JP2023168230A - toner binder - Google Patents

Abstract

To provide a toner binder that ensures excellent dispersion of crystalline polyester resin in amorphous polyester resin.SOLUTION: A toner binder includes a crystalline polyester resin (A), an amorphous polyester resin (B), and a graft polymer (C). The crystalline polyester resin (A) is a polyester resin obtained by reacting an alcohol component (x) with a carboxylic acid component (y). (x) contains a C2-36 aliphatic diol (x1). The content of (x1) in (x) is 20-80 mol%. (y) contains a C4-36 aliphatic dicarboxylic acid (y1). The content of (y1) in (y) is 20-80 mol%. (A) has a peak top temperature (Tm) of an endothermic peak of 50°C to 85°C. The endothermic peak of (A) has a half-width of 7°C or lower. (C) is a polymer with a side chain branched from a polyolefin.SELECTED DRAWING: None

Description

The present invention relates to toner binders.

In recent years, along with the promotion of smaller size, higher speed, higher image quality, and higher reliability of electrophotographic equipment, there has been a strong demand for improved low-temperature fixing properties of toner from the perspective of energy saving by reducing energy consumption in the fixing process. .
Toner binders have a large effect on toner properties as described above, and known materials include polystyrene resin, styrene-acrylic resin, polyester resin, epoxy resin, polyurethane resin, and polyamide resin. Polyester resin is attracting particular attention because it is easy to balance properties and fixability.
For example, for the purpose of low-temperature fixability, a toner using a crystalline polyester resin and an amorphous resin with excellent melting properties has been proposed (see Patent Document 1). Furthermore, a toner composition containing a hybrid polyester of crystalline polyester and amorphous polyester has been proposed for the purpose of improving low-temperature fixing properties and charging properties (see Patent Document 2).
However, when toner particles are made smaller in size in order to meet the demand for higher image quality, toners using the above-mentioned crystalline polyester resin cannot be said to have sufficient dispersibility of the crystalline polyester resin in the toner. Improvement is desired.

JP2002-287426A Patent No. 6485155

An object of the present invention is to provide a toner binder with excellent dispersibility of crystalline polyester resin in amorphous polyester resin.

As a result of intensive study, the present inventor has arrived at the present invention.
That is, the present invention provides a toner binder containing a crystalline polyester resin (A), an amorphous polyester resin (B), and a graft polymer (C), wherein the crystalline polyester resin (A) contains an alcohol component (x). It is a polyester resin obtained by reacting a carboxylic acid component (y) with a carboxylic acid component (y) as a raw material, the alcohol component (x) contains an aliphatic diol (x1) having 2 to 36 carbon atoms, and (x) of (x1) The content in is 20 to 80 mol% based on the total number of moles of (x), the carboxylic acid component (y) contains an aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms, and (y1) The content in (y) is 20 to 80 mol% based on the total number of moles of (y), and the endothermic peak measured by a differential scanning calorimeter (DSC) of the crystalline polyester resin (A) is The peak top temperature (Tm) is 50°C to 85°C, the half width of the endothermic peak of the crystalline polyester resin (A) is 7°C or less, and the graft polymer (C) contains ethylene and/or propylene. It is a polymer having side chains branching from polyolefin, which is an essential constituent monomer.

The toner binder of the present invention exhibits the effect of excellent dispersibility of crystalline polyester resin in amorphous polyester resin.

The present invention provides a toner binder containing a crystalline polyester resin (A), an amorphous polyester resin (B), and a graft polymer (C), in which the crystalline polyester resin (A) contains an alcohol component (x). A polyester resin obtained by reacting a carboxylic acid component (y) as a raw material, wherein the alcohol component (x) contains an aliphatic diol (x1) having 2 to 36 carbon atoms, and in (x) of (x1) The content is 20 to 80 mol% based on the total number of moles of (x), the carboxylic acid component (y) contains an aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms, and The content in (y) is 20 to 80 mol% based on the total number of moles of (y), and the peak of the endothermic peak measured by a differential scanning calorimeter (DSC) of the crystalline polyester resin (A) The top temperature (Tm) is 50°C to 85°C, the half width of the endothermic peak of the crystalline polyester resin (A) is 7°C or less, and the graft polymer (C) essentially contains ethylene and/or propylene. The toner binder is a polymer having side chains branched from polyolefin as a constituent monomer.

The present invention is a toner binder containing a crystalline polyester resin (A), an amorphous polyester resin (B), and a graft polymer (C).
In the present invention, "crystallinity" means that a DSC curve has a peak top temperature (Tm) of an endothermic peak in differential scanning calorimetry (also referred to as DSC measurement).
A method for measuring the peak top temperature (Tm) of an endothermic peak will be described below.
Measurement is performed using a differential scanning calorimeter (for example, DSC Q20 manufactured by TA Instruments Co., Ltd.). The sample was heated for the first time from 30°C to 180°C at 10°C/min, then cooled from 180°C to 0°C at 10°C/min, and then from 0°C to 10°C/min. The top temperature of the endothermic peak in the second heating process when the temperature is raised to 180°C for the second time under the condition of 180° C. is defined as the peak top temperature (Tm) of the endothermic peak.

The crystalline polyester resin (A) in the present invention is a polyester resin obtained by reacting an alcohol component (x) and a carboxylic acid component (y) as raw materials, and the alcohol component (x) has a carbon number of 2 to 36. contains an aliphatic diol (x1), the content of (x1) in (x) is 20 to 80 mol% based on the total number of moles of (x), and the carboxylic acid component (y) has 4 carbon atoms. -36 aliphatic dicarboxylic acids (y1), and the content of (y1) in (y) is 20 to 80 mol% based on the total number of moles of (y). The alcohol component (x) and the carboxylic acid component (y) may be used alone or in combination of two or more.

The alcohol component (x) of the crystalline polyester resin (A) in the present invention includes, in addition to the essential constituent aliphatic diol (x1) having 2 to 36 carbon atoms, the aliphatic diol having 2 to 36 carbon atoms ( Diols other than x1) and/or polyols having a valence of 3 or more may be mentioned. Furthermore, monoalcohol may be used as the alcohol component (x) if necessary.

The aliphatic diol (x1) having 2 to 36 carbon atoms includes straight chain aliphatic diols having 2 to 36 carbon atoms (ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol). , 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,18-octadecanediol , 1,19-nonadecanediol and 1,20-eicosandiol), branched aliphatic diols having 3 to 36 carbon atoms (propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2 -hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, etc.) and alicyclic diols having 4 to 36 carbon atoms (e.g. 1,4- cyclohexanedimethanol, hydrogenated bisphenol A, etc.).

Among the aliphatic diols (x1) having 2 to 36 carbon atoms, straight-chain aliphatic diols having 2 to 36 carbon atoms are preferred from the viewpoint of crystallinity.

Diols other than aliphatic diols having 2 to 36 carbon atoms (x1) include alkylene ether glycols having 4 to 36 carbon atoms (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol). etc.), alkylene oxide adducts of the above alicyclic diols (preferably 1 to 30 moles added), alkylene oxide adducts of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (preferably 2 to 30 moles added), 30), polylactone diol (poly ε-caprolactone diol, etc.), polybutadiene diol, and the like.

In alkylene oxide adducts of alicyclic diols or bisphenols, the alkylene oxide (hereinafter "alkylene oxide" may be abbreviated as AO) is ethylene oxide (hereinafter "ethylene oxide" may be abbreviated as EO). ) adducts, propylene oxide (hereinafter "propylene oxide" is abbreviated as PO) adducts, butylene oxide (hereinafter "butylene oxide" is abbreviated as BO) adducts, and the like.

Examples of polyols with a valence of 3 or more include alkane polyols and their intramolecular or intermolecular dehydrates (e.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.), saccharides and their derivatives. (for example, sucrose and methyl glucoside, etc.), alkylene oxide adducts of trisphenols (trisphenol PA, etc.) (preferably the number of moles added is 2 to 30), novolac resins (phenol novolak, cresol novolak, etc.), and the average The degree of polymerization is preferably 3 to 60), such as alkylene oxide adducts (the number of moles added is preferably 2 to 30) and acrylic polyols [copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers, etc.]. It will be done.

Monoalcohols include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, etc.) ) etc.

As components other than the aliphatic diol (x1) having 2 to 36 carbon atoms, from the viewpoint of dispersibility, diols other than the aliphatic diol (x1) having 2 to 36 carbon atoms and monoalcohols are preferred, and alkylene oxide of bisphenol A Adducts and straight chain alkyl alcohols having 1 to 30 carbon atoms are more preferred.

The carboxylic acid component (y) of the crystalline polyester resin (A) in the present invention includes, in addition to the essential constituent aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms, the aromatic dicarboxylic acid and/or Examples include polycarboxylic acids having a valence of 3 or higher, anhydrides of these acids, and lower alkyl (1 to 4 carbon atoms) esters (methyl ester, ethyl ester, isopropyl ester, etc.). Moreover, a monocarboxylic acid may be used as the carboxylic acid component (y) if necessary.

As the aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms, alkanedicarboxylic acids having 4 to 36 carbon atoms {alkanedicarboxylic acids having carboxyl groups at both ends of a chain saturated hydrocarbon group (adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,18-octadecanedicarboxylic acid, etc.), alkanedicarboxylic acids having a carboxyl group other than the terminal end of the chain saturated hydrocarbon group (decylsuccinic acid, etc.), and alkenedicarboxylic acids having 4 to 36 carbon atoms. Examples include acids (alkenylsuccinic acids such as dodecenylsuccinic acid, pentadecenylsuccinic acid, and octadecenylsuccinic acid, maleic acid, fumaric acid, and citraconic acid).

Among the aliphatic dicarboxylic acids (y1) having 4 to 36 carbon atoms, alkanedicarboxylic acids having carboxyl groups at both ends of a chain saturated hydrocarbon group are preferred from the viewpoint of crystallinity.

The aromatic dicarboxylic acid is not particularly limited as long as it is a carboxylic acid in which two carboxyl groups are bonded to a conjugated unsaturated ring structure such as a benzene ring or a naphthalene ring. (phthalic acid, isophthalic acid, terephthalic acid, t-butyl isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.).

Examples of polycarboxylic acids having a valence of 3 or higher include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexanetricarboxylic acid, etc.) ) and vinyl polymers of unsaturated carboxylic acids [number average molecular weight (Mn): 450 to 10,000] (styrene/maleic acid copolymers, styrene/acrylic acid copolymers, styrene/fumaric acid copolymers, etc.) ) etc.

Examples of monocarboxylic acids include aromatic monocarboxylic acids having 7 to 37 carbon atoms (including the carbon of the carbonyl group) (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), carbon atoms 2 to 37; 50 aliphatic monocarboxylic acids (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, behenic acid) , (meth)acrylic acid [(meth)acrylic means acrylic or methacryl], crotonic acid, isocrotonic acid, cinnamic acid, etc.).

As components other than the aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms, from the viewpoint of dispersibility, aromatic dicarboxylic acids and polycarboxylic acids having a valence of 3 or more are preferable, and aromatic dicarboxylic acids having 8 to 36 carbon atoms are preferable. More preferred are group dicarboxylic acids and aromatic polycarboxylic acids having 9 to 20 carbon atoms.

The content of the aliphatic diol (x1) having 2 to 36 carbon atoms in the alcohol component (x) is 20 to 80 mol% based on the total number of moles of (x) from the viewpoint of crystallinity and dispersibility, Preferably it is 40 to 60 mol%.

The content of the aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms in the carboxylic acid component (y) is 20 to 80 mol% based on the total number of moles of (y) from the viewpoint of crystallinity and dispersibility. It is preferably 40 to 60 mol%.

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

In the present invention, the crystalline polyester resin (A) can be produced by polycondensation reaction, transesterification reaction, etc., but from the viewpoint of crystallinity, it is preferable to produce it by combining polycondensation reaction and transesterification reaction. For example, a method of producing by transesterification of a crystalline part (a1) obtained by a polycondensation reaction and an amorphous part (a2) can be mentioned.
The crystalline part (a1) has a peak top temperature (Tm) of an endothermic peak measured by a differential scanning calorimeter (DSC), and is obtained by reacting an alcohol component and a carboxylic acid component as raw materials. It is polyester. In addition, the amorphous part (a2) is a polyester obtained by reacting an alcohol component and a carboxylic acid component as raw materials, in which the peak top temperature (Tm) of the endothermic peak is not observed by a differential scanning calorimeter (DSC). It is about.

In the production of the crystalline polyester resin (A) of the present invention, when obtaining the crystalline polyester resin (A) by a transesterification reaction between the crystalline part (a1) and the amorphous part (a2), an inert gas ( The reaction can be carried out in an atmosphere (such as nitrogen gas) at a reaction temperature of preferably 120 to 280°C, more preferably 130 to 250°C, and still more preferably 140 to 235°C. In addition, the reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of ensuring the transesterification reaction. It is also effective to reduce the pressure in order to improve the reaction rate at the final stage of the reaction.

At this time, an esterification catalyst can also be used if necessary.
Examples of esterification catalysts include tin-containing catalysts (such as dibutyltin oxide), antimony trioxide, titanium-containing catalysts [such as titanium alkoxides, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, JP 2006-243715A Catalysts described in the publication (titanium diisopropoxy bistriethanolaminate, titanium dihydroxybistriethanolaminate, titanium monohydroxytristriethanolaminate, titanyl bistriethanolaminate, and intramolecular polycondensates thereof, etc.), and special Catalysts described in Japanese Patent Publication No. 2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.), zirconium-containing catalysts (for example, zirconyl acetate, etc.), and zinc acetate.
Among the esterification catalysts, preferred are titanium-containing catalysts from the viewpoint of low-temperature fixability, and more preferred are the catalysts described in JP-A No. 2006-243715 and the catalysts described in JP-A No. 2007-11307. .

The peak top temperature (Tm) of the endothermic peak of the crystalline polyester resin (A) in the present invention measured by a differential scanning calorimeter (DSC) is 50 to 85°C, preferably 60 to 80°C, and more Preferably it is 70 to 80°C.
If Tm is 50°C or higher, the crystallinity will be good, and if it is 85°C or lower, the dispersibility will be good. Tm can be adjusted by the content and number of carbon atoms of the aliphatic diol (x1) having 2 to 36 carbon atoms and the content and number of carbon atoms of the aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms.
For example, as the content and carbon number of the aliphatic diol (x1) and aliphatic dicarboxylic acid (y1) increase, the peak top temperature (Tm) increases.
Furthermore, if the crystalline polyester resin (A) is a resin obtained by a transesterification reaction between a crystalline part (a1) and an amorphous part (a2), an aliphatic diol (x1), an aliphatic dicarboxylic acid (y1) Since crystallinity is easily maintained even when the content and number of carbon atoms are small, it becomes easy to achieve the peak top temperature (Tm) of the endothermic peak.

The half width of the endothermic peak indicating the peak top temperature (Tm) of the crystalline polyester resin (A) in the present invention is 7°C or less, preferably 6°C or less, particularly preferably 2 to 6°C. The half-width of the endothermic peak indicating the peak top temperature (Tm) is calculated from the baseline of the endothermic peak to half the maximum height of the endothermic peak, based on the DSC curve obtained by measuring the peak top temperature (Tm) of the endothermic peak. Let it be the temperature width of the peak in height. The half width of the endothermic peak depends on the content of aliphatic diol (x1) having 2 to 36 carbon atoms, the number of carbon atoms and the content of aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms, the number of carbon atoms, polycondensation reaction, and ester. It can be adjusted by reaction conditions such as exchange reaction.
For example, as the content and carbon number of the aliphatic diol (x1) and aliphatic dicarboxylic acid (y1) increase, the half-width of the endothermic peak decreases. In addition, if the crystalline polyester resin (A) is a resin obtained by transesterification between the crystalline part (a1) and the amorphous part (a2), aliphatic diol (x1), aliphatic dicarboxylic acid ( Even when the content of y1) and the number of carbon atoms are small, crystallinity is easily maintained, making it easy to achieve the half-width of the endothermic peak.
For example, the crystalline polyester resin (A) is a resin obtained by a transesterification reaction between the crystalline part (a1) and the amorphous part (a2), and the crystalline part (a1) and the amorphous part (a2) If the weight ratio (a1/a2) is between 20/80 and 70/30, the above half width can be easily achieved.

From the viewpoint of crystallinity, it is preferable that the endothermic amount of the crystalline polyester resin (A) based on the endothermic peak measured by a differential scanning calorimeter (DSC) is 20 to 90 J/g.

The acid value of the crystalline polyester resin (A) is preferably 0 to 30 mgKOH/g, more preferably 0 to 10 mgKOH/g from the viewpoint of crystallinity.

The hydroxyl value of the crystalline polyester resin (A) is preferably 0 to 100 mgKOH/g, more preferably 20 to 50 mgKOH/g from the viewpoint of crystallinity.

The number average molecular weight (hereinafter sometimes abbreviated as Mn) of the crystalline polyester resin (A) is preferably from 1,000 to 1,000,000, more preferably from 3,000 to 10 ,000.

The weight average molecular weight (hereinafter sometimes abbreviated as Mw) of the crystalline polyester resin (A) is preferably from 2,000 to 2,000,000, more preferably from 6,000 to 20,000 from the viewpoint of crystallinity. ,000.

The amorphous polyester resin (B) in the present invention is a polyester resin obtained by reacting an alcohol component (X) and a dicarboxylic acid component (Y) as raw materials, and the alcohol component (X) is an alkylene oxide of bisphenol A. It is preferable to contain the adduct (X1) from the viewpoint of chargeability and storage stability. The alcohol component (X) and the carboxylic acid component (Y) may be used alone or in combination of two or more.

The alcohol component (X) of the amorphous polyester resin (B) in the present invention includes, in addition to the alkylene oxide adduct of bisphenol A (X1), a diol other than (X1) described below and/or a valence of 3 or more. Examples include polyols. Moreover, a monoalcohol may be used as the alcohol component (X) if necessary.

The alkylene oxide adduct (X1) of bisphenol A is a compound obtained by adding an alkylene oxide to bisphenol A, and includes, for example, an EO adduct of bisphenol A, a PO adduct of bisphenol A, and a BO adduct of bisphenol A. etc.

Among the alkylene oxide adducts (X1) of bisphenol A, EO adducts of bisphenol A and PO adducts of bisphenol A are preferred from the viewpoint of chargeability and storage stability.

The number of moles of alkylene oxide added in the alkylene oxide adduct (X1) of bisphenol A is preferably 2 to 30, more preferably 2 to 10, and even more preferably 2 from the viewpoint of chargeability and storage stability. ~5.

Diols other than the alkylene oxide adduct (X1) of bisphenol A include straight chain aliphatic diols having 2 to 36 carbon atoms (ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexane). Diol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,18-octadecane branched aliphatic diols having 3 to 36 carbon atoms (propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1, 2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, etc.), alicyclic diols having 4 to 36 carbon atoms (e.g. 1,4 -cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene ether glycols having 4 to 36 carbon atoms (e.g. diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), the above alicyclic Alkylene oxide [EO, PO, BO, etc.] adducts (preferably the number of moles added is 1 to 30) of the formula diol, alkylene oxide (EO, PO, BO, etc.) adducts of bisphenols (bisphenol F, bisphenol S, etc.) ( Preferably, the number of moles added is 2 to 30), polylactone diol (poly ε-caprolactone diol, etc.), polybutadiene diol, and the like.

As the polyol having a valence of 3 or more, those similar to those exemplified for the crystalline polyester resin (A) can be used.

As the monoalcohol, the same ones as those exemplified for the crystalline polyester resin (A) can be used.

When the alcohol component (X) contains a component other than the alkylene oxide adduct of bisphenol A (X1), from the viewpoint of low-temperature fixability, diols are preferred, such as linear aliphatic diols having 2 to 36 carbon atoms, and straight-chain aliphatic diols having 2 to 36 carbon atoms. More preferred are 3 to 36 branched aliphatic diols.

As the carboxylic acid component (Y) of the amorphous polyester resin (B) in the present invention, the same carboxylic acid component (y) as exemplified for the crystalline polyester resin (A) can be used, and the carboxylic acid component Preferred as (Y) are aromatic dicarboxylic acids having 8 to 36 carbon atoms, alkanedicarboxylic acids having 4 to 36 carbon atoms, and aromatic polycarboxylic acids having 9 to 20 carbon atoms.

From the viewpoint of chargeability and storage stability, the content of the alkylene oxide adduct (X1) of bisphenol A in the alcohol component (X) is preferably determined by the total number of moles of the alcohol component (X) that is a constituent component of the polyester resin. The amount is 90 to 100 mol%, more preferably 95 to 100 mol%, and even more preferably 100 mol%.

From the viewpoint of chargeability and storage stability, the content of aromatic dicarboxylic acid in the carboxylic acid component (Y) is preferably 70% based on the total number of moles of the carboxylic acid component (Y) that is a constituent component of the polyester resin. ~100 mol%.

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

In the present invention, the amorphous polyester resin (B) can be produced in the same manner as known polyester production methods. For example, a component containing an alcohol component (X) and a carboxylic acid component (Y) is reacted in an inert gas (nitrogen gas, etc.) atmosphere at a reaction temperature of preferably 150 to 280°C, more preferably 160 to 250°C, More preferably, the reaction can be carried out at 170 to 235°C. In addition, the reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of ensuring the polycondensation reaction. It is also effective to reduce the pressure in order to improve the reaction rate at the final stage of the reaction.

At this time, an esterification catalyst can also be used if necessary. As the esterification catalyst, the same ones as the esterification catalysts exemplified for the crystalline polyester resin (A) can be used, and preferred ones are also the same.

The glass transition temperature (hereinafter abbreviated as Tg) of the amorphous polyester resin (B) is preferably 20 to 90°C, more preferably 40 to 80°C. If the temperature is 20° C. or higher, the heat-resistant storage stability is excellent, and if the temperature is 90° C. or lower, there is little inhibition on low-temperature fixing properties.

The acid value of the amorphous polyester resin (B) is preferably 0 to 75 mgKOH/g, more preferably 8 to 23 mgKOH/g from the viewpoint of charging property and heat-resistant storage stability.

The hydroxyl value of the amorphous polyester resin (B) is preferably from 0 to 120 mgKOH/g, more preferably from 1 to 55 mgKOH/g, from the viewpoint of chargeability and heat-resistant storage stability.

The number average molecular weight (hereinafter sometimes abbreviated as Mn) of the amorphous polyester resin (B) is preferably 1,000 to 100,000, more preferably 2 , 500 to 65,000.

The weight average molecular weight (hereinafter sometimes abbreviated as Mw) of the amorphous polyester resin (B) is preferably 2,000 to 200,000, more preferably 5 ,000 to 130,000.

The 1/2 drop temperature of the amorphous polyester resin (B) is preferably 80 to 170°C from the viewpoint of heat-resistant storage stability and low-temperature fixability, and more preferably 97 to 150°C.

Two or more types of amorphous polyester resin (B) with different 1/2 drop temperatures may be used in combination; one with a 1/2 drop temperature of 80°C or more and less than 110°C and one with a 110°C or more and less than 170°C. From the viewpoint of low-temperature fixing properties, the combination is preferred, and the combination of one with a 1/2 drop temperature of 85°C to 105°C and one with a 115°C to 160°C is more preferred.

The graft polymer (C) in the present invention is a polymer having a side chain branching from a polyolefin containing ethylene and/or propylene as an essential constituent monomer. Examples of polyolefins containing ethylene and/or propylene as essential constituent monomers include polyethylene and polypropylene.

The side chain branched from the polyolefin is a polymer whose constituent monomers are monomers having vinyl groups. The monomer having a vinyl group is not particularly limited as long as it forms a side chain branching from the polyolefin, and can be appropriately selected from known monomers depending on the purpose. For example, the following (1) ~(10) can be mentioned.
(1) Vinyl Hydrocarbons Vinyl hydrocarbons include (1-1) aliphatic vinyl hydrocarbons, (1-2) alicyclic vinyl hydrocarbons, and (1-3) aromatic vinyl hydrocarbons.
(1-1) Aliphatic vinyl hydrocarbons Examples of aliphatic vinyl hydrocarbons include alkenes and alkadienes.
Specific examples of alkenes include propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and other α-olefins.
Specific examples of alkadienes include butadiene, isoprene, 1,4-pentadiene, 1,6-heptadiene, and 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons Examples of alicyclic vinyl hydrocarbons include mono- or di-cycloalkenes and alkadienes, and specific examples include cyclohexene, (di)cyclopentadiene, and vinylcyclohexene. , ethylidene bicycloheptene, and terpenes (pinene, limonene, indene, etc.).
(1-3) Aromatic vinyl hydrocarbons Examples of aromatic vinyl hydrocarbons include styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and/or alkenyl) substituted products, specifically α-methyl Styrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, vinylnaphthalene, etc. can be mentioned.

(2) Carboxyl group-containing vinyl monomers and their salts Carboxyl group-containing vinyl monomers and their salts include unsaturated monocarboxylic acids (salts) having 3 to 30 carbon atoms, unsaturated dicarboxylic acids (salts), their anhydrides, and their salts. Examples include monoalkyl (1 to 24 carbon atoms) esters or salts thereof.
Specifically, (meth)acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, Examples include carboxyl group-containing vinyl monomers such as citraconic acid, citraconic acid monoalkyl ester, and cinnamic acid, and metal salts thereof.

In the present invention, "(salt)" means a salt of a compound.
For example, an unsaturated monocarboxylic acid (salt) having 3 to 30 carbon atoms means an unsaturated monocarboxylic acid or a salt thereof.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters, and salts thereof Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters, and salts thereof include alkenesulfonic acids (salts) having 2 to 14 carbon atoms, styrene, Sulfonic acid (salt), C2-24 alkyl derivative of styrene sulfonic acid (salt), sulfo(hydroxy)alkyl-(meth)acrylate (salt), sulfo(hydroxy)alkyl-(meth)acrylamide (salt), Examples include sulfuric acid esters of alkylarylsulfosuccinic acid and polyoxyalkylene mono(meth)acrylate.
Specifically, vinylsulfonic acid, (meth)allylsulfonic acid, methylvinylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, sulfopropyl (meth)acrylate, 2-hydroxy-3-(meth)acryloxy Propylsulfonic acid, 2-(meth)acryloylamino-2,2-dimethylethanesulfonic acid, 2-(meth)acryloyloxyethanesulfonic acid, 3-(meth)acryloyloxy-2-hydroxypropanesulfonic acid, 2-( meth)acrylamido-2-methylpropanesulfonic acid, 3-(meth)acrylamido-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly(n=2 to 30) oxyalkylene (ethylene, Propylene, butylene: mono(meth)acrylate sulfate ester (may be individual, random, or block) [poly(n=5-15) oxypropylene monomethacrylate sulfate ester, etc.] and polyoxyethylene polycyclic phenyl ether sulfate ester, etc. It will be done.

(4) Phosphoric acid group-containing vinyl monomer and its salt:
Examples of the phosphoric acid group-containing vinyl monomer and its salt include (meth)acryloyloxyalkyl (carbon number 1 to 24) phosphoric acid monoester (salt) and (meth)acryloyloxyalkyl (carbon number 1 to 24) phosphonic acid (salt). can be mentioned.
Specific examples include 2-hydroxyethyl (meth)acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, and 2-acryloyloxyethylphosphonic acid.

Examples of the salts (2) to (4) above include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, and quaternary ammonium salts. can be mentioned.

(5) Hydroxyl group-containing vinyl monomer Hydroxyl group-containing vinyl monomers include hydroxystyrene, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, ( meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-buten-1,4-diol, propargyl alcohol, 2-hydroxyethyl propenyl ether and Examples include sucrose allyl ether.

(6) Nitrogen-containing vinyl monomer The nitrogen-containing vinyl monomer includes (6-1) amino group-containing vinyl monomer, (6-2) amide group-containing vinyl monomer, (6-3) nitrile group-containing vinyl monomer, (6- 4) A vinyl monomer containing a quaternary ammonium cation group and (6-5) a vinyl monomer containing a nitro group.
(6-1) As amino group-containing vinyl monomers, aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth)acrylamide , (meth)allylamine, morpholinoethyl (meth)acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N,N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, Examples include N-arylphenylene diamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.
(6-2) Vinyl monomers containing amide groups include (meth)acrylamide, N-methyl(meth)acrylamide, N-butylacrylamide, diacetone acrylamide, N-methylol(meth)acrylamide, N,N'-methylene- Examples include bis(meth)acrylamide, cinnamic acid amide, N,N-dimethylacrylamide, N,N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, and N-vinylpyrrolidone.
(6-3) Examples of the nitrile group-containing vinyl monomer include (meth)acrylonitrile, cyanostyrene, and cyanoacrylate.
(6-4) Examples of the quaternary ammonium cation group-containing vinyl monomer include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and diallylamine. Examples include quaternized products of vinyl monomers containing amine groups (those quaternized using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate).
(6-5) Examples of the nitro group-containing vinyl monomer include nitrostyrene.

(7) Epoxy group-containing vinyl monomer Examples of the epoxy group-containing vinyl monomer include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and p-vinylphenylpropylene oxide.

(8) Vinyl monomer containing halogen element Examples of the vinyl monomer containing halogen element include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromustyrene, dichlorostyrene, chloromethylstyrene, tetrafluoroethylene, fluoroacrylate, Examples include tetrafluorostyrene and chloroprene.

(9) Alkyl ester of (meth)acrylic acid, vinyl ester, vinyl (thio)ether, vinyl ketone (9-1) As the alkyl ester of (meth)acrylic acid, for example, an alkyl group having an alkyl group having 1 to 50 carbon atoms (Meth)acrylate [methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, etc.).
(9-2) Examples of the vinyl ester include vinyl butyrate, vinyl propionate, vinyl butyrate, and the like.
(9-3) Vinyl (thio)ethers include, for example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl Examples include 2-butoxyethyl ether, 3,4-dihydro 1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, and phenoxystyrene.
(9-4) Examples of the vinyl ketone include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.

(10) Other vinyl monomers Examples of other vinyl monomers include isocyanatoethyl (meth)acrylate and m-isopropenyl-α,α-dimethylbenzyl isocyanate.

In the synthesis of the graft polymer (C), one of the above vinyl monomers (1) to (10) may be used alone or in combination of two or more, and from the viewpoint of dispersibility, vinyl hydrocarbon , carboxyl group-containing vinyl monomers and their salts, nitrogen-containing vinyl monomers, and alkyl esters of (meth)acrylic acid are preferred, and more preferred are aromatic vinyl hydrocarbons, unsaturated monocarboxylic acids (salts) having 3 to 30 carbon atoms, Vinyl monomers containing a nitrile group, alkyl (meth)acrylates having an alkyl group having 1 to 50 carbon atoms, and more preferably styrene, acrylic acid, acrylonitrile, methyl methacrylate, and n-butyl acrylate.

The average SP value (solubility parameter) of the monomer constituting the side chain branched from the polyolefin, based on the mole fraction, is preferably 10.3 to 12.3 (cal/cm ³ ) ^1/2 . More preferably, it is 10.5 to 11.8 (cal/cm ³ ) ^1/2 . If the average value based on the molar fraction of SP value is 10.3 to 12.3, the graft polymer (C) has appropriate polarity and the dispersibility of the release agent and crystalline polyester resin (A) in the toner is improved. Becomes good. Note that the SP value in the present invention is determined by the method by Fedors [Polym. Eng. Sci. 14(2) 152, (1974)].

The weight proportion of the polyolefin in the graft polymer (C) is preferably 5 to 15% by weight based on the weight of (C) from the viewpoint of dispersibility. If it is 5% by weight or more, the dispersibility of the mold release agent and the crystalline polyester resin (A) is excellent, and if it is 15% by weight or less, there is little inhibition of low-temperature fixability.

The method for producing the graft polymer (C) is, for example, by dissolving or dispersing a polyolefin in a solvent such as toluene or xylene, heating it to 100°C to 200°C, and then adding a mixture of vinyl group-containing monomers to a peroxide-based polymer. This can be carried out by dropping the polymerization together with an initiator (benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxide benzoate, etc.) and then distilling off the solvent.

The acid value of the graft polymer (C) is preferably 80 mgKOH/g or less, more preferably 63 mgKOH/g or less, still more preferably 0.5 mgKOH/g or less. When the acid value is 80 mgKOH/g or less, the graft polymer (C) becomes hydrophobic and has excellent heat-resistant storage stability.

The number average molecular weight (hereinafter abbreviated as Mn) of the graft polymer (C) is preferably 1,000 to 4,000, more preferably 1,500 to 3,000. If it is 1,000 or more, the heat-resistant storage stability is excellent, and if it is 4,000 or less, there is little inhibition on low-temperature fixing properties.

The weight average molecular weight (hereinafter abbreviated as Mw) of the graft polymer (C) is preferably 8,000 to 40,000, more preferably 8,000 to 39,400. If it is 8,000 or more, it has excellent heat-resistant storage stability, and if it is 40,000 or less, there is little inhibition on low-temperature fixing properties.

The 1/2 drop temperature of the graft polymer (C) is preferably 90 to 140°C, more preferably 110 to 130°C.

The weight ratio of the crystalline polyester resin (A) in the toner binder of the present invention is preferably 5 to 50% by weight from the viewpoint of low-temperature fixability and fixing strength.

The weight proportion of the amorphous polyester resin (B) in the toner binder of the present invention is preferably 47 to 92% by weight from the viewpoint of heat-resistant storage stability.

The weight proportion of the graft polymer (C) in the toner binder of the present invention is preferably 3 to 15% by weight from the viewpoint of dispersibility.

The weight ratio (A/B) of the crystalline polyester resin (A) and the amorphous polyester resin (B) in the toner binder of the present invention is 10/90 to 40 from the viewpoint of low temperature fixability and storage stability. /60 is preferable.

Next, a method for manufacturing the toner binder of the present invention will be explained.
The method for producing the toner binder is not particularly limited as long as the crystalline polyester resin (A), the amorphous polyester resin (B), and the graft polymer (C) are uniformly mixed, and any known mixing method may be used. Examples of the method include powder mixing, melt mixing, and solvent mixing. Further, the crystalline polyester resin (A), the amorphous polyester resin (B), and the graft polymer (C) may be mixed together with other necessary toner raw materials when producing the toner.

Examples of mixing devices for powder mixing include Henschel mixer, Nauta mixer, and Banbury mixer. A Henschel mixer is preferred.
Examples of the mixing device for melt-mixing include batch-type mixing devices such as reaction vessels and continuous-type mixing devices. A continuous mixing device is preferred in order to mix uniformly in a short time at an appropriate temperature. Examples of continuous mixing devices include static mixers, extruders, continuous kneaders, three rolls, and the like.
As a method of solvent mixing, the crystalline polyester resin (A), the amorphous polyester resin (B), and the graft polymer (C) are dissolved or dispersed in an organic solvent (ethyl acetate, THF, acetone, etc.) and homogenized. After that, there are methods of removing solvent and pulverizing, or dissolving or dissolving the crystalline polyester resin (A), amorphous polyester resin (B), and graft polymer (C) in an organic solvent (ethyl acetate, THF, acetone, etc.). Examples include a method of dispersing, dispersing in water, and then granulating and removing the solvent.

The toner binder obtained by the above manufacturing method may be used to obtain resin particles for toner.
The content of the toner binder in the resin particles is preferably 30 to 97% by weight, more preferably 42 to 96% by weight, even more preferably 50 to 95% by weight, based on the weight of the resin particles.

The resin particles can be mixed with various known additives such as a coloring agent, a mold release agent, a charge control agent, and a fluidizing agent, if necessary.

As the colorant, it is preferable to contain one or more types selected from the group consisting of a black colorant, a blue colorant, a red colorant, and a yellow colorant. As the colorant, all dyes, pigments, etc. used as colorants for toners can be used.
Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, and 114, etc.), pigment yellow (12, 14, 17, and 83, etc.), India first orange, Irgasin Red, Paranitaniline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22 and 48.2, etc.), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Solvent Blue (25, 94, 60 and 15.3 etc.), Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B and Oil Pink Examples include OP. Further, if necessary, magnetic powder (ferromagnetic metal powder such as iron, cobalt, and nickel, and compounds such as magnetite, hematite, and ferrite) may be included to serve as a coloring agent.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, based on a total of 100 parts by weight of the toner binder of the present invention. When using magnetic powder, the content of the magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, based on the total 100 parts by weight of the toner binder.

As mold release agents, natural waxes (beeswax, carnauba wax, montan wax, etc.), petroleum waxes (paraffin wax, microcrystalline wax, petrolatum, etc.), synthetic waxes (Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oxidized polyethylene wax, etc.) can be used. wax and oxidized polypropylene wax, etc.), and synthetic ester waxes (fatty acid esters synthesized from fatty acids with 10 to 30 carbon atoms and alcohols with 10 to 30 carbon atoms, etc.), and from the group consisting of these mold release agents. It is preferable to contain one or more selected types. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 1 to 10% by weight, based on a total of 100 parts by weight of the toner binder of the present invention. be.

The charge control agent may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent, such as nigrosine dye, triphenylmethane dye containing a tertiary amine as a side chain, class ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatics Examples include ring-containing polymers. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, based on a total of 100 parts by weight of the toner binder of the present invention. .5% by weight.

Examples of the fluidizing agent include silica, titania, alumina, fatty acid metal salts, silicone resin particles, and fluororesin particles, and two or more types may be used in combination. Silica is preferred from the viewpoint of toner chargeability. Further, the silica is preferably hydrophobic silica from the viewpoint of toner transferability. 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 a total of 100 parts by weight of the toner binder of the present invention. It is.

Further, the total weight of additives such as colorants, mold release agents, charge control agents, and fluidizing agents may be 3 to 70% by weight, preferably 4 to 58% by weight, and more preferably 4 to 58% by weight, based on the weight of the resin particles. Preferably it is 5 to 50% by weight.

The volume average particle diameter (D50) of the resin particles is preferably 1 to 15 μm, more preferably 2 to 10 μm, particularly preferably 3 to 7 μm. By setting it within the above range, low-temperature fixing properties will be good.

There are no particular restrictions on the method for producing resin particles, and there are known kneading and pulverization methods, suspensions described in Japanese Patent Publication No. 36-10231, Japanese Patent Application Laid-Open No. 59-53856, and Japanese Patent Application Laid-Open No. 59-61842. Polymerization methods, emulsion polymerization methods such as the soap-free polymerization method in which the monomer is soluble and is directly polymerized in the presence of a water-soluble polymerization initiator to produce toner, interfacial polymerization methods such as the microcapsule manufacturing method, In-site polymerization method, coacervation method, as disclosed in JP-A-62-106473 and JP-A-63-186253, at least one type of fine particles are aggregated to obtain a desired particle size. Products obtained by the emulsion aggregation method, the dispersion polymerization method characterized by monodispersity, the dissolution suspension method in which the necessary resins are dissolved in a water-insoluble organic solvent and then turned into resin particles in water, and the ester extension polymerization method. Alternatively, it may be produced by a method of dispersing in carbon dioxide in a supercritical state.

When resin particles are used as toner, they are mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with resin (acrylic resin, silicone resin, etc.) as necessary. Used as a developer for electrical latent images. When carrier particles are used, the weight ratio of toner to carrier particles is preferably 1/99 to 99/1. Furthermore, an electrical latent image can also be formed by friction with a member such as a charging blade instead of the carrier particles.
Note that the toner does not need to contain carrier particles.

The toner is fixed on a support (paper, polyester film, etc.) by a copying machine, printer, etc., and is used as a recording material. As a method for fixing to the support, known hot roll fixing methods, flash fixing methods, etc. can be applied.

Toners are used to develop electrostatic images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like. More specifically, it is used for developing electrostatic images or magnetic latent images suitable for full-color printing.

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

Physical property values of the crystalline polyester resin, amorphous polyester resin, graft polymer, toner, etc. were measured by the following method.

<Peak top temperature of endothermic peak of crystalline polyester resin>
Measurement was performed using a differential scanning calorimeter {for example, "DSCQ20" [manufactured by TA Instruments Co., Ltd.]}. The crystalline polyester resin was heated from 30°C to 180°C at 10°C/min for the first time, then cooled from 180°C to 0°C at 10°C/min, and then from 0°C to 180°C. The temperature showing the top of the endothermic peak in the second heating process when the temperature was raised to 180° C. for the second time under the condition of 10° C./min was defined as the peak top temperature of the endothermic peak of the crystalline polyester resin.

<Amount of endotherm at endothermic peak of crystalline polyester resin>
In the DSC curve of the second heating process observed under the same measurement conditions as the measurement of the peak top temperature of the endothermic peak, the point closest to the peak on the baseline below the endothermic start temperature (T0) of the endothermic peak. The endothermic amount at the endothermic peak having the peak top temperature of the endothermic peak was calculated by drawing a straight line connecting the point closest to the peak on the baseline above the end point temperature of the endothermic peak.

<Half width of endothermic peak of crystalline polyester resin>
The temperature width of the peak at half the peak height from the baseline of the endothermic peak was defined as the half width of the endothermic peak.

<Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was measured under the following conditions using a sample solution obtained by dissolving a sample in tetrahydrofuran (THF) and filtering out insoluble matter through a glass filter.
Equipment: HLC-8120 manufactured by Tosoh Corporation
Column: TSK GEL GMH6 2 pieces [manufactured by Tosoh Corporation]
Measurement temperature: 40℃
Sample solution: 0.25% by weight THF solution Solution injection amount: 100μl
Detection device: Refractive index detector Reference material: 12 points of TSK standard POLYSTYRENE manufactured by Tosoh Corporation (molecular weight 500 1,050 2,800 5,970 9,100 18,100 37,900 96,400 190,000 355,000 1,090,000 2,890,000)

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

<1/2 temperature drop>
Using a constant test force extrusion type capillary rheometer flow tester {manufactured by Shimadzu Corporation, CFT-500D}, while heating 1 g of the measurement sample at a heating rate of 6°C/min, a plunger of 1.96 MPa was applied. Apply a load, extrude through a nozzle with a diameter of 1 mm and a length of 1 mm, and draw a graph of "plunger descent amount (flow value)" and "temperature", which corresponds to 1/2 of the maximum plunger descent amount. The temperature at which the sample was measured was read from the graph, and this value (the temperature when half of the measurement sample flowed out) was defined as the 1/2 drop temperature.

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

<Toner volume average particle size (D50) (μm), number average particle size (μm), particle size distribution (volume average particle size/number average particle size)>
Measurement was performed using a Coulter counter [trade name: Multisizer III (manufactured by Beckman Coulter, Inc.)].
First, 0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) as a dispersant was added to 100 to 150 mL of ISOTON-II (manufactured by Beckman Coulter), which is an electrolytic aqueous solution. Furthermore, 2 to 20 mg of the measurement sample was added, and the electrolyte in which the sample was suspended was dispersed for about 1 to 3 minutes using an ultrasonic disperser. The number was measured and the volume distribution and number distribution were calculated. From the obtained distribution, the volume average particle diameter (D50) (μm), number average particle diameter (μm), and particle size distribution (volume average particle diameter/number average particle diameter) of the toner were determined.

<Production Example 1> [Synthesis of crystalline polyester resin (A-1)]
<Synthesis of crystal part (a1)>
231 parts (50 mol%) of 1,12-dodecanediol, 259 parts (58 mol%) of dodecanedioic acid, and behenyl alcohol were placed in a reaction tank equipped with a cooling tube, heating/cooling device, thermometer, stirrer, and nitrogen introduction tube. 10 parts (1 mol %) and 1.5 parts of titanium dihydroxybis(triethanolaminate) as a condensation catalyst were added, and the mixture was reacted at 170° C. under a nitrogen stream for 8 hours while distilling off the produced water. Next, while gradually raising the temperature to 220°C, the reaction was carried out for 4 hours under a nitrogen stream while distilling off the generated water, and further the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa until the acid value was 1 mgKOH/g. I took it out when it arrived. The resin taken out was cooled to room temperature and then crushed to form particles to obtain a crystal part (a1). The weight average molecular weight (Mw) of the crystal part (a1) is 39,000, the peak top temperature (Tm) of the endothermic peak is 84 ° C., the amount of heat absorbed at the endothermic peak is 116 J/g, the acid value is 1 mgKOH/g, and the hydroxyl value is It was 6mgKOH/g.

<Synthesis of amorphous part (a2)>
In a separate reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 153 parts (19 mol %) of bisphenol A/PO 2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P"), 209 parts (29 mol%) of bisphenol A/EO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BPE-20"), 132 parts (41 mol%) of terephthalic acid, titanium dihydroxybis(triethanol) as a condensation catalyst. amine) and reacted while raising the temperature to 230°C under a reduced pressure of 0.5 to 2.5 kPa and distilling off the water produced until the acid value became less than 2 mgKOH/g. Made it react. The mixture was then cooled to 180° C., 6 parts (2 mol %) of trimellitic anhydride was added, reacted for 1 hour under normal pressure, and then taken out. The resin taken out was cooled to room temperature and then crushed to form particles to obtain an amorphous part (a2). The 1/2 drop temperature of the amorphous part (a2) is 97°C, the glass transition temperature (Tg) is 58°C, the acid value is 8mgKOH/g, the hydroxyl value is 55mgKOH/g, and the weight average molecular weight (Mw) is 5,000. was.

<Synthesis of crystalline polyester resin (A-1)>
500 parts of the crystalline part (a1) and 500 parts of the amorphous part (a2) were placed in a reaction tank equipped with a cooling tube, a heating/cooling device, a thermometer, a stirrer, and a nitrogen introduction tube, and the mixture was heated at 150°C under a nitrogen stream. Then, transesterification reaction was carried out for 30 hours. The resin taken out was cooled to room temperature and then ground into particles to obtain a crystalline polyester resin (A-1). The weight average molecular weight (Mw) of the crystalline polyester resin (A-1) is 11,400, the peak top temperature (Tm) of the endothermic peak is 78°C, the amount of heat absorbed at the endothermic peak is 56 J/g, and the half-width at the endothermic peak is 5. ℃, the acid value was 2 mgKOH/g, and the hydroxyl value was 27 mgKOH/g.

<Production Example 2> [Synthesis of crystalline polyester resin (A-2)]
After obtaining the crystalline part (a1) and the amorphous part (a2) in the same manner as in Production Example 1 except that the raw materials listed in Production Example 2 in Table 1 were used, 500 parts of the crystalline part (a1) and the amorphous part were obtained. 500 parts of part (a2) were placed in a reaction tank equipped with a cooling tube, a heating/cooling device, a thermometer, a stirrer and a nitrogen introduction tube, and transesterification was carried out at 150° C. under a nitrogen stream for 30 hours. The resin taken out was cooled to room temperature and then ground into particles to obtain a crystalline polyester resin (A-2). The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, half-width at the endothermic peak, acid value, and hydroxyl value of the obtained crystalline polyester resin are listed in Table 1.

<Production Example 3> [Synthesis of crystalline polyester resin (A-3)]
After obtaining the crystalline part (a1) and the amorphous part (a2) in the same manner as in Production Example 1 except that the raw materials listed in Production Example 3 in Table 1 were used, 200 parts of the crystalline part (a1) and the amorphous part were obtained. 800 parts of part (a2) were placed in a reaction tank equipped with a cooling tube, a heating/cooling device, a thermometer, a stirrer, and a nitrogen introduction tube, and the transesterification reaction was carried out at 150° C. under a nitrogen stream for 30 hours. The resin taken out was cooled to room temperature and then ground into particles to obtain a crystalline polyester resin (A-3). The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, half-width at the endothermic peak, acid value, and hydroxyl value of the obtained crystalline polyester resin are listed in Table 1.

<Production Example 4> [Synthesis of crystalline polyester resin (A-4)]
After obtaining the crystalline part (a1) and the amorphous part (a2) in the same manner as in Production Example 1 except that the raw materials listed in Production Example 4 in Table 1 were used, 700 parts of the crystalline part (a1) and the amorphous part were obtained. 300 parts of part (a2) were placed in a reaction tank equipped with a cooling tube, a heating/cooling device, a thermometer, a stirrer, and a nitrogen introduction tube, and transesterification reaction was carried out at 150° C. under a nitrogen stream for 30 hours. The resin taken out was cooled to room temperature and then ground into particles to obtain a crystalline polyester resin (A-4). The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, half-width at the endothermic peak, acid value, and hydroxyl value of the obtained crystalline polyester resin are listed in Table 1.

<Production Example 5> [Synthesis of crystalline polyester resin (A-5)]
After obtaining the crystalline part (a1) and the amorphous part (a2) in the same manner as in Production Example 1 except that the raw materials listed in Production Example 5 in Table 1 were used, 700 parts of the crystalline part (a1) and the amorphous part were obtained. 300 parts of part (a2) were placed in a reaction tank equipped with a cooling tube, a heating/cooling device, a thermometer, a stirrer, and a nitrogen introduction tube, and transesterification reaction was carried out at 150° C. under a nitrogen stream for 30 hours. The resin taken out was cooled to room temperature and then ground into particles to obtain a crystalline polyester resin (A-5). The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, half-width at the endothermic peak, acid value, and hydroxyl value of the obtained crystalline polyester resin are listed in Table 1.

<Comparative Production Example 1> [Synthesis of polyester resin (AR-1)]
A polyester resin (AR-1) was obtained in the same manner as in Production Example 1 <Synthesis of crystal part (a1)> except that the raw materials listed in Comparative Production Example 1 in Table 1 were used. The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, half-width at the endothermic peak, acid value, and hydroxyl value of the obtained polyester resin are listed in Table 1.

<Comparative Production Example 2> [Synthesis of polyester resin (AR-2)]
A polyester resin (AR-2) was obtained in the same manner as in Production Example 1 <Synthesis of amorphous part (a2)> except that the raw materials listed in Comparative Production Example 2 in Table 1 were used. The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, half-width at the endothermic peak, acid value, and hydroxyl value of the obtained polyester resin are listed in Table 1. Note that (AR-2) did not have an endothermic peak.

<Comparative Production Example 3> [Synthesis of polyester resin (AR-3)]
A polyester resin (AR-3) was obtained in the same manner as in Production Example 1 <Synthesis of amorphous part (a2)> except that the raw materials listed in Comparative Production Example 3 in Table 1 were used. The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, half-width at the endothermic peak, acid value, and hydroxyl value of the obtained polyester resin are listed in Table 1. Note that (AR-3) did not have an endothermic peak.

<Comparative Production Example 4> [Synthesis of polyester resin (AR-4)]
A polyester resin (AR-4) was obtained in the same manner as in Production Example 1 <Synthesis of crystal part (a1)> except that the raw materials listed in Comparative Production Example 4 in Table 1 were used. The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, half-width at the endothermic peak, acid value, and hydroxyl value of the obtained polyester resin are listed in Table 1.

Table 1 shows the composition and resin physical properties of the crystalline polyester resins (A) obtained in Production Examples 1 to 5 and the polyester resins (AR) obtained in Comparative Production Examples 1 to 4.

<Production Example 6> [Synthesis of amorphous polyester resin (B-1)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 193 parts (14.6 mol%) of bisphenol A/PO 2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P"), 539 parts (35.4 mol%) of bisphenol A/PO 3 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-3P"), 173 parts (26.7 mol%) of terephthalic acid, 67 parts of adipic acid ( 11.8 mol%), 86 parts (11.5 mol%) of trimellitic anhydride, and 3.6 parts of titanium dihydroxybis(triethanolaminate) as a condensation catalyst were reacted at 220°C, and the resulting water was The reaction was continued for 20 hours while distilling off. The reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa, and when the 1/2 temperature drop reached 150°C, it was taken out using a steel belt cooler. The resin taken out was pulverized into particles to obtain an amorphous polyester resin (B-1). The amorphous polyester resin (B-1) has a 1/2 drop temperature of 150°C, a glass transition temperature Tg of 60°C, an acid value of 23mgKOH/g, a hydroxyl value of 1mgKOH/g, and a weight average molecular weight Mw of 130,000. was.

<Production Example 7> [Synthesis of amorphous polyester resin (B-2)]
In a separate reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 324 parts (20.0 mol %) of bisphenol A/PO 2 molar adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BP-2P") were added. ), 443 parts (30.0 mol%) of bisphenol A/EO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Himer BPE-20"), 280 parts (47.7 mol%) of terephthalic acid, as a condensation catalyst Add 3.0 parts of titanium dihydroxybis(triethanolaminate) and react while raising the temperature to 230°C under a reduced pressure of 0.5 to 2.5 kPa while distilling off the water produced to obtain an acid value of 2 mgKOH. The reaction was carried out until the concentration was less than /g. The mixture was then cooled to 180° C., 14 parts (2.3 mol %) of trimellitic anhydride was added, reacted for 1 hour under normal pressure, and then taken out. The resin taken out was cooled to room temperature and then ground into particles to obtain an amorphous polyester resin (B-2). The 1/2 drop temperature of the amorphous polyester resin (B-2) is 97°C, the glass transition temperature (Tg) is 58°C, the acid value is 8mgKOH/g, the hydroxyl value is 55mgKOH/g, and the weight average molecular weight (Mw) was 5,000.

Table 2 shows the composition and resin physical properties of the amorphous polyester resin (B) obtained in Production Examples 6 and 7.

<Production Example 8> [Synthesis of graft polymer (C-1)]
An autoclave was charged with 300 parts of xylene and 100 parts of low molecular weight polyethylene (Sunwax 151P manufactured by Sanyo Chemical Industries, Ltd., softening point 107°C), and after purging with nitrogen, the temperature was raised to 165°C in a closed state with stirring. Acrylonitrile [manufactured by Nacalai Tesque Co., Ltd.] 100 parts, styrene [manufactured by Idemitsu Kosan Co., Ltd.] 850 parts, butyl acrylate 50 parts, di-t-butyl peroxide [Perbutyl D, manufactured by NOF Corporation, hereinafter the same] A mixed solution of 37 parts of xylene and 80 parts of xylene was added dropwise at 165° C. over 3 hours to polymerize, and the mixture was further maintained at this temperature for 30 minutes. Next, the solvent was removed to obtain a graft polymer (C-1). Graft polymer (C-1) has a 1/2 drop temperature of 112°C, a glass transition temperature (Tg) of 65°C, an acid value of 0mgKOH/g, a weight average molecular weight (Mw) of 19,200, and a side chain. The average SP value of the monomers based on the mole fraction was 10.9 (cal/cm ³ ) ^1/2 .

<Production Examples 9 to 13> [Synthesis of graft polymers (C-2) to (C-6)]
Graft polymers (C-2) to (C-6) were obtained in the same manner as Production Example 8 except that the raw materials listed in Production Examples 9 to 13 in Table 3 were used. The average value based on the mole fraction of the 1/2 drop temperature, glass transition temperature (Tg), acid value, weight average molecular weight (Mw), and SP value of the monomer constituting the side chain of the obtained graft polymer is It is listed in Table 3.

<Example 1> [Preparation of toner binder (D-1)]
20 parts of crystalline polyester resin (A-1), 30 parts of amorphous polyester resin (B-1), 70 parts of amorphous polyester resin (B-2), 5 parts of graft polymer (C-1), After preliminary mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Kakoki Co., Ltd.], the mixture was kneaded with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.] to obtain a toner binder (D-1). .

<Examples 2 to 10> [Preparation of toner binders (D-2) to (D-10)]
Toner binders (D-2) to (D-10) were obtained in the same manner as in Example 1 except that the raw materials listed in Examples 2 to 10 in Table 4 were used.

<Comparative Examples 1 to 6> [Preparation of toner binders (D'-1) to (D'-6)]
Toner binders (D'-1) to (D'-6) were obtained in the same manner as in Example 1, except that the raw materials listed in Comparative Examples 1 to 6 in Table 4 were used.

Table 4 shows the compositions and evaluation results of the toner binders (D) obtained in Examples 1 to 10 and the toner binders (D') obtained in Comparative Examples 1 to 6.

[Evaluation method]
Toners were prepared by the following method using the toner binders obtained in Examples 1 to 10 and Comparative Examples 1 to 6, and the dispersibility, low temperature fixing properties, charging properties, heat resistant storage stability, and fixing strength were evaluated. .
[Manufacture of toner]
100 parts of toner binder, 8 parts of pigment carbon black "MA-100" [manufactured by Mitsubishi Chemical Corporation] as a coloring agent, 4 parts of paraffin wax "HNP-9" [manufactured by Nippon Seirin Co., Ltd.] as a mold release agent , 1 part by weight of charge control agent "T-77" [manufactured by Hodogaya Chemical Co., Ltd.] was added, and after premixing using a Henschel mixer [FM10B, manufactured by Mitsui Miike Kakoki Co., Ltd.], a twin-screw kneader [( PCM-30 manufactured by Ikegai Co., Ltd.].
Next, it was finely pulverized using a supersonic jet pulverizer Labojet [manufactured by Nippon Pneumatic Industries Co., Ltd.], and then classified using an air classifier [MDS-I, manufactured by Nippon Pneumatic Industries Co., Ltd.] to determine the volume average particle size. Resin particles having a diameter of 5 μm and a particle size distribution of 1.2 were obtained. 1 part of hydrophobic silica "Aerosil R972" [manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent was mixed with 99 parts of the obtained resin particles in a sample mill to obtain a toner.

<Dispersibility> (Maximum particle size of crystalline polyester resin, average particle size of crystalline polyester resin)
A cross section of the toner observed with a transmission electron microscope (TEM) was prepared as follows. The obtained toner was embedded in a visible light curable embedding resin (D-800, manufactured by Nissin EM), cut into a 60 nm thick piece using an ultrasonic ultramicrotome (EM5, manufactured by Leica), and placed in a vacuum dyeing machine ( Ruthenium staining was performed using Filgen Co., Ltd.). Thereafter, the dispersion state of the crystalline polyester resin was observed from a cross section of the obtained toner using a transmission electron microscope (H7500, manufactured by Hitachi High-Technologies Corporation) at an accelerating voltage of 120 kV. Among the entire observed images, the crystalline polyester resin having the largest major axis was defined as the maximum particle size. In addition, image processing was performed on a randomly selected enlarged image (x1000) using the free software "image J" according to the following procedure, and the calculated "mean feret" was calculated as the average particle size of the crystalline polyester resin. did. Under these evaluation conditions, the maximum particle size of the crystalline polyester resin is preferably 1.0 μm or less, and the maximum particle size of the crystalline polyester resin is preferably 0.5 μm or less. Note that in the toner binders of Comparative Examples 4 and 5, no dispersion of the crystalline polyester resin could be confirmed.

1. image type → 8bit
2. line → analyze → set scale
→ known distance 5.0
3. process → binary → median filter 10
4. image → adjust → threshold
5. process → binary → fill hole
6. analyze particle
(set mesearements → feret diameter)

<Low temperature fixability> (MFT)
The toner was uniformly placed on the paper surface at a concentration of 0.6 mg/cm ² . At this time, the powder was placed on the paper using a printer without a heat fixing device. Other methods may be used as long as the powder can be placed uniformly at the above weight density. This paper was placed on a pressure roller at a fixing speed (heating roller circumferential speed) of 213 mm/sec and a fixing pressure (pressure roller pressure) of 10 kg/ ^cm2 , and the heating roller temperature ranged from 90 to 230°C in 5°C increments. A fixed image was created at each temperature. Next, the presence or absence of cold offset in each fixed image was visually confirmed in descending order of heating roller temperature, and the temperature at which cold offset no longer occurred is shown in Table 4 as MFT (° C.).
The lower the temperature at which cold offset does not occur, the better the low-temperature fixing properties are. Under these evaluation conditions, the MFT is generally preferably 125° C. or lower.

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

<Heat-resistant storage stability> (degree of agglomeration)
Mix 1 g of toner and 0.013 g of Aerosil R8200 (manufactured by Evonik Japan Co., Ltd.) in a shaker for 1 hour, put the mixture in an airtight container, let it stand for 48 hours in an atmosphere with a temperature of 45°C and a humidity of 80%, and then mix it with a powder tester. The degree of aggregation was measured and the heat-resistant storage stability was evaluated.
The lower the value of the cohesion test determined by the method below, the better the heat-resistant storage stability. Under this evaluation condition, it is preferably 3% or less.
Equipment: POWDER TESTER model PT-X (manufactured by Hosokawa Micron)
Sieve opening: 355μm, 250μm, 150μm
Vibration width: 1mm
Vibration time: 30 seconds Operation method: Set the sieves in the order of 355 μm in the upper stage, 250 μm in the middle stage, and 150 μm in the lower stage on the vibration table of the powder tester, place 1 g of toner on the upper sieve, and vibrate for 30 seconds at a vibration width of 1 mm. , measure the weight of toner remaining on each sieve.
Cohesion degree: Calculated from the weight of toner used for measurement and the weight of toner remaining after sieving.
Cohesion degree (%) = (U/N + M/N x 3/5 + L/N x 1/5) x 100
U: Weight of upper tier, M: Weight of middle tier, L: Weight of lower tier, N: Weight of sample (1 g)

<Fixing strength> (tape peeling)
Evaluation of low-temperature adhesion properties The fixing strength of the prepared MFT-fixed image was evaluated by a tape peel test. After applying a tape ("Scotch Mending Tape" manufactured by 3M) to the fixed image, the tape is peeled off and the image density (ID) of the image adhered to the tape is measured using a reflection densitometer (product name: "X-Rite"). model 404, manufactured by X-Rite). The smaller the image density (value) of the attached image, the higher the fixing strength. Under this evaluation condition, it is preferably 0.2 or less.

<Fixing strength> (Pencil hardness)
The MFT fixed image created in the above low-temperature low adhesion evaluation was applied with a 10 g load from directly above a pencil fixed at an angle of 45 degrees in accordance with JIS K5600-5-4 (1999). A scratch hardness test was conducted using a manual scratching method, and the image strength was evaluated based on the pencil hardness without scratches. The higher the pencil hardness, the better the image strength. Generally, it is preferable that it is HB or more.

As is clear from the evaluation results in Table 4, toner binders (D-1) to (D-10) had good dispersibility, and excellent results were obtained in all performance evaluations.
On the other hand, toner binders (D'-1) to (D'-6) did not have sufficient dispersibility and were poor in several other performance items.

The toner binder of the present invention can be suitably used as an electrophotographic toner used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like.
Furthermore, it is suitable for use as additives for paints, additives for adhesives, particles for electronic paper, etc.

Claims (6)

A toner binder containing a crystalline polyester resin (A), an amorphous polyester resin (B), and a graft polymer (C), wherein the crystalline polyester resin (A) contains an alcohol component (x) and a carboxylic acid component ( y) as a raw material, the alcohol component (x) contains an aliphatic diol (x1) having 2 to 36 carbon atoms, and the content of (x1) in (x) is ( 20 to 80 mol% based on the total number of moles of x), the carboxylic acid component (y) contains an aliphatic dicarboxylic acid (y1) having 4 to 36 carbon atoms, The content is 20 to 80 mol% based on the total number of moles of (y), and the peak top temperature (Tm) of the endothermic peak measured by a differential scanning calorimeter (DSC) of the crystalline polyester resin (A) is ) is 50°C to 85°C, the half width of the endothermic peak of the crystalline polyester resin (A) is 7°C or less, and the graft polymer (C) contains ethylene and/or propylene as an essential constituent monomer. A toner binder that is a polymer having side chains branched from a polyolefin. The toner binder according to claim 1, wherein the crystalline polyester resin (A) has an endothermic amount of 20 to 90 J/g based on an endothermic peak measured by a differential scanning calorimeter (DSC). The crystalline polyester resin (A) is a resin obtained by a transesterification reaction between a crystalline part (a1) and an amorphous part (a2), and the crystalline part (a1) and the amorphous part (a2) The toner binder according to claim 1, which has a weight ratio (a1/a2) of 20/80 to 70/30. The toner binder according to claim 1, wherein the weight ratio (A/B) of the crystalline polyester resin (A) and the amorphous polyester resin (B) is 10/90 to 40/60. The graft polymer (C) is a polymer of a monomer whose side chain has a vinyl group, and the average value based on the molar fraction of the SP value of the monomer is 10.3 to 12.3 (cal/ The toner binder according to claim 1, wherein the toner binder has a particle size of ^1/2 cm ³ ). The amorphous polyester resin (B) is a polyester resin obtained by reacting an alcohol component (X) and a dicarboxylic acid component (Y) as raw materials, and the alcohol component (X) is an alkylene oxide adduct of bisphenol A ( The toner binder according to claim 1, containing X1).