JP2022111067A - Method for producing polyester resin and method for producing resin particle - Google Patents

Abstract

To provide a method for producing a polyester resin which is excellent in emulsion stability, compatibility with a crystalline polyester resin and colorability, and resin particles which are excellent in low temperature fixability and charging properties.SOLUTION: A method for producing a polyester resin subjects an alcohol component (x) containing an alkylene oxide adduct (x1) of bisphenol A and a carboxylic acid component (y) containing an aromatic dicarboxylic acid (y1) to polycondensation, wherein the alkylene oxide adduct (x1) of the bisphenol A is 90-100 mol%, the aromatic dicarboxylic acid (y1) is 80-100 mol%, the aromatic carboxylic acid (y1) contains an isophthalic acid, and the production method includes a first polycondensation step of performing polycondensation in the presence of a titanium compound and an amine compound having an acid dissociation constant (pKa) of 7-10 until an acid value of a reactant becomes 2 mgKOH/g or less, and a second polycondensation step of adding an isophthalic acid to the reactant obtained in the first polycondensation step.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a polyester resin and a method for producing resin particles.

Polyester resins are mostly made up of carbon-carbon bonds and are therefore hydrophobic and hardly soluble in water. Therefore, 1) forced emulsification and 2) self-emulsification are generally known methods for preparing an aqueous dispersion of a polyester resin.
1) Forced emulsification is a method in which polyester resin is dissolved in an organic solvent or melted to liquefy, and then forcibly dispersed in water using surfactants such as emulsifiers and dispersants (patented Reference 1). In this method, since a large amount of a low-molecular-weight hydrophilic compound (surfactant) is used, there is a problem that water resistance, storage stability, electrical properties, etc. are significantly inferior.
2) The self-emulsification method involves dissolving a polyester resin having a polar group (carboxylic acid group, sulfonic acid group, etc.) in the molecule in a mixed solution consisting of an organic solvent and water, and then adding water. It is a method of phase inversion and self-emulsification (Patent Document 2). Problem 1) can be overcome by not using a surfactant, but conversely, the control of the physical properties of the resin greatly affects emulsifiability, so the stability of the resin becomes an issue.

In order to solve these problems, for example, toner binders (Patent Document 3) and composite resins (Patent Document 4) in which fatty acids are introduced through multistage reactions have been proposed. However, particularly in low-molecular-weight polyester resins, residual low-molecular-weight components, residual monomer amounts, and the like pose problems of emulsion stability.
In recent years, along with the promotion of miniaturization, high speed, and high image quality of electrophotographic apparatuses, there is a strong demand for improved low-temperature fixability of toner from the viewpoint of energy saving, i.e., reduction of energy consumption in the fixing process. Excellent low-temperature fixability, such as hybrid resins in which crystalline polyesters are chemically bonded to the side chains of amorphous polyester resins (Patent Document 5), and resins with specific sharp-melting structures (Patent Document 6). Other toner compositions are known, but are still unsatisfactory.
On the other hand, as an esterification catalyst conventionally used in the production of polyester resins for toners, the development of titanium-based catalysts with relatively high activity and less burden on the environment is progressing. Conventional alkoxide-based titanium catalysts have a sufficiently high initial activity, but have a problem that they are weak in hydrolysis resistance and are deactivated by condensed water generated during the reaction. On the other hand, a water-based chelate titanium catalyst with high hydrolysis resistance was developed (Patent Document 7). However, since it comes into contact with the condensed water generated during the reaction at a high temperature, it inevitably becomes inactive at the end of the reaction, which prolongs the reaction time. I have a problem with coloring. As a countermeasure against deactivation, there is a method of increasing the amount of catalyst in consideration of the amount of deactivation. Also, there are problems such as generation of oppositely charged toner.
On the other hand, a composition composed of a titanium catalyst and an amine, which is a combination of a polymerization catalyst and a co-catalyst, has been proposed (Patent Document 8), but the amount of the titanium catalyst is still large, and a small amount that does not affect the chargeability is used. Development of highly active esterification catalysts and co-catalysts is required.

JP 2007-333977 A JP 2006-290963 A JP-A-2008-115333 JP 2014-38218 A JP 2016-183996 A Japanese Patent Application Laid-Open No. 2020-109530 JP 2006-243715 A JP 2007-333977 A

An object of the present invention is to provide a polyester resin excellent in emulsification stability, compatibility with a crystalline polyester resin, and colorability, and a method for producing resin particles capable of obtaining a toner excellent in low-temperature low-adhesiveness and chargeability. intended to provide

The present inventor has arrived at the present invention as a result of intensive studies.
That is, the present invention is a method for producing a polyester resin in which an alcohol component (x) containing an alkylene oxide adduct (x1) of bisphenol A and a carboxylic acid component (y) containing an aromatic dicarboxylic acid (y1) are polycondensed. It is a method for producing a polyester resin that satisfies the following (1) to (5).
(1) The alkylene oxide adduct (x1) of bisphenol A contained in the alcohol component (x) is 90 to 100 mol % based on the total number of moles of the alcohol component (x).
(2) The aromatic dicarboxylic acid (y1) contained in the carboxylic acid component (y) is 80 to 100 mol % based on the total number of moles of the carboxylic acid component (y).
(3) The aromatic carboxylic acid (y1) contains isophthalic acid.
(4) In the presence of a titanium compound and an amine compound having an acid dissociation constant (pKa) of 7 to 10, there is a first polycondensation step of polycondensing the reaction product until the acid value is 2 mgKOH/g or less.
(5) A second polycondensation step of adding isophthalic acid to the reactant obtained in the first polycondensation step and further polycondensing it.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyester resin excellent in emulsification stability, compatibility with a crystalline polyester resin, and colorability, and a method for producing resin particles excellent in low-temperature adhesion properties and chargeability. .

The present invention will be described in detail below.
The polyester resin obtained by the production method of the present invention is obtained by polycondensation of an alcohol component (x) containing an alkylene oxide adduct (x1) of bisphenol A and a carboxylic acid component (y) containing an aromatic dicarboxylic acid (y1). It is a polyester resin obtained by

The alcohol component (x) constituting the polyester resin includes, in addition to the alkylene oxide adduct (x1) of bisphenol A, which is an essential component, a diol (x2) other than the alkylene oxide adduct (x1) of bisphenol A described later and/or Alternatively, a polyol (x3) having a valence of 3 or more can be used. Moreover, a monoalcohol (x4) may be used as the alcohol component, if necessary.

The alkylene oxide adduct (x1) of bisphenol A is a compound obtained by adding an alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenol A. For example, propylene of bisphenol A Oxide (hereinafter, "propylene oxide" is abbreviated as PO) adduct (x11), ethylene oxide of bisphenol A (hereinafter, "ethylene oxide" is abbreviated as EO) adduct (x12), and butylene oxide of bisphenol A (hereinafter, "butylene oxide" is abbreviated as BO) adduct (x13) and the like.

The number of moles of alkylene oxide added in the alkylene oxide adduct (x1) of bisphenol A is preferably 2 to 30, more preferably 2 to 10, and still more preferably 2, from the viewpoint of chargeability and storage stability. ~5.

Examples of the diol (x2) other than the alkylene oxide adduct (x1) of bisphenol A include alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octane Diol, 1,10-decanediol, 1,12-dodecanediol, propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2 -octanediol, 1,2-nonanediol, 1,2-decanediol), alkylene ether glycols having 4 to 36 carbon atoms (eg diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether) glycol, etc.), alicyclic diols having 4 to 36 carbon atoms (eg, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene oxide [EO, PO, BO, etc.] adducts of the above alicyclic diols ( preferably 1 to 30 moles), alkylene oxide (EO, PO, BO, etc.) adducts of bisphenols (bisphenol F, bisphenol S, etc.) (preferably 2 to 30 moles), polylactone diol (poly ε -caprolactone diol, etc.) and polybutadiene diol.

Polyols with a valence of 3 or higher (x3) include alkane polyols and their intramolecular or intermolecular dehydrates (e.g. glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.), sugars and derivatives thereof (e.g., sucrose and methylglucoside), alkylene oxide adducts of trisphenols (trisphenol PA, etc.) (addition mole number is preferably 2 to 30), novolac resins (phenol novolak, cresol novolak, etc.). The average degree of polymerization is preferably 3 to 60) alkylene oxide adducts (addition mole number is preferably 2 to 30) and acrylic polyols [copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers, etc.] etc.

Monoalcohols (x4) include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and ligno ceryl alcohol, etc.).

When a component other than the alkylene oxide adduct of bisphenol A (x1) is included as the alcohol component (x), from the viewpoint of emulsion stability, the diol (x2) is preferable, and an alkylene glycol having 2 to 12 carbon atoms is more preferable. .

As the carboxylic acid component (y) of the polyester resin, in addition to the aromatic dicarboxylic acid (y1) which is an essential component, a dicarboxylic acid (y2) and/or a polycarboxylic acid (y3) having a valence of 3 or more, which will be described later. and anhydrides and lower alkyl (C 1-4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these acids. Moreover, a monocarboxylic acid (y4) may be used as the carboxylic acid component (y), if necessary.

Examples of the aromatic dicarboxylic acid (y1) include, in addition to isophthalic acid, which is an essential component, aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalene dicarboxylic acid and 4,4'-biphenyldicarboxylic acid) and the like.

As the aromatic dicarboxylic acid (y1), when a component other than isophthalic acid is included, terephthalic acid is preferable from the viewpoint of compatibility with the crystalline polyester and chargeability.

Examples of dicarboxylic acids (y2) other than the above aromatic dicarboxylic acids include alkanedicarboxylic acids having 2 to 50 carbon atoms {alkanedicarboxylic acids having carboxyl groups at both ends of a chain saturated hydrocarbon group (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,18-octadecanedicarboxylic acid, etc.), alkanedicarboxylic acids having a carboxyl group other than the end of the chain saturated hydrocarbon group (decylsuccinic acid, etc.)}, C4-50 Alkenedicarboxylic acids (alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid and citraconic acid, etc.), alicyclic dicarboxylic acids having 6 to 40 carbon atoms [dimer acid (dimerized linoleic acid, etc.)] and the like. Anhydrides and lower alkyl esters of these acids may also be used.

Examples of polycarboxylic acids (y3) having a valence of 3 or more include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexane tricarboxylic acid, etc.) and unsaturated carboxylic acid vinyl polymers [number average molecular weight (Mn): 450 to 10,000] (styrene/maleic acid copolymer, styrene/acrylic acid copolymer, and styrene/fumaric acid copolymer polymers, etc.). Anhydrides and lower alkyl esters of these acids may also be used.

The monocarboxylic acid (y4) includes aromatic monocarboxylic acids (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.) having 7 to 37 carbon atoms (including the carbon of the carbonyl group), carbon Number 2 to 50 aliphatic monocarboxylic acids (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid , behenic acid, (meth)acrylic acid ["(meth)acrylic" means acrylic or methacrylic], crotonic acid, isocrotonic acid, cinnamic acid, etc.).

When a component other than the aromatic dicarboxylic acid (y1) is included as the carboxylic acid component (y), from the viewpoint of emulsion stability and chargeability, an alkanedicarboxylic acid having a carbon number of 2 to 50, a trivalent or higher valence poly Carboxylic acid (y3) is preferred, more preferably an alkanedicarboxylic acid having a carboxyl group at both ends of a chain saturated hydrocarbon group, and an aromatic polycarboxylic acid having 9 to 20 carbon atoms, more preferably adipic acid , and trimellitic anhydride.

The alkylene oxide adduct (x1) of bisphenol A contained in the alcohol component (x) is 90 to 100 mol% based on the total number of moles of the alcohol component (x), and has compatibility with the crystalline polyester resin and low-temperature fixing. From the viewpoint of sexuality, it is preferably 95 to 100 mol %, more preferably 100 mol %.

The alkylene oxide adduct (x1) of bisphenol A preferably contains 50 to 100 mol% of the propylene oxide adduct (x11) of bisphenol A based on the total number of moles of (x1), from the viewpoint of chargeability. More preferably 80 to 100 mol %, still more preferably 80 to 90 mol %.

The aromatic dicarboxylic acid (y1) contained in the carboxylic acid component (y) is 80 to 100 mol% based on the total number of moles of the carboxylic acid component (y), and from the viewpoint of chargeability, preferably 90 to 100 mol. %, more preferably 100 mol %.

From the viewpoint of compatibility with the crystalline polyester resin, the isophthalic acid contained in the carboxylic acid component (y) is preferably 10 to 100 mol% based on the total number of moles of the carboxylic acid component (y). It is preferably 30 to 70 mol %.

When the aromatic dicarboxylic acid contains isophthalic acid and terephthalic acid, the weight ratio of isophthalic acid and terephthalic acid (isophthalic acid/terephthalic acid) is 30/70 to 70 from the viewpoint of chargeability and compatibility with the crystalline polyester resin. /30, more preferably 30/70 to 50/50.

The reaction ratio between the alcohol component (x) and the carboxylic acid component (y) is preferably 1/2 to 2/1, more preferably 1/2 to 2/1, as the molar ratio {[OH]/[COOH]} between the hydroxyl group and the carboxyl group. is 1/1.3 to 1.5/1, more preferably 1/1.2 to 1.4/1. The hydroxyl group is a hydroxyl group derived from the alcohol component (x).

The method for producing a polyester resin of the present invention comprises polycondensation of an alcohol component (x) containing an alkylene oxide adduct (x1) of bisphenol A and a carboxylic acid component (y) containing an aromatic dicarboxylic acid (y1). A method for producing a resin, wherein the first polymerization is carried out by polycondensation in the presence of a titanium compound and an amine compound having an acid dissociation constant (pKa) of 7 to 10 until the acid value of the reactant is 2 mgKOH/g or less. It has a condensation step and a second polycondensation step of adding isophthalic acid to the reactant obtained in the first polycondensation step and further polycondensing it.

[First polycondensation step]
The first polycondensation step is a step of polycondensing in the presence of a titanium compound and an amine compound having an acid dissociation constant (pKa) of 7 to 10 until the acid value of the reactant becomes 2 mgKOH/g or less.

In the first polycondensation step, an alcohol component and a carboxylic acid component are polycondensed in the presence of a titanium compound and an amine compound having an acid dissociation constant (pKa) of 7 to 10, so that the titanium compound undergoes an esterification reaction. It acts as a catalyst, and by using the amine compound together, the deactivation of the titanium compound is suppressed, the catalytic activity is increased, and the alcohol component (x) and the carboxylic acid component (y) can be reacted in a short time. , a polyester resin with little coloring can be obtained. In addition, by using the titanium compound and the amine compound together, the formation of side reaction products derived from the titanium compound is suppressed compared to the case where the amine compound is not used, and a polyester resin excellent in chargeability and emulsion stability is obtained. be able to. Furthermore, by polycondensing until the acid value of the reactant becomes 2 mgKOH/g or less, unreacted carboxylic acid components and alcohol components are reduced, and a polyester resin having excellent chargeability and emulsion stability can be obtained. It is more preferable to carry out polycondensation until the acid value of the product becomes 1 mgKOH/g or less.

The titanium compound may be any compound as long as it contains a titanium element and is used as an esterification catalyst. Catalysts described in 2006-243715 {titanium diisopropoxybis (triethanolamine), titanyl bis (triethanolamine) and their intramolecular polycondensates, etc.}, and described in JP 2007-11307 catalysts (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate and titanium diisopropoxy diterephthalate, etc.), titanium dihydroxybis (triethanolamine), titanium dihydroxy (diethanolamine), titanium monohydroxy tris (triethanolamine) , titanium tetrakis (ethanolamine), titanylhydroxytriethanolamine, titanylbis (triethanolamine), intramolecular or intermolecular polycondensates of titanium dihydroxybis (triethanolamine), titanium monohydroxytris (triethanol amines) intramolecular polycondensates, and the like. One of the titanium compounds may be used alone, or two or more thereof may be used in combination.
From the viewpoint of catalytic activity, titanium dihydroxybis(triethanolamine), titanium dihydroxy(diethanolamine), and intramolecular polycondensates of titanium dihydroxybis(triethanolamine) are preferred.

In the method for producing the polyester resin of the present invention, from the viewpoint of adjusting the catalytic activity and colorability, the amount of the titanium compound is 0.01 to 0.01 based on the total weight of the alcohol component (x) and the carboxylic acid component (y). It is preferably 0.4% by weight, more preferably 0.01 to 0.2% by weight. When the amount of the titanium compound present is 0.01% by weight or more, the catalytic activity becomes good, and the speed of the esterification reaction improves. When the amount of the titanium compound present is 0.4% by weight or less, the coloring of the resin becomes good.

In addition, the amine compound has an acid dissociation constant (pKa) that satisfies 7 to 10, and may be any amine compound other than the above titanium compounds. amines, etc.), cyclic amines (alicyclic amines, heterocyclic amines, aromatic amines, etc.), and the like. The above amine compounds may be used singly or in combination of two or more.
The acid dissociation constant (pKa) can be determined by neutralization titration and the Henderson-Hasselbalch equation. Specifically, the amine compound is precisely weighed in a beaker, and tetrahydrofuran (THF) is added to dissolve it. A pH electrode is placed in this solution to read the pH of the amine compound. Then, it is titrated with a 0.1 mol/L potassium hydroxide ethanol solution to obtain a titration curve of titration amount and pH. From the obtained titration curve, the point where the slope of pH is largest is taken as the neutralization point, and the pH at half the amount of 0.1 mol/L potassium hydroxide ethanol solution required to reach the neutralization point is read from the titration curve. , the pH value read is taken as the acid dissociation constant (pKa).
When the acid is represented by HA, it becomes the following general formula (1), and the Henderson-Hasselbalch formula becomes the following general formula (2). (at neutralization point, pH = pKa)
HA ⇔ H ⁺ + A ^- general formula (1)
pH = pKa + log [A ^- ] / [HA] general formula (2)

Examples of alkylamines having an acid dissociation constant (pKa) of 7 to 10 include alkylamines having 2 to 30 carbon atoms (for example, trimethylamine (pKa 9.8), dimethylisobutylamine (pKa 9.9) and tripentylamine (pKa 9.8). ) etc.).

Alkanolamines having an acid dissociation constant (pKa) of 7 to 10 include alkanolamines having 2 to 30 carbon atoms (e.g., monoethanolamine (pKa 9.5), diethanolamine (pKa 8.9) and triethanolamine (pKa 7.8). ) etc.).

Alicyclic amines having an acid dissociation constant (pKa) of 7 to 10 include alicyclic amines having 6 to 20 carbon atoms (eg, cyclohexylamine (pKa 9.8), cyclodecylamine (pKa 9.9) and cyclooctadecyl amine (pKa 9.5), etc.).

Heterocyclic amines having an acid dissociation constant (pKa) of 7 to 10 include 1,4-diazabicyclo[2.2.2]octane (DABCO), pyrrolidine, piperidine, piperazine, morpholine, pyrrole, pyrazole, imidazole, Heterocyclic amines with pyridine, pyridazine, pyrazine, oxazole and thiazole such as DABCO (pKa 8.8), morpholine (pKa 8.4), N-methylmorpholine (pKa 7.4), 4-allylmorpholine (pKa 7.1) ), benzoylpiperazine (pKa 7.8) and 2-(p-tolyl)pyridine (pKa 7.6), etc.).

Examples of aromatic amines having an acid dissociation constant (pKa) of 7 to 10 include aromatic amines having 6 to 30 carbon atoms (eg, dimethylbenzylamine (pKa 8.9), diethylbenzylamine (pKa 9.5), 2-phenyl ethylamine (pKa 9.8), adrenaline (pKa 8.6), etc.).

Among the above amine compounds, from the viewpoint of reactivity with acids, alkylamines, alkanolamines and heterocyclic amines are preferred, and 1,4-diazabicyclo[2.2.2]octane and 4-allyl are more preferred. morpholine, tripentylamine, diethanolamine and triethanolamine.

In the method for producing a polyester resin of the present invention, from the viewpoint of adjusting the catalytic activity and the colorability of the resin, the total weight of the amine compound used in the first polycondensation step and the amine compound used in the second polycondensation step described later is , based on the total weight of the alcohol component (x) and the carboxylic acid component (y), preferably 0.01 to 0.4 wt%, more preferably 0.01 to 0.2 wt% . When the amount of the titanium compound present is 0.01% by weight or more, the catalytic activity becomes good, and the speed of the esterification reaction improves. When the amount of the titanium compound present is 0.4% by weight or less, the coloring of the resin becomes good.

Furthermore, the weight of the amine compound used in the first polycondensation step is 0.01 to 0.3% by weight based on the total weight of the alcohol component (x) and the carboxylic acid component (y). And from the viewpoint of colorability, it is more preferably 0.01 to 0.2% by weight.

[Second double condensation step]
The second polycondensation step is a step of adding isophthalic acid to the reactant obtained in the first polycondensation step and further polycondensing it.

In the second polycondensation step, when the acid value of the reactant obtained in the first polycondensation step is 2 mgKOH/g or less, isophthalic acid, which is a dicarboxylic acid with low sublimability and high reactivity, is added. By polycondensation, it is possible to introduce carboxyl groups into the polyester resin while reducing unreacted alcohol component (x) and carboxylic acid component (y). It is possible to obtain a polyester resin without

In the second polycondensation step, the ratio of isophthalic acid added when the acid value is 2 mgKOH/g or less is based on the total number of moles of the carboxylic acid component (y) from the viewpoint of compatibility with the crystalline polyester resin. is preferably 10 to 50 mol %, more preferably 20 to 40 mol %.

Furthermore, the second polycondensation step preferably includes a step of adding an amine compound having an acid dissociation constant (pKa) of 7 to 10 after adding isophthalic acid from the viewpoint of colorability and emulsion stability. By adding an amine compound with an acid dissociation constant (pKa) of 7 to 10 after the addition of isophthalic acid, the catalytic activity is further increased and the esterification reaction can be completed in a short time, so that the resin can be colored due to heat history. can be suppressed.

Further, the weight of the amine compound having an acid dissociation constant (pKa) of 7 to 10 used in the second polycondensation step is 0.01 to 0.01 based on the total weight of the alcohol component (x) and the carboxylic acid component (y). From the viewpoint of catalytic activity and colorability, 0.3% by weight is preferable, and 0.01 to 0.2% by weight is more preferable.

Furthermore, in the second polycondensation step, the temperature in the reaction system immediately before adding isophthalic acid is 225 to 235°C, and the polymerization temperature in the second polycondensation step after adding isophthalic acid is 200 to 217°C. °C from the viewpoint of catalytic activity and colorability.
Coloration of resin is mainly due to oxidative decomposition of resin due to heat history, and can be suppressed by lowering the reaction temperature. Since highly reactive isophthalic acid is used as the acid to be added, even if the reaction temperature is lowered to the above range, coloration can be suppressed without lowering the reactivity.

In the production of the polyester resin of the present invention, production conditions other than the above steps can be the same as those of known polyester production methods. For example, a component containing an alcohol component (x) and a carboxylic acid component (y) is reacted in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280°C, more preferably 160 to 250°C. More preferably, the reaction can be carried out at 170-235°C. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of ensuring the polycondensation reaction. It is preferable to have a step of reducing the pressure in order to improve the reaction rate, and the degree of pressure reduction is preferably 0.5 to 20 kPa, more preferably 0.2 to 15 kPa, and still more preferably 0.1 to 10 kPa. . From the viewpoint of the emulsion stability of the resulting polyester resin, the process time at a pressure of 80 to 120 kPa is preferably 8 hours or less.

In the present invention, the glass transition temperature (Tg) of the polyester resin is preferably 45 to 80°C, more preferably 50 to 70°C, from the viewpoint of low temperature fixability. The glass transition temperature (Tg) can be measured by a method (DSC method) specified in ASTM D3418-82 using DSC Q20 manufactured by TA Instruments Co., Ltd., for example.

In the present invention, the acid value of the polyester resin is preferably 5 to 40 mgKOH/g, more preferably 6 to 30 mgKOH/g, still more preferably 7 to 15 mgKOH/g. The acid value of the polyester resin can be measured by the method specified in JIS K0070 (1992 edition).

In the present invention, the weight average molecular weight of the polyester resin measured by gel permeation chromatography (GPC) is preferably 4,000 to 100,000, more preferably 4,000 to 50,000, from the viewpoint of emulsion stability. , more preferably 4,000 to 40,000, and most preferably 5,000 to 30,000.

[Resin particles]
The resin particles obtained by the production method of the present invention contain the polyester resin obtained by the production method of the present invention as an essential component. The content of the polyester resin obtained by the production method of the present invention in the resin particles is preferably 30 to 97% by weight, more preferably 40 to 80% by weight, based on the weight of the resin particles. If necessary, various additives such as known resins other than the polyester resin of the present invention, colorants, release agents, and charge control agents can be mixed.

Examples of the resin other than the polyester resin obtained by the production method of the present invention include polyester resins other than the polyester resin obtained by the production method of the present invention, vinyl resins, urethane resins, epoxy resins, and the like. From the viewpoint of dispersion stability, it is preferably a polyester resin other than the polyester resin obtained by the production method of the present invention, and more preferably a crystalline polyester resin (C) other than the polyester resin obtained by the production method of the present invention. . The content of the resin other than the polyester resin obtained by the production method of the present invention in the resin particles is preferably 0 to 60% by weight, more preferably 8 to 55% by weight, based on the weight of the resin particles.

In the present invention, the crystalline polyester resin (C) means one exhibiting crystallinity and having an endothermic peak top temperature Tp (°C) in the range of 40 to 100°C.
In the present invention, "crystallinity" refers to a resin having a clear endothermic peak instead of a stepwise endothermic change in the second heating process of differential scanning calorimeter (DSC) measurement described later.
In the present invention, when the temperature Tp indicating the endothermic peak top is measured by DSC, for example, DSC Q20 manufactured by TA Instruments can be used. As for the temperature rising/cooling conditions, the temperature is raised to 180° C. at a rate of 10° C./min (first temperature raising process). Next, after standing at 180° C. for 10 minutes, it is cooled to 0° C. at 10° C./min (first cooling process). Next, after being left at 0° C. for 10 minutes, the temperature is raised to 180° C. at 10° C./min (second temperature raising process).

As the crystalline polyester resin (C), the same alcohol component (x) and carboxylic acid component (y) as exemplified for the polyester resin obtained by the production method of the present invention can be used. is preferably an alkylene glycol having 2 to 12 carbon atoms, more preferably ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol. The carboxylic acid component (y) is preferably an alkanedicarboxylic acid having 2 to 50 carbon atoms, more preferably an alkanedicarboxylic acid having a carboxyl group at both ends of a chain saturated hydrocarbon group (succinic acid, adipic acid , sebacic acid, azelaic acid, dodecanedioic acid, 1,18-octadecanedicarboxylic acid).
The content of the crystalline polyester resin (C) in the resin particles is preferably 2 to 20% by weight, more preferably 4 to 10% by weight, based on the weight of the resin particles.

As the colorant, all dyes and pigments used as colorants for toners can be used. Specifically, carbon black, iron black, Sudan black SM, fast yellow G, benzidine yellow, pigment yellow, India first orange, irgasin red, paranitroaniline red, toluidine red, carmine FB, pigment orange R, lake red. 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B and Oil Pink OP, etc., and these are used alone. Alternatively, two or more kinds can be mixed and used. If necessary, magnetic powder (powder of ferromagnetic metals such as iron, cobalt, nickel, etc., or compounds such as magnetite, hematite, ferrite, etc.) can also be incorporated as a coloring agent.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the polyester resin of the present invention. When magnetic powder is used, the content of the magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, with respect to 100 parts by weight of the total polyester resin.

Release agents include natural waxes (beeswax, carnauba wax, montan wax, etc.), petroleum waxes (paraffin wax, microcrystalline wax, petrolatum, etc.), synthetic waxes (Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polyethylene oxide, etc.). waxes, oxidized polypropylene waxes, etc.), and synthetic ester waxes (fatty acid esters synthesized from fatty acids having 10 to 30 carbon atoms and alcohols having 10 to 30 carbon atoms, etc.). It is preferable to contain one or more selected types. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and still more preferably 1 to 10% by weight, based on 100 parts by weight of the polyester resin of the present invention. be.

The charge control agent may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent. ammonium salts, polyamine resins, imidazole derivatives, polymers containing quaternary ammonium groups, metal-containing azo dyes, copper phthalocyanine dyes, metal salicylates, boron complexes of benzylic acid, polymers containing sulfonic acid groups, fluorine-containing polymers, halogen-substituted aromatics ring-containing polymers and the like. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, based on the total 100 parts by weight of the polyester resin of the present invention. .5% by weight.

The method for producing the resin particles of the present invention is not particularly limited as long as it comprises a step of mixing the organic solvent solution of the polyester resin obtained by the production method of the present invention with an aqueous medium. 62-106473 and JP-A-63-186253, as disclosed in JP-A-63-186253, an emulsification-aggregation method in which at least one or more kinds of fine particles are aggregated to obtain a desired particle size, and a dispersion polymerization characterized by monodispersion. Examples include a dissolution suspension method in which the necessary resins are dissolved in a water-insoluble organic solvent and then formed into resin particles in water, and an ester extension polymerization method disclosed in JP-A-2002-284881.
Among the above production methods, the emulsification aggregation method in which at least one kind of fine particles are aggregated to obtain a desired particle size is preferred from the viewpoint of controlling the particle size of the resin particles.

Among the methods for producing the resin particles of the present invention, the emulsion aggregation method, which is a preferred production method, includes a step of mixing an organic solvent solution of the polyester resin of the present invention with an aqueous medium to obtain resin fine particles containing the polyester resin, and aggregating the resin fine particles. It includes a step of allowing (also referred to as an aggregation step).

The method of mixing an organic solvent solution of a polyester resin with an aqueous medium to obtain fine resin particles containing a polyester resin is not particularly limited, but includes the following [1] and [2].

[1] A method of mixing an organic solvent solution of a polyester resin with an aqueous medium to disperse the polyester resin in the aqueous solvent, and then removing the organic solvent to produce a dispersion of fine resin particles.

[2] A solution of a polyester resin in an organic solvent is mixed with an aqueous medium, then the carboxyl groups in the polyester resin are salted with a neutralizing agent, the polyester resin is dispersed in the aqueous solvent, and then the organic solvent is removed to obtain a resin. A method for producing a fine particle dispersion.

Among the above methods [1] to [2], the method [2] is preferable from the viewpoint of ease of production of resin fine particles.

Moreover, when an additive is used, a dispersion liquid of fine resin particles containing a polyester resin and an additive dispersion liquid (colorant dispersion liquid, release agent dispersion liquid, etc.) may be mixed and used.

Examples of the organic solvent in the organic solvent solution of the polyester resin in the method for producing resin particles of the present invention include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogen solvents, esters, ester ether solvents, and ethers. Solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, mixed solvents of two or more of these, and the like.
Specific examples of organic solvents include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, tetralin, etc.); aliphatic or alicyclic hydrocarbon solvents (n-hexane, n-heptane, mineral spirits, cyclohexane, etc.); Halogen solvents such as methyl, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichlorethylene and perchlorethylene; esters or ester ethers such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate. Solvent; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol , isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethylsulfoxide; Examples include cyclic compound solvents and mixed solvents of two or more thereof. Among the above organic solvents, volatile ones having a boiling point of less than 100°C are preferred. Preferred organic solvents include ethyl acetate, acetone and methyl ethyl ketone.

The amount of the organic solvent to be used is preferably 25 to 300 parts by weight, more preferably 25 to 100 parts by weight, still more preferably 25 to 70 parts by weight, based on 100 parts by weight of the polyester resin.

As the aqueous solvent in the step of mixing the organic solvent solution of the polyester resin with the aqueous solvent in the method for producing the resin particles of the present invention, any liquid containing water as an essential component can be used without limitation. Aqueous solutions of solvents, aqueous solutions of surfactant (s), aqueous solutions of water-soluble polymer (t), mixtures of two or more of these, and the like can be used.

From the viewpoint of improving the dispersibility of the polyester resin in the aqueous solvent, a neutralizing agent may be used to neutralize the carboxyl groups of the polyester resin. Examples of neutralizing agents include organic compounds such as ammonia and triethylamine, and inorganic compounds such as sodium hydroxide.

From the viewpoint of dispersibility, the amount of the neutralizing agent used is preferably 1 to 150 mol %, more preferably 5 to 100 mol %, based on the carboxyl groups of the polyester resin.

When dispersing the resin in an aqueous solvent, known surfactants (s) and inorganic dispersants can be used as emulsifiers or dispersants as necessary.

The surfactant (s) is not particularly limited, and includes an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3) and a nonionic surfactant ( s-4) and the like. The surfactant (s) may be a combination of two or more surfactants.

Examples of the anionic surfactant (s-1) include carboxylic acids or salts thereof, sulfate ester salts, carboxymethylated salts, sulfonates and phosphate ester salts.
Cationic surfactants (s-2) include quaternary ammonium salt surfactants and amine salt surfactants.
Examples of amphoteric surfactants (s-3) include carboxylate type amphoteric surfactants, sulfate type amphoteric surfactants, sulfonate type amphoteric surfactants and phosphate type amphoteric surfactants. mentioned.
Nonionic surfactants (s-4) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.
Specific examples of these surfactants (s) include those described in JP-A-2002-284881.

Examples of inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, polyvalent metal phosphates such as hydroxyapatite, carbonates such as calcium carbonate and magnesium carbonate, calcium metasilicate, and sulfuric acid. Examples include inorganic salts such as calcium and barium sulfate, and inorganic compounds such as magnesium hydroxide and aluminum hydroxide.

A known water-soluble polymer (t) can be used as an emulsifier or dispersant when dispersing the resin in an aqueous solvent. The use of the water-soluble polymer (t) is preferable because the volume average particle size of the fine resin particles tends to be small, and the particle size distribution (volume average particle size/number average particle size) tends to be small.

Examples of the water-soluble polymer (t) include cellulose compounds (e.g., methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, and chitosan. , polyethylene glycol and the like.

When the organic solvent solution of the polyester resin of the present invention is mixed with an aqueous medium, the dispersion method is not particularly limited, but low-speed shearing, high-speed shearing, friction, high-pressure jet, ultrasonic waves, etc. known equipment can be applied. A high shear method is preferred to reduce the particle size of the fine particles in the dispersion. When a high-speed shearing disperser is used, the rotation speed is not particularly limited, but is generally 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but is generally 0.1 to 5 minutes in the batch method. The temperature is preferably 5 to 200°C, more preferably 20 to 100°C.
Dispersing devices include, for example, a homogenizer (manufactured by IKA), a polytron (manufactured by Kinematica), a batch-type emulsifier such as TK Auto Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and an Ebara Milder (manufactured by Ebara Corporation). ], TK Filmix, TK Pipeline Homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.], Colloid Mill [manufactured by Shinko Pantech Co., Ltd.], Ultra Visco Mill (manufactured by Aimex Co., Ltd.), Slasher, Trigonal wet mill Pulverizer [manufactured by Nippon Coke Industry Co., Ltd.], Capitron (manufactured by Eurotech), Continuous emulsifier such as Fine Flow Mill [manufactured by Taiheiyo Kiko Co., Ltd.], Microfluidizer [manufactured by Mizuho Industry Co., Ltd.], High-pressure emulsifiers such as Nanomizer (manufactured by Nanomizer) and APV Gaurin (manufactured by Gaurin), membrane emulsifiers such as membrane emulsifiers [manufactured by Reika Kogyo Co., Ltd.], vibro mixers [manufactured by Reika Kogyo Co., Ltd.], etc. and an ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson). Among these, APV Gaulin, Homogenizer, TK Auto Homomixer, Ebara Milder, TK Filmix and TK Pipeline Homomixer are preferred from the viewpoint of uniformity of particle size.

The amount of the aqueous medium to be used is preferably 100 to 500 parts by weight, more preferably 150 to 400 parts by weight, and still more preferably 150 to 300 parts by weight with respect to 100 parts by weight of the organic solvent solution of the polyester resin.

The solid content concentration and volatile content of resin particles and the like in the dispersion liquid in the production method of the present invention are obtained by the following methods.
About 2.00 g of the sample before drying is weighed and dried at 120° C. for 1 hour while taking care not to precipitate resin particles. The sample after drying is taken out and the weight is measured to the second decimal place, and the solid content concentration (% by weight) is calculated from (weight of the sample after drying / weight of the sample before drying) x 100, {(before drying The volatile content (% by weight) is calculated from (weight of sample−weight of sample after drying)/weight of sample before drying}×100.

The method of aggregating the resin fine particles obtained in the step of obtaining the resin fine particles is not particularly limited. Examples include a method of heating the dispersion, a method of adding the flocculant without heating, and a method of combining heating and addition of the flocculant.
When attempting to obtain an aggregate of a desired size by aggregating resin fine particles under stirring, the particle size of the aggregate is controlled by the balance between the cohesive force between the particles and the shearing force due to stirring. Alternatively, the cohesive force can be increased by adding a cohesive agent.

As flocculating agents, acids (hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, etc.), inorganic acid metal salts (sodium chloride, magnesium chloride, calcium chloride, aluminum chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate , copper sulfate, sodium carbonate, etc.), fatty acid metal salts (sodium acetate, potassium formate, sodium oxalate, etc.), aromatic fatty acid metal salts (sodium benzoate, sodium phthalate, potassium salicylate, etc.), phenolic metals Salts (sodium phenolate, etc.), amine salts (metal salts of amino acids, triethanolamine hydrochloride, aniline hydrochloride, etc.) and the like.
Among these, metal salts of inorganic acids and metal salts of fatty acids are preferred, and metal salts of inorganic acids are more preferred.

The temperature of the dispersion put in the tank when the resin fine particles are aggregated is preferably 5 to 100° C., more preferably 20 to 100° C., from the viewpoint of controlling the volume average particle diameter and particle size distribution of the resin particles.
In the step of forming aggregates, the pH of the dispersion is preferably 2 to 10, more preferably 3 to 6, from the viewpoint of controlling the volume average particle size and particle size distribution of the resin particles.

The amount of the aggregating agent to be added is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the fine resin particles, from the viewpoint of controlling the volume average particle size and particle size distribution of the resin particles. .

When the aggregation is performed only by heating without using an aggregating agent, the aggregation temperature is preferably 40 to 100°C, more preferably 50 to 100°C.
The time required for agglomeration is optimized depending on the shape of the device and the scale of treatment, but in order for the particle size of the resin particles to reach the target particle size, it is necessary to hold the resin particles at the predetermined temperature for at least 30 minutes or longer. desirable. The temperature may be raised at a constant rate until the temperature reaches a predetermined temperature, or may be raised stepwise.

In order to increase the stability of the aggregates obtained in the aggregation step, it is preferred to carry out the aging step after the aggregation step.
The aging step is a step of fusing and integrating the fine resin particles in the aggregate by heat treatment or the like, and the shape becomes nearly spherical. Aggregates before the aging process are considered to be aggregates due to electrostatic or physical aggregation of fine resin particles. can be made nearly spherical. According to such a ripening process, by controlling the temperature, time, etc. of the ripening process, it is possible to obtain various shapes such as a grape-shaped shape in which resin fine particles are aggregated, a potato-shaped shape in which fusion has progressed, a spherical shape in which fusion has progressed, and the like. Resin particles having various shapes can be produced according to the purpose.

The temperature at which the aggregates are fused is preferably 5 to 200° C., more preferably 30 to 100° C., from the viewpoint of shape controllability of the resulting resin particles. The pH of the liquid for fusing the aggregates is preferably 3-10, more preferably 5-10. The time required for the aging process varies depending on the desired shape of the resin particles, but it is desirable to hold the particles at the predetermined temperature for 0.1 to 10 hours, preferably 1 to 6 hours.

After the aggregating step, preferably before or during the aging step, it is preferable to add a surfactant or raise the pH value. As the surfactant used here, a known surfactant (s) can be used, but it is particularly preferable to use the same surfactant (s) as used when producing the resin fine particles. After the aggregation step, by adding a surfactant or increasing the pH value before the completion of the aging step, it is possible to suppress the aggregation of the aggregates aggregated in the aggregation step, and the coarsening after the aging step. In some cases, particle generation can be suppressed.

From the standpoint of low-temperature fixability, the method for producing resin particles of the present invention preferably further includes a step of removing the aqueous solvent from the aggregate dispersion obtained by the step of aggregating the resin fine particles.

As a method for removing the aqueous solvent from the dispersion, the following methods [3] to [5] and a combination of two or more of them can be applied.
[3] A method of drying the dispersion under reduced pressure or normal pressure.
[4] A method of subjecting the dispersion to solid-liquid separation using a centrifugal separator, a Spakura filter and/or a filter press, etc., adding water or the like as necessary, repeating the solid-liquid separation, and then drying the obtained solid.
[5] A method of freezing and drying the dispersion (so-called freeze-drying).

In the above methods [3] and [4], drying can be performed using known equipment such as a fluidized bed dryer, a vacuum dryer, and a circulation dryer. In addition, if necessary, it can be classified using an air classifier, a sieve, or the like to obtain a predetermined particle size distribution.

From the viewpoint of low-temperature fixability, the amount of the aqueous solvent remaining with respect to 100 parts by weight of the resin particles is preferably 0 to 2 parts by weight, more preferably 0 to 1 part by weight, still more preferably 0 to 0.1 parts by weight, and particularly preferably 0 to 0.01 parts by weight.

The resin particles obtained by the production method of the present invention can be used as a toner by adding known fluidizing agents (silica, titania, alumina, calcium carbonate, fatty acid metal salts, silicone resin particles, fluororesin particles, etc.). It is fixed on a support (paper, polyester film, etc.) by a copier, printer, etc. and used as a recording material. As a method for fixing onto the support, a known hot roll fixing method, flash fixing method, or the like can be applied.

The resin particles obtained by the production method of the present invention can be preferably used for developing electrostatic charge images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like. More preferably, it can be used for developing full-color electrostatic images or magnetic latent images.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these. Hereinafter, "parts" means parts by weight unless otherwise specified.

Each physical property value of the polyester resin and the like was measured by the following methods.

<Method for measuring glass transition temperature (Tg)>
Using a differential scanning calorimeter (manufactured by TA Instruments, DSC Q20), measurement was performed under the following conditions according to the method (DSC method) specified in ASTM D3418-82.
(1) Heating from 30 ° C. to 150 ° C. at 20 ° C./min (2) Holding at 150 ° C. for 10 minutes (3) Cooling at 20 ° C./min to -35 ° C. (4) Holding at -35 ° C. for 10 minutes (5 ) The glass transition temperature was obtained by analyzing the differential scanning calorimetry curve measured in the process of (6) and (5), which was heated up to 150°C at 20°C/min.

<Method for measuring acid value>
It was measured by the method specified in JIS K0070 (1992 edition). However, the solvent for acid value measurement was acetone, a mixed solvent of methanol and toluene (acetone:methanol:toluene=12.5:12.5:75), and the solvent for hydroxyl value measurement was THF.

<Method for measuring weight average molecular weight (Mw)>
The molecular weight was measured by dissolving the polyester resin in THF and filtering the undissolved matter through a glass filter to obtain a sample solution under the following conditions.
Apparatus: HLC-8120 manufactured by Tosoh Corporation
Column: TSK GEL GMH6 2 [manufactured by Tosoh Corporation]
Measurement temperature: 40°C
Sample solution: 0.25% by weight THF solution Solution injection volume: 100 μl
Detection device: Refractive index detector Reference material: 12 points of standard polystyrene (TSKstandard POLYSTYRENE) manufactured by Tosoh Corporation (molecular weight 500 1,050 2,800 5,970 9,100 18,100 37,900 96,400 190,000 355,000 1,090,000 2,890,000)

<Method for measuring peak top temperature of endothermic peak of crystalline polyester resin (C)>
It was measured using a differential scanning calorimeter {for example, "DSCQ20" [manufactured by TA Instruments]}. The crystalline polyester resin (C) is first heated from 20° C. to 150° C. at a rate of 10° C./min, then cooled from 150° C. to 0° C. at a rate of 10° C./min. The temperature indicating the top of the endothermic peak in the process of the second heating when the temperature was raised from 0°C to 150°C for the second time under the conditions of 10°C/min was taken as the endothermic peak temperature of the crystalline polyester resin (C). It was taken as the peak top temperature.

<Production Example 1> [Production of titanium compound (titanium dihydroxybis(triethanolamine))]
634.0 parts (33.3 mol %) of ORGATICS TC-310 (manufactured by ORGATIC), 366.0 parts (66.6 mol %) of triethanolamine are placed in a reactor equipped with a condenser, stirrer and nitrogen inlet tube. %) was added and reacted at 80° C. for about 1 hour to obtain titanium dihydroxybis(triethanolamine).

<Production Example 2> [Production of titanium compound (intramolecular polycondensate of titanium dihydroxybis(triethanolamine))]
Titanium dihydroxybis(triethanolamine) was further heated to 100° C. and dehydrated under reduced pressure to obtain an intramolecular polycondensate of titanium dihydroxybis(triethanolamine).

<Production Example 3> [Production of crystalline polyester resin (C)]
392.1 parts (51.1 mol %) of 1,6-hexanediol, 731.2 parts (48.9 mol %) of dodecanedioic acid, 1.5 parts of titanium dihydroxybis(triethanolamine) was added as a titanium compound, and reacted for 4 hours under normal pressure at 180° C. under a nitrogen stream while distilling off the generated water. Further, the temperature was raised to 200° C. under a reduced pressure of 0.5 to 2.5 kPa, and the mixture was reacted at 200° C. for 10 hours. The titanium compound of Production Example 1 was used as titanium dihydroxybis(triethanolamine).
The crystalline polyester resin (C) had an acid value of 8 mgKOH/g, an endothermic peak top temperature of 72° C., and a weight average molecular weight (Mw) of 20,000.

<Production Example 4> [Production of polyester resin (H)]
757.6 parts (51.8 mol%) of bisphenol A/PO3 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-3P") was added to a reaction tank equipped with a cooling tube, a stirrer and a nitrogen inlet tube. ), 270.4 parts (43.4 mol %) of terephthalic acid, 34.7 parts (4.8 mol %) of trimellitic anhydride, and 2.5 parts of titanium dihydroxybis(triethanolamine) as a condensation catalyst. The reaction was carried out for 4 hours at normal pressure and 180° C. under a nitrogen stream while distilling off the water produced. Furthermore, the temperature was raised to 200° C. under a reduced pressure of 0.5 to 2.5 kPa, and the mixture was allowed to react at 200° C. for 10 hours.
The polyester resin (H) had an acid value of 12 mgKOH/g, a glass transition temperature (Tg) of 61.2°C, and a weight average molecular weight (Mw) of 50,000.

<Example 1> [Production of polyester resin (L-1)]
103.3 parts (15.0 mol%) of bisphenol A/PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P") is placed in a reactor equipped with a cooling tube, a stirrer and a nitrogen inlet tube. ), bisphenol A · PO 3 mol adduct (manufactured by Sanyo Chemical Industries Co., Ltd., "Hymer BP-3P") 539.6 parts (70.0 mol%), bisphenol A · EO 2 mol adduct (Sanyo Chemical Industries Co., Ltd. ), "Hymer BPE-20") 97.1 parts (15.0 mol%), terephthalic acid 197.3 parts (60.0 mol%), isophthalic acid 65.8 parts (20.0 mol%), As a titanium compound, 1.3 parts of titanium dihydroxybis(triethanolamine) and 0.3 parts of triethanolamine are added, the temperature is raised to 227° C. under a reduced pressure of 0.5 to 2.5 kPa, and the water produced is distilled off. The reaction was allowed to proceed for 8 hours while removing the gas. When the acid value was measured, it was 1.0 mgKOH/g. Furthermore, 65.8 parts (20.0 mol%) of isophthalic acid and 1.0 part of triethanolamine are added and reacted at 217°C for 8 hours under a reduced pressure of 0.5 to 2.5 kPa to give an acid value of 11 mgKOH/ It was taken out at the time of reaching g to obtain a polyester resin (L-1).
The polyester resin (L-1) had an acid value of 11 mgKOH/g, a glass transition temperature (Tg) of 63.7° C., and a weight average molecular weight Mw of 13,000.

<Examples 2 to 23> [Production of polyester resins (L-2) to (L-23)]
Polyester resins (L-2) to (L-23) were obtained in the same manner as in Example 1 except that the raw materials described in Examples 2 to 23 in Table 1 were used. Table 1 shows the acid value, Tg and Mw of the obtained polyester resin.

<Comparative Examples 1 and 2> [Production of polyester resins (LR-1) to (LR-2)]
Polyester resins (LR-1) to (LR-2) were obtained in the same manner as in Example 1 except that the raw materials described in Comparative Examples 1 and 2 in Table 1 were used. Table 1 shows the acid value, Tg and Mw of the obtained polyester resin.

<Comparative Example 3> [Production of polyester resin (LR-3)]
103.3 parts (15.0 mol%) of bisphenol A/PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P") is placed in a reactor equipped with a cooling tube, a stirrer and a nitrogen inlet tube. ), bisphenol A · PO 3 mol adduct (manufactured by Sanyo Chemical Industries Co., Ltd., "Hymer BP-3P") 539.6 parts (70.0 mol%), bisphenol A · EO 2 mol adduct (Sanyo Chemical Industries Co., Ltd. ), “Hymer BPE-20”) 97.1 parts (15.0 mol%), terephthalic acid 197.3 parts (60.0 mol%), isophthalic acid 131.6 parts (40.0 mol%), As titanium compounds, 1.3 parts of titanium dihydroxybis(triethanolamine) and 1.3 parts of triethanolamine are added, the temperature is raised to 227° C. under a reduced pressure of 0.5 to 2.5 kPa, and the water produced is distilled off. The mixture was allowed to react for 10 hours while removing the water, and when the acid value reached 11 mgKOH/g, the mixture was taken out to obtain a polyester resin (LR-3).
The polyester resin (LR-3) had an acid value of 11 mgKOH/g, a glass transition temperature (Tg) of 63.7° C., and a weight average molecular weight Mw of 13,000.

<Comparative Example 4> [Production of polyester resin (LR-4)]
A polyester resin (LR-4) was obtained in the same manner as in Example 1, except that the raw materials described in Comparative Example 4 in Table 1 were used without using an amine compound. Table 1 shows the acid value, Tg and Mw of the obtained polyester resin.

<Comparative Example 5> [Production of polyester resin (LR-5)]
A polyester resin (LR-5) was obtained in the same manner as in Example 1 except that the raw material described in Comparative Example 5 in Table 1 was used and the acid value when isophthalic acid was added was 10 mgKOH/g. . Table 1 shows the acid value, Tg and Mw of the obtained polyester resin.

Table 1 shows the number of parts, reaction conditions, reaction temperature and physical properties of the polyester resins (L-1) to (L-23) and (LR-1) to (LR-5).

<Example 24> [Resin particles (Z-1)]
[Production of Dispersion (Clb-1) of Resin Fine Particles (Cl-1)]
100 parts of polyester resin (L-1) and 100 parts of methyl ethyl ketone are charged into a reaction vessel equipped with a stirring device, a heating/cooling device, a cooling pipe and a thermometer, and stirred and homogenized to obtain an organic solvent of polyester resin (L-1). A solution was obtained. The temperature of the organic solvent solution of the polyester resin (L-1) was adjusted to 25° C., 2.2 parts of 10.0% by weight ammonia water was added as a neutralizing agent, and the mixture was stirred for 5 minutes. Thereafter, 300 parts of ion-exchanged water at 25° C. is added dropwise over 1 hour for phase inversion emulsification, and methyl ethyl ketone is distilled off under reduced pressure of 30 kPa at 40° C. to obtain a dispersion (Clb) of fine resin particles (Cl-1). -1) was obtained. The volume-based median diameter of the fine resin particles (Cl-1) was 0.15 μm, and the solid content concentration of the dispersion (Clb-1) was 20% by weight.

[Production of Dispersion Liquid (Chb) of Resin Fine Particles (Ch)]
In the same manner as in the production of the dispersion (Clb-1) of the resin fine particles (Cl-1), except that the polyester resin (L-1) was replaced with the polyester resin (H), a resin fine particle dispersion (Chb) was prepared. Obtained. The volume-based median diameter of the fine resin particles (Ch) was 0.15 μm, and the solid content concentration of the dispersion (Chb) was 20% by weight.

[Production of Dispersion Liquid (Ccb) of Resin Fine Particles (Cc)]
100 parts of the crystalline polyester resin (C) and 100 parts of methyl ethyl ketone are charged into a reaction vessel equipped with a stirring device, a heating/cooling device, a cooling pipe and a thermometer, and stirred and homogenized to form an organic solvent for the crystalline polyester resin (C). A solution was obtained. The temperature of the organic solvent solution of the crystalline polyester resin (C) was adjusted to 50° C., 2.2 parts of 10.0% by weight ammonia water was added as a neutralizing agent, and the mixture was stirred for 5 minutes. Thereafter, 300 parts of ion-exchanged water at 50°C is added dropwise over 1 hour for phase inversion emulsification, and methyl ethyl ketone is distilled off under reduced pressure of 30 kPa at 40°C to obtain a dispersion (Ccb) of fine resin particles (Cc). Obtained. The volume-based median diameter of the fine resin particles (Cc) was 0.15 μm, and the solid content concentration of the dispersion (Ccb) was 20% by weight.

[Production of colorant dispersion]
10 parts of carbon black [manufactured by Mitsubishi Chemical Corporation: MA100], 0.5 parts of sodium dodecylbenzenesulfonate, and 40 parts of ion-exchanged water were placed in a reaction vessel equipped with a stirrer, a heating/cooling device, a cooling tube, and a thermometer. The temperature was raised to 30° C. while stirring at a rotation speed of 300 rpm, and after stirring at the same temperature for 30 minutes, the mixture was further wet pulverized with an Ultra Viscomil to obtain a black colorant dispersion. The black colorant dispersion thus obtained had a volume-based median diameter of 0.05 μm and a solid content concentration of 20% by weight.

[Production of Release Agent Dispersion]
10 parts of Fischer-Tropsch wax [manufactured by Nippon Seiro Co., Ltd.: FT-0070], 0.5 parts of sodium dodecylbenzenesulfonate, 15 parts of ion-exchanged water was added, and the temperature was raised to 95°C while stirring at 300 rpm. After stirring at the same temperature for 30 minutes, the mixture was cooled to 30°C over 1 hour to crystallize the Fischer-Tropsch wax into fine particles. The mixture was precipitated and wet pulverized with an Ultravisco mill to obtain a release agent dispersion. The obtained releasing agent dispersion had a volume-based median diameter of 0.25 μm and a solid content concentration of 50% by weight.

[Production of resin particles (Z-1)]
A dispersion (Clb-1) of fine resin particles (Cl-1), a dispersion (Chb) of fine resin particles (Ch), and A dispersion (Ccb) of fine resin particles (Cc), a colorant dispersion, and a release agent dispersion were charged so that the solid content was the number of parts shown in Table 2, 300 parts of ion-exchanged water was charged, and the liquid temperature was 30°C. After adjusting the pH to 10, an aqueous sodium hydroxide solution having a concentration of 25% by weight was added with stirring to adjust the pH to 10 to obtain a dispersion liquid.
Next, in order to coagulate the resin fine particles (Cl-1), the resin fine particles (Ch), the resin fine particles (Cc), the colorant, and the release agent, a coagulant having a concentration of 10% by weight was stirred at a rotation speed of 300 rpm. After adding an aqueous solution of magnesium chloride and appropriately sampling to confirm that the volume average particle diameter became 5 μm, the temperature of the system was adjusted to 60° C. The pH was adjusted to 4.5 and after 30 minutes the pH was adjusted to 4.0. Fusion and spheronization were achieved by holding the stirring for 3 hours.
Thereafter, the mixture was cooled to 30° C. to obtain an aqueous dispersion of resin particles containing a colorant. Next, after repeating filtration and washing with water three times, the resin particles are separated by filtration and dried for 18 hours in a circulating air dryer at 40° C. Resin particles having a volatile content of 0.5% by weight or less ( Z-1) was obtained.

<Examples 25 to 33> [Resin particles (Z-2) to (Z-10)]
In the same manner as in the production of the dispersion (Clb-1) of the fine resin particles (Cl-1), except that the polyester resin (L-1) is replaced with the polyester resins (L-2) to (L-10), After obtaining resin fine particle dispersions (Clb-2) to (Clb-10),
In Example 24, the dispersion (Clb-1) of the resin fine particles (Cl-1) was changed to the dispersion (Clb-2) of the resin fine particles (Cl-2) to the dispersion of the resin fine particles (Cl-10) (Clb- Resin particles (Z-2) to (Z-10) were obtained in the same manner as in Example 24, except that each was replaced with 10).

<Comparative Examples 6 to 8> [Resin particles (Z'-1) to (Z'-3)]
In the same manner as in the production of the dispersion (Clb-1) of the fine resin particles (Cl-1), except that the polyester resin (L-1) is replaced with the polyester resins (LR-1) to (LR-3), After obtaining resin fine particle dispersions (Clrb-1) to (Clrb-3),
In Example 24, the dispersion (Clb-1) of the fine resin particles (Cl-1) was changed to the dispersion (Clrb-1) of the fine resin particles (Clr-1) to the dispersion (Clrb-1) of the fine resin particles (Clr-3). Resin particles (Z'-1) to (Z'-3) were obtained in the same manner as in Example 24, except that 3) was substituted.

<Example 34> [Resin particles (Z-11)]
[Manufacture of MB1]
1200 parts of water, 40 parts of carbon black (manufactured by Mitsubishi Chemical Corporation, MA100), and 20 parts of the polyester resin (L-11) produced in Example 11 were mixed in a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After kneading at 90° C. for 30 minutes using this roll, the mixture was rolled, cooled, and pulverized with a pulperizer to obtain a pigment masterbatch [MB1].

[Production of fine particle dispersion [PD1]]
780 parts of water and 8 parts of sodium alkylallyl sulfosuccinate (manufactured by Sanyo Chemical Industries, Ltd., Eleminol JS-20) are charged into a reaction vessel equipped with a stirrer, a heating/cooling device and a thermometer, and stirred at 200 rpm for homogenization. did. After heating this to raise the system temperature to 85° C., 9 parts of a 10% by weight ammonium persulfate aqueous solution is added, and then a monomer mixture consisting of 30 parts of styrene, 40 parts of butyl acrylate, and 30 parts of methacrylic acid. was added dropwise over 2 hours. After the dropwise addition, the fine particle dispersion was obtained by aging at 85° C. for 4 hours. The volume average particle size of the fine particles contained in the fine particle dispersion was 0.031 μm. A portion of the fine particle dispersion was dried to isolate the resin. The resin component had an Mn of 18700, an Mw of 154000, a Tg of 64° C. and an acid value of 196 mgKOH/g.

[Production of aqueous phase s1]
955 parts of water, 15 parts of fine particle dispersion liquid [PD1], and 30 parts of sodium dodecyldiphenyl ether disulfonate aqueous solution (Eleminol MON7, manufactured by Sanyo Chemical Industries) were added to a container equipped with a stirring rod to form a milky white liquid [aqueous phase s1]. got

[Production of Wax Dispersion]
15 parts of Fischer-Tropsch wax [manufactured by Nippon Seiro Co., Ltd.: FT-0070] and 85 parts of ethyl acetate are added to a reaction vessel equipped with a cooling pipe, a thermometer and a stirrer, and the mixture is heated to 80°C. The mixture was melted and cooled to 30° C. over 1 hour to crystallize the Fischer-Tropsch wax into fine particles, which were then wet pulverized with "Ultraviscomil" (manufactured by Imex) to prepare a [wax dispersion].

[Production of resin particles (Z-11)]
Polyester resin (L-11), polyester resin (H), crystalline polyester resin (C), pigment masterbatch [MB1], and wax dispersion were charged in a beaker so that the solid content was the number of parts shown in Table 2, and 50 Ethyl acetate was added so as to obtain a weight % ethyl acetate solution, and the mixture was dissolved, mixed and homogenized to obtain an oil phase. Add 600 parts of [aqueous phase s1] to this oil phase, use a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 25 ° C., perform a dispersion operation for 1 minute at a rotation speed of 12000 rpm, and further with a film evaporator. The solvent was removed for 30 minutes at a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40° C., and a rotation speed of 100 rpm to obtain a dispersion of resin particles.
After repeating the process of centrifuging 100 parts of the dispersion, adding 60 parts of water and centrifuging to separate solid and liquid twice, drying at 35 ° C. for 1 hour, a classifier [elbow jet [Matsubo ( Co., Ltd.]] to remove fine powder and coarse powder so that fine powder of 3.17 μm or less is 12% by number or less, and coarse powder of 8.0 μm or more is 3% by volume or less, and resin particles (Z-11 ).

<Examples 35 to 37> [Resin particles (Z-12) to (Z-14)]
Resin particles (Z-12) to (Z-14) were obtained in the same manner as in Example 34, except that the polyester resin (L-11) was replaced with polyester resins (L-12) to (L-14). rice field.

<Example 38> [Resin particles (Z-15)]
Polyester resin (L-13), crystalline polyester resin (C), pigment masterbatch [MB1], and wax dispersion were charged in a beaker so that the solid content was the number of parts shown in Table 2, and a 50% by weight ethyl acetate solution and Ethyl acetate was added so as to dissolve and mix and homogenize to obtain an oil phase. Add 600 parts of [aqueous phase s1] to this oil phase, use a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 25 ° C., perform a dispersion operation at a rotation speed of 12000 rpm for 1 minute, and further with a film evaporator. The solvent was removed for 30 minutes at a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40° C., and a rotation speed of 100 rpm to obtain a dispersion of resin particles.
After repeating the process of centrifuging 100 parts of the dispersion, adding 60 parts of water and centrifuging to separate solid and liquid twice, drying at 35 ° C. for 1 hour, a classifier [elbow jet [Matsubo ( Co., Ltd.]] to remove fine powder and coarse powder so that fine powder of 3.17 μm or less is 12% by number or less, and coarse powder of 8.0 μm or more is 3% by volume or less, and resin particles [Z-15 ] was obtained.

<Comparative Examples 9 to 10> [Resin particles (Z'-4) to (Z'-5)]
Resin particles (Z′-4) to (Z′-5) were prepared in the same manner as in Example 34, except that polyester resin (L-11) was replaced with polyester resins (LR-4) to (LR-5). Obtained.

<Comparative Example 11> [Resin particles (Z'-6)]
Polyester resin (LR-1), crystalline polyester resin (C), pigment masterbatch [MB1], and wax dispersion were charged in a beaker so that the solid content was the number of parts shown in Table 2, and a 50% by weight ethyl acetate solution and Ethyl acetate was added so as to dissolve and mix and homogenize to obtain an oil phase. Add 600 parts of [aqueous phase s1] to this oil phase, use a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), perform a dispersion operation at a rotation speed of 12000 rpm at 25 ° C. for 1 minute, and further reduce the pressure with a film evaporator. The solvent was removed for 30 minutes at a temperature of -0.05 MPa (gauge pressure), a temperature of 40°C, and a rotation speed of 100 rpm to obtain a dispersion of resin particles.
After repeating the process of centrifuging 100 parts of the dispersion, adding 60 parts of water and centrifuging to separate solid and liquid twice, drying at 35 ° C. for 1 hour, a classifier [elbow jet [Matsubo ( Co., Ltd.]], resin particles [Z'- 6] was obtained.

<Examples 39 to 47> [Resin particles (Z-16) to (Z-24)]
In the same manner as in the production of the dispersion (Clb-1) of the fine resin particles (Cl-1), except that the polyester resin (L-1) is replaced with the polyester resins (L-15) to (L-23), After obtaining resin fine particle dispersions (Clb-15) to (Clb-23),
In Example 24, the dispersion (Clb-1) of the resin fine particles (Cl-1) was changed to the dispersion (Clb-15) of the resin fine particles (Cl-15) to the dispersion of the resin fine particles (Cl-23) (Clb- Resin particles (Z-16) to (Z-24) were obtained in the same manner as in Example 24, except that each was replaced with 23).

Table 2 shows the number of resin particles to be blended and the evaluation results obtained in each example and comparative example.

[Evaluation method]
Methods for measuring and evaluating the emulsion stability, colorability b, compatibility (ΔTg) with the crystalline polyester resin, chargeability, low-temperature fixability, and hot offset resistance of the resin particles are described below. explain.

<Emulsion stability>
Emulsion stability was evaluated by the rate of change (%) in the median diameter immediately after making the polyester resin obtained by the present invention into a dispersion liquid by the following method and after standing at room temperature for one week.
Specifically, each polyester resin (L) is made into a dispersion liquid of fine resin particles according to the procedure for producing a dispersion liquid (Clb-1) of fine resin particles (Cl-1), and the solid content concentration becomes 10% by weight. After adjusting with ion-exchanged water as above, the median diameter immediately after making the dispersion liquid was measured using a dynamic light scattering type particle distribution analyzer "SZ-100" (manufactured by HORIBA, Ltd.). After that, the median diameter of the dispersion was measured again after standing at room temperature for one week. The rate of change was calculated using the following formula.
Rate of change (%) = (|median diameter after 1 week-median diameter immediately after dispersion |/particle diameter immediately after dispersion) × 100 (%)
A smaller rate of change indicates better emulsification stability.

<Colorability>
Methyl ethyl ketone (MEK) is added to the polyester resin (L) and dissolved to prepare a 10 wt% solution, and colored by the Saybolt color measurement method using a color meter (manufactured by NIPPON DENSHOKU, “OME”-2000”). The properties (L, a, b) were measured. In particular, the value of b, which indicates the yellowness of the resin, is used for evaluation, and the lower the value, the better the colorability.

<Compatibility with crystalline polyester resin (ΔTg)>
The compatibility with the crystalline polyester resin was evaluated by comparing the amount of change in Tg (ΔTg) of the polyester resin when the crystalline polyester resin was added.
First, the polyester resin (L) of the present invention and the polyester resin (H) which is another resin
was charged so as to have the number of parts shown in Table 2, and tetrahydrofuran was added to make a 20% by weight tetrahydrofuran solution, uniformly dissolved, and the solvent was removed. Resin composition containing polyester resin (H) and polyester resin (L) of the present invention was measured.
Next, the polyester resin (L) of the present invention, the polyester resin (H) which is another resin, and the crystalline polyester resin are charged so as to have the parts number shown in Table 2, and tetrahydrofuran is added so as to obtain a 20% by weight tetrahydrofuran solution. Measure the Tg (2) of the resin composition containing the crystalline polyester resin, the polyester resin (H), and the polyester resin (L) of the present invention that are uniformly dissolved and solvent removed, and the crystalline polyester resin is determined by the following formula. The amount of change in Tg of the polyester resin upon addition was calculated.
Under these evaluation conditions, the larger the difference in Tg, the better the compatibility, and when the temperature is 10° C. or higher, the compatibility with the crystalline polyester resin is good.
The Tg was measured by the same method as for the Tg of the polyester resin of the present invention.
Compatibility with crystalline polyester resin (ΔTg) = |Tg (2) - Tg (1)|

Regarding the evaluation of the chargeability and low-temperature fixability of the resin particles, the obtained resin particles (Z-1) to (Z-24) and (Z'-1) to (Z'-6) were mixed with hydrophobic silica. Evaluation was made by uniformly mixing the following blending ratios to obtain a toner.
Resin particles (Z): Hydrophobic silica [Nippon Aerosil Co., Ltd., Aerosil R972]
= 99 parts by weight: 1 part by weight.

<Chargeability> (charge amount)
(1) 0.5 g of toner and 10 g of ferrite carrier (F-150, manufactured by Powdertech Co., Ltd.) were placed in a 50 ml glass bottle and conditioned at 23° C. and a relative humidity of 50% for 8 hours or more.
(2) Friction-stirred with a Turbula shaker mixer at 90 rpm for 2 minutes, 0.2 g of the mixed powder after stirring was loaded into a blow-off powder charge amount measuring device equipped with a 20 μm mesh stainless steel mesh, and the blow pressure was 10 KPa. , and a suction pressure of 5 KPa, the charge amount of the residual ferrite carrier was measured, and the charge amount (μC/g) of the toner was calculated by a standard method. For toners, the higher the negative charge amount, the better the charge characteristics, and it is preferably -15 μC/g or less.
A blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement.

<Low temperature fixability>
The toner was evenly placed on the paper so as to be 0.6 mg/cm ² . At this time, a printer without a heat fixing device was used as the method of placing the powder on the paper surface. Other methods may be used as long as the powder can be uniformly placed at the above weight density. The paper is passed through a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm/sec and a fixing pressure (pressure roller pressure) of 10 kg/cm ² to measure the low-temperature fixing temperature, which is the temperature at which cold offset occurs. did. It means that the lower the low-temperature fixing temperature, the better the low-temperature fixability. The low temperature fixing temperature (°C) of the toner is shown in Table 2 as low temperature fixability (°C).

<Hot offset resistance>
The toner was evenly placed on the paper so as to be 0.6 mg/cm ² . At this time, a printer without a heat fixing device was used as the method of placing the powder on the paper surface. Other methods may be used as long as the powder can be uniformly placed at the above weight density. This paper was passed through a pressure roller under the conditions of a fixing speed (heating roller peripheral speed) of 213 mm/sec and a fixing pressure (pressure roller pressure) of 10 kg/cm ² , and the temperature at which hot offset occurred was measured. Higher hot offset temperature means better hot offset resistance. The hot offset resistance temperature (°C) of the toner is shown in Table 2 as hot offset resistance temperature (°C).

The polyester resin of the present invention has excellent emulsification stability, compatibility with crystalline polyester resins, and excellent colorability. The resin particles have excellent low-temperature fixability and chargeability, and are used in electrophotography, electrostatic recording, electrostatic printing, and the like. It can be suitably used as a toner. Furthermore, it is useful as an additive for paints, an additive for adhesives, particles for electronic paper, and the like.

Claims (5)

A method for producing a polyester resin by polycondensing an alcohol component (x) containing an alkylene oxide adduct (x1) of bisphenol A and a carboxylic acid component (y) containing an aromatic dicarboxylic acid (y1), comprising: A method for producing a polyester resin that satisfies 1) to (5).
(1) The alkylene oxide adduct (x1) of bisphenol A contained in the alcohol component (x) is 90 to 100 mol % based on the total number of moles of the alcohol component (x).
(2) The aromatic dicarboxylic acid (y1) contained in the carboxylic acid component (y) is 80 to 100 mol % based on the total number of moles of the carboxylic acid component (y).
(3) The aromatic carboxylic acid (y1) contains isophthalic acid.
(4) In the presence of a titanium compound and an amine compound having an acid dissociation constant (pKa) of 7 to 10, there is a first polycondensation step of polycondensing the reaction product until the acid value is 2 mgKOH/g or less.
(5) A second polycondensation step of adding isophthalic acid to the reactant obtained in the first polycondensation step and further polycondensing it. 2. The method for producing a polyester resin according to claim 1, wherein the second polycondensation step comprises adding an amine compound having an acid dissociation constant (pKa) of 7 to 10 after adding isophthalic acid. The total weight of the amine compound used in the first polycondensation step and the amine compound used in the second polycondensation step is 0.01 to 0.01 based on the total weight of the alcohol component (x) and the carboxylic acid component (y). 3. The method for producing a polyester resin according to claim 2, wherein the content is 0.4% by weight. The production of the polyester resin according to any one of claims 1 to 3, wherein the ratio of the isophthalic acid added in the second polycondensation step to the total number of moles of the carboxylic acid component (y) is 10 to 50 mol%. Method. A method for producing resin particles, comprising the step of mixing an organic solvent solution of the polyester resin according to any one of claims 1 to 4 with an aqueous medium.