JP2020187341A - Method for manufacturing toner binder and toner - Google Patents

Abstract

To provide a toner binder and a toner that satisfy all of crushability, heat-resistant storage property, charge characteristics, image conveyance resistance, and durability, while maintaining low-temperature fixability and hot offset resistance.SOLUTION: There is provided a method for manufacturing a toner binder containing a saturated polyester resin (A) and a vinyl resin (B). The saturated polyester resin (A) is a polyester resin obtained through polycondensation of a carboxylic acid component (y) and an alcohol component (x) containing an alkylene oxide adduct of bisphenol A in which the addition mol number of alkylene oxide is 2 to 5. The saturated polyester resin (A) has a hydroxyl value of 3 mgKOH/g or more, and the method for manufacturing a toner binder includes a step of polymerizing constituent monomers of the vinyl resin (B) at a temperature of 100°C or higher under the presence of the saturated polyester resin (A) to obtain the vinyl resin (B).SELECTED DRAWING: None

Description

The present invention relates to a toner binder and a method for producing a toner.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic devices such as copiers and laser printers has been rapidly increasing, and the demand for their performance is also increasing.
Conventionally, for full-color electrophotographic, 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 are known methods and devices for obtaining a multicolor image by heating and fixing a toner image on a transfer material after repeating an image forming step such as transferring the image onto the material.

In order to pass through these processes without any problem, the toner first needs to maintain a stable charge amount, and then needs to have good fixability to paper. Further, since the apparatus has a heating body in the fixing portion, the temperature rises in the apparatus, so that the toner is required not to be blocked in the apparatus.

Further, from the viewpoint of energy saving of reducing energy consumption in the fixing process as well as promoting miniaturization, high speed, and high image quality of the electrophotographic apparatus, improvement of low temperature fixability of toner is strongly required.
Recently, as a transfer material, many types of paper such as recycled paper having a large surface unevenness and coated paper having a smooth surface are used. In order to cope with the surface properties of these transfer materials, a fuser having a wide nip width such as a soft roller or a belt roller is preferably used. However, if the nip width is widened, the contact area between the toner and the fixing roller increases, and a so-called high temperature offset phenomenon occurs in which molten toner adheres to the fixing roller. Therefore, it is a prerequisite that offset resistance is required.
In addition to the above, multicolor images (full color) are required to have much higher gloss than black and white images (monochrome) due to reproduction of photographic images, etc., and it is necessary to make the toner layer of the obtained image smooth. is there.
Therefore, it is necessary to develop low-temperature fixability while maintaining offset resistance while having high gloss, and a high-gloss toner image is required in a wide working range.

The toner binder has a great influence on the toner characteristics as described above, and polystyrene resin, styrene-acrylic resin, polyester resin, epoxy resin, polyurethane resin, polyamide resin and the like are known, but recently, they are stored. Polyester resin has attracted particular attention because it is easy to balance property and fixability.

As a method for expanding the fixing temperature range, a toner using a polyester resin containing an unsaturated carboxylic acid as a constituent component has been proposed (Patent Document 1).
However, although this method can prevent the offset phenomenon at a high temperature to some extent, the lower limit temperature for fixing is insufficient, and the demands for high speed and energy saving have not yet been sufficiently met.

On the other hand, many toners using a hybrid resin in which a polyester component and a styrene acrylic component are chemically bonded have been proposed (Patent Documents 2 to 6).
However, although this method improves hot offset resistance, charging characteristics, and pulverization property, low temperature fixability is still insufficient.

As described above, toner binders and toners that satisfy all of crushability, heat storage resistance, charging characteristics, image transfer resistance and durability while maintaining low temperature fixability and hot offset resistance have been used so far. There wasn't.

JP-A-2017-003985 Japanese Unexamined Patent Publication No. 2007-286562 Japanese Unexamined Patent Publication No. 2014-235362 Japanese Unexamined Patent Publication No. 2008-009171 Japanese Unexamined Patent Publication No. 2010-128466 Japanese Unexamined Patent Publication No. 2006-047585

An object of the present invention is to provide a toner binder and a toner that satisfy all of pulverization property, heat storage property, charging property, image transport property and durability while maintaining low temperature fixability and hot offset resistance. To do.

The present inventors have arrived at the present invention as a result of diligent studies to solve these problems.
That is, the present invention is a method for producing a toner binder containing a saturated polyester resin (A) and a vinyl resin (B), wherein the saturated polyester resin (A) has 2 to 5 additional moles of alkylene oxide. A polyester resin obtained by polycondensing an alcohol component (x) containing an alkylene oxide adduct and a carboxylic acid component (y). The saturated polyester resin (A) has a hydroxyl value of 3 mgKOH / g or more. This is a method for producing a toner binder, which comprises a step of polymerizing a constituent monomer of a vinyl resin (B) at a temperature of 100 ° C. or higher in the presence of a saturated polyester resin (A) to obtain a vinyl resin (B).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a toner binder and a toner having excellent pulverizability, heat storage resistance, charging characteristics, image transfer resistance and durability while maintaining low temperature fixability and hot offset resistance.

The method for producing a toner binder of the present invention is a method for producing a toner binder containing a saturated polyester resin (A) and a vinyl resin (B), wherein the saturated polyester resin (A) has 2 to 2 moles of alkylene oxide added. It is a polyester resin obtained by polycondensing an alcohol component (x) containing an alkylene oxide adduct of bisphenol A, which is 5, and a carboxylic acid component (y), and the saturated polyester resin (A) has a hydroxyl value of 3 mgKOH /. Production of a toner binder having a step of obtaining a vinyl resin (B) by polymerizing a constituent monomer of the vinyl resin (B) at a temperature of 100 ° C. or higher in the presence of a saturated polyester resin (A) having a weight of g or more. The method.
The method for producing the toner binder of the present invention will be sequentially described below.

The toner binder obtained by the production method of the present invention contains a saturated polyester resin (A), and the saturated polyester resin (A) contains an alcohol component (x) and a carboxylic acid component (y) containing an alkylene oxide adduct of bisphenol A. ), Which is a polyester resin obtained by polycondensing with), and contains an alkylene oxide adduct of bisphenol A having an addition molar number of 2 to 5 mol as an essential component.

The saturated polyester resin (A) may be an amorphous polyester resin or a crystalline polyester resin, and an amorphous polyester resin is preferable from the viewpoint of pulverizability. These may be one kind alone or a combination of two or more kinds.
The saturated polyester resin in the present invention is a polyester resin that does not have a radically polymerizable carbon-carbon double bond, and the unsaturated polyester resin is a polyester resin that has a radically polymerizable carbon-carbon double bond. That is. Double bonds of aromatic rings and heterocycles are not considered in determining whether the polyester resin is an unsaturated polyester resin or a saturated polyester resin.
Further, "crystallinity" in the present invention means that the DSC curve has a peak top temperature (Tm) of an endothermic peak in the differential scanning calorimetry (also referred to as DSC measurement) described below. Further, "amorphous" means that the peak top temperature of the endothermic peak does not exist when the transition temperature of the sample is measured using the differential scanning calorimeter described below.
Measurement is performed using a differential scanning calorimeter {for example, "DSC210" [manufactured by Seiko Instruments Inc.]}. The crystalline resin was first heated from 20 ° C. to 10 ° C./min to 150 ° C., then cooled to 0 ° C. from 150 ° C. to 10 ° C./min, and then from 0 ° C. to 10 ° C. The temperature indicating the top of the endothermic peak in the second temperature raising process when the temperature is raised to 150 ° C. under the condition of ° C./min is defined as the peak top temperature of the endothermic peak of the crystalline resin.

Examples of the alcohol component (x) include monool (x1), diol (x2), and a polyol (x3) having a valence of trivalent or higher.
These may be one kind alone or a combination of two or more kinds as long as they contain the alkylene oxide adduct of bisphenol A which has 2 to 5 addition moles of the alkylene oxide described below. ..

Monool (x1) includes linear or branched alkyl alcohols (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and ligno) having 1 to 30 carbon atoms. Ceryl alcohol, etc.) and the like.
From the viewpoint of image strength and heat storage stability, among these monools, a linear or branched alkyl alcohol having 8 to 24 carbon atoms is preferable, a linear alkyl alcohol having 8 to 24 carbon atoms is more preferable, and further, a linear alkyl alcohol having 8 to 24 carbon atoms is preferable. Preferred are dodecyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lignoceryl alcohol.

The diol (x2) contains an alkylene oxide adduct of bisphenol A having an addition mole number of 2 to 5 as an essential component. The alkylene oxide adduct of bisphenol A is obtained by adding an alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenol A.

By containing the alkylene oxide adduct of bisphenol A, which has 2 to 5 moles of alkylene oxide, as an essential component, low temperature fixability, charging characteristics and durability are improved.
The alkylene oxide to be added to bisphenol A is preferably an alkylene oxide having 2 to 4 carbon atoms, for example, ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), propylene oxide ("propylene oxide"). ”, Which may be abbreviated as PO below), butylene oxide, tetrahydrofuran, and a combination of two or more of these.
From the viewpoint of low temperature fixability, the AO constituting the AO adduct of bisphenol A having 2 to 5 moles of alkylene oxide is preferably EO and / or PO.

The number of moles of alkylene oxide added in the AO adduct of bisphenol A is 2 to 5, and the number of moles of alkylene oxide added is 2 to 5 from the viewpoint of low temperature fixability, charging characteristics and durability, preferably 2 to 3. is there. When the number of added moles is 2 or more, the low temperature fixability is good, and when the number of added moles is 5 or less, the charging characteristics and durability are good.

As the diol (x2) other than the AO adduct of bisphenol A having an addition molar number of 2 to 5 of the alkylene oxide, an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-) Propropylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.) (x21), alkylene ether glycols with 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene) Glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) (x22), alicyclic diol having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.) (x23), alicyclic diol. (Poly) alkylene oxide adduct (preferably 1 to 30 moles added) (x24), aromatic diol [monocyclic dihydric phenol (eg hydroquinone, etc.) and bisphenols, etc.] (x25) and alkylene oxide adduct molars. Examples thereof include an alkylene oxide adduct of the above aromatic diol (preferably the number of addition moles 2 to 30) (x26) excluding the AO adduct of bisphenol A having a number of 2 to 5.

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. , 2'-diethylbisphenol F and the like, and these can be used in combination of two or more.

Among the diols (x2) other than the AO adduct of bisphenol A having 2 to 5 moles of alkylene oxide, the alkylene glycol (x21) having 2 to 36 carbon atoms is used from the viewpoint of low temperature fixability and heat storage stability. preferable.

Examples of the trivalent or higher valence polyol (x3) include trivalent or higher valent aliphatic polyhydric alcohols (x31) having 3 to 36 carbon atoms, saccharides and derivatives thereof (x32), and aliphatic polyhydric alcohols. AO adduct (preferably 1 to 30 moles added) (x33), AO adduct (preferably 2 to 30 moles added) (x34) of trisphenols (trisphenol PA, etc.), novolak resin (phenol) Novolac, cresol novolak and the like are included, and examples thereof include AO adducts (preferably 2 to 30 addition moles) (x35) having an average degree of polymerization of 3 to 60).

Aliphatic polyhydric alcohols (x31) having trivalent or higher valences having 3 to 36 carbon atoms include alkane polyols and their intramolecular or intermolecular dehydrations, and examples thereof include glycerin, trimethylolethane, and trimethylolpropane. Examples thereof include pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol.

Examples of the saccharide and its derivative (x32) include sucrose and methyl glucoside.

Of the trivalent or higher valence polyols (x3), an aliphatic polyhydric alcohol (x31) having a trivalent or higher valence having 3 to 36 carbon atoms is used from the viewpoint of achieving both low temperature fixability and hot offset resistance. And a novolak resin (containing phenol novolac, cresol novolak, etc., preferably 3 to 60 degrees of polymerization), an AO adduct (preferably 2 to 30 additional moles) (x35).

Among the alkylene oxide adducts of bisphenol A, which is an essential component (the number of moles added is 2 to 5), the ethylene oxide adduct of bisphenol A (which is preferable from the viewpoint of achieving both low temperature fixability, hot offset resistance and heat storage stability) The number of added moles is 2 to 3) and the propylene oxide adduct of bisphenol A (the number of added moles is 2 to 3).

As a diol (x2) other than the AO adduct of bisphenol A in which the addition mole number of the alkylene oxide contained in the alcohol component (x) is 2 to 5, and a polyol (x3) having a valence of 3 or more, it is heat-preservable. From the viewpoint, preferred ones include alkylene glycol having 2 to 10 carbon atoms, 3 to 8 valent aliphatic polyhydric alcohol having 3 to 36 carbon atoms, and novolak resin (phenol novolac, cresol novolak, etc.), and the average degree of polymerization is It is preferably an AO adduct of 3 to 60) (the number of addition moles is preferably 2 to 30).
More preferably, it is an alkylene glycol having 2 to 6 carbon atoms and a trivalent aliphatic polyhydric alcohol having 3 to 36 carbon atoms, and even more preferably, ethylene glycol, propylene glycol, and trimethylolpropane.

As the alcohol component (x), a diol (x2) and a polyol (x3) having a valence of trivalent or higher can be used in combination. The molar ratio [(x2) / (x3)] of the diol (x2) and the polyol (x3) having a valence of trivalent or higher when used in combination is 80/20 to 99 / from the viewpoint of low temperature fixability and hot offset resistance. 1 is preferable, 85/15 to 98/2 is more preferable, and 90/10 to 97/3 is particularly preferable.

Examples of the carboxylic acid component (y) include aromatic carboxylic acid (y1) and aliphatic carboxylic acid (y2). One type of carboxylic acid component (y) may be used, or two or more types may be used in combination.

Examples of the aromatic carboxylic acid (y1) include aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and trivalent or higher valent aromatic acids having 9 to 20 carbon atoms. Examples thereof include polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.).
Examples of the aliphatic carboxylic acid (y2) include an aliphatic dicarboxylic acid having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, lepargic acid and sebacic acid), and a fat having 6 to 36 carbon atoms. Vinyl polymers of group tricarboxylic acids (hexanetricarboxylic acids, etc.) and unsaturated carboxylic acids [Mn: 450-10,000] (styrene / malonic acid copolymers, styrene / acrylic acid copolymers, and styrene / fumaric acids Polymers, etc.) and the like.

As the carboxylic acid component (y), an anhydride of these carboxylic acids, a lower alkyl (carbon number 1 to 4) ester (methyl ester, ethyl ester, isopropyl ester, etc.) may be used, or in combination with these carboxylic acids. You may.

Among these carboxylic acid components (y), an aliphatic dicarboxylic acid having 2 to 50 carbon atoms, an aromatic dicarboxylic acid having 8 to 36 carbon atoms, and carbon are preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance. It is a trivalent or higher aromatic polycarboxylic acid having a number of 9 to 20, more preferably adipic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and a combination thereof.
Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Anhydrides and lower alkyl esters of these acids are similarly preferred.

In the present invention, the hydroxyl value of the saturated polyester resin (A) is 3 mgKOH / g or more from the viewpoint of pulverizability, charging characteristics and image transfer resistance. More preferably, it is 22 to 55 mgKOH / g. The hydroxyl value of the saturated polyester resin (A) can be measured by the method specified in JIS K0070 (1992).

In the present invention, the acid value of the saturated polyester resin (A) is preferably 30 mgKOH / g or less, more preferably 15 to 29 mgKOH / g. The acid value of the saturated polyester resin (A) can be measured by the method specified in JIS K0070 (1992).

In the present invention, the glass transition temperature (Tg _A ) of the saturated polyester resin (A) is preferably 50 to 70 ° C, more preferably 60 to 70 ° C. When the glass transition temperature is 70 ° C. or lower, the low-temperature fixability is good, and when the glass transition temperature is 50 ° C. or higher, the heat-resistant storage stability is good.
The glass transition temperature (Tg _A ) can be measured by a method (DSC method) specified in ASTM D3418-82, for example, using DSC Q20 manufactured by TA Instruments Co., Ltd.

In the present invention, the peak top molecular weight (Mp) of the saturated polyester resin (A) in gel permeation chromatography (GPC) is 3,000 to 10, from the viewpoint of low temperature fixability, hot offset resistance and heat storage stability. It is preferably 000, more preferably 5,000 to 10,000.

In the present invention, the peak top molecular weight (Mp), number average molecular weight (hereinafter, may be abbreviated as Mn), and weight average molecular weight (hereinafter, may be abbreviated as Mw) of the saturated polyester resin (A) are determined. , GPC can be used for measurement under the following conditions.
Equipment (example): HLC-8120 [manufactured by Tosoh Corporation]
Column (example): 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution filtered through a glass filter Solution injection volume: 100 μL
Detector: Refractive index detector Reference material: 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, 090,280,000) [manufactured by Tosoh Corporation]

In the present invention, the saturated polyester resin (A) can be produced in the same manner as known polyesters.
For example, it can be carried out by reacting the constituents in an atmosphere of an inert gas (nitrogen gas or the like) at a reaction temperature of preferably 150 to 280 ° C., more preferably 160 to 250 ° C., still more preferably 170 to 235 ° C. it can. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

At this time, an esterification catalyst can be used if necessary.
Examples of esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide, etc.), antimony trioxide, titanium-containing catalysts [eg, titanium alkoxide, potassium titanate oxalate, titanium terephthalate, titanium terephthalate alkoxide, JP-A-2006-243715. The catalysts described in Japanese Patent Publication No. {Titanium diisopropoxybis (triethanolaminete), titaniumdihydroxybis (triethanolamineate), titanium monohydroxytris (triethanolamineate), titanylbis (triethanolamineate) and theirs. Intramolecular polycondensate, etc.} and catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyterephthalate, etc.), etc.], zirconium-containing catalysts (eg, zirconyl acetate, etc.) ) And zinc acetate and the like. Of these, a titanium-containing catalyst is preferable.

The total charge ratio of the alcohol component (x) and the carboxylic acid component (y) of the saturated polyester resin (A) is preferably 1/2 to the equivalent ratio of hydroxyl groups and carboxyl groups ([OH] / [COOH]). It is 2/1, more preferably 1 / 1.3 to 1.5 / 1, and even more preferably 1 / 1.2 to 1.4 / 1.

The toner binder obtained by the production method of the present invention contains a vinyl resin (B). The vinyl resin (B) is a resin containing a polyfunctional vinyl monomer (a) and / or a monofunctional vinyl monomer (b) as a constituent monomer. Further, from the viewpoint of hot offset resistance and durability, the vinyl resin (B) preferably contains a polyfunctional vinyl monomer (a) as a constituent monomer. Further, the weight ratio of the polyfunctional vinyl monomer (a) to the monomer constituting the vinyl resin (B) is preferably 0.1 to 10% by weight based on the weight of the vinyl resin (B). Since the vinyl resin contains the polyfunctional vinyl monomer (a) as a constituent component and has the above weight ratio, the pulverizability is maintained and the hot offset resistance is improved.

Examples of the polyfunctional vinyl monomer (a) include a divalent vinyl monomer and a trivalent or higher valent vinyl monomer.
These may be one kind alone or a combination of two or more kinds.

Divalent vinyl monomers include divinylbenzene, 1,5-hexadiene, di (meth) acrylate of glycerin, di (meth) acrylate of trimethylolpropane, and di (meth) acrylate of 3-hydroxy-1,5-pentanediol. , 2-Hydroxy-2-ethyl-1,3-propanediol di (meth) acrylate and the like.

Examples of trivalent or higher vinyl monomers include trimethylol propan tri (meth) acrylate, triallyl 1,3,5-benzenetricarboxylic acid, tri (meth) acrylate of glycerin, tri (meth) acrylate of pentaerythritol, and trimethylol propane. Tri (meth) acrylate of ethylene oxide adduct, tetra (meth) acrylate of pentaerythritol, penta (meth) acrylate of dipentaerythritol, hexa (meth) acrylate of dipentaerythritol, tetra of ethylene oxide adduct of dipentaerythritol Examples thereof include (meth) acrylate, penta (meth) acrylate of ethylene oxide adduct of dipentaerythritol, and penta (meth) acrylate of propylene oxide adduct of dipentaerythritol.

Of these polyfunctional vinyl monomers (a), divinylbenzene and trimethylolpropane triacrylate are preferable from the viewpoint of low temperature fixability, hot offset resistance and pulverization property.

Examples of the monofunctional vinyl monomer (b) include a styrene-based monomer (b1), a (meth) acrylic-based monomer (b2), a vinyl ester monomer (b3), and a monomer having a nitrile group (b4). As the monofunctional vinyl monomer (b), one type may be used alone, or two or more types may be used in combination.

Examples of the styrene-based monomer (b1) include styrene and alkylstyrene having an alkyl group having 1 to 3 carbon atoms (for example, α-methylstyrene and p-methylstyrene).

Examples of the (meth) acrylic monomer (b2) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl (meth) acrylate, and ethyl-2- ( Examples thereof include hydroxymethyl) acrylicate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate.

Examples of the vinyl ester monomer (b3) include vinyl acetate, vinyl propionate, isopropenyl acetate and the like.

Examples of the monomer (b4) having a nitrile group include acrylonitrile and methacrylonitrile.

Among these monofunctional vinyl monomers (b), styrene-based monomers (b1), (meth) acrylic-based monomers (b2), from the viewpoints of toner hot offset resistance, heat-resistant storage stability, grindability, and charge stability. And a monomer having a nitrile group (b4) is preferable, and styrene, acrylic acid, butyl acrylate, ethyl acrylate and acrylonitrile are more preferable.

As described above, the weight ratio of the polyfunctional vinyl monomer (a) in the monomer constituting the vinyl resin (B) is 0.1 to 10% by weight based on the weight of the vinyl resin (B). Is preferable. When it is 0.1% by weight or more, the hot offset resistance is good, and when it is 10% by weight or less, the pulverizability is good. The weight ratio of the monofunctional vinyl monomer (b) in the monomer constituting the vinyl resin (B) is preferably 90 to 99.9% by weight based on the weight of the vinyl resin (B).

The weight ratio of the polyfunctional vinyl monomer (a) in the monomer constituting the vinyl resin (B) can be quantified by measuring the thermal decomposition GC / MS. BUNSKI KAGAKU Vol. 48, No. 4, PP. The measurement was performed under the following conditions with reference to 449-456 (1999).
<Pyrolysis type pyrolysis gas chromatograph-mass spectrometry (pyrolysis GC / MS)>
1. 1. Pyrolysis equipment and conditions Equipment: Perkin Elmer Japan's TurboMatrix40
Pyrolysis temperature: 180 ° C
Pyrolysis time: 60 min
2. 2. GC / MS equipment and conditions Equipment: GCMS QP-2010 manufactured by Shimadzu Corporation
Column: ZB-5 (30 m x 0.25 mm x 1 μm)
Oven temperature: 40 ° C (3 min) -2 ° C / min (70 ° C) -5 ° C / min (150 ° C) -10 ° C / min (300 ° C) -30 min
Carrier gas: He (pressure 100 kPa)
Interface temperature: 250 ° C
Injection method: Total injection Inlet temperature: 200 ° C
Detector (MS): GCMS QP-2010 manufactured by Shimadzu Corporation
MS temperature: Ion source 200 ° C
Scan range: EI (Electron Ionization): m / z (mass / charge of ions) 33-500
3. 3. Sampling conditions Vial bottle size: 20 ml Headspace vial Sample volume: 100 mg
Sample pretreatment: A toner binder to which 3 ml of a 25 wt% methanol solution of tetramethylammonium hydroxide was added was used.

In the present invention, the glass transition temperature (Tg _B ) of the vinyl resin (B) is preferably 35 to 47 ° C.
When Tg _B is 47 ° C. or lower, the low-temperature fixability is good, and when it is −35 ° C. or higher, the heat-resistant storage stability is good. The glass transition temperature (Tg _B ) of the vinyl resin (B) is a value calculated by the Fox-Fory equation, 1 / Tg12 = φ (1) / Tg1 + φ (2) / Tg2. Tg12 corresponds to Tg at the absolute temperature (unit K) of the vinyl resin (B), and Tg1 and Tg2 are the glass transition temperatures (unit K) of the homopolymers of the monomers constituting the vinyl resin (B). , Φ (1) and φ (2) are weight percentages of the monomers constituting the vinyl resin (B).

The glass transition temperature of the monomeric homopolymer constituting the vinyl resin (B) is calculated using the software of Polymer Design Tools (DTW Associates, Inc. versior 1.1).

The acid value of the vinyl resin (B) is preferably 55 mgKOH / g or less from the viewpoint of low-temperature fixability.
The acid value of the vinyl resin (B) is calculated by weight percentage using the acid value of each of the monomers used for the polymerization of the vinyl resin (B) and the weight of the monomer.

The toner binder obtained by the production method of the present invention may contain a saturated polyester resin (A) and a vinyl resin (B), but resins other than the saturated polyester resin (A) and the vinyl resin (B) and known additions It may contain an agent (release agent, etc.).

In the present invention, the weight ratio [(A) / (B)] of the saturated polyester resin (A) and the vinyl resin (B) is 50 / from the viewpoint of achieving both low temperature fixability, hot offset resistance, and heat storage stability. It is preferably 50 to 90/10.

The toner binder obtained by the production method of the present invention preferably satisfies the following relational expression (1) from the viewpoint of low temperature fixability and hot offset resistance. By satisfying the relational expression (1), the compatibility between the saturated polyester resin (A) and the vinyl resin (B) is improved, and a sufficient fixing region is secured. In order to satisfy the relational expression (1), the SP values of the saturated polyester resin (A) and the vinyl resin (B) may be brought close to each other, and in particular, the weight of the monofunctional vinyl monomer (b) used for the vinyl resin (B). The ratio needs to be considered. Specifically, the SP value of the saturated polyester resin (A) should be 11.0 to 12.0 (cal / cm ³ ) ^0.5, and the SP value of the vinyl resin (B) should be 9.7 to 11. 7 (cal / cm ³ ) ^0.5 , acrylonitrile (SP value:) which is a monofunctional vinyl monomer (b) having a higher SP value than the saturated polyester resin (A) when designing the vinyl resin (B). 14.4) and acryloacid (SP value: 14.0), styrene (SP value: 10.6), butyl acrylate, which is a monofunctional vinyl monomer (b) having a lower SP value than the saturated polyester resin (A). Consideration of the weight ratio of (SP value: 9.8) and ethyl acrylate (SP value: 10.2) can be mentioned.
Relational expression (1): | SP (A) -SP (B) | ≤ 1.3

In the relational expression (1), SP (A) is the solubility parameter (SP value) (cal / cm ³ ) ^0.5 of the saturated polyester resin (A), and SP (B) is the SP value of the vinyl resin (B). (Cal / cm ³ ) ^0.5 .
The SP value (cal / cm ³ ) ^0.5 in the toner binder of the present invention was calculated by the method described in Polymer engineering and science Vol. 14, pp. 151-154 by Robert F Fedors et al. 25. It is a value at ° C.

The glass transition temperature (Tg) of the toner binder obtained by the production method of the present invention is preferably 50 to 70 ° C.
When the Tg of the toner binder is 70 ° C. or lower, the low-temperature fixability is good, and when the Tg is 50 ° C. or higher, the heat-resistant storage stability is good. The glass transition temperature (Tg) is measured by a method (DSC method) specified in ASTM D3418-82 using, for example, DSC Q20 manufactured by TA Instruments Co., Ltd.

Toner binder obtained by the method of the present invention, the difference in glass transition temperature (Tg _B) of the glass transition temperature of the saturated polyester resin _(A) (Tg A) and the vinyl resin _{(B) [(Tg A)} - (Tg _B )] is preferably 15 ° C. or higher from the viewpoint of low-temperature fixability. The larger the difference in the glass transition temperature, the more effective the low temperature fixability is, and the reason for this will be explained below.
The viscosity of the toner binder is the dominant factor for low temperature fixability. On the other hand, when comparing the viscosities of the saturated polyester resin (A) and the vinyl resin (B), the vinyl resin (B) has a higher viscosity. By lowering the glass transition temperature (Tg _B ) of the vinyl resin (B), the viscosity of the vinyl resin (B) in the fixing temperature range can be lowered, and thus the viscosity of the toner binder can be lowered. Further, when the vinyl resin (B) contains the polyfunctional vinyl monomer (a), it has a crosslinked structure and satisfies the heat-resistant storage property even if the glass transition temperature is low.
In order to satisfy this range, it is particularly preferable to lower the glass transition temperature of the vinyl resin (B), which is a monomer having a lower glass transition temperature than the saturated polyester resin (A) (single amount). Body homopolymer glass transition temperature: 10 ° C), butyl acrylate (monomeric homopolymer glass transition temperature: -17 ° C) and ethyl acrylate (monomeric homopolymer glass transition temperature: 11 ° C) ) Etc. can be easily controlled.

The acid value of the toner binder obtained by the production method of the present invention is preferably 10 to 30 mgKOH / g or less.
The acid value of the toner binder can be measured by the method specified in JIS K0070 (1992).

The toner binder obtained by the production method of the present invention may contain a THF insoluble matter.
The content (% by weight) of the THF insoluble matter in the toner binder is preferably 50% by weight or less, more preferably 5 to 30% by weight, from the viewpoint of achieving both hot offset resistance and low temperature fixability. Is.

The content (% by weight) of the THF insoluble matter in the toner binder was determined by the following method.
50 mL of THF is added to 0.5 g of the sample, and the mixture is stirred and refluxed for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter, and the resin component 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 defined as the weight of THF insoluble, and the weight obtained by subtracting the weight of THF insoluble from the weight of the sample is defined as the weight of THF insoluble and THF soluble. Calculate the weight percent of the minute.

A method for manufacturing a toner binder will be described.
In the toner binder obtained by the production method of the present invention, the constituent monomers of the vinyl resin (B) are polymerized at a temperature of 100 ° C. or higher in the presence of the saturated polyester resin (A) to obtain the vinyl resin (B). Has a process. Producing the vinyl resin (B) in the presence of the saturated polyester resin (A) allows the vinyl resin (B) to be uniformly polymerized in the saturated polyester resin (A), and has pulverizability and hot offset properties. It is preferable from the viewpoint of compatibility. Further, the saturated polyester resin (A) can be reduced in viscosity by polymerizing the constituent monomers of the vinyl resin (B) at a temperature of 100 ° C. or higher, and the saturated polyester resin (A) can be made without using a solvent. ), The vinyl resin (B) can be uniformly polymerized.

Examples of the polymerization apparatus include a batch type polymerization apparatus and a continuous type polymerization apparatus. Examples of the batch type polymerization apparatus include a reaction vessel such as an autoclave. Examples of the continuous polymerization apparatus include a static mixer, an extruder, a continuous sneaker, and a triple roll.

Specific methods for obtaining the vinyl resin (B) by polymerizing the constituent monomers of the vinyl resin (B) in the presence of the saturated polyester resin (A) include the following method (1) or method (2). ) Is preferable.
Method (1) A mixture of a saturated polyester resin (A) and a monomer constituting the vinyl resin (B) is charged into a batch polymerization apparatus and heated to a temperature at which it becomes a solution to form the vinyl resin (B). A method for obtaining a vinyl resin (B) by polymerizing a monomer.
Method (2) The saturated polyester resin (A) and the monomers constituting the vinyl resin (B) are each injected into a continuous polymerization apparatus at a temperature at which they are in a solution state, and the constituent monomers of the vinyl resin (B) are injected. A method for obtaining a vinyl resin (B) by polymerizing.

The temperature at which the constituent monomers of the vinyl resin (B) are polymerized is preferably 100 to 200 ° C., more preferably 100 to 160 ° C. from the viewpoint of hot offset resistance, image transfer resistance and heat storage stability. is there. When the polymerization temperature is 200 ° C. or lower, the vinyl resin (B) is less likely to be decomposed and the heat-resistant storage stability is good. When the polymerization temperature is 100 ° C. or higher without using a known solvent, the constituent monomers The reactivity of the above is good, and the hot offset property and the image transfer resistance are good.

The time for polymerizing the constituent monomers of the vinyl resin (B) using the batch type polymerization apparatus is preferably 30 minutes or more, more preferably 1 to 20 minutes from the viewpoint of the uniformity and productivity of the vinyl resin (B). It's time.
The time for polymerizing the constituent monomers of the vinyl resin (B) using the continuous polymerization apparatus is preferably 1 to 300 minutes, more preferably 4 to 3 from the viewpoint of the uniformity and productivity of the vinyl resin (B). It is 120 minutes.

When the constituent monomers of the vinyl resin (B) are polymerized in the presence of the saturated polyester resin (A) to obtain the vinyl resin (B), the use of the radical reaction initiator (c) causes a polymerization reaction. It is preferable from the viewpoint of surely performing. The radical reaction initiator (c) is not particularly limited, and examples thereof include an inorganic peroxide (c1), an organic peroxide (c2), and an azo compound (c3). In addition, these radical reaction initiators may be used in combination.

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, and for example, benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α-bis (t-butyl). Peroxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t- Butyl peroxyhexin-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t -Butylperoxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5 Examples thereof include -trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropylmonocarbonate and t-butylperoxyacetate.

The azo compound (c3) is not particularly limited, but for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis. (Cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like can be mentioned.

Among these, organic peroxide (c2) is preferable because it has high initiator efficiency and does not produce toxic by-products such as cyanide compounds, and t-butylperoxy-2-ethylhexanoate and dit. -Butyl peroxide and t-butyl peroxyisopropyl monocarbonate are more preferred.

The amount of the radical reaction initiator (c) used is not particularly limited, but is preferably 0.01 to 10% by weight based on the total weight of the constituent monomers of the saturated polyester resin (A) and the vinyl resin (B). ..

The method of adding the radical reaction initiator (c) is not particularly limited, but in the case of the method (1), it is preferable to add the radical reaction initiator (c) alone without using a solvent such as xylene. In the case of 2), it is preferable to add the radical reaction initiator (c) alone without using a solvent such as xylene, and further uniformly mix it with the saturated polyester resin (A).

When the radical reaction initiator (c) is used, it has a step of reducing the pressure in the reaction system during and / or after the polymerization of the constituent monomers of the vinyl resin (B) in order to remove the initiator decomposition residue and the like. Is preferable. The depressurization step may be started at the same time as the start of the polymerization, during or after the polymerization.

The temperature of the depressurizing step is preferably 100 to 200 ° C., more preferably 120 to 195 ° C., further preferably 130 to 190 ° C., and particularly preferably 140 to 190 ° C. from the viewpoint of volatilization efficiency and productivity. ℃. When the temperature at the time of depressurization is 200 ° C. or less, the vinyl resin is less likely to decompose and the heat-resistant storage stability is good. When the temperature at the time of decompression is 100 ° C. or more, the resin viscosity becomes low, and the vapor of the volatilized product Efficiency is improved because it is easy to volatilize from the viewpoint of pressure.

The time of the depressurizing step is preferably 1 to 300 minutes, more preferably 4 to 120 minutes from the viewpoint of heat-resistant storage and productivity.

The degree of decompression in the depressurization step is preferably 0.01 to 30 kPa, more preferably 0.1 to 5 kPa, from the viewpoint of heat storage resistance, hot offset resistance and productivity.

The toner obtained by the production method of the present invention contains a toner binder.

The toner obtained by the production method of the present invention may contain one or more known additives selected from a colorant, a mold release agent, a charge control agent, a fluidizing agent, and the like, if necessary, in addition to the toner binder. Good.

As the colorant, all of the dyes and pigments used as the colorant for toner can be used. For example, Carbon Black, Iron Black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmin FB, Pigment Orange R, Lake Red 2G, Rhodamin. FB, Rhodamin B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, Oil Pink OP, etc., and these are the only colorants. It may be a mixture of two or more kinds. Further, if necessary, a magnetic powder (powder of a ferromagnetic metal such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) can be contained also as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the toner binder. When magnetic powder is used, it is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight.

As the release agent, those having a flow softening point (T1 / 2) of 50 to 170 ° C. by a flow tester are preferable, and fatty acid hydrocarbon waxes such as polyolefin wax, microcrystallin wax, paraffin wax, Fishertropch wax and the like and them. Oxides, carnauba wax, montan wax and their deoxidizing waxes, ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and mixtures thereof.

The flow softening point (T1 / 2) of the release agent was measured under the following conditions.
<Measurement method of flow softening point (T1 / 2)>
Using a descent type flow tester [for example, CFT-500D manufactured by Shimadzu Corporation], a load of 1.96 MPa is applied by a plunger while heating 1 g of the measurement sample at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger drop amount (flow value)" and "temperature", and graph the temperature corresponding to 1/2 of the maximum value of the plunger drop amount. This value (the temperature at which half of the measurement sample flows out) is defined as the flow softening point (T1 / 2).

As the polyolefin wax, those obtained by (co) copolymerization of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and mixtures thereof). And those obtained by further heat-decomposing them], (eg, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer), oxidation of (co) copolymers of olefins with oxygen and / or ozone. Maleic anhydride modified products of (co) polymers of olefins [eg maleic anhydride and derivatives thereof (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.)], olefins and unsaturated carboxylic acids [ (Meta) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl ester [(meth) alkyl acrylate (1-18 carbon atoms of alkyl) ester and alkyl maleate (alkyl carbon number 1) ~ 18) Esters, etc.] and the like, and examples thereof.

Examples of microcrystalline wax include Hi-Mic-2095, Hi-Mic-1090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, and Hi-Mic- manufactured by Nippon Seiro Co., Ltd. 1045, Hi-Mic-2045 and the like can be mentioned.

Examples of the paraffin wax include Paraffin WAX-155, Paraffin WAX-150, Paraffin WAX-145, Paraffin WAX-140, Paraffin WAX-135, HNP-3, HNP-5, and HNP-manufactured by Nippon Seiwa Co., Ltd. 9, HNP-10, HNP-11, HNP-12, HNP-51 and the like.

Examples of Fischer-Tropsch wax include Sasolwax C80 manufactured by Sazole.

Examples of carnauba wax include refined carnauba wax specially manufactured No. 1 manufactured by Hiroyuki Kato Co., Ltd.

Examples of the ester wax include fatty acid ester waxes (for example, Nissan Electol WEP-2, WEP-3, WEP-4, WEP-5, WEP-8, etc. manufactured by Nichiyu Co., Ltd.).

Examples of higher alcohols include aliphatic alcohols having 30 to 50 carbon atoms, and examples thereof include triacontanol. Examples of the fatty acid include fatty acids having 30 to 50 carbon atoms, and examples thereof include triacontane carboxylic acid.

Examples of the fatty acid amide include Diamid Y and Diamid 200 manufactured by Mitsubishi Chemical Corporation.

As the charge control agent, either a positive charge charge control agent or a negative charge charge control agent may be contained, and a niglosin dye, a triphenylmethane dye containing a tertiary amine as a side chain, and a quaternary ammonium salt. , Polyamine resin, imidazole derivative, quaternary ammonium base-containing polymer, metal-containing azo dye, copper phthalocyanine dye, salicylic acid metal salt, boron complex of benzylic acid, sulfonic acid group-containing polymer, fluorine-containing polymer, halogen-substituted aromatic ring-containing polymer, etc. Can be mentioned.

Examples of the fluidizing agent include silica, titania, alumina, calcium carbonate, fatty acid metal salt, silicone resin particles, fluororesin particles, and the like, and two or more of them may be used in combination. Silica is preferable from the viewpoint of toner chargeability. Further, the silica is preferably hydrophobic silica from the viewpoint of toner transferability.

The content of the toner binder in the toner is preferably 45 to 92% by weight based on the weight of the toner.
The content of the colorant is preferably 0.5 to 50% by weight based on the weight of the toner.
The content of the release agent is preferably 1 to 10% by weight based on the weight of the toner.
The content of the charge control agent is preferably 0.5 to 7.5% by weight based on the weight of the toner.
The content of the fluidizing agent is preferably 0.1 to 4% by weight based on the weight of the toner.
The total content of the additives is preferably 8 to 55% by weight based on the weight of the toner.
By setting the composition ratio of the toner in the above range, it is possible to easily obtain a toner having good hot offset resistance, heat storage stability, and charge stability.

The toner obtained by the production method of the present invention may be obtained by any of known methods such as a kneading and pulverizing method, an emulsion phase inversion method and a polymerization method.
For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended, melt-kneaded, then roughly pulverized, and finally atomized using a jet mill pulverizer or the like. By further classifying, the particles have a volume average particle diameter (D50) of preferably 5 to 20 μm, and then mixed with a fluidizing agent to produce the particles.
The volume average particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III [manufactured by Beckman Coulter Co., Ltd.].

When toner is obtained by the emulsification phase inversion method, the components constituting the toner excluding the fluidizing agent can be dissolved or dispersed in an organic solvent, then emulsified by adding water or the like, and then separated and classified for production. it can. The volume average particle size of the toner is preferably 3 to 15 μm.

If necessary, the toner of the present invention is mixed with carrier particles such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite and resin (acrylic resin, silicone resin, etc.) to form an electrically latent image. It is used as a developer for. When carrier particles are used, the weight ratio of the toner to the carrier particles is preferably 1/99 to 99/1. Further, instead of the carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.
The toner of the present invention does not have to contain carrier particles.

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

The toner and toner binder of the present invention are used for developing electrostatically charged images or magnetic latent images in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, and the like. More specifically, it is used for developing an electrostatic charge image or a magnetic latent image particularly suitable for full color.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, "parts" indicates parts by weight.

<Manufacturing Example 1> [Manufacturing of saturated polyester resin (A-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 326 parts of EO2 mol adduct of bisphenol A, 415 parts of PO2 mol adduct of bisphenol A, 274 parts of terephthalic acid, and titanium diisopropoxy as a catalyst. 2.5 parts of bis (triethanolaminate) was added, and the mixture was reacted at 230 ° C. under a nitrogen stream for 3 hours while distilling off the generated water. Next, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 6 hours, and then the temperature was lowered to 180 ° C. 42 parts of trimellitic anhydride was added, and the mixture was reacted under normal pressure for 1 hour and then taken out to obtain a saturated polyester resin (A-1).

<Manufacturing Example 2> [Manufacturing of saturated polyester resin (A-2)]
470 parts of EO2 mol adduct of bisphenol A, 240 parts of propylene glycol, 382 parts of terephthalic acid, 84 parts of adipic acid, and titanium diisopropoxy as a catalyst in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. 2.5 parts of bis (triethanolaminate) was added, and the mixture was reacted at 230 ° C. under a nitrogen stream for 3 hours while distilling off the generated water. Next, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 6 hours, and then the temperature was lowered to 180 ° C. 34 parts of trimellitic anhydride was added, and the mixture was reacted under normal pressure for 1 hour and then taken out to obtain a saturated polyester resin (A-2). The amount of propylene glycol that flowed out was 109 parts.

<Manufacturing Examples 3 to 5> [Manufacturing of saturated polyester resins (A-3) to (A-5)]
The alcohol component (x) and the carboxylic acid component (y) shown in Table 1 were charged in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and the other reactions were carried out in the same manner as in Production Example 1. Saturated polyester resins (A-3) to (A-5) were obtained.

<Comparative Production Example 1> [Production of unsaturated polyester resin (A'-1)]
620 parts of PO2 mol adduct of bisphenol A, 163 parts of PO3 mol adduct of bisphenol A, 245 parts of terephthalic acid, and titanium diisopropoxy as a catalyst in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. 2.5 parts of bis (triethanolaminate) was added, and the mixture was reacted at 230 ° C. under a nitrogen stream for 3 hours while distilling off the generated water. Next, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 5 hours, and then the temperature was lowered to 180 ° C. 1 part of tert-butylcatechol was added as a polymerization inhibitor, 19 parts of fumaric acid was added, and the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 8 hours, and then 9 parts of trimellitic anhydride was added under normal pressure. After reacting for 1 hour with, the resin was taken out to obtain an unsaturated polyester resin (A'-1) having a radically polymerizable carbon-carbon double bond.

<Comparative Production Example 2> [Production of Saturated Polyester Resin (A'-2)]
1 part of EO2 mol adduct of bisphenol A, 122 parts of PO2 mol adduct of bisphenol A, 620 parts of PO3 mol adduct of bisphenol A, 243 parts of terephthalic acid in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. A part, 6 parts of trimellitic anhydride, and 3 parts of tetrabutoxytitanate as a condensation catalyst were added and reacted at 220 ° C. under pressure, and the reaction was carried out for 10 hours while distilling off the produced water. Then, the pressure was gradually released and returned to normal pressure, and the reaction was further promoted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours. After normal pressure with nitrogen, it was cooled to 180 ° C. 73 parts of trimellitic anhydride was added, the temperature was raised to 210 ° C., the reaction was further promoted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours, and then the reaction was taken out to obtain a saturated polyester resin (A'-2).

<Comparative Production Example 3> [Production of Saturated Polyester Resin (A'-3)]
728 parts of EO1 mol adduct of bisphenol A, 344 parts of terephthalic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube at 220 ° C. under pressure. The reaction was carried out for 10 hours while distilling off the produced water. Then, the pressure was gradually released and returned to normal pressure, and the reaction was further promoted under a reduced pressure of 0.5 to 2.5 kPa for 4 hours. The pressure was adjusted to normal pressure with nitrogen and then taken out to obtain a saturated polyester resin (A'-3) having a 1 mol adduct of alkylene oxide of bisphenol A.

Table 1 shows the composition and physical property values of the polyester resin.

<Example 1> [Manufacturing of toner binder (C-1)]
At room temperature, 700 parts of saturated polyester resin (A-1) was added to the autoclave, 103 parts of styrene as a monomer constituting the vinyl resin (B-1) [manufactured by Idemitsu Kosan Co., Ltd., the same applies hereinafter], butyl acrylate. [Mitsubishi Chemical Co., Ltd., same below] 103 parts, acrylonitrile [Nakalitex Co., Ltd., same below] 88 parts, trimethylolpropane triacrylate [New Nakamura Chemical Industry Co., Ltd., same below] 5.4 Part, t-butylperoxyisopropyl monocarbonate as the radical polymerization initiator (c) [Perbutyl I, manufactured by Nichiyu Co., Ltd., the same applies hereinafter] 3 parts were charged in the above order, replaced with nitrogen, and then at 70 ° C. The mixture was uniformly stirred for 30 minutes. Then, the temperature was raised to 120 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 6 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing a saturated polyester resin (A-1) and a vinyl resin (B-1) was added. -1) was obtained.

<Example 2> [Manufacturing of toner binder (C-2)]
At room temperature, 600 parts of saturated polyester resin (A-1), 251 parts of butyl acrylate as a monomer constituting vinyl resin (B-2), 146 parts of acrylonitrile, and 3.6 parts of trimethylolpropane triacrylate in an autoclave. 2 parts of t-butylperoxyisopropyl monocarbonate as a radical polymerization initiator (c) were charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 140 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 2 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing the saturated polyester resin (A-1) and the vinyl resin (B-2) was contained. -2) was obtained.

<Example 3> [Manufacturing of toner binder (C-3)]
At room temperature, 800 parts of saturated polyester resin (A-2) was added to the autoclave, 11 parts of styrene as a monomer constituting the vinyl resin (B-3), 94 parts of butyl acrylate, 62 parts of acrylonitrile, and acrylic acid [Mitsubishi. Chemical Co., Ltd., same below] 14 parts, divinylbenzene [Tokyo Kasei Kogyo Co., Ltd., same below] 20 parts, t-butylperoxyisopropyl monocarbonate 1.5 parts as radical polymerization initiator (c) Was charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 120 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 6 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing a saturated polyester resin (A-2) and a vinyl resin (B-3) was added. -3) was obtained.

<Example 4> [Manufacturing of toner binder (C-4)]
At room temperature, 750 parts of saturated polyester resin (A-3), 92 parts of styrene as a monomer constituting vinyl resin (B-4), 104 parts of butyl acrylate, 46 parts of acrylonitrile, and 9 parts of divinylbenzene were added to the autoclave. , 1 part of t-butylperoxyisopropyl monocarbonate as the radical polymerization initiator (c) was charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 130 ° C. over 1 hour in a sealed state. After further maintaining the temperature at the same temperature for 3 hours to complete the polymerization, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing a saturated polyester resin (A-3) and a vinyl resin (B-4) was subjected to. -4) was obtained.

<Example 5> [Manufacturing of toner binder (C-5)]
At room temperature, 500 parts of saturated polyester resin (A-3) was added to the autoclave, 299 parts of butyl acrylate as a monomer constituting the vinyl resin (B-5), ethyl acrylate [manufactured by Tokyo Kasei Kogyo Co., Ltd., The same applies hereinafter] 199 parts, 2 parts of trimethylolpropane triacrylate, and 5 parts of t-butylperoxyisopropyl monocarbonate as the radical polymerization initiator (c) are charged in the above order, replaced with nitrogen, and then replaced with nitrogen at 70 ° C. for 30 minutes. Stirred uniformly. Then, the temperature was raised to 120 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 6 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing a saturated polyester resin (A-3) and a vinyl resin (B-5) was added. -5) was obtained.

<Example 6> [Manufacturing of toner binder (C-6)]
At room temperature, 900 parts of saturated polyester resin (A-3), 5.4 parts of styrene as a monomer constituting vinyl resin (B-3), 47 parts of butyl acrylate, 31 parts of acrylonitrile, acrylic acid in an autoclave. 7 parts, 9.8 parts of divinylbenzene, 2 parts of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator (c) [Perbutyl O, manufactured by Nichiyu Co., Ltd., the same applies hereinafter] The mixture was charged in order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 100 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 5 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing the saturated polyester resin (A-3) and the vinyl resin (B-3) was subjected to. -6) was obtained.

<Example 7> [Manufacturing of toner binder (C-7)]
At room temperature, 700 parts of saturated polyester resin (A-4), 103 parts of styrene as a monomer constituting vinyl resin (B-1), 103 parts of butyl acrylate, 88 parts of acrylonitrile, trimethylolpropane tri 5.4 parts of acrylate and 1 part of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator (c) were charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 110 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 3 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing a saturated polyester resin (A-4) and a vinyl resin (B-1) was added. -7) was obtained.

<Example 8> [Manufacturing of toner binder (C-8)]
At room temperature, 800 parts of saturated polyester resin (A-3) was added to the autoclave, 73 parts of styrene as a monomer constituting the vinyl resin (B-4), 83 parts of butyl acrylate, 37 parts of acrylonitrile, and divinylbenzene. 2 parts, di-t-butyl peroxide as a radical polymerization initiator (c) [Perbutyl D, manufactured by Nichiyu Co., Ltd., the same applies hereinafter] 2 parts were prepared in the above order, replaced with nitrogen, and then at 70 ° C. The mixture was uniformly stirred for 30 minutes. Then, the temperature was raised to 160 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 2 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing the saturated polyester resin (A-3) and the vinyl resin (B-4) was subjected to. -8) was obtained.

<Example 9> [Manufacturing of toner binder (C-9)]
At room temperature, 850 parts of saturated polyester resin (A-2) was added to the autoclave, 98 parts of styrene as a monomer constituting the vinyl resin (B-6), 52 parts of butyl acrylate, and as a radical polymerization initiator (c). 1 part of the di-t-butyl peroxide of No. 1 was charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 150 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 5 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing a saturated polyester resin (A-2) and a vinyl resin (B-6) was added. -9) was obtained.

<Example 10> [Manufacturing of toner binder (C-10)]
At room temperature, 700 parts of saturated polyester resin (A-5) was added to the autoclave, 103 parts of styrene as a monomer constituting the vinyl resin (B-1), 103 parts of butyl acrylate, 88 parts of acrylonitrile, and trimethylolpropane tri. 5.4 parts of acrylate and 3 parts of t-butylperoxyisopropyl monocarbonate as the radical polymerization initiator (c) were charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 120 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 6 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing a saturated polyester resin (A-5) and a vinyl resin (B-1) was added. -10) was obtained.

<Comparative Example 1> [Manufacturing of toner binder (C'-1)]
At room temperature, 700 parts of unsaturated polyester resin (A'-1), 188 parts of butyl acrylate as a monomer constituting the vinyl resin (B-2), 109 parts of acrylonitrile, and trimethylolpropane triacrylate 2 in an autoclave. .7 parts, 3 parts of t-butylperoxyisopropyl monocarbonate as the radical polymerization initiator (c) were charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 120 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 6 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and a toner binder containing an unsaturated polyester resin (A'-1) and a vinyl resin (B-2) was added. (C'-1) was obtained.

<Comparative Example 2> [Manufacturing of Toner Binder (C'-2)]
At room temperature, 700 parts of saturated polyester resin (A'-2) was added to the autoclave, 188 parts of butyl acrylate as a monomer constituting the vinyl resin (B-2), 109 parts of acrylonitrile, and trimethylolpropane triacrylate. Seven parts and three parts of t-butylperoxyisopropyl monocarbonate as the radical polymerization initiator (c) were charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 120 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 6 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and a toner binder containing a saturated polyester resin (A'-2) and a vinyl resin (B-2) was used. C'-2) was obtained.

<Comparative Example 3> [Manufacturing of Toner Binder (C'-3)]
At room temperature, 700 parts of saturated polyester resin (A'-3), 195 parts of styrene as a monomer constituting vinyl resin (B-6), 105 parts of butyl acrylate, radical polymerization initiator (c) in an autoclave. 3 parts of t-butylperoxyisopropyl monocarbonate was charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 120 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 6 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and a toner binder containing a saturated polyester resin (A'-3) and a vinyl resin (B-6) was used. C'-3) was obtained.

<Comparative Example 4> [Manufacturing of Toner Binder (C'-4)]
At room temperature, 700 parts of saturated polyester resin (A-1) was added to the autoclave, 103 parts of styrene as a monomer constituting the vinyl resin (B-1), 103 parts of butyl acrylate, 88 parts of acrylonitrile, and trimethylolpropane tri. 5.4 parts of acrylate and 3 parts of t-butylperoxyisopropyl monocarbonate as the radical polymerization initiator (c) were charged in the above order, replaced with nitrogen, and then uniformly stirred at 70 ° C. for 30 minutes. Then, the temperature was raised to 90 ° C. over 1 hour in a sealed state. After the polymerization was completed by keeping the temperature at the same temperature for 6 hours, the pressure was reduced to 0.5 to 2.5 kPa for 3 hours, and the toner binder (C) containing a saturated polyester resin (A-1) and a vinyl resin (B-1) was added. '-4) was obtained.

The toner binder (C'-1) contains an unsaturated polyester resin (A') having a radically polymerizable carbon-carbon double bond, but does not contain the saturated polyester resin (A), and (C'-2). In (), the hydroxyl value of the saturated polyester resin (A) is less than 3 mgKOH / g, and in (C'-3), the saturated polyester resin (A) does not contain 2 to 5 mol of alkylene oxide of bisphenol A. C'-4) is a toner binder polymerized at a temperature of less than 100 ° C.
The radical reaction initiator (c) in Table 3 is as follows.
(C-1): t-Butylperoxyisopropyl monocarbonate (c-2): t-butylperoxy-2-ethylhexanoate (c-3): di-t-butylperoxide

Table 2 shows the composition and physical property values of the vinyl resin, and Table 3 shows the composition and physical property values of the toner binder.

<Example 11> [Manufacturing of toner (T-1)]
For 88 parts of the toner binder (C-1) according to Example 1, 7 parts of carbon black pigment [manufactured by Mitsubishi Chemical Corporation, MA-100] and paraffin wax as a release agent [Nippon Seiwa Co., Ltd.] HNP-9] and 1 part of the charge control agent [Hodoya Chemical Industry Co., Ltd., T-77] were added to make toner by the following method.
First, it was premixed using a Henschel mixer [manufactured by Nippon Coke Industries Co., Ltd., FM10B] and then kneaded with a twin-screw kneader [manufactured by Ikekai Co., Ltd., PCM-30]. Then, after pulverizing using a supersonic jet crusher Lab Jet [Kurimoto, Ltd., KJ-25], an elbow jet classifier [Matsubo Co., Ltd., EJ-L-3 (LABO) type) ] To obtain toner particles having a volume average particle diameter D50 of 6 μm.
Then, 1 part of colloidal silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] was mixed with 100 parts of the toner particles by a sample mill to obtain the toner (T-1) according to Example 11.

<Examples 12 to 20> [Manufacturing of toners (T-2) to (T-10)]
Toners were produced in the same manner as in Example 11 with the number of parts of the raw materials blended shown in Table 4, and toners (T-2) to (T-10) according to Examples 12 to 20 were obtained.

<Comparative Examples 5 to 8> [Manufacturing of toners (T'-1) to (T'-4)]
Toners were produced in the same manner as in Example 11 with the number of parts of the raw materials blended shown in Table 4, and toners (T'-1) to (T'-4) according to Comparative Examples 5 to 8 were obtained.

[Evaluation methods]
Below, the obtained toners (T-1) to (T-10) and (T'-1) to (T'-4) have low temperature fixability, hot offset resistance, pulverization property, heat storage property, and charging. The measurement method and evaluation method of characteristics, image transfer resistance and durability will be described including judgment criteria.

<Low temperature fixability>
The toner was evenly placed on the paper surface so as to have a concentration of 1.00 mg / cm ² . At this time, as a method of placing the powder on the paper surface, a printer with the heat fixing machine removed was used.
This paper was passed through a soft roller in a fixing speed (peripheral speed of a heating roller) of 213 mm / sec and a heating roller temperature in the range of 100 to 200 ° C. in 5 ° C. increments.
Next, the presence or absence of cold offset on the fixed image was visually observed, and the temperature at which the cold offset occurred (MFT) was measured.
The lower the temperature at which the cold offset is generated, the better the low temperature fixability.
Under these evaluation conditions, the MFT is generally preferably 130 ° C. or lower.

<Hot offset resistance>
Toner is placed on the paper surface by the same method as described in the above low temperature fixability, and the paper is placed on a soft roller with a fixing speed (peripheral speed of the heating roller) of 213 mm / sec and a heating roller temperature in the range of 100 to 200 ° C. It was passed in 5 ° C increments.
Next, the presence or absence of hot offset on the fixed image was visually observed, and the temperature at which the hot offset occurred was measured.
The higher the temperature at which hot offset occurs, the better the hot offset resistance. Under these evaluation conditions, it is preferably 180 ° C. or higher.

<Crushability>
For 89 parts of each toner binder used for the toners (T-1) to (T-10) and (T'-1) to (T'-4), the pigment carbon black [manufactured by Mitsubishi Chemical Corporation] , MA-100] 7 parts, release agent paraffin wax [Nippon Seiwa Co., Ltd., HNP-9] 3 parts, charge control agent [Hodogaya Chemical Industry Co., Ltd., T-77] 1 part In addition, after pre-mixing using a Henshell mixer Nippon Coke Industries Co., Ltd., FM10B], the mixture obtained by kneading with a twin-screw kneader [Ikekai Co., Ltd., PCM-30] is cooled and then 8.6. Mesh pass ~ 30 mesh-on size crushed and classified as particles for crushability evaluation, and these crushability evaluation particles are used as supersonic jet crusher Lab Jet [Kuji-25, manufactured by Kurimoto Iron Works Co., Ltd.] ], It was finely pulverized under the following conditions.
Crushing pressure: 0.64 MPa
Grinding time: 15 minutes Separater frequency: 150Hz
Adjuster ring: 15mm
Luber size: Medium As particles for evaluation of pulverizability, finely pulverized particles are used as they are without classification, and the volume average particle size (μm) is used as a Coulter counter [Product name: Multisizer III (Beckman Coulter Co., Ltd.) ) Made)].
The smaller the volume average particle size, the better the pulverizability. Under this evaluation condition, it is preferably 8.0 μm or less.

<Heat-resistant storage>
1 g of toner was placed in a closed container and allowed to stand for 24 hours in an atmosphere of a temperature of 50 ° C. and a humidity of 50%, the degree of blocking was visually judged, and the heat-resistant storage stability was evaluated according to the following criteria.

[Criteria]
◯: No blocking has occurred and excellent heat-resistant storage stability.
Δ: Blocking has occurred in a part, and the heat-resistant storage property is inferior.
X: Blocking occurs on the whole, and the heat-resistant storage stability is significantly inferior.

<Charging characteristics>
0.5 g of toner and 20 g of ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) were placed in a 50 mL glass bottle, and the humidity was adjusted at 23 ° C. and 50% relative humidity for 8 hours or more. Then, friction stir welding was performed at 50 rpm for 10 minutes and 60 minutes with a tubler shaker mixer, and the amount of charge at each time was measured.
A blow-off charge measuring device [manufactured by Kyocera Chemical Co., Ltd.] was used for the measurement.
(1) Charge amount after 10 minutes The "charge amount after 10 minutes of friction time" is defined as the charge amount after 10 minutes, and the smaller this value is, the stronger the negative charge property is and the better the initial charge amount is. Under this evaluation condition, it is preferably −10 μC / g or less.
(2) Charging stability "Charging amount after 60 minutes of friction time / Charging amount after 10 minutes of friction time" was calculated and used as the charging stability index. The larger the charge stability index, the better the charge stability. Under this evaluation condition, it is preferably 0.8 or more.

<Image transport resistance>
A solid image on the entire surface of the paper was prepared using a commercially available monochrome copying machine [AR5030, manufactured by Sharp Corporation] as a two-component developer, and the degree of image transport scratches caused by the paper ejection roller was evaluated according to the following criteria.

[Evaluation criteria]
⊚: No image transport scratches ○: Part of the image transport scratches can be confirmed when magnified 30 times Δ: Image transport scratches can be visually confirmed in part ×: Image transport scratches can be visually confirmed as a whole

<Durability>
Continuous copying was performed using a commercially available monochrome copier [Sharp Co., Ltd., AR5030] using toner as a two-component developer, and the durability was evaluated according to the following criteria.

[Criteria]
⊚: There is no change in image quality and no fog even after copying 10,000 sheets.
◯: Fog has occurred after copying 10,000 sheets.
Δ: Fog has occurred after copying 6,000 sheets.
X: Fog has occurred after copying 2,000 sheets.

As is clear from the evaluation results in Table 4, all the performance evaluations of the toners (T-1) to (T-10) according to Examples 11 to 20 were excellent.
On the other hand, the toners (T'-1) to (T'-4) according to Comparative Examples 5 to 8 were defective in some performance items.

The toner binder and toner of the present invention are excellent in crushability, heat storage resistance, charge characteristics, image transfer resistance and durability while maintaining low temperature fixability and hot offset resistance, and are excellent in electrophotographic, electrostatic recording and static electricity. It can be suitably used as a toner binder and toner for static charge image development used for electroprinting and the like.
Further, it is suitable for applications such as paint additives, adhesive additives, and electronic paper particles.

Claims (9)

A method for producing a toner binder containing a saturated polyester resin (A) and a vinyl resin (B).
A polyester obtained by polycondensing an alcohol component (x) containing an alkylene oxide adduct of bisphenol A in which the saturated polyester resin (A) has an alkylene oxide adduct of 2 to 5 and a carboxylic acid component (y). It is a resin
The saturated polyester resin (A) has a hydroxyl value of 3 mgKOH / g or more.
A method for producing a toner binder, which comprises a step of polymerizing a constituent monomer of a vinyl resin (B) at a temperature of 100 ° C. or higher in the presence of a saturated polyester resin (A) to obtain a vinyl resin (B). The vinyl resin (B) contains the polyfunctional vinyl monomer (a) as a constituent monomer, and the weight ratio of the polyfunctional vinyl monomer (a) to the monomer constituting the vinyl resin (B) is the vinyl resin (B). The method for producing a toner binder according to claim 1, wherein the content is 0.1 to 10% by weight based on the weight of the above. The method for producing a toner binder according to claim 1 or 2, wherein the saturated polyester resin (A) is an amorphous saturated polyester resin. The method for producing a toner binder according to any one of claims 1 to 3, which satisfies the following relational expression (1).
Relational expression (1): | SP (A) -SP (B) | ≤ 1.3
[In the relational expression (1), SP (A) is the solubility parameter (SP value) (cal / cm ³ ) ^0.5 of the saturated polyester resin (A), and SP (B) is the SP of the vinyl resin (B). The value (cal / cm ³ ) is ^0.5 . ] Method for producing a toner binder according to any one of claims 1 to 4 a glass transition temperature (Tg _B) is -35～47 ° C. vinyl resin (B). Difference in glass transition temperature (Tg _B) of the glass transition temperature of the saturated polyester resin _(A) (Tg A) and the vinyl resin (B) - claim _{1 [(Tg A) (Tg} B)] is 15 ℃ or higher The method for producing a toner binder according to any one of 5 to 5. The method for producing a toner binder according to any one of claims 1 to 6, wherein the saturated polyester resin (A) has a peak top molecular weight (Mp) of 3,000 to 10,000 in gel permeation chromatography (GPC). .. The toner binder according to any one of claims 1 to 7, wherein the weight ratio [(A) / (B)] of the saturated polyester resin (A) to the vinyl resin (B) is 50/50 to 90/10. Production method. A method for producing a toner containing the toner binder according to any one of claims 1 to 8.