JP2018131544A - Method for producing polyester latex dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyester latex dispersion having little variation in particle diameter of a polyester resin.SOLUTION: There is provided a method for producing a polyester latex dispersion using a phase inversion emulsification method, which comprises the following steps: step 1: a step of mixing a polyester resin and an organic solvent to prepare a dissolution liquid 13; step 2: a step of mixing a dissolution liquid 13 obtained in the step 1 with a neutralizer (1) 14 in an amount so that the liquid viscosity is in the range of 5 to 500 mPa s; step 3: a step of adding and mixing a neutralizer (2) 16 at least once by determining the addition amount of the neutralizer (2) 16 so that the liquid viscosity is in the range of 50 to 1000 mPa s by confirming the state of a solution 15 obtained in the step 2; step 4: a step of continuously adding pure water 18 to a solution 17 obtained in the step 3 to form resin particles and obtain a resin particle dispersion 19; and step 5: a step of removing an organic solvent 12 from the resin particle dispersion 19 obtained in the step 4.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a polyester latex dispersion and a toner production method using the obtained dispersion.

  In recent years, in an electrophotographic image forming apparatus, an electrostatic charge image developing toner (heat-fixed at a lower temperature) in order to further save energy for the purpose of increasing the printing speed and reducing the environmental load ( Hereinafter, it is simply called “toner”). For such toner, it is necessary to lower the melting temperature and melt viscosity of the binder resin, and by adding a sharp melt material such as polyester resin as a plasticizer (fixing aid), low temperature fixability can be achieved. Improved toners have been proposed.

  For example, in Patent Document 1, a crystalline polyester, an amorphous polyester, and a vinyl chloride resin are mixed at a specific ratio and used to adjust the amount of compatibility between the crystalline polyester and the amorphous polyester. The low-temperature fixability is achieved.

JP 2014-119554 A

  In the toner using the polyester resin as described above, the arrangement of the resin particles in the toner particles and the toner structure is important. However, in Patent Document 1, when preparing a dispersion of polyester resin particles, the size of the polyester resin particles in the dispersion varies due to process variations and resin physical properties (particle size variations occur), When a toner is prepared using a dispersion, there is a problem that the toner structure and physical properties (low-temperature fixability and heat resistance) vary. Specifically, the phase inversion emulsification method is used in the preparation of the polyester resin particle dispersion of Patent Document 1. In such a phase inversion emulsification method, a latex dispersion containing polyester resin particles is formed in the following flow.

  1. A state (W / O) in which water droplets are dispersed in an oil phase in which a polyester resin is dissolved in an organic solvent is formed.

  2. On the other hand, neutralizing agent is added to dissociate the polyester end group (COOH group) to lower the interfacial tension between the oil phase and the water phase, and the oil phase and water phase are mixed (co-phase). To do.

  3. Then, when water is continuously dripped, the polyester end groups are dissociated and self-emulsifying property is imparted, so that a state (O / W) in which the resin particles are dispersed in the aqueous phase is formed. At that time, the electrostatic stability of the resin particles is determined according to the amount of the terminal group dissociated from the polyester, and the particle size is determined.

  4). The obtained dispersion is desolubilized to form a latex dispersion in which the polyester resin particles are dispersed.

  From the above, the amount of neutralizing agent when forming the co-phase determines the final particle size, but there are always process variations (such as variations in the amount of water, resin and solvent contained in the system) at the production site. Therefore, it has been found that even if the amount of the neutralizing agent is the same, the same co-phase state is not formed and there is a problem (problem) that the particle size varies. In addition, there is a problem (problem) that it is easy to make a bias in the formation of a common phase state with only one injection of the neutralizing agent as in the existing phase inversion emulsification method (see paragraph “0047” of Patent Document 1). Found that there is.

  As a countermeasure against the above-mentioned problems (problems), a method of tightening management of raw material variations and process variations is also conceivable. However, since an increase in costs is expected, the increase in management costs is suppressed, and polyester resin particles This led to the idea that it is desirable to suppress the variation in particle size.

  Therefore, the present invention has been made in view of the above problems and situations, and an object of the present invention is to provide a method for producing a polyester latex dispersion that can suppress the variation in the particle size of the polyester resin even if the process varies. To do.

  In the phase-inversion emulsification of polyester (PES), the present inventors detected a state in the system by adding a neutralizing agent once to the PES solution in the examination process to solve the above problems, By adding the neutralizing agent one or more times, there is a production process variation (specifically, the amount of water contained in the organic solvent and the acid value variation due to polyester resin lot fluctuation). Has also found that the particle size of the PES resin particles can be stabilized, leading to the present invention.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A method for producing a polyester latex dispersion using a phase inversion emulsification method including the following steps:
Step 1: A step of mixing a polyester resin and an organic solvent to prepare a solution,
Step 2: Mixing the solution obtained in Step 1 with a neutralizing agent (1) in an amount such that the liquid viscosity is in the range of 5 to 500 mPa · s,
Step 3: Check the state of the solution obtained in Step 2, determine the amount of neutralizer (2) to be added so that the liquid viscosity is in the range of 50 to 1000 mPa · s, and at least once the neutralizer (2 )
Step 4: Pure water is continuously added to the solution obtained in Step 3 to form resin particles to obtain a resin particle dispersion, and Step 5: Organic from the resin particle dispersion obtained in Step 4 A process for desolvating the solvent.

  2. In the step 1, the neutralizing agent (3) is added in an amount such that the degree of neutralization in the solution before desorption is 3 to 25% before desolvating the organic solvent in the step 5. The manufacturing method of the polyester latex dispersion of description.

  3. 3. The method for producing a polyester latex dispersion as described in 1 or 2 above, wherein the neutralizing agent used in the steps 2 and 3 is a strongly alkaline compound having a pH of 11 or more.

  4). 4. The method for producing a polyester latex dispersion according to any one of items 1 to 3, wherein the neutralization degree in the solution obtained in the step 3 is 25 to 100%.

  5. The above-mentioned 1-4, wherein the ratio of the neutralizing agent (1) is 55 to 95% by mass with respect to the total amount of the neutralizing agents (1) and (2) mixed in the steps 2 and 3. The manufacturing method of the polyester latex dispersion liquid of any one of these.

  6). A polyester latex dispersion is produced by the production method according to any one of 1 to 5 above, and a toner forming solution containing the obtained polyester latex dispersion is used, and at least resin particles contained in the latex dispersion A method for producing a toner, comprising aggregating and fusing the toner.

  According to the present invention, the state of the system is observed by the first charging of the neutralizing agent, and the amount of the neutralizing agent in the second and subsequent times is determined, thereby suppressing the variation in the particle diameter of the polyester resin particles even if there is a process variation. A process for producing a polyester latex dispersion is provided.

It is process schematic of the manufacturing method of the polyester latex dispersion liquid of this invention.

The method for producing a polyester latex dispersion of the present invention is characterized by using a phase inversion emulsification method including the following steps;
Step 1: A step of mixing a polyester resin and an organic solvent to prepare a solution,
Step 2: Mixing the solution obtained in Step 1 with a neutralizing agent (1) in an amount such that the liquid viscosity is in the range of 5 to 500 mPa · s,
Step 3: Check the state of the solution obtained in Step 2, determine the amount of neutralizer (2) to be added so that the liquid viscosity is in the range of 50 to 1000 mPa · s, and at least once the neutralizer (2 )
Step 4: Pure water is continuously added to the solution obtained in Step 3 to form resin particles to obtain a resin particle dispersion, and Step 5: Organic from the resin particle dispersion obtained in Step 4 This is a step of desolvating the solvent.

  By having such a configuration, the effects of the invention can be effectively expressed. That is, in the phase inversion emulsification of polyester, a neutralizing agent is added once to the polyester (PES) solution to detect the state (liquid viscosity) in the system, and the neutralizing agent is further added one or more times. , To stabilize the particle size of PES resin particles even if there is a production process variation (specifically, the amount of water contained in the organic solvent or the acid value variation due to lot fluctuation of the polyester resin). Can do. As a result, a PES latex dispersion in which PES resin particles with little variation in particle size are dispersed in water is obtained.

  The expression mechanism or action mechanism of the effect of the present invention is as follows. That is, a common phase (solution) is formed by the first neutralization, but the physical properties of the common phase change according to variations in the system. By adjusting the amount of the neutralizing agent to be added after the second time according to the physical properties, the same common phase state (to obtain the same particle size every time for each production lot) can be formed. The physical properties of the common phase (state in the system) are detected by the liquid viscosity, the stirring torque, and the like, and the amount of the neutralizing agent after the second time can be determined. In the present invention, since the viscosity with low measurement sensitivity is easy to read the measured value difference, the liquid viscosity is detected and the neutralizing agent amount for the second and subsequent times is determined. As described above, the state of the system (physical properties of the common phase) is observed by the first charging of the neutralizing agent, and the amount of the neutralizing agent in the second and subsequent times is determined, so that there is little particle size variation even if there is a process variation. A PES latex dispersion in which PES resin particles (with a particle size range close to each production lot) is dispersed in water is obtained. Further, the second and subsequent neutralizing agent amounts are divided into two or more times (for example, the second and subsequent neutralizing agent amounts are added separately for the second time and the third time). Phase formation is performed, and the reproducibility of the particle size is increased.

  Specifically, the following operation is performed as a method of adjusting the amount of the neutralizing agent to be added after the second time according to the physical properties of the co-phase (state in the system) by the first neutralization.

  1. The viscosity (liquid viscosity) data of the co-phase corresponding to the acid value and the degree of neutralization is previously collected for each type of polyester resin.

  2. Even if the acid value of the polyester resin used for phase inversion emulsification is unknown, when the first neutralizing agent (fixed amount) is added, the acid value of the polyester resin can be calculated back from the viscosity value of the common phase Create.

  3. In order to observe the state of the system (physical properties of the common phase) by the first neutralization, measure the viscosity in the system and adjust the viscosity to the target particle size. Determine the amount of the summing agent and add the second and subsequent neutralizing agents.

  That is, if the AV (acid value) is known, the degree of neutralization for achieving the target particle size can be known (the data on the relationship between the degree of neutralization and the particle size needs to be made in advance). Can be determined. In addition, since the relationship between the degree of neutralization and the viscosity at each AV (acid value) has been made into data, the procedure is such that it can be estimated (based on the data) how much viscosity will be obtained after the second neutralizing agent is added. It has become.

  Hereinafter, constituent elements of the present invention (each component and process used in the present invention), and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[Method for producing polyester latex dispersion]
FIG. 1 is a process schematic diagram of the method for producing a polyester latex dispersion of the present invention. As shown in FIG. 1, in the method for producing a polyester latex dispersion of the present invention, a phase inversion emulsification method including the following steps 1 to 5 is used.

  In step 1, as shown in FIG. 1, a polyester resin (PES powder) 11 and an organic solvent (oil phase) 12 are mixed to prepare a PES solution (oil phase) 13 (step 1).

  In step 2, the PES solution (oil phase) 13 obtained in step 1 is mixed with an amount of neutralizing agent (1) 14 having a liquid viscosity in the range of 5 to 500 mPa · s (step 2). Thereby, the neutralization liquid (cophase) 15 is produced.

  In step 3, the state of the solution (neutralization liquid (common phase) 15) obtained in step 2 is confirmed, and the addition amount of neutralizing agent (2) 16 in which the liquid viscosity is in the range of 50 to 1000 mPa · s is determined. Decide and mix at least once (step 3). Thereby, the neutralization liquid (common phase) 17 is produced.

  In step 4, pure water 18 is continuously added to the solution obtained in step 3 (neutralization solution (common phase) 17) to form resin particles (step 4). Thereby, a PES particle dispersion (aqueous phase) 19 is prepared (emulsification is completed).

  In step 5, the organic solvent 12 is dissolved from the resin particle dispersion (PES particle dispersion (aqueous phase) 19) obtained in step 4 (step 5). In this way, a PES particle dispersion (aqueous phase) 22 is produced (desolubilization complete).

  In Step 5, before the organic solvent 12 is dissolved, an amount of neutralizing agent in which the degree of neutralization in the solution (PES particle dispersion (water phase) 19) before the dissolution is 3 to 25%. (3) 20 may be input. Thereby, a PES particle dispersion (aqueous phase) 21 is prepared (processing of the emulsion is completed). In this case, as shown in FIG. 1, instead of the resin particle dispersion (PES particle dispersion (water phase) 19) obtained in step 4, a resin particle dispersion (PES particle dispersion (water phase) 21). Then, the organic solvent 12 is dissolved. In this way, the PES particle dispersion (aqueous phase) 22 may be produced.

≪Process 1≫
Step 1 is a step of preparing a solution by mixing a polyester resin and an organic solvent (solution preparation step). In this step 1, as shown in FIG. 1, a polyester resin (PES powder) 11 and an organic solvent (oil phase) 12 are mixed to obtain a solution (PES solution (oil phase) 13).

<Polyester resin (PES powder) 11>
The polyester resin that can be used in this step is not particularly limited, but is preferably used as a binder resin for toner base particles, and is preferably an amorphous polyester resin or a hybrid amorphous polyester. Resins, crystalline polyester resins, hybrid crystalline polyester resins, and the like can be used.

  The polyester resin used in this step preferably has an acid group at the end of the molecular chain from the viewpoint of facilitating emulsification of the resin particle dispersion and enhancing dispersion stability. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphonic acid group, a sulfinic acid group, and the like. From the point that the dispersion stability of the resin can be obtained and the heat storage stability of the obtained soot can be improved. A carboxyl group is preferred.

  The content of the polyester resin having an acid group facilitates emulsification of the resin particle dispersion, can improve the dispersion stability, and further improves the dot reproducibility and charging stability of the obtained toner. From the point which can be performed, it is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, still more preferably 95 parts by mass or more, further preferably 100 parts by mass of the resin constituting the resin particles in the polyester latex dispersion. 100 parts by mass. The raw material monomer of the polyester resin having an acid group is not particularly limited, and any alcohol component and any carboxylic acid component can be used. Hereinafter, based on these points, each of the above-described polyester resin components will be described.

[Amorphous polyester resin]
The amorphous polyester resin is a polyester resin, and has a relatively high glass transition temperature (Tg) without having a melting point when differential scanning calorimetry (DSC) is performed. At this time, the glass transition temperature (Tg) is preferably 30 to 80 ° C, particularly preferably 40 to 64 ° C. The glass transition temperature (Tg) can be measured with a differential calorimeter (DSC). Specifically, it can be measured using a commercially available apparatus such as “Diamond DSC” (manufactured by PerkinElmer). First, 3.0 mg of a measurement sample (resin) is sealed in an aluminum pan and set in a “diamond DSC” sample holder. The reference uses an empty aluminum pan. Then, a first temperature raising process for raising the temperature from 0 ° C. to 200 ° C. at a temperature raising rate of 10 ° C./min, a cooling process for cooling from 200 ° C. to 0 ° C. at a cooling rate of 10 ° C./min, and a temperature raising rate of 10 ° C./min. A DSC curve is obtained according to the measurement conditions (temperature increase / cooling conditions) in which the second temperature increase process of increasing the temperature from 0 ° C. to 200 ° C. in this order is performed in this order. Based on the DSC curve obtained by this measurement, the maximum between the rising line of the first peak and the peak peak before the rising of the first endothermic peak in the second temperature rising process and the peak peak. A tangent line indicating an inclination is drawn, and the intersection is defined as a glass transition temperature (Tg). Moreover, since the monomer which comprises an amorphous polyester resin differs from the monomer which comprises a crystalline polyester resin, it can distinguish from a crystalline polyester resin by analysis, such as NMR, for example. Furthermore, those skilled in the art can control the glass transition temperature by the resin composition.

  The amorphous polyester resin is obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyvalent carboxylic acid) and a divalent or higher alcohol (polyhydric alcohol). There is no restriction | limiting in particular about an amorphous polyester resin, The conventionally well-known amorphous polyester resin in this technical field can be used.

  Examples of the polyvalent carboxylic acid and polyhydric alcohol used for the preparation of the amorphous polyester resin are not particularly limited, but include the following.

  As the polyvalent carboxylic acid used for the preparation of the amorphous polyester resin, it is preferable to use unsaturated aliphatic polyvalent carboxylic acid, aromatic polyvalent carboxylic acid, and derivatives thereof. A saturated aliphatic polyvalent carboxylic acid may be used in combination as long as an amorphous resin can be formed.

  Examples of the unsaturated aliphatic polycarboxylic acid include methylene succinic acid, fumaric acid, maleic acid, 3-hexenedioic acid, 3-octenedioic acid, and an alkenyl group having 2 to 20 carbon atoms. Unsaturated aliphatic dicarboxylic acids such as succinic acid: unsaturated aliphatic tricarboxylic acids such as 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid, aconitic acid; 4 -Unsaturated aliphatic tetracarboxylic acid such as pentene-1,2,3,4-tetracarboxylic acid, and the like, and lower alkyl esters and acid anhydrides thereof can also be used.

  Examples of the aromatic polycarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, t-butylisophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylenediacetic acid, and 2,6-naphthalenedicarboxylic acid. Aromatic dicarboxylic acids such as acid, 4,4′-biphenyldicarboxylic acid, anthracene dicarboxylic acid; 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid (trimesic acid), Aromatic tricarboxylic acids such as 1,2,4-naphthalene tricarboxylic acid and hemimellitic acid; Aromatic tetracarboxylic acids such as pyromellitic acid and 1,2,3,4-butanetetracarboxylic acid; Aromatics such as melittic acid Hexacarboxylic acid and the like, and these lower alkyl esters and acid anhydrides are used. You can also.

  The above polyvalent carboxylic acids may be used alone or in combination of two or more.

  As the polyhydric alcohol used for the preparation of the amorphous polyester resin, it is preferable to use an unsaturated aliphatic polyhydric alcohol, an aromatic polyhydric alcohol and derivatives thereof from the viewpoint of chargeability and toner strength. Saturated aliphatic polyhydric alcohols may be used in combination as long as a water-soluble resin can be formed.

  Examples of the unsaturated aliphatic polyhydric alcohol include 2-butene-1,4-diol, 3-butene-1,4-diol, 2-butyne-1,4-diol, and 3-butyne-1,4. -Unsaturated aliphatic diols such as diol and 9-octadecene-7,12-diol, and the like, and these derivatives can also be used.

  Examples of the aromatic polyhydric alcohol include bisphenols such as bisphenol A and bisphenol F, and alkylene oxide adducts of bisphenols such as ethylene oxide adducts and propylene oxide adducts, 1,3,5-benzene. Examples include triol, 1,2,4-benzenetriol, 1,3,5-trihydroxymethylbenzene, and derivatives thereof can also be used. Among these, it is preferable to use a bisphenol A compound such as an ethylene oxide adduct or a propylene oxide adduct of bisphenol A from the viewpoint that it is particularly easy to optimize thermal characteristics.

  The number of carbons of the trihydric or higher polyhydric alcohol is not particularly limited, but is particularly preferably 3 to 20 because it is easy to optimize the thermal characteristics.

  The polyhydric alcohols may be used alone or in admixture of two or more.

(Weight average molecular weight, number average molecular weight of amorphous polyester resin)
The weight average molecular weight (Mw) of the amorphous polyester resin is not particularly limited, but is preferably in the range of 5,000 to 100,000, and more preferably in the range of 5,000 to 50,000. preferable. If the weight average molecular weight (Mw) is 5,000 or more, the heat-resistant storage property of the toner can be improved, and if it is 100,000 or less, the low-temperature fixability can be further improved. The number average molecular weight (Mn) of the resin is not particularly limited, but is preferably in the range of 1,500 to 25,000. The weight average molecular weight (Mw) and number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC). Specifically, it can be measured by the following method.

(Measurement method of weight average molecular weight and number average molecular weight of resin)
The molecular weight (weight average molecular weight and number average molecular weight) of each resin (amorphous polyester resin, hybrid amorphous polyester resin, crystalline polyester resin, hybrid crystalline polyester resin, etc.) by GPC is measured as follows. . That is, using an apparatus “HLC-8120GPC” (manufactured by Tosoh Corporation) and a column “TSKguardcolumn + TSKgelSuperHZ-M3 series” (manufactured by Tosoh Corporation), while maintaining the column temperature at 40 ° C., tetrahydrofuran (THF) was used as a carrier solvent at a flow rate. Run at 0.2 mL / min. The measurement sample (resin) is dissolved in tetrahydrofuran so as to have a concentration of 1 mg / ml. The solution is prepared by performing treatment at room temperature for 5 minutes using an ultrasonic disperser. Next, a sample solution is obtained by processing with a membrane filter having a pore size of 0.2 μm, 10 μL of this sample solution is injected into the apparatus together with the carrier solvent, and detected using a refractive index detector (RI detector). The molecular weight distribution of the measurement sample is calculated based on a calibration curve created using monodisperse polystyrene standard particles. Ten points are used as polystyrene for the calibration curve measurement.

(Acid value of amorphous polyester resin)
Further, the amorphous polyester resin preferably has an acid value of 5 to 50 mgKOH / g. By setting it within such a range, the dispersion stability of the polyester latex dispersion can be improved. Further, the low-temperature fixability of the soot can be improved. Furthermore, the binder resin and the release agent (such as ester wax) containing the amorphous polyester resin are easily dispersed uniformly during toner production. Therefore, the release agent (ester wax or the like) is difficult to be exposed on the surface of the toner particles, so that occurrence of image noise (fogging) is suppressed. In addition, the acid value of resin (amorphous polyester resin, amorphous polyester resin, hybrid resin etc.) can be measured by the method as described in an Example.

  The acid value (and hydroxyl value) of the polyester resin (amorphous polyester resin, hybrid amorphous polyester resin, crystalline polyester resin, hybrid crystalline polyester resin, etc.) is the type and composition ratio of the alcohol component and carboxylic acid component, It can be controlled by adjusting the amount of catalyst and the like, and selecting reaction conditions such as reaction temperature, reaction time and reaction pressure.

(Method for producing amorphous polyester resin)
The production method of the amorphous polyester resin is not particularly limited, and the resin is produced by polycondensation (esterification) of the polyvalent carboxylic acid and the polyhydric alcohol using a known esterification catalyst. Can do.

  Catalysts that can be used in the production include alkali metal compounds such as sodium and lithium; compounds containing Group 2 elements such as magnesium and calcium; aluminum, zinc, manganese, antimony, titanium, tin, zirconium, germanium, and the like Metal compounds; phosphorous acid compounds; phosphoric acid compounds; and amine compounds. Considering availability, dibutyltin oxide, tin octylate, tin dioctylate, salts thereof, tetranormal butyl titanate (tetrabutyl orthotitanate), tetraisopropyl titanate (titanium tetraisopropoxide), tetramethyl titanate, etc. Is preferably used. You may use these individually by 1 type or in combination of 2 or more types.

  The temperature of polycondensation (esterification) is not particularly limited, but is preferably 150 to 250 ° C. The time for polycondensation (esterification) is not particularly limited, but is preferably 0.5 to 15 hours. During the polycondensation, the reaction system may be depressurized as necessary.

[Hybrid amorphous polyester resin]
The hybrid amorphous polyester resin is a hybrid amorphous polyester resin in which the amorphous polyester resin is chemically bonded to an amorphous polyester resin segment and another resin segment. By having such a configuration, the ratio of the polyester resin segment to the whole is reduced, whereby the moisture adsorption property can be reduced, and the decrease in the resistance value of the toner can be reduced. In addition, it is preferable that the other resin segment in a hybrid amorphous polyester resin exists in the range of 5-30 mass%. By being in this range, it is possible to efficiently exhibit the effect of reducing moisture adsorption and improve the low-temperature fixability. The hybrid amorphous polyester resin can also be said to be a modified amorphous polyester resin that is partially modified. That is, “partially modified” means that the amorphous polyester resin includes “other resin segments” as “amorphous polyester resin segments”, and the “other resin segments” include vinyl resins. This is because it includes segments, crystalline polyester resin segments, and the like. In the present invention, the hybrid amorphous polyester resin includes not only a graft type but also a block type.

(Weight average molecular weight of hybrid amorphous polyester resin)
The weight average molecular weight (Mw) of the hybrid amorphous polyester resin is in the range of 5,000 to 100,000 from the viewpoint of ensuring both sufficient low-temperature fixability and excellent long-term storage stability. Preferably, it is 5,000-50,000. By setting the weight average molecular weight (Mw) of the hybrid amorphous polyester resin to 100,000 or less, sufficient low-temperature fixability can be obtained. On the other hand, by setting the weight-average molecular weight (Mw) of the hybrid amorphous polyester resin to 5,000 or more, the heat-resistant storage property of the toner can be improved, and image defects due to fusion between the toners can be effectively suppressed. can do. The number average molecular weight (Mn) of the resin is not particularly limited, but is preferably in the range of 1,500 to 25,000.

(Acid value of hybrid amorphous polyester resin)
The hybrid amorphous polyester resin preferably has an acid value of 5 to 50 mgKOH / g. By setting it within such a range, the dispersion stability of the polyester latex dispersion can be improved. Further, the low-temperature fixability of the soot can be improved. Furthermore, the binder resin and the release agent (such as ester wax) containing the hybrid amorphous polyester resin are easily dispersed uniformly during the production of the toner. Therefore, the release agent (ester wax or the like) is difficult to be exposed on the surface of the toner particles, so that occurrence of image noise (fogging) is suppressed. The acid value of the resin (amorphous polyester resin, hybrid amorphous polyester resin, crystalline polyester resin, hybrid crystalline polyester resin, etc.) can be measured by the method described in the examples.

(Other resin segments in hybrid amorphous polyester resin)
Examples of the other resin segment in the hybrid amorphous polyester resin include a vinyl resin segment and a crystalline polyester resin segment. According to a preferred embodiment, the other resin segment is a vinyl resin segment. Since the resin component having a vinyl resin segment has a low moisture adsorptivity, the hybrid amorphous polyester resin can reduce a decrease in the resistance value of the toner by having the vinyl resin segment.

  As such a hybrid amorphous polyester resin, according to a more preferred embodiment, the other resin segment includes, for example, a styrene- (meth) acrylic resin segment (vinyl resin segment).

  The styrene- (meth) acrylic resin has a molecular structure of a radical polymer of a compound having a radical polymerizable unsaturated bond, and can be synthesized, for example, by radical polymerization of the compound. One or more compounds may be used, and examples thereof include styrene and its derivatives, and (meth) acrylic acid and its derivatives.

  Examples of the styrene and its derivatives include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, pn. -Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-lauryl styrene, 2,4- Dimethylstyrene and 3,4-dichlorostyrene are included.

  Examples of the above (meth) acrylic acid and derivatives thereof include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, methacrylic acid Examples include ethyl, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

(Amorphous polyester resin segment in hybrid amorphous polyester resin)
The amorphous polyester resin segment is a portion derived from an amorphous polyester resin other than the above-mentioned other resins in the hybrid amorphous polyester resin. The amorphous polyester resin segment has a function of controlling the affinity between these resins when a hybrid amorphous polyester resin and a crystalline resin are used in combination as a binder resin. By using the resin segment, when the hybrid amorphous polyester resin and the crystalline resin are used in combination as a binder resin for the toner, the affinity between these improves, and the hybrid amorphous polyester resin is contained in the crystalline resin. It becomes easy to be taken in, and the charging uniformity can be improved. The crystalline resin that can be used when the hybrid amorphous polyester resin and the crystalline resin are used in combination includes a crystalline polyester resin (including a hybrid crystalline polyester resin), a crystalline polyurethane resin, and a crystalline polyurea. Examples thereof include resins, crystalline polyamide resins, and crystalline polyether resins. From the viewpoint of chargeability and low-temperature fixability, it is particularly preferable to use crystalline polyester resins (including hybrid crystalline polyester resins).

  The inclusion of the amorphous polyester resin segment in the hybrid amorphous polyester resin (and also in the toner) is determined by specifying the chemical structure using, for example, NMR measurement or methylation reaction Py-GC / MS measurement. Can be confirmed.

  The amorphous polyester resin segment does not have a melting point and has a relatively high glass transition temperature (Tg) when differential scanning calorimetry (DSC) is performed on a resin having the same chemical structure and molecular weight as the segment. It is a resin segment. At this time, for the resin having the same chemical structure and molecular weight as the segment, the glass transition temperature (Tg1) in the first temperature rising process in DSC measurement is preferably in the range of 30 to 80 ° C., particularly 40 to 40 ° C. It is preferably within the range of 65 ° C.

  The amorphous polyester resin segment is a portion derived from a known polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyvalent carboxylic acid) and a divalent or higher alcohol (polyhydric alcohol). When the above differential scanning calorimetry (DSC) is performed, the resin segment does not have a melting point and has a relatively high glass transition temperature (Tg).

  Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and the like; maleic anhydride, fumaric acid, succinic acid, Examples thereof include aliphatic carboxylic acids such as alkenyl succinic anhydride and adipic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid; their anhydrides and lower (1 to 5 carbon atoms) alkyl esters thereof. Among these polycarboxylic acids, it is desirable to include an aromatic carboxylic acid.

  As the polyvalent carboxylic acid, a tri- or higher-valent carboxylic acid (trimellitic acid or acid anhydride thereof) having a crosslinked structure or a branched structure may be used in combination with the dicarboxylic acid in order to ensure fixability. These polyvalent carboxylic acids may be used alone or in combination of two or more.

  Examples of the polyhydric alcohol include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, and glycerin; cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct. Among these polyhydric alcohols, aromatic diols and alicyclic diols are desirable, and aromatic diols are more desirable.

  As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a cross-linked structure or a branched structure (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol, in order to ensure fixability. These polyhydric alcohols may be used alone or in combination of two or more.

  The content of the amorphous polyester resin segment is preferably in the range of 1 to 30% by mass with respect to the total amount of the hybrid amorphous polyester resin. By setting it as the range of such content, the effect that moderate compatibility with the styrene acrylic resin which is a main binder can be maintained is acquired.

(Method for producing hybrid amorphous polyester resin)
The method for producing a hybrid amorphous polyester resin is particularly limited as long as it can form a polymer having a structure in which the above amorphous polyester resin segment and another resin segment are chemically bonded. is not. As a specific method for producing the hybrid amorphous polyester resin, the same method as that of the hybrid crystal polyester resin described later can be used.

  (1) A method of producing a hybrid amorphous polyester resin by polymerizing other resin segments in advance and performing a polymerization reaction to form an amorphous polyester resin segment in the presence of the other resin segments.

  In this method, first, a monomer (preferably a vinyl monomer such as a styrene monomer and a (meth) acrylic acid ester monomer) constituting another resin segment described above is subjected to an addition reaction to form another resin. Form a segment. Next, in the presence of another resin segment, a polyvalent carboxylic acid and a polyhydric alcohol are subjected to a polycondensation reaction to form an amorphous polyester resin segment. At this time, a hybrid amorphous polyester resin is formed by a condensation reaction of the polyvalent carboxylic acid and the polyhydric alcohol, and an addition reaction of the polyvalent carboxylic acid or the polyhydric alcohol to the other resin segments. .

  In this method, it is preferable to incorporate a site where these segments can react with each other in the amorphous polyester resin segment or other resin segments.

  Specifically, when the other resin segment is formed, in addition to the monomer constituting the other resin segment, a carboxy group [—COOH] or a hydroxy group [—OH] remaining in the amorphous polyester resin segment A compound having a site capable of reacting and a site capable of reacting with other resin segments is also used. That is, when this compound reacts with a carboxy group [—COOH] or a hydroxy group [—OH] in an amorphous polyester resin segment, the amorphous polyester resin segment chemically bonds with other resin segments. Can do.

  Or you may use the compound which can react with a polyhydric alcohol or polyhydric carboxylic acid at the time of formation of an amorphous polyester resin segment, and has a site | part which can react with another resin segment.

  By using this method, a hybrid amorphous polyester resin having a structure (graft structure) in which an amorphous polyester resin segment is chemically bonded to another resin segment can be formed.

  (2) A method of producing a hybrid amorphous polyester resin by forming an amorphous polyester resin segment and another resin segment and combining them.

  In this method, first, an amorphous polyester resin segment is formed by a condensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol. In addition to the reaction system for forming the amorphous polyester resin segment, the other resin segments are formed by addition polymerization of the monomers constituting the other resin segments described above. At this time, it is preferable to incorporate a site where the amorphous polyester resin segment and the other resin segment can react with each other. In addition, since the method of incorporating such a reactive site is as described above, detailed description thereof is omitted.

  Next, by reacting the amorphous polyester segment formed above with another resin segment, a hybrid amorphous polyester resin having a structure in which the amorphous polyester resin segment and the other resin segment are chemically bonded is obtained. Can be formed.

  In addition, when the reactive site is not incorporated in the amorphous polyester resin segment and other resin segments, a system in which the amorphous polyester resin segment and other resin segments coexist is formed, You may employ | adopt the method of throwing in the compound which has a site | part which can be couple | bonded with an amorphous polyester resin segment and another resin segment. And the hybrid amorphous polyester resin of the structure which the amorphous polyester resin segment and the other resin segment chemically bonded can be formed through the said compound.

  (3) A method in which an amorphous polyester resin segment is formed in advance and a hybrid amorphous polyester resin is produced by performing a polymerization reaction to form another resin segment in the presence of the amorphous polyester resin segment. is there.

  In this method, first, a polyvalent carboxylic acid and a polyhydric alcohol are subjected to a condensation reaction for polymerization to form an amorphous polyester resin segment. Next, in the presence of the amorphous polyester resin segment, a monomer constituting another resin segment is polymerized to form another resin segment. At this time, similarly to the above (1), it is preferable to incorporate a site where these segments can react with each other in the amorphous polyester resin segment or other resin segments. In addition, since the method of incorporating such a reactive site is as described above, detailed description thereof is omitted.

  By using the above method, a hybrid amorphous polyester resin having a structure (graft structure) in which another resin segment is chemically bonded to the amorphous polyester resin segment can be formed.

  Among the forming methods (1) to (3), the method (1) is easy to form and produce a hybrid amorphous polyester resin having a structure in which an amorphous polyester resin chain is grafted to another resin chain. This is preferable because the process can be simplified. In the method (1), since the amorphous polyester resin segments are bonded after the other resin segments are formed in advance, the orientation of the amorphous polyester resin segments tends to be uniform. Therefore, it is preferable because a hybrid amorphous polyester resin suitable for the toner defined in the present invention can be reliably formed.

[Crystalline polyester resin]
In the present invention, the crystalline polyester resin is a known polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyvalent carboxylic acid) and a divalent or higher alcohol (polyhydric alcohol). A resin having a clear endothermic peak. Specifically, the “clear endothermic peak” means a peak in which the half-value width of the endothermic peak is within 15 ° C. when measured at a heating rate of 10 ° C./min in differential scanning calorimetry (DSC). means.

  By including the crystalline polyester resin (domain thereof) in the toner particles, the sharp melt property of the toner particles (binder resin in the toner particles) can be improved, and the low-temperature fixing property and the fixing separation property can be improved. . In addition, since the crystalline polyester resin has an ester bond, it is easy to adsorb moisture, thereby further promoting the charge release and further suppressing the sticking of the paper having the image on which the toner is thermally fixed. It is also preferable from the viewpoint.

  The polyvalent carboxylic acid used for the preparation of the crystalline polyester resin is a compound containing two or more carboxy groups in one molecule, and can form a crystalline resin by polycondensation reaction. That's fine.

  Specifically, for example, saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and n-dodecyl succinic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; phthalates Aromatic dicarboxylic acids such as acid, isophthalic acid and terephthalic acid; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides of these carboxylic acid compounds or alkyl esters having 1 to 3 carbon atoms Etc. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The polyhydric alcohol used for the preparation of the crystalline polyester resin is a compound containing two or more hydroxy groups in one molecule and can form a crystalline resin by polycondensation reaction. Good.

  Specifically, for example, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, neopentyl glycol, 1,4-butenediol, and other aliphatic diols; trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol. These may be used individually by 1 type and may be used in combination of 2 or more type.

(Melting point of crystalline polyester resin)
The melting point of the crystalline polyester resin is preferably in the range of 60 to 90 ° C, more preferably 70 to 85 ° C, from the viewpoint that sufficient low-temperature fixability can be obtained. The melting point of the crystalline polyester resin can be controlled by the resin composition.

  The melting point of the crystalline polyester resin indicates the temperature at the peak top of the endothermic peak, and is a value measured by DSC by differential scanning calorimetry using “Diamond DSC” (manufactured by PerkinElmer). Specifically, 1.0 mg of a measurement sample (crystalline polyester resin) is sealed in an aluminum pan (KITNO.B0143013), and this is set in a sample holder of “Diamond DSC” at a measurement temperature of 0 to 200 ° C. The temperature control of heating-cooling-heating is performed under the measurement conditions of a heating rate of 10 ° C./min and a cooling rate of 10 ° C./min, and the analysis is performed based on the data in the second heating.

(Weight average molecular weight, number average molecular weight of crystalline polyester resin)
The weight average molecular weight (Mw) of the crystalline polyester resin is not particularly limited, but is preferably in the range of 5,000 to 100,000, and more preferably in the range of 5,000 to 50,000. . If the weight average molecular weight (Mw) is 5,000 or more, the heat-resistant storage property of the toner can be improved, and if it is 100,000 or less, the low-temperature fixability can be further improved. The number average molecular weight (Mn) of the resin is preferably 1,000 to 15,000 from the viewpoint of low-temperature fixability and gloss stability. The number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC). Specifically, it is a value measured by the method described in the above “Method for measuring weight average molecular weight and number average molecular weight of resin”.

(Acid value of crystalline polyester resin)
Further, the crystalline polyester resin preferably has an acid value of 5 to 50 mgKOH / g. By setting it within such a range, the dispersion stability of the polyester latex dispersion can be improved. Further, the low-temperature fixability of the soot can be improved. Further, the binder resin and the release agent (such as ester wax) containing the crystalline polyester resin can be easily dispersed uniformly during toner production. Therefore, the release agent (ester wax or the like) is difficult to be exposed on the surface of the toner particles, so that occurrence of image noise (fogging) is suppressed. In addition, the acid value of crystalline polyester resin can be measured by the method as described in an Example.

(Method for producing crystalline polyester resin)
The method for producing the crystalline polyester resin is not particularly limited, and the resin can be produced by polycondensation (esterification) of the polyvalent carboxylic acid and the polyhydric alcohol using a known esterification catalyst. it can.

  Catalysts that can be used in the production include alkali metal compounds such as sodium and lithium; compounds containing Group 2 elements such as magnesium and calcium; aluminum, zinc, manganese, antimony, titanium, tin, zirconium, germanium, and the like Metal compounds; phosphorous acid compounds; phosphoric acid compounds; and amine compounds. Considering availability, dibutyltin oxide, tin octylate, tin dioctylate, salts thereof, tetranormal butyl titanate (tetrabutyl orthotitanate), tetraisopropyl titanate (titanium tetraisopropoxide), tetramethyl titanate, etc. Is preferably used. You may use these individually by 1 type or in combination of 2 or more types.

  The temperature of polycondensation (esterification) is not particularly limited, but is preferably 150 to 250 ° C. The time for polycondensation (esterification) is not particularly limited, but is preferably 0.5 to 15 hours. During the polycondensation, the reaction system may be depressurized as necessary.

[Hybrid crystalline polyester resin]
A hybrid crystalline polyester resin (also abbreviated as a hybrid resin) is a resin in which a crystalline polyester resin segment and an amorphous resin segment are chemically bonded.

  The crystalline polyester resin segment refers to a molecular chain constituting the crystalline polyester resin. The amorphous resin segment refers to a molecular chain that constitutes an amorphous resin (a resin that cannot take a crystal structure).

(Weight average molecular weight of hybrid resin)
The weight average molecular weight (Mw) of the hybrid resin is preferably in the range of 5,000 to 100,000 from the viewpoint of ensuring both sufficient low-temperature fixability and excellent long-term storage stability. More preferably, it is 000-50,000, and it is especially preferable in the range of 8,000-40,000. By setting the weight average molecular weight (Mw) of the hybrid resin to 100,000 or less, sufficient low-temperature fixability can be obtained. On the other hand, by setting the weight average molecular weight (Mw) of the hybrid resin to 5,000 or more, when the hybrid resin and the amorphous resin are used as a binder resin at the time of toner storage, the compatibility of these resins is reduced. Is suppressed from proceeding excessively, and image defects due to fusion between toners can be effectively suppressed.

(Acid value of hybrid resin)
Furthermore, the hybrid resin preferably has an acid value of 5 to 50 mgKOH / g. By setting it within such a range, the dispersion stability of the polyester latex dispersion can be improved. Further, the low-temperature fixability of the soot can be improved. Further, the binder resin and the release agent (such as ester wax) containing the hybrid resin are easily dispersed uniformly during toner production. Therefore, the release agent (ester wax or the like) is difficult to be exposed on the surface of the toner particles, so that occurrence of image noise (fogging) is suppressed. The acid value of the resin (amorphous polyester resin, hybrid amorphous polyester resin, crystalline polyester resin, hybrid crystalline polyester resin, etc.) can be measured by the method described in the examples.

(Crystalline polyester resin segment in hybrid resin)
The crystalline polyester resin segment is a portion derived from a known polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyvalent carboxylic acid) and a divalent or higher alcohol (polyhydric alcohol). In the differential scanning calorimetry of the toner, it refers to a resin segment having a clear endothermic peak rather than a stepwise endothermic change.

  The crystalline polyester resin segment is not particularly limited as long as it is defined above. For example, this resin (or resin having a structure in which other components are copolymerized with a main chain of a crystalline polyester resin segment, or a resin having a structure in which a crystalline polyester resin segment is copolymerized with a main chain composed of other components) If the toner containing the resin has a clear endothermic peak as described above, the resin corresponds to a hybrid resin having a crystalline polyester resin segment in the present invention.

  Further, the valences of the polyvalent carboxylic acid component and the polyhydric alcohol component are each preferably 2 to 3, particularly preferably 2 respectively. , Dicarboxylic acid component, diol component).

  As the dicarboxylic acid component, an aliphatic dicarboxylic acid is preferably used, and an aromatic dicarboxylic acid may be used in combination. As the aliphatic dicarboxylic acid, it is preferable to use a linear one. By using a linear type, there is an advantage that crystallinity is improved. The dicarboxylic acid component is not limited to one type, and two or more types may be mixed and used.

  Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. Acid (dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid (tetradecanedioic acid), 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecane Examples thereof include dicarboxylic acid and 1,18-octadecanedicarboxylic acid, and these lower alkyl esters and acid anhydrides can also be used.

  Among the above aliphatic dicarboxylic acids, aliphatic dicarboxylic acids having 6 to 12 carbon atoms are preferable because the above-described effects are easily obtained.

  Examples of the aromatic dicarboxylic acid that can be used with the aliphatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. Is mentioned. Among these, terephthalic acid, isophthalic acid, and t-butylisophthalic acid are preferably used from the viewpoints of availability and emulsification ease.

  As the dicarboxylic acid component for forming the crystalline polyester resin segment, the content of the aliphatic dicarboxylic acid is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol%. % Or more, and particularly preferably 100 mol%. When the content of the aliphatic dicarboxylic acid in the dicarboxylic acid component is 50 mol% or more, the crystallinity of the crystalline polyester resin segment can be sufficiently ensured.

  Moreover, it is preferable to use aliphatic diol as a diol component, and you may contain diols other than aliphatic diol as needed. As the aliphatic diol, a linear diol is preferably used. By using a linear type, there is an advantage that crystallinity is improved. A diol component may be used individually by 1 type and may be used 2 or more types.

  Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18- Examples include octadecanediol and 1,20-eicosanediol.

  Among the aliphatic diols, the diol component is preferably an aliphatic diol having 2 to 12 carbon atoms, more preferably an aliphatic diol having 6 to 12 carbon atoms, because the above-described effects are easily obtained.

  Examples of the diol other than the aliphatic diol used as necessary include a diol having a double bond and a diol having a sulfonic acid group. Specifically, examples of the diol having a double bond include 2 -Butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like.

  As the diol component for forming the crystalline polyester resin segment, the content of the aliphatic diol is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more. And particularly preferably 100 mol%. When the content of the aliphatic diol in the diol component is 50 mol% or more, the crystallinity of the crystalline polyester resin segment can be ensured. As a result, the toner produced using the dispersion of the present invention has excellent low-temperature fixability and excellent gloss of the finally formed image.

  The use ratio of the diol component to the dicarboxylic acid component is such that the equivalent ratio [OH] / [COOH] of the hydroxy group [OH] of the diol component to the carboxy group [COOH] of the dicarboxylic acid component is 1.5 / 1. It is preferable to be within a range of ˜1 / 1.5, and more preferably within a range of 1.2 / 1 to 1 / 1.2.

  The method for forming the crystalline polyester resin segment is not particularly limited, and the segment is formed by polycondensation (esterification) of the polyvalent carboxylic acid and the polyhydric alcohol using a known esterification catalyst. Can do.

  Catalysts that can be used in the production of the crystalline polyester resin segment include alkali metal compounds such as sodium and lithium; group 2 metal compounds of the periodic table of elements such as magnesium and calcium; aluminum, zinc, manganese, and antimony Metal compounds such as titanium, tin, zirconium and germanium; phosphorous acid compounds; phosphoric acid compounds; and amine compounds.

  Specifically, examples of the tin compound include dibutyltin oxide, tin octylate, tin dioctylate, and salts thereof. Titanium compounds include titanium alkoxides such as tetranormal butyl titanate, tetraisopropyl titanate, tetramethyl titanate, and tetrastearyl titanate; titanium acylates such as polyhydroxy titanium stearate; titanium tetraacetylacetonate, titanium lactate, titanium triethanolamine Examples thereof include titanium chelates such as nates. Examples of germanium compounds include germanium dioxide. Furthermore, examples of the aluminum compound include oxides such as polyaluminum hydroxide, aluminum alkoxide, and the like, and tributylaluminate and the like can be given. You may use these individually by 1 type or in combination of 2 or more types.

  The polymerization temperature is not particularly limited, but is preferably in the range of 150 to 250 ° C. Moreover, although superposition | polymerization time is not specifically limited, It is preferable to exist in the range of 0.5 to 10 hours. During the polymerization, the pressure in the reaction system may be reduced as necessary.

  The constituent component and the content ratio of each segment in the hybrid resin can be specified by, for example, NMR measurement or methylation reaction Py-GC / MS measurement.

  Here, the hybrid resin includes an amorphous resin segment described in detail below in addition to the crystalline polyester resin segment. The hybrid resin may be in any form such as a block copolymer or a graft copolymer as long as it includes the crystalline polyester resin segment and the amorphous resin segment, and is a graft copolymer. preferable. By using a graft copolymer, the orientation of the crystalline polyester resin segment can be easily controlled, and sufficient crystallinity can be imparted to the hybrid resin.

  Furthermore, from the above viewpoint, it is preferable that the crystalline polyester resin segment is grafted with the amorphous resin segment as a main chain. That is, the hybrid crystalline polyester resin is preferably a graft copolymer having an amorphous resin segment as a main chain and a crystalline polyester resin segment as a side chain.

  By setting it as the said form, the orientation of a crystalline polyester resin segment can be raised more and the crystallinity of hybrid resin can be improved.

  In addition, substituents, such as a sulfonic acid group, a carboxy group, and a urethane group, may be further introduced into the hybrid resin. The introduction of the substituent may be in the crystalline polyester resin segment or in the amorphous resin segment described below.

(Amorphous resin segment in hybrid resin)
The amorphous resin segment is a portion derived from an amorphous resin other than the crystalline polyester resin in the hybrid resin. The amorphous resin segment has a function of controlling the affinity between these resins when a hybrid resin and an amorphous resin are used in combination as a binder resin, and the amorphous resin segment is present. Therefore, when a hybrid resin and an amorphous resin are used in combination as a toner binder resin, the affinity between them is improved, and the hybrid resin is easily incorporated into the amorphous resin, improving the charging uniformity and the like. Can be made.

  The inclusion of an amorphous resin segment in the hybrid resin (and also in the toner) can be confirmed by specifying the chemical structure using, for example, NMR measurement or methylation reaction Py-GC / MS measurement. .

  The amorphous resin segment does not have a melting point and has a relatively high glass transition temperature (Tg) when differential scanning calorimetry (DSC) is performed on a resin having the same chemical structure and molecular weight as the segment. It is a resin segment. At this time, for the resin having the same chemical structure and molecular weight as the segment, the glass transition temperature (Tg1) in the first temperature rising process in DSC measurement is preferably in the range of 30 to 80 ° C., particularly 40 to 40 ° C. It is preferably within the range of 65 ° C.

  The amorphous resin segment is not particularly limited as long as it is defined above. For example, for a resin having a structure in which a main chain of an amorphous resin segment is copolymerized with other components, or a resin having a structure in which an amorphous resin segment is copolymerized with a main chain composed of other components, this resin ( If the toner containing the resin has an amorphous resin segment as described above, the resin corresponds to the hybrid resin having an amorphous resin segment in the present invention.

  The amorphous resin segment is preferably composed of the same type of resin as the amorphous resin contained in the binder resin used for toner production. By adopting such a form, the affinity between the hybrid resin and the amorphous resin is further improved, the hybrid resin is further easily taken into the amorphous resin, and the charging uniformity is further improved.

  Here, “the same kind of resin” means that a characteristic chemical bond is commonly contained in the repeating unit. Here, “characteristic chemical bond” is described in the National Institute for Materials Science (NIMS) Substance / Material Database (http://polymer.nims.go.jp/PoLyInfo/guide/jp/term_polymer.html). According to “Polymer classification”. That is, polyacryl, polyamide, polyanhydride, polycarbonate, polydiene, polyester, polyhaloolefin, polyimide, polyimine, polyketone, polyolefin, polyether, polyphenylene, polyphosphazene, polysiloxane, polystyrene, polysulfide, polysulfone, polyurethane, polyurea Chemical bonds constituting polymers classified according to a total of 22 types of polyvinyl and other polymers are referred to as “characteristic chemical bonds”.

  In addition, the “same kind of resin” in the case where the resin is a copolymer is characteristic when the monomer type having the above chemical bond is used as a constituent unit in the chemical structure of a plurality of monomer types constituting the copolymer. Refers to resins having common chemical bonds. Therefore, even if the characteristics of the resin itself are different from each other, or even when the molar component ratios of the monomer species constituting the copolymer are different from each other, the same type of chemical bonds are used as long as they have a common chemical bond. Considered resin.

  For example, a resin (or resin segment) formed of styrene, butyl acrylate and acrylic acid and a resin (or resin segment) formed of styrene, butyl acrylate and methacrylic acid have at least chemical bonds constituting polyacryl. These are the same kind of resins. To further illustrate, a resin (or resin segment) formed of styrene, butyl acrylate and acrylic acid and a resin (or resin segment) formed of styrene, butyl acrylate, acrylic acid, terephthalic acid and fumaric acid are mutually As a common chemical bond, it has a chemical bond constituting at least polyacryl. Therefore, these are the same kind of resins.

  The resin component constituting the amorphous resin segment is not particularly limited, and examples thereof include a vinyl resin segment, a urethane resin segment, and a urea resin segment. Among these, a vinyl resin segment is preferable because it is easy to control thermoplasticity.

  The vinyl resin segment is not particularly limited as long as a vinyl compound is polymerized, and examples thereof include an acrylic ester resin segment, a styrene / acrylic ester resin segment, and an ethylene-vinyl acetate resin segment. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the vinyl resin segments, a styrene / acrylic acid ester resin segment (styrene / acrylic resin segment) is preferable from the viewpoint of forming a uniform and fine domain structure of the plasticizer. Therefore, the styrene / acrylic resin segment as the amorphous resin segment will be described below.

The styrene / acrylic resin segment is formed by addition polymerization of at least a styrene monomer and a (meth) acrylic acid ester monomer. The styrene monomer here includes, in addition to styrene represented by the structural formula of CH ₂ ═CH—C ₆ H ₅ , those having a structure having a known side chain or functional group in the styrene structure. In addition, the (meth) acrylic acid ester monomer mentioned here is an acrylic acid ester compound or a methacrylic acid compound in addition to an acrylic acid ester compound or a methacrylic acid ester compound represented by CH ₂ = CHCOOR (R is an alkyl group). It includes an ester compound having a known side chain or functional group in the structure of an ester derivative or the like.

  Specific examples of styrene monomers and (meth) acrylate monomers that can form styrene / acrylic resin segments are shown below, but they can be used to form styrene / acrylic resin segments used in the present invention. These are not limited to those shown below.

  First, specific examples of the styrene monomer include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4- Examples thereof include dimethyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, and pn-dodecyl styrene. These styrene monomers can be used alone or in combination of two or more.

  Specific examples of the (meth) acrylic acid ester monomer include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate. Acrylate monomers such as stearyl acrylate, lauryl acrylate, and phenyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, Stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl meta Relate, methacrylic acid esters such as dimethyl aminoethyl methacrylate.

  In this specification, “(meth) acrylic acid ester monomer” is a general term for “acrylic acid ester monomer” and “methacrylic acid ester monomer”. “Methyl acrylate” is a general term for “methyl acrylate” and “methyl methacrylate”.

  These acrylic acid ester monomers or methacrylic acid ester monomers can be used alone or in combination of two or more. That is, a copolymer is formed using a styrene monomer and two or more acrylate monomers, and a copolymer is formed using a styrene monomer and two or more methacrylic ester monomers. Either a coalescence can be formed, or a copolymer can be formed by using a styrene monomer, an acrylate monomer, and a methacrylate ester monomer in combination.

  It is preferable that the content rate of the structural unit derived from the styrene monomer in an amorphous resin segment exists in the range of 40-90 mass% with respect to the whole quantity of an amorphous resin segment. Moreover, the content rate of the structural unit derived from the (meth) acrylic acid ester monomer in an amorphous resin segment may be in the range of 10-60 mass% with respect to the whole quantity of an amorphous resin segment. preferable. By making it within such a range, it becomes easy to control the plasticity of the hybrid resin.

  Further, the amorphous resin segment is preferably formed by addition polymerization of a compound for chemically bonding to the crystalline polyester resin segment in addition to the styrene monomer and the (meth) acrylate monomer. . Specifically, it is preferable to use a compound that is ester-bonded to a polyhydric alcohol-derived hydroxy group [—OH] or a polyvalent carboxylic acid-derived carboxy group [—COOH] contained in the crystalline polyester resin segment. Therefore, the amorphous resin segment can be addition-polymerized with respect to the styrene monomer and the (meth) acrylate monomer, and has a carboxy group [—COOH] or a hydroxy group [—OH]. It is preferable to further polymerize the compound.

  Examples of such compounds include compounds having a carboxy group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester; 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate And compounds having a hydroxy group, such as polyethylene glycol mono (meth) acrylate.

  It is preferable that the content rate of the structural unit derived from the said compound in an amorphous resin segment exists in the range of 0.5-20 mass% with respect to the whole quantity of an amorphous resin segment.

  The method for forming the styrene / acrylic resin segment is not particularly limited, and examples thereof include a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator. Specific examples of the oil-soluble polymerization initiator include the following azo or diazo polymerization initiators and peroxide polymerization initiators.

  As the azo or diazo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1) -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  As the peroxide polymerization initiator, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4 -Dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4,4-t-butylperoxycyclohexyl) propane, tris- (t-butylperoxy) triazine and the like.

  Moreover, when forming resin particles by an emulsion polymerization method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide, and the like.

  The content of the amorphous resin segment is preferably 20% by mass or less with respect to the total amount of the hybrid resin. Thereby, the effect that a more uniform crystalline polyester resin domain can be formed while maintaining sufficient crystallinity is obtained.

(Method for producing hybrid resin)
The method for producing the hybrid resin is not particularly limited as long as it can form a polymer having a structure in which the crystalline polyester resin segment and the amorphous resin segment are chemically bonded. Specific examples of the method for producing the hybrid resin include the following methods.

  (1) A method of producing a hybrid resin by polymerizing an amorphous resin segment in advance and performing a polymerization reaction to form a crystalline polyester resin segment in the presence of the amorphous resin segment.

  In this method, first, a monomer (preferably a vinyl monomer such as a styrene monomer and a (meth) acrylic acid ester monomer) constituting the above-described amorphous resin segment is subjected to an addition reaction to form an amorphous material. A conductive resin segment is formed. Next, in the presence of the amorphous resin segment, a polyvalent carboxylic acid and a polyhydric alcohol are polymerized to form a crystalline polyester resin segment. At this time, a polyhydric carboxylic acid and a polyhydric alcohol are subjected to a condensation reaction, and a polycarboxylic acid or a polyhydric alcohol is added to the amorphous resin segment to form a hybrid resin.

  In this method, it is preferable to incorporate a site where these segments can react with each other in the crystalline polyester resin segment or the amorphous resin segment.

  Specifically, when the amorphous resin segment is formed, in addition to the monomer constituting the amorphous resin segment, a carboxy group [—COOH] or a hydroxy group [—OH] remaining in the crystalline polyester resin segment A compound having a site capable of reacting with the non-crystalline resin segment and a site capable of reacting with the amorphous resin segment is also used. That is, when this compound reacts with the carboxy group [—COOH] or the hydroxy group [—OH] in the crystalline polyester resin segment, the crystalline polyester resin segment may be chemically bonded to the amorphous resin segment. it can.

  Alternatively, a compound having a site capable of reacting with a polyhydric alcohol or polyvalent carboxylic acid and capable of reacting with an amorphous resin segment may be used during the formation of the crystalline polyester resin segment.

  By using this method, a hybrid resin having a structure (graft structure) in which a crystalline polyester resin segment is chemically bonded to an amorphous resin segment can be formed.

  (2) A method of producing a hybrid resin by forming a crystalline polyester resin segment and an amorphous resin segment, respectively, and combining them.

  In this method, a polyvalent carboxylic acid and a polyhydric alcohol are first subjected to a condensation reaction to form a crystalline polyester resin segment. In addition to the reaction system for forming the crystalline polyester resin segment, the above-described monomer constituting the amorphous resin segment is subjected to addition polymerization to form the amorphous resin segment. At this time, it is preferable to incorporate a site where the crystalline polyester resin segment and the amorphous resin segment can react with each other. In addition, since the method of incorporating such a reactive site is as described above, detailed description thereof is omitted.

  Next, the crystalline polyester resin segment formed above and the amorphous resin segment are reacted to form a hybrid resin having a structure in which the crystalline polyester resin segment and the amorphous resin segment are chemically bonded. Can do.

  In addition, when the reactive site is not incorporated in the crystalline polyester resin segment and the amorphous resin segment, a system in which the crystalline polyester resin segment and the amorphous resin segment coexist is formed, You may employ | adopt the method of throwing in the compound which has a site | part which can be combined with a crystalline polyester resin segment and an amorphous resin segment. Then, a hybrid resin having a structure in which the crystalline polyester resin segment and the amorphous resin segment are chemically bonded can be formed via the compound.

  (3) A method for producing a hybrid resin by forming a crystalline polyester resin segment in advance and performing a polymerization reaction to form an amorphous resin segment in the presence of the crystalline polyester resin segment.

  In this method, first, a polyvalent carboxylic acid and a polyhydric alcohol are subjected to a condensation reaction for polymerization to form a crystalline polyester resin segment. Next, in the presence of the crystalline polyester resin segment, a monomer constituting the amorphous resin segment is polymerized to form an amorphous resin segment. At this time, it is preferable to incorporate a site where these segments can react with each other in the crystalline polyester resin segment or the amorphous resin segment, as in the above (1). In addition, since the method of incorporating such a reactive site is as described above, detailed description thereof is omitted.

  By using the above method, a hybrid resin having a structure (graft structure) in which an amorphous resin segment is chemically bonded to a crystalline polyester resin segment can be formed.

  Among the methods (1) to (3), the method (1) facilitates the formation of a hybrid resin having a structure in which a crystalline polyester resin chain is grafted to an amorphous resin chain, and simplifies the production process. This is preferable because it is possible. In the method (1), since the amorphous resin segment is formed in advance and then the crystalline polyester resin segment is bonded, the orientation of the crystalline polyester resin segment tends to be uniform. Therefore, it is preferable because a hybrid resin suitable for the toner specified in the present invention can be reliably formed.

<Organic solvent (oil phase) 12>
The organic solvent used for the preparation of the PES solution (oil phase) 13 is preferably one having a low boiling point and low solubility in water from the viewpoint of easy removal after phase inversion emulsification, Specific examples include methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and the like. These can be used alone or in combination of two or more. The amount of the organic solvent used is usually in the range of 1 to 300 parts by mass, preferably in the range of 1 to 100 parts by mass, and more preferably in the range of 25 to 70 parts by mass with respect to 100 parts by mass of the polyester resin. .

(Preparation of PES solution (oil phase) 13)
The polyester resin (PES powder) 11 and the organic solvent (oil phase) 12 are mixed. This produces a solution (PES solution (oil phase) 13). As the mixing (stirring) conditions, from the viewpoint of the solubility of the resin, mixing is performed at a temperature (liquid temperature) of 25 to 80 ° C., preferably 28 to 75 ° C., for 10 to 120 minutes, preferably 20 to 90 minutes ( Stirring). The mixing and stirring device is not particularly limited and may be appropriately selected according to the production scale. That is, as a method of obtaining the PES solution (oil phase) 13, the organic solvent (oil phase) 12 is put in a container and heated to the above temperature (liquid temperature). There is a method in which the polyester resin (PES powder) 11 is added and mixed, and the polyester resin (PES powder) 11 is dissolved in the organic solvent (oil phase) 12 and uniformly mixed while stirring with a stirrer. preferable. However, after the polyester resin (PES powder) 11 and the organic solvent (oil phase) 12 are put in a container in advance, the polyester resin (PES powder) 11 is organically heated and stirred at the above temperature (liquid temperature). There is no particular limitation such that the solvent (oil phase) 12 may be dissolved and mixed uniformly.

≪Process 2≫
Step 2 is a step (first neutralization step) in which the solution obtained in step 1 is mixed with an amount of neutralizing agent (1) having a liquid viscosity in the range of 5 to 500 mPa · s. In this step 2, as shown in FIG. 1, the PES solution (oil phase) 13 obtained in step 1 is mixed with a neutralizing agent (1) 14 in an amount such that the liquid viscosity is in the range of 5 to 500 mPa · s. (Step 2). Thereby, the neutralization liquid (cophase) 15 is produced. Preferably, a surfactant (aqueous solution) is added to and mixed with a solution (oil phase) 13 in which a polyester resin is dissolved in an organic solvent, and a solution (emulsion) in which water droplets are dispersed in the oil phase (W / O). ). A predetermined amount of neutralizing agent (1) is added to the W / O solution (emulsion) to dissociate the polyester terminal group (COOH group), thereby lowering the interfacial tension between the oil phase and the water phase, It is preferable to form the neutralized liquid 15 in a state where the phase and the aqueous phase are mixed (cophase). However, a solution (emulsion) in a state where water droplets are dispersed in the oil phase (W / O) by adding a predetermined amount of the neutralizing agent (1) aqueous solution to the PES solution (oil phase) 13. Furthermore, by dissociating the polyester terminal group (COOH group), the interfacial tension between the oil phase and the aqueous phase is lowered, and the neutralized solution 15 in a state where the oil phase and the aqueous phase are mixed (co-phase) is formed. May be.

<Surfactant (aqueous solution)>
In this step 2, before adding the neutralizing agent (1) as described above, the surfactant (aqueous solution) is added to and mixed with the solution (oil phase) 13 in which the polyester resin is dissolved in the organic solvent, and the oil is added. It is preferable to form a solution (emulsion) in which water droplets are dispersed in the phase (W / O).

  The surfactant is not particularly limited, and known surfactants can be used, and are selected from cationic surfactants, anionic surfactants, nonionic surfactants, and the like. Can be used. Two or more of these surfactants may be used in combination. The surfactant can also be used in a dispersion liquid such as a colorant or an offset preventing agent used in the production of the toner. The surfactant is used as an aqueous solution from the viewpoint of forming a solution (emulsion) in a state where water droplets are dispersed in the oil phase (W / O). Also in the examples, a surfactant polyoxyethylene (2) sodium lauryl ether sulfate (manufactured by Kao Corporation, product name: Emar E-27C) was diluted with water, and an aqueous solution having a surfactant concentration of 15% by mass. Is used.

  Specific examples of the cationic surfactant include dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, and hexadecyl trimethyl ammonium bromide.

  Specific examples of nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, norylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, styrylphenyl poly Examples thereof include oxyethylene ether and monodecanoyl sucrose.

  Specific examples of the anionic surfactant include aliphatic soaps such as sodium stearate and sodium laurate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, and polyoxyethylene (2) sodium lauryl ether sulfate (Kao Corporation). Manufactured, product name: Emar E-27C) and the like.

  These surfactants can be used alone or in combination of two or more as required.

  From the viewpoint of forming a solution in which water droplets are dispersed in the oil phase (W / O) with respect to 100 parts by mass of the polyester resin in the PES solution (oil phase) 13, Preferably it is 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass. It is below mass parts.

<Neutralizing agent (1) 14>
In the present invention, the neutralizing agent (1) for neutralizing the polyester resin can obtain a polyester latex dispersion having a small particle size and a narrow particle size distribution, and from the viewpoint of ease of handling, as an aqueous solution. It is preferable to be used. When the surfactant (aqueous solution) is used to form a W / O solution, the polyester end groups (COOH groups) are dissociated by adding a predetermined amount of the neutralizing agent (1) to the solution. Thus, the interfacial tension between the oil phase and the water phase can be lowered, and the neutralized solution 15 in a state where the oil phase and the water phase are mixed (common phase) can be formed. Moreover, when not adding surfactant with respect to the solution (oil phase) 13, the state by which the water droplet is disperse | distributing to the oil phase by adding predetermined amount neutralizing agent (1) aqueous solution ( W / O) solution and further dissociating the polyester end group (COOH group) to lower the interfacial tension between the oil phase and the water phase, and the oil phase and the water phase are mixed (co-phase). A neutralizing solution 15 can also be formed.

  When the neutralizing agent (1) is used as an aqueous solution, the pH at 25 ° C. is preferably 8.5 or more, more preferably 10.0 or more, even more preferably from the viewpoint of forming a stable cophase state as soon as possible. Is 11.0 or more, more preferably 12.0 or more. Thus, when using neutralizer (1) as aqueous solution, it is preferable that it is a strong alkaline compound (aqueous solution) whose pH in 25 degreeC is 11 or more. This is because the use of a strong alkaline neutralizer can form a stable co-phase state faster than when a weak alkaline neutralizer is used. The upper limit of pH is not particularly limited, but is preferably 13.5 or less, more preferably 13.0 or less, from the same viewpoint as described above.

  The neutralizing agent (1) may be an alkaline compound, and any of an inorganic alkaline compound and an organic alkaline compound may be used. Examples of the inorganic alkaline compound include alkali metal hydroxide salts such as potassium, sodium, and lithium, carbonates, bicarbonates, and ammonia. Specific examples of the alkali metal hydroxide salt, carbonate, and bicarbonate include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Examples of the organic alkaline compound include alkanolamines such as diethylethanolamine. Further, from the viewpoint of controlling the pH of the alkaline aqueous solution without reducing the neutralization reaction efficiency, a buffer solution obtained by mixing a strongly alkaline compound and a weakly acidic compound may be used. For example, potassium hydroxide And a buffer solution obtained by mixing phosphoric acid. Among these, from the viewpoint of forming a stable cophase state earlier, sodium hydroxide and potassium hydroxide, which are strongly alkaline compounds having a pH of 11 or higher at 25 ° C., are preferable, and sodium hydroxide is more preferable.

  When the neutralizing agent (1) is used as an aqueous solution, the concentration of the neutralizing agent (1) (alkaline compound) in the aqueous solution is preferably 1% by mass or more from the viewpoint of forming a stable cophase state earlier. Preferably it is 5 mass% or more, More preferably, it is 8 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 30 mass% or less.

  In this step 2, as described in the method of adjusting the amount of neutralizing agent to be added after the second time according to the physical properties of the co-phase (state in the system) by the first neutralization described above, the target particle size and It is preferable to set the liquid viscosity in a range lower than the viscosity value at that time. From this viewpoint, a surfactant (aqueous solution) was added to and mixed with the solution (oil phase solution) 13 obtained in step 1 or, if necessary, the solution (oil phase solution) 13. A neutralizing agent (1) is mixed with the W / O solution (emulsion) in such an amount that the liquid viscosity is in the range of 5 to 500 mPa · s. Here, when the liquid viscosity is less than 5 mPa · s, it is not preferable in terms of measurement stability. Moreover, when a liquid viscosity exceeds 500 mPa * s, it is unpreferable at the point of the mixing property of a solution. From this viewpoint, the liquid viscosity is preferably in the range of 10 to 400 mPa · s, more preferably in the range of 12 to 390 mPa · s.

  In addition, regarding the relationship between the liquid viscosity of the common phase and the input amount of the neutralizing agent, the above-described “neutralizing agent to be added after the second time depending on the physical properties of the common phase by the first neutralization (state in the system)” As described in “Method of adjusting the amount”, the viscosity (liquid viscosity) data of the common phase corresponding to the acid value and the degree of neutralization may be previously obtained for each resin type of the polyester resin. Moreover, even if the acid value of the polyester resin used for phase inversion emulsification is unknown for the next step, when the first neutralizing agent (fixed amount) is added, the polyester resin is determined from the viscosity value of the common phase. It is necessary to create a calculation formula that can calculate the acid value of.

(Measurement of liquid viscosity)
The liquid viscosity can be measured using an existing viscometer that can be measured even in a liquid. For example, using a shield-type vibration viscometer (for example, VM-200T2 manufactured by Seconic Co., Ltd.) that can measure even when the liquid is stirred and can output real-time data, in solution (reaction system) It can be measured by directly inserting (immersing) the detection terminal (probe) of the viscometer into The liquid viscosity measuring method described above can be applied to any solution such as the neutralized solution obtained in Step 2 and the neutralized solution obtained in Step 3.

(Preparation of neutralization solution (common phase) 15 (including preparation of W / O solution))
The above solution to the solution (PES solution (oil phase) 13) or to a W / O solution (emulsion) formed by adding and mixing a dispersion stabilizer (surfactant) if necessary. Neutralizing agent (1) 14 in an amount in the viscosity range is mixed. Thereby, the neutralization liquid (cophase) 15 is produced. The mixing (stirring) conditions after the addition of the surfactant (aqueous solution) are from 25 to 80 ° C., preferably from 28 to 75 ° C. (liquid temperature) for 10 to 180 minutes from the viewpoint of uniform dispersibility of the solution. Preferably, mixing (stirring) may be performed for 20 to 90 minutes. Moreover, as mixing (stirring) conditions after addition of the neutralizing agent (1) 14, stirring is performed in a temperature (liquid temperature) range of 25 to 80 ° C., preferably 28 to 75 ° C., from the viewpoint of uniform dispersibility of the solution. However, a predetermined amount of the neutralizing agent (1) 14 may be added. Any method of adding a predetermined amount of surfactant or neutralizing agent (1) 14 may be added all at once, or may be added in small portions over a certain period of time, or divided into several times. There is no particular limitation such as adding them. The mixing and stirring device for the surfactant is not particularly limited, and may be appropriately selected depending on the production scale. The reaction vessel and mixing and stirring apparatus used for neutralization are not particularly limited as long as they have sufficient resistance to the strong alkaline neutralizing agent (1), and may be appropriately selected according to the production scale. . That is, as a method of obtaining the neutralization liquid (cophase) 15, a surfactant (aqueous solution) is added to the PES solution (oil phase liquid) 13 heated to the above temperature (liquid temperature) as necessary. To form a W / O solution (emulsion). During this time, the temperature (liquid temperature) is heated (held). Next, the W / O solution is transferred to a reaction vessel, a predetermined amount of neutralizing agent (1) 14 is added thereto, and the polyester end groups (COOH groups) are dissociated while stirring with a stirrer. A method of reducing the interfacial tension between the oil phase and the aqueous phase and forming the neutralized solution 15 in a state where the oil phase and the aqueous phase are mixed (common phase) is preferable. However, a predetermined amount of the neutralizing agent (1) 14 was transferred to the reaction vessel after the dissolution liquid (oil phase liquid) 13 was transferred to the reaction vessel without using a surfactant, while heating and stirring to the above temperature (liquid temperature). Is added to form a solution in which water droplets are dispersed in the oil phase (W / O), and further, the polyester terminal groups (COOH groups) in the oil phase are dissociated, so that the oil phase and the water phase The neutralization liquid 15 in a state where the oil phase and the aqueous phase are mixed (co-phase) may be formed.

≪Process 3≫
Step 3 is a step of confirming the state of the solution obtained in Step 2, determining the addition amount of the neutralizing agent (2) in which the liquid viscosity is in the range of 50 to 1000 mPa · s, and charging and mixing at least once ( (Second neutralization step). In this process 3, as shown in FIG. 1, the state of the solution (neutralization liquid (cophase) 15) obtained in the process 2 is confirmed, and the liquid viscosity is in the range of 50 to 1000 mPa · s. (2) Decide the addition amount of 16 and mix at least once (step 3). Thereby, the neutralization liquid (common phase) 17 is produced. Here, as a method (means) for confirming the state of the solution (neutralization solution (co-phase) 15) obtained in step 2 (physical properties of the co-phase), the liquid viscosity, the stirring torque, etc. are adjusted within a predetermined range A method (means) for (control) is mentioned. In the present invention, the viscosity with low measurement sensitivity is easy to read the measured value difference. Therefore, the method of adjusting the liquid viscosity to a predetermined range is applied, but other methods (means) can also be used. In this embodiment, in order to confirm the state of the solution obtained in step 2, the liquid viscosity of the solution may be measured (monitored) and confirmed to be in the range of 5 to 500 mPa · s. Moreover, in order to determine the addition amount of the neutralizing agent (2) 16 in which the liquid viscosity is in the range of 50 to 1000 mPa · s, according to the above-described “physical properties (state in the system) of the co-phase by the first neutralization” The method of adjusting the amount of neutralizing agent to be added after the second time can be determined. That is, since the amount of the neutralizing agent when forming the neutralizing solution (cophase) 17 determines the final particle size, it depends on the acid value and the degree of neutralization for each resin type acquired in advance. The amount of neutralizing agent for the second and subsequent times is determined based on the viscosity data of the common phase and, further, a calculation formula that allows the resin acid value to be calculated backward from the viscosity value of the common phase so that the viscosity value becomes the target particle size. be able to. As a result, PES resin particles with small particle size variations (with a particle size range close to each production lot) are dispersed in water even if there are process variations (such as variations in the amount of water, resin or solvent contained in the system). A PES latex dispersion is obtained.

<Neutralizing agent (2) 16>
In the present invention, the neutralizing agent (2) for neutralizing the polyester resin can also obtain a polyester latex dispersion having a small particle size and a narrow particle size distribution, and from the viewpoint of ease of handling, an aqueous solution. It is preferable to be used as The state of the system (liquid viscosity) is checked by adding the neutralizing agent (1) for the first time, and the amount of the neutralizing agent (2) for the second and subsequent times is further determined (data and calculation formulas obtained in advance as described above) Based on the above, the amount of neutralizing agent (2) after the second time is determined so that the viscosity value becomes the target particle size), so that there is little particle size variation (every production lot) A PES latex dispersion in which PES resin particles (with a close particle size range) are dispersed in water is obtained. Furthermore, by dividing the neutralizing agent (2) into two or more degrees (see Examples 6, 7, 9, 14, 15, 17), a more uniform co-phase is formed, and the reproducibility of the particle size is high. Become.

  When the neutralizing agent (2) is used as an aqueous solution, the pH at 25 ° C. stably forms the same co-phase state as soon as possible (to obtain the same particle size every production lot) even if there is a process variation. From the viewpoint, it is preferably 8.5 or more, more preferably 10.0 or more, still more preferably 11.0 or more, and particularly preferably 12.0 or more. Thus, when using a neutralizing agent (2) as aqueous solution, what contains the strong alkaline compound whose pH in 25 degreeC is 11 or more (= aqueous solution of strong alkaline compound) is preferable. This is because the use of a strong alkaline neutralizing agent makes it possible to maintain the same co-phase state (to obtain the same particle size every production lot) with a weak alkaline neutralizing agent even if there is a process variation. This is because it can be formed more quickly and stably than when it is used. The upper limit of pH is not particularly limited, but is preferably 13.5 or less, more preferably 13.0 or less, from the same viewpoint as described above.

  As a neutralizing agent (2), what is necessary is just an alkaline compound, and the thing similar to a neutralizing agent (1) can be used. Similar to the neutralizer (1), the neutralizer (2) has the same co-phase state (to obtain the same particle size every production lot) even if there is a process variation. From the standpoint of forming the mixture more quickly and stably than when using, sodium hydroxide and potassium hydroxide, which are strongly alkaline compounds having a pH of 11 or more at 25 ° C., are preferred, and sodium hydroxide is more preferred.

  When the neutralizing agent (2) is used as an aqueous solution, the concentration of the neutralizing agent (2) (alkaline compound) in the aqueous solution is the same (in order to obtain the same particle size every production lot) even if there is a process variation. From the viewpoint of stably forming the co-phase state earlier than when a weak alkaline neutralizer is used, it is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more. In addition, it is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

  In this step 3, as described in the method of adjusting the amount of neutralizing agent to be added after the second time according to the physical properties of the common phase (state in the system) by the first neutralization described above, What is necessary is just to determine the viscosity value (liquid viscosity) when becoming. From this viewpoint, the liquid viscosity is in the range of 50 to 1000 mPa · s with respect to the solution (neutralization liquid (common phase) 17) obtained in step 2 (viscosity value when the target particle diameter is reached). The amount of neutralizing agent (2) to be added is added in one or more portions and mixed. Here, when the liquid viscosity is less than 50 mPa · s, it is not preferable in terms of measurement stability. Moreover, when a liquid viscosity exceeds 1000 mPa * s, it is unpreferable at the point of uniform mixing property. From this viewpoint, the liquid viscosity is preferably in the range of 70 to 950 mPa · s, more preferably in the range of 90 to 940 mPa · s.

  In addition, regarding the relationship between the liquid viscosity of the common phase and the amount of the neutralizing agent, the above-described “neutralization to be charged after the second time depending on the physical properties of the common phase by the first neutralization (state in the system)” As described in “Method of adjusting the amount of agent”, the viscosity (liquid viscosity) data of the cophase corresponding to the acid value and the degree of neutralization may be previously obtained for each resin type of the polyester resin. Moreover, even if the acid value of the polyester resin used for phase inversion emulsification is unknown for the next step, when the first neutralizing agent (fixed amount) is added, the polyester resin is determined from the viscosity value of the common phase. It is sufficient to create a formula that can calculate the acid value of.

(Degree of neutralization in the solution obtained in step 3)
The degree of neutralization in the solution obtained in step 3 (neutralization solution (common phase) 17) is preferably 25 to 100%, more preferably 30 to 70%. By adjusting (limiting) the degree of neutralization in the solution obtained in step 3 to the above range, PES resin particles having a desirable particle size range can be formed.

(Neutralization degree)
Degree of neutralization (%) is (substance amount of neutralized COOH group of polyester resin in solution (mol)) / (substance amount of COOH group in polyester resin before neutralization in solution (mol)) It can be calculated by a formula of × 100. The degree of neutralization in the solution (before desolubilization) in step 5 can be calculated in the same manner.

(Ratio of neutralizing agent (1) to the total amount of neutralizing agents (1) and (2))
The ratio of the neutralizing agent (1) to the total amount of the neutralizing agents (1) and (2) mixed in the steps 2 and 3 is preferably 55 to 95% by mass, and preferably 70 to 95% by mass. More preferred. By adjusting (restricting) the ratio of the neutralizing agent (1) to the total amount of the neutralizing agents (1) and (2) within the above range, a more stable common phase state can be formed and the particle size can be made uniform precisely. This is preferable because it is possible.

(Preparation of neutralization liquid (common phase) 17)
The neutralizing liquid (cophase) 15 is charged with a neutralizing agent (2) 16 having an amount in the range of the liquid viscosity. Thereby, the neutralization liquid (common phase) 17 is produced. Moreover, as mixing (stirring) conditions after addition of the neutralizing agent (2) 16, from the viewpoint of uniform mixing properties, stirring is performed in a temperature (liquid temperature) range of 25 to 85 ° C, preferably 28 to 75 ° C. A predetermined amount of the neutralizing agent (2) 16 may be added. The predetermined amount of the neutralizing agent (2) 16 may be added all at once, or may be added in small portions over a fixed time, or may be added in several portions. There is no particular limitation. Dividing into several times (dividing into two or more times) is excellent in that a more uniform co-phase is formed and the reproducibility of the particle size is improved. The reaction vessel and the mixing and stirring device used for neutralization are not particularly limited as long as they have sufficient resistance to the strong alkaline neutralizing agent (2), and may be appropriately selected according to the production scale. . That is, as a method of obtaining the neutralizing solution 17, the neutralizing solution 15 is added with an amount of the neutralizing agent (2) 16 which becomes a viscosity value when the target particle size is reached, and the polyester end groups are added while stirring. By dissociating, the interfacial tension between the oil phase and the aqueous phase is lowered, and there is a method for obtaining the neutralized solution 17 in the same co-phase state (in order to obtain the same particle diameter every production lot) even if there is a process variation. It is done.

≪Process 4≫
Step 4 is a step (phase inversion emulsification step) in which pure water is continuously added to the solution obtained in step 3 to form resin particles. In this step 4, as shown in FIG. 1, pure water 18 is continuously added to the solution obtained in step 3 (neutralization liquid (cophase) 17) to form resin particles (PES particles) ( Step 4). Thereby, phase inversion emulsification is completed, and PES particle dispersion liquid (aqueous phase) 19 can be obtained. Here, when pure water is continuously added dropwise to the solution obtained in Step 3 (neutralization solution (cophase) 17), the polyester end groups are dissociated and imparted with self-emulsifying properties. A dispersion (emulsion) in a state (O / W) in which PES particles are dispersed is formed. In that case, the electrostatic stability of the resin particles is determined according to the amount of dissociated end groups, and the particle size is determined. In the present invention, even if there is a process variation, the phase inversion emulsification (existing process operation) of the present step 4 is performed on the neutralized solution 17 in the same co-phase state even if there is a process variation. Resin particles (PES particles) having a small particle size (with a particle size range close to each production lot) can be obtained.

<Pure water 18>
In this step (phase inversion emulsification step) 4, pure water is used from the viewpoint of easy preparation of a dispersion (water phase) 19 of PES particles having a small particle size and a narrow particle size distribution. The pure water is not particularly limited, and conventionally known water can be used. For example, RO water (water through a reverse osmosis membrane) obtained by a method of removing impurities from water (clean water, etc.), deionized water (water from which ions have been removed by an ion exchange resin, etc.), distilled water (with a distiller) Distilled water) can be used.

  The temperature at which pure water is added (liquid temperature) is preferably equal to or higher than the glass transition temperature of the polyester resin from the viewpoint of obtaining a dispersion (aqueous phase) 19 of PES particles having a narrow particle size distribution. Below the boiling point of water is preferred. More preferably, from the viewpoint of stabilizing the interfacial tension in the solution, the temperature is in the range of ± 10 ° C. which is the same as the temperature (liquid temperature) of the solution obtained in Step 3 defined above. Specifically, it is preferably 50 ° C or higher, more preferably 60 ° C or higher, and preferably 98 ° C or lower, more preferably 80 ° C or lower.

  From the viewpoint of obtaining a dispersion (aqueous phase) 19 of PES particles having a narrow particle size distribution, the addition speed when continuously adding pure water is obtained in Step 3 until phase inversion emulsification is completed (terminated). Preferably, it is 0.1 parts by weight / minute or more, more preferably 1 part by weight / minute or more, and further preferably 3 parts by weight / minute or more with respect to 100 parts by weight of the resin constituting the resin particles in the solution 17. In addition, it is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, further preferably 15 parts by weight or less, and still more preferably 8 parts by weight or less. That is, pure water can be continuously added by the operation of adding pure water at the above addition rate. In addition, there is no restriction | limiting in the addition speed | rate of the pure water after completion | finish of phase inversion emulsification (It is preferable to finish addition of the pure water after completion | finish of phase inversion emulsification as quickly as possible). Completion of phase inversion emulsification can be confirmed by SEM images.

  The amount of pure water used is 100 parts by mass of the resin constituting the resin particles in the solution 17 obtained in step 3 from the viewpoint of improving the storage stability of latex and the production efficiency of the PES particle dispersion (aqueous phase) 19. Is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 150 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 500 parts by mass. It is below mass parts.

(Preparation of PES particle dispersion (aqueous phase) 19)
Pure water 18 is continuously added to the neutralization liquid (common phase) 17 within the range of the temperature (liquid temperature) and the amount used, specifically, at the addition rate, and mixed. Thus, an emulsified PES particle dispersion (aqueous phase) 19 (emulsion) is prepared. Moreover, as mixing (stirring) conditions during continuous addition of pure water 18, from the viewpoint of stability of interfacial tension in the solution, the solution obtained in Step 3 on the side where pure water 18 is added is 25 to 85. A predetermined amount of pure water 18 may be continuously added while stirring while maintaining the temperature (liquid temperature) in the range of ° C, preferably 28 to 75 ° C. The reaction vessel used for phase inversion emulsification is not particularly limited, but the reaction vessel used in Step 2 to Step 4 is preferably used as it is. The emulsification and dispersion can be performed using mechanical energy, and the disperser (mixing and stirring device) for performing emulsification and dispersion is not particularly limited. Examples include a shearing disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. Specifically, for example, a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) can be used.

  The dispersion diameter of the oil droplets in the emulsion (PES particle dispersion (water phase) 19) is preferably in the range of 60 to 1000 nm, more preferably in the range of 80 to 500 nm.

  The dispersion diameter of the oil droplets is determined by a particle size distribution measuring device (for example, Nanotrack Wave (manufactured by Microtrack Bell)) or a laser diffraction / scattering type particle size distribution measuring device (for example, LA-750, LA-960 (both Co., Ltd.). Volume average particle diameter measured using HORIBA, Ltd.).

≪Process 5≫
Step 5 is a step of removing an organic solvent from the resin particle dispersion obtained in Step 4 (desolubilization step). In this process 5, as shown in FIG. 1, the organic solvent 12 is dissolved from the resin particle dispersion (PES particle dispersion (aqueous phase) 19) obtained in the process 4 (step 5). As a result, demelting is completed, and a PES particle dispersion (aqueous phase) 22 can be obtained. In the present invention, by removing the obtained resin particle dispersion (PES particle dispersion (aqueous phase) 19), there is little particle size variation even if there are process variations (particle size range close to each production lot). The latex dispersion liquid in which the resin particles (PES particles) are dispersed in water can be formed.

  Furthermore, it is preferable to add the neutralizing agent (3) in an amount such that the degree of neutralization in the solution before desorption is 3 to 25% before desolvating the organic solvent in this step 5. This is because by introducing the neutralizing agent (3) before demelting, the electrostatic stability of the resin particle surface can be improved, and the long-term storage property of the latex dispersion is improved. That is, in this step 5, as shown in FIG. 1, before the organic solvent 12 is dissolved from the resin particle dispersion (PES particle dispersion (aqueous phase) 19) obtained in the step 4, before the dissolution. The amount of neutralizing agent (3) 20 in which the degree of neutralization in the solution (and after the addition of neutralizing agent (3)) (PES particle dispersion (aqueous phase) 21) is 3 to 25% is charged. preferable. Thereby, the process of an emulsion liquid is completed and the PES particle dispersion liquid (aqueous phase) 21 can be obtained. Here, completion of the processing of the emulsion can be confirmed by SEM image or particle size distribution measurement. When the neutralizing agent (3) 20 is added, “the organic solvent is removed from the resin particle dispersion (reference numeral 19) obtained in step 4” means “the resin particle dispersion obtained in step 4”. The organic solvent is de-solubilized from the resin particle dispersion (symbol 21) obtained by further neutralizing the liquid (symbol 19) to the range of the above neutralization degree.

<Neutralizing agent (3) 20>
In the present invention, the neutralizing agent (3) for completing the treatment of the emulsion is preferably used as an aqueous solution from the viewpoint of uniform mixing properties and ease of handling. By introducing the neutralizing agent (3), the electrostatic stability of the surface of the resin particles can be increased, and the long-term storage property of the latex dispersion can be improved (improved).

  When the neutralizing agent (3) is used as an aqueous solution, the pH at 25 ° C. is preferably 8.5 or more from the viewpoint of quickly and stably neutralizing action and increasing the electrostatic stability of the resin particle surface. Preferably it is 10.0 or more, More preferably, it is 11.0 or more, Most preferably, it is 12.0 or more. Thus, when using neutralizer (3) as aqueous solution, what contains the strong alkaline compound whose pH in 25 degreeC is 11 or more (= aqueous solution of strong alkaline compound) is preferable. This is because the use of a strongly alkaline neutralizing agent can quickly and stably improve the neutralizing action and the electrostatic stability of the resin particle surface. The upper limit of pH is not particularly limited, but is preferably 13.5 or less, more preferably 13.0 or less, from the same viewpoint as described above.

  As a neutralizing agent (3), what is necessary is just an alkaline compound, and the thing similar to a neutralizing agent (1) can be used. In the neutralizing agent (3), from the viewpoint of quick and stable neutralizing action and electrostatic stability on the surface of the resin particles, sodium hydroxide or hydroxide which is a strongly alkaline compound having a pH of 11 or more at 25 ° C. Potassium is preferred, and sodium hydroxide is more preferred.

  When the neutralizing agent (3) is used as an aqueous solution, the concentration of the neutralizing agent (3) (alkaline compound) in the aqueous solution is quick and stable from the viewpoint of increasing the neutralizing action and electrostatic stability of the resin particle surface. , Preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less. It is.

  In this step 5, from the viewpoint of increasing the electrostatic stability on the surface of the resin particles, the resin particle dispersion (PES particle dispersion (aqueous phase) 19) obtained in step 4 is used before and after desorption. The neutralizing agent (3) 20 is added in such an amount that the degree of neutralization in the solution (PES particle dispersion (aqueous phase) 21) after the addition of the compatibilizer (3) is 3 to 25%. Here, if the degree of neutralization is 3% or more, it is excellent in terms of storage stability due to electrostatic stability. If the said neutralization degree is 25% or more, it is excellent at the point of the storage stability by ionic strength fall. From this viewpoint, the neutralization degree is preferably in the range of 5 to 20%.

(Preparation of PES particle dispersion (aqueous phase) 21)
A neutralizing agent (3) 20 having an amount in the range of the neutralization degree is added to and mixed with the PES particle dispersion (aqueous phase) 19. In this way, a PES particle dispersion (aqueous phase) 21 is prepared. The mixing (stirring) conditions for the neutralizing agent (3) 20 are from 25 to 85 ° C., preferably from 28 to 75 ° C. in the temperature (liquid temperature) range from the viewpoint of uniform mixing, while stirring. A fixed amount of neutralizing agent (3) 20 may be added. The predetermined amount of the neutralizing agent (3) 20 may be added all at once, or may be added in small portions over a fixed time, or may be added in several portions. There is no particular limitation. The reaction vessel and the mixing and stirring device used for neutralization are not particularly limited, and the reaction vessel used in Step 2 to Step 4 is preferably used as it is.

(Preparation of PES particle dispersion (aqueous phase) 22)
The organic solvent 12 is dissolved from the PES particle dispersion (aqueous phase) 19 or the PES particle dispersion (aqueous phase) 21. In this way, a PES particle dispersion (aqueous phase) 22 is prepared. There are no particular limitations on the desolubilization method, and examples include a method of removing by distillation (desolubilization) under reduced pressure, a method of spraying in a mist state and drying. From the viewpoint of particle stability and efficiency, a method of removing by distillation (desolubilization) under reduced pressure is preferred. In such a method of removing by distillation (desolubilization) under reduced pressure, the organic solvent can be removed by distillation (desolution) by stirring for 0.5 to 6 hours under reduced pressure of 10 to 95 kPa, preferably 13 to 80 kPa. it can. The decompression (vacuum) apparatus used for decompression is not particularly limited, and may be appropriately selected according to the production scale. However, the present invention is not limited to the above desorption method. The organic solvent distilled off (desolubilized) may be recovered and reused from the viewpoint of reducing the environmental load.

(Solid content concentration of PES particle dispersion (aqueous phase) 22)
The solid content concentration of the polyester latex dispersion (PES particle dispersion (aqueous phase) 22) obtained in this step 5 improves the productivity of the soot and improves the dispersion stability of the resin particles (PES particles). From the viewpoint of making it preferable, it is preferably 7% by mass or more, more preferably 10% by mass or more, still more preferably 13% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30%. It is below mass%. In addition, solid content is the total amount of non-volatile components, such as resin and surfactant.

(Volume average particle diameter of resin particles (PES particles) in PES particle dispersion (water phase) 22)
The volume average particle size of the resin particles (PES particles) in the polyester latex dispersion (PES particle dispersion (aqueous phase) 22) obtained in this step 5 is to sharpen the particle size distribution of From the viewpoint of improving dot reproducibility, charging stability, etc., it is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm. It is as follows. Here, the volume average particle size is determined by a particle size distribution measuring device such as a particle size distribution measuring device (for example, Nanotrack Wave (manufactured by Microtrack Bell)) or a laser diffraction particle size distribution measuring device (for example, laser diffraction / scattering). It can be measured using a particle size distribution analyzer LA-750, LA-960 (manufactured by Horiba, Ltd.).

  The polyester latex dispersion liquid of the present invention can be produced by the steps 1 to 5 described above. Next, a toner manufacturing method using this will be described.

<< Method for producing toner for developing electrostatic image >>
The method for producing a toner for developing an electrostatic charge image (also simply referred to as “toner”) of the present invention comprises producing a polyester latex dispersion by the production method described above, and preparing a toner forming solution containing the obtained polyester latex dispersion. It is characterized in that at least the resin particles contained in the latex dispersion are agglomerated and fused. Here, the polyester latex dispersion liquid obtained above is an aqueous dispersion liquid in which PES particles (hereinafter also referred to as “binder resin fine particles (1)”), which is one kind of binder resin, are dispersed. . Examples of the toner forming solution include binder resins other than PES particles, for example, acrylic resins such as styrene resins and alkyl acrylates and alkyl methacrylates, styrene / acrylic resins, silicone resins, olefin resins, and amide resins. And an aqueous dispersion in which resin particles such as epoxy resin (hereinafter also referred to as “binder resin fine particles (2)”) are dispersed; fine particles of colorant (hereinafter also referred to as “colorant fine particles”) are dispersed. An aqueous dispersion obtained by dispersing fine particles of a release agent (hereinafter also referred to as “release agent fine particles”) or the like may be mixed. That is, in the toner production method of the present invention, the binder resin fine particles (2) can be added to the polyester latex dispersion obtained above (aqueous dispersion in which the binder resin fine particles (1) are dispersed) as necessary. A toner-forming solution is prepared by mixing an aqueous dispersion in which colorant fine particles are dispersed, an aqueous dispersion in which fine colorant particles are dispersed, an aqueous dispersion in which release agent fine particles are dispersed, and the like. The toner particles are formed by agglomerating and fusing the binder resin fine particles (1) (further, the binder resin fine particles (2), the colorant fine particles, the release agent fine particles, etc.) contained in the solution. It is a manufacturing method.

An example of a toner production method (an example in which an amorphous resin (binding resin fine particle (2) forming resin) and a crystalline polyester resin (binding resin fine particle (1) forming resin) are used as a binding resin). Specifically,
(A) forming a precursor (I) (core particle) of the binder resin fine particles (2);
(B) forming a precursor (II) of the binder resin fine particles (2) (intermediate layer covering the core particle surface; intermediate layer-coated particles);
(C) Binder resin fine particles (2) (core particles / intermediate layer / by formation of precursor (III) of binder resin fine particles (2) (outermost layer covering intermediate layer coated particle surface; outermost layer coated particles) A step of forming the outermost three-layer particles),
(D) a step of preparing an aqueous dispersion in which fine particles (binder resin fine particles (1)) of a crystalline polyester resin are dispersed as the polyester latex dispersion obtained above,
(E) a step of preparing an aqueous dispersion in which colorant fine particles are dispersed in an aqueous medium;
(F) a step of forming toner particles;
(G) a step of cooling the dispersion of toner particles;
(H) separating the toner particles from the aqueous medium and removing the surfactant from the toner particles;
(I) drying the washed toner particles;
If necessary, (j) a step of adding an external additive to the dried toner particles can be added.

  Here, the “aqueous dispersion” is a dispersion in which a dispersion (fine particles) is dispersed in an aqueous medium, and the aqueous medium is one in which a main component (50% by mass or more) is water. .

  Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, are particularly preferable.

(A) Binder resin fine particle (2) precursor (I) (core particle) forming step (first polymerization)
In this step, the precursor (I) (core particle) of the binder resin fine particles (2) is formed by emulsion polymerization according to a conventional method.

  Specifically, the polymerization initiator is added to the surfactant solution and heated, and the monomer solution for forming the core particles of the binder resin fine particles (2) is dropped and reacted while stirring.

  The reaction temperature is preferably in the range of 70 to 90 ° C, for example.

  The average particle diameter of the precursor (I) (core particle) of the binder resin fine particles (2) is preferably in the range of 50 to 150 nm in terms of volume-based median diameter. The volume-based median diameter of the precursor (I) (core particle) of the binder resin fine particles (2) is a value measured using “UPA-150” (manufactured by Microtrack).

(B) Step of forming precursor (II) of binder resin fine particles (2) (intermediate layer covering core particle surface; intermediate layer coated particles) (second polymerization)
In this step, the binder resin fine particles (2) containing a polymerization initiator and a release agent in a dispersion of the precursor (I) (core particles) of the binder resin fine particles (2) formed by the first polymerization. The intermediate layer-coated particles are formed by adding the polymerizable monomer for forming the intermediate layer to form the precursor (II) (intermediate layer) of the binder resin fine particles (2).

  Specifically, a binder resin fine particle (2) in which a surfactant solution is added to a dispersion of the precursor (I) (core particle) of the binder resin fine particles (2) and a release agent are dissolved. The intermediate layer forming polymerizable monomer is heated, mixed and dispersed by a mechanical disperser, added with a polymerization initiator, and polymerized by stirring while heating.

  Moreover, the amount of the dispersion liquid in which the precursor (I) (core particle) of the binder resin fine particles (2) is dispersed is in the range of 5 to 50 parts by mass in the total solvent for performing the second polymerization. It is preferable in that both elasticity and low temperature fixability can be maintained.

  The reaction temperature is preferably in the range of, for example, 70 to 95 ° C.

(C) Binder resin fine particles (2) (core particle / intermediate layer / outermost layer 3 layers) by forming precursor (III) of binder resin fine particles (2) (outermost layer covering the surface of the intermediate layer coated particles) Structure particle) formation step (third polymerization)
In this step, a binder resin fine particle (2) precursor (II) (intermediate layer coated particle) dispersion formed by the second polymerization is further added to the outermost layer forming polymerization of the binder resin fine particles (2). The binder resin fine particles (2) (core particle / intermediate layer / outermost layer, three layers) are formed by adding a functional monomer to form the precursor (III) (outermost layer) of the binder resin fine particles (2). Structure particles).

  Specifically, a polymerization initiator is added to the dispersion of the heated binder resin fine particle (2) precursor (II), and the polymerizable monomer for forming the binder resin fine particles (2) is added while stirring. Drop and polymerize.

  The reaction temperature is preferably in the range of, for example, 70 to 95 ° C.

<Binder Resin Used for Binder Resin Fine Particles (2)>
The binder resin is preferably a thermoplastic resin, and can be used without particular limitation as long as it is other than a polyester resin among those generally used as a binder resin constituting a toner. Specific examples include styrene resins, acrylic resins such as alkyl acrylates and alkyl methacrylates, styrene / acrylic resins, silicone resins, olefin resins, amide resins, and epoxy resins. These resins can be used alone or in combination of two or more.

  The binder resin (amorphous resin) of the binder resin fine particles (2) includes those used for the binder resin fine particles (1) (crystalline polyester resin) from the viewpoint of achieving both cost and thermal characteristics. It is preferably 50 to 95% by mass, more preferably 55 to 92% by mass, particularly preferably 60 to 89% by mass, and 65 to 87% by mass with respect to the entire binder resin. Most preferred.

  The binder resin particularly preferably contains a styrene / acrylic resin obtained by polymerizing a styrene monomer and an acrylic monomer. Since the styrene / acrylic resin is a resin having a characteristic of high elasticity at a high temperature, the effect of improving the fixing separation property and the high temperature offset property can be obtained.

  The binder resin preferably contains 30% by mass or more of styrene / acrylic resin from the viewpoint of manifesting the above effects.

  The weight average molecular weight (Mw) of the styrene / acrylic resin is in the range of 25,000 to 60,000, and the number average molecular weight (Mn) is in the range of 8,000 to 15,000. This is preferable from the viewpoint of securing low temperature properties and glossiness stability.

  Examples of polymerizable monomers used in styrene / acrylic resins include aromatic vinyl monomers and (meth) acrylic acid ester monomers, and ethylenically unsaturated bonds capable of radical polymerization. Those having the following are preferred.

  Styrene monomers include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2,4-dimethylstyrene 3,4-dichlorostyrene and the like and derivatives thereof. These aromatic vinyl monomers can be used alone or in combination of two or more.

  Examples of acrylic monomers include acrylic acid ester monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and phenyl acrylate. As ester monomers, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, methacrylic acid Examples thereof include dimethylaminoethyl and diethylaminoethyl methacrylate. These (meth) acrylic acid ester monomers can be used alone or in combination of two or more. Among the above, it is preferable to use a styrene monomer in combination with at least one of an acrylate monomer or a methacrylic acid monomer.

  As the polymerizable monomer, a third vinyl monomer can also be used. Examples of the third vinyl monomer include acid monomers such as acrylic acid, methacrylic acid, maleic anhydride, and vinyl acetic acid, and acrylamide, methacrylamide, acrylonitrile, ethylene, propylene, butylene, vinyl chloride, and N-vinylpyrrolidone. And butadiene.

  As the polymerizable monomer, a polyfunctional vinyl monomer may be further used. Examples of the polyfunctional vinyl monomer include diacrylates such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol, and dimethacrylates and trimethacrylates of tertiary or higher alcohols such as divinylbenzene, pentaerythritol, and trimethylolpropane. Etc. The copolymerization ratio of the polyfunctional vinyl monomer to the entire polymerizable monomer is usually within the range of 0.001 to 5% by mass, preferably within the range of 0.003 to 2% by mass, more preferably 0. Within the range of 0.01 to 1% by mass. Although the gel component insoluble in tetrahydrofuran is generated by using the polyfunctional vinyl monomer, the proportion of the gel component in the whole polymer is usually 40% by mass or less, preferably 20% by mass or less.

  The binder resin is preferably prepared by an emulsion polymerization method according to the forming steps (a) to (c) described as an example of the toner production method. Emulsion polymerization can be obtained by dispersing and polymerizing a polymerizable monomer such as styrene or acrylate in an aqueous medium. In order to disperse the polymerizable monomer in the aqueous medium, it is preferable to use a surfactant. For the polymerization (for example, the first polymerization to the third polymerization in the forming steps (a) to (c) above), polymerization is performed. An initiator, a chain transfer agent, etc. can be used.

(Polymerization initiator)
The polymerization initiator used for the polymerization of the binder resin (the first polymerization to the third polymerization in the forming steps (a) to (c) above) is not particularly limited, and a known one is used. can do. Specifically, for example, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, peroxide Lauroyl, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid tert-hydroperoxide, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) palmitate; 2,2 '-Azobis (2 -Aminodipropane) hydrochloride, 2,2'-azobis- (2-aminodipropane) nitrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 4,4'- And azo compounds such as azobis-4-cyanovaleric acid and poly (tetraethylene glycol-2,2′-azobisisobutyrate). The addition amount of the polymerization initiator varies depending on the desired molecular weight and molecular weight distribution, but specifically, it is preferably added in the range of 0.1 to 5% by mass with respect to the polymerizable monomer.

(Chain transfer agent)
In the production of the binder resin (the first polymerization to the third polymerization in the forming steps (a) to (c) above), it is also preferable to add a chain transfer agent together with the polymerizable monomer. The molecular weight of the polymer can be controlled by adding a chain transfer agent. In the polymerization step of polymerizing the aromatic vinyl monomer and the (meth) acrylic acid ester monomer, the molecular weight of the styrene / acrylic polymerizable monomer is generally adjusted for the purpose of adjusting the molecular weight. The chain transfer agent used can be used. The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans and mercapto fatty acid esters.

  The addition amount of the chain transfer agent varies depending on the desired molecular weight and molecular weight distribution, but specifically, it is preferably added in the range of 0.1 to 5% by mass with respect to the polymerizable monomer.

(Surfactant)
When the binder resin is dispersed in an aqueous medium and polymerized by an emulsion polymerization method (the first polymerization to the third polymerization in the forming steps (a) to (c) above), in order to prevent aggregation of the dispersed droplets, Usually a dispersion stabilizer is added. As the dispersion stabilizer, a known surfactant can be used, and a dispersion stabilizer selected from a cationic surfactant, an anionic surfactant, a nonionic surfactant and the like can be used. Two or more of these surfactants may be used in combination. The dispersion stabilizer can also be used in a dispersion liquid such as a colorant and an offset preventing agent.

  Specific examples of the cationic surfactant include dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, and hexadecyl trimethyl ammonium bromide.

  Specific examples of nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, norylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, styrylphenyl poly Examples thereof include oxyethylene ether and monodecanoyl sucrose.

  Specific examples of anionic surfactants include aliphatic soaps such as sodium stearate and sodium laurate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, and polyoxyethylene (2) sodium lauryl ether sulfate. Can do. These surfactants can be used alone or in combination of two or more as required.

<Release agent>
The release agent may be contained in the toner particles. That is, in the production of the binder resin (the first polymerization to the third polymerization in the forming steps (a) to (c) above), it is also preferable to add a release agent together with the polymerizable monomer. However, it may be used as an aqueous dispersion in which release agent fine particles are dispersed, or may be mixed with an aqueous dispersion in which binder resin fine particles (1) are dispersed to prepare a toner forming solution. . By containing the release agent in the toner particles, it becomes difficult to be compatible with the crystalline polyester resin (one kind of binder resin) contained in the toner particles, and it is easy to ooze out during heat fixing. High fixing separation can be obtained.

  The content of the release agent is preferably 5 to 20% by mass with respect to the total amount of toner particles excluding the colorant. Thereby, it is possible to obtain an effect that fixing separation property can be improved while suppressing a decrease in heat resistance and durability due to the addition of a release agent.

  The average particle diameter of the release agent contained in the binder resin (or toner particles) is not particularly limited, but for example, it is preferably 3 μm or less in volume-based median diameter.

  As the releasing agent, various known waxes can be used. From the viewpoint of improving the low-temperature fixability and releasing property of the toner, a hydrocarbon wax or an ester wax is preferable.

  Specifically, for example, low molecular weight polyethylene wax, low molecular weight polypropylene wax, Fischer-Tropsch wax, microcrystalline wax, hydrocarbon waxes such as paraffin wax, carnauba wax, pentaerythritol behenate, behenyl behenate, And ester waxes such as behenyl citrate. These can be used alone or in combination of two or more.

  Of these waxes, it is particularly preferable to use microcrystalline wax. The microcrystalline wax is not stably crystallized inside the toner and tends to grow into a domain having a large aspect ratio, and at a normal temperature, the domain is difficult to be exposed on the surface of the toner particle. As a result, it is possible to obtain an effect of suppressing a decrease in durability due to heat resistance or photoconductor filming / carrier spent.

  Microcrystalline wax has a branched structure and is less likely to gather inside the toner due to steric hindrance, and is thus considered to grow easily into a domain having a large aspect ratio.

  Of these waxes, from the viewpoint of releasability during low-temperature fixing, it is preferable to use a wax having a low melting point, specifically, a melting point in the range of 40 to 90 ° C.

  Further, it is preferable to form an independent domain different from the domain of the crystalline polyester resin (binder resin) as the state of presence of the release agent in the toner particles. The release agent and the crystalline polyester resin (binder resin) form different independent domains, so that each function is easily exhibited.

  In the production method of the present invention, when toner particles are produced in a state where a wax (release agent) is coated with the binder resin, domains different from the crystalline polyester resin (binder resin) are likely to be formed. Since the crystalline polyester resin (binder resin) and the release agent are not compatible with each other and exist in the matrix as different independent domains, the functions of the crystalline polyester resin (binder resin) and the release agent can be achieved. Since the respective functions can be fully exhibited without being impaired, a toner having good low-temperature fixability, fixing separation property and offset property on rough paper can be obtained.

(D) Step of preparing an aqueous dispersion of crystalline polyester resin fine particles In this step, an aqueous dispersion of crystalline polyester resin fine particles using a crystalline polyester resin is prepared by the method for producing a polyester latex dispersion described above. Then, prepare an aqueous dispersion. In detail, it is as having demonstrated with the manufacturing method of the above-mentioned polyester latex dispersion liquid.

  The content of the crystalline polyester resin is preferably in the range of 5 to 20% by mass, particularly preferably 5 to 18% by mass, based on the total amount of toner particles excluding the colorant, and 6 to 15 Most preferably, it is mass%. Thereby, while obtaining the effect of improving the low-temperature fixability by improving the sharp melt property of the binder resin, it is possible to suppress a decrease in heat resistance due to the addition of the crystalline polyester resin.

(E) Preparation Step of Aqueous Dispersion of Colorant Fine Particles This step is a step that is performed as necessary when toner particles containing a colorant are desired, and the colorant is finely divided in an aqueous medium. In which an aqueous dispersion of fine colorant particles is prepared.

  The aqueous dispersion of colorant fine particles can be obtained by dispersing the colorant in an aqueous medium in which a surfactant is added to a critical micelle concentration (CMC) or higher.

  The colorant can be dispersed using mechanical energy, and the disperser to be used is not particularly limited. However, an ultrasonic disperser, a mechanical homogenizer, a manton gourin or a pressure homogenizer is preferably used. Examples thereof include medium dispersers such as a pressure disperser, a sand grinder, a Getzman mill, and a diamond fine mill.

  In the dispersed state, the colorant fine particles preferably have a volume-based median diameter in the range of 10 to 300 nm, more preferably in the range of 100 to 200 nm, and particularly preferably in the range of 100 to 150 nm. The volume-based median diameter of the colorant fine particles is a value measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.).

<Colorant>
As the colorant, various known pigments and dyes can be used.

  Examples of the carbon black that is one of the colorants include channel black, furnace black, acetylene black, thermal black, lamp black, and the like. Examples of black iron oxide include magnetite, hematite, and iron titanium trioxide. Can be mentioned.

  Examples of the dye include C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 and the like.

  Examples of the pigment include C.I. I. Pigment Red 5, 48: 1, 48: 3, 53: 1, 57: 1, 81: 4, 122, 139, 144, 149, 150, 166, 177, 178, 222, 238, 269, C.I. I. Pigment Orange 31 and 43, C.I. I. Pigment yellow 14, 17, 74, 93, 94, 138, 155, 156, 158, 180, 185, C.I. I. Pigment green 7, C.I. I. Pigment Blue 15: 3, 60, and the like.

  The colorant for obtaining the toner of each color by the toner production method of the present invention can be used singly or in combination of two or more for each color.

  The colorant used in the method for producing a toner of the present invention is obtained by dispersing fine colorant particles in the obtained toner particles so as to be preferably in the range of 1 to 10% by mass, more preferably in the range of 2 to 8% by mass. It is preferable to prepare a toner-forming solution containing the aqueous dispersion. When the content of the colorant is within the above range, the desired toner can be obtained with a desired coloring power, and the influence on the chargeability from the release of the colorant or adhesion to the carrier is minimized. Can do.

  In this step, an aqueous dispersion containing other additives than the colorant may be prepared. For example, when a toner particle containing a charge control agent is desired, an aqueous solution of the charge control agent containing the charge control agent in an aqueous medium may be prepared as necessary.

<Charge control agent>
Various known compounds can be used as the charge control agent. In the production method of the present invention, from the viewpoint of charge controllability and charge stability, the toner particles are preferably prepared so that the toner particles obtained by the production method of the present invention contain a charge control agent.

  The content of the charge control agent is preferably in the range of 0 to 5% by mass in the toner particles obtained by the production method of the present invention, and more preferably in the range of 0 to 0.5% by mass. In addition, it is preferable to prepare a toner forming solution containing an aqueous solution of a charge control agent.

(F) Toner particle forming step In this step, the crystalline polyester resin fine particles prepared in the step (d) are formed on the surface of the binder resin fine particles (2) formed by the third polymerization in the step (c). The colorant fine particles prepared in the step (e) are aggregated and further fused by heating to form toner particles.

  Specifically, a coagulant having a critical coagulation concentration or more is added to an aqueous dispersion in which the binder resin fine particles (2), the crystalline polyester resin fine particles, and the colorant fine particles are dispersed, and then aggregated by heating. , Fuse. This forms toner particles.

  The fusing temperature is preferably in the range of 70 to 95 ° C, for example.

(Flocculant)
The flocculant used in this step is not particularly limited, but those selected from metal salts such as alkali metal salts and alkaline earth metal salts are preferably used.

  Examples of the metal salt include monovalent metal salts such as sodium, potassium, and lithium; divalent metal salts such as calcium, magnesium, manganese, and copper; and trivalent metal salts such as iron and aluminum.

  Specific metal salts can include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, and the like. It is particularly preferable to use a divalent metal salt. These can be used alone or in combination of two or more.

  In addition to the toner particle forming step, it is also preferable to provide an aging step.

  In the aging step, the toner particles obtained in the toner particle forming step are aged by heat energy until a desired shape is obtained.

  Specifically, the aging treatment is performed by heating and stirring the system in which the toner particles are dispersed, thereby adjusting the shape of the toner particles by a heating temperature, a stirring speed, a heating time and the like until a desired circularity is obtained. Done.

(G) Cooling Step This step is a step of cooling the toner particle dispersion.

  As a condition for the cooling treatment, it is preferable to cool at a cooling rate within a range of 1 to 20 ° C./min. The specific method of the cooling treatment is not particularly limited, and examples include a method of cooling by introducing a refrigerant from the outside of the reaction vessel, a method of cooling by directly introducing cold water into the reaction system, and the like. it can.

(H) Filtration / Washing Step This step involves solid-liquid separation of the toner particles from the cooled dispersion of toner particles, and a toner cake obtained by solid-liquid separation (aggregating toner particles in a wet state in a cake form) This is a step of removing adhering substances such as a surfactant and an aggregating agent from the aggregate).

  The solid-liquid separation is not particularly limited, and a centrifugal separation method, a vacuum filtration method using Nutsche or the like, a filtration method using a filter press, or the like can be used. Further, in washing, it is preferable to wash with water until the electric conductivity of the filtrate reaches 10 μS / cm.

(I) Drying Step This step is a step of drying the washed toner cake, and can be carried out according to a drying step in a generally-known method for producing toner particles.

  Specifically, examples of the dryer used for drying the toner cake include a spray dryer, a vacuum freeze dryer, and a vacuum dryer, and a stationary shelf dryer, a mobile shelf dryer, a fluidized bed, and the like. It is preferable to use a dryer, a rotary dryer, a stirring dryer or the like.

  The moisture of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less. In addition, when the dried toner particles are aggregated by a weak interparticle attractive force, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.

(J) External additive addition step This step is a step that is performed as necessary when an external additive is added to the toner particles.

  The above toner particles can be used as toners as they are, but in order to improve fluidity, chargeability, cleaning properties, etc., external additives such as fluidizing agents and cleaning aids are added to the toner particles. You may use it in the state.

<External additive>
Various external additives may be used in combination.

  The total addition amount of these external additives is preferably in the range of 0.05 to 5 parts by mass, more preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner particles. It is said.

  As the external additive mixing device, a mechanical mixing device such as a Henschel mixer or a coffee mill can be used.

  In the toner production method of the present invention, a toner-forming solution may be prepared by further mixing an aqueous dispersion of amorphous polyester resin fine particles, which is one of the polyester latex dispersions obtained above. Good. By containing an amorphous polyester resin, it is preferable in that the obtained toner particles have good heat storage stability and can be fixed at low temperature by being compatible with the crystalline polyester resin.

[Toner for developing an electrostatic image obtained by the production method of the present invention]
The “electrostatic image developing toner” obtained by the production method of the present invention refers to an aggregate of toner particles. The toner particles obtained by the production method of the present invention are particles comprising a binder resin, a colorant and a release agent, and the binder resin is a polyester resin derived from the polyester latex dispersion obtained above. including. Further, as described above, the toner particles obtained by the production method of the present invention may further contain other components such as a charge control agent as necessary, so-called fluidizing agents, cleaning aids, etc. These external additives may be externally added.

<Glass transition temperature of toner>
The toner obtained by the production method of the present invention preferably has a glass transition temperature (Tg) in the range of 50 to 70 ° C, more preferably in the range of 55 to 65 ° C. When the glass transition temperature of the toner is in the above range, sufficient low-temperature fixing property and heat-resistant storage property can be reliably achieved. Further, when the glass transition temperature of the toner is in the above range, the heat resistance (thermal strength) of the toner is maintained, and as a result, sufficient heat storage stability and hot offset resistance can be reliably obtained. Conceivable.

<Melting point of toner>
The toner obtained by the production method of the present invention preferably has a melting point (Tm) in the range of 60 to 90 ° C, more preferably in the range of 65 to 80 ° C. When the melting point of the toner is in the above range, sufficient low-temperature fixing property and heat-resistant storage property can be surely achieved. In addition, by setting the melting point of the toner within the above range, it is considered that the heat resistance (thermal strength) of the toner is maintained well, and thereby sufficient heat storage stability can be secured. The glass transition temperature and melting point of the toner are measured in the same manner as the crystalline polyester resin.

<Toner particle size>
In the toner obtained by the production method of the present invention, the average particle diameter is preferably in the range of 3 to 8 μm, and more preferably in the range of 5 to 8 μm, for example, on a volume basis median diameter. This average particle size can be controlled by the concentration of the flocculant used in the production, the amount of organic solvent added, the fusing time, and / or the composition of the binder resin. When the volume-based median diameter is in the above range, a very small dot image of 1200 dpi level can be faithfully reproduced.

  The volume-based median diameter of the toner is measured and calculated using a measuring apparatus in which a computer system equipped with data processing software “Software V3.51” is connected to “Multisizer 3” (manufactured by Beckman Coulter). Value.

  Specifically, 0.02 g of a measurement sample (toner) was added to 20 mL of a surfactant solution (for example, a surfactant obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing toner particles). The mixture is allowed to acclimate to the solution, and then subjected to ultrasonic dispersion for 1 minute to prepare a toner dispersion. This beaker containing “ISOTONII” (manufactured by Beckman Coulter) in the sample stand Then, inject with a pipette until the displayed concentration of the measuring device is 8%. By using this concentration, a reproducible measurement value can be obtained.

  In the measurement apparatus, the measurement particle count is 25000, the aperture diameter is 100 μm, the frequency range is calculated by dividing the range of 2 to 60 μm, which is the measurement range, into 256, and the volume integrated fraction is 50 % Particle diameter is defined as the volume-based median diameter.

<Average circularity of toner>
In the toner obtained by the production method of the present invention, the average circularity of the individual toner particles constituting the toner is in the range of 0.930 to 1.000 from the viewpoint of stability of charging characteristics and low-temperature fixability. Is preferably within the range of 0.950 to 0.995. When the average circularity is within the above range, the individual toner particles are less likely to be crushed, the contamination of the frictional charge imparting member is suppressed, the toner chargeability is stabilized, and the image quality of the formed image is high. It will be a thing.

  The average circularity of the toner is a value measured using “FPIA-2100” (manufactured by Sysmex).

  Specifically, the measurement sample (toner) was blended with an aqueous solution containing a surfactant, dispersed by performing ultrasonic dispersion for 1 minute, and then subjected to measurement conditions HPF by “FPIA-2100” (manufactured by Sysmex). In the (high-magnification imaging) mode, imaging is performed in an appropriate density range of 3000 to 10,000 HPF detections, and the circularity is calculated for each toner particle according to the following equation (y). The average circularity of the toner is a value calculated by adding the circularity of each toner particle and dividing by the total number of toner particles. If the number of HPF detections is in the above range, reproducibility can be obtained.

<Developer>
The toner obtained by the production method of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.

  When the toner is used as a two-component developer, the carrier uses magnetic particles made of a conventionally known material such as a metal such as iron, ferrite, or magnetite, or an alloy of such a metal with a metal such as aluminum or lead. In particular, ferrite particles are preferred.

  Further, as the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a dispersion type carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.

  The average particle diameter of the carrier is preferably in the range of 20 to 100 μm, more preferably in the range of 25 to 80 μm in terms of volume-based median diameter.

  The volume-based median diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

≪Acid value of resin and mold release agent≫
(Reagent preparation)
A phenolphthalein solution was prepared by dissolving 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and adding ion-exchanged water to 100 mL. 7 g of JIS special grade potassium hydroxide was dissolved in 5 mL of ion-exchanged water, and ethyl alcohol (95% by volume) was added to make 1 liter. In order not to touch the carbon dioxide gas, it was placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to prepare a potassium hydroxide solution. The orientation was in accordance with the description of JIS K0070-1966.

(main exam)
2.0 g of the pulverized sample was precisely weighed in a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (volume ratio 2: 1) was added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution prepared as an indicator was added and titrated with the prepared potassium hydroxide solution. The end point of the titration was when the light red color of the indicator lasted for about 30 seconds.

(Blank test)
The same operation as in the above test was performed except that no sample was used (that is, only a mixed solution of toluene / ethanol (volume ratio 2: 1) was used).

(Calculation of acid value)
The acid value was calculated by substituting the titration results of this test and blank test into the following formula (1).

<Hybrid amorphous polyester resin [a] and its synthesis method>
(Preparation of hybrid amorphous polyester resin [a1-1], [a1-2], [a1-3])
The following addition polymerization resin (styrene / acrylic resin: StAc) segment raw material monomer and radical polymerization initiator containing both reactive monomers were placed in a dropping funnel.

-Styrene 80 mass parts-N-butyl acrylate 20 mass parts-Acrylic acid 10 mass parts-Polymerization initiator (di-t-butyl peroxide) 16 mass parts.

  In addition, the raw material monomer of the following polycondensation resin (non-crystalline polyester resin: APEs) segment is put into a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170 ° C. Dissolved.

-66.9 mass parts of terephthalic acid-47.4 mass parts of fumaric acid-285.7 mass parts of bisphenol A propylene oxide 2 mol addition products.

  Next, under stirring, the raw material monomer and radical polymerization initiator of the addition polymerization resin (styrene / acrylic resin: StAc) segment placed in the dropping funnel were dropped over 90 minutes, and after aging for 60 minutes, the pressure was reduced. The unreacted addition polymerization monomer was removed at (8 kPa).

Thereafter, 0.4 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, the temperature was raised to 235 ° C., and the reaction was performed at normal pressure (101.3 kPa) for 5 hours and further under reduced pressure (8 kPa) for 1 hour. went.

  Next, after cooling to 200 ° C., the reaction was performed under reduced pressure (20 kPa) until the desired acid value (AV [mg KOH / g-pes]) shown in Table 1 was reached. At this time, the reaction time under reduced pressure (20 kPa) was 7 hours. Subsequently, the solvent was removed to obtain a hybrid amorphous polyester resin [a1-1]. Similarly, the reaction time was changed as shown in Table 1 under reduced pressure (20 kPa) to obtain hybrid amorphous polyester resins [a1-2] and [a1-3] having different acid values shown in Table 1.

(Synthesis of Hybrid Amorphous Polyester Resin [a2-1] to [a4-2])
In the method for synthesizing the hybrid amorphous polyester resin [a1-1], the hybrid amorphous polyester resins [a2-1], [a3-1] and [a4-1] are synthesized according to the conditions shown in Table 1 below. Each went. Similarly, in the synthesis method of [a2-1], the reaction time was changed as shown in Table 1 under reduced pressure (20 kPa), and the hybrid amorphous polyester resin [a2-2] having different acid values shown in Table 1 was obtained. , [A2-3] were obtained. Further, in the synthesis method of [a3-1], the reaction time was changed as shown in Table 1 under reduced pressure (20 kPa) to obtain a hybrid amorphous polyester resin [a3-2] having different acid values shown in Table 1. It was. In the synthesis method [a4-1], the reaction time was changed as shown in Table 1 under reduced pressure (20 kPa) to obtain hybrid amorphous polyester resins [a4-2] having different acid values shown in Table 1. . In Table 1, monomer 1, monomer 2, monomer 3, polymerization initiator, acid monomer 1, acid monomer 2, acid monomer 3, alcohol monomer 1, alcohol monomer 2 are styrene, n-butyl acrylate, acrylic acid, di- t-Butyl peroxide, terephthalic acid, fumaric acid, succinic acid, bisphenol A propylene oxide 2 mol adduct, bisphenol A ethylene oxide 2 mol adduct.

<Preparation of aqueous dispersion of resin particle [A] containing hybrid amorphous polyester resin [a]>
(Preparation of aqueous dispersion of resin particles [A3] containing hybrid amorphous polyester resin [a1-3]) (Example 3)
(Process 1)
72.6 parts by mass of the hybrid amorphous polyester resin [a1-3] obtained by the above synthesis was dissolved in 72.6 parts by mass of methyl ethyl ketone at 66 ° C. for 30 minutes. This obtained the 1st step solution.

(Process 2)
Next, 44.8 parts by mass of 15% by mass of Emar E-27C (manufactured by Kao Corporation) is added and mixed as a surfactant to the solution obtained in Step 1, and this solution is stirred. While stirring, 1.91 parts by mass of a 25% by mass aqueous sodium hydroxide solution was added as a neutralizing agent (1).

  Here, the amount in which the liquid viscosity is in the range of 5 to 500 mPa · s by previously collecting the viscosity (liquid viscosity) data of the co-phase corresponding to the acid value and the degree of neutralization for each resin type of the polyester resin. The amount of neutralizing agent (1) added was determined. This obtained the neutralization liquid by the process 2.

(Process 3)
Measure the viscosity of the neutralized solution (dissolved solution) obtained in step 2 (viscosity is shown in Table 2), and consider the acid value (AV) of the resin estimated from the viscosity so that the target particle size is 120 nm. While stirring, 1.37 parts by mass of a 25% by mass aqueous sodium hydroxide solution was added as the neutralizing agent (2) -1. Thereby, the neutralization liquid by the process 3 was obtained.

  Here, the acid value (AV) of the resin estimated from the viscosity was estimated from the viscosity (liquid viscosity) data of the common phase corresponding to the acid value and the degree of neutralization for each resin type of the polyester resin obtained in advance. . Furthermore, the addition amount of the neutralizing agent (2) -1 in which the liquid viscosity is in the range of 50 to 1000 mPa · s (in other examples, the neutralizing agent (2) is divided into two or more times to obtain the neutralizing agent (2 ) -1, (2) -2, and in the case of using the neutralizing agent (2) -3, the total addition amount of the neutralizing agent (2) is the acid value of the resin (AV ) In consideration of AV (acid value), neutralization degree, particle size, and viscosity (the above-mentioned experimental data) so that the viscosity value at the target particle size (120 nm) is obtained. Relational expression obtained by performing the operations 1 to 3 specifically described as a method of adjusting the amount of the neutralizing agent to be added after the second time according to the physical properties (state in the system) of the first phase neutralization. Hereinafter the same).

(Process 4)
Subsequently, 210 parts by mass of pure water heated to 66 ° C. was added dropwise to the neutralized solution obtained in Step 3 over 70 minutes. During the dropping, the liquid in the container became white turbid, and after the entire amount was dropped, a uniformly emulsified state (a dispersion in which resin particles were formed) was obtained.

  As a result of measuring the particle size of the oil droplets of the emulsion (resin particle dispersion) obtained in step 4 with a particle size distribution analyzer “Nanotrack Wave (manufactured by Microtrack Bell)”, the volume average particle size was 128 nm. It was.

(Step 5) (Form using neutralizer (3))
Subsequently, 0.51 mass part of 25 mass% sodium hydroxide aqueous solution was added as a neutralizing agent (3), keeping the emulsion (resin particle dispersion liquid) obtained at the process 4 at 66 degreeC. Using a diaphragm type vacuum pump “V-700” (manufactured by BUCHI), stirring at 15 kPa (150 mbar) under reduced pressure for 3 hours distilled off methyl ethyl ketone, and resin particles having a solid content of 13.5% by mass An aqueous dispersion [A3] in which [a1-3] was dispersed was prepared.

  As a result of measurement with the particle size distribution analyzer, the volume average particle size of the resin fine particles [A3] was 124 nm.

(Preparation of aqueous dispersion of resin particles [A15] containing hybrid amorphous polyester resin [a3-2]) (Comparative Example 4)
(Step 1) (Form in which neutralizing agent is added before dissolution)
87.2 parts by mass of the hybrid amorphous polyester resin [a3-2] obtained by the above synthesis was mixed with 58.1 parts by mass of methyl ethyl ketone and 1.83 parts by mass of 25% by mass sodium hydroxide, and the mixture was mixed at 66 ° C for 30 minutes. Stir for minutes to dissolve. This obtained the 1st step solution.

(Process 2)
Next, 17.9 parts by mass of 15% by mass of Emar E-27C (manufactured by Kao Corporation) is added and mixed as a surfactant to the solution obtained in Step 1, and this solution is stirred. While stirring, 1.83 parts by mass of a 25% by mass aqueous sodium hydroxide solution was added as a neutralizing agent (1).

  Here, the total addition amount of the neutralizing agent before dissolution in step 1 and the neutralizing agent (1) in this step 2 is AV (acid), which is experimental data stored in advance so that the target particle size is 250 nm. Value), degree of neutralization, particle size and viscosity. Thereby, the neutralization liquid by the process 2 was obtained.

(Step 4) (Perform step 4 without performing step 3)
Subsequently, 210 parts by mass of pure water heated to 66 ° C. was added dropwise to the neutralized solution obtained in Step 2 over 70 minutes. During the dropping, the liquid in the container became white turbid, and after the entire amount was dropped, a uniformly emulsified state (a dispersion in which resin particles were formed) was obtained.

  As a result of measuring the particle size of the oil droplets of the emulsion (resin particle dispersion) obtained in step 4 with a particle size distribution analyzer “Nanotrack Wave (manufactured by Microtrack Bell)”, the volume average particle size was 221 nm. It was.

(Step 5) (Form not using neutralizer (3))
Next, while maintaining the temperature of the emulsion obtained in Step 4 at 66 ° C., a diaphragm vacuum pump “V-700” (manufactured by BUCHI) is used and stirred at 15 kPa (150 mbar) under reduced pressure for 3 hours. Then, methyl ethyl ketone was distilled off to prepare an aqueous dispersion [A15] in which resin particles [a3-2] having a solid content of 16.3% by mass were dispersed.

  As a result of measurement with the particle size distribution analyzer, the volume average particle size of the resin fine particles [A15] was 210 nm.

(Preparation of aqueous dispersions [A1] to [A2] and [A4] to [A14] of resin particles [a1-1] to [a4-2]) (Examples 1-2, 4-11, and Comparative Example 1) ~ 3)
In the method for preparing the above hybrid amorphous polyester resin fine particles [A3] and [A15] (preparation of aqueous dispersion of resin particles [A3] and [A15]), a hybrid amorphous polyester resin according to the conditions shown in Table 2 below Fine particles [A1] to [A2] and [A4] to [A14] were synthesized (preparation of aqueous dispersions of resin particles [A1] to [A2] and [A4] to [A14]). The strong alkali and the weak alkali in Table 2 are a 25 mass% sodium hydroxide aqueous solution and a 30 mass% ammonia aqueous solution, respectively. Moreover, it shows in Table 2 (Table 2-1-Table 2-3) about the liquid viscosity at the time of throwing in neutralizing agent (1) and (2).

<Hybrid Crystalline Polyester Resin [c] and Synthesis Method thereof>
(Synthesis of hybrid crystalline polyester resin [c2-1], [c2-2])
The following addition polymerization resin (styrene / acrylic resin: StAc) segment raw material monomer and radical polymerization initiator containing both reactive monomers were placed in a dropping funnel.

-Styrene 43 mass parts-N-butyl acrylate 15 mass parts-Acrylic acid 6 mass parts-Polymerization initiator (di-t-butyl peroxide) 7 mass parts.

  In addition, the following polycondensation resin (crystalline polyester resin: CPEs) segment raw material monomer is put into a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170 ° C. to dissolve. I let you.

-Sebacic acid 281 mass parts-1,12-dodecanediol 283 mass parts.

  Next, the raw material monomer and radical polymerization initiator of the addition polymerization resin (styrene / acrylic resin: StAc) segment placed in the dropping funnel under stirring were added dropwise over 90 minutes, and after aging for 60 minutes, under reduced pressure ( The unreacted addition polymerization monomer was removed at 8 kPa). The amount of monomer removed at this time was very small with respect to the raw material monomer ratio of the resin.

Thereafter, 0.8 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, the temperature was raised to 235 ° C., and the reaction was performed at normal pressure (101.3 kPa) for 5 hours and further under reduced pressure (8 kPa) for 1 hour. went.

  Next, after cooling to 200 ° C., the reaction was carried out under reduced pressure (20 kPa) until the desired acid value shown in Table 3 was reached, thereby obtaining a hybrid crystalline polyester resin [c2-1]. Similarly, the reaction time was changed as shown in Table 3 under reduced pressure (20 kPa) to obtain hybrid crystalline polyester resins [c2-2] having different acid values shown in Table 3.

(Synthesis of Hybrid Crystalline Polyester Resins [c1-1] to [c5-3])
In the method for synthesizing the hybrid crystalline polyester resin [c2-1], crystalline polyester resins [c1-1], [c3-1], [c4-1] and [c5-1] according to the conditions shown in Table 3 below. Were synthesized respectively. Similarly, in the synthesis method of [c1-1], the reaction time was changed as shown in Table 3 under reduced pressure (20 kPa), and the hybrid crystalline polyester resins [c1-2] having different acid values shown in Table 3 were changed. Obtained. Moreover, in the synthesis method of [c3-1], the reaction time was changed as shown in Table 3 under reduced pressure (20 kPa) to obtain hybrid crystalline polyester resins [c3-2] having different acid values shown in Table 3. . Furthermore, in the synthesis method of [c4-1], the reaction time was changed as shown in Table 3 under reduced pressure (20 kPa) to obtain hybrid crystalline polyester resins [c4-2] having different acid values shown in Table 3. . In the synthesis method of [c5-1], the reaction time was changed as shown in Table 3 under reduced pressure (20 kPa), and the hybrid crystalline polyester resins [c5-2], [c5-2], [ c5-3] were obtained. In Table 3, monomer 1, monomer 2, monomer 3, polymerization initiator, acid monomer 3, acid monomer 4, acid monomer 5, alcohol monomer 3, alcohol monomer 4, alcohol monomer 5, and alcohol monomer 6 are styrene, n- Butyl acrylate, acrylic acid, di-t-butyl peroxide, succinic acid, sebacic acid, hexadecanedioic acid, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, 1,14-tetradecane Diol.

<Preparation of aqueous dispersion of resin particles [C] containing hybrid crystalline polyester resin [c]>
(Preparation of aqueous dispersion of resin particles [C8] containing hybrid crystalline polyester resin [c4-2]) (Example 19)
(Process 1)
87.2 parts by mass of the crystalline polyester resin [c4-2] obtained by the above synthesis was dissolved in 58.1 parts by mass of methyl ethyl ketone at 66 ° C. for 30 minutes and dissolved. This obtained the 1st step solution.

(Process 2)
Next, 17.9 parts by mass of 15% by weight Emar E-27C (manufactured by Kao Corporation) is added to and mixed with the solution obtained in Step 1, and this solution is added to a reaction vessel having a stirrer. While stirring, 1.29 parts by mass of a 25% by mass aqueous sodium hydroxide solution was added.

  Here, by collecting the viscosity (liquid viscosity) data of the co-phase according to the acid value and the degree of neutralization for each resin type of the polyester resin in advance, the liquid viscosity is in the range of 5 to 500 mPa · s. The amount of neutralizing agent (1) added was determined. This obtained the neutralization liquid by the process 2. Thereby, the neutralization liquid by the process 2 was obtained.

(Process 3)
The viscosity of the neutralized solution (dissolved solution) obtained in step 2 is measured (viscosity is shown in Table 2), and the acid value (AV) of the resin estimated from the viscosity is taken into consideration so that the target particle size is 300 nm. While stirring, 0.87 part by mass of a 25% by mass aqueous sodium hydroxide solution was added as the neutralizing agent (2) -1. Thereby, the neutralization liquid by the process 3 was obtained.

  Here, the acid value (AV) of the resin estimated from the viscosity was estimated from co-phase viscosity (liquid viscosity) data corresponding to the acid value and the degree of neutralization of the polyester resin obtained in advance. Furthermore, the addition amount of the neutralizing agent (2) -1 in which the liquid viscosity is in the range of 50 to 1000 mPa · s (in other examples, the neutralizing agent (2) is divided into two or more times to obtain the neutralizing agent (2 ) -1, (2) -2, and in the case of using the neutralizing agent (2) -3, the total addition amount of the neutralizing agent (2) is the acid value of the resin (AV ) Is taken into consideration by the relational expression of AV (acid number), neutralization degree, particle size and viscosity, which are experimental data set in advance so that the viscosity value becomes the target particle size (300 nm). .

(Process 4)
Subsequently, 210 parts by mass of pure water heated to 66 ° C. was added dropwise to the neutralized solution obtained in Step 3 over 70 minutes. During the dropping, the liquid in the container became white turbid, and after the entire amount was dropped, a uniformly emulsified state (a dispersion in which resin particles were formed) was obtained.

  As a result of measuring the particle size of the oil droplets of the emulsion (resin particle dispersion) obtained in step 4 with a particle size distribution analyzer “Nanotrack Wave (manufactured by Microtrack Bell)”, the volume average particle size was 324 nm. It was.

(Step 5) (Form using neutralizer (3))
Subsequently, 0.51 mass part of 25 mass% sodium hydroxide aqueous solution was added, keeping the emulsion (resin particle dispersion liquid) obtained at the process 4 at 66 degreeC. Using a diaphragm type vacuum pump “V-700” (manufactured by BUCHI), the mixture is stirred at 15 kPa (150 mbar) under reduced pressure for 3 hours to distill off methyl ethyl ketone, and resin particles having a solid content of 15.4% by mass An aqueous dispersion [C8] in which [c4-2] was dispersed was prepared.

  As a result of measurement using the particle size distribution analyzer, the volume average particle size of the resin fine particles [c4-2] was 311 nm.

(Preparation of aqueous dispersions [C1] to [C7], [C9] to [C14] of resin particles [c1-1] to [c5-2]) (Examples 12 to 18, 20 to 22 and Comparative Example 5) ~ 7)
In the above method for preparing hybrid crystalline polyester resin fine particles [C8] (preparation of aqueous dispersion of resin particles [C8]), hybrid crystalline polyester resin fine particles [C1] to [C7], [C7], [C7], C9] to [C14] were synthesized (preparation of aqueous dispersions of resin particles [C1] to [C7] and [C9] to [C14]). The strong alkali and the weak alkali in Table 4 are a 25 mass% sodium hydroxide aqueous solution and a 30 mass% ammonia aqueous solution, respectively. Moreover, it shows in Table 4 (Table 4-1-Table 4-3) also about the liquid viscosity at the time of throwing in neutralizing agent (1) and (2).

≪Evaluation method≫
Using the produced dispersions A1 to A15 and C1 to C14, the volume average particle diameter of the resin particles was measured with Nanotrack Wave (manufactured by Microtrack Bell), and the following was evaluated.

<Particle size variation>
When the particle sizes of the dispersions using resins having different acid values synthesized with the same composition were compared, the particle size variation from the target particle size was evaluated in the following four ranks. The obtained results are shown in Tables 2 and 4 above.

(Evaluation criteria for particle size variation)
◎: Within ± 10 nm ○: Within ± 25 nm (excluding the range within ± 10 nm) Δ: Within ± 50 nm (excluding the range within ± 25 nm) ×: Within ± 50 nm The range is out of range.

<Repeatability>
When resin particles were produced twice or more under the same conditions using the same resin and the particle diameters were compared, the particle size variation was evaluated in the following four ranks. The obtained results are shown in Tables 2 and 4 above.

(Evaluation criteria for repeatability)
A: Reproduced within a range of ± 5 nm ○: Reproduced within a range of ± 10 nm (excluding a range of ± 5 nm) Δ: Reproduced within a range of ± 15 nm (excluding a range of ± 10 nm) ×: It varies in a range outside the range of ± 15 nm.

<Storage>
When comparing the particle size measured immediately after production with the particle size measured after storage for 1 month in a high-temperature and high-humidity environment at a temperature of 50 ° C. and a humidity of 85% RH, Rated by rank. The obtained results are shown in Tables 2 and 4 above.

(Storage criteria)
A: The range is within ± 10 nm. A: The range is within ± 25 nm (excluding the range within ± 10 nm). Δ: The range is within ± 50 nm (excluding the range within ± 25 nm).

  As is clear from the results shown in Tables 2 and 4, each of the dispersions A1 to A11 and C1 to C11 of Examples 1 to 22 is compared to each of the dispersions A12 to A15 and C12 to C14 of Comparative Examples 1 to 7. As a result, the particle size variation, the repeatability and the storage stability were all excellent (evaluation of ◯ or higher). In contrast, each of the dispersions A12 to A15 and C12 to C14 of Comparative Examples 1 to 7 was evaluated to be inferior in evaluation of particle size variation (x evaluation). From this, neutralization only once as in the case of phase inversion emulsification of existing polyester (however, even if neutralization was performed before dissolution in step 1 as in comparative example 4, the process was the same as in other comparative examples. If neutralization of 3 is not performed, a single phase is formed), but the physical properties of the common phase change according to variations in the system. The amount of neutralizing agent when forming this co-phase determines the final particle size, but there are always process variations (such as variations in the amount of water, resin and solvent contained in the system) at the production site. It was confirmed that even if the amount of the neutralizing agent was the same, the same co-phase state was not formed, and there was a problem that the particle size varied. Moreover, in each dispersion A12-A15 of Comparative Examples 1-7, C12-C14, it has confirmed that it was evaluation (x or (triangle | delta) evaluation) inferior also in evaluation of reproducibility.

[Styrene-acrylic resin particle dispersion (B1)]
(First polymerization)
A 5 L reaction vessel equipped with a stirrer, temperature sensor, cooling pipe and nitrogen introduction device was charged with 8 g of sodium dodecyl sulfate and 3 L of ion-exchanged water, and the internal temperature was 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. The temperature was raised to. After adding a solution prepared by dissolving 10 g of potassium persulfate in 200 g of ion-exchanged water, the liquid temperature was again set to 80 ° C., and a mixed solution of the following raw material monomers was added dropwise over 1 hour. Then, it superposed | polymerized by heating and stirring at 80 degreeC for 2 hours, and prepared the dispersion liquid of the styrene-acrylic resin particle.

・ Styrene (St) 480g
・ N-butyl acrylate (BA) 250g
-68 g of methacrylic acid (MAA).

(Second polymerization)
A solution of 7 g of polyoxyethylene (2) sodium dodecyl ether sulfate dissolved in 3 L of ion-exchanged water was charged into a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introducing device. After heating the solution to 98 ° C., 280 g of a dispersion of styrene-acrylic resin particles obtained by the first polymerization and a solution in which the following raw material monomers and a release agent are dissolved at 90 ° C. are added, and a circulation route is added. A dispersion liquid containing emulsified particles (oil droplets) was prepared by mixing and dispersing for 1 hour using a mechanical disperser CLEARMIX (manufactured by M Technique Co., Ltd.).

・ Styrene (St) 256g
・ N-butyl acrylate (BA) 115g
・ Methacrylic acid (MAA) 21g
N-octyl-3-mercaptopropionate 5 g
124 g of microcrystalline wax (release agent with a melting point of 73 ° C.)

  A polymerization initiator solution in which 6 g of potassium persulfate was dissolved in 200 mL of ion-exchanged water was added to the prepared dispersion, and the system was polymerized by heating and stirring at 84 ° C. for 1 hour. A dispersion of resin particles was prepared.

(Third polymerization)
After adding 400 mL of ion-exchanged water to the dispersion of styrene-acrylic resin particles obtained by the second polymerization and mixing well, a solution prepared by dissolving 11 g of potassium persulfate in 400 mL of ion-exchanged water was added, and the temperature was 82 ° C. Under the temperature conditions, a mixture of the following raw material monomers was added dropwise over 1 hour.

・ Styrene (St) 435g
・ N-butyl acrylate (BA) 157 g
・ Methacrylic acid (MAA) 41g
-13 g of n-octyl-3-mercaptopropionate.

  After completion of the dropwise addition, the mixture was heated and stirred for 2 hours, and then cooled to 28 ° C. to prepare a styrene-acrylic resin particle dispersion (B1).

  The volume-based median diameter of the styrene-acrylic resin particles in the dispersion (B1) was 220 nm, the glass transition temperature (Tg) was 55 ° C., and the weight average molecular weight (Mw) was 38000.

[Colorant fine particle dispersion (Bk)]
90 g of sodium dodecyl sulfate was dissolved in 1600 g of ion-exchanged water with stirring. While stirring the resulting solution, 420 g of Legal 330R (Cabot carbon black) was gradually added and dispersed using a stirrer CLEARMIX (M Technique Co., Ltd.). A dispersion (Bk) was prepared.

  It was 120 nm when the volume-based median diameter of the colorant fine particles in the colorant fine particle dispersion (Bk) was measured using an electrophoretic light scattering photometer ELS-800 (manufactured by Otsuka Electronics Co., Ltd.).

[Toner (1) and Developer (1)] (Example A1)
Into a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling tube, 147 parts by mass (in terms of solid content) of styrene-acrylic resin particle dispersion (B1) and 2000 parts by mass of ion-exchanged water were added and then 5 mol / L. Was added to adjust the pH to 10.

  Thereafter, 40 parts by mass of the colorant fine particle dispersion (Bk) (in terms of solid content) was added, and an aqueous solution in which 60 parts by mass of magnesium chloride was dissolved in 60 parts by mass of ion-exchanged water was stirred at 30 ° C. for 10 minutes. Added. The system was heated to 70 ° C. over 50 minutes, and 98 parts by mass (in terms of solid content) of a dispersion (C7) of crystalline polyester resin particles was added over 10 minutes, and then heated to 83 ° C. over 20 minutes. did. In this state, the particle size of the associated particles was measured with Coulter Multisizer 3 (manufactured by Beckman Coulter), and when the volume-based median diameter reached 6.0 μm, a dispersion of amorphous polyester resin particles ( A1) 98 parts by mass (in terms of solid content) was added over 60 minutes, and an aqueous solution in which 190 parts by mass of sodium chloride was dissolved in 760 parts by mass of ion-exchanged water was added to stop particle growth. The temperature of the toner was further increased, and the particles were fused by heating and stirring at 80 ° C., and the toner measured using a measuring device FPIA-2100 (manufactured by Sysmex) with an HPF detection count of 4000. When the average circularity reached 0.945, it was cooled to 30 ° C. at a cooling rate of 2.5 ° C./min.

  Thereafter, the solid-liquid separated, dehydrated toner cake is re-dispersed in ion-exchanged water, and the operation of solid-liquid separation is repeated three times, followed by washing at 40 ° C. for 24 hours to obtain black toner particles. Got.

  To 100 parts by mass of the obtained toner particles, 0.6 part by mass of hydrophobic silica (number average primary particle size: 12 nm, degree of hydrophobicity: 68) and hydrophobic titanium oxide (number average primary particle size = 20 nm, degree of hydrophobicity) : 63) 1.0 part by mass was added. Next, after mixing for 20 minutes at a rotating blade peripheral speed of 35 mm / sec and 32 ° C. with a Henschel mixer (manufactured by Nihon Coke Kogyo Co., Ltd.), an external additive treatment is performed to remove coarse particles using a 45 μm sieve. Thus, toner (1) was produced.

  A developer (1) was produced by adding and mixing a toner carrier (1) with a ferrite carrier having a volume average particle diameter of 60 μm coated with a silicone resin so that the toner concentration is 6% by mass.

[Toners (2) to (29) and developers (2) to (29)] (Examples A2 to A22 and Comparative Examples A1 to A7))
In the production of the toner (1) and the developer (1), each toner (2) is the same as the toner (1) except that the type of the dispersion of polyester resin particles is changed as shown in Table 5 below. ) To (29) and their developers (2) to (29).

  In Table 5, “APES dispersion” is an abbreviation for a dispersion of amorphous polyester resin particles. “CPES dispersion” is an abbreviation for dispersion of crystalline polyester resin particles.

[Evaluation]
Using the developers (1) to (29) of the produced toners (1) to (29), the low-temperature fixability and heat resistance of the toners (1) to (29) were evaluated as toner performance.

(Low temperature fixability)
In the copying machine bizhub PRO (registered trademark) C6501 (manufactured by Konica Minolta Co., Ltd.), the fixing device was modified so that the surface temperature of the fixing heat roller could be changed in the range of 100 to 210 ° C. Developers (1) to (29) were loaded in this modified machine, and a solid image with a toner adhesion amount of 11 mg / 10 cm ² was formed on A4 size plain paper (basis weight 80 g / m ² ). The fixing experiment for fixing processing was repeatedly performed while increasing the fixing temperature to be set from 85 ° C. to 130 ° C. by 5 ° C.

  The paper after the fixing experiment at each fixing temperature was folded by a folding machine so as to apply a load to the solid image on the paper, and compressed air of 0.35 MPa was sprayed. The solid image of the crease portion of the paper was evaluated in five ranks 1 to 5 according to the following evaluation criteria.

(Evaluation criteria)
Rank 5: No crease Rank 4: Partial peeling according to the fold Rank 3: Fine linear peeling according to the fold Rank 2: Thick linear peeling according to the fold Rank 1 : There is large peeling at the fold.

  Of the fixing temperatures of the fixing experiments in which the evaluation results were ranked 3, the lowest fixing temperature was ranked as the lower limit fixing temperature as follows. The lower the lower limit fixing temperature, the better the low-temperature fixability. The obtained results are shown in Table 5 above.

(Rank evaluation of low-temperature fixability)
A: The lower limit fixing temperature is 110 ° C. or lower, and the low temperature fixing property is very good. ○: The lower limit fixing temperature is higher than 110 ° C. and not higher than 120 ° C., and the low temperature fixing property is good. Higher than ℃, poor low-temperature fixability.

<Stability of low-temperature fixability>
When arbitrary toners were compared, the low-temperature fixability variation was evaluated according to the following three ranks. The obtained results are shown in Table 5 above. As shown in Table 5, the optional toners are those using the same APES dispersion (for example, Examples A12 and A13 using APES dispersion (A10)), or CPES dispersion. (For example, Examples A1 to A3 using a CPES dispersion (C7)), and these arbitrary toners were evaluated.

(Evaluation criteria for low-temperature fixability variation (repeated reproducibility; stability of low-temperature fixability))
◎: More than half in the above low-temperature fixability rank evaluation is ◎, and the others are good. ○: In the low-temperature fixability rank evaluation, less than half is ◎, and the others are good. X: In the rank evaluation of the low temperature fixability, x is partially included.

(Heat-resistant)
Each of the produced toners (1) to (29) was used. First, 0.5 g of toner is taken into a 10 mL glass bottle with an inner diameter of 21 mm, the lid is closed, shaken 600 times at room temperature with a tap denser KYT-2000 (manufactured by Seishin Enterprise), and then removed at 55 ° C. and 35 with the lid removed. It was left for 2 hours in an environment of% RH. Next, place the toner on a 48-mesh (mesh 350 μm) sieve, taking care not to crush the toner agglomerates, set the powder tester (manufactured by Hosokawa Micron), and fix it with a press bar and knob nut. Then, after applying vibration for 10 seconds at a vibration intensity of 1 mm in feed width, the amount of toner remaining on the sieve was measured.

  From the measured toner amount, the toner aggregation rate (%) was calculated by the following formula.

  From this toner aggregation rate (%), the heat resistance of the toner was evaluated according to the following criteria, and ◎ and ○ were judged to be acceptable levels that could be used practically without problems.

(Rank evaluation of heat resistance)
A: The toner aggregation rate is less than 15% by mass and the heat resistance is very high. O: The toner aggregation rate is 15% by mass or more and 20% by mass or less, and the heat resistance is high. X: The toner aggregation rate is 20% by mass. Exceeded heat resistance and cannot be used.

<Stability of heat resistance>
When arbitrary toners were compared, the heat resistance variation was evaluated in the following three ranks. The obtained results are shown in Table 5 above. As shown in Table 5, the optional toners are those using the same APES dispersion (for example, Examples A12 and A13 using APES dispersion (A10)), or CPES dispersion. (For example, Examples A1 to A3 using a CPES dispersion (C7)), and these arbitrary toners were evaluated.

(Evaluation criteria for heat resistance variation (repeated reproducibility; heat resistance stability))
◎: More than half in the above heat resistance rank evaluation is ◎, and the others are ◯. ○: In the heat resistance rank evaluation, less than half are ◎, and the others are ◯. In the heat resistance rank evaluation, “X” is partially included.

  As is apparent from the results shown in Table 5, the toners (1) to (22) and the developers (1) to (22) of Examples A1 to A22 have different particle diameters, repeated reproducibility and storage. The evaluation of the properties is made using any one of the dispersions A1 to A11 and any one of the dispersions C1 to C11, all of which show excellent performance. On the other hand, each of the toners (23) to (29) and the developers (23) to (29) of Comparative Examples A1 to A7 is any one of each of the dispersions A12 to A15 having an inferior particle size variation evaluation, or It is produced using any one of the dispersions C12 to C14. Therefore, the toners (1) to (22) and the developers (1) to (22) in Examples A1 to A22 are the same as the toners (23) to (29) and the developers in Comparative Examples A1 to A7. Compared with (23) to (29), evaluation of low temperature fixability, low temperature fixability variation (low temperature fixability stability), heat resistance and heat resistance variation (heat resistance stability) are all excellent. (Evaluation of ◯ or higher). On the other hand, each of the toners (23) to (29) and the developers (23) to (29) of Comparative Examples A1 to A7 exhibit a variation in low temperature fixability and low temperature fixability (low temperature fixability stability). It was confirmed that the evaluation was inferior or the evaluation of the variation in heat resistance and heat resistance (stability of heat resistance) was inferior. Therefore, when a toner is prepared using a dispersion having excellent particle size variation, reproducibility and storage stability of polyester resin particles, toner structure / physical properties, particularly low temperature fixability, low temperature fixability variation ( It was confirmed that the low temperature fixing stability), heat resistance and heat resistance variation (heat stability) can all exhibit excellent performance.

11 Polyester resin (PES powder),
12 Organic solvent (oil phase),
13 PES solution (oil phase),
14 Neutralizing agent (1),
15 Solution obtained in step 2; neutralization solution (cophase);
16 Neutralizing agent (2),
17 Solution obtained in step 3; neutralization solution (cophase),
18 Pure water,
19 Resin particle dispersion obtained in step 4; PES particle dispersion (aqueous phase),
20 Neutralizing agent (3),
21 resin particle dispersion after neutralization with neutralizer (3); PES particle dispersion (aqueous phase),
22 Resin particle dispersion obtained in step 5; PES particle dispersion (aqueous phase).

Claims (6)

A method for producing a polyester latex dispersion using a phase inversion emulsification method including the following steps:
Step 1 A step of mixing a polyester resin and an organic solvent to prepare a solution,
Process 2 The process of mixing the neutralizer (1) of the quantity from which a liquid viscosity becomes the range of 5-500 mPa * s with the solution obtained at the process 1,
Step 3 The state of the solution obtained in Step 2 is confirmed, the amount of the neutralizing agent (2) in which the liquid viscosity is in the range of 50 to 1000 mPa · s is determined, and the neutralizing agent (2) is determined at least once. Charging and mixing the process,
Step 4 Pure water is continuously added to the solution obtained in Step 3 to form resin particles to obtain a resin particle dispersion, and Step 5 An organic solvent is removed from the resin particle dispersion obtained in Step 4. Desolubilization process.   The neutralizing agent (3) in an amount that makes the degree of neutralization in the solution before desolubilization 3 to 25% is added before desolvating the organic solvent in the step 5. The manufacturing method of the polyester latex dispersion liquid of description.   The method for producing a polyester latex dispersion according to claim 1 or 2, wherein the neutralizing agent used in the steps 2 and 3 is a strongly alkaline compound having a pH of 11 or more.   The method for producing a polyester latex dispersion according to any one of claims 1 to 3, wherein the degree of neutralization in the solution after the step 3 is 25 to 100%.   The ratio of the neutralizing agent (1) is 55 to 95% by mass with respect to the total amount of the neutralizing agents (1) and (2) mixed in the steps 2 and 3. 5. A method for producing a polyester latex dispersion according to any one of 4 above.   A polyester latex dispersion is produced by the production method according to claim 1, and a toner forming solution containing the obtained polyester latex dispersion is used, and at least a resin contained in the latex dispersion A method for producing a toner, comprising aggregating and fusing particles.