JP2022111083A - Polyester resin composition and resin particle - Google Patents

Abstract

To provide a polyester resin composition which has good emulsion stability and reduces variation in a particle diameter when forming the polyester resin composition into particles, and has good compatibility with other resin, and resin particles which are excellent in particle size distribution and low temperature fixability.SOLUTION: A polyester resin composition contains a polyester resin obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y), in which the alcohol component (x) contains an AO additive (x1) of bisphenol A, a content of the (x1) is 90-100 mol%, a content of a PO additive (x11) of the bisphenol A in the (x1) is 80-100 mol%, the carboxylic acid component (y) contains an aromatic dicarboxylic acid (y1), a content of the (y1) is 80-100 mol%, and a ratio of a terephthalic acid to an isophthalic acid in the (y1) is 30/70 to 70/30.SELECTED DRAWING: None

Description

The present invention relates to a polyester resin composition and 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 a polyester resin is dissolved in an organic solvent or melted to liquefy, and then forcibly dispersed in water using a surfactant such as an emulsifier or dispersant. . 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 (for example, Patent Document 1). 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.
Further, when the polyester resin is used for toner applications, the compatibility with other resins contained in the toner is important, but the compatibility of the polyester resin is still insufficient.

JP 2006-290963 A

An object of the present invention is to provide a polyester resin composition having good emulsion stability, reduced variation in particle size when granulated, and good compatibility with other resins, and a particle size distribution and low-temperature fixability. An object of the present invention is to provide excellent resin particles.

The present inventor has arrived at the present invention as a result of intensive studies. That is, the present invention is a polyester resin composition containing a polyester resin obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y), wherein the alcohol component (x) is an alkylene oxide adduct of bisphenol A (x1 ), the content of (x1) in (x) is 90 to 100 mol% based on the total number of moles of (x), and the propylene oxide adduct of bisphenol A (x11) in (x1) The content is 80 to 100 mol% based on the total number of moles of (x1), the carboxylic acid component (y) contains the aromatic carboxylic acid (y1), and the content of (y1) in (y) is 80 to 100 mol% based on the total number of moles of (y), and the molar ratio of terephthalic acid and isophthalic acid in (y1) (terephthalic acid/isophthalic acid) is 30/70 to 70/30, When the acid value of the polyester resin is α (mgKOH/g) and the total amount of terephthalic acid and isophthalic acid in the polyester resin is β (ppm), the following formulas (1) and (2) are satisfied. Polyester resin composition: Resin particles containing the polyester resin composition.
7≦α≦15 (1)
β≦α×250-1000 (2)

According to the present invention, a polyester resin composition having good emulsion stability, reduced variation in particle size when granulated, and good compatibility with other resins, and excellent particle size distribution and low temperature fixability It becomes possible to provide resin particles.

The present invention will be described in detail below.
[Polyester resin composition]
The polyester resin composition of the present invention is a polyester resin composition containing a polyester resin obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y), wherein the alcohol component (x) is an alkylene oxide of bisphenol A. containing the adduct (x1), the content of (x1) in (x) is 90 to 100 mol% based on the total number of moles of (x), and the propylene oxide adduct of bisphenol A (x11) The content in (x1) is 80 to 100 mol% based on the total number of moles of (x1), the carboxylic acid component (y) contains an aromatic carboxylic acid (y1), and (y) of (y1) is 80 to 100 mol% based on the total number of moles of (y), and the molar ratio of terephthalic acid and isophthalic acid in (y1) (terephthalic acid/isophthalic acid) is 30/70 to 70/ 30.
The polyester resin may be used alone or in combination of two or more. The alcohol component (x) and the carboxylic acid component (y) may be used alone or in combination of two or more. good.

The alcohol component (x) of the polyester resin in the present invention 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 a polyol (x3) having a valence of 3 or more. Moreover, a monoalcohol (x4) may be used as the alcohol component (x) 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, and bisphenol is an essential constituent. In addition to the propylene oxide (hereinafter "propylene oxide" is abbreviated as PO) adduct (x11) of A, for example, bisphenol A with ethylene oxide (hereinafter "ethylene oxide" is abbreviated as EO) adduct (x12) , and butylene oxide of bisphenol A (hereinafter, “butylene oxide” is abbreviated as BO) adduct (x13).

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 adduct (addition mole number is preferably 2 to 30) and 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 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.

As the aromatic dicarboxylic acid (y1), in addition to terephthalic acid and isophthalic acid, which are essential constituents, for example, aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, t-butylisophthalic acid, 2,6-naphthalene dicarboxylic acid and 4,4'-biphenyldicarboxylic acid) and the like.

Examples of the dicarboxylic acid (y2) other than the aromatic dicarboxylic acid (y1) 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.)}, 4 carbon atoms ~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 acid [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), an alkanedicarboxylic acid having 2 to 50 carbon atoms is preferable from the viewpoint of emulsion stability and compatibility with other resins, and more An alkanedicarboxylic acid having a carboxyl group at both ends of a chain saturated hydrocarbon group is preferred, and adipic acid is more preferred.

The alcohol component (x) contains an alkylene oxide adduct (x1) of bisphenol A, the content of (x1) in (x) is 90 to 100 mol% based on the total number of moles of (x), and other From the viewpoint of compatibility with the resin, it is preferably 95 to 100 mol%, more preferably 100 mol%.

The content of the propylene oxide adduct (x11) of bisphenol A in (x1) is 80 to 100 mol% based on the total number of moles of (x1), from the viewpoint of emulsion stability and compatibility with other resins. , preferably 90 to 100 mol %, more preferably 100 mol %.

The carboxylic acid component (y) contains an aromatic dicarboxylic acid (y1), the content of (y1) in (y) is 80 to 100 mol% based on the total number of moles of (y), and the emulsion stability from the viewpoint of, preferably 90 to 100 mol%, more preferably 99 to 100 mol%, still more preferably 100 mol%.

The molar ratio of terephthalic acid and isophthalic acid (terephthalic acid/isophthalic acid) in the aromatic dicarboxylic acid (y1) is 30/70 to 70/30, from the viewpoint of emulsion stability and compatibility with other resins. , preferably 50/50 to 70/30.

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).

In the present invention, the polyester resin can be produced in the same manner as 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, still more preferably 20 to 40 hours, from the viewpoints of ensuring the polycondensation reaction and emulsification stability. 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 0.5 to 15 kPa, and still more preferably 0.5 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.

At this time, an esterification catalyst can also be used as needed.
Examples of esterification catalysts include tin-containing catalysts (e.g., dibutyltin oxide, etc.), antimony trioxide, titanium-containing catalysts [e.g., titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, JP-A-2006-243715, The catalyst described in the publication {titanium diisopropoxybis (triethanolamine), titanium dihydroxybis (triethanolamine), titanium monohydroxy tris (triethanolamine), titanylbis (triethanolamine) and their intramolecular polycondensates, etc.], catalysts described in JP-A-2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy di terephthalate, etc.)], zirconium-containing catalysts (for example, zirconyl acetate etc.) and zinc acetate. Among these, titanium-containing catalysts are preferred.

The polyester resin of the present invention is represented by the following formulas (1) and (2), where α (mgKOH/g) is the acid value of the polyester resin and β (ppm) is the total amount of terephthalic acid and isophthalic acid in the polyester resin. meet.
7≦α≦15 (1)
β≦α×250-1000 (2)
The total amount of terephthalic acid and isophthalic acid in the polyester resin is calculated from the peak area obtained by LC-MS measurement of the solution obtained by dissolving the polyester resin in THF, forming a precipitate with methanol, and extracting it by filtration.
By setting the acid value α of the polyester resin and the total amount β of terephthalic acid and isophthalic acid in the polyester resin within the ranges of the formulas (1) and (2), the emulsifiability of the resin is improved.
When α<7, the hydrophilicity of the resin is too low and emulsification becomes difficult. On the other hand, when α>15, the hydrophilicity is too high and the dispersed particle size becomes too fine due to emulsification, making it impossible to control the particle size well.
If β>α×250-1000, the remaining unreacted terephthalic acid and carboxylic acid such as isophthalic acid become factors that hinder the emulsion stability when the resin is emulsified, resulting in deterioration of the emulsion stability.
For example, the acid value α of the polyester resin can be controlled by the reaction ratio between the alcohol component (x) and the carboxylic acid component (y) and the reaction rate of the esterification reaction. The total amount β of terephthalic acid and isophthalic acid in the polyester resin can be controlled by adjusting the amount of terephthalic acid and isophthalic acid added and the total amount of unreacted terephthalic acid and isophthalic acid. Further, the above range can be easily achieved by introducing a step of controlling the equilibrium time in the esterification reaction, specifically by introducing a step of stabilizing the equilibrium at the reaction temperature.

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 α of the polyester resin is 7 to 15 mgKOH/g, preferably 8 to 14 mgKOH/g, more preferably 8 to 13 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 40,000, more preferably 4,000, from the viewpoint of emulsion stability and low temperature fixability. ~35,000, more preferably 4,000 to 30,000, most preferably 5,000 to 25,000. When the weight average molecular weight is 4000 or more and the acid value α of the polyester resin and the total amount β of terephthalic acid and isophthalic acid in the polyester resin are within the ranges of the formulas (1) and (2), the emulsion stability is improved. When the weight-average molecular weight is 40,000 or less, the low-temperature fixability is improved.

The polyester resin composition of the present invention may contain a polyester resin other than the above, if necessary, in addition to the essential polyester resins described above. It is preferable from the viewpoint of the properties and compatibility.

In the present invention, the polyester resin (H) is a polyester resin obtained by polycondensation of the alcohol component (X) and the carboxylic acid component (Y). The same as component (y) can be used.
The alcohol component (X) is preferably an alkylene oxide adduct of bisphenol A (x1), more preferably a PO adduct of bisphenol A (x11) or an EO adduct of bisphenol A (x12).
Preferred as the carboxylic acid component (Y) are aromatic dicarboxylic acids (y1) (terephthalic acid, isophthalic acid), alkanedicarboxylic acids having 2 to 50 carbon atoms, and aromatic polycarboxylic acids having 9 to 20 carbon atoms.

The alcohol component (X) preferably contains an alkylene oxide adduct (x1) of bisphenol A, and the content of (x1) in (X) is 90 to 100 mol% based on the total number of moles of (X). From the viewpoint of compatibility with other resins, the content is more preferably 95 to 100 mol %, and still more preferably 100 mol %. In addition, the content of the propylene oxide adduct (x11) of bisphenol A in (x1) is preferably 80 to 100 mol% based on the total number of moles of (x1). From the viewpoint of compatibility, it is more preferably 90 to 100 mol %, still more preferably 100 mol %.

The carboxylic acid component (Y) preferably contains an aromatic dicarboxylic acid (y1), and the content of (y1) in (Y) is 80 to 100 mol% based on the total number of moles of (Y). is preferred, and from the viewpoint of emulsion stability, it is more preferably 90 to 100 mol %, and still more preferably 100 mol %. Further, the molar ratio of terephthalic acid and isophthalic acid (terephthalic acid/isophthalic acid) in the aromatic dicarboxylic acid (y1) is preferably 70/30 to 99/1. From the viewpoint of compatibility, it is more preferably 70/30 to 95/5.

From the viewpoint of emulsifiability, the polyester resin (H) has an acid value of α (mgKOH/g) and a total amount of terephthalic acid and isophthalic acid in the polyester resin (H) as β (ppm). Then, it is preferable to satisfy the following formulas (3) and (4).
7≦α≦15 (3)
β≤α×250-1000 (4)
The total amount of terephthalic acid and isophthalic acid in the polyester resin (H) is calculated from the peak area obtained by LC-MS measurement of the solution obtained by dissolving the polyester resin (H) in THF, forming a precipitate with methanol, and extracting by filtration. It's about what you did.
By setting the acid value α of the polyester resin (H) and the total amount β of terephthalic acid and isophthalic acid in the polyester resin (H) to the ranges of formulas (1) and (2), even when the weight average molecular weight is low The emulsifiability of the resin becomes good.

The acid value of the polyester resin (H) is preferably 7-15 mgKOH/g, more preferably 7-14 mgKOH/g, still more preferably 7-12 mgKOH/g. The acid value of the polyester resin can be measured by the method specified in JIS K0070 (1992 edition).

The weight average molecular weight of the polyester resin (H) in gel permeation chromatography (GPC) is preferably 40,000 to 100,000, more preferably 40,000 to 80, from the viewpoint of emulsion stability and compatibility. ,000, more preferably 40,000 to 75,000, and most preferably 40,000 to 70,000.

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 of the present invention can be used. 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-dodecane is a diol. 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).

In the polyester resin composition of the present invention, the weight ratio [(L)/(H)] of the polyester resin (L), which is the essential polyester resin, and the polyester resin (H), which is the other polyester resin, is 30/ 70 to 70/30 is preferred, and 40/60 to 60/40 is more preferred.

In the polyester resin composition of the present invention, the content of the polyester resin (L), which is an essential polyester resin, in the polyester resin composition is preferably 20 to 100% by weight, more preferably 20 to 100% by weight, based on the weight of the polyester resin composition. 20 to 75% by weight, more preferably 30 to 65% by weight.

The content of the polyester resin (H) in the polyester resin composition is preferably 20 to 75% by weight, more preferably 30 to 65% by weight, based on the weight of the polyester resin composition.

The content of the crystalline polyester resin (C) in the polyester resin composition is preferably 3 to 20% by weight, more preferably 5 to 15% by weight, based on the weight of the polyester resin composition.

[Resin particles]
The resin particles of the present invention contain the polyester resin composition of the present invention as an essential component. If necessary, various additives such as known resins other than the polyester resin composition of the present invention, colorants, release agents, and charge control agents can be mixed.

Resins other than the polyester resin composition of the present invention include vinyl resins, urethane resins, epoxy resins, and the like. Vinyl resins and urethane resins are preferred from the viewpoint of dispersion stability.

The content in the resin particles of the polyester resin composition of the present invention is preferably 30 to 97% by weight, more preferably 70 to 90% 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, per 100 parts by weight of the polyester resin composition of the present invention. When magnetic powder is used, the content of 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 composition.

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.), etc., from the group consisting of these release agents 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 with respect to the total 100 parts by weight of the polyester resin composition of the present invention. %.

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% by weight, based on the total 100 parts by weight of the polyester resin composition of the present invention. ~7.5% by weight.

The method for producing the resin particles of the present invention is not particularly limited. a dispersion polymerization method characterized by monodispersion; a dissolution suspension method in which the necessary resins are dissolved in a non-water-soluble organic solvent and then formed into resin particles in water; Examples thereof include the ester extension polymerization method disclosed in JP-A-2002-284881.
Among the above-mentioned production methods, the emulsion aggregation method is preferable from the viewpoint of particle size control of resin particles and low-temperature fixability, in which at least one kind of fine particles are aggregated to obtain particles having a desired particle size.

The emulsion aggregation method, which is a preferred production method among the methods for producing resin particles of the present invention, includes a step of mixing an organic solvent solution of a polyester resin with an aqueous medium to obtain resin fine particles containing a polyester resin composition, and aggregating the resin fine particles. including a step (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 composition is not particularly limited, but includes the following [1] to [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.

Further, when a plurality of polyester resins are contained, the polyester resins may be dispersed separately, or may be dispersed after being mixed in advance, but from the viewpoint of particle size distribution, it is preferable to disperse the polyester resins separately. .
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 the resin particles and the like in the dispersion in the method for producing resin particles 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 diameter 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 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 being fixed on a support (paper, polyester film, etc.) by a printer or the like. 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 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 version). 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 sample in THF and filtering the undissolved matter through a glass filter to obtain a sample solution, and measured the molecular weight 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>
It was measured using a differential scanning calorimeter {for example, "DSCQ20" [manufactured by TA Instruments]}. The sample was first heated from 20°C to 150°C at a rate of 10°C/min, then cooled from 150°C to 10°C/min to 0°C, and then from 0°C to 10°C/min. The temperature indicating the top of the endothermic peak in the process of the second temperature rise when the second temperature was raised to 150° C. under the condition of 150° C. was taken as the peak top temperature of the endothermic peak of the sample.

<Method for measuring the total amount of terephthalic acid and isophthalic acid>
The total amount of terephthalic acid and isophthalic acid remaining in the polyester resin was determined by a quantitative method using a liquid chromatograph/mass spectrometer (LC/MS).
<Adjustment of sample solution>
After about 0.2 g of polyester resin was dissolved in 1 ml of THF, 10 g of methanol was added dropwise at 10 g/min while stirring with a stirrer to precipitate the resin, and terephthalic acid and isophthalic acid remaining in the resin were dissolved in methanol. Extracted. A sample solution was obtained by filtering the methanol soluble matter through a 0.4 μ filter.
<Equipment conditions for LC/MS>
Apparatus: LCMS-8030 (manufactured by Shimadzu Corporation)
Column: Inert Sustain C18 (2.0 μm×2.1 mm×10 cm)
Mobile phase A: 10 mM ammonium acetate/methanol = 80/20
Mobile phase B: Methanol Flow rate: 0.2 ml/min
Injection volume: 0.1 μl
Detector: MS
Ion source: ESI (±)
A standard solution of terephthalic acid and isophthalic acid was prepared, and the total amount of terephthalic acid and isophthalic acid in the polyester resin was calculated by the calibration curve method.

<Production Example 1> [Production of titanium-containing catalyst (titanium dihydroxybis(triethanolamine))]
634.0 parts (33.3 mol%) of TC-310 (manufactured by ORGATIC) and 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 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 an esterification catalyst, and the mixture was reacted at normal pressure at 180° C. under a nitrogen stream for 4 hours 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-containing catalyst 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 3> [Production of polyester resin (L-1)]
401.1 parts (26.0 mol%) of bisphenol A/PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P") was added to a reaction tank equipped with a cooling tube, a stirrer and a nitrogen inlet tube. ), bisphenol A · PO 3 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-3P") 172.7 parts (10.0 mol%), bisphenol A · EO 2 mol adduct (Sanyo Chemical Industries Co., Ltd. ), “Hymer BPE-20”) 130.5 parts (9.0 mol%), ethylene glycol 13.7 parts (5.0 mol%), terephthalic acid 210.6 parts (28.7 mol%), isophthalic 90.3 parts (12.3 mol %) of acid, 58.1 parts (9.0 mol %) of adipic acid, and 2.5 parts of titanium dihydroxybis(triethanolamine) as an esterification catalyst were added, and the reaction was carried out under normal pressure. The reaction was carried out at 180° C. for 4 hours under a nitrogen stream while distilling off the generated water. Furthermore, the temperature is raised to 200°C under a reduced pressure of 0.5 to 2.5 kPa, and the reaction is performed at 200°C for 20 hours. After equilibration and stabilization for 4 hours, the mixture was taken out to obtain a polyester resin (L-1).
Polyester resin (L-1) has an acid value (α) of 12 mgKOH/g, a glass transition temperature (Tg) of 62° C., a weight average molecular weight (Mw) of 11,000, and the sum of terephthalic acid and isophthalic acid in the polyester resin. The amount (β) was 1750 ppm.

<Production Examples 4 to 20> [Production of polyester resins (L-2) to (L-18)]
Polyester resins (L-2) to (L-18) were obtained in the same manner as in Production Example 3 except that the raw materials described in Production Examples 4 to 20 in Table 1 were used. Table 1 shows the acid value (α), Tg, Mw, the right side of formula (2), and the total amount (β) of terephthalic acid and isophthalic acid in the polyester resin.

<Production Example 21> [Production of polyester resin (H-1)]
94.4 parts (7.2 mol%) of bisphenol A/PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P") was added to a reactor equipped with a cooling tube, stirrer and nitrogen inlet tube. ), bisphenol A · PO 3 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-3P") 660.0 parts (44.8 mol%), terephthalic acid 200.9 parts (32.0 mol%) , 67.0 parts (10.7 mol%) of isophthalic acid, 39.4 parts (5.4 mol%) of trimellitic anhydride, and 2.5 parts of titanium dihydroxybis(triethanolamine) as an esterification catalyst, The reaction was carried out for 4 hours under normal pressure at 180° C. under a nitrogen stream while distilling off the generated water. Furthermore, the temperature was raised to 200°C under a reduced pressure of 0.5 to 2.5 kPa, and the reaction was performed at 200°C for 18 hours. After equilibration and stabilization for 4 hours, the mixture was taken out to obtain a polyester resin (H-1).
Polyester resin (H-1) has an acid value of 12 mgKOH/g, a glass transition temperature (Tg) of 59°C, a weight average molecular weight (Mw) of 55,000, and a total amount of terephthalic acid and isophthalic acid in the polyester resin (β ) was 1500 ppm.

<Production Examples 22 to 29> [Production of polyester resins (H-2) to (H-9)]
Polyester resins (H-2) to (H-9) were obtained in the same manner as in Production Example 21 except that the raw materials described in Production Examples 22 to 29 in Table 2 were used. Table 2 shows the acid value (α), Tg, Mw, the right side of formula (2), and the total amount (β) of terephthalic acid and isophthalic acid in the polyester resin.

<Production Example 30> [Production of polyester resin (H-10)]
280.2 parts (20.7 mol%) of bisphenol A/PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P") was 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, Ltd., "Hymer BP-3P") 470.5 parts (31.1 mol%), terephthalic acid 175.7 parts (27.0 mol%) , isophthalic acid 75.3 parts (11.6 mol%) trimellitic anhydride 36.3 parts (4.8 mol%), adipic acid 27.6 parts (4.8 mol%) titanium dihydroxy bis as an esterification catalyst 2.5 parts of (triethanolamine) was added and reacted for 4 hours under normal pressure at 180° C. under a nitrogen stream while distilling off the water produced. 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 6 hours. rice field.
The polyester resin (HR-1) has an acid value (α) of 12 mgKOH/g, a glass transition temperature (Tg) of 60°C, a weight average molecular weight (Mw) of 51,000, and the sum of terephthalic acid and isophthalic acid in the polyester resin. The amount (β) was 3000 ppm.

<Comparative Production Examples 1 to 6> [Production of polyester resins (LR-1) to (LR-6)]
Polyester resins (LR-1) to (LR-6) were obtained in the same manner as in Production Example 3 except that the raw materials described in Comparative Production Examples 1 to 6 in Table 1 were used. Table 1 shows the acid value (α), Tg, Mw, the right side of formula (2), and the total amount (β) of terephthalic acid and isophthalic acid in the polyester resin.

<Comparative Production Example 7> [Production of polyester resin (LR-7)]
135.6 parts (10.0 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, Ltd., "Hymer BP-3P") 607.2 parts (39.9 mol%), terephthalic acid 113.9 parts (17.6 mol%) , 211.5 parts (32.6 mol%) of isophthalic acid, and 2.5 parts of titanium dihydroxybis(triethanolamine) as an esterification catalyst are added, and the water produced is removed at normal pressure at 180 ° C. under a nitrogen stream. The reaction was continued for 4 hours while distilling off. Furthermore, the temperature was raised to 220°C under a reduced pressure of 0.5 to 2.5 kPa, and the reaction was allowed to proceed at 220°C for 30 hours. After equilibration and stabilization for 10 hours, the mixture was taken out to obtain a polyester resin (LR-7).
Polyester resin (LR-7) has an acid value (α) of 6 mgKOH/g, a glass transition temperature (Tg) of 62°C, a weight average molecular weight (Mw) of 15,000, and the sum of terephthalic acid and isophthalic acid in the polyester resin. The amount (β) was 150 ppm.

<Comparative Production Example 8> [Production of polyester resin (LR-8)]
135.7 parts (10.0 mol%) of bisphenol A/PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P") was 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, Ltd., "Hymer BP-3P") 607.9 parts (39.9 mol%), terephthalic acid 113.5 parts (17.5 mol%) , 210.7 parts (32.5 mol%) of isophthalic acid, and 2.5 parts of titanium dihydroxybis(triethanolamine) as an esterification catalyst are added, and the water produced is removed under normal pressure at 180 ° C. under a nitrogen stream. The reaction was continued for 4 hours while distilling off. Furthermore, 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 8 hours. rice field.
The polyester resin (LR-8) has an acid value (α) of 7 mgKOH/g, a glass transition temperature (Tg) of 62°C, a weight average molecular weight Mw of 13,000, and the total amount of terephthalic acid and isophthalic acid in the polyester resin ( β) was 1400 ppm.

<Comparative Production Examples 9 to 10> [Production of polyester resins (LR-9) to (LR-10)]
Polyester resins (LR-9) to (LR-10) were obtained in the same manner as in Comparative Production Example 8 except that the raw materials described in Comparative Production Examples 9 to 10 in Table 1 were used. Table 1 shows the acid value (α), Tg, Mw, the right side of formula (2), and the total amount (β) of terephthalic acid and isophthalic acid in the polyester resin.

Table 1 shows the number of parts and physical properties of the polyester resins (L-1) to (L-18) and (LR-1) to (LR-10).

Table 2 shows the number of parts and physical properties of the polyester resins (H-1) to (H-10).

<Example 1> [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-1) of Resin Fine Particles (Ch-1)]
Fine resin particles (Ch-1) were prepared 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) was replaced with the polyester resin (H-1). A dispersion (Chb-1) was obtained. The volume-based median diameter of the fine resin particles (Ch-1) was 0.15 μm, and the solid concentration of the dispersion (Chb-1) 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) and a dispersion (Chb -1), 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 3, and 300 parts of ion-exchanged water was charged, and the liquid After adjusting the temperature to 30° C., a sodium hydroxide aqueous 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-1), the resin fine particles (Cc), the colorant, and the release agent, a concentration of 10 wt. % magnesium chloride aqueous solution, and after confirming that the volume average particle diameter is 5 μm by appropriately sampling, the temperature of the system is adjusted to 60° C., and then 0.3 M nitric acid aqueous solution is added. The pH was adjusted to 4.5 by 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 polyester resin composition (P-1), a release agent, and 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 2 to 3> [Resin particles (Z-2) to (Z-3)]
In the production of the dispersion (Chb-1) of the fine resin particles (Ch-1) in Example 1, except that the polyester resin (H-1) was replaced with the polyester resins (H-2) to (H-3). After obtaining dispersions (Chb-2) to (Chb-3) of fine resin particles in the same manner,
In Example 1, the dispersion (Chb-1) of the resin fine particles (Ch-1) was changed to the dispersion (Chb-2) of the resin fine particles (Ch-2), the dispersion of the resin fine particles (Ch-3) (Chb- Resin particles (Z-2) to (Z-3) containing the polyester resin compositions (P-2) to (P-3) were obtained in the same manner, except that 3) was substituted.

<Examples 4 to 8> [Resin particles (Z-4) to (Z-8)]
In the production of the dispersion (Clb-1) of the fine resin particles (Cl-1) in Example 1, except that the polyester resin (L-1) was replaced with the polyester resins (L-2) to (L-6). After obtaining dispersions (Clb-2) to (Clb-6) of fine resin particles in the same manner,
In Example 1, 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-6) (Clb- Resin particles (Z-4) to (Z-8) containing the polyester resin compositions (P-4) to (P-8) were obtained in the same manner except that the resin particles (Z-4) to (Z-8) were respectively replaced with 6).

<Examples 13 to 20> [Resin particles (Z-13) to (Z-20)]
Except for replacing the polyester resin (L-1) with the polyester resins (L-11) to (L-18) in the production of the dispersion (Clb-1) of the fine resin particles (Cl-1) in Example 1 After obtaining dispersions (Clb-11) to (Clb-18) of fine resin particles in the same manner,
In Example 1, the dispersion (Clb-1) of the fine resin particles (Cl-1) was changed to the dispersion (Clb-11) of the fine resin particles (Cl-11) to the dispersion (Clb-18) of the fine resin particles (Cl-18). Resin particles (Z-13) to (Z-20) containing the polyester resin compositions (P-13) to (P-20) were obtained in the same manner, except that the polyester resin compositions (P-13) to (P-20) were respectively replaced with 18).

<Examples 21 to 27> [Resin particles (Z-21) to (Z-27)]
Except for replacing the polyester resin (H-1) with the polyester resins (H-4) to (H-10) in the production of the dispersion (Chb-1) of the fine resin particles (Ch-1) in Example 1 Similarly, after obtaining dispersions (Chb-4) to (Chb-10) of fine resin particles,
In Example 1, the dispersion (Chb-1) of the resin fine particles (Ch-1) was changed to the dispersion (Chb-4) of the resin fine particles (Ch-4), the dispersion of the resin fine particles (Ch-10) (Chb- Resin particles (Z-21) to (Z-27) containing the polyester resin compositions (P-21) to (P-27) were obtained in the same manner, except that 10) was substituted.

<Comparative Examples 1 to 8> [Resin particles (Z'-1) to (Z'-8)]
In the production of the dispersion (Clb-1) of the resin fine particles (Cl-1) in Example 1, the polyester resin (L-1) was replaced with the polyester resins (LR-1) to (LR-8), respectively, and the resin fine particles Dispersion of fine resin particles (Clrb-1) was prepared in the same manner as above, except that polyester resin (H-1) was replaced with polyester resin (H-10) in the production of dispersion (Chb-1) of (Ch-1). After obtaining ~ (Clrb-8), (Chb-10),
In Example 1, 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-8). In 8), polyester resin composition (P Resin particles (Z'-1) to (Z'-8) containing '-1) to (P'-8) were obtained.

<Example 9> [Resin particles (Z-9)]
[Production of Pigment Masterbatch [MB1]]
1200 parts of water, 40 parts of carbon black (manufactured by Mitsubishi Chemical Corporation: MA100), and 20 parts of the polyester resin (L-7) produced in Example 7 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 part of the fine particle dispersion was dried to isolate the resin, which 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-9)]
Polyester resin (L-7), polyester resin (H-1), crystalline polyester resin (C), pigment masterbatch [MB1], and wax dispersion were charged into a beaker so that the solid content was the number of parts shown in Table 3. Ethyl acetate was further added to obtain a 50% by weight ethyl acetate solution, followed by dissolution, mixing and homogenization 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 under the conditions of 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 containing the polyester resin composition (P-9).
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-9 ).

<Examples 10 to 12> [Resin particles (Z-10) to (Z-12)]
Polyester resin compositions (P-10) to (P-12) were prepared in the same manner as in Example 9, except that the polyester resin (L-7) was replaced with the polyester resins (L-8) to (L-10). Resin particles (Z-10) to (Z-12) containing

<Comparative Examples 9 to 10> [Resin particles (Z'-9) to (Z'-10)]
In Example 9, the same procedure was repeated except that polyester resin (L-7) was replaced with polyester resins (LR-9) to (LR-10) and polyester resin (H-1) was replaced with polyester resin (H-10). Thus, resin particles (Z'-9) to (Z'-10) containing the polyester resin compositions (P'-9) to (P'-10) were obtained.

Table 3 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, compatibility, and low-temperature fixability of resin particles of the obtained polyester resin composition are described below.

<Emulsion stability>
The emulsion stability of the polyester resin composition of the present invention was evaluated by the change rate (%) of the median diameter immediately after making the polyester resin of the present invention into a dispersion liquid by the following method and after standing at room temperature for one week.
Specifically, each polyester resin is used as a dispersion liquid of resin particles according to the procedure for producing a dispersion liquid (Clb-1) of fine resin particles (Cl-1), and the solid content concentration is 10% by weight. After adjustment with exchanged water, 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.). Thereafter, the median diameter of the dispersion after standing at room temperature for 1 week was measured again, and the rate of change was calculated by 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.

<Particle size distribution>
The particle size distribution of the resin particles (Z) in the present invention was calculated from the volume average particle diameter and number average particle diameter of the resin particles (Z) obtained in each example and comparative example using the following formula.
Particle size distribution=volume average particle size/number average particle size The volume average particle size and number average particle size of the resin particles (Z) were measured using "Multisizer IV" (manufactured by Coulter, Inc.) or the like.
Specifically, 0.1 to 5 mL of a surfactant (alkylbenzenesulfonate) as a dispersant was added to 100 to 150 mL of ISOTON-II (manufactured by Beckman Coulter, Inc.), which is an electrolytic aqueous solution. Furthermore, 2 to 20 mg of the measurement sample is added, and the electrolytic solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser. , the number was measured and the volume distribution and the number distribution were calculated. From the obtained distribution, the volume average particle diameter and number average particle diameter of the resin particles were determined.
If the volume average particle size/number average particle size is 1.20 or less, it means that the particle size distribution is excellent.

<Compatibility (ΔTg)>
Compatibility with other resins was evaluated by comparing the amount of change in Tg (ΔTg) of the polyester resin of the present invention when the crystalline polyester resin was added.
First, the polyester resin (L) and the polyester resin (H) of the present invention were prepared in the number of parts shown in Table 3, and tetrahydrofuran was added to form a 20% by weight tetrahydrofuran solution, uniformly dissolved, and the solvent was removed from the polyester resin. Tg was measured. Next, the polyester resin (L), the polyester resin (H) and the crystalline polyester resin of the present invention were added in the parts shown in Table 3, and tetrahydrofuran was added to obtain a 20% by weight tetrahydrofuran solution, followed by uniform dissolution, The Tg of the resin composition containing the solvent-removed crystalline polyester resin was measured, and the difference between the Tg of the polyester resin and the Tg of the polyester resin composition containing the crystalline polyester resin was calculated by the following formula.
Under these evaluation conditions, the greater the difference in Tg, the more excellent the compatibility.
The Tg was measured by the same method as for the Tg of the polyester resin of the present invention.
Compatibility (ΔTg) = | Tg of polyester resin composition containing polyester resin and crystalline polyester resin - Tg of polyester resin |

<Low temperature fixability>
Regarding the evaluation of the low-temperature fixability of the resin particles, the obtained resin particles (Z-1) to (Z-27) and (Z'-1) to (Z'-10) and hydrophobic silica were blended as follows. Evaluation was made by uniform mixing at a ratio to obtain a toner.
Resin particles (Z): Hydrophobic silica [Nippon Aerosil Co., Ltd., Aerosil R972]
= 99 parts by weight: 1 part by weight.
The toner was evenly placed on the paper so as to be 0.85 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.
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 , and the temperature at which cold offset occurred (MFT) was measured.
The lower the temperature at which cold offset occurs, the better the low-temperature fixability.

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

Claims (2)

A polyester resin composition containing a polyester resin obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y),
The alcohol component (x) contains an alkylene oxide adduct (x1) of bisphenol A, the content of (x1) in (x) is 90 to 100 mol% based on the total number of moles of (x), and The content of the propylene oxide adduct (x11) of bisphenol A in (x1) is 80 to 100 mol% based on the total number of moles of (x1),
The carboxylic acid component (y) contains an aromatic dicarboxylic acid (y1), the content of (y1) in (y) is 80 to 100 mol% based on the total number of moles of (y), and (y1 ) has a molar ratio of terephthalic acid and isophthalic acid (terephthalic acid/isophthalic acid) of 30/70 to 70/30,
When the acid value of the polyester resin is α (mgKOH/g) and the total amount of terephthalic acid and isophthalic acid in the polyester resin is β (ppm), the following formulas (1) and (2) are satisfied. Polyester resin composition.
7≦α≦15 (1)
β≤α×250-1000 (2) Resin particles containing the polyester resin composition according to claim 1 .