JP6021333B2 - Toner production method - Google Patents

Description

  The present invention relates to a toner production method using an aqueous medium of resin fine particles.

  Aqueous dispersions of resin fine particles are used in various fields such as toner, ink for inkjet printers, liquid developers for electrostatic printing, and the like. In any field, control of the particle size and particle size distribution of the resin fine particles in the aqueous dispersion of resin fine particles is important. Particularly, resin fine particles having a small particle size and a sharp particle size distribution are desired.

  When an aqueous dispersion of resin fine particles is used in the production of toner, an aqueous dispersion of resin fine particles having a more precisely controlled particle size is desired. This is because the particle size and particle size distribution of the resin fine particles greatly affect the toner particle size distribution, shape, and the like, and greatly affect the developability of the toner.

  Patent Document 1 proposes a method using an organic solvent called a phase inversion emulsification method as a method for producing resin fine particles. Patent Documents 2 and 3 propose a solvent-free emulsification method in which a resin dispersion is obtained without using an organic solvent from the viewpoint of reducing environmental burden and saving resources.

JP-A-8-21655 JP2004-189765 JP 2007-106906 A

  In the methods described in Patent Documents 1 to 3, when emulsifying a resin having an acid group, adsorption of the surfactant to the resin is inhibited by electrostatic repulsion between the negative charge derived from the acid group and the negative charge of the surfactant. As a result, the adhesion amount of the surfactant becomes uneven. For this reason, the amount of the surfactant adhering to the surface of the dispersion becomes non-uniform, so that the particle size distribution of the resin fine particles to be formed becomes wide and a toner having a desired particle size may not be obtained.

  In recent years, in order to achieve both low-temperature fixability and storage stability in the electrophotographic field, core-shell toners having a structure in which a core made of a low softening point resin is covered with a shell made of a high softening point resin have been widely used. When an aqueous dispersion of resin fine particles having a large particle size and a wide particle size distribution is used as a constituent material of the shell, shell particle adhesion to the core particles becomes non-uniform, and the storage stability of the toner decreases. In order to solve the above problem, it is conceivable to increase the coating amount of the shell, but in this case, the softening point of the entire toner is increased, and the low-temperature fixability is deteriorated. Therefore, in order to achieve both storage stability and low-temperature fixability, it is a big problem to make the resin fine particles sufficiently small and narrow the particle size distribution.

  The present invention solves the above problems. That is, an object of the present invention is to provide a method for producing an aqueous dispersion of resin fine particles having a small particle size and a narrow particle size distribution. Another object of the present invention is to provide a toner production method that is excellent in low-temperature fixability and storage stability by using an aqueous dispersion of the resin fine particles.

The present invention
Producing an aqueous dispersion of resin fine particles;
An aqueous dispersion of the resin fine particles and a colorant are mixed, and the resin fine particles and the colorant are aggregated in an aqueous medium to obtain an aggregate having a weight average particle diameter (D4) of 4.5 μm or more and 7.0 μm or less. An aggregation process to form;
A fusing step of heating and fusing the aggregates;
In a method for producing a toner having
The step of producing an aqueous dispersion of the resin fine particles includes:
(I) a mixing step of mixing a resin having an acid group, an anionic surfactant, an aqueous medium, an acid and a tertiary amine represented by the following formula 1 to obtain a mixture;
NR ¹ R ² R ³ Formula 1
[In Formula 1, R ¹ , R ² , and R ³ each represent a hydrocarbon group having 1 to 8 carbon atoms that may have a hydroxyl group. ]
(Ii) Stirring the mixture at a temperature equal to or higher than the glass transition point of the resin having an acid group to obtain an aqueous dispersion of the resin fine particles having a 50% particle size of 0.02 μm or more and 1.00 μm or less based on volume distribution. An emulsifying step to obtain, wherein in the emulsifying step, the concentration of the amino cation generated from the tertiary amine and the acid in the aqueous phase of the aqueous dispersion is equal to or less than the following critical aggregation concentration. Toner manufacturing method.
[Critical coagulation concentration refers to the volume distribution standard 50% particle size of resin fine particles of an aqueous dispersion of resin fine particles to which an aqueous solution prepared by dissolving tertiary amine and acid in water is added. This is the amino cation concentration in the aqueous phase of the aqueous dispersion at a time when it exceeds 1.5 times the 50% particle diameter of the resin fine particles in the aqueous dispersion of the resin fine particles. ].
Furthermore, the present invention provides
Producing an aqueous dispersion of resin fine particles;
An aqueous dispersion of the resin fine particles and a colorant are mixed, and the resin fine particles and the colorant are aggregated in an aqueous medium to obtain an aggregate having a weight average particle diameter (D4) of 4.5 μm or more and 7.0 μm or less. An aggregation process to form;
A fusing step of heating and fusing the aggregates;
In a method for producing a toner having
The step of producing an aqueous dispersion of the resin fine particles includes:
(I) a mixing step of mixing a resin having an acid group, a solvent in which the resin having an acid group is soluble, and an anionic surfactant to obtain a mixture;
(Ii) An aqueous system of the resin fine particles in which 50% particle size based on volume distribution is 0.02 μm or more and 1.00 μm or less by adding acid, water and a tertiary amine represented by the following formula 1 to the mixture and stirring the mixture. It has an emulsification step to obtain a dispersion. NR ¹ R ² R ³ Formula 1
[In Formula 1, R ¹ , R ² , and R ³ each represent a hydrocarbon group having 1 to 8 carbon atoms that may have a hydroxyl group. ]
In the emulsification step, the concentration of an amino cation generated from the tertiary amine and the acid in the aqueous phase of the aqueous dispersion is not more than a critical aggregation concentration.
[Critical coagulation concentration refers to the volume distribution standard 50% particle size of resin fine particles of an aqueous dispersion of resin fine particles to which an aqueous solution prepared by dissolving tertiary amine and acid in water is added. This is the amino cation concentration in the aqueous phase of the aqueous dispersion at a time when it exceeds 1.5 times the 50% particle diameter of the resin fine particles in the aqueous dispersion of the resin fine particles. ].

  According to the present invention, even when an acid group-containing resin is used, it is possible to provide an aqueous dispersion of resin fine particles having a smaller particle size and a narrower particle size distribution than before. Further, by producing a toner using an aqueous dispersion of resin fine particles having a small particle size and a narrow particle size distribution produced according to the present invention, a toner excellent in low-temperature fixability and storage stability can be obtained.

<Method for producing aqueous dispersion of resin fine particles>
First, the first aspect of the method for producing an aqueous dispersion of resin fine particles will be described.

  The 1st aspect of the manufacturing method of this invention has the mixing process of mixing resin which has an acid group, and anionic surfactant, and obtaining a mixture.

  The resin having an acid group used in the present invention means a resin having a carboxyl group, a sulfo group, or a salt thereof at the end or side chain of a molecular chain. Specifically, an acrylic resin, a methacrylic resin, a styrene-acrylic copolymer, a styrene-methacrylic copolymer, a polyester resin, a polyamic acid resin, and the like can be preferably exemplified. Among these, when used as a toner material, a polyester resin is preferable from the viewpoint that the difference between the softening temperature (Tm) of the toner and the glass transition point (Tg) can be reduced.

  The polyester resin is obtained by polycondensing an acid component and an alcohol component. When the polyester resin is produced, the acid component includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, In addition to dicarboxylic acids such as undecane dicarboxylic acid, dodecane dicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecyl succinic acid, n-dedecenyl succinic acid, cyclohexane dicarboxylic acid, Trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1, 3-dicarboxyl-2-methyl-2-methylenecarb Propane, tri- or higher carboxylic acid, and derivatives such as their anhydrides or lower alkyl esters.

  Examples of the alcohol component include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, , 9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, In addition to aliphatic diols such as 20-eicosanediol, dihydric alcohols such as polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, 1,4-cyclohexanedimethanol, 1,3,5-trihydroxy Aromatic alcohols such as methylbenzene, pentaerythritol Dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane Trivalent alcohol such as trimethylolpropane may be used.

  When used as a toner, the glass transition point (Tg) of the resin having an acid group used in the present invention is preferably 50 ° C. or higher from the viewpoint of blocking prevention, and 80 ° C. or lower from the viewpoint of low-temperature fixability. It is preferable that

  The softening temperature (Tm) of the resin having an acid group used in the present invention is preferably 150 ° C. or less from the viewpoint of low-temperature fixability when used as a toner, and from the viewpoint of heat-resistant storage properties of the toner. 90 degreeC or more is preferable.

  The resin having an acid group used in the present invention has a molecular weight range of 3,500 to 15,000 in the molecular weight distribution measured by gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF) of the resin. It is preferable to have a peak top of the main peak. When the peak top of the main peak is within the above range, the thermal stability is high when an aqueous dispersion of resin fine particles is used in the production of the aggregated toner.

The resin having an acid group used in the present invention preferably has an acid value of 1 mgKOH / g or more and 30 mgKOH / g or less . When the acid value of the resin is 1 or more, the chargeability is high when the toner is used, and scattering and fogging are suppressed. Further, if the acid value is 30 or less, the moisture absorption of the resin is suppressed, and the toner characteristics hardly change even in environments with different temperatures.

  The anionic surfactant used in the present invention includes, as a hydrophobic substituent, a hydrocarbon group having a linear or branched structure, a fluorocarbon chain, or a hydrophobic group having an aromatic ring such as benzene or naphthalene, and a sulfonic acid A compound having an ester, a carboxylic acid, or a hydrophilic group having a sulfonic acid is preferable. Examples of the anionic surfactant include sulfate ester salt, sulfonate salt, phosphate ester, soap, amine salt type, and quaternary ammonium salt type. Specifically, fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonylphenyl ether sulfate; lauryl sulfonate, dodecylbenzene sulfonate, tri Alkylnaphthalene sodium sulfonates such as isopropyl naphthalene sulfonate and dibutyl naphthalene sulfonate; sulfonates such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate; lauryl phosphate; Phosphoric acid esters such as isopropyl phosphate and nonylphenyl ether phosphate Le ethers; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; sulfosuccinate salts such as sulfosuccinate lauryl disodium and the like. The surfactant is preferably added so that the concentration in the liquid is equal to or higher than the critical micelle concentration. Surfactant may be used individually by 1 type and may use 2 or more types together.

  In the mixing step in the present invention, the acid group-containing resin and the anionic surfactant may be mixed as they are, or these materials may be mixed in the presence of water.

In the first aspect of the production method of the present invention, the aqueous medium, the acid, the tertiary amine represented by NR ¹ R ² R ³ and the mixture are stirred at a temperature equal to or higher than the glass transition point of the resin having an acid group, An emulsification step of obtaining a resin emulsion.

  Examples of the stirring device include a high-speed rotation type homogenizer and a high-pressure type homogenizer.

  In the present invention, in the emulsification step, the amino cation generated by the tertiary amine and the acid shields the negative charge derived from the acid group of the resin having an acid group. Thereby, the electrostatic repulsion between the negative charge derived from the acid group of the resin and the anionic surface activity is weakened, and it is considered that the surfactant adheres to the resin surface in a state where the amount of the surface active agent is larger and nearly uniform. Therefore, an aqueous dispersion of resin fine particles having a small particle size and a sharp particle size distribution can be obtained. On the other hand, when the concentration of the amino cation in the aqueous medium is too high, the charge shielding effect of the amino cation with respect to the resin having an acid group becomes too strong, causing aggregation of resin fine particles. As a result, the resin fine particles have a large particle size and a broad dispersion of resin fine particles is obtained.

  Therefore, in the emulsification step of the present invention, the concentration of the amino cation generated from the tertiary amine and acid in the aqueous phase needs to be not more than the critical aggregation concentration. The concentration of amino cation in the present invention means the lower concentration of the tertiary amine and acid in the aqueous phase.

  Specifically, the critical aggregation concentration is measured by the following method.

  First, an aqueous dispersion of resin fine particles prepared without adding a tertiary amine and an acid is prepared, and a volume distribution reference 50% particle diameter of the resin fine particles in the aqueous dispersion of the resin fine particles is measured.

  Next, at 20 ° C., while stirring the aqueous dispersion of the resin fine particles with Claremix 2.2S (manufactured by M Technique Co., Ltd.) at a rotation speed of 10,000 r / min, the concentration of amino cation is 5.0 mol. An aqueous solution prepared by dissolving equimolar tertiary amine and hydrochloric acid in water so as to be / L is gradually added, and the volume distribution standard 50% particle diameter of the resin fine particles is measured as needed.

  The volume distribution standard 50% particle size of the resin fine particles in the aqueous dispersion to which the aqueous solution is added is 1.5 times the volume distribution standard 50% particle size of the resin fine particles in the resin emulsion before the aqueous solution is added. The concentration of the amino cation in the aqueous phase at the time when the concentration is exceeded is defined as the critical aggregation concentration.

  For measuring the particle size of the resin fine particles, a dynamic light scattering particle size distribution measuring device (Nanotrack UPA150: manufactured by Nikkiso Co., Ltd.) is used, and the particle size is measured according to the operation manual of the device.

In the present invention, the amount of the tertiary amine and the acid may be such that the concentration of the amino cation in the aqueous phase is equal to or less than the critical aggregation concentration. If the amount of either the tertiary amine or the acid is large, for example, a resin polyester is used. If you, pH of the aqueous phase, may Ru polarized in basic or acidic, thereby promoting the hydrolysis of resin. From this, it is preferable to add equimolar amounts of the tertiary amine and the acid. In the emulsification step in the present invention, an aqueous medium, an acid, a tertiary amine represented by the following formula 1 and a mixture are stirred.
NR ¹ R ² R ³ Formula 1
[In formula ^1, R ^{1, R} 2, and R ^3, respectively, to display the good number 1 to 8 hydrocarbon group carbon atoms which may have a hydroxyl group. ]

^{R 1,} R 2, ^{R 3} in Formula 1, respectively, is preferably a hydrocarbon group having 1 to 3 carbon atoms having a hydrocarbon group or a hydroxyl group, having 1 to 8 carbon atoms. R ¹ , R ² and R ³ in Formula 1 are each more preferably a hydrocarbon group having 1 to 8 carbon atoms or a hydrocarbon group having 2 carbon atoms having a hydroxyl group. Specific examples of the tertiary amine include the following compounds. 2- (dimethylamino) ethanol, 2-diethylaminoethanol, 2- (dibutylamino) ethanol, N-ethyldiethanolamine, triethanolamine, triethylamine, tripropylamine, triamylamine, trihexylamine, tri-n-octylamine , Tridodecylamine. Among these tertiary amines, the group consisting of 2- (dimethylamino) ethanol, 2-diethylaminoethanol, 2- (dibutylamino) ethanol, and N-ethyldiethanolamine from the viewpoint of storage stability of the aqueous dispersion of resin fine particles. It is particularly preferred to use one or more tertiary amines selected from

The tertiary amine preferably has an SP value of 17 or more and 28 or less , and more preferably 19 or more and 25 or less . When the SP value of the tertiary amine is within the above range, the storage stability of the aqueous dispersion of resin fine particles is improved.

  The SP value (solubility parameter (δ)) is one of the indexes serving as a measure of the affinity of two or more compounds, and is represented by the square root of the cohesive energy of molecules. The SP value is calculated from the structural formula of the compound using the Hansen solubility parameter (HSPiP 3rd edition, Ver. 3.1.14). In addition, the SP value of amine is calculated in the state of an amine that is not neutralized with an acid.

  Examples of the acid used in the present invention include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid; and organic acids such as acetic acid, lactic acid, glycolic acid, citric acid, succinic acid and maleic acid.

  In the emulsification step, a basic substance may be added as necessary. When an acid group-containing resin is atomized in an aqueous medium as it is, the pH becomes 3-4. For example, when the acid group-containing resin is a hydrolyzable resin such as a polyester resin, the hydrolysis of the resin is accelerated. Resulting in. Therefore, it is preferable to add a basic substance, particularly when using a hydrolyzable resin. Basic substances include inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; organic bases such as dimethylamine, diethylamine, and triethylamine. Can be mentioned. Among these, from the viewpoint of inhibiting hydrolysis under basic conditions, it is preferable to use weak bases such as dimethylamine and triethylamine. When using a basic substance, it is preferable to adjust the addition amount so that the pH in the aqueous medium is 6 to 11.

  An example of detailed procedures of the mixing step and the emulsification step in the first aspect of the present invention will be described. A resin having an acid group, a surfactant, an acid and a tertiary amine are put into an aqueous medium in which a basic substance is present, and then mixed. Next, it heats to temperature higher than the glass transition point (Tg) of resin which has this acid group, stirs a mixture, applying a shear force, and obtains an emulsion. Further, the obtained emulsion is cooled with stirring while applying a shearing force to a temperature not higher than the glass transition point of the resin to obtain an aqueous dispersion of resin fine particles.

In the emulsification step, when the melt viscosity of the resin having an acid group is greater than 10 ³ Pa · s, it may be difficult to obtain an emulsion having a target particle size. Therefore, in the emulsification step of the first aspect, the mixture is stirred while heating at a temperature equal to or higher than the softening point of the resin having an acid group in order to reduce the resin melt viscosity to 10 ³ Pa · s or less. The resin melt viscosity means the resin melt viscosity in water. The temperature in the emulsification step is preferably a high temperature, but a temperature at which the resin melt viscosity is 10 ³ Pa · s or less is sufficient. Conversely, if the temperature in the emulsification step is too high, the hydrolysis of the resin may be promoted, and therefore the temperature during emulsification is preferably 150 ° C. or lower.

  When the heating temperature is 100 ° C. or higher in the emulsification step, the emulsification step may be performed in a container that can be hermetically pressurized.

  In the method for producing an aqueous dispersion of resin fine particles of the present invention, after the emulsification step, the obtained emulsion is cooled to a temperature not higher than Tg of the resin having an acid group while applying a shearing force. Is preferred. The cooling rate in the cooling step is preferably from 0.5 ° C./min to 10.0 ° C./min, more preferably from 1.0 ° C./min to 10.0 ° C./min, It is particularly preferable that the temperature is from 0 ° C / min to 5.0 ° C / min. When the cooling rate is within the above range, generation of coarse particles and broadening of the particle size distribution of resin fine particles can be suppressed. In addition, when cooling the aqueous dispersion of resin fine particles from a temperature of Tg or less to room temperature, the cooling rate is not particularly limited.

  The resin fine particles contained in the aqueous dispersion of resin fine particles preferably have a volume distribution standard 50% particle size of 0.02 μm or more and 1.00 μm or less, and more preferably 0.02 μm or more and 0.40 μm or less. If the volume distribution reference 50% particle diameter of the resin fine particles is within the above range, the stability of the resin fine particles is good, and sedimentation separation hardly occurs. Further, when used for the production of toner by the aggregation method, it becomes easy to maintain the uniformity of the toner composition among the toner particles.

  In order to adjust the volume distribution standard 50% particle size of the resin fine particles to the above range, the amount of surfactant, the amount of basic substance, the amount of tertiary amine, the amount of acid, the heating temperature during the emulsification step, And it is good to adjust suitably the strength of the shearing force in an emulsification process or a cooling process.

  Next, a second aspect of the method for producing an aqueous dispersion of resin fine particles will be described.

  In the second embodiment, after the mixing step of mixing a resin having an acid group and a solvent in which the resin having an acid group is soluble to obtain a mixture, a shearing force is applied to stir the mixture to obtain a resin emulsion. An emulsification step is performed. In that case, an emulsification process is performed in presence of water, an acid, an anionic surfactant, and a tertiary amine.

  Regarding the resin having an acid group, the anionic surfactant, the basic substance, the acid, and the tertiary amine in the second embodiment, the same as those described in the first embodiment can be used.

  The resin-soluble solvent used in the second embodiment is a solvent capable of dissolving 10 parts by mass of an acid group-containing resin with respect to 100 parts by mass of the solvent in a range from room temperature to an emulsification temperature. means. The solvent may be water-soluble or water-insoluble, but a water-soluble solvent having a relatively low boiling point is preferable from the viewpoint of removing the solvent. Specific examples include ethyl acetate, butyl acetate, methyl ethyl ketone, tetrahydrofuran, dioxane, methanol, ethanol and isopropyl alcohol. These solvents can be used alone or in admixture of two or more.

  In the emulsification step in the second aspect, the same emulsification apparatus, basic substance, and water-soluble inorganic salt as in the first aspect can be used.

  An example of detailed procedures of the mixing step and the emulsification step in the second aspect will be described. A resin having an acid group, an anionic surfactant, a basic substance, and a solvent in which the resin is soluble are added, and stirring is performed until the resin is uniformly dissolved in the solvent. Next, while applying a shearing force, a mixture of an acid, water and a tertiary amine is added dropwise to phase inversion emulsify the resin. The temperature at which phase inversion emulsification is carried out is preferably below the boiling point of the solvent from the viewpoint of handling, and more preferably at room temperature. Thereafter, the solvent is removed by heating or decompression to obtain an aqueous dispersion of resin fine particles.

  In order to adjust the volume distribution reference 50% particle size of the resin fine particles to a desired range, the amount of surfactant, the amount of basic substance, the amount of tertiary amine, the amount of acid, the solvent in which the resin is soluble And the strength of the shearing force during the emulsification step may be appropriately adjusted.

  In the second embodiment, the anionic surfactant is not necessarily added from the mixing step, and may be added together with water, acid, and tertiary amine in the emulsification step, for example.

<Toner production method>
The aqueous dispersion of resin fine particles obtained in the present invention can be used for toner production such as an agglomeration method. When the toner is produced by a coagulation method, by mixing the colorant with an aqueous dispersion of the resin fine particles, aggregating step of forming an aggregate of the resin fine particles and colorant are aggregated in an aqueous medium, heating the aggregates and, through the fusion process Ru fused to obtain toner. Hereinafter, the toner production method will be described in detail, but the toner production method in the present invention is not limited to the following method.

  In the agglomeration step, the above-mentioned aqueous dispersion of resin fine particles, an aqueous dispersion of colorant fine particles, and, if necessary, a toner component such as a release agent are mixed to prepare a liquid mixture. The particles contained in the particles are aggregated to form aggregates. Examples of the method for forming the aggregate include a method in which a flocculant is added and mixed in the above-mentioned mixed solution, the temperature is adjusted, and mechanical power is appropriately applied.

  The colorant may be a pigment or a dye, but a pigment is preferably used from the viewpoint of light resistance and the like. In this case, the pigment is an organic or inorganic colored compound that is insoluble in water.

  The following are mentioned as an inorganic pigment. Oxide pigments such as cobalt blue, celsian blue, cobalt violet, cobalt green, zinc white, titanium white, light red, chrome oxide green, and mars black; hydroxide pigments such as viridan, yellow ocher, and alumina white; ultramarine Silicate pigments such as talc and white carbon; metal powders such as gold powder, silver powder and bronze powder; carbon black. The following are mentioned as an organic pigment. β-naphthol azo compounds, naphthol AS azo compounds, monoazo or disazo acetoacetate allylide azo compounds, pyrazone azo compounds, condensed azo pigments, phthalocyanine compounds, subphthalocyanine compounds, porphyrin compounds, quinacridone compounds , Isoindoline compounds, isoindolinone compounds, selenium compounds, perylene compounds, perinone compounds, thioindigo compounds, dioxazine compounds, quinophthalone compounds, diketopyrrolopyrrole compounds. The following are examples of commercially available color materials for black, cyan, magenta, and yellow.

  Raven1060, Raven1080, Raven1170, Raven1200, Raven1250, Raven1255, Raven1500, Raven2000, Raven3500, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000, Raven5000 , MOGUL-L, Regal 400R, Regal 660R, Regal 330R, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1300, Monarch 1400 (above, manufactured by Cabot Corporation); Color Black F 1, Color Black FW2, Color Black FW200, Color Black 18, Color Black S160, Color Black S170, Special Black 4P, Special Black 4A, Special Black 140P, BlackPr 140, Color Black S170, Color Black S170, Color Black S170, Special Black No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical Corporation).

  Examples of cyan color materials include C.I. I. Pigment Blue-1, C.I. I. Pigment Blue-2, C.I. I. Pigment Blue-3, C.I. I. Pigment Blue-15, C.I. I. Pigment Blue-15: 2, C.I. I. Pigment Blue-15: 3, C.I. I. Pigment Blue-15: 4, C.I. I. Pigment Blue-16, C.I. I. Pigment Blue-22, C.I. I. Pigment Blue-60 and the like.

  Examples of the magenta color material include C.I. I. Pigment Red-5, C.I. I. Pigment Red-7, C.I. I. Pigment Red-12, C.I. I. Pigment Red-48, C.I. I. Pigment Red-48: 1, C.I. I. Pigment Red-57, C.I. I. Pigment Red-112, C.I. I. Pigment Red-122, C.I. I. Pigment Red-123, C.I. I. Pigment Red-146, C.I. I. Pigment Red-168, C.I. I. Pigment Red-184, C.I. I. Pigment Red-202, C.I. I. Pigment Red-207 and the like.

  Examples of yellow color materials include C.I. I. Pigment Yellow-12, C.I. I. Pigment Yellow-13, C.I. I. Pigment Yellow-14, C.I. I. Pigment Yellow-16, C.I. I. Pigment Yellow-17, C.I. I. Pigment Yellow-74, C.I. I. Pigment Yellow-83, C.I. I. Pigment Yellow-93, C.I. I. Pigment Yellow-95, C.I. I. Pigment Yellow-97, C.I. I. Pigment Yellow-98, C.I. I. Pigment Yellow-114, C.I. I. Pigment Yellow-128, C.I. I. Pigment Yellow-129, C.I. I. Pigment Yellow-151, C.I. I. Pigment Yellow-154 and the like.

  Examples of the release agent include the following. Low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point); fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; ester waxes such as stearyl stearate; carnauba wax Plant waxes such as rice wax, candelilla wax, tree wax and jojoba oil; animal waxes such as beeswax; minerals such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax and ester wax Petroleum wax; and modified products thereof.

  A charge control agent may be added to the toner as necessary. As the charge control agent, a chrome azo dye, an iron azo dye, an aluminum azo dye, a salicylic acid metal complex, a polymer charge control agent, or the like can be used.

  Examples of the flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum. When adding and mixing the flocculant, the temperature is preferably equal to or lower than the glass transition point (Tg) of the resin particles (resin having an acid group) contained in the mixed solution. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The said mixing can be performed using a well-known mixing apparatus, a homogenizer, a mixer, etc.

  The average particle size of the aggregate formed here is not particularly limited, but it is usually preferable to control the average particle size to be approximately the same as the average particle size of the toner particles to be obtained. The average particle size of the aggregate can be easily controlled by, for example, appropriately setting / changing the temperature at the time of addition / mixing of the flocculant or the like and the conditions of the stirring / mixing.

The fusing step, the aggregate, by heating the glass transition point (Tg) or more of the first resin, obtained in Rukoto fused, toner particles aggregate surface was smoothed (core particles) process is there. By this step, the surface area of the agglomerates is reduced, and toner particles having a good shape can be obtained. In addition, when shell particles are attached in the attaching step described later, the shell particles are efficiently attached to the core particles. Before entering the primary fusing step, a chelating agent, a pH adjusting agent, a surfactant and the like can be appropriately added in order to prevent fusion between toner particles.

  Examples of chelating agents include alkali metal salts such as ethylenediaminetetraacetic acid and its Na salt, sodium gluconate, sodium tartrate, potassium citrate, sodium citrate, nitrotriacetate salts, many containing both functionality of COOH and OH. And water-soluble polymers (polyelectrolytes).

  The heating temperature in the fusion step may be between the glass transition point (Tg) of the resin having an acid group contained in the aggregate and the temperature at which the resin is thermally decomposed. As the heating / fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the heating / fusion time depends on the temperature of heating and cannot be defined unconditionally, but is generally 10 minutes to 10 hours. Note that the toner cooling step described below may be performed as necessary after the fusing step.

  The toner cooling step is a step of cooling the temperature of the aqueous medium containing the toner particles to a temperature lower than the glass transition point (Tg) of the resin having an acid group. If the aqueous medium is not cooled to a temperature lower than Tg, coarse particles are generated when the flocculant is added when the adhesion step described later is performed. A specific cooling rate is 0.1 to 50 ° C./min. In addition, as a core particle, what was obtained through the aggregation process and fusion process mentioned above is preferable, However, You may use the core particle obtained by the other manufacturing method.

  Next, the attaching process for attaching the shell particles to the core particles will be described in detail. The adhesion step refers to an aqueous dispersion of the second resin fine particles having the second resin and the core at a temperature lower than the glass transition point (Tg) of the resin having the acid group (first resin) contained in the core particles. In this step, the particles and the aggregating agent are mixed to attach the second resin fine particles in the aqueous dispersion to the surface of the core particles. The adhering step is preferably performed after the toner cooling step.

  Examples of the flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum. The flocculant may be mixed simultaneously with the aqueous dispersion of the second resin fine particles, or may be mixed before and after that. In addition, you may perform the following secondary fusion process, washing | cleaning, and a secondary cooling process as needed after an adhesion process.

The secondary fusing step, the resulting shell adhering member by adhesion process, by heating the glass transition point (Tg) or more of the resin (first resin) having an acid group, in Rukoto fusing, the particle surface This is a smoothing process. The core resin and the shell resin are sufficiently fixed by the secondary fusion process, and the shell is prevented from being detached from the core particles by operations such as washing and filtration described later. Before entering the secondary fusion step, a chelating agent, a pH adjuster, a surfactant, and the like can be appropriately added in order to prevent fusion between toner particles.

  The heating temperature in the secondary fusion step may be between the glass transition point (Tg) of the resin having an acid group contained in the aggregate and the temperature at which the resin is thermally decomposed. As the heating / fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the heating / fusion time depends on the temperature of heating and cannot be defined unconditionally, but is generally 10 minutes to 10 hours.

  After the secondary coalescence step, the obtained particles are cooled to room temperature under appropriate conditions, and washed, filtered, dried, etc. to obtain toner particles. Further, inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester resin and silicone resin may be added to the surface of the obtained toner particles. These inorganic particles and resin particles function as external additives such as fluidity aids and cleaning aids.

  The weight average particle diameter (D4) of the toner is preferably 4.5 to 7.0 μm, and more preferably 5.0 to 6.5 μm.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to these.

<Measurement of Molecular Weight Distribution, Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn), etc. Measured by Gel Permeation Chromatography (GPC) of Resin Tetrahydrofuran (THF)>
The molecular weight distribution, weight average molecular weight (Mw), number average molecular weight (Mn) and the like measured by GPC of the THF soluble content of the resin fine particles are determined as follows.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and about 100 μl of THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko is preferably used. is there. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. Examples include combinations of TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and TSKguardcolumn.

The sample is prepared as follows.
Place the resin (sample) in tetrahydrofuran (THF), leave it for several hours, shake well, mix well with THF until the sample is no longer united, and let stand for more than 12 hours. At this time, the standing time in THF is set to be 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5: manufactured by Tosoh Corporation, Excro Disc 25CR: manufactured by Gelman Science Japan Co., Ltd., etc. can be used) is passed. This is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

<Measurement of acid value of resin>
The acid value of the resin is determined as follows. The basic operation conforms to JIS-K0070. The acid value indicates the number of mg of potassium hydroxide required to neutralize the acid group contained in 1 g of the sample.
(1) Reagent (a) Solvent: N / 10 potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use of ethyl ether-ethyl alcohol mixture (1 + 1 or 2 + 1) or benzene-ethyl alcohol mixture (1 + 1 or 2 + 1) Neutralize with.
(B) Phenolphthalein solution: 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
(C) N / 10 potassium hydroxide-ethyl alcohol solution: Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 v / v%) to 1 liter, leave it for 2 to 3 days, and filter. . The standardization is performed according to JIS K 8006 (basic matters concerning titration during the reagent content test).

(2) Operation Weigh 1-20 g of resin (sample) correctly, add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this was titrated with a 0.1 mol / L potassium hydroxide ethyl alcohol solution, and the end point of neutralization was reached when the indicator was slightly red for 30 seconds.

(3) Calculation formula The acid value is calculated by the following formula.

A = B × f × 5.661 / S
A: Acid value B: Amount used of 0.1 mol / L potassium hydroxide ethyl alcohol solution (ml)
f: Factor of 0.1 mol / L potassium hydroxide ethyl alcohol solution S: Sample (g)

<Particle size distribution analysis of resin fine particles and colorant fine particles>
For the analysis of the particle size distribution, a dynamic light scattering type particle size distribution measuring device (Nanotrack UPA150: manufactured by Nikkiso Co., Ltd.) is used, and the particle size distribution is measured according to the operation manual of the device. As a specific measurement method, a surfactant aqueous solution is dropped into ion-exchanged water, and then the resin fine particle or colorant fine particle dispersion is adjusted to the optimum concentration of the device, and the dispersion treatment is performed for 30 seconds with an ultrasonic disperser. The obtained dispersion treatment liquid is measured, and the 50% particle size and coefficient of variation based on the volume distribution are obtained.

<Toner particle size distribution analysis>
The particle size distribution of the toner is measured by particle size distribution analysis by the Coulter method. As a measuring device, Multisizer IV (manufactured by Coulter, Inc.) is used, and measurement is performed according to the operation manual of the device. About 1% sodium chloride aqueous solution is prepared using 1st grade sodium chloride as electrolyte solution. As the electrolytic solution, for example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. Specifically, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant in 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample (toner) is further added. Add. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. The obtained dispersion treatment liquid is subjected to measurement of the volume and number of toners of 2.00 μm or more by means of the measurement apparatus equipped with a 100 μm aperture as an aperture, and the volume distribution and number distribution of the toner are calculated. From the calculation result, the weight average particle diameter (D4) of the toner is obtained.

<Measurement of glass transition point (Tg) of resin>
The glass transition point (Tg) of the resin is measured using a differential scanning calorimeter (DSC) measuring device (DSC822: manufactured by METTLER TOLEDO). In the DSC measurement, measurement is performed with a differential scanning calorimeter of high accuracy internal heat input compensation type from the measurement principle. The measurement method is performed according to ASTM D3418-82. Specifically, Tg is calculated from the DSC curve measured when the temperature is raised and lowered once, the previous history is taken, and the temperature is raised at 10 ° C./min. The central value of the intersection point between the baseline before and after the endotherm and the tangent to the endothermic curve is defined as Tg (° C.).

<Measurement of softening temperature (Tm) of resin>
The softening temperature (Tm) of the resin is measured using a flow tester (CFT-500D: manufactured by Shimadzu Corporation). Weigh 1.5 g of the sample (resin) to be measured, use a die with a height of 1.0 mm and a diameter of 1.0 mm, a heating rate of 4.0 ° C./min, a preheating time of 300 seconds, a load of 5 kg, and a measurement temperature. The measurement is performed in the range of 60.0 to 200.0 ° C. An intermediate value between the melting start temperature and the melting end temperature is defined as a softening temperature (Tm).

<Production of aqueous dispersion of resin fine particles>
[Resin production example 1]
Three-neck flask containing 50 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 28 parts by mass of terephthalic acid, 20 parts by mass of isophthalic acid, and 0.03 parts by mass of dibutyltin oxide After stirring at 230 ° C. for 24 hours under a nitrogen stream, 2 parts by weight of trimellitic acid was added, and stirring was performed at 200 ° C. for 1 hour. Thereafter, the polyester resin 1 having an Mw of 20,500, an Mn of 7,200, a Tg of 71 ° C., and an acid value of 9 mgKOH / g was obtained by stirring for 4 hours under reduced pressure conditions of 3 mmHg while maintaining the temperature. .

[Resin production example 2]
Three-neck flask containing 50 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 28 parts by mass of terephthalic acid, 20 parts by mass of isophthalic acid, and 0.03 parts by mass of dibutyltin oxide After stirring at 230 ° C. for 24 hours under a nitrogen stream, 1 part by weight of trimellitic acid was added and stirring was performed at 200 ° C. for 1 hour. Then, the polyester resin 2 having Mw of 21,500, Mn of 7,400, Tg of 73 ° C., and acid value of 2 mgKOH / g was obtained by stirring for 4 hours while reducing the pressure at 1 mmHg.

[Resin Production Example 3]
Three-neck flask containing 50 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 28 parts by mass of terephthalic acid, 20 parts by mass of fumaric acid, and 0.03 parts by mass of dibutyltin oxide After stirring at 230 ° C. for 24 hours under a nitrogen stream, 3 parts by weight of trimellitic acid was added and stirred at 200 ° C. for 30 minutes. Then, the polyester resin 3 with Mw of 22,500, Mn of 7,200, Tg of 65 ° C., and acid value of 13 mgKOH / g was obtained by stirring for 2 hours under a reduced pressure of 5 mmHg while maintaining the temperature.

[Example 1]
-Polyester resin 1 430 parts by mass-Aqueous medium (ion-exchanged water) 490.6 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 86.0 parts by mass-Basic substance for resin neutralization ( 2-Diethylaminoethanol) 12.13 parts by weight Material for producing amino cation
-Tertiary amine (2- (dimethylamino) ethanol, SP value: 23.2) 13.37 parts by mass-Acid (1 mol / L hydrochloric acid) 150 parts by mass in a 1500 ml pressure-resistant round bottom stainless steel container and mixed did. The amino cation concentration in the aqueous phase was 0.234 mol / L.

  Next, a high-speed shearing emulsifier CLEARMIX (M Technique Co., Ltd .: CLM-2.2S) was hermetically connected to the pressure-resistant round bottom stainless steel container. While the mixture in the sealed container was heated to 140 ° C., the Claremix rotor was rotated at a rotational speed of 20,000 r / min for 10 minutes and subjected to shear dispersion. Thereafter, cooling is performed at a cooling rate of 1.0 ° C./min while maintaining rotation of 20,000 r / min until 50 ° C., and the 50% particle size based on the volume distribution of the resin fine particles is 0.20 μm, An aqueous dispersion 1 of resin fine particles having a variation coefficient of 28% was obtained. When the critical aggregation concentration under the above emulsification conditions was separately measured, the critical aggregation concentration was 0.73 mol / L.

  The resin fine particle aqueous dispersion 1 was allowed to stand for one month, and then the particle size of the resin fine particle was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particle was 0.20 μm. The state was kept.

[Comparative Example 1]
An aqueous dispersion 2 of resin fine particles was obtained in the same manner as in Example 1 except that the tertiary amine and acid for generating the amino cation were not added and ion-exchanged water corresponding to the mass was added. The obtained resin fine particles had a volume distribution standard 50% particle size of 0.35 μm and a coefficient of variation of 110%, which was larger than that of Example 1 and a broad particle size distribution.

  In addition, after the aqueous dispersion 2 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.46 μm. Also increased in particle size.

[Example 2]
In order to adjust the amino cation concentration in the aqueous phase to 0.077 mol / L, 4.46 parts by mass of 2- (dimethylamino) ethanol as a tertiary amine and 50 parts by mass of 1 mol / L hydrochloric acid as an acid were used. Except for adding ion-exchanged water with a difference in total mass, the same procedure as in Example 1 was performed, and the resin fine particles having a 50% particle size of 0.30 μm based on the volume distribution standard of the resin fine particles and a coefficient of variation of 75% An aqueous dispersion 3 was obtained.

  The resin fine particle aqueous dispersion 3 was allowed to stand for one month, and then the particle size of the resin fine particle was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particle was 0.32 μm. The state was kept.

Example 3
In order to correspond to an amino cation concentration in the aqueous phase of 0.155 mol / L, 8.91 parts by mass of 2- (dimethylamino) ethanol as a tertiary amine and 100 parts by mass of 1 mol / L hydrochloric acid as an acid were used. Resin fine particles having a 50% particle diameter of 0.22 μm and a coefficient of variation of 34% based on the volume distribution of the resin fine particles, except that ion exchange water having a difference in total mass is added. An aqueous dispersion 4 was obtained.

  The aqueous dispersion 4 of resin fine particles was allowed to stand for one month, and then the particle size of the resin fine particles was measured again. As a result, the 50% particle size of the resin fine particles based on the volume distribution was 0.24 μm, and the good dispersion was obtained. The state was kept.

Example 4
In order to adjust the amino cation concentration in the aqueous phase to 0.314 mol / L, 17.83 parts by mass of 2- (dimethylamino) ethanol as a tertiary amine and 200 parts by mass of 1 mol / L hydrochloric acid as an acid were used. Except that the ion exchange water of the total mass difference was reduced, the conditions were the same as in Example 1, and the resin fine particles having a 50% particle size of 0.23 μm based on the volume distribution standard of resin fine particles and a coefficient of variation of 32% were used. An aqueous dispersion 5 was obtained.

  The resin fine particle aqueous dispersion 5 was allowed to stand for one month, and then the particle size of the resin fine particle was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particle was 0.25 μm, indicating good dispersion. The state was kept.

Example 5
In order to adjust the amino cation concentration in the aqueous phase to 0.647 mol / L, 35.66 parts by mass of 2- (dimethylamino) ethanol as a tertiary amine and 400 parts by mass of 1 mol / L hydrochloric acid as an acid were used. Except that the ion exchange water of the difference in total mass was reduced, it was performed under the same conditions as in Example 1, and the resin fine particles having a volume distribution standard 50% particle size of 0.33 μm and a coefficient of variation of 102% were used. An aqueous dispersion 6 was obtained.

  Incidentally, after the aqueous dispersion 6 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.41 μm. The particle size was slightly larger.

[Comparative Example 2]
In order to adjust the amino cation concentration in the aqueous phase to 0.785 mol / L, 42.79 parts by mass of 2- (dimethylamino) ethanol as a tertiary amine and 480 parts by mass of 1 mol / L hydrochloric acid as an acid were used. Except that the ion exchange water of the difference in total mass was reduced, it was performed under the same conditions as in Example 1, and the resin fine particles having a 50% particle size of 0.47 μm based on the volume distribution standard of the resin fine particles and a coefficient of variation of 122%. An aqueous dispersion 7 was obtained. It is considered that this is because aggregation occurs during emulsification, the particle size is larger than that of Comparative Example 1, and the particle size distribution is widened.

  Incidentally, after the aqueous dispersion 7 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.55 μm. Also increased in particle size.

[Comparative Example 3]
An aqueous dispersion 8 of resin fine particles was obtained in the same manner as in Example 1 except that the acid for generating the amino cation was not added and ion-exchanged water corresponding to the mass was added. The obtained resin fine particles had a 50% particle size of 0.40 μm based on volume distribution and a coefficient of variation of 136%, which were larger than those of Example 1 and Comparative Example 1, and the particle size distribution was broad.

  In addition, after the aqueous dispersion 8 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.56 μm. Also increased in particle size.

Example 6
Except that 17.58 parts by mass of 2-diethylaminoethanol (SP value = 20.6) was used as the tertiary amine and the total mass was adjusted by the amount of ion-exchanged water, the same procedure as in Example 1 was carried out. An aqueous dispersion 9 of resin fine particles having a 50% particle size on the distribution basis of 0.21 μm and a coefficient of variation of 32% was obtained. The amino cation concentration in the aqueous phase was 0.236 mol / L.

  After the aqueous dispersion 9 of the resin fine particles was allowed to stand for 1 month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particles was 0.23 μm. The state was kept.

Example 7
Using 2- (dibutylamino) ethanol (SP value = 19.3) as a tertiary amine, 26.00 parts by mass, and adjusting the total mass with the amount of ion-exchanged water, it was carried out under the same conditions as in Example 1, An aqueous dispersion 10 of resin fine particles having a 50% particle size of 0.23 μm and a coefficient of variation of 31% based on the volume distribution of resin fine particles was obtained. The amino cation concentration in the aqueous phase was 0.239 mol / L.

  The resin fine particle aqueous dispersion 10 was allowed to stand for one month, and then the particle size of the resin fine particle was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particle was 0.24 μm. The state was kept.

Example 8
Using N-ethyldiethanolamine (SP value = 24.6) as a tertiary amine, 19.98 parts by mass, and adjusting the total mass with the amount of ion-exchanged water, the same procedure as in Example 1 was performed. An aqueous dispersion 11 of resin fine particles having a 50% particle size of 0.22 μm based on volume distribution and a variation coefficient of 33% was obtained. The amino cation concentration in the aqueous phase was 0.237 mol / L.

  The resin fine particle aqueous dispersion 11 was allowed to stand for one month, and then the particle size of the resin fine particle was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particle was 0.22 μm, indicating good dispersion. The state was kept.

Example 9
The volume of the resin fine particles is the same as in Example 1 except that triethanolamine (SP value = 28.2) and 22.38 parts by mass are used as the tertiary amine and the total mass is adjusted by the amount of ion-exchanged water. An aqueous dispersion 12 of resin fine particles having a distribution basis 50% particle size of 0.22 μm and a coefficient of variation of 35% was obtained. The amino cation concentration in the aqueous phase was 0.237 mol / L.

  In addition, after the aqueous dispersion 12 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 1.21 μm. Also increased in particle size.

Example 10
The same procedure as in Example 1 was carried out except that triethylamine (SP value = 15.5) and 15.18 parts by mass were used as the tertiary amine, and the total mass was adjusted with the amount of ion-exchanged water. An aqueous dispersion 13 of resin fine particles having a 50% particle size of 0.24 μm and a coefficient of variation of 42% was obtained. The amino cation concentration in the aqueous phase was 0.235 mol / L.

  In addition, after the aqueous dispersion 13 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 1.17 μm. Also increased in particle size.

Example 11
Except that tripropylamine (SP value = 16.4) and 21.49 parts by mass were used as the tertiary amine and the total mass was adjusted by the amount of ion-exchanged water, the same procedure as in Example 1 was carried out. An aqueous dispersion 14 of resin fine particles having a 50% particle size on the basis of distribution of 0.21 μm and a coefficient of variation of 38% was obtained. The amino cation concentration in the aqueous phase was 0.237 mol / L.

  After the aqueous dispersion 14 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 1.16 μm. Also increased in particle size.

Example 12
The volume of the resin fine particles is the same as in Example 1 except that triamylamine (SP value = 15.9) and 34.11 parts by mass are used as the tertiary amine and the total mass is adjusted by the amount of ion-exchanged water. An aqueous dispersion 15 of resin fine particles having a distribution standard 50% particle size of 0.25 μm and a coefficient of variation of 40% was obtained. The amino cation concentration in the aqueous phase was 0.242 mol / L.

  In addition, after the aqueous dispersion 15 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 1.13 μm. Also increased in particle size.

Example 13
The volume of the resin fine particles is the same as in Example 1 except that trihexylamine (SP value = 16.1) and 40.43 parts by mass are used as the tertiary amine and the total mass is adjusted by the amount of ion-exchanged water. An aqueous dispersion 16 of resin fine particles having a distribution standard 50% particle size of 0.26 μm and a coefficient of variation of 70% was obtained. The amino cation concentration in the aqueous phase was 0.244 mol / L.

  Incidentally, after the aqueous dispersion 16 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 1.29 μm. Also increased in particle size.

Example 14
Resin was used under the same conditions as in Example 1 except that tri-n-octylamine (SP value = 16.3), 53.05 parts by mass was used as the tertiary amine, and the total mass was adjusted with the amount of ion-exchanged water. An aqueous dispersion 17 of resin fine particles having a 50% particle size of 0.28 μm and a coefficient of variation of 88% based on the volume distribution of the fine particles was obtained. The amino cation concentration in the aqueous phase was 0.250 mol / L.

  In addition, after the aqueous dispersion 17 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 1.27 μm. Also increased in particle size.

[Comparative Example 4]
The same procedure as in Example 1 was conducted except that 78.30 parts by mass of tridodecylamine was used as the tertiary amine and the total mass was adjusted by the amount of ion-exchanged water. An aqueous dispersion 18 of resin fine particles having 0.39 μm and a coefficient of variation of 115%, which is larger than that of Example 1 and has a broad particle size distribution, was obtained. The amino cation concentration in the aqueous phase was 0.261 mol / L.

Example 15
-Polyester resin 2 430 parts by mass-Aqueous medium (ion exchange water) 554.5 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 86.0 parts by mass-Basic substance for resin neutralization ( 2-diethylaminoethanol) 2.69 parts by mass Material for generating an amino cation Tertiary amine (2- (dimethylamino) ethanol, SP value = 23.2) 8.91 parts by mass Acid (1 mol / L) Hydrochloric acid) 100 parts by mass was placed in a 1,500 ml pressure-resistant round bottom stainless steel container and mixed. The amino cation concentration in the aqueous phase was 0.153 mol / L.

  Next, a high-speed shearing emulsifier CLEARMIX (M Technique Co., Ltd .: CLM-2.2S) was hermetically connected to the pressure-resistant round bottom stainless steel container. While the mixture in the sealed container was heated to 140 ° C., the Claremix rotor was rotated at a rotational speed of 20,000 r / min for 10 minutes and subjected to shear dispersion. Thereafter, cooling is performed at a cooling rate of 1.0 ° C./min while maintaining rotation at 20,000 r / min until 50 ° C., and the 50% particle size based on the volume distribution of the resin fine particles is 0.24 μm, An aqueous dispersion 19 of resin fine particles having a variation coefficient of 48% was obtained. When the critical aggregation concentration under the above emulsification conditions was separately measured, the critical aggregation concentration was 0.42 mol / L.

  The resin fine particle aqueous dispersion 19 was allowed to stand for one month, and then the particle size of the resin fine particle was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particle was 0.23 μm. The state was kept.

[Comparative Example 5]
Emulsification was carried out in the same manner as in Example 15 except that the tertiary amine and acid were not added, and the total mass was adjusted with the amount of ion-exchanged water, to obtain an aqueous dispersion 20 of resin fine particles. The resin fine particles obtained had a 50% particle diameter of 1.32 μm and a coefficient of variation of 125% based on the volume distribution.

  In addition, after the aqueous dispersion 20 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 1.42 μm. Also increased in particle size.

Example 16
The same as Example 15 except that 17.83 parts by mass of tertiary amine (2- (dimethylamino) ethanol) and 200 parts by mass of acid (1 mol / L hydrochloric acid) were used and the total mass was adjusted with the amount of ion-exchanged water. Thus, an aqueous dispersion 21 of resin fine particles having a 50% particle size of 0.36 μm and a coefficient of variation of 72% based on the volume distribution of the resin fine particles was obtained. The amino cation concentration in the aqueous phase was 0.310 mol / L.

  The resin fine particle aqueous dispersion 21 was allowed to stand for one month, and then the particle size of the resin fine particle was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particle was 0.37 μm. The state was kept.

[Comparative Example 6]
The same as Example 15 except that 26.74 parts by mass of tertiary amine (2- (dimethylamino) ethanol) and 300 parts by mass of acid (1 mol / L hydrochloric acid) were used and the total mass was adjusted with the amount of ion-exchanged water. Thus, an aqueous dispersion 22 of resin fine particles having a 50% particle diameter of 1.45 μm and a coefficient of variation of 144% based on the volume distribution of the resin fine particles was obtained. This is considered that aggregation occurred during emulsification, the particle size was larger than that of Comparative Example 5, and the particle size distribution was widened. The amino cation concentration in the aqueous phase was 0.471 mol / L.

  In addition, after the aqueous dispersion 22 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 1.88 μm. Also increased in particle size.

Example 17
-Polyester resin 3 430 parts by mass-Aqueous medium (ion exchange water) 430.8 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 86.0 parts by mass-Basic substance for resin neutralization ( 10% ammonia water) 20.0 parts by mass Material for producing amino cation, tertiary amine (2- (dimethylamino) ethanol SP value = 23.2) 17.83 parts by mass, acid (1 mol / L hydrochloric acid) ) 200 parts by mass was placed in a 1,500 ml pressure-resistant round bottom stainless steel container and mixed. The amino cation concentration in the aqueous phase was 0.318 mol / L.

  Next, a high-speed shearing emulsifier CLEARMIX (M Technique Co., Ltd .: CLM-2.2S) was hermetically connected to the pressure-resistant round bottom stainless steel container. While the mixture in the sealed container was heated to 140 ° C., the Claremix rotor was rotated at a rotational speed of 20,000 r / min for 10 minutes and subjected to shear dispersion. Thereafter, cooling is performed at a cooling rate of 1.0 ° C./min while maintaining a rotation of 20,000 r / min until 50 ° C., and the 50% particle size based on the volume distribution of the resin fine particles is 0.04 μm, An aqueous dispersion 23 of resin fine particles having a variation coefficient of 32% was obtained. When the critical aggregation concentration under the above emulsification conditions was separately measured, the critical aggregation concentration was 0.87 mol / L.

  After the aqueous dispersion 23 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particles was 0.04 μm, indicating good dispersion The state was kept.

[Comparative Example 7]
Emulsification was carried out in the same manner as in Example 17 except that the tertiary amine and acid were not added, and the total mass was adjusted with the amount of ion-exchanged water, to obtain an aqueous dispersion 24 of resin fine particles. The obtained resin fine particles had a 50% particle size of 0.06 μm based on volume distribution and a coefficient of variation of 66%, which was larger than Example 17 and broad in particle size distribution.

  In addition, after the aqueous dispersion 24 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.08 μm. Also increased in particle size.

Example 18
The same as Example 17 except that 44.57 parts by mass of tertiary amine (2- (dimethylamino) ethanol) and 500 parts by mass of acid (1 mol / L hydrochloric acid) were used and the total mass was adjusted with the amount of ion-exchanged water. Thus, an aqueous dispersion 25 of resin fine particles having a 50% particle size of 0.05 μm based on the volume distribution of the resin fine particles and a coefficient of variation of 45% was obtained. The amino cation concentration in the aqueous phase was 0.831 mol / L.

  Incidentally, after the aqueous dispersion 25 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particles was 0.05 μm. The state was kept.

[Comparative Example 8]
The same as Example 17 except that 49.03 parts by mass of tertiary amine (2- (dimethylamino) ethanol) and 550 parts by mass of acid (1 mol / L hydrochloric acid) were used and the total mass was adjusted with the amount of ion-exchanged water. Thus, an aqueous dispersion 26 of resin fine particles having a 50% particle size based on the volume distribution of resin fine particles of 0.33 μm and a coefficient of variation of 102% was obtained. This is considered that aggregation occurred during emulsification, the particle size was larger than that of Comparative Example 7, and the particle size distribution was widened. The amino cation concentration in the aqueous phase was 0.921 mol / L.

  Incidentally, after the aqueous dispersion 26 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.41 μm. Also increased in particle size.

Example 19
100 parts by weight of polyester resin 1, 2.0 parts by weight of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK), 1.20 parts by weight of basic substance for resin neutralization (sodium hydroxide), The mixture was put into a 500 ml beaker, and mixed at 95 ° C. for 120 minutes with a chi-type stirrer while stirring at 200 r / min.

  Thereafter, while maintaining the temperature, 3.12 parts by mass of tertiary amine (2- (dimethylamino) ethanol) and 35 parts by mass of acid (1 mol / L hydrochloric acid) were stirred with a chi-type stirrer at 200 r / min. An aqueous solution heated to 95 ° C. dissolved in 200 parts by mass of ion-exchanged water is dropped over 2 hours, and aqueous dispersion of resin fine particles having a 50% particle size of 0.27 μm and a coefficient of variation of 50% based on volume distribution. A body 27 was obtained. The amino cation concentration in the aqueous phase was 0.149 mol / L. Moreover, when the critical aggregation concentration in the said emulsification conditions was measured separately, the critical aggregation concentration was 0.71 mol / L.

  The resin fine particle aqueous dispersion 27 was allowed to stand for one month, and then the particle size of the resin fine particle was measured again. As a result, the 50% particle size on the basis of the volume distribution of the resin fine particle was 0.27 μm. The state was kept.

[Comparative Example 9]
Emulsification was carried out in the same manner as in Example 19 except that the tertiary amine and acid were not added, to obtain an aqueous dispersion 28 of resin fine particles. The obtained resin fine particles had a 50% particle size based on volume distribution of 0.48 μm and a coefficient of variation of 152%, which was larger than that of Example 19, and the particle size distribution was broad.

  In addition, after the aqueous dispersion 28 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.59 μm. Also increased in particle size.

Example 20
60 parts by mass of polyester resin 1, 7.2 parts by mass of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK), 1.12 parts by mass of basic substance for resin neutralization (10% ammonia water), methyl ethyl ketone 150 parts by mass and 50 parts by mass of isopropyl alcohol are mixed and dissolved. K. The mixture was stirred at 4,000 r / min using Robomix (manufactured by Primics).

  Further, 2.46 parts by mass of tertiary amine (2- (dimethylamino) ethanol) and 21 parts by mass of acid (1 mol / L hydrochloric acid) (corresponding to 0.035 mol as an amino cation with respect to 100 parts by mass of the polyester resin). An aqueous solution in which the addition amount was dissolved in 177.8 parts by mass of ion-exchanged water was dropped, and then the tetrahydrofuran was removed using an evaporator. Then, an aqueous dispersion 29 of resin fine particles having a 50% particle size based on the volume distribution of resin fine particles of 0.21 μm and a variation coefficient of 26% was obtained. The amino cation concentration in the aqueous phase was 0.106 mol / L. Moreover, when the critical aggregation density | concentration in the said emulsification conditions was measured separately, the critical aggregation density | concentration was 0.72 mol / L.

  After the aqueous dispersion 29 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.21 μm, indicating good dispersion. The state was kept.

[Comparative Example 10]
Emulsification was carried out in the same manner as in Example 20 except that the tertiary amine and acid were not added, to obtain an aqueous dispersion 30 of resin fine particles. The obtained resin fine particles had a volume distribution standard 50% particle size of 0.31 μm and a coefficient of variation of 111%, which was larger than Example 20 and a broad particle size distribution.

  In addition, after the aqueous dispersion 30 of the resin fine particles was allowed to stand for one month, the particle size of the resin fine particles was measured again. As a result, the 50% particle size based on the volume distribution of the resin fine particles was 0.34 μm. Also increased in particle size.

  Tables 1 and 2 show the materials used in Examples 1 to 20 and Comparative Examples 1 to 10, physical properties of the obtained resin fine particles, and the like. In Tables 1 and 2, “amino cation amount” represents the amount (mol) of amino cation with respect to 100 parts by mass of the polyester resin. From the results of Examples 1-20 and Comparative Examples 1-10, by adding an amino cation, the resin fine particles of the aqueous dispersion can be made small, and the particle size of the resin fine particles can be controlled in a nearly uniform state. Indicated.

<Manufacture of agglomerated toner>
Example 21
(Preparation of release agent aqueous dispersion)
・ Ester wax (behenyl behenate, melting point: 75 ° C.) 100 parts by mass ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 10 parts by mass ・ Ion-exchanged water 890 parts by mass After charging, while heating to 90 ° C. and circulating with a metering pump, using CLEARMIX W-Motion (M Technique Co., Ltd.), rotor rotation speed 19,000r / min, screen rotation speed 19,000r / The mixture was stirred for 60 minutes and dispersed for 60 minutes. After the dispersion treatment for 60 minutes, the release agent aqueous dispersion is subsequently cooled to 40 ° C. under conditions of a rotor rotation speed of 1,000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 ° C./min. Obtained. When this sample was measured using a dynamic light scattering type particle size distribution analyzer (Nanotrack UPA150: manufactured by Nikkiso Co., Ltd.), the 50% particle size based on volume distribution was 0.15 μm, and the coarseness was 0.8 μm or more. Particles were 0.01 volume% or less.

(Preparation of colorant aqueous dispersion)
-Cyan pigment (CI Pigment Blue 15: 3) 100 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 10 parts by mass-Ion-exchanged water 890 parts by mass The above materials are mixed and a homogenizer (IKA: Ultra Turrax T50) was used for dispersion for 30 minutes at a rotation speed of 24,000 r / min. Thereafter, using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), dispersion was performed under a pressure condition of 200 MPa to prepare a colorant aqueous dispersion in which a cyan pigment was dispersed. The 50% particle size based on the volume distribution of the colorant (cyan pigment) in the colorant aqueous dispersion was 0.12 μm, and the colorant concentration was 10% by mass.

(Aggregation process)
-Resin fine particle aqueous dispersion 23 50 parts-Colorant aqueous dispersion 10 parts by weight-Release agent aqueous dispersion 20 parts by weight-1% by weight magnesium sulfate aqueous solution 20 parts by weight-Ion-exchanged water 100 parts by weight The components were put into a round stainless steel flask, and mixed and dispersed at 5,000 r / min for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50). Then, it heated to 48 degreeC, adjusting suitably the rotation speed so that a liquid mixture might be stirred using the stirring blade in the water bath for heating. After maintaining at 48 ° C. for 1 hour, the volume average particle diameter of the formed aggregated particles was measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. As a result, it was confirmed that aggregated particles having a volume average particle diameter of about 5.1 μm were formed.

<Fusion process>
Thereafter, an aqueous solution in which 2 parts by mass of trisodium citrate was dissolved was added to 38 parts by mass of ion-exchanged water, and then the mixture was heated to 75 ° C. and kept for 2 hours while continuing stirring. The volume average particle diameter and average circularity of the obtained particles were measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. As a result, it was confirmed that sufficiently fused and united particles having a volume average particle diameter of about 5.4 μm and an average circularity of 0.963 were formed.
<Filtering, washing, drying process>
Then, the obtained liquid was cooled and filtered. The filter cake was sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles 1.

(Production of toner)
To 100 parts by mass of the toner particles, 1.8 parts by mass of hydrophobized silica fine powder having a specific surface area measured by the BET method of 200 m ² / g is dry-mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the toner is mixed. It was. Then, the fixing property was evaluated by the following method.

An unfixed toner image (0.6 mg / cm ² ) was formed on plain paper (64 g / m ² ) using a commercially available full color digital copying machine (CLC1100, manufactured by Canon Inc.). Next, a fixing unit removed from a commercially available color laser printer (LBP-5500, manufactured by Canon Inc.) was modified so that the fixing temperature could be adjusted, and a fixing test for an unfixed image was performed using this. At that time, the fixing test was performed under normal temperature and humidity, and the process speed was set to 100 mm / second. Further, the fixing temperature was increased by 10 ° C., and an unfixed image was fixed at each fixing temperature. When the presence or absence of an offset in the fixed image when the unfixed image was fixed was visually confirmed, the fixing temperature range in which no offset occurred was 105 to 145 ° C.

[Comparative Example 11]
Toner particles 2 were obtained in the same manner as in Example 21 except that the aqueous dispersion 23 of resin fine particles was changed to the aqueous dispersion 24. The filtrate in the filtration step became a cloudy liquid due to the release of the release agent dispersion. When the release agent component in the white turbid liquid was analyzed, 35% of the release agent used for the toner particle production flowed out. When a fixing test of the toner particles was performed in the same procedure as in Example 21, the fixing temperature range was 105 to 120 ° C.

[Example 22]
The process up to the fusion process was performed under the same conditions as in Example 21, and the adhesion process described below was further performed.

(Adhesion process)
After fusing the particles in the same manner as in the fusing step of Example 21, water was placed in a water bath while stirring was continued, and the core particles were cooled to 25 ° C. Next, 7.7 parts by mass of the aqueous dispersion 1 of resin fine particles was added. The addition amount of the resin fine particle aqueous dispersion 1 is assumed to be an amount necessary to cover the 5.5 μm core particles with one layer of 0.20 μm shell particles, assuming that the core particles are spherical particles. .

  Then, it stirred for 10 minutes, and also 60 mass parts of 2 mass% calcium chloride aqueous solution was dripped, and it heated up at 35 degreeC. In this state, a small amount of the liquid was extracted at any time, passed through a 2 μm microfilter, and stirring was continued at 35 ° C. until the filtrate became transparent. After confirming that the filtrate became transparent, the mixture was heated to 40 ° C. and stirred for 1 hour, and then 35 parts by mass of a 5 mass% trisodium citrate aqueous solution was added, and the temperature was raised to 65 ° C. Stir for hours.

(Filtration, washing, drying process)
Then, the obtained liquid was cooled and filtered. The filter cake was sufficiently washed with ion-exchanged water, and dried using a vacuum dryer to obtain toner particles 3. The weight average particle diameter (D4) of the toner particles 3 was 5.9 μm.

  Next, when the toner particles were observed with a reflection electron microscope, the core particles were sufficiently covered with the shell particles. The obtained toner particles were stored for 1 week in an environment of a temperature of 40 ° C. and a relative humidity of 80%. As a result, no toner aggregation occurred and the toner had good storage stability. It was shown that.

[Comparative Example 12]
Except that the aqueous dispersion 1 of resin fine particles was changed to the aqueous dispersion 2, an adhesion process was performed in the same manner as in Example 22 to obtain toner particles 4. When the toner particles after drying were observed with a reflection electron microscope, the coating of the shell particles onto the core particles was insufficient. When the obtained toner particles were stored for 1 week in an environment of 40 ° C. and 80% relative humidity, the toner particles began to fuse from the third day and became agglomerated after the fourth day. However, the toner shape could not be maintained.

The aqueous dispersion of resin fine particles obtained by the present invention can be suitably used for the production of electrophotographic toners, inks, paints, adhesives, pressure-sensitive adhesives, fiber processing, papermaking, paper processing and the like.

Claims (10)

Producing an aqueous dispersion of resin fine particles;
An aqueous dispersion of the resin fine particles and a colorant are mixed, and the resin fine particles and the colorant are aggregated in an aqueous medium to obtain an aggregate having a weight average particle diameter (D4) of 4.5 μm or more and 7.0 μm or less. An aggregation process to form;
A fusing step of heating and fusing the aggregates;
In a method for producing a toner having
The step of producing an aqueous dispersion of the resin fine particles includes:
(I) a resin having an acid group, an anionic surfactant, a mixing step of obtaining an aqueous medium, a mixture of tertiary amines Tables acid and the following formula 1 mixture
NR ¹ R ² R ³ Formula 1
[In Formula 1, R ¹ , R ² , and R ³ each represent a hydrocarbon group having 1 to 8 carbon atoms that may have a hydroxyl group. ]
(Ii) Stirring the mixture at a temperature equal to or higher than the glass transition point of the resin having an acid group to obtain an aqueous dispersion of the resin fine particles having a 50% particle size of 0.02 μm or more and 1.00 μm or less based on volume distribution. An emulsifying step to obtain, wherein in the emulsifying step, the concentration of the amino cation generated from the tertiary amine and the acid in the aqueous phase of the aqueous dispersion is equal to or less than the following critical aggregation concentration. Toner manufacturing method.
[Critical coagulation concentration refers to the volume distribution standard 50% particle size of resin fine particles of an aqueous dispersion of resin fine particles to which an aqueous solution prepared by dissolving tertiary amine and acid in water is added. This is the amino cation concentration in the aqueous phase of the aqueous dispersion at a time when it exceeds 1.5 times the 50% particle diameter of the resin fine particles in the aqueous dispersion of the resin fine particles. ]. Producing an aqueous dispersion of resin fine particles;
An aqueous dispersion of the resin fine particles and a colorant are mixed, and the resin fine particles and the colorant are aggregated in an aqueous medium to obtain an aggregate having a weight average particle diameter (D4) of 4.5 μm or more and 7.0 μm or less. An aggregation process to form;
A fusing step of heating and fusing the aggregates;
In a method for producing a toner having
The step of producing an aqueous dispersion of the resin fine particles includes:
(I) a mixing step of mixing a resin having an acid group, a solvent in which the resin having an acid group is soluble, an anionic surfactant and a basic substance to obtain a mixture;
(Ii) An aqueous system of the resin fine particles in which 50% particle size based on volume distribution is 0.02 μm or more and 1.00 μm or less by adding acid, water and a tertiary amine represented by the following formula 1 to the mixture and stirring the mixture. Having an emulsification step to obtain a dispersion
NR ¹ R ² R ³ Formula 1
[In Formula 1, R ¹ , R ² , and R ³ each represent a hydrocarbon group having 1 to 8 carbon atoms that may have a hydroxyl group. ]
In the emulsification step, the concentration of an amino cation generated from the tertiary amine and the acid in the aqueous phase of the aqueous dispersion is not more than a critical aggregation concentration.
[Critical coagulation concentration refers to the volume distribution standard 50% particle size of resin fine particles of an aqueous dispersion of resin fine particles to which an aqueous solution prepared by dissolving tertiary amine and acid in water is added. This is the amino cation concentration in the aqueous phase of the aqueous dispersion at a time when it exceeds 1.5 times the 50% particle diameter of the resin fine particles in the aqueous dispersion of the resin fine particles. ].   The toner production method according to claim 1, wherein the resin having an acid group has a glass transition point of 50 ° C. or more and 80 ° C. or less.   The toner production method according to claim 1, wherein the resin having an acid group is a hydrolyzable resin.   The toner production method according to claim 3, wherein a basic substance is added in the emulsification step.   The method for producing a toner according to claim 1, wherein the resin having an acid group is a polyester resin.   The method for producing a toner according to claim 1, wherein the acid value of the resin having an acid group is 1 mgKOH / g or more and 30 mgKOH / g or less.   The toner production method according to claim 1, wherein the tertiary amine has an SP value of 17 or more and 28 or less.   The tertiary amine is 2- (dimethylamino) ethanol, 2-diethylaminoethanol, 2- (dibutylamino) ethanol, N-ethyldiethanolamine, triethanolamine, triethylamine, tripropylamine, triamylamine, trihexylamine, The toner production method according to claim 1, wherein the toner is one or more tertiary amine selected from the group consisting of tri-n-octylamine. The method for producing a toner according to claim 1, wherein the acid is hydrochloric acid.