JP4662475B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic charge image that has both hot offset resistance and low-temperature fixability and hardly contaminates a contact partner.

(Dispersed state of release agent)
It is known to add a fixing release material such as wax to the toner to prevent offset during fixing, but if the characteristics of the wax or the state of dispersion in the toner are inappropriate, it will With long-term use, the phenomenon of wax detaching from or exuding from the toner surface occurs, and in two-component developers, contamination of the carrier surface occurs, thereby deteriorating the charging characteristics of the toner. In addition, in the case of a one-component developer, the toner is often fused to a developing roller or a blade for thinning the toner, thereby hindering uniform development of the toner.

  Toners obtained by the conventional kneading and pulverization method are generally irregular in shape, the particle size distribution is broad, the fluidity is low, the transferability is low, the fixing energy is high, and the charge amount between the toner particles is high. There was a problem that it was non-uniform and charging stability was low. Particularly in fixing, a kneading and pulverizing type toner prepared by a pulverization method has a large amount on the surface because the pulverization is broken at the interface of the release agent (wax), so that a release effect is easily produced. Furthermore, adhesion to the blade was likely to occur, and the performance was unsatisfactory.

On the other hand, in order to overcome the problems of the toner by the kneading and pulverizing method, a method for producing the toner by the polymerization method has been proposed. Since this method does not include a pulverization step, the toner does not require a kneading step and a pulverization step, which contributes to cost savings such as energy saving, production time reduction, and product yield improvement. large. In addition, the particle size distribution in the polymerized toner particles obtained by such a polymerization method is easy to form a sharp distribution as compared with the particle size distribution of the toner by the pulverization method, and it is easy to encapsulate the wax. It is possible to greatly improve the performance. It is also easy to obtain a spherical toner.
However, there are many problems that have not yet been solved in the toner produced by the polymerization method.

(Suspension polymerization toner)
The suspension polymerization method is a method in which a toner composition such as a polymerizable monomer, a polymerization initiator and a colorant is suspended in an aqueous medium containing a dispersant and then polymerized to obtain toner particles. . In this production method, a binder resin is produced substantially by a polymerization reaction of a styrene monomer and an acrylic monomer. However, since this method is difficult to control the molecular weight, fixing characteristics, that is, low-temperature fixability, hot offset resistance, and fixing There is a problem that it is difficult to design the viscoelasticity of the resin so as to satisfy both the bleeding property of the release agent and the glossiness of the image at the same time. Another problem is that styrene monomers and acrylic monomers are harmful to the human body. Patent Document 1 (Japanese Patent Laid-Open No. 2005-148455), Patent Document 2 (Japanese Patent Laid-Open No. 2004-333841), Patent Document 3 (Japanese Patent No. 3308918), Patent Document 4 (Japanese Patent Laid-Open No. 10-171156), Patent Document 5 (Japanese Patent Laid-Open No. 10-282822) appropriately defines the viscoelastic characteristics of the toner, but none of them satisfy the image glossiness and the fixing characteristics required for full color at the same time.

  Further, since this manufacturing method does not have means for finely dispersing the wax in the toner, the obtained toner is encapsulated without finely dispersing the wax, and the outer shell is made of binder resin and the inner shell is made of wax. A core-shell structure is formed. Therefore, when the toner is used in an actual machine, the adhesion of the wax to the photoreceptor is reduced, but the toner fixing property is encapsulated as compared with the pulverization method in which the wax exists in the form of a particle interface. As a result, the wax is less likely to seep onto the toner surface. Therefore, if the binder resin is not properly viscoelastically designed to sufficiently exude the wax, the toner has poor releasability and poor fixing efficiency, that is, a toner that is disadvantageous for power consumption. End up.

(Dissolved suspension toner)
The dissolution suspension method, as disclosed in Patent Document 6 (Patent No. 3521659), disperses and dissolves a polymer as a binder resin and a toner composition in a volatile solvent such as a low-boiling organic solvent, This is an underwater granulation method in which a volatile solvent is removed after emulsification and droplet formation in an aqueous medium in which a dispersant is present, and is not accompanied by a polymerization reaction. This method is excellent in that a polyester having excellent low-temperature fixability and glossiness can be used. However, in the step of dispersing or dissolving the toner composition in a solvent, it does not dissolve or dissolves when a high molecular weight resin or a crosslinkable resin is added. However, since the viscosity of the liquid is increased, the productivity of the toner is remarkably deteriorated. Therefore, there is a problem in that the fixing characteristics cannot be sufficiently controlled because the high molecular weight resin or the cross-linked resin cannot be used freely.

Further, as described in Patent Document 7 (Japanese Patent No. 3225889) and Patent Document 8 (Japanese Patent No. 3456372), the obtained toner uniformly and finely disperses wax. Therefore, unlike the wax-encapsulated toner obtained by the suspension polymerization method, the wax exposed on the toner surface is partially present, and the releasing effect is likely to occur like the pulverized toner. The margin for adhesion is small.
In addition, if the wax does not exude effectively, the wax domain remains in the toner layer even after fixing to paper or OHP, and the scattering of incident light in the image increases, and There is a problem that color reproducibility and transparency of OHP deteriorate. Since light scattering occurs at the wax-resin interface, the smaller the wax dispersion diameter, the larger the area of the interface, which is disadvantageous for light scattering.

From the above, if there is a precondition that the wax can be sufficiently oozed out during fixing, it is considered preferable that the wax in the toner is contained in the center of the toner like a suspension polymerization toner. .
JP 2005-148455 A JP 2004-333841 A Japanese Patent No. 3308918 Japanese Patent Laid-Open No. 10-171156 Japanese Patent Laid-Open No. 10-282822 Japanese Patent No. 3521659 Japanese Patent No. 3225899 Japanese Patent No. 3456372

  An object of the present invention is to provide a toner that simultaneously satisfies the contamination of a photoreceptor, a carrier, a blade, and the like by wax, and the releasability at the time of fixing, and also provides image color reproducibility and transparency of OHP. It is to provide a toner excellent in the above.

To solve the problem of contamination of the photoreceptor, carrier, blade, etc. due to the wax, the wax may be completely encapsulated to form a core-shell structure in which the outer shell is a binder resin and the inner shell is a wax.
However, if the wax does not bleed out sufficiently at the time of fixing, not only the releasability at the time of fixing can be exhibited, but also the wax remains in the toner layer after fixing, and the color reproducibility on paper and the transparency of OHP deteriorate. End up.
Accordingly, the present inventors have found a viscoelastic property of a resin that is effective for exuding wax and that is excellent in low-temperature fixability and hot offset resistance.

That is, the said subject is solved by the following this invention.
(1) “In a toner containing at least a binder resin, a colorant, and a wax,
The wax exists as one domain in one toner particle, and is included in the center.
The storage elastic modulus G ′ (100 ° C.) at 100 ° C. of the toner is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ (Pa),
The storage elastic modulus G ′ (150 ° C.) at 150 ° C. of the toner is 1.0 × 10 ^{2 to} 1.0 × 10 ³ (Pa),
The ratio G ′ (150 ° C.) / G ′ (200 ° C.) of the storage elastic modulus G ′ (150 ° C.) of the toner at 150 ° C. and the storage elastic modulus G ′ (200 ° C.) of the toner at 200 ° C. is 0.5-2. And
An electrostatic charge characterized in that a temperature T (° C.) at which tan δ = 1 is 110 <T <130, tan δ> 1 at T-10 (° C.), and tan δ <1 at T + 10 (° C.). Image developing toner ",
(2) "The toner for developing an electrostatic charge image according to item (1), wherein the binder resin of the toner is a polyester resin",
(3) “The electrostatic image developing toner according to (1) or (2) above, wherein the polyester resin has at least a non-crosslinking component and a crosslinking component”;
(4) “Granulated in an O / W type dispersion liquid in which an oily phase of a toner material containing at least a binder resin or its precursor or monomer and a wax is dispersed in an aqueous medium in the form of droplets. The toner for developing an electrostatic charge image according to any one of (1) to (3), wherein the toner is basically composed of toner particles.
( 5 ) "The toner for developing an electrostatic charge image according to the above item (4), wherein the oily phase of the toner material is precipitated after the wax is dissolved by heating ",
( 6 ) "The polyester resin includes a urea-modified polyester, and the urea-modified polyester is obtained by crosslinking and / or stretching. The electrostatic image developing toner according to item (5) "
( 7 ) "The electrostatic charge image developing toner according to any one of items (1) to ( 6 ), wherein the wax content is 5 to 30% by weight of the total toner" ,
( 8 ) The electrostatic charge according to any one of (1) to ( 7 ), wherein the wax includes any one of paraffin wax, polyethylene wax, and polypropylene wax. Image Developing Toner "

  According to the present invention, it is possible to obtain a toner that simultaneously satisfies the contamination of a photoreceptor or the like with wax and good fixing properties, and is excellent in image color reproducibility and OHP transparency.

(Wax dispersion state)
In the toner of the present invention, the wax exists as one domain in one toner particle, and is contained in the center. This dispersion state can be confirmed by the following method.
The toner was embedded in an epoxy resin, sliced to about 100 μm, stained with ruthenium tetroxide, and then observed with a transmission electron microscope (TEM: H-9000H manufactured by Hitachi, Ltd.) at a magnification of 10000, and photographed. The dispersion state of the wax can be observed by image evaluation of this photograph.
Here, the definition of “wax exists as one domain in one toner particle” is as follows. That is, among the toner cross-sections observed by TEM, when 10 arbitrary toner particles whose major axis of the toner cross-section is “toner volume average particle diameter ± 0.5 μm” are observed, only one wax domain is contained. It means that there are 9 or more toner particles.
The definition of “enclosed in the center” is as follows. That is, among the toner cross sections observed by TEM, when 10 arbitrary toner particles whose major axis of the toner cross section is “volume average particle diameter of toner ± 0.5 μm” are observed, the distance from the toner surface to 0.5 μm is observed. This means that there are 9 or more toner particles in the surface layer where no wax is present.

(Viscoelastic properties of toner)
The toner of the present invention is a toner comprising at least a binder resin, a colorant, and a wax, and has the following viscoelastic characteristics.
(1) The storage elastic modulus G ′ (100 ° C.) at 100 ° C. of the toner is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ (Pa).
It is an index of low-temperature fixability and ease of wax exudation, and if it is less than 1.0 × 10 ³ , there is no problem with fixability and gloss, but the heat-resistant storage stability of the toner is not satisfied. If it is larger than 1.0 × 10 ⁴ , sufficient melting characteristics for the exudation of wax cannot be obtained.
(2) The storage elastic modulus G ′ (150 ° C.) at 150 ° C. of the toner is 1.0 × 10 ^{2 to} 1.0 × 10 ³ (Pa).
It is an index of low-temperature fixability and hot offset resistance. If it is less than 1.0 × 10 ² , hot offset resistance is not sufficient. If it is larger than 1.0 × 10 ³ , the low-temperature fixability is not sufficient.
(3) The ratio G ′ (150 ° C.) / G ′ (200 ° C.) of the storage elastic modulus G ′ (150 ° C.) of the toner at 150 ° C. and the storage elastic modulus G ′ (200 ° C.) of the toner at 200 ° C. is 0. 5-2
It is an index of hot offset resistance. If it is larger than 2, the hot offset resistance is not sufficient.
(4) When the temperature at which tan δ = 1 is assumed to be T (° C.), 110 <T <130, tan δ> 1 is always below T (° C.), and tan δ <1 is always above T (° C.) It is an index of ease of removal, and the wax tends to ooze out in a region where tan δ is greater than 1.

  The viscoelastic property of the toner is obtained by using HAAKE RheoStress RS50, fixing 1 g of a sample to a 20 mm parallel plate, and measuring at a frequency of 1 Hz, a temperature of 70 to 210 ° C., and a temperature increase rate of 3 ° C./min.

(Binder resin)
As the binder resin of the toner of the present invention, polyester is preferably used.
(polyester)
The polyester is obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyhydric alcohol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

The polycondensation reaction between a polyhydric alcohol (PO) and a polycarboxylic acid (PC) is carried out in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and heated to 150 to 280 ° C. while reducing the pressure as necessary. The produced water is distilled off to obtain a polyester having a hydroxyl group. The hydroxyl value of the polyester is preferably 5 or more, and the acid value of the polyester is usually 1 to 30, preferably 5 to 20. By giving an acid value, the toner tends to be negatively charged, and further, when fixing to a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly environmental fluctuation.
The weight average molecular weight is 10,000 to 400,000, preferably 20,000 to 200,000. A weight average molecular weight of less than 10,000 is not preferable because offset resistance deteriorates. On the other hand, if it exceeds 400,000, the low-temperature fixability is deteriorated.

  In addition to the unmodified polyester obtained by the above polycondensation reaction, the polyester preferably contains a urea-modified polyester. The urea-modified polyester is obtained by reacting a terminal carboxyl group or hydroxyl group of the polyester obtained by the above polycondensation reaction with a polyvalent isocyanate compound (PIC) to obtain a polyester prepolymer (A) having an isocyanate group. It is obtained by cross-linking and / or extending the molecular chain by the reaction of the amine with amines.

  Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

  The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

  The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acids (B5), and (B6) in which the amino group of (B1) to (B5) is blocked.

Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), And oxazolidine compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.
When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.

  The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  The urea-modified polyester is produced by a one-shot method or the like. Polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with polyvalent isocyanate (PIC), and the polyester prepolymer (A) which has an isocyanate group is obtained. Further, this (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a urea-modified polyester.

  When reacting (PIC) and when reacting (A) and (B), a solvent may be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran).

  In addition, in the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B), a reaction terminator can be used as necessary to adjust the molecular weight of the resulting urea-modified polyester. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester or the like is not particularly limited when the above-mentioned unmodified polyester is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. When the urea-modified polyester is used alone, its number average molecular weight is usually 2000 to 20000, preferably 2000 to 10000, more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

  By using the unmodified polyester and the urea-modified polyester in combination, the low-temperature fixability and the glossiness when used in a full-color image forming apparatus are improved. Therefore, it is preferable to use the urea-modified polyester alone. The unmodified polyester may include polyester modified with a chemical bond other than a urea bond.

  The unmodified polyester and the urea-modified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, it is preferable that the unmodified polyester and the urea-modified polyester have a similar composition.

  The weight ratio of unmodified polyester to urea-modified polyester is usually 20/80 to 95/5, preferably 70/30 to 95/5, more preferably 75/25 to 95/5, and particularly preferably 80 /. 20-93 / 7. When the weight ratio of the urea-modified polyester is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The glass transition point (Tg) of the binder resin containing unmodified polyester and urea-modified polyester is usually 45 to 65 ° C, preferably 45 to 60 ° C. If it is less than 45 ° C., the heat resistance of the toner deteriorates, and if it exceeds 65 ° C., the low-temperature fixability becomes insufficient.
In addition, since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the heat-resistant storage stability tends to be good even when the glass transition point is low as compared with known polyester-based toners.

(Toner production method)
Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.

(1) A toner material liquid (oil phase) is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

The toner material liquid has at least the wax dispersed in the oily phase. The volume average particle diameter of the dispersed particles of the wax is not particularly limited and may be appropriately selected according to the purpose. However, in the present invention, the wax is present as one domain in one toner particle. Since it is the characteristic, 0.6-3 micrometers is preferable. If the volume average particle size of the dispersed particles of the wax is less than 0.6 μm, the release performance may not be sufficiently obtained. If the volume average particle size exceeds 3 μm, the uniform dispersibility of the wax between the toner particles is deteriorated. There is. That is, particles containing no wax are likely to be generated.
As a method of dispersing wax, how to deposit by cooling after dissolved by heating in an organic solvent is employed.
The volume average particle diameter (Dv) of the wax dispersed particles contained in the wax dispersion is measured by a particle size distribution measuring apparatus (“LA-920”; manufactured by Horiba, Ltd.) using a laser light scattering method.

(2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Here, the “oil phase” and “aqueous medium” in the present invention are relative, and therefore, the toner material liquid does not contain moisture, while the aqueous medium is alcohol or acetone. Naturally, an organic solvent such as THF may be mixed.

Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.) 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries) Manufactured), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footgent F-300 (Neos), and the like.

The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium. For this reason, it is preferable to add so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%. For example, polymethyl methacrylate fine particles 1 μm and 3 μm, polystyrene fine particles 0.5 μm and 2 μm, poly (styrene-acrylonitrile) fine particles 1 μm, trade names are PB-200H (manufactured by Kao Corporation), SGP (manufactured by Soken Co., Ltd.), Techno Examples include polymer SB (manufactured by Sekisui Chemical Co., Ltd.), SGP-3G (manufactured by Sokensha), and micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.).
In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxypropyl , 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

(3) At the same time as the preparation of the emulsion, the amines (B) are added to react with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

(4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and toner base particles can be produced by removing the solvent.
In order to encapsulate the wax domains in the toner particles near the center and to fuse them when there are a plurality of domains in one toner particle, the temperature of the system is higher than the wax melting point after desolvation. It is better to mature for an appropriate time.
Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

(5) A charge control agent is injected into the toner base particles obtained above as required, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

(wax)
The wax is not particularly limited as long as it can be dispersed in the oil-based medium, and can be appropriately selected according to the purpose. Examples thereof include long-chain hydrocarbons, carbonyl group-containing waxes, and polyolefin waxes. These may be used individually by 1 type and may use 2 or more types together. Of these, long chain hydrocarbons are preferred.
Examples of the long chain hydrocarbon include paraffin wax, polyethylene wax, polypropylene wax, and sazol wax. Among these, paraffin wax having a low melting point is preferable from the viewpoint of improving low-temperature fixability.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

(Coloring agent)
As the colorant, known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR), Permanent yellow (NCG), Vulcan fast yellow (5G, R) ), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Se Red, parachlor ortho nitroa Lynn Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Po Azo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalo Anine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded together with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, 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, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

  The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite.

(External additive)
An external additive for assisting the fluidity, developability and chargeability of the toner particles can be used. In the present invention, “consisting essentially of toner particles” means that the use of such external additives is not excluded. As the external additive, inorganic fine particles are preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 × ¹⁰ -3 ~2μm, it is particularly preferably 5 × ¹⁰ -3 ~0.5μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%.

Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, as the fluidity imparting agent, it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination. In particular, when stirring and mixing are performed using particles having an average particle diameter of 5 × 10 ⁻² μm or less, the electrostatic force and van der Waals force with the toner are remarkably improved. Even when stirring and mixing inside the developing device is performed to obtain a good image quality that does not cause the release of the fluidity imparting agent from the toner and does not generate firefly, etc., and further reduces the residual toner. It is done.

Titanium oxide fine particles are excellent in environmental stability and image density stability, but have a tendency to deteriorate the charge rise characteristics. Therefore, if the amount of titanium oxide fine particles added is larger than the amount of silica fine particles added, this side effect is affected. It can be considered large.
However, when the added amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 to 1.5 wt%, the charge rising characteristics are not greatly impaired, and the desired charge rising characteristics can be obtained, that is, repeated copying. Even if it performs, stable image quality is obtained.

<Toner Production Example 1>
(Preparation of [fine particle dispersion 1])
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and then an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The volume average particle size of the [fine particle dispersion 1] measured with a laser diffraction / scattering particle size distribution analyzer (LA-920: manufactured by Horiba, Ltd.) was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin component was 58 ° C., and the weight average molecular weight was 130,000.

(Preparation of [Aqueous Phase 1])
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white liquid. Got. This is designated as [Aqueous Phase 1].

(Synthesis of [Low molecular polyester 1])
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 206 parts of bisphenol A ethylene oxide 2 mol adduct, 509 parts of bisphenol A propylene oxide 2 mol adduct, 200 parts terephthalic acid, 41 parts trimellitic anhydride, 44 parts of adipic acid and 2 parts of dibutyltin oxide were added, polycondensed at 230 ° C. for 7 hours under normal pressure, and further reacted for 5 hours under reduced pressure of 10 to 15 mmHg to obtain [Low molecular polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 3300, a weight average molecular weight of 6900, a peak molecular weight of 3800, a Tg of 43 ° C., and an acid value of 24.

(Synthesis of [Intermediate Polyester 1])
Place 463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and stack for 8 hours at 230 ° C under normal pressure. Condensation was carried out, and [Intermediate polyester 1] was obtained by reacting under reduced pressure of 10 to 15 mmHg for 5 hours. [Intermediate Polyester 1] had a weight average molecular weight of 28000, Tg of 36 ° C., an acid value of 0.5, and a hydroxyl value of 16.5.

(Synthesis of [Prepolymer 1])
Next, 413 parts of [Intermediate polyester 1], 87 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained.

[Synthesis of ketimine]
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 hours and half to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

(Synthesis of master batch)
1200 parts of water, 540 parts of carbon black (Printex 60: manufactured by Degussa) and 1200 parts of [low molecular weight polyester 1] are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture is 1 at 130 ° C. using two rolls. After kneading for a time, rolling and cooling and pulverizing with a pulverizer to obtain [Master Batch 1].

[Production of oil phase]
A reaction vessel equipped with a stir bar and a thermometer was charged with 378 parts of [low molecular weight polyester 1], 500 parts of carnauba wax (RN-05: manufactured by Celalica Noda), and 947 parts of ethyl acetate, and the temperature was raised to 80 ° C. with stirring. Then, it was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and wax were dispersed under the conditions of filling and one pass. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was subjected to two passes by the bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] was 50%.

([Emulsification]-[Desolvation])
[Pigment / wax dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [ketimine compound] 2.9 parts were put in a container and stirred at 5000 rpm for 2 minutes with a TK homomixer (manufactured by Tokushu Kika). 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at a rotational speed of 13000 rpm for 25 minutes to obtain [Emulsified slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirring bar and a thermometer, and after removing the solvent at 30 ° C. for 7 hours, aging was carried out at 90 ° C. for 7 hours to obtain [Dispersion slurry 1].

(Washing-drying)
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(I): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(II): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (I), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered under reduced pressure.
(III): 100 parts of 10% hydrochloric acid was added to the filter cake of (II), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(IV): 300 parts of ion-exchanged water was added to the filter cake of (III), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain [Filter cake 1]. .
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain [Toner Base Particles 1]. Thereafter, 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide were mixed with 100 parts of [toner base particle 1] using a Henschel mixer to obtain [Toner 1].

<Toner Production Example 2>
In Toner Production Example 1, [Toner 2] was obtained in the same manner as in Production Example 1 except that the oil phase production process was changed to the following conditions.
(Production of oil phase)
A reaction vessel equipped with a stirrer and a thermometer was charged with 378 parts of [Low molecular weight polyester 1], 500 parts of paraffin wax (HNP-11: manufactured by Nippon Seiki), and 947 parts of ethyl acetate, and the temperature was raised to 80 ° C. with stirring. Then, it was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 2].
[Raw material solution 2] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and the mixture was subjected to 2 passes with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 2]. The solid content concentration of [Pigment / Wax Dispersion 2] was 50%.

<Toner Production Example 3>
In Toner Production Example 2, [Toner 3] was obtained in the same manner as in Production Example 1 except that the steps of emulsification to solvent removal were changed to the following conditions.
(Emulsification to solvent removal)
[Pigment / Wax Dispersion 2] 867 parts are put in a container, and stirred at 5000 rpm for 2 minutes with a TK homomixer (manufactured by Tokushu Kika), then 1200 parts of [Aqueous Phase 1] are added to the container, and a TK homomixer is used. [Emulsion slurry 3] was obtained by mixing for 25 minutes at a rotational speed of 13000 rpm.
[Emulsion slurry 3] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 7 hours, aging was carried out at 90 ° C for 7 hours to obtain [Dispersion slurry 3].

<Comparative Toner Production Example 4>
3 parts of tricalcium phosphate was added to 900 g of water and stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo) to prepare an aqueous medium.
Next, 160 parts of styrene, 40 parts of n-butyl acrylate, 16 parts of carbon black (Printex 60: manufactured by Degussa), 4 parts of aluminum salicylate compound (Bontron E-88: manufactured by Orient Chemical Co., Ltd.), saturated polyester resin (propylene oxide modified bisphenol) A polycondensate of A and isophthalic acid, Tg = 65 ° C., Mw = 10000) 20 parts, paraffin wax (HNP-11: manufactured by Nippon Seiki Co., Ltd.) 30 parts, divinylbenzene 0.6 parts are added and heated to 60 ° C. It was heated and uniformly dissolved and dispersed at 9000 rpm using a TK homomixer to obtain a polymerizable monomer composition.
To this, 6 parts of a polymerization initiator (perbutyl PV: manufactured by NOF Corporation) obtained by mixing with an isoparaffin solvent was added and uniformly dissolved and dispersed. Next, the mixture was poured into the aqueous medium in the reaction vessel, and granulated by stirring at 6000 rpm using a TK homomixer at 60 ° C. in a nitrogen atmosphere.
Thereafter, the mixture was transferred to a propeller type agitator and stirred, and the temperature was raised to 70 ° C. in 2 hours. After 4 hours, the temperature was raised to 80 ° C. at a heating rate of 40 ° C./Hr and reacted for 5 hours. After completion of the polymerization reaction, the mixture was cooled and diluted hydrochloric acid was added to dissolve the dispersant. Thereafter, the solid and liquid were separated, washed with 10 times the amount of water as the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain toner base particles.
Thereafter, 100 parts of toner base particles were mixed with 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide by a Henschel mixer to obtain [Toner 4].

<Comparative Toner Production Example 5>
In Toner Production Example 2, [Toner 5] was obtained in the same manner as in Production Example 2 except that Prepolymer 1 was changed to Prepolymer 2 obtained as follows.
(Synthesis of intermediate polyester)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride, 2 parts of dibutyltin oxide was added, polycondensed under normal pressure at 230 ° C. for 7 hours, and further reacted for 5 hours under reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] The number average molecular weight was 3,400, the weight average molecular weight was 11,000, the peak molecular weight was 3000, Tg was 52 ° C., the acid value was 1, and the hydroxyl value was 52.
Next, 413 parts of [Intermediate polyester 1], 87 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polymer 2] was obtained.

<Comparative Toner Production Example 6>
In Comparative Toner Production Example 5, [Toner 6] was obtained in the same manner as in Production Example 5 except that the number of bead mill passes of the raw material solution was changed from 1 pass to 3 passes in the oil phase production step.

<Comparative Toner Production Example 7>
In Toner Production Example 3, [Toner 7] was obtained in the same manner as in Production Example 3 except that the number of bead mill passes of the raw material solution in the oil phase production step was changed from 1 pass to 3 passes.

<Evaluation items>
(Fixing characteristics)
Using Ricoh's imgio Neo C385, a plain image and thick paper transfer paper (Ricoh Type 6200 and NBS Ricoh's copy printing paper <135>) with a solid image of 0.8 ± 0.05 mg / cm ² of toner Adjustment was made so that the image was developed, and the fixing device 40 was adjusted so that the temperature of the fixing belt was variable, and the temperature at which hot offset and winding did not occur with plain paper was measured, and the fixing lower limit temperature was measured with cardboard. . The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

(Contamination)
The presence or absence of toner filming on the developing roller or the photoreceptor was observed. ○ indicates no filming, Δ indicates filming on streaks, and × indicates filming as a whole.

(Haze degree)
Using a Ricoh color copier pre-tail 550, adjustment is made so that 1.0 ± 0.1 mg / cm ² of toner is developed, and a Ricoh OHP sheet (type PPC-DX) is used as transfer paper. Remodeled to increase the spring pressure of the fixing device so that the nip width is 1.6 times. When the surface temperature of the fixing roller is 160 ° C, the image is output in the OHP mode, and the haze degree is directly read by Suga Test Instruments Co., Ltd. The haze degree was measured by a computer HGM-2DP type.
This haze degree is also referred to as haze, and is measured as a measure of the transparency of the toner. The lower the value, the higher the transparency, and the better the color developability when using an OHP sheet, and the layers are laminated. In addition, the color development of the lower layer of the toner becomes good, and an image with a wide color reproduction range can be obtained. Further, the haze value indicating good color developability is preferably 30% or less, particularly preferably 20% or less.
The evaluation rank is as follows.
10% or less: ◎
10-15%: ○
15-20%: △
20-25%: ×
25% or more: XX
Tables 1 and 2 show the toner characteristics, and Table 3 shows the evaluation results.

Claims (8)

In a toner containing at least a binder resin, a colorant, and a wax,
The wax exists as one domain in one toner particle, and is included in the center.
The storage elastic modulus G ′ (100 ° C.) at 100 ° C. of the toner is 1.0 × 10 ^{3 to} 1.0 × 10 ⁴ (Pa),
The storage elastic modulus G ′ (150 ° C.) at 150 ° C. of the toner is 1.0 × 10 ^{2 to} 1.0 × 10 ³ (Pa),
The ratio G ′ (150 ° C.) / G ′ (200 ° C.) of the storage elastic modulus G ′ (150 ° C.) of the toner at 150 ° C. and the storage elastic modulus G ′ (200 ° C.) of the toner at 200 ° C. is 0.5-2. And
An electrostatic charge characterized in that a temperature T (° C.) at which tan δ = 1 is 110 <T <130, tan δ> 1 at T-10 (° C.), and tan δ <1 at T + 10 (° C.). Toner for image development. The electrostatic charge image developing toner according to claim 1, wherein the binder resin of the toner is a polyester resin. The electrostatic image developing toner according to claim 1, wherein the polyester resin has at least a non-crosslinking component and a crosslinking component. From toner particles granulated in an O / W type dispersion liquid in which an oily phase of a toner material containing at least a binder resin or a precursor or monomer thereof and a wax is dispersed in a droplet form in an aqueous medium. The electrostatic image developing toner according to claim 1, wherein the toner for developing an electrostatic image according to claim 1. The electrostatic charge developing toner according to claim 4, wherein the oily phase of the toner material is a wax that is dissolved by heating and then precipitated. 6. The electrostatic charge developing device according to claim 4, wherein the polyester resin contains a urea-modified polyester, and the urea-modified polyester is obtained by crosslinking and / or stretching. toner. The toner according to any one of claims 1 to 6, wherein the amount of said wax is from 5 to 30% by weight of the total toner. The wax is paraffin wax, polyethylene wax, toner according to any one of claims 1 to 7, characterized in that it contains one of polypropylene wax.