JP7402214B2 - Method for producing polyester resin and method for producing resin particles - Google Patents

Description

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

Since polyester resin is mostly formed of carbon-carbon bonds, it is hydrophobic and hardly dissolves in water. Therefore, generally known methods for preparing an aqueous dispersion of polyester resin are 1) forced emulsification method and 2) self-emulsification method.
1) Forced emulsification method is a method in which polyester resin is dissolved or melted in an organic solvent and liquefied, and then this is forcibly dispersed in water using a surfactant such as an emulsifier or a dispersant (a patented method). Reference 1). Since this method uses a large amount of a low molecular weight hydrophilic compound (surfactant), there is a problem that water resistance, storage stability, electrical properties, etc. are significantly inferior.
2) Self-emulsification method involves dissolving a polyester resin that has polar groups (carboxylic acid groups, sulfonic acid groups, etc.) in its molecules in a mixed solution consisting of an organic solvent and water, and then adding water. This is a method of phase inversion and self-emulsification (Patent Document 2). Problem 1) can be overcome by not using a surfactant, but on the other hand, controlling the physical properties of the resin has a large effect on emulsifying properties, so stabilizing the resin becomes an issue.

In order to achieve these problems, for example, toner binders (Patent Document 3) and composite resins (Patent Document 4) in which fatty acids are introduced in a multi-stage reaction have been proposed. However, especially in low-molecular polyester resins, residual low-molecular weight components and residual monomer amounts pose problems in emulsion stability.
Furthermore, in recent years, along with the promotion of smaller size, higher speed, and higher image quality of electrophotographic devices, there has been a strong demand for improved low-temperature fixing properties of toners from the viewpoint of energy saving by reducing energy consumption in the fixing process. Hybrid resins that have crystalline polyester chemically bonded to the side chains of amorphous polyester resin (Patent Document 5) and resins that have a specific structure with sharp melt properties (Patent Document 6) have excellent low-temperature fixing properties. Although similar toner compositions are known, they are still insufficient.
On the other hand, as esterification catalysts that have been conventionally used in producing polyester resins for toners, titanium-based catalysts that have less environmental impact and relatively high activity are being developed. Although conventional alkoxide-based titanium catalysts have sufficiently high initial activity, they have a problem in that they have poor hydrolysis resistance and are deactivated by condensed water generated during the reaction. In response, a titanium catalyst which is a water-based chelate and has high hydrolysis resistance has been developed (Patent Document 7). However, since it comes into contact with the condensed water generated during the reaction at high temperatures, it inevitably becomes deactivated at the end of the reaction, prolonging the reaction time, and the resin itself undergoes side reactions such as oxidative decomposition reactions, causing it to turn yellow. There is a problem with coloring. As a countermeasure against deactivation, there is a method of increasing the amount of catalyst to account for the amount of deactivation, but the resin itself becomes hazy due to the catalyst residue deactivated during the reaction, and charging stability decreases due to increasing the amount of catalyst. However, there are problems such as the generation of reversely charged toner.
On the other hand, a composition consisting of a titanium catalyst and an amine in combination with a polymerization catalyst and a co-catalyst has been proposed (Patent Document 8), but the amount of titanium catalyst is still large, and a small amount that does not affect charging properties is proposed. There is a need for the development of highly active esterification catalysts and promoters.

Japanese Patent Application Publication No. 2007-333977 Japanese Patent Application Publication No. 2006-290963 Japanese Patent Application Publication No. 2008-115333 Japanese Patent Application Publication No. 2014-38218 Japanese Patent Application Publication No. 2016-183996 JP2020-109530A Japanese Patent Application Publication No. 2006-243715 Japanese Patent Application Publication No. 2007-333977

An object of the present invention is to provide a polyester resin with excellent emulsion stability, compatibility with crystalline polyester resins, and coloring properties, and a method for producing resin particles capable of producing toners with excellent low-temperature adhesion properties and charging properties. The purpose is to provide

As a result of intensive study, the present inventor has arrived at the present invention.
That is, the present invention is a method for producing a polyester resin, which comprises polycondensing an alcohol component (x) containing an alkylene oxide adduct of bisphenol A (x1) and a carboxylic acid component (y) containing an aromatic dicarboxylic acid (y1). This 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) Aromatic carboxylic acid (y1) contains isophthalic acid.
(4) A first polycondensation step of polycondensing the reactant 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.
(5) A second polycondensation step is performed in which isophthalic acid is added to the reaction product obtained in the first polycondensation step and further polycondensed.

The present invention makes it possible to provide a polyester resin that has excellent emulsion stability, compatibility with crystalline polyester resin, and colorability, and a method for producing resin particles that have excellent low-temperature adhesion and electrostatic properties. .

The present invention will be explained in detail below.
The polyester resin obtained by the production method of the present invention is obtained by polycondensing an alcohol component (x) containing an alkylene oxide adduct of bisphenol A (x1) 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 of bisphenol A (x1), which is an essential component, a diol (x2) other than the alkylene oxide adduct of bisphenol A (x1), which will be described later. Alternatively, a polyol (x3) having a valence of 3 or more may be mentioned. Furthermore, 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 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), bisphenol A ethylene oxide (hereinafter "ethylene oxide" is abbreviated as EO) adduct (x12), and bisphenol A butylene oxide (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 even more preferably 2 from the viewpoint of chargeability and storage stability. ~5.

Diols (x2) other than alkylene oxide adducts of bisphenol A (x1) 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 (e.g. diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether) glycol, etc.), alicyclic diols having 4 to 36 carbon atoms (e.g. 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene oxide [EO, PO, BO, etc.] adducts of the above alicyclic diols ( Preferably, the number of moles added is 1 to 30), alkylene oxide (EO, PO, BO, etc.) adducts of bisphenols (bisphenol F, bisphenol S, etc.) (preferably the number of moles added is 2 to 30), polylactone diol (poly ε -caprolactone diol, etc.) and polybutadiene diol.

Polyols with a valence of 3 or more (x3) include alkane polyols and their intramolecular or intermolecular dehydrates (e.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.), sugars and its derivatives (such as sucrose and methyl glucoside), alkylene oxide adducts of trisphenols (such as trisphenol PA) (preferably the number of moles added is 2 to 30), novolac resins (including phenol novolak and cresol novolak, etc.) and an alkylene oxide adduct (with an average degree of polymerization of preferably 3 to 60) (the number of moles added is preferably 2 to 30) and an acrylic polyol [copolymer of hydroxyethyl (meth)acrylate and other vinyl monomer, 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 lignosyl alcohol). ceryl alcohol, etc.).

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

The carboxylic acid component (y) of the polyester resin includes, in addition to the aromatic dicarboxylic acid (y1) which is an essential component, a dicarboxylic acid (y2) and/or a polycarboxylic acid with a valence of 3 or more (y3), which will be described later. and anhydrides and lower alkyl (1 to 4 carbon atoms) 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.

In addition to isophthalic acid, which is an essential component, aromatic dicarboxylic acids (y1) include, for example, aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, terephthalic acid, t-butyl isophthalic acid, 2,6-naphthalene). dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.).

When the aromatic dicarboxylic acid (y1) contains a component other than isophthalic acid, terephthalic acid is preferred from the viewpoint of compatibility with crystalline polyester and chargeability.

Dicarboxylic acids (y2) other than the above-mentioned 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 terminal end of the chain saturated hydrocarbon group (decylsuccinic acid, etc.), Alkenyl dicarboxylic acids (alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, etc.), alicyclic dicarboxylic acids having 6 to 40 carbon atoms [dimer acid (dimerized linoleic acid), etc.). Further, anhydrides and lower alkyl esters of these acids may also be used.

Examples of the polycarboxylic acid (y3) having a valence of 3 or higher 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 vinyl polymers of unsaturated carboxylic acids [number average molecular weight (Mn): 450 to 10,000] (styrene/maleic acid copolymer, styrene/acrylic acid copolymer, and styrene/fumaric acid copolymer) polymers, etc.). Further, anhydrides and lower alkyl esters of these acids may also be used.

As the monocarboxylic acid (y4), aromatic monocarboxylic acids having 7 to 37 carbon atoms (including the carbon of the carbonyl group) (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), 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 methacryl), crotonic acid, isocrotonic acid, cinnamic acid, etc.).

When the carboxylic acid component (y) contains a component other than the aromatic dicarboxylic acid (y1), from the viewpoint of emulsion stability and charging property, an alkanedicarboxylic acid having 2 to 50 carbon atoms, a polyvalent dicarboxylic acid having a valence of 3 or more, Carboxylic acid (y3) is preferable, 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, and even 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 good compatibility with crystalline polyester resin and low temperature fixing. From the viewpoint of properties, the content is preferably 95 to 100 mol%, more preferably 100 mol%.

The alkylene oxide adduct of bisphenol A (x1) is preferably 50 to 100 mol% of the propylene oxide adduct of bisphenol A (x1) 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 preferably 90 to 100 mol from the viewpoint of chargeability. %, 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), and more preferably Preferably it is 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 is preferable, and more preferably 30/70 to 50/50.

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

The method for producing a polyester resin of the present invention involves polycondensing an alcohol component (x) containing an alkylene oxide adduct of bisphenol A (x1) with a carboxylic acid component (y) containing an aromatic dicarboxylic acid (y1). A method for producing a resin, comprising a first polycondensation process in which the reactant is polycondensed 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. The method includes a condensation step and a second polycondensation step in which isophthalic acid is added to the reaction product obtained in the first polycondensation step and further polycondensation is performed.

[First polycondensation step]
The first polycondensation step is a step in which polycondensation is performed 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, the alcohol component and the carboxylic acid component are polycondensed in the presence of a titanium compound and an amine compound with an acid dissociation constant (pKa) of 7 to 10, so that the titanium compound undergoes the esterification reaction. It acts as a catalyst, and by using the amine compound in combination, it suppresses the deactivation of the titanium compound, and also increases the catalytic activity, allowing the alcohol component (x) and the carboxylic acid component (y) to react in a short time. , a polyester resin with little coloring can be obtained. In addition, by using a titanium compound and the amine compound in combination, the generation of side reaction products derived from the titanium compound is suppressed compared to when the amine compound is not used, and a polyester resin with excellent charging properties and emulsion stability is obtained. be able to. Furthermore, by polycondensing the reactants until the acid value becomes 2 mgKOH/g or less, unreacted carboxylic acid components and alcohol components are reduced, making it possible to obtain a polyester resin with excellent charging properties and emulsion stability. More preferably, the step is polycondensation until the acid value of the product becomes 1 mgKOH/g or less.

The titanium compound may be any compound containing the element titanium and used as an esterification catalyst, such as titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, JP-A Catalysts described in No. 2006-243715 {titanium diisopropoxybis(triethanolaminate), titanyl bis(triethanolaminate), intramolecular polycondensates thereof, etc.}, and those described in JP-A No. 2007-11307 catalysts (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.), titanium dihydroxybis (triethanolaminate), titanium dihydroxy (diethanolaminate), titanium monohydroxytris (triethanolaminate) , titanium tetrakis (ethanolaminate), titanium hydroxytriethanolaminate, titanylbis (triethanolaminate), intramolecular or intermolecular polycondensate of titanium dihydroxybis (triethanolaminate), titanium monohydroxytris (triethanolaminate) amines), and the like. The above titanium compounds may be used alone or in combination of two or more.
From the viewpoint of catalytic activity, intramolecular polycondensates of titanium dihydroxybis(triethanolaminate), titanium dihydroxy(diethanolaminate), and titanium dihydroxybis(triethanolaminate) are preferred.

In the method for producing a polyester resin of the present invention, from the viewpoint of adjusting catalytic activity and colorability, the amount of the titanium compound is from 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. If the amount of the titanium compound is 0.01% by weight or more, the catalyst activity will be good and the speed of the esterification reaction will be improved, and if the amount of the titanium compound is 0.4% by weight or less, the coloring property of the resin will be improved. becomes good.

Further, the amine compound is one having an acid dissociation constant (pKa) of 7 to 10, and may be any amine compound other than the titanium compounds mentioned above, such as acyclic amines (alkyl amines, alkanols, etc.). amines), cyclic amines (alicyclic amines, heterocyclic amines, aromatic amines, etc.), and the like. The above amine compounds may be used alone or in combination of two or more.
Note that the acid dissociation constant (pKa) can be determined by neutralization titration and the Henderson-Hasselbalch equation. Specifically, an amine compound is accurately weighed in a beaker, and tetrahydrofuran (THF) is added to dissolve it. A pH electrode is placed in this solution and the pH of the amine compound is read. Thereafter, titration is performed 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, take the point where the pH slope is the greatest as the neutralization point, and read the pH at half the amount of 0.1 mol/L potassium hydroxide ethanol solution required to reach the neutralization point from the titration curve. , the read pH value is taken as the acid dissociation constant (pKa).
When acid is represented by HA, it becomes the following general formula (1), and the Henderson-Hasselbalch equation becomes the following general formula (2). (At the 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 (pKa9.8), dimethylisobutylamine (pKa9.9), and tripentylamine (pKa9.8)). ), etc.).

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

Examples of alicyclic amines having an acid dissociation constant (pKa) of 7 to 10 include alicyclic amines having 6 to 20 carbon atoms (for example, cyclohexylamine (pKa 9.8), cyclodecylamine (pKa 9.9), and cyclooctadecyl amine (pKa9.5), etc.).

Examples of 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 (e.g. DABCO (pKa 8.8), morpholine (pKa 8.4), N-methylmorpholine (pKa 7.4), 4-allylmorpholine (pKa 7.1) ), benzoylpiperazine (pKa 7.8), 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 (for example, 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 to be described later is , preferably from 0.01 to 0.4% by weight, more preferably from 0.01 to 0.2% by weight, based on the total weight of the alcohol component (x) and the carboxylic acid component (y). . If the amount of the titanium compound is 0.01% by weight or more, the catalyst activity will be good and the speed of the esterification reaction will be improved, and if the amount of the titanium compound is 0.4% by weight or less, the coloring property of the resin will be improved. becomes good.

Further, it is important that 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). The amount is preferably 0.01 to 0.2% by weight, and more preferably 0.01 to 0.2% by weight.

[Second condensation step]
The second polycondensation step is a step in which isophthalic acid is added to the reaction product obtained in the first polycondensation step, and further polycondensation is performed.

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 sublimation property and high reactivity, is added. By polycondensation, carboxyl groups can be introduced into the polyester resin while reducing unreacted alcohol components (x) and carboxylic acid components (y), resulting in crosslinking with excellent emulsion stability and charging properties. No polyester resin can be obtained.

In addition, 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. The amount is preferably 10 to 50 mol%, more preferably 20 to 40 mol%.

Furthermore, it is preferable from the viewpoint of colorability and emulsion stability that the second polycondensation step includes a step of further adding an amine compound having an acid dissociation constant (pKa) of 7 to 10 after adding isophthalic acid. 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, thereby reducing the coloring of the resin due to thermal history. It can be suppressed.

Furthermore, 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 100% based on the total weight of the alcohol component (x) and the carboxylic acid component (y). The content is preferably 0.3% by weight from the viewpoint of catalytic activity and colorability, and more preferably 0.01 to 0.2% by weight.

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. ℃ is preferable from the viewpoint of catalytic activity and colorability.
Coloring of the resin is mainly due to oxidative decomposition of the resin due to thermal history, and can be suppressed by lowering the reaction temperature. Since the added acid is highly reactive isophthalic acid, coloring can be suppressed without reducing the reactivity even if the reaction temperature is lowered to the above range.

In the production of the polyester resin of the present invention, production conditions other than the above steps can be produced in the same manner as in 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, etc.) 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 to 235°C. In addition, 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 even more preferably 0.1 to 10 kPa. . From the viewpoint of 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. Note that the glass transition temperature (Tg) can be measured by the method specified in ASTM D3418-82 (DSC method) using, for example, DSC Q20 manufactured by TA Instruments.

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, and still more preferably 7 to 15 mgKOH/g. The acid value of 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 in 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. Further, if necessary, various additives such as known resins other than the polyester resin of the present invention, colorants, mold release agents, and charge control agents can be mixed.

Examples of resins other than polyester resins obtained by the production method of the present invention include polyester resins other than the polyester resins 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 excluding the polyester resin obtained by the production method of the present invention, and more preferably a crystalline polyester resin (C) excluding the polyester resin obtained by the production method of the present invention. . The content of resin other than 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 that exhibits crystallinity and has an endothermic peak top temperature Tp (°C) in the range of 40 to 100°C.
Note that "crystalline" in the present invention refers to a resin that has a clear endothermic peak rather than a stepwise change in endothermic amount in the second temperature raising process of differential scanning calorimeter (DSC) measurement, which will be described later.
In the present invention, when measuring the temperature Tp indicating the endothermic peak top by DSC, for example, DSC Q20 manufactured by TA Instruments Co., Ltd. can be used. Further, as the temperature raising/cooling conditions, the temperature is raised to 180° C. at a rate of 10° C./min (first temperature raising step). Next, after being left at 180°C for 10 minutes, it is cooled to 0°C at a rate of 10°C/min (first cooling process). Next, after being left at 0° C. for 10 minutes, the temperature is raised to 180° C. at a rate of 10° C./min (second temperature raising step).

As the crystalline polyester resin (C), those similar to the alcohol component (x) and carboxylic acid component (y) exemplified in the polyester resin obtained by the production method of the present invention can be used, and the alcohol component (x) Preferred are alkylene glycols having 2 to 12 carbon atoms, more preferably ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, It is 1,12-dodecanediol. Preferred carboxylic acid components (y) are alkanedicarboxylic acids having 2 to 50 carbon atoms, more preferably 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).
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, pigments, etc. used as colorants for toners can be used. Specifically, carbon black, iron black, Sudan black SM, first 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, Orazole Brown B, and Oil Pink OP, etc. Alternatively, two or more types can be used in combination. Further, if necessary, magnetic powder (ferromagnetic metal powder such as iron, cobalt, nickel, etc., or compound such as magnetite, hematite, ferrite, etc.) may be included to also function 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 a total of 100 parts by weight of the polyester resin of the present invention. When using magnetic powder, the content of the magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, based on the total 100 parts by weight of the polyester resin.

As mold release agents, 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, oxidized polyethylene wax, etc.) can be used. wax and oxidized polypropylene wax, etc.), and synthetic ester waxes (fatty acid esters synthesized from fatty acids with 10 to 30 carbon atoms and alcohols with 10 to 30 carbon atoms, etc.), and from the group consisting of these mold release agents. It is preferable to contain one or more selected types. The content of the mold release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and even 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, such as nigrosine dye, triphenylmethane dye containing a tertiary amine as a side chain, class ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatics Examples include ring-containing polymers. 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 a total of 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 includes a step of mixing an organic solvent solution of the polyester resin obtained by the production method of the present invention with an aqueous medium. The emulsion aggregation method for agglomerating at least one type of fine particles to obtain a desired particle size, as disclosed in Japanese Patent Application Laid-open No. 62-106473 and Japanese Patent Application Laid-open No. 63-186253, and the dispersion polymerization method characterized by monodispersion. Legal methods include a dissolution suspension method in which necessary resins are dissolved in a water-insoluble organic solvent and then turned into resin particles in water, and an ester extension polymerization method disclosed in JP-A No. 2002-284881.
Among the above manufacturing methods, from the viewpoint of controlling the particle size of resin particles, an emulsion aggregation method is preferred in which at least one type of fine particles are aggregated to obtain a desired particle size.

The emulsion aggregation method, which is a preferred manufacturing method among the methods for manufacturing resin particles of the present invention, is a process of mixing an organic solvent solution of the polyester resin of the present invention with an aqueous medium to obtain resin fine particles containing a polyester resin, and aggregating the resin fine particles. (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 resin particles containing a polyester resin is not particularly limited, but the following methods [1] and [2] can be mentioned.

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

[2] Mix an organic solvent solution of polyester resin with an aqueous medium, then salt the carboxyl groups in the polyester resin with a neutralizing agent, disperse the polyester resin in the aqueous solvent, and remove the organic solvent to form the resin. A method for producing a dispersion of fine particles.

Among the methods [1] to [2] above, method [2] is preferred from the viewpoint of ease of manufacturing resin particles.

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

Examples of the organic solvent in the organic solvent solution of 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. Examples include solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more thereof.
Specific examples of organic solvents include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, tetralin, etc.); aliphatic or alicyclic hydrocarbon solvents (n-hexane, n-heptane, mineral spirit, cyclohexane, etc.); chloride 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 Solvents: 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, alcohol solvents such as 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, and complex solvents such as N-methylpyrrolidone. Examples include cyclic compound solvents and mixed solvents of two or more of these solvents. Among the above organic solvents, volatile ones with a boiling point of less than 100°C are preferred. Preferred organic solvents include ethyl acetate, acetone, and methyl ethyl ketone.

The amount of organic solvent used per 100 parts by weight of the polyester resin is preferably 25 to 300 parts by weight, more preferably 25 to 100 parts by weight, even more preferably 25 to 70 parts by weight.

In the method for producing resin particles of the present invention, the aqueous solvent used in the step of mixing an organic solvent solution of a polyester resin with an aqueous solvent can be used without any restriction as long as it is a liquid containing water as an essential component. An aqueous solution of a solvent, an aqueous solution of a surfactant (s), an aqueous solution of a water-soluble polymer (t), a mixture of two or more of these, and the like can be used.

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

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, from the viewpoint of dispersibility.

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

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

Examples of the anionic surfactant (s-1) include carboxylic acids or their salts, sulfate ester salts, carboxymethylated salts, sulfonates, and phosphate ester salts.
Examples of the cationic surfactant (s-2) include quaternary ammonium salt type surfactants and amine salt type surfactants.
Examples of amphoteric surfactants (s-3) include carboxylate type amphoteric surfactants, sulfate ester salt type amphoteric surfactants, sulfonate type amphoteric surfactants, and phosphate ester salt type amphoteric surfactants. Can be mentioned.
Examples of the nonionic surfactant (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 No. 2002-284881.

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.

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

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

Dispersion methods used when mixing the organic solvent solution of the polyester resin of the present invention with an aqueous medium are not particularly limited, but include low-speed shearing, high-speed shearing, friction, high-pressure jet, and ultrasonic waves. Known equipment can be applied. A high-speed shearing method is preferred in order to reduce the particle size of the fine particles in the dispersion. When a high-speed shear type disperser is used, the rotation speed is not particularly limited, but is generally 1,000 to 30,000 rpm, preferably 5,000 to 20,000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is generally 0.1 to 5 minutes. The temperature is preferably 5 to 200°C, more preferably 20 to 100°C.
Dispersion devices include, for example, a homogenizer (manufactured by IKA), a polytron (manufactured by Kinematica), a batch emulsifier such as a 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 Imex Co., Ltd.), Thrasher, Trigonal Wet Micromixer Continuous emulsifiers such as crushers [manufactured by Nippon Coke Industry Co., Ltd.], Capitolon (manufactured by Eurotech), Fine Flow Mill [manufactured by Taiheiyo Kiko Co., Ltd.], microfluidizers [manufactured by Mizuho Industries, Ltd.], High-pressure emulsifiers such as Nanomizer (manufactured by Nanomizer), APV Gaulin (manufactured by Gaulin), membrane emulsifiers such as membrane emulsifier [manufactured by Reika Kogyo Co., Ltd.], vibromixer [manufactured by Reika Kogyo Co., Ltd.], etc. Examples include ultrasonic emulsifiers such as a vibrating emulsifier and an ultrasonic homogenizer (manufactured by Branson). Among these, preferred from the viewpoint of particle size uniformity are APV Gaulin, Homogenizer, TK Auto Homo Mixer, Ebara Milder, TK Filmix, and TK Pipeline Homo Mixer.

The amount of the aqueous medium used per 100 parts by weight of the polyester resin solution in an organic solvent is preferably 100 to 500 parts by weight, more preferably 150 to 400 parts by weight, even more preferably 150 to 300 parts by weight.

The solid concentration and volatile content of resin particles, etc. in the dispersion in the production method of the present invention were determined by the following method.
About 2.00 g of the sample before drying is weighed out, taking care not to cause precipitation of resin particles, etc., and dried at 120° C. for 1 hour. Take out the sample after drying, measure its weight to the second decimal place, calculate the solid content concentration (weight%) from (weight of sample after drying/weight of sample before drying) x 100, The volatile content (weight %) is calculated from sample weight−sample weight after drying)/sample weight before drying}×100.

The method of aggregating the resin particles obtained in the step of obtaining the resin particles is not particularly limited, and the resin particles obtained by the methods [1] to [2] etc. are placed in a tank equipped with a stirring device. Examples include a method of heating the dispersion, a method of adding a flocculant without heating, and a method of combining heating and addition of a flocculant.
When attempting to obtain aggregates of a desired size by aggregating resin fine particles while stirring, the particle size of the aggregates is controlled by the balance between the cohesive force between the particles and the shearing force caused by stirring. Alternatively, the cohesive force can be increased by adding a coagulant.

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

The temperature of the dispersion liquid placed in the tank when agglomerating the resin particles is preferably 5 to 100°C, more preferably 20 to 100°C, from the viewpoint of controlling the volume average particle size and particle size distribution of the resin particles.
Further, in the step of forming aggregates, the pH of the dispersion liquid 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 flocculant added is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin particles, from the viewpoint of controlling the volume average particle size and particle size distribution of the resin particles. .

The aggregation temperature when aggregation is carried out only by heating without using a coagulant is preferably 40 to 100°C, more preferably 50 to 100°C.
The time required for aggregation is optimized depending on the equipment shape and processing scale, but in order for the resin particles to reach the desired particle size, it is necessary to hold the resin particles at the above-mentioned predetermined temperature for at least 30 minutes or more. desirable. The temperature may be raised at a constant rate or may be raised in steps until the predetermined temperature is reached.

In order to increase the stability of the aggregates obtained in the aggregation step, it is preferable to carry out a ripening step after the aggregation step.
The aging step is a step in which the fine resin particles in the aggregate are fused and integrated by heat treatment or the like, and the shape becomes nearly spherical. Aggregates before the aging process are thought to be aggregates of resin fine particles that are electrostatically or physically agglomerated, but after the aging process, the resin fine particles that make up the aggregates are fused to each other, and the resin particles are It becomes possible to make the shape close to spherical. According to such a ripening process, by controlling the temperature, time, etc. of the ripening process, resin particles can be shaped into grape-shaped aggregates, potato-shaped with advanced fusion, spherical with further fused, etc. Resin particles of various shapes can be manufactured depending on 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 when fusing the aggregates is preferably 3 to 10, more preferably 5 to 10. Further, the time required for the aging step varies depending on the shape of the target resin particles, but it is desirable to maintain the temperature at the above-mentioned predetermined temperature for 0.1 to 10 hours, preferably 1 to 6 hours.

Note that it is preferable to add a surfactant or increase the pH value after the aggregation step, preferably before or during the ripening step. 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. By adding a surfactant after the aggregation process and before the completion of the ripening process, or by increasing the pH value, it is possible to suppress the agglomeration of the aggregates that aggregated in the aggregation process, and reduce the coarseness after the ripening process. Particle generation may be suppressed.

From the viewpoint of low-temperature fixability, it is preferable that the method for producing resin particles of the present invention further includes a step of removing an aqueous solvent from the dispersion of aggregates obtained by the step of aggregating resin fine particles.

As a method for removing the aqueous solvent from the dispersion, the following methods [3] to [5] and combinations of two or more of these methods can be applied.
[3] A method of drying the dispersion under reduced pressure or normal pressure.
[4] A method in which the dispersion is subjected to solid-liquid separation using a centrifugal separator, a spackle filter, and/or a filter press, etc., water, etc. are added as necessary, the solid-liquid separation is repeated, and then the obtained solid is dried.
[5] A method of freezing and drying the dispersion (so-called freeze-drying).

In methods [3] and [4] above, drying can be carried out using known equipment such as a fluidized bed dryer, a vacuum dryer, and a circulating air dryer. Further, if necessary, the particles can be classified using a wind classifier or a sieve to obtain a predetermined particle size distribution.

From the viewpoint of low-temperature fixability, the amount of the remaining aqueous solvent based on 100 parts by weight of the resin particles is preferably 0 to 2 parts by weight, more preferably 0 to 1 part by weight, even more preferably 0 to 0.1 part by weight, and particularly preferably It is 0 to 0.01 part 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 used as a recording material by fixing it on a support (paper, polyester film, etc.) using a copying machine, printer, etc. As a method for fixing to the support, known hot roll fixing methods, flash fixing methods, etc. can be applied.

The resin particles obtained by the production method of the present invention can be preferably used for developing electrostatic 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 Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Hereinafter, "parts" refer to parts by weight unless otherwise specified.

Each physical property value of the polyester resin etc. was measured by the following method.

<Method for measuring glass transition temperature (Tg)>
It was measured using a differential scanning calorimeter (manufactured by TA Instruments, DSC Q20) according to the method specified in ASTM D3418-82 (DSC method) under the following conditions.
(1) Raise temperature from 30℃ to 150℃ at 20℃/min (2) Hold at 150℃ for 10 minutes (3) Cool to -35℃ at 20℃/min (4) Hold at -35℃ for 10 minutes (5 ) The glass transition temperature was determined by analyzing the differential scanning calorimetry curve measured in the process of raising the temperature to 150° C. at 20° C./min (6) and (5).

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

<Method for measuring weight average molecular weight (Mw)>
The molecular weight was measured under the following conditions using a sample solution in which the polyester resin was dissolved in THF and the insoluble matter was filtered out using a glass filter.
Equipment: HLC-8120 manufactured by Tosoh Corporation
Column: TSK GEL GMH6 2 pieces [manufactured by Tosoh Corporation]
Measurement temperature: 40℃
Sample solution: 0.25% by weight THF solution Solution injection amount: 100μl
Detection device: Refractive index detector Reference material: 12 points of TSK standard 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)>
Measurement was performed using a differential scanning calorimeter {for example, "DSCQ20" [manufactured by TA Instruments Co., Ltd.]}. The crystalline polyester resin (C) was heated from 20°C to 150°C at 10°C/min for the first time, then cooled from 150°C to 0°C at 10°C/min, and then When the temperature is raised from 0°C to 150°C for the second time under the conditions of 10°C/min, the temperature showing the top of the endothermic peak in the second heating process is calculated as the endothermic peak of the crystalline polyester resin (C). It was taken as the peak top temperature.

<Production Example 1> [Production of titanium compound (titanium dihydroxybis(triethanolaminate))]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 634.0 parts (33.3 mol%) of ORGATIX TC-310 (manufactured by ORGATIC) and 366.0 parts (66.6 parts of triethanolamine) were placed. % by mole) and reacted at 80° C. for about 1 hour to obtain titanium dihydroxybis(triethanolaminate).

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

<Production Example 3> [Production of crystalline polyester resin (C)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 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(triethanolaminate) was added as a titanium compound, and the mixture was reacted for 4 hours at normal pressure and 180° C. under a nitrogen stream while distilling off the produced water. Further, the temperature was raised to 200° C. under reduced pressure of 0.5 to 2.5 kPa, and the mixture was reacted at 200° C. for 10 hours, and when the acid value reached 8, it was taken out to obtain a crystalline polyester resin (C). Note that the titanium compound of Production Example 1 above was used as titanium dihydroxybis(triethanolaminate).
The acid value of the crystalline polyester resin (C) was 8 mgKOH/g, the peak top temperature of the endothermic peak was 72°C, and the weight average molecular weight (Mw) was 20,000.

<Production Example 4> [Production of polyester resin (H)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 757.6 parts (51.8 mol%) of bisphenol A/PO 3 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-3P") were added. ), 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(triethanolaminate) as a condensation catalyst. The mixture was reacted for 4 hours at normal pressure and 180° C. under a nitrogen stream while distilling off the produced 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, and when the acid value reached 12 mgKOH/g, it was taken out to obtain a polyester resin (H).
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)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 103.3 parts (15.0 mol %) of bisphenol A/PO 2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P") were added. ), 539.6 parts (70.0 mol%) of bisphenol A/PO 3 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-3P"), 539.6 parts (70.0 mol%), bisphenol A/EO 2 mol adduct (Sanyo Chemical Industries, Ltd.) ), "Himer BPE-20") 97.1 parts (15.0 mol%), terephthalic acid 197.3 parts (60.0 mol%), isophthalic acid 65.8 parts (20.0 mol%), 1.3 parts of titanium dihydroxybis(triethanolaminate) and 0.3 parts of triethanolamine were added as titanium compounds, and the temperature was raised to 227°C under reduced pressure of 0.5 to 2.5 kPa, and the water produced was distilled. The mixture was allowed to react for 8 hours while being removed. 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 were added and reacted at 217°C for 8 hours under reduced pressure of 0.5 to 2.5 kPa, so that the acid value was 11 mgKOH/ It was taken out at the time when the weight reached 1.5 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 listed in Examples 2 to 23 in Table 1 were used. The acid value, Tg, and Mw of the obtained polyester resin are listed in Table 1.

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

<Comparative Example 3> [Manufacture of polyester resin (LR-3)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 103.3 parts (15.0 mol %) of bisphenol A/PO 2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P") were added. ), 539.6 parts (70.0 mol%) of bisphenol A/PO 3 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-3P"), 539.6 parts (70.0 mol%), bisphenol A/EO 2 mol adduct (Sanyo Chemical Industries, Ltd.) ), "Himer BPE-20") 97.1 parts (15.0 mol%), terephthalic acid 197.3 parts (60.0 mol%), isophthalic acid 131.6 parts (40.0 mol%), 1.3 parts of titanium dihydroxybis(triethanolaminate) and 1.3 parts of triethanolamine were added as titanium compounds, and the temperature was raised to 227°C under reduced pressure of 0.5 to 2.5 kPa, and the water produced was distilled. The mixture was allowed to react for 10 hours while being removed, and when the acid value reached 11 mgKOH/g, it was taken out to obtain a polyester resin (LR-3).
The acid value of the polyester resin (LR-3) was 11 mgKOH/g, the glass transition temperature (Tg) was 63.7°C, and the weight average molecular weight Mw was 13,000.

<Comparative Example 4> [Manufacture of polyester resin (LR-4)]
A polyester resin (LR-4) was obtained in the same manner as in Example 1, except that the amine compound was not used and the raw materials listed in Comparative Example 4 in Table 1 were used. The acid value, Tg, and Mw of the obtained polyester resin are listed in Table 1.

<Comparative Example 5> [Manufacture of polyester resin (LR-5)]
A polyester resin (LR-5) was obtained in the same manner as in Example 1, except that the raw materials listed in Comparative Example 5 in Table 1 were used and the acid value when adding isophthalic acid was 10 mgKOH/g. . The acid value, Tg, and Mw of the obtained polyester resin are listed in Table 1.

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

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

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

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

[Manufacture of colorant dispersion]
In a reaction vessel equipped with a stirring device, a heating/cooling device, a cooling tube, and a thermometer, 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 added. The mixture was heated to 30° C. with stirring at a rotational speed of 300 rpm, stirred at the same temperature for 30 minutes, and then wet-pulverized using an Ultra Visco Mill to obtain a black colorant dispersion. The volume-based median diameter of the obtained black colorant dispersion was 0.05 μm, and the solid content concentration was 20% by weight.

[Manufacture of release agent dispersion]
In a reaction vessel equipped with a stirring device, a heating/cooling device, a cooling tube, and a thermometer, 10 parts of Fischer-Tropsch wax [FT-0070 manufactured by Nippon Seiro Co., Ltd.], 0.5 part of sodium dodecylbenzenesulfonate, 15 parts of ion-exchanged water was added, and the temperature was raised to 95°C while stirring at a rotational speed of 300 rpm. After stirring at the same temperature for 30 minutes, the Fischer-Tropsch wax was cooled to 30°C over 1 hour to crystallize the Fischer-Tropsch wax into fine particles. The mixture was further wet-pulverized using an Ultra Visco Mill to obtain a release agent dispersion. The volume-based median diameter of the obtained mold release agent dispersion was 0.25 μm, and the solid content concentration was 50% by weight.

[Manufacture of resin particles (Z-1)]
A dispersion of resin fine particles (Cl-1) (Clb-1), a dispersion of resin fine particles (Ch) (Chb), A dispersion liquid (Ccb) of resin fine particles (Cc), a colorant dispersion liquid, and a mold release agent dispersion liquid were prepared so that the solid content became the parts shown in Table 2, 300 parts of ion-exchanged water was prepared, and the liquid temperature was set at 30°C. After adjusting the pH to 10, an aqueous sodium hydroxide solution having a concentration of 25% by weight was added while stirring to obtain a dispersion.
Next, in order to agglomerate the resin fine particles (Cl-1), resin fine particles (Ch), resin fine particles (Cc), colorant, and mold release agent, a flocculant with a concentration of 10% by weight was added while stirring at a rotation speed of 300 rpm. After adding the magnesium chloride aqueous solution and confirming that the volume average particle size was 5 μm by sampling appropriately, the temperature of the system was adjusted to 60 ° C., and then by adding a 0.3 M nitric acid aqueous solution, The pH was adjusted to 4.5 and after 30 minutes the pH was adjusted to 4.0. Fusion and spheroidization were performed by maintaining stirring for 3 hours.
Thereafter, it was cooled to 30° C. to obtain an aqueous dispersion of resin particles containing a colorant. Next, the resin particles were filtered and washed with water three times, separated by filtration, and dried for 18 hours in a blower circulation dryer at 40°C to obtain resin particles with 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 production of a dispersion (Clb-1) of resin fine particles (Cl-1), the same procedure was carried out except that the polyester resin (L-1) was replaced with polyester resins (L-2) to (L-10), respectively. After obtaining dispersions (Clb-2) to (Clb-10) of resin fine particles,
In Example 24, a dispersion (Clb-1) of resin fine particles (Cl-1) was mixed with a dispersion (Clb-2) of resin fine particles (Cl-2) to a dispersion (Clb-1) of resin fine particles (Cl-10). Resin particles (Z-2) to (Z-10) were obtained in the same manner as in Example 24, except for replacing each with 10).

<Comparative Examples 6 to 8> [Resin particles (Z'-1) to (Z'-3)]
In the production of a dispersion liquid (Clb-1) of resin fine particles (Cl-1), the same procedure was carried out except that the polyester resin (L-1) was replaced with polyester resins (LR-1) to (LR-3), respectively. After obtaining dispersions of resin fine particles (Clrb-1) to (Clrb-3),
In Example 24, a dispersion (Clb-1) of resin fine particles (Cl-1) was mixed with a dispersion (Clrb-1) of resin fine particles (Clr-1) to a dispersion (Clrb-3) of resin fine particles (Clr-3). Resin particles (Z'-1) to (Z'-3) were obtained in the same manner as in Example 24 except for replacing with 3).

<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) manufactured in Example 11 were mixed in a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After kneading for 30 minutes at 90°C using this roll, the mixture was rolled, cooled, and pulverized using a pulperizer to obtain a pigment masterbatch [MB1].

[Manufacture of fine particle dispersion [PD1]]
780 parts of water and 8 parts of sodium alkylallylsulfosuccinate (Eleminol JS-20, manufactured by Sanyo Chemical Industries, Ltd.) were placed in a reaction vessel equipped with a stirrer, a heating/cooling device, and a thermometer, and the mixture was homogenized by stirring at 200 rpm. did. After heating this to raise the system internal temperature to 85°C, 9 parts of a 10% by weight ammonium persulfate aqueous solution was 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. was added dropwise over 2 hours. After dropping, the mixture was aged at 85° C. for 4 hours to obtain a fine particle dispersion. The volume average particle diameter of the fine particles contained in the fine particle dispersion was 0.031 μm. Further, a portion of the fine particle dispersion was dried to isolate the resin. The resin content had an Mn of 18,700, an Mw of 154,000, a Tg of 64° C., and an acid value of 196 mgKOH/g.

[Manufacture of water phase s1]
955 parts of water, 15 parts of fine particle dispersion liquid [PD1], and 30 parts of sodium dodecyl diphenyl ether disulfonate aqueous solution (Eleminol MON7, manufactured by Sanyo Chemical Industries) were put into a container equipped with a stirring bar, and a milky white liquid [aqueous phase s1] was added. I got it.

[Manufacture of wax dispersion]
15 parts of Fischer-Tropsch wax (manufactured by Nippon Seiro Co., Ltd.: FT-0070) and 85 parts of ethyl acetate were placed in a reaction vessel equipped with a cooling tube, a thermometer, and a stirrer, and the mixture was heated to 80°C. The mixture was dissolved and cooled to 30° C. over 1 hour to crystallize the Fischer-Tropsch wax into fine particles, which were then wet-pulverized using “Ultra Viscomil” (manufactured by Imex) to prepare a [wax dispersion].

[Manufacture of resin particles (Z-11)]
Pour polyester resin (L-11), polyester resin (H), crystalline polyester resin (C), pigment masterbatch [MB1], and wax dispersion into a beaker so that the solid content becomes the number of parts shown in Table 2. Ethyl acetate was added to give a weight percent ethyl acetate solution, and the mixture was homogenized by dissolving and mixing to obtain an oil phase. 600 parts of [aqueous phase s1] was added to this oil phase, and dispersion was performed using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 25°C and a rotational speed of 12,000 rpm for 1 minute, and further in 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 steps of centrifuging 100 parts of the dispersion, adding 60 parts of water, centrifuging and solid-liquid separation twice, and drying at 35°C for 1 hour, a classifier [Elbojet] Co., Ltd.], the fine powder and coarse powder were removed and resin particles (Z-11 ) was obtained.

<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 polyester resin (L-11) was replaced with polyester resins (L-12) to (L-14), respectively. Ta.

<Example 38> [Resin particles (Z-15)]
In a beaker, put polyester resin (L-13), crystalline polyester resin (C), pigment masterbatch [MB1], and wax dispersion so that the solid content is in the parts shown in Table 2, and add 50% by weight ethyl acetate solution. Ethyl acetate was added to dissolve and mix to make the mixture homogeneous to obtain an oil phase. 600 parts of [aqueous phase s1] was added to this oil phase, and dispersion was performed using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 25°C and a rotational speed of 12,000 rpm for 1 minute, and further in 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 steps of centrifuging 100 parts of the dispersion, adding 60 parts of water, centrifuging and solid-liquid separation twice, and drying at 35°C for 1 hour, a classifier [Elbojet] Co., Ltd.], the fine powder and coarse powder are removed so that the fine powder of 3.17 μm or less is 12% by number or less and the coarse powder of 8.0 μm or more is 3% by volume or less. ] was obtained.

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

<Comparative Example 11> [Resin particles (Z'-6)]
In a beaker, put polyester resin (LR-1), crystalline polyester resin (C), pigment masterbatch [MB1], and wax dispersion so that the solid content is in the parts shown in Table 2, and add a 50% by weight ethyl acetate solution. Ethyl acetate was added to dissolve and mix to make the mixture homogeneous 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.) to perform a dispersion operation at 25°C for 1 minute at a rotation speed of 12,000 rpm, 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 steps of centrifuging 100 parts of the dispersion, adding 60 parts of water, centrifuging and solid-liquid separation twice, and drying at 35°C for 1 hour, a classifier [Elbojet] Co., Ltd.], the fine powder and coarse powder are removed so that the fine powder of 3.17 μm or less is 12% by number or less, and the coarse powder of 8.0 μm or more is 3% by volume or less. 6] was obtained.

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

Table 2 shows the blended parts and evaluation results of resin particles obtained in each Example and Comparative Example.

[Evaluation method]
Below, the methods for measuring and evaluating the emulsion stability, colorability b, compatibility with crystalline polyester resin (ΔTg) of the obtained resin, and the charging property, low temperature fixing property, and hot offset resistance of the resin particles are explained. explain.

<Emulsification stability>
The emulsion stability was evaluated by the rate of change (%) in the median diameter immediately after the polyester resin obtained according to the present invention was made into a dispersion liquid by the method described below and after it was left standing at room temperature for one week.
Specifically, each polyester resin (L) is made into a dispersion of resin fine particles according to the procedure for manufacturing a dispersion of resin fine particles (Cl-1) (Clb-1), and the solid content concentration is 10% by weight. After adjusting with ion-exchanged water as described above, the median diameter of the dispersion was measured using a dynamic light scattering particle distribution analyzer "SZ-100" (manufactured by Horiba, Ltd.). Thereafter, the median diameter of the dispersion liquid was remeasured after being allowed to stand 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 size immediately after dispersion) x 100 (%)
The smaller the rate of change, the better the emulsion stability.

<Colorability>
Methyl ethyl ketone (MEK) was added and dissolved in polyester resin (L) 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, evaluation is performed using the value of b, which represents the yellowness of the resin, and the lower the value, the better the coloring property.

<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 other resin (H)
A resin composition containing the polyester resin (H) and the polyester resin (L) of the present invention, which were prepared in the number of parts shown in Table 2, and uniformly dissolved by adding tetrahydrofuran to make a 20% by weight tetrahydrofuran solution, and the solvent was removed. The Tg(1) of the sample was measured.
Next, the polyester resin (L) of the present invention, the other resin polyester resin (H), and the crystalline polyester resin were charged in the parts shown in Table 2, and tetrahydrofuran was added to make a 20% by weight tetrahydrofuran solution. 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 which had been homogeneously dissolved and solvent removed was measured, and the Tg (2) of the crystalline polyester resin was determined using the following formula. The amount of change in Tg of the polyester resin upon addition was calculated.
Under these evaluation conditions, a larger difference in Tg means better compatibility, and a temperature of 10° C. or higher results in better compatibility with the crystalline polyester resin.
Note that Tg was measured using the same measuring method as 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 resin particles, the obtained resin particles (Z-1) to (Z-24), (Z'-1) to (Z'-6) and hydrophobic silica were evaluated. The toner was evaluated by uniformly mixing the toner at the following blending ratio.
Resin particles (Z): Hydrophobic silica [manufactured by Nippon Aerosil Co., Ltd., Aerosil R972]
=99 parts by weight: 1 part by weight.

<Charging property> (Charging amount)
(1) 0.5 g of toner and 10 g of ferrite carrier (manufactured by Powder Tech Co., Ltd., F-150) were placed in a 50 ml glass bottle, and the bottle was conditioned at 23° C. and relative humidity of 50% for 8 hours or more.
(2) Frictionally stirred at 90 rpm for 2 minutes using a Turbler shaker mixer, and 0.2 g of the mixed powder after stirring was loaded into a blow-off powder charge measuring device equipped with a stainless steel wire mesh with an opening of 20 μm, and a blow pressure of 10 KPa was applied. , the amount of charge on the remaining ferrite carrier was measured under the conditions of a suction pressure of 5 KPa, and the amount of charge on the toner (μC/g) was calculated by a standard method. Note that for toners, the higher the negative charge amount, the better the charging characteristics, and it is preferably −15 μC/g or less.
A blow-off charge measuring device [manufactured by Toshiba Chemical Corporation] was used for the measurement.

<Low temperature fixability>
The toner was uniformly placed on the paper surface at a concentration of 0.6 mg/cm ² . At this time, the powder was placed on the paper using a printer without a heat fixing device. Other methods may be used as long as the powder can be placed uniformly at the above weight density. The low-temperature fixing temperature, which is the temperature at which cold offset occurs, was measured when this paper was passed through a pressure roller at a fixing speed (heating roller circumferential speed) of 213 mm/sec and a fixing pressure (pressure roller pressure) of 10 kg/ ^cm2 . did. The lower the low-temperature fixing temperature, the better the low-temperature fixing properties. The low-temperature fixing temperature (°C) of the toner is shown in Table 2 as the low-temperature fixability (°C).

<Hot offset resistance>
The toner was uniformly placed on the paper surface at a concentration of 0.6 mg/cm ² . At this time, the powder was placed on the paper using a printer without a heat fixing device. Other methods may be used as long as the powder can be placed uniformly at the above weight density. The temperature at which hot offset occurs was measured when this paper was 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 . The higher the hot offset temperature, the better the hot offset resistance. The hot offset resistance temperature (°C) of the toner is shown in Table 2 as the hot offset resistance temperature (°C).

The polyester resin of the present invention has excellent emulsion stability, compatibility with crystalline polyester resin, and colorability, and the resin particles have excellent low-temperature fixing properties and charging properties, and are used for electrophotography, electrostatic recording, electrostatic printing, etc. 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 of bisphenol A (x1) and a carboxylic acid component (y) containing an aromatic dicarboxylic acid (y1), the method 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) Aromatic dicarboxylic acid (y1) contains isophthalic acid.
(4) A first polycondensation step in which the reactants are polycondensed 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. , the titanium compound is at least one compound selected from the group consisting of titanium dihydroxybis(triethanolaminate), titanium dihydroxy(diethanolaminate), and intramolecular polycondensate of titanium dihydroxybis(triethanolaminate). and the amine compound is at least one compound selected from the group consisting of alkylamines, alkanolamines, and heterocyclic amines, and the weight of the amine compound used in the first polycondensation step is greater than the alcohol component. (x) and the carboxylic acid component (y), and the weight of the titanium compound is 0.01 to 0.3% by weight based on the total weight of the alcohol component (x) and the carboxylic acid component (y). Based on weight, it is 0.01 to 0.4% by weight .
(5) A second polycondensation step is performed in which isophthalic acid is added to the reaction product obtained in the first polycondensation step and further polycondensed. The method for producing a polyester resin according to claim 1, wherein the second polycondensation step includes a step of 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 The method for producing a polyester resin according to claim 2, wherein the content is 0.4% by weight. Production of a polyester resin according to any one of claims 1 to 3, wherein the ratio of 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.