JP2007114740A - Toner for electrostatic image development and method for manufacturing same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic image development excellent in color reproducibility, color developing property and transmittance, and having satisfactory color developing property and good image properties while using a small amount of a colorant. <P>SOLUTION: The toner for electrostatic image development is manufactured as follows; an organic pigment or carbon black dispersion (A) obtained by adsorbing an organic dye derivative or a triazine derivative having a basic or acidic functional group on an organic pigment or carbon black in an organic solvent in the presence of an acid or a base is added to a solution (C) of a styrenic resin or polyester resin (B), mixed and freed of the solvent, and the resultant colored resin composition (D) is pulverized and classified. By using the dispersion (A), the colored resin composition in which the organic pigment or carbon black is uniformly dispersed as fine particles in the resin is obtained. Additives such as a charge control agent and a release agent may be added to the resin solution (C) or kneaded with the formed colored resin composition (D) under heating. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic charge image used in a copying machine, a printer or the like in which an image is formed using an electrophotographic method, an electrostatic recording method or the like, a method for producing the same, a resin-coated colorant for toner, and It relates to the manufacturing method.

  Conventionally, as a method for developing an electrostatic latent image formed on an electrostatic charge image bearing member such as an electrophotographic photosensitive member or an electrostatic recording member, it is roughly classified into a liquid in which fine toner is dispersed in an electrically insulating liquid. Two methods are known: a method using a developer (wet development method) and a method using a dry toner in which a colorant such as an organic pigment is dispersed in a binder resin (dry development method). Typical examples of dry development methods include a method using a two-component developer composed of carrier particles and a toner, and a method using a one-component developer composed of only a toner.

  The toner used in the dry development method usually uses a styrene resin or polyester resin as a binder resin, kneaded with a colorant such as a dye or pigment, cooled, and then pulverized, classified, and further It is manufactured through a post-treatment process in which external additives are added and mixed. In recent years, it is also produced by a chemical method such as a polymerization method or a chemical milling method. These toners usually have an average particle size of about 1 to 20 μm. Further, as carrier particles used in the two-component developer, iron powder, ferrite, magnetite, etc., which are coated with a hydrophobic resin as required, are used.

  Furthermore, as for office or personal copiers, printers, and their combined machines, those using dry toner have become mainstream recently. Furthermore, copiers and printers having color and full-color functions are also widely used, but images obtained by these copiers, printers and multi-function machines that use dry toner can be used for offset printing and liquid developers. Compared to the above, image quality such as color reproducibility, color development, and transparency is inferior. This is because the dry toner has a particle size larger than that of a liquid developer or printing ink, and it is difficult to uniformly disperse a colorant such as an organic pigment in a finely divided state in the toner. Is.

  On the other hand, in the case of a color toner (including a black toner used together), good color developability and color reproducibility, and light transmittance in an OHP sheet or the like are required. In order to satisfy such characteristics, it is important to select and use a pigment with sufficient consideration of characteristics such as the type and particle size of the pigment, and to disperse the pigment well in the binder resin. For this reason, many studies have been made on the selection and treatment of pigments.

Specifically, a wet pigment and a solid resin at room temperature are kneaded by applying high-speed shear stress, and by removing moisture, a colorant with less pigment aggregation is obtained, and color reproducibility using this colorant It has been proposed to obtain a color toner having excellent color development and transparency (see, for example, Patent Document 1). In addition, by treating the surface of the pigment with a nonionic surfactant, the pigment is well dispersed in the binder resin and compatibility with the binder resin is improved, and the charge amount distribution of the color toner is sharpened. It has been proposed that fog can be reduced (see, for example, Patent Document 2). Further, it has been proposed to obtain a color toner excellent in transparency, coloring power, and saturation by containing an organic pigment having an average major axis of 0.2 μm or less in the binder resin (see, for example, Patent Document 3). . Furthermore, it has been proposed that a good color toner can be obtained by using the specific surface area of the pigment particles in the range of 30 to 300 m ² / g (see, for example, Patent Document 4).

JP-A-9-288376 JP 2005-62517 A JP-A-6-250444 Japanese Patent Laid-Open No. 2003-98753

  As described above, various techniques for uniformly dispersing fine pigments in the toner have been proposed in the production of color toners. However, in the conventional method, the particle size of the obtained colorant, the state of aggregation, the coloring, There are still various problems such as the fact that the uniform dispersibility of the agent in the resin is not sufficient, or even if it is obtained, the production method is complicated, and good color reproduction is not possible. In addition to this, it has not yet been sufficient to obtain a toner that sufficiently satisfies other characteristics such as electrical characteristics in a simple and stable manner. Therefore, it is desired to easily and stably produce a color toner that solves these problems and is excellent in color reproducibility, color developability, and transparency in which a colorant is finely dispersed. It is also desired to obtain a color toner excellent in color reproducibility, color developability and transparency by using a small amount of colorant. The demand for such a fine and uniform dispersion of the pigment applies not only to the color toner but also to the black toner using carbon black.

  In view of such a current situation, an object of the present invention is to provide an electrostatic image in which an organic pigment or carbon black is uniformly and finely dispersed, has excellent color reproducibility, color development, and transparency, and has excellent toner electrical characteristics. It is to provide a developing toner and a method for producing the same.

  Another object of the present invention is to provide a colored resin composition capable of producing a toner for developing an electrostatic image having excellent characteristics.

  Another object of the present invention is to provide an electrostatic charge image developing toner capable of obtaining an image satisfying sufficient color developability and color reproducibility with the use of a small amount of organic pigment or carbon black, and a method for producing the same, and It is to provide a colored resin composition used in the production of toner.

  As a result of intensive studies, the present inventors have determined that an organic pigment or carbon black dispersion (A) in which an organic dye derivative or triazine derivative having a basic or acidic functional group is adsorbed under a specific condition is used as a styrene resin and It has been found that the above object can be achieved by producing a toner using a colored resin composition obtained by mixing with a resin solution selected from polyester resins and removing the solvent, and has led to the present invention. is there.

That is, the present invention relates to the following inventions (1) to (11).
(1) An organic pigment or carbon black obtained by adsorbing an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group to an organic pigment or carbon black in an organic solvent in the presence of an acid Dispersion of organic pigment or carbon black obtained by adsorbing organic pigment derivative having acidic functional group or triazine derivative having acidic functional group to organic pigment or carbon black in organic solvent in the presence of base It contains a colored resin composition obtained by mixing the liquid (A) with a solution (C) of a resin (B) selected from styrene resins and polyester resins and removing the solvent. Toner for developing electrostatic images.

(2) The electrostatic image developing toner according to 1 above, wherein the resin solution (C) further contains at least one of a charge control agent and a release agent. .

(3) The electrostatic image developing toner according to 1 or 2 above, wherein the adsorption treatment is performed using a media type dispersing machine.

(4) The electrostatic charge image developing toner according to any one of (1) to (3), wherein the organic solvent used in the organic pigment or the carbon black dispersion (A) contains a protic solvent. Toner for image development.

(5) The electrostatic image developing toner according to any one of (1) to (4), wherein the organic solvent used in the resin solution is a hydrocarbon solvent.

(6) An organic pigment or carbon black obtained by adsorbing an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group to an organic pigment or carbon black in an organic solvent in the presence of an acid Dispersion of organic pigment or carbon black obtained by adsorbing organic pigment derivative having acidic functional group or triazine derivative having acidic functional group to organic pigment or carbon black in organic solvent in the presence of base A colored resin composition (D) is formed by mixing the liquid (A) with a solution (C) of a resin (B) selected from a styrene resin and a polyester resin, and removing the solvent. A method for producing a toner for developing an electrostatic charge image, comprising pulverizing a product.

(7) In the method for producing a toner for developing an electrostatic charge image according to (6), at least one of a charge control agent and a release agent is further added to and mixed with the resin solution (C). A method for producing a toner for developing a charge image.

(8) The method for producing a toner for developing an electrostatic charge image according to the item 6 or 7, wherein the adsorption treatment is performed using a media type dispersing machine.

(9) In the electrostatic image developing toner according to any one of 6 to 8, the organic solvent used in the organic pigment or the carbon black dispersion (A) includes a protic solvent. A method for producing a developing toner.

(10) The method for producing a toner for developing an electrostatic charge image according to any one of the above items 6 to 9, wherein the solvent used in the resin solution is a hydrocarbon solvent.

(11) An organic pigment or carbon black obtained by adsorbing an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group to an organic pigment or carbon black in an organic solvent in the presence of an acid Dispersion of organic pigment or carbon black obtained by adsorbing organic pigment derivative having acidic functional group or triazine derivative having acidic functional group to organic pigment or carbon black in organic solvent in the presence of base A colored resin composition for toner obtained by mixing the liquid (A) with a solution (C) of a resin (B) selected from styrene resins and polyester resins and removing the solvent.

  In the present invention, an organic pigment or carbon black obtained by adsorbing an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group to an organic pigment or carbon black in an organic solvent in the presence of an acid. Dispersion of organic pigment or carbon black obtained by adsorbing organic pigment derivative having acidic functional group or triazine derivative having acidic functional group to organic pigment or carbon black in organic solvent in the presence of base The liquid (A) is mixed with a solution (C) of a resin (B) selected from a styrene resin and a polyester resin, and the solvent is removed, whereby an organic pigment or carbon black is contained in the styrene resin or polyester resin solution. Uniformly dispersed, distributed and blended, and thus obtained after solvent removal Also in the colored resin composition, an organic pigment or carbon black of fine particle size is uniformly dispersed in the resin, it is dispensed formulation. As a result, in the color toner formed using the colored resin composition for toner of the present invention, good color reproducibility, color developability and transparency can be obtained, and a small amount of pigment is used compared to conventional toners. Even in an amount, sufficient colorability can be obtained. In addition, since organic pigment or carbon black having a fine particle size is uniformly dispersed and distributed in toner particles, it has excellent electrical characteristics and other characteristics required for toner, and has uniform quality. An electrostatic charge image developing toner can be easily formed. Such an excellent toner can be obtained by adsorbing an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group to an organic pigment or carbon black in an organic solvent in the presence of an acid. Obtained by adsorbing the obtained organic pigment or carbon black dispersion, organic dye derivative having acidic functional group or triazine derivative having acidic functional group to organic pigment or carbon black in an organic solvent in the presence of a base. In the obtained organic pigment or carbon black dispersion liquid, the organic pigment or carbon black undergoes a wet dispersion treatment, and the presence of counter ions in the wet treatment solution causes dispersion of the pigment used in the conventional toner. Compared to the state, it is obtained with a much smaller particle size, and further mixed with the resin solution The Rukoto, because due to its excellent dispersion state is directly transferred into the resin.

Specific embodiments for carrying out the invention

Hereinafter, the present invention will be described in more detail.
The pigment dispersion (A) used for forming the colored resin composition used in the toner for developing an electrostatic charge image of the present invention comprises an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group. Adsorption treatment to an organic pigment or carbon black in an organic solvent in the presence of an acid, or an organic pigment derivative having an acidic functional group or a triazine derivative having an acidic functional group in an organic solvent in the presence of a base Alternatively, it can be obtained by adsorption treatment on carbon black. At this time, the organic pigment or carbon black subjected to the adsorption treatment is obtained as a dispersion finely dispersed in a dispersion medium, which is an organic pigment derivative or triazine introduced on the surface of the organic pigment or carbon black by the adsorption treatment. Due to the charge repulsion caused by the basic or acidic functional groups of the derivatives and the presence of counter ions consisting of acids or bases in the dispersion, the resulting organic pigment or carbon black dispersion does not cause aggregation and is well dispersed. It is by maintaining.

  The adsorption treatment of the present invention will be described more specifically. For example, when the adsorption treatment is performed using an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group, a general method is an organic solvent. An organic dye derivative or triazine derivative having an acid or a basic functional group is added to the mixture, and after mixing and stirring, an organic pigment or carbon black is added, followed by sufficient mixing and dispersion to perform adsorption. When the adsorption treatment is performed using an organic dye derivative having an acidic functional group or a triazine derivative having an acidic functional group, a base may be used in place of the acid in the above method.

  The organic pigment or carbon black in the dispersion obtained by such a method becomes basic when the adsorbed material has a basic functional group, while the adsorbed material has an acidic functional group. When it has, it will have acidity. The acid or base contained in the dispersion (A) of the organic pigment or carbon black that has been subjected to the adsorption treatment plays a major role in uniformly dispersing the organic pigment that has been subjected to the adsorption treatment and whose surface polarity is controlled. . For example, an organic pigment or carbon black that has been adsorbed with an organic dye derivative or triazine derivative having a basic functional group has a positively charged surface polarity. On the other hand, the acid present in the organic solvent has negative chargeability and is present as a counter ion, so that the organic pigment or carbon black can be dispersed in a fine state without agglomeration. Furthermore, it is possible to have excellent temporal stability or storage stability (no aggregation or precipitation over a long period of time). On the other hand, organic pigments or carbon blacks that have been adsorbed with organic dye derivatives or triazine derivatives having acidic functional groups have negatively charged surface polarity, whereas bases present in dispersions are positively charged. And the presence of counter ions makes it possible to disperse without agglomeration, which makes it possible to achieve excellent dispersibility and refinement of the pigment, and excellent stability over time or storage stability (long Over a period of time without aggregation or precipitation).

  Here, the organic pigment or carbon black dispersion (A) obtained by the adsorption treatment is added to and mixed with the solution (C) of the resin (B) selected from the styrene resin and the polyester resin to remove the solvent. As a result, the organic pigment or carbon black adsorbed with the organic dye derivative or triazine derivative having a basic or acidic functional group is dispersed in the resin in a finely dispersed state in the dispersion (A), and is removed by solvent removal. A solid colored resin composition is obtained. At this time, a charge control agent and / or a release agent may be contained in the resin solution (C). If necessary, after the colored resin composition is once formed, the colored resin composition, the charge control agent and / or the release agent may be further heated and kneaded. The charge control agent and the release agent may be used simultaneously, or may be separately heated and kneaded. Of course, if a charge control agent or a release agent is not required in toner production, it may not be used. Thereafter, a toner for developing an electrostatic image having excellent characteristics can be obtained by subjecting it to a post-treatment step in which a pulverization step, a classification step, an external additive and the like are added and mixed.

  In the following, first, an organic pigment, a material constituting the carbon black dispersion (A), a pigment such as an organic pigment or carbon black, an organic dye derivative or triazine derivative having a basic or acidic functional group, an acid, a base, The organic solvent that is the dispersion medium will be described more specifically. Thereafter, together with the organic pigment dispersion (A), a styrene resin and a polyester resin constituting the colored resin composition for toner of the present invention, an organic solvent used to form a solution of these resins, and a toner The materials used, such as charge control agents, mold release agents, and other internal or external additives, will be described in detail.

  As the organic pigment and carbon black used in the present invention, any of those conventionally used for forming a toner for developing an electrostatic charge image can be used, and among them, yellow, magenta, cyan and black shown below. Organic pigments and carbon black are preferred.

  First, as the yellow organic pigment, compounds represented by benzimidazolone compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex compounds, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 168, 174, 176, 180, 181 and 191 are preferably used. Among them, it is preferable to use a benzimidazolone compound.

  As magenta organic pigments, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, etc. are preferably used. Among them, it is preferable to use a quinacridone compound.

  As the cyan organic pigment, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are preferably used. Among these, it is preferable to use a copper phthalocyanine compound.

  As the black organic pigment, aniline black, iron black or the like is preferably used. Carbon black can be any of furnace black, channel black, acetylene black, etc. However, furnace black carbon is preferred because it has the effect of reducing fog (soil on the white background) in image characteristics. is there.

  These organic pigments or carbon blacks use organic pigments that have not been surface-treated such as rosin treatment or neutral carbon blacks with few surface functional groups, considering the adsorptivity and desorption properties of organic dye derivatives or triazine derivatives. It is preferable to do. The particle size of the organic pigment and carbon black is not particularly limited, but is preferably 0.01 to 1 μm, as in the particle size range of the organic pigment or carbon black used for a normal toner. However, the particle diameter here refers to the average primary particle diameter measured with a transmission electron microscope or the like.

  The organic pigment and carbon black subjected to the adsorption treatment can be used alone or in admixture of two or more, and when used as a toner, usually 0.5 to 20 with respect to 100 parts by weight of the binder resin. It is preferably present in an addition amount of parts by weight, preferably 1 to 10 parts by weight.

  The slurry concentration of the organic pigment to be adsorbed and the organic solvent dispersion (A) of carbon black is a characteristic value unique to the organic pigment, and the type and addition of an organic dye derivative or triazine derivative having a basic or acidic functional group. Since the appropriate concentration varies depending on the amount and the like, it is not particularly limited, but 5 to 50% by weight is preferable. If the content of the organic pigment in the slurry of the organic solvent dispersion is less than 5% by weight, the grinding efficiency is poor. In some cases, the organic pigment is fused in the pulverizer.

  The organic dye derivative having a basic functional group and the triazine derivative having a basic functional group used in the present invention are represented by the following general formula (1) or (3).

General formula (1):

The symbol in a formula represents the following meaning.
Q ₁ ; aryl group having organic dye residue, anthraquinone residue or amino group X ₁ ; direct bond, —CONH—Y ₂ —, —SO ₂ NH—Y ₂ — or —CH ₂ NHCOCH ₂ NH—Y ₁ — (Y ₂ represents an alkylene group or an arylene group which may have a substituent.)
Y ₁ ; —NH— or —O—
Z ₁ ; a hydroxyl group, an alkoxy group or a group represented by the following general formula (2), and n represents an integer of 1 to 4. In the case of n = 1, it may be —NH—X ₁ -Q ₁ .
R ₁ and R ₂ each independently a substituted or unsubstituted alkyl group m; an integer of 1 to 6

General formula (2):

The symbol in General formula (2) represents the following meaning.
Y ₃ ; —NH— or —O—
R ₃ and R ₄ ; each independently a substituted or unsubstituted alkyl group, or a heterocycle o formed by combining R ₃ and R ₄ ; an integer of 1 to 6

General formula (3):

The symbol in a formula represents the following meaning.
Q ₂ ; organic dye residue or anthraquinone residue X ₂ ; direct bond, —CONH—Y ₅ —, —SO ₂ NH—Y ₅ — or —CH ₂ NHCOCH ₂ NH—Y ₅ — (Y ₅ represents a substituent. Represents an alkylene group or an arylene group which may have.)
Y ₄ ; group p represented by the following general formula (4); an integer of 1 to 4

General formula (4):

The symbol in General formula (4) represents the following meaning.
R ₅ and R ₆ each independently a substituted or unsubstituted alkyl group q; an integer of 1 to 6

Examples of the organic dye residue in Q ₁ of the general formula (1) and Q ₂ of (3) include phthalocyanine dyes, azo dyes, quinacridone dyes, dioxazine dyes, anthrapyrimidine dyes, anthanthrone dyes, Examples thereof include pigments or dyes such as indanthrone dyes, flavanthrone dyes, perylene dyes, perinone dyes, thioindico dyes, isoindolinone dyes, and triphenylmethane dyes. In addition, examples of the aryl group having an amino group in Q ₁ of the general formula (1) include an aminophenyl group and an aminonaphthyl group. At this time, in addition to the amino group, the benzene ring can be substituted with other groups. You may have a substituent in any one of a halogen group, an amino group, a nitro group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an alkoxy group, a substituted or unsubstituted alkyl group.

  The concentration of the organic dye derivative having a basic functional group or the triazine derivative having a basic functional group in the organic solvent solution is preferably 1 to 100 mmol / L, and more preferably 1 to 50 mmol / L. Most preferably, it is 5-20 mmol / L.

  On the other hand, the organic dye derivative having an acidic functional group and the triazine derivative having an acidic functional group used in the present invention are represented by the following general formula (5) or (6).

General formula (5):

The symbol in a formula represents the following meaning.
Q ₃ ; an organic dye residue, an anthraquinone residue, an optionally substituted heterocyclic ring, or an optionally substituted aromatic ring R ₇ ; —O—R ₈ , —NH -R < ₈ >, a halogen group, -X < ₃ > -R < ₈ >, -X < ₄ > -Y < ₆ > -Z < ₂ > (R < ₈ > represents the alkyl group and alkenyl group which may have a hydrogen atom or a substituent.)
_{X 3; -NH -, - O} -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or _{-X 5 -Y 6 -X 6 - (} X 5 and X ₆ each independently represents —NH— or —O—.
_{X 4; -CONH -, - SO} 2 NH -, - CH 2 NH -, - NHCO- or -NHSO ₂ -
Y ₆ ; an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group which may have a substituent, or an arylene group Z ₂ which may have a substituent; -SO ₃ M, -COOM (M represents one equivalent of a monovalent to trivalent cation.)

The organic pigment residue at Q ₃ in the above general formula (5), phthalocyanine dyes, azo dyes, quinacridone dyes, dioxazine dyes, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone Examples thereof include pigments or dyes such as throne dyes, perylene dyes, perinone dyes, thioindico dyes, isoindolinone dyes, and triphenylmethane dyes.

Examples of the heterocyclic ring or aromatic ring in Q ₃ of the general formula (5) include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, Indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene and the like can be mentioned.

General formula (6):

The symbol in a formula represents the following meaning.
Q _4; organic pigment residue or anthraquinone residue _{X 7;} direct _{bond, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or - _{X 8 -Y 7 -X 9 - (} X 8 and _{X 9} each independently represent a -NH- or -O-, _{Y 7} represents an alkylene group or an arylene group which may have a substituent.)
Z ₃ ; —SO ₃ M, —COOM (M represents 1 equivalent of a 1 to 3 valent cation)
r; an integer from 1 to 4

Examples of the organic dye residue in Q ₄ of the general formula (6) include phthalocyanine dyes, azo dyes, quinacridone dyes, dioxazine dyes, anthrapyrimidine dyes, ansanthrone dyes, indanthrone dyes, and flavans. Examples thereof include pigments or dyes such as throne dyes, perylene dyes, perinone dyes, thioindico dyes, isoindolinone dyes, and triphenylmethane dyes.

  The concentration of the organic dye derivative having an acidic functional group or the triazine derivative having an acidic functional group in the organic solvent solution is preferably 1 to 100 mmol / L, and more preferably 1 to 50 mmol / L. Most preferably, it is 5-20 mmol / L.

  The organic solvent used when forming the organic pigment or carbon black dispersion (A) in the present invention also functions as a dispersion aid for the organic pigment and carbon black, and has a dielectric constant of 15 or more. It is preferable to use 20 or more polar solvents. When the dielectric constant is less than 15, the solubility of the organic dye derivative or triazine derivative having a basic or acidic functional group is significantly lowered. In the present invention, the organic solvent is not particularly limited as long as the dielectric constant satisfies the above conditions. Specifically, for example, alcohol such as methanol, ethanol, propyl alcohol, butanol; 1,2-ethane Glycol solvents such as diol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and diethylene glycol; ketones such as acetone and methyl ethyl ketone; other N-methylpyrrolidone, acetonitrile, N, N -Dimethylformamide, sulfolane, dimethyl sulfoxide and the like. These solvents can be used singly or in combination of two or more, but in use, it is preferable to contain a protic solvent such as alcohols or glycols. In consideration of mixing with a styrenic resin or a polyester resin described later, it is more preferable to use alcohols among the protic solvents. Further, viscous glycerin or the like can be dissolved in the above solvent at room temperature.

  Examples of the acid added to dissolve the organic dye derivative having a basic functional group and the triazine derivative having a basic functional group in the present invention include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, salts obtained by the reaction of a strong acid and a weak base. Inorganic compounds, carboxylic acids, organic acids such as sulfonic acids, and the like can be used. Organic acids are preferred, and carboxylic acids are particularly preferred. In addition, these acids preferably have a molecular weight of 300 or less, more preferably 200 or less.

  As the addition amount of the acid used in the present invention, 0.1 to 10 equivalents is added with respect to the acidic functional group amount contained in the organic dye derivative having a basic functional group or the triazine derivative having a basic functional group. I can do it. More preferably, it is 0.5 to 5 equivalents.

  In the present invention, the base added to dissolve the organic dye derivative having an acidic functional group and the triazine derivative having an acidic functional group is generated by a reaction between a metal hydroxide such as an alkali metal, a weak acid and a strong base. Various bases such as salts, ammonia, amino group-containing organic compounds and the like can be mentioned. Alkali metals, ammonia, and amino group-containing organic compounds are preferred. Further, these bases preferably have a molecular weight of 300 or less, more preferably 200 or less.

  When the base is added, it can be added in an amount of 0.1 to 10 equivalents relative to the amount of acidic functional group contained in the organic dye derivative having acidic functional group or the triazine derivative having acidic functional group. More preferably, it is 0.5 to 5 equivalents.

  Adsorption treatment of an organic dye derivative or triazine derivative having a basic or acidic functional group onto an organic pigment or carbon black is carried out in an organic solvent in the presence of an acid or base. At this time, the organic pigment or carbon black is pulverized. It is preferable to mix and stir the dispersion (that is, to disperse) while (for example, grinding). The disperser used for the adsorption treatment is not particularly limited. For example, a paint conditioner (manufactured by Red Devil), a ball mill, a sand mill (such as “Dynomill” manufactured by Shinmaru Enterprises), an attritor, a pearl mill (Such as “DCP mill” manufactured by Eirich), coball mill, basket mill, homomixer, homogenizer (such as “Creamix” manufactured by M Technique), wet jet mill (“Genus PY” manufactured by Genus, “Nanomizer manufactured by Nanomizer”) Or the like. In view of cost, processing capability, etc., a media type disperser using dispersed media particles is preferable. As the media, glass beads, zirconia beads, alumina beads, magnetic beads, stainless beads, etc. can be used. Since the media-type disperser has a completely sealed structure, there is no loss of balance due to foaming or solvent evaporation, and stable pulverization is possible.

  The organic pigment and carbon black adsorbed by a disperser are preferably refined to a dispersed particle size of 0.5 μm or less, preferably 0.2 μm or less, in order to exhibit their performance. The dispersed particle size here is an average particle size (D50 value) measured by a general particle size distribution meter, for example, a dynamic light scattering type particle size distribution meter (for example, “Microtrac UPA” manufactured by Nikkiso Co., Ltd.). is there.

  In the media-type disperser used in the present invention, the major factors that determine the dispersibility include the type of dispersion media, the particle size of the dispersion media, the filling rate of the dispersion media in the disperser, the solution concentration of the sample to be dispersed, the solvent concentration Types are listed. Among these, the type of dispersed media and the particle size of the media greatly contribute to the dispersibility.

The types of dispersion media include glass beads (SiO ₂ 70-80%, NaO 12-16%, etc.), zircon beads (ZrO ₂ 69%), depending on the viscosity (specific gravity) of the dispersion (A) and the required particle size for dispersion. , SiO ₂ 31%), zirconia beads (ZrO ₂ 95% or more), alumina (Al ₂ O ₃ 90% or more), titania (TiO ₂ 77.7%, Al ₂ O ₃ 17.4%), steel balls, etc. However, in order to obtain good dispersibility, it is preferable to use zirconia beads or zircon beads.

  The particle diameter (diameter) of the dispersion medium can be used in the range of 0.1 mm to 3.0 mm, but in particular, the range of 0.3 to 1.4 mm is preferable. If it is smaller than 0.1 mm, the load in the pulverizer increases, and heat generation causes organic pigments, carbon black, organic dye derivatives, triazine derivatives, etc. to be fused, making dispersion difficult, and from 3.0 mm Is too large, preferable dispersion cannot be performed. The filling rate of the dispersion medium is preferably 60 to 85%. If it exceeds 85%, the load in the disperser will increase, and heat generation will cause organic pigments, carbon black, organic dye derivatives, triazine derivatives, etc. to be fused, making dispersion difficult, and below 60%. If it becomes, dispersion efficiency will fall and uniform dispersion will become difficult. Moreover, when the density | concentration of the organic pigment or carbon black in a dispersion liquid (A) is high (concentration of 40 to 50 weight%), it is good to make a filling rate into 60 to 70%.

  Here, in the dispersion step for obtaining the dispersion liquid (A), the pigment, adsorbate, acid or base, and organic solvent are charged into the disperser to form a slurry, which is then dispersed in the disperser. The temperature is preferably cooled to 50 ° C. or lower in order to prevent an increase in the viscosity of the slurry and a decrease in fluidity. Dispersion at a temperature exceeding 50 ° C. is not preferable because the organic pigment, carbon black, organic dye derivative, and triazine derivative in the disperser aggregate.

  The styrene resin solution used in the present invention can be used by dissolving the styrene resin described below in an organic solvent, but the state before the styrene resin is synthesized in solution polymerization and the solvent is removed (desolvent). It is also preferable to use in the above. The resin concentration in the styrene resin solution is preferably about 3 to 30% by weight, more preferably 5 to 25% by weight, based on the resin solution.

Examples of polystyrene resins used in the invention include homopolymers of styrene and its derivatives such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer Styrene-styrene derivative copolymer such as coalescence; styrene-vinyl naphthalene copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene -Acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile -Indene copolymerization And styrene copolymers and the like as preferred. Among these, styrene homopolymers, styrene-styrene derivative copolymers, styrene-acrylic acid copolymers, and styrene-methacrylic acid copolymers are particularly preferable. Moreover, it is preferable that these weight average molecular weights (Mw) are the range of 1 * 10 < ⁴ > -5 * 10 < ⁶ > normally.

  As the copolymer component other than styrene when the styrene resin is a copolymer, the vinyl monomer includes methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, acrylic acid Acrylic esters such as cyclohexyl, lauryl acrylate, stearyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methyl methacrylate, ethyl methacrylate, Propyl methacrylate, butyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, furfuryl methacrylate, methacrylate Methacrylic acid esters such as tetrahydrofurfuryl phosphate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, aromatic vinyl monomers such as vinyltoluene, α-methylstyrene, chlorostyrene, Unsaturated dibasic acid dialkyl esters such as dibutyl maleate, dioctyl maleate, dibutyl fumarate, dioctyl fumarate, vinyl esters such as vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile, methacrylamide, acrylamide, etc. Nitrogen-containing vinyl monomers, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and cinnamic acid, unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid and itaconic acid, monomethyl maleate and maleic acid Examples thereof include unsaturated dicarboxylic acid monoesters such as monoethyl acid, monobutyl maleate, monooctyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate and monooctyl fumarate.

  The styrenic resin solution of the present invention may be a solution-polymerized solution or a solution prepared by dissolving a resin produced by bulk polymerization, suspension polymerization, or emulsion polymerization in the above-mentioned solvent. It is efficient to use the obtained resin together with the solution used for polymerization.

The styrene resin has a molecular weight distribution measured by GPC and has at least one peak in the region of 3 × 10 ^{3 to} 5 × 10 ⁴ and at least one peak or shoulder in the region of 10 ⁵ or more. A copolymer is preferred from the viewpoint of fixability. A binder resin having such a molecular weight distribution can be produced by mixing two or more resins having different average molecular weights.

In addition, the molecular weight distribution by said GPC is measured on condition of the following, using HLC-8120 (made by Tosoh Corporation) as a measuring apparatus, for example.
The column is stabilized in a 40 ° C. heat chamber, and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and about 100 μl of a sample solution dissolved in THF is injected for measurement. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.

As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is suitably used. . An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, combinations of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL) manufactured by Tosoh Corporation, A combination of G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and TSKguardcolumn can be given.

  The measurement sample is prepared as follows. That is, after putting a sample in THF and leaving it to stand for several hours, the sample is sufficiently shaken, mixed well with THF until the sample is no longer united, and further allowed to stand for 12 hours or more. At this time, the standing time in THF is set to be 24 hours or longer. Then, GPC measurement was performed on a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Ltd., etc.). Sample for use. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

  In the production of the vinyl polymer, a polymerization initiator is used. Any conventionally known polymerization initiator can be used as the polymerization initiator. Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, tertiary butyl hydroperoxide, tertiary butyl peroxybenzoate, ditertiary butyl peroxide, cumene hydroperoxide, dicumyl peroxide, azoisobutyro Nitrile, azobisvaleronitrile and the like are usually preferably used. The use ratio of the initiator to the vinyl monomer is generally 0.2 to 5% by weight. The polymerization temperature is appropriately selected according to the type of monomer and initiator used.

  Examples of the organic solvent used in forming the styrene resin solution of the present invention include hydrocarbon solvents such as benzene, toluene, xylene, and cyclohexane, methanol, ethanol, iso-propyl alcohol, n-butyl alcohol, sec-butyl. Alcohol solvents such as alcohol, iso-butyl alcohol, amyl alcohol, cyclohexanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ester solvents such as ethyl acetate, n-butyl acetate, cellosolve acetate, methyl And ether solvents such as cellosolve, ethyl cellosolve, and butyl cellosolve. Among them, it is preferable to use a hydrocarbon solvent in view of compatibility when mixing with the dispersion liquid (A).

  On the other hand, the polyester resin solution used in the present invention is produced by dissolving the polyester resin described below in an organic solvent. The resin concentration in the polyester resin solution is preferably about 3 to 40% by weight, more preferably 5 to 30% by weight, based on the resin solution.

  The polyester resin used in the present invention may be any one that is conventionally known as a binder resin for dry toners for developing electrostatic images. As the alcohol component constituting the polyester resin of the present invention, the monoalcohol component is a glycidyl ester of a tertiary fatty acid, and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol. 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, etc. Examples of the aliphatic diol having 2 to 10 carbon atoms and the crosslinking component include polyhydric alcohols such as glycerin, sorbit, sorbitan, butanetriol, trimethylolethane, pentaerythritol, and trimethylolpropane. These may be used alone or in combination of two or more. By using a glycidyl ester of a tertiary fatty acid together with an aliphatic diol having 2 to 10 carbon atoms, offset resistance and blocking resistance can be improved.

  The acid component constituting the polyester includes a monocarboxylic acid, a disproportionated rosin, and a divalent carboxylic acid such as benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; Alkyl dicarboxylic acids such as acids, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; and succinic acid or anhydrides further substituted with an alkyl group having 16 to 18 carbon atoms; fumaric acid, maleic acid, citraconic acid, Examples thereof include unsaturated dicarboxylic acids such as itaconic acid or anhydrides thereof. Examples of the trivalent or higher carboxylic acid as a crosslinking component include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, butanetricarboxylic acid, hexanetricarboxylic acid, Benzophenone tetracarboxylic acid, tetra (methyle Carboxyl) methane, octane tetracarboxylic acid, and benzophenone tetracarboxylic acid anhydride, and the like. It is also preferable to use a monocarboxylic acid disproportionated rosin in combination with a divalent carboxylic acid for the purpose of achieving a balance between fixability and offset resistance. These may be used alone or in combination of two or more.

  The polyester resin may be a homopolyester or a copolyester alone or a blend of two or more of these. The polyester resin preferably has a weight average molecular weight (Mw) of 5,000 or more in terms of molecular weight measured by gel permeation chromatography (GPC) from the viewpoint of offset resistance and low-temperature fixability. The thing of 000-1,000,000 is more preferable. When the weight average molecular weight of the polyester resin decreases, the offset resistance of the toner tends to decrease, and when the weight average molecular weight increases, the fixability tends to decrease. The thermoplastic polyester resin used is a type having a molecular weight distribution curve of two peaks comprising a specific low molecular weight condensation polymer component and a specific high molecular weight condensation polymer component, or a single molecular weight distribution curve. Any of the types having

From the viewpoint of preventing toner aggregation, the polyester resin preferably has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 45 to 70 ° C., preferably 50 to 65 ° C. Furthermore, the true density of the resin is preferably 1.1 to 1.3 g / cm ³ . When the true density of the resin is low, the toner can be used in a small amount when an image having the same density is formed, and as a result, economical copying can be performed.

  In addition, other than polyester resins conventionally used as binder resins for toner, such as polystyrene polymers, polystyrene copolymers such as styrene-acrylic resins, and the like within the scope of achieving the object of the present invention. You may use together with resin.

  The polyester resin used in the present invention is prepared by a known and usual production method using the predetermined acid component and alcohol component as raw materials, and any of transesterification reaction or direct esterification reaction can be applied as the reaction method. is there. In addition, polycondensation can be promoted by a method of increasing the reaction temperature by pressurization, a pressure reduction method, or a method of flowing an inert gas under normal pressure. In the above reaction, a known and commonly used reaction catalyst such as at least one metal compound selected from antimony, titanium, tin, zinc and manganese may be used to accelerate the reaction. Specific examples of the reaction catalyst include di-n-butyltin oxide, stannous oxalate, antimony trioxide, titanium tetrabutoxide, manganese acetate, and zinc acetate. The amount of these reaction catalysts added is usually preferably about 0.001 to 0.5 mol% in the resulting polyester resin.

  Examples of the organic solvent used in producing the polyester resin solution of the present invention include hydrocarbon solvents such as benzene, toluene, xylene, and cyclohexane, methanol, ethanol, iso-propyl alcohol, n-butyl alcohol, and sec-butyl alcohol. Alcohol solvents such as iso-butyl alcohol, amyl alcohol and cyclohexanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate, n-butyl acetate and cellosolve acetate, methyl cellosolve And ether solvents such as ethyl cellosolve and butyl cellosolve. Among these, use of a carbon-based solvent is preferable in view of compatibility when mixed with the organic pigment dispersion (A).

  The electrostatic charge image developing toner of the present invention contains a charge control agent as required. By using a charge control agent, a toner having a stable charge amount can be obtained. At this time, in order not to impair the hue of the toner, it is necessary to use a white or light color as the charge control agent. In the toner of the present invention, any conventionally known white or light color positive or negative charge control agent can be used as the charge control agent.

  When the electrostatic charge image developing toner of the present invention is used as a positively chargeable toner, any of conventionally known white or light color positive charge control agents may be used as the charge control agent. Compounds are preferred. Examples of the quaternary ammonium salt compound that can be used in the present invention include a salt-forming compound comprising a quaternary ammonium salt and an organic sulfonic acid or molybdic acid. As the organic sulfonic acid, naphthol sulfonic acid is preferably used.

  Specific quaternary ammonium salt compounds include tributylbenzylammonium-1-hydroxy-4-naphthalenesulfonate, tributylbenzylammonium-2-hydroxy-8-naphthalenesulfonate, triethylbenzylammonium-1-hydroxy-4. -Naphthalenesulfonate, tripropylbenzylammonium-1-hydroxy-4-naphthalenesulfonate, tripropylbenzylammonium-2-hydroxy-6-naphthalenesulfonate, trihexylbenzylammonium-1-hydroxy-4-naphthalene Examples include sulfonate, tetrabutylammonium-1-hydroxy-4-naphthalenesulfonate, tetraoctylammonium-1-hydroxy-4-naphthalenesulfonate, and the like.

  On the other hand, when used as a negatively chargeable toner, a salicylic acid derivative metal salt compound, a salicylic acid derivative metal complex, a phenol-based condensate, a phosphonium compound, and the like are preferable as a charge control agent. As the metal used for the metal salt compound of the salicylic acid derivative and the metal complex of the salicylic acid derivative, zinc, calcium, magnesium, titanium, chromium, aluminum, silicon and the like are preferable. As the salicylic acid derivative, those having a tert-butyl group or a tert-octyl group are preferable. Specifically, salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid, 3- Phenylsalicylic acid is a particularly preferred compound. As the phenol condensate, a calixarene compound is preferable. As these charge control agents, those obtained by a known production method can be used.

The charge control agent can be used more effectively by pulverizing with a pulverizer and adjusting to a desired particle size distribution. In the present invention, a good particle size distribution as a charge control agent is 0.5 to 40 μm, more preferably 1 to 20 μm in volume average particle size. When the volume average particle diameter is larger than 40 μm, it becomes difficult to disperse the charge control agent in the binder resin, and it becomes difficult to disperse the charge control agent in the toner. In addition, the content of the charge control agent per toner particle is biased, leading to an increase in fog and scattering in the apparatus. On the other hand, when a material having a volume average particle size of less than 0.5 μm is used, although the dispersion in the binder resin is good, the specific surface area of the charge control agent is increased and the toner is excessively charged. In some cases, the charge amount increases and the image density decreases.
The addition amount of the charge control agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 0.8 to 3 parts by weight with respect to 100 parts by weight of the solid content in the resin solution. It is.

Further, instead of using the charge control agent, a resin charge control agent that does not affect the hue can be used. For positive charging, the general formula — [CH ₂ —CH (C ₆ H ₅ ) _a ] — [CH ₂ —CH (COOC ₄ H ₉ )] _b — [CH ₂ —C (CH ₃ ) COOC ₂ H _{4 ^{N + CH 3 (C 2 H}} 5) 2 ] _{cCH 3 (C 6 H 4)} SO 3 - ( these are parts quaternary ammonium salt 3 to 35 parts by weight of styrene-acrylic portion be 97 to 65 parts by weight , Thereby determining the values of a, b, and c), and a styrene / acrylic polymer copolymerized with a styrene / acrylic resin using a quaternary ammonium salt as a functional group.

On the other hand, for negative charging, the general formula — [CH ₂ —CH (C ₆ H ₅ ) _a ] — [CH ₂ —CHCOOCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] _b — [CH ₂ —CHCONHC] (CH ₃ ) ₂ CH ₂ SO ₃ H] _c — (of which 2 to 20 parts by weight of the sulfonic acid part and 98 to 80 parts by weight of the styrene / acryl part determine the values of a, b and c) And styrene / acrylic polymers copolymerized with styrene / acrylic resins using sulfonic acid as a functional group, and polymeric ammonium compounds.

  Specifically, 2-ethylhexyl acrylate / acryloylamino-2-methyl-1-propanesulfonic acid / styrene copolymer, butyl acrylate / N, N-diethyl-N-methyl-2- (methacryloyloxy) ethyl Ammonium = p-toluenesulfonate / styrene copolymer, benzalkonium chloride salt and poly (diallyldimethylammonium chloride). The resin charge control agent is usually 0.5 to 20 parts by weight, preferably 1.0 to 8.0 parts by weight with respect to 100 parts by weight of the solid content in the resin solution.

The charge control agent is preferably added to the polyester resin solution together with the organic pigment dispersion (A) in the process of obtaining the colored resin composition (D), in order to obtain good dispersion of the charge control agent. In addition, after obtaining the colored resin composition (D), a charge control agent may be further added and mixed, and then added through a kneading step.

  In the electrostatic charge image developing toner of the present invention, a release agent can be used. The release agent is selected from the group consisting of hydrocarbon waxes such as polypropylene wax, polyethylene wax and Fiescher-Tropsch wax, and natural ester waxes such as synthetic ester waxes, carnauba wax and rice wax. A mold is used. Since it is often difficult to uniformly disperse and disperse the release agent uniformly in the resin, it is preferable to produce the toner after pulverizing the release agent to 10 μm or less.

  The release agent is preferably added to the styrene resin solution or the polyester resin solution together with the organic pigment dispersion (B) in the process of obtaining the colored resin composition (D) as in the case of the charge control agent. In addition, after obtaining the colored resin assembly composition (D), a release agent may be further added and mixed, and then added through a kneading step. The addition amount of the release agent is not particularly limited, but is usually 0.1 to 5 parts by weight with respect to 100 parts by weight of solid content in the resin solution, that is, 0.1 to 5 parts by weight with respect to 100 parts by weight of the binder resin. Part. It is preferable to add a release agent to the styrene-based resin solution or the polyester resin solution because the release agent is uniformly dispersed in the resin without causing phase separation between the resin and the release agent.

  The colored resin composition (D) of the present invention can be obtained by mixing a styrene resin or polyester resin solution and a pigment dispersion (A), if necessary, a charge control agent and a release agent, and removing the solvent. Usually, the pigment dispersion (A) and, if necessary, a charge control agent and a release agent are added to a styrene resin or polyester resin solution and mixed. The content of the organic pigment or carbon black contained in the colored resin composition (D) is preferably in the range of 0.5 to 25% by weight. More preferably, it is in the range of 1 to 20% by weight. When the amount is less than 0.5% by weight, it is difficult to obtain the effect as an organic pigment, and when the amount is more than 25% by weight, dispersion in the resin becomes difficult. In the present invention, desolvation refers to a step of desolvation at normal pressure or depressurization at 100 to 250 ° C. In particular, in order to prevent thermal deterioration of the resin and the organic pigment and sufficiently perform the solvent removal, it is preferable to perform the solvent removal under reduced pressure at 120 to 220 ° C.

The composition (D) obtained here is used as an electrostatic image developing toner after toner base particles are obtained by the following method (1) or (2).
(1) The colored resin composition (D) is roughly pulverized, finely pulverized, and classified to obtain toner base particles. At this time, at the stage of obtaining the composition (D), it is preferable to add both a charge control agent and a release agent as necessary. In the coarse crushing step, the composition (D) is adjusted to 10 mm or less using a sample mill, a drum flaker or the like and sent to the fine crushing step. In the fine pulverization and classification step, the toner particles are pulverized to a desired toner particle size of 15 μm or less using a jet mill, a mechanical pulverizer or the like, and classified. Usually, an airflow classifier, a rotary classifier, an elbow jet classifier or the like can be used for classification.
(2) The colored resin composition (D) is mixed with internal additives used for toner preparation such as a charge control agent and a release agent, and after melt-kneading, cooling, coarse pulverization, fine pulverization, classification are performed, Toner mother particles are obtained. The mixing step is performed by mixing with a conventionally known mixer such as a Henschel mixer or a super mixer, and the melt kneading is a batch kneader such as a heating kneader or a Banbury mixer, or an extruder such as a single or twin screw extruder. Any of continuous kneaders such as the above may be used. In general, some organic pigments, particularly yellow pigments, may change color when the kneading temperature exceeds 150 ° C., and kneading at a temperature exceeding 150 ° C. may not be preferable. is there.

  The toner base particles thus obtained can be sufficiently mixed as necessary using a mixer such as an external additive and a Henschel mixer, and the toner for electrostatic charge development of the present invention can be produced through a sieving step. .

  Examples of the external additive used in the toner for developing an electrostatic charge image of the present invention include a lubricant, a fluidizing agent, an abrasive, a conductivity-imparting agent, and an image peeling prevention agent, which are used as necessary. As the agent, any of known additives conventionally used in the production of toners may be used. As examples of these additives, as the lubricant, polyvinylidene fluoride, zinc stearate, etc., as the fluidity improver (fluidizing agent), silica, aluminum oxide, titanium oxide produced by a dry method or a wet method, Silicon-aluminum co-oxide, silicon-titanium co-oxide, and those hydrophobized, such as silicon nitride, cerium oxide, silicon carbide, strontium titanate, tungsten carbide, calcium carbonate and hydrophobizing these Examples of the conductivity imparting agent include tin oxide and the like.

  The toner for developing an electrostatic charge image of the present invention preferably contains, as a fluidizing agent, hydrophobized silica, silicon aluminum co-oxide, and silicon titanium co-oxide fine powder as external additives. Examples of the hydrophobic treatment of these fine powders include treatment with a silane coupling agent such as silicon oil, tetramethyldisilazane, dimethyldichlorosilane, and dimethyldimethoxysilane. The amount of the hydrophobized fine powder such as silica subjected to hydrophobization treatment is 0.01 to 20%, preferably 0.03 to 5%, based on the developer weight.

  The particle diameter of the toner for developing an electrostatic charge image of the present invention is desirably 1 to 15 μm, preferably 3 to 12 μm in volume average particle diameter. In the toner of the present invention, the organic pigment and carbon black are more finely dispersed than in the conventional toner, so that the dispersibility, distribution, and compoundability of the organic pigment and carbon black that are very preferable can be obtained even in a small particle size toner. It can be done. The toner particle size distribution can be measured using, for example, a Coulter counter (multisizer).

  The electrostatic image developing toner of the present invention can be mixed with a carrier and used as a two-component developer. The carrier that can be used together with the toner of the present invention may be any conventionally known carrier. Examples of the carrier that can be used include magnetic powders such as iron powder, ferrite powder, and nickel powder, and those whose surfaces are treated with a resin or the like. Examples of the resin covering the carrier surface include styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, acrylic acid ester copolymer, methacrylic acid ester copolymer, fluorine-containing resin, silicone-containing resin, and polyamide. Examples thereof include a resin, an ionomer resin, a polyphenylene sulfide resin, and a mixture thereof. Among these, a silicone-containing resin is particularly preferable because the formation of spent toner is small. Moreover, it is preferable that the weight average particle diameter of a carrier is the range of 30-100 micrometers.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples. However, the present invention is not limited to the following examples. In the following examples, “parts” means “parts by weight” unless otherwise specified.

[Example 1]
To a glass bottle, 89.9 parts of methanol, 0.1 part of hydrogen chloride, and 0.5 part of a dispersant represented by the following general formula (7) were added, mixed and stirred, and then phthalocyanine blue (Pigment Blue 15: 3) was added. 5 parts were added, and zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain an organic pigment dispersion 1. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, the particle size of the dispersion was 80 nm.

General formula (7):

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Furthermore, 30 parts of the organic pigment dispersion 1 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 1 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 1 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm.

  Furthermore, using this cyan toner and developer, a real-life test was performed in a single color mode using a commercially available full-color copying machine (CLC-800 manufactured by Canon Inc.), and image density (initial and values after 30000 sheets), fog (initial) And values after 30000 sheets), evaluation of in-flight scattering gave good results. Further, when the image was confirmed after being left for 14 days in the state after 30000 sheets, a satisfactory result was obtained without any decrease in image density or increase in fog due to charge decay. The results are shown in Table 1.

The particle size distribution of the organic pigment subjected to the adsorption treatment in the dispersion 1 was measured using a Microtrac particle size analyzer UPA150 (manufactured by Nikkiso Co., Ltd.). The measurement conditions at this time were as follows.
Transparent Particles: Yes
Spherical Particles: Yes
Part Reflective Index: 1.50
Part. Density: 1.00g / cm ³
Fluid: Methanol
Fluid Refractive Index: 1.33
Measurement time: 180s
As for the average particle diameter, D50 and a cumulative 50 percent diameter (volume distribution) were used as indicators of the average particle diameter.

  Here, the image density was measured using a Macbeth photometer. The concentration may be 1.35 or more. The fog was measured by measuring the reflectance with a photovolt. 1.5% or less is a good value. Further, the scattering of the toner in the machine was performed by checking whether or not the scattered toner was present on the transfer charger of the copying machine. When toner scattering is observed on the transfer charger, image contamination is caused.

[Example 2]
To a glass bottle, 89.9 parts of n-butanol, 0.1 part of glacial acetic acid and 0.5 part of a dispersant represented by the above general formula (7) are added, and after mixing and stirring, phthalocyanine blue (Pigment Blue 15: 3) is added. 9.5 parts were added, and zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain an organic pigment dispersion 2. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, the particle diameter of the dispersion was 154 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 2 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a composition 2 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 2 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results are shown in Table 1.

[Example 3]
To a glass bottle, 79.8 parts of methyl ethyl ketone, 0.2 part of glacial acetic acid and 1.0 part of a dispersant represented by the above general formula (7) were added, mixed and stirred, and then 19 parts of phthalocyanine blue (Pigment Blue 15: 3). In addition, zirconia beads were dispersed as media (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain organic pigment dispersion 3. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, the particle size of the dispersion was 125 nm.

  On the other hand, 10 parts of styrene-butyl acrylate copolymer resin was added to 90 parts of xylene in a flask and mixed while dissolving the resin at a temperature of 90 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 3 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 3 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 3 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results are shown in Table 1.

[Example 4]
89.9 parts of methanol, 0.1 part of glacial acetic acid and 0.5 part of a dispersant represented by the following general formula (8) were added to a glass bottle, mixed and stirred, and then 9.5 parts of quinacridone pigment (Pigment Red 122). In addition, zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain an organic pigment dispersion 4. When the dispersibility of the organic pigment subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 121 nm.

General formula (8):

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 4 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 4 for magenta toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized by a jet mill pulverizer and classified by an airflow classifier to obtain magenta toner mother particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged magenta toner 4 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results are shown in Table 1.

[Example 5]
Add 89.9 parts of methanol, 0.1 part of glacial acetic acid and 0.5 part of a dispersant represented by the following general formula (9) to a glass bottle, and after mixing and stirring, add 9.5 parts of carbon black, and add zirconia beads. Dispersion was carried out as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain a carbon black dispersion 5. When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 155 nm.

General formula (9):

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 5 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin 2 parts of wax (Fischer-Tropsch wax) was added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a composition 5 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 5 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results are shown in Table 1.

[Example 6]
To a glass bottle, 89.9 parts of methanol, 0.1 part of glacial acetic acid and 0.5 part of a dispersant represented by the following general formula (10) were added, mixed and stirred, and then benzimidazolone pigment (Pigment yellow 180) was added. 5 parts were added, and zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain an organic pigment dispersion liquid 6. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, the particle size of the dispersion was 130 nm.

General formula (10):

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Furthermore, 30 parts of the organic pigment dispersion 6 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding 2 parts of wax (Fischer-Tropsch wax) to the flask and mixing, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 6 for yellow toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, yellow toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the yellow toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged yellow toner 6 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results are shown in Table 1.

[Example 7]
Add 89.9 parts of ethanol, 0.1 part of glacial acetic acid and 0.5 part of a dispersant represented by the following general formula (11) to a glass bottle, and after mixing and stirring, add 9.5 parts of carbon black, and add zirconia beads. As a medium (diameter: 1.25 mm, filling rate: 70%), a carbon black dispersion liquid 7 was obtained by dispersing for 30 minutes with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can). When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 160 nm.

General formula (11):

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 7 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a composition 7 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added, mixed with a Henschel mixer, and then a negatively charged black toner 7 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results are shown in Table 1.

[Example 8]
In a flask, 10 parts of a styrene-methyl methacrylate copolymer resin was added to 90 parts of toluene, and mixing was performed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-methyl methacrylate copolymer resin solution. .
30 parts (solid content 10%) of the organic pigment dispersion 1 produced in Example 1, 940 parts (solid content 10%) of the above styrene-methyl methacrylate copolymer resin solution, and further an aromatic hydroxycarboxylic acid calcium salt 1 part of a compound and 2 parts of paraffin wax (Fischer-Tropsch wax) were added to and mixed in a flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system. 8 was obtained. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 8 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results are shown in Table 1.

[Comparative Example 1]
90.0 parts of methanol and 10 parts of phthalocyanine blue (Pigment Blue 15: 3) are added to a glass bottle, and a paint conditioner (Red Devil 5410 single type, 28) using zirconia beads as a medium (diameter 1.25 mm, filling rate 70%). An organic pigment dispersion 8 was obtained by dispersing with an on-mill for 30 minutes. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, agglomeration that could be visually confirmed was observed.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 8 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a cyan toner composition 9. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 9 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
Add 89.9 parts of methanol, 0.1 part of glacial acetic acid and 10 parts of phthalocyanine blue (Pigment Blue 15: 3) to a glass bottle, and paint conditioner with zirconia beads as media (diameter 1.25 mm, filling rate 70%). (Red Devil 5410 single type, 28 ounce mill can) was dispersed for 30 minutes to obtain an organic pigment dispersion 9. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, agglomeration that could be visually confirmed was observed.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 9 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 10 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 10 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3]
Add 90 parts of methanol and 0.5 part of the dispersant represented by the above general formula (7) to a glass bottle, mix and stir, then add 9.5 parts of phthalocyanine blue (Pigment Blue 15: 3), and add zirconia beads to the media. Dispersion was carried out for 30 minutes with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) as (diameter 1.25 mm, filling rate 70%) to obtain organic pigment dispersion 10. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, the particle size of the dispersion was 576 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 10 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 11 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 11 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 4]
To a glass bottle, add 80 parts of methanol, 10 parts of Solsperse 20000 (manufactured by Avicia, alcohol-soluble resin dispersant), 10 parts of benzimidazolone pigment (Pigment yellow 180), and add zirconia beads to media (diameter 1.25 mm, The organic pigment dispersion 11 was obtained by dispersing with a paint conditioner (Red Devil 5410 single type, 28 ounce mill) for 30 minutes. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, the particle size of the dispersion was 286 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 11 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 12 for yellow toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, yellow toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the yellow toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable yellow toner 12 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 5]
To a glass bottle, 90 parts of methanol and 0.5 part of the dispersant represented by the above general formula (8) were added, mixed and stirred, 10 parts of quinacridone pigment (Pigment red 122) was added, and zirconia beads were added to the media (diameter 1.25 mm). The organic pigment dispersion 12 was obtained by dispersing for 30 minutes using a paint conditioner (Red Devil 5410 single type, 28 ounce mill can). When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, the particle diameter of the dispersion was 610 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 12 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a magenta toner composition 13. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged magenta toner 13 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 6]
Add 80 parts of methanol, 10 parts of Solsperse 20000 (manufactured by Avicia, alcohol-soluble resin type dispersant) and 10 parts of quinacridone pigment (Pigment red 122) to a glass bottle, and add zirconia beads to media (diameter: 1.25 mm, filling factor) 70%) was dispersed for 30 minutes with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) to obtain an organic pigment dispersion 13. When the dispersibility of the adsorbed organic pigment in the dispersion was confirmed, the particle size of the dispersion was 372 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Furthermore, 30 parts of the organic pigment dispersion 13 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding 2 parts of wax (Fischer-Tropsch wax) to the flask and mixing, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a magenta toner composition 14. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable magenta toner 14 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 9]
89.9 parts of methanol, 0.1 part of sodium hydroxide and 0.75 part of a dispersant represented by the following general formula (12) are added to a glass bottle, and after mixing and stirring, 9.25 parts of carbon black (Monarch 880) is added. In addition, zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain a carbon black dispersion 14. When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 153 nm.

Formula (12):

The particle size distribution of the carbon black subjected to adsorption treatment in the dispersion 14 was measured using a Microtrac particle size analyzer UPA150 (manufactured by Nikkiso Co., Ltd.). The measurement conditions at this time were as follows.
Transparent Particles: Yes
Spherical Particles: Yes
Part Reflective Index: 1.50
Part. Density: 1.00g / cm ³
Fluid: Methanol
Fluid Refractive Index: 1.33
Measurement time: 180s
As for the average particle diameter, D50 and a cumulative 50 percent diameter (volume distribution) were used as indicators of the average particle diameter.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 14 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) into the flask, the solvent was removed from the system while recovering the solvent at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 15 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 15 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm.

  Further, when this black toner and developer were used in the same manner as in Example 1, evaluation of image density (initial and values after 30000 sheets), fog (initial and values after 30000 sheets), and in-machine scattering was evaluated. As a result, good results were obtained. Further, when the image was confirmed after being left for 14 days in the state after 30000 sheets, a satisfactory result was obtained without any decrease in image density or increase in fog due to charge decay. The results at this time are shown in Table 2.

[Example 10]
89.9 parts of ethanol, 0.1 part of DMAE (dimethylaminoethanol) and 0.75 part of the dispersant represented by the above general formula (12) were added to a glass bottle, and after mixing and stirring, 9 parts of carbon black (Monarch 880) was added. .25 parts were added, and zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain a carbon black dispersion 15. When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 189 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 15 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a black toner composition 16. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added, mixed with a Henschel mixer, and then a negatively chargeable black toner 16 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 2.

[Example 11]
89.9 parts of methanol, 0.1 part of DMAE (dimethylaminoethanol) and 0.5 part of a dispersant represented by the general formula (12) were added to a glass bottle, mixed and stirred, and then phthalocyanine blue (Pigment Blue 15: 3). 9.5 parts of zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain an organic pigment dispersion liquid 16 . When the dispersibility of the pigment subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 94 nm.

  On the other hand, 10 parts of styrene-butyl acrylate copolymer resin was added to 90 parts of xylene in a flask and mixed while dissolving the resin at a temperature of 90 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Furthermore, 30 parts of the organic pigment dispersion 16 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed while recovering the solvent outside at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 17 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 17 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 2.

[Example 12]
79.8 parts of ethylene glycol, 0.2 part of DMAE (dimethylaminoethanol) and 1.0 part of a dispersant represented by the general formula (12) were added to a glass bottle, mixed and stirred, and then phthalocyanine blue (Pigment Blue 15: 3). 19.0 parts), and zirconia beads as a medium (diameter: 1.25 mm, filling rate: 70%) are dispersed for 30 minutes with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) to obtain an organic pigment dispersion liquid 17 It was. When the dispersibility of the pigment subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 85 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 15 parts of organic pigment dispersion 17 (solid content 20%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax 2 parts of (Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a composition 18 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner mother particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 18 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 2.

[Example 13]
89.9 parts of methanol, 0.1 part of DMAE (dimethylaminoethanol) and 0.5 part of a dispersant represented by the following general formula (13) are added to a glass bottle, and after mixing and stirring, a quinacridone pigment (Pigment Red 122) is added. 9.5 parts were added, and zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain an organic pigment dispersion 18. When the dispersibility of the adsorption-treated pigment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 105 nm.

General formula (13):

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 18 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed from the system while recovering the solvent at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a magenta toner composition 19. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable magenta toner 19 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 2.

[Example 14]
89.9 parts of methyl ethyl ketone, 0.1 part of sodium hydroxide and 0.5 part of a dispersant represented by the following general formula (14) are added to a glass bottle, and after mixing and stirring, 9.5 parts of carbon black (Monarch 280) are added. In addition, zirconia beads were dispersed as media (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain a carbon black dispersion liquid 19. When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 105 nm.

General formula (14):

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 19 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a black toner composition 20. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 20 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 2.

[Example 15]
To a glass bottle, 89.9 parts of methanol, 0.1 part of DMAE (dimethylaminoethanol) and 0.5 part of a dispersant represented by the following general formula (15) were added, mixed and stirred, and then benzimidazolone pigment (Pigment yellow 180). 9.5 parts), and zirconia beads as a medium (diameter: 1.25 mm, filling rate: 70%) are dispersed with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain an organic pigment dispersion 20 It was. When the dispersibility of the pigment subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 85 nm.

Formula (15):

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 20 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding 2 parts of wax (Fischer-Tropsch wax) to the flask and mixing, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 21 for yellow toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, yellow toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the yellow toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged yellow toner 21 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 2.

[Example 16]
Add 89.9 parts of ethanol, 0.1 part of sodium hydroxide and 0.5 part of the dispersant represented by the general formula (16) to a glass bottle, and after mixing and stirring, add 9.5 parts of carbon black (Monarch 280). Then, zirconia beads were dispersed as a medium (diameter: 1.25 mm, filling rate: 70%) with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) for 30 minutes to obtain a carbon black dispersion liquid 21. When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 113 nm.

Formula (16):

  On the other hand, 10 parts of a styrene-methyl methacrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-methyl methacrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 21 (solid content 10%), 940 parts of the styrene-methyl methacrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 22 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 22 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 2.

[Comparative Example 7]
90.0 parts of methanol and 10 parts of carbon black (Monarch 880) are added to a glass bottle, and paint conditioner (Red Devil 5410 single type, 28 ounce mill can) with zirconia beads as media (diameter 1.25 mm, filling rate 70%) For 30 minutes to obtain a carbon black dispersion 22. When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion was confirmed, agglomeration that could be visually confirmed was observed.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 22 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 23 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 23 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 2.

[Comparative Example 8]
Add 89.9 parts of methanol, 0.1 part of DMAE (dimethylaminoethanol) and 10 parts of carbon black (Monarch 880) to a glass bottle, and paint conditioner using zirconia beads as media (diameter 1.25 mm, filling rate 70%). (Red Devil 5410 single type, 28 ounce mill can) was dispersed for 30 minutes to obtain a carbon black dispersion liquid 23. When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion was confirmed, agglomeration that could be visually confirmed was observed.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 23 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed from the system while recovering the solvent at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 24 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added, mixed with a Henschel mixer, and then a negatively charged black toner 24 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 2.

[Comparative Example 9]
Add 80 parts of methanol, 10 parts of Solsperse 20000 (manufactured by Abyssia, alcohol-soluble resin dispersant) and 10 parts of carbon black (Monarch 880) to a glass bottle, and add zirconia beads to media (diameter 1.25 mm, filling rate 70 %) Was dispersed for 30 minutes with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can) to obtain a carbon black dispersion liquid 24. When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 286 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 24 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a black toner composition 25. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 25 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 2.

[Comparative Example 10]
To a glass bottle, 90 parts of methanol and 0.5 part of a dispersant represented by the general formula (12) were added, mixed and stirred, 9.5 parts of carbon black (Monarch 880) was added, and zirconia beads were added to the medium (diameter 1. The carbon black dispersion liquid 25 was obtained by dispersing for 30 minutes with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can). When the dispersibility of the carbon black subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 576 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the carbon black dispersion 25 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed from the system while recovering the solvent at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 26 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable black toner 26 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 2.

[Comparative Example 11]
90 parts of methanol and 10 parts of phthalocyanine blue (Pigment Blue 15: 3) are added to a glass bottle, and paint conditioner (Red Devil 5410 single type, 28 ounce mill can) using zirconia beads as media (diameter 1.25 mm, filling rate 70%) For 30 minutes to obtain an organic pigment dispersion 26. When the dispersibility of the pigment subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 610 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Furthermore, 30 parts of the organic pigment dispersion 26 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) into the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 27 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 27 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, evaluation was performed in the same manner as in Example 2. The results at this time are shown in Table 2.

[Comparative Example 12]
Add 80 parts of methanol, 10 parts of Solsperse 20000 (manufactured by Avicia, alcohol-soluble resin type dispersant) and 10 parts of phthalocyanine blue (Pigment Blue 15: 3) to a glass bottle, and add zirconia beads to media (diameter: 1.25 mm, The organic pigment dispersion liquid 27 was obtained by dispersing for 30 minutes with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can). When the dispersibility of the adsorption-treated pigment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 372 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 27 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 28 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 28 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 2.

[Comparative Example 13]
Add 89.9 parts of methanol, 0.1 part of DMAE (dimethylaminoethanol) and 10 parts of quinacridone pigment (Pigment Red 122) to a glass bottle and paint with zirconia beads as media (diameter 1.25 mm, filling rate 70%). The organic pigment dispersion liquid 28 was obtained by dispersing for 30 minutes with a conditioner (Red Devil 5410 single type, 28 ounce mill can). When the dispersibility of the pigment subjected to the adsorption treatment in the dispersion was confirmed, agglomeration that could be visually confirmed was observed.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 28 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a magenta toner composition 29. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable magenta toner 29 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 2.

[Comparative Example 14]
In a glass bottle, 90 parts of methanol and 0.5 part of a dispersant represented by the general formula (13) were added, mixed and stirred, 9.5 parts of quinacridone pigment (Pigment Red 122) was added, and zirconia beads were added to the media (diameter 1 And an organic pigment dispersion 29 was obtained by dispersing for 30 minutes with a paint conditioner (Red Devil 5410 single type, 28 ounce mill can). When the dispersibility of the pigment subjected to the adsorption treatment in the dispersion liquid was confirmed, the particle diameter of the dispersion liquid was 985 nm.

  On the other hand, 10 parts of a styrene-butyl acrylate copolymer resin was added to 90 parts of toluene in a flask and mixed while dissolving the resin at a temperature of 80 ° C. to obtain a styrene-butyl acrylate copolymer resin solution. Obtained.

  Further, 30 parts of the organic pigment dispersion 29 (solid content 10%), 940 parts of the styrene-butyl acrylate copolymer resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin After adding and mixing 2 parts of wax (Fischer-Tropsch wax) in the flask, the solvent was removed while recovering the solvent outside at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a magenta toner composition 30. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged magenta toner 30 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 2.

[Example 17]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 1 produced in Example 1, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 31 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged cyan toner 31 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm.

  Further, using this cyan toner and developer, evaluation was performed in the same manner as in Example 1, and image density (initial value and value after 30000 sheets), fog (initial value and value after 30000 sheets), and in-machine scattering were evaluated. As a result, good results were obtained. Further, when the image was confirmed after being left for 14 days in the state after 30000 sheets, a satisfactory result was obtained without any decrease in image density or increase in fog due to charge decay. The results at this time are shown in Table 3.

[Example 18]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 2 produced in Example 2, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 32 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 32 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 3.

[Example 19]
Add 10 parts of a non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of xylene in a flask and heat the resin at a temperature of 90 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 3 produced in Example 3, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a cyan toner composition 33. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 33 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 3.

[Example 20]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 4 produced in Example 4, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed while collecting the solvent outside at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a magenta toner composition 34. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized by a jet mill pulverizer and classified by an airflow classifier to obtain magenta toner mother particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged magenta toner 34 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 3.

[Example 21]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts of carbon black dispersion 5 produced in Example 5 (solid content 10%), 940 parts of the above polyester resin solution (solid content 10%), 1 part of aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a composition 35 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 35 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 3.

[Example 22]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 6 produced in Example 6, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 140 ° C. and a pressure of 20 mmHg to obtain a composition 36 for yellow toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, yellow toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the yellow toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged yellow toner 36 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 3.

[Example 23]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the carbon black dispersion 7 produced in Example 7, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 37 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable black toner 37 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 3.

[Example 24]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, pentaerythritol) into 90 parts of toluene, and dissolve the resin at a temperature of 80 ° C. The polyester resin solution was obtained while mixing.

  30 parts (solid content 10%) of the organic pigment dispersion 1 produced in Example 1, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a cyan toner composition 38. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 38 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 3.

[Comparative Example 15]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 8 produced in Comparative Example 1, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 39 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 39 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 3.

[Comparative Example 16]
Meanwhile, 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) was added to 90 parts of toluene in a flask at a temperature of 80 ° C. Mixing was performed while dissolving the resin to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 9 produced in Comparative Example 2, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 40 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 40 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 3.

[Comparative Example 17]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 10 produced in Comparative Example 3, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while collecting the solvent out of the system to obtain a composition 41 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 41 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 3.

[Comparative Example 18]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 11 produced in Comparative Example 4, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 42 for yellow toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, yellow toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the yellow toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged yellow toner 42 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 3.

[Comparative Example 19]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 12 produced in Comparative Example 5, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a magenta toner composition 43. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable magenta toner 43 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 3.

[Comparative Example 20]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 13 produced in Comparative Example 6, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a magenta toner composition 44. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable magenta toner 44 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 3.

[Example 25]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the carbon black dispersion 14 produced in Example 9, 940 parts of the above polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax ( 2 parts of Fischer-Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a composition 45 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 45 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm.

  Furthermore, using this black toner and developer, a real-life test was performed in a single color mode using a commercially available full-color copying machine (CLC-800 manufactured by Canon Inc.), and the image density (initial and values after 30000 sheets), fog (initial) And values after 30000 sheets), evaluation of in-flight scattering gave good results. Further, when the image was confirmed after being left for 14 days in the state after 30000 sheets, a satisfactory result was obtained without any decrease in image density or increase in fog due to charge decay. The results at this time are shown in Table 4.

[Example 26]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts of carbon black dispersion 15 produced in Example 10 (solid content 10%), polyester resin solution 940 parts (solid content 10%), 1 part of aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a black toner composition 46. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 46 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 4.

[Example 27]
Add 10 parts of a non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of xylene in a flask and heat the resin at a temperature of 90 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 16 produced in Example 11 and 940 parts of a polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a composition 47 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 47 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 4.

[Example 28]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  15 parts (solid content 20%) of the organic pigment dispersion 17 produced in Example 12, 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added to and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 48 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner mother particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable cyan toner 48 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 4.

[Example 29]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts of organic pigment dispersion 18 produced in Example 13 (solid content 10%), 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a magenta toner composition 49. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged magenta toner 49 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 4.

[Example 30]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the carbon black dispersion 19 produced in Example 14, 940 parts of a polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added to and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 50 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added, mixed with a Henschel mixer, and then a negatively charged black toner 50 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 4.

[Example 31]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts of the organic pigment dispersion 20 produced in Example 15 (solid content 10%), 940 parts of a polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 140 ° C. and a pressure of 20 mmHg to obtain a composition 51 for yellow toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, yellow toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the yellow toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged yellow toner 51 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 4.

[Example 32]
Add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, pentaerythritol) in 90 parts of toluene and dissolve the resin at a temperature of 80 ° C. The polyester resin solution was obtained while mixing.

  30 parts (solid content 10%) of the carbon black dispersion 21 produced in Example 16 and 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added to and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 52 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added, mixed with a Henschel mixer, and then a negatively charged black toner 52 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Further, when the evaluation was made in the same manner as in Example 1, good results were obtained. The results at this time are shown in Table 4.

[Comparative Example 21]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the carbon black dispersion 22 produced in Comparative Example 7, 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added to and mixed with the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a black toner composition 53. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added, mixed with a Henschel mixer, and then a negatively charged black toner 53 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 4.

[Comparative Example 22]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the carbon black dispersion 23 produced in Comparative Example 8, 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added to and mixed in the flask, and then the solvent was removed while recovering the solvent outside the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 54 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 54 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 4.

[Comparative Example 23]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the carbon black dispersion 24 produced in Comparative Example 9, 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added to and mixed in the flask, and then the solvent was removed while recovering the solvent outside the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 55 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 55 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 4.

[Comparative Example 24]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts of carbon black dispersion 25 produced in Comparative Example 10 (solid content 10%), 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 56 for black toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, black toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the black toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged black toner 56 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 4.

[Comparative Example 25]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 26 prepared in Comparative Example 11, 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added to and mixed with the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a composition 57 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged cyan toner 57 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 4.

[Comparative Example 26]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts of organic pigment dispersion 27 produced in Comparative Example 12 (solid content 10%), 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed at a temperature of 150 ° C. and a pressure of 20 mmHg while recovering the solvent out of the system to obtain a composition 58 for cyan toner. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, after finely pulverizing with a jet mill pulverizer and classification with an airflow classifier, cyan toner base particles having a volume average particle diameter of 10.5 μm were obtained.

  To 100 parts by weight of the cyan toner base particles, 0.25 part by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively charged cyan toner 58 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 4.

[Comparative Example 27]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 28 produced in Comparative Example 13, 940 parts of a polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg to obtain a magenta toner composition 59. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable magenta toner 59 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 4.

[Comparative Example 28]
In a flask, add 10 parts of non-linear polyester resin (synthesized from disproportionated rosin, terephthalic acid, neopentyl glycol, neodecanoic acid glycidyl ester, trimellitic acid) into 90 parts of toluene, and heat the resin at a temperature of 80 ° C. Mixing was performed while dissolving to obtain a polyester resin solution.

  30 parts (solid content 10%) of the organic pigment dispersion 29 produced in Comparative Example 14, 940 parts of polyester resin solution (solid content 10%), 1 part of an aromatic hydroxycarboxylic acid calcium salt compound, paraffin wax (Fischer) 2 parts of Tropsch wax) were added and mixed in the flask, and then the solvent was removed while recovering the solvent out of the system at a temperature of 150 ° C. and a pressure of 20 mmHg. Thus, a magenta toner composition 60 was obtained. And after cooling, the chip | tip was obtained and it grind | pulverized to 3 mm or less with the sample mill, and the chip | tip was obtained. Subsequently, the mixture was finely pulverized with a jet mill pulverizer and classified with an airflow classifier to obtain magenta toner base particles having a volume average particle diameter of 10.5 μm.

  To 100 parts by weight of the magenta toner base particles, 0.25 parts by weight of hydrophobic silica (Aerosil R974) was added and mixed with a Henschel mixer, and then a negatively chargeable magenta toner 60 was obtained through a sieving step. A developer was prepared at a toner concentration of 4% using a silicone resin-coated ferrite carrier having a weight average particle diameter of 60 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The results at this time are shown in Table 4.

The toner for developing an electrostatic charge image of the present invention can be preferably used in an electrophotographic dry developer, a copying machine using the toner, a printer, and the like, and uniformly in a binder resin in a state in which the organic pigment in the toner is miniaturized. Therefore, it is possible to provide a toner having excellent color developability, transparency, color reproducibility, and image quality.

Claims (11)

  An organic pigment or a carbon black dispersion obtained by adsorbing an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group to an organic pigment or carbon black in an organic solvent in the presence of an acid; Alternatively, an organic pigment or carbon black dispersion (A) obtained by adsorbing an organic dye derivative having an acidic functional group or a triazine derivative having an acidic functional group to an organic pigment or carbon black in an organic solvent in the presence of a base. And a colored resin composition (D) obtained by mixing and removing a solution (C) of a resin (B) selected from a styrene-based resin and a polyester resin. Toner for developing electrostatic images.   2. The electrostatic image developing toner according to claim 1, wherein the resin solution (C) further contains at least one of a charge control agent and a release agent. 3.   The electrostatic image developing toner according to claim 1, wherein the adsorption treatment is performed using a media type disperser.   4. The electrostatic image developing toner according to claim 1, wherein the organic solvent used in the organic pigment or the carbon black dispersion (A) contains a protic solvent. Toner.   5. The electrostatic charge image developing toner according to claim 1, wherein the solvent used in the resin solution is a hydrocarbon solvent.   An organic pigment or a carbon black dispersion obtained by adsorbing an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group to an organic pigment or carbon black in an organic solvent in the presence of an acid; Alternatively, an organic pigment or carbon black dispersion (A) obtained by adsorbing an organic dye derivative having an acidic functional group or a triazine derivative having an acidic functional group to an organic pigment or carbon black in an organic solvent in the presence of a base. ) And a solution of a resin (B) selected from a styrene-based resin and a polyester resin, and by removing the solvent, a colored resin composition (C) is formed and the colored resin composition is pulverized. A method for producing a toner for developing an electrostatic charge image.   The method for producing a toner for developing an electrostatic charge image according to claim 6, wherein at least one of a charge control agent and a release agent is further added to and mixed with the resin solution (C). A method for producing a developing toner.   8. The method for producing a toner for developing an electrostatic charge image according to claim 6, wherein the adsorption treatment is performed using a media type dispersing machine.   9. The electrostatic image developing toner according to claim 6, wherein the organic solvent used in the organic pigment or the carbon black dispersion (A) contains a protic solvent. Toner manufacturing method.   10. The method for producing an electrostatic charge image developing toner according to claim 6, wherein the solvent used in the resin solution (C) is a hydrocarbon solvent. . An organic pigment or a carbon black dispersion obtained by adsorbing an organic dye derivative having a basic functional group or a triazine derivative having a basic functional group to an organic pigment or carbon black in an organic solvent in the presence of an acid; Alternatively, an organic pigment or carbon black dispersion (A) obtained by adsorbing an organic dye derivative having an acidic functional group or a triazine derivative having an acidic functional group to an organic pigment or carbon black in an organic solvent in the presence of a base. ) And a solution (C) of a resin (B) selected from styrene-based resins and polyester resins, and the solvent is removed to obtain a colored resin composition for toner.