JP2008129395A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which is superior in anti-electrostatic offset characteristics in a low-humidity environment and provides superior and stable images over a long period of time, even under a high-temperature environment. <P>SOLUTION: The toner contains at least a coloring agent, an inorganic powder material and a resin; wherein the weight-average particle size (D4) is 3-10 μm; the ratio D4/D1 of the weight-average particle size (D4) to number average particle size (D1) is at least 1 and at most 1.8; the glass transition temperature is 30-65°C, and the average circularity is 0.950-0.999; and further, the resin contains a polycondensed polyester resin, and the polycondensed polyester resin is a resin which is formed in the presence of a specific titanium-containing catalyst. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or a toner jet recording method.

  Conventionally, many methods are known as electrophotographic methods. Generally, there is a known method for obtaining a toner image by using a photoconductive substance, forming an electric latent image on a photoreceptor, transferring the toner image onto a transfer material such as paper, and fixing it by heat or pressure. It has been.

  Various methods and apparatuses have been developed as a fixing method, but the most common method at present is a pressure heating method using a heated roller, film or belt. In particular, pressure heating using a film is widely used because it can be fixed with a relatively low amount of heat.

  In recent years, copying apparatuses and printers using electrophotography have been required to have higher speed and higher image quality, and it has been necessary to provide high-definition images while accelerating the process speed of the apparatus. However, as the speed increases, the load on the toner increases and the time for the toner to obtain a charge is shortened, so that the image density is lowered and the fog is easily deteriorated due to toner wear and unstable charging. . In particular, the temperature rise in a high temperature environment tends to increase, and the developability is likely to deteriorate due to acceleration of aggregation and toner wear due to surface alteration due to heat. On the other hand, when fixing at high speed and continuously in an environment where the chargeability of the toner is likely to increase, such as under low humidity, a phenomenon called electrostatic offset occurs in which the toner adheres to the fixing roller as the excessively charged component of the toner increases. It becomes easy.

  A toner capable of preventing these phenomena as much as possible is indispensable for high speed and high stability, and improvement is desired.

  For example, in Patent Document 1, Ti is used as a catalyst for a polyester resin and a ligand is an alkylamine group, an alkoxy group, an alkenyloxy group, or an acyloxy group. Thus, proposals have been made to improve toner durability, particularly wear resistance. Patent Document 2 discloses an invention that imparts long-term stability, particularly filming resistance, to a toner by using a titanium catalyst at the time of polyester production and further controlling the titanium content in the resulting resin. However, these inventions still have problems in terms of image quality such as density stability during long-term printing and suppression of fog deterioration.

  There has also been an invention in which a polycondensation resin using a titanium catalyst and a composite oxide are combined (Patent Document 3). This improvement improves the development performance under high temperature and high humidity, but leaves room for further improvement in terms of electrostatic offset resistance.

In improving the developability, Patent Document 4 uses a polyester resin whose physical properties are limited as a toner binder,
A technique of mixing and using a high softening point and low softening point polyester produced in the presence of a titanium catalyst having a specific ligand as in Patent Document 5,
Furthermore, as disclosed in Patent Document 6, there is a proposal achieved by a technique in which a polyester resin having a limited amount of tetrahydrofuran and insoluble matter and a monomer structure is used as a toner binder. These proposals have obtained satisfactory performance at room temperature, but are insufficient in terms of durable development performance at high temperatures assuming in-machine temperature rise. Further, in a configuration in which a load is applied to the toner, there is a concern that the developability is deteriorated due to insufficient wear resistance of the toner.

Japanese Patent Registration No. 3623480 JP 2004-133320 A Japanese Patent Laid-Open No. 2004-177607 JP 2004-258627 A JP 2005-91696 A JP 2005-195684 A

  An object of the present invention is to provide a toner that solves the above problems.

  An object of the present invention is to provide a toner that has excellent electrostatic offset resistance in a low-humidity environment and can stably obtain an excellent image over a long period of time even in a high-temperature environment.

As a result of intensive studies, the present inventors can satisfy the above requirements by using a polyester resin synthesized with a specific polymerization catalyst as a binder resin and further adjusting the toner physical properties to optimum ones. And found the present invention. That is, the above object can be achieved by the following toner.
(1) A toner containing at least a colorant, an inorganic fine powder, and a resin,
The weight average particle diameter (D4) of the toner is 3 to 10 μm, and the ratio D4 / D1 of the weight average particle diameter (D4) to the number average particle diameter (D1) is 1 or more and 1.8 or less.
The toner has a glass transition temperature of 30 to 65 ° C .;
The toner has an average circularity of 0.950 to 0.999,
The resin contains a polycondensed polyester resin;
A toner wherein the polycondensation polyester resin is a resin formed in the presence of at least one titanium-containing catalyst (a) represented by the following general formula (I) or (II).
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[In the formula, X is a residue obtained by removing H of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, and other OH groups of the polyalkanolamine are directly bonded to the same Ti atom. An OH group may be polycondensed in the molecule to form a ring structure, or an OH group directly bonded to another Ti atom may be polycondensed between molecules to form a repeating structure. The degree of polymerization in the case of forming a repeating structure is 2-5. R is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]
(2) The toner according to (1), wherein the toner contains 3.0% by volume or less of particles having a particle size of 12.7 μm or more and 20% by number or less of particles having a particle size of 4.0 μm or less. toner.
(3) The toner according to (1) or (2), wherein the toner contains toner particles generated in an aqueous medium.
(4) The toner contains toner particles produced by dispersing a polymerizable monomer composition in an aqueous medium, granulating the polymerized monomer, and (1). The toner according to (3).
(5) The toner according to (1) to (4), wherein the colorant contained in the toner contains at least a magnetic substance.

  According to the present invention, it is possible to provide a toner which is excellent in electrostatic offset resistance under a low humidity environment and can stably obtain an excellent image for a long time even under a high temperature environment.

  As a result of intensive investigations on improvement of electrostatic offset resistance and durability developability in a high temperature environment, the present inventors have used a polyester resin synthesized in the presence of a specific titanium catalyst as a toner binder resin, and the toner surface. It has been found that it is important to control the shape and physical properties.

  The outline of the relationship between the performance of the toner of the present invention and each component will be described below.

  The toner of the present invention has a weight average particle diameter (D4) of 3 to 10 μm and a ratio D4 / D1 of the weight average particle diameter (D4) to the number average particle diameter (D1) of 1 or more and 1.8 or less. .

  In the case of D4> 10 μm, the chargeability is lowered, and the image density is remarkably lowered due to an increase in low charge components. In the case of D4 <3 μm, the excessively charged component is increased, so that the electrostatic offset resistance is greatly deteriorated.

  D4 / D1 represents the sharpness of the particle size distribution of the toner. The closer the value is to 1, the sharper the value, and the larger the value, the broader the value. When this D4 / D1 exceeds 1.8, the toner charge amount distribution becomes broad, so that the remarkable destabilization of the developability due to the low charge component and the static resistance due to the overcharge component. Decrease in electric offset is observed.

  By including the polyester resin in the toner, excellent charging performance can be imparted to the toner. Furthermore, by using a titanium compound having a polyalkanol aminate as a ligand as a polyester polymerization catalyst, it becomes possible to give the resin an appropriate strength and charge stabilization effect. This is because a titanium compound having a polyalkanol aminate as a ligand reacts while being incorporated into the resin during the reaction, and takes a specific structure due to titanium and the ligand, thereby improving the resin strength and charging. We believe that it has a stabilizing effect.

  Furthermore, the toner shape is important in order to sufficiently exhibit the effect of the polyester resin. Specifically, by bringing the toner close to a spherical shape by a manufacturing method or heat treatment, the polyester of the present invention exhibits the charging and stabilizing effect and further wear resistance. This is considered to be effective because the specific structure of the polyester resin is efficiently present in the vicinity of the surface.

  Further, from the viewpoint of the wear resistance and charging performance of the toner, the glass transition point of the toner needs to be 30 ° C. to 65 ° C. If it is less than 30 ° C., the wear resistance and the storage stability at high temperatures are remarkably lowered, so the effects of the present invention cannot be obtained. Further, if the temperature exceeds 65 ° C., the toner becomes too hard, so that proper charging cannot be obtained at the time of frictional charging, and the developing property deteriorates because the charge distribution is greatly broadened, and the excessively charged components also increase. As a result, the electrostatic offset resistance is significantly reduced.

  That is, the present invention is realized by using a polyester resin synthesized in the presence of a specific titanium catalyst as a binder resin for a toner, making the toner surface shape as spherical as possible, and setting the glass transition point in an appropriate range.

  The material used by this invention is explained in full detail below.

  The titanium-containing catalyst (a) used in the present invention is a compound represented by the formula (I) or (II), and two or more kinds may be used in combination.

  In the general formulas (I) and (II), X is a residue obtained by removing one OH group H from a mono- or polyalkanolamine having 2 to 12 carbon atoms. When the number of carbon atoms is less than 2, the hydrophobicity of the titanium compound is reduced, so that the polyester resin is easily affected by humidity, destabilization of charge and developability in a high humidity environment. On the other hand, when the number of carbon atoms exceeds 12, it tends to be excessively charged, and the durability developability tends to decrease. The number of nitrogen atoms in the catalyst, that is, the total number of primary, secondary, and tertiary amino groups is usually 1 to 2, but preferably 1 from the viewpoint of the reaction activity of the titanium-containing catalyst.

  Preferred as X are residues of dialkanolamine (particularly diethanolamine) and residues of trialkanolamine (particularly triethanolamine), and particularly preferred are residues of triethanolamine.

  As said monoalkanolamine, arbitrary alkanolamines, such as ethanolamine and a propanolamine, can be used.

  Examples of polyalkanolamines include dialkanolamines (such as diethanolamine, N-methyldiethanolamine, and N-butyldiethanolamine), trialkanolamines (such as triethanolamine, and tripropanolamine), and tetraalkanolamines (N, N, N). ', N'-tetrahydroxylethylethylenediamine and the like).

  In the case of polyalkanolamine, at least one OH group is present in addition to the OH group that is a residue other than H used to form a Ti—O—C bond with a Ti atom, and this is the same Ti atom. A ring structure may be formed by polycondensation with a directly bonded OH group in the molecule. In addition, a repeating structure may be formed by polycondensation between molecules with OH groups directly bonded to other Ti atoms. The ring structure is a structure that can be easily formed when a hydroxyl group that is not involved in the binding of polyalkanolamine and other hydroxyl groups in the molecule are polycondensed, but the presence or absence of the ring structure does not affect the activity of the catalyst. Even if the repeating structure is formed, the performance is not affected, but the degree of polymerization is preferably 2 to 5 from the viewpoint of catalytic activity.

  R represents H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. Specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, β-methoxyethyl group and β -An ethoxyethyl group etc. are mentioned. R is preferably H and an alkyl group having 1 to 4 carbon atoms that does not contain an ether bond, and more preferably H, an ethyl group, and an isopropyl group.

  In the formula (I), m is an integer of 1 to 4, and the sum of m and n is 4.

  In formula (II), p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2.

  m or p is preferably 2 or more. When m or p is 1 or less, the activity of the catalyst is slightly lowered, so that the polyester resin tends to have a slightly low molecular weight. There is a tendency to weaken. A plurality of X may be the same or different, but the same X is preferable from the viewpoint of stability and activity of the titanium-containing catalyst (a).

  Specific examples of the titanium-containing catalyst (a) in the present invention represented by the general formula (I) include titanium dihydroxybis (triethanolamate), titanium trihydroxydiethanolamate, titanium trihydroxymonoethanol. Aminate, titanium trihydroxytriethanolaminate, titanium dihydroxybis (diethanolamate), titanium dihydroxybis (monoethanolamate), titanium dihydroxybis (monopropanolamate), titanium dihydroxybis (N-methyldiethanolamate), Titanium dihydroxybis (N-butyldiethanolamate), tetrahydroxytitanium and N, N, N ′, N′-tetrahydroxyethylethylenedi Min and reaction products, and polycondensates between within or molecules of these molecules.

  Specific examples of those represented by the general formula (II) include titanyl bis (triethanolamate), titanyl bis (diethanolamate), titanyl bis (monoethanolamate), titanylhydroxyethanolamate, titanylhydroxydiethanolamate, titanylhydroxy Examples include triethanolaminate, titanylethoxydiethanolamate, titanylethoxytriethanolamate, titanylisopropoxytriethanolaminate, and intramolecular or intermolecular polycondensates thereof.

  Preferred as the titanium-containing catalyst (a) are titanium dihydroxybis (triethanolamate), titanium dihydroxybis (diethanolamate), titanyl bis (triethanolamate), a polycondensate thereof, and a combination thereof. More preferably, it is titanium dihydroxybis (triethanolaminate). When the catalyst structure contains an alkanolamine group, the higher the number of alkanolamine groups and the carbon number of the alkanolamine group, the higher the resistance to humidity of the part that maintains the catalyst structure in the resin, and it can be applied as a toner material. In this case, the durable developability of the toner tends to be improved.

  These titanium-containing catalysts (a) can be stably obtained by, for example, reacting titanium dialkoxybis (alcohol aminate) at 70 to 90 ° C. in the presence of water.

  The polycondensation polyester resin contained in the toner of the present invention is obtained by reacting a polyester resin that is a polycondensate of a divalent or higher alcohol monomer component and a divalent or higher carboxylic acid monomer component, or a polyepoxide. A modified polyester resin and a polyester resin obtained by modifying the polyester resin with a vinyl monomer such as styrene or butyl acrylate may also be contained.

Specific examples of the dihydric or higher alcohol monomer component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3. 3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene Alkylene oxide adducts of bisphenol A such as (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane,
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1, Examples include 6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, and hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol monomer component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Is mentioned.

Examples of the divalent or higher carboxylic acid monomer component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, or anhydrides thereof;
Alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof;
Succinic acid or anhydride thereof substituted with an alkyl or alkenyl group having 6 to 18 carbon atoms;
And unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof.

Examples of other monomers include glycerin, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ethers of novolak type phenol resins;
Polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and its anhydrides;
Examples thereof include hydroxycarboxylic acids such as hydroxystearic acid and hydrogenated castor oil fatty acid; and lactones such as caprolactone.

  Among them, in particular, a bisphenol derivative represented by the following general formula (a) is a dihydric alcohol monomer component, and a carboxylic acid component (a divalent or higher carboxylic acid or acid anhydride thereof, or a lower alkyl ester thereof) ( For example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) are used as acid monomer components, and resins obtained by condensation polymerization with these polyester unit components have good charging characteristics. Therefore, it is preferable.

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  Regarding the physical properties of the polycondensed polyester of the present invention, preferred ranges for use as a toner material are described below.

  The peak top molecular weight of the polycondensed polyester resin is preferably 1000 to 30000, more preferably 1500 to 25000, and particularly 1800 to 20000.

  The acid value (mgKOH / g) of the polycondensed polyester resin is preferably 0.1 to 60, more preferably 0.2 to 50, and particularly 0.5 to 40.

  The hydroxyl value (mgKOH / g) of the polycondensed polyester resin is preferably 1 to 70, more preferably 3 to 60, particularly 5 to 55.

  The glass transition point of the polycondensed polyester resin is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, particularly 55 to 75 ° C.

  The polycondensation polyester resin in the present invention can be produced in the same manner as in the usual polyester production method. For example, it can be carried out by reacting at a reaction temperature of 150 to 280 ° C. in the presence of a titanium-containing catalyst (a) in an inert gas (such as nitrogen gas) atmosphere. Moreover, it is preferable that reaction time shall be about 2 to 40 hours from a viewpoint of performing a polycondensation reaction reliably. It is also effective to reduce the pressure (for example, 1 to 50 mmHg) in order to improve the reaction rate at the end of the reaction.

  The addition amount of (a) is preferably 0.0001 to 0.8%, more preferably 0.0002 to 0.6%, particularly preferably, based on the weight of the polymer obtained from the viewpoint of polymerization activity. Is 0.0015 to 0.55%.

  In addition, other esterification catalysts can be used in combination as long as the catalytic effect of (a) is not impaired. Examples of other esterification catalysts include tin-containing catalysts, trimonic acid antimony, titanium-containing catalysts other than (a) (for example, titanium alkoxide, titanyl potassium oxalate, and titanium terephthalate), zirconium-containing catalysts, and germanium-containing catalysts. , Alkali (earth) metal catalyst, zinc acetate and the like. The addition amount of these other catalysts is preferably 0 to 0.6% with respect to the obtained polymer. The content of (a) in all the added catalysts is preferably 50 to 100%.

  As the resin constituting the toner, in addition to the above-mentioned condensation-polymerized polyester, a vinyl resin such as styrene / acrylic resin may be used in combination.

Examples of vinyl resins include polystyrene; homopolymers of styrene-substituted products such as poly-p-chlorostyrene and polyvinyltoluene;
Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylic acid Acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene Styrene copolymers such as copolymers, styrene-acrylonitrile-indene copolymers;
Acrylic resin; Methacrylic resin; Polyvinyl acetate; Silicone resin; Polyester resin; Polyamide resin; Furan resin; Epoxy resin; These resins are used alone or in combination.

As monomers for the styrene monomer of the styrene-based copolymer, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, A monocarboxylic acid having a double bond such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof;
Dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate and dimethyl maleate, and their substitutes; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate;
Examples thereof include ethylene-based olefins such as ethylene, propylene, and butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

  The main component of the toner resin component is preferably a polyester resin and / or a styrene copolymer which is a copolymer of styrene and another vinyl monomer.

  The styrenic copolymer is preferably cross-linked with a cross-linkable monomer as required in order to improve the durability developability.

  Crosslinkable monomers include aromatic divinyl compounds, diacrylate compounds linked by alkyl chains, diacrylate compounds linked by alkyl chains containing ether bonds, and chains containing aromatic groups and ether bonds. Diacrylate compounds, polyester-type diacrylates and the like are preferably used. Each crosslinkable monomer is exemplified below.

Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene;
Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6 hexanediol. Diacrylate, neopentylglycol diacrylate, and those obtained by replacing acrylate of the above compound with methacrylate;
Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, And those in which propylene glycol diacrylate and acrylate of the above compounds are replaced by methacrylate;
Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2. , 2-bis (4-hydroxyphenyl) propane diacrylate and the above compounds in which the acrylate is replaced by methacrylate;
Examples of polyester diacrylates include trade name MANDA (Nippon Kayaku).

  As the colorant used in the toner of the present invention, the following yellow / magenta / cyan colorants can be used. As the black colorant, carbon black and a magnetic material can be used as the main colorant. However, when a magnetic material is used, a large charge stabilization effect is obtained when combined with the polyester of the present invention, which is preferable.

Examples of the magnetic material used in the present invention include iron oxides such as magnetite, maghemite and ferrite, and iron oxides including other metal oxides;
Metals such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, Examples thereof include alloys with metals such as V, and mixtures thereof.

Specifically, as a material of the magnetic substance, triiron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), iron oxide zinc (ZnFe ₂ O ₄ ), iron yttrium oxide (Y ₃ Fe ₅ O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), iron oxide copper (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), oxidation Iron nickel (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron oxide manganese (MnFe ₂ O ₄ ), oxidation Examples thereof include iron lanthanum (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), and nickel powder (Ni). The magnetic materials described above are used alone or in combination of two or more. A particularly suitable material is a fine powder of triiron tetroxide or γ-iron sesquioxide.

These magnetic materials have an average particle diameter of 0.05 to 2 μm, magnetic properties of 795.8 kA / m applied, coercive force of 1.6 to 12.0 kA / m, saturation magnetization of 50 to ²⁰⁰ Am ² / kg (preferably 50 to 100 Am ² / kg) and residual magnetization of ^{2 to 20} Am ² / kg are preferable.

  The magnetic material is used in an amount of 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the binder resin.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, C.I. I. Pigment Yellow 3.7.10.12.12.14.15.17.233.24.60.62.7.74.75.5.83.93.95.99.9.100.101.104.108.109.110 111.117.123.128.129.138.139.147.148.1500.155.166.168.169.177.179.180.181.183.185.191: 1.191.192.193 .199 or the like is preferably used. Examples of the dye system include C.I. I. solvent Yellow 33.567.79.93.112.162.163, C.I. I. disperse Yellow 42.64.2011.211 etc. are mentioned. By including such a yellow colorant in the toner, a yellow toner can be obtained.

  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, 238, 254, 269, C.I. I. Pigment Bio Red 19 is particularly preferable. By including such a magenta colorant in the toner, a magenta toner can be obtained.

  As the cyan colorant, 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. By incorporating such a cyan colorant into the toner, a cyan toner can be obtained.

  A full color toner that forms a full color image can be obtained by combining the black toner, yellow toner, magenta toner, and cyan toner.

  The toner of the present invention may contain a charge control agent in order to stabilize the charge characteristics. A well-known thing can be utilized as a charge control agent.

  For example, organometallic compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

  Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, resin charge control agents, and the like can be given.

  The following substances are used to control the toner to be positively charged.

Nigrosine-modified products of nigrosine and fatty acid metal salts, etc .; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and lake lake pigments thereof;
Triphenylmethane dyes and their lake pigments (for example, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide);
Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate;
Examples thereof include resin-based charge control agents such as polar polymers having a sulfonic acid or carboxylic acid group in the side chain. These can be used alone or in combination of two or more.

  When a 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 suitable, and a polar polymer or a metal-containing salicylic acid compound is suitable. Is preferred.

  The charge control agent is used in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the resin.

  The toner of the present invention preferably contains 1 to 50% by weight of a release agent with respect to the binder resin.

A known wax can be used as a release agent that can be used in the toner of the present invention. For example, paraffin wax, microcrystalline wax, petroleum wax such as petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method,
Examples thereof include polyolefin waxes and their derivatives represented by polyethylene, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof. Derivatives here include oxides, block copolymers with vinyl monomers, and graft modified products. It is also possible to control the state of dispersion of iron oxide in the toner by adjusting the acid value and the degree of modification of the wax. Furthermore, higher aliphatic alcohols, higher fatty acids or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant-based waxes, and animal waxes can also be used.

  As a method for producing the toner particles contained in the toner of the present invention, a known method can be used. However, when the toner of the present invention contains toner particles generated in an aqueous medium, the polycondensation polyester of the present invention is used. It is preferable because it is easily present in the vicinity of the toner surface. Among them, the method of dispersing a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium, granulating, and polymerizing the polymerizable monomer is easy to control the toner shape to an optimum one. preferable.

  Specific examples of the method for producing toner particles in the aqueous medium include suspension polymerization, dissolution suspension, emulsion aggregation, association polymerization, and the like. The suspension polymerization method, which is a method for dispersing, granulating and polymerizing a polymerizable monomer in an aqueous medium, is most preferably used in the present invention. This is because, when the suspension polymerization method is used, the structure derived from the Ti catalyst having a high charge stabilizing effect can be uniformly present in the vicinity of the surface, so that the effect of the present invention can be sufficiently obtained.

  A method for producing toner particles by the suspension polymerization method will be described below.

  In the suspension polymerization method, a polymerizable monomer, a colorant, a release agent, and other additives as necessary are uniformly added by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser. The dissolved or dispersed monomer system is suspended in an aqueous medium containing a dispersion stabilizer. The polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

As the polymerizable monomer used in the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate Acrylic polymerizable monomers such as n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate Methacrylic polymerizable monomers such as n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate;
Methylene aliphatic monocarboxylic acid ester; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether;
Examples thereof include vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  In the present invention, the above monofunctional polymerizable monomers are used singly or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are combined. use. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

As the polymerization initiator used in the polymerization of the polymerizable monomer described above, an oil-soluble initiator and / or a water-soluble initiator is used. For example, as the oil-soluble initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) Azo compounds such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile;
Acetylcyclohexylsulfonyl peroxide, diisopropyl peroxide, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t -Peroxide initiators such as butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide .

  Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salts, sodium azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

  In the present invention, in order to control the polymerization degree of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.

As the crosslinking agent used in the toner of the present invention, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate;
And divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  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, the polymerized toner particles are preferably filtered, washed and dried by a known method, and then a classification step is performed to cut coarse powder and fine powder.

  In the present invention, the amount of coarse powder and fine powder is important from the viewpoint of toner performance. The toner of the present invention contains 3.0% by volume or less of particles having a particle size of 12.7 μm or more and 20 number% of particles having a particle size of 4.0 μm or less by adjusting the toner production method and the classification process. It is preferable to contain below. When the coarse powder of 12.7 μm or more exceeds 3.0% by volume, the chargeability of the toner tends to decrease and the density tends to become unstable. On the other hand, when the amount of fine powder of 4.0 μm or less exceeds 20% by number, excessively charged components increase and electrostatic offset is likely to occur.

  The toner of the present invention can be obtained by externally mixing and adhering inorganic fine particles such as a fluidity imparting agent and abrasive and resin fine particles to the toner particles, if necessary.

  The above-mentioned inorganic fine particles preferably used in the present invention are described below.

  Examples of the charge controllable particles among the inorganic fine particles include metal oxides (such as tin oxide, titania, zinc oxide, silica, alumina) and carbon black.

  Abrasives include metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, etc.) , Calcium carbonate, etc.). Of these, strontium titanate is preferably used as the abrasive.

  Examples of the fluidity-imparting agent include metal oxides (silica, alumina, titania, etc.), carbon fluoride, and the like. Each of them is more preferably hydrophobized.

  The total amount of the inorganic fine powder added to the toner in the present invention is preferably 0.5 to 4.5 parts by mass, more preferably 0.8 to 3.5 parts by mass with respect to 100 parts by mass of the toner particles. When the total amount of the inorganic fine powder is less than 0.5 parts by mass, the fluidity of the toner becomes insufficient, fogging caused by a decrease in chargeability, and toner scattering may occur, and the effects of the present invention can be sufficiently exerted. Absent. On the other hand, when the total addition amount is more than 4.5 parts by mass, adverse effects such as toner scattering, deterioration of fixability, fusion of the photosensitive member, and reduction of the toner charge amount due to contamination of the charging member occur.

Titania, silica, and alumina preferably added as the inorganic fine particles have a specific surface area of 20 to 400 m ² / g, more preferably 35 to 300 m ² / g, more preferably 50 to 230 m ² / g as measured by the BET method. Those within the range are good.

  The inorganic fine particles as the fluidity-imparting agent are silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, and others for the purpose of improving hydrophobicity, chargeability, and transferability. The treatment is preferably performed by using a treating agent such as an organosilicon compound alone or in combination.

  Other inorganic fine particles include an anti-caking agent; a conductivity imparting agent such as zinc oxide, antimony oxide, tin oxide; and a developability improver.

  Moreover, resin fine particles can be added as necessary. For example, resin fine particles obtained by homopolymerizing or copolymerizing monomer components used in a binder resin for toner, such as styrene, acrylic acid, methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate, by an emulsion polymerization method.

  The addition amount of these additives is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the toner.

  Examples of image forming methods to which the toner of the present invention can be applied are shown below.

  In the image forming apparatus of FIG. 1, reference numeral 100 denotes a photosensitive drum, and a primary charging roller 117, a developing device 140, a transfer charging roller 114, a cleaner 116, a register roller 124, and the like are provided around the photosensitive drum. The photoreceptor 100 is charged to, for example, −700 V by the primary charging roller 117 (applied voltages are AC voltage −2.0 kVpp, DC voltage −700 Vdc). Then, exposure is performed by irradiating the photosensitive member 100 with a laser beam 123 by the laser generator 121. The electrostatic latent image on the photoconductor 100 is developed with a one-component magnetic developer by the developing device 140 and transferred onto the transfer material by the transfer roller 114 in contact with the photoconductor via the transfer material. The transfer material on which the toner image is placed is conveyed to the fixing device 126 by the conveying belt 125 or the like and fixed on the transfer material. In addition, toner remaining on a part of the photoreceptor is cleaned by the cleaning unit 116. As shown in FIG. 2, the developing device 140 is provided with a cylindrical toner carrier 102 (hereinafter referred to as a developing sleeve) made of a nonmagnetic metal such as aluminum or stainless steel in the vicinity of the photosensitive member 100. The gap between 100 and the developing sleeve 102 is maintained at about 300 μm by a sleeve / photoreceptor gap holding member (not shown). A magnet roller 104 is fixed and disposed concentrically with the developing sleeve 102 in the developing sleeve. However, the developing sleeve 102 is rotatable. The magnet roller 104 is provided with a plurality of magnetic poles as shown in the figure, where S1 affects development, N1 regulates the toner coat amount, S2 takes in / conveys toner, and N2 affects toner blowout prevention. The toner is applied to the developing sleeve 102 by the toner application roller 141, and is adhered and conveyed. An elastic blade 103 is provided as a member for regulating the amount of toner conveyed, and the amount of toner conveyed to the development area is controlled by the contact pressure of the elastic blade 103 against the developing sleeve 102. In the development region, a DC and AC development bias is applied between the photoconductor 100 and the development sleeve 102, and the developer on the development sleeve flies onto the photoconductor 100 in accordance with the electrostatic latent image and becomes a visible image. .

  Next, measurement methods of various materials and toner physical property data in the present invention will be described in detail below.

(1) Average circularity of toner The circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles. In the present invention, flow type particle image analyzer FPIA- manufactured by Toa Medical Electronics Co., Ltd. is used. The particle shape is measured using 2100, and the circularity is obtained by the following equation. Furthermore, as shown by the following equation, a value obtained by dividing the total roundness of all the measured particles by the total number of particles is defined as the average circularity.

(2) Toner particle size distribution A Coulter Counter TA-II type (manufactured by Coulter Inc.) is used as a measuring device, and an interface (manufactured by Nikkiki) that outputs number distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) are provided. Connect and prepare 1% NaCl aqueous solution using 1st grade sodium chloride as electrolyte. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and the number of toners are measured by measuring the volume and number of toners using the Coulter counter TA-II type with a 100 μm aperture as the aperture. Calculate the volume distribution and number distribution of particles of ˜40 μm. Then, the weight-based weight average diameter D4 obtained from the number average particle diameter (D1) volume distribution (the median value of each channel is the representative value for each channel), and the weight-based weight of 12.7 μm or more obtained from the volume distribution. Find the distribution.

(3) Measurement of magnetic properties of iron oxide Magnetic properties of iron oxide were measured using an “vibrating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.) under an external magnetic field of 79.6 kA / m. It is a measured value.

(4) Measurement of acid value and hydroxyl value of resin <Acid value>
The acid value is determined as follows. Basic operation conforms to JIS-K0070.
(A) As the reagent (I) solvent, an ethyl ether-ethyl alcohol mixed solution (1 + 1 or 2 + 1) or a benzene-ethyl alcohol mixed solution (1 + 1 or 2 + 1) is used. Neutralize with 1 mol / liter potassium hydroxide ethyl alcohol solution.
(II) Phenolphthalein solution: 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 vol%).
(III) 0.1 mol / liter potassium hydroxide-ethyl alcohol solution: Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 vol%) to 1 liter, leave it for 2 to 3 days, and filter. . The standardization is performed according to JIS K 8006 (basic matters concerning titration during the reagent content test).
(B) Operation: 1-20 g of a sample (toner or binder resin) is weighed correctly, 100 ml of a solvent and a few drops of a phenolphthalein solution as an indicator are added thereto, and shaken sufficiently until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this is titrated with a 0.1 mol / liter potassium hydroxide ethyl alcohol solution, and the end point of neutralization is taken when the indicator is slightly red for 30 seconds.
(C) Calculation formula The acid value is calculated by the following formula.

here,
A: Acid value (mgKOH / g)
B: Amount of 0.1 mol / liter potassium hydroxide ethyl alcohol solution (ml)
f: 0.1 mol / liter of potassium hydroxide ethyl alcohol solution, factor S: sample (g)

<Hydroxyl value>
The hydroxyl value is determined as follows. Basic operation conforms to JIS-K0070.
(A) Reagent (I) Acetylation reagent: Add 25 g of acetic anhydride to a 100 ml volumetric flask, add pyridine to make a total volume of 100 ml, and shake well. The acetylating reagent should be kept away from moisture, carbon dioxide and acid vapors and stored in a brown bottle.
(II) Phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 vol%).
(III) N / 2 potassium hydroxide-ethyl alcohol solution Dissolve 35 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 vol%) to 1 liter, leave it for 2 to 3 days, and filter. The orientation is performed according to JIS K 8006.
(B) Operation: 0.5-2.0 g of a sample is correctly weighed in a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. Put a small funnel over the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at 95-100 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disk with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. In order to further complete the decomposition, the flask was again heated in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the wall of the flask were washed with 5 ml of ethyl alcohol, and N / 2 potassium hydroxide ethyl alcohol using a phenolphthalein solution as an indicator. Titrate with solution. A blank test is performed in parallel with the main test.
(C) Calculation formula The hydroxyl value is calculated by the following formula.

here,
A: Hydroxyl value (mgKOH / g)
B: Amount used of N / 2 potassium hydroxide ethyl alcohol solution for blank test (ml)
C: Amount of use of N / 2 potassium hydroxide ethyl alcohol solution in this test (ml)
f: Factor of N / 2 potassium hydroxide ethyl alcohol solution S: Sample (g)
D: Acid value

(5) Molecular Weight Measurement of Toner and Resin In the present invention, the molecular weight distribution of the chromatogram by GPC (gel permeation chromatography) using THF as a solvent for the tetrahydrofuran (THF) of the toner binder resin is as follows. Measured.

  Preparation of measurement sample: A toner sample and THF are mixed at a concentration of about 0.5 to 5 mg / ml (for example, about 5 mg / ml) and left at room temperature for several hours (for example, 5 to 6 hours). Shake and mix the THF and sample well (until the sample is no longer united), and let stand at room temperature for 12 hours or longer (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the end of standing is set to 24 hours or longer. Then, GPC was passed through a sample processing filter (pore size 0.45-0.5 μm, for example, Mysori Disc H-25-2 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Ltd., etc.). This sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

Measurement of GPC: The column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a THF sample solution of the resin. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3. It is appropriate to use 9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. In addition, as a column, in order to measure a molecular weight area | region of 10 < ³ > -2 * 10 < ⁶ > correctly, it is good to combine several commercially available polystyrene gel columns, and in this invention, it measures on the following conditions. .

GPC measurement conditions:
Equipment LC-GPC 150C (manufactured by Waters)
Column KF801, 802, 803, 804, 805, 806, 807 (manufactured by Shodex) Column temperature 40 ° C
solv. THF (tetrahydrofuran)
In the measurement of the GPC chromatogram, the high molecular weight side starts measurement from the starting point where the chromatogram rises from the baseline, and the low molecular weight side measures up to a molecular weight of about 400.

(6) Measurement of glass transition point of toner and resin Measured in accordance with ASTM D3418-82. In the present invention, “DSC-7” (manufactured by PerkinElmer) is used. The melting point of indium and zinc is used for temperature correction of the device detection unit, and the heat of fusion of indium is used for correction of heat quantity. The measurement sample is accurately weighed within the range of 10 mg. Obtained when a sample in an aluminum pan and a sample containing only an aluminum pan (empty pan) are set for control and the temperature of a 30 to 200 ° C. measurement region is raised at a rate of 10 ° C./min. The main endothermic peak value is determined from the DSC curve obtained as the endothermic peak value of the release agent used in the present invention. The half-value width of the endothermic peak is the temperature width of the endothermic chart at a portion corresponding to one half of the peak height from the base line in the endothermic peak.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way.

[Synthesis of titanium-containing catalyst]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube capable of bubbling in the liquid, 1617 parts by mass of titanium diisopropoxybis (triethanolaminate) and 126 parts by mass of ion-exchanged water are placed, and the solution is liquid with nitrogen. Under moderate bubbling, the temperature was gradually raised to 90 ° C. and reacted (hydrolyzed) at 90 ° C. for 4 hours to obtain titanium dihydroxybis (triethanolamate) [catalyst a-1]. Regarding the ligand and structure, the catalyst having the structure of the general formula (I) is shown in Table 1, and the catalyst having the structure of the general formula (II) is shown in Table 2.

  Further, a-2 to a-6 are synthesized by changing the reagent and performing the same operation, and further a step of dehydrating a hydroxyl group is added to thereby add a titanium-containing catalyst a-7 to a-13 having a titanyl structure. Got.

[Synthesis of polyester resins 1 to 13]
The following components were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted for 10 hours while distilling off the water produced at 230 ° C. under a nitrogen stream.
Bisphenol A EO 2 mol adduct 350 parts by mass Bisphenol A PO 2 mol adduct 326 parts by mass Terephthalic acid 278 parts by mass Titanium-containing catalyst a-1 2 parts by mass

  Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg, and when the acid value becomes 2 or less, it is cooled to 180 ° C., 62 parts by mass of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. Thereafter, it was pulverized to obtain a polyester resin 1. Table 3 shows the correspondence between the resin and the catalyst and the resin properties.

  Moreover, except having changed the catalyst like Table 3, the same operation was performed and the polyester resins 2, 3 and 5-13 were synthesize | combined.

  The polyester resin 4 was synthesized in the same manner as in the production of the polyester resin 1 except that the catalysts shown in Table 3 were used and trimellitic anhydride was not added.

[Synthesis of polyester resins 4 ′ to 6 ′ and 11 ′ to 13 ′]
The following components were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted for 10 hours while distilling off water produced at 220 ° C. under a nitrogen stream.
Bisphenol A PO 2 mol adduct 430 parts by mass Bisphenol A PO 3 mol adduct 350 parts by mass Terephthalic acid 207 parts by mass Isophthalic acid 65 parts by mass Dodecenyl succinic anhydride 20 parts by mass Maleic anhydride 10 parts by mass Titanium-containing catalyst a-4 2 Parts by mass

  Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value reached 5, it was taken out, cooled to room temperature and pulverized to obtain a polyester resin 4 '. Table 3 shows the correspondence between the resin and the catalyst and the resin properties.

  Similarly, polyester resins 5 ', 6', 11 'to 13' were synthesized by changing the catalyst as shown in Table 3.

[Manufacture of magnetic materials]
An aqueous solution containing ferrous hydroxide was prepared by mixing 1.0 to 1.1 equivalents of a caustic soda solution with respect to iron ions in an aqueous ferrous sulfate solution. While maintaining the aqueous solution at pH 9, air was blown and an oxidation reaction was performed at 80 to 90 ° C. to prepare a slurry liquid for generating seed crystals.

Subsequently, after adding ferrous sulfate aqueous solution so that it may become 0.9-1.2 equivalent with respect to the original alkali amount (sodium component of caustic soda) to this slurry liquid, the slurry liquid is maintained at pH 8 and air is supplied. The oxidation reaction is advanced while blowing, the pH is adjusted to about 6 at the end of the oxidation reaction, and the silane coupling agent [n-C ₆ H ₁₃ Si (OCH ₃ ) ₃ ] is 0.6 per 100 parts by mass of iron oxide. Part by mass was added and stirred well. The produced hydrophobic iron oxide particles were washed, filtered and dried by a conventional method, and then the aggregated particles were crushed to obtain a hydrophobic magnetic material. BET of the magnetic body magnetic properties in 6.1m ² /g,79.6kA/m was ^{σs = 69.0Am 2 /kg,σr=3.0Am 2 / kg} .

(Production of polar polymer)
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts by mass of methanol as a solvent, 150 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, As a monomer, 94.8 parts by mass of styrene, 5 parts by mass of 2-ethylhexyl acrylate, and 0.2 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature while stirring. A solution obtained by diluting 5 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 4 hours. Further, t-butylperoxy was further added. A solution obtained by diluting 0.50 parts by mass of 2-ethylhexanoate with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization to obtain a polar polymer.

[Example 1]
<Manufacture of toner 1>
After adding 451 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 709 parts by mass of ion-exchanged water and heating to 60 ° C., 67.7 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution is gradually added. Thus, an aqueous medium containing Ca ₃ (PO ₄ ) ₂ was obtained.

  On the other hand, the following prescription was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.).

Styrene 78 parts by mass n-butyl acrylate 22 parts by mass Polyester resin 1 5 parts by mass Magnetic substance 90 parts by mass Polar polymer 1 part by mass The monomer composition was heated to 60 ° C., and ester wax (mp.73) was added thereto. C.) 15 parts by mass were mixed and dissolved. A polymerizable monomer system was obtained by dissolving 2 parts by mass of a polymerization initiator butyl peroxide.

The polymerizable monomer system was charged into the aqueous medium and granulated by stirring at 10,000 rpm for 15 minutes in a TK homomixer (Special Machine Industries Co., Ltd.) at 60 ° C. in an N ₂ atmosphere. . Thereafter, the mixture was reacted at 80 ° C. for 1 hour while stirring with a paddle stirring blade. Thereafter, the liquid temperature was raised to 80 ° C., and stirring was further continued for 10 hours. After completion of the reaction, the suspension was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water, and dried to obtain toner particles.

A Henschel mixer (Mitsui Mitsui) was added 100 parts by weight of the toner particles and 0.8 parts by weight of a hydrophobic silica fine powder having a treated BET specific surface area of 120 m ² / g, which was treated with hexamethyldisilazane and then with silicone oil. The toner 1 (weight average particle diameter D ₄ : 7.0 μm) was prepared by mixing using a chemical machine. Table 4 shows the physical properties of Toner 1.

Evaluation 1. Image Density Evaluation Image density tends to decrease due to insufficient charge when the amount of moisture in the air is large. In particular, in the case of outputting an image such as a solid image in which the developer is rapidly changed, since the charging start-up time is short, it is difficult to obtain a uniform and sufficient charge amount, and the image density is likely to decrease. Therefore, in the present invention, in order to evaluate the performance under severe conditions, an evaluation method in which a solid black image is continuously drawn under a high temperature and high humidity environment is adopted.

  800 g of toner 1 is weighed, a commercially available laser beam printer LaserJet 4300n (manufactured by Hewlett Packard) is modified to have a process speed of 350 mm / sec, and the thickness of the elastic blade in contact with the 4300n CRG sleeve is 3 The blade contact pressure was increased by changing to an increased one, and the temperature and humidity were adjusted for 12 hours in a high temperature and high humidity environment (32.5 ° C., 82.5%, hereinafter referred to as H / H). After that, the toner 1 was put into the developing unit and installed at 4300n, and a solid black image was printed at 10,000 A4. The obtained solid black image was sampled at the beginning and last 10 of the endurance, and the density of 6 points per sheet was measured with a reflection densitometer RD918 (manufactured by Macbeth). The density measurement position was set at the center of each of six rectangles formed by dividing the long side of A4 paper into three and the short side into two. An average value was calculated for the obtained data of 60 points at the beginning and the end of each end, and recorded as “before endurance” and “after endurance” concentrations.

Evaluation 2. Electrostatic offset resistance test Electrostatic offset is a phenomenon that occurs when toner is electrostatically attached to the fixing roller side when a paper carrying toner passes through the fixing device. Therefore, the evaluation under the environment where excessive charging is promoted such as a low humidity environment and the situation where the fixing roller is charged after continuous paper passing is the strictest against electrostatic offset. In addition, when the paper to be passed is coated on the surface, both the toner and the fixing roller are more easily charged than normal paper such as recycled paper, and thus electrostatic offset is likely to occur. In consideration of these points, the toner of the present invention was evaluated.

1) Recycled paper evaluation Weighing 800 g of toner 1 and modifying a laser beam printer LaserJet 4300 n (manufactured by Hewlett Packard) to change the process speed to 550 mm / sec, together with CRG for 4300 n , a high temperature and low humidity environment (32. The temperature and humidity were adjusted to 5 ° C., 5%, hereinafter H / L) for 12 hours. Thereafter, the toner 1 was put into the CRG, installed at 4300n, and a solid white image was continuously passed through A4 paper (recycled paper EW100 manufactured by Canon Inc.) 1000 sheets. Thereafter, 100 images were continuously drawn using an electrostatic offset test chart in which the first half of the image was solid black and the second half was white, and the electrostatic offset resistance was visually evaluated.

2) Evaluation of coated paper Using CRG after evaluation of recycled paper, the paper was changed to coated paper (Image Coat Gloss 100, manufactured by Canon Inc.), and 1000 solid white images were continuously passed again. Thereafter, 100 continuous images were drawn using the same electrostatic offset test chart as that for recycled paper evaluation, and the electrostatic offset resistance was visually evaluated.

In addition, the evaluation criteria of the electrostatic offset resistance in 1) and 2) were determined as follows.
A It is not seen at all.
B Can be seen faintly on a white background.
C Can be seen in a small part on the white background.
D It is faintly seen in a slightly wide area on the white background.
E Faint over a wide area of white background.
F Appears clearly in a wide area of white background.
G Remarkably appears on the white background.

[Examples 2 to 8]
Toners 2 to 8 were produced and evaluated in the same manner as in Example 1 except that the polyester resin used was changed as shown in Table 4. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 9]
Toner 9 was produced in the same manner as in Example 6 except that the colorant and amount used were changed from 90 parts by mass of magnetic material to 5 parts by mass of carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation].

  In the evaluation of the image density, a laser beam printer HP Color LaserJet 4700dn (manufactured by Hewlett Packard) was modified so that the process speed was 350 mm / sec, and the elastic blade in contact with the 4700 dn CRG sleeve was used. Evaluation was performed in the same manner as in Example 1 except that a blade whose contact pressure was increased by changing the thickness to 30% was used.

  Further, in the electrostatic offset resistance test, evaluation was performed in the same manner as in Example 1 except that a laser beam printer HP Color LaserJet 4700dn (manufactured by Hewlett Packard) was modified to use a process speed of 550 mm / sec. It was.

  The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 10]
<Manufacture of Toner 10>
Polyester 4 40 parts by weight Polyester 4 ′ 40 parts by weight Methyl ethyl ketone 80 parts by weight Ethyl acetate 80 parts by weight Ester wax (melting point 73 ° C.) 15 parts by weight Carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] 5 parts by weight Polar compound 1 part by weight The mixture consisting of parts was dispersed for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.) to prepare a dispersion.

In a 2 liter four-necked flask equipped with a high-speed stirrer TK-homomixer, 350 parts by mass of ion-exchanged water and 225 parts by mass of a 0.1 mol / liter-Na ₃ PO ₄ aqueous solution were added. Was adjusted to 10,000 rpm and heated to 65 ° C. To this, 34 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a minute hardly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ .

  272 parts by weight of the dispersion was put into a high-speed stirrer, and granulated for 15 minutes at 65 ° C. with stirring while maintaining a rotational speed of 10,000 rpm. Thereafter, the high-speed stirrer is changed to a normal propeller stirrer, the rotation speed of the stirrer is maintained at 150 rpm, the internal temperature is raised to 95 ° C. and held for 3 hours to remove the solvent from the dispersion, and the toner A particle dispersion was prepared.

  The toner particle dispersion was cooled to 25 ° C. Dilute hydrochloric acid was added to the aqueous dispersion medium to dissolve the hardly water-soluble dispersant. It was dissolved, filtered, washed with water, and dried to obtain toner particles.

A Henschel mixer (Mitsui Mitsui) was added 100 parts by weight of the toner particles and 0.8 parts by weight of a hydrophobic silica fine powder having a treated BET specific surface area of 120 m ² / g, which was treated with hexamethyldisilazane and then with silicone oil. The toner 10 (weight average particle diameter D ₄ : 7.2 μm) was prepared by mixing using a chemical machine.

  Evaluation was performed using the toner 10 in the same manner as in Example 9. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 11]
<Manufacture of toner 11>
Polyester resin 4 50 parts by weight Polyester resin 4 ′ 50 parts by weight Carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] 8 parts by weight Ester wax (melting point 73 ° C.) 15 parts by weight Polar polymer 3 parts by weight Material of the above prescription After mixing well with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a biaxial kneader (PCM-30 type, manufactured by Ikekai Tekko Co., Ltd.) set at a temperature of 130 ° C. Kneaded. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less using a hammer mill. The coarsely pulverized product was finely pulverized using a jet mill which is a mechanical pulverizer. Then, the hot spheronization process was performed with hot air of 300 degreeC.

The obtained heat spheronized product was classified with an airflow classifier to obtain a toner classified product. A Henschel mixer (Mitsui Co., Ltd.) was added 100 parts by weight of this toner classified product and 1.0 part by weight of a hydrophobic silica fine powder treated with hexamethyldisilazane and then with silicone oil and having a treated BET specific surface area of 120 m ² / g. The toner 11 (weight average particle diameter 7.1 μm) was prepared by mixing with Miike Chemical Co., Ltd.).

  Evaluation was performed using the toner 11 in the same manner as in Example 9. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 12]
<Manufacture of toner 12>
In the production of the toner 11, the toner 11 is processed in the same manner as the toner 11 except that the number of particles of 4 μm or less is adjusted to about 22 number% and the number of particles of 12.7 μm or more is set to about 5 volume% by adjusting the classification process. 12 (weight average particle diameter 7.8 μm) was prepared.

  Evaluation was performed using the toner 12 in the same manner as in Example 9. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 13]
<Manufacture of toner 13>
A toner 13 (weight average particle diameter 7.8 μm) was prepared in the same manner as in Example 12 except that the polyester resin used was changed to polyester resin 5 and polyester resin 5 ′.

  Evaluation was performed using the toner 13 in the same manner as in Example 9. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 14]
A toner 14 (weight average particle diameter 7.9 μm) was prepared in the same manner as in Example 12 except that the polyester resin used was polyester resin 6 and polyester resin 6 ′.

  Evaluation was performed in the same manner as in Example 9 using the toner 14. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 15]
A toner 15 (weight average particle diameter 7.7 μm) was prepared in the same manner as in Example 12 except that the polyester resin used was polyester resin 11 and polyester resin 11 ′.

  Evaluation was performed using toner 15 in the same manner as in Example 9. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Example 16]
A toner 16 (weight average particle diameter of 7.7 μm) was prepared in the same manner as in Example 12 except that the polyester resin used was polyester resin 12 and polyester resin 12 ′.

  Evaluation was performed using toner 16 in the same manner as in Example 9. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Comparative Example 1]
<Manufacture of Comparative Toner 1>
Polyester resin 13 20 parts by weight Polyester resin 13 ′ 80 parts by weight Magnetic substance 1 90 parts by weight Ester wax (melting point 73 ° C.) 15 parts by weight Azo-based iron complex (T-77 manufactured by Hodogaya Chemical Co., Ltd.) 1 part by weight Material of the above prescription After mixing well with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a biaxial kneader (PCM-30 type, manufactured by Ikekai Tekko Co., Ltd.) set at a temperature of 130 ° C. Kneaded. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less using a hammer mill. The coarsely pulverized product was finely pulverized using a jet mill which is a mechanical pulverizer.

The obtained finely pulverized product is classified while being adjusted with an airflow classifier, and the number of particles of 4 μm or less is set to 5.5% by number, and the number of particles of 12.7 μm or more is set to 0.8% by volume. Got. A Henschel mixer (Mitsui Co., Ltd.) was added 100 parts by weight of this toner classified product and 1.0 part by weight of a hydrophobic silica fine powder treated with hexamethyldisilazane and then with silicone oil and having a treated BET specific surface area of 120 m ² / g. The toner 1 for comparison (weight average particle diameter 7.2 μm) was prepared by mixing with Miike Chemical Co., Ltd.).

  Evaluation was performed in the same manner as in Example 1 using the comparative toner 1. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

[Comparative Example 2]
<Production of Comparative Toner 2>
Polyester resin 13 100 parts by mass Carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] 8 parts by mass Ester wax (melting point 73 ° C.) 15 parts by mass Azo-based iron complex (T-77 by Hodogaya Chemical Co., Ltd.) 1 part by mass Was used in the same manner as in Comparative Example 1 to prepare a comparative toner 2 (weight average particle size 9.8 μm).

  Evaluation was performed in the same manner as in Example 1 using the comparative toner 2. The toner physical properties are shown in Table 4, and the evaluation results are shown in Table 5.

It is an explanatory diagram of an image forming apparatus that can use the toner of the present invention. It is explanatory drawing of a developing device.

Explanation of symbols

100 photoconductor (image carrier, charged body)
102 Developing sleeve (magnetic toner carrier)
114 Transfer roller (transfer member)
116 Cleaner 117 Charging roller (contact charging member)
121 Laser beam scanner (latent image forming means, exposure device)
124 Feed roller 125 Conveying member 126 Fixing device 140 Developing device 141 Stirring member

Claims (5)

A toner containing at least a colorant, an inorganic fine powder, and a resin,
The weight average particle diameter (D4) of the toner is 3 to 10 μm, and the ratio D4 / D1 of the weight average particle diameter (D4) to the number average particle diameter (D1) is 1 or more and 1.8 or less.
The toner has a glass transition temperature of 30 to 65 ° C .;
The toner has an average circularity of 0.950 to 0.999,
The resin contains a polycondensed polyester resin;
A toner wherein the polycondensed polyester resin is a resin formed in the presence of at least one titanium-containing catalyst (a) represented by the following general formula (I) or (II).
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[Wherein X is a residue obtained by removing H of one OH group from mono- or polyalkanolamine having 2 to 12 carbon atoms, and other OH groups of polyalkanolamine are directly bonded to the same Ti atom. An OH group may be polycondensed in the molecule to form a ring structure, or an OH group directly bonded to another Ti atom may be polycondensed between molecules to form a repeating structure. The degree of polymerization in the case of forming a repeating structure is 2-5. R is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]   2. The toner according to claim 1, wherein the toner contains 3.0% by volume or less of particles having a particle size of 12.7 μm or more and 20% by number or less of particles having a particle size of 4.0 μm or less. .   The toner according to claim 1, wherein the toner contains toner particles generated in an aqueous medium.   The toner contains toner particles formed by dispersing a polymerizable monomer composition containing at least a polymerizable monomer in an aqueous medium, granulating the polymerized monomer, and then polymerizing the polymerizable monomer. The toner according to claim 1.   The toner according to claim 1, wherein the colorant contained in the toner contains at least a magnetic substance.

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