JP5402583B2 - Toner, developer, and image forming method - Google Patents

Description

  The present invention relates to a toner, a developer containing the toner, and an image forming method using the toner, and more particularly to an image forming apparatus using a so-called electrophotographic method such as an electrostatic copying machine or a laser beam printer. The present invention relates to a full-color toner to be used, a developer containing the toner, and an image forming method using the toner.

  Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, and the like, an electrical or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating. The toner used for electrostatic image development is generally colored particles in which a binder, a charge control agent, and other additives are contained in a binder resin. And a polymerization method.

In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. Yes.
According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limit to the selection of the toner material. For example, a composition obtained by melt mixing needs to be pulverized and classified by an economically usable apparatus, and the melt-mixed composition must be made sufficiently brittle. For this reason, when the composition is pulverized into particles, the particle size distribution of the pulverized particles tends to be wide, and a copy image having good resolution and gradation can be obtained. The fine powder of 5 μm or less, particularly 3 μm or less, and the coarse powder of 20 μm or more must be removed by classification, and there is a disadvantage that the yield becomes very low. In the pulverization method, it is difficult to uniformly disperse a release agent, a colorant (pigment) and the like in the thermoplastic resin. In addition, since the colorant added to the toner is exposed on the surface of the obtained toner, the toner surface is unevenly charged, the toner charge distribution becomes wide, and the development characteristics deteriorate. There is. Therefore, due to these problems, the pulverization method cannot sufficiently meet the demand for high performance.

In recent years, in order to overcome the problems in the pulverization method, for example, toner particles are obtained by a suspension polymerization method.
However, the toner particles obtained by the suspension polymerization method have a drawback that they are spherical and have poor cleaning properties. In development / transfer with a low image area ratio, there is little transfer residual toner and there is no problem with poor cleaning. However, in development / transfer with a high image area ratio, such as photographic images, untransferred images due to poor paper feed, etc. The formed toner may be generated as a transfer residual toner on the photosensitive member, and if the transfer residual toner is accumulated, the background stain of the image is generated.
In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. Furthermore, since the resin is polymerized at the same time as the preparation of the toner, there are many cases where the materials used in the conventional toner cannot be used. Even those that can be polymerized using conventional materials may not be able to adequately control the particle size due to the influence of additives such as resins and colorants. There is a problem that the degree is small.
Particularly problematic is that the polyester resin that has conventionally exhibited excellent fixing performance and color suitability by the kneading and pulverization method cannot be basically used, and therefore it can sufficiently cope with downsizing, speeding up, colorization, etc. It is a point that cannot be done.

For this reason, a method has been disclosed in which resin fine particles obtained by an emulsion polymerization method are associated to obtain amorphous toner particles (see, for example, Patent Document 1). As magenta pigments, naphthol pigments are disclosed as pigments having high color reproducibility and weather resistance (see, for example, Patent Document 2).
However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. There is a problem in that the amount distribution is widened and the resulting image is poorly stained. In addition, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, and the like, and the original charging ability cannot be exhibited. In addition, even in the emulsion polymerization method in which the colorant component is hardly exposed on the toner surface, the colorant is easily aggregated, so that it is difficult to add and disperse the colorant uniformly in the toner. Due to the difference, there is a problem that the non-uniformity of charging occurs and the stability when used for a long time is lowered. In the case of color output, a slight deterioration in developability and transferability causes a problem in color balance and gradation. Furthermore, since the colorant in the toner is generally hydrophilic and incompatible with the resin, there is a problem that the transmitted light is irregularly reflected at the interface and the transparency of OHP or the like is hindered.

As a toner production method for solving these problems, a so-called dissolution suspension method is disclosed in which an oily component liquid (oil phase) in which a toner component is dissolved is particulated in an aqueous medium, and after removing the solvent, the powder is pulverized (for example, And Patent Documents 3 to 6).
However, while the dissolution suspension method has an advantage that the toner can be easily spheroidized, particularly when the mixture of the aqueous medium and the oil component is vigorously stirred in order to reduce the average particle diameter of the toner. The colorant (pigment) contained in the toner tends to segregate at the interface between the aqueous medium and the oil component during atomization, and the colorant (pigment) is exposed on the toner surface or the colorant (pigment) is not dispersed in the toner. There is a problem that it becomes uniform. In particular, the magenta pigment has a problem that it easily segregates on the toner particle surface due to its structure as compared with carbon black and phthalocyanine pigment.
As a means for improving the colorant (pigment) dispersibility, a technique using a polymer dispersant as a colorant (pigment) dispersant is disclosed, and by defining the acid value and amine value of the polymer dispersant, There has been disclosed a toner having excellent offset property, charging property and storage property, and good color development and OHP permeability (see, for example, Patent Document 7). However, when preparing a toner by suspending and granulating in an aqueous system, it is not sufficient to specify the acid value and amine value of the polymer dispersant, and colorant (pigment) aggregation occurs during toner preparation, and the toner Color developability, transparency after fixing the toner deteriorates, and color reproducibility decreases.

On the other hand, for the purpose of improving color reproducibility, a technique for adjusting the hue by using two or more kinds of colorants (pigments) has been widely used. And a quinacridone pigment in a ratio of 80:20 to 50:50 is disclosed (for example, see Patent Document 8).
However, in the dissolution suspension method, the quinacridone pigment has a hydrophilic group portion exposed on the skeleton, approaches the aqueous phase during granulation, and segregates on the toner surface layer. If the colorant is segregated, it tends to aggregate, resulting in poor color development and a problem of affecting the chargeability.

Furthermore, a magenta toner having a working mass ratio of 50:50 to 60:40 using Pigment Red 31 and Pigment Red 150 which are naphthol pigments is disclosed (for example, see Patent Document 9).
However, among the naphthol pigments, Pigment Red 150 has a high coloring power, but has an amine group that is unstable on the molecular skeleton and active against water on the relatively outer side of the skeleton. The water resistance is poor, and there is a problem that the solution suspension method tends to segregate on the toner surface layer due to the water phase side during granulation.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner having high saturation, excellent hue, no scumming under high temperature and high humidity, a developer containing the toner, and an image forming method using the toner. And

Means for solving the problems are as follows. That is,
<1> A toner that is granulated by dispersing an oil phase containing at least a binder resin, a colorant, and a release agent in an aqueous medium, wherein the colorant includes Pigment Red 31 and Pigment Red 269. The mixing ratio of the pigment red 31 and the pigment red 269 is 1:99 to 50:50 by mass ratio, and the content of the colorant is 3% by mass to the binder resin. The toner is 12% by mass.
<2> Granulation in an aqueous medium includes, in an organic solvent, at least an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound as a binder resin, and unmodified A polyester resin, a colorant, and a release agent are dissolved or dispersed, and the dissolved or dispersed material is dispersed in an aqueous medium to prepare a dispersion. In the aqueous medium, the active hydrogen group-containing compound and The toner according to <1>, wherein the toner is formed by crosslinking or extending a polymer having a site capable of reacting with the active hydrogen group-containing compound and removing the organic solvent from the obtained dispersion.
<3> The toner according to <2>, wherein the acid value of the unmodified polyester resin is 5 KOHmg / g to 40 KOHmg / g.
<4> The toner according to any one of <1> to <3>, wherein the colorant is surface-treated with an acidic surface treatment agent.
<5> The toner according to <4>, wherein the acid value of the surface treatment agent is 3 KOHmg / g to 20 KOHmg / g.
<6> The toner according to any one of <4> to <5>, wherein the surface treatment agent has a melting point of 70 ° C to 110 ° C.
<7> The toner according to any one of <4> to <6>, wherein the melting point of the surface treatment agent is lower than the melting point of the unmodified polyester resin.
<8> The toner according to any one of <2> to <7>, wherein the toner is granulated using a master batch in which a colorant is dispersed in an unmodified polyester resin.
<9> The toner according to <8>, wherein the toner is granulated using a master batch in which a colorant and a surface treatment agent are dispersed in an unmodified polyester resin.
<10> The toner according to any one of <8> to <9>, wherein the dispersion is performed by melt kneading using an open type melt kneader.
<11> The toner according to any one of <1> to <10>, wherein the toner is granulated using a pigment press cake as a colorant.
<12> A developer comprising the toner according to any one of <1> to <11>.
<13> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <11> The image forming apparatus includes at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. An image forming method.
<14> The electrostatic latent image forming step is a step of forming an electrostatic latent image on each of the plurality of electrostatic latent image carriers, and the developing step is to convert each electrostatic latent image to the electrostatic latent image. <13, which is a step of forming a visible image by developing with different color toner for each carrier, and the transfer step is a step of transferring the visible image to a recording medium via an intermediate transfer member. >.

  According to the present invention, it is possible to solve the above-described problems and achieve the above-described object, to achieve a toner having high saturation, excellent hue, and no scumming under high temperature and high humidity, and the toner. An image forming method using the developer and the toner can be provided.

FIG. 1 is a diagram illustrating an example of an image forming apparatus according to the present invention. FIG. 2 is a diagram showing another example of the image forming apparatus of the present invention. FIG. 3 is a diagram showing the tandem developing device of FIG.

(toner)
The toner of the present invention is granulated by dispersing an oil phase in an aqueous medium, and includes at least a binder resin, a colorant, and a release agent, and includes an active hydrogen group-containing compound, a surface treatment agent, and a charge control agent. , External additives, and other components as necessary.

<Binder resin>
The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an unmodified polyester resin obtained by dehydration condensation of a polyhydric alcohol component and a polyhydric acid component, an active hydrogen group Examples thereof include a polymer having a site capable of reacting with the containing compound, and a mixture thereof. In the case of producing a toner by the dissolution suspension method, for example, a styrene resin, an acrylic resin, and the like can be given.

-Unmodified polyester resin-
The unmodified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of dispersibility of the colorant, a propylene oxide adduct of bisphenols as a polyhydric alcohol component is all polyvalent. Polyester resin polymerized using 50 mol% or more with respect to the alcohol component is preferable, and polyester resin polymerized using 70 mol% or more of the propylene oxide adduct of bisphenols as the polyhydric alcohol component with respect to the total polyhydric alcohol component. A polyester resin obtained by polymerizing a propylene oxide adduct of bisphenol as a polyhydric alcohol component with 80 mol% or more based on the total polyhydric alcohol component is particularly preferable.

--Polyhydric alcohol component--
There is no restriction | limiting in particular as said polyhydric alcohol component, According to the glass transition point of the resin (for example, polyester resin) obtained, molecular weight, a softening point, it can select suitably, For example, diol, trihydric or more alcohol , Etc.

The diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6 -Alkylene glycol such as hexanediol; diol having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc. Alicyclic diols; those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to alicyclic diols; bisphenol A, bisphenol F, bisphenol S Bisphenols; the bisphenols include ethylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide; and the like. In addition, it is preferable that carbon number of the said alkylene glycol is 2-12.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. And a mixture thereof is more preferable.

The trihydric or higher alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, trihydric or higher aliphatic alcohol, trihydric or higher polyphenol, alkylene of trihydric or higher polyphenols. And oxide adducts.
The trihydric or higher aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
The trihydric or higher polyphenols are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trisphenol PA, phenol novolac, and cresol novolak.
The alkylene oxide adduct of the trihydric or higher polyphenols is not particularly limited and can be appropriately selected depending on the purpose. For example, trihydric or higher polyphenols include ethylene oxide, propylene oxide, butylene oxide, The thing which added the alkylene oxide etc. are mentioned.

  When a polyester resin containing a certain amount or more of the propylene oxide adduct as the polyhydric alcohol component is combined with a polymer dispersant which is a polyester derivative having a predetermined acid value and amine value, a colorant (pigment) Dispersibility is excellent and toner color reproducibility is improved. Although this reason is not certain, it is considered that the affinity between the polyester resin and the polymer dispersant is increased, and the colorant (pigment) is stabilized.

--Polyacid component--
There is no restriction | limiting in particular as said polyvalent acid component, According to the objective, it can select suitably, For example, polycarboxylic acid is mentioned.
The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicarboxylic acids, trivalent or higher carboxylic acids, and mixtures of dicarboxylic acids and trivalent or higher carboxylic acids. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, a dicarboxylic acid, a mixture of a dicarboxylic acid and a small amount of a tricarboxylic or higher polycarboxylic acid is preferable.
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, bivalent alkanoic acid, bivalent alkenoic acid, aromatic dicarboxylic acid, etc. are mentioned.
The divalent alkanoic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid and sebacic acid.
There is no restriction | limiting in particular as said bivalent alkenoic acid, Although it can select suitably according to the objective, A C4-C20 bivalent alkenoic acid is preferable. The divalent alkenoic acid having 4 to 20 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include maleic acid and fumaric acid.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, Although it can select suitably according to the objective, C8-C20 aromatic dicarboxylic acid is preferable. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. .
The trivalent or higher carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trivalent or higher aromatic carboxylic acids.
There is no restriction | limiting in particular as said trivalent or more aromatic carboxylic acid, Although it can select suitably according to the objective, C9-C20 aromatic carboxylic acid is preferable. The aromatic carboxylic acid having 9 to 20 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimellitic acid and pyromellitic acid.
The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid may be used. And acid anhydrides or lower alkyl esters.
There is no restriction | limiting in particular as said lower alkyl ester, According to the objective, it can select suitably, For example, methyl ester, ethyl ester, isopropyl ester, etc. are mentioned.
When the dicarboxylic acid and the trivalent or higher carboxylic acid are used as a mixture, the mass ratio of the trivalent or higher carboxylic acid to the dicarboxylic acid is not particularly limited and may be appropriately selected depending on the purpose. However, 0.01 mass%-10 mass% are preferable, and 0.01 mass%-1 mass% are more preferable.
The equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid in the polycondensation of the polyol and the polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Is preferable, 1 to 1.5 is more preferable, and 1.02 to 1.3 is particularly preferable.

The hydroxyl value and acid value of the unmodified polyester resin can be arbitrarily adjusted by adding a trivalent or higher alcohol or a trivalent or higher acid.
There is no restriction | limiting in particular as an acid value of the said non-modified polyester resin, Although it can select suitably according to the objective, 5 KOHmg / g-40 KOHmg / g are preferable. If the acid value of the polyester resin is less than 5 KOHmg / g, it may be difficult to disperse the colorant and the release agent, and if it exceeds 40 KOHmg / g, it may be easily affected by the external environment. For example, the charge may decrease under high temperature and high humidity, resulting in scumming or scattering. However, within the above preferable range, the dispersibility of the release agent and the colorant is improved, and coloring and releasability are achieved. Thus, a toner having excellent storage stability and chargeability under high temperature and high humidity can be obtained.

There is no restriction | limiting in particular as a weight average molecular weight of the said unmodified polyester resin, Although it can select suitably according to the objective, 1,000-30,000 are preferable and 1,500-15,000 are more preferable.
When the weight average molecular weight is less than 1,000, the heat-resistant storage stability may be lowered, and when it exceeds 30,000, the low-temperature fixability may be lowered.
There is no restriction | limiting in particular as content of the component whose said weight average molecular weight is less than 1,000, Although it can select suitably according to the objective, 8 mass%-28 mass% are preferable.

There is no restriction | limiting in particular as a glass transition temperature of the said unmodified polyester resin, Although it can select suitably according to the objective, 30 to 70 degreeC is preferable, 35 to 60 degreeC is more preferable, and 35 to 55 degreeC. ° C is particularly preferred.
When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.

-Polymer having a site capable of reacting with active hydrogen group-containing compound-
The polymer having a site capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include resins, polyacrylic resins, polyester resins, epoxy resins, and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together.
Among these, a polyester resin is preferable in terms of high fluidity and transparency at the time of melting.

Examples of the site capable of reacting with the active hydrogen group-containing compound of the prepolymer include an isocyanate group, an epoxy group, a carboxyl group, and a functional group represented by -COCl. These may be used individually by 1 type and may use 2 or more types together.
Among these, an isocyanate group is preferable.

  The prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is easy to adjust the molecular weight of the polymer component, and oilless low-temperature fixing characteristics in dry toners, particularly for fixing heating media. Even in the absence of a release oil application mechanism, a polyester resin having an isocyanate group or the like capable of generating a urea bond is preferable in terms of ensuring good release properties and fixing properties.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent or the like when a polymer having a site capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium.

  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 and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

The active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. The polymer having a site capable of reacting with the active hydrogen group-containing compound is a polyester prepolymer having an isocyanate group. In some cases, amines are preferred because they can be made to have a high molecular weight by an extension reaction, a crosslinking reaction or the like with the polyester prepolymer.
The amines are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those amino groups blocked. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of a diamine and a small amount of trivalent or higher amine are preferable.

  There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine, etc. are mentioned. There is no restriction | limiting in particular as said aromatic diamine, According to the objective, it can select suitably, For example, phenylenediamine, diethyltoluenediamine, 4,4'- diaminodiphenylmethane, etc. are mentioned. The alicyclic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane and isophorone diamine. Can be mentioned. There is no restriction | limiting in particular as said aliphatic diamine, According to the objective, it can select suitably, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc. are mentioned.

  The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.

  The amino alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.

  The amino mercaptan is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.

  The amino acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.

  There is no restriction | limiting in particular as what blocked the said amino group, According to the objective, it can select suitably, For example, it is obtained by blocking an amino group with ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples thereof include ketimine compounds and oxazolidone compounds.

--Polyester resin containing isocyanate group--
There is no restriction | limiting in particular as the polyester resin containing the said isocyanate group, According to the objective, it can select suitably, For example, the polyester resin which has an active hydrogen group obtained by polycondensing a polyol and polycarboxylic acid, And reaction products with polyisocyanates.

--- Polyol ---
There is no restriction | limiting in particular as said polyol, According to the objective, it can select suitably, For example, diol, trihydric or more alcohol, the mixture of diol and trihydric or more alcohol, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diol, and a mixture of diol and a small amount of trihydric or higher alcohol are preferable.

The diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6 -Alkylene glycol such as hexanediol; diol having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc. Alicyclic diols; those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to alicyclic diols; bisphenol A, bisphenol F, bisphenol S Bisphenols; the bisphenols include ethylene oxide, propylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide; and the like. In addition, there is no restriction | limiting in particular as carbon number of the said alkylene glycol, Although it can select suitably according to the objective, 2-12 are preferable.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. And a mixture thereof is more preferable.

The trihydric or higher alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, trihydric or higher aliphatic alcohol, trihydric or higher polyphenol, alkylene of trihydric or higher polyphenols. And oxide adducts.
The trihydric or higher aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
The trihydric or higher polyphenols are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trisphenol PA, phenol novolac, and cresol novolak.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to trihydric or higher polyphenols.
When the diol and the trihydric or higher alcohol are mixed and used, the mass ratio of the trihydric or higher alcohol to the diol is not particularly limited and may be appropriately selected depending on the intended purpose. % To 10% by mass is preferable, and 0.01% to 1% by mass is more preferable.

--- Polycarboxylic acid ---
The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicarboxylic acids, trivalent or higher carboxylic acids, and mixtures of dicarboxylic acids and trivalent or higher carboxylic acids. It is done. These may be used individually by 1 type and may use 2 or more types together.
Among these, a dicarboxylic acid, a mixture of a dicarboxylic acid and a small amount of a tricarboxylic or higher polycarboxylic acid is preferable.

There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, bivalent alkanoic acid, bivalent alkenoic acid, aromatic dicarboxylic acid, etc. are mentioned.
The divalent alkanoic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid and sebacic acid.
There is no restriction | limiting in particular as said bivalent alkenoic acid, Although it can select suitably according to the objective, C4-C20 bivalent alkenoic acid is preferable. There is no restriction | limiting in particular as said C4-C20 bivalent alkenoic acid, According to the objective, it can select suitably, For example, a maleic acid, a fumaric acid, etc. are mentioned.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, Although it can select suitably according to the objective, C8-C20 aromatic dicarboxylic acid is preferable. There is no restriction | limiting in particular as said C8-C20 aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.

The trivalent or higher carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trivalent or higher aromatic carboxylic acids.
There is no restriction | limiting in particular as said trivalent or more aromatic carboxylic acid, Although it can select suitably according to the objective, C9-C20 trivalent or more aromatic carboxylic acid is preferable. There is no restriction | limiting in particular as said C9-C20 trivalent or more aromatic carboxylic acid, According to the objective, it can select suitably, For example, trimellitic acid, pyromellitic acid, etc. are mentioned.

As the polycarboxylic acid, an acid anhydride or a lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid may be used.
There is no restriction | limiting in particular as said lower alkyl ester, According to the objective, it can select suitably, For example, methyl ester, ethyl ester, isopropyl ester, etc. are mentioned.
When the dicarboxylic acid and the trivalent or higher carboxylic acid are used in combination, the mass ratio of the trivalent or higher carboxylic acid to the dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. 0.01 mass% to 10 mass% is preferable, and 0.01 mass% to 1 mass% is more preferable.

  The equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid in the polycondensation of the polyol and the polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. ˜2 is preferable, 1 to 1.5 is more preferable, and 1.02 to 1.3 is particularly preferable.

There is no restriction | limiting in particular as content of the structural unit derived from the polyol in the polyester prepolymer which has the said isocyanate group, Although it can select suitably according to the objective, 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 lowered, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. When the content exceeds 40% by mass, Low temperature fixability may be reduced.

--- Polyisocyanate ---
The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and phenol derivatives thereof. , Oxime, caprolactam and the like blocked.
The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene Examples thereof include diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.
The alicyclic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanato Examples include diphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like.
The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α ′, α′-tetramethylxylylene diisocyanate.
There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris (isocyanatoalkyl) isocyanurate, a tris (isocyanatocycloalkyl) isocyanurate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is not particularly limited and may be appropriately selected depending on the purpose. 1-5 are preferable, 1.2-4 are more preferable, and 1.5-3 are especially preferable. When the equivalent ratio is less than 1, offset resistance may be lowered. When the equivalent ratio is more than 5, low-temperature fixability may be lowered.

  There is no restriction | limiting in particular as content of the structural unit derived from polyisocyanate in the polyester prepolymer containing the said isocyanate group, Although it can select suitably according to the objective, 0.5 mass%-40 mass% are Preferably, 1-30 mass% is more preferable, and 2-20 mass% is especially preferable. When the content is less than 0.5% by mass, the hot offset resistance may be deteriorated, and when it exceeds 40% by mass, the low-temperature fixability may be deteriorated.

  There is no restriction | limiting in particular as an average number of the isocyanate groups which the said polyester prepolymer has per molecule, Although it can select suitably according to the objective, 1 or more are preferable, 1.2-5 are more preferable, 1 .5-4 are particularly preferred. When the average number is less than 1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be lowered.

  The mass ratio of the polyester prepolymer having an isocyanate group to the polyester resin containing a propylene oxide adduct of bisphenol in the polyhydric alcohol component and having a specific hydroxyl value and an acid value is particularly limited. However, it may be appropriately selected according to the purpose, but is preferably less than 5/95 to more than 25/75, more preferably 10/90 to 25/75. When the mass ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

-Adhesive substrate-
The adhesive substrate is not particularly limited as long as it is generated by an extension reaction and / or a crosslinking reaction between the active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound. However, a polyester prepolymer obtained by reacting a polycondensate of bisphenol A propylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate and uread with isophoronediamine, for example, Mixture of bisphenol A propylene oxide 2 mol adduct and polycondensate of isophthalic acid; polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with isophorone diisocyanate with urea And what Mixtures of spunol A propylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate reacted with isophorone diisocyanate Polyester prepolymer urealated with isophorone diamine, bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct (bisphenol A propylene oxide 2 mol adduct mixture ratio is 50 mol% or more) and terephthal Mixture with acid polycondensate; bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate were mixed with isophorone diisocyanate. A mixture of a polyester prepolymer that has been reacted with an acrylate with isophorone diamine and a polycondensate of bisphenol A propylene oxide 2 mol adduct and terephthalic acid; a mixture of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a condensate with isophorone diisocyanate and uread with hexamethylenediamine, a 2-condensate of bisphenol A propylene oxide and a polycondensate of terephthalic acid; Polyester prepolymer obtained by reacting a polycondensate of styrene and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and 2 mol of bisphenol A ethylene oxide added Product / bisphenol A propylene oxide 2 mol adduct (mixture ratio of bisphenol A propylene oxide 2 mol adduct is 50 mol% or more) and polycondensate of terephthalic acid; bisphenol A ethylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a polycondensate with isophorone diisocyanate with ethylenediamine and a 2-condensate of bisphenol A propylene oxide and a polycondensate of terephthalic acid; a bisphenol A ethylene oxide 2-mole adduct and A polyester prepolymer obtained by reacting a polycondensate of isophthalic acid with diphenylmethane diisocyanate and uread with hexamethylene diamine, a 2-mole bisphenol A propylene oxide adduct and Polyester prepolymer obtained by reacting a polycondensate of isophthalic acid with a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Polycondensation of urethanized with hexamethylenediamine, bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct (mixing ratio of bisphenol A propylene oxide 2-mole adduct is 50 mol% or more) and terephthalic acid A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with toluene diisocyanate. Of urethanized with bisphenol A propylene oxide 2 mol adduct and isophthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid, trimellitic acid A polyester prepolymer obtained by reacting a polycondensate of the above with an isophorone diisocyanate and uread with a ketimine compound in which an amino group is blocked with a ketone, and a bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct ( Bisphenol A propylene oxide 3 mol adduct mixture ratio is 50 mol% or more) and a mixture of polycondensates of terephthalic acid, adipic acid and trimellitic acid.
Here, the adhesive base material is a base material having adhesiveness to a recording medium such as paper.

In addition, when reacting the said active hydrogen group containing compound and the said isocyanate group containing polyester resin, you may form a urethane bond by adding alcohol.
The molar ratio of the urethane bond to the urea bond thus formed (to distinguish it from the urethane bond of the isocyanate group-containing polyester resin) is not particularly limited and can be appropriately selected according to the purpose. 0-9 are preferable, 1 / 4-4 are more preferable, and 2 / 3-7 / 3 are especially preferable. If the molar ratio is greater than 9, the hot offset resistance may decrease.

In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer having a site capable of reacting with the active hydrogen group-containing compound. When the reaction terminator is used, the molecular weight and the like of the adhesive substrate produced by the extension reaction and / or the crosslinking reaction can be controlled within a desired range.
The reaction terminator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, ketimine compounds in which these amino groups are blocked, and the like. Can be mentioned.

  In a modified polyester resin (hereinafter sometimes referred to as “prepolymer”) as a polymer having a site capable of reacting with the active hydrogen group-containing compound with respect to the equivalent of the amino group in the amine as the active hydrogen group-containing compound. There is no restriction | limiting in particular as an equivalent ratio of an isocyanate group, Although it can select suitably according to the objective, 1 / 3-3 are preferable, 1 / 2-2 are more preferable, and 2 / 3-1.5 are. Particularly preferred. If the equivalent ratio is less than 1/3, the low-temperature fixability may be lowered. If the equivalent ratio is more than 3, the molecular weight of the urea-modified polyester resin may be lowered, and the hot offset resistance may be lowered.

<Colorant>
The colorant includes at least pigment red 31 and pigment red 269, which are naphthol pigments as magenta pigments, and further includes other components as necessary.
Among the naphthol pigments, Pigment Red 31 and Pigment Red 269 have relatively good dispersion in the oil phase or resin, and have high coloring power. Since Pigment Red 269 has strong absorption on the short wavelength side, it has a strong yellowishness as a magenta pigment and has a hue close to red, and therefore magenta color reproducibility is poor. On the other hand, Pigment Red 31 has a strong bluish color due to its strong color on the short wavelength side, but has an absorption on the long wavelength side, so if it is added too much, the saturation of the magenta color is lowered. By using together Pigment Red 31 and Pigment Red 269 as the colorant, it becomes possible to obtain a magenta toner having a good hue, coloring degree and chargeability.

The mixing ratio of Pigment Red 31 and Pigment Red 269 is not particularly limited as long as the mass ratio is 1:99 to 50:50, and can be appropriately selected according to the purpose, but is 5:95 to 45. : 55 is preferable, and 5:95 to 15:85 is more preferable.
By setting the mixing ratio of Pigment Red 31 and Pigment Red 269 to 1:99 to 50:50 by mass ratio, it is possible to obtain a magenta toner having a good hue, coloring degree, and chargeability.

The addition amount of the colorant is not particularly limited as long as it is 3% by mass to 12% by mass with respect to the binder resin, and can be appropriately selected according to the purpose. Although it can select suitably according to, 5 mass%-8 mass% are preferable.
When the addition amount of the colorant is less than 3% by mass with respect to the binder resin, the colorability is not sufficient, and the toner has low coloration and low saturation. Due to the absorption of the region, saturation and secondary color developability are reduced, and since the absolute amount of the colorant is increased, the chargeability of the toner is lowered, the oil phase viscosity is increased, and the productivity is deteriorated.

The colorant is preferably dispersed in advance in the unmodified polyester resin before adjusting the oil phase, and more preferably melted and kneaded in advance in the unmodified polyester resin.
That is, in the preparation of the toner of the present invention, it is preferable to use a master batch in which a colorant is previously dispersed in an unmodified polyester resin. By using the masterbatch, a magenta toner having a good hue, coloring degree, and charging property can be obtained by reducing the shock when the coloring agent is dispersed in the oil phase to prevent aggregation of the coloring agent and improving the dispersibility of the coloring agent. Can be obtained.

  It is preferable to prepare a master batch in which a colorant is previously dispersed in an unmodified polyester resin by melt kneading. The master batch prepared by melt kneading can be effectively dispersed by further adding a surface treatment agent to be described later, and re-aggregation of the colorant does not occur as in the case of solvent-based dispersion. No colorant is required, and stable colorant dispersibility can be obtained.

  In preparing a master batch in which a colorant is dispersed in advance in an unmodified polyester resin, it is preferable to use a washed pigment press cake as the colorant. The pigment presscake contains water between the pigment particles, and this water is replaced with an unmodified polyester resin during melt kneading. Thus, a toner having excellent pigment dispersibility can be obtained without aggregation of the pigment.

The melt kneader for melt kneading is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a single screw extruder kneader, a twin screw extruder kneader, a two roll, a three roll, and the like. Is mentioned.
Among these, an open-type melt kneader such as a continuous open-type two-roll kneader is preferable in terms of improving dispersibility.
Since the open-type melt kneader can release heat generated during shearing, it can be kneaded at a relatively low temperature. Since kneading at a low temperature can impart high resilience to the raw material, it is possible to obtain a toner with more excellent colorant (pigment) dispersibility.

  In the melt kneader, by making the roll gap on the kneaded product discharge side wider than the roll gap on the raw material charging side, the kneading force of the open roll type kneader, which usually applies a strong shearing force over the entire kneading section, is increased. , It can be concentrated in the raw material charging part in the first half of the kneading part. Further, since the latter half of the kneading part is mainly mixed by melting, generation of kneading heat itself can be suppressed, and the kneading effect can be increased. Two rolls arranged close to each other are heated rolls in which one roll passes a heating medium, and the other roll is a cooling roll passed through a cooling medium, thereby giving a stronger elasticity. Thus, the dispersibility of a release agent and a colorant (pigment) described later is improved.

<Release agent>
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably, For example, natural wax, synthetic wax, etc. are mentioned.
The natural wax is not particularly limited and may be appropriately selected depending on the intended purpose. For example, beeswax derived from animals, whale wax, shellac wax, carnauba wax derived from plants, wood wax, rice bran wax (rice wax), Candelilla wax, petroleum-derived paraffin wax, microcrystalline wax, mineral-derived montan wax, ozokerite, and the like.
The synthetic wax is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include Fischer-Tropsch wax, polyethylene wax, oil-based synthetic wax (ester, ketones, amide), hydrogenated wax, and the like. Can be mentioned.

The type of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of releasability, a hydrocarbon obtained by separating and purifying a vacuum distillation distillate of petroleum. What modified | denatured wax with carboxylic acid etc. is preferable.
The paraffin wax has a low viscosity at a relatively low temperature, has a low penetration, and is denatured, so that the acid value can be controlled relatively easily.

  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, It is preferable that it is lower than melting | fusing point of the said unmodified polyester resin from the point of mold release property, and 70 to 110 degreeC. ° C is more preferred.

The addition amount of the release agent is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of release properties, storage stability under high temperature and high humidity, and chargeability, the binder resin is added. On the other hand, 1 mass%-20 mass% are preferable, and 3 mass%-10 mass% are more preferable.
When the addition amount of the release agent is less than 1% by mass with respect to the binder resin, the release effect may be small, and when it exceeds 20% by mass, it may be easily influenced by the environment. .

  There is no restriction | limiting in particular as an acid value of the said mold release agent, Although it can select suitably according to the objective, 3KOHmg / g-20KOHmg / g are preferable.

  The viscosity of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, the viscosity at 90 ° C. is 5 cP to 50 cP in terms of bleedability so as not to inhibit charging. preferable.

<Surface treatment agent>
The surface treating agent is not particularly limited as long as it is an acidic surface treating agent for surface treating a colorant, and can be appropriately selected according to the purpose.

  By treating the colorant with an acidic surface treatment agent (acid treatment), the dispersibility of the colorant in the unmodified polyester resin is improved, and a magenta toner having a good hue, coloration degree, and chargeability. Can be obtained.

There is no restriction | limiting in particular as an acid value of the said surface treating agent, Although it can select suitably according to the objective, 3KOHmg / g-20KOHmg / g are preferable.
When the acid value of the surface treatment agent is less than 3 KOHmg / g, the colorant may not be sufficiently dispersed. When it exceeds 20 KOHmg / g, the surface treatment agent may be easily affected by the external environment. Under high temperature and high humidity, electrification may decrease, resulting in scumming or scattering. On the other hand, when the content is within the preferable range, the dispersibility of the colorant is improved, and a toner excellent in actual machine running property under high temperature and high humidity can be obtained.

There is no restriction | limiting in particular as melting | fusing point of the said surface treating agent, Although it can select suitably according to the objective, The temperature lower than melting | fusing point of the said unmodified polyester resin is preferable, and 70 to 110 degreeC is more preferable.
When the melting point of the surface treatment agent is equal to or higher than the melting point of the unmodified polyester resin, the surface treatment agent may not be effectively adsorbed on the surface of the colorant (pigment) during melt kneading. When the temperature is lower than the melting point of the resin, the surface treatment agent melts at the time of melt kneading and can be adsorbed on the particle surface in a state of being mixed with the colorant, and a great effect on the colorant (pigment) dispersibility is obtained.

  When the melting point of the surface treatment agent is lower than 70 ° C., the storage stability under high temperature and high humidity may be adversely affected, and the toner may solidify. When the melting point is higher than 110 ° C., the surface treatment agent is present during melt kneading. It is necessary to make the temperature high in order to melt the resin, and the viscosity of the unmodified polyester resin is lowered, and high shear may not be imparted.

  There is no restriction | limiting in particular as a viscosity of the said surface treating agent, Although it can select suitably according to the objective, It is preferable that the viscosity in 90 degreeC is 5 cP-50 cP. If the viscosity at 90 ° C. is less than 5 cP, the surface treatment agent exposed on the toner surface may adversely affect the storage stability under high temperature and high humidity, and the toner may solidify. If it exceeds, the viscosity is too high, it is difficult to mix with the colorant (pigment) at the time of melting, and it is difficult to adsorb on the surface of the colorant (pigment), so the effect of dispersibility of the colorant (pigment) may be small.

<Charge control agent>
The charge control agent is not particularly limited and may be appropriately selected depending on the purpose. However, a colorless or white charge control agent is used in that the color tone changes when a colored charge control agent is used. preferable.
The colorless or white charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, and fluorine-modified agents. Examples include quaternary ammonium salts including quaternary ammonium salts, alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine-based surfactants, 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.

A commercial product may be used as the charge control agent.
There is no restriction | limiting in particular as said commercial item, According to the objective, it can select suitably, For example, Bontron P-51 of a quaternary ammonium salt, E-82 of an oxynaphthoic acid type metal complex, Salicylic acid type metal complex E-84, phenol-based condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industries, Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 of boron complex (Japan) Carlit), quinacridone, azo pigments, other sulfonic acid groups, carbo Sill group, a polymer having a functional group such as quaternary ammonium salts, and the like.

The content of the charge control agent is not particularly limited and may be appropriately selected depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like. % By mass to 10% by mass is preferable, and 0.2% by mass to 5% by mass is more preferable.
When the content of the charge control agent is less than 0.1% by mass, the charge controllability may not be obtained. When the content exceeds 10% by mass, the chargeability of the toner becomes too high, and The electrostatic attractive force may increase, leading to a decrease in developer fluidity and a decrease in image density.

<External additive>
There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably, For example, an organic particle, an inorganic particle, etc. are mentioned.

  There is no restriction | limiting in particular as said organic particle, According to the objective, it can select suitably, For example, PMMA etc. are mentioned.

The inorganic particles are not particularly limited and can be appropriately selected according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, Etc. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a primary particle diameter of the said inorganic particle, Although it can select suitably according to the objective, 5 nm-2 micrometers are preferable, and 5 nm-500 nm are more preferable.
The BET specific surface area of the inorganic particles is not particularly limited and may be appropriately selected depending on the ^purpose, 20m ² / ^g~500m 2 / g are preferred.
There is no restriction | limiting in particular as content in the toner of the said inorganic particle, Although it can select suitably according to the objective, 0.01 mass%-5.0 mass% are preferable, 0.01 mass%-5 0.0 mass% is more preferable.
The inorganic particles are preferably used after being subjected to a surface treatment from the viewpoints of improving fluidity and blocking properties, storage resistance and water resistance.
There is no restriction | limiting in particular as a processing agent used for the said surface treatment, According to the objective, it can select suitably, For example, a silane coupling agent, a silylating agent, the silane coupling agent which has a fluorinated alkyl group, organic Examples include titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils.

<Oil phase>
The oil phase is not particularly limited as long as it contains at least a toner material containing a binder resin, a colorant, and a release agent, and can be appropriately selected according to the purpose. It is preferable that the material is dissolved or dispersed in a solvent.

  There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, It is preferable to contain an organic solvent. The organic solvent is preferably removed when forming the toner base particles or after forming the toner base particles.

There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The organic solvent whose boiling point is less than 150 degreeC is preferable at the point which is easy to remove.
The organic solvent having a boiling point of less than 150 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

  There is no restriction | limiting in particular as the usage-amount of the said organic solvent, Although it can select suitably according to the objective, 40 mass parts-300 mass parts are preferable with respect to 100 mass parts of toner materials, and 60 mass parts-140 mass parts. Mass parts are more preferable, and 80 to 120 parts by mass are particularly preferable.

  The toner material is not particularly limited as long as it contains at least a binder resin, a colorant, and a release agent, and can be appropriately selected according to the purpose. May further be contained.

The mixing ratio of the colorant and the organic solvent in the oil phase containing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5:95 to 50:50. .
When the mixing ratio of the colorant and the organic solvent is less than 5: more than 95, the amount of the organic solvent is increased during the production of the toner, and the production efficiency of the toner may be reduced. If so, the colorant may not be sufficiently dispersed.

  When emulsifying or dispersing the toner material in the aqueous medium using the oil phase containing the toner material, it is preferable to disperse the oil phase containing the toner material in the aqueous medium while stirring.

The disperser for the dispersion is not particularly limited and may be appropriately selected depending on the purpose. For example, a low speed shear disperser, a high speed shear disperser, a friction disperser, and a high pressure jet disperser. And an ultrasonic disperser.
Among these, a high-speed shearing disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like are not particularly limited and can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as said rotation speed, Although it can select suitably according to the objective, 1,000 rpm-30,000 rpm are preferable, and 5,000 rpm-20,000 rpm are more preferable.
There is no restriction | limiting in particular as said dispersion | distribution time, Although it can select suitably according to the objective, In the case of a batch system, it is preferable that it is 0.1 minute-5 minutes.
There is no restriction | limiting in particular as said dispersion | distribution temperature, Although it can select suitably according to the objective, 0 degreeC-150 degreeC is preferable under pressure, and 40 degreeC-98 degreeC is more preferable. In general, dispersion is easier when the dispersion temperature is higher.

<Aqueous medium>
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, water is preferable.
The solvent miscible with water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, methanol, isopropanol, ethylene glycol, etc. are mentioned. The lower ketones are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acetone and methyl ethyl ketone.

<Toner production method>
An example of the method for producing the toner is a known dissolution suspension method.
As another example of the method for producing the toner, a method for forming toner base particles while producing an adhesive substrate will be described below. In such a method, preparation of an aqueous medium, preparation of an oil phase containing a toner material, emulsification or dispersion of the toner material, formation of an adhesive substrate, removal of a solvent, a site capable of reacting with an active hydrogen group-containing compound Synthesis of a polymer having a hydrogen atom, synthesis of an active hydrogen group-containing compound, and the like.

  The aqueous medium can be prepared by dispersing resin particles in an aqueous medium. There is no restriction | limiting in particular in the addition amount in the aqueous medium of the said resin particle, Although it can select suitably according to the objective, 0.5 mass%-10 mass% are preferable.

  The oil phase containing the toner material is prepared in a solvent by containing an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, a colorant, a release agent, a charge control agent, The toner material containing a modified polyester resin can be dissolved or dispersed. In the toner material, components other than the binder resin and the colorant may be added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium, or the oil phase containing the toner material is added to the aqueous medium. When added to the aqueous medium, it may be added to the aqueous medium.

  The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when the toner material is emulsified or dispersed, the adhesive base material is obtained by subjecting the active hydrogen group-containing compound and the polymer having a site capable of reacting with the active hydrogen group-containing compound to an extension reaction and / or a crosslinking reaction. Generate.

  The adhesive base material is an aqueous medium containing an oil phase containing a polymer having reactivity to active hydrogen groups such as a polyester prepolymer having an isocyanate group, together with a compound containing active hydrogen groups such as amines. An aqueous medium in which an oil phase containing a toner material is added in advance with a compound having an active hydrogen group may be produced by emulsifying or dispersing in the aqueous medium and subjecting both to an extension reaction and / or a cross-linking reaction in an aqueous medium. It may be produced by emulsifying or dispersing in an aqueous medium and subjecting both to an extension reaction and / or a crosslinking reaction in an aqueous medium. After the oil phase containing a toner material is emulsified or dispersed in an aqueous medium, You may produce | generate by adding the compound which has a hydrogen group, and carrying out an elongation reaction and / or a crosslinking reaction of both from a particle interface in an aqueous medium. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.

The reaction conditions (reaction time, reaction temperature) for producing the adhesive substrate are not particularly limited, and include an active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound. Depending on the combination, it can be appropriately selected.
There is no restriction | limiting in particular as said reaction time, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
There is no restriction | limiting in particular as said reaction temperature, Although it can select suitably according to the objective, 0 to 150 degreeC is preferable and 40 to 98 degreeC is more preferable.

  There is no particular limitation on the method for stably forming a dispersion containing a polymer having a site capable of reacting with an active hydrogen group-containing compound such as a polyester prepolymer having an isocyanate group in the aqueous medium. For example, an oil phase prepared by dissolving or dispersing a toner material containing a binder resin, a colorant, a release agent, and a charge control agent in a solvent is added to an aqueous medium phase. And a method of dispersing by shearing force.

The disperser for the dispersion is not particularly limited and may be appropriately selected depending on the purpose. For example, a low speed shear disperser, a high speed shear disperser, a friction disperser, and a high pressure jet disperser. And an ultrasonic disperser.
Among these, a high-speed shearing disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of rotations, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as said rotation speed, Although it can select suitably according to the objective, 1,000 rpm-30,000 rpm are preferable, and 5,000 rpm-20,000 rpm are more preferable.
There is no restriction | limiting in particular as said dispersion | distribution time, Although it can select suitably according to the objective, In the case of a batch system, 0.1 minute-5 minutes are preferable.
There is no restriction | limiting in particular as said dispersion | distribution temperature, Although it can select suitably according to the objective, 0 degreeC-150 degreeC is preferable under pressure, and 40 degreeC-98 degreeC is more preferable. In general, dispersion is easier when the dispersion temperature is higher.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose. It is 50 to 2 parts by mass with respect to 100 parts by mass of the toner material. 1,000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass is more preferable.
When the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated, and toner mother particles having a predetermined particle size may not be obtained, and the amount exceeds 2,000 parts by mass. The production cost may increase.

-Dispersant-
When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution. .
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, surfactants are preferable.

--Surfactant--
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, etc. Can be used.
There is no restriction | limiting in particular as said anionic surfactant, According to the objective, it can select suitably, For example, alkylbenzene sulfonate, (alpha) -olefin sulfonate, phosphate ester, etc. are mentioned.
Among these, those having a fluoroalkyl group are preferable.

  The anionic surfactant having a fluoroalkyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, perfluoro Octanesulfonyl glutamate disodium, sodium 3- [ω-fluoroalkyl (C6-C11) oxy] -1-alkyl (C3-C4) sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino ] 1-propane sulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (C7-C13) or its metal salt, perfluoroalkyl (C4-C12) sulfonic acid or its Metal salts, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, mono And perfluoroalkyl (C6-C16) ethyl phosphate.

  There is no restriction | limiting in particular as a commercial item of the surfactant which has the said fluoroalkyl group, According to the objective, it can select suitably, For example, Surflon S-111, S-112, S-113 (above, Asahi Glass Co., Ltd.) Manufactured), FLORARD FC-93, FC-95, FC-98, FC-129 (above, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries), MegaFuck F-110 F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products Co., Ltd.), Footage 100, 150 (above, manufactured by Neos), and the like.

There is no restriction | limiting in particular as said cationic surfactant, According to the objective, it can select suitably, For example, amine salt type surfactants, such as an alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative, imidazoline; And quaternary ammonium salt type surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, and benzethonium chloride.
Among these, aliphatic primary, secondary or tertiary amino acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, chlorides Benzethonium, pyridinium salts and imidazolinium salts are preferred.
There is no restriction | limiting in particular as a commercial item of the said cationic surfactant, According to the objective, it can select suitably, For example, Surflon S-121 (made by Asahi Glass Co., Ltd.); Florard FC-135 (made by Sumitomo 3M Co., Ltd.) Unidyne DS-202 (manufactured by Daikin Industries, Ltd.), Mega-Fac F-150, F-824 (manufactured by Dainippon Ink &Co.); Xtop EF-132 (manufactured by Tochem Products); Etc.);

  There is no restriction | limiting in particular as said nonionic surfactant, According to the objective, it can select suitably, For example, a fatty-acid amide derivative, a polyhydric alcohol derivative, etc. are mentioned.

  The amphoteric surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N -Dimethylammonium betaine, etc. are mentioned.

--Slightly water-soluble inorganic compound dispersant--
The poorly water-soluble inorganic compound dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite. It is done.

-Polymer protective colloid-
The polymer-based protective colloid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a monomer having a carboxyl group, an alkyl (meth) acrylate having a hydroxyl group, a vinyl ether, a vinyl carboxylate, an amide Examples thereof include homopolymers or copolymers obtained by polymerizing monomers, acid chloride monomers, monomers having a nitrogen atom or its heterocyclic ring, polyoxyethylene resins, celluloses, and the like. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

  The monomer having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid , Fumaric acid, maleic acid, maleic anhydride, and the like.

  The (meth) acrylic monomer containing a hydroxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, acrylic acid β-hydroxypropyl, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, Examples include diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, and glycerin monomethacrylate.

  There is no restriction | limiting in particular as said vinyl ether, According to the objective, it can select suitably, For example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc. are mentioned.

  There is no restriction | limiting in particular as said vinyl carboxylate, According to the objective, it can select suitably, For example, vinyl acetate, vinyl propionate, vinyl butyrate, etc. are mentioned.

  There is no restriction | limiting in particular as said amide monomer, According to the objective, it can select suitably, For example, acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide, etc. are mentioned.

  The acid chloride monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acrylic acid chloride and methacrylic acid chloride.

  There is no restriction | limiting in particular as a monomer which has the said nitrogen atom or its heterocyclic ring, According to the objective, it can select suitably, For example, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine etc. are mentioned.

  The polyoxyethylene resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene Examples thereof include alkylamides, polyoxypropylene alkylamides, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearate phenyl, polyoxyethylene pelargonate phenyl, and the like.

  There is no restriction | limiting in particular as said cellulose, According to the objective, it can select suitably, For example, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc. are mentioned.

  Other examples of the dispersant are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acids such as calcium phosphate salts and those that are soluble in alkali. When a calcium phosphate salt is used as the dispersant, the calcium phosphate salt can be removed using a method in which the calcium salt is dissolved with hydrochloric acid or the like, washed with water, or decomposed with an enzyme.

-Catalyst-
A catalyst can be used for the elongation reaction and / or the cross-linking reaction in producing the adhesive substrate.
The catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, Examples thereof include a method of evaporating the organic solvent, a method of spraying the dispersion liquid in a dry atmosphere, and removing the organic solvent in the oil droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, or may be performed after drying.

The obtained toner base particles may be mixed with particles such as a release agent and a charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose. For example, a method for applying the impact force to the mixture using blades rotating at high speed, And a method of causing the particles to collide with each other or a suitable collision plate.
The apparatus used in the above method is not particularly limited and may be appropriately selected depending on the purpose. Examples of such devices include a device with a lowered heel, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

<Toner characteristics>
Since the toner of the present invention has a smooth surface, it has excellent properties such as transferability and chargeability, and can form a high-quality image. Further, when the toner of the present invention contains an adhesive base obtained by reacting an active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound in an aqueous medium, Further, it is further excellent in various properties such as fixing properties. Therefore, the toner of the present invention can be used in various fields and can be suitably used for image formation by electrophotography.

-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, 3 micrometers-8 micrometers are preferable, and 4 micrometers-7 micrometers are more preferable.
When the volume average particle diameter is less than 3 μm, in the two-component developer, the toner may be fused to the surface of the carrier during long-term stirring in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur. When the developer exceeds 8 μm, a high-resolution and high-quality image can be obtained. It becomes difficult to obtain, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may become large.

The ratio of the volume average particle diameter to the number average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.00 to 1.25, 1.05 to 1. 25 is more preferable.
When the ratio of the volume average particle diameter to the number average particle diameter of the toner is within the above preferable range, in the two-component developer, the fluctuation of the toner particle diameter in the developer is maintained even if the toner balance is performed over a long period of time. Even with long-term agitation in the developing device, good and stable developability can be obtained, and with a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, Suppresses filming of toner on the developing roller and fusion of toner to a member such as a blade for thinning the toner, and good and stable developability can be obtained even in long-term use (stirring) of the developing device. High-quality images can be obtained.
When the ratio of the volume average particle diameter to the number average particle diameter of the toner exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of the toner in the developer is performed. In some cases, the toner particle size varies greatly.

  The ratio of the volume average particle diameter to the volume average particle diameter and the number average particle diameter of the toner can be measured as follows using a particle size measuring device Multisizer III (manufactured by Beckman Coulter). First, 0.1 mL to 5 mL of a surfactant such as an alkyl benzene sulfonate is added as a dispersing agent to 100 mL to 150 mL of an electrolyte aqueous solution such as an about 1 mass% sodium chloride aqueous solution. Next, about 2 mg to 20 mg of a measurement sample is added. The aqueous electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and then the volume and number of toners are measured using a 100 μm aperture to determine the volume distribution and number distribution. Is calculated. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.

  According to the present invention, it is possible to obtain a magenta toner that is free from uneven distribution of colorants, has excellent color developability and colorability, is excellent in chargeability, and has no image contamination such as ground fog.

(Developer)
The developer contains at least the toner of the present invention, and optionally contains other components such as a carrier as necessary.
For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.
When the developer is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle size of the toner, and members such as a filming of the toner on the developing roller and a blade for thinning the toner The toner is less fused to the toner, and good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer is used as a two-component developer, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter is small, and good and stable developability and images can be obtained even with long-term stirring in the developing device. can get.
When the toner is used for a two-component developer, it may be used by mixing with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 90% by mass to 98% by mass, and 93% by mass to 97% by mass. More preferred.

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

--- Core material--
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, 50 emu / g-90 emu / g manganese-strontium type material, manganese-magnesium type material, etc. are mentioned. . In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.
These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable. When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. When the volume average particle diameter is more than 150 μm, the specific surface area is decreased, and the toner In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

--- Resin layer--
The material of the resin layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, amino resin, polyvinyl resin, polystyrene resin, polyhalogenated olefin, polyester Resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, Examples include fluoroterpolymers such as copolymers of tetrafluoroethylene, vinylidene fluoride, and monomers having no fluoro group, silicone resins, and the like.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said amino-type resin, According to the objective, it can select suitably, For example, a urea-formaldehyde resin, a melamine resin, a benzoguanamine resin, a urea resin, a polyamide resin, an epoxy resin etc. are mentioned.
There is no restriction | limiting in particular as said polyvinyl-type resin, According to the objective, it can select suitably, For example, an acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc. are mentioned. .
There is no restriction | limiting in particular as said polystyrene resin, According to the objective, it can select suitably, For example, a polystyrene, a styrene-acryl copolymer, etc. are mentioned.
The polyhalogenated olefin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyvinyl chloride.
There is no restriction | limiting in particular as said polyester-type resin, According to the objective, it can select suitably, For example, a polyethylene terephthalate, a polybutylene terephthalate, etc. are mentioned.

  The resin layer may contain conductive powder or the like as necessary. There is no restriction | limiting in particular as said electrically conductive powder, According to the objective, it can select suitably, For example, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide, etc. are mentioned. The conductive powder preferably has an average particle size of 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.

The resin layer is formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then coating and drying the coating solution on the surface of the core using a known coating method, followed by baking. Can do.
There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, a dip coating method, a spray method, a brush coating method etc. can be used.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl cellosolve, etc. are mentioned.
The baking may be an external heating method or an internal heating method. For example, a method using a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, The method used, etc. are mentioned.

  There is no restriction | limiting in particular as content of the resin layer in the said carrier, Although it can select suitably according to the objective, 0.01 mass%-5.0 mass% are preferable. When the content is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer is thick and the carrier Fusion may occur between them, and the uniformity of the carrier may decrease.

(Image forming method, image forming apparatus)
The image forming method of the present invention preferably includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further includes a cleaning step, and other types appropriately selected as necessary. The process includes, for example, a static elimination process, a recycling process, a control process, and the like.
The image forming apparatus used in the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further includes a cleaning unit. And other means appropriately selected as necessary, for example, a static elimination means, a recycling means, a control means, and the like.
The image forming method of the present invention can be carried out by the image forming apparatus used in the present invention. The electrostatic latent image forming step uses an electrostatic latent image forming unit, and the developing step uses a developing unit. The transfer step can be performed using a transfer unit, the fixing step can be performed using a belt fixing unit, and the other steps can be performed using other units.

  In the image forming method, the electrostatic latent image forming step is a step of forming an electrostatic latent image on each of a plurality of electrostatic latent image carriers, and the developing step is a step of forming each electrostatic latent image. Development of a different color toner for each electrostatic latent image carrier to form a visible image, and the transfer step transfers the visible image to a recording medium via an intermediate transfer member It is preferable that it is a process.

-Electrostatic latent image formation process-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image carrier such as a photoconductive insulator or a photoconductor. The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. The photoconductor is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. . Among these, an amorphous silicon photoconductor is preferable because it has a long lifetime.

The electrostatic latent image is formed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then exposing it like an image, and can be formed using electrostatic latent image forming means. . The electrostatic latent image forming means includes, for example, a charger that applies a voltage to the surface of the electrostatic latent image carrier and uniformly charges it, and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise And at least.
The charger is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a known contact charger or corotron provided with a conductive or semiconductive roll, brush, film, rubber blade, or the like. And a non-contact charger using corona discharge such as Scorotron.
The exposure device is not limited as long as it can be exposed like an image to be formed on the surface of the electrostatic latent image carrier charged by the charger, and can be appropriately selected according to the purpose. And 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. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of an electrostatic latent image carrier.

-Development process-
The developing step is a step of developing an electrostatic latent image with the toner of the present invention to form a visible image, and the visible image can be formed using a developing unit. The developing unit is not particularly limited as long as it can be developed with the toner of the present invention, and can be appropriately selected according to the purpose. For example, the developer of the present invention is accommodated, and the electrostatic latent image is converted into toner. And a developer having at least a developing device capable of being contacted or non-contacted. Among these, a developing device provided with the developer container of the present invention is preferable.
The developing device is not particularly limited and can be appropriately selected depending on the purpose.For example, a developing device having a stirrer for charging the developer of the present invention by friction stirring and a rotatable magnet roller, etc. Can be mentioned. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. The magnet roller is disposed in the vicinity of the electrostatic latent image carrier, and a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted by the electrostatic latent image carrier. Move to the surface. As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the electrostatic latent image carrier.

-Transfer process-
The transfer step is a step of transferring the toner image to a recording medium by charging the electrostatic latent image carrier on which the toner image is formed using, for example, a transfer charger. can do. At this time, the transfer step preferably includes a primary transfer step of transferring the toner image onto the intermediate transfer member, and a secondary transfer step of transferring the toner image transferred onto the intermediate transfer member onto the recording medium. Further, the transfer step includes a primary transfer step in which a toner image of two or more colors, preferably a full color toner, is used to transfer a toner image of each color onto an intermediate transfer member to form a composite toner image; It is more preferable to have a secondary transfer step of transferring the composite toner image formed on the recording medium.

The transfer means includes a primary transfer means for transferring a toner image onto an intermediate transfer member to form a composite toner image, and a secondary transfer means for transferring the composite toner image formed on the intermediate transfer member onto a recording medium. It is preferable to have. The intermediate transfer member is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an endless transfer belt. The transfer means (primary transfer means and secondary transfer means) preferably has at least a transfer device that charges and separates the toner image formed on the electrostatic latent image carrier on the recording medium side. The transfer means can have one or more transfer devices.
There is no restriction | limiting in particular as said transfer device, According to the objective, it can select suitably, For example, the corona transfer device by a corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, an adhesive transfer device etc. are mentioned.
The recording medium is not particularly limited, and can be appropriately selected from known recording media (recording paper).

-Fixing process-
The fixing step is a step of fixing the toner image transferred to the recording medium, and can be fixed by a fixing belt method. The fixing unit used in the fixing belt method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a combination of a heating roller, a pressure roller, and an endless belt. At this time, heating temperature is 80 degreeC-200 degreeC normally.

-Static elimination process-
The neutralization step is a step of neutralizing by applying a neutralization bias to the electrostatic latent image carrier, and can be neutralized using a neutralization unit. The neutralization means is not particularly limited as long as a neutralization bias can be applied to the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include a neutralization lamp.

-Cleaning process-
The cleaning step is a step of removing toner remaining on the electrostatic latent image carrier and can be cleaned using a cleaning unit. The cleaning means is not particularly limited as long as the toner remaining on the electrostatic latent image carrier can be removed, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush Examples include cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, and web cleaners.

-Recycling process-
The recycling step is a step of recycling the toner removed in the cleaning step to the developing means, and can be recycled using the recycling means. There is no restriction | limiting in particular as said recycling means, According to the objective, it can select suitably, For example, a well-known conveyance means etc. can be used.

-Control process-
The said control process is a process of controlling each process, and can be controlled using a control means. The control means is not particularly limited as long as the operation of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include a sequencer and a computer.

FIG. 1 shows an example of an image forming apparatus of the present invention. The image forming apparatus 100A includes a photosensitive drum 10 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, an exposure device (not shown) as an exposure unit, and a developing device (for black) as a developing unit. Developing unit 45K, yellow developing unit 45Y, magenta developing unit 45M, cyan developing unit 45C), intermediate transfer member 50, cleaning device 60 having a cleaning blade as a cleaning unit, and neutralizing lamp 70 as a neutralizing unit. Have
The intermediate transfer member 50 is an endless belt, is stretched by three rollers 51 arranged on the inner side thereof, and can move in the arrow direction. A part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50.
Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. Further, a transfer roller 80 as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) the toner image to the recording medium 95 is disposed to face the intermediate transfer member 50.
Further, around the intermediate transfer member 50, a corona charger 52 for applying a charge to the toner image on the intermediate transfer member 50, a contact portion between the photosensitive drum 10 and the intermediate transfer member 50, and the intermediate transfer member 50 are provided. And the contact portion of the recording medium 95.
Black (K), yellow (Y), magenta (M), and cyan (C) developer units (black developer unit 45K, yellow developer unit 45Y, magenta developer unit 45M, cyan developer unit 45C) , A developer container (42K, 42Y, 42M, 42C), a developer supply roller (43K, 43Y, 43M, 43C), and a developing roller (44K, 44Y, 44M, 44C).
In the image forming apparatus 100A, the photosensitive drum 10 is uniformly charged by the charging roller 20, and then the exposure light 30 is exposed imagewise on the photosensitive drum 10 by an exposure device (not shown) to form an electrostatic latent image. Form. Next, a developer is supplied to the electrostatic latent image formed on the photosensitive drum 10 from a developing device (black developing device 45K, yellow developing device 45Y, magenta developing device 45M, cyan developing device 45C). Then, after developing and forming a toner image, the toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the transfer bias applied from the roller 51. Further, the toner image on the intermediate transfer member 50 is given a charge by the corona charger 52 and then transferred (secondary transfer) onto the recording medium 95. The toner remaining on the photosensitive drum 10 is removed by the cleaning device 60, and the photosensitive drum 10 is once discharged by the discharging lamp 70.

FIG. 2 shows another example of the image forming apparatus of the present invention. The image forming apparatus 100B is a tandem 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 copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can rotate in the direction of the arrow.

  A cleaning device 17 for removing the toner remaining on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. Further, four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other on the intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 along the conveyance direction. A tandem developing device 120 is disposed. As shown in FIG. 3, the image forming means 18 for each color includes a photosensitive drum 10, a charging roller 20 that uniformly charges the photosensitive drum 10, and a black electrostatic latent image formed on the photosensitive drum 10. (K), yellow (Y), magenta (M), and cyan (C) are developed with each color developer to form a toner image, and each color toner image is transferred onto the intermediate transfer member 50. A transfer roller 62, a cleaning device 63, and a static elimination lamp 64.

An exposure device 21 is disposed in the vicinity of the tandem developing device 120. The exposure device 21 exposes the exposure light L on the photoconductor drum 10 (black photoconductor 10K, yellow photoconductor 10Y, magenta photoconductor 10M, cyan photoconductor 10C) to form an electrostatic latent image. .
Further, a secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. The secondary transfer device 22 includes a secondary transfer belt 24 that is an endless belt stretched between a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It has become.
A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26.

Further, in the vicinity of the secondary transfer device 22 and the fixing device 25, a reversing device 28 for reversing the recording paper in order to form images on both sides of the recording paper is disposed.
Next, full color image formation (color copy) in the image forming apparatus 100B will be described. First, a 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 document is set on the contact glass 32 of the scanner 300. close up. Next, when a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is placed on the contact glass 32. When set, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is emitted from the first traveling body 33, and reflected light from the document surface is reflected by a mirror in the second traveling body 34 and received by the reading sensor 36 through the imaging lens 35. . Thus, a color original (color image) is read, and image information of each color of black, yellow, magenta, and cyan is obtained.

  Further, after an electrostatic latent image of each color is formed on the photosensitive drum 10 based on the obtained image information of each color by the exposure device 21, the electrostatic latent image of each color is supplied from the developing device 61 of each color. The developed developer is used to form a toner image of each color. The formed toner images of the respective colors are sequentially transferred (primary transfer) on the intermediate transfer member 50 that is rotated and moved by the support rollers 14, 15, and 16, thereby forming a composite toner image on the intermediate transfer member 50. .

  In the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143 and separated one by one by the separation roller 145. Then, the sheet is fed to the sheet feeding path 146, conveyed by the conveying roller 147, guided to the sheet feeding path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the recording paper on the manual feed tray 151 is fed out, separated one by one by the separation roller 58, put into the manual 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 to remove paper dust from the recording paper.

Then, the registration roller 49 is rotated in synchronization with the composite toner image formed on the intermediate transfer member 50, and the recording paper is sent between the intermediate transfer member 50 and the secondary transfer device 22, so that the composite toner image is transferred onto the recording paper. Transfer to (secondary transfer).
The recording sheet on which the composite toner image has been transferred is conveyed by the secondary transfer device 22 and sent out to the fixing device 25. In the fixing device 25, the composite toner image is fixed on the recording paper by being heated and pressed by the fixing belt 26 and the pressure roller 27. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55, reversed by the reversing device 28, guided again to the transfer position, formed on the back surface, discharged by the discharge roller 56, and stacked on the discharge tray 57.
The toner remaining on the intermediate transfer member 50 after the composite toner image is transferred is removed by the cleaning device 17.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. Further, unless otherwise specified, “part” indicates mass part, and “%” indicates mass%.

(Synthesis example 1 of polyester resin)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts of a 2-mole adduct of bisphenol A, 84 parts of a 3-mole adduct of bisphenol A, 274 parts of terephthalic acid and 2 parts of dibutyltin oxide are added. And allowed to react at 230 ° C. for 8 hours under normal pressure. Next, polyester resin A was synthesized by reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours. The obtained polyester resin A had an acid value of 15.3 mg KOH / g and a melting point of 95 ° C.

(Synthesis example 2 of polyester resin)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 77 parts of a 2-mole addition product of ethylene oxide of bisphenol A, 74 parts of a 3-mole addition product of propion oxide of bisphenol A, 289 parts of terephthalic acid and 2 parts of dibutyltin oxide And allowed to react at 230 ° C. for 10 hours under normal pressure. Next, polyester resin B was synthesized by reacting under reduced pressure of 10 mmHg to 15 mmHg for 6 hours. The obtained polyester resin B had an acid value of 4.7 mgKOH / g and a melting point of 118 ° C.

(Synthesis example 3 of polyester resin)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 82 parts of a 2-mole addition product of ethylene oxide of bisphenol A, 69 parts of a 3-mole addition product of propion oxide of bisphenol A, 294 parts of terephthalic acid and 2 parts of dibutyltin oxide are added. And allowed to react at 230 ° C. for 8 hours under normal pressure. Next, polyester resin C was synthesized by reacting under reduced pressure of 10 mmHg to 15 mmHg for 6 hours. The obtained polyester resin C had an acid value of 46 mgKOH / g and a melting point of 123 ° C.

The acid values of the polyester resins A to C were measured as follows.
<Method for measuring acid value>
Measurement was performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of sample is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation was performed as follows.
Titration was carried out with N / 10 caustic potash-alcohol solution standardized in advance, and the acid value was determined from the consumption of alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample mass (where N is a factor of N / 10 KOH)

The melting points of the polyester resins A to C were measured as follows.
<Measuring method of melting point>
In the differential scanning calorimetry (DSC), the melting point is determined by the peak top indicating the maximum endotherm of the DSC curve. Moreover, the measurement was performed on the following measurement conditions using TA-60WS and DSC-60 by Shimadzu Corporation.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

(Production Examples of Toners of Examples 1-13 and Comparative Examples 1-4)
<Preparation of master batch>
50% by mass of any one of polyester resins A, B, and C synthesized by the methods shown in Synthesis Examples 1 to 3, and C.I. I. Pigment red 31 (manufactured by Fuji Pigment) and C.I. I. Pigment Red 269 (manufactured by Dainichi Seika Co., Ltd.) mixed at a ratio shown in Table 1 and 40% by mass of magenta pigment and 10% by mass of any one of the following surface treatment agents A to F are manufactured by Henschel mixer (Mitsui Mining Co., Ltd.). ) At 1,000 rpm for 5 minutes, then kneaded with an open roll kneader (Mitsui Mine Co., Ltd.), and a colorant (pigment) dispersion powder having a diameter of 2 mm is produced with a rotoplex grinder. And a master batch.
The surface treatment agents A to F are as follows.
The surface treating agent A has a melting point of 76 ° C. and an acid value of 12.4.
The surface treating agent B has a melting point of 81 ° C. and an acid value of 1.2.
The surface treating agent C has a melting point of 93 ° C. and an acid value of 23.
The surface treating agent D has a melting point of 105 ° C. and an acid value of 18.9.
The surface treating agent E has a melting point of 63 ° C. and an acid value of 9.6.
The surface treating agent F has a melting point of 120 ° C. and an acid value of 22.3. The acid values and melting points of the surface treatment agents A to F were measured in the same manner as the polyester resins A to C.

<Preparation of toner material liquid (oil phase)>
In a beaker, 10 parts of a polyester prepolymer, 75 parts of the same polyester resin (any one of polyester resins A to C) contained in the masterbatch, and 130 parts of ethyl acetate as a solvent are stirred and stirred. Dissolved. Next, 5 parts of paraffin wax and the above master batch are added so as to have the colorant concentration shown in Table 1 (mass% with respect to the binder resin (the total of the prepolymer and the polyester resins A to C)). 3 passes under the condition that 80% by volume of zirconia beads having a particle diameter of 0.5 mm were filled at a liquid feeding speed of 1 kg / hour, a peripheral speed of the disk of 6 m / second using an ultra visco mill (made by Imex Co., Ltd.). did. Further, 2.7 parts of a ketimine compound was added and dissolved to prepare a toner material liquid (oil phase).

<Preparation of emulsified slurry>
Add 150 parts of an aqueous medium to a container, add 100 parts of toner material liquid (oil phase) while stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and mix for 10 minutes. Thus, an emulsified slurry was prepared.

<Preparation of dispersion slurry>
In a Kolben equipped with a stirrer and a thermometer, 100 parts of the prepared emulsified slurry was charged, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.

<Preparation of filter cake>
After filtering 100 parts of the dispersion slurry under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10 wt% aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. Furthermore, 20 parts of 10 mass% hydrochloric acid was added to the obtained filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, the mixture was filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake.

<Preparation of toner for evaluation>
The prepared final filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner mother particles. To 100 parts of the obtained toner base particles, 1.0 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide are added as external additives, and mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). A toner for evaluation was prepared.

(Evaluation of toner)
<Color reproducibility evaluation>
The toner obtained above and a 60 μm ferrite carrier were stirred and mixed for 20 minutes at a toner concentration of 4% by volume to obtain a two-component developer. This two-component developer was charged into a copying machine (Imagio Neo C355) manufactured by Ricoh Co., Ltd., and adjusted so that the adhesion amount was 0.4 mg / cm ² on Tokishi Art N 110 Kg (manufactured by Mitsubishi Paper Industries). Thereafter, 100 solid images of 5 cm × 5 cm were printed. After printing 100 sheets, three solid images of 5 cm × 5 cm were output in the same manner as above, and used as image samples for evaluation.
The chromaticness index a * and b * in the L * a * b * color system (CIE: 1976) was measured for the solid image formed using a chromaticity meter (X-Rite 938, manufactured by X-Rite). Then, the value of C * represented by the following formula (1) was obtained, and the saturation of each color toner was evaluated.
C * = [(a *) ² + (b *) ² ] ^1/2 (1)

The evaluation criteria for saturation are as follows.
A: Very good. C * is 75 or more.
○: Good. C * is 73 or more and less than 75.
Δ: Slightly poor C * is 70 or more and less than 73.
X: Defect. C * is less than 70.
In the measurement, an average of five points of each image sample was calculated, and an average value of three images was calculated.
The results are shown in Table 2.

Further, from the calculated a * b *, the color difference from JapanColor was calculated from the following formula (2), and ΔE was evaluated.
ΔE = [(a *) ² − (b *) ² ] ^1/2 (2)

The evaluation criteria for color difference are as follows.
A: Very good. ΔE is less than 1.
○: Good. ΔE is 1 or more and less than 3.
Δ: Slightly poor ΔE is 3 or more and less than 5.
X: Defect. ΔE is 5 or more.
The results are shown in Table 2.

<Coloring degree evaluation>
Similarly to the color reproducibility evaluation, five solid images of each image sample were measured using a chromaticity meter (X-Rite 938 manufactured by X-Rite), and an average value of the three samples was calculated to obtain an image density. .

The image density evaluation criteria are as follows.
A: Very good. Image density of 1.5 or more ○: Good. C * is 1.4 or more and less than 1.5.
Δ: Slightly poor C * is 1.3 or more and less than 1.4.
X: Defect. C * is less than 1.3.
The results are shown in Table 2.

<Evaluation of soiling under high temperature and high humidity>
The toner obtained above and a 60 μm ferrite carrier were stirred and mixed at a toner concentration of 4% by mass for 20 minutes to obtain a two-component developer. The two-component developer was subjected to a printing durability test of 50,000 sheets at a document density of 5% using a copying machine (Imagio Neo C355) manufactured by Ricoh Co., Ltd. in an environment of 40 ° C./80%.
After printing 50,000 sheets, print a blank sheet and turn off the power during printing. After the power is turned off, the photosensitive member is taken out, and the front portion of the cleaning portion is peeled off after applying a low-adhesive transparent tape (Printac C, manufactured by Nitto Denko Corporation), and then attached to a white paper. Using a transparent tape that is not affixed to the photoconductor as a reference, the reference and the transparent tape after being affixed to the photoconductor are each measured using a chromaticity meter (X-Rite 938), and the average value is calculated. Calculated as soil dirt.

The evaluation criteria for soiling are as follows.
A: Very good. Soil less than 0.010: Good. Dirt 0.010 or more and less than 0.015.
Δ: Slightly poor Dirt from 0.015 to less than 0.025.
X: Defect. Dirt 0.025 or more.
The results are shown in Table 2.

According to the evaluation results, the toner of Comparative Example 1 was a toner having a low bluish color and a large color difference from Japan color because the ratio of Pigment Red 31 in the naphthol pigment was low.
Since the ratio of Pigment Red 31 in the naphthol pigment is high, the toner of Comparative Example 2 has a high bluish color, a large color difference from Japan color, and a long wavelength side absorption, resulting in a low chroma toner.
The toner of Comparative Example 3 was a toner having a low color saturation and coloration due to a low amount of magenta pigment added and a large color difference from Japan color.
The toner of Comparative Example 4 was a toner that had a large color difference from Japan color due to the high amount of magenta pigment added, and low chargeability, and thus caused a background stain under high temperature and high humidity.
In the toners of Comparative Examples 5 and 6, since the colorant (pigment) is segregated by using the quinacridone pigment (Pigment Red 122) or Pigment Red 150 as the magenta pigment, the saturation is low and the charging property is low. The toner was soiled under moisture.
On the other hand, the toners of Examples 1 to 13 were high in saturation, excellent in hue, and free from background stains during running under high temperature and high humidity.

  Since the toner of the present invention has high saturation, excellent hue, and no background stains due to running under high temperature and high humidity, for example, laser printers, direct digital machines, direct or indirect electrophotographic multicolor image development systems Can be used widely for full-color copiers, full-color laser printers, full-color plain paper fax machines, etc.

DESCRIPTION OF SYMBOLS 10 Photosensitive drum 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14, 15, 16 Support roller 17 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 Reversing device 30 Exposure light 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 42K, 42Y, 42M, 42C Development Agent container 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Development roller 45K Black developer 45Y Yellow developer 45M Magenta developer 45C Cyan developer 49 Registration roller 5 Intermediate transfer member 51 Roller 52 Corona charger 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Separation roller 60 Cleaning device 61 Developer 62 Transfer roller 63 Cleaning device 64 Static discharge lamp 70 Static discharge lamp 80 Transfer roller 90 Cleaning Device 95 Recording medium 100A, 100B Image forming device 120 Tandem developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying apparatus main body 151 Manual tray 200 Paper feeding table 300 Scanner 400 Automatic document feeder L Exposure

Japanese Patent No. 2537503 JP 59-165069 A JP-A-50-120632 JP 63-25664 A Japanese Patent Laid-Open No. 5-127422 JP-A-8-179556 Japanese Patent No. 3661422 JP 2003-215847 A Japanese Patent No. 3927998

Claims (14)

A toner granulated by dispersing an oil phase containing at least a binder resin, a colorant, and a release agent in an aqueous medium,
The colorant includes pigment red 31 and pigment red 269, and a mixing ratio of the pigment red 31 and the pigment red 269 is 1:99 to 50:50 in terms of mass ratio.
The toner according to claim 1, wherein the content of the colorant is 3% by mass to 12% by mass with respect to the binder resin.   Granulation in an aqueous medium is carried out in an organic solvent at least with an active hydrogen group-containing compound, as a binder resin, a polymer having a site capable of reacting with the active hydrogen group-containing compound, and an unmodified polyester resin; The colorant and the release agent are dissolved or dispersed, the dissolved or dispersed material is dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and the active hydrogen are prepared in the aqueous medium. The toner according to claim 1, wherein the toner is formed by crosslinking or extending a polymer having a site capable of reacting with a group-containing compound and removing the organic solvent from the obtained dispersion.   The toner according to claim 2, wherein the acid value of the unmodified polyester resin is 5 KOH mg / g to 40 KOH mg / g.   The toner according to claim 1, wherein the colorant is surface-treated with an acidic surface treatment agent.   The toner according to claim 4, wherein the acid value of the surface treatment agent is 3 KOH mg / g to 20 KOH mg / g.   The toner according to claim 4, wherein the melting point of the surface treatment agent is 70 ° C. to 110 ° C.   The toner according to claim 4, wherein the melting point of the surface treatment agent is lower than the melting point of the unmodified polyester resin.   The toner according to claim 2, wherein the toner is granulated using a master batch in which a colorant is dispersed in an unmodified polyester resin.   The toner according to claim 8, wherein the toner is granulated using a master batch in which a colorant and a surface treatment agent are dispersed in an unmodified polyester resin.   The toner according to claim 8, wherein the dispersion is performed by melt kneading using an open type melt kneader.   The toner according to claim 1, wherein the toner is granulated using a pigment press cake as a colorant.   A developer comprising the toner according to claim 1.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to claim 1 to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. The electrostatic latent image forming step is a step of forming an electrostatic latent image on each of the plurality of electrostatic latent image carriers,
The developing step is a step of developing each electrostatic latent image using a toner of a different color for each electrostatic latent image carrier to form a visible image,
The image forming method according to claim 13, wherein the transfer step is a step of transferring the visible image to a recording medium via an intermediate transfer member.