JP2007178630A - Electrophotographic toner and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an electrophotographic toner for which a polyester aqueous dispersion is used and which has excellent low-temperature fixability while assuring satisfactory heat resistant storage property and mechanical strength without burdening a process. <P>SOLUTION: The electrophotographic toner manufactured by using the water dispersion of a polyester resin having a polar group within the molecule is characterized in that the relation between the particle diameter (D50V) of cumulation 50% of the volume particle diameter of the polyester resin particles in the water dispersion and the particle diameter (D50P) of cumulation 50% of the number particle diameter satisfies formula: 1≤(D50V/D50P)≤1.25. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrophotographic toner, and in particular, an electrophotographic toner using a polyester aqueous dispersion has a low process load, and further has excellent low temperature while ensuring good heat storage stability and mechanical strength. An object is to obtain a toner having fixing properties.

  Polyester resin composed of a polybasic acid component and a polyhydric alcohol component is used as a film-forming resin. Film processability, resistance to organic solvents (solvent resistance), weather resistance, adhesion to various substrates, etc. Therefore, it is used in large quantities as a binder component in fields such as paints, inks, adhesives, and coating agents. In recent years, the use of organic solvents has tended to be restricted from the standpoints of environmental protection, resource conservation, dangerous goods regulations by the Fire Service Act, and workplace environment improvement. A polyester resin aqueous dispersion finely dispersed in an aqueous medium has been actively developed (for example, see Patent Document 1).

  On the other hand, in the field of electrophotographic toner, a toner using a polyester resin that is superior in low-temperature fixability and image gloss as compared to a styrene / acrylic copolymer resin that has been used in the past due to recent increases in speed and color. Has been actively developed (see Patent Documents 2 and 3). In addition, since the polyester resin has a polar group in the molecule, it is advantageous for pigment dispersion and that a sufficient mechanical strength can be obtained even when a low molecular weight resin is used.

  Regarding the toner manufacturing method, conventionally, as a toner, a so-called pulverization method in which a colorant, a charge control agent, a fluidity modifier, a pulverization aid, etc. are added to a thermoplastic resin and then kneaded and further classified. The toner produced was mainstream. However, such a pulverization method requires a lot of energy for pulverization and melt kneading. In addition, the toner tends to have a smaller particle size year by year, but there is a concern that the required energy greatly increases as the particle size decreases in the pulverization method.

On the other hand, a fine particle resin dispersed in a solvent such as water is used as a starting material, and a colorant dispersion or a wax dispersion is mixed to produce agglomerated particles by chemical aggregation, and then heated to fuse and combine the agglomerated particles. Recently, so-called polymerized toner, which is used as a toner, has attracted attention in recent years. Since the polymer toner can form a spherical toner with a small particle size of several microns and high uniformity, the image quality of a color print can be made particularly clear. Also, in production, compared to the mechanical energy consumption used in the conventional kneading and pulverization methods, the chemical manufacturing plant requires less energy consumption, and the generation of CO ₂ can be greatly reduced. In addition, when printing, the toner transfer efficiency to the paper is high, so the residual toner is reduced. As a result, the toner consumption can be suppressed, and the toner transferred to the paper more uniformly can also have a lower fixing temperature. There is an advantage over the grinding method. That is, when producing a polymerized toner having the above-described characteristics, a polyester resin dispersed in a solvent mainly containing water is used as a starting atomization resin, so that there is very little environmental load and excellent low-temperature fixability. A polymerized toner can be produced. Therefore, the influence on the industry is very large from the environmental aspect and the toner physical aspect.

  However, in producing a polyester aqueous dispersion as a starting material, for example, in a polyester aqueous dispersion as shown in Patent Document 1, when stored for a long period of time, the molecular weight of the polyester resin tends to decrease, When a toner is prepared using such an aqueous dispersion, there is a possibility that the storage stability of the toner and further the physical properties of the toner will be greatly affected.

Among the methods for obtaining a polyester resin aqueous dispersion, as a method of using an organic solvent,
(1) A method of obtaining an aqueous dispersion of a polyester resin by dissolving the polyester resin in an organic solvent and adding water with stirring.
(2) A method of obtaining an aqueous dispersion of a polyester resin by dissolving and dispersing the polyester resin in a mixture of an organic solvent and water,
As such a method, for example, a production method using an organic solvent having a boiling point of 60 to 200 ° C. and a solubility of 20 g or more in 1 liter of water at 20 ° C. is known (for example, (See Patent Document 4). However, when the aqueous dispersion polyester resin is simply dispersed in an aqueous medium containing an organic solvent as described above, the stability as a dispersion is governed by the presence of the organic solvent. When the composition of the medium is changed by dilution with water or the like, the composition may become unstable and the viscosity becomes very high, or the particles of the dispersion may be coalesced to form a precipitate or an aggregate. Also, when a toner is prepared using an aqueous dispersion polyester resin containing an organic solvent, it takes time to remove the solvent in the toner forming process, particularly when the organic solvent is a high boiling point solvent of 100 ° C. or higher. However, this is not preferable in terms of process or cost. Furthermore, if residual solvent remains in the toner particles, the toner physical properties may be affected.

  On the other hand, in Patent Document 5, the polyester resin whose acid value and weight average molecular weight are controlled is dispersed in an aqueous medium containing an organic solvent, and then the organic solvent is removed from the obtained polyester resin aqueous medium. A production method for obtaining an aqueous dispersion by reducing the content of the organic solvent has been proposed, but in such a production method, vigorous stirring is required when the polyester is dispersed in an aqueous medium, and It takes time to disperse uniformly. In addition, when a basic substance for neutralization is charged all at once, the basic substance may volatilize during stirring. Furthermore, since dispersion is performed with a mechanical share, there is a problem that poor dispersion is likely to occur, and from the viewpoint of particle size distribution, it is difficult to form uniform particles. As a result, it is difficult to uniformly control the size and shape of the toner produced using the polyester aqueous dispersion produced by such a method, and it is not suitable from the viewpoint of storage stability of the toner.

  Further, in Patent Document 6, there is a method in which a polyester resin is dissolved in an organic good solvent, and then a poor solvent that does not dissolve the polyester resin is added to form a mixed solution, and then this solution is added to water while stirring. Although proposed, in such a technique, there is a possibility that the resin may precipitate upon addition of a poor solvent or addition to water. In addition, since stirring in the system tends to be uneven, it is difficult to control the fine particle formation process, and it is difficult to obtain an aqueous dispersion having a narrow particle size distribution. Furthermore, in the dissolution of the polyester resin in the initial good solvent and the poor solvent, if the dissolution concentration is too high, not only the handling property is bad, but it takes time to diffuse into water. In addition, there is a problem that the resin precipitates and the concentration of fine particles in the system increases during particle generation, and adhesion between particles is promoted. That is, when a toner is prepared using a polyester aqueous dispersion prepared by such a method, the storage stability of the toner is poor as in the above example, and it is difficult to control the shape of the toner.

  Furthermore, in Patent Document 7, after dissolving a carboxyl group-containing polyester resin whose composition and physical properties are defined in a ketone solvent, a neutralizing agent is added, then water is added, and then the ketone solvent is distilled off. Thus, a method for producing an aqueous dispersion to be phase-inverted into an aqueous system has been proposed. However, in the case of phase inversion using only a ketone solvent as described above, phase inversion to the aqueous phase does not proceed smoothly, and an aqueous dispersion having a wide particle size distribution tends to be formed. There was also a problem that sediment was formed during phase inversion. In addition, when the polyester resin is dissolved only in the ketone solvent at a high dissolution concentration, the process of phase inversion from the oil phase to the aqueous phase by adding water does not proceed quickly because the hydrophilicity in the system is low, As a result, there is a risk of poor dispersion. Furthermore, from the state in which the concentration of the polyester resin dissolved in the organic solvent is low as described in the examples, all the carboxyl groups of the resin are neutralized with a basic compound and phase-shifted to an aqueous system. There is a problem that a dispersion having a very wide particle size distribution occurs because a large amount of small particles formed by association of resins having hydrophilic groups or small particles formed by the resin having hydrophilic groups themselves are generated. . These small particles are usually ionic substances, and are particularly prominent when trying to produce a dispersion having a large particle size. The presence of such small particles is a major factor in fluctuations in physical properties due to the lot of the aqueous dispersion, and when toner is produced, the toner physical properties are greatly affected, for example, the variation in charge amount becomes large. Such small particles can be removed by providing a washing step at the time of toner preparation, but this is not desirable because the yield decreases and the manufacturing cost increases.

JP-A-9-296100 (Claims) JP-A-4-86744 (Claims) JP-A-11-302361 (Claims) Japanese Patent Publication No. 61-58092 (Claims) JP 2002-173582 A (Claims) Japanese Patent Publication No. 7-216210 (Claims) Japanese Patent Publication No. 5-295100 (Claims)

  An object of the present invention is to obtain an electrophotographic toner having an excellent low-temperature fixability while ensuring a good heat-resistant storage property and mechanical strength with a small process load.

As a result of intensive studies and studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention relates to an electrophotographic toner produced using an aqueous dispersion of a polyester resin having a polar group in the molecule, and a particle diameter (D50V) of 50% cumulative volume particle diameter of the polyester resin particles in the aqueous dispersion. The present invention relates to an electrophotographic toner produced using an aqueous polyester resin dispersion wherein the relationship between the particle diameter and the particle diameter (D50P) of 50% cumulative number particle diameter satisfies the following formula.
1 ≦ (D50V / D50P) ≦ 1.25
The present invention also relates to a method for producing an electrophotographic toner, comprising mixing the polyester resin aqueous dispersion described above and a colorant fine particle dispersion, and aggregating and fusing each fine particle to produce toner particles.

  In the present invention, an aqueous dispersion having a very narrow particle size distribution can be produced by adding water and inversion in a state where the resin dissolution concentration is increased as a polyester resin aqueous dispersion having a polar group. In addition, when the polar group is a carboxyl group, a small particle in which resins having hydrophilic groups are associated with each other by neutralizing and reversing the amount of all the carboxyl groups from a state where the resin dissolution concentration is increased. Can be prevented. Furthermore, aqueous dispersions having a narrow particle size distribution and various sizes can be prepared, and the storage stability is improved. Accordingly, when a toner is prepared using the polyester aqueous dispersion, the load on the process is small, the size and shape are uniform, and lot blurring is reduced. Furthermore, it is possible to produce a highly practical toner having excellent low-temperature fixability while ensuring good heat-resistant storage properties and mechanical strength.

Hereinafter, the present invention will be described in detail.
As the polyester resin used in the present invention, a polyester resin obtained by condensation polymerization of a polyester raw material comprising a polycarboxylic acid component and a polyol component can be used.

  Examples of divalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid as aromatic dicarboxylic acids. Examples of the aliphatic carboxylic acid include succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid and the like. Examples of the alicyclic polycarboxylic acid include alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and dimer acid. These can use 1 type (s) or 2 or more types arbitrarily.

  When the total amount of the polycarboxylic acid component is 100 mol%, the amount of aromatic dicarboxylic acid is preferably 80 mol% or more. Preferably, it is 85 mol% or more, and more preferably 90 mol%. If the total of the above aromatic dicarboxylic acids is less than 80 mol%, the hydrolysis resistance of the resulting polyester resin and the hardness of the resulting coating film may be insufficient. Moreover, it is particularly preferable to use terephthalic acid and isophthalic acid in combination from the viewpoint of achieving both impact resistance and hardness of the resulting coating film, and the dispersibility and stability during the preparation of the aqueous dispersion are excellent.

  Among the above polycarboxylic acids, aliphatic dicarboxylic acids other than aromatic dicarboxylic acids and alicyclic dicarboxylic acids are sebacic acid and cyclohexanedicarboxylic acid from the viewpoint of hydrolysis resistance of the resulting polyester resin and weather resistance of the resulting coating film. Acids are preferred.

  Examples of the polyol include divalent aliphatic glycols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, triethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 2-methyl- 3-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and the like. Further, as glycols containing a divalent aromatic structure, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, p-xylene-α, α′-diol, m-xylene-α, α′-diol, etc. Is mentioned.

  Examples of the divalent alicyclic glycol include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, hydrogenated bisphenol-A, and dimer diol.

Moreover, you may use together polyvalent carboxylic acid and a polyol compound in the range which does not impair the effect of this invention.
Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylene Carboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid and the like, and anhydrides or lower alkyl esters of these acids.

  Examples of the trihydric or higher polyhydric alcohol 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.

  When performing condensation polymerization of a polyester resin, a polymerization catalyst may be used. Examples of the polymerization catalyst include titanium compounds (tetra-n-butyl titanate, tetraisopropyl titanate, titanium oxyacetylacetonate, etc.), antimony compounds (tributoxyantimony, antimony trioxide, etc.), germanium compounds (tetra-n- Butoxy germanium, germanium oxide and the like), zinc compounds (zinc acetate and the like), and the like. You may use the said polymerization catalyst 1 type (s) or 2 or more types. Titanium compounds are preferred from the viewpoint of polymerization reactivity.

  The polyester resin used in the present invention is obtained by co-condensation polymerization of the above raw material monomers, and the polymerization method is not particularly limited, and a known method is used.

In the polyester resin used in the present invention, it is necessary to introduce a polar group such as an ionic group in order to increase the affinity for water when dispersed in water. As the polar group, a salt of a carboxyl group or a sulfonyl group is generally used. In the present invention, a salt of a carboxyl group is preferably used from the viewpoint of narrowing the particle size distribution.
As a method for introducing a carboxyl group into a polyester resin, after polymerizing the resin, under atmospheric pressure and nitrogen atmosphere, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1,8-naphthalic anhydride 1,2-cyclohexanedicarboxylic anhydride, cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-anhydride, ethylene glycol bisanhydro trimellitate, 5- (2,5-dioxo One or more selected from tetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, naphthalene 1,8: 4,5-tetracarboxylic dianhydride, etc. After the polycondensation, these acid anhydrides are introduced into the oligomer state before adding the acid anhydrides and before the resin is made high molecular weight, and then reduced. By high molecular weight by polycondensation of lower, there is a method of introducing a carboxyl group into the resin. Of these, the acid value targeted by the former method is easily obtained, which is preferable.

  The polyester resin preferably has an acid value of 3 to 25 mgKOH / g, and more preferably 4 to 20 mgKOH / g, from the viewpoints of stability of the aqueous dispersion and solvent resistance. When the acid value is less than 3 mgKOH / g, the storage stability of the aqueous dispersion may be lowered. Moreover, when an acid value exceeds 25 mgKOH / g, there exists a possibility that the water resistance of the coating film obtained may be inferior.

  The polyester resin may contain polar groups other than carboxyl groups. For example, a sulfonic acid metal base, a phosphoric acid group, etc. are mentioned, These can have 1 type, or 2 or more types. As a method for introducing a sulfonic acid metal base, a metal salt such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- [4-sulfophenoxy] isophthalic acid, or 2-sulfo-1, A dicarboxylic acid or glycol containing a sulfonic acid metal base such as a metal salt such as 4-butanediol, 2,5-dimethyl-3-sulfo-2,5-hexanediol, etc. is converted into a polycarboxylic acid component or a polyol component. The method of using in 10 mol% or less of the sum total of these, Preferably it is 7 mol% or less, More preferably, it is 5 mol% or less. If it exceeds 10 mol%, the hydrolysis resistance of the resin itself and the water resistance of the coating film tend to decrease.

The aqueous dispersion used for this invention is manufactured using the above polyester resins. The present invention is characterized in that the relational expression of the relationship between the 50% cumulative particle diameter of the polyester resin particles (D50V) and the 50% cumulative particle diameter of the number particle diameter (D50P) satisfies the following formula: To do.
1 ≦ (D50V / D50P) ≦ 1.25
The cumulative volume particle size and the like of the aqueous dispersion used in the present invention is based on the particle size range (channel) divided on the basis of the particle size distribution measured by a measuring device of a Coulter counter (LS13 320 manufactured by Beckman Coulter, Inc.). , The cumulative distribution is drawn from the smaller diameter side, and the particle diameters that become 50% cumulative are defined as D50V and D50P. Using these, the particle size distribution index is obtained as follows by the ratio of the particle size having a volume accumulation of 50% to the particle size having a number accumulation of 50% (DP defined).
DP = D50V / D50P
The particle size distribution index DP is desirably 1.25 or less, and more desirably 1.20 or less. The lower limit is preferable because it approaches monodispersion as it approaches 1.

  The aqueous dispersion of the polyester resin used in the present invention is, for example, a polyester resin obtained by condensation polymerization of a polyester raw material comprising a polycarboxylic acid component and a polyol component, a good solvent for dissolving the polyester resin, or a good solvent and a polyester. After being dissolved in a mixed solvent with a poor solvent that does not dissolve the resin at a solid concentration of 35% by mass or more, the acid value of the resin is neutralized with 0.4 to 0.95 equivalent of a basic compound, and water is added. It is desirable to produce by phase inversion by adding and then removing the organic solvent. The method for removing the organic solvent may be removed outside the system by heating, or may be removed outside the system in a vacuum.

 The dissolution of the polyester resin in the process of producing the aqueous dispersion used in the present invention is carried out with a good organic solvent that dissolves the polyester or a mixed solvent of a good organic solvent and a poor organic solvent that does not dissolve the polyester resin. When using a mixed solvent, the content of the organic poor solvent contained in the total organic solvent is preferably 25% or less, more preferably 20% or less. If the poor solvent is more than 25%, the resin may precipitate during dissolution. When the amount of the poor solvent is 25% or less in the total organic solvent, there is no fear of resin precipitation. Further, when a solvent having high solubility in water is used as the poor solvent, the oil phase is changed to the aqueous phase. Since phase inversion occurs smoothly, particles with a very narrow particle size distribution can be produced.

  In the process of preparing the aqueous dispersion used in the present invention, the solvent used for dissolving the polyester resin includes n-butanol, isopropyl alcohol, diacetone alcohol, 2-ethylhexanol, methyl ethyl ketone, acetonitrile, dimethylacetamide, dimethyl Formamide, N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, 1,3-oxolane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, propylene glycol monopropyl ether, propylene Glycol monobutyl ether can be used. There is no problem even if two or more of these solvents are used in combination. Among these, methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and isopropyl alcohol having a boiling point of 100 ° C. or lower are preferable. By using these, the organic solvent remaining in the system can be reduced in a short time in the solvent removal step in the subsequent step. On the other hand, when a high boiling point solvent having a boiling point higher than 100 ° C. is used, it becomes difficult to completely remove the organic solvent in the system, and these residual organic solvents may have a great influence on the physical properties of the toner later.

  When the polyester resin is dissolved using the above-mentioned solvent, the concentration can be arbitrarily selected, but is preferably 35% by mass or more, particularly preferably 45% to 70%. If it is lower than 35%, a large amount of water and time are required until the phase is inverted by adding water, which is not preferable in the production process. Further, if the dissolved concentration is low, a large amount of organic solvent is used, which is not desirable from the viewpoint of cost and environment. Furthermore, when the phase is changed from a low dissolved concentration to an aqueous system, the low molecular weight hydrophilic component contained in the polyester shifts to the aqueous phase, so that the hydrophilic component that does not contribute to particle formation is dispersed in water. It will exist in the body. Furthermore, since the water dispersion does not proceed uniformly and a large amount of small particles are formed in which the resins having hydrophilic groups are associated with each other, the particle size distribution of the finished water dispersion becomes wide. On the other hand, when phase inversion is performed from a state in which the dissolved concentration is high, a hydrophilic component having a low molecular weight or a hydrophobic resin to which a hydrophilic group has not been added can be encased in the particles without being lost. An aqueous dispersion having a narrow particle size distribution can be produced. However, if the dissolution concentration exceeds 70%, it takes time for dissolution, and the entanglement between the particles becomes remarkable, and phase inversion does not proceed easily. As a result, poor dispersion may occur.

  When water dispersion is performed using a polyester resin into which a carboxyl group has been introduced, the carboxyl group is preferably neutralized by a basic compound. The basic compound is added preferably after the polyester resin is dissolved in an organic solvent until water is added to perform phase inversion. When a polyester resin, an organic solvent, and a basic compound are mixed at the time of dissolution, it takes time to dissolve, so that a highly volatile basic compound may volatilize out of the system. The reason why it is not preferable to add the basic compound after the phase inversion is that the particle size of the aqueous dispersion is determined by the neutralization amount of the carboxyl group before the phase inversion. This is because the addition of a substance does not contribute to particle formation. That is, the basic compound is preferably added in a predetermined amount all at once after the polyester is dissolved and before water is added. However, there is no problem in adding a basic substance after phase inversion or after distilling off the solvent in order to improve dispersion stability. This is because the hydrophilicity can be enhanced and aggregation between particles can be prevented by electrostatic repulsion between the generated carboxyl anions.

  Examples of basic substances that can be used for neutralization include amine compounds typified by ammonia and triethylamine, and inorganic bases typified by sodium hydroxide and potassium hydroxide. In order to eliminate remaining in the film, it is preferable that the amine compound is highly volatile.

  Specific examples of the highly volatile amine compound include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-n-propylamine, dimethyl-n-propylamine, monoethanolamine, Diethanolamine or triethanolamine, N-methanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamon, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, or N, N -Dimethylpropanolamine etc. can be mentioned. Particularly preferred are triethylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine and the like. Most preferred are triethanolamine, triethylamine and ammonia. Two or more of these highly volatile amine compounds may be used in combination.

  As the usage-amount of the said basic substance, 0.4-0.95 times equivalent is preferable with respect to the quantity of the carboxyl group contained in a polyester resin, and 0.5-0.90 times equivalent is more preferable. If it is lower than 0.4 equivalent, sufficient hydrophilicity cannot be imparted to the resin, which may cause precipitation in the water dispersion step. Moreover, since it is 0.95 times equivalent or more, ie, when neutralizing nearly 100% of the carboxyl group which resin has, since the hydrophilic property of resin will increase, resin which has a hydrophilic group assembled together. There is a possibility that a large amount of small particles are produced, and the particle size distribution tends to be wide.

The aqueous dispersion used in the present invention is manufactured by adding the basic substance to the polyester resin dissolved in the solvent and neutralizing it, and then adding water to perform phase inversion. It is desirable to be at least room temperature and below the boiling point of the organic solvent or basic compound. Furthermore, it is preferably not less than the glass transition temperature of the polyester resin and not more than the boiling point of the organic solvent or basic compound.
Although a method of adding a polyester resin solution to water can also be used, in such a case, particularly when the solid content concentration at the time of dissolution is high, not only the handling property is bad, but also the time for diffusion into water is long. Cost. Furthermore, since vigorous stirring is required, uniform particles are hardly generated. From such a viewpoint, it is preferable to add water to the polyester resin solution.

In preparing the aqueous dispersion used in the present invention, water is added for phase inversion, and as an addition method, it is desirable to add in particular until phase inversion. This is because the rate of water addition affects particle formation during phase inversion. When all the amount of water is added at once after neutralization, the temperature in the system temporarily drops, and the phase inversion from the oil phase to the water phase becomes insufficient. Occurs. On the other hand, even if the rate of water addition until phase inversion is too slow, phase inversion does not proceed smoothly, so that an aqueous dispersion having a very wide particle size distribution may be formed.
For these reasons, it is desirable to add a predetermined amount of water at a certain speed so as not to lower the temperature in the system until phase inversion. Moreover, there is no problem even if hot water is added to maintain the temperature in the system.

  The aqueous dispersion used in the present invention is preferably neutralized and phase-inverted, and the solvent is removed after adding a predetermined amount of water. The removal of the organic solvent may be removed outside the system by heating, or may be removed outside the system in a vacuum. The amount of residual organic solvent in the aqueous dispersion used in the present invention is desirably 2% or less. More preferably, it is 1% or less. If the organic solvent is contained in an amount of more than 2%, the hydrolyzability of the resin may be promoted. In addition, the stability as a dispersion may be governed by the presence of the organic solvent, the composition of the medium changes due to evaporation of the organic solvent, the system becomes unstable and the viscosity becomes very high, This is because there is a possibility that the particles may coalesce and precipitates may be generated. Also from the environmental viewpoint, it is preferable that the amount of the organic solvent is small. Furthermore, when an electrophotographic toner is produced using the polyester resin, the remaining organic solvent may affect the toner physical properties. The amount of the organic solvent can be controlled by ordinary methods such as increasing the heating temperature, increasing the heating time, and adjusting the degree of vacuum.

  The removed organic solvent can be used again for dissolving the resin. Although water remains in the removed solvent, the water can be controlled and used as needed. In dissolving the polyester resin using the removed organic solvent, the proportion of water is preferably 30% or less, more preferably 10% or less, based on the total solvent. When the proportion of water is more than 30%, the solubility of the resin is remarkably deteriorated, and a precipitate may be generated during the phase transition. If it is 10% or less, the solubility is not particularly affected, and further, because water is contained, the phase inversion proceeds rapidly in the phase inversion process, and an aqueous dispersion having an extremely good particle size distribution is obtained. Obtainable.

  Although the method for producing the polyester resin aqueous dispersion used in the present invention has been described above, the polyester resin aqueous dispersion of the present invention can be produced without adopting all of these, but by combining the above, further DP Small aqueous dispersions can be produced.

 The polyester aqueous dispersion produced according to the above method can suppress the formation of extremely small particles having a particle size of 50 (nm) or less. The content of the small particles is, for example, in the supernatant when the aqueous dispersion whose solid content is adjusted to 30% is separated into the supernatant and the sediment by a centrifuge (CP70MX (manufactured by Hitachi High-Technologies)). Solid content concentration is an indicator. This is because small particles are formed by the resin itself having a hydrophilic group that does not contribute to particle formation or by the association of resins having a hydrophilic group with each other. This is to shift to the side. The solid content concentration of the supernatant after centrifugation is preferably 4% or less, more preferably 2% or less when the aqueous dispersion having a solid content concentration of 30% is centrifuged at 20000 rpm for 2 hours. Moreover, when the solid content concentration of the aqueous dispersion before centrifugation is different from 30%, it can be centrifuged after adding water for dilution. Moreover, water may be distilled off to increase the solid content concentration of the aqueous dispersion. In addition, as an index of the supernatant liquid solid content concentration when centrifugation is performed at different solid content concentrations, when the solid content concentration of the aqueous dispersion is 10, 20, and 40%, 1%, 2%, and 5%, respectively. The following is desirable.

  In the aqueous dispersion used in the present invention, coarse particles of 1 μm or more are 1% or less, preferably 0.5% or less, more preferably 0.2% or less, and still more preferably 0.01% or less in the total resin. It is. If it is present in an amount of 1% or more, precipitates are generated over time, resulting in poor storage stability and lot blurring during toner production.

  The average particle diameter of the polyester resin aqueous dispersion thus obtained is desirably 60 (nm) or less as the lower limit and 500 (nm) as the upper limit. If the average particle size is less than 60 (nm), the aqueous dispersion has a high viscosity, the high-form content concentration is lowered, and workability may be reduced. If it exceeds 500 (nm), the dispersibility is lowered, for example, a precipitate is generated during storage. The upper limit of the average particle diameter is preferably 400 (nm), and more preferably 300 (nm). The lower limit of the average particle is preferably 70 (nm), and more preferably 80 (nm).

  The solid content concentration of the aqueous dispersion is desirably 15 to 60%. If the solid content concentration is lower than 15%, it is not preferable because it not only wastes transportation and storage costs but also consumes extra energy and time in the drying process when the aqueous dispersion is used. . On the other hand, if the solid content concentration is higher than 60%, the viscosity of the aqueous dispersion may be very high. Further, it is not preferable from the viewpoint of storage stability.

  The water dispersion is neutralized in a polyester resin having a carboxyl group polar group in a state where the resin dissolution concentration is increased, and by adding water, the phase inversion proceeds uniformly due to the entanglement effect of the resin. An aqueous dispersion having a narrow particle size distribution can be produced. Furthermore, since the hydrophilicity can be controlled by neutralizing the carboxyl group of the resin by a necessary amount, the resin itself having a hydrophilic group or a hydrophilic group can be added. Generation | occurence | production of the small particle which the resin which had had associated was able to be prevented.

  The polyester resin preferably has a number average molecular weight of 2000 or more, more preferably 3000 or more. Although the upper limit of the number average molecular weight is not particularly limited, it is preferably substantially 30000 or less from the viewpoint of solvent solubility. When the number average molecular weight is less than 2000, the processability, impact resistance, corrosion resistance, and dispersion stability of the resulting coating film may be lowered. The said number average molecular weight can be determined by the polystyrene conversion value by a gel permeation chromatography measurement.

  The polyester resin preferably has a glass transition temperature of a lower limit of 20 ° C. and an upper limit of 100 ° C. If the glass transition temperature is less than 20 ° C, the resulting coating film will have insufficient hardness and may not have good corrosion resistance. If it exceeds 100 ° C, the processability and impact resistance of the resin itself will be reduced. There is a case. Preferably, the lower limit is preferably 30 ° C, more preferably 40 ° C. The upper limit is preferably 90 ° C, and more preferably 80 ° C. In addition, when using the said polyester resin for a toner use, it is preferable that a glass transition temperature is 50 to 80 degreeC. When the temperature is lower than 50 ° C., the heat aggregation property as a toner becomes poor, and when it is made into a toner, there is a tendency to block, causing a problem in storage stability. If it is higher than 80 ° C., the fixing property becomes poor. The glass transition temperature can be determined by measurement with a differential scanning calorimeter.

  When the polyester resin is used for toner applications, the softening point is preferably in the range of 80 ° C to 150 ° C. When the softening point is less than 80 ° C., the toner using the polyester resin tends to aggregate during handling or storage, and the fluidity may deteriorate particularly during long-term storage. On the other hand, if the softening point exceeds 150 ° C., the toner using the polyester resin may have a problem in fixing characteristics at low temperatures. In addition, since the fixing roll needs to be heated to a high temperature, the material of the fixing roll and the material of the base material to be copied may be limited.

Further the polyester resin, when used in toner applications, the melt viscosity at 100 ° C. of the resin is preferably from 10 ⁴ to 10 ⁶ poise, more preferably from 5 × 10 ⁴ to 5 × 10 ⁵ poise. If it is not in the above range, the fixing characteristics may be inferior, which is not preferable.

  The polyester resin is preferably amorphous. If it is amorphous, the solvent solubility is high, which is extremely advantageous in controlling the particle size. However, this is not the case when used as a toner application. The term “amorphous” as used in the present invention means that there is no clear endothermic peak in the measurement with a differential scanning calorimeter.

  In the present invention, it is preferable to use 100% of the polyester as described above, but other resins may be added if necessary as long as it is less than 35%. Although it does not specifically limit as such a thing, A styrene-acryl resin, an alkyd resin, an epoxy resin, a urethane resin, a styrene butadiene resin, a petroleum resin etc. can be used.

  The toner is produced by aggregating / drying the aqueous dispersion and the pigment, wax, charge control material, etc. by utilizing the above-mentioned characteristics of the aqueous dispersion having a narrow particle size distribution and excellent adhesion to the substrate. be able to.

  When producing the toner of the present invention using such an aqueous dispersion, a nonionic sea surface active agent may be used. This is used for the purpose of stabilizing the dispersion of each fine particle in the aggregation step and adjusting the cohesive force of the dispersed fine particles. In other words, since nonionic surfactants have a markedly reduced dispersion stabilizing power above their cloud point, an appropriate amount can be coexisting with the ionic surfactant when preparing the fine particle dispersion, By adding an appropriate amount in advance, it becomes possible to adjust the cohesive force between particles based on the control of the coagulation temperature, and it is possible to realize the uniformity and efficiency of cohesion of particles.

  Examples of the nonionic surfactant include polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene oxide. Examples thereof include esters and sorbitan esters, but an ionic surfactant may be used in combination as necessary.

  Examples of ionic surfactants include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6 Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, etc.), sulfuric acid Ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, stearic acid) Potassium, calcium oleate), and the like.

  There is no problem even if an appropriate dispersion stabilizer is added to the aqueous dispersion. For example, polyvinyl alcohol, gelatin, gum arabic, methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, sodium salt of carboxymethyl cellulose, sodium dodecylbenzene sulfate, sodium dodecylbenzenesulfonate, sodium octyl sulfate, sodium laurate, calcium phosphate, magnesium phosphate, Examples thereof include aluminum phosphate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite and the like. These dispersion stabilizers can be used in an amount of 0.05 to 3% by mass.

  As the colorant used when producing the toner of the present invention using an aqueous dispersion, known pigments conventionally used as colorants for full-color toners can be used. For example, carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, duPont oil red, quinoline yellow, methylene blue chloride, copper phthalocyanine, malachite green oxalate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 184, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 17, C.I. I. Solvent Yellow 162, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment blue 15: 1, C.I. I. And CI Pigment Blue 15: 3. There is no problem even if these are used in combination of two or more.

  The colorant fine particle dispersion can be prepared by dispersing a colorant in an aqueous medium. The dispersion treatment of the colorant is performed in a state where the surfactant concentration is set to a critical micelle concentration (CMC) or more in water. As the surfactant to be used, anionic surfactants and nonionic surfactants can be used, and these may be used alone or mixed in an appropriate composition. The disperser used for the dispersion treatment of the colorant is not particularly limited, but preferably an ultrasonic disperser, a pressure disperser such as a mechanical homogenizer or a pressure homogenizer, a medium disperser such as a sand grinder or a diamond fine mill. Can be mentioned. Moreover, as a surfactant used, the same thing as the above-mentioned surfactant can be mentioned.

  In the present invention, the toner particles may contain a release agent, a charge control agent, magnetic powder and the like. In particular, when the toner of the present invention is used as a full-color toner used in a full-color image forming apparatus, and an image forming apparatus having a fixing device of a type in which the amount of release oil applied to a fixing member such as a roller is reduced. When used in the apparatus, the release agent is preferably contained in the toner particles.

  Wax is used as a mold release agent. As the wax, waxes known in the field of electrostatic charge image developing toners can be used. For example, polyolefin waxes such as polyethylene wax and polypropylene wax, natural waxes such as carnauba wax and rice wax, montan wax, and Fischer-Tropsch wax. And paraffin wax. When a polyester resin is used as the binder resin, it is preferable to use an oxidized wax from the viewpoint of improving dispersibility.

  The release agent dispersion treatment can be performed in the same manner as in the preparation of the colorant dispersion.

  The addition amount of the release agent is 0.5 to 12 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. When using 2 or more types of wax as a mold release agent, those total amounts should just be in the said range.

  As the charge control agent, a known charge control agent that has been conventionally added to control the chargeability in the field of electrostatic image developing toners can be used. For example, fluorine-containing surfactants, metal-containing dyes such as salicylic acid metal complexes, azo-based metal compounds, polymer acids such as copolymers containing maleic acid as a monomer component, quaternary ammonium salts, nigrosine, etc. An azine dye, carbon black, or the like can be used. The charge control agent may be used in a proportion of 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, based on the total mass of the binder resin used.

  As an example in the case of producing the toner of the present invention using an aqueous dispersion, a process in which a polyester aqueous dispersion and a colorant fine particle dispersion are mixed, and the fine particles are aggregated and fused to produce toner particles, It comprises a filtration / washing process for removing the surfactant from the toner particles and a drying process for drying the washed toner particles.

  As a method for agglomerating and fusing each fine particle, a salting-out agent composed of an alkali metal salt or an alkaline earth metal salt or the like in an aqueous medium in which resin fine particles, colorant fine particles, etc. are present exceeds the critical aggregation concentration. The method of heating the medium after adding as a flocculant is illustrated.

  Examples of the salting-out agent used herein include alkali metal salts and alkaline earth metal salts. Examples of alkali metals include monovalent metals such as lithium, potassium and sodium, and alkaline earth metals include magnesium and calcium. And divalent metals such as strontium and barium, and salts such as divalent and higher aluminum can also be used. Preferably, potassium, sodium, magnesium, calcium, barium and the like can be mentioned. Examples of constituents of the salt include chlorine salts, bromine salts, iodine salts, carbonates and sulfates.

  The filtration / washing step removes the surfactant and salting-out agent coexisting from the filtered toner particles filtered from the toner particle dispersion obtained in the above step and the filtered toner particles. The cleaning process is performed. Here, examples of the filtration method include, but are not limited to, a centrifugal separation method, a vacuum filtration method using Nutsche and the like, a filtration method using a filter press and the like.

  The drying step is a step of drying the washed toner particles. Examples of dryers used in this process include spray dryers, vacuum freeze dryers, vacuum dryers, etc., stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers A stirring dryer or the like is preferably used. The water content of the dried toner particles is preferably 5% by mass or less, and more preferably 2% by mass or less. In addition, when the toner particles that have been dried are aggregated due to weak interparticle attraction, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill or a Henschel mixer can be used.

  As an external additive used when externally treating the toner particles produced in the above-described steps, known inorganic fine particles used as a fluidity adjusting agent in the field of electrostatic image developing toners are used. For example, silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, diamond carbon lactam, etc. Various nitrides such as carbide, boron nitride, titanium nitride, zirconium nitride, various borides such as zirconium boride, titanium oxide (titania), calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica, colloidal silica Various oxides such as calcium titanate, magnesium titanate Various titanate compounds such as strontium, strontium titanate, sulfides such as molybdenum disulfide, various fluorides such as magnesium fluoride and carbon fluoride, various types such as aluminum stearate, calcium stearate, zinc stearate, magnesium stearate Various nonmagnetic inorganic fine particles such as metal soap, talc and bentonite can be used alone or in combination. Inorganic fine particles, especially silica, titanium oxide, alumina, zinc oxide, etc. are conventionally used hydrophobizing agents such as silane coupling agents, titanate coupling agents, silicone oils, silicone varnishes, and fluorine-based silanes. It is preferable that the surface treatment is carried out by a known method using a coupling agent or a fluorine-based silicone oil, a coupling agent having an amino group or a quaternary ammonium base, or a modified silicone oil.

  The average primary particle size of the inorganic fine particles used as the external additive is 5 to 100 nm, preferably 10 to 50 nm, and more preferably 20 to 40 nm.

  Organic fine particles are granulated by emulsion polymerization, soap-free emulsion polymerization, wet polymerization such as non-aqueous dispersion polymerization, gas phase method, etc. for the purpose of cleaning aids, styrene, (meth) acrylic Fine particles such as benzoguanamine, melamine, Teflon (registered trademark), silicon, polyethylene, and polypropylene can be used.

  The relationship between the 50% cumulative particle diameter (D50V) of the polyester resin particles described above and the 50% cumulative particle diameter (D50P) of the number particle diameter satisfies 1 ≦ (D50V / D50P) ≦ 1.25. When electrophotographic toner is produced using an aqueous dispersion of polyester resin, a very favorable electrophotographic toner is produced because there are very few small-sized particles, which are ionic substances, and thus there is little variation in charge amount and less blur due to lots. can do. Small particles can be removed by providing a washing process in the toner forming process, but this is not desirable because the yield decreases and the manufacturing cost increases. Further, since the aqueous dispersion of the present invention has a very narrow particle size distribution, a toner having a uniform shape and size can be produced as a result.

  The toner of the present invention may be used as a full color toner used in a full color image forming apparatus, or may be used as a monochrome toner used in a monochrome image forming apparatus.

The toner of the present invention may be used in an image forming apparatus having any type of fixing device, but the type of fixing device in which the amount of releasing oil applied to a fixing member such as a roller is reduced, That is, it is preferably used for an image forming apparatus having a fixing device in which the amount of release oil applied is 4 mg / m ² or less, particularly a fixing device of a type that does not apply release oil.

Next, the present invention will be specifically described using the following examples and comparative examples, but the present invention is not limited thereto. The characteristic value evaluation was performed by the following method. In the examples and comparative examples, “parts” simply means “parts by mass”.
In the examples, the properties of polyester and polyester aqueous dispersion were measured as follows.

(1) Reduced viscosity (ηsp / c, unit dl / g): 0.10 g of a polyester resin was dissolved in 25 cc of a mixed solvent of phenol / tetrachloroethane (mass ratio 6/4) and measured at 30 ° C. using an Ubbelohde viscosity tube. did.

(2) Acid value: 0.2 g of a sample was precisely weighed and dissolved in 20 ml of chloroform. Subsequently, it titrated with 0.01N potassium hydroxide (ethanol solution). Phenolphthalein was used as an indicator.

(3) Glass transition temperature: 5 mg of sample was put in an aluminum sample pan and sealed, and the differential scanning calorimetry (DSC) DSC-220 manufactured by Seiko Instruments Inc. was used to increase the temperature up to 200 ° C. and the heating rate was 20 ° C. Measured at / min, it was determined at the temperature of the intersection of the base line extension below the glass transition temperature and the tangent indicating the maximum slope at the transition.

(4) Resin composition: ¹ H-NMR analysis was performed using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian in a chloroform D solvent, and the integral ratio was determined.

(5) Specific gravity: A 500 ml graduated cylinder containing approximately 20% calcium chloride aqueous solution is prepared at 30 ± 0.05 ° C., and a sample without air bubbles (polyester) is placed therein so that the sample stays in the middle of the graduated cylinder. Adjust the specific gravity of calcium chloride. The specific gravity of the calcium chloride aqueous solution at this time was measured with a hydrometer, and this was used as the specific gravity of the sample.

(6) Number average molecular weight: Calculated from the results of GPC measurement at a column temperature of 35 ° C. and a flow rate of 1 ml / min using Waters Gel Permeation Chromatography (GPC) 150c with tetrahydrofuran as an eluent, A measurement value in terms of polystyrene was obtained. However, Showa Denko Co., Ltd. shodex KF-802, 804, 806 was used for the column.

(7) Particle size and particle size distribution: The aqueous dispersion was adjusted to a solid concentration of 0.1% by mass using only distilled water, and measured at 25 ° C. with a Coulter counter LS13 320 (manufactured by Beckman).

(8) Residual organic solvent content in the aqueous dispersion: gas chromatograph HP5890 (manufactured by HEWLETT PACKARD), filled capillary PORAPLOT-Q (φ0.32 mm × 10 m), injection temperature 220 ° C., detect temperature 220 ° C. 1,4-Dioxane was used as an internal standard substance, and an aqueous dispersion diluted with ion-exchanged water was directly put into the apparatus, and the content of the organic solvent was determined.

(9) Supernatant solid content concentration: The aqueous dispersion was centrifuged at 20000 rpm × 2 hours using CP70MX (manufactured by Hitachi High-Technologies). Thereafter, only the supernatant was collected and the nonvolatile content was measured.

  In the examples, the volume average particle diameter (D) of the toner was measured using a Coulter counter LS13 320 (manufactured by Beckman).

[Production Example of Polyester Resin (A-1)]
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 318 parts of terephthalic acid, 318 parts of isophthalic acid, 7.7 parts of trimellitic anhydride, 322 parts of ethylene glycol, an ethylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Co., Ltd .: BPE-20F) 1152 parts were added, and the esterification reaction was performed from 160 ° C. to 230 ° C. over 3 hours under a pressure of 2 atmospheres of nitrogen atmosphere. After releasing the pressure, 0.42 part of tetrabutyl titanate was charged, and then the pressure inside the system was gradually reduced to 5 mmHg over 20 minutes, and then the pressure was reduced to 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. A condensation reaction was performed. The mixture was cooled to 220 ° C. under a nitrogen stream, 23 parts of trimellitic anhydride was added, and the reaction was performed for 30 minutes. As a result of NMR compositional analysis, the obtained polyester resin (A-3) has an acid component in a molar ratio of terephthalic acid / isophthalic acid / trimellitic acid = 48/48/4 and a glycol component in a molar ratio of ethylene glycol. / Ethylene oxide adduct of bisphenol A = 10/90. Further, the reduced viscosity was measured and found to be 0.25 dl / g, glass transition temperature 58 ° C., acid value 18 mgKOH / g, specific gravity 1.23, and number average molecular weight 3700.

[Production Example of Polyester Resin (A-2)]
In a reaction vessel equipped with a stirrer, condenser and thermometer, 385 parts of terephthalic acid, 126 parts of isophthalic acid, 88 parts of fumaric acid, 322 parts of ethylene glycol, ethylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Co., Ltd .: BPE-20F) The esterification reaction was performed for 3 hours from 160 ° C. to 230 ° C. under a pressure of 1152 parts and 2 atmospheres of nitrogen atmosphere. After releasing the pressure, 0.42 part of tetrabutyl titanate was charged, and then the pressure inside the system was gradually reduced to 5 mmHg over 20 minutes, and then the pressure was reduced to 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. A condensation reaction was performed. The mixture was cooled to 220 ° C. under a nitrogen stream, and 31 parts of trimellitic anhydride was added to react for 30 minutes. As a result of NMR compositional analysis, the obtained polyester resin (A-2) has a molar ratio of terephthalic acid / isophthalic acid / fumaric acid / trimellitic acid = 58/19/19/4, and the glycol component is The molar ratio was ethylene glycol / bisphenol A ethylene oxide adduct = 10/90. Further, the reduced viscosity was measured and found to be 0.21 dl / g, glass transition temperature 51 ° C., acid value 12 mgKOH / g, specific gravity 1.26, and number average molecular weight 3500.

[Production Example of Polyester Resin (A-3)]
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 352 parts of terephthalic acid, 303 parts of 1,4-cyclohexanedicarboxylic acid, 322 parts of ethylene glycol, 1152 parts of an ethylene oxide adduct of bisphenol A, under a 2 atmosphere pressure of nitrogen atmosphere, 160 The esterification reaction was carried out from 0 ° C. to 230 ° C. over 3 hours. After releasing the pressure, 0.42 part of tetrabutyl titanate was charged, and then the pressure inside the system was gradually reduced to 5 mmHg over 20 minutes, and then the pressure was reduced to 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. A condensation reaction was performed. The mixture was cooled to 220 ° C. under a nitrogen stream, 23 parts of trimellitic anhydride was added, and the reaction was performed for 30 minutes. As a result of NMR compositional analysis, the resulting polyester resin (A-3) has a molar ratio of terephthalic acid / 1,4-cyclohexanedicarboxylic acid / trimellitic acid = 53/44/3, and a glycol component. The molar ratio was ethylene glycol / bisphenol A ethylene oxide adduct = 10/90. Further, the reduced viscosity was measured and found to be 0.20 dl / g, glass transition temperature 51 ° C., acid value 7.8 mgKOH / g, specific gravity 1.24, number average molecular weight 3300.

[Production Example of Polyester Resin (A-4)]
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 385 parts of terephthalic acid, 126 parts of isophthalic acid, 99 parts of itaconic acid, 310 parts of ethylene glycol, propylene oxide adduct of bisphenol A (manufactured by Asahi Denka Co., Ltd .: BPX-11) 1368 Part, under a nitrogen atmosphere at 2 atm pressure, an esterification reaction was performed from 160 ° C. to 230 ° C. over 3 hours. After releasing the pressure, 0.42 part of tetrabutyl titanate was charged, and then the pressure inside the system was gradually reduced to 5 mmHg over 20 minutes, and then the pressure was reduced to 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. A condensation reaction was performed. The mixture was cooled to 220 ° C. under a nitrogen stream, 27 parts of trimellitic anhydride was added, and the reaction was performed for 30 minutes. As a result of NMR compositional analysis, the obtained polyester resin (A-4) was found to have a molar ratio of terephthalic acid / isophthalic acid / itaconic acid / trimellitic acid = 59 / 19.6 / 19.6 / 1.8. The glycol component was a propylene oxide adduct of ethylene glycol / bisphenol A = 5/95 in molar ratio. Further, the reduced viscosity was measured and found to be 0.22 dl / g, glass transition temperature 52 ° C., acid value 5.3 mgKOH / g, specific gravity 1.25, number average molecular weight 3100.

[Production Example of Polyester Resin (A-5)]
In a reaction vessel equipped with a stirrer, condenser and thermometer, 385 parts of terephthalic acid, 126 parts of isophthalic acid, 88 parts of fumaric acid, 322 parts of ethylene glycol, ethylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Co., Ltd .: BPE-20F) The esterification reaction was performed for 3 hours from 160 ° C. to 230 ° C. under a pressure of 1152 parts and 2 atmospheres of nitrogen atmosphere. After releasing the pressure, 0.42 part of tetrabutyl titanate was charged, and then the pressure inside the system was gradually reduced to 5 mmHg over 20 minutes, and then the pressure was reduced to 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. A condensation reaction was performed. The mixture was cooled to 220 ° C. under a nitrogen stream, and 31 parts of trimellitic anhydride was added to react for 30 minutes. As a result of NMR compositional analysis, the obtained polyester resin (A-5) has an acid component in a molar ratio of terephthalic acid / isophthalic acid / fumaric acid / trimellitic acid = 58/19/19/4, and a glycol component. The molar ratio was ethylene glycol / bisphenol A ethylene oxide adduct = 10/90. Further, the reduced viscosity was measured and found to be 0.21 dl / g, a glass transition temperature of 65 ° C., and an acid value of 10.4. It was mgKOH / g, specific gravity 1.26, number average molecular weight 3400.

[Production Example of Polyester Resin (A-6)]
In a reaction vessel equipped with a stirrer, condenser and thermometer, 318 parts of terephthalic acid, 318 parts of isophthalic acid, 7.7 parts of trimellitic anhydride, 447 parts of ethylene glycol, 70 parts of 2-methyl-1,3-propanediol, nitrogen The esterification reaction was carried out from 160 ° C. to 230 ° C. over 3 hours under an atmospheric pressure of 2 atm. After releasing the pressure, 0.42 part of tetrabutyl titanate was charged, and then the pressure inside the system was gradually reduced to 5 mmHg over 20 minutes, and then the pressure was reduced to 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. A condensation reaction was performed. The mixture was cooled to 220 ° C. under a nitrogen stream, 4 parts of trimellitic anhydride was added, and the reaction was performed for 30 minutes. As a result of NMR compositional analysis, the obtained polyester resin (A-6) was found to have an acid component in a molar ratio of terephthalic acid / isophthalic acid / trimellitic acid = 49/49/2 and a glycol component in a molar ratio of ethylene glycol. / 2-methyl-1,3-propanediol = 85/15. Further, the reduced viscosity was measured to be 0.36 dl / g, glass transition temperature 57 ° C., acid value 2.5 mgKOH / g, specific gravity 1.24, and number average molecular weight 9000.

[Production Example 1 of Polyester Water Dispersion]
Into a container equipped with a stirrer, a condenser, and a thermometer, 100 parts of the polyester resin (A-1) was added, 145 parts of methyl ethyl ketone and 40 parts of isopropyl alcohol were added, and the polyester was dissolved at 70 ° C. After cooling, when the internal temperature reached 55 ° C., 10 parts of 2.8% ammonia water was added, 370 parts of ion-exchanged water at 55 ° C. was added 25 parts per minute, over a total of 15 minutes, An aqueous dispersion containing the residual solvent was obtained. Subsequently, the container was gradually heated and cooled when about 333 parts of solvent and water were distilled off, and taken out when the temperature reached 35 ° C. Finally, it was filtered through a 200 mesh nylon mesh to obtain an aqueous dispersion E1 of a polyester resin. The water dispersion E1 had a non-volatile content of 30.0%, D50V measured with a Coulter counter was 160 nm, and the particle size distribution index DP was 1.24. Thus, a good water dispersion was obtained.

[Production Examples 2-8 of Polyester Water Dispersion]
Polyester resin water dispersions E2 to 8 were obtained by performing the same operations as in Example 1 using the polyester resin (A-1 to 5) with the charging composition and the neutralization rate shown in Table 1. Table 1 shows the charged composition for obtaining each aqueous dispersion, and the particle diameters and solid content concentrations of the obtained polyester resin aqueous dispersions E2 to E8.

[Production Example 9 of Polyester Water Dispersion]
Into a container equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen introduction tube, 100 parts of polyester resin (A-2) was added, and then 80 parts of methyl ethyl ketone and 20 parts of tetrahydrofuran were added. The resin was dissolved. Then, when the internal temperature reached 55 ° C., 9 parts of 2.8% ammonia water was added, and 305 parts of ion-exchanged water at 55 ° C. was added 20 parts per minute for a total of 15 minutes. An aqueous dispersion containing the residual solvent was obtained. Next, the container was gradually heated, cooled when about 148 parts of solvent and water were distilled off, and taken out when the temperature reached 35 ° C. Finally, it was filtered through a 200 mesh nylon mesh to obtain an aqueous dispersion E9 of a polyester resin. The water dispersion E9 had a nonvolatile content of 10.0%, D50V measured with a Coulter counter was 150 nm, and the particle size distribution index DP was 1.14. Thus, a good water dispersion was obtained.

[Production Example 10 of Polyester Water Dispersion]
Into a container equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen introduction tube, 100 parts of polyester resin (A-2) was added, and then 47 parts of methyl ethyl ketone and 7 parts of isopropyl alcohol acetone were added, The polyester resin was dissolved in After cooling, when the internal temperature reached 55 ° C., 2.1 parts of triethylamine was added, 277 parts of ion-exchanged water at 55 ° C. was added 18 parts per minute, 15 minutes in total, and the remaining solvent was removed. An aqueous dispersion containing was obtained. Subsequently, the container was gradually heated and cooled when about 97 parts of the solvent and water were distilled off, and the container was taken out when the temperature reached 35 ° C. Finally, it was filtered through a 200 mesh nylon mesh to obtain an aqueous dispersion E10 of a polyester resin. The water dispersion E10 had a non-volatile content of 30.0%, D50V measured with a Coulter counter was 350 nm, and the particle size distribution index DP was 1.25. Thus, a good water dispersion was obtained.

[Production Example 11 of Polyester Water Dispersion]
Into a container equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen introducing tube, 100 parts of polyester resin (A-3) was added, and then 75 parts of methyl ethyl ketone and 7 parts of acetone were added. The resin was dissolved. After cooling, when the internal temperature reached 40 ° C., 2.1 parts of triethylamine was added, 300 parts of ion-exchanged water at 40 ° C. was added 18 parts per minute, 15 minutes in total, and the remaining solvent was removed. An aqueous dispersion containing was obtained. Next, the container was gradually heated, cooled when about 148 parts of solvent and water were distilled off, and taken out when the temperature reached 35 ° C. Finally, it was filtered through a 200 mesh nylon mesh to obtain an aqueous dispersion E11 of a polyester resin. The water dispersion E11 had a nonvolatile content of 30.1%, D50V measured with a Coulter counter was 220 nm, and the particle size distribution index DP was 1.24. Thus, a good water dispersion was obtained.

[Production Example 12 of Polyester Water Dispersion]
100 parts of polyester resin (A-2) is charged into a container equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen introducing tube, and then 85 parts of methyl ethyl ketone, 10 parts of isopropyl alcohol and 5 parts of water are added. The polyester resin was dissolved at 70 ° C. After cooling, when the internal temperature reached 55 ° C., 10.2 parts of 2.8% ammonia water was added, and 294 parts of ion-exchanged water at 55 ° C. was added 20 parts per minute over a total of 15 minutes Then, an aqueous dispersion containing the residual solvent was obtained, and then the container was gradually heated, cooled when about 171 parts of the solvent and water were distilled off, and taken out when the temperature reached 35 ° C. Finally, it was filtered through a 200 mesh nylon mesh to obtain an aqueous dispersion E12 of a polyester resin. The water dispersion E12 had a nonvolatile content of 30.5%, D50V measured with a Coulter counter was 140 nm, and the particle size distribution index DP was 1.12. Thus, a good water dispersion was obtained.

[Production Example 13 of Polyester Water Dispersion]
After 100 parts of polyester resin (A-6) was added to a container equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen introduction tube, 60 parts of methyl ethyl ketone and 20 parts of isopropyl alcohol were added, Dissolved. After cooling, when the internal temperature reaches 55 ° C, 2.0 parts of 2.8% ammonia water is added, and 300 parts of ion-exchanged water at 55 ° C is added 20 parts per minute over a total of 15 minutes. However, the viscosity in the container rapidly increased with the addition of ion exchange water, and the phase was changed in a non-uniform state. The vessel was gradually heated to distill off the solvent, but the operation was stopped because resin precipitation occurred during the removal of the solvent.

[Production Example 14 of Polyester Water Dispersion]
Into a container equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introducing tube, 100 parts of polyester resin (A-2) was added, and then 98 parts of methyl ethyl ketone and 2 parts of isopropyl alcohol were added. Dissolved. After cooling, when the internal temperature reaches 55 ° C, 4.5 parts of 2.8% ammonia water is added, and 300 parts of ion-exchanged water at 55 ° C is added 20 parts per minute over a total of 15 minutes. However, the viscosity in the container rapidly increased with the addition of ion exchange water, and the phase was changed in a non-uniform state. The vessel was gradually heated to distill off the solvent, but the operation was stopped because resin precipitation occurred during the removal of the solvent.

[Production Example 15 of Polyester Water Dispersion]
Into a container equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, 100 parts of polyester resin (A-2) was added, and then 181 parts of methyl ethyl ketone and 5 parts of isopropyl alcohol were added, Dissolved. After cooling, when the internal temperature reached 55 ° C., 19 parts of 2.8% ammonia water was added, and 360 parts of ion-exchanged water at 55 ° C. was added 25 parts per minute for a total of 15 minutes. An aqueous dispersion containing the residual solvent was obtained. Subsequently, the container was gradually heated and cooled when about 335 parts of the solvent and water were distilled off, and taken out when the temperature reached 35 ° C. Finally, it was filtered through a 200 mesh nylon mesh to obtain an aqueous dispersion E13 of a polyester resin. The non-volatile content of the aqueous dispersion E13 was 30.1%, D50V measured with a Coulter counter was 280 nm, and the particle size distribution index DP was 1.37.

[Production Example 16 of Polyester Water Dispersion]
Into a container equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, 100 parts of polyester resin (A-4) was added, and then 99 parts of methyl ethyl ketone and 1 part of isopropyl alcohol were added. Dissolved. After cooling, when the internal temperature reached 55 ° C., 8.7 parts of 2.8% ammonia water was added, and 150 parts of ion-exchanged water at 55 ° C. was added 8 parts per minute over a total of 15 minutes. Thus, an aqueous dispersion containing a residual solvent was obtained. Subsequently, the container was gradually heated, and when about 100 solvent and water were distilled off, the container was cooled and taken out when the temperature reached 35 ° C. Finally, it was filtered through a 200 mesh nylon mesh to obtain an aqueous dispersion E14 of a polyester resin. The non-volatile content of the aqueous dispersion E14 was 40.0%, D50V measured with a Coulter counter was 185 nm, and the particle size distribution index DP was 1.32.

[Production Example 17 for polyester aqueous dispersion]
Into a container equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introducing tube, 100 parts of polyester resin (A-3) was added, and then 87 parts of methyl ethyl ketone and 5 parts of isopropyl alcohol were added at 70 ° C. Dissolved. Thereafter, the temperature was raised, and when the internal temperature reached 85 ° C., 7.7 parts of 2.8% ammonia water was added, and 307 parts of ion-exchanged water at 85 ° C. was added 20 parts per minute for a total of 15 minutes. The aqueous dispersion containing the residual solvent was added. Subsequently, the container was gradually heated and cooled when about 166 parts of the solvent and water were distilled off. When the temperature reached 35 ° C., the container was taken out. Finally, it was filtered through a 200 mesh nylon mesh to obtain an aqueous dispersion E15 of a polyester resin. The non-volatile content of the aqueous dispersion E15 was 30.7%, D50V measured with a Coulter counter was 360 nm, and the particle size distribution index DP was 3.58.

[Production Example 18 of Polyester Water Dispersion]
Into a container equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introducing tube, 100 parts of polyester resin (A-1) was added, and then 30 parts of methyl ethyl ketone and 3 parts of isopropyl alcohol were added. Dissolved. After cooling, when the internal temperature reached 55 ° C., 11.8 parts of 2.8% ammonia water was added and 260 parts of 55 ° C. ion exchange water was added over 20 parts per minute over a total of 15 minutes. However, the viscosity in the container rapidly increased with the addition of ion exchange water, and the phase was changed in a non-uniform state. The vessel was gradually heated to distill off the solvent, but the operation was stopped because resin precipitation occurred during the removal of the solvent.

[Production Example 19 of Polyester Water Dispersion]
After 100 parts of polyester resin (A-4) was put into a container equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen introducing tube, 61 parts of methyl ethyl ketone and 7 parts of acetone were added and dissolved at 70 ° C. did. After cooling, when the internal temperature reached 55 ° C., 0.9 part of triethylamine was added and 290 parts of ion-exchanged water at 55 ° C. was added all at once, but no increase in viscosity in the container was observed. . Thereafter, the vessel was gradually heated to distill off the solvent, but the operation was stopped because resin deposition occurred during the removal of the solvent.

[Production Example 20 of Polyester Water Dispersion]
Into a container equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen introducing tube, 100 parts of polyester resin (A-1) was added, and then 20 parts of methyl ethyl ketone and 46 parts of isopropyl alcohol were added, at 70 ° C. Dissolved. After cooling, when the internal temperature reached 55 ° C, 12 parts of 2.8% ammonia water was added, and 285 parts of ion-exchanged water at 55 ° C was added 19 parts per minute, 15 minutes in total. The viscosity in the container increased rapidly with the addition of ion-exchanged water, and the phase was changed in a non-uniform state. The vessel was gradually heated to distill off the solvent, but the operation was stopped because resin precipitation occurred during the removal of the solvent.

[Production Example 21 of Polyester Water Dispersion]
Into a container equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen inlet tube, 100 parts of polyester resin (A-5) was added, and then 45 parts of methyl ethyl ketone, 5 parts of isopropyl alcohol and 50 parts of water were added. The polyester resin was dissolved at 70 ° C. After cooling, when the internal temperature reached 55 ° C, 10.1 parts of 2.8% ammonia water was added, and 213 parts of ion-exchanged water at 55 ° C was added 14 parts per minute over a total of 15 minutes. However, the viscosity in the container rapidly increased with the addition of ion exchange water, and the phase was changed in a non-uniform state. The vessel was gradually heated to distill off the solvent, but the operation was stopped because resin precipitation occurred during the removal of the solvent.

[Production Example 22 of Polyester Water Dispersion]
A stirrer equipped with a jacketed glass container that can be sealed is charged with 100 parts of a polyester resin (A-1), 60 parts of isopropyl alcohol, 4.1 g of triethylamine, and 170 g of distilled water, and stirred at a rotational speed of 7000 rpm. did. Next, heating was performed 10 minutes later, the system temperature was kept at 75 ° C., and the mixture was further stirred for 30 minutes. Thereafter, the rotation speed was lowered to 4000 rpm and the mixture was cooled to room temperature with stirring to obtain a milky white uniform polyester aqueous dispersion. It was. Next, 230 g of this polyester aqueous dispersion and 120 g of distilled water were charged into a container equipped with a stirrer, a condenser and a thermometer. Thereafter, the container was gradually heated, and when about 120 g of the aqueous medium was distilled off, the container was cooled and taken out when the temperature reached 35 ° C. Finally, filtration was performed with a 200 mesh nylon mesh to obtain an aqueous dispersion E16 of a polyester resin. The non-volatile content of the aqueous dispersion E16 was 30.1%, the volume particle size measured with a Coulter counter was 160 nm, and the particle size distribution index DP was 1.28.

[Production Example 23 of Polyester Water Dispersion]
In a container equipped with a stirrer, a condenser and a thermometer, 20 parts of polyester resin (A-1) and 380 parts of tetrahydrofuran were dissolved. To this solution, 210 parts of acetonitrile and 1 part of triethylamine were added and mixed and stirred. Next, the mixed solution was gradually added to 440 parts of water while stirring to precipitate fine particles. The mixed solution containing the fine particles thus obtained was gradually heated and cooled when about 850 parts of the solvent and water were distilled off, and taken out when the temperature reached 35 ° C. Finally, filtration was performed with a 200 mesh nylon mesh to obtain an aqueous dispersion E17 of a polyester resin. The non-volatile content of the aqueous dispersion E17 was 10.1%, the volume particle size measured with a Coulter counter was 260 nm, and the particle size distribution index DP was 1.35.

[Production Example 24 of Polyester Water Dispersion]
In a container equipped with a stirrer, a condenser and a thermometer, 100 parts of polyester resin (A-1) and 567 parts of methyl ethyl ketone were dissolved. To this solution, 4.1 parts of triethylamine was added for neutralization, and then 2000 parts of distilled water was added, followed by mixing and stirring. Subsequently, this mixed solution was gradually heated, and when about 1790 parts of the solvent and water were distilled off, the mixture was cooled and taken out when the temperature reached 35 ° C. Finally, filtration was performed with a 200 mesh nylon mesh to obtain an aqueous dispersion E18 of a polyester resin. The non-volatile content of the aqueous dispersion E18 was 10.0%, the volume particle size measured with a Coulter counter was 450 nm, and the particle size distribution index DP was 1.76.

  Solvent composition ratio, preparation solvent solid content concentration, neutralization rate with respect to polyester acid value, volume particle diameter, DP, solid content concentration of water dispersion E1 to E18, remaining in water dispersion Table 1 shows the amount of organic solvent and the solid concentration of the supernatant after centrifugation.

Abbreviations in the table are as follows.
MEK: Methyl ethyl ketone
IPA: isopropyl alcohol THF: tetrahydrofuran Ac: acetone ANT: acetonitrile Anm: aqueous ammonia (2.8 wt% solution)
TEA: Triethylamine

(Preparation of wax dispersion (1))
680 parts of distilled water, 180 parts of carnauba wax (manufactured by Celarica Noda), 17 parts of sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku) are mixed and emulsified and dispersed by applying high-pressure shear to obtain a wax fine particle dispersion. Obtained. When the particle size of the wax fine particles was measured using a dynamic light scattering particle size distribution analyzer, LB-500 (manufactured by Horiba Seisakusho), the average particle size was 110 nm.

(Preparation of wax dispersion (2))
680 parts of distilled water, 180 parts of pentaerythritol ester (Unistar H476 manufactured by NOF Corporation) and 17 parts of sodium dodecylbenzenesulfonate (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are mixed, emulsified and dispersed by applying high-pressure shear, and wax fine particles. A dispersion was obtained. When the particle size of the wax fine particles was measured using a dynamic light scattering particle size distribution analyzer, LB-500 (manufactured by Horiba Seisakusho), the average particle size was 130 nm.

(Colorant fine particle dispersion (1))
10 parts of sodium dodecylbenzenesulfonate (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved in 180 parts of distilled water, and 25 parts of carbon black (Regal 330R; manufactured by Cabot Corporation) is added and dispersed therein as fine colorant particles. A colorant fine particle dispersion (1) was obtained. When the particle size of the dispersed carbon black was measured using a dynamic light scattering particle size distribution analyzer, LB-500 (manufactured by Horiba, Ltd.), the average particle size was 106 nm.

(Colorant fine particle dispersion (2))
10 parts of sodium dodecylbenzenesulfonate (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved in 180 parts of distilled water, and 25 parts of cyan pigment (copper phthalocyanine B15: 3; manufactured by Dainichi Seika Co., Ltd.) is used as fine colorant particles. In addition, it was dispersed to obtain a colorant fine particle dispersion (2). When the particle size of the dispersed cyan pigment was measured using a dynamic light scattering particle size distribution analyzer, LB-500 (manufactured by Horiba, Ltd.), the average particle size was 110 nm.

[Example 1]
In a reaction vessel (four-necked flask) equipped with a stirrer, a condenser, a nitrogen introducing device, and a temperature sensor, 420.7 g of polyester water dispersion E1 (solid content conversion), 166 g of colorant dispersion (1), 95 g of wax dispersion (1) was added and stirred. After adjusting the internal temperature to 30 ° C., a 2M sodium hydroxide aqueous solution was added to this solution to adjust the pH to 11.0. Next, an aqueous solution in which 12.1 g of magnesium chloride hexahydrate was dissolved in 1000 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, temperature increase was started, and the system was heated to 90 ° C. over 6 minutes (temperature increase rate: 10 ° C./min). In this state, the particle size of the associated particles was measured, and when the volume average particle size reached 4.1 μm, an aqueous solution in which 80.4 g of sodium chloride was dissolved in 1000 ml of ion-exchanged water was added to stop particle growth. Furthermore, as a ripening treatment, the mixture was heated and stirred for 2 hours at a liquid temperature of 85 ° C. to promote spheroidization. Then, it cooled to 40 degreeC on the conditions of 8 degreeC / min, hydrochloric acid was added, pH was adjusted to 2.0, and stirring was stopped. The produced associated particles were filtered, washed repeatedly with ion-exchanged water whose temperature was adjusted to 45 ° C., and then dried with hot air at 40 ° C., to obtain toner particles T1 having a volume average particle size of 4.4 μm. To 100 parts by mass of the obtained toner particles T1, 0.5 part by mass of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part by mass of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate ( After adding 1.0 part by mass of (average particle size 0.2 μm) and mixing with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), the mixture was sieved with a sieve having an opening of 90 μm to obtain a toner.

[Example 2]
In Example 1, instead of using the polyester aqueous dispersion E1, E2 was used, and instead of using the colorant fine particle dispersion (1), the same procedure was performed using the colorant fine particle dispersion (2). Toner particles T2 having a diameter of 4.6 μm were obtained. To 100 parts by mass of the toner particles T2, 0.5 part by mass of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part by mass of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate After adding 1.0 part by mass (average particle size 0.2 μm) and mixing with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), the mixture was sieved with a sieve having an opening of 90 μm to obtain a toner.

[Example 3]
In Example 1, instead of using the polyester water dispersion E1, E3 was used, and instead of using the wax dispersion (1), the volume average particle size was 4.8 μm by the same operation using the wax dispersion (2). Toner particles T3 were obtained. To 100 parts by mass of toner particles T3, 0.5 part by mass of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part by mass of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate After adding 1.0 part by mass (average particle size 0.2 μm) and mixing with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), the mixture was sieved with a sieve having an opening of 90 μm to obtain a toner.

[Examples 4 to 12]
In Example 1, instead of using the polyester water dispersion E1, E4 to 12 were used, and the colorant fine particle dispersion and the wax dispersion were each subjected to the same procedure using the types shown in Table 2, and the volumes shown in Table 2 were used. Toner particles T4 to T12 having a particle size were obtained. With respect to 100 parts by mass of these toner particles, 0.5 part by mass of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part by mass of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate ( After adding 1.0 part by mass of (average particle size 0.2 μm) and mixing with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), the mixture was sieved with a sieve having an opening of 90 μm to obtain a toner.
Got.

[Comparative Example 1]
In a reaction vessel (four-necked flask) equipped with a stirrer, a cooling tube, a nitrogen introducing device, and a temperature sensor, 420.7 g of polyester water dispersion E13 (in terms of solid content), 166 g of colorant dispersion (1), 95 g of wax dispersion (1) was added and stirred. After adjusting the internal temperature to 30 ° C., a 2M sodium hydroxide aqueous solution was added to this solution to adjust the pH to 11.0. Next, an aqueous solution in which 12.1 g of magnesium chloride hexahydrate was dissolved in 1000 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, temperature increase was started, and the system was heated to 90 ° C. over 6 minutes (temperature increase rate: 10 ° C./min). In this state, the particle size of the associated particles was measured, and when the volume average particle size reached 4.9 μm, an aqueous solution in which 80.4 g of sodium chloride was dissolved in 1000 ml of ion-exchanged water was added to stop particle growth. Furthermore, as a ripening treatment, the mixture was heated and stirred for 2 hours at a liquid temperature of 85 ° C. to promote spheroidization. Then, it cooled to 40 degreeC on the conditions of 8 degreeC / min, hydrochloric acid was added, pH was adjusted to 2.0, and stirring was stopped. The produced association particles were filtered, washed repeatedly with ion-exchanged water whose temperature was adjusted to 45 ° C., and then dried with hot air at 40 ° C., to obtain toner particles T13 having a volume average particle size of 5.1 μm. To 100 parts by mass of the obtained toner particles T13, 0.5 part by mass of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part by mass of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate ( After adding 1.0 part by mass of (average particle size 0.2 μm) and mixing with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), the mixture was sieved with a sieve having an opening of 90 μm to obtain a toner.

[Comparative Example 2]
In Comparative Example 1, instead of using the polyester water dispersion E13, E14 was used, and instead of using the colorant fine particle dispersion (1), the same procedure was performed using the colorant fine particle dispersion (2). Toner particles T14 having a diameter of 4.8 μm were obtained. With respect to 100 parts by mass of the toner particles, 0.5 part by mass of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part by mass of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate (average) 1.0 part by mass) was added and mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds).

[Comparative Example 3]
In Comparative Example 2, instead of using the polyester water dispersion E13, E15 was used, and instead of using the wax dispersion (1), the wax dispersion (2) was used in the same manner, and the volume average particle size was 5.8 μm. Toner particles T15 were obtained. With respect to 100 parts by mass of the toner particles, 0.5 part by mass of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part by mass of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate (average) After adding 1.0 part by mass of a particle size of 0.2 μm and mixing with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), the mixture was sieved with a sieve having an opening of 90 μm to obtain a toner.

[Comparative Examples 4 to 6]
In Comparative Example 1, instead of using the polyester water dispersion E13, E16 to 18 are used, and the colorant fine particle dispersion and the wax dispersion are each of the types shown in Table 2, and the toner particles shown in the table are operated in the same manner. T16 to T18 were obtained. With respect to 100 parts by mass of these toner particles, 0.5 part by mass of hydrophobic silica (H-2000; manufactured by Clariant), 1.0 part by mass of titanium oxide (STT30A: manufactured by Titanium Industry Co., Ltd.), strontium titanate ( After adding 1.0 part by mass of (average particle size 0.2 μm) and mixing with a Henschel mixer (peripheral speed 40 m / sec, 60 seconds), the mixture was sieved with a sieve having an opening of 90 μm to obtain a toner.

(Manufacture of binder type carrier)
In order to use the toners obtained in the above Examples and Comparative Examples as a two-component developer for evaluation, binder type carriers were produced.
100 parts by mass of a polyester resin, 700 parts by mass of magnetic particles (magnetite; EPT-1000: manufactured by Toda Kogyo Co., Ltd.) and 2 parts by mass of carbon black (Mogal L; manufactured by Cabot) are sufficiently mixed with a Henschel mixer and biaxial extrusion kneading. The cylinder part was set at 180 ° C. and the cylinder head part at 170 ° C., and melt kneaded. The kneaded product was cooled, then coarsely pulverized with a hammer mill, finely pulverized with a jet pulverizer, and classified to obtain a binder-type carrier having a volume average particle size of 40 μm.

(Toner characteristics evaluation method)
Heat Resistance 10 g of toner was allowed to stand at a high temperature of 50 ° C. for 24 hours, and then the toner was visually observed and evaluated.
○: No aggregates were observed Δ: Less than 10 aggregates were present ×: 10 or more aggregates were present In the following evaluation, the toner concentration was 6% by mass of toner and carrier. A developer obtained by mixing with the above was used.
Fixability Fixability was evaluated comprehensively from the evaluation results of peel resistance and offset resistance.
○: The result of all items was “◎” or “○” △: “△” was included in addition to “◎” or “○” ×: At least one “×” was included Peel resistance With a digital copying machine (DIALTA Di350; manufactured by Minolta Co., Ltd.) equipped with an oil-less fixing device while changing the fixing temperature in the range of 80 to 130 ° C. in increments of 2 ° C., 1.5 cm × 1.5 cm Were taken (attachment amount 2.0 mg / cm ² ), and each image was folded in half from the middle, and the peel resistance of the image was visually evaluated. The temperature between the fixing temperature when the image was slightly peeled off and the lower fixing temperature at which the image was not peeled at all was defined as the fixing lower limit temperature.
A: The fixing lower limit temperature was less than 102 ° C. ○: The fixing lower limit temperature was 102 ° C. or more and less than 106 ° C. Δ: The fixing lower limit temperature was 106 ° C. or more and less than 112 ° C. x: The fixing lower limit temperature was It was 112 ° C or higher.
Offset resistance Offset the digital copier (DIALTA Di350; manufactured by Minolta) by 1/2 and take a halftone image while changing the fixing temperature in the range of 90 ° C to 150 ° C in 5 ° C increments. This state was visually observed to evaluate the temperature at which high temperature offset occurs (offset temperature).
A: Offset temperature was 128 ° C. or higher. ○: Offset temperature was 120 ° C. or higher and lower than 128 ° C. Δ: Offset temperature was 115 ° C. or higher and lower than 120 ° C. x: Offset temperature was lower than 115 ° C. there were.
Stress Resistance Stress resistance was evaluated by the presence or absence of a phenomenon in which crushed or worn toner particles adhere to the surface of the organic photoconductor in a thin layer due to continuous use of the toner.

  Table 2 shows the physical properties of the resin particles and toners of Examples 1 to 12 and Comparative Examples 1 to 6 prepared using the aqueous dispersions E1 to E18.

  From Table 2, it can be seen that the toner of the present invention is an electrostatic charge developing toner that achieves excellent low-temperature fixability while ensuring good heat storage stability and mechanical strength.

  In the present invention, in a polyester resin having a polar group, an aqueous dispersion having a very narrow particle size distribution can be produced by adding water and inversion in a state where the resin dissolution concentration is increased. In addition, when the polar group is a carboxyl group, by neutralizing the necessary amount of all the carboxyl groups from a state in which the resin dissolution concentration is increased and performing phase inversion, there are few small particles and a narrow particle size distribution. A water dispersion having a size can be produced. The aqueous dispersion thus prepared has good storage stability. When a toner is prepared using the polyester aqueous dispersion, the environmental load is small in the process, the size and shape are uniform, and lot blurring is small. Furthermore, since excellent low-temperature fixability can be achieved while ensuring good heat-resistant storage properties and mechanical strength, it contributes greatly to the industry.

Claims (17)

In an electrophotographic toner produced using an aqueous dispersion of a polyester resin having a polar group in the molecule, the particle diameter (D50V) and the number particle diameter are 50% of the volume particle diameter of the polyester resin particles in the aqueous dispersion. A toner for electrophotography produced using an aqueous polyester resin dispersion, wherein the relationship of 50% cumulative particle diameter (D50P) satisfies the following formula.
1 ≦ (D50V / D50P) ≦ 1.25   The toner for electrophotography produced using the polyester resin aqueous dispersion according to claim 1, wherein the polyester resin is amorphous.   The toner for electrophotography produced using the aqueous polyester resin dispersion according to claim 1 or 2, wherein the polar group is a carboxyl group salt, and the acid value of the polyester resin is 3 to 25 mgKOH / g. . The polyester resin particles having a particle diameter of 1 µm or more are 1% by mass or less of the total polyester resin particles, and for electrophotography produced using the polyester resin aqueous dispersion according to any one of claims 1 to 3. toner.   5. The toner for electrophotography produced using the aqueous polyester resin dispersion according to claim 3, wherein the carboxyl group salt is an amine salt.   6. The toner for electrophotography produced using the polyester resin aqueous dispersion according to claim 5, wherein the amine compound is at least one member selected from the group consisting of triethanolamine, triethylamine and ammonia.   The volume average particle diameter of the polyester resin particles is 60 nm to 500 nm, The toner for electrophotography produced using the polyester resin aqueous dispersion according to claim 1.   The residual organic solvent amount is 2% by mass or less, The electrophotographic toner produced using the polyester resin aqueous dispersion according to any one of claims 1 to 7.   9. The supernatant solid content concentration when the aqueous dispersion adjusted to a solid content concentration of 30% by mass is separated into a supernatant and a sediment by a centrifuge, and is 4% by mass or less. An electrophotographic toner produced using the aqueous polyester resin dispersion according to claim 1.   The polyester resin aqueous dispersion according to any one of claims 1 to 9, wherein the polyester resin is neutralized by adding an amine compound in an amount of 0.4 to 0.95 equivalent to the acid value of the polyester resin. An electrophotographic toner produced using the same.   The polyester resin is dissolved in an organic solvent in a solid content concentration range of 35% by mass or more and 70% by mass or less, and water is added to the varnish to thereby perform phase inversion and self-emulsification. An electrophotographic toner produced using the polyester resin aqueous dispersion according to any one of 1 to 10.   The organic solvent is a mixed solvent composed of an organic good solvent that dissolves the polyester resin and an organic poor solvent that does not dissolve the polyester resin, and is produced using the aqueous polyester resin dispersion according to claim 11. Toner for electrophotography.   The electrophotographic produced using the polyester resin aqueous dispersion according to claim 12, wherein the amount of the organic poor solvent is 25% by mass or less based on the total amount of the organic solvent when the polyester resin is dissolved. Toner.   The polyester resin water according to any one of claims 11 to 13, wherein the organic solvent is selected from at least two kinds selected from the group consisting of methyl ethyl ketone, tetrahydrofuran, acetone, dioxane, ethyl acetate and isopropyl alcohol. An electrophotographic toner produced using a dispersion.   The toner for electrophotography produced using the polyester resin aqueous dispersion according to claim 11, wherein the organic solvent has a boiling point of 100 ° C. or less.   The solvent used at the time of melt | dissolving a polyester resin is a mixed solvent of an organic solvent and water, Comprising: Water is contained 30 mass% or less with respect to all the solvents, The any one of Claims 11-15 characterized by the above-mentioned. An electrophotographic toner produced using an aqueous polyester resin dispersion.   An electrophotographic toner comprising: mixing the polyester resin aqueous dispersion according to any one of claims 1 to 16 and a colorant fine particle dispersion; and aggregating and fusing each fine particle to produce toner particles. Production method.