JP4627233B2 - Toner manufacturing method and toner base particle manufacturing method - Google Patents

Description

  The present invention relates to an electrostatic latent image developing toner and toner base particles used for image formation by an electrostatic copying process such as a copying machine, a facsimile machine, and a printer, and also relates to an image forming apparatus using the toner. is there.

  Electrophotography uses a photoconductive material to form an electrical latent image on a photoreceptor, develop the latent image with toner, transfer the toner image to a recording material such as paper, and then heat and This is a method of fixing by pressure or the like.

In recent years, high-speed copying and high image quality have been demanded for electrophotography.
As a method for producing a toner, a colorant such as a dye and a pigment and an additive such as a charge control agent are melt-mixed in a thermoplastic resin and uniformly dispersed, and then pulverized and classified by a fine pulverizer and a classifier. There is known a pulverization method for producing toner by performing the above.

In these pulverized toners, when a releasable substance such as wax is added,
It is necessary to make the dispersibility of the releasable substance to a sufficient level. For this reason, it is necessary to maintain a certain degree of viscosity at the kneading temperature with the resin, and the content of the releasable substance to be about 5 parts by mass or less per 100 parts by mass of the toner. Due to such restrictions, there is a limit to the toner fixability by the pulverization method.

  In this kneading and pulverizing method, if the solid fine particles such as the colorant are not completely uniformly dispersed in the resin, the toner composition may be distributed and the toner development characteristics may be changed. In addition, image resolution, solid area uniformity, gradation reproducibility, and the like largely depend on the toner characteristics, particularly the particle size, and a smaller particle size particle provides a higher quality image. And high-quality copiers often use small particle size toner. However, when the toner particles are reduced in size by the pulverization method, the volume average particle size is about 5.0 μm.

  In order to obtain a predetermined particle size and particle size distribution with the pulverized toner, a classification step is essential, and fine powder and coarse powder are generated in addition to the predetermined particle size toner. Various ideas have been made for the reuse, and the coarse powder is pulverized again into a fine powder in the manufacturing process. However, as described in Patent Document 1 and the like, the toner fine powder is environmentally friendly, Recycled to the raw material mixing process due to production costs. However, when the toner fine powder is melted and kneaded again by the kneader, the resin molecular cutting in the toner fine powder occurs again, and the fixing performance such as hot offset occurs when the toner is fixed on the paper. Deterioration of durability performance occurred and was not preferable. Thus, various ideas have been proposed, such as processing the fine powder before putting it into the kneading process (Patent Document 2), and it has been widely practiced as a known technique.

  On the other hand, Patent Document 3 and the like propose a method for producing a polymerized toner in which a polymerizable monomer composition having at least a polymerizable monomer is subjected to suspension polymerization, and at the same time, toner particles are obtained. In this suspension polymerization method, a polymerizable monomer and a colorant are uniformly dissolved or dispersed to form a polymerizable monomer composition, and then the polymerizable monomer composition contains a dispersion stabilizer. It is dispersed in a continuous phase such as an aqueous phase using an appropriate stirrer and simultaneously undergoes a polymerization reaction to obtain toner particles having a desired particle size. Because of its advantages, it is attracting attention.

  With polymerized toner, the release agent component can be included in the toner particles with respect to the content and dispersibility of the release agent, so that the content can be increased compared to the pulverized toner and the dispersibility must be satisfied at the same time. Can do. Moreover, about the dispersibility of a coloring agent, it can melt | dissolve or disperse | distribute uniformly with another additive in a polymerizable monomer. Furthermore, a desired particle size and particle size distribution can be obtained depending on the dispersion / granulation conditions, and the toner can be made smaller.

However, this polymerized toner also has the following problems.
Depending on the polymerization reaction conditions and the toner formulation, particle agglomeration occurs during the reaction, and the polymer particle agglomerates adhere to the reaction vessel wall surface, the stirring blade, or the like. Even under production conditions in which the particle size distribution width is sharp and particle aggregation is suppressed as much as possible, the mixing of these coarse particles cannot be completely excluded.

  In addition, in the case of polymerized toner, when toner particles other than predetermined are generated in some form, the particles are designed as a core-shell structure of at least two layers by inclusion of a releasable component, a low energy fixing component and the like. Therefore, it cannot be simply reused like pulverized toner. This is an important examination item to be solved in terms of toner yield. In Patent Document 4, it is proposed to dissolve non-predetermined toner particles in a polymerizable monomer and reuse them. However, only a soluble component in the non-predetermined toner is used for the polymerizable monomer. Insoluble components cannot be used. Further, Patent Document 5 describes a technique of kneading and pulverizing an extra THF-insoluble matter generated at the time of producing a polymerized toner, and charging it into a single monomer or a composition for reuse. However, in recent years when higher image quality is required, image quality problems such as insufficient image density and insufficient fogging have occurred due to reuse, and improvements have been desired.

Japanese Patent Laid-Open No. 5-34976 JP-A-8-69126 Japanese Patent Publication No. 36-10231 JP-A-10-301330 Japanese Patent Laid-Open No. 2004-4798

  Accordingly, the present invention has been made in view of the above problems, and reuses non-predetermined particles generated at the time of preparation of the polymerized toner, so that toner and toner base particles that are environmentally friendly, have high image density, and do not cause fogging. The issue is to provide.

As means for solving the above problems, the present invention has the following features.
In the method for producing a toner of the present invention, a resin dispersion is obtained by dissolving or dispersing a masterbatch containing at least 30 wt% of colorant A in a binder resin in a water-insoluble organic solvent or a polymerizable monomer. the method of manufacturing a toner having a step, the masterbatch, of Nozomu Tokoro toner particle size of the toner you a coloring agent B at least a binder resin fine side and / or the coarse particles side of the waste toner particles C or granulated It is obtained by kneading the granules and the colorant A.
In the method for producing a toner of the present invention, the production method further comprises a volume average particle diameter E of the unnecessary toner particles C on the fine powder side with respect to the volume average particle diameter D of the desired toner. 9 × D.
In the method for producing a toner of the present invention, the production method further comprises a volume average particle size F of the unwanted toner particles C on the coarse powder side of 1.1 × D to 10 to the volume average particle size D of the desired toner. It is xD.
In the toner production method of the present invention, the production method is further characterized in that the volume average particle diameter E of the unnecessary toner particles C on the fine powder side is 0.5 to 5 μm.
In the method for producing a toner of the present invention, the production method is further characterized in that the volume average particle size F of the unnecessary toner particles C on the coarse powder side is 50 μm or less.
In the method for producing a toner of the present invention, the colorant A and the colorant B are further the same colorant.
The toner production method of the present invention is further characterized in that the particles C are non-predetermined particles obtained by toner classification.
The toner production method of the present invention is further characterized in that the particles C are particles obtained by a dry process by melt kneading.

In the manufacturing method of the toner of the present invention, furthermore, the particles C are characterized by a particle obtained in non-aqueous organic solvent.
In the toner manufacturing method of the present invention, the master batch is further obtained by a flushing method.
In the method for producing a toner of the present invention, the master batch is further obtained by particles C and a colorant A.
The toner manufacturing method of the present invention is further characterized in that the toner is a color toner.

The toner production method of the present invention, furthermore, the toner over at least a polymer having a site reactive with a compound having an active hydrogen group, a polyester, a colorant, respectively and a releasing agent in an organic solvent the dissolution or toner over composition dispersed is dispersed in an aqueous medium is extended and / or crosslinking reaction, characterized in that it is obtained by.
In the manufacturing method of the toner of the present invention, furthermore, the toner chromatography is characterized by containing a release agent.
In the manufacturing method of the toner of the present invention, furthermore, the toner over the average circularity is characterized in that at least 0.94.
In the manufacturing method of the toner of the present invention, furthermore, the toner chromatography, the ratio of the volume average particle size in 3.0～8.0Myuemu, volume average particle diameter and (Dv) to the number average particle diameter (Dn) (Dv / Dn) is it being in the range of 1.00 to 1.40.

The toner manufacturing method of the present invention is further characterized in that the toner has a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180.
In the toner manufacturing method of the present invention, the toner has a spindle shape, and the spindle shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (provided that r1 ≧ r2 ≧ r3). ), The ratio (r2 / r1) of the minor axis r2 to the major axis r1 is in the range of 0.5 to 1.0, and the ratio (r3 / r2) of the thickness r3 to the minor axis r2 is 0.7 to It is characterized by being in the range of 1.0.

In the method for producing toner base particles according to the present invention , at least a master batch containing 30 wt% or more of the colorant A in the binder resin is dissolved or dispersed in a water-insoluble organic solvent or a polymerizable monomer. in the production method of the toner base particles having a step of obtaining, the master batch, of Nozomu Tokoro toner particle size of the toner you a coloring agent B at least a binder resin fine side and / or the waste toner particles of the coarse powder side It is obtained by kneading C or a granulated product thereof and colorant A.

As described above, according to the means for solving the above problems, the present invention can provide toner and toner base particles that are excellent in low-temperature fixability and are not limited to styrene / acrylic.
The image forming apparatus of the present invention can provide a good image having a high image density and no fogging.

The toner production method and the toner base particle production method of the present invention involve dissolving or dispersing a master batch containing at least 30 wt% of the colorant A in a binder resin in a water-insoluble organic solvent or a polymerizable monomer. A method for producing a toner having a step of obtaining a resin dispersion and a method for producing toner base particles, wherein the master batch comprises at least a fine powder side and / or a coarse particle having a desired toner particle size containing at least a binder resin and a colorant B. It is obtained by kneading the powder-side unnecessary toner particles C or a granulated product thereof and the colorant A.
The master batch is obtained by combining a colorant and a binder resin. Although the production method will be described later, in the present invention, this is a method for producing a polymerized toner using the master batch, and the toner batch color reproducibility by kneading the particles C or the granulated product thereof, The effect of improving the image density and eliminating the occurrence of fog is obtained. (See Table 1 in the Examples).

The volume average particle diameter E of the unnecessary toner particles C on the fine powder side is preferably 0.1 × D to 0.9 × D with respect to the volume average particle diameter D of the desired toner. When the master batch is formed with a volume average particle diameter E of 0.9 × D or less, color reproducibility is appropriately dispersed when the unnecessary toner particles C on the fine powder side are mixed with the resin and the colorant. Improvement of image density and generation of fog can be suppressed.
The volume average particle diameter E of the unnecessary toner particles C on the fine powder side is more preferably 0.5 to 5 μm.
The volume average particle diameter F of the unwanted toner particles C on the coarse powder side is preferably 1.1 × D to 10D with respect to the volume average particle diameter D of the desired toner. This is because the low-temperature fixability equivalent to that of the predetermined particles can be maintained by reducing the polymer that tends to be a coarse component during toner granulation and the remaining undissolved component in which the toner particles are not uniformly dispersed during oil layer formation. More preferably, the volume average particle size F of the unnecessary toner particles C on the coarse powder side is 50 μm or less.

  Further, the present invention includes a case where the colorant A and the colorant B are the same colorant.

Further, the present invention is characterized in that the particles C are non-predetermined particles obtained in a classification process of toner production.
The non-predetermined particles, which are the particles C of the present invention, are obtained in the process of producing a pulverized toner, and are characterized by being obtained by dry classification by melt kneading. The predetermined outside particles are specifically toner fine powder, and the toner fine powder is not used again in the kneading process, but is used as a raw material in the master batch manufacturing process to produce toner. As a result, there is no occurrence of molecular cutting of the resin in the toner fine powder due to remelting and kneading in the toner fine powder kneading machine as described in the background art, and deterioration of fixing performance such as hot offset when fixing the toner to paper, Further, it is possible to prevent deterioration of the durability performance of the toner.

The predetermined outer particles, which are the particles C of the present invention, are obtained by a step of classifying the particles after dispersing the resin dispersion in an aqueous medium to obtain an emulsion.
This classification step is preferably wet classification. That is, in the PxP method, classification is preferably performed from the end of solvent removal to the time of water washing, and in the suspension polymerization step, from the end of polymerization to the time of water washing. More preferably, after washing once, classification is performed at the second washing. This is because if a dispersant for water is present around the toner particles, the dispersant is also mixed into the master batch.

  In the present invention, the master batch is a flushing method. The flushing method is a method of mixing and kneading an aqueous paste containing a colorant water together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the (wet-classified non-predetermined particles) can be used as they are, it is not necessary to dry them and is preferably used.

  The present invention is characterized in that the total amount of the master batch other than the colorant A is particles C. The binder resin that is the raw material of the masterbatch is configured to be only the binder resin contained in the particles C.

  The present invention is a method for producing a full color toner. When the coloring agent A and the coloring agent B are the same, the case where they are different is included.

  In the present invention, color particles C that cannot be reused may be used for the black toner. In other words, in a full-color image forming apparatus, only black is pulverized toner, and the particles other than the predetermined particles for polymerization are added at the time of premixing in the manufacture of black pulverized toner.

In the present invention, after the non-predetermined particles containing polyester are put into the masterbatch preparation step, dissolved in an organic solvent together with a toner constituent material such as a resin and a release agent, and then granulated and then granulated. There is an effect that the selectivity of the resin is improved by the turbidity method and the PxP method.
The PxP method is one of polymerization methods, and can use a polyester different from the styrene / acrylic resin of the existing polymerization method as a resin, and is a toner production method advantageous for low-temperature fixing and colorization and high gloss. There is a feature that the molecular weight of the toner can be controlled by an extension reaction.

Constituent materials and manufacturing methods of the toner and toner base particles of the present invention will be described.
First, the toner and toner base particles obtained by the PxP method will be described, and then the toner and toner base particles obtained by the suspension polymerization method will be described.
(Modified polyester)
The PxP toner of the present invention contains a modified polyester (i) as a binder resin. The modified polyester (i) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.

  Examples of the modified polyester (i) include urea-modified polyester obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B). As the polyester prepolymer (A) having an isocyanate group, a polyester having a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and having an active hydrogen group is further added to a polyvalent isocyanate compound (PIC). And those reacted with. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

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

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

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

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

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

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

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

The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The modified polyester (i) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10000. When the molecular weight is less than 1000, the elongation reaction hardly occurs, the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (i), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

(Unmodified polyester)
In the present invention, not only the modified polyester (i) is used alone, but also the unmodified polyester (ii) can be contained as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to the single use. Examples of (ii) include polycondensates of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC), which are the same as the polyester component (i), and preferred ones are also the same as (i). . Further, (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, for example, may be modified with a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, the polyester component (i) and (ii) preferably have similar compositions. In the case of containing (ii), the weight ratio of (i) to (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is 1000-10000 normally, Preferably it is 2000-8000, More preferably, it is 2000-5000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. As for the acid value of (ii), 1-5 are preferable, More preferably, it is 2-4. Since a high acid value wax is used as the wax, the low acid value binder leads to electrification and high volume resistance, so that it is easy to match the toner used for the two-component developer.

  The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If the temperature is lower than 35 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.

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

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

  The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant under high shear. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.
The amount of the charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite.

(Release agent)
As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. The effect on high temperature offset is exhibited without applying a release agent such as oil. Examples of such a wax component include the following. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.

(External additive)
Inorganic fine particles are preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner particles. The primary particle diameter of the inorganic fine particles is preferably 5 × ¹⁰ -3 ~2μm, it is particularly preferably 5 × ¹⁰ -3 ~0.5μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.

Such external additives can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
In particular, it is preferable to use hydrophobic silica and hydrophobic titanium oxide obtained by subjecting silica and titanium oxide to the above surface treatment.

Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.
(Production method of toner binder)
The toner binder can be manufactured by the following method. Polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with a polyvalent isocyanate compound (PIC), and the prepolymer (A) which has an isocyanate group is obtained. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond.
When reacting (PIC) and when reacting (A) and (B), a solvent may be used if necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers Inactive to polyvalent isocyanate compounds (PIC) such as benzene (such as tetrahydrofuran).
When the unmodified polyester (ii) is used in combination, (ii) is produced in the same manner as the polyester having a hydroxyl group, and this is dissolved and mixed in the solution after the completion of the reaction (i).

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

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

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

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

As the cationic surfactants, aliphatic primary to have a fluoroalkyl group, 2 primary or secondary amine acids, aliphatic quaternary ammonium, such as perfluoroalkyl (C6 ~ C10) sulfonamide propyl trimethyl ammonium salt Salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries) Smoke), Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footage F-300 (Neos), and the like.

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

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

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

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

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . In addition, when a calcium phosphate salt or other acid that is soluble in alkali is used as the dispersion stabilizer, the calcium phosphate salt is removed from the toner base particles by dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.

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

Next, a constituent material and a manufacturing method of a toner obtained by the suspension polymerization method (in the following description, used to mean including toner base particles) will be described.
In this case, examples of the unnecessary toner particles C include coarse particles, fine particles, and ultrafine particles separated and removed by the classification step. Also, due to fluctuations in manufacturing conditions, toner particles out of the predetermined particle size distribution, particle size distribution range, or abnormalities occurred during the reaction of the polymerized toner, and differed from the predetermined toner physical properties (for example, molecular weight and molecular weight distribution). (Polymer physical properties) polymerized toner particles and the like can also be used as this mixture. Further, deposits on the wall surface of the polymerization tank can also be used as non-predetermined toner.

(Suspension polymerization method) An oil-soluble polymerization initiator, an emulsification method to be described later in an aqueous medium in which a colorant, a release agent and the like are dispersed in a polymerizable monomer and a surfactant and other solid dispersants are contained. To emulsify and disperse. Thereafter, after the polymerization reaction to form particles, a wet treatment for attaching the inorganic fine particles A to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing. Polymerizable monomers such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, acrylamide, methacrylamide, diacetone Functional groups can be introduced on the surface of toner particles by using a part of acrylate or methacrylate such as acrylamide or these methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other amino groups. . Further, by selecting a dispersant having an acid group or a basic group as a dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

Hereinafter, the constituent material and manufacturing method of the suspension polymerization toner will be described in detail.
Examples of the colorant that can be suitably used as a method for producing the suspension polymerization toner include carbon black and the following yellow / magenta / cyan colorants.
As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180, etc. are preferably used.
As the magenta colorant, 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, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.
As the cyan colorant, 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 particularly preferably used.

These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

Release agents usable for the suspension polymerization toner include petroleum wax such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method, polyethylene And natural waxes and derivatives thereof such as carnauba wax and candelilla wax, which include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can also be used.

A charge control agent may be blended in the suspension polymerization toner. A well-known thing can be utilized as a charge control agent. Further, when the toner is produced using a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include, as negative charge control agents, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid and dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, sulfones Examples thereof include a polymer compound having an acid or carboxylic acid group in the side chain, a boron compound, a urea compound, a silicon compound, and a calixarene. Examples of positive charge control agents include quaternary ammonium salts, polymer compounds having the quaternary ammonium salt in the side chain, guanidine compounds, nigrosine compounds, imidazole compounds, and the like.

As a method of adding a charge control agent to the toner, there are a method of adding it inside the toner base particles and a method of adding it externally. The amount of these charge control agents used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. When added internally, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. In addition, when externally added, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner.

Examples of the polymerizable monomer constituting the polymerizable monomer system used in the suspension polymerization toner include the following.
Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, Acrylic esters such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. , Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, Methacrylic acid dimethyl aminoethyl methacrylate esters such as diethylaminoethyl methacrylate and other acrylonitrile-methacrylonitrile-monomer acrylamide.

In the production of the suspension polymerization toner, a resin may be added to the monomer system for polymerization. For example, it contains hydrophilic functional groups such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups that cannot be used because monomers are water-soluble and dissolve in aqueous suspension to cause emulsion polymerization. In order to introduce these monomer components into the toner, random copolymers of these with vinyl compounds such as styrene or ethylene, block copolymers, graft copolymers, or the like, or polyester It can be used in the form of a polycondensate such as polyamide, or a polyaddition polymer such as polyether or polyimine.

Examples of the alcohol component and the acid component constituting the polyester resin used in the suspension polymerization toner are shown below. As alcohol components, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Examples include diol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, and hydrogenated bisphenol A.

As the divalent carboxylic acid, benzene dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or the anhydride thereof; alkyl dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid or the anhydride, Furthermore, succinic acid substituted with an alkyl or alkenyl group having 6 to 18 tannes or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or an anhydride thereof.

In addition, polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolac type phenol resins can be cited as the alcohol component, and trimellitic acid, pyromellitic acid, 1,2,3,4- Examples thereof include polyvalent carboxylic acids such as butanetetracarboxylic acid, benzophenonetetracarboxylic acid and anhydrides thereof.

It is preferable that 45-55 mol% of the said polyester resin is an alcohol component, and 55-45 mol% is an acid component in all the components.

In suspension polymerization, two or more polyester resins may be used in combination as long as the physical properties of the resulting toner particles are not adversely affected, or the physical properties may be adjusted by modification with, for example, silicone or a fluoroalkyl group-containing compound. It is suitably performed.

Moreover, when using the high molecular polymer containing such a polar functional group, the average molecular weight is preferably 5,000 or more.

In addition, resins other than those mentioned above may be added to the monomer system. Examples of the resin used include styrene such as polystyrene and polyvinyltoluene, and homopolymers of substitution products thereof; styrene-propylene copolymer, styrene -Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer Polymer, styrene-vinyl methyl ether copolymer, steel -Vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, Phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins and the like can be used alone or in combination.

As addition amount of these resin, 1-20 mass parts is preferable with respect to 100 mass parts of monomers. If it is less than 1 part by mass, the effect of addition is small, while if it exceeds 20 parts by mass, it becomes difficult to design various physical properties of the polymerized toner.

Further, a polymer having a molecular weight different from the molecular weight range of the toner obtained by polymerizing the monomer may be dissolved in the monomer for polymerization.

The polymerization initiator used in the production of the suspension polymerization toner has a half-life of 0.5 to 30 hours during the polymerization reaction, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the polymerization reaction is carried out in an added amount, a polymer having a maximum between 10,000 and 100,000 in molecular weight can be obtained, and desired strength and suitable melting characteristics can be imparted to the toner. Examples of polymerization initiators include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, Examples thereof include peroxide-based polymerization initiators such as cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, and t-butylperoxy 2-ethylhexanoate.

In producing the suspension polymerization toner, a crosslinking agent may be added, and the preferable addition amount is 0.001 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

Here, as the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used, for example, an aromatic divinyl compound such as divinylbenzene, divinylnaphthalene, etc .; for example, ethylene glycol diacrylate, ethylene glycol diester Carboxylic acid ester having two double bonds such as methacrylate, 1,3-butanediol dimethacrylate, etc .; Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, etc .; and having three or more vinyl groups Are used alone or as a mixture.

In the suspension polymerization toner, a seed polymerization method in which a monomer is further adsorbed to the once obtained polymer particles and then polymerized using a polymerization initiator can be suitably used in the present invention. At this time, it is also possible to use a compound having polarity dispersed or dissolved in the monomer to be adsorbed.

In suspension polymerization, generally the above-mentioned toner composition, that is, components necessary for the toner such as pigment, mold release agent, plasticizer, charge control agent, cross-linking agent and other additives in the polymerizable monomer, for example, An aqueous system containing a dispersion stabilizer is a monomer system in which an organic solvent, a high molecular weight polymer, a dispersing agent, etc., which are added to lower the viscosity of the polymer produced by the polymerization reaction, are added as appropriate and uniformly dissolved or dispersed. Suspend in medium. At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size at a stretch. The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Further, during the granulation, a polymerization initiator dissolved in a polymerizable monomer or a solvent can be added immediately after the granulation and before starting the polymerization reaction.

After granulation, stirring may be performed using a normal stirrer to such an extent that the particle state is maintained and particle floating and sedimentation are prevented.

In the case of producing a suspension polymerization toner, known surfactants and organic / inorganic dispersants can be used as dispersion stabilizers. In particular, inorganic dispersants are unlikely to produce harmful ultrafine powders, and their steric hindrance prevents dispersion stability. Therefore, even if the reaction temperature is changed, the stability is not easily lost, the washing is easy and the toner is not adversely affected. Examples of such inorganic dispersants include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate, carbonates such as calcium carbonate and magnesium carbonate, calcium metasuccinate, calcium sulfate and barium sulfate. Inorganic oxides such as inorganic salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina can be mentioned.

These inorganic dispersants are desirably used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. However, although it is difficult to generate ultrafine particles, it is somewhat difficult to atomize the toner. Therefore, you may use 0.001-0.1 mass part surfactant together.

Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, the inorganic dispersant particles can be generated and used in an aqueous medium. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed with high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At the same time, a water-soluble sodium chloride salt is produced as a by-product. However, if a water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and an ultrafine toner based on emulsion polymerization is produced. Since it becomes difficult to generate | occur | produce, it is more convenient. Since it becomes an obstacle when removing the remaining polymerizable monomer at the end of the polymerization reaction, it is better to replace the aqueous medium or desalinate with an ion exchange resin. The inorganic dispersant can be almost completely removed by dissolving with an acid or alkali after completion of the polymerization.

In the polymerization step, the polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. When the polymerization is carried out in this temperature range, the release agent and wax to be sealed inside are precipitated by phase separation, and the encapsulation is more complete. In order to consume the remaining polymerizable monomer, the reaction temperature can be increased to 90 to 150 ° C. at the end of the polymerization reaction.

After the polymerization is completed, the polymerized toner particles are filtered, washed and dried by a known method to obtain toner base particles, and further, inorganic fine powder is mixed and adhered to the surface to obtain a toner. Moreover, it is one of the desirable forms of this invention to put a classification process in a manufacturing process and to cut coarse powder and fine powder.

In the suspension polymerization toner, an inorganic fine powder having a number average primary particle size of 4 to 80 nm is preferably added as a fluidizing agent.
As the inorganic fine particles used, silica, alumina, titanium oxide and the like can be used. For example, as the silicic acid fine powder, both a so-called dry method produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass or the like can be used. However, dry silica is preferred because it has few silanol groups on the surface and inside of the silica fine powder, and few production residues such as Na ₂ O, SO ₃ ^— . In dry silica, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Is also included.

The addition amount of inorganic fine particles having an average primary particle size of 4 to 80 nm is preferably 0.1 to 3.0% by mass with respect to the toner base particles, and the effect is obtained when the addition amount is less than 0.1% by mass. It is not sufficient, and if it exceeds 3.0% by mass, the fixing property is deteriorated.
In addition, content of inorganic fine powder can be quantified using the analytical curve created from the standard sample using the fluorescent X ray analysis.
The inorganic fine particles are preferably hydrophobized in view of characteristics in a high temperature and high humidity environment.

As treatment agents for hydrophobic treatment, treatment agents such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds may be used alone or in combination. And may be processed.
As a method for treating inorganic fine particles, for example, a silylation reaction can be performed as a first-stage reaction to eliminate silanol groups by chemical bonding, and then a hydrophobic thin film can be formed on the surface with silicone oil as a second-stage reaction. .
The silicone oil preferably has a viscosity at 25 ° C. of 10 to 200,000 mm ² / s, more preferably 3,000 to 80,000 mm ² / s. If it is less than 10 mm ² / s, the inorganic fine particles are not stable, and the image quality tends to deteriorate due to heat and mechanical stress. If it exceeds 200,000 mm ² / s, uniform processing tends to be difficult.

As the silicone oil used, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.
As a method for treating silicone oil, for example, silica treated with a silane compound and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or a method of spraying silicone oil on silica may be used. Also good. Alternatively, after dissolving or dispersing silicone oil in a suitable solvent, silica fine powder may be added and mixed to remove the solvent. A method using a sprayer is more preferable in that the formation of inorganic fine particle aggregates is relatively small.

The treatment amount of the silicone oil is 1 to 40 parts by mass, preferably 3 to 35 parts by mass with respect to 100 parts by mass of silica.
Silica used in the suspension polymerization toner preferably has a specific surface area measured by the BET method by nitrogen adsorption in the range of ²⁰ to 350 m ² / g in order to impart good fluidity to the toner. The thing of 25-300 m < ² > / g is still better.
In accordance with the BET method, the specific surface area is obtained by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) and calculating the specific surface area using the BET multipoint method.

The suspension polymerization toner can be used as a one-component developer. For example, in the case of a polymerized toner in which a magnetic material is contained in the toner as a one-component developer, there is a method of transporting and charging the polymerized toner using a magnet incorporated in the developing sleeve. However, the developer is not necessarily limited to the one-component developer as described above, and may be used as a two-component developer.

When used as a two-component developer, a carrier is used as a developer together with a suspension polymerization toner. The magnetic carrier is composed of an element composed of iron, copper, zinc, nickel, cobalt, manganese, chromium element alone or in a composite ferrite state. The magnetic carrier has a spherical shape, a flat shape, or an indeterminate shape. Furthermore, it is preferable to control the fine structure (for example, surface unevenness) of the surface state of the magnetic carrier particles. In general, after the inorganic oxide is fired and granulated, magnetic carrier core particles are generated in advance and then coated on a resin. From the viewpoint of reducing the load on the toner of the magnetic carrier, a method of obtaining a low density dispersion carrier by kneading and classifying the inorganic oxide and the resin, and further kneading the inorganic oxide and the monomer directly. A method of obtaining a true spherical magnetic carrier by suspension polymerization in an aqueous medium can also be used.

The average circularity of the toner is preferably in the range of 0.94 to 1.00. When the average circularity is less than 0.94 and the toner has a shape separated from the spherical shape, it is difficult to obtain a satisfactory transfer property or a high-quality image without dust. Such irregularly shaped particles have many points of contact with the smooth medium on the photoreceptor and the charge concentrates on the tip of the protrusion, so van der Waals force and mirror force are more than those with relatively spherical particles. Wearing power is high. For this reason, in the electrostatic transfer process, the spherical particles are selectively moved in the toner in which the amorphous particles and the spherical particles are mixed, and the character portion and the line portion image are lost. In addition, the remaining toner must be removed for the next development process, and there is a problem that a cleaning device is required or the toner yield (the ratio of toner used for image formation) is low. .
The circularity of the toner is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, the measurement is performed using a flow particle image analyzer (FPIA-2100; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 mL of water from which impure solids are removed in advance is added, 0.1 to 0.5 mL of a surfactant is added as a dispersant, and about 0.1 to 9.5 g of a measurement sample is further added. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration and dispersion of the dispersion are set to 3,000 to 10,000 / μL, and the shape and distribution of the toner are measured.

The toner has a volume average particle diameter (Dv) of 3.0 to 8.0 μm and a ratio (Dv / Dn) to the number average particle diameter (Dn) of 1.00 to 1.40. Preferably, the toner has a volume average particle size of 3.0 to 6.0 μm and a Dv / Dn of 1.00 to 1.15, so that any of heat resistant storage stability, low temperature fixability and hot offset resistance can be obtained. In particular, when used in a full-color copying machine, the glossiness of the image is excellent.
Generally, it is said that the smaller the toner particle size, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced. When used as a system developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
In addition, these phenomena are greatly related to the content of fine powder. Particularly, when the particle diameter of the toner exceeds 3%, the adhesion to the magnetic carrier and the stability of charging at a high level are hindered. Become.
Conversely, when the volume average particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of the toner in the developer is performed. In many cases, the variation in the particle diameter of the toner increases. Further, when Dv / Dn exceeds 1.40, the resolving power decreases. When the volume average particle size is less than 3.0 μm, there is a concern about the influence on the human body due to the floating of the toner. When the volume average particle size exceeds 8.0 μm, the sharpness of the toner image on the photoreceptor is lowered and the resolution is also lowered.

  The average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter), laser diffraction / scattering LA-920 (manufactured by Horiba). . In the present invention, a Coulter counter TA-II type was used and connected to an interface (manufactured by Nikka Giken) and a PC9801 personal computer (manufactured by NEC) to output the number distribution and volume distribution.

The toner of the present invention is preferably a toner having a shape factor SF-1 in the range of 100 to 180 and SF-2 in the range of 100 to 180.
The shape factors SF-1 and SF-2 are represented by the following formulas (1) and (2).
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1)
SF-2 = {(PERI) ² / AREA} × (100 / 4π) (2)
When the value of SF-1 is 100, the shape of the toner becomes a true sphere, and becomes larger as the value of SF-1 increases. Further, when the value of SF-2 is 100, the unevenness does not exist on the toner surface, and as the SF-2 value increases, the unevenness of the toner surface becomes more prominent. FIG. 1A is a schematic diagram of a toner shape for explaining SF-1 and FIG. 1B is a diagram for explaining SF-2.
Specifically, the shape factor is measured by taking a photograph of the toner with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.), introducing it into an image analyzer (LUSEX 3: manufactured by Nireco) and analyzing it. Calculated.

  When the shape factors SF-1 and SF-2 are both close to 100 and the shape of the toner is close to a true sphere, the contact between the toner and the toner or the toner and the image carrier becomes a point contact. Accordingly, the fluidity is increased and the adhesion between the toner and the image carrier is also weakened, and the transfer rate is increased. The dot reproducibility is also improved. On the other hand, when the toner shape factors SF-1 and SF-2 are large to some extent, the margin for cleaning increases, and there is no problem such as defective cleaning. Therefore, it is preferable that the shape factors SF-1 and SF-2 are in the range of 100 to 180 as a range in which the image quality is not deteriorated from the balance between the two.

The toner of the present invention has a spindle shape and can be represented by the following shape rule.
FIG. 2 is a diagram schematically showing the shape of the toner of the present invention. In FIG. 2, when a spindle-shaped toner is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), the toner of the present invention has a minor axis and a major axis. The ratio (r2 / r1) (see FIG. 2B) is 0.5 to 1.0, and the ratio of thickness to minor axis (r3 / r2) (see FIG. 2C) is 0.7 to 1. Preferably it is in the range of 0.0. If the ratio of the minor axis to the major axis (r2 / r1) is less than 0.5, the distance from the true spherical shape is inferior, so that dot reproducibility and transfer efficiency are inferior, and high quality image quality cannot be obtained. If the ratio of thickness to short axis (r3 / r2) is less than 0.7, the shape is close to a flat shape, and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the minor axis (r3 / r2) is 1.0, the rotating body has a major axis as a rotation axis, and the fluidity of the toner can be improved.
Note that r1, r2, and r3 were measured with a scanning electron microscope (SEM) while changing the angle of field of view and taking pictures.

The toner produced as described above can also be used as a one-component magnetic toner that does not use a magnetic carrier or a non-magnetic toner.
When used in a two-component developer, it may be used by mixing with a magnetic carrier, and the magnetic carrier is a ferrite containing a divalent metal such as iron, magnetite, Mn, Zn, Cu, A volume average particle size of 20 to 100 μm is preferred. If the average particle size is less than 20 μm, carrier adhesion is likely to occur on the photoreceptor during development, and if it exceeds 100 μm, the miscibility with the toner is low, the toner charge amount is insufficient, and charging failure during continuous use is likely to occur. . Further, Cu ferrite containing Zn is preferable because of high saturation magnetization, but can be appropriately selected according to the process of the image forming apparatus. The resin for coating the magnetic carrier is not particularly limited, and examples thereof include silicone resin, styrene-acrylic resin, fluorine-containing resin, and olefin resin. The manufacturing method may be that the coating resin is dissolved in a solvent, sprayed into the fluidized bed and coated on the core, or the resin particles are electrostatically attached to the core particles and then melted by heat to coat. You may do. The resin to be coated has a thickness of 0.05 to 10 μm, preferably 0.3 to 4 μm.

An image forming apparatus using the toner of the present invention as a developer will be described.
FIG. 3 is a schematic diagram showing the configuration of an embodiment of the image forming apparatus according to the present invention. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which it is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) further mounted thereon.
The copying apparatus main body 100 has a tandem type in which four image forming units 18 each having various units for performing an electrophotographic process such as charging, developing, and cleaning are arranged in parallel around a photosensitive member 40 as a latent image carrier. An image forming apparatus 20 is provided. Above the tandem image forming apparatus 20, there is provided an exposure apparatus 21 that exposes the photoreceptor 40 with laser light based on image information to form a latent image. Further, an intermediate transfer belt 10 made of an endless belt member is provided at a position facing each photoconductor 40 of the tandem type image forming apparatus 20. A primary transfer unit 62 for transferring the toner images of the respective colors formed on the photoconductor 40 to the intermediate transfer belt 10 is disposed at a position facing the photoconductor 40 via the intermediate transfer belt 10.
A secondary transfer device 22 that collectively transfers the toner images superimposed on the intermediate transfer belt 10 onto transfer paper conveyed from the paper feed table 200 is disposed below the intermediate transfer belt 10. The secondary transfer device 22 is configured by spanning a secondary transfer belt 24 that is an endless belt between two rollers 23, and is disposed by pressing against the support roller 16 via the intermediate transfer belt 10. The toner image on 10 is transferred onto a transfer sheet. A fixing device 25 for fixing the image on the transfer paper is provided beside the secondary transfer device 22.
The secondary transfer device 22 described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveyance function together.
In the illustrated example, a sheet reversing device 28 for reversing the transfer paper so as to record an image on both sides of the transfer paper is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. Prepare.

For the developing device of the image forming means 18, the developer containing the toner is used. In the developing device, the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 40 to develop the latent image on the photoconductor 40. By applying the alternating electric field, the developer is activated, the charge amount distribution of the toner can be narrowed, and the developability can be improved.
In addition, the photosensitive member 40 and the developing device are integrally supported, and the process cartridge can be formed to be detachable from the main body of the image forming apparatus. In addition, the process cartridge may include a charging unit and a cleaning unit.

The operation of the image forming apparatus is as follows.
First, a document is set on the document table 30 of the automatic document feeder 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. Hold it down.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34 and reflects by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.

  When a start switch (not shown) is pressed, one of the support rollers 14, 15 and 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer belt 10 is rotated and conveyed. To do. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer belt 10, the monochrome images are sequentially transferred to form a composite color image on the intermediate transfer belt 10.

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one and put into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer belt 10, the sheet is fed between the intermediate transfer belt 10 and the secondary transfer device 22, and is transferred by the secondary transfer device 22. A color image is recorded on the sheet.

The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
On the other hand, the intermediate transfer belt 10 after image transfer is removed by the intermediate transfer belt cleaning device 17 to remove residual toner remaining on the intermediate transfer belt 10 after image transfer, and is prepared for re-image formation by the tandem image forming apparatus 20. .

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. “Part” means part by weight.
[Comparative Example 1]
After warming the 0.1 M -Na ₃ PO ₄ aqueous solution 451 parts of the closing and 60 ° C. in deionized water 709 parts and stirred at 12,000rpm using a TK homomixer. To this, 68 parts of 1.0 M CaCl ₃ aqueous solution was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ . 170 parts of styrene, 30 parts of 2-ethylhexyl acrylate, 10 parts of magenta pigment (CI Pigment Red 122), 60 parts of paraffin wax (sp. 70 ° C.), 5 parts of a metal compound of di-tert-butylsalicylate, styrene-methacryl 10 parts of an acid copolymer (Mw 50,000, acid value 20 mgKOH / g) was put into a TK homomixer, heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm. In this, 10 parts of a polymerization initiator, 2,2′-azobis (2,4-dimethylvaleronitrile), was dissolved to prepare a polymerizable monomer system. The polymerizable monomer system was put into the aqueous medium and stirred at 10,000 rpm for 20 minutes in a TK homomixer at 60 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer system. Then, after making it react with a paddle stirring blade for 3 hours at 60 degreeC, liquid temperature was made 80 degreeC and it was made to react for 10 hours. After completion of the polymerization reaction, the mixture is cooled and hydrochloric acid is added to dissolve calcium phosphate, followed by filtration, washing with water, drying and classification, Dv = 5.9 μm, Dv / Dn = 1.11, 4 μm or less = 6 number%, 12. 7 μm or more = 0.4% by number of [Toner Base 1] was obtained. Further, the toner adhering to the fine powder side, the coarse powder side, and the classifier generated as a by-product during classification was collected and uniformly mixed to obtain [predetermined outer particle 1]. The predetermined outer particles had Dv = 7.6 μm, Dv / Dn = 1.40, 4 μm or less = 30 number%, and 12.7 μm or more = 10 number%.

[Comparative Example 2]
After warming the 0.1M-Na ₃ PO ₄ aqueous solution 451 parts of the closing and 60 ° C. in deionized water 709 parts and stirred at 12,000rpm using a TK homomixer. To this, 68 parts of 1.0 M CaCl ₃ aqueous solution was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ . 153 parts of styrene, 27 parts of 2-ethylhexyl acrylate, 9 parts of magenta pigment (CI Pigment Red 122) and [predetermined outer particle 1] are kneaded at 150 ° C. for 30 minutes using two rolls, rolled, cooled and pulverized with a pulverizer. [ Kneaded particles 1 of non-predetermined particles] 29 parts (10% by weight based on the toner raw material), 54 parts of paraffin wax (sp. 70 ° C.), 5 parts of di-tert-butylsalicylic acid metal compound, styrene-methacrylic acid 9 parts of a copolymer (Mw 50,000, acid value 20 mgKOH / g) was put into a TK homomixer, heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm. A polymerization initiator, 9 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), was dissolved in this to prepare a polymerizable monomer system. The polymerizable monomer system was put into the aqueous medium and stirred at 10,000 rpm for 20 minutes with a TK homomixer at 60 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer system. Then, after making it react with a paddle stirring blade for 3 hours at 60 degreeC, liquid temperature was made 80 degreeC and it was made to react for 10 hours. After completion of the polymerization reaction, the mixture was cooled and hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water, drying and classification, Dv = 6.0 μm, Dv / Dn = 1.12, 4 μm or less = 5% by number, 12.7 μm. Above = 0.4% by number of [Toner Base 2] was obtained.
Non-prescribed particle reuse example 1
120 parts of water, 20 parts of [predetermined outer particle 1], 90 parts of magenta pigment (CI Pigment Red 122), styrene-methacrylic acid copolymer (Mw 50,000, acid value 20 mgKOH)
/ G) Add 90 parts, mix with a Henschel mixer (Mitsui Mining Co., Ltd.), knead the mixture for 30 minutes at 150 ° C. using two rolls, roll cool and crush with a pulverizer to obtain [Masterbatch 1] It was.

[Example 1]
After warming the 0.1M-Na ₃ PO ₄ aqueous solution 451 parts of the closing and 60 ° C. in deionized water 709 parts and stirred at 12,000rpm using a TK homomixer. To this, 68 parts of 1.0 M CaCl ₃ aqueous solution was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ . 153 parts of styrene, 27 parts of 2-ethylhexyl acrylate, 20 parts of [Masterbatch 1], 54 parts of paraffin wax (sp. 70 ° C.), 5 parts of metal compound of di-tert-butylsalicylate, styrene-methacrylic acid copolymer 9 parts (Mw 50,000, acid value 20 mgKOH / g) was put into a TK homomixer, heated to 60 ° C., and uniformly dissolved and dispersed at 12,000 rpm. A polymerization initiator, 9 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), was dissolved in this to prepare a polymerizable monomer system. The polymerizable monomer system was put into the aqueous medium and stirred at 10,000 rpm for 20 minutes in a TK homomixer at 60 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer system. Then, after making it react with a paddle stirring blade for 3 hours at 60 degreeC, liquid temperature was made 80 degreeC and it was made to react for 10 hours. After completion of the polymerization reaction, the mixture was cooled and hydrochloric acid was added to dissolve calcium phosphate, followed by filtration, washing with water, drying and classification, Dv = 5.9 μm, Dv / Dn = 1.11, 4 μm or less = 6 number%, 12.7 μm. Above = 0.4% by number of [Toner Base 3] was obtained.

[Comparative Example 3]
(1)-Synthesis of organic fine particle emulsion 1-
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 15 parts of a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [resin fine particle dispersion 1] was obtained. The weight average particle diameter of the [resin fine particle dispersion 1] measured by LA-920 was 60 nm. A portion of [resin fine particle dispersion 1] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase-
990 parts of water, [resin fine particle dispersion 1 83 parts of a 48.5% aqueous solution of dodecyl diphenyl ether sodium Terujisuruhon acid (ELEMINOL MON-7: Sanyo Chemical Industries, Ltd.) 37 parts, were mixed and stirred to 90 parts of ethyl acetate, milky Obtained liquid. This is designated as [Aqueous Phase 1].
(3)-Synthesis of low molecular weight polyester 1-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then put 44 parts of trimellitic anhydride into the reaction vessel, and at 180 ° C. under normal pressure. The mixture was reacted for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.
(4) Synthesis of intermediate polyester and prepolymer
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 682 parts bisphenol A ethylene oxide 2-mole adduct, 81 parts bisphenol A propylene oxide 2-mole adduct, 283 parts terephthalic acid, 22 parts trimellitic anhydride and 2 parts of dibutyltin oxide was added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1].
[Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.
(5)-Synthesis of ketimine-
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.
(6)-Synthesis of master batch-
Add 1200 parts of water, 800 parts of magenta pigment (CI Pigment Red 180) and 1200 parts of polyester resin, mix with a Henschel mixer (Mitsui Mining Co., Ltd.), and knead the mixture at 150 ° C. for 30 minutes using two rolls. Then, after rolling and cooling, the mixture was pulverized with a pulverizer to obtain [Masterbatch 2].
(7)-Creation of oil phase-
A container equipped with a stir bar and a thermometer was charged with 378 parts of [low molecular polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 2] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.
[Toner Base 4] was obtained using the following materials by the following operating means.
(8)-Emulsification->Aging-> Solvent removal-
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute After mixing, 1200 parts of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsified Slurry 1].
[Emulsion slurry 1] is put into a container in which a stirrer with a vertical blade and a thermometer is set, and is aged for 90 minutes at 200 rpm and 28 ° C. Then, after removing the solvent at 30 ° C. for 8 hours, [dispersion Slurry 1] was obtained.
(9) ~ Cleaning ⇒ Drying ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure, a: 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed 12,000 rpm for 10 minutes), and then filtered.
b: 100 parts of 10% hydrochloric acid was added to the filter cake of a and mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), followed by filtration.
c: 300 parts of ion exchange water at 25 ° C. is added to the filter cake of b, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice to obtain [Filter cake 1]. It was. [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and classified, and Dv = 5.8 μm, Dv / Dn = 1.12, 4 μm or less = 7% by number, 12.7 μm or more = 0. 5% by number of [Toner Base 4] was obtained. Further, the fine particles, the coarse particles, and the toner adhering to the classifier, which are generated as by-products during classification, are collected, and Dv = 3.2 μm, Dv / Dn = 1.28, 4 μm or less = 75. Number%, 12.7 μm or more = 0% by weight [predetermined outer particle 2], Dv = 13.9 μm, Dv / Dn = 3.43, 4 μm or less = 45.7 number%, 12.7 μm As above, [predetermined outer particles 4] on the number side of 50% by number coarse powder was obtained.

[Comparative Example 4]
[Synthesis of Toner Base 5]
In Comparative Example 3 (7)-Preparation of oil phase-[Master batch 2] 500 parts, magenta pigment (CI Pigment Red 180) 90 parts, [predetermined outer particle 2] 10 parts (10% relative to the toner raw material) In the same manner as in Comparative Example 3, Dv = 5.9 μm, Dv / Dn = 1.13, 4 μm or less = 6 number%, 12.7 μm or more = 0.4 number% [toner base 5 ] Was obtained.

[Example 2]
Non-specified particle reuse example 2
~ Master batch synthesis ~
Add 1200 parts of water, 720 parts of magenta pigment (CI Pigment Red 180), 480 parts of [low molecular weight polyester 1] and 800 parts of [predetermined outer particle 2], and mix with a Henschel mixer (Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 3] was obtained.
[Synthesis of Toner Base 6]
Dv = 5.8 μm in the same manner as in Comparative Example 3 except that 500 parts of [Masterbatch 2] was changed to 500 parts of [Masterbatch 3] in (7) of Comparative Example 3—Preparation of oil phase— Dv / Dn = 1.12, 4 μm or less = 7% by number, and 12.7 μm or more = 0.4% by number [Toner Base 6].

[Example 3]
Reuse of non-specified particles of pulverized toner 90 parts of [low molecular weight polyester], 10 parts of magenta pigment (CI Pigment Red 180), 2 parts of di-tert-butylsalicylic acid zinc compound (BONTRON E-84) in a Henschel mixer After sufficiently stirring and mixing, the mixture is heated and melted at a temperature of 130 to 140 ° C. for about 30 minutes with a roll mill, cooled to room temperature, the obtained kneaded product is pulverized and classified with a jet mill, classified, and [toner base], The toner adhered to the fine powder side, the coarse powder side, and the classifier generated as a by-product during classification was collected and mixed uniformly to obtain [predetermined outer particle 3]. The predetermined outer particles had Dv = 8.4 μm, Dv / Dn = 1.55, 4 μm or less = 45 number%, 12.7 μm or more = 10 number%.
Reuse of non-specified particles 3
~ Master batch synthesis ~
Add 1200 parts of water, 720 parts of magenta pigment (CI Pigment Red 180), 480 parts of [low molecular weight polyester 1] and 800 parts of [predetermined outer particle 3], and mix with a Henschel mixer (Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 4] was obtained.
[Synthesis of Toner Base 7]
Dv = 5.7 μm, in the same manner as in Example 2 except that (Master batch 3) 500 parts was changed to [Master batch 4] 500 parts in (7)-Preparation of oil phase in Example 2 [Toner base 7] having Dv / Dn = 1.13, 4 μm or less = 9% by number, and 12.7 μm or more = 0.3% by number was obtained.

[Example 4]
Non-specified particle reuse example 4
~ Master batch synthesis ~
Add 1200 parts of water, 720 parts of magenta pigment (CI Pigment Red 180), 480 parts of [low molecular weight polyester 1] and 800 parts of [predetermined outer particle 4], and mix with a Henschel mixer (Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 5] was obtained.
[Synthesis of Toner Base 6]
Dv = 5.9 μm in the same manner as in Comparative Example 3, except that 500 parts of [Masterbatch 2] was changed to 500 parts of [Masterbatch 5] in (7) of the Comparative Example 3 to creation of the oil phase. Dv / Dn = 1.11, 4 μm or less = 8 number%, and 12.7 μm or more = 0.5 number% [Toner Base 8].

  Next, 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) is added to 100 parts of each of the obtained toner bases (1) to (8), and the peripheral speed is 30 m / sec using a Henschel mixer. As a result, 30 cycles of mixing and 1 minute of rest were performed for 5 cycles to obtain toners a to h.

[Example of carrier production]
Silicone resin (organostraight silicone) 100 parts Toluene 100 parts γ- (2-Aminoethyl) aminopropyltrimethoxysilane 5 parts Carbon black 10 parts The above mixture was dispersed with a homomixer for 20 minutes to prepare a coating layer forming solution. This coating layer forming liquid was coated on the surface of 1,000 parts of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus to obtain a magnetic carrier A. The toner a to g 5 parts and the magnetic carrier A 95 parts were mixed with a ball mill to prepare two-component developers 1 to 8, and the following evaluation was performed.

The evaluation results are shown in Table 1.
(Evaluation item)
The developers 1 to 7 were set in an IPSIO color 8000 machine manufactured by Ricoh, and the following evaluation was performed after outputting 50000 charts with a 5% image area ratio.
(Color reproducibility)
The color reproducibility was evaluated by creating a solid image with an adhesion amount of 0.40 ± 0.03 mg / cm ^{2 on} a transfer paper (TYPE 6000 <70 W>, manufactured by Ricoh), and the saturation of the solid image at this time. (C *) was measured by X-Rite 938 and ranked by the following 5 criteria. Here, the higher the saturation, the better the color reproducibility.
(Image density)
After outputting a solid image, the image density was measured by X-Rite (manufactured by X-Rite). This was measured at five points, and the average was obtained. A practical level of 1.4 or higher.
(Fog)
The blank paper image was stopped during development, the developer on the photoconductor after development was transferred to tape, and the difference from the image density of the untransferred tape was measured with a 938 spectrocytometer (manufactured by X-Rite). Evaluation was made with “◯ (good)” when the difference from the image density of the untransferred tape was 0.05 or less, and “× (defective)” when the difference was higher.
A: 76 or more B: 72-76
□: 68-72
Δ: 64-68
X: Less than 64

The shape factor SF-1, is a view schematically showing a shape of the toner over to for explaining the shape factor SF-2. The shape of the toner over according to the present invention is a diagram schematically showing. Is a schematic structural view showing an embodiment of an image forming apparatus using a toner over according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Intermediate transfer belts 14, 15, 16 Support roller 17 Intermediate transfer belt cleaning device 18 Image forming means 20 Tandem type image forming device 21 Exposure device 22 Secondary transfer device 23 Support roller 24 Secondary transfer belt 25 Fixing device 27 Pressure roller 28 Sheet reversing device 30 Document table 31 Document discharge tray 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Photosensitive member (latent image carrier)
42, 50 Paper feed roller 43 Paper bank 44 Paper feed cassette 45, 52 Separation rollers 46, 48 Paper feed path 47 Transport roller 49 Registration roller 51 Manual feed tray 53 Manual paper feed path 55 Switching claw 56 Paper discharge roller 57 Paper output tray 62 Primary Transfer device 100 Copying device main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (19)

In a toner production method comprising a step of dissolving or dispersing a master batch containing at least 30% by weight of colorant A in a binder resin in a water-insoluble organic solvent or a polymerizable monomer to obtain a resin dispersion,
The masterbatch, kneading at least unnecessary toner particles of the binder fines side of Nozomu Tokoro toner particle size of the resin and toner you a coloring agent B and / or coarse particles side C or its granulated substance and colorant A And a toner production method. The toner production method according to claim 1, wherein:
In the production method, the volume average particle diameter E of the unnecessary toner particles C on the fine powder side is 0.1 × D to 0.9 × D with respect to the volume average particle diameter D of the desired toner. Manufacturing method. In the toner production method according to claim 1 or 2,
In the production method, the volume average particle diameter F of the unnecessary toner particles C on the coarse powder side is 1.1 × D to 10 × D with respect to the volume average particle diameter D of the desired toner. Production method. The method for producing a toner according to any one of claims 1 to 3,
In the production method, the volume average particle diameter E of the unnecessary toner particles C on the fine powder side is 0.5 to 5 μm. The method for producing a toner according to any one of claims 1 to 4,
In the production method, the volume average particle size F of the unnecessary toner particles C on the coarse powder side is 50 μm or less. The method for producing a toner according to any one of claims 1 to 5,
The method for producing a toner, wherein the colorant A and the colorant B are the same colorant. The method for producing a toner according to any one of claims 1 to 6,
The method for producing toner, wherein the particles C are particles other than predetermined particles obtained by classification of toner. The toner production method according to claim 7, wherein:
The method for producing a toner, wherein the particles C are particles obtained by a dry method by melt kneading. The toner production method according to claim 7, wherein:
The method for producing a toner, wherein the particles C are particles obtained in a non-aqueous organic solvent. In the toner manufacturing method according to claim 9,
The method for producing toner, wherein the master batch is obtained by a flushing method. The toner production method according to claim 1,
The method for producing a toner, wherein the master batch is obtained by particles C and a colorant A. 12. The method for producing a toner according to claim 1, wherein:
The toner is a color toner. The method for producing a toner according to any one of claims 1 to 12,
The toner over at least a polymer having a site reactive with a compound having an active hydrogen group, a polyester, a colorant, a release agent dissolved respectively in an organic solvent and or dispersed so the toner - the composition, A method for producing a toner, wherein the toner is obtained by dispersing in an aqueous medium and subjecting it to elongation and / or crosslinking. The method for producing a toner according to claim 1,
The toner over the method for producing a toner which is characterized by containing a release agent. The method for producing a toner according to any one of claims 1 to 14,
The toner over the method for producing a toner, wherein the average circularity is 0.94 or more. The method for producing a toner according to any one of claims 1 to 15,
The toner chromatography is a volume average particle size 3.0～8.0Myuemu,
A toner production method, wherein the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.40. The method for producing a toner according to any one of claims 1 to 16,
The toner over the shape factor SF-1 is in the range of 100 to 180, the production method of the toner shape factor SF-2 is characterized in that in the range of 100 to 180. The method for producing a toner according to any one of claims 1 to 17,
The toner chromatography is and in spindle shape,
The spindle shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), and the ratio (r2 / r1) between the minor axis r2 and the major axis r1 is 0.5. A method for producing a toner, wherein the ratio of the thickness r3 to the minor axis r2 (r3 / r2) is in the range of 0.7 to 1.0. A method for producing toner base particles comprising a step of obtaining a resin dispersion by dissolving or dispersing a master batch containing at least 30 wt% of colorant A in a binder resin in a water-insoluble organic solvent or a polymerizable monomer In
The masterbatch, kneading at least unnecessary toner particles of the binder fines side of Nozomu Tokoro toner particle size of the resin and toner you a coloring agent B and / or coarse particles side C or its granulated substance and colorant A A process for producing toner base particles, wherein the toner base particles are obtained .

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