JP6405655B2 - Full-color image forming device - Google Patents

Description

  The present invention relates to a full-color image forming apparatus used for electrophotographic image formation such as copying machines, electrostatic printing, facsimiles, printers, electrostatic recording and the like.

  In electrophotographic image formation, an electrostatic charge image (latent image) is formed on an electrostatic latent image carrier, charged toner is conveyed by a developer carrier, and the latent image is developed to form a toner image. After the formation, the toner image is transferred onto a recording medium such as paper and fixed by a method such as heating to obtain an output image. Further, the toner remaining on the electrostatic latent image carrier after the transfer is collected from the electrostatic latent image carrier by the cleaning member and discharged to a waste toner storage unit.

  In the heat-fixing type image forming apparatus, since a large amount of electric power is required in the process of heat-melting the toner and fixing it on a recording medium such as paper, the toner has a low-temperature fixability from the viewpoint of energy saving. Is one of the important characteristics.

  In order to improve the low-temperature fixability of the toner, it is necessary to control the thermal characteristics of the binder resin that occupies most of the toner. For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 2010-077419), low-temperature fixability and heat resistance are determined by defining the composition and thermal characteristics of a crystalline resin in a toner having a crystalline resin as a main component of a binder resin. It has been proposed that both storability can be achieved. In Patent Document 2 (Japanese Patent Laid-Open No. 2010-151996), two types of crystalline polyester resins having different storage elastic modulus at 160 ° C. are contained as a binder resin, so that both low temperature fixability and storage stability can be achieved. It has been proposed that Further, in Patent Document 3 (Japanese Patent Laid-Open No. 2012-83714), a specific relationship is satisfied with respect to the viscosity η of the toner measured with a rheometer and the amount of wax exuded from the toner when fixed at 170 ° C. Therefore, a toner that can achieve both low-temperature fixability and heat-resistant storage has been proposed.

While the present inventors are studying further low-temperature fixing of the toner, the present inventors have found a problem of image peeling in a low-temperature region as a new problem that has not existed before. In the conventional study of low-temperature fixing, generally, a so-called cold offset in which the toner on the recording medium adheres to the fixing member side when passing through the fixing nip and is fixed on the recording medium after one round is a problem. It was. In this case, when a sufficient amount of heat is applied to the toner at the time of fixing as the fixing temperature rises, the cold offset is eliminated and a good fixing state is obtained. However, it was found that as the temperature is further lowered, there is a different problem of image peeling in the fixing temperature range between the cold offset and the good fixing state. Image peeling is due to moderate melting of the toner on the recording medium at low temperatures, but it passes through the fixing nip due to insufficient releasability from the fixing member and insufficient adhesion to the recording medium (paper). Sometimes the toner layer is pulled to the fixing member side and peeled off from the recording medium to form a local convex portion on the image, and this convex portion separates the recording medium from the fixing member after passing through the fixing nip. It is a fixing failure that becomes apparent when it comes into contact with the separation member and is destroyed. When this problem occurs, even if the cold offset is improved, this image peeling increases the temperature at which a good fixing state can be achieved, thus preventing energy saving of the image forming apparatus.
Therefore, this invention makes it a subject to solve the said problem and to achieve the following objectives. That is, according to the present invention, when a full-color image is formed, even in a low temperature range, good fixability without causing image peeling due to insufficient releasability from a fixing member and insufficient adhesion to a recording medium (paper). The first object is to provide an excellent full-color image forming apparatus having In addition, it has sufficient heat-resistant storage stability even in storage in a high-temperature and high-humidity environment, suppresses the occurrence of abnormal images due to toner aggregates, and provides a partial high-gloss image (spot gloss). It is a second and third object to provide an excellent full-color image forming apparatus that can be produced satisfactorily.

  As a result of intensive studies in view of the above problems, the present inventors have found that the value of W satisfies a specific range for the amount W of the release agent at 100 ° C. of the full-color toner used in the image forming apparatus, and By transferring the toner on the recording medium in order of increasing W value from the fixing unit side, good releasability from the fixing member is maintained, especially during color superposition during full color image formation. However, it has been found that good adhesion to the recording medium (paper) can be maintained, the formation of local convex portions that cause image peeling can be suppressed, and the occurrence of image peeling can be suppressed.

The present invention is based on the above findings by the present inventors, and specific means for solving the above problems are as described in (1) below. That is, the full-color image forming apparatus of the present invention comprises (1) “an electrostatic latent image carrier, a charging means for charging the surface of the electrostatic latent image carrier, and the charged electrostatic latent image carrier surface. An exposure unit that forms an electrostatic latent image by exposure, a developing unit that sequentially develops the electrostatic latent image with a plurality of colors of toner to form a visible image, and a transfer that transfers the visible image to a recording medium And an image forming apparatus having at least fixing means for fixing the transferred image transferred to the recording medium,
The multi-color toner comprises a toner base containing at least a binder resin, a colorant and a release agent, and an external additive,
When the amount of exudation of the release agent at 100 ° C. for each of the toners of the plurality of colors is W, the W satisfies the following relational expression (1) and the stacking order of the toner on the recording medium is The full-color image forming apparatus, wherein the toner is transferred in order from the toner having the larger W value from the fixing unit side.
0.30 ≦ W ≦ 0.50 (1) ”

  As will be apparent from the following detailed and specific description, according to the present invention, firstly, when a full-color image is formed, the releasability from the fixing member is insufficient and the recording medium (paper) It has good fixability without causing image peeling due to insufficient adhesiveness, and secondly, it has sufficient heat-resistant storage stability even in storage in a high-temperature and high-humidity environment. Thirdly, it is possible to provide an excellent full-color image forming apparatus capable of suppressing the occurrence of an abnormal image due to this and thirdly producing a partial high gloss image (spot gloss).

1 is a schematic explanatory diagram illustrating an example of a full-color image forming apparatus of the present invention. It is a schematic explanatory drawing which shows the other example of the full-color image forming apparatus of this invention. It is a schematic explanatory drawing which shows an example using the tandem type color image forming apparatus of the full color image forming apparatus of this invention. FIG. 4 is a partially enlarged schematic explanatory diagram of the full-color image forming apparatus shown in FIG. 3.

The present invention relates to the “full-color image forming apparatus” described in (1) above. As will be understood from the following detailed description, the “full-color image forming apparatus” includes the following (2) to (2) to (5) The mode of the “full-color image forming apparatus” described in (5)
(2) “W1 is the amount of the release agent present in the vicinity of the toner surface at normal temperature and humidity, and W2 is the amount of the release agent present in the vicinity of the toner surface after storage at high temperature and high humidity. The full-color image forming apparatus according to (1), wherein W2 satisfies the following relational expression (2).
1.0 <= W2 / W1 <= 1.3 ... Relational expression (2). "
(3) The full-color image forming apparatus according to (1) or (2), wherein the binder resin contains at least a crystalline polyester resin.
(4) The full-color image forming apparatus according to any one of (1) to (3), wherein the weight average molecular weight (Mw) corresponding to the binder resin in the toner is 5000 to 18000. "
(5) “Transparent toner (hereinafter referred to as“ clear ”in the specification) comprising a toner base material containing at least a binder resin and a release agent and not containing a colorant, and an external additive. The full-color image forming apparatus according to any one of the above (1) to (4), which may be expressed as “toner”. "

  The material constituting the toner mounted on the image forming apparatus of the present invention, the carrier contained in the developer mounted on the image forming apparatus of the present invention, and the image forming apparatus of the present invention will be described. It is easy for those skilled in the art to change or modify the present invention within the scope of the claims to form other embodiments, and these changes and modifications are included in the scope of the claims. The following description is an example of a preferred embodiment of the present invention, and is not intended to limit the scope of the claims.

(toner)
The toner mounted on the image forming apparatus of the present invention includes at least a binder resin, toner base particles containing a colorant and a release agent, and an external additive, and further includes other components as necessary.

<Toner base particles>
The toner base particles contain at least a binder resin, a colorant, and a release agent. Furthermore, a charge control agent, a layered inorganic mineral, etc. can be contained as needed.

<< Binder resin >>
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably. For example, polyester resin, silicone resin, styrene / acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amidoimide resin, butyral resin, urethane resin, ethylene vinyl acetate resin, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, polyester resin, polyester resin and the above-mentioned other binder resins are combined in that they have excellent low-temperature fixability, can smooth the image surface, and have sufficient flexibility even when the molecular weight is lowered. Resins are preferred.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, Although it can select suitably according to the objective, An unmodified polyester resin and a modified polyester resin are preferable. These may be used individually by 1 type and may use 2 or more types together.

--Unmodified polyester resin--
The unmodified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include resins obtained by polyesterifying carboxylic acid and crystalline polyester resins.
According to the present invention, a toner having excellent low-temperature fixability using a crystalline polyester resin that is likely to cause abnormal images due to toner aggregates and in which variations in image density and transferability are more noticeable is mounted. Even in a high-speed machine, generation of abnormal images can be similarly suppressed over time, and image density stability and transferability can be maintained well.

前記一般式（１）中、Ａは、炭素数１〜２０のアルキル基、アルキレン基、置換基を有してもよい芳香族基又はヘテロ環芳香族基を表し、ｍは、２〜４の整数を表す。
ただし、前記一般式（２）中、Ｂは、炭素数１〜２０のアルキル基、アルキレン基、置換基を有してもよい芳香族基又はヘテロ環芳香族基を表し、ｎは、２〜４の整数を表す。

In the general formula (1), A represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, an aromatic group that may have a substituent, or a heterocyclic aromatic group, and m represents 2 to 4 Represents an integer.
However, in said general formula (2), B represents the C1-C20 alkyl group, alkylene group, the aromatic group which may have a substituent, or a heterocyclic aromatic group, and n is 2-2. Represents an integer of 4.

There is no restriction | limiting in particular as a polyol represented by the said General formula (1), According to the objective, it can select suitably. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, Pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2, -Butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A oxidation Examples include ethylene adducts, hydrogenated bisphenol A propylene oxide adducts, and the like.
These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as polycarboxylic acid represented by the said General formula (2), According to the objective, it can select suitably. For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid , Isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2, , 5,7-Naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl- 2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, te La (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, etc., cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, And ethylene glycol bis (trimellitic acid). These may be used alone or in combination of two or more.

--- Crystalline polyester resin ---
The polyester resin preferably contains a crystalline polyester resin.
Examples of the crystalline polyester resin include saturated aliphatic diol compounds having 2 to 12 carbon atoms as alcohol components, particularly 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10- Decanediol, 1,12-dodecandiol and derivatives thereof, and a dicarboxylic acid having 2 to 12 carbon atoms or a saturated dicarboxylic acid having 2 to 12 carbon atoms having at least a double bond (C═C bond) as an acidic component Especially using fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1, -8 octanedioic acid, 1,10-decanedioic acid, 1,12 dodecanedioic acid and their derivatives Synthesized crystalline polyester is preferred.

  Among these, in particular, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and the like in terms of reducing the difference between the endothermic peak temperature and the endothermic shoulder temperature in the DSC chart. Any one alcohol component of 1,12-dodecanediol, fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid , 1,12-dodecanedioic acid is preferably composed of only one kind of dicarboxylic acid component.

  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 and a trivalent or higher polyvalent such as trimellitic anhydride as an acid component can be used during polyester synthesis. Examples thereof include a method of designing and using a non-linear polyester that has been subjected to condensation polymerization by adding a polyvalent carboxylic acid.

  The molecular structure of the crystalline polyester resin of 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.

  The content of the crystalline polyester resin in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3% by weight to 15% by weight, and more preferably 5% by weight to 10% by weight. preferable. When the content is 3% by weight or more, the effect on the low-temperature fixability is sufficiently obtained, and preferably 15% by weight or less, an abnormal image due to toner aggregation over time is less likely to occur, This is preferable because variations in image density and deterioration in transferability are less likely to occur.

  “Crystallinity” in the present invention is the ratio of the softening temperature measured by the Koka flow tester to the maximum peak temperature (melting point) of the heat of fusion measured by a differential scanning calorimeter (DSC) (softening temperature / The maximum melting temperature (melting heat peak temperature) is 0.80 to 1.55, and it is a property that softens sharply by heat. A polyester resin having this property is referred to as a “crystalline polyester resin”.

  The softening temperature of the resin and toner can be measured using a Koka flow tester (for example, CFT-500D (manufactured by Shimadzu Corporation)). While heating 1 g of resin as a sample at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. Plotting was performed, and the temperature at which half the sample flowed out was defined as the softening temperature.

  The maximum peak temperature (melting point) of the heat of fusion of the resin and toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). As a pretreatment, a sample to be used for measurement of the maximum peak temperature of heat of fusion is melted at 130 ° C., then lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./minute, and then from 70 ° C. to 10 ° C. The temperature is lowered at a rate of 0.5 ° C./min. Here, by DSC, the temperature is increased at a rate of temperature increase of 20 ° C./min to measure the endothermic change, and a graph of “endothermic amount” and “temperature” is drawn. The endothermic peak temperature at 100 ° C. is defined as “Ta *”. When there are a plurality of endothermic peaks, the temperature of the peak with the largest endothermic amount is Ta *. Thereafter, the sample is stored at (Ta * −10) ° C. for 6 hours, and further stored at (Ta * −15) ° C. for 6 hours. Next, the sample was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, and then the temperature was increased at a temperature increase rate of 20 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak of the calorific value was taken as the maximum peak temperature of the heat of fusion.

--Modified polyester resin--
There is no restriction | limiting in particular as said modified polyester resin, According to the objective, it can select suitably. For example, an active hydrogen group-containing compound, a resin obtained by subjecting a polyester capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “polyester prepolymer”) to an extension reaction and / or a crosslinking reaction, etc. Can be mentioned. The extension reaction and / or the cross-linking reaction may be stopped by a reaction terminator (blocked monoamine such as diethylamine, dibutylamine, butylamine, laurylamine, ketimine compound, etc.) as necessary.

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent or the like when the polyester prepolymer undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous phase.

  The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. However, when the polyester prepolymer is an isocyanate group-containing polyester prepolymer described later. An amine is preferable in that a high molecular weight can be obtained.

  There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be contained singly or in combination of two or more.

  The amines that are the active hydrogen group-containing compounds are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, and the like. The thing etc. which blocked the amino group of amines are mentioned. Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine, etc.); aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetramine. Examples of the amino alcohol include ethanolamine and hydroxyethylaniline. Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid include aminopropionic acid and aminocaproic acid. Examples of the blocked amino groups of these amines include, for example, any of these amines (diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, etc.) and ketones (acetone, methyl ethyl ketone, And ketimine compounds and oxazolyzone compounds obtained from methyl isobutyl ketone and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, the amines are particularly preferably diamine and a mixture of a diamine and a small amount of a trivalent or higher polyamine.

--- Polymer capable of reacting with active hydrogen group-containing compound ---
The polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited as long as it is a polymer having at least a group capable of reacting with the active hydrogen group-containing compound, and can be appropriately selected according to the purpose. . Urea bond-forming group-containing polyester resin (RMPE) is superior in terms of high fluidity and transparency during melting, easy adjustment of the molecular weight of the polymer component, and excellent oil-less low-temperature fixability and releasability in dry toners. Preferably, an isocyanate group-containing polyester prepolymer is more preferable.

  The isocyanate group-containing polyester prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polycondensate of a polyol and a polycarboxylic acid, a reactive hydrogen group-containing polyester resin is reacted with a polyisocyanate. And the like.

  There is no restriction | limiting in particular as said polyol, According to the objective, it can select suitably. For example, 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 alicyclic diol, alkylene oxide of the bisphenol Diols such as adducts (ethylene oxide, propylene oxide, butylene oxide, etc.); polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), trivalent or higher phenols (phenol novolac) , Cresol novolac, etc.) trihydric or higher polyols such as alkylene oxide adducts of trihydric or higher polyphenols; mixtures of diols and trihydric or higher polyols. These may be used individually by 1 type and may use 2 or more types together. Among these, the polyol is preferably the diol alone or a mixture of the diol and a small amount of the trivalent or higher polyol. Examples of the diol include alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols (bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, etc.) Is preferred.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer of the said polyol, According to the objective, it can select suitably. For example, 0.5 mass%-40 mass% are preferable, 1 mass%-30 mass% are more preferable, and 2 mass%-20 mass% are especially preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both the storage stability of the toner and the low-temperature fixability. Fixability may deteriorate.

  There is no restriction | limiting in particular as said polycarboxylic acid, According to the objective, it can select suitably. For example, alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.); Examples thereof include polycarboxylic acids (such as aromatic polycarboxylic acids having 9 to 20 carbon atoms such as trimellitic acid and pyromellitic acid). These may be used individually by 1 type and may use 2 or more types together. Among these, the polycarboxylic acid is preferably an alkenylene dicarboxylic acid having 4 to 20 carbon atoms and an aromatic dicarboxylic acid having 8 to 20 carbon atoms. In place of the polycarboxylic acid, an anhydride of polycarboxylic acid, a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.

  The mixing ratio of the polyol and the polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. The mixing ratio of the hydroxyl group [OH] of the polyol and the carboxyl group [COOH] of the polycarboxylic acid is not limited. The equivalent ratio [OH] / [COOH] is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

  The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene Diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, etc .; alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane) Diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4, '-Diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, etc .; araliphatic diisocyanate (α, α , Α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates (tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, etc.); these phenol derivatives; blocked with oximes, caprolactam, etc. And the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a mixing ratio of the said polyisocyanate and the said active hydrogen group containing polyester resin (hydroxyl group containing polyester resin), According to the objective, it can select suitably. The equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] of the polyisocyanate and the hydroxyl group [OH] of the hydroxyl group-containing polyester resin is preferably 5/1 to 1/1, and 4/1 to 1.2. / 1 is more preferable, and 3/1 to 1.5 / 1 is particularly preferable. When the equivalent ratio [NCO] / [OH] is less than 1/1, the offset resistance may be deteriorated, and when it exceeds 5/1, the low-temperature fixability may be deteriorated.

  There is no restriction | limiting in particular as content of the said polyisocyanate in the said isocyanate group containing polyester prepolymer, According to the objective, it can select suitably. 0.5 mass%-40 mass% are preferable, 1 mass%-30 mass% are more preferable, 2 mass%-20 mass% are especially preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both storage stability and low-temperature fixability. May get worse.

  The average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the polyester resin (RMPE) modified with a urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  There is no restriction | limiting in particular as a mixing ratio of the said isocyanate group containing polyester prepolymer and the said amines, According to the objective, it can select suitably. The mixing equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the isocyanate group-containing polyester prepolymer and the amino group [NHx] in the amines is preferably 1/3 to 3/1. / 2 to 2/1 is more preferable, and 1 / 1.5 to 1.5 / 1 is particularly preferable. If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be reduced. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin is reduced. Hot offset resistance may deteriorate.

--- Method for synthesizing polymer capable of reacting with active hydrogen group-containing compound ---
There is no restriction | limiting in particular as a synthesis method of the polymer which can react with the said active hydrogen group containing compound, According to the objective, it can select suitably. For example, in the case of the isocyanate group-containing polyester prepolymer, the polyol and the polycarboxylic acid are heated to 150 ° C. to 280 ° C. in the presence of a known esterification catalyst (titanium tetrabutoxide, dibutyltin oxide, etc.). And a method of synthesizing by reacting the polyisocyanate with the hydroxyl group-containing polyester at 40 ° C. to 140 ° C. after the water is distilled off to obtain the hydroxyl group-containing polyester. .

  There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the polymer which can react with the said active hydrogen group containing compound, According to the objective, it can select suitably. The molecular weight distribution by GPC (gel permeation chromatography) of the soluble portion of tetrahydrofuran (THF) is preferably 3,000 to 40,000, more preferably 4,000 to 30,000. When the weight average molecular weight (Mw) is less than 3,000, the storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated. The weight average molecular weight (Mw) can be measured, for example, as follows. First, the column was stabilized in a 40 ° C. heat chamber, and at this temperature, tetrahydrofuran (THF) as a column solvent was flowed at a flow rate of 1 mL / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 μL to 200 μL of a tetrahydrofuran sample solution. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared by several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Alternatively, the molecular weights of Toyo Soda Kogyo Co., Ltd. are 6 × 10 2, 2.1 × 10 2, 4 × 10 2, 1.75 × 10 4, 1.1 × 10 5, 3.9 × 10 5, 8.6 × 10 5, 2 × 10 6 And 4.48 × 10 6, and at least about 10 standard polystyrene samples are preferably used. An RI (refractive index) detector can be used as the detector.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably. For example, plant wax (carnauba wax, cotton wax, wood wax, rice wax, etc.), animal wax (beeswax, lanolin, etc.), mineral wax (ozokerite, cercin etc.), petroleum wax (paraffin, microcrystalline, petrolatum, etc.) Waxes and waxes; synthetic hydrocarbon waxes (Fischer-Tropsch wax, polyethylene wax, etc.), synthetic waxes (esters, ketones, ethers, etc.) other than natural waxes; 1,2-hydroxystearic acid amide , Stearic acid amide, phthalic anhydride imide, fatty acid amides such as chlorinated hydrocarbons; polyacrylates such as poly (n-stearyl methacrylate) and poly (n-lauryl methacrylate) which are low molecular weight crystalline polymers (Acrylic acid n Crystalline polymer of the side chain stearyl over ethyl methacrylate copolymer, etc.) and the like having a long chain alkyl group; and the like. Among these, ester waxes are particularly preferable.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 90 degreeC is preferable and 60 to 80 degreeC is more preferable. When the melting point is less than 50 ° C., the release agent is likely to ooze out from the toner base during high temperature storage of about 30 to 50 ° C., which may adversely affect the heat resistant storage stability. However, it is not preferable because it may cause a cold offset at the time of fixing at a low temperature. The melting point of the release agent is determined by measuring the maximum endothermic peak using a differential scanning calorimeter (TG-DSC system, TAS-100, manufactured by Rigaku Corporation).

  There is no restriction | limiting in particular as melt viscosity of the said mold release agent, Although it can select suitably according to the objective, As a measured value in 100 degreeC, 5 cps-100 cps are preferable, and 5 cps-50 cps are more preferable. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 100 cps, adhesion between paper and toner may be hindered in a low temperature range, and image peeling is likely to occur. It is not very preferable.

  The release agent is preferably present in a dispersed state in the toner base particles, and for this purpose, the release agent and the binder resin are preferably incompatible with each other. The method for finely dispersing the release agent in the toner base particles is not particularly limited and may be appropriately selected depending on the purpose. For example, the release agent is dispersed by applying a kneading shear force during toner production. The method etc. are mentioned.

  The dispersion state of the release agent can be confirmed by observing a thin film slice of toner particles with a transmission electron microscope (TEM). The dispersion diameter of the release agent is preferably small, but if it is too small, there are cases where bleeding during fixing is insufficient. Therefore, if the release agent can be confirmed at a magnification of 10,000, the release agent is present in a dispersed state. When the release agent cannot be confirmed at 10,000 times, even when finely dispersed, the dyeing at the time of fixing becomes insufficient.

  There is no restriction | limiting in particular as content in the said toner of the said release agent, Although it can select suitably according to the objective, 3 mass%-20 mass% are preferable, and 5 mass%-15 mass% are more preferable. . When the content is less than 3% by mass, the hot offset resistance tends to deteriorate and image peeling tends to occur in a low temperature range. When the content exceeds 20% by mass, heat resistant storage stability, image density stability, transfer This is not preferable because the property tends to deteriorate.

―Release agent dispersion resin―
The toner base particles preferably contain a release agent-dispersing resin for the purpose of controlling the dispersion state / existence state of the release agent in the toner base particles. Although there is no restriction | limiting in particular as this mold release agent dispersion resin, The graft polymer which consists of polyolefin resin and vinyl resin is preferable.

-Graft polymer-
The graft polymer has a structure in which a vinyl resin is grafted on at least a main chain made of a polyolefin resin, and can be produced by a conventionally known method. That is, the polyolefin resin constituting the main chain of the graft polymer is dissolved in an organic solvent, and the vinyl monomer for the vinyl resin constituting the side chain is added to this solution, and these polyolefin resin and vinyl monomer are added to the organic solvent. The graft polymerization is carried out in the presence of a polymerization initiator such as an organic peroxide. The weight ratio of the polyolefin resin and the vinyl monomer is preferably 1 to 30:70 to 99, more preferably 5 to 25:75 to 95 from the viewpoint of filming resistance.

  In the graft polymer, an unreacted polyolefin resin and an ungrafted vinyl resin formed by polymerization of vinyl monomers are mixed. In the present invention, it is not necessary to separate and remove these resins. The coalescence can be preferably used as a mixed resin containing these resins. In this mixed resin, the content of the unreacted polyolefin resin is 5% by weight or less, preferably 3% by weight or less. The content of the ungrafted vinyl resin is 10% by weight or less, preferably 5% by weight or less. The proportion of the graft polymer in the mixed resin is 85% by weight or more, preferably 90% by weight or more. The ratio of the graft polymer in the mixed resin, the molecular weight thereof, the molecular weight of the vinyl polymer, and the like can be appropriately adjusted depending on conditions such as the charging ratio of the reaction raw material, the polymerization reaction temperature, and the reaction time.

  Examples of the olefins constituting the polyolefin resin include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and the like.

  Examples of the polyolefin resin include polymers of olefins, thermal degradation products, oxides, modified products, and copolymers with other monomers copolymerizable with olefins.

  Examples of the olefin polymers include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, propylene / 1-hexene copolymer, and the like.

  A heat-degraded product of an olefin polymer is a polyolefin resin obtained by heating a polyolefin resin having a weight average molecular weight (Mw) of 50,000 to 5,000,000 to 250 ° C. to 450 ° C. to reduce the molecular weight. The double bond content per molecule corresponding to the number of molecules derived from the molecular weight (Mn) is preferably 30 to 70%.

  Examples of the olefin polymer oxide include oxides of the exemplified olefin polymers.

  Examples of the modified product of the olefin polymer include a maleic acid derivative adduct of the olefin polymer exemplified above. Examples of the maleic acid derivative include maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate and the like.

  Examples of the copolymer with other monomers copolymerizable with olefins include copolymers of olefins with monomers such as unsaturated carboxylic acids and unsaturated carboxylic acid alkyl esters. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, maleic anhydride, and the like. Examples of the unsaturated carboxylic acid alkyl ester include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms and maleic acid alkyl esters having 1 to 18 carbon atoms.

  The polyolefin resin used in the present invention may have a polymer structure having a polyolefin structure, and the monomer does not necessarily have an olefin structure. For this reason, for example, polymethylene such as sasol wax can also be used.

  The softening point of the polyolefin resin is usually preferably 60 to 170 ° C. in order to improve the fluidity of the toner, and more preferably 70 to 150 ° C. from the viewpoint of exhibiting an effective release effect. 130 ° C. is more preferable.

  The molecular weight of the polyolefin resin is usually from 500 to 20,000 for the number average molecular weight (Mn) and 800 to 100,000 for the weight average molecular weight (Mw) from the viewpoint of filming to the carrier and releasability. , Mn is preferably 1,000 to 15,000, Mw is preferably 1,500 to 60,000, Mn is preferably 1,500 to 10,000, and Mw is particularly preferably 2,000 to 30,000. preferable.

  As the vinyl resin, conventionally known homopolymers or copolymers of vinyl monomers can be used. Specifically, styrene monomers, alkyl esters of unsaturated carboxylic acids having 1 to 18 carbon atoms, vinyl ester monomers, vinyl ether monomers, halogen element-containing vinyl monomers, diene monomers, (meth) acrylonitrile, cyano Examples thereof include unsaturated nitrile monomers such as styrene. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the styrene monomer include styrene, α-methyl styrene, p-methyl styrene, m-methyl styrene, p-methoxy styrene, p-hydroxy styrene, p-acetoxy styrene, ethyl styrene, phenyl styrene, benzyl styrene, and the like. Is mentioned.

  Examples of the alkyl ester of an unsaturated carboxylic acid having 1 to 18 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

  Examples of the vinyl ester monomer include vinyl acetate, the vinyl ether monomer includes vinyl methyl ether, and the halogen element-containing vinyl monomer includes vinyl chloride. Examples of the diene monomer include butadiene and isobutylene.

  Among these, a styrene monomer, an unsaturated carboxylic acid alkyl ester, (meth) acrylonitrile, and a combination thereof are preferable, and a combination of styrene; styrene and a (meth) acrylic acid alkyl ester or (meth) acrylonitrile is particularly preferable.

  The SP value (solubility parameter) of the vinyl resin is selected in consideration of the SP value of the amorphous polyester resin (a) as the binder resin. The SP value can be calculated by a known Fedors method.

  As for the molecular weight of the vinyl resin, the number average molecular weight (Mn) is usually 1,500 to 100,000, the weight average molecular weight (Mw) is 5,000 to 200,000, and Mn is 2,500 to 50,000. Mw is preferably 6,000 to 100,000, particularly preferably Mn is 2,800 to 20,000, and Mw is 7,000 to 50,000.

  The Tg (glass transition point) of the vinyl resin is preferably 50 to 80 ° C. and more preferably 55 to 70 ° C. from the viewpoints of good storage stability and good low-temperature fixability.

Specific examples of the graft polymer used in the present invention include those comprising the following polyolefin resin (R) and vinyl resin (S).
(R): polyethylene and (S): styrene / acrylonitrile / butyl acrylate copolymer, (R): polyethylene and (S): styrene / acrylonitrile / butyl acrylate / acrylic acid copolymer, (R): polypropylene And (S): styrene / acrylonitrile / butyl acrylate copolymer, (R): polypropylene and (S): styrene / acrylonitrile / butyl acrylate / acrylic acid copolymer, (R): polypropylene and (S): Styrene / acrylonitrile / butyl acrylate / monobutyl maleate copolymer, (R): oxidized polypropylene and (S): styrene / acrylonitrile copolymer, (R): polyethylene / polypropylene mixture and (S): styrene / acrylonitrile Copolymer, (R): ethylene / propylene copolymer And (S): styrene / acrylic acid / butyl acrylate copolymer, (R): ethylene / propylene copolymer and (S): styrene / acrylonitrile / butyl acrylate copolymer, (R): maleic acid Modified polypropylene and (S): styrene / acrylonitrile / acrylic acid / butyl acrylate copolymer, (R): maleic acid modified polypropylene and (S): styrene / acrylonitrile / acrylic acid / -2-ethylhexyl acrylate copolymer , (R): polyethylene / maleic acid modified polypropylene mixture and (S): acrylonitrile / butyl acrylate / styrene / monobutyl maleate copolymer.

As the method for producing the graft polymer, for example, first, a polyolefin resin is dissolved or dispersed in a solvent such as toluene or xylene, heated to 100 to 200 ° C., and then a vinyl monomer is dropped together with a peroxide-based initiator. For example, and then the solvent is distilled off to obtain a graft polymer. Examples of the peroxide initiator include benzoyl peroxide, di-t-butyl peroxide, di-t-butylperoxyhexahydroterephthalate, and t-butyl peroxide benzoate.
The amount of the peroxide-based initiator can be appropriately adjusted based on the weight of the reaction raw material, and is usually 0.2 to 10% by weight, preferably 0.5 to 5% by weight.

  Moreover, the addition amount of the graft polymer including the unreacted polyolefin resin and vinyl resin is usually preferably 30 to 120 parts by mass with respect to 100 parts by mass of the release agent from the viewpoint of dispersion stability of the release agent. 35-100 mass parts is more preferable.

―Colorant―
There is no restriction | limiting in particular as a coloring agent used for the said toner, According to the objective, it can select suitably from a well-known coloring agent.

  The color of the colorant of the toner is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, Each color toner can be obtained by appropriately selecting the type of colorant, but is preferably a color toner.

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

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited, but it is preferable to use a binder resin or a resin having a structure similar to the binder resin from the viewpoint of compatibility with the binder resin.

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

-Charge control agent-
Further, in order to impart an appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary.
Any known charge control agent can be used as the charge control agent. Since the color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, a triphenylmethane dye, a molybdate chelate pigment, a rhodamine dye, an alkoxyamine, a quaternary ammonium salt (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. 01 mass%-5 mass% are preferable, and 0.02 mass%-2 mass% are more preferable. When the addition amount exceeds 5% by mass, 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 reduced, and the image The density may be lowered, and if it is less than 0.01% by mass, the charge start-up property and the charge amount are not sufficient, and the toner image may be easily affected.

-Layered inorganic mineral-
The layered inorganic mineral is not particularly limited as long as it is an inorganic mineral in which layers having a thickness of several nm are laminated, and can be appropriately selected according to the purpose. Examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and a mixture thereof. These may be used alone or in combination of two or more. Among these, a modified layered inorganic mineral is preferable because it can be modified when the toner is granulated, has a charge control function, and is excellent in low-temperature fixing, and a layered inorganic mineral having a montmorillonite-based basic crystal structure is an organic cation. Organic modified montmorillonite and bentonite are particularly preferred from the viewpoint that the modified layered inorganic mineral modified with the above is more preferable, and the viscosity can be easily adjusted without affecting the toner characteristics.

  The modified layered inorganic compound preferably modifies at least part of the layered inorganic mineral with organic ions. By modifying at least a part of the layered inorganic mineral with organic ions, the layer has an appropriate hydrophobicity, the oil phase containing the toner composition and / or the toner composition precursor has a non-Newtonian viscosity, Can be modified.

  There is no restriction | limiting in particular as content in the toner base particle of the said modified | denatured layered inorganic mineral, Although it can select suitably according to the objective, 0.05 mass%-5 mass% are preferable.

<External additive>

-External additive-
The toner preferably contains inorganic fine particles having a number average particle diameter of 30 nm to 60 nm, more preferably 30 nm to 50 nm, as an external additive. By containing inorganic fine particles in the above particle size range, the fluidity of the toner is improved, and an abnormal image is generated due to the deterioration of the cohesiveness of the toner without being embedded in the toner base due to external stress over time. Can be suppressed.

  The toner preferably further contains inorganic fine particles having a number average particle diameter of 80 nm to 200 nm as an external additive, and more preferably 100 nm to 180 nm. By containing the inorganic fine particles in the particle size range, it is possible to suppress the burying of the external additive in the toner base due to external stress and to suppress the occurrence of an abnormal image due to the deterioration of the toner cohesiveness.

  There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably from well-known things. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoro Examples thereof include polymers. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the hydrophobized silica fine particles include HDK H2000T, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303VP (all manufactured by Clariant Japan); R972, R974, RX200, RY200, R202, R805, R812, NX90G (all manufactured by Nippon Aerosil Co., Ltd.) and the like. Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.

  There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.3 mass part-3.0 mass parts are preferable with respect to 100 mass parts of toner base particles. 0.5 parts by mass to 2.0 parts by mass is more preferable.

  The total coverage of the external additive with respect to the toner base particles is not particularly limited, but is preferably 50% to 90%, and more preferably 60% to 80%.

-Toner production method-
The toner production method and materials in the present invention can be any known ones as long as they satisfy the conditions, and are not particularly limited. For example, the toner particles may be mixed in a kneading and pulverization method or an aqueous medium. There is a so-called chemical method of granulating.
Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, etc., in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent and the like in an aqueous medium. Dispersing or emulsifying dissolution suspension method; in the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group is contained in resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting the active hydrogen group-containing compound and the reactive group-containing prepolymer in the aqueous medium (production method (I)); Phase inversion emulsification method in which water is added to a solution composed of an emulsifier; the resin particles obtained by these methods are aggregated in a state of being dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting. Aggregation And the like. Among these, the toner obtained by the dissolution suspension method, the production method (I), and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.), and the production method (I). The resulting toner is more preferred.
In the following, a detailed description of these production methods will be given.

  The kneading and pulverizing method is, for example, a method of producing the toner base particles by pulverizing and classifying a toner material having at least a colorant, a binder resin, and a release agent melted and kneaded.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, a Kneader manufactured by Buss, etc. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  In the dissolution suspension method, for example, an oil phase composition in which a toner composition containing at least a binder resin or a resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is used. This is a method for producing toner base particles by dispersing or emulsifying in a medium.

The organic solvent used for dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later.
Examples of the organic solvent include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve (registered trademark), and butyl cellosolve. (Registered trademark), ether solvents such as propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, Examples include alcohol solvents such as isobutanol, t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol, and mixed solvents of two or more of these. .

In the dissolution suspension method, when the oil phase composition is dispersed or emulsified in an aqueous medium, an emulsifier or a dispersant may be used as necessary.
As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used. The surfactant is not particularly limited, and is an anionic surfactant (alkyl benzene sulfonic acid, phosphate ester, etc.), a cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), an amphoteric surfactant (carbon carboxyl). Acid salt type, sulfate ester type, sulfonate salt type, phosphate ester salt type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.) and the like. One surfactant may be used alone, or two or more surfactants may be used in combination.
Examples of the water-soluble polymer include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan. , Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid) , Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer ( Min) neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.
Moreover, said organic solvent, a plasticizer, etc. can also be used together as an auxiliary | assistant of emulsification or dispersion | distribution.

  The toner according to the present invention includes at least a binder resin, a binder resin precursor having a functional group capable of reacting with an active hydrogen group (reactive group-containing prepolymer), a colorant, and a release agent in a dissolution suspension method. An active phase group-containing prepolymer and an active hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium are dispersed or emulsified in an aqueous medium containing resin fine particles. It is preferable to obtain the toner base particles by a method of reacting with (the production method (I)).

The resin fine particles can be formed using a known polymerization method, but is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).
(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method.
(B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in an aqueous medium, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent to cure.
(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method for preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heated to a solvent in advance. By cooling the dissolved resin solution, the resin fine particles are precipitated, the solvent is removed to form the resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to disperse the resin fine particles in water. A method for preparing a liquid.
(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

  The volume average particle diameter of the resin fine particles is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 120 nm or less. When the volume average particle size of the resin fine particles is less than 10 nm or more than 300 nm, the particle size distribution of the toner may be deteriorated.

  The solid content concentration of the oil phase is preferably about 40 to 80%. If the concentration is too high, dissolution or dispersion becomes difficult, and the viscosity becomes high and difficult to handle. If the concentration is too low, the productivity of the toner decreases.

  The toner composition other than the binder resin such as the colorant and the release agent, and the masterbatch thereof are individually dissolved or dispersed in an organic solvent, and then mixed with the binder resin solution or dispersion. May be.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The dispersion or emulsification method in the aqueous medium is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  In order to remove the organic solvent from the obtained emulsified dispersion, there is no particular limitation, and a known method can be used. For example, the whole system is gradually raised while stirring the whole system under normal pressure or reduced pressure. A method of warming and completely evaporating and removing the organic solvent in the droplets can be employed.

  As a method of washing and drying the toner base particles dispersed in the aqueous medium, a known technique is used. That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

  In the agglomeration method, for example, a toner base particle is produced by mixing and aggregating a resin fine particle dispersion comprising at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion as necessary. is there. The resin fine particle dispersion is obtained by a known method such as emulsion polymerization, seed polymerization, phase inversion emulsification, and the like. The colorant particle dispersion and the release agent particle dispersion are obtained by a known wet dispersion method. It can be obtained by dispersing a colorant or a release agent in an aqueous medium.

For the control of the aggregation state, methods such as applying heat, adding a metal salt, and adjusting pH are preferably used.
There is no restriction | limiting in particular as said metal salt, The monovalent metal which comprises salts, such as sodium and potassium; The bivalent metal which comprises salts, such as calcium and magnesium; The trivalent metal which comprises salts, such as aluminum, etc. Is mentioned.
Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion. Among these, magnesium chloride, aluminum chloride, and complexes and multimers thereof are preferable. .
Also, heating between the agglomeration and after completion of the agglomeration can promote fusion between the resin fine particles, which is preferable from the viewpoint of toner uniformity. Furthermore, the shape of the toner can be controlled by heating. Normally, the toner becomes more spherical when heated further.

  As the method for washing and drying the toner base particles dispersed in the aqueous medium, the above-described method and the like can be used.

Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the coalesced particles are added to and mixed with the toner base particles produced as described above. Inorganic fine particles may be added and mixed.
For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

-Extruding amount of release agent at 100 ° C of toner W-
The amount of exudation of the release agent W at 100 ° C. of the toner satisfies the following relational expression (1).
0.30 ≤ W ≤ 0.50 ... Relational expression (1)
When the W is less than 0.30, the release agent is not sufficiently oozed out particularly at the time of fixing in a low temperature range, the releasability from the fixing member is deteriorated, and image peeling occurs. On the other hand, when the W exceeds 0.50, the releasability is good, but a large amount of the release agent elutes at the paper / toner interface and hinders the adhesion between the paper and the toner. Arise.

As a method for measuring the amount W of the release agent exuded at 100 ° C. of the toner, for example, the toner is molded into a cylindrical sample having a diameter of about 8 [mm] and a height of 3 [mm]. Is heated on a heating stage capable of temperature control at 100 ° C. for 10 minutes.
Then, it can quantify by measuring the surface opposite to the heating surface of the heated cylindrical sample by the FTIR-ATR method. As an example of an apparatus used for the FTIR-ATR method, a MultiScope FTIR unit is installed in Spectrum One manufactured by PERKIN ELMER, a micro ATR of a germanium (Ge) crystal having a diameter of 100 μm, an incident angle of infrared rays of 41.5 °, The measurement was performed with a resolution of 4 cm −1 and a total of 20 times. The intensity ratio (P2850 / P828) between the peak (2850 cm-1) derived from the obtained release agent and the peak (828 cm-1) derived from the binder resin is the relative amount of the release agent near the toner particle surface, that is, The amount of the release agent oozing out. In addition, as said W, the average value after measuring 3 times by changing a measurement place was used. In the heating mode, the amount (percentage) of all toner particles in the toner layer transferred and laminated on the recording medium averages (totally), and the amount of wax that exudes in the cylindrical sample of the size. It is a necessary and sufficient time to be reflected as (ratio).

  The method for controlling the amount of exudation of the release agent W at 100 ° C. of the toner is not particularly limited. For example, the type of the release agent, the content of the release agent, or the content of the release agent-dispersing resin is included. In the method of controlling by appropriately selecting the amount, or in the chemical method of toner, after the washing step for removing the surfactant used in the emulsification or dispersion step, the toner filter cake is reslurried and predetermined at a predetermined temperature. There is a method of controlling by adding a process of heating for a time. In the heating step, it is preferable to perform the heating at an arbitrary temperature and time of 40 to 65 ° C. and a heating time of 5 minutes to 2 hours.

-Change in the amount of release agent near the toner surface before and after storage at high temperature and high humidity (W2 / W1)-
When the amount of the release agent present in the vicinity of the toner surface at normal temperature and normal humidity is W1, and the amount of the release agent present in the vicinity of the toner surface after storage at high temperature and high humidity is W2, the relationship between W1 and W2 is as follows. It is preferable to satisfy the formula (2).
1.00 ≦ W2 / W1 ≦ 1.30 ... Relational expression (2)
When W2 / W1 exceeds 1.30, the heat resistant storage stability may deteriorate, which is not preferable.

As a method for measuring the W1, for example, a toner is molded into a cylindrical sample having a diameter of about 8 [mm] and a height of 3 [mm] at room temperature and normal humidity. It can be calculated by measuring by the same FTIR-ATR method as the method for measuring the exuding amount W of the mold release agent.
As a method for measuring W2, for example, a toner stored at 40 ° C. and 70% RH for 2 weeks is molded in the same manner as W1 and measured by the FTIR-ATR method.

-Weight average molecular weight (Mw) of toner-
The weight average molecular weight (Mw) of the toner is preferably 5000 to 18000. When the Mw is 5000 or more, toner aggregates are less likely to be generated, and abnormal image generation can be sufficiently suppressed. When the Mw is 18000 or less, the low-temperature fixability of the toner is improved, and particularly the toner layer on the recording medium side (lower side) where the fixing member does not directly contact is sufficiently melted in the low-temperature region, and image peeling occurs. This is preferable.
As a measuring method of the weight average molecular weight (Mw) of the toner, for example, it can be measured by gel permeation chromatography (GPC). Specifically, the column is stabilized in a 40 ° C. heat chamber. To the column stabilized at this temperature, tetrahydrofuran (THF) as a solvent is flowed at a flow rate of 1 mL / min, and a THF sample solution of toner adjusted to a sample concentration of 0.05% to 0.6% by weight is 50 μL to 200 μL. Inject and measure.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical co. The molecular weights manufactured by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ It is appropriate to use 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

  The shape, size, etc. of the toner are not particularly limited and can be appropriately selected according to the purpose. The average circularity, volume average particle size, volume average particle size and number are as follows. It is preferable to have a ratio (volume average particle diameter / number average particle diameter) to the average particle diameter.

-Average circularity of toner-
The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles. For example, 0.950 to 0.980 is preferable, and 0.960 to 0 is preferable. .975 is more preferred. In addition, it is preferable that the particles having an average circularity of less than 0.95 are 15% or less.
When the average circularity is less than 0.950, satisfactory transferability and a high-quality image free from dust may not be obtained. When the average circularity exceeds 0.980, image formation employing blade cleaning or the like is employed. In the system, defective cleaning on the photoconductor and transfer belt occurs, and in the case of image formation with a high image area ratio such as photographic images, an untransferred image is formed due to poor paper feed, etc. The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.

  The average circularity is measured using a flow particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). It was. Specifically, 0.1 to 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and each toner 0 is added. 0.1 to 0.5 g was added, and the mixture was mixed with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured with the FPIA-2100 until the concentration of 5,000 to 15,000 / μL was obtained. In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of average circularity. In order to obtain the concentration of the dispersion, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. The amount of toner added varies depending on the particle size, and is small when the particle size is small, and needs to be increased when the particle size is large. By adding 5 g, the dispersion concentration can be adjusted to 5,000 / μl to 15,000 / μl.

-Volume average particle diameter of toner-
There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3 micrometers-10 micrometers are preferable, and 4 micrometers-7 micrometers are more preferable. When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. Therefore, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle size may increase.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, and more preferably 1.00 to 1.15.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). Then, measurement was performed with an aperture diameter of 100 μm, and analysis was performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and 0.5 g of each toner is added. The mixture was stirred with a micropartel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

(Developer)
The developer mounted on the image forming apparatus of the present invention contains at least the toner, and optionally contains other appropriately selected components such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

  In the case of the one-component developer using the toner, toner aggregation does not easily occur over time against stress caused by the developing means, and toner filming on the developing roller as the developer carrying member In addition, there is no fusion of toner to a layer thickness regulating member such as a blade for thinning the toner, and good and stable image quality can be obtained by maintaining good image density stability and transferability. . In addition, in the case of the two-component developer using the toner, toner aggregation does not easily occur over time even with agitation stress caused by the developing means, and the occurrence of abnormal images is suppressed, and the image density is stable. Good and stable image quality can be obtained by maintaining good properties and transferability.

(Career)
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core particle and the resin layer (coating layer) which coat | covers this core particle is preferable.

<Core particles>
The core particles are not particularly limited as long as they are magnetic core particles, and can be appropriately selected according to the purpose. For example, ferromagnetic metals such as iron and cobalt; oxidation of magnetite, hematite, ferrite, and the like Iron; resin particles in which magnetic materials such as various alloys and compounds are dispersed in a resin. Among these, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr-based ferrite and the like are preferable from the viewpoint of environmental considerations.

-Weight average particle diameter Dw of core particles-
The weight average particle diameter Dw of the core particles refers to the particle diameter at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction or scattering method. There is no restriction | limiting in particular as the weight average particle diameter Dw of the said core particle, Although it can select suitably according to the objective, 10 micrometers-80 micrometers are preferable, and 20 micrometers-65 micrometers are more preferable.

The weight average particle diameter Dw of the core particles is measured by using a microtrac particle size distribution meter (HRA9320-X100, manufactured by Honeywell) as a particle size distribution (relationship between number frequency and particle size) of particles measured on a number basis. And measured under the conditions described below, and calculated using the following relational expression (3). Each channel represents a length for dividing the particle size range in the particle size distribution chart into measurement width units, and the lower limit value of the particle size stored in each channel is adopted as the representative particle size.
Dw = {1 / Σ (nD3)} × {Σ (nD4)} (Expression 3)
However, in said formula relational expression (3), D represents the representative particle diameter (micrometer) of the core particle which exists in each channel, and n represents the total number of the core particle which exists in each channel.
[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

<Coating layer>
The coating layer contains at least a resin, and may contain other components such as a filler as necessary.

-Resin-
There is no restriction | limiting in particular as resin for forming the coating layer of a carrier, According to the objective, it can select suitably. For example, a crosslinkable copolymer containing polyolefin (for example, polyethylene, polypropylene, etc.) or a modified product thereof, polystyrene, acrylic resin, acrylonitrile, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; consisting of an organosiloxane bond Silicone resins or modified products thereof (for example, modified products by alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.); polyamide; polyester; polyurethane; polycarbonate; urea resin; melamine resin; benzoguanamine resin; Examples thereof include polyimide resins and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is preferable.

There is no restriction | limiting in particular as said silicone resin, According to the objective, it can select suitably from the silicone resin generally known. For example, a straight silicone resin composed only of an organosiloxane bond and a silicone resin modified with alkyd, polyester, epoxy, acrylic, urethane, etc. can be mentioned.
Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone). Specific examples of the modified silicone resin include epoxy-modified product: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-. 305 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.

  The silicone resin can be used alone, but a crosslinking reactive component, a charge amount adjusting component, and the like can be used at the same time. Examples of the crosslinking reactive component include a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent, and the like.

-Filler-
There is no restriction | limiting in particular as said filler, According to the objective, it can select suitably, For example, a conductive filler, a nonelectroconductive filler, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to contain a conductive filler and a non-conductive filler in the coating layer.

The conductive filler refers to a filler having a powder specific resistance value of 100 Ω · cm or less.
The said nonelectroconductive filler points out the filler whose powder specific resistance value exceeds 100 ohm * cm.
The powder specific resistance value of the filler is measured by a powder resistance measuring system (MCP-PD51, manufactured by Dia Instruments) and a resistivity meter (4-terminal 4-probe system, Loresta GP, manufactured by Mitsubishi Chemical Analytech). Was measured under the conditions of a sample of 1.0 g, an electrode interval of 3 mm, a sample radius of 10.0 mm, and a load of 20 kN.

--Conductive filler--
There is no restriction | limiting in particular as said electroconductive filler, According to the objective, it can select suitably. For example, a conductive filler formed by forming a layer of tin dioxide or indium oxide on a substrate such as aluminum oxide, titanium oxide, zinc oxide, barium sulfate, silicon oxide, or zirconium oxide; a conductive filler formed using carbon black, or the like It is done. Among these, a conductive filler containing aluminum oxide, titanium oxide, and barium sulfate is preferable.

--Non-conductive filler--
There is no restriction | limiting in particular as said nonelectroconductive filler, According to the objective, it can select suitably. For example, a non-conductive filler formed using aluminum oxide, titanium oxide, barium sulfate, zinc oxide, silicon dioxide, zirconium oxide, or the like can be given. Among these, non-conductive fillers containing aluminum oxide, titanium oxide, and barium sulfate are preferable.

<Carrier manufacturing method>
There is no restriction | limiting in particular as a manufacturing method of the said carrier, Although it can select suitably according to the objective, The said resin and the said filler are contained in the surface of the said core particle using a fluid bed type coating apparatus. The method of manufacturing by apply | coating a coating layer forming solution is preferable. In addition, when apply | coating the said coating layer forming solution, you may advance condensation of the resin contained in the said coating layer, and after apply | coating the said coating layer forming solution, condensation of the resin contained in the said coating layer You may proceed. There is no restriction | limiting in particular as the condensation method of the said resin, According to the objective, it can select suitably, For example, the method etc. which give a heat | fever, light, etc. to the said coating layer formation solution, etc. are mentioned. .

-Weight average particle diameter Dw of carrier-
The weight average particle diameter Dw of the carrier refers to the particle diameter at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction / scattering method. There is no restriction | limiting in particular as the weight average particle diameter Dw of the said carrier, Although it can select suitably according to the objective, 10 micrometers-80 micrometers are preferable, and 20 micrometers-65 micrometers are more preferable.

For the measurement of the weight average particle diameter Dw of the carrier, the particle size distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number is used using a Microtrac particle size distribution meter (HRA9320-X100, manufactured by Onewell). Measured under the conditions described below and calculated using the following relational expression (4). Each channel represents a length for dividing the particle size range in the particle size distribution chart into measurement width units, and the lower limit value of the particle size stored in each channel is adopted as the representative particle size.
Dw = {1 / Σ (nD3)} × {Σ (nD4)} (Expression 4)
In the relational expression (4), D represents the representative particle diameter (μm) of carriers present in each channel, and n represents the total number of carriers present in each channel.
[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

  When the developer is a two-component developer, the mixing ratio of the toner and the carrier in the two-component developer is preferably such that the mass ratio of the toner to the carrier is 2.0 to 12.0% by mass, More preferably, it is 2.5-10.0 mass%.

(Image forming method and image forming apparatus)
The image forming method used in the present invention includes at least an electrostatic latent image forming step (charging step and exposure step), a developing step, a transfer step, and a fixing step, and other types appropriately selected as necessary. The process includes, for example, a static elimination process, a cleaning process, a recycling process, a control process, and the like.
The image forming apparatus of the present invention includes an electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, and exposing the surface of the electrostatic latent image carrier to expose the electrostatic latent image. An exposure means for forming the electrostatic latent image, a developing means for sequentially developing the electrostatic latent image with a plurality of colors of toner to form a visible image, a transfer means for transferring the visible image to a recording medium, and a recording medium. And at least fixing means for fixing the transferred image, and other means appropriately selected as necessary, for example, static elimination means, cleaning means, recycling means, control means, and the like.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape thereof is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like. Is mentioned. Among these, an organic photoreceptor (OPC) is preferable in that a higher definition image can be obtained.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by electrostatic latent image forming means. Can do.
The electrostatic latent image forming unit includes, for example, a charging unit (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure that exposes the surface of the electrostatic latent image carrier imagewise. Means (exposure unit).

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.
The charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying a direct current and an alternating voltage.
Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

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

-Development process and development means-
The developing step is a step of developing the electrostatic latent image with the toner to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner, and can be performed by the developing unit.
The developing unit preferably includes, for example, at least a developing unit that accommodates the toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner, and includes a toner-containing container. Etc. are more preferable.

The developing device may be a monochromatic developing device or a multi-color developing device, and has, for example, an agitator that frictionally agitates and charges the toner and a rotatable magnet roller. A thing etc. are mentioned suitably.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

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

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

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the developer of each color is transferred to the recording medium, or the developer of each color. On the other hand, it may be carried out at the same time in a state where these are laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed. The heating in the heating and pressing means 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 step and the fixing unit depending on the purpose.

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

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

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
The control step is a step of controlling each step, and each step can be suitably performed by a control means.
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  FIG. 1 shows a first example of an image forming apparatus of the present invention. The image forming apparatus 100A includes a photosensitive drum 10, a charging roller 20, an exposure device (not shown), a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70. Prepare.

  The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged on the inner side, and can move in the direction of the arrow in the figure. A part of the three rollers 51 also functions as a transfer bias roller that can apply a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is disposed to face the intermediate transfer belt 50. Further, around the intermediate transfer belt 50, a corona charging device 58 for applying a charge to the toner image transferred to the intermediate transfer belt 50 is connected to the photosensitive drum 10 with respect to the rotation direction of the intermediate transfer belt 50. It is disposed between the contact portion of the intermediate transfer belt 50 and the contact portion of the intermediate transfer belt 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 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 41. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller (developer carrier) 44. The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in the figure. Further, a part of the developing belt 41 is in contact with the photosensitive drum 10.

  Next, a method for forming an image using the image forming apparatus 100A will be described. First, the charging roller 20 is used to uniformly charge the surface of the photosensitive drum 10, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the transfer bias applied from the transfer roller 80 is used. Then, it is transferred (secondary transfer) onto the transfer paper 95. On the other hand, the photosensitive drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is discharged by the discharging lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

  FIG. 2 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than that, the configuration is the same as that of the image forming apparatus 100A.

FIG. 3 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100 </ b> C is a tandem type color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The intermediate transfer belt 50 provided at the center of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15 and 16, and can move in the direction of the arrow in the figure. In the vicinity of the roller 15, a cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred onto the recording paper is disposed. The image forming units 120Y, 120C, 120M, and 120K for yellow, cyan, magenta, and black are juxtaposed along the conveying direction while facing the intermediate transfer belt 50 stretched by the rollers 14 and 15. An exposure device 21 is disposed in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is disposed. The secondary transfer belt 24 is an endless belt stretched around a pair of rollers 23, and the recording paper and the intermediate transfer belt 50 conveyed on the secondary transfer belt 24 are between the rollers 16 and 23. Can touch. Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26 that is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26. Is arranged. A sheet reversing device 28 for reversing the recording paper when an image is formed on both sides of the recording paper is disposed in the vicinity of the secondary transfer belt 24 and the fixing device 25.

  Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color document is set on the contact glass 32 of the scanner 300 to automatically convey the document. The device 400 is closed. When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the contact glass 32. In this case, the scanner 300 is immediately driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, the reflected light from the original surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34 and then received by the reading sensor 36 via the imaging lens 35, whereby the original is received. It is read and image information of black, yellow, magenta and cyan is obtained.

The image information for each color is transmitted to the image forming unit 120 for each color, and a toner image for each color is formed. As shown in FIG. 9, the image forming units 120 for each color each include a photosensitive drum 10, a charging roller 160 that uniformly charges the photosensitive drum 10, and image information for each color. An exposure device that exposes the exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; A transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a static elimination lamp 64 are provided.
The toner images of the respective colors formed by the image forming units 120 of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is stretched and moved by the rollers 14, 15, and 16, and superimposed to form a composite toner image. It is formed.

In the image forming apparatus of the present invention, the recording order is such that the order in which the toner is stacked on the recording medium is in order from the fixing unit side to the toner having the largest amount of the release agent W of the release agent at 100 ° C. Transferred onto the medium. In the image forming apparatus shown in FIG. 8, the value of W of toner is the smallest for black toner, and the value of W increases in the order of cyan toner, magenta toner, and yellow toner. Cyan toner, magenta toner, and yellow toner are transferred in this order.
In the present invention, the arrangement of black, cyan, magenta, and yellow in the image forming apparatus may be adjusted by W, or the toner W may be adjusted by the arrangement of the apparatus.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied in order to remove paper dust from the recording paper. Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is sent. The toner image is transferred onto the recording paper (secondary transfer). The toner remaining on the intermediate transfer belt 50 to which the composite toner image has been transferred is removed by the cleaning device 17.

  The recording paper on which the composite toner image has been transferred is conveyed by the secondary transfer belt 24 and then the composite toner image is fixed by the fixing device 25. Next, the conveyance path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. Alternatively, the recording path of the recording paper is switched by the switching claw 55, reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then discharged onto the discharge tray 57 by the discharge roller 56. .

  The image forming apparatus of the present invention can provide high-quality images over a long period of time.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. In addition, the part in an Example represents a mass part unless there is particular description, and% represents the mass%.

[Production Example 1; Production of crystalline polyester resin 1]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 202 parts by mass (1.00 mol) of sebacic acid, 154 parts by mass (1.30 mol) of 1,6-hexanediol, and tetrabutoxy titanate as a condensation catalyst 0.5 part by mass was added, and the reaction was carried out for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw was about 15 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [crystalline polyester resin 1] was obtained. The obtained [Crystalline Polyester Resin 1] had Mw of 14,000, a maximum peak temperature (melting point) of melting heat of 66 ° C., a softening temperature of 75 ° C., and a maximum softening temperature / melting heat peak temperature of 1.14.

[Production Example 2; Production of amorphous polyester resin 1 (unmodified polyester resin)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube, 282 parts by mass of bisphenol A EO 2 mol adduct, 161 parts by mass of bisphenol A PO 2 mol adduct, 150 parts by mass of terephthalic acid, 15 parts by mass of adipic acid, and tetrabutoxy 0.5 parts by mass of titanate was added, and the reaction was carried out for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg. When the acid value reached 2, the mixture was cooled to 180 ° C., 13 parts by weight of trimellitic anhydride was added, and the reaction was carried out at normal pressure for 3 hours. Polyester resin 1] was obtained. [Amorphous polyester resin 1] obtained had Mw of 6,000 and Tg of 54 ° C.

[Production Example 3; Production of amorphous polyester resin 2 (unmodified polyester resin)]
[Amorphous polyester resin 2] was obtained in the same manner as in Production Example 2, except that the addition amount of bisphenol A EO 2 mol adduct was changed to 294 parts by mass and the addition amount of bisphenol A PO 2 mol adduct was changed to 167 parts by mass. . The obtained [Amorphous polyester resin 2] had Mw of 5,000 and Tg of 54 ° C.

[Production Example 4; Production of amorphous polyester resin 3 (unmodified polyester resin)]
[Amorphous polyester resin 3] was obtained in the same manner as in Production Example 2, except that the addition amount of bisphenol A EO 2 mol adduct was changed to 303 parts by mass and the addition amount of bisphenol A PO 2 mol adduct was changed to 174 parts by mass. . The obtained [Amorphous polyester resin 3] had Mw of 4,000 and Tg of 53 ° C.

[Production Example 5; Production of amorphous polyester resin 4 (unmodified polyester resin)]
[Amorphous polyester resin 4] was obtained in the same manner as in Production Example 2, except that the addition amount of bisphenol A EO 2 mol adduct was changed to 315 parts by mass and the addition amount of bisphenol A PO 2 mol adduct was changed to 180 parts by mass. . The obtained [Amorphous polyester resin 4] had Mw of 3,000 and Tg of 52 ° C.

[Production Example 6; Production of amorphous polyester resin 5 (unmodified polyester resin)]
[Amorphous polyester resin 5] was obtained in the same manner as in Production Example 2 except that the addition amount of bisphenol A EO 2 mol adduct was changed to 327 parts by mass and the addition amount of bisphenol A PO 2 mol adduct was changed to 187 parts by mass. . The obtained [Amorphous polyester resin 5] had Mw of 2,000 and Tg of 51 ° C.

[Production Example 7; Production of amorphous polyester resin 6 (unmodified polyester resin)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube, 210 parts by mass of bisphenol A EO 2 mol adduct, 121 parts by mass of bisphenol A PO 2 mol adduct, 150 parts by mass of terephthalic acid, 15 parts by mass of adipic acid, and tetrabutoxy 0.5 parts by mass of titanate was added, and the reaction was carried out for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg, the reaction is carried out until Mw reaches approximately 14,000, then cooled to 180 ° C., 13 parts by weight of trimellitic anhydride is added, and the reaction is carried out at normal pressure for 3 hours. [Amorphous polyester resin 6] was obtained. The obtained [Amorphous polyester resin 6] had Mw of 14,000 and Tg of 60 ° C.

[Production Example 8; Production of amorphous polyester resin 7 (unmodified polyester resin)]
In Production Example 7, the addition amount of bisphenol A EO 2 mol adduct was changed to 222 parts by mass, the addition amount of bisphenol A PO 2 mol adduct was changed to 128 parts by mass, and the reaction time under reduced pressure of 5 to 20 mmHg was about 13 [Amorphous polyester resin 7] was obtained in the same manner except that the amount was changed to reach 000. The obtained [Amorphous polyester resin 7] had a Mw of 13,000 and a Tg of 60 ° C.

[Production Example 9; Production of amorphous polyester resin 8 (unmodified polyester resin)]
In Production Example 7, the addition amount of the bisphenol A EO 2 mol adduct was changed to 234 parts by mass, the addition amount of the bisphenol A PO 2 mol adduct was changed to 134 parts by mass, and the reaction time under reduced pressure of 5 to 20 mmHg was about 12, [Amorphous polyester resin 8] was obtained in the same manner except that the amount was changed to reach 000. The obtained [Amorphous polyester resin 8] had Mw of 12,000 and Tg of 59 ° C.

[Production Example 10; Production of amorphous polyester resin 9 (unmodified polyester resin)]
In Production Example 7, the addition amount of bisphenol A EO 2 mol adduct was changed to 246 parts by mass, the addition amount of bisphenol A PO 2 mol adduct was changed to 141 parts by mass, and the reaction time under reduced pressure of 5 to 20 mmHg was about 11, [Amorphous polyester resin 9] was obtained in the same manner except that the amount was changed to reach 000. The obtained [Amorphous polyester resin 9] had Mw of 11,000 and Tg of 58 ° C.

[Production Example 11; Production of amorphous polyester resin 10 (unmodified polyester resin)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube, 204 parts by mass of bisphenol A EO 2 mol adduct, 115 parts by mass of bisphenol A PO 2 mol adduct, 166 parts by mass of terephthalic acid, and 0.5 parts by mass of tetrabutoxy titanate The reaction was carried out for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and it reacted until Mw reached about 40,000, and [Amorphous polyester resin 10] was obtained. The obtained [Amorphous polyester resin 10] had an Mw of 40,000 and a Tg of 65 ° C.

[Production Example 12; Production of amorphous polyester resin 11 (unmodified polyester resin)]
In Production Example 11, the addition amount of the bisphenol A EO 2 mol adduct was changed to 210 parts by mass, the addition amount of the bisphenol A PO 2 mol adduct was changed to 121 parts by mass, and the reaction time under reduced pressure of 5 to 20 mmHg was about 38, [Amorphous polyester resin 11] was obtained in the same manner except that the amount was changed to reach 000. The obtained [Amorphous polyester resin 11] had Mw of 38,000 and Tg of 64 ° C.

[Production Example 13; Production of amorphous polyester resin 12 (unmodified polyester resin)]
In Production Example 11, the addition amount of bisphenol A EO 2 mol adduct was changed to 222 parts by mass, the addition amount of bisphenol A PO 2 mol adduct was changed to 128 parts by mass, and the reaction time under reduced pressure of 5 to 20 mmHg was approximately 36, [Amorphous polyester resin 12] was obtained in the same manner except that the amount was changed to reach 000. The obtained [Amorphous polyester resin 12] had Mw of 36,000 and Tg of 64 ° C.

[Production Example 14; Production of amorphous polyester resin 13 (unmodified polyester resin)]
In Production Example 11, the addition amount of the bisphenol A EO 2 mol adduct was changed to 234 parts by mass, the addition amount of the bisphenol A PO 2 mol adduct was changed to 134 parts by mass, and the reaction time under reduced pressure of 5 to 20 mmHg was approximately 34, [Amorphous polyester resin 13] was obtained in the same manner except that the amount was changed to reach 000. The obtained [Amorphous polyester resin 13] had Mw of 34,000 and Tg of 63 ° C.

[Production Example 15; Production of amorphous polyester resin 14 (unmodified polyester resin)]
In Production Example 11, the addition amount of bisphenol A EO 2 mol adduct was changed to 240 parts by mass, the addition amount of bisphenol A PO 2 mol adduct was changed to 138 parts by mass, and the reaction time under reduced pressure of 5 to 20 mmHg was about 33, [Amorphous polyester resin 14] was obtained in the same manner except that the amount was changed to reach 000. The obtained [Amorphous polyester resin 14] had Mw of 33,000 and Tg of 63 ° C.

[Production Example 16; Production of polyester prepolymer 1]
660 parts by mass of bisphenol A EO 2 mol adduct, 82 parts by mass of bisphenol A PO 2 mol adduct, 291 parts by mass of terephthalic acid, and 1 part by mass of tetrabutoxy titanate are placed in a reaction vessel equipped with a condenser, a stirrer and a nitrogen insertion tube. The reaction was carried out for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 10-15 mmHg for 7 hours, and [Intermediate polyester 1] was obtained. [Intermediate polyester 1] was Mw12,600.
Next, 400 parts by mass of the obtained [intermediate polyester 1], 95 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen insertion tube. Was reacted at 80 ° C. for 8 hours to obtain a 50% by mass ethyl acetate solution of [polyester prepolymer 1] having an isocyanate group at the terminal. [Polyester prepolymer 1] had a free isocyanate mass% of 1.41%.

[Production Example 17; Production of polyester prepolymer 2]
In Production Example 16, except that the addition amount of bisphenol A EO 2 mol adduct was changed to 720 parts by mass, and the addition amount of bisphenol A PO 2 mol adduct was changed to 89 parts by mass to obtain [Intermediate polyester 2], Finally, a 50% by mass ethyl acetate solution of [Polyester Prepolymer 2] was obtained. The obtained [intermediate polyester 2] was Mw 9,300, and the [polyester prepolymer 2] had a free isocyanate mass% of 1.47%.

[Production Example 18; Production of polyester prepolymer 3]
In Production Example 16, except that the addition amount of bisphenol A EO 2 mol adduct was changed to 780 parts by mass and the addition amount of bisphenol A PO 2 mol adduct was changed to 95 parts by mass, [Intermediate Polyester 3] was obtained in the middle. Finally, a 50% by mass ethyl acetate solution of [Polyester Prepolymer 3] was obtained. The obtained [Intermediate polyester 3] was Mw8,200, and the [polyester prepolymer 3] had a free isocyanate mass% of 1.52%.

[Production Example 19; Production of graft polymer]
In a reaction vessel equipped with a stir bar and a thermometer, 480 parts by mass of xylene and 100 parts by mass of low molecular weight polyethylene (Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 128 ° C.) are sufficiently dissolved and purged with nitrogen. After that, a mixed solution of 740 parts by mass of styrene, 100 parts by mass of acrylonitrile, 60 parts by mass of butyl acrylate, 36 parts by mass of di-t-butylperoxyhexahydroterephthalate, and 100 parts by mass of xylene was dropped at 170 ° C. for 3 hours. The polymer was polymerized and held at this temperature for 30 minutes. Next, the solvent was removed to synthesize [graft polymer]. The obtained [graft polymer] had Mw of 24,000 and Tg of 67 ° C.

[Manufacture of black toner matrix]
[Production Example 20; Production of Black Toner Base 1 (Ester Elongation Method)]
-Preparation of release agent dispersion 1-
50 parts by weight of paraffin wax (HNP-9, manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.), 30 parts by weight of [graft polymer], and 420 parts of ethyl acetate are placed in a container equipped with a stirring bar and a thermometer. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), the liquid feeding speed was 1 kg / hr, and the disk peripheral speed. Dispersion was carried out under the conditions of 3 volume filling with 80% by volume of 6 m / sec, 0.5 mm zirconia beads to obtain [Partitioner Dispersion Liquid 1].

-Preparation of black masterbatch 3-
Amorphous polyester resin 3 100 parts by mass Carbon black (Printex 35, manufactured by Degussa) 100 parts by mass (DBP oil absorption: 42 mL / 100 g, pH: 9.5)
-Ion exchange water 50 mass parts Said raw material was mixed using the Henschel mixer (made by Mitsui Mining Co., Ltd.). The obtained mixture was kneaded using two rolls. The kneading temperature started kneading from 90 ° C., and then gradually cooled to 50 ° C. The obtained kneaded material was pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Black Masterbatch 3].

-Preparation of black oil phase 1-
In a container equipped with a thermometer and a stirrer, 113 parts by weight of [Amorphous Polyester Resin 3], 75 parts by weight of [Releasing Agent Dispersion 1], 20 parts by weight of [Black Masterbatch 3], 68 parts by weight of ethyl acetate And pre-dispersed with a stirrer, and then stirred with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotational speed of 5,000 rpm to uniformly dissolve and disperse [Black oil phase 1] Got.

-Production of aqueous dispersion of resin fine particles-
In a reaction vessel equipped with a stirrer and a thermometer, 600 parts by mass of water, 120 parts by mass of styrene, 100 parts by mass of methacrylic acid, 45 parts by mass of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, Sanyo Chemical Industries) When 10 parts by mass and 1 part by mass of ammonium persulfate were charged and stirred at 400 rpm for 20 minutes, a white emulsion was obtained. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts by mass of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 6 hours to obtain [Aqueous dispersion of resin fine particles]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion] was 60 nm, the weight average molecular weight of the resin component was 140,000, and Tg was 73 ° C.

-Preparation of aqueous phase 1-
990 parts by weight of water, 83 parts by weight of an aqueous dispersion of resin fine particles, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 90 ethyl acetate Mass parts were mixed and stirred to obtain [Aqueous Phase 1].

-Emulsification or dispersion-
To 275 parts by mass of [Black Oil Phase 1], 32 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 3] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine were added. Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Black oil phase 1 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Black oil phase 1 ′] was added and emulsified for 1 minute to obtain [Black emulsified slurry 1].

-Solvent removal-Washing-Drying-
[Black emulsified slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Black slurry 1]. The obtained [Black slurry 1] was filtered under reduced pressure, and then the following washing treatment was performed.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) 100 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake of (1) and mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), followed by filtration under reduced pressure.
(3) 100 parts by mass of 10 mass% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(4) 300 parts by mass of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered twice.
(5) 300 parts by mass of ion-exchanged water was added to the filter cake of (4), heated at 50 ° C. for 5 minutes with stirring, and then filtered again to obtain filter cake 1.
The obtained filter cake 1 was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the mixture was sieved with a mesh having a mesh size of 75 μm to prepare a black toner base 1.

[Production Example 21; Production of black toner base material 2 (ester elongation method)]
-Preparation of crystalline polyester resin dispersion 1-
100 parts by weight of [Crystalline Polyester Resin 1] and 400 parts of ethyl acetate are placed in a container in which a stir bar and a thermometer are set. Using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), dispersion was performed for 5 hours under the conditions of a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% by volume of 0.5 mm zirconia beads. A polyester resin dispersion 1] was obtained.

-Preparation of black oil phase 2-
In a container equipped with a thermometer and a stirrer, 97 parts by mass of [Amorphous polyester resin 3], 68 parts by mass of [Crystalline polyester resin dispersion 1], 75 parts by mass of [Releasing agent dispersion 1], [Black Master batch 3] 20 parts by mass and 16 parts by mass of ethyl acetate were added and pre-dispersed with a stirrer, and then stirred at a rotational speed of 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) It was uniformly dissolved and dispersed to obtain [Black oil phase 2].

-Emulsification or dispersion-
36 parts by mass of an ethyl acetate solution of [Polyester prepolymer 2] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine were added to 275 parts by mass of [Black oil phase 2]. Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Black oil phase 2 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Black oil phase 2 ′] was added and emulsified for 1 minute to obtain [Black emulsified slurry 2].

-Solvent removal-Washing-Drying-
[Black emulsified slurry 2] was subjected to solvent removal, washing, drying, air sieving, and black toner under the same conditions as [Black emulsified slurry 1] except that the heating temperature of (5) was changed to 45 ° C. A mother body 2 was produced.

[Production Example 22: Production of black toner base 3 (ester elongation method)]
-Preparation of release agent dispersion 2-
In a container equipped with a stir bar and a thermometer, 50 parts by weight of paraffin wax (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C.), 22.5 parts by weight of [graft polymer], and 427.5 parts of ethyl acetate The mixture was heated to 80 ° C. with stirring and held at 80 ° C. for 5 hours, then cooled to 30 ° C. in 1 hour, and a liquid feed rate of 1 kg / hr using a bead mill (Ultra Visco Mill, manufactured by IMEX). Dispersion was carried out under conditions of a disk peripheral speed of 6 m / sec, filling with 80% by volume of 0.5 mm zirconia beads and 3 passes to obtain [Partitioner Dispersion Liquid 2].

-Production of black oil phase 3-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 21, the oil phase was produced under the same conditions except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2] and the heating temperature of (5) was changed to 55 ° C. Emulsification or dispersion, solvent removal, washing, drying, air sieving, and black toner base 3 were produced.

[Production Example 23; Production of black toner base 4 (ester elongation method)]
-Preparation of black oil phase 4-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 21, except that the heating temperature of (5) was changed to 50 ° C., oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving were carried out to produce a black toner base 4 did.

[Production Example 24; Production of black toner base 5 (ester elongation method)]
-Preparation of black oil phase 5-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 21, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 20 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A black toner base 5 was produced.

[Production Example 25; Production of Black Toner Base 6 (Ester Elongation Method)]
-Production of black oil phase 6-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 21, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 10 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A black toner base 6 was produced.

[Production Example 26; Production of Black Toner Base 7 (Ester Elongation Method)]
-Preparation of black oil phase 7-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 21, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 15 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A black toner base 7 was prepared.

[Production Example 27; Production of black toner base 8 (ester elongation method)]
-Preparation of black oil phase 8-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 21, except that the heating time of (5) was changed to 15 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving were performed to produce a black toner base 8 did.

[Production Example 28; Production of black toner base material 9 (ester elongation method)]
-Production of black oil phase 9-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 21, the oil phase was produced under the same conditions except that [release agent dispersion 1] was changed to [release agent dispersion 2] and the heating temperature of (5) was changed to 40 ° C. Emulsification or dispersion, solvent removal, washing, drying, air sieving, and black toner base 9 were produced.

[Production Example 29; Production of black toner base material 10 (dissolution suspension method)]
-Preparation of black oil phase 10-
In a container equipped with a thermometer and a stirrer, 110 parts by weight of [Amorphous polyester resin 3], 19 parts by weight of [Amorphous polyester resin 14], 75 parts by weight of [Releasing agent dispersion 1], [Black master] Batch 3] 20 parts by mass and 92 parts by mass of ethyl acetate were added and pre-dispersed with a stirrer, and then stirred at a rotational speed of 5,000 rpm with a TK homomixer (made by Tokushu Kika Co., Ltd.) Were dissolved and dispersed in [Black Oil Phase 10].

-Emulsification or dispersion-
In a separate container equipped with a stirrer and a thermometer, 400 parts by mass of [Aqueous Phase 1] was placed, and while stirring at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [black oil Phase 10] was added and emulsified for 1 minute to obtain [Black Emulsion Slurry 10].

-Solvent removal-Washing-Drying-
[Black emulsified slurry 10] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] to prepare a black toner base 10.

[Production Example 30; Production of black toner base 11 (dissolution suspension method)]
-Preparation of black oil phase 11-
In a container equipped with a thermometer and a stirrer, 96 parts by mass of [Amorphous polyester resin 3], 19 parts by mass of [Amorphous polyester resin 14], 68 parts by mass of [Crystalline polyester resin dispersion 1], Mold Dispersion Liquid 1] 75 parts by mass, [Black Masterbatch 3] 20 parts by mass, and ethyl acetate 38 parts by mass were pre-dispersed with a stirrer, and then TK homomixer (manufactured by Tokushu Kika Co., Ltd.). ) At a rotation speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Black oil phase 11].

-Emulsification or dispersion-
In a separate container equipped with a stirrer and a thermometer, 400 parts by mass of [Aqueous Phase 1] was placed, and while stirring at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [black oil Phase 11] was added and emulsified for 1 minute to obtain [Black Emulsion Slurry 11].

-Solvent removal-Washing-Drying-
[Black emulsified slurry 11] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as in [Black emulsified slurry 1] to prepare a black toner base 11.

[Production Example 31; Production of Black Toner Base 12 (Emulsion Aggregation Method)]
-Preparation of amorphous polyester resin dispersion 9-
[Amorphous polyester resin 9] 60 parts by mass of ethyl acetate was added to 60 parts by mass and dissolved. Next, 120 parts by weight of water, 2 parts by weight of an anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution were mixed in [Aqueous phase] 120 parts by mass of the resin solution was added and emulsified using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then emulsified with a Manton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an [emulsified slurry].
Next, the [emulsified slurry] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 4 hours to obtain [Amorphous polyester resin dispersion 9]. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in the obtained [amorphous polyester resin dispersion liquid 9] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

-Preparation of amorphous polyester resin dispersion 14-
[Amorphous Polyester Resin Dispersion 9] In the same manner as in [Amorphous Polyester Resin Dispersion 9] except that [Amorphous Polyester Resin 9] is replaced with [Amorphous Polyester Resin 14]. ] Was obtained. It was 0.16 micrometer when the volume average particle diameter of the particle | grains in the obtained [amorphous polyester resin dispersion liquid 14] was measured with the particle size distribution measuring apparatus (LA-920, Horiba, Ltd. make).

-Preparation of release agent dispersion 3-
25 parts by mass of paraffin wax (HNP-9, manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.), 1 part by mass of an anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 200 parts by mass of water are mixed, and 90 ° C. And melted. Next, this melt was emulsified with a homogenizer (IKA, Ultra Tarrax T50), and then emulsified with a Menton Gorin high-pressure homogenizer (Gorin) to obtain [Releasing Agent Dispersion 3].

-Preparation of colorant dispersion 1-
Carbon black (Printtex35, manufactured by Degussa) 20 parts by mass, anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by mass, and water 80 parts by mass are mixed together, and a TK homomixer (special machine) And [Colorant Dispersion 1] was obtained.

-Aggregation-
In a container equipped with a thermometer and a stirrer, 235 parts by mass of [Amorphous polyester resin dispersion 9], 57 parts by mass of [Amorphous polyester resin dispersion 14], and 45 parts by mass of [release agent dispersion 3] [Colorant dispersion 1] 34 parts by mass and 600 parts by mass of water were added and stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, the dispersion was heated to 45 ° C. while gradually dropping 50 parts by mass of a 5% by mass magnesium chloride aqueous solution while stirring at 5000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). The aggregated particles were kept at 45 ° C. until the volume average particle diameter grew to 5.1 μm. Heated to 90 ° C. while maintaining pH 9 by adding 2% by weight aqueous sodium hydroxide solution to this, kept in this state for 2 hours, cooled to 20 ° C. at 1 ° C./min, [Black Slurry 12] Got.

-Solvent removal-Washing-Drying-
[Black slurry 12] was washed, dried, and air sieved under the same conditions as in [Black slurry 1] to prepare a black toner base 12.

[Production Example 32; Production of Black Toner Base 13 (Emulsion Aggregation Method)]
-Preparation of crystalline polyester resin dispersion 2-
[Crystalline Polyester Resin 1] 60 parts by mass of ethyl acetate was added to 60 parts by mass and mixed and stirred at 60 ° C. to dissolve. Next, 120 parts by weight of water, 2 parts by weight of an anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution were mixed in [Aqueous phase] 120 parts by mass of the resin solution was added and emulsified using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then emulsified with a Manton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an [emulsified slurry].
Next, the [emulsified slurry] was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 60 ° C. for 4 hours to obtain [Crystalline polyester resin dispersion 2]. It was 0.17 micrometer when the volume average particle diameter of the particle | grains in the obtained [crystalline polyester resin dispersion liquid 2] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

-Aggregation-
In a container equipped with a thermometer and a stirrer, 207 parts by mass of [Amorphous polyester resin dispersion 9], 57 parts by mass of [Amorphous polyester resin dispersion 14], 28 parts of [crystalline polyester resin dispersion 2] Part, [release agent dispersion 3] 45 parts by mass, [colorant dispersion 1] 34 parts by mass and water 600 parts by mass were stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, the dispersion was heated to 45 ° C. while gradually dropping 50 parts by mass of a 5% by mass magnesium chloride aqueous solution while stirring at 5000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). The aggregated particles were kept at 45 ° C. until the volume average particle diameter grew to 4.9 μm. This was cooled to 20 ° C. to obtain [Black Slurry 13].

-Solvent removal-Washing-Drying-
[Black slurry 13] was washed, dried, and air sieved under the same conditions as [Black slurry 1] except that the heating time of (5) was changed to 15 minutes to produce a black toner base 13.

[Production Example 33; Production of black toner base material 14 (pulverization method)]
-Production of Black Master-Batch 9-
[Black masterbatch 9] was obtained in the same manner as in [Black masterbatch 3] except that [amorphous polyester resin 3] was changed to [amorphous polyester resin 9].

-Melt kneading, grinding, classification-
44 parts by mass of [Amorphous polyester resin 9], 28 parts by mass of [Amorphous polyester resin 13], 6 parts by mass of paraffin (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C.), and [Black Masterbatch 9] ] 12 parts by mass were premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.), and then uniaxial kneader (compact bus co-kneader, manufactured by Buss). The mixture was melted and kneaded under the conditions of set temperature (inlet part 90 ° C.), outlet part (60 ° C.) and feed amount (10 kg / Hr). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulverizer (manufactured by Hosokawa Micron). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, under conditions of air pressure (6.0 atm / cm @ 2) and feed amount (0.5 kg / hr). Finely pulverized and further classified by a classifier (manufactured by Alpine, 132MP) to obtain [Black Toner Base 14].

[Production Example 34; Production of Black Toner Base 15 (Crushing Method)]
-Melt kneading, grinding, classification-
[Amorphous Polyester Resin 9] 42 parts by mass, [Amorphous Polyester Resin 13] 25 parts by mass, [Crystalline Polyester Resin 1] 5 parts by mass, paraffin (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C. ) After 6 parts by weight and 12 parts by weight of [Black Masterbatch 9] were premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.), a uniaxial kneader (small bus) -It melted and kneaded | mixed on condition of preset temperature (inlet part 90 degreeC), outlet part (60 degreeC), and feed amount (10 kg / Hr) in the co-kneader (Buss make). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulverizer (manufactured by Hosokawa Micron). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, under conditions of air pressure (6.0 atm / cm @ 2) and feed amount (0.5 kg / hr). Finely pulverized and further classified by a classifier (manufactured by Alpine, 132MP) to obtain [Black Toner Base 15].

[Production Example 35; Production of black toner base material 16 (ester elongation method)]
-Preparation of black masterbatch 4-
[Black masterbatch 4] was obtained in the same manner as in [Black masterbatch 3] except that [amorphous polyester resin 3] was changed to [amorphous polyester resin 4].

-Preparation of black oil phase 16-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is changed to 117 parts by mass of [Amorphous Polyester Resin 4], and [Black Masterbatch 3] is changed to [Black Masterbatch 4]. [Black oil phase 16] was obtained in the same manner except that the amount of ethyl acetate added was changed to 64 parts by mass.

-Emulsification or dispersion-
To 275 parts by mass of [Black oil phase 16], 24 parts by mass of an ethyl acetate solution of [Polyester prepolymer 3] and 1.5 parts by mass of a 50% by mass ethyl acetate solution of isophorone diamine were added. The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Black oil phase 16 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Black oil phase 16 ′] was added and emulsified for 1 minute to obtain [Black emulsified slurry 16].

-Solvent removal-Washing-Drying-
[Black emulsified slurry 16] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as in [Black emulsified slurry 1] to prepare a black toner base 16.

[Production Example 36; Production of Black Toner Base 17 (Ester Elongation Method)]
-Preparation of black oil phase 17-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 106 parts by mass of [Amorphous Polyester Resin 9], [Black Masterbatch 3] is [Black Masterbatch 9], [Black oil phase 17] was obtained in the same manner except that the amount of ethyl acetate added was changed to 74 parts by mass.

-Emulsification or dispersion-
To 275 parts by mass of [Black Oil Phase 17], 45 parts by mass of [Polyester Prepolymer 2] in ethyl acetate and 3 parts by mass of 50% by mass of isophoronediamine in ethyl acetate were added. Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Black oil phase 17 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Black oil phase 17 ′] was added and emulsified for 1 minute to obtain [Black emulsified slurry 17].

-Solvent removal-Washing-Drying-
[Black Emulsion Slurry 17] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black Slurry 1] except that the heating time of (5) was changed to 20 minutes. Produced.

[Production Example 37; Production of black toner base 18 (ester elongation method)]
−Preparation of black masterbatch 5−
[Black masterbatch 5] was obtained in the same manner as in [Black masterbatch 3] except that [amorphous polyester resin 3] was changed to [amorphous polyester resin 5].

-Preparation of black oil phase 18-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 123 parts by mass of [Amorphous Polyester Resin 5], [Black Masterbatch 3] is [Black Masterbatch 5], [Black oil phase 18] was obtained in the same manner except that the amount of ethyl acetate added was changed to 73 parts by mass.

-Emulsification or dispersion-
To 290 parts by mass of [Black Oil Phase 18], 12 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 3] and 1.2 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine were added, and a TK homomixer (special (Manufactured by Kikai Co., Ltd.) at a rotation speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Black oil phase 18 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Black oil phase 18 ′] was added and emulsified for 1 minute to obtain [Black emulsified slurry 18].

-Solvent removal-Washing-Drying-
[Black emulsified slurry 18] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as in [Black emulsified slurry 1] to prepare a black toner base 18.

[Production Example 38; Production of Black Toner Base 19 (Ester Elongation Method)]
-Preparation of black masterbatch 6-
[Black Masterbatch 6] was obtained in the same manner as in [Black Masterbatch 3] except that [Amorphous Polyester Resin 3] was changed to [Amorphous Polyester Resin 6].

-Preparation of black oil phase 19-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 106 parts by mass of [Amorphous Polyester Resin 6], [Black Masterbatch 3] is [Black Masterbatch 6], [Black oil phase 19] was obtained in the same manner except that the amount of ethyl acetate added was changed to 71 parts by mass.

-Emulsification or dispersion-
To 271 parts by mass of [Black Oil Phase 19], 46 parts by mass of [Polyester Prepolymer 1] in ethyl acetate and 3.5 parts by mass of 50% by mass of isophoronediamine in ethyl acetate were added. The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Black oil phase 19 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Black oil phase 19 ′] was added and emulsified for 1 minute to obtain [Black emulsified slurry 19].

-Solvent removal-Washing-Drying-
[Black emulsified slurry 19] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black slurry 1] except that the heating time of (5) was changed to 20 minutes. Produced.

[Production Example 39; Production of Black Toner Base 20 (Ester Elongation Method)]
In Production Example 21, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 25 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A black toner base 20 was produced.

[Production Example 40; Production of black toner base material 21 (ester elongation method)]
In Production Example 21, the same conditions were used except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2], the heating temperature of (5) was changed to 55 ° C., and the heating time was changed to 20 minutes. Then, an oil phase was prepared, emulsified or dispersed, solvent removed, washed, dried, and air sieved to prepare a black toner base 21.

[Production Example 41; Production of Black Toner Base 22 (Ester Elongation Method)]
In Production Example 21, a black toner base 22 was produced under the same conditions except that the heat treatment of (5) was changed to no, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving. .

[Manufacture of yellow toner matrix]
[Production Example 42; Production of Yellow Toner Base 1 (Ester Elongation Method)]
-Preparation of yellow masterbatch 2-
In the production of [Black Masterbatch 3], [Amorphous Polyester Resin 3] was changed to [Amorphous Polyester Resin 2] and carbon black was changed to C.I. I. [Yellow Masterbatch 2] was obtained in the same manner except that it was changed to CI Pigment Yellow 185 (D1155 manufactured by BASF Japan).

-Preparation of yellow oil phase 1-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 111 parts by mass of [Amorphous Polyester Resin 2], and 20 parts by mass of [Black Masterbatch 3] is [Yellow Masterbatch 2]. [Yellow oil phase 1] was obtained in the same manner except that the amount of ethyl acetate added was changed to 16 parts by mass to 74 parts by mass.

-Emulsification or dispersion-
40 parts by mass of an ethyl acetate solution of [Polyester prepolymer 3] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added to 275 parts by mass of [Yellow oil phase 1]. Co., Ltd.) and stirred and dispersed uniformly to obtain [Yellow oil phase 1 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Yellow oil phase 1 ′] was added and emulsified for 1 minute to obtain [Yellow emulsion slurry 1].

-Solvent removal-Washing-Drying-
[Yellow Emulsion Slurry 1] is the same as [Black Emulsion Slurry 1] except that the heating time in (5) is changed to 15 minutes. Solvent removal, washing, drying and air sieving 1 was produced.

[Production Example 43; Production of yellow toner base material 2 (ester elongation method)]
-Preparation of Yellow Masterbatch 1-
[Yellow Master Batch 1] was obtained in the same manner as in [Yellow Master Batch 2] except that [Amorphous Polyester Resin 2] was changed to [Amorphous Polyester Resin 1].

-Preparation of yellow oil phase 2-
In the production of [Black Oil Phase 2], 97 parts by mass of [Amorphous Polyester Resin 3] is 94 parts by mass of [Amorphous Polyester Resin 1] and 20 parts by mass of [Black Masterbatch 3] is [Yellow Masterbatch 1]. [Yellow oil phase 2] was obtained in the same manner except that the amount of ethyl acetate added was changed to 16 parts by mass and 22 parts by mass.

-Emulsification or dispersion-
45 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 2] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added to 275 parts by mass of the [Yellow oil phase 2]. Co., Ltd.) at a rotation speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Yellow oil phase 2 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Yellow oil phase 2 ′] was added and emulsified for 1 minute to obtain [Yellow emulsion slurry 2].

-Solvent removal-Washing-Drying-
[Yellow emulsion slurry 2] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsion slurry 1] to produce yellow toner base 2.

[Production Example 44; Production of yellow toner base 3 (ester elongation method)]
-Preparation of yellow oil phase 3-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 43, the same conditions were used except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2], the heating temperature of (5) was changed to 55 ° C., and the heating time was changed to 15 minutes. Then, an oil phase was prepared, emulsified or dispersed, solvent removed, washed, dried, and air sieved to prepare a yellow toner base 3.

[Production Example 45: Production of yellow toner base 4 (ester elongation method)]
-Preparation of yellow oil phase 4-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 43, the yellow toner base 4 is produced under the same conditions except that the heating time of (5) is changed to 10 minutes under the same conditions, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving. did.

[Production Example 46; Production of yellow toner base 5 (ester elongation method)]
-Preparation of yellow oil phase 5-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 43, under the same conditions except that the heating time of (5) was changed to 30 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving were carried out to produce yellow toner base 5 did.

[Production Example 47; Production of yellow toner base 6 (ester elongation method)]
-Preparation of yellow oil phase 6-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 43, the yellow toner base 6 was produced under the same conditions except that the heating time of (5) was changed to 15 minutes under the same conditions, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving. did.

[Production Example 48; Production of Yellow Toner Base 7 (Ester Elongation Method)]
-Preparation of yellow oil phase 7-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 43, the yellow toner base 7 is produced under the same conditions except that the heating time of (5) is changed to 20 minutes under the same conditions as in oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving. did.

[Production Example 49; Production of Yellow Toner Base 8 (Ester Elongation Method)]
-Preparation of yellow oil phase 8-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 43, except that the heating temperature of (5) was changed to 45 ° C. and the heating time was changed to 15 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A yellow toner base 8 was produced.

[Production Example 50; Production of yellow toner base material 9 (ester elongation method)]
-Preparation of yellow oil phase 9-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 43, the same conditions were used except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2], the heating temperature of (5) was changed to 40 ° C., and the heating time was changed to 10 minutes. Then, an oil phase was prepared, emulsified or dispersed, solvent removed, washed, dried, and air sieved to prepare a yellow toner base 9.

[Production Example 51; Production of yellow toner base material 10 (dissolution suspension method)]
-Preparation of yellow oil phase 10-
In the production of [Black Oil Phase 10], 110 parts by mass of [Amorphous Polyester Resin 3] is added to 108 parts by mass of [Amorphous Polyester Resin 1] and 23 parts by mass of [Amorphous Polyester Resin 14] is added. In addition, [Yellow oil phase 10] was obtained in the same manner except that 20 parts by mass of [Black masterbatch 3] was changed to 16 parts by mass of [Yellow masterbatch 1] and the addition amount of ethyl acetate was changed to 98 parts by mass. .

-Emulsification or dispersion-
In a separate container with a stirrer and a thermometer, 400 parts by mass of [Aqueous Phase 1] was placed, and while stirring at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [yellow oil Phase 10] was added and emulsified for 1 minute to obtain [Yellow Emulsion Slurry 10].

-Solvent removal-Washing-Drying-
[Yellow Emulsion Slurry 10] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black Emulsion Slurry 1] except that the heating time of (5) was changed to 15 minutes. Was made.

[Production Example 52; Production of Yellow Toner Base 11 (Dissolution Suspension Method)]
-Production of yellow oil phase 11-
In the production of [Black Oil Phase 11], 96 parts by mass of [Amorphous Polyester Resin 3] is added to 94 parts by mass of [Amorphous Polyester Resin 1] and 23 parts by mass of [Amorphous Polyester Resin 14] is added. In addition, [Yellow oil phase 11] was obtained in the same manner except that 20 parts by weight of [Black masterbatch 3] was changed to 16 parts by weight of [Yellow masterbatch 1] and the addition amount of ethyl acetate was changed to 44 parts by weight. .

-Emulsification or dispersion-
In a separate container with a stirrer and a thermometer, 400 parts by mass of [Aqueous Phase 1] was placed, and while stirring at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [yellow oil Phase 11] was added and emulsified for 1 minute to obtain [Yellow Emulsion Slurry 11].

-Solvent removal-Washing-Drying-
[Yellow Emulsion Slurry 11] was subjected to solvent removal, washing, drying and air sieving under the same conditions as [Black Emulsion Slurry 1] except that the heating time of (5) was changed to 15 minutes. Was made.

[Production Example 53; Production of yellow toner base 12 (emulsion aggregation method)]
-Preparation of amorphous polyester resin dispersion 6-
[Amorphous Polyester Resin Dispersion 9] was similarly produced except that [Amorphous Polyester Resin 9] was replaced with [Amorphous Polyester Resin 6]. ] Was obtained. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in the obtained [amorphous polyester resin dispersion 6] was measured with the particle size distribution measuring apparatus (LA-920, Horiba, Ltd. make).

-Preparation of Colorant Dispersion 2-
In the preparation of [Colorant Dispersion Liquid 1], carbon black was changed to C.I. I. [Colorant dispersion 2] was obtained in the same manner except that it was changed to CI Pigment Yellow 185 (D1155 manufactured by BASF Japan Ltd.).

-Aggregation-
In a container equipped with a thermometer and a stirrer, 235 parts by mass of [Amorphous polyester resin dispersion 6], 57 parts by mass of [Amorphous polyester resin dispersion 14], and 45 parts by mass of [release agent dispersion 3] [Colorant dispersion 2] 26 parts by mass and 600 parts by mass of water were added and stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, the dispersion was heated to 45 ° C. while gradually dropping 50 parts by mass of a 5% by mass magnesium chloride aqueous solution while stirring at 5000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). The aggregated particles were kept at 45 ° C. until the volume average particle diameter grew to 5.1 μm. Heated to 90 ° C. while keeping pH 9 by adding 2% by weight aqueous sodium hydroxide solution to this, kept in this state for 2 hours, then cooled to 20 ° C. at 1 ° C./min, [Yellow slurry 12] Got.

-Solvent removal-Washing-Drying-
[Yellow slurry 12] was washed, dried, and air sieved under the same conditions as [Black slurry 1] except that the heating time of (5) was changed to 15 minutes, and yellow toner base 12 was produced.

[Production Example 54; Production of Yellow Toner Base 13 (Emulsion Aggregation Method)]
-Aggregation-
In a container equipped with a thermometer and a stirrer, 207 parts by mass of [Amorphous polyester resin dispersion 6], 57 parts by mass of [Amorphous polyester resin dispersion 14], 28 parts of [crystalline polyester resin dispersion 2] Part, [release agent dispersion 3] 45 parts by mass, [colorant dispersion 2] 26 parts by mass, and 600 parts by mass of water were stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, the dispersion was heated to 45 ° C. while gradually dropping 50 parts by mass of a 5% by mass magnesium chloride aqueous solution while stirring at 5000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). The aggregated particles were kept at 45 ° C. until the volume average particle diameter grew to 4.9 μm. This was cooled to 20 ° C. to obtain [Yellow slurry 13].

-Solvent removal-Washing-Drying-
[Yellow slurry 13] was washed, dried, and air sieved under the same conditions as [Black slurry 1] except that the heating time of (5) was changed to 20 minutes, and yellow toner base 13 was produced.

[Production Example 55; Production of Yellow Toner Base 14 (Crushing Method)]
-Preparation of yellow masterbatch 6-
[Yellow masterbatch 6] was obtained in the same manner as in [Yellow masterbatch 2] except that [amorphous polyester resin 2] was changed to [amorphous polyester resin 6].

-Melt kneading, grinding, classification-
[Amorphous polyester resin 6] 46 parts by mass, [Amorphous polyester resin 10] 28 parts by mass, paraffin (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C.) 6 parts by mass, and [Yellow Masterbatch 6] ] 8 parts by mass was premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.), and then in a single-screw kneader (compact bus co-kneader, manufactured by Buss). The mixture was melted and kneaded under the conditions of set temperature (inlet part 90 ° C.), outlet part (60 ° C.) and feed amount (10 kg / Hr). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulverizer (manufactured by Hosokawa Micron). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, the air pressure (6.0 atm / cm ² ) and feed amount (0.5 kg / hr) were set. The mixture was finely pulverized and further classified by a classifier (manufactured by Alpine, 132MP) to obtain [Yellow Toner Base 14].

[Production Example 56; Production of yellow toner base material 15 (pulverization method)]
-Melt kneading, grinding, classification-
[Amorphous Polyester Resin 6] 44 parts by mass, [Amorphous Polyester Resin 10] 25 parts by mass, [Crystalline Polyester Resin 1] 5 parts by mass, paraffin (HNP-9, manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C. ) After 6 parts by weight and 8 parts by weight of [Yellow Masterbatch 6] were premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.), -It melted and kneaded | mixed on condition of preset temperature (inlet part 90 degreeC), outlet part (60 degreeC), and feed amount (10 kg / Hr) in the co-kneader (Buss make). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulverizer (manufactured by Hosokawa Micron). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, under conditions of air pressure (6.0 atm / cm @ 2) and feed amount (0.5 kg / hr). Fine pulverization was carried out, and further classification was carried out with a classifier (manufactured by Alpine, 132 MP) to obtain [Yellow Toner Base 15].

[Production Example 57; Production of yellow toner base material 16 (ester elongation method)]
-Preparation of yellow masterbatch 4-
[Yellow masterbatch 4] was obtained in the same manner as in [Yellow masterbatch 2] except that [amorphous polyester resin 2] was changed to [amorphous polyester resin 4].

-Preparation of yellow oil phase 16-
In the production of [Black Oil Phase 1], 113 parts by weight of [Amorphous Polyester Resin 3] is 116 parts by weight of [Amorphous Polyester Resin 4], and 20 parts by weight of [Black Masterbatch 3] is [Yellow Masterbatch 4]. [Yellow oil phase 16] was obtained in the same manner except that the amount of ethyl acetate added was changed to 69 parts by mass.

-Emulsification or dispersion-
30 parts by mass of [Polyester Prepolymer 3] in ethyl acetate and 1.5 parts by mass of 50% by weight ethyl acetate solution of isophoronediamine are added to 275 parts by mass of [Yellow oil phase 16], and a TK homomixer (special The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Yellow oil phase 16 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Yellow oil phase 16 ′] was added and emulsified for 1 minute to obtain [Yellow emulsion slurry 16].

-Solvent removal-Washing-Drying-
[Yellow Emulsion Slurry 16] was subjected to solvent removal, washing, drying and air sieving under the same conditions as [Black Emulsion Slurry 1] except that the heating time of (5) was changed to 10 minutes. Was made.

[Production Example 58; Production of Yellow Toner Base 17 (Ester Elongation Method)]
-Preparation of yellow oil phase 17-
In the production of [Black Oil Phase 1], 113 parts by weight of [Amorphous Polyester Resin 3] is 108 parts by weight of [Amorphous Polyester Resin 6], and 20 parts by weight of [Black Masterbatch 3] is [Yellow Masterbatch 6]. [Yellow oil phase 17] was obtained in the same manner except that the amount of ethyl acetate added was changed to 16 parts by mass to 76 parts by mass.

―Emulsification or dispersion―
To 275 parts by mass of [Yellow Oil Phase 17], 45 parts by mass of [Polyester Prepolymer 2] in ethyl acetate and 3 parts by mass of 50% by mass of isophoronediamine in ethyl acetate were added. Co., Ltd.) and stirred and dispersed uniformly to obtain [Yellow oil phase 17 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Yellow oil phase 17 ′] was added and emulsified for 1 minute to obtain [Yellow emulsion slurry 17].

-Solvent removal-Cleaning-Drying-
[Yellow Emulsion Slurry 17] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black Emulsion Slurry 1] except that the heating time of (5) was changed to 25 minutes. Was made.

[Production Example 59; Production of yellow toner base 18 (ester elongation method)]
-Production of yellow masterbatch 5-
[Yellow masterbatch 5] was obtained in the same manner as in [Yellow masterbatch 2] except that [amorphous polyester resin 2] was changed to [amorphous polyester resin 5].

-Preparation of yellow oil phase 18-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 121 parts by mass of [Amorphous Polyester Resin 5], and 20 parts by mass of [Black Masterbatch 3] is [Yellow Masterbatch 5]. [Yellow oil phase 18] was obtained in the same manner except that the amount of ethyl acetate added was changed to 79 parts by mass to 16 parts by mass.

―Emulsification or dispersion―
To 290 parts by weight of [Yellow oil phase 18], 20 parts by weight of an ethyl acetate solution of [Polyester prepolymer 3] and 1.2 parts by weight of a 50% by weight ethyl acetate solution of isophoronediamine are added. The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Yellow oil phase 18 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Yellow oil phase 18 ′] was added and emulsified for 1 minute to obtain [Yellow emulsion slurry 18].

-Solvent removal-Cleaning-Drying-
[Yellow Emulsion Slurry 18] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black Emulsion Slurry 1] except that the heating time of (5) was changed to 10 minutes. Was made.

[Production Example 60; Production of yellow toner base 19 (ester elongation method)]
-Preparation of yellow oil phase 19-
In the production of [Black Oil Phase 1], 113 parts by weight of [Amorphous Polyester Resin 3] is added to 100 parts by weight of [Amorphous Polyester Resin 6], and 20 parts by weight of [Black Masterbatch 3] is set to [Yellow Masterbatch 6]. [Yellow oil phase 19] was obtained in the same manner except that the amount of ethyl acetate added was changed to 81 parts by mass to 16 parts by mass.

―Emulsification or dispersion―
62 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 1] and 5.5 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added to 271 parts by mass of [Yellow oil phase 19], and a TK homomixer (special The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Yellow oil phase 19 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Yellow oil phase 19 ′] was added and emulsified for 1 minute to obtain [Yellow emulsion slurry 19].

-Solvent removal-Cleaning-Drying-
[Yellow Emulsion Slurry 19] was subjected to solvent removal, washing, drying and air sieving under the same conditions as [Black Emulsion Slurry 1] except that the heating temperature of (5) was changed to 55 ° C. Was made.

[Production Example 61; Production of yellow toner base 20 (ester elongation method)]
In Production Example 43, the yellow toner base 20 is produced under the same conditions except that the heating temperature of (5) is changed to 45 ° C. under the same conditions, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving. did.

[Production Example 62; Production of Yellow Toner Base 21 (Ester Elongation Method)]
In Production Example 43, the same conditions were used except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2], the heating temperature of (5) was changed to 55 ° C., and the heating time was changed to 30 minutes. Then, an oil phase was prepared, emulsified or dispersed, solvent removed, washed, dried, and air sieved to prepare a yellow toner base 21.

[Production Example 63; Production of yellow toner base 22 (ester elongation method)]
In Production Example 43, an oil phase was prepared, emulsified or dispersed, solvent-removed, washed, dried, and air-screened under the same conditions except that the heat treatment of (5) was changed to none to prepare a yellow toner base 22. .

[Manufacture of magenta toner matrix]
[Production Example 64; Production of magenta toner base 1 (ester elongation method)]
-Production of magenta masterbatch 2-
In the production of [Black Masterbatch 3], [Amorphous Polyester Resin 3] is changed to [Amorphous Polyester Resin 2], and 100 parts by mass of carbon black is added to C.I. I. Pigment Red 122 (RTS manufactured by DIC) 20 parts by mass, C.I. I. [Magenta masterbatch 2] was obtained in the same manner except that the pigment red 269 (1022 manufactured by DIC) was changed to 80 parts by mass.

-Preparation of magenta oil phase 1-
In the production of [Black Oil Phase 1], 113 parts by weight of [Amorphous Polyester Resin 3] is 111 parts by weight of [Amorphous Polyester Resin 2], and 20 parts by weight of [Black Masterbatch 3] is [Magenta Masterbatch 2]. [Magenta oil phase 1] was obtained in the same manner except that the amount of ethyl acetate added was changed to 20 parts by mass and 70 parts by mass of ethyl acetate.

-Emulsification or dispersion-
To 275 parts by mass of [Magenta Oil Phase 1], 36 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 3] and 3 parts by mass of an isophoronediamine 50% by mass ethyl acetate solution were added, and a TK homomixer (specialized machine) was added. (Made by Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [magenta oil phase 1 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Magenta oil phase 1 ′] was added and emulsified for 1 minute to obtain [Magenta emulsified slurry 1].

-Solvent removal-Washing-Drying-
[Magenta Emulsion Slurry 1] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black Emulsion Slurry 1] except that the heating time of (5) was changed to 10 minutes. 1 was produced.

[Production Example 65; Production of magenta toner base material 2 (ester elongation method)]
-Preparation of magenta oil phase 2-
In the production of [Black Oil Phase 2], 97 parts by mass of [Amorphous Polyester Resin 3] is 92 parts by mass of [Amorphous Polyester Resin 2], and 20 parts by mass of [Black Masterbatch 3] is [Magenta Masterbatch 2]. [Magenta oil phase 2] was obtained in the same manner except that the amount of ethyl acetate added was changed to 20 parts by mass.

-Emulsification or dispersion-
To 275 parts by mass of [Magenta Oil Phase 2], 45 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 2] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine were added, and a TK homomixer (specialized machine) was added. (Made by Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [magenta oil phase 2 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Magenta oil phase 2 ′] was added and emulsified for 1 minute to obtain [Magenta emulsified slurry 2].

-Solvent removal-Washing-Drying-
[Magenta emulsified slurry 2] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 2] except that the heating time of (5) was changed to 15 minutes. 2 was produced.

[Production Example 66; Production of Magenta Toner Base 3 (Ester Elongation Method)]
-Preparation of magenta oil phase 3-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 65, the oil phase was prepared under the same conditions except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2] and the heating temperature of (5) was changed to 55 ° C. Emulsification or dispersion, solvent removal, washing, drying, air sieving, and magenta toner base 3 were produced.

[Production Example 67; Production of magenta toner base 4 (ester elongation method)]
-Preparation of magenta oil phase 4-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 65, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 10 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A magenta toner base 4 was produced.

[Production Example 68; Production of magenta toner base 5 (ester elongation method)]
-Preparation of magenta oil phase 5-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 65, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 25 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A magenta toner base 5 was produced.

[Production Example 69: Production of magenta toner base 6 (ester elongation method)]
-Preparation of magenta oil phase 6-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 65, under the same conditions except that the heating temperature of (5) was changed to 50 ° C., oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, and magenta toner base 6 were produced. did.

[Production Example 70; Production of Magenta Toner Base 7 (Ester Elongation Method)]
-Preparation of magenta oil phase 7-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 65, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 20 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A magenta toner base 7 was produced.

[Production Example 71; Production of magenta toner base 8 (ester elongation method)]
-Preparation of magenta oil phase 8-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 65, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 5 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A magenta toner base 8 was produced.

[Production Example 72; Production of magenta toner base material 9 (ester elongation method)]
-Preparation of magenta oil phase 9-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 65, the oil phase was prepared under the same conditions except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2] and the heating time of (5) was changed to 10 minutes. Emulsification or dispersion, solvent removal, washing, drying, air sieving, and magenta toner base 9 were produced.

[Production Example 73; Production of Magenta Toner Base 10 (Dissolution Suspension Method)]
-Preparation of magenta oil phase 10-
In the production of [Black Oil Phase 10], 110 parts by mass of [Amorphous Polyester Resin 3] is 106 parts by mass of [Amorphous Polyester Resin 2], and 23 parts by mass of [Amorphous Polyester Resin 14] is added. In addition, [Magenta oil phase 10] was obtained in the same manner except that 20 parts by mass of [Black masterbatch 3] was changed to 20 parts by mass of [Magenta masterbatch 2] and the addition amount of ethyl acetate was changed to 96 parts by mass. .

-Emulsification or dispersion-
Put 400 parts by mass of [Aqueous Phase 1] in another container in which a stirrer and a thermometer are set and stir at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Phase 10] was added and emulsified for 1 minute to obtain [Magenta emulsified slurry 10].

-Solvent removal-Washing-Drying-
[Magenta emulsified slurry 10] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] except that the heating time of (5) was changed to 10 minutes. Was made.

[Production Example 74; Production of Magenta Toner Base 11 (Dissolution Suspension Method)]
-Preparation of magenta oil phase 11-
In the production of [Black Oil Phase 11], 96 parts by mass of [Amorphous Polyester Resin 3] is added to 92 parts by mass of [Amorphous Polyester Resin 2], and 23 parts by mass of [Amorphous Polyester Resin 14] is added. In addition, [Magenta oil phase 11] was obtained in the same manner except that 20 parts by mass of [Black Masterbatch 3] was changed to 20 parts by mass of [Magenta Masterbatch 2] and the addition amount of ethyl acetate was changed to 42 parts by mass. .

-Emulsification or dispersion-
Put 400 parts by mass of [Aqueous Phase 1] in another container in which a stirrer and a thermometer are set and stir at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Phase 11] was added and emulsified for 1 minute to obtain [Magenta emulsified slurry 11].

-Solvent removal-Washing-Drying-
[Magenta emulsified slurry 11] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] except that the heating time of (5) was changed to 10 minutes. Was made.

[Production Example 75; Production of Magenta Toner Base 12 (Emulsion Aggregation Method)]
-Preparation of amorphous polyester resin dispersion 7-
[Amorphous Polyester Resin Dispersion 9] was similarly prepared except that [Amorphous Polyester Resin 9] was replaced with [Amorphous Polyester Resin 7]. ] Was obtained. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in the obtained [amorphous polyester resin dispersion liquid 7] was measured with the particle size distribution measuring apparatus (LA-920, Horiba, Ltd. make).

-Preparation of Colorant Dispersion 3-
In the preparation of [Colorant Dispersion Liquid 1], 20 parts by mass of carbon black was added to C.I. I. Pigment Red 122 (RTS manufactured by DIC) 4 parts by mass, C.I. I. [Colorant dispersion 3] was obtained in the same manner except that the pigment red 269 (1022 manufactured by DIC) was changed to 16 parts by mass.

-Aggregation-
In a container equipped with a thermometer and a stirrer, 235 parts by mass of [Amorphous polyester resin dispersion 7], 57 parts by mass of [Amorphous polyester resin dispersion 14], and 45 parts by mass of [release agent dispersion 3] [Colorant dispersion 3] 34 parts by mass and 600 parts by mass of water were added and stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, the dispersion was heated to 45 ° C. while gradually dropping 50 parts by mass of a 5% by mass magnesium chloride aqueous solution while stirring at 5000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). The aggregated particles were kept at 45 ° C. until the volume average particle diameter grew to 5.1 μm. Heated to 90 ° C. while maintaining pH 9 by adding a 2% by weight aqueous sodium hydroxide solution to this, kept in this state for 2 hours, then cooled to 20 ° C. at 1 ° C./min, [magenta slurry 12] Got.

-Solvent removal-Washing-Drying-
[Magenta slurry 12] was washed, dried, and air sieved under the same conditions as [Black slurry 1] except that the heating time of (5) was changed to 10 minutes, and a magenta toner base 12 was produced.

[Production Example 76; Production of Magenta Toner Base 13 (Emulsion Aggregation Method)]
-Aggregation-
In a container equipped with a thermometer and a stirrer, 207 parts by mass of [Amorphous polyester resin dispersion 7], 57 parts by mass of [amorphous polyester resin dispersion 14], 28 parts of [crystalline polyester resin dispersion 2] Part, [Partitioner Dispersion Liquid 3] 45 parts by mass, [Colorant Dispersion Liquid 3] 34 parts by mass, and water 600 parts by mass were stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, the dispersion was heated to 45 ° C. while gradually dropping 50 parts by mass of a 5% by mass magnesium chloride aqueous solution while stirring at 5000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). The aggregated particles were kept at 45 ° C. until the volume average particle diameter grew to 4.9 μm. This was cooled to 20 ° C. to obtain [Magenta slurry 13].

-Solvent removal-Washing-Drying-
[Magenta slurry 13] was washed, dried, and air sieved under the same conditions as [Black slurry 1] except that the heating time of (5) was changed to 20 minutes to produce magenta toner base 13.

[Production Example 77; Production of Magenta Toner Base 14 (Crushing Method)]
-Production of magenta masterbatch 7-
[Magenta masterbatch 7] was obtained in the same manner as in [Magenta masterbatch 2] except that [amorphous polyester resin 2] was changed to [amorphous polyester resin 7].

-Melt kneading, grinding, classification-
[Amorphous polyester resin 7] 44 parts by mass, [Amorphous polyester resin 11] 28 parts by mass, paraffin (HNP-9, manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.) 6 parts by mass, and [magenta masterbatch 7 ] 12 parts by mass were premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.), and then uniaxial kneader (compact bus co-kneader, manufactured by Buss). The mixture was melted and kneaded under the conditions of set temperature (inlet part 90 ° C.), outlet part (60 ° C.) and feed amount (10 kg / Hr). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulverizer (manufactured by Hosokawa Micron). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, the air pressure (6.0 atm / cm ² ) and feed amount (0.5 kg / hr) were set. The mixture was finely pulverized and further classified by a classifier (manufactured by Alpine, 132 MP) to obtain [Magenta Toner Base 14].

[Production Example 78; Production of Magenta Toner Base 15 (Crushing Method)]
-Melt kneading, grinding, classification-
[Amorphous Polyester Resin 7] 42 parts by mass, [Amorphous Polyester Resin 11] 25 parts by mass, [Crystalline Polyester Resin 1] 5 parts by mass, paraffin (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C. ) 6 parts by mass and 12 parts by mass of [magenta masterbatch 7] were premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.), -It melted and kneaded | mixed on condition of preset temperature (inlet part 90 degreeC), outlet part (60 degreeC), and feed amount (10 kg / Hr) in the co-kneader (Buss make). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulverizer (manufactured by Hosokawa Micron). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, under conditions of air pressure (6.0 atm / cm @ 2) and feed amount (0.5 kg / hr). Fine pulverization was carried out, and further classification was carried out with a classifier (manufactured by Alpine, 132 MP) to obtain [Magenta Toner Base 15].

[Production Example 79; Production of magenta toner base material 16 (ester elongation method)]
-Production of magenta masterbatch 4-
[Magenta masterbatch 4] was obtained in the same manner as in [Magenta masterbatch 2] except that [amorphous polyester resin 2] was changed to [amorphous polyester resin 4].

-Production of magenta oil phase 16-
In the production of [Black Oil Phase 1], 113 parts by weight of [Amorphous Polyester Resin 3] is 115 parts by weight of [Amorphous Polyester Resin 4], and 20 parts by weight of [Black Masterbatch 3] is [Magenta Masterbatch 4]. [Magenta oil phase 16] was obtained in the same manner except that the amount of ethyl acetate added was changed to 20 parts by mass and 66 parts by mass.

-Emulsification or dispersion-
To 275 parts by mass of [Magenta oil phase 16], 28 parts by mass of [polyester prepolymer 3] in ethyl acetate and 1.5 parts by mass of 50% by mass of isophoronediamine in ethyl acetate were added. The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Magenta oil phase 16 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Magenta oil phase 16 ′] was added and emulsified for 1 minute to obtain [Magenta emulsified slurry 16].

-Solvent removal-Washing-Drying-
[Magenta emulsified slurry 16] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] except that the heating time of (5) was changed to 10 minutes. Was made.

[Production Example 80; Production of Magenta Toner Base 17 (Ester Elongation Method)]
-Preparation of magenta oil phase 17-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 106 parts by mass of [Amorphous Polyester Resin 7], and 20 parts by mass of [Black Masterbatch 3] is [Magenta Masterbatch 7]. [Magenta oil phase 17] was obtained in the same manner except that the amount of ethyl acetate added was changed to 20 parts by mass and 74 parts by mass.

―Emulsification or dispersion―
To 275 parts by mass of [Magenta Oil Phase 17], 45 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 2] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added, and a TK homomixer (specialized machine) is added. (Made by Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [magenta oil phase 17 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Magenta oil phase 17 ′] was added and emulsified for 1 minute to obtain [Magenta emulsified slurry 17].

-Solvent removal-Cleaning-Drying-
[Magenta emulsified slurry 17] was subjected to solvent removal, washing, drying and air sieving under the same conditions as [Black emulsified slurry 1] except that the heating time of (5) was changed to 25 minutes. Was made.

[Production Example 81; Production of Magenta Toner Base 18 (Ester Elongation Method)]
-Magenta masterbatch 5 production-
[Magenta masterbatch 5] was obtained in the same manner as in [Magenta masterbatch 2] except that [amorphous polyester resin 2] was changed to [amorphous polyester resin 5].

-Preparation of magenta oil phase 18-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 121 parts by mass of [Amorphous Polyester Resin 5], and 20 parts by mass of [Black Masterbatch 3] is [Magenta Masterbatch 5]. [Magenta oil phase 18] was obtained in the same manner except that the amount of ethyl acetate added was changed to 20 parts by mass and 75 parts by mass.

―Emulsification or dispersion―
To 290 parts by mass of [Magenta oil phase 18], 16 parts by mass of [polyester prepolymer 3] in ethyl acetate and 1.2 parts by mass of isophoronediamine in 50% by mass ethyl acetate were added. (Machika Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [magenta oil phase 18 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Magenta oil phase 18 ′] was added and emulsified for 1 minute to obtain [Magenta emulsified slurry 18].

-Solvent removal-Cleaning-Drying-
[Magenta emulsified slurry 18] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] except that the heating time of (5) was changed to 10 minutes. Was made.

[Production Example 82; Production of magenta toner base material 19 (ester elongation method)]
-Magenta master batch 6 production-
[Magenta masterbatch 6] was obtained in the same manner as in [Magenta masterbatch 2] except that [amorphous polyester resin 2] was changed to [amorphous polyester resin 6].

-Preparation of magenta oil phase 19-
In the production of [Black Oil Phase 1], 113 parts by weight of [Amorphous Polyester Resin 3] is 101 parts by weight of [Amorphous Polyester Resin 6], and 20 parts by weight of [Black Masterbatch 3] is [Magenta Masterbatch 6]. [Magenta oil phase 19] was obtained in the same manner except that the amount of ethyl acetate added was changed to 20 parts by mass and 76 parts by mass.

―Emulsification or dispersion―
To 271 parts by mass of [Magenta Oil Phase 19], 56 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 1] and 5.5 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine were added, and a TK homomixer (special (Machika Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [magenta oil phase 19 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Magenta oil phase 19 ′] was added and emulsified for 1 minute to obtain [Magenta emulsified slurry 19].

-Solvent removal-Cleaning-Drying-
[Magenta emulsified slurry 19] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] except that the heating time of (5) was changed to 20 minutes. Was made.

[Production Example 83; Production of magenta toner base 20 (ester elongation method)]
In Production Example 65, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 10 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A magenta toner base 20 was produced.

[Production Example 84; Production of magenta toner base material 21 (ester elongation method)]
In Production Example 65, the same conditions were used except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2], the heating temperature of (5) was changed to 55 ° C., and the heating time was changed to 30 minutes. Thus, the magenta toner base 21 was prepared by preparing an oil phase, emulsifying or dispersing, removing the solvent, washing, drying, and air sieving.

[Production Example 85; Production of magenta toner base material 22 (ester elongation method)]
In Production Example 65, a magenta toner base 22 was produced under the same conditions except that the heat treatment of (5) was changed to none, under the same conditions, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, and air sieving. .

[Manufacture of cyan toner matrix]
[Production Example 86; Production of Cyan Toner Base 1 (Ester Elongation Method)]
-Preparation of cyan master batch 3-
In the production of [Black Masterbatch 3], carbon black was changed to C.I. I. [Cyan Masterbatch 3] was obtained in the same manner except that it was changed to CI Pigment Blue 15: 3 (Toyo Ink Co., Ltd. 7919).

-Preparation of cyan oil phase 1-
In the production of [Black Oil Phase 1], the addition amount of [Amorphous Polyester Resin 3] is 112 parts by mass, [Black Masterbatch 3] is 20 parts by mass, [Cyan Masterbatch 3] is 18 parts by mass, and ethyl acetate is added. [Cyan oil phase 1] was obtained in the same manner except that the addition amount of was changed to 71 parts by mass.

-Emulsification or dispersion-
To 275 parts by mass of [Cyan Oil Phase 1], 36 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 3] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine were added, and a TK homomixer (specialized mechanized) was added. Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Cyan oil phase 1 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Cyan oil phase 1 ′] was added and emulsified for 1 minute to obtain [Cyan emulsified slurry 1].

-Solvent removal-Washing-Drying-
[Cyan emulsified slurry 1] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] to prepare cyan toner base 1.

[Production Example 87; Production of cyan toner base 2 (ester elongation method)]
-Preparation of cyan oil phase 2-
In the production of [Black Oil Phase 2], the addition amount of [Amorphous Polyester Resin 3] is 93 parts by mass, [Black Masterbatch 3] is 20 parts by mass, [Cyan Masterbatch 3] is 18 parts by mass, and ethyl acetate is added. [Cyan oil phase 2] was obtained in the same manner except that the addition amount of was changed to 21 parts by mass.

-Emulsification or dispersion-
45 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 2] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added to 275 parts by mass of [Cyan oil phase 2], and a TK homomixer (specialized machine) is added. Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Cyan oil phase 2 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Cyan oil phase 2 ′] was added and emulsified for 1 minute to obtain [Cyan emulsified slurry 2].

-Solvent removal-Washing-Drying-
[Cyan emulsified slurry 2] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 2] to prepare cyan toner base 2.

[Production Example 88; Production of cyan toner base 3 (ester elongation method)]
-Production of Cyan Oil Phase 3-Emulsification or Dispersion-Solvent Removal-Washing-Drying-
In Production Example 87, the oil phase was prepared under the same conditions except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2] and the heating temperature of (5) was changed to 55 ° C. Emulsification or dispersion, solvent removal, washing, drying, air sieving, and cyan toner base 3 were produced.

[Production Example 89; Production of cyan toner base 4 (ester elongation method)]
-Production of Cyan Oil Phase 4-Emulsification or Dispersion-Solvent Removal-Washing-Drying-
In Production Example 87, except that the heating temperature of (5) was changed to 50 ° C., oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, and cyan toner base 4 were produced. did.

[Production Example 90; Production of cyan toner base 5 (ester elongation method)]
-Production of Cyan Oil Phase 5-Emulsification or Dispersion-Solvent Removal-Washing-Drying-
In Production Example 87, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 25 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A cyan toner base 5 was prepared.

[Production Example 91; Production of cyan toner base 6 (ester elongation method)]
-Production of Cyan Oil Phase 6-Emulsification or Dispersion-Solvent Removal-Washing-Drying-
In Production Example 87, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 10 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A cyan toner base 6 was prepared.

[Production Example 92; Production of cyan toner base 7 (ester elongation method)]
-Preparation of cyan oil phase 7-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 87, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 15 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A cyan toner base 7 was prepared.

[Production Example 93; Production of cyan toner base 8 (ester elongation method)]
-Preparation of cyan oil phase 8-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 87, except that the heating time of (5) was changed to 15 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving were carried out to prepare cyan toner base 8 did.

[Production Example 94; Production of Cyan Toner Base 9 (Ester Elongation Method)]
-Preparation of cyan oil phase 9-emulsification or dispersion-solvent removal-washing-drying-
In Production Example 87, the oil phase was prepared under the same conditions except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2] and the heating time of (5) was changed to 10 minutes. Emulsion or dispersion, solvent removal, washing, drying, air sieving, and cyan toner base 9 were produced.

[Production Example 95; Production of cyan toner base material 10 (dissolution suspension method)]
-Preparation of cyan oil phase 10-
In the production of [Black Oil Phase 10], the addition amount of [Amorphous Polyester Resin 3] is 107 parts by mass, the addition amount of [Amorphous Polyester Resin 14] is 23 parts by mass, [Black Masterbatch 3] [Cyan oil phase 10] was obtained in the same manner except that 20 parts by mass was changed to 18 parts by mass of [Cyan Masterbatch 3] and the amount of ethyl acetate added was changed to 97 parts by mass.

-Emulsification or dispersion-
In a separate container with a stirrer and a thermometer, 400 parts by weight of [Aqueous Phase 1] was placed, and while stirring at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [Cyan oil Phase 10] was added and emulsified for 1 minute to obtain [Cyan emulsified slurry 10].

-Solvent removal-Washing-Drying-
[Cyan emulsified slurry 10] was removed under the same conditions as [Black emulsified slurry 1] except that the heating temperature of (5) was changed to 45 ° C and the heating time was changed to 20 minutes. Thus, a cyan toner base 10 was produced.

[Production Example 96; Production of cyan toner base 11 (dissolution suspension method)]
-Preparation of cyan oil phase 11-
In the production of [Black Oil Phase 11], the addition amount of [Amorphous Polyester Resin 3] is 93 parts by mass, the addition amount of [Amorphous Polyester Resin 14] is 23 parts by mass, [Black Masterbatch 3] [Cyan oil phase 11] was obtained in the same manner except that 20 parts by mass was changed to 18 parts by mass of [Cyan Masterbatch 3] and the amount of ethyl acetate added was changed to 43 parts by mass.

-Emulsification or dispersion-
In a separate container with a stirrer and a thermometer, 400 parts by weight of [Aqueous Phase 1] was placed, and while stirring at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [Cyan oil Phase 11] was added and emulsified for 1 minute to obtain [Cyan emulsified slurry 11].

-Solvent removal-Washing-Drying-
[Cyan emulsified slurry 11] was removed under the same conditions as [Black emulsified slurry 1] except that the heating temperature of (5) was changed to 45 ° C and the heating time was changed to 20 minutes. Thus, a cyan toner base 11 was produced.

[Production Example 97; Production of cyan toner base 12 (emulsion aggregation method)]
-Preparation of amorphous polyester resin dispersion 8-
[Amorphous Polyester Resin Dispersion 9] was similarly prepared except that [Amorphous Polyester Resin 9] was replaced with [Amorphous Polyester Resin 8]. ] Was obtained. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in the obtained [amorphous polyester resin dispersion liquid 8] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

-Preparation of Colorant Dispersion 4-
In the preparation of [Colorant Dispersion Liquid 1], carbon black was changed to C.I. I. [Colorant dispersion 4] was obtained in the same manner except that the pigment was changed to CI Pigment Blue 15: 3 (7919 manufactured by Toyo Ink Co., Ltd.).

-Aggregation-
In a container equipped with a thermometer and a stirrer, 235 parts by mass of [Amorphous polyester resin dispersion 8], 57 parts by mass of [Amorphous polyester resin dispersion 14], and 45 parts by mass of [release agent dispersion 3] [Colorant dispersion 4] 30 parts by mass and 600 parts by mass of water were added and stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, the dispersion was heated to 45 ° C. while gradually dropping 50 parts by mass of a 5% by mass magnesium chloride aqueous solution while stirring at 5000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). The aggregated particles were kept at 45 ° C. until the volume average particle diameter grew to 5.1 μm. Heated to 90 ° C. while keeping pH 9 by adding 2% by mass aqueous sodium hydroxide solution to this, kept in this state for 2 hours, cooled to 20 ° C. at 1 ° C./min, [Cyan slurry 12] Got.

-Solvent removal-Washing-Drying-
[Cyan Slurry 12] was washed, dried, and air sieved under the same conditions as [Black Slurry 1] to prepare Cyan Toner Base 12.

[Production Example 98; Production of Cyan Toner Base 13 (Emulsion Aggregation Method)]
-Aggregation-
In a container equipped with a thermometer and a stirrer, 207 parts by mass of [Amorphous polyester resin dispersion 8], 57 parts by mass of [Amorphous polyester resin dispersion 14], and 28 parts of [crystalline polyester resin dispersion 2] Part, [Partitioner dispersion liquid 3] 45 parts by mass, [Colorant dispersion liquid 4] 30 parts by mass and water 600 parts by mass were stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, the dispersion was heated to 45 ° C. while gradually dropping 50 parts by mass of a 5% by mass magnesium chloride aqueous solution while stirring at 5000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50). The aggregated particles were kept at 45 ° C. until the volume average particle diameter grew to 4.9 μm. This was cooled to 20 ° C. to obtain [Cyan Slurry 13].

-Solvent removal-Washing-Drying-
[Cyan Slurry 13] was washed, dried, and air sieved under the same conditions as [Black Slurry 1] except that the heating time of (5) was changed to 15 minutes to produce cyan toner base 13.

[Production Example 99; Production of Cyan Toner Base 14 (Crushing Method)]
-Preparation of cyan master batch 8-
[Cyan master batch 8] was obtained in the same manner as in [Cyan master batch 3] except that [Amorphous polyester resin 3] was changed to [Amorphous polyester resin 8].

-Melt kneading, grinding, classification-
[Amorphous Polyester Resin 8] 45 parts by mass, [Amorphous Polyester Resin 12] 28 parts by mass, paraffin (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C.) 6 parts by mass, and [Cyan Masterbatch 8] ] 10 parts by mass was premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.), and then uniaxial kneader (compact bus co-kneader, manufactured by Buss). The mixture was melted and kneaded under the conditions of set temperature (inlet part 90 ° C.), outlet part (60 ° C.) and feed amount (10 kg / Hr). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulverizer (manufactured by Hosokawa Micron). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, the air pressure (6.0 atm / cm ² ) and feed amount (0.5 kg / hr) were set. The mixture was finely pulverized and further classified by a classifier (manufactured by Alpine, 132 MP) to obtain [Cyan Toner Base 14].

[Production Example 100; Production of Cyan Toner Base 15 (Crushing Method)]
-Melt kneading, grinding, classification-
[Amorphous Polyester Resin 8] 43 parts by mass, [Amorphous Polyester Resin 12] 25 parts by mass, [Crystalline Polyester Resin 1] 5 parts by mass, paraffin (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C. ) After 6 parts by weight and 10 parts by weight of [Cyan Masterbatch 8] were premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.), a uniaxial kneader (small bus) -It melted and kneaded | mixed on condition of preset temperature (inlet part 90 degreeC), outlet part (60 degreeC), and feed amount (10 kg / Hr) in the co-kneader (Buss make). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulverizer (manufactured by Hosokawa Micron). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, under conditions of air pressure (6.0 atm / cm @ 2) and feed amount (0.5 kg / hr). Finely pulverized and further classified by a classifier (manufactured by Alpine, 132 MP) to obtain [Cyan Toner Base 15].

[Production Example 101; Production of Cyan Toner Base 16 (Ester Elongation Method)]
-Production of cyan master batch 4-
[Cyan master batch 4] was obtained in the same manner as in [Cyan master batch 3] except that [Amorphous polyester resin 3] was changed to [Amorphous polyester resin 4].

-Preparation of cyan oil phase 16-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 117 parts by mass of [Amorphous Polyester Resin 4], and 20 parts by mass of [Black Masterbatch 3] is [Cyan Masterbatch 4]. [Cyan oil phase 16] was obtained in the same manner except that the amount of ethyl acetate added was changed to 18 parts by mass and 66 parts by mass.

-Emulsification or dispersion-
To 275 parts by mass of [Cyan Oil Phase 16], 26 parts by mass of [Polyester Prepolymer 3] in ethyl acetate and 1.5 parts by mass of 50% by mass of isophoronediamine in ethyl acetate were added. The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Cyan oil phase 16 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Cyan oil phase 16 ′] was added and emulsified for 1 minute to obtain [Cyan emulsified slurry 16].

-Solvent removal-Washing-Drying-
[Cyan emulsified slurry 16] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] to produce cyan toner base 16.

[Production Example 102; Production of Cyan Toner Base 17 (Ester Elongation Method)]
-Preparation of cyan oil phase 17-
In the production of [Black Oil Phase 1], 113 parts by weight of [Amorphous Polyester Resin 3] is 107 parts by weight of [Amorphous Polyester Resin 8], and 20 parts by weight of [Black Masterbatch 3] is [Cyan Masterbatch 8]. [Cyan oil phase 17] was obtained in the same manner except that the amount of ethyl acetate added was changed to 18 parts by mass and 75 parts by mass.

―Emulsification or dispersion―
45 parts by mass of an ethyl acetate solution of [polyester prepolymer 2] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added to 275 parts by mass of [Cyan oil phase 17], and a TK homomixer (specialized mechanization) is added. Co., Ltd.) and stirred and dispersed uniformly to obtain [Cyan oil phase 17 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Cyan oil phase 17 ′] was added and emulsified for 1 minute to obtain [Cyan emulsified slurry 17].

-Solvent removal-Cleaning-Drying-
[Cyan emulsified slurry 17] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] except that the heating time of (5) was changed to 20 minutes. Was made.

[Production Example 103; Production of cyan toner base 18 (ester elongation method)]
―Preparation of Cyan Masterbatch 5―
[Cyan master batch 5] was obtained in the same manner as in [Cyan master batch 3] except that [Amorphous polyester resin 3] was changed to [Amorphous polyester resin 5].

-Production of cyan oil phase 18-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 123 parts by mass of [Amorphous Polyester Resin 5], and 20 parts by mass of [Black Masterbatch 3] is [Cyan Masterbatch 5]. [Cyan oil phase 18] was obtained in the same manner except that the amount of ethyl acetate added was changed to 18 parts by mass.

―Emulsification or dispersion―
To 290 parts by mass of [Cyan oil phase 18], 14 parts by mass of [polyester prepolymer 3] in ethyl acetate and 1.2 parts by mass of isophoronediamine in 50% by mass ethyl acetate were added. The mixture was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Cyan oil phase 18 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Cyan oil phase 18 ′] was added and emulsified for 1 minute to obtain [Cyan emulsified slurry 18].

-Solvent removal-Cleaning-Drying-
[Cyan emulsified slurry 18] was removed under the same conditions as [Black emulsified slurry 1] except that the heating temperature of (5) was changed to 45 ° C and the heating time was changed to 15 minutes. Thus, a cyan toner base 18 was produced.

[Production Example 104; Production of Cyan Toner Base 19 (Ester Elongation Method)]
-Production of cyan master batch 6-
[Cyan master batch 6] was obtained in the same manner as in [Cyan master batch 3] except that [Amorphous polyester resin 3] was changed to [Amorphous polyester resin 6].

-Production of cyan oil phase 19-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] is 105 parts by mass of [Amorphous Polyester Resin 6], and 20 parts by mass of [Black Masterbatch 3] is [Cyan Masterbatch 6]. [Cyan oil phase 19] was obtained in the same manner except that the amount of ethyl acetate added was changed to 74 parts by mass to 18 parts by mass.

―Emulsification or dispersion―
50 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 1] and 5.5 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added to 271 parts by mass of [Cyan oil phase 19], and a TK homomixer (special (Chemical Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Cyan oil phase 19 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Cyan oil phase 19 ′] was added and emulsified for 1 minute to obtain [Cyan emulsified slurry 19].

-Solvent removal-Cleaning-Drying-
[Cyan emulsified slurry 19] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black emulsified slurry 1] except that the heating time of (5) was changed to 25 minutes. Was made.

[Production Example 105; Production of Cyan Toner Base 20 (Ester Elongation Method)]
In Production Example 87, except that the heating temperature of (5) was changed to 50 ° C. and the heating time was changed to 20 minutes, oil phase preparation, emulsification or dispersion, solvent removal, washing, drying, air sieving, A cyan toner base 20 was produced.

[Production Example 106; Production of Cyan Toner Base 21 (Ester Elongation Method)]
In Production Example 87, the same conditions were used except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2], the heating temperature of (5) was changed to 55 ° C., and the heating time was changed to 25 minutes. Then, an oil phase was prepared, emulsified or dispersed, solvent removed, washed, dried, and air sieved to prepare a cyan toner base 21.

[Production Example 107; Production of cyan toner base 22 (ester elongation method)]
In Production Example 87, an oil phase was prepared, emulsified or dispersed, solvent-removed, washed, dried, and air-screened under the same conditions except that the heat treatment of (5) was changed to none to prepare cyan toner base 22. .

[Production Example 108; Production of Clear Toner (No Colorant) Base 1 (Ester Elongation Method)]
-Preparation of clear oil phase 1-
In the production of [Black Oil Phase 1], 113 parts by mass of [Amorphous Polyester Resin 3] was changed to 123 parts by mass of [Amorphous Polyester Resin 1] and 20 parts by mass of [Black Masterbatch 3] were added without addition. [Clear oil phase 1] was obtained in the same manner.

―Emulsification or dispersion―
30 parts by mass of [Polyester Prepolymer 3] in ethyl acetate and 3 parts by mass of 50% by mass of isophoronediamine in ethyl acetate are added to 265 parts by mass of [Clear Oil Phase 1], and a TK homomixer (specialized mechanized) is added. Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Clear oil phase 1 ′]. Then, 400 parts by mass of [Aqueous Phase 1] is put in another container in which a stirrer and a thermometer are set, and stirred at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Clear oil phase 1 ′] was added and emulsified for 1 minute to obtain [Clear emulsified slurry 1].

-Solvent removal-Cleaning-Drying-
[Clear Emulsion Slurry 1] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as [Black Emulsion Slurry 1] except that the heating time of (5) was changed to 20 minutes. 1 was produced.

[Production of Black Toner 1 to Black Toner 22 and Clear Toner 1]
[Black Toner Base 2] to [Black Toner Base 9], [Black Toner Base 16] to [Black Toner Base 19], [Black Toner Base 1], [Black Toner Base 10] to [Black Toner Base 15] ], [Black Toner Base 20] to [Black Toner Base 22], and [Clear Toner Base 1] are used in the order of the relationship between the toner base and the toner as shown in Table 1, and 100 parts by weight of each toner base is used. On the other hand, 1.15 parts by mass of UFP-35, 1.10 parts by mass of H2000, and 0.70 parts by mass of JMT-150IB (manufactured by Teica) were added, and the Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was added. After mixing, the mixture was passed through a sieve having an opening of 500 mesh to obtain black toners 1 to 22 and clear toner. Table 1 shows the physical properties of the obtained black toners 1 to 22 and clear toner 1.

[Preparation of Yellow Toner 1 to Yellow Toner 22]
[Yellow Toner Base 2] to [Yellow Toner Base 9], [Yellow Toner Base 16] to [Yellow Toner Base 19], [Yellow Toner Base 1], [Yellow Toner Base 10] to [Yellow Toner Base 15] ], [Yellow Toner Base 20] to [Yellow Toner Base 22] are used in the order of the relationship between the toner base and the toner as shown in Table 2, and UFP-35 is added to 100 parts by mass of each toner base. 1.15 parts by mass, 1.10 parts by mass of H2000, 0.70 parts by mass of JMT-150IB (manufactured by Teika), and mixing with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), then opening 500 mesh And yellow toners 1 to 22 were obtained. Table 2 shows the physical properties of the obtained yellow toners 1 to 22.

[Production of Magenta Toner 1 to Magenta Toner 22]
[Magenta Toner Base 2] to [Magenta Toner Base 9], [Magenta Toner Base 16] to [Magenta Toner Base 19], [Magenta Toner Base 1], [Magenta Toner Base 10] to [Magenta Toner Base 15] ], [Magenta Toner Base 20] to [Magenta Toner Base 22] are used in the order of the relationship between the toner base and the toner as shown in Table 3, and UFP-35 is used for 100 parts by mass of each toner base. 1.15 parts by mass, 1.10 parts by mass of H2000, 0.70 parts by mass of JMT-150IB (manufactured by Teika), and mixing with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), then opening 500 mesh To obtain magenta toners 1 to 22. Table 3 shows the physical properties of the obtained magenta toners 1 to 22.

[Preparation of Cyan Toner 1 to Cyan Toner 22]
[Cyan Toner Base 2] to [Cyan Toner Base 9], [Cyan Toner Base 16] to [Cyan Toner Base 19], [Cyan Toner Base 1], [Cyan Toner Base 10] to [Cyan Toner Base 15] ], [Cyan toner base 20] to [Cyan toner base 22] are used in the order of the relationship between the toner base and the toner as shown in Table 4, and UFP-35 is added to 100 parts by weight of each toner base. 1.15 parts by mass, 1.10 parts by mass of H2000, 0.70 parts by mass of JMT-150IB (manufactured by Teika), and mixing with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), then opening 500 mesh The cyan toners 1 to 22 were obtained. Table 4 shows the physical properties of the obtained cyan toners 1 to 22.

<Method for Measuring Toner Weight Average Molecular Weight (Mw)>
The weight average molecular weight (Mw) of the toner was measured by gel permeation chromatography (GPC). The column was stabilized in a 40 ° C. heat chamber. To the column stabilized at this temperature, tetrahydrofuran (THF) as a solvent is flowed at a flow rate of 1 mL / min, and a THF sample solution of toner adjusted to a sample concentration of 0.05% to 0.6% by weight is 50 μL to 200 μL. Injected and measured.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical co. Manufactured by Toyo Soda Industry Co., Ltd. and having molecular weights of 6 × 10 2, 2.1 × 10 3, 4 × 10 3, 1.75 × 10 4, 5.1 × 10 4, 1.1 × 10 5, 3.9 × 10 5, It is appropriate to use 8.6 × 10 5, 2 × 10 6, 4.48 × 10 6, and use at least about 10 standard polystyrene samples. An RI (refractive index) detector was used as the detector.

[Production Example 109; Production of Carrier 1]
26 parts by mass of a silicone resin solution (solid content 23%, SR2410, manufactured by Toray Dow Corning), acrylic resin (Hitaroid 3001, solid content 50% by mass, manufactured by Hitachi Chemical Co., Ltd.) 2.5 parts by mass, benzoguanamine resin ( My coat 106, solid content 77% by mass, manufactured by Mitsui Cytec Co., Ltd.) 5 parts by mass, alumina particles (0.3 μm, specific resistance 1014 Ω · cm) 18 parts by mass, titanium diisopropoxybis (ethylacetoacetate) TC- as a catalyst 750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 2 parts by mass, SH6020 (manufactured by Toray Dow Corning Co., Ltd.) 0.2 part by mass as a silane coupling agent, diluted with toluene, dispersed with a homomixer for 10 minutes, solid content 10 mass % Resin solution was obtained. The resin solution was baked ferrite powder [(MgO) 1.8 (MnO) 49.5 (Fe2O3) 48.0: weight average particle diameter; 35 μm], 1000 parts by mass, and the coating layer thickness on the core particle surface was 0.15 μm. Then, it was applied with a Spira coater (Okada Seiko Co., Ltd.) and dried to obtain a coated ferrite powder. The obtained coated ferrite powder was fired at 180 ° C. for 2 hours in an electric furnace. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier 1 having a weight average particle diameter of 35 μm.

<Production of developer>
Example 1 Production of Black Developer 1, Yellow Developer 1, Magenta Developer 1 and Cyan Developer 1
70 parts by mass of black toner 1, yellow toner 1, magenta toner 1, cyan toner 1 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. By mixing, each developer 1 containing each toner was prepared.

Example 2 Production of Black Developer 2, Yellow Developer 2, Magenta Developer 2, and Cyan Developer 2
70 parts by mass of black toner 2, yellow toner 2, magenta toner 2 and cyan toner 2 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. By mixing, each developer 2 containing each toner was produced.

Example 3 Production of Black Developer 3, Yellow Developer 3, Magenta Developer 3, and Cyan Developer 3
70 parts by mass of black toner 3, yellow toner 3, magenta toner 3, cyan toner 3 and 930 parts by mass of carrier 1 are put in four commercially available ointment bottles, respectively, and a tumbler mixer is used at 81 rpm for 5 minutes. By mixing, each developer 4 containing each toner was prepared.

Example 4 Production of Black Developer 4, Yellow Developer 4, Magenta Developer 4, and Cyan Developer 4
70 parts by mass of black toner 4, yellow toner 4, magenta toner 4 and cyan toner 4 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. By mixing, each developer 4 containing each toner was prepared.

[Example 5: Production of black developer 5, yellow developer 5, magenta developer 5 and cyan developer 5]
70 parts by mass of black toner 5, yellow toner 5, magenta toner 5, cyan toner 5 and 930 parts by mass of carrier 1 are put in four commercially available ointment bottles, respectively, and a tumbler mixer is used at 81 rpm for 5 minutes. Each developer 5 containing each toner was prepared by mixing.

[Example 6: Production of black developer 6, yellow developer 6, magenta developer 6 and cyan developer 6]
70 parts by mass of black toner 6, yellow toner 6, magenta toner 6 and cyan toner 6 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. By mixing, each developer 6 containing each toner was produced.

[Example 7: Production of black developer 7, yellow developer 7, magenta developer 7 and cyan developer 7]
70 parts by mass of black toner 7, yellow toner 7, magenta toner 7, cyan toner 7 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and 81 minutes with a tumbler mixer at 81 rpm. Each developer 7 containing each toner was prepared by mixing.

[Example 8: Production of black developer 8, yellow developer 8, magenta developer 8 and cyan developer 8]
70 parts by mass of black toner 8, yellow toner 8, magenta toner 8, cyan toner 8 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. By mixing, each developer 8 containing each toner was produced.

[Example 9: Production of black developer 9, yellow developer 9, magenta developer 9 and cyan developer 9]
70 parts by mass of black toner 9, yellow toner 9, magenta toner 9, cyan toner 9 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. The respective developers 9 containing the respective toners were prepared by mixing.

Example 10 Production of Black Developer 10, Yellow Developer 10, Magenta Developer 10, and Cyan Developer 10
70 parts by mass of black toner 10, yellow toner 10, magenta toner 10, cyan toner 10 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. By mixing, each developer 10 containing each toner was produced.

Example 11 Production of Black Developer 11, Yellow Developer 11, Magenta Developer 11, and Cyan Developer 11
In four commercially available ointment bottles, 70 parts by weight of black toner 11, yellow toner 11, magenta toner 11, cyan toner 11 and 930 parts by weight of carrier 1 were placed, respectively, and turbuler mixer at 81 rpm for 5 minutes. The respective developers 11 containing the respective toners were prepared by mixing.
Example 12 Production of Black Developer 12, Yellow Developer 12, Magenta Developer 12, and Cyan Developer 12
In four commercially available ointment bottles, 70 parts by mass of black toner 12, yellow toner 12, magenta toner 12, cyan toner 12 and 930 parts by mass of carrier 1 were placed, respectively, and turbuler mixer at 81 rpm for 5 minutes. The respective developers 12 containing the respective toners were prepared by mixing.

Example 13 Production of Black Developer 13, Yellow Developer 13, Magenta Developer 13, and Cyan Developer 13
70 parts by mass of black toner 13, yellow toner 13, magenta toner 13, cyan toner 13 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and 81 minutes at 81 rpm with a tumbler mixer. The respective developers 13 containing the respective toners were prepared by mixing.

Example 14 Production of Black Developer 14, Yellow Developer 14, Magenta Developer 14, and Cyan Developer 14
70 parts by mass of black toner 14, yellow toner 14, magenta toner 14 and cyan toner 14 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. The respective developers 14 containing the respective toners were prepared by mixing.

Example 15 Production of Black Developer 15, Yellow Developer 15, Magenta Developer 15, and Cyan Developer 15
70 parts by mass of black toner 15, yellow toner 15, magenta toner 15 and cyan toner 15 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, at 81 rpm for 5 minutes with a tumbler mixer. The respective developers 15 containing the respective toners were prepared by mixing.

Example 16 Production of Black Developer 16, Yellow Developer 16, Magenta Developer 16, and Cyan Developer 16
70 parts by mass of black toner 16, yellow toner 16, magenta toner 16, cyan toner 16 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. By mixing, each developer 16 containing each toner was produced.

Example 17 Production of Black Developer 17, Yellow Developer 17, Magenta Developer 17, and Cyan Developer 17
In four commercially available ointment bottles, 70 parts by mass of black toner 17, yellow toner 17, magenta toner 17, cyan toner 17 and 930 parts by mass of carrier 1 were placed, respectively, and turbuler mixer at 81 rpm for 5 minutes. The respective developers 17 containing the respective toners were prepared by mixing.

Example 18 Production of Black Developer 18, Yellow Developer 18, Magenta Developer 18, and Cyan Developer 18
70 parts by mass of black toner 18, yellow toner 18, magenta toner 18 and cyan toner 18 and 930 parts by mass of carrier 1 are put in four commercially available ointment bottles, respectively, and a tumbler mixer is used at 81 rpm for 5 minutes. Each developer 18 containing each toner was prepared by mixing.

Example 19 Production of Black Developer 19, Yellow Developer 19, Magenta Developer 19, and Cyan Developer 19
70 parts by mass of black toner 19, yellow toner 19, magenta toner 19 and cyan toner 19 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. The respective developers 19 containing the respective toners were prepared by mixing.

Example 20 Production of Black Developer 5, Yellow Developer 5, Magenta Developer 5, Cyan Developer 5, and Clear Developer 1
In five commercially available ointment bottles, 70 parts by mass of black toner 5, yellow toner 5, magenta toner 5, cyan toner 5, clear toner 1 and 930 parts by mass of carrier 1 are put in a tumbler mixer. Each developer 5 and clear developer 1 containing each toner were prepared by mixing at 81 rpm for 5 minutes.

[Comparative Example 1; Production of black developer 20, yellow developer 20, magenta developer 20 and cyan developer 20]
70 parts by mass of black toner 20, yellow toner 20, magenta toner 20, cyan toner 20 and 930 parts by mass of carrier 1 are put in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. The respective developers 20 containing the respective toners were prepared by mixing.

[Comparative Example 2; Production of Black Developer 21, Yellow Developer 21, Magenta Developer 21, and Cyan Developer 21]
70 parts by mass of black toner 21, yellow toner 21, magenta toner 21, cyan toner 21 and 930 parts by mass of carrier 1 are placed in four commercially available ointment bottles, respectively, and a tumbler mixer at 81 rpm for 5 minutes. The respective developers 21 containing the respective toners were prepared by mixing.

[Comparative Example 3; Production of Black Developer 22, Yellow Developer 22, Magenta Developer 22, and Cyan Developer 22]
In each of four commercially available ointment bottles, 70 parts by mass of black toner 22, yellow toner 22, magenta toner 22, cyan toner 22 and 930 parts by mass of carrier 1 are placed, and turbuler mixer at 81 rpm for 5 minutes. The respective developers 22 containing the respective toners were prepared by mixing.

  Next, the obtained developer is set in the image forming apparatuses 1 to 23 in accordance with the toner combinations shown in Table 5, and image peeling (low temperature fixability), heat resistant storage stability, and glossiness are as follows. An evaluation was made and an overall judgment was made. The results are shown in Table 5. “Cl” in the table indicates clear toner.

<Image peeling in low temperature range (low temperature fixability)>
Using the image forming apparatuses 1 to 23 of the present invention, a copy test was performed on copy paper TYPE 6000 <70W> (manufactured by Ricoh Co., Ltd.). The evaluation conditions for the minimum fixing temperature are as follows: copy paper TYPE 6000 <70 W> (manufactured by Ricoh Co., Ltd.), 3 cm × 10 cm R (Y + M), G (with a toner adhesion amount of 0.70 ± 0.05 mg / cm ² ). Y + C) and B (M + C), which are two-color superposition charts, with a linear velocity of paper feed of 260 mm / sec to 280 mm / sec, a surface pressure of 1.2 kgf / cm ² and a nip width of 11 mm, The temperature at which image peeling disappeared when fixing was performed by changing the fixing temperature (fixing lower limit temperature) was determined. Evaluation of low-temperature fixability was evaluated according to the following criteria. The lower the fixing minimum temperature, the better the low-temperature fixability.
[Evaluation criteria]
A: Very good, B: Good, B: Acceptable, B: Unusable for practical use A: B, B, C: Passed and x: Fail.
A: R, G, and B all have a fixing lower limit temperature of less than 120 ° C. ○: No color having a fixing lower limit temperature of 130 ° C. or higher.
One or more colors having a fixing lower limit temperature of 120 ° C. or higher and lower than 130 ° C. Δ: No color having a fixing lower limit temperature of 140 ° C. or higher.
One or more colors with a minimum fixing temperature of 130 ° C. or higher and lower than 140 ° C. ×: One or more colors with a minimum fixing temperature of 140 ° C. or higher

<Heat resistant storage stability>
For each of the color toners 1 to 22 and clear toner 1 mounted on the image forming apparatus of the present invention, 10 g of each was weighed into a 200 CC screw vial and left in a 35 ° C./80% environment for one month to obtain an evaluation toner. The toner for evaluation was spread on an opening of 75 μm, and the state of the toner remaining on the shaker was observed by shaking for 1 minute.
[Evaluation criteria]
A: Very good, B: Good, B: Acceptable, B: Unusable for practical use A: B, B, C: Passed and x: Fail.
A: Not observed at all O: Agglomerated toner was slightly observed Δ: Agglomerated toner was slightly observed ×: Agglomerated toner was scattered a lot

<Glossiness>
Using the image forming apparatuses 1 to 23 of the present invention, a copy test was performed on POD gloss coated paper (basis weight: 128 g / m @ 2) made by Oji Paper. The evaluation images of the glossiness of the image forming apparatuses 1 to 19 and the image forming apparatuses 21 to 23 are obtained by applying an adhesion amount of 0.40 ± 0.02 mg / cm 2 to POD gloss coated paper (basis weight: 128 g / m 2) manufactured by Oji Paper. A 3 cm × 10 cm solid image of the chromatic color toner was formed. The evaluation image of the glossiness of the image forming apparatus 20 is 3 cm × 10 cm of chromatic toner having an adhesion amount of 0.40 ± 0.02 mg / cm 2 on POD gloss coated paper (basis weight: 128 g / m 2) manufactured by Oji Paper. An image was formed on the solid image so that a 3 cm × 10 cm solid image of a transparent toner having an adhesion amount of 0.40 ± 0.02 mg / cm 2 overlapped. These images were fixed at a linear velocity of paper feed: 280 mm / second, surface pressure: 1.2 kgf / cm 2, nip width: 11 mm, fixing temperature: 180 ° C., and used as gloss evaluation images. The glossiness was evaluated by measuring 60 ° glossiness at any 10 locations using a gloss meter VG-7000 (manufactured by Nippon Denshoku Industries Co., Ltd.), obtaining the average glossiness, and evaluating it according to the following criteria.
[Evaluation criteria]
A: Very good, B: Good, B: Acceptable, B: Unusable for practical use A: B, B, C: Passed and x: Fail.
◎: Average glossiness of 80% or more ○: Average glossiness of 50% or more and less than 80% △: Average glossiness of 20% or more and less than 50% ×: Average glossiness of less than 20%

<Comprehensive judgment>
Based on the evaluation of the initial image density stability, the image density stability over time, the initial transferability, the transfer stability over time, and the image peeling in a low temperature range, a comprehensive determination was made.
◎: There are two or more ◎, and Δ, × None ○: Other △: There are two or more △ and none ×: One or more × ◎: Very good, ○: Good, △: Acceptable , X: a level that cannot be used practically, ◎, ○, △ was passed and x was rejected.

  From Table 5, the image forming apparatuses of Examples 1 to 19 do not cause image peeling in a low temperature range and have excellent heat-resistant storage stability and generally good results as compared with the image forming apparatuses of Comparative Examples 1 to 3. was gotten. Further, in the image forming apparatus of Example 20, in addition to the above, a result capable of forming a high gloss image was obtained.

10 Electrostatic latent image carrier (photosensitive drum)
10K Black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer Supply roller 44K Developing roller 44Y Developing roller 44M Developing row 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer belt 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona Charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoconductor cleaning device 64 Static discharge lamp 70 Static discharge lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 120 Image forming unit 130 Document base 142 Paper feed roller 143 Paper bank 144 Paper cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device main body 160 Charging device 200 Paper feed tray Le 300 Scanner 400 automatic document feeder (ADF)

JP 2010-0777419 A JP 2010-151996 A JP 2012-83714 A

Claims (4)

An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, exposure means for exposing the charged surface of the electrostatic latent image carrier to form an electrostatic latent image, and Developing means for sequentially developing the electrostatic latent image with a plurality of colors of toner to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit,
The multi-color toner comprises a toner base containing at least a binder resin, a colorant and a release agent, and an external additive,
When the amount of exudation of the release agent at 100 ° C. for each toner of the plurality of colors is W,
The toner is transferred such that W satisfies the following relational expression (1), and the order of stacking of toner on the recording medium is from the fixing unit to the toner having the largest value of W ,
When the amount of the release agent present in the vicinity of the toner surface at normal temperature and humidity of the toner is W1, the release agent amount present in the vicinity of the toner surface after storage for 2 weeks at 40 ° C. and 70% RH, A full-color image forming apparatus, wherein W1 and W2 satisfy the following relational expression (2) .
0.30 ≤ W ≤ 0.50 ... Relational expression (1)
1.00 ≦ W2 / W1 ≦ 1.30 ... Relational expression (2) The full-color image forming apparatus according to claim 1, wherein the binder resin contains at least a crystalline polyester resin. 3. The full-color image forming apparatus according to claim 1, wherein a weight average molecular weight (Mw) corresponding to a binder resin in the toner is 5000 to 18000. 4. 4. The toner according to claim 1, further comprising a transparent toner comprising a toner base material containing at least a binder resin and a release agent and no colorant, and an external additive. The full-color image forming apparatus described in 1.

Images