JP2003241438A - Positive charge toner and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive charge toner having excellent stability of the charge amount and excellent dispersibility of a coloring agent, causing no fog, having high printing density and excellent balance in low temperature fixing property and high temperature storage property, and hardly causing color transfer or sticking to a resin sheet, and to provide a method for manufacturing the toner. <P>SOLUTION: The toner comprises a binder resin, an electrification controlling resin and a coloring agent. When the toner is melted by heating to form a film of 20 μm film thickness, the number of the coloring agent particles having ≥0.2 μm major diameter observed in a 100 μm×100 μm area is ≤50. The electrification controlling resin is a polyester resin produced by condensation polymerization of a polyvalent carboxylic acid compound (A1) having an amino group or its salt and/or a polyhydric alcohol (A2) having an amino group or its salt. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positively chargeable toner and a method for manufacturing the same. More specifically, the present invention relates to a positively chargeable toner having a clear color tone, stable charging, and excellent transferability, regardless of whether it is a one-component system or a two-component system, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, full-color electrophotographic apparatuses, particularly digitized full-color electrophotographic apparatuses, have been attracting attention, and are being widely spread on the market with the development of OA. The electrophotographic toner used in an electrophotographic apparatus (hereinafter, may be simply referred to as “toner”) is mainly prepared by adding a colorant, a charge control agent, etc. to a binder resin, kneading, and then pulverizing, Further classification, particles produced by a so-called pulverization method (pulverization method particles) or a mixture of a polymerizable monomer, a colorant, a charge control agent, etc. is polymerized by a method such as suspension polymerization, emulsion polymerization, dispersion polymerization, etc. Then, particles (polymerized particles) produced by causing them to associate with each other are mainly used. Also, depending on the charging method of the photoconductor,
The toner used for this purpose is different, and is classified into negatively charged toner and positively charged toner.

In the electrophotographic method, colorization has recently progressed, and a color toner corresponding to a color image forming apparatus is required. The color image forming apparatus includes a plurality of image forming units, each of which forms a toner image of a different color, and the color toner images of yellow, magenta, cyan, black, etc. are sequentially superposed on the same recording medium. It is known to transfer and perform color printing. Regardless of whether a pulverized toner or a polymerized toner is used, the following is required to be used as a color toner.

(1) The toner has high transparency in order to superpose multiple colors. (2) Spectral reflection characteristics are excellent in order to reproduce colors. (3) To precisely control the positive or negative charging of the toner. (4) Low temperature fixing is possible. (5) Easy manufacture of color toner.

Various studies have been conducted to meet these demands. For example, in JP-A-61-149969, an additive for enhancing charging such as a homopolymer of an amine-containing monomer and a pigment are prepared by mixing them in a halogenated hydrocarbon such as chloroform by a roll mill. A toner composition is disclosed in which a pigment treated with an additive for enhancing charging is melt-mixed with resin particles and then pulverized. Japanese Patent Laid-Open No. 62-1195
No. 49, a binder resin is dissolved in a solvent, a colorant and a charge control agent are added to the solution, the mixture is stirred and mixed, the solvent is removed by a freeze-drying method, and then the obtained toner is pulverized and classified. A method of making a toner is disclosed. Japanese Patent Laid-Open No. 03-1
In the 55568 publication, a binder resin, at least one of a dye and a pigment, and an organic solvent are mixed and kneaded to produce a master batch of a dye or a pigment, and the master batch is further prepared with a binder resin, and if necessary. And other additives are mixed, kneaded, and pulverized and classified. Further, in Japanese Patent Laid-Open No. 4-242755,
A method for producing a color toner in which a resin-dispersed pigment obtained by heating and press-kneading a pigment in a binder resin is melted and kneaded with the binder resin and dispersed, and a circle equivalent to the circle present in the binder resin. A color toner is disclosed in which the number ratio of pigment particles having a diameter of 0.3 μm or more is dispersed at 0.1% or less.

However, even by these methods, it is considerably difficult to simultaneously satisfy various requirements of the color toner. In particular, it has been difficult to produce a color toner having stable chargeability, excellent transparency, and good spectral reflection characteristics.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to obtain a positive image in electrophotography, and a positively chargeable toner whose chargeability does not change even when placed in different environments, and its production. To provide a method. Especially when applied to color toner, it has excellent spectral characteristics such as transparency necessary for reproducing a clear color tone of a color image, has less fog, can increase printing density, and has excellent durable printing characteristics. An object of the present invention is to provide a chargeable toner and a manufacturing method thereof. The present inventor has conducted extensive studies in order to achieve the above object, and by using a charge control resin composition comprising a specific polyester resin, a charge control resin and a colorant, and optionally an organic solvent, The inventors have found that the above objects can be achieved and completed the present invention.

[0008]

Thus, according to the present invention, (1) a toner containing a binder resin, a charge control resin and a colorant and melted at a temperature of 170 ° C. to a film thickness of 20 μm, an area of 100 μm. The major axis of 0.
The number of colorant particles of 2 μm or more is 50 or less, and the polyhydric carboxylic acid compound (A1) in which the charge control resin contains an amino group or a salt thereof and / or a polyhydric alcohol containing an amino group or a salt thereof. A positively chargeable toner which is a polyester resin obtained by polycondensing (A2), (2) a polyvalent carboxylic acid compound (A1) containing an amino group or a salt thereof and / or a polyvalent containing an amino group or a salt thereof. 100 parts by weight of a charge control resin made of a polyester resin obtained by polycondensing alcohol (A2), and a colorant 10.
To 200 parts by weight and 0 to 100 parts by weight of an organic solvent capable of dissolving the charge control resin to obtain a charge control resin composition, the method for producing a positively chargeable toner, Will be provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The positively chargeable toner of the present invention contains at least a binder resin, a charge control resin and a colorant.
The charge control resin contained in the toner of the present invention is a polyvalent carboxylic acid compound (A containing an amino group or a salt thereof).
1) and / or a polyester resin obtained by polycondensing a polyhydric alcohol (A2) containing an amino group or a salt thereof. Incidentally, a polyvalent carboxylic acid compound (A1) containing an amino group or a salt thereof and / or another polyvalent carboxylic acid compound capable of copolycondensing with a polyhydric alcohol (A2) containing an amino group or a salt thereof, which will be described later, or The polyhydric alcohol does not contain an amino group or a salt thereof.

As the polyvalent carboxylic acid compound (A1) containing an amino group or a salt thereof constituting the polyester resin, aminoterephthalic acid, 5-aminoisophthalic acid, 5-aminoisophthalic acid methyl ester, 4-aminophthalic acid, Aromatic polycarboxylic acids such as 4-aminophthalic anhydride, 4-aminonaphthalene-2,7 dicarboxylic acid and 5- [4-aminophenoxy] isophthalic acid; 5
-Aminohexahydroisophthalic acid, 5-aminohexahydroisophthalic acid methyl ester, 4-aminohexahydrophthalic acid, 4-aminohexahydrophthalic anhydride; 5-aminotetrahydroisophthalic acid, 5-aminotetrahydroisophthalic acid methyl ester Alicyclic polyvalent carboxylic acids such as 4-aminotetrahydrophthalic acid and 4-aminotetrahydrophthalic anhydride; and the like.
Further, as the polyhydric alcohol (A2) containing an amino group or a salt thereof, 2-amino-2-methyl-1,3
-Chain aliphatic polyhydric alcohols such as propanediol and diethanolamine; 2-amino-4-hydroxymethylbenzyl alcohol, 2-amino-3-hydroxymethylbenzyl alcohol, 4-amino-2-hydroxymethylbenzyl alcohol, 5- Aromatic polyhydric alcohols such as amino-3-hydroxymethylbenzyl alcohol;
Examples thereof include alicyclic polyhydric alcohols such as 2,4-bis (hydroxyethyl) -1-aminocyclohexane; and ammonium salts thereof.

The polyester resin having an ammonium salt may be one obtained by copolycondensing the polyvalent carboxylic acid compound (A1) having an ammonium salt and / or the polyhydric alcohol (A2) having an ammonium salt as described above. The polycarboxylic acid compound having an amino group (A
1) and / or a polyhydric alcohol having an amino group (A
It may be obtained by copolycondensing 2) and then ammonium chloride. In the polyester resin contained in the toner of the present invention, the amount of the polyvalent carboxylic acid compound (A1) containing an amino group or a salt thereof and / or the polyhydric alcohol (A2) containing an amino group or a salt thereof is the polyester. It is usually 0.2 to 30 mol%, preferably 0.5 to 10 mol% of all monomers (the total of all carboxylic acid components and all alcohol components) constituting the resin. By containing the polyhydric carboxylic acid compound (A1) and / or the polyhydric alcohol (A2) as a polycondensation component, the dispersibility of the pigment in the toner is improved and the chargeability of the toner can be controlled. .

It is preferable that the polyester resin is further copolycondensed with the cyclic divalent carboxylic acid compound (B). Examples of the cyclic divalent carboxylic acid compound (B) include aromatic divalent carboxylic acid compounds and alicyclic divalent carboxylic acid compounds, and alicyclic divalent carboxylic acid compounds are preferable.
Examples of the aromatic divalent carboxylic acid compound include 1,5-naphthalic acid, 2,6-naphthalic acid, diphenic acid, terephthalic acid, isophthalic acid, phthalic acid and their alkyl-substituted compounds, and their acid anhydrides and halogens. And derivatives such as compounds, esters and amides.

The alicyclic divalent carboxylic acid compound is a compound having an alicyclic structure and two carboxyl groups or carboxylic acid derivative groups in the molecular structure. As an alicyclic structure,
Examples thereof include monocyclic rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclohexene ring; and polycyclic rings such as norbornane ring and norbornene ring. Suitable alicyclic divalent carboxylic acid compounds include a carboxyl group or a carboxylic acid derivative group (amide group, ester group, acid anhydride group, acid halide) at each of the two carbon atoms constituting the alicyclic ring. An alicyclic divalent carboxylic acid compound formed by bonding; in particular, an alicyclic divalent carboxylic acid represented by the general formula (1) or (2) or an alkyl group such as an anhydride thereof is a substituent on the alicyclic ring Are combined as. The alkyl group preferably has 1 to 8 carbon atoms,
Specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group.

[0014]

[Chemical 1]

[0015]

[Chemical 2]

R in the formula (1) or (2) is an alkyl group.

The alicyclic divalent carboxylic acid compound preferably used for the polyester resin is, for example, butadiene,
It can be obtained by reacting a diene compound such as isoprene, piperylene, cyclopentadiene and the like; maleic anhydride, and optionally hydrogenating. Specific examples of the alicyclic divalent carboxylic acid compound include tetrahydroterephthalic acid, tetrahydroisophthalic acid, tetrahydrophthalic acid; hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid; 3-alkyltetrahydroterephthalic acid, 4- Alkyltetrahydroterephthalic acid, 3-alkyltetrahydroisophthalic acid, 4-alkyltetrahydroisophthalic acid, 3-alkyltetrahydrophthalic acid, 4-alkyltetrahydrophthalic acid;
3-alkylhexahydroterephthalic acid, 4-alkylhexahydroterephthalic acid, 3-alkylhexahydroisophthalic acid, 4-alkylhexahydroisophthalic acid, 3-alkylhexahydrophthalic acid, 4-alkylhexahydrophthalic acid; 3, 6-Endomethylene-tetrahydroterephthalic acid, 3,6-Endomethylene-tetrahydroisophthalic acid, 3,6-Endomethylene-tetrahydrophthalic acid; 3,6-Endomethylene-hexahydroterephthalic acid, 3,6-Endomethylene- Hexahydroisophthalic acid, 3,6-endomethylene-hexahydrophthalic acid;

2-alkyl-3,6-endomethylene-
Tetrahydroterephthalic acid, 3-alkyl-3,6-endomethylene-tetrahydroterephthalic acid, 2-alkyl-3,6-endomethylene-tetrahydroisophthalic acid, 3-alkyl-3,6-endomethylene-tetrahydroisophthalic acid, 2 -Alkyl-3,6-endomethylene-tetrahydrophthalic acid, 3-alkyl-3,6-
Endomethylene-tetrahydrophthalic acid; 2-alkyl-3,6-endomethylene-hexahydroterephthalic acid, 3-alkyl-3,6-endomethylene-hexahydroterephthalic acid; 2-alkyl-3,6-endomethylene- Hexahydroisophthalic acid, 3-alkyl-3,
6-endomethylene-hexahydroisophthalic acid, 2-
Alkyl-3,6-endomethylene-hexahydrophthalic acid, 3-alkyl-3,6-endomethylene-hexahydrophthalic acid;

Specific examples of the derivative of the alicyclic divalent carboxylic acid compound include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-alkyltetrahydrophthalic anhydride and 3-alkylhexahydrophthalic anhydride. ,
Acid anhydrides such as 4-alkyltetrahydrophthalic anhydride and 4-alkylhexahydrophthalic anhydride; halides, esters, amides and the like. They are,
Each can be used alone or in combination of two or more. Among these, 3-alkyltetrahydrophthalic acid, 3-alkylhexahydrophthalic acid,
4-alkyltetrahydrophthalic acid, 4-alkylhexahydrophthalic acid and their anhydrides have high melting characteristics, and when the polyester resin is used in the toner, a toner having excellent dispersibility of the colorant can be obtained. preferable. The amount of the cyclic divalent carboxylic acid compound (B) is usually 7 in the total polyvalent carboxylic acid component constituting the polyester resin.
It is preferably 0 to 100 mol%, particularly preferably 80 to 100 mol%. If this ratio is too small, the toner may not have sufficient storage stability.

As a carboxylic acid component constituting the polyester resin, a chain divalent carboxylic acid compound (D) or a trivalent or higher valent carboxylic acid compound (F) may be copolycondensed, if necessary. Examples of the chain polyvalent carboxylic acid compound (D) capable of copolycondensation include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid and itaconic acid. Examples of the trivalent or higher polycarboxylic acid compound (F) include trimellitic acid, pyromellitic acid, and trimesic acid. The proportion of the chain-type divalent carboxylic acid compound (D) is preferably 30 mol% or less of all carboxylic acid components. When this ratio is high, the glass transition temperature and the melt viscosity are low, so that the blocking resistance of the toner may be lowered or hot offset may occur. The proportion of the trivalent or higher polycarboxylic acid compound (F) is preferably 5 mol% or less of the total carboxylic acid component. When this ratio is high, the weight average molecular weight of the polyester resin is high, so that the melt viscosity of the toner is high and the fixing property of the toner may be deteriorated.

The polyester resin contained in the toner of the present invention is preferably further copolycondensed with a cyclic dihydric alcohol (C). Examples of the cyclic dihydric alcohol (C) include aromatic dihydric alcohols and alicyclic dihydric alcohols, and alicyclic dihydric alcohols are preferable. As the aromatic dihydric alcohol, paraxylylene glycol,
Metaxylylene glycol, orthoxylylene glycol
And ethylene oxide adducts of 1,4-phenylene glycol, bisphenol A ethylene oxide adducts and propylene oxide adducts. As the alicyclic dihydric alcohol, 2,2-bis (4
-Hydroxycyclohexyl) -propane (i.e.
Hydrogenated bisphenol A), 1,4-bis (hydroxymethyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, 1,2-bis (hydroxymethyl) cyclohexane, 2,2,4,4-tetramethyl-
1,3-Cyclohexanediol, 1,4-Cyclohexanediol, Hydrogenated bisphenol A ethylene oxide adduct and propylene oxide adduct, tricyclodecanediol, tricyclodecane dimethano-
And dicyclohexyl 4,4′-diol and the like. Of these, bis (hydroxycyclohexyl) -alkanes such as hydrogenated bisphenol A are preferred.
The amount of the cyclic dihydric alcohol (C) is preferably 2 to 60 mol%, and more preferably 3 to 50 mol% of the total polyhydric alcohol component constituting the polyester resin. If the amount of the cyclic dihydric alcohol (C) is too small, the glass transition temperature and the melt viscosity may be lowered, the blocking resistance may be lowered, and hot offset may occur. When the amount of the hydric alcohol is too large, the melt viscosity becomes high and the fixability may decrease.

It is preferable that a chain dihydric alcohol (E) is further copolycondensed as another alcohol component constituting the polyester resin. Further, trihydric or higher alcohol (G) may be copolycondensed. As the chain dihydric alcohol (E), ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, diethylene glycol, polyethylene glycol, polytetramethylene glycol, and other linear aliphatic glycols; propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 2,2,4 -Trimethyl-1,3-
Pentanediol, 2-ethyl-2-butyl-1,3-
Examples thereof include branched chain aliphatic glycols such as propanediol. Among these, linear aliphatic glycols are preferable, and among them, ethylene glycol is particularly preferable. The amount of the chain-type dihydric alcohol (E) is preferably 40 to 98 mol% of the total polyhydric alcohol components constituting the polyester resin, and more preferably 50 to 97 mol%. If the amount of the chain dihydric alcohol (E) is too small, the melt viscosity may be increased and the fixability may be deteriorated. Conversely, if the amount of the chain dihydric alcohol is too large,
The glass transition temperature and the melt viscosity may be lowered, the blocking resistance may be lowered, and hot offset may occur. Examples of the trihydric or higher alcohol (G) include trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, trimethylolethane,
Examples include cyclohexane triol and tris (hydroxymethyl) cyclohexane. The proportion of trihydric or higher alcohol (G) is preferably 5 mol% or less of all alcohol components. When this ratio is high, the weight average molecular weight of the polyester resin is high, so that the melt viscosity of the toner is high and the fixing property of the toner may be deteriorated.

The molecular weight of the polyester resin contained in the toner of the present invention is, when measured by gel permeation chromatography (GPC), a number average molecular weight in terms of polystyrene of 1,500 to 20,000, preferably It is 2,000 to 10,000 and the weight average molecular weight is preferably 5,000 to 300,000, preferably 7,000 to 100,000. When the molecular weight is within this range, a toner excellent in low-temperature fixing property and hot offset resistance can be obtained. If the number average molecular weight or the weight average molecular weight is smaller than the above range, the cohesive force of the resin may be reduced, and the storage stability may be deteriorated. There is. The glass transition temperature of the polyester resin is preferably 40 to 90 ° C, particularly preferably 50 to 8 ° C.
It is 0 ° C. When the glass transition temperature is within the above range, the storage stability of the toner is improved.

The polyester resin usually has a hydroxyl value of 1 to
100 mgKOH / g, preferably 5-80 mg
KOH / g. When the hydroxyl value is small, the fixability may be deteriorated, and large unevenness may occur on the surface of the image to deteriorate the smoothness. On the other hand, when it is large, the hot offset generation temperature becomes low, the hydrophilicity becomes high, and the charge amount tends to change due to environmental changes. Also,
The charge control resin preferably has fewer aromatic rings in order to reduce the influence of water in a high temperature and high humidity environment.

The polyester resin contained in the toner of the present invention can be produced by a known method, that is, a polycondensation method. In polycondensing the polyhydric carboxylic acid component and the polyhydric alcohol component, the total number of hydroxyl values of the alcoholic reactive groups [X] in all the monomers obtained by summing the polyhydric carboxylic acid component and the polyhydric alcohol component. Is preferable under the condition that the total acid value of the carboxylic acid-reactive groups is not smaller than the total number [Y] of the carboxylic acid, since the molecular weight of the polyester and the hydroxyl value can be increased. The ratio of the total number [X] of hydroxyl groups of alcoholic reactive groups to the total number [Y] of acid values of carboxylic acid reactive groups is preferably [X] / [Y] equivalent ratio of 1.00 or more. 01-1.5 are more preferable, and the range of 1.03-1.3 is especially preferable.
Here, the alcoholic reactive group refers to an alcoholic functional group that forms an ester bond, and typically includes a hydroxyl group and the like. Carboxylic acid reactive group refers to a carboxylic acid functional group that forms an ester bond,
Usually, a carboxyl group or a carboxylic acid derivative group and the like can be mentioned.

The polycondensation reaction is carried out, for example, at a reaction temperature of 100 to
It is carried out at 300 ° C., preferably 150 to 280 ° C., particularly preferably in the presence of an inert gas. If necessary, a water-insoluble organic solvent that is azeotropic with water, such as toluene or xylene, may be used. The polycondensation reaction is carried out under reduced pressure (usually 0.1 to 500 mmHg, preferably 0.5 to 500 mmHg).
200 mmHg, more preferably 1 to 50 mmHg). An esterification catalyst is usually used in this polycondensation reaction. Examples of the esterification catalyst include Bronsted acids such as paratoluenesulfonic acid, sulfuric acid, and phosphoric acid; calcium acetate, zinc acetate, manganese acetate, zinc stearate; iron and zinc acetylacetonates; metal alkoxides; alkyltin oxides. , Organoalkyl compounds such as dialkyltin oxide and organotitanium compounds: metal oxides such as tin oxide, antimony oxide, titanium oxide and vanadium oxide: heteropolyacids, etc. Alkoxides, heteropoly acids or iron acetylacetonates are preferred.

In order to obtain the polyester resin contained in the toner of the present invention, the above-mentioned carboxylic acid compound and alcohol may be charged in a desired composition ratio and reacted in a lump, and in order to adjust the molecular weight, Methods can also be used. That is, the cyclic divalent carboxylic acid compound (B) and the cyclic divalent alcohol (C) are preferably used as the cyclic divalent carboxylic acid compound (B), the cyclic divalent alcohol (C) and the chain formula 2. The carboxylic acid compound (D) and / or the chain dihydric alcohol (E) is polycondensed to obtain a precursor, and then the polycarboxylic acid compound containing the precursor and an amino group or a salt thereof ( A1) and / or a polyhydric alcohol (A2) containing an amino group or a salt thereof, and a polycarboxylic acid compound (H) and / or a polyhydric alcohol (I) are polycondensed.

The precursor has a number average molecular weight of 1,500 to 5,000 in terms of polystyrene when measured by gel permeation chromatography (GPC).
It is preferably 2,000 to 4,000. When the molecular weight is in this range, the dispersibility of the resin is high. The glass transition temperature of the precursor is preferably 40 ° C. or higher, particularly preferably 50 to 80 ° C. Glass transition temperature is 40
When it is at least ℃, the storage stability of the toner is improved.

A polyvalent carboxylic acid compound (A1) containing a precursor and an amino group or a salt thereof and / or a polyvalent carboxylic acid compound (A2) copolycondensed with a polyhydric alcohol (A2) containing an amino group or a salt thereof ( H) is not particularly limited, and as described above, a cyclic divalent carboxylic acid compound (B) such as an aromatic divalent carboxylic acid compound and an alicyclic dicarboxylic acid compound, a chain divalent carboxylic acid compound ( D),
Examples thereof include trivalent or higher carboxylic acid compounds (F). Of these, cyclic divalent carboxylic acid compounds such as terephthalic acid, tetrahydroterephthalic acid, and hexahydroterephthalic acid, in which a carboxyl group or a carboxylic acid derivative group is bonded to two non-adjacent carbon atoms forming a ring, respectively. preferable. Polyhydric carboxylic acid compound (A1) containing precursor and amino group or salt thereof and / or polyhydric alcohol (I) copolycondensed with polyhydric alcohol (A2) containing amino group or salt thereof
Is not particularly limited, and as described above, a cyclic dihydric alcohol (C) such as an aromatic dihydric alcohol or an alicyclic dihydric alcohol, a chain dihydric alcohol (E), or a trihydric or higher alcohol. (G) etc. can be mentioned. The total amount of the polyvalent carboxylic acid compound (H) or the polyhydric alcohol (I) used for copolycondensation with the precursor is preferably 10 to 50 parts by weight, particularly preferably 100 parts by weight of the precursor. 20 to 40 parts by weight. When the amount of the polyvalent carboxylic acid compound or the polyhydric alcohol is in the above range, it is possible to increase the molecular weight without impairing the melting property, which is preferable.

In the toner of the present invention, the above polyester resin is usually added to 100 parts by weight of the binder resin described below.
It is contained in an amount of 0.01 to 20 parts by weight, preferably 0.03 to 10 parts by weight. If the amount of the polyester resin is small, the charge control performance is not revealed, and if it is too large, the range of change in the charge amount due to environmental changes tends to be large.

The toner of the present invention exhibits a practically sufficient charging property without using any other charge control agent in addition to the above polyester resin. However, a conventional charge control agent may be used together for the purpose of fine adjustment. As the other charge control agent, it is possible to use various charge control agents having positive or negative chargeability. Examples thereof include metal complexes of organic compounds having a carboxyl group or a nitrogen-containing group, metal-containing dyes, nigrosine and the like. More specifically, Spiron Black TRH (Hodogaya Chemical Co., Ltd.), T-7
7 (Hodogaya Chemical Co., Ltd.), Bontron S-34 (Orient Chemical Co., Ltd.), Bontron E-84 (Orient Chemical Co., Ltd.), Bontron N-01 (Orient Chemical Co., Ltd.), Copy Blue-PR ( Clariant) and / or other charge control resins such as quaternary ammonium (salt) group-containing (meth) acrylate copolymers and sulfonic acid (salt) group-containing acrylate copolymers. be able to.

As the binder resin contained in the toner of the present invention, a polymer usually used as a binder resin for toner can be used. Specifically, polystyrene, styrene- (meth) acrylate copolymer resin, polyester resin other than the above, polyurethane, epoxy resin, polyolefin, polyamide, polysulfone, polycyanoaryl ether, (meth) acrylate resin, norbornene resin, styrene. Examples include nuclear hydrogenated products of system resins and nuclear hydrogenated products of styrene-isoprene-styrene block polymers.

The colorants contained in the toner of the present invention include black colorants, yellow colorants, magenta colorants and cyan colorants. Examples of the black colorant include carbon black and nigrosine-based dyes and pigments; magnetic particles such as cobalt, nickel, ferrosoferric oxide, manganese iron oxide, zinc iron oxide and nickel iron oxide. When using carbon black, the primary particle size is 20-
It is preferable to use one having a thickness of 40 nm because good image quality is obtained and the safety of the toner to the environment is improved. As the yellow colorant, compounds such as azo pigments and condensed polycyclic pigments are used. Specifically, C.I. I. Pigment Yellow 3, 12, 13, 14, 15, 17, 62, 6
5, 73, 83, 90, 93, 97, 120, 138,
155, 180, 181 and the like. As the magenta colorant, compounds such as azo pigments and condensed polycyclic pigments are used. Specifically, C.I. I. Pigment Red 48, 57, 58, 60, 63, 64, 68, 81, 8
3, 87, 88, 89, 90, 112, 114, 12
2, 123, 144, 146, 149, 163, 17
0, 184, 185, 187, 202, 206, 20
7, 209, 251, C.I. I. Pigment Violet 19 and the like. As the cyan colorant, a copper phthalocyanine compound and its derivative, an anthraquinone compound or the like can be used. Specifically, C.I. I. Pigment Blue 2, 3, 6, 15, 15: 1, 15: 2, 15: 3,
15: 4, 16, 17, and 60 and the like. The amount of these colorants is usually 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the binder resin.

The toner of the present invention may contain a release agent from the viewpoint of improving low temperature fixing property and preventing filming. Examples of the release agent include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and low molecular weight polybutylene; plant-based natural waxes such as candelilla, carnauba, rice, and wax; petroleum oils such as paraffin, microcrystalline, petrolactam, etc. Examples of the wax include synthetic waxes such as Fischer-Tropsch wax; and polyfunctional ester compounds such as pentaerythritol tetramyristate, pentaerythritol tetrapalmitate, and dipentaerythritol hexamyristate. These can be used alone or in combination of two or more.

Of these, synthetic waxes (particularly Fischer-Tropsch wax), petroleum waxes, polyfunctional ester compounds and the like are preferable. Among these, in the DSC curve measured by a differential scanning calorimeter, the endothermic peak temperature during heating is 30 to 200 ° C., preferably 50.
To 180 ° C., particularly preferably 60 to 160 ° C., and a multifunctional ester compound such as dipentaerythritol ester having an endothermic peak temperature in the range of 50 to 80 ° C. is fixed as a toner. It is particularly preferable in terms of balance of releasability. In particular, it has a molecular weight of 1,000 or more, dissolves in 5 parts by weight or more at 25 ° C. in 100 parts by weight of styrene, and has an acid value of 10 mg / KO.
The dipentaerythritol ester having an H or less is significantly effective in lowering the fixing temperature. Endothermic peak temperature is ASTM
It is the value measured by D3418-82. The amount of the release agent is usually 100 parts by weight of the binder resin,
It is 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight.

The toner of the present invention has a volume average particle diameter (dv).
Is usually 1 to 10 μm, preferably 3 to 8 μm, and the ratio of the volume average particle diameter to the number average particle diameter (dp) (dv /
dp) is 1 to 2.0, preferably 1 to 1.5. In addition, a value obtained by dividing the major axis rl of the toner by the minor axis rs (rl / r
s) is preferably in the range of 1 to 1.3. If this ratio becomes large, the transferability of transferring the toner image on the photoconductor to a transfer material such as paper is deteriorated, or the friction between the toners becomes large when the toner is stored in the toner storage portion of the image forming apparatus. Therefore, the external additive may peel off and the durability may be reduced.

The melt viscosity of the toner of the present invention at 120 ° C. is usually 10,000 Pa · s or less, preferably 10
0 to 10,000 Pa · s, more preferably 1,000
~ 8,000 Pa · s. With the toner having such a melt viscosity, high image quality can be achieved even by printing at high speed. Viscosity can be measured using a flow tester. Also, the softening temperature by the flow tester is
Usually, it is 50 to 80 ° C, preferably 60 to 70 ° C,
The outflow starting temperature is usually 90 to 150 ° C., preferably 10
It is 0 to 130 ° C. If the softening temperature is low, the storability may decrease, and conversely, if the softening temperature is high, the fixability may decrease. If the outflow starting temperature is low, the hot offset resistance may decrease, and conversely, if it is high, the fixability may decrease. The toner of the present invention has a glass transition temperature of usually 0 to 80 ° C., preferably 40 to 70 ° C., as measured by a differential scanning calorimeter.
Is. If the glass transition temperature is low, the storability may be lowered, and conversely, if it is high, the fixability may be lowered.

The toner of the present invention has a tetrahydrofuran (THF) insoluble content of usually 0 to 50%, preferably 0 to 20%. If it is 50% or more, the gloss decreases and the transparency deteriorates. The amount of THF-insoluble matter can be measured by the method described below. A preferred toner used in the present invention is a volume resistivity value (lo
g (Ω · cm)) is usually 10 to 13, preferably 1
0.5-12.5. If the volume resistivity value is small, fog may occur, and if it is large, toner scattering, fog, filming, or poor cleaning may occur. Further, it is preferable that the toner of the present invention has a small change in charge amount in a high temperature and high humidity environment (H / H environment) and a low temperature and low humidity environment (L / L environment), that is, high so-called environmental stability. At that time, it is preferable that the amount of change in the charge amount between the environments is 5 μC / g or less. Fogging may occur if environmental stability is low.

The toner of the present invention has a film thickness of 20 after being melted by heating.
The number of colorant particles having a major axis of 0.2 μm or more observed in an area of 100 μm × 100 μm of the toner having a size of 50 μm is 50 or less, preferably 30 or less, more preferably 20 or less. If this number is large, the spectral characteristics such as transparency necessary for reproducing a clear color tone of a color image may be deteriorated, fog may be increased, and the print density may be lowered. The spectral characteristics can be measured by printing a solid image with a commercially available printer and measuring the color tone with a spectral color difference meter.

The toner of the present invention can be made into particles having a core-shell structure (also referred to as a capsule structure) by coating the outside of the above-mentioned toner with another polymer. In the core-shell structure particles, by encapsulating the low softening point substance inside (core layer) with a substance having a higher softening point, it is possible to balance the lowering of the fixing temperature and the prevention of aggregation during storage. Therefore, it is preferable.

In the case of core-shell type toner, the glass transition temperature of the polymer constituting the core layer is usually 0 to 80 ° C, preferably 40 to 60 ° C. If the glass transition temperature is too high, the fixing temperature may increase, and if it is too low, the storage stability may decrease. Further, the glass transition temperature of the polymer forming the shell layer needs to be set to be higher than the glass transition temperature of the polymer forming the core layer as the binder resin. The glass transition temperature of the polymer constituting the shell layer is usually 50 to 130 ° C., preferably 60 to 120 ° C., and more preferably 80 to 110 ° C. in order to improve the storage stability of the toner. If it is lower than this, the storage stability may decrease, and if it is higher than this, the fixing property may decrease. The difference between the glass transition temperature of the polymer forming the core layer and the glass transition temperature of the polymer forming the shell layer is usually 10 ° C or higher, preferably 20 ° C or higher, more preferably 3 ° C.
It is 0 ° C or higher. If it is smaller than this difference, the balance between the preservability and the fixability may decrease.

The weight ratio of the core layer and the shell layer of the core-shell type toner is not particularly limited, but is usually 80/20 to 9
It is used at 9.9 / 0.1. If the ratio of the shell layer is less than the above ratio, the storability is deteriorated, and conversely, if it is more than the above ratio, fixing at low temperature may be difficult.

Further, it is desirable to limit the amount of residual metal (ions) in the toner. Especially when metal (ion) such as magnesium or calcium remains in the developer, it absorbs moisture under high humidity conditions, which lowers the fluidity of the developer,
The image quality may be adversely affected. Even if the content of magnesium or calcium (hereinafter, simply referred to as residual metal) in the developer is small, the content of the developer is 30 per minute even under high temperature and high humidity conditions.
A high-speed machine capable of printing more than one sheet can provide high print density and good image quality without fog. The residual metal amount is preferably 170 ppm or less, more preferably 150 pp
m or less, particularly preferably 120 ppm or less. In order to reduce the residual metal, for example, in the dehydration stage of the toner manufacturing process, dehydration and cleaning may be repeatedly performed using a cleaning dehydrator such as a continuous belt filter or a siphon peeler type centrifuge, and then dried.

In the toner of the present invention, for example, a colorant, a charge control resin, a release agent and the like are melt-mixed in a thermoplastic resin as a binder resin component and uniformly dispersed to form a composition, A pulverization method of obtaining a toner by pulverizing and classifying the composition, dissolving or dispersing a colorant, a charge control resin, a release agent, etc. in a polymerizable monomer which is a binder resin raw material,
After adding the polymerization initiator, it is suspended in an aqueous dispersion medium containing a dispersion stabilizer, and heated to a predetermined temperature to start the polymerization,
After the polymerization is finished, filtration, washing, dehydration, a polymerization method for obtaining a toner by drying, particles of a binder resin obtained by emulsion polymerization or suspension polymerization, and particles containing a colorant and a charge control resin, The associated particles are subjected to an association method of obtaining a toner by filtering and drying, a hydrophilic group-containing resin is used as a binder resin, and a colorant, a charge control resin, etc. are added thereto and dissolved in an organic solvent. It can be produced by a phase inversion emulsification method or the like in which the resin is neutralized, the phase is inverted, and then the toner is dried to obtain a toner. Among these, the toner obtained by the polymerization method is preferable from the viewpoint of obtaining a toner that gives an image quality with good dot reproducibility.

The method for producing a positively chargeable toner of the present invention comprises a polyvalent carboxylic acid compound (A1) containing the above-mentioned amino group or a salt thereof and / or a polyhydric alcohol (A2) containing an amino group or a salt thereof. 100 parts by weight of a charge control resin composed of a polyester resin obtained by polycondensation of 10 to 200 parts by weight of a colorant, and 0 to 100 parts by weight of an organic solvent capable of dissolving the charge control resin are mixed to control charge. There is a step of obtaining a resin composition. In the toner manufacturing method of the present invention, 100 parts by weight of the charge control resin and the coloring agent 2 are used.
It is preferable to use a charge control resin composition obtained by mixing 0 to 150 parts by weight. By producing the toner using the charge control resin composition, the colorant can be uniformly dispersed in the toner.

When an organic solvent is used in the production of the charge control resin composition used in the present invention, the charge control resin can be dissolved or swollen to mix the resin in a soft state, and the colorant can be uniformly dispersed. Therefore, it is preferable. When the organic solvent is not used, it is necessary to heat and mix the resin to a temperature at which the resin becomes soft, and it may be difficult to control the temperature. When an organic solvent is used, the organic solvent may evaporate due to heating, especially when the boiling point of the organic solvent is low. Therefore, it is preferable to obtain the charge control resin composition at room temperature or by cooling. If the organic solvent remains in the toner, an odor problem may occur, so the organic solvent may be removed either during the production of the charge control resin composition or during the production of the toner. preferable. The amount of the organic solvent is 0 to 100 parts by weight of the charge control resin.
The amount is 100 parts by weight, preferably 5 to 80 parts by weight, and more preferably 10 to 60 parts by weight. Within this range, the balance between dispersibility and processability is excellent. At this time, the organic solvent may be added all at once, or may be added in several divided portions while checking the kneading state.

When an organic solvent is used, its solubility coefficient (hereinafter referred to as SP value) is 8 to 15 [cal / c].
m ³ ] ^1/2 and the boiling point is preferably in the range of 50 to 150 ° C. If the SP value is less than 8 [cal / cm ³ ] ^1/2 , the polarity may be too small to dissolve the charge control resin, and conversely, the SP value may be 15
If it is larger than [cal / cm ³ ] ^1/2 , the polarity becomes high and the charge control resin may not be dissolved. On the other hand, if the boiling point is lower than 50 ° C, the organic solvent may evaporate due to the heat generated by the kneading, while if it is higher than 150 ° C, it may be difficult to remove the organic solvent after the kneading. Specific examples of the organic solvent (SP value / boiling point), methanol (14.5 / 65 ° C.), ethanol (10.0 / 78.3 ° C.), propanol (11.9 /
97.2 ° C), diethyl ketone (8.8 / 102 ° C),
Di-n-propyl ketone (8.0 / 144 ° C), di-i
So-propyl ketone (8.0 / 124 ° C), methyl-
n-Propyl ketone (8.3 / 102 ° C), methyl-
iso-propyl ketone (8.5 / 95 ° C), methyl-
n-butyl ketone (8.5 / 127 ° C), methyl-i
So-butyl ketone (8.4 / 117 ° C), toluene (8.9 / 110 ° C), tetrahydrofuran (9.1 /
65 ° C.), methyl ethyl ketone (9.3 / 80 ° C.), acetone (9.9 / 56 ° C.), cyclohexanone (9.9)
/ 156 ° C.) and the like, and these may be used alone or in combination of two or more kinds. Among these, considering the solubility in the charge control resin and the removal after kneading, diethyl ketone, methyl-n-propyl ketone, methyl-n-
Butyl ketone, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / propanol mixed solvent, methyl ethyl ketone / methanol mixed solvent are preferable.

Mixing is carried out by using a roll, a plastic coder (manufactured by Brabender), a Labo Plastomill (manufactured by Toyo Seiki),
It can be performed using a kneader, a single screw extruder, a twin screw extruder, a Banbury, a Bus Cokneader, or the like. When an organic solvent is used, there is a problem of odor and toxicity, and thus a closed mixer that does not leak the organic solvent is preferable. Further, it is preferable that a torque meter is installed in the mixer because the dispersibility can be controlled by the torque level.

The charge control resin composition used in the present invention was prepared by adding an organic solvent to the composition to prepare a 5% resin solution, and the resin solution was then applied onto a glass plate with a doctor blade having a gap of 30 μm. The major axis of the film obtained by coating and drying is 100 .mu.m.times.100 .mu.m.
The number of colorant particles of 2 μm or more is usually 20 or less, preferably 10 or less, and more preferably 5 or less. If this number is large, the spectral characteristics such as transparency necessary for reproducing a clear color tone of a color image may be deteriorated, fog may be increased, and the print density may be lowered. For the spectral characteristics, solid printing is performed with a commercially available printer, and the color tone is measured with a spectral color difference meter. After adding an organic solvent to make a 5% resin solution,
The major axis 0.2 observed in a unit area of 100 μm × 100 μm of a film having a thickness of 30 μm obtained by coating and drying.
By using a charge control resin composition having 20 or less colorant particles having a particle size of 20 μm or more, the film is heated and melted to a film thickness of 20 μm.
In addition, a toner in which the number of colorant particles having a major axis of 0.2 μm or more observed in an area of 100 μm × 100 μm is 50 or less can be relatively easily obtained.

In the method for producing a positively chargeable toner of the present invention, in order to include the charge control resin composition in the toner, the binder resin, the charge control resin composition and, if necessary, other additives are added. After melt-kneading, etc., the mixture is cooled and then pulverized and classified so as to obtain a desired particle size distribution, a polymerizable monomer as a raw material of a binder resin and a charge control resin composition in an appropriate aqueous dispersion medium. And a polymerization method of polymerizing a polymerizable monomer composition containing other additives as necessary, but the toner is produced by a polymerization method because a toner giving good image quality with dot reproducibility can be obtained. Preferably.

In the method for producing a positively chargeable toner of the present invention, the polymerizable monomer composition is prepared by mixing 2 to 20 parts by weight of the charge control resin composition and 100 parts by weight of the polymerizable monomer. Then, it is preferable to polymerize this in an aqueous dispersion medium to produce a positively chargeable toner.

The polymerization method is not particularly limited, and any of emulsion polymerization, suspension polymerization, precipitation polymerization and soap-free polymerization may be used, but it is possible to improve the charging property and transfer property by uniformly incorporating a colorant. Therefore, the suspension polymerization method is preferable, and specifically, polymerization containing a polymerizable monomer, a charge control resin composition, a molecular weight adjusting agent, a release agent, and, if necessary, an additive such as a charge control agent. The polymerizable monomer composition is polymerized in an aqueous medium.

A more preferable method for producing a core-shell type toner by suspension polymerization will be described below. A polymerizable monomer composition containing a polymerizable monomer (polymerizable monomer for core), a charge control resin composition, and other additives in an aqueous dispersion medium containing a dispersion stabilizer (core Monomer composition)
By suspending and polymerizing using a polymerization initiator,
A capsule toner can be obtained by producing core particles, and further adding a polymerizable monomer for forming a shell (polymerizable monomer for shell) and a polymerization initiator and polymerizing. As a specific method for forming the shell, a method of continuously adding a polymerizable monomer for shell to the reaction system of the polymerization reaction carried out to obtain the core particles, or continuously polymerizing it, or using another reaction system Examples thereof include a method of charging the obtained core particles, adding a polymerizable monomer for shell to the core particles, and performing stepwise polymerization. The shell component monomer can be added all at once to the reaction system, or can be added continuously or intermittently using a pump such as a plunger pump.

Examples of the polymerizable monomer for the core include a monovinyl type monomer, a crosslinkable monomer and a macromonomer. This polymerizable monomer is polymerized to form a binder resin component. Specific examples of the monovinyl monomer include styrene, vinyltoluene, α-methylstyrene and other styrene monomers; (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, ( Propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, (meth)
Examples thereof include (meth) acrylic acid derivatives such as dimethylaminoethyl acrylate and (meth) acrylamide; monoolefin monomers such as ethylene, propylene and butylene. The monovinyl-based monomer may be used alone or in combination of a plurality of monomers. Of these monovinyl-based monomers, styrene-based monomers alone, and a combination of styrene-based monomers and (meth) acrylic acid derivatives are preferably used.

The use of a crosslinkable monomer and a polymer together with a monovinyl monomer is effective for improving hot offset. The crosslinkable monomer is a monomer having two or more polymerizable carbon-carbon unsaturated double bonds. Specifically, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and their derivatives; diethylenically unsaturated carboxylic acid esters such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate; N, N-
2 vinyl groups such as divinylaniline and divinyl ether
Examples thereof include compounds having three or more vinyl groups such as pentaerythritol triallyl ether and trimethylolpropane triacrylate. The crosslinkable polymer is a polymer having two or more vinyl groups in the polymer, and specifically, polyethylene, polypropylene having two or more hydroxyl groups in the molecule,
Examples thereof include esters obtained by subjecting a polymer such as polyester and polyethylene glycol and an unsaturated carboxylic acid monomer such as acrylic acid and methacrylic acid to a condensation reaction. These crosslinkable monomers and crosslinkable polymers may be used alone or in combination of two or more. The amount used is monovinyl monomer 1
It is usually 10 parts by weight or less, preferably 100 parts by weight,
It is 0.1 to 2 parts by weight.

Further, it is preferable to use a macromonomer together with the monovinyl-based monomer because a good balance between storability and low-temperature fixability can be obtained. The macromonomer has a vinyl polymerizable functional group at the end of the molecular chain, and is usually an oligomer or polymer having a number average molecular weight of 1,000 to 30,000. When a polymer having a small number average molecular weight is used, the surface portion of the polymer particles becomes soft and the storage stability is deteriorated. On the contrary, when a polymer having a large number average molecular weight is used, the meltability of the macromonomer is deteriorated, and the fixability and storage stability are deteriorated. Examples of the vinyl polymerizable functional group at the end of the macromonomer molecular chain include an acryloyl group and a methacryloyl group, and a methacryloyl group is preferable from the viewpoint of ease of copolymerization.

The macromonomer preferably has a glass transition temperature higher than the glass transition temperature of the polymer obtained by polymerizing the monovinyl monomer. Specific examples of the macromonomer used in the present invention include a polymer obtained by polymerizing styrene, a styrene derivative, a methacrylic acid ester, an acrylic acid ester, acrylonitrile, methacrylonitrile or the like, or a polysiloxane skeleton. Among them, hydrophilic monomers, particularly polymers obtained by polymerizing methacrylic acid esters or acrylic acid esters alone or in combination thereof are preferable.
When the macromonomer is used, the amount thereof is usually 0.01 to 10 with respect to 100 parts by weight of the monovinyl monomer.
It is 0.03 to 5 parts by weight, and more preferably 0.05 to 1 part by weight. If the amount of macromonomer is small, the storage stability of the toner will not be improved. If the amount of macromonomer becomes extremely large, the fixing property of the toner will be deteriorated.

Among the polymerizable monomers for the core, those capable of forming a polymer having a glass transition temperature of usually 60 ° C. or lower, preferably 40 to 60 ° C. are suitable as the core monomer. If the glass transition temperature is too high, the fixing temperature will increase,
On the contrary, if it is too low, the storage stability of the toner deteriorates. Usually, the core monomer may be used alone or in combination of two or more kinds.

The polymerizable monomer for shell is preferably one which gives a polymer having a glass transition temperature higher than that of the polymer constituting the core particle. As a monomer constituting the polymerizable monomer for shell, styrene, acrylonitrile, methyl methacrylate or the like which forms a polymer having a glass transition temperature of higher than 80 ° C. is used alone or in combination of two or more kinds. Can be used. The glass transition temperature of the polymer obtained from the polymerizable monomer for shell is usually 50 to 130 ° C., preferably 60 to 120 ° C., more preferably 80 to 110 ° C. in order to improve the storage stability of the polymerized toner. Is. If it is lower than this, storage stability may be lowered, and conversely, if it is higher, fixing property may be lowered. The difference in glass transition temperature between the polymer composed of the polymerizable monomer for the core and the polymer composed of the polymerizable monomer for the shell is usually 10 ° C.
Or higher, preferably 20 ° C. or higher, more preferably 30 ° C. or higher. If it is smaller than this difference, the storage stability is reduced.

As the polymerization initiator, persulfates such as potassium persulfate; 4,4′-azobis (4-cyanovaleric acid),
2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide, 2,2'-azobis (2
-Amidinopropane) dihydrochloride, 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,
Azo compounds such as 2'-azobisisobutyronitrile; lauroyl peroxide, benzoyl peroxide, t-
Butyl peroxy-2-ethyl hexanoate, t-hexyl peroxy-2-ethyl hexanoate, t-butyl peroxypivalate, di-isopropyl peroxydicarbonate, 1,1,3,3-tetramethyl Examples thereof include peroxides such as butylperoxy-2-ethylhexanoate and t-butylperoxyisobutyrate.

Among these, it is preferable to select an oil-soluble polymerization initiator for the polymerizable monomer composition for core.
It is preferable to select a water-soluble polymerization initiator for the polymerizable monomer composition for shell. The polymerization initiator for the core is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the monovinyl monomer. The polymerization initiator can be added in advance to the polymerizable monomer composition, but in some cases, it can be added to the suspension after the completion of the granulation step. The amount of the polymerization initiator for shells is usually 0.001 to 1% by weight based on the aqueous medium. If the amount is too small, the polymerization will not proceed and the productivity will be reduced.

A dispersion stabilizer can be added to the reaction solution for stable polymerization. Examples of the dispersion stabilizer include sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate and magnesium carbonate; phosphates such as calcium phosphate; metal oxides such as aluminum oxide and titanium oxide; Metal compounds and metal hydroxides such as aluminum hydroxide, magnesium hydroxide and ferric hydroxide; water-soluble polymers such as polyvinyl alcohol, methyl cellulose, gelatin; anionic surfactants, nonionic surfactants, amphoteric Examples thereof include surfactants, which may be used alone or in combination of two or more kinds. Among these, a dispersion stabilizer containing a metal compound, particularly a colloid of a poorly water-soluble metal hydroxide, can narrow the particle size distribution of polymer particles,
In addition, the residual amount of the dispersant after washing is small, and an image can be clearly reproduced, which is preferable.

The dispersion stabilizer containing a colloid of a poorly water-soluble metal hydroxide is not limited by its production method, but it is obtained by adjusting the pH of the aqueous solution of the water-soluble polyvalent metal compound to 7 or more. Metal hydroxide colloid,
In particular, it is preferable to use a poorly water-soluble metal hydroxide colloid produced by the reaction of the water-soluble polyvalent metal compound and the alkali metal hydroxide in the aqueous phase.

In the colloid of the poorly water-soluble metal compound, in the number particle size distribution, the cumulative number calculated from the small particle size side is 50.
It is preferable that the particle diameter Dp50, which is%, is 0.5 μm or less, and the particle diameter Dp90, which is 90%, is 1 μm or less. If the particle size of the colloid becomes large, the stability of polymerization is impaired and the storage stability of the toner is deteriorated.

The dispersion stabilizer is a monovinyl monomer 10
It is usually used in a proportion of 0.1 to 20 parts by weight with respect to 0 parts by weight. If this ratio is less than 0.1 part by weight, it is difficult to obtain sufficient polymerization stability, and polymer aggregates are easily generated. On the other hand, if it exceeds 20 parts by weight, the toner particle size after polymerization becomes too fine, which is not practical.

As the molecular weight modifier, for example, t
-Dodecyl mercaptan, n-dodecyl mercaptan,
Examples thereof include mercaptans such as n-octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide. These molecular weight modifiers can be added before the start of the polymerization or during the polymerization. The molecular weight modifier is 100 parts by weight of the monovinyl monomer,
Usually, it is used in a proportion of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

The toner of the present invention can be used as it is for the development of electrophotography, but in general, in order to adjust the charging property, fluidity, storage stability and the like of the toner, the toner particles are not Fine particles having a particle size smaller than that of the toner particles (hereinafter referred to as an external additive) are used by adhering or embedding. Examples of the external additive include inorganic particles and organic resin particles. Examples of the inorganic particles include silicon dioxide, aluminum oxide, titanium oxide, zinc oxide, tin oxide, barium titanate, and strontium titanate. As the organic resin particles, methacrylic acid ester polymer particles, acrylic acid ester polymer particles, styrene-methacrylic acid ester copolymer particles, styrene-acrylic acid ester copolymer particles, zinc stearate, calcium stearate, shell is methacrylic acid Examples thereof include core-shell type particles having an acid ester copolymer and a core formed of a styrene polymer. In the case of a magnetic one-component developer, iron, cobalt, nickel, an alloy mainly containing them, or an oxide such as ferrite may be contained. Among these, inorganic oxide particles, particularly silicon dioxide particles are preferable. Further, the surface of these fine particles can be subjected to a hydrophobizing treatment, and hydrophobized silicon dioxide particles are particularly preferable. The amount of the external additive is not particularly limited, but is usually 0.1 to 6 parts by weight with respect to 100 parts by weight of the toner particles. The external additives may be used in combination of two or more kinds. When an external additive is used in combination, a method of combining inorganic particles having different average particle diameters or combining inorganic particles and organic resin particles is suitable. To attach the external additive to the toner particles, the external additive and the toner particles are usually charged in a mixer such as a Henschel mixer and stirred. When the toner is prepared by polymerization in water as described above, it is possible to use a wet method in which an external additive is dispersed in water, mixed with an aqueous dispersion of toner particles, stirred, and then spray dried.

[0068]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Parts and percentages in these examples are by weight unless otherwise stated. In this example, the following methods were used for evaluation. 1. Polyester resin characteristics (1) Number average molecular weight and weight average molecular weight The number average molecular weight and weight average molecular weight of polyester are G
It was calculated as a standard polystyrene conversion amount according to the PC method. (2) Hydroxyl value The hydroxyl value of polyester is "standard oil and fat analysis test method"
The measurement was carried out according to the method described in paragraphs 2, 4, 9, 2-83 of the Japan Oil Chemists' Society. The unit is mgKOH / g. (3) Glass transition temperature The glass transition temperature (Tg) of polyester resin is JIS
It was measured according to the DSC method defined in K 7121. The unit is ° C.

2. Characteristics of Charge Control Resin Composition (1) Dispersion of Colorant 1 After taking out a part of the charge control resin composition, toluene which dissolves the charge control resin was added to form a 5% solution of the charge control resin composition. . The mixed solution was applied on a glass plate with a doctor blade having a gap of 30 μm and dried to prepare a sheet. This sheet is observed with an optical microscope and 100μ
The number of colorant particles having a major axis of 0.2 μm or more existing in m squares was counted.

3. Toner characteristics (1) Toner particle size The volume average particle size (dv) and number average particle size (dp) of polymer particles were measured with a Multisizer (manufactured by Beckman Coulter, Inc.). The measurement with this Multisizer was carried out using an aperture diameter of 100 μm, a medium of Isoton II,
The number of particles measured: 100,000. (2) Toner shape The shape of the toner was photographed by a scanning electron microscope, the photograph was read by a Nexus 9000 type image processing device, and the value (rl / rs) obtained by dividing the major axis of the toner by the minor axis was measured. The number of toners measured at this time was 100. (3) Melt viscosity flow tester (manufactured by Shimadzu Corporation, model name "CFT-50"
0C ”) and the sample amount is 1.0 to 1.3 g,
The melt viscosity at 120 ° C was measured under the following measurement conditions. Starting temperature: 35 ° C, heating rate: 3 ° C / min, preheating time: 5
Min, cylinder pressure: 10.0 Kgf / cm ² , die diameter: 0.5 mm, die length 1.0 mm, shear stress:
2.451 × 10 ⁵ Pa (4) THF insoluble content 1 g of toner is precisely weighed and put into a cylindrical filter paper (86R size 28 × 100 mm, manufactured by Advantech Co., Ltd.), which is applied to a Soxhlet extractor, and THF is placed in the lower flask. Add and extract for 6 hours. After the extraction, the extraction solvent was recovered, and the soluble resin component extracted in the extraction solvent was separated by an evaporator, precisely weighed, and calculated from the following calculation. THF insoluble amount (%) = ((T−S) / T) × 100 T: toner sample amount (g) S: extracted resin amount (g)

(5) Volume resistivity value The volume resistivity value of toner is about 3 g of toner and 5 cm in diameter.
In a tablet molding machine, a test piece is prepared by applying a load of about 100 kg for 1 minute, and a dielectric loss measuring device (manufactured by Ando Electric Co., model name "TRS-10 type") is used at a temperature of 30 ° C. ,
The measurement was performed under the condition of a frequency of 1 kHz. (6) Charge amount L / L (temperature 10 ° C, humidity 20%), H / H (temperature 35
The amount of electrification under the environment (° C, humidity 80%) was measured, and the state of the environmental fluctuation was evaluated. The charge amount of the toner is determined by putting the toner in a commercially available non-magnetic one-component developing type printer (trade name "HL1670N" manufactured by Brother Industries, Ltd.) and leaving it in the environment for one day and night, and then printing five halftone print patterns. After printing, the toner on the developing roller was sucked into a suction type charge amount measuring device, and the charge amount per unit weight was measured from the charge amount and the suction amount. (7) Dispersion of colorant 2 Place an appropriate amount of toner on a slide glass, put a cover glass on it, heat it to 170 ° C on a hot plate to melt the toner, and then apply force with a cover glass. In addition, the toner was crushed. Thickness meter (made by Anritsu Corporation,
The toner thickness measured with the product name: K-402B) is 20.
The μm portion was observed with an optical microscope, and the number of colorant particles having a major axis of 0.2 μm or more and existing in 100 μm square was counted.

4. Image quality evaluation (1) Color tone Set the printing paper in the above-mentioned printer, put the toner in the developing device, and the temperature is 35 ° C and the humidity is 80% (H / H).
After left in the environment for a whole day and night, solid printing was performed at a density of 5% and measured with a spectral color difference meter (manufactured by Nippon Denshoku Co., Ltd., model name "SE2000"). (2) Printing density Set the printing paper in the above-mentioned printer, put the toner in the developing device, and the temperature is 35 ° C and the humidity is 80% (H / H).
After left in the environment for a whole day and night, 5% density is used for continuous printing from the beginning, and solid printing is performed when printing the 20,000th sheet. Black toner is McBeth transmission type image density measuring machine, color toner is color reflection type densitometer ( X-Light, model name "4
04A ") was used to measure the print density. (3) Fog Using the printer described above, a temperature of 35 ° C. and a humidity of 80
%, (H / H) environment, left for 24 hours, continuously printed at a density of 5%, printed 20,000 sheets, then solid printed, stopped printing halfway, and left on the photoreceptor after development. The toner in the non-image area was peeled off with an adhesive tape (Scotch Mending Tape 810-3-18 manufactured by Sumitomo 3M Ltd.), and the toner was attached to a new printing paper. Black toner
Whiteness (B) of the printing paper to which the adhesive tape is attached
Was measured with a whiteness meter (manufactured by Nippon Denshoku Co., Ltd.), and similarly,
The whiteness (A) of the printing paper to which only the adhesive tape was attached was measured. The difference ΔY between the whiteness (A) and the whiteness (B) was calculated as the fog value. On the other hand, for the color toner, in the same manner as the black toner, the color tone is measured instead of the whiteness by using the above-described spectral color difference meter, and the color tone is expressed as the coordinates in the Lab space, and the color difference ΔE is calculated, and the fog value is calculated. And A smaller value indicates less fog.

(4) Fixing temperature The temperature of the fixing roll was changed to 5 ° C. by modifying it so that the temperature of the fixing roll of the printer can be changed.
Measure the fixing rate of the developer at each temperature in steps,
A fixing test was conducted to find the relationship between temperature and fixing rate. The fixing rate is 5 to stabilize the changed fixing roll temperature.
After leaving for more than a minute, solid printing was performed on the printing paper with a modified printer, and the solid area of the printed paper was calculated from the ratio of the print density before and after the tape peeling operation. That is, the fixing ratio was calculated from the following equation, where the image density before peeling the tape is before ID and the image density after the tape peeling is after ID. Fixing rate (%) = (After ID / Before ID) × 100 Here, the tape peeling operation is to stick the above-mentioned adhesive tape to the measurement portion of the test paper and press it with a constant pressure to adhere it, and then to a constant speed. Is a series of operations for peeling the adhesive tape in the direction along the paper. In this fixing test, the fixing roll temperature corresponding to a fixing ratio of 80% was defined as the fixing temperature of the developer. (5) Hot offset temperature In the same way as fixing temperature measurement, the fixing roll temperature is changed to
Solid printing was performed and the temperature at which hot offset occurred was measured. The fixing roll temperature when the hot offset occurred was defined as the hot offset temperature.

[Synthesis of bis (β-hydroxyethyl) hexahydroterephthalate] 557 parts of 1,4-cyclohexanedicarboxylic acid was placed in a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing pipe and a nitrogen gas introducing pipe. ,
And 443 parts of ethylene glycol were charged. Stirring was carried out while introducing nitrogen gas, and the reaction was carried out at 180 ° C. for 5 hours while removing water produced during the reaction. Reaction temperature 20
Raise it to 0 ° C and gradually reduce the pressure in the flask to 1.5.
After the lapse of time, the pressure was adjusted to 5 mmHg or less, and the reaction was further continued for 2 hours to obtain bis (β-hydroxyethyl) hexahydroterephthalate. Bis (β-hydroxyethyl) hexahydroterephthalate was a colorless transparent liquid.

[Synthesis of Polyester Resin] (Synthesis Example 1) A three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube and a nitrogen gas inlet tube was charged with 366 parts of 4-methyl-hexahydrophthalic anhydride. Hexahydroterephthalate bis (β-hydroxyethyl) 100
Parts, 5-aminohexahydroisophthalic acid dimethyl ester 100 parts, 2,2-bis (4-hydroxycyclohexyl) -propane 284 parts, and ethylene glycol 150 parts. The ratio of the total number of hydroxyl values [X] / the total number of acid values [Y] is 1.19. Stirring was carried out while introducing nitrogen gas, and the reaction was carried out at 200 ° C. for 3 hours while removing alcohol produced during the reaction. Next, 5 parts of tetrabutoxy titanate was added, the reaction temperature was raised to 220 ° C., and the pressure in the flask was gradually reduced.
After the pressure was adjusted to mHg or less, the reaction was continued for another 3 hours to obtain a polyester resin (1). The obtained polyester resin (1) had a number average molecular weight of 3,100, a weight average molecular weight of 10,300, a hydroxyl value of 68 mgKOH / g, and a glass transition temperature of 62 ° C.

(Synthesis Example 2) 317 parts of hexahydrophthalic acid and 3 parts of terephthalic acid were placed in a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing pipe and a nitrogen gas introducing pipe.
29 parts, 304 parts of neopentyl glycol and 50 parts of trimethylolpropane were charged. The ratio of the total number of hydroxyl values [X] / the total number of acid values [Y] is 1.10. Stirring was carried out while introducing nitrogen gas, and the reaction was carried out at 200 ° C. for 3 hours while removing alcohol produced during the reaction. Next, 0.5 part of zinc acetate was added, the reaction temperature was raised to 220 ° C. and the pressure in the flask was gradually decreased to 1.5 mmHg or less after 1.5 hours, and then the reaction was continued for another 3 hours to obtain a polyester resin ( 2) was obtained. The obtained polyester resin (2) has a number average molecular weight of 2,900, a weight average molecular weight of 5,500, and a hydroxyl value of 72 mgKOH / g.
The glass transition temperature was 53 ° C.

Example 1 [Production of Charge Control Resin Composition] As a charge control resin, 24 parts of methyl ethyl ketone and 6 parts of methanol were dispersed in 100 parts of the polyester resin (1) obtained in Synthesis Example 1,
The mixture was kneaded with a roll while cooling. When the charge control resin is wrapped around the roll, a magenta pigment (manufactured by Client Co., trade name “CI Pigment Violet 1
9 ") 100 parts by weight was gradually added and kneading was carried out for 1 hour to produce a charge control resin composition. At this time, the roll gap was initially 1 mm, then gradually widened and finally expanded to 3 mm, and the organic solvent (methyl ethyl ketone /
Methanol = 4/1 mixed solvent) was added several times according to the kneading state of the charge control resin. After taking out a part of the charge control resin composition, toluene was added and dissolved to obtain a 5% solution of the charge control resin composition in toluene. A resin solution was applied onto a glass plate with a doctor blade having a gap of 30 μm and dried to prepare a sheet. When this sheet is observed with an optical microscope, it exists in 100 μm square,
There were no colorant particles with a major axis of 0.2 μm or more.

[Production of Toner] An aqueous solution of 9.8 parts of magnesium chloride (water-soluble polyvalent metal salt) dissolved in 250 parts of ion-exchanged water, and 50 parts of ion-exchanged water with sodium hydroxide (alkali metal hydroxide) 6 An aqueous solution having 9 parts dissolved therein was gradually added under stirring to prepare a magnesium hydroxide colloid (poorly water-soluble metal hydroxide colloid) dispersion. The particle size distribution of the produced colloid was calculated by using D50 (50% cumulative value of number particle size distribution) and D90
(90% cumulative value of number particle size distribution) is a particle size distribution measuring device (manufactured by Shimadzu Corporation, model name "SALD2000A
Mold ”). In the measurement by this particle size distribution measuring device, the refractive index was 1.55 to 0.20i, the ultrasonic wave irradiation time was 5 minutes, and 10% saline was used as a dispersion medium at the time of droplet measurement. 80.5 parts of styrene, 19.5 parts of butyl acrylate, 0.5 parts of divinylbenzene and 0.3 parts of polymethacrylic acid ester macromonomer (trade name "AA6" manufactured by Toagosei Co., Ltd., Tg = 94 ° C) Wet pulverization of the polymerizable monomer for core consisting of 12 parts of the charge control resin composition described above, 2 parts of t-dodecyl mercaptan and 10 parts of dipentaerythritol hexamyristate using a media type wet pulverizer. A polymerizable monomer composition for core was obtained. On the other hand, 2 parts of methyl methacrylate and 100 parts of water were finely dispersed by an ultrasonic emulsifying machine to obtain an aqueous dispersion of a polymerizable monomer for shell. The particle size of the droplets of the polymerizable monomer for shell was Dp90 of 1.6 μm as measured by the above particle size distribution analyzer.

The core monomer composition was added to the magnesium hydroxide colloidal dispersion obtained above, and the mixture was stirred until the droplets became stable, and t-butylperoxy-2-ethylhexano was added thereto. After adding 5 parts of ate (Nippon Yushi Co., Ltd., trade name "Perbutyl O"), using Ebara Milder (Ebara Corporation, model name "MDN303V"), high shear for 30 minutes at 15,000 rpm The mixture was stirred to granulate the droplets of the monomer composition. This granulated aqueous dispersion of the polymerizable monomer composition for the core was placed in a reactor equipped with a stirring blade, and the polymerization reaction was started at 90 ° C. When the polymerization conversion rate reached almost 100%. , Sampled,
The particle size of the core was measured. As a result, the volume average particle size (d
v) was 7.2 μm. Further, an aqueous dispersion of the polymerizable monomer for shell, and 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide (manufactured by Wako Pure Chemical Industries, Ltd., trade name “VA- 086 ") 0.2 part was dissolved in 65 parts of distilled water, and an aqueous solution was placed in the reactor.
After continuing the polymerization for 8 hours, the reaction was stopped to obtain an aqueous dispersion of toner particles having a pH of 9.5.

While stirring the aqueous dispersion of the toner particles obtained above, the system pH was adjusted to 5 or less with sulfuric acid, acid washing (25 ° C., 10 minutes) was performed, and water was separated by filtration, and then fresh. Ion-exchanged water (500 parts) was added to re-slurry and washed with water. After that, dehydration and water washing were repeated several times again to separate solids by filtration, and then dried at 45 ° C. for 2 days in a dryer to obtain toner particles. The dried toner particles were taken out and the volume average particle diameter (d
v) was 7.2 μm, and the volume average particle diameter (dv) / number average particle diameter (dp) was 1.23. The rl / rs was 1.1, and the gel amount was 11%. Further, the number of colorant particles having a major axis of 0.2 μm or more present in a unit area is 1
It was an individual. To 100 parts of the toner particles obtained above, 0.6 part of hydrophobized colloidal silica (trade name "HDK2150" manufactured by Clariant Co., Ltd.) was added,
Toner was prepared by mixing using a Henschel mixer. Table 1 shows the characteristics of the obtained toner and the evaluation of images and the like.

(Examples 2-3) In Example 1, instead of the magenta pigment (trade name "CI Pigment Violet 19" manufactured by Client Co.) as a colorant, a yellow pigment (trade name manufactured by Client Co., Ltd.) was used. "C.
I. Pigment Yellow 180 ″) or a cyan pigment (trade name “CI Pigment Blue 15: 3” manufactured by Client Co.) was used to obtain a toner in the same manner as in Example 1. Table 1 shows the characteristics of the obtained toner and the evaluation results of images.

Comparative Example 1 Instead of using the polyester resin (1) in Example 1 to prepare the charge control resin composition, the polyester resin (2) obtained in Synthesis Example 2 was used. A composition was prepared, and 12 parts of this polyester resin composition and 2 parts of a quaternary ammonium salt charge control agent (trade name "Bontron P-51" manufactured by Orient Chemical Industry Co., Ltd.) as a charge control agent were used for the core. A toner was obtained in the same manner as in Example 1 except that the polymerizable monomer composition was prepared. Table 1 shows the characteristics of the obtained toner and the evaluation of images and the like.

(Comparative Examples 2 to 3) In Comparative Example 1, a yellow pigment (trade name, manufactured by Client Co., Ltd., trade name: CI Pigment Violet 19 manufactured by Client Co., Ltd.) was used as a coloring agent. "C.
I. Pigment Yellow 180 ") or a cyan pigment (trade name" CI Pigment Blue 15: 3 "manufactured by Client Co.) was used to obtain a toner in the same manner as in Comparative Example 1. Table 1 shows the characteristics of the obtained toner and the evaluation results of images.

(Comparative Example 4) In Example 1, instead of using the charge control resin composition, styrene / butyl acrylate / N, N-diethyl-N-methyl-2- (methacryloyloxy) was used as the charge control resin. Ethyl ammonium p-toluene sulfone copolymer (weight average molecular weight 18,
000, glass transition temperature 60 ° C., functional group amount 3%) 6 parts, and magenta pigment (trade name “CI Pigment Violet 19” manufactured by Client Co., Ltd.) as a colorant were used as a core polymerizable monomer. Other than making and using the body composition,
A toner was obtained in the same manner as in Example 1. Table 1 shows the characteristics of the obtained toner and the evaluation of images and the like.

[0085]

[Table 1]

From Table 1, the charge control resin is obtained by polycondensing a polyvalent carboxylic acid compound (A1) containing an amino group or a salt thereof and / or a polyhydric alcohol (A2) containing an amino group or a salt thereof. Area of toner 10 containing no polyester resin and heat-melted to a film thickness of 20 μm
The positively chargeable toners of Comparative Examples 1 to 4 in which the number of colorant particles having a major axis of 0.2 μm or more observed in 0 μm × 100 μm is 50 or more, the pigment dispersibility and color tone are poor, the printing density is low, and the fog is low. You can see that there are many. On the other hand, it can be seen that the positively chargeable toner of the present invention has high environmental stability, good pigment dispersibility and color tone, high print density, and reduced fog.

[0087]

The positively chargeable toner of the present invention has a wide interval between the fixing start temperature and the offset start temperature even in a fixing device in which a heat-resistant film capable of power saving and quick start and a thermal head are combined, and is excellent. It exhibits excellent low temperature fixing characteristics, high surface smoothness of fixed images, and high temperature storability. In addition, the stability of the charge amount is excellent and the dispersibility of the colorant is excellent, so that the reproducibility of the color image is high, a clear image can be obtained, the fog is small, and the printing density can be increased. Difficult to cause color transfer and sticking to vinyl resin sheet.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 G03G 9/08 351 9/087 384 9/09 361 F term (reference) 2H005 AA06 AA11 AB02 AB06 CA08 CA21 CA30 DA03 EA05 EA07 4J002 CF131 FD096 GS00 GT00 4J029 AA02 AB07 AC02 AE18 BA02 BD02 BD06 BD10 BH01 CB05 CB06 CB10 CC06 CD03 CH01 DA01 DA02 HA01 HB01 HB02 HB06

Claims (17)

[Claims] 1. An area 1 of a toner containing a binder resin, a charge control resin and a colorant, which is heated and melted to a film thickness of 20 μm.
The number of colorant particles having a major axis of 0.2 μm or more observed in 00 μm × 100 μm is 50 or less, and the charge control resin contains a polyvalent carboxylic acid compound (A1) containing an amino group or a salt thereof and / or A positively chargeable toner which is a polyester resin obtained by polycondensing a polyhydric alcohol (A2) containing an amino group or a salt thereof. 2. The positively chargeable toner according to claim 1, wherein the charge control resin is a polyester resin obtained by further polycondensing the cyclic divalent carboxylic acid compound (B). 3. The positively chargeable toner according to claim 2, wherein the charge control resin is a polyester resin obtained by polycondensing a cyclic dihydric alcohol (C). 4. The positively chargeable toner according to claim 3, wherein the charge control resin is a polyester resin obtained by polycondensing a chain dihydric alcohol (E). 5. The positively chargeable toner according to claim 2, wherein the cyclic divalent carboxylic acid compound (B) is an alicyclic divalent carboxylic acid compound. 6. The positively charged compound according to claim 5, wherein the alicyclic divalent carboxylic acid compound is a compound in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two adjacent carbon atoms forming an alicycle. Toner. 7. The cyclic dihydric alcohol (C) is alicyclic 2
The positively chargeable toner according to claim 3, wherein the positively chargeable toner is a hydric alcohol. 8. The positively chargeable toner according to claim 7, wherein the alicyclic dihydric alcohol is bis (hydroxycyclohexyl) -alkane. 9. A charge control comprising a polyester resin obtained by polycondensing a polyvalent carboxylic acid compound (A1) containing an amino group or a salt thereof and / or a polyhydric alcohol (A2) containing an amino group or a salt thereof. A step of mixing 100 parts by weight of a resin, 10 to 200 parts by weight of a colorant, and 0 to 100 parts by weight of an organic solvent capable of dissolving the charge control resin to obtain a charge control resin composition. Method for producing positively chargeable toner. 10. The method for producing a positively chargeable toner according to claim 9, wherein the charge control resin is a polyester resin obtained by further polycondensing the cyclic divalent carboxylic acid compound (B). 11. The method for producing a positively chargeable toner according to claim 10, wherein the charge control resin is a polyester resin obtained by further polycondensing a cyclic dihydric alcohol (C). 12. The method for producing a positively chargeable toner according to claim 11, wherein the charge control resin is a polyester resin obtained by polycondensing a chain dihydric alcohol (E). 13. The cyclic divalent carboxylic acid compound (B) is
The method for producing a positively chargeable toner according to claim 10, which is an alicyclic divalent carboxylic acid compound. 14. The positively charged compound according to claim 13, wherein the alicyclic divalent carboxylic acid compound is a compound in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two adjacent carbon atoms forming an alicycle. Method for producing a volatile toner. 15. The method for producing a positively chargeable toner according to claim 11, wherein the cyclic dihydric alcohol (C) is an alicyclic dihydric alcohol. 16. The method for producing a positively chargeable toner according to claim 15, wherein the alicyclic dihydric alcohol is bis (hydroxycyclohexyl) -alkane. 17. A polymerizable monomer composition is obtained by mixing 2 to 20 parts by weight of the charge control resin composition with 100 parts by weight of a polymerizable monomer, and polymerized in an aqueous dispersion medium. 17. The method for producing a positively chargeable toner according to claim 9, which comprises: