JP7513643B2 - Polyester resin composition and resin particles - Google Patents

Description

The present invention relates to a polyester resin composition and resin particles.

Since polyester resins are mostly formed from carbon-carbon bonds, they are hydrophobic and hardly dissolve in water. Therefore, the methods generally known for preparing aqueous dispersions of polyester resins are 1) forced emulsification and 2) self-emulsification.
1) The forced emulsification method is a method in which polyester resin is dissolved or melted in an organic solvent to make it liquefied, and then this is forcibly dispersed in water using a surfactant such as an emulsifier or dispersant. This method has the problem that water resistance, storage stability, electrical properties, etc. are significantly inferior because a large amount of low molecular weight hydrophilic compound (surfactant) is used in this method.
2) The self-emulsification method is a method in which a polyester resin having polar groups (such as carboxylic acid groups or sulfonic acid groups) in the molecule is dissolved in a mixed solution of an organic solvent and water, and then water is added to cause phase inversion and self-emulsification (for example, Patent Document 1). By not using a surfactant, the problem of 1) can be overcome, but conversely, control of the physical properties of the resin has a large effect on the emulsification properties, so stabilization of the resin becomes an issue.
Furthermore, when a polyester resin is used in toner applications, compatibility with other resins contained in the toner becomes important, but the compatibility of the polyester resins is not yet sufficient.

JP 2006-290963 A

An object of the present invention is to provide a polyester resin composition containing a polyester resin having good emulsion stability, and resin particles having excellent particle size distribution and low-temperature fixability.

The present inventors have conducted extensive research and have arrived at the present invention. That is, the present invention relates to a polyester resin composition comprising a polyester resin obtained by polycondensation of an alcohol component (x) and a carboxylic acid component (y),
The polyester resin comprises a polyester resin (L), a polyester resin (H) and a crystalline polyester resin (C),
the alcohol component (x) of the polyester resin (L) contains an alkylene oxide adduct of bisphenol A (x1), the content of (x1) in (x) being 90 to 100 mol % based on the total number of moles of (x), and the content of a propylene oxide adduct of bisphenol A (x11) in (x1) being 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), the molar ratio of terephthalic acid to isophthalic acid in (y1) (terephthalic acid/isophthalic acid) is 30/70 to 70/30, and the weight average molecular weight of the polyester resin (L) is 4,000 to 35,000;
When the acid value of the polyester resin (L) is α _L (mg KOH/g) and the total amount of terephthalic acid and isophthalic acid in the polyester resin (L) is β _L (ppm), the following formulas (1) and (2) are satisfied:
the alcohol component of the polyester resin (H) contains an alkylene oxide adduct of bisphenol A (x1), the content of (x1) in (x) being 90 to 100 mol % based on the total number of moles of (x), and the content of a propylene oxide adduct of bisphenol A (x11) in (x1) being 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), the molar ratio of terephthalic acid to isophthalic acid in (y1) (terephthalic acid/isophthalic acid) is 70/30 to 95/5, and the weight average molecular weight of the polyester resin (H) is 40,000 to 100,000;
When the acid value of the polyester resin (H) is α _H (mg KOH/g) and the total amount of terephthalic acid and isophthalic acid in the polyester resin (H) is β _H (ppm), the following formula (3) is satisfied:
The alcohol component (x) of the crystalline polyester resin (C) is an alkylene glycol having 2 to 12 carbon atoms, and the carboxylic acid component (y) of the crystalline polyester resin (C) is an alkanedicarboxylic acid having 2 to 50 carbon atoms; and
The content of the polyester resin (L) in the polyester resin composition is 20 to 75% by weight, the content of the polyester resin (H) in the polyester resin composition is 20 to 75% by weight, and the content of the crystalline polyester resin (C) in the polyester resin composition is 3 to 20% by weight;
and resin particles containing the polyester resin composition.
7≦α _L ≦15 (1)
β _L ≦α _L × 250-1000 (2)
7≦α _H ≦15 (3)

According to the present invention, it is possible to provide a polyester resin composition containing a polyester resin having good emulsion stability, and resin particles having excellent particle size distribution and low-temperature fixability.

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 polycondensing an alcohol component (x) and a carboxylic acid component (y), wherein the alcohol component (x) contains 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 content of a propylene oxide adduct of bisphenol A (x11) 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), 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 to 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 kinds. The alcohol component (x) and the carboxylic acid component (y) may be used alone or in combination of two or more kinds.

The alcohol component (x) of the polyester resin in the present invention includes the alkylene oxide adduct (x1) of bisphenol A, which is an essential component, as well as diols (x2) other than the alkylene oxide adduct (x1) of bisphenol A and/or polyols (x3) having a valence of three or more, which will be described later. In addition, monoalcohols (x4) may be used as the alcohol component (x) if necessary.

The alkylene oxide adduct of bisphenol A (x1) is a compound obtained by adding an alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenol A. In addition to the essential component propylene oxide (hereinafter, "propylene oxide" will be abbreviated as PO) adduct of bisphenol A (x11), examples include ethylene oxide (hereinafter, "ethylene oxide" will be abbreviated as EO) adduct of bisphenol A (x12) and butylene oxide (hereinafter, "butylene oxide" will be abbreviated as BO) adduct of bisphenol A (x13).

From the viewpoints of chargeability and storage stability, the number of moles of alkylene oxide added in the alkylene oxide adduct of bisphenol A (x1) is preferably 2 to 30, more preferably 2 to 10, and even more preferably 2 to 5.

Diols (x2) other than the alkylene oxide adduct of bisphenol A (x1) include alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 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 (for example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene oxide (EO, PO, BO, etc.) adducts of the above alicyclic diols (preferably 1 to 30 moles added), alkylene oxide (EO, PO, BO, etc.) adducts of bisphenols (bisphenol F, bisphenol S, etc.) (preferably 2 to 30 moles added), polylactone diols (poly ε-caprolactone diol, etc.), and polybutadiene diols.

Examples of trivalent or higher polyols (x3) include alkane polyols and their intramolecular or intermolecular dehydration products (e.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.), sugars and their derivatives (e.g., sucrose and methyl glucoside, etc.), alkylene oxide adducts of trisphenols (trisphenol PA, etc.) (the number of moles added is preferably 2 to 30), alkylene oxide adducts of novolac resins (including phenol novolac and cresol novolac, etc., with an average degree of polymerization of preferably 3 to 60) (the number of moles added is preferably 2 to 30), and acrylic polyols [copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers, etc.].

Examples of 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 lignoceryl 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 preferred, and an alkylene glycol having 2 to 12 carbon atoms is more preferred.

The carboxylic acid component (y) of the polyester resin includes, in addition to the essential aromatic dicarboxylic acid (y1), dicarboxylic acid (y2) and/or trivalent or higher polycarboxylic acid (y3), as described below, and anhydrides and lower alkyl (carbon number 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these acids. In addition, monocarboxylic acid (y4) may be used as the carboxylic acid component (y) if necessary.

Examples of aromatic dicarboxylic acids (y1) include terephthalic acid and isophthalic acid, which are essential components, as well as aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid).

Examples of dicarboxylic acids (y2) other than the aromatic dicarboxylic acids (y1) include alkane dicarboxylic acids having 2 to 50 carbon atoms (alkane dicarboxylic 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-octadecane dicarboxylic acid, etc.), alkane dicarboxylic acids having carboxyl groups at other ends of a chain saturated hydrocarbon group (decyl succinic acid, etc.)), alkene dicarboxylic acids having 4 to 50 carbon atoms (alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, etc.), and alicyclic dicarboxylic acids having 6 to 40 carbon atoms (dimer acids (dimerized linoleic acid, etc.)). In addition, anhydrides or lower alkyl esters of these acids may also be used.

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

Examples of monocarboxylic acids (y4) include aromatic monocarboxylic acids having 7 to 37 carbon atoms (including the carbonyl group carbon) (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), and aliphatic monocarboxylic acids having 2 to 50 carbon atoms (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 the carboxylic acid component (y) contains a component other than the aromatic dicarboxylic acid (y1), from the viewpoint of emulsion stability and compatibility with other resins, an alkanedicarboxylic acid having 2 to 50 carbon atoms is preferred, more preferably an alkanedicarboxylic acid having carboxyl groups at both ends of a chain saturated hydrocarbon group, and even more preferably adipic acid.

The alcohol component (x) 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), and from the viewpoint of compatibility with other resins, it is preferably 95 to 100 mol%, and more preferably 100 mol%.

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

The carboxylic acid component (y) 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), and from the viewpoint of emulsion stability, it is preferably 90 to 100 mol%, more preferably 99 to 100 mol%, and even more preferably 100 mol%.

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

The reaction ratio of the alcohol component (x) and the carboxylic acid component (y) is preferably 1/2 to 2/1, more preferably 1/1.3 to 1.5/1, and even more preferably 1/1.2 to 1.4/1, in terms of the molar ratio of hydroxyl groups to carboxyl groups {[OH]/[COOH]}. The above hydroxyl groups are hydroxyl groups 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, the reaction can be carried out by reacting components containing an alcohol component (x) and a carboxylic acid component (y) in an inert gas (nitrogen gas, etc.) atmosphere at a reaction temperature of preferably 150 to 280°C, more preferably 160 to 250°C, and even more preferably 170 to 235°C. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, and even more preferably 20 to 40 hours, from the viewpoint of ensuring the polycondensation reaction and emulsion stability. It is preferable to have a process of reducing pressure in order to improve the reaction rate, and the degree of reduction in pressure is preferably 0.5 to 20 kPa, more preferably 0.5 to 15 kPa, and even more preferably 0.5 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 this case, an esterification catalyst can be used as necessary.
Examples of the esterification catalyst include tin-containing catalysts (e.g., dibutyltin oxide, etc.), antimony trioxide, titanium-containing catalysts [e.g., titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium alkoxide terephthalate, catalysts described in JP-A-2006-243715 {titanium diisopropoxybis(triethanolaminate), titanium dihydroxybis(triethanolaminate), titanium monohydroxytris(triethanolaminate), titanyl bis(triethanolaminate) and intramolecular polycondensates thereof, etc.}, and catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.)], zirconium-containing catalysts (e.g., zirconyl acetate, etc.), and zinc acetate, etc. Among these, titanium-containing catalysts are preferred.

The polyester resin of the present invention satisfies the following formulas (1) and (2) when the acid value of the polyester resin is α _L (mg KOH/g) and the total amount of terephthalic acid and isophthalic acid in the polyester resin is β _L (ppm).
7≦α _L ≦15 (1)
β _L ≦α _L × 250-1000 (2)
The total amount of terephthalic acid and isophthalic acid in the polyester resin is calculated from the peak area obtained by dissolving the polyester resin in THF, precipitating with methanol, filtering and extracting the solution, and subjecting the solution to LC-MS measurement.
By setting the acid value α of the polyester resin and the total amount _βL of terephthalic acid and isophthalic acid in the polyester resin within the ranges of formulas (1) and (2), the emulsifiability of the resin becomes good.
If α _L < 7, the hydrophilicity of the resin is too low, making emulsification difficult, while if α _L > 15, the hydrophilicity is too high, so that the dispersed particle size upon emulsification becomes too fine, making it difficult to control the particle size.
If β _L > α _L × 250-1000, the remaining unreacted terephthalic acid and carboxylic acids such as isophthalic acid become factors that inhibit emulsion stability when the resin is emulsified, resulting in deterioration of emulsion stability.
For example, the acid value α of the polyester resin can be controlled by the reaction ratio of the alcohol component (x) and the carboxylic acid component (y) or 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 the amount of terephthalic acid and isophthalic acid added or the total amount of unreacted terephthalic acid and isophthalic acid. The above range can be easily achieved by controlling the equilibrium time in the esterification reaction, specifically by introducing a process 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 the method specified in ASTM D3418-82 (DSC method) using, for example, DSC Q20 manufactured by TA Instruments Co., Ltd.

In the present invention, the acid value α of the polyester resin is 7 to 15 mgKOH/g, preferably 8 to 14 mgKOH/g, and 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 as measured by gel permeation chromatography (GPC) is preferably 4,000 to 40,000, more preferably 4,000 to 35,000, even more preferably 4,000 to 30,000, and most preferably 5,000 to 25,000, from the viewpoints of emulsion stability and low-temperature fixability. 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 formulas (1) and (2), emulsion stability is improved, and when the weight average molecular weight is 40,000 or less, low-temperature fixability is improved.

The polyester resin composition of the present invention may contain polyester resins other than the above-mentioned essential polyester resins as necessary, and preferably contains polyester resin (H) and crystalline polyester resin (C) from the viewpoints of low-temperature fixability and compatibility.

In the present invention, the polyester resin (H) is a polyester resin obtained by polycondensation of an alcohol component (X) and a carboxylic acid component (Y), and the same alcohol component (x) and carboxylic acid component (y) as exemplified for the polyester resin of the present invention 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 of bisphenol A (x1), and the content of (x1) in (X) is preferably 90 to 100 mol% based on the total number of moles of (X), and from the viewpoint of compatibility with other resins, it is more preferably 95 to 100 mol%, and even more preferably 100 mol%. The content of the propylene oxide adduct of bisphenol A (x11) in (x1) is preferably 80 to 100 mol% based on the total number of moles of (x1), and from the viewpoint of emulsion stability and compatibility with other resins, it is more preferably 90 to 100 mol%, and even more preferably 100 mol%.

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

From the viewpoint of emulsifiability, it is preferable that polyester resin (H) satisfies the following formulas (3) and (4), where α _H (mg KOH/g) is the acid value of polyester resin (H) and β _H (ppm) is the total amount of terephthalic acid and isophthalic acid in polyester resin (H).
7≦α _H ≦15 (3)
β _H ≦α _H × 250-1000 (4)
The total amount of terephthalic acid and isophthalic acid in polyester resin (H) is calculated from the peak area obtained by dissolving polyester resin (H) in THF, precipitating with methanol, filtering and extracting the solution, and subjecting the solution to LC-MS measurement.
By setting the acid value _αH of polyester resin (H) and the total amount _βH of terephthalic acid and isophthalic acid in polyester resin (H) within the ranges of formula ( 3 ) and formula ( 4 ), the emulsifiability of the resin becomes good even when the weight average molecular weight is low.

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

From the viewpoints of emulsion stability and compatibility, the weight average molecular weight of polyester resin (H) as measured by gel permeation chromatography (GPC) is preferably 40,000 to 100,000, more preferably 40,000 to 80,000, even 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 which exhibits crystallinity and has an endothermic peak top temperature Tp (°C) in the range of 40 to 100°C.
In the present invention, "crystalline" refers to a resin that has a clear endothermic peak, rather than a stepwise change in endothermic heat, during the second heating process in a differential scanning calorimeter (DSC) measurement described below.
In the present invention, when the temperature Tp showing the endothermic peak top is measured by DSC, for example, DSC Q20 manufactured by TA Instruments Co., Ltd. can be used. The heating and cooling conditions are as follows: heating to 180°C at 10°C/min (first heating process); then, leaving at 180°C for 10 minutes, cooling to 0°C at 10°C/min (first cooling process); then, leaving at 0°C for 10 minutes, heating to 180°C at 10°C/min (second heating process).

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

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

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 75% by weight, and even more preferably 30 to 65% by weight, based on the weight of the polyester resin composition.

The content of 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, and may further contain various additives such as known resins other than the polyester resin composition of the present invention, colorants, release agents, charge control agents, etc., if necessary.

Examples of resins other than the polyester resin composition of the present invention include vinyl resins, urethane resins, and epoxy resins. From the viewpoint of dispersion stability, vinyl resins and urethane resins are preferred.

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 of the dyes and pigments used as toner colorants can be used. Specific examples include carbon black, iron black, Sudan Black SM, Fast Yellow G, Benzidine Yellow, Pigment Yellow, India Fast 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. These can be used alone or in combination of two or more. If necessary, magnetic powder (powder of ferromagnetic metals such as iron, cobalt, and nickel, or compounds such as magnetite, hematite, and ferrite) can be included to function as a colorant.

The content of the colorant is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the polyester resin composition of the present invention. When magnetic powder is used, the content of the magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight of the polyester resin composition.

Examples of 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, oxidized polyethylene wax, oxidized polypropylene wax, 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.), and it is preferable to contain one or more types selected from the group consisting of these release agents. The content of the 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 total polyester resin composition of the present invention.

The charge control agent may be either a positively charged charge control agent or a negatively charged charge control agent, and examples thereof include nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salts, polyamine resins, imidazole derivatives, polymers containing quaternary ammonium bases, metal-containing azo dyes, copper phthalocyanine dyes, metal salicylic acid salts, boron complexes of benzilic acid, polymers containing sulfonic acid groups, fluorine-containing polymers, and polymers containing halogen-substituted aromatic rings. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 7.5% by weight, based on 100 parts by weight of the polyester resin composition of the present invention.

The method for producing the resin particles of the present invention is not particularly limited, and examples thereof include the well-known emulsion aggregation method disclosed in JP-A-62-106473 and JP-A-63-186253 in which at least one type of fine particles is aggregated to obtain particles of a desired particle size, the dispersion polymerization method characterized by monodispersion, the dissolution suspension method in which necessary resins are dissolved in a water-insoluble organic solvent and then resin particles are formed in water, and the ester elongation polymerization method disclosed in JP-A-2002-284881.
Among the above manufacturing methods, the emulsion aggregation method is preferred from the viewpoints of controlling the particle size of resin particles and low-temperature fixability, in which at least one type of fine particles is aggregated to obtain particles of a desired particle size.

The emulsion aggregation method, which is a preferred 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 microparticles containing a polyester resin composition, and a step of aggregating the resin microparticles (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 microparticles containing a polyester resin composition is not particularly limited, but examples include the following [1] and [2].

[1] A method of producing a dispersion of resin microparticles by 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.

[2] A method in which an organic solvent solution of a polyester resin is mixed with an aqueous medium, the carboxyl groups in the polyester resin are converted into salts using a neutralizing agent, the polyester resin is dispersed in an aqueous solvent, and the organic solvent is then removed to produce a dispersion of resin fine particles.

Of the above methods [1] and [2], method [2] is preferred from the viewpoint of ease of producing resin microparticles.

In addition, when a plurality of polyester resins are contained, the polyester resins may be dispersed separately, or may be mixed in advance and then dispersed. From the viewpoint of particle size distribution, however, it is preferable to disperse the polyester resins separately.
When additives are used, a dispersion of resin fine particles containing a polyester resin and an additive dispersion (such as a colorant dispersion and a release agent dispersion) may be mixed and used.

In the method for producing resin particles of the present invention, examples of the organic solvent for the organic solvent solution of the polyester resin include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogenated solvents, esters, ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more of these.
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.); halogenated solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, and perchloroethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl ether ... Examples of the organic solvent include ether solvents such as Rosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohol solvents such as 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, heterocyclic compound solvents such as N-methylpyrrolidone, and mixed solvents of two or more of these. 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 organic solvent used per 100 parts by weight of polyester resin is preferably 25 to 300 parts by weight, more preferably 25 to 100 parts by weight, and even more preferably 25 to 70 parts by weight.

In the resin particle manufacturing method of the present invention, the aqueous solvent used in the step of mixing the organic solvent solution of the polyester resin with the aqueous solvent can be any liquid containing water as an essential component, and examples of the aqueous solvent that can be used include water, an aqueous solution of an organic solvent, an aqueous solution of a surfactant (s), an aqueous solution of a water-soluble polymer (t), and mixtures of two or more of these, as described below.

In order to improve 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 the neutralizing agent include organic compounds such as ammonia and triethylamine, and inorganic compounds such as sodium hydroxide.

From the viewpoint of dispersibility, the amount of neutralizing agent used is preferably 1 to 150 mol %, and more preferably 5 to 100 mol %, relative to 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 examples thereof include anionic surfactants (s-1), cationic surfactants (s-2), amphoteric surfactants (s-3), and nonionic surfactants (s-4). 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 salts, salts of carboxymethyl compounds, sulfonates, and phosphate salts.
Examples of the cationic surfactant (s-2) include quaternary ammonium salt type surfactants and amine salt type surfactants.
Examples of the amphoteric surfactant (s-3) include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-type amphoteric surfactants.
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 polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasilicate, calcium sulfate, 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. Using a water-soluble polymer (t) is preferable because it reduces the volume average particle size of the resin microparticles and tends to reduce the particle size distribution (volume average particle size/number average particle size).

Examples of the water-soluble polymer (t) include cellulose compounds (e.g., methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, and saponified products thereof, etc.), gelatin, starch, dextrin, gum arabic, chitin, chitosan, polyethylene glycol, etc.

The dispersion method when mixing the organic solvent solution of the polyester resin of the present invention with an aqueous medium is not particularly limited, but known equipment such as low-speed shear type, high-speed shear type, friction type, high-pressure jet type, and ultrasonic type can be applied. A high-speed shear type is preferred 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 1000 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, homogenizers (manufactured by IKA), Polytrons (manufactured by Kinematica), TK Auto Homo Mixers (manufactured by Tokushu Kika Kogyo Co., Ltd.), and other batch-type emulsifiers, Ebara Milders (manufactured by Ebara Corporation), TK Filmix, TK Pipeline Homo Mixers (manufactured by Tokushu Kika Kogyo Co., Ltd.), colloid mills (manufactured by Kobe Steel Pantech Co., Ltd.), Ultra Visco Mills (manufactured by Imex Co., Ltd.), slashers, and trigonal wet fine grinding mills (manufactured by Nippon Coke Works Co., Ltd.), Examples of such emulsifiers include continuous emulsifiers such as Ebara Microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), Capitron (manufactured by Eurotech Co., Ltd.), and Fine Flow Mill (manufactured by Pacific Machinery Co., Ltd.); high-pressure emulsifiers such as Microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), Nanomizer (manufactured by Nanomizer Co., Ltd.), and APV Gaulin (manufactured by Gaulin Co., Ltd.); membrane emulsifiers such as Membrane Emulsifier (manufactured by Reika Kogyo Co., Ltd.); vibration emulsifiers such as Vibro Mixer (manufactured by Reika Kogyo Co., Ltd.); and ultrasonic emulsifiers such as Ultrasonic Homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaulin, homogenizer, TK Auto Homo Mixer, Ebara Milder, TK Filmix, and TK Pipeline Homo Mixer are preferred from the viewpoint of particle size uniformity.

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

In the method for producing resin particles of the present invention, the solid content concentration and volatile content of the resin particles and the like in the dispersion liquid are determined by the following methods.
Taking care not to cause precipitation of resin particles, etc., weigh out about 2.00 g of the sample before drying and dry it for 1 hour at 120° C. After drying, remove the sample and measure its weight to two decimal places. Calculate the solid content concentration (wt%) from (weight of sample after drying/weight of sample before drying) x 100, and calculate the volatile content (wt%) from {(weight of sample before drying-weight of sample after drying)/weight of sample before drying} x 100.

The method for aggregating the resin microparticles obtained in the step of obtaining the resin microparticles is not particularly limited, and examples thereof include a method of heating a dispersion of resin microparticles obtained by methods (1) to (2) placed in a tank equipped with a stirrer, a method of adding an aggregating agent without heating, and a method of combining heating and adding an aggregating agent.
When resin microparticles are aggregated under stirring to obtain aggregates of the desired size, the particle size of the aggregates is controlled by the balance between the cohesive force between the particles and the shear force caused by stirring, but the cohesive force can be increased by heating or adding an aggregating agent.

Examples of the flocculant 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.), metal salts of phenols (sodium phenolate, etc.), and amine salts (metal salts of amino acids, triethanolamine hydrochloride, aniline hydrochloride, etc.).
Of 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 liquid placed 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 size and particle size distribution of the resin particles.
In the step of forming the 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.

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, and more preferably 1 to 15 parts by weight, per 100 parts by weight of the resin microparticles.

When aggregation is carried out 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 aggregation is optimized depending on the shape of the apparatus and the processing scale, but in order for the particle size of the resin particles to reach the target particle size, it is desirable to maintain the above-mentioned predetermined temperature for at least 30 minutes or more. The temperature may be raised at a constant rate until the predetermined temperature is reached, or the temperature may be raised in stages.

In order to increase the stability of the aggregates obtained in the aggregation step, it is preferable to carry out an aging step after the aggregation step.
The aging process is a process in which the resin fine particles in the aggregate are fused together by heating or the like, and the shape becomes nearly spherical. The aggregate before the aging process is considered to be an assembly of the resin fine particles due to electrostatic or physical aggregation, but after the aging process, the resin fine particles constituting the aggregate are fused together, and the shape of the resin particles can be made nearly spherical. According to this aging process, by controlling the temperature and time of the aging process, it is possible to produce resin particles of various shapes according to the purpose, such as grape-shaped, which is an aggregated shape of resin fine particles, potato-shaped, which is a fused shape, and spherical, which is a fused shape.

From the viewpoint of shape controllability of the resulting resin particles, the temperature when fusing the aggregates is preferably 5 to 200°C, and more preferably 30 to 100°C. The pH of the liquid when fusing the aggregates is preferably 3 to 10, and more preferably 5 to 10. The time required for the aging step varies depending on the shape of the desired resin particles, but it is desirable to maintain the above-mentioned specified temperature for 0.1 to 10 hours, and preferably 1 to 6 hours.

After the aggregation step, preferably before or during the aging step, it is preferable to add a surfactant or increase the pH value. The surfactant used here may be any known surfactant (s), but it is preferable to use the same surfactant (s) as that used when producing the resin microparticles. By adding a surfactant or increasing the pH value after the aggregation step and before the completion of the aging step, it is possible to suppress the aggregation of the aggregates that were aggregated in the aggregation step, and in some cases, it is possible to suppress the generation of coarse particles after the aging step.

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

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 used.
[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 centrifuge, a sparkler filter and/or a filter press, water or the like is added as necessary to repeat the solid-liquid separation, and the obtained solid is then dried.
[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 reduced pressure dryer, or a circulating air dryer. If necessary, classification can be performed using an air classifier or a sieve to obtain a predetermined particle size distribution.

From the viewpoint of low-temperature fixability, the amount of remaining aqueous solvent per 100 parts by weight of 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 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 a known fluidizing agent (silica, titania, alumina, calcium carbonate, fatty acid metal salts, silicone resin particles, fluororesin particles, etc.), and are fixed to a support (paper, polyester film, etc.) by a copier, printer, etc. and used as a recording material. As a method for fixing to a support, known heat roll fixing method, flash fixing method, etc. can be applied.

The resin particles of the present invention can be preferably used for developing electrostatic images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, etc. More preferably, they can be used for developing full-color electrostatic images or magnetic latent images.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. In the following, "parts" refers to parts by weight unless otherwise specified.

The physical properties of polyester resins, etc. were measured using the following methods.

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

<Method of measuring acid value>
The measurement was performed according to the method specified in JIS K0070 (1992 edition), except that the measurement solvent for the acid value was a mixed solvent of acetone, methanol, and toluene (acetone:methanol:toluene=12.5:12.5:75), and the measurement solvent for the hydroxyl value was THF.

<Method for measuring weight average molecular weight (Mw)>
The molecular weight was measured under the following conditions: a sample was dissolved in THF, and the insoluble matter was filtered off using a glass filter to obtain a sample solution.
Equipment: Tosoh Corporation HLC-8120
Column: TSK GEL GMH6 x 2 (Tosoh Corporation)
Measurement temperature: 40°C
Sample solution: 0.25% by weight THF solution Injection amount: 100 μl
Detector: Refractive index detector Reference material: 12 standard polystyrenes (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 the peak top temperature of the endothermic peak>
The measurement was performed using a differential scanning calorimeter {e.g., "DSCQ20" [manufactured by TA Instruments, Inc.]}. The sample was first heated from 20°C to 150°C at 10°C/min, then cooled from 150°C to 0°C at 10°C/min, and then heated a second time from 0°C to 150°C at 10°C/min. The temperature showing the top of the endothermic peak during the second heating process was determined 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).
<Preparation of sample solution>
About 0.2 g of polyester resin was dissolved in 1 ml of THF, and then 10 g of methanol was added dropwise at 10 g/min while stirring with a stirrer to precipitate the resin, and the terephthalic acid and isophthalic acid remaining in the resin were extracted into methanol. The methanol-soluble portion was filtered through a 0.4 μm filter to obtain a sample solution.
<LC/MS Instrument Conditions>
Apparatus: LCMS-8030 (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 (±)
Standard solutions of terephthalic acid and isophthalic acid were 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(triethanolaminate))]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 634.0 parts (33.3 mol %) of TC-310 (manufactured by Orgatec) and 366.0 parts (66.6 mol %) of triethanolamine were placed and reacted at 80° C. for about 1 hour to obtain titanium dihydroxybis(triethanolaminate).

<Production Example 2> [Production of Crystalline Polyester Resin (C)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 392.1 parts (51.1 mol%) of 1,6-hexanediol, 731.2 parts (48.9 mol%) of dodecanedioic acid and 1.5 parts of titanium dihydroxybis(triethanolamine) as an esterification catalyst were placed, and the mixture was reacted for 4 hours at normal pressure and 180°C under a nitrogen stream while distilling off the water produced. The mixture was then heated to 200°C under a reduced pressure of 0.5 to 2.5 kPa, reacted at 200°C for 10 hours, and taken out when the acid value reached 8 to obtain a crystalline polyester resin (C). The titanium-containing catalyst of Production Example 1 was used for the 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)]
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 401.1 parts (26.0 mol%) of bisphenol A·PO 2-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P"), 172.7 parts (10.0 mol%) of bisphenol A·PO 3-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-3P"), 172.7 parts (10.0 mol%) of bisphenol A·EO 2-mol adduct (manufactured by Sanyo Chemical Industries, 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 acid 90.3 parts (12.3 mol%), adipic acid 58.1 parts (9.0 mol%), titanium dihydroxybis (triethanol aminate) 2.5 parts as an esterification catalyst were added, and the mixture was reacted for 4 hours while distilling off the generated water at normal pressure and 180 ° C. under a nitrogen stream. Further, the mixture was heated to 200 ° C. under a reduced pressure of 0.5 to 2.5 kPa, and reacted at 200 ° C. for 20 hours. When the acid value became 12 mg KOH / g, the reduced pressure was released, and the mixture was equilibrated and stabilized at normal pressure and 200 ° C. for 4 hours, and then taken out to obtain polyester resin (L-1).
The polyester resin (L-1) had an acid value (α) of 12 mg KOH/g, a glass transition temperature (Tg) of 62° C., a weight average molecular weight (Mw) of 11,000, and a total amount (β) of terephthalic acid and isophthalic acid in the polyester resin of 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 shown in Production Examples 4 to 20 in Table 1 were used. The acid value (α), Tg, Mw, right side of formula (2), and the total amount (β) of terephthalic acid and isophthalic acid in the polyester resin obtained are shown in Table 1.

<Production Example 21> [Production of Polyester Resin (H-1)]
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 94.4 parts (7.2 mol%) of bisphenol A·PO 2-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P"), 660.0 parts (44.8 mol%) of bisphenol A·PO 3-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-3P"), 200.9 parts (32.0 mol%) of terephthalic acid, 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(triethanolaminate) as an esterification catalyst were placed, and the mixture was reacted for 4 hours at normal pressure and 180° C. under a nitrogen stream while distilling off the water produced. The temperature was then raised to 200°C under reduced pressure of 0.5 to 2.5 kPa, and the reaction was carried out at 200°C for 18 hours. When the acid value reached 12 mgKOH/g, the reduced pressure was released, and the mixture was allowed to equilibrate and stabilize at normal pressure and 200°C for 4 hours. The mixture was then taken out and a polyester resin (H-1) was obtained.
The polyester resin (H-1) had 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 (β) of terephthalic acid and isophthalic acid in the polyester resin of 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 shown in Production Examples 22 to 29 in Table 2 were used. The acid value (α), Tg, Mw, right side of formula (2), and the total amount (β) of terephthalic acid and isophthalic acid in the polyester resin obtained are shown in Table 2.

<Production Example 30> [Production of polyester resin (H-10)]
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 280.2 parts (20.7 mol%) of bisphenol A·PO 2-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P"), 470.5 parts (31.1 mol%) of bisphenol A·PO 3-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-3P"), 175.7 parts (27.0 mol%) of terephthalic acid, 75.3 parts (11.6 mol%) of isophthalic acid, 36.3 parts (4.8 mol%) of trimellitic anhydride, 27.6 parts (4.8 mol%) of adipic acid, and 2.5 parts of titanium dihydroxybis(triethanolaminate) as an esterification catalyst were placed, and the mixture was reacted for 4 hours at normal pressure and 180° C. under a nitrogen stream while distilling off the water produced. The temperature was then raised to 200° C. under reduced pressure of 0.5 to 2.5 kPa, and the reaction was continued at 200° C. for 6 hours. When the acid value reached 12 mgKOH/g, the resin was taken out to obtain a polyester resin (HR-1).
The polyester resin (HR-1) had 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 a total amount (β) of terephthalic acid and isophthalic acid in the polyester resin of 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 shown in Comparative Production Examples 1 to 6 in Table 1 were used. The acid value (α), Tg, Mw, right side of formula (2), and the total amount (β) of terephthalic acid and isophthalic acid in the polyester resin obtained are shown in Table 1.

Comparative Production Example 7 Production of Polyester Resin (LR-7)
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 135.6 parts (10.0 mol %) of a bisphenol A·PO 2-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P"), 607.2 parts (39.9 mol %) of a bisphenol A·PO 3-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-3P"), 113.9 parts (17.6 mol %) of terephthalic acid, 211.5 parts (32.6 mol %) of isophthalic acid, and 2.5 parts of titanium dihydroxybis(triethanolaminate) as an esterification catalyst were placed, and the mixture was reacted for 4 hours at normal pressure and 180° C. under a nitrogen stream while distilling off the generated water. Further, the temperature was raised to 220°C under a reduced pressure of 0.5 to 2.5 kPa, and the reaction was carried out at 220°C for 30 hours. When the acid value reached 6 mgKOH/g, the reduced pressure was released, and the mixture was allowed to equilibrate and stabilize at normal pressure and 200°C for 10 hours, and then taken out to obtain a polyester resin (LR-7).
The polyester resin (LR-7) had an acid value (α) of 6 mg KOH/g, a glass transition temperature (Tg) of 62° C., a weight average molecular weight (Mw) of 15,000, and a total amount (β) of terephthalic acid and isophthalic acid in the polyester resin of 150 ppm.

Comparative Production Example 8 Production of Polyester Resin (LR-8)
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 135.7 parts (10.0 mol %) of a bisphenol A·PO 2-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P"), 607.9 parts (39.9 mol %) of a bisphenol A·PO 3-mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-3P"), 113.5 parts (17.5 mol %) of terephthalic acid, 210.7 parts (32.5 mol %) of isophthalic acid, and 2.5 parts of titanium dihydroxybis(triethanolaminate) as an esterification catalyst were placed, and the mixture was reacted for 4 hours at normal pressure and 180° C. under a nitrogen stream while distilling off the water produced. The temperature was then raised to 200° C. under reduced pressure of 0.5 to 2.5 kPa, and the reaction was continued at 200° C. for 8 hours. When the acid value reached 7 mgKOH/g, the mixture was taken out to obtain a polyester resin (LR-8).
The polyester resin (LR-8) had an acid value (α) of 7 mg KOH/g, a glass transition temperature (Tg) of 62° C., a weight average molecular weight Mw of 13,000, and a total amount (β) of terephthalic acid and isophthalic acid in the polyester resin of 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 shown in Comparative Production Examples 9 to 10 in Table 1 were used. The acid value (α), Tg, Mw, right side of formula (2), and the total amount (β) of terephthalic acid and isophthalic acid in the polyester resin obtained are shown in Table 1.

The blending amounts and resin properties of polyester resins (L-1) to (L-18) and (LR-1) to (LR-10) are shown in Table 1.

The blending amounts and resin properties of polyester resins (H-1) to (H-10) are shown in Table 2.

Example 1 Resin Particles (Z-1)
[Preparation of Dispersion (Clb-1) of Resin Fine Particles (Cl-1)]
A reaction vessel equipped with a stirrer, a heating/cooling device, a cooling tube and a thermometer was charged with 100 parts of polyester resin (L-1) and 100 parts of methyl ethyl ketone, and the mixture was stirred and homogenized to obtain an organic solvent solution of polyester resin (L-1). The organic solvent solution of polyester resin (L-1) was adjusted to 25°C, and 2.2 parts of 10.0 wt% ammonia water was added as a neutralizing agent, and the mixture was stirred for 5 minutes. Thereafter, 300 parts of 25°C ion-exchanged water 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 (Clb-1) of resin fine particles (Cl-1). The volume-based median diameter of the resin fine particles (Cl-1) was 0.15 μm, and the solids concentration of the dispersion (Clb-1) was 20 wt%.

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

[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 charged into a reaction vessel equipped with a stirring device, a heating and cooling device, a cooling tube and a thermometer, and the mixture was stirred and homogenized to obtain an organic solvent solution of crystalline polyester resin (C). The organic solvent solution of crystalline polyester resin (C) was adjusted to 50°C, and 2.2 parts of 10.0 wt% ammonia water was added as a neutralizing agent and stirred for 5 minutes. Then, 300 parts of 50°C ion-exchanged water was dropped over 1 hour to cause 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 resin fine particles (Cc). The volume-based median diameter of the resin fine particles (Cc) was 0.15 μm, and the solid content concentration of the dispersion (Ccb) was 20 wt%.

[Preparation of colorant dispersion]
In a reaction vessel equipped with a stirrer, a heating/cooling device, a cooling tube, and a thermometer, 10 parts of carbon black [MA100 manufactured by Mitsubishi Chemical Corporation], 0.5 parts of sodium dodecylbenzenesulfonate, and 40 parts of ion-exchanged water were added, and the mixture was heated 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 Ultraviscomill 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 was 20% by weight.

[Preparation of release agent dispersion]
In a reaction vessel equipped with a stirrer, 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 parts of sodium dodecylbenzenesulfonate, and 15 parts of ion-exchanged water were added, and the temperature was raised to 95°C while stirring at a rotation speed of 300 rpm, and after stirring at the same temperature for 30 minutes, the temperature was cooled to 30°C over 1 hour to crystallize the Fischer-Tropsch wax into fine particles, which were then wet-pulverized with an Ultraviscomill to obtain a release agent dispersion. The volume-based median diameter of the obtained release agent dispersion was 0.25 μm, and the solid content concentration was 50% by weight.

[Production of resin particles (Z-1)]
A reaction vessel equipped with a stirrer, a heating/cooling device, a cooling tube, a thermometer and a nitrogen inlet tube was charged with the dispersion liquid (Clb-1) of resin fine particles (Ch-1), the dispersion liquid (Chb-1) of resin fine particles (Cc), the dispersion liquid of a colorant, and the dispersion liquid of a release agent so as to have solid contents in parts as shown in Table 3, 300 parts of ion-exchanged water was charged, the liquid temperature was adjusted to 30° C., and then a 25% by weight aqueous sodium hydroxide solution was added with stirring to adjust the pH to 10, thereby obtaining a dispersion liquid.
Next, in order to aggregate the resin fine particles (Cl-1), resin fine particles (Ch-1), resin fine particles (Cc), colorant, and release agent, a magnesium chloride aqueous solution having a concentration of 10% by weight was added as an aggregating agent while stirring at a rotation speed of 300 rpm, and after appropriate sampling was performed to confirm that the volume average particle size had reached 5 μm, the temperature of the system was adjusted to 60° C., and then a 0.3 M nitric acid aqueous solution was added to adjust the pH to 4.5, and after 30 minutes, the pH was adjusted to 4.0. Fusion and spheroidization were performed by maintaining 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. The resin particles were then filtered and washed with water three times, and then filtered and dried for 18 hours in a 40° C. air circulation dryer to obtain resin particles (Z-1) having a volatile content of 0.5% by weight or less.

<Examples 2 to 3> [Resin particles (Z-2) to (Z-3)]
In the production of the dispersion liquid (Chb-1) of the resin fine particles (Ch-1) in Example 1, the polyester resin (H-1) was replaced with the polyester resins (H-2) to (H-3), respectively, to obtain dispersion liquids (Chb-2) to (Chb-3) of the resin fine particles in the same manner as in Example 1, and then
Resin particles (Z-2) to (Z-3) containing polyester resin compositions (P-2) to (P-3) were obtained in the same manner as in Example 1, except that the dispersion liquid (Chb-1) of resin fine particles (Ch-1) was replaced with the dispersion liquid (Chb-2) of resin fine particles (Ch-2) and the dispersion liquid (Chb-3) of resin fine particles (Ch-3), respectively.

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

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

<Examples 21 to 27> [Resin particles (Z-21) to (Z-27)]
In the production of the dispersion liquid (Chb-1) of the resin fine particles (Ch-1) in Example 1, the polyester resin (H-1) was replaced with the polyester resins (H-4) to (H-10), respectively, to obtain dispersion liquids (Chb-4) to (Chb-10) of the resin fine particles.
Resin particles (Z-21) to (Z-27) containing polyester resin compositions (P-21) to (P-27) were obtained in the same manner as in Example 1, except that the dispersion liquid (Chb-1) of resin fine particles (Ch-1) was replaced with the dispersion liquid (Chb-4) of resin fine particles (Ch-4) and the dispersion liquid (Chb-10) of resin fine particles (Ch-10), respectively.

Comparative Examples 1 to 8 [Resin Particles (Z'-1) to (Z'-8)]
In the production of dispersion liquid (Clb-1) of resin fine particles (Cl-1) in Example 1, polyester resin (L-1) was replaced with polyester resin (LR-1) to (LR-8), respectively, and in the production of dispersion liquid (Chb-1) of resin fine particles (Ch-1), polyester resin (H-1) was replaced with polyester resin (H-10). In the same manner as in Example 1, dispersion liquids (Clrb-1) to (Clrb-8) and (Chb-10) of resin fine particles were obtained, and then,
Resin particles (Z'-1) to (Z'-8) containing polyester resin compositions (P'-1) to (P'-8) were obtained in the same manner as in Example 1, except that the dispersion liquid (Clb-1) of resin fine particles (Cl-1) was replaced with the dispersion liquids (Clrb-1) to (Clr-8) of resin fine particles (Clr-1) to (Clrb-8) of resin fine particles, and the dispersion liquid (Chb-1) of resin fine particles (Ch-1) was replaced with the dispersion liquid (Chb-10) of resin fine particles (Ch-10).

Example 9 Resin Particles (Z-9)
[Production of pigment master batch [MB1]]
1,200 parts of water, 40 parts of carbon black (MA100 manufactured by Mitsubishi Chemical Corporation), and 20 parts of the polyester resin (L-7) manufactured in Example 7 were mixed in a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded using a three-roll mill at 90° C. for 30 minutes, then cooled by rolling, and pulverized in a pulverizer to obtain a pigment master batch [MB1].

[Production of fine particle dispersion [PD1]]
In a reaction vessel equipped with a stirrer, a heating/cooling device, and a thermometer, 780 parts of water and 8 parts of sodium alkylarylsulfosuccinate (Eleminol JS-20, manufactured by Sanyo Chemical Industries) were charged, and the mixture was homogenized by stirring at 200 rpm. This was heated to raise the temperature in the system to 85° C., and then 9 parts of a 10% by weight aqueous solution of ammonium persulfate was added, followed by dropping a monomer mixture consisting of 30 parts of styrene, 40 parts of butyl acrylate, and 30 parts of methacrylic acid 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. In addition, the resin was isolated by drying a portion of the fine particle dispersion, and the resin had an Mn of 18700, an Mw of 154000, a Tg of 64° C., and an acid value of 196 mg KOH/g.

[Preparation of aqueous phase s1]
Into a vessel equipped with a stirring rod were added 955 parts of water, 15 parts of the fine particle dispersion [PD1], and 30 parts of an aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON7, manufactured by Sanyo Chemical Industries) to obtain a milky white liquid [aqueous phase s1].

[Production of wax dispersion]
Into a reaction vessel equipped with a cooling tube, a thermometer, and a stirrer, 15 parts of Fischer-Tropsch wax [FT-0070, manufactured by Nippon Seiro Co., Ltd.] and 85 parts of ethyl acetate were placed, heated to 80°C and dissolved, and cooled to 30°C over one hour to crystallize the Fischer-Tropsch wax into fine particles, which were then wet-pulverized in an "Ultra Viscomill" (manufactured by Imex) to produce a [wax dispersion].

[Production of resin particles (Z-9)]
In a beaker, polyester resin (L-7), polyester resin (H-1), crystalline polyester resin (C), pigment master batch [MB1], and wax dispersion were charged so that the solid content was the number of parts in Table 3, and ethyl acetate was further added to obtain a 50 wt% ethyl acetate solution, and the mixture was dissolved and mixed uniformly to obtain an oil phase. 600 parts of [water phase s1] were added to this oil phase, and a dispersion operation was performed at 25°C and 12,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and the solvent was removed for 30 minutes using a film evaporator under 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 a polyester resin composition (P-9).
The process of centrifuging 100 parts of the dispersion, adding 60 parts of water, and centrifuging to separate the solid and liquid was repeated twice, and then drying at 35° C. for 1 hour. Then, using a classifier [Elbow Jet [manufactured by Matsubo Co., Ltd.]], fine powders and coarse powders were removed so that fine powders of 3.17 μm or less constituted 12% by number or less and coarse powders of 8.0 μm or more constituted 3% by volume or less, thereby obtaining resin particles (Z-9).

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

Comparative Examples 9 to 10 [Resin Particles (Z'-9) to (Z'-10)]
In Example 9, resin particles (Z'-9) to (Z'-10) containing polyester resin compositions (P'-9) to (P'-10) were obtained in the same manner as in Example 9, 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).

The blended amounts of resin particles obtained in each Example and Comparative Example and the evaluation results are shown in Table 3.

[Evaluation method]
The methods for measuring and evaluating the emulsion stability, compatibility, and low-temperature fixability of the resin particles of the resulting polyester resin composition will be described below.

<Emulsion stability>
The emulsion stability of the polyester resin composition of the present invention was evaluated based on the rate of change (%) in the median diameter immediately after the polyester resin of the present invention was made into a dispersion by the following method and after it was left standing at room temperature for 1 week.
Specifically, each polyester resin was made into a dispersion of resin particles according to the procedure for producing the dispersion (Clb-1) of resin fine particles (Cl-1), and the solid content was adjusted with ion-exchanged water to 10% by weight, and the median diameter immediately after the dispersion was made was measured using a dynamic light scattering particle distribution measuring device "SZ-100" (manufactured by Horiba, Ltd.) After that, the median diameter of the dispersion after standing at room temperature for one week was measured again, and the rate of change was calculated using the following formula.
Rate of change (%) = (|median diameter after 1 week - median diameter immediately after dispersion|/particle diameter immediately after dispersion) x 100 (%)
The smaller the rate of change, the more excellent the emulsion stability.

<Particle size distribution>
The particle size distribution of the resin particles (Z) in the present invention was calculated from the volume average particle size and number average particle size of the resin particles (Z) obtained in each of the Examples and Comparative Examples according to 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 a Multisizer IV (manufactured by Coulter) or the like.
Specifically, 0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) was added as a dispersant to 100 to 150 mL of an aqueous electrolyte solution of ISOTON-II (manufactured by Beckman Coulter, Inc.). 2 to 20 mg of a measurement sample was then added, and the electrolyte solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser. The volume and number of resin particles were measured using a 50 μm aperture as the aperture using the measurement device, and the volume distribution and number distribution were calculated. From the obtained distribution, the volume average particle size and number average particle size of the resin particles were obtained.
A volume average particle size/number average particle size ratio of 1.20 or less means that the particle size distribution is excellent.

<Compatibility (ΔTg)>
The compatibility with other resins was evaluated by comparing the amount of change (ΔTg) in Tg of the polyester resin of the present invention when a crystalline polyester resin was added.
First, polyester resin (L) and polyester resin (H) of the present invention were charged so as to obtain the parts shown in Table 3, and tetrahydrofuran was added to obtain a 20 wt% tetrahydrofuran solution to uniformly dissolve the polyester resin, and the Tg of the polyester resin after desolvation was measured. Next, polyester resin (L) and polyester resin (H) of the present invention and a crystalline polyester resin were charged so as to obtain the parts shown in Table 3, and tetrahydrofuran was added to obtain a 20 wt% tetrahydrofuran solution to uniformly dissolve the polyester resin, and the Tg of the resin composition containing the crystalline polyester resin after desolvation 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, a larger difference in Tg indicates better compatibility, and a difference of 10° C. or more indicates good compatibility with other resins.
The Tg was measured in the same manner as that 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>
The low temperature fixing property of the resin particles was evaluated by uniformly mixing the obtained resin particles (Z-1) to (Z-27), (Z'-1) to (Z'-10) with hydrophobic silica in the following blending ratio to prepare a toner.
Resin particles (Z): Hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.]
= 99 parts by weight: 1 part by weight.
The toner was uniformly placed on the paper surface to a density of 0.85 mg/cm ^2. The method for placing the powder on the paper surface was a printer without a thermal fixing unit.
The temperature at which cold offset occurs (MFT) was measured when the paper was passed through a pressure roller under conditions of a fixing speed (heat roller peripheral speed) of 213 mm/sec and a fixing pressure (pressure roller pressure) of 10 kg/cm ² .
The lower the temperature at which cold offset occurs, the better the low-temperature fixing property.

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, etc. Furthermore, they are useful as additives for paints, additives for adhesives, particles for electronic paper, etc.

Claims (2)

The polyester resin composition includes a polyester resin obtained by polycondensing an alcohol component (x) and a carboxylic acid component (y),
The polyester resin comprises a polyester resin (L), a polyester resin (H) and a crystalline polyester resin (C),
the alcohol component (x) of the polyester resin (L) contains an alkylene oxide adduct of bisphenol A (x1), the content of (x1) in (x) being 90 to 100 mol % based on the total number of moles of (x), and the content of a propylene oxide adduct of bisphenol A (x11) in (x1) being 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), the molar ratio of terephthalic acid to isophthalic acid in (y1) (terephthalic acid/isophthalic acid) is 30/70 to 70/30, and the weight average molecular weight of the polyester resin (L) is 4,000 to 35,000;
When the acid value of the polyester resin (L) is α _L (mg KOH/g) and the total amount of terephthalic acid and isophthalic acid in the polyester resin (L) is β _L (ppm), the following formulas (1) and (2) are satisfied:
the alcohol component of the polyester resin (H) contains an alkylene oxide adduct of bisphenol A (x1), the content of (x1) in (x) being 90 to 100 mol % based on the total number of moles of (x), and the content of a propylene oxide adduct of bisphenol A (x11) in (x1) being 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), the molar ratio of terephthalic acid to isophthalic acid in (y1) (terephthalic acid/isophthalic acid) is 70/30 to 95/5, and the weight average molecular weight of the polyester resin (H) is 40,000 to 100,000;
When the acid value of the polyester resin (H) is α _H (mg KOH/g) and the total amount of terephthalic acid and isophthalic acid in the polyester resin (H) is β _H (ppm), the following formula (3) is satisfied:
The alcohol component (x) of the crystalline polyester resin (C) is an alkylene glycol having 2 to 12 carbon atoms, and the carboxylic acid component (y) of the crystalline polyester resin (C) is an alkanedicarboxylic acid having 2 to 50 carbon atoms; and
The content of the polyester resin (L) in the polyester resin composition is 20 to 75% by weight, the content of the polyester resin (H) in the polyester resin composition is 20 to 75% by weight, and the content of the crystalline polyester resin (C) in the polyester resin composition is 3 to 20% by weight;
A polyester resin composition comprising:
7≦α _L ≦15 (1)
β _L ≦α _L × 250-1000 (2)
7≦α _H ≦15 (3) Resin particles comprising the polyester resin composition according to claim 1.