant, a release agent, and a charge control agent.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably from well-known coloring agents. 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, Iso Indolinone Yellow, Bengala, Pangdan, Lead Red, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilli Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon , Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine oren , Perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, Ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc white, litbon, a mixture thereof and the like can be mentioned.

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

The colorant can also be used as a master batch combined with a resin.
The resin kneaded with the master batch is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a modified polyester resin obtained by modifying a polyester resin with an isocyanate group or an epoxy, a polyester resin and a polycarboxylic acid An unmodified polyester resin consisting of In addition to the modified and unmodified polyester resins, for example, polymers of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and the like, and substituted polymers thereof; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer , Styrene-vinyl methyl ketone copolymer, Styrene copolymers such as lene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate , Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic chain Examples thereof include alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The masterbatch can be obtained by mixing and kneading the masterbatch resin and a colorant with a high shear force.
At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a method of removing water and organic solvent components by mixing and kneading an aqueous paste containing water together with a resin and an organic solvent and transferring the colorant to the resin side, can be used. According to this method, since the wet cake of the colorant can be used as it is, there is no need to dry it.
For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.

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

The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and the colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is It is more preferable that the colorant is used in a dispersion of 10 to 50.
When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered and the pigment dispersibility may be insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient.
The acid value can be measured, for example, by the method described in JIS K0070 in the same manner as described above, and the amine value can be measured, for example, by the method described in JIS K7237.

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

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

  The addition amount of the pigment dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 1 part by mass to 200 parts by mass with respect to 100 parts by mass of the colorant. More preferably, it is -80 mass parts. When the addition amount is less than 1 part by mass, the dispersibility may be lowered, and when it exceeds 200 parts by mass, the chargeability may be lowered.

<< Releasing agent >>
Examples of the release agent include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, and sazol wax; aliphatic hydrocarbon waxes such as oxidized polyethylene wax. Oxides of these or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal waxes such as beeswax, lanolin, spermaceti; mineral systems such as ozokerite, ceresin, petrolatum Waxes; waxes mainly composed of fatty acid esters such as montanic acid ester wax and caster wax; various synthetic ester waxes and synthetic amide waxes.

  Other examples of the release agent include palmitic acid, stearic acid, montanic acid, and other saturated straight chain fatty acids such as straight chain alkyl carboxylic acids having a straight chain alkyl group; prundic acid, eleostearic acid, valinaline Unsaturated fatty acids such as acids; stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesilyl alcohol, and other long-chain alkyl alcohols; saturated alcohols such as sorbitol; linoleic acid amides; Fatty acid amides such as olefinic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bislauric acid amide and hexamethylene bisstearic acid amide; ethylene bisoleic acid amide and hexamethylene bisolei Unsaturated fatty acid amides such as acid amides, N, N′-dioleyl adipic acid amides, N, N′-dioleyl sepasic acid amides; m-xylene bisstearic acid amides, N, N-distearyl isophthalic acid amides, etc. A fatty acid metal salt such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate; a wax grafted with an aliphatic hydrocarbon wax using a vinyl monomer such as styrene or acrylic acid; Examples thereof include partial ester compounds of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities removed are preferably used as the release agent.

The melting point of the release agent is preferably less than 65 ° C., more preferably in the range of 69 ° C. to 120 ° C., in order to balance the fixability and the offset resistance. When the melting point is 65 ° C. or higher, the blocking resistance does not decrease, and when it is 120 ° C. or lower, the offset resistance effect is sufficiently exhibited.
In the present invention, the melting point of the release agent is defined as the peak top temperature of the maximum peak of the endothermic peak of the wax measured by differential scanning calorimetry (DSC).

As the DSC measuring instrument for measuring the melting points of the release agent and the toner, a highly accurate internal heat input compensation type differential scanning calorimeter is preferable. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after raising and lowering the temperature once and taking a previous history.
The content of the release agent varies depending on the melt viscoelasticity and fixing method of the amorphous resin, but a range of 1 to 50 parts by mass is preferable with respect to 100 parts by mass of the amorphous resin.

<< Charge Control Agent >>
There is no restriction | limiting in particular as said charge control agent, According to the objective, a well-known thing can be selected suitably. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like.

  Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries); TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.); Copy charge PSY VP2038 of ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst); LRA-901, LR- which is a boron complex 147 (manufactured by Nippon Carlit); copper phthalocyanine, perylene, quinacrid And azo pigments, other high molecular compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts, phenolic resins, and fluorine compounds.

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

<Toner characteristics>
In the toner of the present invention, in the cut-section image of the toner in a transmission electron microscope (TEM),
The number average particle diameter of the crystalline substance existing in the depth region Aa from the toner surface to 1/6 (1 / 6d) of the toner diameter d is CDa,
The relationship between CDa and CDc when the number average particle diameter of the crystalline substance existing in a circular central region Ac having a radius of 1 / 6d and centering on the toner is CDc satisfies the following relationship. It is characterized by.
CDa <CDc

Further, as a more preferable aspect, in the toner region, when the region other than the Aa and the Ac is Ab, the CDa when the number average particle diameter of the crystalline substance existing in the Ab is CDb, The relationship between CDb and CDc satisfies the following relationship.
CDa <CDb <CDc

  The toner exhibiting the above properties is a toner excellent in all of low-temperature fixability, blocking resistance, and image stability.

  The above-mentioned Aa, Ab, Ac, CDa, CDb, and CDc can be determined based on a transmission electron microscope (TEM) photograph of a fractured surface of toner particles by a method described later.

  The crystalline substance in the toner of the present invention is characterized in that it has an inclined structure so that the particle diameter increases from the toner surface toward the toner center in the TEM image. By adopting such a structure, it is possible to suppress the exposure to the toner surface while maintaining the effect of exuding the crystalline substance at the time of fixing, and it is possible to prevent the toner charge from being lowered and the occurrence of character smearing. .

In order to obtain the desired toner defined in the present invention, it is necessary to sufficiently consider the kind and content of the amorphous resin, the crystalline substance, and other components contained in the toner. And in this invention, it manufactures suitably by using the manufacturing method mentioned later. At that time, it is preferable to consider the type of the organic solvent in the toner composition liquid and the solubility of the amorphous resin or the crystalline substance in the organic solvent.
In particular, in the present invention, a crystalline substance having high solubility in an organic solvent at a high temperature is used to control the presence state of the crystalline substance in the toner, and the temperature condition in the toner composition liquid in the droplet solidification step and the drying condition are controlled. Another characteristic is that the conditions are set to a higher temperature range.

  Furthermore, in the manufacturing method described later, when the recrystallization temperature of the crystalline substance is Tc (° C.), the droplets may be dried in an atmosphere adjusted to (Tc-5) ° C. or higher. Alternatively, even in an atmosphere of less than (Tc-5) ° C., the droplets may be dried in an atmosphere in which the relative humidity based on the organic solvent in the toner composition liquid is adjusted to 10% to 40%. .

An example of a toner cross-sectional view of the present invention is shown in FIG.
FIG. 2A is a diagram in which the contour of the toner is emphasized by adjusting the contrast of FIG. From this figure, the relationship between Aa, Ab, and Ac can be seen.
The Aa region is a region having a depth from the surface of the toner to 1/6 (1 / 6d) of the toner diameter d (the toner diameter d is a straight line passing through the center of the toner and connecting both ends of the toner).
The Ac region refers to a central region from the toner center to 1/6 (1 / 6d) of the toner diameter d, that is, a circular central region having a radius of 1 / 6d centered on the toner center.
The Ab region refers to a region other than the Aa and the Ac in the toner region.
FIG. 2B is a diagram in which the crystalline substance in the region Ac in the toner particle of FIG. 1 is emphasized. In these figures, the image may be binarized as necessary. An image processing method can be appropriately selected so that the presence state of the crystalline substance can be understood.

The number average particle diameters CDa, CDb, CDc of the crystalline substances in the toner particles satisfy CDa <CDb <CDc.
If this condition is not satisfied, the crystalline substance is likely to be exposed on the surface, and toner charge reduction and background contamination are likely to occur.

  As said CDa, the range of 60 nm-140 nm is preferable, and 60 nm-100 nm are more preferable. When the CDa is less than 60 nm, the effect of the crystalline substance disposed on the toner surface is hardly exhibited, and the offset property may be deteriorated by inhibiting the bleeding at the time of fixing. On the other hand, when the CDa is larger than 140 nm, the crystalline substance is likely to be exposed on the surface, and toner charge lowering and scumming are liable to occur.

  The CDb is preferably in the range of 200 nm to 240 nm. If the CDb is less than 200 nm, the effect of the crystalline substance disposed on the toner surface is difficult to be exhibited, and the seepage at the time of fixing may be hindered to deteriorate the offset property. On the other hand, when the CDb is larger than 240 nm, the crystalline substance is likely to be exposed on the surface, and the toner charge is likely to be lowered and the background is easily soiled.

  The CDc is preferably in the range of 210 nm to 350 nm. When the CDc is less than 210 nm, the effect of the crystalline substance disposed on the toner surface is hardly exhibited, and the offset property may be deteriorated by inhibiting the seepage during fixing. On the other hand, if CDc is larger than 350 nm, the crystalline substance is likely to be exposed on the surface, and toner charge reduction and background contamination are likely to occur.

The ratio of CDc to CDa (CDc / CDa) is preferably in the range of 3.0 to 3.5. When CDc / CDa is less than 3.0, the effect of the crystalline substance disposed on the toner surface is difficult to be exhibited, and the seepage at the time of fixing may be hindered to deteriorate the offset property. On the other hand, if CDc / CDa is greater than 3.5, the crystalline substance is likely to be exposed on the surface, and toner charge reduction and background contamination are likely to occur.
Measurement of Aa, Ab, Ac, CDa, CDb, and CDc is performed as follows based on a transmission electron microscope (TEM) photograph of a fractured surface of toner particles.

[Measurement of Aa, Ab, Ac, CDa, CDb, CDc]
Here, as a TEM observation, for example, after embedding the toner in an epoxy resin, an ultramicrotome (ultrasonic) is sliced in a cross section passing through the center of the toner to produce a toner flake, and this is dyed with RuO ₄ Then, using a transmission electron microscope (TEM), the magnification of the microscope is adjusted, and the Aa, Ab, and Ac regions, and the number average particle diameters of CDa, CDb, and CDc are determined from the cut section of the toner.
For each of the 50 toners, a split surface of the toner is prepared.
The field of view of the microscope is expanded until Aa, Ab, Ac, CDa, CDb, and CDc can be measured, and the fractured surface is observed, and the 50 fractured surfaces of the toner are extracted as measurement samples. After the extraction, the Ac, Ab, Ac, CDa, CDb, and CDc are obtained from the image files using, for example, image analysis software ImageJ.
In the toner of the present invention, the values of CDa, CDb, and CDc are obtained for each of the 50 cut surfaces of the sample, and it is checked whether the average value of the 50 points is CDa <CDb <CDc.

  The heat generation peak temperature, melting point, and glass transition temperature (Tg) of the toner and each material in the present invention are measured using, for example, a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation). be able to.

[Measurement of exothermic peak temperature, melting point, and glass transition temperature (Tg)]
The exothermic peak temperature, melting point, and glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the sample is heated from 0 ° C. to 200 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. Thereafter, the temperature is cooled to 0 ° C. at a temperature drop rate of 10 ° C./min from 200 ° C., and further heated to 200 ° C. at a temperature rise rate of 10 ° C./min. ) To measure the DSC curve.
From the obtained DSC curve, using the analysis program “endothermic shoulder temperature” in the DSC-60 system, the DSC curve at the first temperature rise is selected, and the glass transition temperature at the first temperature rise of the target sample is obtained. Can do. Further, by using the “endothermic shoulder temperature”, a DSC curve at the second temperature rise can be selected, and the glass transition temperature at the second temperature rise of the target sample can be obtained.
Further, from the obtained DSC curve, the DSC curve at the first temperature rise is selected using the analysis program “peak temperature analysis program” in the DSC-60 system, and the melting point at the first temperature rise of the target sample is obtained. be able to. Further, by using the “endothermic peak temperature”, a DSC curve at the second temperature rise can be selected, and the melting point at the second temperature rise of the target sample can be obtained.
Similarly, using the “peak temperature analysis program”, a DSC curve at the first temperature drop can be selected, and the exothermic peak temperature at the first temperature drop of the target sample can be obtained.
In the present invention, the glass transition temperature at the first temperature rise when the toner is used as the target sample is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
Moreover, in this invention, melting | fusing point and Tg at the time of the 2nd temperature rise of each structural component are made into melting | fusing point and Tg of each object sample.

<Toner shape>
The volume average particle diameter of the toner of the present invention is preferably 1 μm to 8 μm from the viewpoint of forming a high-resolution, high-definition and high-quality image.
Further, the particle size distribution (volume average particle size / number average particle size) of the toner is preferably 1.00 to 1.15 from the viewpoint of maintaining a stable image over a long period of time.

Further, the toner of the present invention has a distribution in which the number particle diameter and frequency (number) of the toner are plotted, which is 1.21 times the number particle diameter (also referred to as “mode diameter”) having the highest frequency (number). It is preferable to have a second frequency (number) peak in the range of 1.31 times the number particle diameter.
When the second frequency (number) peak is not exhibited, particularly when the particle size distribution (volume average particle size / number average particle size) approaches 1.00 (monodisperse), the fine packing property of the toner is improved. Since it becomes very high, initial fluidity reduction and poor cleaning are likely to occur. On the other hand, when the number particle size larger than 1.31 times has a second frequency (number) peak, the image quality granularity is lowered due to the presence of a large amount of coarse powder as toner, which is not preferable.
The particle size and particle size distribution are measured as follows.

[Measurement of particle size and particle size distribution of toner]
The volume average particle diameter (Dv) and number average particle diameter (Dn) of the toner of the present invention are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) at an aperture diameter of 50 μm. After measuring the volume and number of toner particles, the volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained. For the particle size distribution, Dv / Dn obtained by dividing the volume average particle size (Dv) of the toner by the number average particle size (Dn) is used. If it is completely monodisperse, it becomes 1, and the larger the value, the wider the distribution.

  External additives such as a fluidity improver and a cleaning property improver can be added to the toner of the present invention as necessary.

<< Flowability improver >>
A fluidity improver may be added to the toner according to the present invention. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
There is no restriction | limiting in particular as said fluid improvement agent, According to the objective, it can select suitably. For example, fine powder silica such as wet process silica and dry process silica, fine powder of metal oxide such as fine powder unoxidized titanium and fine powder unalumina, and surface thereof with silane coupling agent, titanium coupling agent, silicone oil, etc. Treated silica, treated titanium oxide, treated alumina; fluorine resin powders such as fine vinylidene fluoride powder and fine polytetrafluoroethylene powder. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.

  There is no restriction | limiting in particular as a particle size of the said fluid improvement agent, Although it can select suitably according to the objective, 0.001 micrometer-2 micrometers are preferable as an average primary particle diameter, and 0.002 micrometer-0.2 micrometer are more preferable.

  The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, for example, AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80. , -COK84; Ca-O-SiL (trade name of CABOT) -M-5, -MS-7, -MS-75, -HS-5, -EH-5; Wacker HDK (trade name of WACKER-CHEMIE) -N20 V15, -N20E, -T30, -T40; D-CFineSi1ica (trade name of Dow Corning); Franco1 (trade name of Franci1) and the like.

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

  Examples of the organosilicon compound include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and dimethyl. Vinylchlorosilane, divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethyl Chlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethyl L-chlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxy Silane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, Examples thereof include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  There is no restriction | limiting in particular as a number average particle diameter of the said fluid improvement agent, Although it can select suitably according to the objective, 5 nm-100 nm are preferable, and 5 nm-50 nm are more preferable.

As the specific surface area of the flowability improving agent, a specific surface area by nitrogen adsorption measured by the BET method, preferably at least ^{30m 2 / g, 60m 2 /} g~400m 2 / g is more preferable.
For fine powder the flowability improver is treated surfaces, the specific surface area is preferably at least ^{20m 2 / g, 40m 2 /} g~300m 2 / g is more preferable.

  There is no restriction | limiting in particular as an application quantity of the said fluid improvement agent, Although it can select suitably according to the objective, 0.03 mass part-8 mass parts are preferable with respect to 100 mass parts of toner particles.

<< Cleaning improver >>
There is no particular limitation on the cleaning property improving agent for improving the removability of the toner remaining on the electrostatic latent image carrier or the primary transfer medium after the toner is transferred to recording paper or the like, and it is appropriately selected according to the purpose. can do. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a weight average particle size of 0.01 μm to 1 μm.

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

(Toner production method)
The toner production method of the present invention includes at least a droplet forming step and a droplet solidifying step, and further includes other steps as necessary.
In order to obtain a toner having the characteristics of the present invention, it is preferable to produce the toner by the droplet forming step and the droplet solidifying step.
In particular, the present invention is characterized in that the temperature of the toner composition liquid is set in a high temperature range, and the drying temperature in the droplet solidification step is set in a high temperature range.

<Droplet formation process>
The droplet forming step is a step of forming droplets by discharging a toner composition liquid in which at least an amorphous resin and a crystalline substance are dissolved or dispersed in an organic solvent.

  The toner composition liquid contains at least the amorphous resin and the crystalline substance, and further contains a toner such as other colorant, pigment dispersant, release agent, charge control agent, etc., if necessary. The composition can be obtained by dissolving or dispersing in an organic solvent.

  The temperature of the toner composition liquid is appropriately adjusted depending on the material constituting the toner composition liquid, but is preferably set to a high temperature range of 45 ° C to 65 ° C.

In addition, it is possible to dissolve the crystalline substance by heating the organic solvent and the toner composition liquid. When the boiling point of the organic solvent is Tb (° C.), it is preferably less than Tb-15 ° C.
By setting the temperature to less than Tb−15 ° C., bubbles are not generated in the toner composition liquid due to evaporation of the organic solvent, and the toner composition liquid is not dried and narrows the discharge holes in the vicinity of the discharge holes. Can be done.

The crystalline substance needs to be dissolved in the toner composition liquid in order to prevent clogging of the discharge holes, but without phase separation from the amorphous resin dissolved in the toner composition liquid. The dissolution is important for obtaining uniform toner particles. Furthermore, it is important that the amorphous resin and the crystalline substance are phase-separated in the toner particles from which the organic solvent has been removed, in order to exhibit releasability during fixing and prevent offset. If the crystalline material is not phase-separated from the amorphous resin, not only can the mold release be exhibited, but the viscosity and elasticity at the time of melting of the amorphous resin will be lowered, and hot offset will be more likely to occur. End up.
Therefore, an optimal crystalline substance is selected depending on the organic solvent and amorphous resin used.

The organic solvent is a volatile solvent capable of dissolving or dispersing the toner composition in the toner composition liquid, and the amorphous resin and the crystalline material in the toner composition liquid are phase-separated. There is no particular limitation as long as it can be dissolved without any limitation, and it can be appropriately selected according to the purpose.
For example, organic solvents such as ethers, ketones, esters, hydrocarbons, and alcohols are preferably used, and tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), ethyl acetate, toluene, water and the like are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.

-Preparation method of toner composition liquid-
A toner composition liquid can be obtained by dissolving or dispersing the toner composition in an organic solvent. For the preparation of the toner composition liquid, it is important to prevent the clogging of the discharge holes by using a homomixer, a bead mill, or the like so that the colorant dispersion is sufficiently fine with respect to the nozzle opening diameter. .

The solid content of the toner composition liquid is preferably 3% by mass to 40% by mass. When the solid content is less than 3% by mass, not only the productivity is lowered, but also the dispersion such as the colorant is liable to settle or agglomerate, so that the composition of each toner particle tends to be nonuniform and the toner quality is improved. May decrease. When the solid content exceeds 40% by mass, a toner having a small particle size may not be obtained.
The step of discharging the toner composition liquid to form droplets can be performed by discharging droplets using a droplet discharge unit.

<< Droplet ejection means >>
The droplet discharge means is not particularly limited as long as the particle size distribution of the discharged droplets is narrow, and can be appropriately selected according to the purpose. Examples thereof include membrane vibration type discharge means, Rayleigh splitting type discharge means, liquid vibration type discharge means, and liquid column resonance type discharge means.

  As the membrane vibration type discharge means, for example, the discharge means described in Japanese Patent Application Laid-Open No. 2008-292976, and as the Rayleigh split type discharge means, for example, the discharge means described in Japanese Patent No. 4647506 is the liquid. Examples of the vibration type discharge means include the discharge means described in JP 2010-102195 A.

  In order to narrow the particle size distribution of the droplets and ensure the productivity of the toner, it is possible to use droplet-formed liquid column resonance using the liquid column resonance type discharge means. Specifically, a standing wave due to liquid column resonance is formed by applying vibration to the toner composition liquid in the liquid column resonance liquid chamber in which at least one or more discharge ports are formed. In other words, the toner composition liquid is ejected from the ejection port disposed in the region to form droplets.

<<< Liquid Column Resonant Discharge Unit >>>
The liquid column resonance discharge means that discharges using the resonance of the liquid column will be described.
FIG. 3 is a schematic cross-sectional view showing an example of a liquid column resonance droplet forming unit. The liquid column resonance droplet forming unit 11 includes a liquid column resonance liquid chamber 18 that stores the toner composition liquid therein, and a liquid common supply path 17. The liquid column resonance liquid chamber 18 communicates with a liquid common supply path 17 provided on one of the wall surfaces at both ends in the longitudinal direction. Further, the liquid column resonance liquid chamber 18 is provided on a wall surface facing the discharge hole 19 and a discharge hole 19 for discharging the droplet 21 to one wall surface of the wall surfaces connected to both ends. Vibration generating means 20 for generating high-frequency vibrations to form a standing wave. The vibration generating means 20 is connected to a high frequency power source (not shown).
The state of the toner composition liquid discharged by the discharge means is a state in which the fine particle component to be obtained is dissolved or dispersed, a so-called “particulate component-containing liquid” state, or a condition under which it is discharged. As long as it is liquid, it does not need to contain an organic solvent, and includes a state in which the fine particle component is melted, a so-called “fine particle component melt” state.

  The toner composition liquid 14 flows through the liquid supply pipe by a liquid circulation pump (not shown) and flows into the liquid common supply path 17 of the liquid column resonance droplet forming unit 10 shown in FIG. 4, and the liquid column resonance liquid shown in FIG. It is supplied to the liquid column resonance liquid chamber 18 of the droplet discharge means 11. A pressure distribution is formed in the liquid column resonance liquid chamber 18 filled with the toner composition liquid 14 by the liquid column resonance standing wave generated by the vibration generating means 20. Then, the droplet 21 is ejected from the ejection hole 19 arranged in a region where the amplitude of the liquid column resonance standing wave is large and the pressure fluctuation is large and which is an antinode of the standing wave. The region that becomes the antinode of the standing wave due to the liquid column resonance means a region other than the node of the standing wave. Preferably, it is a region where the pressure fluctuation of the standing wave has an amplitude large enough to discharge the liquid, and more preferably a position where the amplitude of the pressure standing wave becomes a maximum (a section as a velocity standing wave). ) To a minimum position in a range of ± 1/4 wavelength. If the region is an antinode of a standing wave, even if there are a plurality of discharge holes, substantially uniform droplets can be formed from each, and moreover, the droplets can be discharged efficiently. And clogging of the discharge holes is less likely to occur. The toner composition liquid 14 that has passed through the liquid common supply path 17 flows through a liquid return pipe (not shown) and is returned to the raw material container. When the amount of the toner composition liquid 14 in the liquid column resonance liquid chamber 18 decreases due to the discharge of the liquid droplets 21, a suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 18 acts, and the liquid common supply The flow rate of the toner composition liquid 14 supplied from the passage 17 increases, and the toner composition liquid 14 is replenished in the liquid column resonance liquid chamber 18. When the toner composition liquid 14 is replenished in the liquid column resonance liquid chamber 18, the flow rate of the toner composition liquid 14 passing through the liquid common supply path 17 is restored.

  Each of the liquid column resonance liquid chambers 18 in the liquid column resonance droplet discharge means 11 has a frame formed of a material having such a high rigidity that does not affect the resonance frequency of the liquid at a driving frequency such as metal, ceramics, or silicone. It is formed by bonding. Further, as shown in FIG. 3, the length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 is determined based on the liquid column resonance principle as described later. Further, the width W of the liquid column resonance liquid chamber 18 shown in FIG. 4 is desirably smaller than one half of the length L of the liquid column resonance liquid chamber 18 so as not to give an extra frequency to the liquid column resonance. . Furthermore, it is preferable that a plurality of liquid column resonance liquid chambers 18 are arranged for one droplet forming unit in order to dramatically improve productivity. The range is not limited, but one droplet forming unit provided with 100 to 2,000 liquid column resonance liquid chambers 18 is most preferable because both operability and productivity can be achieved. In addition, for each liquid column resonance liquid chamber, a flow path for supplying liquid is connected from the common liquid supply path 17, and the common liquid supply path 17 communicates with a plurality of liquid column resonance liquid chambers 18. .

Further, the vibration generating means 20 in the liquid column resonant droplet discharging means 11 is not particularly limited as long as it can be driven at a predetermined frequency, but a form in which a piezoelectric body is bonded to the elastic plate 9 is desirable. The elastic plate constitutes a part of the wall of the liquid column resonance liquid chamber so that the piezoelectric body does not come into contact with the liquid. Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, the piezoelectric body is often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO _{3, and the} like can be given. Furthermore, it is desirable that the vibration generating means 20 is arranged so that it can be individually controlled for each liquid column resonance liquid chamber. In addition, a configuration in which the block-shaped vibrating member made of one material described above is partially cut in accordance with the arrangement of the liquid column resonance liquid chambers, and each liquid column resonance liquid chamber can be individually controlled via an elastic plate. desirable.

Furthermore, the diameter of the opening of the discharge hole 19 is desirably in the range of 1 μm to 40 μm. If the particle size is smaller than 1 μm, the formed droplets may be very small so that the toner may not be obtained. In the case of a toner containing solid fine particles such as a pigment, the discharge holes 19 are frequently clogged. In addition, productivity may be reduced. When the particle diameter is larger than 40 μm, the diameter of the droplet is large, and when this is dried and solidified to obtain a desired toner particle diameter of 3 μm to 6 μm, it is necessary to dilute the toner composition with an organic solvent to a very dilute liquid. In some cases, a large amount of drying energy is required to obtain a certain amount of toner, which is inconvenient.
Further, as can be seen from FIG. 4, adopting a configuration in which the discharge holes 19 are provided in the width direction in the liquid column resonance liquid chamber 18 can provide a large number of openings of the discharge holes 19, thereby increasing the production efficiency. Therefore, it is preferable. Further, since the liquid column resonance frequency varies depending on the arrangement of the discharge holes 19, it is desirable to appropriately determine the liquid column resonance frequency after confirming the discharge of the droplet.
The sectional shape of the discharge hole 19 is described as a tapered shape such that the diameter of the opening is reduced in FIG. 3 and the like, but the sectional shape can be appropriately selected.

FIG. 5A to FIG. 5D show schematic views of the shape of the discharge holes as seen from the cross section of the liquid column resonance liquid chamber. Each figure of FIG. 5 shows a cross-sectional shape that the discharge hole 19 can take.
FIG. 5A shows a shape in which the opening diameter becomes narrow while having a round shape from the liquid contact surface of the discharge hole 19 toward the discharge port, and near the outlet of the discharge hole 19 when the thin film 41 vibrates. Since the pressure applied to the liquid is maximized, it is the most preferable shape for stabilizing the discharge.
FIG. 5B has a shape such that the opening diameter becomes narrower from the liquid contact surface of the discharge hole 19 toward the discharge port, and the nozzle angle 24 can be changed as appropriate. Similar to FIG. 5A, the pressure applied to the liquid can be increased in the vicinity of the outlet of the discharge hole 19 when the thin film 41 vibrates due to this nozzle angle, but the range of the nozzle angle is preferably 60 ° to 90 °. 60 ° or less is not preferable because it is difficult for pressure to be applied to the liquid and the processing of the thin film 41 is difficult. When the nozzle angle 24 is 90 °, which corresponds to the case of FIG. 5C, it is difficult to apply pressure to the outlet, and 90 ° is the maximum value. When the angle is 90 ° or more, no pressure is applied to the outlet of the hole 12, so that the droplet discharge becomes very unstable.
FIG. 5D shows a shape combining FIG. 5A and FIG. 5B. In this way, the shape may be changed step by step.

-Mechanism of droplet formation-
Next, the mechanism of droplet formation by the droplet formation unit in liquid column resonance will be described.
First, the principle of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 18 in the liquid column resonance droplet discharge means 11 of FIG. 3 will be described. When the sound velocity of the toner composition liquid in the liquid column resonance liquid chamber is c, and the driving frequency applied from the vibration generating means 20 to the toner composition liquid 14 as a medium is f, the wavelength λ at which the liquid resonance occurs is as follows. It has the relationship of (Formula 1).
λ = c / f (Formula 1)

Further, in the liquid column resonance liquid chamber 18 of FIG. 3, the length from the end of the frame on the fixed end side to the end on the common liquid supply path 17 side is L, and further, the end of the frame on the common liquid supply path 17 side The height h1 (= about 80 μm) is about twice the communication port height h2 (= about 40 μm). In the case of a both-side fixed end that is assumed to be equivalent to a closed fixed end on the liquid common supply path 17 side, resonance occurs when the length L matches an even multiple of a quarter of the wavelength λ. Most efficiently formed. That is, it is expressed by the following (Formula 2).
L = (N / 4) λ (Expression 2)
(However, N represents an even number.)

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

For the drive frequency f with the highest efficiency, the following (Expression 3) is derived from the above (Expression 1) and the above (Expression 2).
f = N × c / (4L) (Formula 3)
(However, L represents the length of the liquid column resonance liquid chamber in the longitudinal direction, c represents the velocity of the sound wave of the toner composition liquid, and N represents an integer.)
However, in reality, since the liquid has a viscosity that attenuates the resonance, the vibration is not amplified infinitely, and has a Q value. Resonance also occurs at a frequency in the vicinity of the drive frequency f with the highest efficiency shown in Equation 3).

FIGS. 6A to D show the velocity and pressure fluctuation standing wave shape (resonance mode) when N = 1, 2, and 3, and FIGS. 7A to 7C show the velocity when N = 4 and 5. The shape of the standing wave of pressure fluctuation (resonance mode) is shown.
Although it is originally a sparse / dense wave (longitudinal wave), it is generally expressed as in FIGS. 6A to 6D and FIGS. 6A to 6D and FIGS. 7A to 7C, the solid line is the velocity standing wave, and the dotted line is the pressure standing wave.

For example, as can be seen from FIG. 6A showing the case of a fixed end with N = 1, in the case of velocity distribution, the amplitude of the velocity distribution is zero at the closed end and the amplitude is maximum at the open end, which is intuitively easy to understand.
When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, the wavelength at which the liquid resonates is λ, and the standing wave is most efficiently generated when the integer N is 1 to 5. . In addition, since the standing wave pattern varies depending on the open / closed state of both ends, they are also shown. As will be described later, the condition of the end is determined by the state of the opening of the discharge hole and the opening of the supply side.
In acoustics, the open end is an end where the moving speed of the medium (liquid) in the longitudinal direction becomes zero, and conversely, the pressure becomes maximum. Conversely, the closed end is defined as an end where the moving speed of the medium becomes zero. The closed end is considered as an acoustically hard wall and wave reflection occurs. When ideally completely closed or open, resonance standing waves having the forms shown in FIGS. 6A to 6D and FIGS. 7A to 7C are generated by superposition of waves. The standing wave pattern also varies depending on the position, and the resonance frequency appears at a position deviated from the position obtained from the above (Equation 3), but a stable ejection condition can be created by appropriately adjusting the driving frequency.

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

  The liquid column resonance liquid chamber 18 in the liquid column resonance droplet discharge means 11 shown in FIG. 3 can be described as an acoustically soft wall due to the fact that both ends are equivalent to the closed end state or the opening of the discharge hole 19. Although it is preferable for the frequency to increase, it is not limited to this, but it may be an open end. The influence of the opening of the discharge hole 19 here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. Therefore, forming wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 as shown in FIG. 6B and FIG. 7A means that the resonance mode of the both-side fixed end and the one-side open end where the discharge hole side is regarded as an opening. This is preferable because all of the resonance modes can be used.

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

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

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

Using the principle of the liquid column resonance phenomenon described above, a liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 18 of FIG. 3, and the discharge hole 19 disposed in a part of the liquid column resonance liquid chamber 18. In this case, droplet discharge occurs continuously. Note that it is preferable to dispose the discharge hole 19 at a position where the pressure of the standing wave fluctuates the most, since the discharge efficiency is increased and the driving can be performed with a low voltage.
Further, one discharge hole 19 may be provided for one liquid column resonance liquid chamber 18, but it is preferable to arrange a plurality of discharge holes 19 from the viewpoint of productivity. Specifically, it is preferably between 2 and 100.
By setting the number to 100 or less, the voltage applied to the vibration generating means 20 can be kept low when a desired droplet is formed from the discharge port 19, and the behavior of the piezoelectric body as the vibration generating means 20 can be stabilized. Can do. Moreover, when opening the some discharge port 19, it is preferable that the pitch between discharge ports is 20 micrometers or more and below the length of a liquid column resonance liquid chamber. By setting the pitch between the discharge ports to 20 μm or more, it is possible to reduce the probability that droplets discharged from adjacent discharge ports collide with each other to form large droplets, and the toner particle size distribution is improved. can do.

Next, in the liquid column resonance droplet forming method, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge head in the droplet forming unit will be described with reference to FIGS. To do.
8A to 8E, the solid line written in the liquid column resonance liquid chamber is a velocity obtained by plotting the velocity at each arbitrary measurement position from the fixed end side to the end on the liquid common supply path side in the liquid column resonance liquid chamber. The distribution is shown, and the direction from the common liquid supply path to the liquid column resonance liquid chamber is “+”, and the opposite direction is “−”. In addition, the dotted line marked in the liquid column resonance liquid chamber indicates a pressure distribution in which the pressure value at each arbitrary measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted. The positive pressure is “+” with respect to the atmospheric pressure, and the negative pressure is “−”. Moreover, if it is a positive pressure, a pressure will be applied to the downward direction in the figure, and if it is a negative pressure, a pressure will be applied to the upward direction in the figure.
8A to 8E, the liquid common supply path side is opened as described above, but the height of the opening where the liquid common supply path 17 and the liquid column resonance liquid chamber 18 communicate with each other (height h2 shown in FIG. 3). ) Is approximately twice or more the height of the frame serving as the fixed end (height h1 shown in FIG. 3), so that the approximate condition that the liquid column resonance liquid chamber 18 is substantially fixed on both sides is obtained. The changes in the original velocity distribution and pressure distribution over time are shown.

  FIG. 8A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 at the time of droplet discharge. In FIG. 8B, the meniscus pressure increases again after the liquid is drawn immediately after the droplet is discharged. As shown in FIGS. 8A and 8B, the pressure in the flow path provided with the discharge hole 19 in the liquid column resonance liquid chamber 18 is maximum. Thereafter, as shown in FIG. 8C, the positive pressure in the vicinity of the discharge hole 19 decreases, and the liquid droplet 21 is discharged in a negative pressure direction.

  And as shown to FIG. 8D, the pressure of the discharge hole 19 vicinity becomes the minimum. From this time, the filling of the toner composition liquid 14 into the liquid column resonance liquid chamber 18 starts. Thereafter, as shown in FIG. 8E, the negative pressure in the vicinity of the discharge hole 19 decreases, and shifts to the positive pressure direction. At this time, the filling of the toner composition liquid 14 is completed. Then, again, as shown in FIG. 8A, the positive pressure in the droplet discharge region of the liquid column resonance liquid chamber 18 becomes maximum, and the droplet 21 is discharged from the discharge hole 19. In this way, a standing wave due to liquid column resonance is generated in the liquid column resonance liquid chamber by high-frequency driving of the vibration generating means, and corresponds to an antinode of standing wave due to liquid column resonance where the pressure changes most. Since the discharge holes 19 are arranged in the droplet discharge region to be discharged, the droplets 21 are continuously discharged from the discharge holes 19 in accordance with the antinode period.

<Droplet solidification process>
The droplet solidifying step is a step of forming toner by solidifying the droplet. Specifically, the toner of the present invention can be obtained by performing a collecting process after solidifying the droplets of the toner composition liquid discharged from the droplet discharging means into the gas.

  The solidification treatment is not particularly limited as long as the toner composition liquid can be in a solid state, and can be appropriately selected depending on the properties of the toner composition liquid. For example, the toner composition liquid can be an organic solvent capable of volatilizing the solid raw material. If it is dissolved or dispersed, it can be achieved by drying the droplets in the carrier air stream after jetting the droplets, that is, volatilizing the organic solvent. In drying the organic solvent, the drying state can be adjusted by appropriately selecting the temperature, vapor pressure, gas type, and the like of the gas to be injected. Further, even if the particles are not completely dried, they may be additionally dried in a separate step after the collection as long as the collected particles maintain a solid state. Moreover, you may form a solidified state by giving a temperature change, a chemical reaction, etc.

Here, in the present invention, the crystalline substance dissolved at the time of solidifying the droplet is recrystallized so that the number average particle diameter of the crystalline substance in the toner particles is CDa <CDc, more preferably CDa <CDb <CDc. Need to grow.
Therefore, the drying temperature in the droplet solidification step is appropriately adjusted depending on the material constituting the toner composition liquid, but is preferably set to a high temperature range of 60 ° C to 70 ° C.
In order to obtain a crystalline substance having a desired size, as a first means, a recrystallization temperature (Tc) of a crystalline substance (in particular, the crystalline substance may be a crystalline polyester resin, the same shall apply hereinafter) is used. ) -5) The droplets are dried in an atmosphere adjusted to be equal to or higher than ° C., or as a second means, the recrystallization temperature of the crystalline substance (Tc) -5) The droplets may be dried in an environment where the relative humidity based on the organic solvent of the toner composition liquid is adjusted to a range of 10% to 40%.

  In either method, sufficient crystal domain growth is promoted by slowing the recrystallization rate of the crystalline substance and the organic solvent drying rate.

Here, the recrystallization temperature of the crystalline substance can be determined by a DSC method. In the present invention, the peak temperature of the exothermic peak observed when heating to 150 ° C. at a rate of temperature increase of 10 ° C./min and then decreasing to 10 ° C./min to 0 ° C. is defined as the recrystallization temperature.
When the atmospheric temperature is lower than the above (recrystallization temperature (Tc) -5 of the crystalline substance), the crystallization speed is increased, and it becomes difficult to form a crystalline substance having a sufficient length or branch.

  Further, in the second means, when the relative humidity based on the organic solvent of the toner composition liquid is less than 10%, the drying speed of the organic solvent is increased, and recrystallization of the crystalline substance is promoted. This is not preferable because a crystalline substance having a small domain is easily formed. On the other hand, when the relative humidity exceeds 40%, the drying speed of the organic solvent is remarkably slowed, and the coalescence and coalescence during drying of the toner particles are promoted, and it becomes difficult to obtain a toner having a desired particle size distribution. .

<< Solid particle collecting means >>
There is no restriction | limiting in particular as the process to collect, It can select suitably, For example, it can collect | recover from air | atmosphere by a cyclone collection, a back filter collection, etc. using a well-known powder collection means. .

<Embodiment of Toner Production Apparatus of the Present Invention>
A specific manufacturing apparatus used in the toner manufacturing method of the present invention will be described with reference to FIG.
The toner manufacturing apparatus 1 of FIG. 9 includes a droplet discharge means 2 and a solidification / collection unit 60.
In the droplet discharge means 2, a raw material container 13 for storing a toner composition liquid 14 and a toner composition liquid 14 stored in the raw material container 13 are supplied to the droplet discharge means 2 through a liquid supply pipe 16. Further, a liquid circulation pump 15 for pumping the toner composition liquid 14 in the liquid supply pipe 16 to return to the raw material container 13 through the liquid return pipe 22 is connected, and the toner composition liquid 14 is discharged as needed. It can be supplied to the means 2. The liquid supply pipe 16 is provided with a pressure measuring device P1 and the dry collection unit is provided with a pressure measuring device P2. Managed by. At this time, if the relationship of P1> P2 is satisfied, the toner composition liquid 1 may ooze out from the hole 12, and if P1 <P2, there is a possibility that gas enters the discharge means and the discharge stops. It is desirable that P1≈P2.
In the chamber 61, a descending airflow 101 created from the carrier airflow inlet 64 is formed. The droplets 21 discharged from the droplet discharge means 2 are transported downward not only by gravity but also by the transport airflow 101 and are collected by the solidified particle collecting means 62.

-Conveyance airflow-
About the said conveyance airflow, it is good also to pay attention to the following points.
When the ejected droplets come into contact with each other before drying, the droplets coalesce into one particle (hereinafter, this phenomenon is also referred to as “coalescence”). In order to obtain solidified particles having a uniform particle size distribution, it is necessary to maintain the distance between the ejected droplets. However, the ejected droplets have a constant initial velocity, but eventually become stalled due to air resistance. The jetted droplets catch up with the stalled particles and coalesce as a result. Since this phenomenon occurs constantly, the particle size distribution is greatly deteriorated when the particles are collected. In order to prevent coalescence, it is necessary to transport the liquid droplets while solidifying the droplets while preventing the liquid droplets from decreasing in speed and preventing the liquid droplets from coming into contact with each other while preventing the coalescence. The solidified particles are conveyed to the collecting means 62.

For example, as shown in FIG. 3, a part of the transport airflow 101 is arranged as a first airflow in the vicinity of the droplet discharge means in the same direction as the droplet discharge direction, thereby reducing the droplet velocity immediately after the droplet discharge. Can be prevented and coalescence can be prevented. Alternatively, as shown in FIG. 10, it may be transverse to the discharge direction. Alternatively, although not shown, it may have an angle, and it is desirable to have an angle at which the droplets are separated from the droplet discharge means. As shown in FIG. 10, when the anti-adhesion airflow is applied from the lateral direction to the droplet discharge, it is desirable that the trajectories do not overlap when the droplets are conveyed by the anti-adhesion airflow from the discharge port. .
After preventing coalescence by the first air stream as described above, the solidified particles may be carried to the solidified particle collecting means by the second air stream.
It is desirable that the velocity of the first air flow is equal to or higher than the droplet jet velocity. If the speed of the anti-adhesion airflow is lower than the droplet ejection speed, it is difficult to exert the function of preventing the droplet particles, which is the original purpose of the anti-adhesion airflow, from contacting.
The property of the first air stream can be added with conditions so that the droplets do not coalesce with each other, and may not necessarily be the same as the second air stream. In addition, a chemical substance that promotes solidification of the particle surface may be mixed in the anti-attachment airflow, or a physical action may be applied.

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

<Other processes>
The method for producing the toner of the present invention may further include a secondary drying step.
For example, if the amount of residual solvent contained in the toner particles obtained by the solidified particle collecting means 62 shown in FIG. 9 is large, secondary drying is performed as necessary to reduce this.
There is no restriction | limiting in particular as secondary drying, A general well-known drying means like fluid bed drying or vacuum drying can be used. If the organic solvent remains in the toner, not only the toner characteristics such as heat resistant storage stability, fixability, and charging characteristics will change over time, but also the organic solvent will volatilize during fixing by heating, adversely affecting the user and peripheral equipment. Sufficient drying is necessary.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and further contains other components such as a carrier as necessary.
The toner of the present invention obtained above can be suitably used for both a one-component developer and a two-component developer mixed with a carrier.

<Career>
There is no restriction | limiting in particular as said carrier, According to the objective, it can select suitably, For example, carriers, such as a ferrite and a magnetite, a resin coat carrier, etc. can be mentioned.
The resin-coated carrier comprises carrier core particles and a resin coating material that is a resin that coats (coats) the surface of the carrier core particles.
Examples of the resin used for the covering material include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers; acrylic acid ester copolymers, methacrylic acid ester copolymers. Preferable examples include acrylic resins such as: fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride; silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins. In addition to these, resins that can be used as coating materials for carriers such as ionomer resins and polyphenylene sulfide resins can be used. These resins may be used alone or in combination of two or more.

As the carrier, a binder type carrier core in which magnetic powder is dispersed in a resin can also be used.
In the resin-coated carrier, as a method of coating the surface of the carrier core with at least a resin coating agent, for example, a method in which a resin is dissolved or suspended in a solvent and adhered to a coated carrier core, or simply in a powder state. The method of mixing is mentioned.

  The ratio of the resin coating material used with respect to the resin-coated carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.01% by mass to 5% by mass with respect to 100 parts by mass of the resin-coated carrier. Preferably, 0.1 mass%-1 mass% are more preferable.

The following (1) and (2) can be mentioned as usage examples in which the magnetic material is coated with the resin coating material of a mixture of two or more.
(1) 100 parts by mass of titanium oxide fine powder treated with 12 parts by mass of a mixture of di, methyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5) (2) with respect to 100 parts by mass of silica fine powder , Treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5) Examples of the resin coating material include styrene-methyl methacrylate copolymer, fluorine-containing resin and styrene copolymer A mixture with a coalescence, a silicone resin or the like is preferably used, and among these, a silicone resin is particularly preferable.

  Examples of the mixture of the fluororesin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, and a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer. , Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-acrylic acid 2-ethylhexyl copolymer (copolymer mass ratio 10:90 to 90:10) and styrene -A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20-60: 5-30: 10: 50) etc. are mentioned. Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.

  Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, and alloys thereof. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Among these magnetic materials, copper-zinc-iron-based ferrites mainly composed of copper, zinc and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium and iron components are particularly preferred. It is done.

The volume resistance value of the carrier can be set by appropriately adjusting the degree of unevenness on the surface of the carrier and the amount of the resin to be coated, and is preferably 10 ⁶ Ω · cm to 10 ¹⁰ Ω · cm, for example.

  There is no restriction | limiting in particular as a particle size of the said carrier, Although it can select suitably according to the objective, 4 micrometers-200 micrometers are preferable, 10 micrometers-150 micrometers are more preferable, 20 micrometers-100 micrometers are more preferable. Among these, as the particle diameter of the resin-coated carrier, a 50% particle diameter is particularly preferably 20 μm to 70 μm. In the two-component developer, the toner of the present invention is preferably used in an amount of 1 part by mass to 200 parts by mass with respect to 100 parts by mass of the carrier, and 2 parts by mass to 50 parts by mass of the toner with respect to 100 parts by mass of the carrier. More preferably it is used.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, thermal CVD (chemical vapor deposition, Chemical Vapor Deposition) is formed on the support. ), A photo-CVD method, a plasma CVD method, or the like, a photoconductor having a photoconductive layer made of a-Si can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

  There is no restriction | limiting in particular as a shape of the said electrostatic latent image carrier, Although it can select suitably according to the objective, A cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and more preferably 10 mm to 30 mm. Particularly preferred.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus.
The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

<< Exposure member and exposure >>
The exposure member is not particularly limited and may be appropriately selected depending on the purpose, as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed like an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
There is no restriction | limiting in particular as a light source used for the said exposure member, According to the objective, it can select suitably, For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser General light emitting materials such as (LD) and electroluminescence (EL).
In addition, various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure member.
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.

<Developing means and development process>
The developing unit is not particularly limited as long as the developing unit includes a developer that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible toner image. And can be appropriately selected according to the purpose.
The development process is not particularly limited as long as the electrostatic latent image formed on the electrostatic latent image carrier is developed using a developer to form a visible toner image. However, it can be appropriately selected depending on the purpose, and for example, it can be carried out by the developing means.

The developing means may be of a dry development type or a wet development type. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.

  In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . The magnet roller is disposed in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by an electric attractive 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.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, and a static elimination means.
Examples of the other processes include a transfer process, a fixing process, a cleaning process, and a static elimination process.

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer member and combined. An embodiment having a primary transfer unit for forming a transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, an intermediate transfer member is used, and the transfer step can be performed on the intermediate transfer member. It is preferable that the visual image is firstly transferred and then the visible image is secondarily transferred onto the recording medium.
The transfer step can be performed by, for example, charging the visible image using a transfer charger and the transfer unit.
Here, when the image to be secondarily transferred onto the recording medium is a color image composed of a plurality of colors of toner, the toner of each color is sequentially superimposed on the intermediate transfer member by the transfer means. An image can be formed on the body, and the image on the intermediate transfer body can be collectively transferred onto the recording medium by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photoconductor toward the recording medium. 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 typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

<< Fixing means and fixing process >>
The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. However, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the recording medium for each color toner May be performed every time the toner is transferred to the toner image, or may be performed simultaneously at the same time in a state where the toners of the respective colors are stacked.
The fixing step can be performed by the fixing unit.
The heating in the heating and pressing member is usually 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 unit depending on the purpose.

The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, is preferably ^{10N / cm 2 ~80N / cm 2} .

<< Cleaning means and cleaning process >>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples thereof include a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning step can be performed by the cleaning unit.

<< Static elimination means and static elimination process >>
The neutralizing means is not particularly limited as long as it is a means for neutralizing by applying a neutralizing bias to the photosensitive member, and can be appropriately selected according to the purpose. Examples thereof include a neutralizing lamp.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the photoconductor, and can be appropriately selected according to the purpose. For example, it can be performed by the neutralization unit. .

  Next, one mode for carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG. A color image forming apparatus 100A shown in FIG. 11 includes a photosensitive drum 100 (hereinafter also referred to as “photosensitive member 100”) as the electrostatic latent image carrier, a charging roller 200 as the charging unit, and the An exposure apparatus 30 as an exposure means, a developing device 40 as the development means, an intermediate transfer member 50, a cleaning device 600 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means. .

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. Also, in the vicinity of the intermediate transfer member 50, there is a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a recording medium. The intermediate transfer member 50 is disposed opposite to the intermediate transfer member 50. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 410 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 410. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 410 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 100.

  In the color image forming apparatus 100A shown in FIG. 11, for example, the charging roller 200 uniformly charges the photosensitive drum 100. The exposure device 30 performs imagewise exposure on the photosensitive drum 100 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 100 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 100 is removed by the cleaning device 600, and the charge on the photoconductor 100 is temporarily removed by the charge eliminating lamp 70.

(Process cartridge)
The process cartridge according to the present invention is detachably molded in various image forming apparatuses, and includes an electrostatic latent image carrier that carries an electrostatic latent image, and an electrostatic latent image carried on the electrostatic latent image carrier. And at least developing means for forming a toner image by developing with the developer of the present invention. The process cartridge of the present invention may further include other means as necessary.

  The developing means includes at least a developer accommodating portion that accommodates the developer of the present invention and a developer carrier that carries and conveys the developer accommodated in the developer accommodating portion. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.

  FIG. 12 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes a photosensitive drum 100, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these. “Part” represents part by mass.
The physical properties of the polymers used in the examples and comparative examples were determined as follows.

<Measurement of toner particle size and particle size distribution>
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner of the present invention were measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 50 μm. After measuring the volume and number of toner particles, the volume distribution and number distribution were calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner were determined. For the particle size distribution, Dv / Dn obtained by dividing the volume average particle size (Dv) of the toner by the number average particle size (Dn) was used.

<Measurement of Aa, Ab, Ac, CDa, CDb, CDc>
Here, as a TEM observation, for example, after embedding the toner in an epoxy resin, an ultramicrotome (ultrasonic) is sliced in a cross section passing through the center of the toner to produce a toner flake, and this is dyed with RuO ₄ Using a transmission electron microscope (TEM), the magnification of the microscope is adjusted, and the number average particle diameters of Aa, Ab, Ac, CDa, CDb, and CDc are measured using the image analysis software ImageJ. Asked.
For each of the 50 toners, a cut section of the toner was prepared.
The 50 fractured surfaces of the toner were extracted as measurement samples, the CDa, CDb, and CDc values were determined for each of the 50 fractured surfaces of the sample, and the average value of the 50 points was calculated.

<Measurement of Content (% by Mass) of Crystalline Polyester Resin in Toner Particles by DSC (Differential Scanning Calorimetry)>
The total amount of the crystalline polyester resin in the toner particles was obtained by a DSC (Differential Scanning Calorimeter) method. Each of the toner sample and the crystalline polyester resin single sample was measured by the following measuring apparatus and conditions, and each was obtained from the ratio of endothermic amounts of the obtained crystalline polyester resin.
Measurement device: DSC device (DSC60; manufactured by Shimadzu Corporation)
-Sample amount: about 5mg
・ Temperature rise temperature: 10 ℃ / min
・ Measurement range: Room temperature to 150 ℃
Measurement environment: In a nitrogen gas atmosphere The total amount of crystalline polyester resin was calculated by the following equation.
Total amount of crystalline polyester resin (% by mass)
= (Endothermic amount of crystalline polyester resin of toner sample (J / g)) × 100)
/ (Endothermic amount of crystalline polyester resin alone (J / g))

(Production Example 1-1)
<Synthesis of amorphous resin>
-Synthesis of Amorphous Polyester Resin A-
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 0.5 mol of bisphenol A propylene oxide adduct and bisphenol A ethylene oxide adduct 0. 5 mol was added as a carboxylic acid component, 0.9 mol of terephthalic acid, and tin octylate was added as an esterification catalyst, and subjected to a condensation polymerization reaction at 180 ° C. for 4 hours in a nitrogen atmosphere. Thereafter, 0.07 mol of trimellitic acid was added, the temperature was raised to 210 ° C., the mixture was reacted for 1 hour, and further reacted at 8 kPa for 1 hour, whereby an amorphous polyester having a weight average molecular weight of 24,000 and Tg of 60 ° C. Resin A was synthesized.

(Production Example 1-2)
<Synthesis of amorphous resin>
-Synthesis of Amorphous Polyester Resin B-
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 0.5 mol of bisphenol A propylene oxide adduct and bisphenol A ethylene oxide adduct 0. 5 mol was added as a carboxylic acid component, 0.9 mol of terephthalic acid, and tin octylate was added as an esterification catalyst, and subjected to a condensation polymerization reaction at 180 ° C. for 4 hours in a nitrogen atmosphere. Thereafter, 0.09 mol of trimellitic acid was added, the temperature was raised to 210 ° C., the mixture was reacted for 2 hours, and further reacted at 8 kPa for 1 hour, whereby an amorphous polyester having a weight average molecular weight of 26,000 and Tg of 60 ° C. Resin B was synthesized.

(Production Example 1-3)
<Synthesis of amorphous resin>
-Synthesis of amorphous styrene acrylic resin A-
In an autoclave reaction vessel equipped with a thermometer, a stirrer, and a nitrogen introduction tube, a mixed monomer of 2610.7 mol of styrene, 651.2 mol of n-butyl acrylate, 0.1 mol of glycidyl methacrylate, and 2 initiators , 2-bis (4,4-di-t-butylperoxycyclohexyl) propane in an amount of 0.3 mol, polymerized in a nitrogen stream at 90 ° C. for 5 hours, and then charged with 820 mol of xylene. After the time polymerization, polymerization was performed at a temperature of 110 ° C. for 1 hour. Further, 0.1 mol of 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and 408 mol of xylene were added, polymerized at 110 ° C. for 4 hours, and then di-t-butyl peroxide at 150 ° C. 2.4 moles and 84 moles of xylene are added and polymerized for 2 hours to complete the polymerization, and the solvent is removed under reduced pressure to form styrene / butyl acrylate having a weight average molecular weight of 26,000 and a glass transition temperature Tg of 62 ° C. Styrene acrylic resin A, which is a copolymer resin, was synthesized.

(Production Example 1-4)
<Synthesis of amorphous resin>
-Synthesis of amorphous polylactic acid resin A-
In a 500 mL four-neck separable flask, 195 g of L-lactide, 105 g of D-lactide (L-form / D-form = 65/35 by weight ratio), and 1.8 g of ethylene glycol were added, and the mixture was heated at 40 ° C. for 5 hours After drying, the internal temperature was gradually raised to 150 ° C., and after confirming that the system had been homogenized by visual observation, 50 mg of tin 2-ethylhexanoate was added to cause a polymerization reaction. At this time, the internal temperature of the system was controlled so as not to exceed 190 ° C. After the reaction time of 2 hours, the system was cooled to 175 ° C., switched to the outflow line again, delactideed under conditions of 10 mmHg for 60 minutes, and the polymerization reaction was completed to obtain polylactic acid A. The weight average molecular weight (Mw) of this resin was 26,000.

(Production Example 1-5)
<Synthesis of amorphous resin>
-Synthesis of amorphous polylactic acid resin B-
In a 500 mL four-necked separable flask, 90 g of L-lactide, 210 g of meso lactide (L isomer / meso isomer 30/70 by weight) and 1.8 g of ethylene glycol were added and dried at 40 ° C. for 5 hours. Thereafter, the internal temperature was gradually raised to 150 ° C., and after confirming that the system had been homogenized by visual observation, 50 mg of tin 2-ethylhexanoate was added to cause a polymerization reaction. At this time, the internal temperature of the system was controlled so as not to exceed 190 ° C. After the reaction time of 2 hours, the system was cooled to 175 ° C., switched to the outflow line again, delactideed under conditions of 10 mmHg for 60 minutes, and the polymerization reaction was completed to obtain polylactic acid B. The weight average molecular weight (Mw) of this resin was 25,000.

(Production Example 2-1)
<Crystalline polyester resin>
-Synthesis of crystalline polyester resin 1-
In a 5 liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, put 2,320 g of sebacic acid, 1,430 g of ethylene glycol, and 4.9 g of hydroquinone, and react at 190 ° C. for 4 hours. Then, the temperature was raised to 220 ° C. and reacted for 3 hours, and further reacted at 7.8 kPa for 1 hour to obtain crystalline polyester resin 1. Table 1 shows the measurement results of melting point, recrystallization temperature, and solubility in organic solvents (solubility per 100 g of ethyl acetate at 45 ° C.).

(Production Example 2-2)
<Crystalline polyester resin>
-Synthesis of crystalline polyester resin 2-
Into a 5 liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,320 g of sebacic acid, 1,430 g of 1,6-hexanediol, and 4.9 g of hydroquinone were added, and 190 ° C. Then, the temperature was raised to 220 ° C. and reacted for 3 hours, and further reacted at 7.8 kPa for 1 hour to obtain crystalline polyester resin 2. Table 1 shows the measurement results of melting point, recrystallization temperature, and solubility in organic solvents (solubility per 100 g of ethyl acetate at 45 ° C.).

(Production Example 2-3)
<Crystalline polyester resin>
-Synthesis of crystalline polyester resin 3-
In a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 2,320 g of 1,10-decanedioic acid, 1,430 g of 1,8-octanediol, 4.9 g of hydroquinone The mixture was reacted at 190 ° C. for 4 hours, heated to 220 ° C., reacted for 3 hours, and further reacted at 7.8 kPa for 1 hour to obtain crystalline polyester resin 3. Table 1 shows the measurement results of melting point, recrystallization temperature, and solubility in organic solvents (solubility per 100 g of ethyl acetate at 45 ° C.).

(Production Example 2-4)
<Crystalline polyester resin>
-Synthesis of crystalline polyester resin 4-
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,320 g of 1,10-decanedioic acid, 1,430 g of ethylene glycol, and 4.9 g of hydroquinone were added. After making it react at 4 degreeC for 4 hours, it heated up at 220 degreeC and made it react for 3 hours, and also it was made to react at 7.8 kPa for 1 hour, and the crystalline polyester resin 4 was obtained. Table 1 shows the measurement results of melting point, recrystallization temperature, and solubility in organic solvents (solubility per 100 g of ethyl acetate at 45 ° C.).

(Production Example 2-5)
<Crystalline polyester resin>
-Synthesis of crystalline polyester resin 5-
Into a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple, 2,320 g of sebacic acid, 1,430 g of ethylene glycol, and 4.9 g of hydroquinone were added and reacted at 200 ° C. for 10 hours. Then, the temperature was raised to 230 ° C. and reacted for 3 hours, and further reacted at 8.3 kPa for 4 hours to obtain crystalline polyester resin 5. Table 1 shows the measurement results of melting point, recrystallization temperature, and solubility in organic solvents (solubility per 100 g of ethyl acetate at 45 ° C.).

(Example 1)
<Preparation of Toner 1>
-Preparation of colorant dispersion-
First, a carbon black dispersion was prepared as a colorant.
20 parts of carbon black (Regal 400, manufactured by Cabot) and 2 parts of a pigment dispersant (Ajisper PB821, manufactured by Ajinomoto Fine Techno Co., Ltd.) were primarily dispersed in 78 parts of ethyl acetate using a mixer having stirring blades. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Further, a carbon black dispersion liquid was prepared by passing through a polytetrafluoroethylene (PTFE) filter (Fluorinert membrane filter FHLP09050, Nihon Millipore Corporation) having 0.45 μm pores and dispersing to a submicron region.

-Preparation of toner composition liquid-
Ester wax having 676.7 parts of ethyl acetate, 30 parts of [Crystalline Polyester Resin 1] as a crystalline substance, 243.3 parts of [Amorphous Polyester Resin A] as an amorphous resin, and the following properties as a release agent 10 parts were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 1] and [Amorphous Polyester Resin A] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.
The release agent is a synthetic ester wax mainly composed of an aliphatic ester having a melting point of 68.9 ° C. and a recrystallization temperature of 61.2 ° C. (WFP-4: manufactured by NOF Corporation).
The boiling point of ethyl acetate is 76.8 ° C.

-Preparation of toner base particles-
The obtained toner composition liquid was discharged under the following conditions using the toner manufacturing apparatus of FIG. 9 having the liquid droplet discharge head shown in FIG. After discharging the droplets, the droplets were dried and solidified by a droplet solidifying means using dry nitrogen, and after the cyclone was collected, they were further subjected to 40 ° C./50% RH for 48 hours at 35 ° C./90% RH. The toner base particles were prepared by air blowing and drying at 50 ° C./50% RH for 24 hours.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.

[Production equipment conditions]
Length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 65 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

  Next, 2.8 parts of commercially available silica fine powder [NAX50] (manufactured by Nippon Aerosil Co., Ltd .; average primary particle size of 30 nm), [H20TM] (manufactured by Clariant) with respect to 100 parts of the toner base particles obtained as described above. 0.9 parts of an average primary particle size of 20 nm) was mixed with a Henschel mixer, and passed through a sieve having an opening of 60 μm to remove coarse particles and aggregates, thereby obtaining [Toner 1].

Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 1] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 1].
With respect to [Toner 1], each physical property value was obtained by the above-described measurement. The results are shown in Table 2.

<Production of developer and evaluation of developer>
<< Preparation and Evaluation of Two-Component Developer >>
4 parts of [Toner 1] and 96 parts of a magnetic carrier described below were mixed by a ball mill to obtain a two-component developer 1.

-Production of carrier-
Silicone resin (organostraight silicone) 100 parts Toluene 100 parts γ- (2-Aminoethyl) aminopropyltrimethoxysilane 5 parts Carbon black 10 parts The above mixture was dispersed with a homomixer for 20 minutes to prepare a coating layer forming solution. This coating layer forming liquid was coated on the surface of 1,000 parts of spherical magnetite having a particle size of 50 μm using a fluid bed type coating apparatus to obtain a magnetic carrier.

  Using an image forming apparatus using [Developer 1] containing [Toner 1], low-temperature fixability, hot offset property, charging stability, background stain, and image stability were evaluated by the evaluation methods described below. The results are shown in Table 3.

[Low temperature fixability]
Using a commercially available copier Ricoh Co. imageo Neo C600 as a developer, an image that forms a 3 cm x 5 cm rectangle on A4 size paper (T6000 70W T, manufactured by Ricoh Co., Ltd.) from the top of the paper. A toner sample having an adhesion amount of 0.85 mg / cm ² was prepared at a position of 5 cm. Subsequently, the temperature of the fixing member was increased from 90 ° C. every 10 ° C. and fixed at a linear speed of 300 mm / sec (toner weight was calculated from the weight of the paper before and after image output). The output image was rubbed by hand, and the temperature at which the toner could not be peeled was evaluated as the minimum fixing temperature.
-Evaluation criteria-
A: Lower fixing temperature is less than 100 ° C .: Lower fixing temperature is 100 ° C. or more and less than 110 ° C. Δ: Lower fixing temperature is 110 ° C. or more and less than 120 ° C. ×: Lower fixing temperature is 120 ° C. or more.

[Hot offset property]
The developer is put into a commercially available copier Ricoh Co. imageo Neo C600, and an image of a 3 cm × 5 cm rectangle is printed on the A4 size paper (T6000 70W T, manufactured by Ricoh Co., Ltd.) 5 cm from the front of the paper. A toner sample with an adhesion amount of 0.85 mg / cm ² was produced at the position of, and an image was output while changing the fixing temperature from a low temperature to a high temperature. The temperature at which the glossiness of the image was lowered or the case where an offset image was seen in the image was taken as the offset generation temperature.
-Evaluation criteria-
○: Offset generation temperature is 200 ° C. or higher. X: Offset generation temperature is lower than 200 ° C.

[Charging stability]
Using a tandem color image forming apparatus (image Neo Neo C600, manufactured by Ricoh Co., Ltd.) as a developer, the toner density is controlled so that the image density is 1.4 ± 0.2 on a chart with a 20% image area. However, the amount of change (μc / g) in the charge amount (μc / g) of the developer for electrophotography after outputting 200,000 sheets (the amount of decrease in charge amount after 200,000 sheets run / charge amount at the beginning of the run) is the initial value before output. And the following criteria. The charge amount was measured by a blow-off method.
-Evaluation criteria-
◎: Less than 15% ○: 15% or more and less than 30% △: 30% or more and less than 50% ×: 50% or more The amount of charge is reduced because the toner adheres to the electrophotographic carrier or the toner itself deteriorates. Therefore, it can be determined that the smaller the change in the charge amount before and after the run, the less the filming of the toner onto the electrophotographic carrier.

[Earth dirt evaluation]
By visually checking the degree of background contamination on the image background when 200,000 sheets of a 5% image area ratio chart are continuously output using a tandem color image forming apparatus (image Neo C600, manufactured by Ricoh Co., Ltd.) It was evaluated by.
-Evaluation criteria-
○: No toner adhesion is observed on the image background portion Δ: Toner adhesion is slightly observed when the image background portion is observed obliquely ×: The toner adhesion is clearly seen on the image background portion

[Image stability evaluation]
The developer is put in a commercially available copying machine (image Neo Neo 455, manufactured by Ricoh Co., Ltd.), and a continuous running test of 50,000 sheets is performed using a type 6000 paper manufactured by Ricoh Co., Ltd. with a printing ratio of 7% image occupancy. The image quality (image density, fine line reproducibility, background stain) on the 50,000th sheet was evaluated according to the following criteria.
-Evaluation criteria-
○: Even when the image is 50,000th, the image was as good as the initial image. Δ: Changed from the initial image in any of the evaluation items of image density, fine line reproducibility, and background stain, but changed from the initial image. X is within 30% x: When an evaluation change of image density, fine line reproducibility, or background stain causes a clear change from the initial image, and the change from the initial image is 30% or more

<< Preparation and Evaluation of One-Component Developer >>
Using an image forming apparatus using a one-component developer composed of [Toner 1], low-temperature fixing property, hot offset property, anti-sticking property, background stain and image stability were evaluated by the evaluation methods described below. The results are shown in Table 3.

[Low temperature fixability]
Prepare a Ricoh IPSiO SP C220 modified so that the fixing roll temperature can be changed to an arbitrary value, set a transfer paper (“TYPE 6200”; manufactured by Ricoh Co., Ltd.), and the amount of each toner attached is 1. A solid image of 00 ± 0.05 mg / cm ² was formed.
The fixing roll temperature was increased from 100 ° C. every 10 ° C., and an image was output. The output image was rubbed by hand, and the temperature at which the toner could not be peeled was evaluated as the minimum fixing temperature.
-Evaluation criteria-
A: Lower fixing temperature is less than 110 ° C .: Lower fixing temperature is 110 ° C. or more and less than 120 ° C. Δ: Lower fixing temperature is 120 ° C. or more and less than 130 ° C. ×: Lower fixing temperature is 130 ° C. or more.

[Hot offset property]
Prepare a Ricoh IPSiO SP C220 modified so that the fixing roll temperature can be changed to an arbitrary value, set a transfer paper (“TYPE 6200”; manufactured by Ricoh Co., Ltd.), and the amount of each toner attached is 1. A solid image of 00 ± 0.05 mg / cm ² was formed, and the image was output while changing the fixing temperature from a low temperature to a high temperature. The temperature at which the glossiness of the image was lowered or the case where an offset image was seen in the image was taken as the offset generation temperature.
-Evaluation criteria-
○: Offset generation temperature is 200 ° C. or higher. X: Offset generation temperature is lower than 200 ° C.

[Stickness resistance]
After outputting 2,000 white solid images using Ricoh Co., Ltd. IPSiO SP C220, the toner adhered to the regulating blade was evaluated in four stages.
The experiment was performed in an environment with a temperature of 27 degrees and a humidity of 40%.
-Evaluation criteria-
◎: Very good level without toner adhesion ○: Level where toner adhesion is not noticeable and does not affect image quality △: Level where toner adhesion is present and affects image quality ×: Level where toner adhesion is noticeable and greatly affects image quality

[Soil dirt]
The toner was put in a Bk cartridge of Ricoh Co., Ltd. IPSiO SP C220, and the white paper and the photoreceptor were observed when the white paper was printed out.
The experiment was performed in an environment with a temperature of 27 degrees and a humidity of 40%.
-Evaluation criteria-
A: No toner adhesion is observed on the white paper or the photoreceptor. B: No toner adhesion is observed on the white paper, but a slight toner adhesion is observed when the photoreceptor is observed obliquely. : Observed with a slight amount of toner when observed with the white paper slanted ×: Clearly toner adhering to the white paper

[Image stability]
Using RICOH Co., Ltd. IPSiO SP C220, 2000 image charts of initial and 1% image area were output, then a black solid image was output to RICOH TYPE 6000 paper, and the image density was measured by a spectral densitometer (X-Rite). The density change before and after the output of 2000 sheets was evaluated.
-Evaluation criteria-
◎: Difference is less than 0.1% ○: Difference is 0.1% or more and less than 0.2% △: Difference is less than 0.2% and less than 0.3% ×: Difference is 0.3% or more

[Comprehensive evaluation score]
About each evaluation result, the comprehensive evaluation score was computed as (double-circle): 3 point, (circle): 2 point, (triangle | delta): 1 point, x: 0 point, and un-evaluable (-): 0 point. A larger overall score indicates a better result.

(Example 2)
[Toner 2] was obtained in the same manner as in Example 1 except that the preparation of the toner composition liquid and the preparation of the toner base particles were performed as follows.

-Preparation of toner composition liquid-
Ester wax of Example 1 as a release agent in 676.7 parts of ethyl acetate, 30 parts of [crystalline polyester resin 2] as a crystalline substance, 243.3 parts of [amorphous polyester resin A] as an amorphous resin 10 parts were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 2] and [Amorphous Polyester Resin A] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
The same manufacturing apparatus as in Example 1 was used, except that the droplet discharge conditions were changed as follows, and the same procedure as in Example 1 was performed. After droplets were discharged, droplet solidification using dry nitrogen was performed. The droplets are dried and solidified by means, and collected in a cyclone, and further blown at 35 ° C./90% RH for 48 hours, 40 ° C./50% RH for 24 hours, and 50 ° C./50% RH for 24 hours. By drying, toner base particles were prepared.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 65 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The toner base particles thus obtained were carried out in the same manner as in Example 1 to obtain toner 2.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 2] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 2].
For [Toner 2], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 2] containing [Toner 2], the low-temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 3)
[Toner 3] was obtained in the same manner as in Example 1 except that the preparation of the toner composition liquid and the preparation of the toner base particles were performed as follows.

-Preparation of toner composition liquid-
Ester wax of Example 1 as a release agent in 676.7 parts of ethyl acetate, 30 parts of [crystalline polyester resin 2] as a crystalline substance, 243.3 parts of [amorphous polyester resin A] as an amorphous resin 10 parts were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 2] and [Amorphous Polyester Resin A] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
The same manufacturing apparatus as in Example 1 was used, except that the droplet discharge conditions were changed as follows, and the same procedure as in Example 1 was performed. After droplets were discharged, droplet solidification using dry nitrogen was performed. The droplets are dried and solidified by means, and collected in a cyclone, and further blown at 35 ° C./90% RH for 48 hours, 40 ° C./50% RH for 24 hours, and 50 ° C./50% RH for 24 hours. By drying, toner base particles were prepared.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 70 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The obtained toner base particles were carried out in the same manner as in Example 1 to obtain toner 3.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 3] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 3].
For [Toner 3], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 3] containing [Toner 3], the low-temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 4
[Toner 4] was obtained in the same manner as in Example 1 except that the preparation of the toner composition liquid and the preparation of the toner base particles were performed as follows.

-Preparation of toner composition liquid-
Ester wax of Example 1 as a release agent in 676.7 parts of ethyl acetate, 10 parts of [crystalline polyester resin 2] as a crystalline substance, 273.3 parts of [amorphous polyester resin A] as an amorphous resin 10 parts were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 2] and [Amorphous Polyester Resin A] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
The same manufacturing apparatus as in Example 1 was used, except that the droplet discharge conditions were changed as follows, and the same procedure as in Example 1 was performed. After droplets were discharged, droplet solidification using dry nitrogen was performed. The droplets are dried and solidified by means, and collected in a cyclone, and further blown at 35 ° C./90% RH for 48 hours, 40 ° C./50% RH for 24 hours, and 50 ° C./50% RH for 24 hours. By drying, toner base particles were prepared.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 60 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The toner base particles thus obtained were carried out in the same manner as in Example 1 to obtain toner 4.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 4] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 4].
With respect to [Toner 4], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 4] containing [Toner 4], the low-temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 5)
[Toner 5] was obtained in the same manner as in Example 1 except that the preparation of the toner composition liquid and the preparation of the toner base particles were performed as follows.

-Preparation of toner composition liquid-
Ester wax of Example 1 as a release agent in 676.7 parts of ethyl acetate, 10 parts of [crystalline polyester resin 3] as a crystalline substance, 273.3 parts of [amorphous polyester resin A] as an amorphous resin 10 parts were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 3] and [Amorphous Polyester Resin A] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
The same manufacturing apparatus as in Example 1 was used, except that the droplet discharge conditions were changed as follows, and the same procedure as in Example 1 was performed. After droplets were discharged, droplet solidification using dry nitrogen was performed. The droplets are dried and solidified by means, and collected in a cyclone, and further blown at 35 ° C./90% RH for 48 hours, 40 ° C./50% RH for 24 hours, and 50 ° C./50% RH for 24 hours. By drying, toner base particles were prepared.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 75 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The toner base particles thus obtained were carried out in the same manner as in Example 1 to obtain toner 5.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 5] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 5].
For [Toner 5], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 5] containing [Toner 5], the low-temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 6)
[Toner 6] was obtained in the same manner as in Example 1, except that the preparation of the toner composition liquid and the preparation of the toner base particles were performed as follows.

-Preparation of toner composition liquid-
Ester wax of Example 1 as a release agent in 676.7 parts of ethyl acetate, 10 parts of [Crystalline Polyester Resin 4] as a crystalline substance, 273.3 parts of [Amorphous Polyester Resin B] as an amorphous resin 10 parts were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 4] and [Amorphous Polyester Resin B] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
Using the same production apparatus as in Example 1, a step of applying ethyl acetate mist was added so that the relative humidity of ethyl acetate with respect to saturation humidity at 60 ° C. was 11%, and the droplet discharge conditions were as follows: Except for such a change, the same operation as in Example 1 was performed, and after the droplets were discharged, the droplets were dried and solidified by a droplet solidifying means using dry nitrogen, and the cyclone was further collected. The toner base particles were prepared by air drying for 48 hours at 40 ° C./90% RH, 24 hours at 40 ° C./50% RH, and 24 hours at 50 ° C./50% RH.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L in the longitudinal direction of the liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 70 ° C
Ethyl acetate relative humidity (in nitrogen stream): 11%
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The toner base particles thus obtained were carried out in the same manner as in Example 1 to obtain toner 6.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 6] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 6].
For [Toner 6], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 6] containing [Toner 6], the low-temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 7)
[Toner 7] was obtained in the same manner as in Example 1 except that the preparation of the toner composition liquid and the preparation of the toner base particles were performed as follows.

-Preparation of toner composition liquid-
To 676.7 parts of ethyl acetate, 10 parts of [crystalline polyester resin 4] as a crystalline substance, 215.6 parts of [amorphous polyester resin B] as an amorphous resin, and 57 of [amorphous styrene acrylic resin A] .7 parts, 10 parts of the ester wax of Example 1 as a release agent were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 4], [Amorphous Polyester Resin B], and [Amorphous Styrene Acrylic Resin A] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
The same manufacturing apparatus as in Example 1 was used, except that the droplet discharge conditions were changed as follows, and the same procedure as in Example 1 was performed. After droplets were discharged, droplet solidification using dry nitrogen was performed. The droplets are dried and solidified by means, and collected in a cyclone, and further blown at 35 ° C./90% RH for 48 hours, 40 ° C./50% RH for 24 hours, and 50 ° C./50% RH for 24 hours. By drying, toner base particles were prepared.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L in the longitudinal direction of the liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 70 ° C
Ethyl acetate relative humidity (in nitrogen stream): 40%
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The toner base particles thus obtained were carried out in the same manner as in Example 1 to obtain toner 7.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 7] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 7].
For [Toner 7], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 7] containing [Toner 7], the low temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Example 8)
[Toner 8] was obtained in the same manner as in Example 1 except that the toner composition liquid was prepared as follows.

-Preparation of toner composition liquid-
In 676.7 parts of ethyl acetate, 30 parts of [crystalline polyester resin 2] as a crystalline substance, 243.3 parts of [amorphous polylactic acid resin A] as an amorphous resin, and the ester of Example 1 as a release agent 10 parts of the wax were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 2] and [Amorphous Polylactic Acid Resin A] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
After the droplets were discharged under the same manufacturing apparatus and droplet discharge conditions as in Example 1, the droplets were dried and solidified by a droplet solidifying means using dry nitrogen, and the cyclone was collected. The toner base particles were produced by blowing and drying at 90% RH for 48 hours, at 40 ° C./50% RH for 24 hours, and at 50 ° C./50% RH for 24 hours.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 65 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The obtained toner base particles were carried out in the same manner as in Example 1 to obtain toner 8.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 8] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 8].
With respect to [Toner 8], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 8] containing [Toner 8], the low-temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Example 9
In [Example 1], [Toner 9] was obtained in the same manner as in Example 1 except that the toner composition liquid was prepared as follows.

-Preparation of toner composition liquid-
In 676.7 parts of ethyl acetate, 30 parts of [crystalline polyester resin 2] as a crystalline substance, 243.3 parts of [amorphous polylactic acid resin B] as an amorphous resin, and the ester of Example 1 as a release agent 10 parts of the wax were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 2] and [Amorphous Polylactic Acid Resin B] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., and 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
After the droplets were discharged under the same manufacturing apparatus and droplet discharge conditions as in Example 1, the droplets were dried and solidified by a droplet solidifying means using dry nitrogen, and the cyclone was collected. The toner base particles were produced by blowing and drying at 90% RH for 48 hours, at 40 ° C./50% RH for 24 hours, and at 50 ° C./50% RH for 24 hours.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 55 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 65 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The toner base particles thus obtained were carried out in the same manner as in Example 1 to obtain toner 9.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 9] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 9].
With respect to [Toner 9], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 9] containing [Toner 9], the low-temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 1)
[Toner 10] was obtained in the same manner as in Example 1 except that the preparation of the toner composition liquid and the preparation of the toner base particles were performed as follows.

-Preparation of toner composition liquid-
Ester wax of Example 1 as a release agent in 676.7 parts of ethyl acetate, 10 parts of [crystalline polyester resin 5] as a crystalline substance, 273.3 parts of [amorphous polyester resin B] as an amorphous resin 10 parts were mixed and dissolved at 70 ° C. using a mixer having stirring blades. Both [Crystalline Polyester Resin 5] and [Amorphous Polyester Resin B] were transparently dissolved in ethyl acetate without phase separation. After dissolution, the liquid temperature was adjusted to 40 ° C., and further 100 parts of the carbon black dispersion was mixed and stirred for 10 minutes to prepare a toner composition liquid.

-Preparation of toner base particles-
The same manufacturing apparatus as in Example 1 was used, except that the droplet discharge conditions were changed as follows, and the same procedure as in Example 1 was performed. After droplets were discharged, droplet solidification using dry nitrogen was performed. The droplets are dried and solidified by means, and collected in a cyclone, and further blown at 35 ° C./90% RH for 48 hours, 40 ° C./50% RH for 24 hours, and 50 ° C./50% RH for 24 hours. By drying, toner base particles were prepared.
Note that the temperature of the toner composition liquid and the member of the toner manufacturing apparatus with which the toner composition liquid comes into contact were controlled at 40 ° C. The toner was continuously produced for 6 hours, but the discharge holes were not clogged.
[Production equipment conditions]
Length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening diameter: 8.0 μm
Drying temperature (nitrogen): 75 ° C
Drive frequency: 340 kHz
Applied voltage to piezoelectric body: 10.0V

The obtained toner base particles were carried out in the same manner as in Example 1 to obtain toner 10.
Table 1 shows the characteristics of the crystalline polyester resin constituting the toner base particles of [Toner 10] and the manufacturing conditions in the droplet solidification step during the manufacturing process of the toner base particles of [Toner 10].
With respect to [Toner 10], each physical property value was determined by the above-described measurement in the same manner as in Example 1. The results are shown in Table 2.
Using an image forming apparatus using [Developer 10] containing [Toner 10], the low-temperature fixing property, hot offset property, charging stability, background stain, and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 3.

Aspects of the present invention are as follows, for example.
<1> A toner containing at least an amorphous resin and a crystalline substance as a binder resin,
In the split cross-sectional image of the toner in the transmission electron microscope (TEM), the crystalline substance is
The number average particle diameter of the crystalline substance existing in the depth region Aa from the toner surface to 1/6 (1 / 6d) of the toner diameter d is CDa,
The relationship between CDa and CDc when the number average particle diameter of the crystalline substance existing in a circular central region Ac having a radius of 1 / 6d and centering on the toner is CDc satisfies the following relationship. The toner is characterized by the following.
CDa <CDc
<2> In the toner region, when the region other than the Aa and the Ac is Ab, the CDa, CDb, and CDc of the crystalline substance existing in the Ab are CDa when the number average particle diameter of the crystalline material is CDb. The toner according to <1>, wherein the relationship satisfies the following relationship.
CDa <CDb <CDc
<3> The toner according to any one of <1> to <2>, wherein the crystalline substance has a solubility of 10 g or more per 100 g of ethyl acetate at 45 ° C.
<4> The toner according to any one of <1> to <3>, wherein the crystalline substance has a melting point of less than 65 ° C.
<5> The toner according to any one of <1> to <4>, wherein the crystalline substance has a number average particle diameter CDa of 60 nm to 140 nm.
<6> The toner according to any one of <1> to <5>, wherein the crystalline substance has a number average particle size CDb of 200 nm to 240 nm.
<7> The toner according to any one of <1> to <6>, wherein the crystalline substance has a number average particle size CDc of 210 nm to 350 nm.
<8> The toner according to any one of <1> to <7>, wherein the ratio of the number average particle diameter CDa to CDc (CDc / CDa) of the crystalline substance is 3.0 to 3.5. .
<9> The toner according to any one of <1> to <8>, wherein the crystalline substance includes a crystalline polyester resin as a main component.
<10> The toner according to any one of <1> to <9>, wherein the amorphous resin contains a polyester resin as a main component.
<11> The molecular weight distribution by GPC of the soluble part of orthodichlorobenzene of the crystalline polyester resin is 3,000 to 30,000 in weight average molecular weight (Mw) and 1,000 to 10 in number average molecular weight (Mn). The toner according to any one of <9> to <10>, wherein the toner is 1 to 10 at 1,000, Mw / Mn.
<12> The content of the crystalline polyester resin is a value obtained by converting the endothermic amount of the crystalline polyester resin obtained by a DSC (differential scanning calorimeter) method into mass, and is 1% by mass to 50% by mass with respect to the toner. The toner according to any one of <9> to <11>.
<13> The volume average particle size of the toner is 1 μm to 8 μm, and the particle size distribution (volume average particle size / number average particle size) is in the range of 1.00 to 1.15. 12>.
<14> In a distribution in which the toner has a number particle diameter and frequency (number) plotted, the toner has a frequency (number) of 1.21 times to 1.31 times the number particle diameter (mode diameter) with the highest frequency (number). The toner according to any one of <1> to <13>, wherein the toner has a second frequency (number) peak in the range of the number particle diameter.
<15> The method for producing a toner according to any one of <1> to <14>,
A droplet forming step of discharging a toner composition solution in which at least an amorphous resin and a crystalline substance as a binder resin are dissolved or dispersed in an organic solvent to form droplets; and solidifying the droplets to form toner particles And a droplet solidifying step of forming the toner.
<16> The liquid droplet forming step forms a standing wave by liquid column resonance by applying vibration to the toner composition liquid in the liquid column resonance liquid chamber in which at least one or more discharge ports are formed. The method for producing a toner according to <15>, wherein the toner composition liquid is ejected from the ejection port arranged in a region where the standing wave becomes an antinode to form droplets.
<17> In the toner composition liquid, the amorphous resin and the crystalline substance are dissolved without phase separation, and the environmental temperature of the droplet solidification step is determined by the DSC method of the crystalline substance. When the crystallization temperature is Tc (° C.), it is (Tc−5) ° C. or more, and in the toner particles in which droplets are solidified, the amorphous resin and the crystalline substance are phase-separated <15 > To <16>.
<18> In the toner composition liquid, the amorphous resin and the crystalline substance are dissolved without phase separation, and the environmental temperature of the droplet solidification step is determined by the DSC method of the crystalline substance. When the crystallization temperature is Tc (° C.), the relative humidity based on the organic solvent of the toner composition liquid in the environment of the droplet solidification step is less than (Tc-5) ° C. and is 10% to 40%. %. The toner production method according to any one of <15> to <16>, wherein the amorphous resin and the crystalline substance are phase-separated in the toner particles in which droplets are solidified. is there.
<19> The <15> to <18>, wherein the temperature of the toner composition liquid at the environmental temperature of the droplet solidifying step is less than (Tb-15) ° C. when the boiling point of the organic solvent is Tb (° C.). Or a toner production method according to any one of the above.
<20> A developer containing at least the toner according to any one of <1> to <14>.
<21> The developer according to <20>, further including a carrier.
<22> an electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising a developer for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image;
An image forming apparatus, wherein the developer is the developer described in any one of <20> to <21>.
<23> an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A development step of developing the electrostatic latent image formed on the electrostatic latent image carrier using a developer to form a toner image,
The image forming method, wherein the developer is the developer according to any one of <20> to <21>.
<24> an electrostatic latent image carrier;
Developing means comprising a developer for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image is integrally supported,
A process cartridge, wherein the developer is the developer according to any one of <20> to <21>.

1: Toner production apparatus 2: Droplet discharge means 9: Elastic plate 10: Liquid column resonance droplet discharge unit 11: Liquid column resonance droplet discharge means 12: Air flow passage 13: Raw material container 14: Toner composition liquid 15: Liquid Circulation pump 16: Liquid supply pipe 17: Liquid common supply path 18: Liquid column resonance flow path 19: Discharge hole 20: Vibration generating means 21: Liquid droplet 22: Liquid return pipe 24: Nozzle angle 30: Exposure device 40: Developer 41: Thin film 50: Intermediate transfer member 51: Roller 58: Corona charger 60: Drying collecting means 61: Chamber 62: Toner collecting means 63: Toner storage part 64: Conveying airflow inlet 65: Conveying airflow outlet 70: Static elimination lamp 80: Transfer roller 90: Cleaning device 95: Transfer paper 100: Photosensitive drum 100A: Color image forming apparatus 101: Downstream air flow 110: Process cartridge 200: Charging roller 410: Developing belt DOO 600: Cleaning apparatus P1: hydraulic pressure gauge P2: chamber pressure gauge

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 05-045929 A JP 11-249339 A JP 2001-117268 A JP 2001-222138 A JP 2007-271789 A Japanese Patent Laid-Open No. 2002-214821

Claims (10)

A toner containing at least an amorphous resin and a crystalline substance as a binder resin,
In the split cross-sectional image of the toner in the transmission electron microscope (TEM), the crystalline substance is
The number average particle diameter of the crystalline substance existing in the depth region Aa from the toner surface to 1/6 (1 / 6d) of the toner diameter d is CDa,
The relationship between CDa and CDc when the number average particle diameter of the crystalline material existing in the circular central region Ac having a radius of 1 / 6d and centering on the toner is CDc satisfies the following relationship. Toner.
CDa <CDc In the toner region, when the region other than the Aa and the Ac is Ab, the relationship between CDa, CDb, and CDc when the number average particle diameter of the crystalline substance existing in the Ab is CDb is The toner according to claim 1, wherein the toner satisfies the following relationship.
CDa <CDb <CDc   The toner according to claim 1, wherein the number average particle diameter CDa of the crystalline substance is 60 nm to 140 nm.   4. The toner according to claim 1, wherein the number average particle diameter CDb of the crystalline substance is 200 nm to 240 nm.   The toner according to claim 1, wherein the crystalline substance has a number average particle diameter CDc of 210 nm to 350 nm. A method for producing the toner according to any one of claims 1 to 5,
A droplet forming step of discharging a toner composition solution in which at least an amorphous resin and a crystalline substance as a binder resin are dissolved or dispersed in an organic solvent to form droplets; and solidifying the droplets to form toner particles And a droplet solidifying step of forming the toner.   A developer comprising at least the toner according to claim 1. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising a developer for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image;
The image forming apparatus according to claim 7, wherein the developer is the developer according to claim 7. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A development step of developing the electrostatic latent image formed on the electrostatic latent image carrier using a developer to form a toner image,
The image forming method according to claim 7, wherein the developer is the developer according to claim 7. An electrostatic latent image carrier;
Developing means comprising a developer for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image is integrally supported,
The process cartridge according to claim 7, wherein the developer is the developer according to claim 7.