WO2019107087A1

WO2019107087A1 - Method for producing resin particles and toner

Info

Publication number: WO2019107087A1
Application number: PCT/JP2018/041205
Authority: WO
Inventors: 前田　真一; 康弘小野; 雄太田畠
Original assignee: 三洋化成工業株式会社
Priority date: 2017-11-28
Filing date: 2018-11-06
Publication date: 2019-06-06
Also published as: JPWO2019107087A1; JP6818162B2

Abstract

The present invention relates to a method for producing resin particles by: obtaining resin microparticles that contain a polyester resin (a) which has a glass transition temperature (Tga) of -20 to 57˚C and which is obtained by polycondensation of an alcohol component (y) and an unsaturated carboxylic acid component (z); and then aggregating and fusing the resin micro particles. The method for producing resin particles comprises a step of producing a modified resin by cross linking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) of the polyester resin (a) after the resin microparticles have been obtained.

Description

Resin particle and method for producing toner

The present invention relates to a method of producing resin particles and toner.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic apparatuses such as copying machines and laser printers has been rapidly increasing, and the demand for their performance has also been advanced.
Conventionally, for full-color electrophotography, a latent image based on color image information is formed on a latent image carrier such as an electrophotographic photosensitive member, the latent image is developed with a toner of a corresponding color, and then the toner image is transferred There is known a method and apparatus for obtaining a multi-color image by heating and fixing a toner image on a transfer material after repeating an image forming process of transferring onto a material.

In order to pass through these processes without problems, it is necessary for the toner to first maintain a stable charge, and then to have good fixability to paper. In addition, since the device has a heater at the fixing portion, the temperature is increased in the device, so that the toner is required not to be blocked in the device.

Further, from the viewpoint of energy saving in which the consumption energy in the fixing step is reduced while the miniaturization, speeding up and image quality enhancement of the electrophotographic apparatus are promoted, the improvement of the low temperature fixability of the toner is strongly demanded.
Recently, as a transfer material to be used, many types of paper such as recycled paper with large surface irregularities and coated paper with a smooth surface are used. In order to cope with the surface properties of these transfer materials, a wide nip fixing device such as a soft roller or a belt roller is preferably used. However, when the nip width is increased, the contact area between the toner and the fixing roller is increased, and a so-called high temperature offset phenomenon occurs in which the molten toner adheres to the fixing roller, so it is premised that offset resistance is required.
In addition to the above, a multi-color image (full color) is required to have a higher gloss than a black and white image (monochrome) from the reproduction of photographic images etc., and it is necessary to make the toner layer of the obtained image smooth. .
Therefore, it is necessary for the toner to be able to exhibit low-temperature fixability while maintaining offset resistance while having high gloss, and it has been required to be able to form high gloss toner images in a wide working range. There is.

The toner binder greatly affects the toner characteristics as described above, and polystyrene resin, styrene-acrylic resin, polyester resin, epoxy resin, polyurethane resin, polyamide resin, etc. are known, but recently, storage Polyester resins are of particular interest because they tend to balance the properties and fixability.

As a method of expanding the fixing temperature range, a toner using a reaction product of a mixture of a resin for polymerization and a polyester resin and an isocyanate has been proposed (Patent Document 1).
However, even if this method can prevent the offset phenomenon at high temperatures to some extent, the lower limit temperature for fixing is also raised at the same time, and low temperature fixing becomes difficult, and the high aggregation of urea groups and urethane groups derived from isocyanate makes the resin There is a problem that the crushability of the Furthermore, the uniformity of the resin is impaired and the heat resistant storage stability is also deteriorated, and the demands for speeding up and energy saving have not been sufficiently answered yet.

On the other hand, methods for producing a toner used for electrostatic charge image development are roughly classified into a pulverization method and a polymerization method.

In the pulverizing method, a toner, a charge control agent, a releasing agent, and the like are melt mixed and uniformly dispersed in a toner binder, and the obtained composition is pulverized and classified to produce a toner. According to the pulverizing method, a toner having excellent characteristics to some extent can be produced, but there is a limitation in selecting a material for toner. For example, the composition obtained by melt mixing should be one that can be crushed and classified by an economically usable device. From this, the melt-blended composition must be sufficiently brittle. For this reason, when the toner binder is actually crushed into particles, a wide range of particle size distribution is easily formed, and when it is intended to obtain an image with good resolution and gradation, the fine powder and the coarse powder are classified. It has the disadvantage that it has to be removed and the toner yield is very low. Further, in the pulverizing method, it is difficult to uniformly disperse the coloring agent, the charge control agent, and the like in the thermoplastic resin, and there is a problem of becoming nonuniform. Unevenness adversely affects toner fluidity, charging stability, image quality and the like.

In order to overcome these problems in the pulverizing method, a method of producing a toner by a polymerization method has been proposed and practiced. Techniques for producing a toner for electrostatic charge image development by a polymerization method are known, and for example, toner particles are obtained by an emulsion polymerization aggregation method (patent document 2) or a dissolution suspension method (patent document 3) .

Patent Document 2 proposes a toner obtained by an emulsion polymerization aggregation method. However, since this method uses a styrene-acrylic resin, the low temperature fixability of the toner is insufficient, and the demands for high image quality, high speed and energy saving have not been sufficiently answered yet. When a polyester resin is used, the low temperature fixability is improved, but the use of a high molecular weight type polyester resin is limited from the viewpoint of the solubility and dispersibility of the resin, and it is difficult to expand the fixing temperature range.

On the other hand, Patent Document 3 proposes a toner obtained by the dissolution suspension method. In this method, a polyester resin, an extending agent, a coloring agent, a releasing agent and the like are added to an aqueous phase containing a dispersion stabilizer with stirring to form oil droplets, and then the temperature is raised to carry out a polymerization reaction. Is a method of obtaining toner particles. According to this dissolution and suspension method, it is possible to achieve both the low temperature fixing property and the hot offset resistance by reducing the particle diameter of the toner particles and making the resin uniform while using the polyester resin, but it is derived from the stretching agent There is a problem that the glossiness is lowered due to (1) high aggregation property of the urea group or the urethane group, and (2) the charge control property is lowered due to the positive chargeability.

As described above, there has been no excellent toner which is excellent in low-temperature fixability, glossiness, hot offset resistance, chargeability and particle size distribution, and which satisfies all of heat-resistant storage stability and charge stability.

Unexamined-Japanese-Patent No. 4-211272 Patent No. 2537503 JP, 2010-152002, A

The present invention provides a method for producing resin particles and toner that are excellent in low temperature fixability, glossiness, hot offset resistance, chargeability and particle size distribution, and satisfy all of heat resistance storage stability, charge stability and cleaning properties. With the goal.

As a result of studying to achieve the above object, the present invention has been achieved.
That is, the present invention provides a polyester resin having a glass transition temperature (Tg _a ) of −20 to 57 ° C. obtained by polycondensation of a component containing an alcohol component (y) and an unsaturated carboxylic acid component (z) The method is a method for producing resin particles in which resin fine particles containing a) are obtained, and then the resin fine particles are aggregated and fused, and after obtaining the resin fine particles, unsaturated carboxylic acid component (z) in the polyester resin (a) A process for producing resin particles including the step of crosslinking the carbon-carbon double bonds derived from each other to form a modified resin, and a process for producing a toner comprising resin particles obtained by the above process for producing resin particles .

It is an object of the present invention to provide a resin particle and a toner manufacturing method which are excellent in low temperature fixability, glossiness, hot offset resistance, chargeability and particle size distribution and satisfy all of heat resistance storage stability, charge stability and cleanability. It will be possible.

The method for producing resin particles of the present invention has a glass transition temperature (Tg _a ) of −20 to 57 ° C. obtained by polycondensation of a component containing an alcohol component (y) and an unsaturated carboxylic acid component (z). The resin fine particles containing the polyester resin (a) of the present invention are obtained, and then the resin fine particles are coagulated and coalesced, and after the resin fine particles are obtained, unsaturated carbon in the polyester resin (a) is obtained. A step of crosslinking the carbon-carbon double bonds derived from the acid component (z) to form a modified resin is characterized.
Below, the manufacturing method of the resin particle of this invention is demonstrated one by one.

The resin particle obtained by the production method of the present invention is a modified resin in which a polyester resin (a) obtained by polycondensation of a component containing an alcohol component (y) and an unsaturated carboxylic acid component (z) is crosslinked. Include as an essential ingredient.
The modified resin in which the polyester resin (a) is crosslinked means an unsaturated carbon in the polyester resin (a) after the polyester resin (a) substantially having carbon-carbon double bonds in its molecule is obtained by polycondensation. The non-linear polyester modified resin (A) is a chemically bonded non-linear polyester modified resin (A) in which a crosslinking reaction occurs at carbon-carbon double bonds derived from the acid component (z).
When the resin particles contain the non-linear polyester modified resin (A), the hot offset resistance, the bending resistance, the document offset property and the image strength of the resin particles and the toner comprising the resin particles become good.
The resin contained in the resin particles may be one type or a mixture of two or more types of resins. For example, a modified resin obtained by crosslinking the polyester resin (a) and a polyester resin (b) {polyester resin described later It may be a combination of a polyester resin except for (a) and a polyester resin obtained by polycondensation of a component containing an alcohol component (y) and a saturated carboxylic acid component (x).
The polyester resin (a) and the polyester resin (b) may be used alone or in combination of two or more.
The polyester resin (a) in the present invention is obtained by polycondensation of a component containing one or more alcohol components (y) and one or more unsaturated carboxylic acid components (z), and is an unsaturated carboxylic acid. It has a carbon-carbon double bond in the molecule derived from the component (z).
Furthermore, the polyester resin (a) is obtained by polycondensation in combination with one or more kinds of saturated carboxylic acid components (x) as a constituent raw material in addition to the alcohol component (y) and the unsaturated carboxylic acid component (z) It may be a polyester resin.

Examples of the alcohol component (y) include monools (y1), diols (y2) and polyols having a valence of 3 or more (y3).

Examples of monools (y1) include alkanols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol and the like) and the like.
Among these monools, preferred are alkanols having 8 to 24 carbon atoms, and more preferred are dodecyl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, and combinations of two or more of these.

The diol (y2) is an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1, 5-Pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.), C4-36 alkylene ether glycol (diethylene glycol, triethylene glycol) , Dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, etc.), alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), Alkylene oxide ((poly) oxyalkylene) adducts (preferably having an average added mole number of 1 to 30), aromatic diols [monocyclic dihydric phenols (eg hydroquinone etc.) and bisphenols etc.] and alkylenes of the above aromatic diols Oxide adducts (preferably, the average addition mole number 2 to 30) and the like can be mentioned.
Among them, alkylene oxide adducts of bisphenols are preferable from the viewpoint of low temperature fixing ability and heat resistant storage stability. In the alkylene oxide, the carbon number of the alkylene group is preferably 2 to 4 (such as ethylene oxide and propylene oxide).

The alkylene oxide adduct of bisphenols is generally obtained by adding an alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenols. As bisphenols, what is shown by following General formula (1) is mentioned.

HO-Ar-P-Ar-OH (1)
[Wherein, P represents an alkylene group having 1 to 3 carbon atoms, -SO _2- , -O-, -S-or a direct bond, and Ar represents a halogen atom or an alkyl having 1 to 30 carbon atoms] Represents a phenylene group which may be substituted by a group. ]

Examples of bisphenols include bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A and 2 And 2'-diethyl bisphenol F etc., and two or more of these can be used in combination.

As the alkylene oxide to be added to these bisphenols, an alkylene oxide having 2 to 4 carbon atoms is preferable, and, for example, ethylene oxide (hereinafter sometimes "ethylene oxide" may be abbreviated as EO), propylene oxide ("1 (Hereinafter, sometimes abbreviated as PO), 1,3-propylene oxide, 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran And combinations of two or more of these.
In terms of heat resistant storage stability and low temperature fixability, AO constituting an AO adduct of bisphenols is preferably EO and PO. The average added mole number of AO is preferably 2 to 30 moles, more preferably 2 to 10 moles.
Among the alkylene oxide adducts of bisphenols, preferred are EO adducts of bisphenol A and PO adducts of bisphenol A (the average addition mole number is preferably 2 to 4, more preferably 2) from the viewpoint of toner fixability. To 3).

Examples of trivalent or higher valence polyols (y3) include trivalent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (y31), saccharides and their derivatives (y32), and aliphatic polyhydric alcohols. AO adduct (average added mole number is preferably 1 to 30) (y33), AO adduct of trisphenols (such as trisphenol PA) (average added mole number is preferably 2 to 30) (y34), novolac resin (Phenol novolak and cresol novolac etc. are included, and the average degree of polymerization is preferably 3 to 60) AO adducts (average added mole number is preferably 2 to 30) (y35), etc. may be mentioned.

Examples of trivalent or higher aliphatic polyhydric alcohol (y31) having 3 to 36 carbon atoms include alkane polyols and intramolecular or intermolecular dehydrated products thereof, and more specifically glycerin, trimethylolethane, Examples thereof include trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol.

Specific examples of the saccharide and its derivative (y32) include sucrose and methyl glucoside. As the AO adduct of aliphatic polyhydric alcohol (y33), the AO adduct of trivalent or higher valence aliphatic polyhydric alcohol (y31) having 3 to 36 carbon atoms as described above (the average addition mole number is preferably 1 to 30).

It is preferable from the viewpoints of heat resistant storage stability and hot offset resistance that a combination of a divalent diol (y2) and a trivalent or higher valence polyol (y3) as the alcohol component (y) is used.

Among these alcohol components (y), the preferred ones from the viewpoint of achieving both low temperature fixing ability and hot offset resistance are alkylene glycols having 2 to 12 carbon atoms; AO adducts of bisphenols (the average addition mole number is preferably AO adducts of 2 to 30); trivalent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms; and novolak resins (including phenol novolaks and cresol novolacs, preferably having an average degree of polymerization of 3 to 60) (The average addition mole number is preferably 2 to 30).

From the viewpoint of heat resistant storage stability, more preferable are alkylene glycols having 2 to 10 carbon atoms, AO adducts of bisphenols (average addition mole number is preferably 2 to 5), trivalent to tetravalent compounds having 3 to 15 carbon atoms Aliphatic polyhydric alcohols and novolak resins (including phenol novolak and cresol novolac, etc., preferably 3 to 60 as the average degree of polymerization) are AO adducts (average added mole number is preferably 2 to 30).
More preferably, they are alkylene glycols having 2 to 6 carbons; trivalent aliphatic polyhydric alcohols having 3 to 10 carbons; and AO adducts of bisphenol A (average added mole number is preferably 2 to 5), Particularly preferred are ethylene oxide, propylene glycol, 3-methyl-1,5-pentanediol, trimethylolpropane and alkylene oxide adducts of bisphenol A (average added mole number: 2 to 3).

The unsaturated carboxylic acid (z) has a polymerizable carbon-carbon double bond.
In the present invention, binding of an aromatic ring is not considered in determining whether it is the unsaturated carboxylic acid component (z) or the saturated carboxylic acid component (x). A compound in which the portion other than the aromatic ring portion is unsaturated carboxylic acid is determined as the unsaturated carboxylic acid component (z), and a compound in which the portion other than the aromatic ring portion is a saturated carboxylic acid is determined as the saturated carboxylic acid component (x).

As the unsaturated carboxylic acid component (z), unsaturated monocarboxylic acid (z1), unsaturated dicarboxylic acid (z2), unsaturated polycarboxylic acid (z3), anhydrides and lower alkyl esters of these acids, etc. may be mentioned. Be One type of unsaturated carboxylic acid component (z) may be used, or two or more types may be used in combination.

Examples of unsaturated monocarboxylic acids (z1) include unsaturated monocarboxylic acids having 2 to 30 carbon atoms, and specific examples include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, and angelic acid. , Tiglic acid, 4-pentenoic acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, 2,4-hexadienoic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vacenic acid, gadeau Examples include acids, eicosenoic acids, erucic acid and nervonic acid.

Examples of unsaturated dicarboxylic acids (z2) include alkene dicarboxylic acids having 4 to 50 carbon atoms. Specifically, alkenyl succinic acids such as dodecenyl succinic acid and pentadecenyl succinic acid, maleic acid, fumaric acid and citraconic acid And mesaconic acid, itaconic acid and glutaconic acid.

Examples of unsaturated polycarboxylic acids (z3) include trivalent or higher unsaturated polycarboxylic acids, and examples thereof include trivalent or higher alkene polycarboxylic acids having 6 to 50 carbon atoms (specifically, aconitic acid, 3 Alkene tricarboxylic acids such as -butene-1,2,3-tricarboxylic acid and 4-pentene-1,2,4-tricarboxylic acid, 1-pentene-1,1,4,4-tetracarboxylic acid, 4-pentene And alkene tetracarboxylic acids such as 1,2,3,4-tetracarboxylic acid and 3-hexene-1,1,6,6-tetracarboxylic acid. The unsaturated polycarboxylic acid (z3) is preferably a trivalent or tetravalent unsaturated polycarboxylic acid.

Among these unsaturated carboxylic acid components (z), preferred are acrylic acid, methacrylic acid, alkenylsuccinic acid, maleic acid and fumaric acid, and two or more of them, from the viewpoint of achieving both low temperature fixability and hot offset resistance. In combination.
More preferable are acrylic acid, methacrylic acid, maleic acid, fumaric acid and a combination of two or more of them. Anhydrides and lower alkyl esters of these acids are also preferred.

Although the unsaturated carboxylic acid component (z) is essential as the carboxylic acid component constituting the polyester resin (a), a saturated carboxylic acid component (x) may be used in combination as a constituent raw material. The saturated carboxylic acid component (x) may be used alone or in combination of two or more.
Examples of such saturated carboxylic acid component (x) include aliphatic carboxylic acids and aromatic carboxylic acids.
Examples of aliphatic carboxylic acids include aliphatic monocarboxylic acids having 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthate, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, Palmitic acid, margaric acid, stearic acid and behenic acid etc.) Aliphatic dicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, repargic acid, sebacic acid and dodecanedioic acid), carbon And aliphatic tricarboxylic acids (eg, hexane tricarboxylic acid etc.) and the like.
Examples of the aromatic carboxylic acid include aromatic monocarboxylic acids having 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid and the like), and aromatic dicarboxylic acids having 8 to 36 carbon atoms Phthalic acid, isophthalic acid, terephthalic acid and naphthalene dicarboxylic acid etc., and trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid and pyromellitic acid etc.) can be mentioned.

As the saturated carboxylic acid component (x), an anhydride of these carboxylic acids, lower alkyl (1 to 4 carbon atoms) esters (such as methyl ester, ethyl ester and isopropyl ester) may be used, or the anhydride or the lower ones. You may use together an alkyl ester and the said carboxylic acid.

Among these saturated carboxylic acid components (x), aliphatic dicarboxylic acids having 2 to 50 carbon atoms and aromatic monocarbons having 7 to 37 carbon atoms are preferable from the viewpoint of achieving both low temperature fixing ability and hot offset resistance. It is an acid, an aromatic dicarboxylic acid having 8 to 20 carbon atoms and a trivalent or higher aromatic polycarboxylic acid having 9 to 20 carbon atoms.
More preferably, benzoic acid, adipic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid and a combination of two or more of them are preferable from the viewpoint of heat resistant storage stability, chargeability and charge stability.
More preferable are adipic acid, terephthalic acid, isophthalic acid, trimellitic acid and a combination of two or more of them. Anhydrides and lower alkyl esters of these acids are likewise preferred.

The polyester resin (a) in the present invention is not particularly limited, but is preferably a non-linear polyester resin from the viewpoint of improving the elasticity at high temperature.
The method for producing the polyester resin (a) in the present invention is not particularly limited, but as described above, it is obtained by polycondensing a component containing the alcohol component (y) and the unsaturated carboxylic acid component (z). Be Furthermore, when the polyester resin (a) is a non-linear polyester resin, for example, when a trivalent or higher polyol is used as the alcohol component (y) in addition to the unsaturated carboxylic acid component (z), a saturated carboxylic acid component (x) As trivalent or higher carboxylic acid or acid anhydride or lower alkyl ester thereof. The polyester resin (a) which is a non-linear polyester resin can also be obtained by using a trivalent or higher unsaturated polycarboxylic acid (z3) as the unsaturated carboxylic acid component (z). By being non-linear, the heat resistant storage stability and the hot offset resistance of the resin particles and the toner are improved.

In the present invention, the polyester resin (a) and the like can be produced in the same manner as known polyester resins.
For example, the reaction temperature of the component containing the alcohol component (y) and the unsaturated carboxylic acid component (z) in an inert gas (nitrogen gas etc.) atmosphere is preferably 150 to 280 ° C., more preferably 160 to It can be carried out by reacting at 250 ° C., more preferably at 170 to 235 ° C. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.

At this time, an esterification catalyst can be used as needed. Examples of esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide etc.), antimony trioxide, titanium-containing catalysts [eg titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, JP-A-2006-243715 Catalysts described in Japanese Patent Application Publication No. JP-A-2006-147-99 [Titanium diisopropoxy bis (triethanolaminate), titanium dihydroxy bis (triethanolaminate), titanium monohydroxytris (triethanolaminate), titanyl bis (triethanolaminate) and their compounds Intramolecular polycondensate etc.], and catalysts described in JP 2007-11307 A (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, and titanium diisopropoxy diterephthalate) ), Etc.], zirconium-containing catalysts (e.g. zirconyl acetate, etc.), and zinc acetate, and the like. Among these, preferred is a titanium-containing catalyst. It is also effective to reduce the pressure to improve the reaction rate at the end of the reaction.

Further, a stabilizer may be added for the purpose of obtaining polyester polymerization stability. As the stabilizer, hydroquinone, methylhydroquinone and hindered phenol compounds may, for example, be mentioned.

The preparation ratio of the alcohol component (y) to the total of the unsaturated carboxylic acid component (z) and the saturated carboxylic acid component (x) is preferably 2 as the equivalent ratio [OH] / [COOH] of hydroxyl group and carboxyl group. It is preferably 1/1/2 to 1/2, more preferably 1.5 / 1 to 1 / 1.3, and still more preferably 1.4 / 1 to 1 / 1.2. The said hydroxyl group is a hydroxyl group derived from alcohol component (y), and a carboxyl group is the sum total of the carboxyl group derived from unsaturated carboxylic acid component (z) and saturated carboxylic acid component (x).
The unsaturated carboxylic acid component (z) used for producing the polyester resin (a) is 3 to 50 moles based on the total number of moles of the unsaturated carboxylic acid component (z) and the saturated carboxylic acid component (x) % Is preferable, 4 to 40 mol% is more preferable, and 5 to 35 mol% is more preferable.

The glass transition temperature (Tg _a ) of the polyester resin (a) is -20 to 57 ° C. When the Tg _a is 57 ° C. or less, the low-temperature fixability is good, and when it is −20 ° C. or more, the heat resistant storage property is good. The Tg _a is preferably −18 to 50 ° C., more preferably −15 to 45 ° C., and still more preferably −10 to 40 ° C.
The glass transition temperature (Tg _a and Tg) can be measured by the method (DSC method) defined in ASTM D3418-82. Glass transition temperature (Tg _a and Tg), for example TA Instruments (Co., Ltd.), can be measured using a DSC Q20. The measurement conditions of glass transition temperature are described.
<Measurement conditions>
(1) Temperature increase from 30 ° C to 20 ° C / min to 150 ° C (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 2.) Analyze the differential scanning calorimetry curve measured in the process of heating up to 150 ° C at 20 ° C / min (6) (5).

The peak top molecular weight of the polyester resin (a) is preferably from 2,000 to 20,000, more preferably from 3,000 to 18, from the viewpoint of coexistence of hot offset resistance, low temperature fixability and glossiness. 000, more preferably 3,500 to 16,000, and particularly preferably a peak top molecular weight of 4,000 to 11,900. In the present invention, the peak top molecular weight of the resin is the peak top molecular weight in gel permeation chromatography (GPC).

Here, the peak top molecular weight (hereinafter sometimes abbreviated as Mp) is obtained by calculating the molecular weight distribution of the sample from the relationship between the logarithmic value of the calibration curve prepared by the standard polystyrene sample and the count number. It is the molecular weight determined from the peak maximum value in the chart of the molecular weight distribution. Since the number of peaks in the chart is not limited to one, when there are a plurality of peaks, it is determined from the peak showing the maximum value among the peak values. In addition, the measurement conditions of GPC measurement are as follows.

In the present invention, the peak top molecular weight, number average molecular weight (hereinafter sometimes abbreviated as Mn) and weight average molecular weight (hereinafter abbreviated as Mw) of resins such as polyester resins are measured using GPC. Measurement under the following conditions. In the present invention, the peak top molecular weight, weight average molecular weight and number average molecular weight are the peak top molecular weight, weight average molecular weight and number average molecular weight of the THF soluble matter.
Device (example): HLC-8120 (manufactured by Tosoh Corporation)
Column (one example): Two TSK GEL GMH6 (made by Tosoh Corp.)
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Injection volume: 100 μL
Detector: Refractive index detector Reference material: Tosoh Co., Ltd. product standard polystyrene (TSK standard POLYSTYRENE) 12 points (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)
To measure the molecular weight, a polyester resin or the like is dissolved in THF so as to be 0.25% by weight, and the insoluble matter is filtered off with a glass filter to obtain a sample solution.

The acid value of the polyester resin (a) is preferably 0 to 30 mg KOH / g, more preferably 0 to 25 mg KOH / g, and still more preferably 0 to 10 mg KOH / g from the viewpoint of chargeability stability.
The acid value of polyester resin (a) etc. can be measured by the method prescribed in JIS K 0070 (1992 version).

The modified resin obtained by crosslinking the polyester resin (a) is, for example, a radical reaction initiator (c) after the polyester resin (a) having carbon-carbon double bonds in the molecule is obtained by polycondensation. It is a modified resin in which a carbon-carbon double bond derived from the unsaturated carboxylic acid component (z) in the polyester resin (a) causes a cross-linking reaction to cause a chemical bond using the generated radicals.

The radical reaction initiator (c) used for the crosslinking reaction of the polyester resin (a) in the present invention is not particularly limited, and inorganic peroxide (c1), organic peroxide (c2) and azo compound (c3) Etc.). The radical reaction initiator (c) may be used alone or in combination of two or more.

The inorganic peroxide (c1) is not particularly limited, and examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.

The organic peroxide (c2) is not particularly limited, but benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t-butylperoxy) ) Diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t-butylper Oxyhexyne-3, acetyl peroxide, isobutyryl peroxide, octaninor peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t-butyl Peroxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecano Aate, t-Butylperoxy 2-ethylhexanoate, t-Butylperoxy 3,5,5-trimethylhexanoate, t-Butylperoxylaurate, t-Butylperoxybenzoate, t-Butylperoxy Isopropyl carbonate and t-butyl peroxy acetate etc. may be mentioned.

Examples of the azo compound and the diazo compound (c3) include, but are not limited to, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2 '-Azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyric acid Ronitrile etc. are mentioned.

The amount of the radical reaction initiator (c) used is not particularly limited, but 100 parts by weight of the unsaturated carboxylic acid component (z) constituting the polyester resin (a) when making the polyester resin (a) a modified resin The preferred amount is 0.1 to 50 parts by weight.
The crosslinking reaction is likely to proceed when the amount of the radical reaction initiator used is 0.1 parts by weight or more based on 100 parts by weight of the unsaturated carboxylic acid component (z) constituting the polyester resin (a) There is a tendency, and when the amount is 50 parts by weight or less, the odor tends to be good. The amount of the radical reaction initiator (c) used is more preferably 30 parts by weight or less, and 20 parts by weight or less based on 100 parts by weight of the unsaturated carboxylic acid component (z) constituting the polyester resin (a) Is more preferably 10 parts by weight or less.

The weight ratio of the tetrahydrofuran insoluble matter to the tetrahydrofuran soluble matter (soluble matter) in the resin particle obtained by the production method of the present invention (THF insoluble matter / THF dissolved matter) is the hot offset resistance, low temperature fixability, From the viewpoint of compatibility with glossiness, it is preferably 5/95 to 60/40, more preferably 5/95 to 50/50, still more preferably 7/93 to 50/50, particularly preferably 9/91 to 40/60.
Here, in addition to the modified resin in which the polyester resin (a) is crosslinked in the resin particles, it is an optional component as needed {polyester resin (b) described later, coloring agent, release agent, charge control agent, fluidizing agent, etc.} If the resin particle contains optional components, the THF insoluble matter and / or the THF solution also contain these optional components.

The weight ratio of the THF insoluble matter to the THF dissolved matter in the resin particle obtained by the production method of the present invention is determined by the following method.
Add 50 mL of THF to 0.5 g of sample and stir at reflux for 3 hours. After cooling, the insolubles are filtered off with a glass filter, and the resin on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The weight of the dried resin on the glass filter is the weight of the THF insolubles, and the weight of the weight of the sample minus the weight of the THF insolubles is the weight of the THF dissolved, the THF insolubles and the THF dissolved Calculate the weight ratio.

It is preferable that the resin particle obtained by the manufacturing method of this invention contains the polyester resin (b) obtained by polycondensing the component containing saturated carboxylic acid component (x) and alcohol component (y).
When the resin particles obtained by the production method of the present invention contain a polyester resin (b), the low temperature fixability is improved.

The polyester resin (b) in the present invention is a polyester resin (other than the polyester resin (a)) excluding the polyester resin (a). The polyester resin (b) does not use the above-mentioned unsaturated carboxylic acid component (z) as a carboxylic acid component, and one or more types of alcohol components (y) and one or more types of saturated carboxylic acid components (x) What is obtained by polycondensing the component containing and the like are mentioned.

Moreover, as polyester resin (b), amorphous polyester resin (b1) and crystalline polyester resin (C) are mentioned.

In the present invention, the crystalline polyester resin (C) indicates crystallinity and means that the temperature Tp (° C.) indicating the endothermic peak top is in the range of 40 to 100 ° C.
The amorphous polyester resin (b1) used in the present invention is a polyester resin (b) other than the crystalline polyester resin (C). In one aspect, the polyester resin (b) is a polyester resin containing an amorphous polyester resin (b1) obtained by polycondensation of a component containing an alcohol component (y) and a saturated carboxylic acid component (x) Is preferred.
In the present invention, “crystallinity” refers to a resin having a clear endothermic peak, not a stepwise endothermic change in the second temperature rising process of differential scanning calorimeter (DSC) measurement described later.
In the present invention, when measuring the temperature Tp indicating the endothermic peak top by DSC, for example, DSC Q20 manufactured by TA Instruments Co., Ltd. can be used. Further, as the temperature raising / cooling conditions, the temperature is raised to 180 ° C. under the condition of 10 ° C./min (first temperature raising process). Next, after standing at 180 ° C. for 10 minutes, it is cooled to 0 ° C. under the condition of 10 ° C./min (first cooling process). Next, after standing at 0 ° C. for 10 minutes, the temperature is raised to 180 ° C. under the condition of 10 ° C./min (second temperature rising process).

Examples of the alcohol component (y) of the amorphous polyester resin (b1) include the same as the alcohol component (y) of the polyester resin (a).
Among these alcohol components (y), preferred from the viewpoint of achieving both low temperature fixability and heat resistant storage stability are AO adducts of alkylene glycols having 2 to 12 carbon atoms and bisphenols (the average addition mole number is preferably 2 To 30).
More preferable from the viewpoint of heat resistant storage stability are alkylene glycols having 2 to 10 carbon atoms and AO adducts of bisphenols (the average addition mole number is preferably 2 to 5).
More preferably, it is an AO adduct of alkylene glycol having 2 to 6 carbon atoms and bisphenol A (average added mole number is preferably 2 to 5), and particularly preferably, an alkylene oxide adduct of propylene glycol and bisphenol A (average The added mole number is 2 to 3).
Further, from the viewpoint of achieving both low temperature fixability and heat resistant storage stability, the alcohol component (y) preferably contains 80 mol% or more, more preferably 90 mol% or more of aromatic diol based on the total number of moles of alcohol component. More preferably, it is 95% or more.

Examples of the carboxylic acid component (x) of the amorphous polyester resin (b1) include the same as the saturated carboxylic acid component (x) of the polyester resin (a).
Among these saturated carboxylic acid components (x), aliphatic carboxylic acids having 2 to 50 carbon atoms and aromatic monocarboxylic acids having 7 to 37 carbon atoms are preferable from the viewpoint of achieving both low temperature fixing ability and heat resistant storage stability. C 8-20 aromatic dicarboxylic acids and C 9-20 trivalent or higher aromatic polycarboxylic acids.
More preferably, benzoic acid, adipic acid, terephthalic acid, isophthalic acid, trimellitic acid and a combination of two or more of them are preferable from the viewpoint of heat resistant storage stability, chargeability and charge stability.
More preferable are terephthalic acid, isophthalic acid, trimellitic acid and a combination of two or more of them. Anhydrides and lower alkyl esters of these acids are likewise preferred.
Further, from the viewpoint of achieving both low temperature fixing ability and heat resistant storage stability, the saturated carboxylic acid component (x) preferably contains 80 mol% or more of aromatic dicarboxylic acid based on the total number of moles of the saturated carboxylic acid component. Is 90 mol% or more, more preferably 95 mol% or more.

As alcohol component (y) of crystalline polyester resin (C), the thing similar to alcohol component (y) of polyester resin (a) is mentioned.
Among these alcohol components (y), preferred are alkylene glycols having 2 to 36 carbon atoms from the viewpoint of achieving both low temperature fixability and heat resistant storage stability. More preferably, it is an alkylene glycol having 2 to 12 carbon atoms. More preferred are alkylene glycols having 2 to 9 carbon atoms, and particularly preferred are 1,6-hexanediol, 1,9-nonanediol and 1,10-decanediol.

As a carboxylic acid component (x) of crystalline polyester resin (C), the thing similar to the saturated carboxylic acid component (x) of polyester resin (a) is mentioned.
Among these saturated carboxylic acid components (x), aliphatic dicarboxylic acids having 2 to 50 carbon atoms are preferable from the viewpoint of achieving both low temperature fixing ability and heat resistant storage stability. More preferred are succinic acid, adipic acid, sebacic acid and dodecanedioic acid. More preferred are sebacic acid and dodecanedioic acid.

The polyester resin (b) may be linear or non-linear, but is preferably linear from the viewpoint of low-temperature fixability and heat resistant storage stability.
Moreover, as polyester resin (b), what does not contain a THF insoluble part substantially is preferable. If it does not contain a THF insoluble matter, it may have a trace amount of crosslinking points, and trimellitic anhydride, phthalic anhydride, and anhydride of saturated polycarboxylic acid (which may be trivalent or higher) at the molecular end It may be modified with maleic anhydride or the like.

The weight ratio (a) / (b) of the polyester resin (a) -derived structural portion in the resin particles to the polyester resin (b) is from the viewpoint of coexistence of low temperature fixability, hot offset resistance and heat resistant storage stability. The ratio is preferably 5/95 to 50/50, more preferably 7/93 to 45/60, and still more preferably 9/90 to 40/60. The structural part derived from the polyester resin (a) is a modified resin obtained by crosslinking the polyester resin (a) and the polyester resin (a). In the production of resin particles, the amounts of each component and polyester resin (b) used to obtain the polyester resin (a) should be set such that the weight ratio (a) / (b) falls within the above range. Is preferred.

The weight ratio (b1) / (C) of the non-crystalline polyester resin (b1) to the crystalline polyester resin (C) in the resin particle is from the point of coexistence of low temperature fixability, hot offset resistance and heat resistant storage stability 100/0 to 50/50 is preferable, more preferably 95/5 to 70/30, and still more preferably 90/10 to 80/20.

When the resin particles contain the polyester resin (b), carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a) in the presence of the polyester resin (b) It is preferable to obtain a modified resin in which the polyester resin (a) is crosslinked by crosslinking reaction between each other, from the viewpoint of coexistence of low temperature fixability, hot offset resistance, and heat resistant storage stability.

The THF soluble portion Mn of the polyester resin (b) is preferably 1,000 to 15,000, more preferably 1,200 to 10,000, from the viewpoint of achieving both the heat resistant storage stability of the toner and the low temperature fixability. More preferably, it is 1,500 to 5,000.

The peak top molecular weight of the THF soluble component of the polyester resin (b) is preferably 2,000 to 30,000, more preferably from the viewpoint of achieving both the hot offset resistance of the toner, the heat resistant storage stability, and the low temperature fixability. It is preferably 2,500 to 20,000, more preferably 3,000 to 10,000.

The temperature Tp showing the endothermic peak top of the crystalline polyester resin (C) is preferably 50 to 90 ° C., more preferably 55 to 85 ° C., still more preferably 60 from the viewpoint of the heat resistant storage stability of the finally obtained toner. It is ~ 80 ° C.

The softening point [Tm] of the crystalline polyester resin (C) by a flow tester is preferably 30 to 170 ° C., more preferably 40 to 130 ° C., still more preferably 50 to 150 ° C. from the viewpoint of low temperature fixability and hot offset resistance. It is 100 ° C.

The softening point [Tm] of the crystalline polyester resin (C) is measured under the following conditions.
<Method of measuring softening point [Tm]>
Using a drop-down flow tester [CFT-500D manufactured by Shimadzu Corporation, for example, apply a load of 1.96 MPa by the plunger while heating 1 g of the measurement sample at a heating rate of 6 ° C./min It extrudes from a nozzle of 1 mm in diameter and 1 mm in length and draws a graph of “Plunger drop amount (flow value)” and “temperature”, and graph the temperature corresponding to half of the maximum drop amount of plunger This value (temperature at which half of the measurement sample flowed out) is taken as the softening point [Tm].

The resin particles obtained by the production method of the present invention are heat resistant to have at least one inflection point indicating a glass transition temperature (Tg) in a chart by differential scanning calorimetry (DSC) in a temperature range of -20 ° C to 80 ° C. The above temperature range is more preferably 30 ° C. to 70 ° C., and still more preferably 40 ° C. to 65 ° C. from the viewpoint of storage stability and low temperature fixability. The resin particles may have two or more inflection points indicating a glass transition temperature (Tg), and one of them may be in this temperature range. The glass transition temperature (Tg) can be determined by the method (DSC method) defined in ASTM D3418-82 as described above. The conditions for measuring the glass transition temperature (Tg) are as described above.

In the resin particles produced in the present invention, at least one known additive selected from the group consisting of a colorant, a mold release agent, a charge control agent, a fluidizing agent and the like is used as needed in addition to the polyester resin. May be

As colorants, 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, indofirst orange, irgasine 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, Oil Pink OP, etc. Or 2 or more types can be mixed and used. If necessary, magnetic powder (powder of a ferromagnetic metal such as iron, cobalt, nickel or the like or a compound such as magnetite, hematite or ferrite) can be contained as well as the function as a colorant.
The content of the colorant is preferably 1 to 40% by weight, more preferably 3 to 10% by weight, based on the weight of resin particles obtained by the production method of the present invention, from the viewpoint of toner image density and low temperature fixability. . When magnetic powder is used, the content of the magnetic powder is preferably 20 to 70% by weight, more preferably 40 to 60% by weight, based on the weight of the resin particles.

As a mold release agent, aliphatic hydrocarbon waxes such as low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and oxides thereof, carnauba Wax, montan wax, sazole wax and their deacidified waxes, ester waxes such as fatty acid ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like.

Polyolefin waxes include (co) polymers [(co) polymerization of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and a mixture of two or more of these, etc.) Products obtained and thermally-deformed polyolefins], oxides of (co) polymers of olefins with oxygen and / or ozone, maleic acid modified products of (co) polymers of olefins [eg maleic acid and its derivatives (anhydride Maleic acid, monomethyl maleate, monobutyl maleate and dimethyl maleate etc.)), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride etc] and / or unsaturated carboxylic acid alkyl esters [Alkyl (meth) acrylate (the carbon number of the alkyl is 1 to 18) Copolymers of ether and maleic acid alkyl (number of carbon atoms in the alkyl 1-18) ester, etc.] or the like, and Sasol wax.

Among them, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, carnauba wax and ester wax are preferable from the viewpoint of low temperature fixing property and hot offset resistance.

The release agent preferably has a softening point [Tm] of 50 to 170 ° C. by a flow tester, and more preferably 50 to 140 ° C., from the viewpoint of low temperature fixing property and hot offset resistance. More preferably, the temperature is 50 to 120 ° C. The softening point [Tm] can be measured under the same conditions as for the crystalline polyester resin (C).

The content of the release agent is preferably 1 to 20% by weight, more preferably 2 to 10% by weight based on the weight of the resin particles obtained by the production method of the present invention, from the viewpoint of low temperature fixability and hot offset resistance. %.

As a charge control agent, nigrosine dye, triphenylmethane dye having tertiary amine as a side chain, quaternary ammonium salt, polyamine resin, imidazole derivative, polymer containing quaternary ammonium base, metal-containing azo dye, copper phthalocyanine dye, Examples thereof include metal salts of salicylic acid, boron complexes of benzyl acid, sulfonic acid group-containing polymers, fluorine-containing polymers, and halogen-substituted aromatic ring-containing polymers.

As a fluidizing agent, colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, barium titanate, magnesium titanate, calcium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, bengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate and barium carbonate.

The charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the weight of the resin particles.
The fluidizing agent may be 0 to 10% by weight, preferably 0 to 5% by weight, more preferably 0.1 to 4% by weight, based on the weight of the resin particles.
In addition, the total amount of additives such as colorant, mold release agent, charge control agent, fluidizing agent and the like may be 3 to 70% by weight, preferably 4 to 58% by weight, based on the weight of resin particles. Preferably, it is 5 to 50% by weight. When the total amount of additives contained in the resin particles is in the above range, it is possible to easily obtain one having good hot offset resistance, chargeability, toner flowability, heat resistant storage stability and charge stability. .

The method for producing resin particles of the present invention has a glass transition temperature (Tg _a ) of −20 to 57 ° C. obtained by polycondensation of a component containing an alcohol component (y) and an unsaturated carboxylic acid component (z). The resin fine particles containing the polyester resin (a) of the present invention are obtained, and then the resin fine particles are coagulated and coalesced, and after the resin fine particles are obtained, unsaturated carbon in the polyester resin (a) is obtained. It is a method for producing resin particles, including the step of crosslinking the carbon-carbon double bonds derived from the acid component (z) to form a modified resin. In the step of crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a) to form a modified resin, resin fine particles of the present invention are finally obtained. It may be carried out at any stage until particles are obtained. The step of crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a) to a modified resin may be performed, for example, before aggregation of the resin fine particles, It may be performed at the time of aggregating the resin fine particles, or may be performed at the time of fusing the aggregated resin fine particles.

From the viewpoints of particle size control, particle size distribution control, shape control, low temperature fixability, hot offset resistance and heat resistant storage stability of the resin particles and toner obtained according to the present invention, the following steps (1) to (1) It is preferable to include 4).
Step (1): Step of obtaining a dispersion containing resin fine particles (X1) containing polyester resin (a) Step (2): Unsaturated carbon in resin fine particles (X1) or polyester resin (a) in dispersion The fine resin particles (X2) containing the modified resin obtained by crosslinking the carbon-carbon double bonds derived from the acid component (z) are aggregated to form aggregates (Y1) of the fine resin particles (X1) or the fine resin particles (X2) Step (3) of forming the aggregate (Y2) of (a) resin particles (Z1) or aggregates (Y2) obtained by fusing the aggregates (Y1) or (Y2) and fusing the aggregates (Y1) Step (4) of obtaining fused resin particles (Z2): step which can be carried out at any stage after completion of the step (1), and may be conducted simultaneously with the step (2) or (3) In the resin fine particles (X1), aggregates (Y1 Polyester resin (a) an unsaturated carboxylic acid component in the (z) from the carbon in or resin particles (Z1) in - a step of crosslinking the carbon-carbon double bond between

More preferably, the production method includes the following steps (1), (2-1) and (3-1), and the production method includes the following steps (1), (2-2) and (3-2). . Steps (2-1) and (2-2) are preferred embodiments of the above step (2), and steps (3-1) and (3-2) are preferred embodiments of the above step (3). It is an example.
Step (1): Step of obtaining dispersion liquid (D1) of resin fine particles (X1) containing polyester resin (a) Step (2-1): aggregation of resin fine particles (X1) in dispersion liquid (D1) Step (2-2) of Forming Aggregate (Y1): Crosslinking Reaction of Carbon-Carbon Double Bonds Derived from Unsaturated Carboxylic Acid Component (z) in Polyester Resin (a) of Dispersion (D1) A step of forming a aggregate (Y2) by aggregating the resin fine particles (X2) after obtaining a dispersion liquid (D2) of resin fine particles (X2) containing the modified resin as a denatured resin : Resin containing a modified resin by fusing the aggregate (Y1) and simultaneously crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a) into a modified resin Process of obtaining particles (3-2): Aggregate ( Here to obtain by fusing resin particles 2), the additive in the resin particles (e.g., coloring agents and / or mold release agents) may be contained. Preferably, an additive dispersion (colorant dispersion, release agent dispersion, etc.) is prepared in advance as a method of incorporating additives (colorant, release agent, etc.) in resin particles, and dispersion (D1) Alternatively, the dispersion liquid (D2) and the additive dispersion liquid are mixed to obtain the dispersion liquid (W1) or (W2), and the dispersion liquids (W1) and (W2) are substituted for the dispersion liquids (D1) and (D2) in the above step. ) Respectively. When the dispersions (W1) and (W2) are used, additives (coloring agent, releasing agent, etc.) can be uniformly dispersed in resin particles, so that low temperature fixing property, glossiness, hot offset resistance, charging From the viewpoint of toner properties, toner fluidity, heat resistant storage stability and charge stability.

The steps (1) and (2) will be described below.
As a dispersion medium which comprises dispersion liquid (D1), (D2), (W1) and (W2), an aqueous solvent is mentioned.
As the aqueous solvent, any liquid containing water as an essential component can be used without limitation, and water, an aqueous solution of an organic solvent, an aqueous solution of surfactant (s), an aqueous solution of water-soluble polymer (t) and these A mixture of two or more of the above can be used. In addition, an organic solvent may be used to dissolve the resin in order to improve the dispersibility of the resin in the aqueous solvent.

As an organic solvent, for example, aromatic hydrocarbon solvent, aliphatic or alicyclic hydrocarbon solvent, halogen solvent, ester or ester ether solvent, ether solvent, ketone solvent, alcohol solvent, amide solvent, sulfoxide solvent, heterocyclic Compound solvents and mixed solvents of two or more of them and the like can be mentioned.
Specific examples of the organic solvent include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene and tetralin etc.); aliphatic or alicyclic hydrocarbon solvents (n-hexane, n-heptane, mineral spirits and cyclohexane etc); Halogen solvents such as methyl, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene and perchloroethylene; esters or ester ethers such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate Solvents; Ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketone solvents such as 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 dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methyl pyrrolidone; and mixed solvents of two or more of these, and the like. Among the above organic solvents, volatile solvents having a boiling point of less than 100 ° C. are preferable. Preferred organic solvents include ethyl acetate, acetone and methyl ethyl ketone.

The amount of the organic solvent used is preferably 0 to 300 parts by weight based on 100 parts by weight of the polyester resin (a) obtained by polycondensation of a component containing the alcohol component (y) and the unsaturated carboxylic acid component (z). More preferably, it is 0 to 100 parts by weight, still more preferably 25 to 70 parts by weight. When an organic solvent is used, it is preferable to remove by heating under normal pressure or reduced pressure after step (1) or step (2).

A neutralizing agent may be used to neutralize the carboxyl groups of the polyester resin in order to improve the dispersibility of the resin in the aqueous solvent. Examples of the neutralizing agent include organic compounds such as ammonia and triethylamine, and inorganic compounds such as sodium hydroxide.

The amount of the neutralizing agent used is preferably 1 to 150 mol%, more preferably 5 to 100 mol%, from the viewpoint of dispersibility with respect to the carboxyl group of the polyester resin.

When dispersing the polyester resin (a) in an aqueous solvent, known surfactants (s) and inorganic dispersants can be used as an emulsifying agent or dispersing agent. It is preferable to use the surfactant (s) and the inorganic dispersant because the volume average particle diameter of the resin fine particles tends to be small.

The surfactant (s) is not particularly limited, and the anionic surfactant (s-1), the cationic surfactant (s-2), the amphoteric surfactant (s-3) and the non-ionic surfactant (s) 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, sulfuric acid ester salts, salts of carboxymethylated substances, sulfonic acid salts and phosphoric acid ester salts.
Examples of the cationic surfactant (s-2) include quaternary ammonium salt surfactants and amine salt surfactants.
Examples of amphoteric surfactants (s-3) include carboxylate-type amphoteric surfactants, sulfate-ester-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-ester-type amphoteric surfactants. It can be mentioned.
Examples of the nonionic surfactant (s-4) include AO-added nonionic surfactants and polyhydric alcohol type nonionic surfactants.
Specific examples of these surfactants (s) include those described in JP-A-2002-284881.

The amount of surfactant (s) used per 100 parts by weight of water as an aqueous solvent is preferably 0 to 300 parts by weight, more preferably 0.001 to 10 parts by weight, still more preferably 0.01 to 5 parts by weight is there.

As the inorganic dispersant, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, polyphosphate metal salts such as hydroxyapatite, etc. carbonates such as calcium carbonate and magnesium carbonate, calcium metaborate, sulfuric acid Inorganic salts such as calcium and barium sulfate; and inorganic compounds such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide.

The amount of the inorganic dispersant used per 100 parts by weight of water as the aqueous solvent is preferably 0 to 300 parts by weight, more preferably 0.001 to 10 parts by weight.

When the polyester resin (a) is dispersed in an aqueous solvent, a known water-soluble polymer (t) can be used as an emulsifying agent or a dispersing agent. The use of the water-soluble polymer (t) is preferable in that the volume average particle size of the resin fine particles is smaller and the particle size distribution (volume average particle size / number average particle size) tends to be smaller.

Examples of water-soluble polymers (t) include cellulose compounds (eg methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose and saponified compounds thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan , Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene imine, polyacrylamide, acrylic acid (salt) containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, sodium hydroxide partially neutralized of polyacrylic acid And sodium acrylate-acrylic acid ester copolymer etc., sodium hydroxide of styrene-maleic anhydride copolymer Partial) neutralization product, water-soluble polyurethane (polyethylene glycol, and the reaction product of polycaprolactone diol with polyisocyanate etc.) and the like.

The amount of water-soluble polymer (t) used is preferably 0 to 5 parts by weight with respect to 100 parts by weight of water as an aqueous solvent.

The volume-based median diameter of the resin fine particles is preferably 0.050 to 1 μm, more preferably 0.07 to 0.5 μm, still more preferably 0.09 to 0, from the viewpoint of controlling the volume particle size and particle size distribution of the resin particles. .3 μm.
The volume-based median diameter of the resin fine particles can be measured using a dynamic light scattering type particle size distribution measuring apparatus “SZ-100” (manufactured by Horiba, Ltd.).

The amount of resin fine particles in 100 parts by weight of the dispersion is preferably 1 to 70 parts by weight (solid content concentration of the resin fine particles in the dispersion is 1 to 70% by weight) from the viewpoint of controlling the volume particle diameter and particle size distribution of the resin particles. More preferably, it is 5 to 65 parts by weight, still more preferably 10 to 60 parts by weight.

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

The method for obtaining the dispersion liquid (D1) of the resin fine particles (X1) containing the polyester resin (a) in the step (1) is not particularly limited, and the following [1] to [7] may be mentioned.
[1] A method of producing a dispersion (D1) by dispersing a component containing a polyester resin (a) and optionally a radical reaction initiator (c), if necessary, in an aqueous solvent in the presence of a suitable dispersant .
[2] An organic solvent solution of a component containing a polyester resin (a) and optionally a radical reaction initiator (c) is dispersed, if necessary, in an aqueous solvent in the presence of a suitable dispersant, to obtain a dispersion (D1) How to manufacture.
[3] An organic solvent solution of a component containing a polyester resin (a) and optionally a radical reaction initiator (c) is dispersed in an aqueous solvent in the presence of a suitable dispersant, if necessary, and then the organic solvent is added A method of producing a dispersion (D1) by removing it.
[4] A precursor of polyester resin (a) and optionally an organic solvent solution of a component containing a radical reaction initiator (c) is dispersed in an aqueous solvent in the presence of a suitable dispersant, if necessary, and thereafter A method of producing a dispersion (D1) by producing a polyester resin (a) from the precursor of (a).
[5] The polyester resin (a) is pulverized using a pulverizer such as a mechanical rotary type or jet type, and then classified, if necessary, a component containing a radical initiator (c) and the presence of a suitable dispersant A method of dispersing in aqueous solvent below to produce a dispersion (D1).
[6] After a resin solution obtained by dissolving a polyester resin (a) in an organic solvent is sprayed in the form of a mist to obtain particles, if necessary a component containing a radical reaction initiator (c) and a suitable dispersant And dispersion in an aqueous solvent to produce a dispersion (D1).
[7] The poor solvent is added to the resin solution in which the polyester resin (a) is dissolved in the organic solvent, or the resin solution in which the resin solution is heated and dissolved in the organic solvent in advance is cooled to precipitate particles. After that, if necessary, it is dispersed in an aqueous solvent in the presence of a component containing a radical reaction initiator (c) and a suitable dispersant, to produce a dispersion (D1).
Among the methods of [1] to [7], the method of [3] is preferable from the viewpoint of easiness of production of the resin fine particles (X1).
In the above-mentioned methods [1] to [7], the “component containing polyester resin (a) and optionally radical reaction initiator (c)” may optionally contain polyester resin (b). It is preferable to contain a polyester resin (b) from the viewpoint of coexistence of low temperature fixability, hot offset resistance and heat resistant storage stability.
Also, a dispersion (D1) of resin fine particles (X1) containing a polyester resin (a) and an additive dispersion (colorant dispersion, release agent dispersion, etc.) are mixed to obtain a dispersion (W1). Hereinafter, the dispersion liquid (W1) may be used instead of the dispersion liquid (D1).
The additive dispersion (colorant dispersion, release agent dispersion, etc.) is obtained by dispersing an additive such as a colorant in an aqueous solvent by a known method, and a dispersant is used if necessary. You may

In the step (2-2), carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a) are cross-linked to form resin fine particles (X2) containing a modified resin as a modified resin Although the method to obtain the dispersion liquid (D2) of is not particularly limited, for example, the following [8] can be mentioned.
[8] A method of producing a dispersion (D2) of resin fine particles (X2) by adding a radical reaction initiator (c) if necessary to the dispersion (D1) and adjusting the temperature to 5 to 200 ° C. if necessary .
In the above [8], the dispersion (W1) may be used instead of the dispersion (D1).
Also, the obtained dispersion liquid (D2) and the crystalline polyester resin (C) dispersion liquid and / or the additive dispersion liquid are mixed to obtain a dispersion liquid (W2), which is replaced with the dispersion liquid (D2) below. Dispersion liquid (W2) may be used.
The crystalline polyester resin (C) dispersion is obtained by dispersing the crystalline polyester resin (C) in an aqueous solvent by a known method, and a dispersing agent may be used if necessary.
Specifically as a method of obtaining a dispersion liquid (W2), the method of following [9] is mentioned preferably.
[9] An organic solvent solution containing a polyester resin (a) and an amorphous polyester resin (b1) and a radical reaction initiator (c) is dispersed in an aqueous solvent, if necessary, in the presence of a suitable dispersant. The dispersion (abD1) of resin fine particles (X1) is obtained, and if necessary, the temperature is adjusted to 5 to 200 ° C., and unsaturated carbon in the polyester resin (a) in the amorphous polyester resin (b1) The carbon-carbon double bonds derived from the acid component (z) are cross-linked to form a modified resin, and the organic solvent is removed to obtain a dispersion (abD2) of resin fine particles (X2). Crystalline polyester resin (C) dispersion in which polyester resin (C) is dispersed, additive dispersion in which additives are dispersed in aqueous solvent (for example, coloring in which colorant is dispersed in aqueous solvent) Agent dispersion and aqueous solution How releasing agent to produce a dispersion by mixing becomes releasing agent dispersion and the like) are dispersed (W2) in the.

The dispersion method in the above methods [1] to [9] 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 waves may be applied. it can. In order to make the particle size of the fine particles in the dispersion 0.05 to 1 μm, a high speed shear type is preferable. When using a high-speed shear disperser, the rotational 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 in the case of a batch system, it is generally 0.1 to 5 minutes. The controlled temperature is selected according to the molecular weight of the radical initiator (c) and the polyester resin (a) used. The temperature is preferably 5 to 200 ° C., more preferably 20 to 100 ° C.
The dispersing apparatus is, for example, a batch type emulsification machine such as a homogenizer (manufactured by IKA), Polytron (manufactured by Kinematica), a TK autohomomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.], Ebara Milder [manufactured by SHINOHARA MFG. ], TK film mix, TK pipeline homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantec Co., Ltd.), ultravisco mill (manufactured by Imex Co., Ltd.), slasher, trigonal wet fine Continuous emulsification machine such as crusher [Nippon Coke Kogyo Co., Ltd.], Capitron (Eurotech Co., Ltd.), Fine Flow Mill [Pacific Kiko Co., Ltd.], Microfluidizer [Mizuho Kogyo Co., Ltd.], Membrane emulsification such as Nanomizer (made by Nanomizer), APV Gaulin (made by Gaulin) etc., high-pressure emulsifying machine, membrane emulsifying machine (made by Cooling Industry Co., Ltd.) etc. , Vibro Mixer [Hiyaka Kogyo Co., Ltd.] vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among them, preferred from the viewpoint of particle size uniformity are APV Gaulin, homogenizer, TK auto homomixer, Ebara milder, TK film mix and TK pipeline homo mixer.

Hereinafter, the “step of forming an aggregate (Y1) of resin fine particles (X1) or an aggregate (Y2) of resin fine particles (X2)” in step (2) will be described.
In the step (2), the resin fine particles (X1) or (X2) in the dispersion {(D1), (D2), (W1) or (W2)} are aggregated to aggregate (Y1) or (Y2) Although the method to obtain is not particularly limited, a method of adding an aggregating agent to the dispersion may be mentioned.
Flocculants include acids (hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid etc.), metal salts of inorganic acids (sodium chloride, magnesium chloride, calcium chloride, aluminum chloride, aluminum sulfate, calcium sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate , Copper sulfate and sodium carbonate etc., metal salts of fatty acids (sodium acetate, potassium formate and sodium oxalate etc), metal salts of aromatic fatty acids (sodium benzoate, sodium phthalate and potassium salicylate etc), metals of phenols Salts (sodium phenolate etc.), amine salts (metal salts of amino acids, triethanolamine hydrochloride, aniline hydrochloride etc.) and the like can be mentioned.
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 in the step (2) is preferably 5 to 100 ° C., more preferably 20 to 100 ° C., from the viewpoint of controlling the volume average particle diameter and the particle size distribution of the resin particles.
Further, in the step of forming aggregates in the step (2), the pH of the dispersion is preferably 2 to 10, more preferably 3 to 6 from the viewpoint of controlling the volume average particle diameter and particle size distribution of the resin particles.

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

The step (3) will be described below.
In the step (3), the temperature at the time of coalescence is preferably 5 to 200 ° C., more preferably 30 to 100 ° C., from the viewpoint of shape controllability of the obtained resin particles and toner. In the step (3), the pH of the solution at the time of fusing the aggregates is preferably 3 to 10, more preferably 5 to 10.

The step (3-2) will be described below.
The temperature in the step of fusing the aggregates (Y2) in the step (3-2) to obtain resin particles is preferably 30 to 100 ° C., more preferably 40 to 100 ° C.

The step (3-1) will be described below.
In the step (3-1), the aggregate (Y1) is fused and simultaneously the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a) are crosslinked to form a modified resin And the step of obtaining resin particles containing the modified resin. In the case of simultaneously carrying out the fusion and the crosslinking reaction, the resin fine particles (X1) are added in advance to the resin fine particles (X1) in the radical reaction initiator (c) or in the step (2) of producing the aggregate (Y1). ) And the radical reaction initiator (c) to form an aggregate (Y1) as an aggregate (Y1) containing resin fine particles (X1) and a radical reaction initiator (c), and the polyester in the aggregate (Y1) The carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the resin (a) are preferably fused while being crosslinked. The temperature is chosen according to the molecular weight of the radical initiator (c) used and the polyester resin (a). In the step (3-1), the temperature is preferably 5 to 200 ° C., more preferably 20 to 100 ° C. The reaction time is preferably 0.1 to 48 hours, more preferably 1 to 24 hours.

The method for producing resin particles of the present invention preferably further comprises the step of removing the aqueous solvent from the dispersion of resin particles from the viewpoint of chargeability, charge stability, and heat resistant storage stability.

As a method of removing the aqueous solvent from the dispersion, the following [10] to [12] and a method of combining two or more of them can be applied.
[10] A method of drying the dispersion under reduced pressure or under normal pressure.
[11] A method of solid-liquid separation of the dispersion by a centrifugal separator, a spatula filter and / or a filter press, adding water etc. as necessary, repeating solid-liquid separation, and then drying the obtained solid.
[12] A method of freezing and drying the dispersion (so-called freeze drying).

In the methods of the above [10] and [11], drying can be performed using a known apparatus such as a fluid bed dryer, a reduced pressure dryer, and a circulating dryer as the dryer. In addition, if necessary, classification can be performed using an air classifier or sieve to obtain a predetermined particle size distribution.

The amount of the aqueous solvent remaining relative 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, and further preferably from the viewpoint of chargeability, charge stability, flowability of the toner and heat resistant storage stability. Is 0 to 0.1 parts by weight, particularly preferably 0 to 0.01 parts by weight.

The particle diameter of the resin particles obtained by the production method of the present invention is preferably 2 to 20 μm, more preferably 3 to 15 μm, still more preferably 4 to 8 μm, from the viewpoint of developability and resolution. The number average particle diameter is preferably 2 to 20 μm, more preferably 3 to 15 μm, and still more preferably 4 to 8 μm. The particle size distribution (volume average particle diameter / number average particle diameter) is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and still more preferably 1.0 to 1.5. The shape is preferably spherical in view of fluidity. Further, it is preferable from the viewpoint of the cleaning property to control the fusion state and to have appropriate unevenness. The volume average particle diameter and the number average particle diameter of the resin particles can be measured with "Multisizer IV" (manufactured by Beckman Coulter, Inc.) or the like.

A method of producing a toner comprising the resin particle obtained by the method of producing a resin particle of the present invention is also one of the present invention.
The toner obtained by the production method of the present invention contains resin particles obtained by the production method of the present invention.

The toner obtained by the production method of the present invention is optionally selected from colorants, release agents, charge control agents, fluidizing agents, etc., as well as resin particles, except in the case where it is previously contained in resin particles. More than one known additive may be included. By containing these, it is possible to easily obtain one having good hot offset resistance, chargeability, toner flowability, heat resistant storage stability, charge stability, image strength, folding resistance and document offsetability.

As a coloring agent, the thing similar to the case of the resin particle is mentioned, A preferable thing is also the same.
The content of the colorant is preferably 1 to 40% by weight, more preferably 3 to 10% by weight, based on the weight of the toner obtained by the production method of the present invention, from the viewpoint of toner image density and low temperature fixability. When magnetic powder is used, the content of the magnetic powder is preferably 20 to 70% by weight, more preferably 40 to 60% by weight, based on the weight of the toner.

As the release agent, the same one as in the case of the resin particle can be mentioned. Among them, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, carnauba wax and ester wax are preferable from the viewpoint of low temperature fixing property and hot offset resistance.

The release agent preferably has a softening point [Tm] of 50 to 170 ° C. by the flow tester, and more preferably 50 to 140 ° C., from the viewpoint of low temperature fixing property and hot offset resistance. More preferably, the temperature is 50 to 120 ° C.

The content of the releasing agent is preferably 1 to 20% by weight, more preferably 2 to 10% by weight, based on the weight of the toner obtained by the production method of the present invention, from the viewpoint of low temperature fixability and hot offset resistance. is there.

As the charge control agent, the same ones as in the case of the resin particles can be mentioned. The charge control agent may be dispersed inside the toner, may coat the toner surface, or may be dispersed inside the toner and coat the toner surface.
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 5% by weight, based on the weight of the toner.

As the fluidizing agent, the same ones as in the case of the resin particles can be mentioned. The content of the fluidizing agent may be 0 to 10% by weight, preferably 0 to 5% by weight, more preferably 0.1 to 4% by weight, based on the weight of the toner.

The toner obtained by the production method of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite coated on the surface with resin (acrylic resin, silicone resin etc.) as necessary. It is used as a developer for an electric latent image. The weight ratio of toner to carrier particles is preferably 1/99 to 100/0. Also, instead of the carrier particles, they can be rubbed with a member such as a charging blade to form an electric latent image.

The method of producing a toner of the present invention is a method of producing a toner comprising resin particles obtained by the method of producing resin particles. The resin particles obtained by the above-mentioned production method may be used as a toner as it is, or the above-mentioned additives may be added by a known method. The above-described method for producing resin particles of the present invention can be used as a method for producing a toner.

The toner obtained by the production method of the present invention is fixed on a support (paper, polyester film or the like) by a copying machine, a printer or the like to be used as a recording material. As a method of fixing on a support, a known heat roll fixing method, flash fixing method and the like can be applied.

The toner obtained by the production method of the present invention can be preferably used to develop an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like. More preferably, it can be used for developing an electrostatic charge image or a magnetic latent image for full color.

Hereinafter, the present invention will be further described by way of examples and comparative examples, but the present invention is not limited thereto. Hereinafter, parts indicate parts by weight unless otherwise specified.

The acid value was measured by the method prescribed in JIS K 0070 (1992 version).
The glass transition temperature was measured by a method (DSC method) defined in ASTM D3418-82 using a differential scanning calorimeter (manufactured by TA Instruments, DSC Q20).
<Measurement conditions of glass transition temperature>
(1) Temperature increase from 30 ° C to 20 ° C / min to 150 ° C (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 2.) The differential scanning calorimetry curve measured in the process of temperature rising to 150 ° C. at 20 ° C./min (6) and (5) was analyzed to determine the glass transition temperature.

The peak top molecular weight was measured using gel permeation chromatography (GPC) under the following conditions. The sample solution was prepared by dissolving the sample (resin) in THF to 0.25 wt% and filtering off the insoluble matter with a glass filter.
Device: HLC-8120 (manufactured by Tosoh Corporation)
Column: Two TSK GEL GMH6 (made by Tosoh Corp.)
Measurement temperature: 40 ° C
Sample solution: THF solution of sample Injection amount of solution: 100 μL
Detection device: Refractive index detector Reference material: Tosoh Co., Ltd. product standard polystyrene (TSK standard POLYSTYRENE) 12 points (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)

The volume-based median diameter of the resin fine particles was measured using a dynamic light scattering type particle size distribution measuring apparatus “SZ-100” (manufactured by Horiba, Ltd.). The solid content concentration of the dispersion was measured by the above method.
The volume average particle size of the resin particles was measured by Coulter Counter Multisizer IV (manufactured by Beckman Coulter, Inc.).

<Production Example 1> [Synthesis of Polyester Resin (a-1)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 772 parts (100 mol%) of bisphenol A · PO3 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., “Hymer BP-3P”), terephthalic acid 236 parts (78.4 mol%), 37 parts (17.5 mol%) of fumaric acid, 14 parts (4.0 mol%) of trimellitic anhydride, titanium dihydroxy bis (triethanolaminate) as a condensation catalyst. 5 parts and 1 part of tert-butyl catechol as a polymerization inhibitor were added, and reacted at 180 ° C. for 4 hours while distilling off generated water under nitrogen stream. The reaction was further allowed to proceed under reduced pressure of 0.5 to 2.5 kPa for 10 hours, and when the acid value reached 5 mg KOH / g, it was taken out to obtain a polyester resin (a-1).
The acid value of the polyester resin (a-1) was 5 mg KOH / g, the glass transition temperature (Tg _a ) was 55 ° C., and the peak top molecular weight was 12,300.

<Production Example 2> [Synthesis of Polyester Resin (a-2)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 755 parts (100 mol%) of bisphenol A · PO3 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., “Hymer BP-3P”), adipic acid 165 parts (75.0 mol%), 44 parts (25.0 mol%) of fumaric acid, 2.5 parts of titanium dihydroxy bis (triethanol aminate) as a condensation catalyst, 1 part of tert-butyl catechol as a polymerization inhibitor The reaction was carried out for 4 hours while distilling off generated water at 180 ° C. under a nitrogen stream. The mixture was further reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value reached 6 mg KOH / g, to obtain a polyester resin (a-2).
The acid value of the polyester resin (a-2) was 6 mg KOH / g, the glass transition temperature (Tg _a ) was 25 ° C., and the peak top molecular weight was 12,000.

<Production Example 3> [Synthesis of Polyester Resin (a-3)]
72 parts (10.0 mol%) of bisphenol A • PO2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd. “Hymer BP-2P”) in a reaction vessel equipped with a condenser, stirrer and nitrogen introduction pipe, 720 parts (90.0 mol%) of bisphenol A • PO 3 mol adduct (“Hymer BP-3P” manufactured by Sanyo Chemical Industries, Ltd.), 218 parts (78.5 mol%) of terephthalic acid, 34 parts of fumaric acid ( 17.5 mol%), 13 parts (4.0 mol%) of trimellitic anhydride, 2.5 parts of titanium dihydroxy bis (triethanol aminate) as a condensation catalyst, 1 part of tert-butyl catechol as a polymerization inhibitor The reaction was carried out for 4 hours while distilling off generated water under a nitrogen stream at 180 ° C. The mixture was further reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value reached 7 mg KOH / g, to obtain a polyester resin (a-3).
The acid value of the polyester resin (a-3) was 7 mg KOH / g, the glass transition temperature (Tg _a ) was 55 ° C., and the peak top molecular weight was 8,000.

<Production Example 4> [Synthesis of Polyester Resin (a-4)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 995 parts (100 mol%) of bisphenol A · PO5 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., “Hymer BP-5P”), terephthalic acid 118 parts (39.2 mol%), 118 parts (39.2 mol%) of isophthalic acid, 37 parts (17.5 mol%) of fumaric acid, 14 parts (4.0 mol%) of trimellitic anhydride, a condensation catalyst Then, 2.5 parts of titanium dihydroxybis (triethanolaminate) and 1 part of tert-butyl catechol as a polymerization inhibitor were added, and reaction was carried out for 4 hours while distilling off generated water under a nitrogen stream at 180.degree. The mixture was further reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value reached 5 mg KOH / g, to obtain a polyester resin (a-4).
The acid value of the polyester resin (a-4) was 5 mg KOH / g, the glass transition temperature (Tg _a ) was −20 ° C., and the peak top molecular weight was 12,500.

<Production Example 5> [Synthesis of Polyester Resin (a-5)]
771 parts (100 mol%) of bisphenol A · PO3 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., “Hymer BP-3P”) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, terephthalic acid 244 parts (78.4 mol%), 32 parts (17.5 mol%) of maleic anhydride, 14 parts (4.0 mol%) of trimellitic anhydride, titanium dihydroxy bis (triethanolaminate) 2 as a condensation catalyst .5 parts, and 1 part of tert-butyl catechol as a polymerization inhibitor were added, and reacted at 180 ° C. for 4 hours while distilling off generated water under nitrogen stream. The mixture was further reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value reached 6 mg KOH / g, to obtain a polyester resin (a-5).
The acid value of the polyester resin (a-5) was 6 mg KOH / g, the glass transition temperature (Tg _a ) was 57 ° C., and the peak top molecular weight was 20,000.

<Production Example 6> [Synthesis of Polyester Resin (a-6)]
812 parts (100 mol%) of bisphenol A · PO3 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., “Hymer BP-3P”), terephthalic acid in a reaction vessel equipped with a condenser, stirrer and nitrogen introduction pipe 201 parts (78.4 mol%), 32 parts (17.5 mol%) of fumaric acid, 12 parts (4.0 mol%) of trimellitic anhydride, titanium dihydroxy bis (triethanol aminate) as a condensation catalyst. 5 parts and 1 part of tert-butyl catechol as a polymerization inhibitor were added, and reacted at 180 ° C. for 4 hours while distilling off generated water under nitrogen stream. The reaction was further allowed to proceed under reduced pressure of 0.5 to 2.5 kPa for 10 hours, and when the acid value reached 5 mg KOH / g, it was taken out to obtain a polyester resin (a-6).
The acid value of the polyester resin (a-6) was 5 mg KOH / g, the glass transition temperature (Tg _a ) was 50 ° C., and the peak top molecular weight was 4,800.

<Production Example 7> [Synthesis of Polyester Resin (a-7)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 708 parts (80 mol%) of bisphenol A · PO3 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., “Hymer BP-3P”), 1, 1 34 parts (20 mol%) of 2-propylene glycol, 274 parts (78.4 mol%) of terephthalic acid, 43 parts (17.5 mol%) of fumaric acid, 16 parts (4.0 mol%) of trimellitic anhydride, 2.5 parts of titanium dihydroxy bis (triethanolaminate) as a condensation catalyst and 1 part of tert-butyl catechol as a polymerization inhibitor are added and reacted for 4 hours while distilling off generated water under nitrogen stream at 180 ° C. The The mixture was further reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value reached 5 mg KOH / g, to obtain a polyester resin (a-7).
The acid value of the polyester resin (a-7) was 5 mg KOH / g, the glass transition temperature (Tg _a ) was 55 ° C., and the peak top molecular weight was 12,100.

<Production Example 8> [Synthesis of Polyester Resin (a-8)]
284 parts (40 mol%) of bisphenol A · PO 2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., “Hymer BP-2P”), bisphenol A in a reaction vessel equipped with a condenser, stirrer and nitrogen introduction pipe · PO 3 molar adduct ("Hymer BP-3P" manufactured by Sanyo Chemical Industries, Ltd.) 486 parts (60 mol%), 201 parts (62.7 mol%) terephthalic acid, 44 parts (15.7 mol) adipic acid %, Fumaric acid 39 parts (17.6 mol%), trimellitic anhydride 15 parts (4.0 mol%), as a condensation catalyst 2.5 parts of titanium dihydroxy bis (triethanol aminate), as a polymerization inhibitor One part of tert-butyl catechol was added, and reaction was performed for 4 hours while distilling off generated water under a nitrogen stream at 180 ° C. The mixture was further reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa, and taken out when the acid value reached 6 mg KOH / g, to obtain a polyester resin (a-8).
The acid value of the polyester resin (a-8) was 6 mg KOH / g, the glass transition temperature (Tg _a ) was 56 ° C., and the peak top molecular weight was 12,400.

Table 1 shows Tg _a , acid value and peak top molecular weight of polyester resins (a-1) to (a-8).

Production Example 9 Synthesis of Amorphous Polyester Resin (b1-1)
281 parts (43.1 mol%) of bisphenol A • PO 2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd. “Hymer BP-2P”) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 471 parts (64.7 mol%) of bisphenol A • PO 3 mol adduct (“Hymer BP-3P” manufactured by Sanyo Chemical Industries, Ltd.), 31 parts (10 mol%) terephthalic acid, 279 parts (90 mol) isophthalic acid %, 2.5 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst, and reacted at 230 ° C. for 4 hours while distilling off generated water under nitrogen stream. The reaction was further allowed to proceed under reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value reached 10 mg KOH / g, it was taken out to obtain an amorphous polyester resin (b1-1).
The acid value of the amorphous polyester resin (b1-1) was 10 mg KOH / g, the glass transition temperature (Tg) was 57 ° C., and the peak top molecular weight was 6,200.

<Production Example 10> [Synthesis of Amorphous Polyester Resin (b1-2)]
308 parts (37.3 mol%) of bisphenol A · PO2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., “Hymer BP-2P”) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 421 parts (45.6 mol%) of bisphenol A • PO 3 mol adduct (“Hymer BP-3P” manufactured by Sanyo Chemical Industries, Ltd.), 31 parts (17.0 mol%) of 1,2-propylene glycol, terephthal 30 parts (10 mol%) of acid, 273 parts (90 mol%) of isophthalic acid, 2.5 parts of titanium dihydroxy bis (triethanol aminate) as a condensation catalyst, and water generated at 230 ° C. under nitrogen stream The reaction was carried out for 4 hours while distilling off. The reaction was further allowed to proceed under reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value reached 10 mg KOH / g, it was taken out to obtain an amorphous polyester resin (b1-2).
The acid value of the amorphous polyester resin (b1-2) was 10 mg KOH / g, the Tg was 56 ° C., and the peak top molecular weight was 6,100.

Preparation Example 11 Synthesis of Amorphous Polyester Resin (b1-3)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 574 parts (75.0 mol%) of bisphenol A • PO2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd. “Hymer BP-2P”), 214 parts (25.0 mol%) of bisphenol A • PO 3 mol adduct (“Hymer BP-3P” manufactured by Sanyo Chemical Industries, Ltd.), 31 parts (11.2 mol%) of terephthalic acid, 190 parts of isophthalic acid 69.1 mol%), 48 parts (19.7 mol%) of adipic acid, 2.5 parts of titanium dihydroxy bis (triethanol aminate) as a condensation catalyst, and the water formed at 230 ° C. under a nitrogen stream The reaction was carried out for 4 hours while distilling off. The reaction was further allowed to proceed under reduced pressure of 0.5 to 2.5 kPa for 4 hours, and when the acid value reached 10 mg KOH / g, it was taken out to obtain an amorphous polyester resin (b1-3).
The acid value of the amorphous polyester resin (b1-3) was 10 mg KOH / g, the Tg was 57 ° C., and the peak top molecular weight was 6,500.

<Production Example 12> [Synthesis of Crystalline Polyester Resin (C-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 614 parts (100.0 mol%) of dodecanedioic acid and 482 parts (113.0 mol%) of 1,9-nonanediol and tetramer as a condensation catalyst 0.5 parts of butoxytitanate was added, and reaction was performed for 8 hours while distilling off generated water under a nitrogen stream at 170 ° C. Next, the temperature is gradually raised to 220 ° C., and reaction is performed for 4 hours while distilling off generated water under a nitrogen stream, and reaction is further performed under reduced pressure of 0.5 to 2.5 kPa, and the acid value is 0.5 mg KOH When it became / g or less, it took out and obtained crystalline polyester resin (C-1). The softening point of the crystalline polyester resin (C-1) was 78 ° C., and the temperature showing the endothermic peak top was 72 ° C.
The softening point was measured by the method of measuring the above-mentioned softening point [Tm] using a descent type flow tester [CFT-500D, manufactured by Shimadzu Corporation]. The temperature showing the endothermic peak top of the crystalline polyester resin (C-1) was measured using DSC Q20 manufactured by TA Instruments. The temperature is raised to 180 ° C. under the conditions of 10 ° C./min (the first temperature rising process) and then left at 180 ° C. for 10 minutes, then the temperature is raised to 0 ° C. under the conditions of 10 ° C./min. It cooled down (the 1st cooling process). Next, after standing at 0 ° C. for 10 minutes, the temperature was raised to 180 ° C. under the condition of 10 ° C./min (second temperature rising process).

<Production Example 13> [Production of Dispersion of Resin Fine Particles (X2-1) (abD2-1)]
15.5 parts of amorphous polyester resin (b1-1), 5.2 parts of polyester resin (a-1), 15.1 parts of methyl ethyl ketone in a reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe and thermometer And 1.7 parts of isopropyl alcohol were charged, stirred and homogenized to obtain an organic solvent solution, and the temperature was adjusted to 25 ° C. To this was added 0.87 parts by weight of 10.0% by weight ammonia water as a neutralizing agent, and 0.4 parts of 2,2'-azobis- (2,4-dimethylvaleronitrile) as a radical reaction initiator (c). And stirred for 5 minutes. Thereafter, 61.7 parts of water at 25 ° C. is added dropwise over 1 hour, phase inversion emulsification is carried out to obtain a dispersion liquid (abD1-1) of resin fine particles (X1-1), and the temperature is gradually raised to 80 ° C. The reaction was allowed to crosslink for 1 hour. Thereafter, methyl ethyl ketone and isopropyl alcohol were distilled off at 40 ° C. under a reduced pressure of 30 kPa. Thus, a modified resin obtained by crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a-1) and the amorphous polyester resin (b1-1) are contained. A dispersion (abD2-1) of resin fine particles (X2-1) was obtained. The volume based median diameter of the resin fine particles (X2-1) was 0.15 μm, and the solid concentration of the dispersion (abD2-1) was 20% by weight.

<Production Example 14> [Production of Dispersion of Resin Fine Particles (X2-2) (abD2-2)]
In Production Example 13, a polyester resin (a-2) was prepared in the same manner as in Production Example 13 except that 5.2 parts of the polyester resin (a-1) was replaced by 5.2 parts of the polyester resin (a-2). Dispersion liquid of resin fine particles (X2-2) containing modified resin obtained by crosslinking carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) and non-crystalline polyester resin (b1-1) (X2-2) abD2-2). The volume based median diameter of the resin fine particles (X2-2) was 0.15 μm, and the solid concentration of the dispersion (abD2-2) was 20% by weight.

<Production example 15> [Production of dispersion liquid (abD2-3) of resin fine particles (X2-3)]
15.5 parts of amorphous polyester resin (b1-1), 5.2 parts of polyester resin (a-3), 15.1 parts of methyl ethyl ketone in a reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe and thermometer And 1.7 parts of isopropyl alcohol were charged, stirred and homogenized to obtain an organic solvent solution, and the temperature was adjusted to 25 ° C. To this, 0.87 parts of 10.0% by weight ammonia water as a neutralizing agent and 0.4 parts of 2,2'-azobis- (2,4-dimethylvaleronitrile) as a radical reaction initiator are added for 5 minutes. It stirred. Thereafter, 61.7 parts of water at 25 ° C. is added dropwise over 1 hour to perform phase inversion emulsification to obtain a dispersion liquid (abD1-3) of resin fine particles (X1-3), and then under reduced pressure of 30 kPa at 40 ° C. Methyl ethyl ketone and isopropyl alcohol were distilled off. Thereafter, while gradually raising the temperature to 80 ° C., the crosslinking reaction is performed for 1 hour to crosslink the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a-3). A dispersion (abD2-3) of resin fine particles (X2-3) containing the modified resin and the amorphous polyester resin (b1-1) was obtained. The volume-based median diameter of the resin fine particles (X2-3) was 0.15 μm, and the solid concentration of the dispersion (abD2-3) was 20% by weight.

<Production Example 16> [Production of Dispersion of Resin Fine Particles (X2-4) (abD2-4)]
In Production Example 15, 5.2 parts of polyester resin (a-3) and 15.5 parts of amorphous polyester resin (b1-1), 2.1 parts of polyester resin (a-1) and amorphous polyester resin ( b1-1) A reaction of crosslinking carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a-1) is carried out in the same manner as in Production Example 15 except that 18.6 parts are substituted. Thus, a dispersion (abD2-4) of resin fine particles (X2-4) containing the modified resin and the amorphous polyester resin (b1-1) was obtained. The volume based median diameter of the resin fine particles (X2-4) was 0.15 μm, and the solid concentration of the dispersion (abD2-4) was 20% by weight.

<Production Example 17> [Production of Dispersion of Resin Fine Particles (X1-5) (abD1-5)]
12.4 parts of amorphous polyester resin (b1-1), 8.3 parts of polyester resin (a-1), 15.1 parts of methyl ethyl ketone in a reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe and thermometer And 1.7 parts of isopropyl alcohol were charged, stirred and homogenized to obtain an organic solvent solution, and the temperature was adjusted to 25 ° C. To this, 0.87 parts of 10.0% by weight ammonia water as a neutralizing agent and 0.4 parts of 2,2'-azobis (2-methylbutyronitrile) as a radical reaction initiator were added and stirred for 5 minutes. . Thereafter, 61.7 parts of water at 25 ° C. was added dropwise over 1 hour to cause phase inversion emulsification. Thereafter, methyl ethyl ketone and isopropyl alcohol were distilled off at 40 ° C. under a reduced pressure of 30 kPa. Thus, a dispersion (abD1-5) of resin fine particles (X1-5) containing the polyester resin (a-1) and the amorphous polyester resin (b1-1) was obtained. The volume based median diameter of the resin fine particles (X1-5) was 0.15 μm, and the solid concentration of the dispersion (abD1-5) was 20% by weight.

<Production Example 18> [Dispersion liquid of resin fine particles (X1-6) (abD1-6)]
In Production Example 17, 8.3 parts of polyester resin (a-1) and 12.4 parts of amorphous polyester resin (b1-1), 5.2 parts of (a-1), and (b1-1) 15.5 A dispersion (abD1-6) of resin fine particles (X1-6) containing a polyester resin (a-1) and an amorphous polyester resin (b1-1) was prepared in the same manner as in Production Example 17 except that parts were replaced by Obtained. The volume-based median diameter of the resin fine particles (X1-2) was 0.15 μm, and the solid concentration of the dispersion (abD1-6) was 20% by weight.

<Production Example 19> [Dispersion liquid of resin fine particles (X2-7) (abD2-7)]
In Production Example 13, 5.2 parts of polyester resin (a-1) and 15.5 parts of amorphous polyester resin (b1-1), 1.5 parts of (a-1), and (b1-1) 19.2 The modified resin obtained by crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a-1) and the non-modified resin are the same as in Production Example 13 except that A dispersion (abD2-7) of resin fine particles (X2-7) containing a crystalline polyester resin (b1-1) was obtained. The volume-based median diameter of the resin fine particles (X2-7) was 0.15 μm, and the solid concentration of the dispersion (abD2-7) was 20% by weight.

<Production example 20> [Dispersion liquid of resin fine particles (X2-8) (abD2-8)]
In Production Example 19, 1.5 parts of a polyester resin (a-1) and 19.2 parts of an amorphous polyester resin (b1-1) (1. 1 parts of (a-1) and (b1-1) 10.3) A modified resin obtained by crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a-1) is produced in the same manner as in Production Example 19 except that the substituted resin is replaced with A dispersion (abD2-8) of resin fine particles (X2-8) containing a crystalline polyester resin (b1-1) was obtained. The volume based median diameter of the resin fine particles (X2-8) was 0.15 μm, and the solid concentration of the dispersion (abD2-8) was 20% by weight.

<Production Example 21> [Dispersion liquid of resin fine particles (X2-9) (abD2-9)]
In Production Example 13, a polyester resin (a-4) was prepared in the same manner as in Production Example 13 except that 5.2 parts of the polyester resin (a-1) was replaced by 5.2 parts of the polyester resin (a-4). Dispersion liquid of resin fine particles (X2-9) containing modified resin formed by crosslinking carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) and non-crystalline polyester resin (b1-1) (X2-9) abD2-9) was obtained. The volume-based median diameter of the resin fine particles (X2-9) was 0.15 μm, and the solid concentration of the dispersion (abD2-9) was 20% by weight.

<Production Example 22> [Dispersion liquid of resin fine particles (X2-10) (abD2-10)]
In Production Example 13, a polyester resin (a-5) is contained in the same manner as in Production Example 13 except that 5.2 parts of the polyester resin (a-1) is replaced by 5.2 parts of the polyester resin (a-5). Dispersion liquid of resin fine particles (X2-10) containing modified resin formed by crosslinking carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) and amorphous polyester resin (b1-1) (X2-10) abD2-10) was obtained. The volume-based median diameter of the resin fine particles (X2-10) was 0.15 μm, and the solid concentration of the dispersion (abD2-10) was 20% by weight.

<Production Example 23> [Dispersion liquid of resin fine particles (X2-11) (abD2-11)]
In Production Example 13, a polyester resin (a-6) is contained in the same manner as in Production Example 13 except that 5.2 parts of the polyester resin (a-1) is replaced by 5.2 parts of the polyester resin (a-6). Dispersion liquid of resin fine particles (X2-11) containing modified resin formed by crosslinking carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) and non-crystalline polyester resin (b1-1) (X2-11) ab D2-11). The volume based median diameter of the resin fine particles (X2-11) was 0.15 μm, and the solid concentration of the dispersion (abD2-11) was 20% by weight.

<Production example 24> [Dispersion liquid of resin fine particles (X2-12) (abD2-12)]
In the same manner as in Production Example 13 except that 5.2 parts of the polyester resin (a-1) is replaced with 5.2 parts of the polyester resin (a-7) in Production Example 13, Dispersion liquid of resin fine particles (X2-12) containing modified resin obtained by crosslinking carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) and non-crystalline polyester resin (b1-1) abD2-12) was obtained. The volume based median diameter of the resin fine particles (X2-12) was 0.15 μm, and the solid concentration of the dispersion (abD2-12) was 20% by weight.

<Production example 25> [Dispersion liquid of resin fine particles (X2-13) (abD2-13)]
In Production Example 13, a polyester resin (a-8) is contained in the same manner as in Production Example 13 except that 5.2 parts of the polyester resin (a-1) is replaced by 5.2 parts of the polyester resin (a-8). Dispersion liquid of resin fine particles (X2-13) containing modified resin formed by crosslinking carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) and amorphous polyester resin (b1-1) (X2-13) abD2-13) was obtained. The volume based median diameter of the resin fine particles (X2-13) was 0.15 μm, and the solid concentration of the dispersion (abD2-13) was 20% by weight.

<Production example 26> [Dispersion liquid of resin fine particles (X2-14) (abD2-14)]
A polyester resin was prepared in the same manner as in Preparation Example 13 except that 15.5 parts of the amorphous polyester resin (b1-1) was replaced with 15.5 parts of the amorphous polyester resin (b1-2). Fine resin particles (X2-) containing a modified resin obtained by crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in a-1) and a non-crystalline polyester resin (b1-2) 14) dispersion liquid (abD2-14) was obtained. The volume based median diameter of the resin fine particles (X2-14) was 0.15 μm, and the solid concentration of the dispersion (abD2-14) was 20% by weight.

<Production Example 27> [Dispersion liquid of resin fine particles (X2-15) (abD2-15)]
A polyester resin was prepared in the same manner as in Preparation Example 13 except that 15.5 parts of the amorphous polyester resin (b1-1) was replaced with 15.5 parts of the amorphous polyester resin (b1-3). Resin fine particles (X2-) containing a modified resin obtained by crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in a-1) and a non-crystalline polyester resin (b1-3) A dispersion (abD2-15) of 15) was obtained. The volume-based median diameter of the resin fine particles (X2-15) was 0.15 μm, and the solid concentration of the dispersion (abD2-15) was 20% by weight.

Production Example 28 Production of Dispersion of Amorphous Polyester Resin (b1-1)
Except that in Production Example 17, 8.3 parts of polyester resin (a-1) and 12.4 parts of amorphous polyester resin (b1-1) were replaced with 20.7 parts of amorphous polyester resin (b1-1). A dispersion (bD-1) of an amorphous polyester resin (b1-1) having a volume based median particle diameter of 0.15 μm of resin fine particles and a solid content concentration of 20% by weight in the same manner as in Production Example 17 Obtained.

<Production Example 29> [Production of Dispersion of Crystalline Polyester Resin (C-1)]
15 parts of crystalline polyester resin (C-1) and 20 parts of ion-exchanged water are charged into a reaction vessel equipped with a stirrer, heating / cooling device, a cooling pipe and a thermometer, and the temperature is raised to 90 ° C. with stirring. After stirring for 30 minutes, the solution is cooled to 10 ° C. over 1 hour to crystallize the crystalline polyester resin in the form of fine particles, and further wet-pulverized with Ultravisco Mill (manufactured by IMEX) to obtain crystalline polyester resin (C-1) Dispersion (CD-1) was obtained. The volume-based median diameter of the crystalline polyester resin (C-1) was 0.10 μm, and the solid concentration of the dispersion (CD-1) was 50% by weight.

<Production Example 30> [Production of Colorant Dispersion]
In a reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe and thermometer, 10 parts of carbon black "MA 100" (manufactured by Mitsubishi Chemical Corporation), 0.5 parts of sodium dodecylbenzene sulfonate, 40 parts of ion exchanged water The temperature was raised to 30 ° C. with stirring at a rotational speed of 300 rpm, and after stirring for 30 minutes at the same temperature, wet pulverization was further performed with an ultravisco mill to obtain a black colorant dispersion. The volume based median diameter of the colorant fine particles of the obtained black colorant dispersion was 0.05 μm, and the solid concentration of the dispersion was 20% by weight.

<Production Example 31> [Production of Release Agent Dispersion]
In a reaction vessel equipped with a stirrer, heating / cooling device, condenser and thermometer, paraffin wax "HNP-9" (maximum heat of fusion heat: 73 ° C, manufactured by Nippon Seiwa Co., Ltd.) 10 parts, dodecylbenzene sulfone Add 0.5 parts of sodium acid and 15 parts of ion-exchanged water, raise the temperature to 78 ° C with stirring at 300 rpm, stir for 30 minutes at the same temperature and cool to 30 ° C over 1 hour to obtain paraffin wax The fine particles were crystallized and further wet-pulverized using an ultravisco mill to obtain a releasing agent dispersion. The volume-based median diameter of the release agent fine particles of the obtained release agent dispersion was 0.25 μm, and the solid content concentration of the dispersion was 50% by weight.

Example 1 Preparation of Toner (T-1)
A reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe, thermometer and nitrogen introducing pipe crosslinks carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) in polyester resin (a-1) Dispersion liquid (abD2-1) of resin fine particles (X2-1) containing modified resin and amorphous polyester resin (b1-1) which are caused to react, dispersion liquid of crystalline resin (C-1), colorant dispersion The solution and the release agent dispersion are charged so that the solid content becomes the number of parts in Table 2, 300 parts of ion exchanged water is charged, and the solution temperature is adjusted to 30 ° C. The pH was adjusted to 10 by adding an aqueous sodium solution to obtain a dispersion (W2-1).
Next, a modified resin obtained by crosslinking the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a-1) and the amorphous polyester resin (b1-1) are contained. In order to coagulate resin fine particles (X2-1), crystalline resin (C-1), coloring agent, and releasing agent, add 10 wt% magnesium chloride aqueous solution as flocculant while stirring at 300 rpm After sampling, it was confirmed that the volume average particle diameter was 5 μm, and then the temperature of the system was adjusted to 60 ° C., and then a pH of 4.5 was obtained by adding a 0.3 M aqueous nitric acid solution. And adjusted to 4.0 after 30 minutes. Fusion (fusion) and spheronization were performed by holding the stirring for 3 hours.
Then, it cooled to 30 degreeC and obtained the aqueous dispersion liquid of the resin particle containing a coloring agent. Next, the resin particles are filtered and washed with water three times, and then separated by filtration and dried for 18 hours with a blower circulating drier at 40 ° C. to reduce volatile matter to 0.5 wt% or less (Z) I got -1). Toner according to the present invention having a volume average particle diameter of 5 μm by uniformly mixing 99 parts by weight of the obtained resin particles (Z-1) and 1 part by weight of colloidal silica (Aerosil R-972) (manufactured by Nippon Aerosil Co., Ltd.) Obtained (T-1).

Examples 2 to 4 Preparation of Toners (T-2) to (T-4)
Dispersions (W2-2) to (W2) are carried out in the same manner as in Example 1 except that dispersion (abD2-1) is replaced with dispersions (abD2-2) to (abD2-4) respectively. -4) After obtaining resin particles (Z-2) to (Z-4), toners (T-2) to (T-4) of the present invention having a volume average particle diameter of 5 μm were obtained.

Example 5 Preparation of Toner (T-5)
Of resin fine particles (X1-5) containing polyester resin (a-1) and amorphous polyester resin (b1-1) in a reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe, thermometer and nitrogen introducing pipe Dispersion (abD1-5), dispersion of crystalline resin (C-1), colorant dispersion, and releasing agent dispersion are charged so that the solid content becomes the number of parts in Table 2, and 300 parts of ion-exchanged water After adjusting the liquid temperature to 30.degree. C., a 25 wt.% Aqueous sodium hydroxide solution was added while stirring at a rotational speed of 300 rpm to adjust the pH to 10 to obtain a dispersion liquid (W1-1).
Next, the resin fine particles (X1-5) containing the polyester resin (a-1) and the amorphous polyester resin (b1-1), the crystalline resin (C-1), the colorant, and the release agent are coagulated. Therefore, while stirring at a rotational speed of 300 rpm, add an aqueous solution of magnesium chloride with a concentration of 10% by weight, and after sampling appropriately to confirm that the volume average particle diameter is 5 μm, adjust the system temperature to 60 ° C. The pH was then adjusted to 4.5 by addition of a 0.3 M aqueous nitric acid solution, and after 30 minutes it was adjusted to 4.0. Then, the cross-linking reaction between carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) in the polyester resin (a-1) is maintained by gradually raising the temperature to 80 ° C. while stirring for 3 hours. The fusion (fusion) and spheronization of the aggregates were performed simultaneously.
Then, it cooled to 30 degreeC and obtained the aqueous dispersion liquid of the resin particle containing a coloring agent. Subsequently, filtration and washing with water were repeated three times, followed by filtration, followed by drying for 18 hours with a blower circulating drier at 40 ° C., and the volatile content was adjusted to 0.5 wt% or less. Toner according to the present invention having a volume average particle diameter of 5 μm by uniformly mixing 99 parts by weight of the obtained resin particles (Z-5) and 1 part by weight of colloidal silica (Aerosil R-972) (manufactured by Nippon Aerosil Co., Ltd.) I got (T-5).

Example 6 Preparation of Toner (T-6)
In Example 5, the dispersion (abD1-5) of resin fine particles (X1-5) containing the polyester resin (a-1) and the amorphous polyester resin (b1-1) is replaced with the dispersion (abD1-6) After the dispersion (W1-2) and the resin particles (Z-6) are obtained in the same manner as in Example 5 except that the dispersion of the crystalline resin (C-1) is not added, the volume average particle diameter is obtained. A 5 μm toner of the present invention (T-6) was obtained.

Examples 7 to 15 [Preparation of Toners (T-7) to (T-15)]
Dispersions (W2-7) to (W2) were prepared in the same manner as in Example 1 except that dispersion (abD2-1) was replaced with dispersions (abD2-7) to (abD2-15), respectively. After obtaining resin particles (Z-7) to (Z-15), toners (T-7) to (T-15) of the present invention having a volume average particle diameter of 5 μm were obtained.

<Comparative Example 1> [Production of Toner (T'-1)]
In Example 5, a dispersion (abD1-5) of resin fine particles (X1-5) containing a polyester resin (a-1) and an amorphous polyester resin (b1-1) is dispersed in a polyester resin (b1-1) Dispersion (W1'-1), resin particles (Z'-1) in the same manner as in Example 5 except that the dispersion (bD-1) was replaced and the dispersion of the crystalline resin (C-1) was not added. After that, a toner (T'-1) having a volume average particle diameter of 5 .mu.m was obtained.

<Comparative Example 2> [Production of Toner (T'-2)]
Twin-screw kneader (S5 KRC kneader, Kurimoto Co., Ltd., 25 parts of the polyester resin (a-1) obtained in Production Example 1 and 75 parts of the amorphous polyester resin (b1-1) obtained in Production Example 9 ) At the same time as the radical initiator (c) and 1.0 part of 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (c-2) as the radical initiator (c). The crosslinking reaction was carried out by feeding at 10 kg / hour and kneading and extruding at 160 ° C. for 15 minutes. The resultant was cooled to obtain a toner binder.
Furthermore, 7 parts of pigment carbon black MA-100 [Mitsubishi Chemical Corporation] and 7 parts of paraffin wax as a releasing agent are added to 100 parts of toner binder, and Henschel mixer [Japan coke industry FM10B] After pre-mixing using the mixture, the mixture was kneaded using a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.].
Next, the mixture is finely pulverized using a supersonic jet crusher Rabojet (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and then classified by an air flow classifier (MDS-I manufactured by Japan Pneumatic Mfg. Co., Ltd.) to obtain volume average particle size. The obtained resin particles (Z'-2) were 5 .mu.m and the particle size distribution was 1.8. 99 parts of the obtained resin particles (Z'-2) and 1 part of colloidal silica (Aerosil R 972: Nippon Aerosil Co., Ltd.) as a fluidizing agent are mixed in a sample mill to obtain a toner (T'-2) Obtained.

Table 2 shows the composition of the polyester resin (a), the polyester resin (b), the radical reaction initiator (c), the coloring agent and the releasing agent for the toners of Examples and Comparative Examples. Table 2 also shows the THF insoluble matter (%) of the resin particles and the glass transition temperature (Tg). The THF insoluble matter (%) was determined by the method described above. The weight ratio of (a) / (b) is the weight ratio of the polyester resin (a) -derived structural portion in the resin particle to the polyester resin (b), and the weight ratio of (b1) / (C) is It is a weight ratio of amorphous polyester resin (b1) and crystalline polyester resin (C).
Next, the toners of Examples and Comparative Examples were evaluated, and the results are shown in Table 3.

[Evaluation method]
The following are the low temperature fixability, glossiness, hot offset resistance, fluidity, heat resistant storage stability, chargeability, charge stability, particle size distribution, folding resistance, document offsetability, image strength, and cleaning ability of the obtained toner. The measurement method and evaluation method will be described including the determination criteria.

<Low temperature fixability>
The toner was uniformly loaded on the paper so as to be 0.85 mg / cm ² . At this time, the powder was put on the paper by using a printer from which the heat fixing device was removed.
The temperature (MFT) at which cold offset occurred when this paper was passed through a pressure roller under the conditions of a fixing speed (heat roller circumferential speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² was measured.
The lower the cold offset occurrence temperature, the better the low-temperature fixability.

<Glossy>
The fixing evaluation was performed in the same manner as the low temperature fixing property. A white cardboard was laid under the image, and the glossiness (%) of the printed image was measured at an incident angle of 60 degrees using a gloss meter ("IG-330" manufactured by Horiba, Ltd.). The higher the degree of gloss, the better the gloss.

<Hot offset resistance (hot offset occurrence temperature)>
The fixation was evaluated in the same manner as the low temperature fixation, and the presence or absence of the hot offset to the fixed image was visually evaluated. After passing through the pressure roller, the temperature at which the hot offset occurred was taken as the hot offset resistance (° C.). In this evaluation condition, it means that the offset is less likely to occur as the temperature is higher, and if the temperature is 180 ° C. or more, the occurrence of the offset can be suppressed in an actual use mode.

<Flowability>
The bulk density (g / 100 mL) of the toner was measured with a powder tester manufactured by Hosokawa Micron Corporation, and the flowability was determined based on the following criteria.

Judgment criteria
○: bulk density is 33 g / 100 mL or more Δ: bulk density is 25 g / 100 mL or more and 33 g / 100 mL or less ×: bulk density is less than 25 g / 100 mL

<Heat resistant storage stability>
1 g of the toner was placed in a closed container and allowed to stand in an atmosphere of temperature 50 ° C. and humidity 50% for 24 hours, the degree of blocking was visually judged, and heat resistance storage stability was evaluated according to the following judgment criteria.
Judgment criteria
○: No blocking occurred at all.
Fair: Blocking has occurred in part.
X: Blocking has occurred on the whole.

<Chargeability> (Charge amount)
(1) 0.5 g of a toner and 10 g of a ferrite carrier (F-150 manufactured by Powder Tech Co., Ltd.) were placed in a 50 mL glass bottle and conditioned at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stir with 90 rpm x 2 minutes with a Tumbler shaker mixer, 0.2 g of the mixed powder after stirring is loaded into a blow-off powder charge amount measuring apparatus in which a 20 μm mesh stainless steel mesh is set, and a blow pressure is 10 KPa The charge amount of the remaining ferrite carrier was measured under the condition of suction pressure 5 KPa, and the charge amount (μC / g) of the resin particles was calculated by a standard method. For toners, the higher the negative charge amount, the better the charging characteristics.
For the measurement, a blow-off charge amount measuring apparatus [manufactured by Toshiba Chemical Co., Ltd.] was used.

Judgment criteria
○: charge amount-less than 15 μC / g Δ: charge amount-15 μC / g or more-less than 5 μC / g ×: charge amount-5 μC / g or more

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (F-150, manufactured by Powder Tech Co., Ltd.) were placed in a 50 mL glass bottle, and conditioned at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stirring was carried out at 50 rpm × 20 minutes and 60 minutes with a Tumbler shaker mixer, and the charge amount at each time was measured.
For the measurement, a blow-off charge amount measuring apparatus [manufactured by Toshiba Chemical Co., Ltd.] was used.
The “charge amount for 60 minutes of friction time / charge amount for 10 minutes of friction time” was calculated and used as an indicator of charge stability.

Judgment criteria
○: 0.7 or more Δ: 0.6 or more and less than 0.7 ×: less than 0.6

<Particle size distribution>
In Comparative Example 2, coarsely pulverized material (from 8.6 mesh pass to 30 mesh on) kneaded and cooled by a twin-screw kneader was subjected to supersonic jet crusher Rabojet (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) It ground finely under the following conditions.
Grinding pressure: 0.5MPa
Grinding time: 15 minutes Adjuster ring: 15 mm
Size of louver: Without classifying this, volume average particle diameter (μm), number average particle diameter (μm), particle size distribution (volume average particle diameter / number average particle diameter) Coulter Counter "Multisizer IV" It measured by (Beckman Coulter Co., Ltd. product), and the particle size distribution was evaluated by the following determination criteria.
In Examples 1 to 15 and Comparative Example 1 in which the pulverizing step was not performed, the dispersion liquid of resin particles was measured.

Judgment criteria
○: Volume average particle diameter less than 5.5 μm and particle size distribution 1.0 or more and less than 1.8 Δ: Volume average particle diameter 5.5 μm or more and less than 6.0 μm and particle size distribution 1.0 or more and less than 1.8 ×: Volume average Particle size 6.0 μm or more or particle size distribution 1.8 or more

<Bending resistance>
The paper was bent so that the image surface was on the inside, and the image fixed by the low temperature fixing evaluation was rubbed twice with a weight of 30 g.
The paper was spread, and the presence or absence of white streaks after bending on the image was visually determined.
Judgment criteria
○: no white streaks △: slightly white streaks ×: white streaks

<Document offset property>
Two sheets of A4 paper on which the images obtained in the low temperature fixing evaluation were fixed were superimposed on each other between fixing surfaces, applied with a weight of 420 g (0.68 g / cm ² ) and allowed to stand at 60 ° C. for 60 minutes .
The document offset property was evaluated according to the following judgment criteria for the state in which the superposed papers were pulled apart.

Judgment criteria
:: no resistance :: a crisp sound but the image does not separate from the paper surface x: the image separates from the paper surface

<Image intensity>
According to JIS K5600, the image fixed by the evaluation of low-temperature fixability was subjected to a scratch test by applying a load of 10 g directly above the pencil fixed at 45 degrees diagonally, and the image strength was evaluated from pencil hardness not scratched. . The higher the pencil hardness, the better the image strength.

Judgment criteria
○: H or more △: B to F
×: 2 B or less

<Cleanability>
The transfer residual toner on the photosensitive member which passed the cleaning process was visually observed using a commercial copying machine [AR 5030; manufactured by Sharp Corp.], and the cleaning property was evaluated according to the following judgment criteria.
Judgment criteria
:: no toner slipped △: toner slipped slightly observed x: toner slipped

[Evaluation results]
As is clear from the evaluation results of Table 3, all the toners obtained by the production method of the present invention obtained excellent results in all performance evaluations. On the other hand, the toner of Comparative Example 1 which does not contain the polyester resin (a) and the toner of Comparative Example 2 manufactured by the pulverization method even if it is contained are not satisfactory in some performance items.

The resin particles and toner obtained by the production method of the present invention are excellent in low temperature fixability, glossiness, hot offset resistance, chargeability and particle size distribution, excellent in heat resistant storage stability, charge stability and cleanability, electrophotography It can be suitably used as a toner used for electrostatic recording, electrostatic printing and the like. Furthermore, it is suitable as applications such as additives for paints, additives for adhesives, and particles for electronic paper.

Claims

Resin containing polyester resin (a) having a glass transition temperature (Tg a ) of −20 to 57 ° C. obtained by polycondensation of a component containing an alcohol component (y) and an unsaturated carboxylic acid component (z) The method is a method for producing resin particles in which resin particles are aggregated and fused after obtaining the particles, and after obtaining the resin particles, carbon-carbon derived from the unsaturated carboxylic acid component (z) in the polyester resin (a) The manufacturing method of the resin particle including the process of making cross-linking reaction of double bond and making it into modified resin.
The method for producing resin particles according to claim 1, wherein the weight ratio of the tetrahydrofuran insoluble matter to the tetrahydrofuran dissolved matter in the resin particles is 5/95 to 50/50.
The method for producing resin particles according to claim 1 or 2, wherein the peak top molecular weight of the polyester resin (a) is 2,000 to 20,000.
The resin fine particles are resin particles further including a polyester resin (b) except the polyester resin (a), wherein the polyester resin (b) is a component containing an alcohol component (y) and a saturated carboxylic acid component (x) The method for producing resin particles according to any one of claims 1 to 3, which is a polyester resin obtained by polycondensation of
The polyester resin (b) is a polyester resin containing an amorphous polyester resin (b1) obtained by polycondensation of a component containing an alcohol component (y) and a saturated carboxylic acid component (x), wherein the alcohol is an alcohol The method for producing resin particles according to claim 4, wherein the component (y) contains 80 mol% or more of an aromatic diol, and the saturated carboxylic acid component (x) contains 80 mol% or more of an aromatic dicarboxylic acid.
6. The method for producing resin particles according to claim 4, wherein the weight ratio of the polyester resin (a) -derived structural portion in the resin particles to the polyester resin (b) is 5/95 to 50/50.
A method for producing a toner comprising resin particles obtained by the method for producing resin particles according to any one of claims 1 to 6.