JP2019049702A - Toner binder and toner composition - Google Patents

Abstract

To provide a toner binder that can achieve both low-temperature fixability and heat-resistant storage stability and is excellent in image quality stability in continuous copying, and a toner composition.SOLUTION: A toner binder contains a polyester resin (A) that is a reactant of a polyol component (x) and a polycarboxylic acid component (y). The polycarboxylic acid component (y) contains at least one selected from the group consisting of an alkylsuccinic acid (y10) having a branched alkyl group having two or more methyl groups and 15 to 32 carbon atoms, an anhydride (y11) of the (y10), an alkenylsuccinic acid (y20) having a branched alkenyl group having two or more methyl groups and 15 to 32 carbon atoms, and an anhydride (y21) of the (y20); the total number of moles of the (y10), (y11), (y20), and (y21) is 3 to 50 mol% based on the total number of moles of the (y).SELECTED DRAWING: None

Description

  The present invention relates to toner binders and toner compositions.

In recent years, the need for environmental impact reduction (energy saving) for copying machines, printers, etc. has become increasingly strong, and development of a toner capable of achieving both low temperature fixability and heat resistant storage stability is required as a toner satisfying this need. ing.
As one of the means for improving the low temperature fixability of the toner, a method using wax is mentioned. However, due to the poor compatibility between the wax and the polyester resin, the wax is not uniformly dispersed in the toner, and a lump of wax bleeds out to the toner surface, resulting in deterioration of the heat-resistant storage stability of the toner. There is a problem that the improvement effect of fixability becomes small.
Patent Document 1 discloses a toner containing an alkylsuccinic acid and / or an alkenylsuccinic acid having a limited number of carbon atoms and a structure as a monomer of a polyester resin, as a countermeasure for improving the dispersibility of a wax. Although both the heat resistance and the storage stability have some effect, the image quality stability during continuous copying is not sufficient, and further improvement of performance is desired.

JP, 2016-38449, A

  An object of the present invention is to provide a toner binder and toner composition which can achieve both low temperature fixing ability and heat resistant storage stability and is excellent in image quality stability at the time of continuous copying.

The present inventors arrived at the present invention as a result of earnest studies to solve these problems. That is, the present invention is the following two inventions.
A toner binder comprising a polyester resin (A) which is a reaction product of a polyol component (x) and a polycarboxylic acid component (y), wherein the polycarboxylic acid component (y) has a branched alkyl group (r1) And an alkyl succinic acid (y10) having 15 to 32 carbon atoms of (r1), a branched alkyl group (r2), and an alkyl succinic anhydride (y11) having 15 to 32 carbon atoms of (r2), a branched Alkenylsuccinic acid (y20) having alkenyl group (r3) and having 15 to 32 carbon atoms of (r3) and branched alkenyl group (r4) and alkenylsuccinic acid having 15 to 32 carbon atoms of (r4) Acid anhydride (y21), mono or diester of (y10) and aliphatic monoalcohol having 1 to 4 carbon atoms, and mono or diester of (y20) and aliphatic monoalcohol having 1 to 4 carbon atoms (R1), (r2), (r3) and (r4) each have two or more methyl groups, and (y10), (y11), (y20) and The toner binder comprises a toner binder having a total number of moles of (y21) of 3 to 50 mole% based on the total number of moles of (y), and a toner composition containing the toner binder and a colorant.

  According to the present invention, it is possible to provide both a low temperature fixability and a heat resistant storage stability, and to provide a toner binder and a toner composition excellent in image quality stability in continuous copying.

Hereinafter, the present invention will be described in detail.
The polyester resin (A) used in the present invention is a reaction product of the polyol component (x) and the polycarboxylic acid component (y).

Examples of the polyol component (x) include diols and polyols having 3 to 8 or 9 or more valences.
As the diol, alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,6 9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,18-octadecanediol, 1,22-docosanediol, 1,30-triacontanediol etc.), having 4 to 36 carbon atoms Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol etc.), alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol and Primed bisphenol A etc., alkylene oxide adducts of the above-mentioned alicyclic diols (preferably with an addition mole number of 1 to 30), aromatic diols [monocyclic dihydric phenols (hydroquinones etc) and bisphenols etc] and the above aromatics Examples thereof include alkylene oxide adducts of diols (preferably with an addition mole number of 2 to 30).
Among these, from the viewpoint of low-temperature fixability and heat resistant storage stability, alkylene glycols having 2 to 36 carbon atoms and aromatic diols are preferable, and alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are more preferable.
In the alkylene oxide, the carbon number of the alkylene group is preferably 2 to 4, and the alkylene oxide is ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3-, 1, Preferred are 3- or iso-butylene oxide and tetrahydrofuran.

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

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

  Specific 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'-diethyl bisphenol F etc. are mentioned, and these can also use 2 or more types together.

  As the alkylene oxide to be added to these bisphenols, an alkylene oxide having 2 to 4 carbon atoms is preferable, and specifically, ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), propylene oxide (Hereinafter, “propylene oxide” may be abbreviated as PO), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran (hereinafter sometimes described as THF), and These 2 or more types of combined use is mentioned. Among these, preferred is EO and / or PO. The addition mole number of AO is preferably 2 to 30 moles, more preferably 2 to 10 moles.

  Among the alkylene oxide adducts of bisphenols, those which are preferable from the viewpoint of toner fixability are EO and / or PO adducts of bisphenol A (average added mole number is preferably 2 to 4, more preferably 2 to 3). is there.

  Examples of trihydric to trihydric polyols include trihydric aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydration products thereof [glycerin, trimethylolethane, trimethylolpropane, pentaerythritol] Sorbitol, sorbitan, polyglycerin and dipentaerythritol etc.], saccharides and derivatives thereof (sucrose and methyl glucoside etc.), alkylene oxide adducts of the above-mentioned aliphatic polyhydric alcohols (AO addition mole number is preferably 1 to 4) 30), alkylene oxide adducts of trisphenols (such as trisphenol PA) (preferably 2 to 30 in terms of added moles of AO), novolak resins (phenol novolak and cresol novolac etc. are included, and the average degree of polymerization is 3 -60) alkylene oxide Id adduct (preferably as an additional molar number of AO is 2 to 30), and the like.

  Examples of the polyol having 9 or more valences include aliphatic polyhydric alcohols having 3 to 36 carbon atoms and having 9 or more carbon atoms (alkane polyols and intramolecular or intermolecular dehydration products thereof [glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, , Sorbitan, polyglycerin and dipentaerythritol etc.), saccharides and derivatives thereof (sucrose and methyl glucoside etc.), alkylene oxide adducts of the above-mentioned aliphatic polyhydric alcohols (preferably 1 to 30 as the added mole number of AO) And alkylene oxide adducts of trisphenols (such as trisphenol PA) (preferably 2 to 30 as the added mole number of AO), novolak resins (phenol novolak and cresol novolac, etc.), and the average degree of polymerization is 3 to 60 ) Alkylene oxide Id adduct (preferably as an additional molar number of AO is 2 to 30), and the like.

  Among the polyol components (x), preferable ones from the viewpoint of coexistence of low temperature fixability and hot offset resistance are alkylene glycols having 2 to 12 carbon atoms, and alkylene oxide adducts of bisphenols (addition molar number of AO is 2 to 30) ), Alkylene oxide adducts of trivalent to trivalent or pentavalent aliphatic polyhydric alcohols (addition molar number of AO: 2 to 30) and alkylene oxide adducts of novolac resin (addition molar number of AO: 2 to 30) And more preferred are alkylene glycols having 2 to 10 carbon atoms, alkylene oxide adducts of bisphenols (additional moles of AO are 2 to 5), trivalent to octavalent aliphatic polyhydric alcohols and alkylene oxides of novolac resins. It is an adduct (addition mole number 2 to 30 of AO), and particularly preferably, an alkyl having 2 to 6 carbon atoms. Glycol, alkylene oxide adduct of bisphenol A (additional mole number of AO is 2 to 5) and trivalent aliphatic polyhydric alcohol, most preferably alkylene oxide adduct of ethylene glycol, propylene glycol, bisphenol A It is the addition mole number 2-3 of AO and trimethylol propane.

The polycarboxylic acid component (y) of the polyester resin (A) used in the present invention is
Alkyl succinic acid (y10) having 15 to 32 carbon atoms having branched alkyl group (r1) and having 15 to 32 carbon atoms (r1), branched alkyl group having (r2) branched alkyl group (r2) and having 15 to 32 carbon atoms Succinic anhydride (y11), branched alkenyl group (r3), (r3) having 15 to 32 carbon atoms of alkenylsuccinic acid (y20) and branched alkenyl group (r4), (r4) C15-32 alkenyl succinic anhydride (y21), mono- or di-ester of (y10) and aliphatic mono-alcohol having 1-4 carbon atoms, and (y20) fatty having 1-4 carbon atoms (R1), (r2), (r3) and (r4) each have two or more methyl groups, containing at least one member selected from the group consisting of mono- or di-esters with monohydric monoalcohols, and (y10) , (Y11 And the total number of moles of (y20) and (y21) is 3 to 50 mole% based on the total number of moles of (y).

As said (y10) and said (y20), the compound etc. which are represented by following General formula (2) are mentioned, For example as said (y11) and said (y21), following General formula (3) And the like. R ¹ in the general formulas (2) and (3) is a C15-32 alkyl or alkenyl group containing two or more methyl groups.

Examples of the mono- or di-ester of (y10) and an aliphatic monoalcohol having 1 to 4 carbon atoms and the mono- or diester of (y20) and an aliphatic monoalcohol having 1 to 4 carbon atoms include The compound etc. which are represented by (4) are mentioned. The mono- or di-ester of (y10) and (y20) used (y10) and (y20) by removing an aliphatic monoalcohol having 1 to 4 carbon atoms after transesterification with a polyol component (x) The same polyester resin (A) as in the case can be obtained, and the same effect can be obtained. R ¹ in the general formula (4) is an alkyl or alkenyl group having 15 to 32 carbon atoms containing two or more methyl groups, and R ² and R ^{3 in} the general formula (4) have 1 to 4 carbon atoms It is an alkyl group.

The number of methyl groups possessed by the alkyl group possessed by (y10) and (y11) and the alkenyl group possessed by (y20) and (y21) is two or more from the viewpoint of heat resistant storage stability, preferably 3 to 3 4 Further, from the viewpoint of low temperature fixability and heat resistant storage stability, R ¹ in the general formulas (2), (3) and (4) is preferably an alkyl group having 15 to 25 carbon atoms or an alkenyl group, It is more preferable that it is the alkyl group or alkenyl group of several 15-18. When the carbon number of the alkyl group of the (y10) and the (y11) and the alkenyl group of the (y20) and the (y21) is less than 15 the low temperature fixability deteriorates, and if it exceeds 32, the heat resistant storage stability Is worse.
Although the reason for this effect is not clear, the alkylsuccinic acid (y10), alkylsuccinic anhydride (y11), alkenylsuccinic acid (y20) or alkenylsuccinic anhydride used as a monomer in the polyester (A) of the present invention It is presumed to be derived from the aliphatic carbon chain of (y21). The (y10), (y11), (y20) and (y21) having a carbon chain according to claim 1 has the affinity of polyester (A) and wax by the bulky and steric hindrance structure of the carbon chain. It can be enhanced. Therefore, it is considered that the bleeding out of the wax can be prevented, and the low temperature fixability, the heat resistant storage stability, and the image quality stability at the time of continuous copying are improved.

The average number of methyl groups possessed by R ¹ in the general formulas (2), (3) and (4) is the following condition for each of (y10), (y11), (y20) and (y21). The NMR is measured by the following equation to calculate the ratio of the peak derived from methyl group (δ = 0.8 to 0.9) to the total peak area derived from other than methyl group (methylene group and methine group). It can be determined by the method described in the calculation method.
< ¹ H-NMR measurement conditions>
Device: "AVANCE 300" manufactured by Bruker Biospin
Integration count: 16 times Sample amount: 10 mg
Solvent: DMSO-d6

<Method of calculating methyl group number>
(1) ¹ H-NMR measurement is performed under the above conditions, and the measurement integral intensity ratio [(methyl group derived peak area) / (total peak area other than methyl group)] is determined from the measurement result.
(2) The obtained measurement integral strength ratio and the theoretical integral strength ratio when the number of methyl radicals is X and X + 1 are compared to determine the number of methyl radicals X satisfying the following inequality 1 relationship. Note that X is an integer.
Theoretical integral intensity ratio in case of methyl radical number X <measured integral intensity ratio <theoretical integral intensity ratio in case of methyl radical number X + 1 (inequality 1)
(3) The measured integral intensity ratio and the number of methyl groups X are substituted into the following formula (1) to obtain the number of methyl groups.
Methyl group number = (measured integral intensity ratio−the theoretical integral intensity ratio in the case of methyl radical number X) / (the theoretical integral intensity ratio in the case of methyl radical number X + 1−the theoretical integral intensity ratio in the case of methyl radical number X) + X (Calculation formula 1 )

From the viewpoint of steric hindrance and the like, it is preferable that (y10), (y11), (y20) and (y21) be a reaction product of at least one selected from maleic acid and fumaric acid with an alkylene compound. Examples of the alkylene compound include those having 15 to 32 carbon atoms having two or more methyl groups, which are obtained by synthesizing from ethylene, propylene, isobutylene, normal butylene and the like, preferably tetramers of these, Pentamers, hexamers and the like can be used. As a synthesis method of these alkylene compounds, the methods described in JP-A-2015-34294, JP-A-2005-15383 and JP-A-1994-65110 can be used.
The alkylene compounds obtained by the methods described in JP-A-2015-34294, JP-A-2005-15383 and JP-A-1994-65110 have two or more methyl groups, and these alkylene compounds are reacted with maleic acid or fumaric acid. As a result, branched alkylene succinic acid having two or more methyl groups or an anhydride thereof is obtained.
The method of reacting the alkylene compound with at least one selected from maleic acid and fumaric acid is not particularly limited, and known methods can be used. From the viewpoint of easiness of production, a method obtained by mixing and heating the above-mentioned alkylene compound and maleic acid or fumaric acid is preferable. The reaction conditions can be referred to JP-A-2004-175804 and the like.

  Preferred as the above (y10) is a reaction product of propylene pentamer, propylene hexamer, butylene pentamer, hexene pentamer or hexentrimer with maleic anhydride, and preferred as the above (y11) Is an anhydride of what is preferable as said (y10). Preferred as the above (y20) are propylene pentamer, propylene hexamer, butylene pentamer, hexene pentamer or a reaction product of hexentrimer and maleic anhydride, and preferred as the above (y21) is the above (y20) Anhydrides of those preferred as

  The polycarboxylic acid component (y) of the polyester resin (A) used in the present invention contains polycarboxylic acid components other than the above (y10), (y11), (y20) and the above (y21). As polycarboxylic acid components other than said (y10), (y11), (y20) and said (y21), dicarboxylic acid and the polycarboxylic acid of 3 to 6 valences or 7 or more valences are mentioned. 1 type may be used for a polycarboxylic acid component (y), and 2 or more types may be used together.

  Examples of the dicarboxylic acids include alkanedicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, repalmic acid and sebacic acid), and alkened dicarboxylic acids having 4 to 50 carbon atoms (maleic acid and fumaric acid) , Citraconic acid, mesaconic acid, itaconic acid and glutaconic acid etc.), aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid and naphthalene dicarboxylic acid etc.) and vinyl polymers of unsaturated carboxylic acids (Alpha) -olefin / maleic acid copolymer etc. whose number average molecular weight is 450-10,000 etc. are mentioned.

Examples of the polycarboxylic acids having 3 to 6 or 7 or more valences include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexane tricarboxylic acid) Acids, etc., vinyl polymers of unsaturated carboxylic acids (styrene / maleic acid copolymers having a number average molecular weight of 450 to 10,000, styrene / acrylic acid copolymers, styrene / fumaric acid copolymers, etc.) It can be mentioned.
As polycarboxylic acid components (y) other than the above (y10), (y11), (y20) and the above (y21), anhydrides of these polycarboxylic acids, lower alkyl (1 to 4 carbon atoms) esters (methyl) Ester, ethyl ester, isopropyl ester etc.) may be used.

  Among the polycarboxylic acid components other than the above (y10), (y11), (y20) and the above (y21), alkanes having a carbon number of 2 to 50 are preferable from the viewpoint of achieving both low temperature fixability and hot offset resistance. Dicarboxylic acids, alkene dicarboxylic acids having 4 to 50 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms, and aromatic polycarboxylic acids having 9 to 20 carbon atoms, and more preferably adipic acid having 16 to 50 carbon atoms Alkenyl succinic acid, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid and combinations thereof, particularly preferably adipic acid, terephthalic acid, isophthalic acid, trimellitic acid and the like It is combined use. Anhydrides and lower alkyl esters of these acids are likewise preferred.

  The total number of moles of (y10), (y11), (y20) and (y21) contained in the polycarboxylic acid component (y) is 3 to 50 mole% based on the total number of moles of (y) Preferably it is 8-40 mol%, More preferably, it is 13-30 mol%. If the total number of moles of (y10), (y11), (y20) and (y21) is less than 3 mole% based on the total number of moles of (y), the low-temperature fixability is deteriorated, 50 If it exceeds mol%, the hot offsetting property is deteriorated.

In the present invention, the polyester resin (A) is obtained by polycondensation of the polyol component (x) and the polycarboxylic acid component (y). It does not restrict | limit especially as a manufacturing method of said (A), A well-known polyester manufacturing method can be used.
For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 240 ° C., more preferably 160 to 225 ° C., particularly preferably 170 to 220 ° C.

  An esterification catalyst can be used as needed at the time of polyester resin manufacture. Examples of esterification catalysts include tin-containing catalysts (such as dibutyltin oxide), antimony trioxide, and titanium-containing catalysts (titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, titanium dihydroxy bis (triethanolaminate) Titanium monohydroxy tris (triethanolaminate), titanyl bis (triethanolaminate), tan tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate etc.], zirconium-containing catalysts (zirconyl acetate etc.) and Zinc acetate etc. are mentioned. Among these, preferred is a titanium-containing catalyst. It is also effective to reduce the pressure to improve the reaction rate at the end of the reaction.

  The reaction ratio of the polyol component (x) to the polycarboxylic acid component (y) is preferably 2/1 to 1/2, more preferably 1., as the equivalent ratio [OH] / [COOH] of hydroxyl group and carboxyl group. It is 4/1 to 1 / 1.2.

The softening point (hereinafter sometimes referred to as Tm) of the polyester resin (A) used in the present invention is preferably 90 to 150 ° C., more preferably 100, from the viewpoint of hot offset resistance and low temperature fixability. It is -140 degreeC, More preferably, it is 110-130 degreeC.
Tm of said (A) can be adjusted with the molecular weight of said (A), and can be made into said preferable range by adjusting the peak top molecular weight of the following THF soluble part in a preferable range.

In the present invention, Tm of the polyester resin (A) can be measured by the following method.
<Method of measuring Tm of polyester resin (A)>
While heating 1 g of the measurement sample at a heating rate of 6 ° C./min using a high-rise flow tester {eg CFT-500 D, manufactured by Shimadzu Corporation), a load of 1.96 MPa is applied by the plunger, It extrudes from a nozzle of 1 mm in diameter and 1 mm in length, draws a graph of "Plunger drop amount (flow value)" and "temperature", and graph the temperature corresponding to 1/2 of the maximum drop amount of plunger. This value (temperature at which half of the measurement sample has flowed out) is taken as Tm.

The acid value of the polyester resin (A) is preferably 7 to 21 mg KOH / g, more preferably 8 to 13 mg KOH / g. When the acid value is 7 to 21 mg KOH / g, the emulsifiability becomes better when the above (A) is used as a chemical toner material.
The acid value of (A) can be adjusted by the feed ratio of the raw materials [reaction ratio of polyol component (x) and polycarboxylic acid component (y)] and reaction time. For example, when it is desired to increase the acid value, the feed ratio of the polycarboxylic acid component (y) is increased or the reaction time is shortened.
The acid value of (A) is measured by the method specified in JIS K 0070 (1992 version).

  The hydroxyl value of the polyester resin (A) is preferably 0 to 50 mg KOH / g, more preferably 5 to 40 mg KOH / g, and particularly preferably 10 to 30 mg KOH / g. The hydroxyl value of (A) can be measured by the method prescribed in JIS K 0070 (1992 version).

The glass transition temperature (hereinafter sometimes referred to as Tg) of the polyester resin (A) is preferably 45 to 75 ° C. When the Tg of (A) is 75 ° C. or less, the low temperature fixability is further improved, and when the Tg is 45 ° C. or more, the preservability is further improved.
In addition, Tg can be measured by the method (DSC method) prescribed | regulated to ASTMD3418-82 using Seiko Instruments Inc. product DSC20, SSC / 580.

  The peak top molecular weight (hereinafter sometimes referred to as Mp) of the THF soluble portion of the polyester resin (A) is preferably 2,000 to 15,000 from the viewpoint of achieving both toner durability and low-temperature fixability. And more preferably 6,000 to 12,000.

  In the present invention, the peak top molecular weight, number average molecular weight (hereinafter sometimes referred to as Mn) and weight average molecular weight (hereinafter sometimes referred to as Mw) of resins such as polyester resin are gel permeation chromatography. It can measure on condition of the following using (GPC).

Device (example): Tosoh Corp. HLC-8120
Column (one example): Two TSK GEL GMH6 (made by Tosoh Corp.)
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Injection volume: 100 μl
Detector: Refractive index detector Reference material: Tosoh Co., Ltd. product standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500 1,050 2,800 5,970 9,100 18,100 37,900 96,400 190,000 355,000 1,090,000 2,890,000)
In the measurement of molecular weight, a polyester resin is dissolved in THF, and the insoluble matter is filtered off with a glass filter to obtain a sample solution.

The toner composition of the present invention contains a toner binder containing a polyester resin (A) and a colorant.
As the colorant, all dyes, pigments and the like used as colorants for toner can be used. Specifically, carbon black, iron black, sudan black SM, fast yellow G, benzidine yellow, pigment yellow, indofirst orange, irgasine red, paranitroaniline red, toluidine red, carmine FB, pigment orange R, lake red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B, Oil Pink OP, etc. Or 2 or more types can be mixed and used. If necessary, magnetic powder (powder of a ferromagnetic metal such as iron, cobalt, nickel or the like or a compound such as magnetite, hematite, ferrite or the like) can be contained in combination with the function as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the toner binder of the present invention. When magnetic powder is used, it is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight.

  In the toner composition of the present invention, a wax can be added to improve low temperature fixability.

  As the wax to be added, hydrocarbon wax (w) having a melting point of 60 to 120 ° C. and polyolefin wax having a melting point of 120 to 170 ° C. can be used, and hydrocarbon wax (w) having a melting point of 60 to 120 ° C. is preferable.

  Examples of hydrocarbon wax (w) having a melting point of 60 to 120 ° C. include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, carnauba wax, montan wax, rice wax, low molecular weight polyethylene and the like.

  The content of the wax in the toner binder is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and still more preferably 1 to 10% by weight.

  The toner composition of the present invention may further contain additives such as a charge control agent and a fluidizing agent.

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, polymers containing quaternary ammonium bases, metal-containing azo dyes, copper phthalocyanine dyes And salicylic acid metal salts, boron complexes of benzyl acid, sulfonic acid group-containing polymers, fluorine-containing polymers, and halogen-substituted aromatic ring-containing polymers.

  The content of the charge control agent in the toner binder is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.5 to 7.5% by weight.

As a fluidizing agent, colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and the like can be mentioned.
The content of the fluidizing agent in the toner binder is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and still more preferably 0.1 to 4% by weight.

  The method for producing the toner composition of the present invention is not particularly limited, and any known production method can be used. For example, it can be obtained by dry blending the components constituting the toner except the fluidizing agent, and then melt-kneading it using a continuous kneader or the like.

The toner composition of the present invention can be coarsely pulverized, atomized and classified using a jet mill or the like, and mixed with a fluidizing agent to obtain a toner. The volume average particle size (D50) of the toner is preferably 5 to 20 μm. The volume average particle diameter (D50) of the toner can be measured using Coulter Counter [trade name: Multisizer III (manufactured by Coulter, Inc.)] or the like.
The obtained toner is mixed with carrier particles such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite and resin (such as acrylic resin and silicone resin) as necessary, and an electric latent image is formed. It is used as a developer of The weight ratio of toner to carrier particles is preferably 1/99 to 100/0. Also, instead of carrier particles, they can be rubbed with a member such as a charging blade to form an electric latent image.

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

  The present invention will be further described by the following examples, but the present invention is not limited thereto.

Preparation Example 1 Preparation of Fluorinated Zeolite Activator Carrier Used for Synthesis of Octene Oligomer Used for Alkenylsuccinic Acid
Preparation of a fluorinated zeolite activator carrier used in synthesis of an alkylene compound was carried out. First, it was fluorinated by impregnating it with an incipient wetness method using ammonium fluoride [Wako Pure Chemical Industries, Ltd.] equivalent to 10% by weight of zeolite "SYLOBEAD (R) [W.R. Grace"]. The material was dried in a vacuum furnace for 8 hours at 100 ° C. 10 g of the dried fluorinated zeolite was placed in a 4.45 cm quartz glass tube attached to the bottom of a sintered quartz disc and the disc dried air The temperature of the quartz glass tube is raised to a final temperature of about 450 ° C. at a rate of about 400 ° C./hour using an electric furnace to dry the zeolite in dry air. The by-produced ammonia was removed while fluorination for 3 hours, and then the zeolite was recovered, stored under dry nitrogen and used without exposure to the atmosphere.

Preparation Example 2 Synthesis of Alkylene Compound (Octene Oligomer) Used for Alkenylsuccinic Acid
Solid addition funnel in which 29.5 g of the fluorozeolite activator carrier obtained in Production Example 1 is charged in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe (same for the reaction vessel used in the following production examples). Attached. Next, the reaction vessel was purged with nitrogen and thoroughly dried by washing with tri-isobutylaluminum 16% by weight hexane solution (TIBA) [Tokyo Kasei Kogyo]. After removing the washed TIBA, 1.1 kg of 1-octene (Wako Pure Chemical Industries, Ltd.) was introduced into the reaction vessel through a cannula. The 1-octene was then heated to 95 ° C. Thereafter, 40.0 g of TIBA 16 wt% hexane solution and then 230 mg of 1,1'-dibutyl zirconocene dichloride [Tokyo Kasei Kogyo] dissolved in a minimum amount of 1-octene were added to the reaction vessel. Thereafter, when the entire amount of the fluorozeolite activator carrier was added while stirring, heat of reaction was generated. The reaction mixture was then heated to 95 ° C. and allowed to react for 6 hours. Thereafter, TIBA was neutralized with 1.74 g of water. Next, this product was filtered, charged in an empty reaction vessel, and subjected to vacuum distillation. The reaction vessel was heated to 150 ° C., stirring was started, and the degree of vacuum was gradually lowered so as not to bump to 0.7 kPa. Thereafter, the temperature was gradually raised, and the fraction at 180 to 200 ° C was recovered as an octene trimer, and the fraction at 220 to 240 ° C as an octene tetramer.

Preparation Example 3 Synthesis of Alkenyl Succinic Acid (y2-1)
In a reaction vessel, 163 parts by weight of maleic anhydride [Mitsui Chemical] and 837 parts by weight of the octene trimmer obtained in Production Example 2 were charged, and pressurized nitrogen substitution was repeated twice to 0.2 MPa. After raising the temperature to 60 ° C., stirring was started, and after raising the temperature to 215 ° C. over 3 hours, reaction was carried out for 7 hours. After completion of the reaction, the reaction was cooled to 150 ° C., and the degree of reduced pressure was gradually lowered so as not to bump to 0.7 kPa. Thereafter, the temperature was gradually raised and distillation under reduced pressure was performed at 0.7 kPa. The fraction up to 200 ° C. or less was recovered as an alkylene compound, 215 ° C. or more was recovered as (y2-1), and the number of methyl groups measured and the carbon chain length are shown in Table 1.

Preparation Example 4 Synthesis of Alkenylsuccinic Acid (y2-2)
In a reaction vessel, 127 parts by weight of maleic anhydride and 873 parts by weight of the octene tetramer obtained in Production Example 2 were charged, and pressurized nitrogen substitution was repeated twice to 0.2 MPa. After raising the temperature to 60 ° C., stirring was started, and after raising the temperature to 215 ° C. over 3 hours, reaction was carried out for 7 hours. After completion of the reaction, the reaction was cooled to 150 ° C., and the degree of reduced pressure was gradually lowered so as not to bump to 0.7 kPa. Thereafter, the temperature was gradually raised and distillation under reduced pressure was performed at 0.7 kPa. The fraction up to 210 ° C. or less was recovered as an alkylene compound, and 215 ° C. or more was recovered as (y2-2).

Preparation Example 5 Synthesis of Alkenylsuccinic Acid (y2-3)
In a reaction vessel, 237 parts by weight of maleic anhydride and 763 parts by weight of propylene pentamer (Parchem Fine & Chemicals) were charged, and pressurized nitrogen substitution was repeated twice to 0.2 MPa. After raising the temperature to 60 ° C., stirring was started, and after raising the temperature to 215 ° C. over 3 hours, reaction was carried out for 7 hours. After completion of the reaction, the reaction was cooled to 150 ° C., and the degree of reduced pressure was gradually lowered so as not to bump to 0.7 kPa. Thereafter, the temperature was gradually raised and distillation under reduced pressure was performed at 0.7 kPa. The fraction up to 195 ° C. or less was recovered as an alkylene compound, and the fraction up to 195 to 210 ° C. was recovered as (y2-3).

Preparation Example 6 Synthesis of Alkyl Succinic Acid (y1-1)
In the reaction layer, 250 parts by weight of the alkenyl succinic acid (y2-3) obtained in Production Example 5 and 750 parts by weight of acetone are charged, and 12.5 parts by weight of Raney nickel (manufactured by Kawaken Fine Chemical Co., Ltd .: NDHT-90) is added , Hydrogen gas was blown into there to 0.3MPa. The temperature was raised to 70 ° C. while stirring, and the reaction was carried out for 4 hours. After completion of the reaction, the reaction solution is cooled to room temperature, the degree of reduced pressure is gradually lowered so as not to bump to 0.7 kPa, and acetone is distilled off by reducing the pressure at 0.7 kPa for 4 hours or more, alkyl succinic acid (y1-1) I got

Preparation Example 7 Synthesis of Alkenylsuccinic Acid (y2-5)
In the reaction layer, 237 parts by weight of maleic acid [Mitsui Chemical] and 763 parts by weight of propylene pentamer were charged, and pressurized nitrogen substitution was repeated twice to 0.2 MPa. After raising the temperature to 60 ° C., stirring was started, and after raising the temperature to 215 ° C. over 3 hours, reaction was carried out for 7 hours. After completion of the reaction, the reaction was cooled to 150 ° C., and the degree of reduced pressure was gradually lowered so as not to bump to 0.7 kPa. Thereafter, the temperature was gradually raised and distillation under reduced pressure was performed at 0.7 kPa. The fractions up to 195 ° C. were recovered as the alkylene compound, and the fractions up to 195-210 ° C. were recovered as (y2-5).

Preparation Example 8 Synthesis of Alkyl Succinic Acid (y1-2)
In the reaction layer, 250 parts by weight of the alkenyl succinic acid (y2-5) obtained in Production Example 7 and 750 parts by weight of acetone are charged, and 12.5 parts by weight of Raney nickel (manufactured by Kawaken Fine Chemical Co., Ltd .: NDHT-90) is added , Hydrogen gas was blown into there to 0.3MPa. The temperature was raised to 70 ° C. while stirring, and the reaction was carried out for 4 hours. After completion of the reaction, the reaction solution is cooled to room temperature, the degree of reduced pressure is gradually lowered so as not to bump to 0.7 kPa, and acetone is distilled off by reducing the pressure at 0.7 kPa for 4 hours or more, alkyl succinic acid (y1-2) I got

Alkenylsuccinic acid (y2-1) to (y2-3), (y2-5) and alkylsuccinic acid (y1-1) to (y1-2) obtained in Preparation Examples and the following compounds used in Examples: The number of methyl groups and the carbon chain length are shown in Table 1.
・ Isooctadecenyl succinic anhydride (y2-4) [Tokyo Chemical Industry]
・ Rikassid DDSA (y2′-1) [New Japan Chemical, 3-dodecenyl succinic anhydride]
・ Rikashid OSA (y2'-2) [New Japan Chemical Industry, octenyl succinic anhydride]

Example 1 Synthesis of Polyester A1
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe (same for the reaction vessel used in the following production examples), the raw materials are charged at the compounding ratio described in Example 1 of Table 2 and heated up to 180 ° C. And allowed to react at normal pressure for 1 hour. Then, while raising the temperature to 215 ° C., the reaction was performed under a reduced pressure of 0.5 to 2.5 kPa. After reaching 215 ° C., the reaction was carried out under reduced pressure as it was, and when Tm reached the target value, it was taken out to obtain polyester A1. The Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester were measured by the methods described later, and the values are shown in Table 2.

Example 2 Synthesis of Polyester A2
A polyester A2 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 2 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 3 Synthesis of Polyester A3
A polyester A3 was obtained in the same manner as <Polyester Production Example 1> except that the raw materials described in Example 3 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 4 Synthesis of Polyester A4
A polyester A4 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 4 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 5 Synthesis of Polyester A5
A polyester A5 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 5 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 6 Synthesis of Polyester A6
Polyester A6 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 6 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 7 Synthesis of Polyester A7
Polyester A7 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 7 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 8 Synthesis of Polyester A8
A polyester A8 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 8 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 9 Synthesis of Polyester A9
A polyester A9 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 9 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 10 Synthesis of Polyester A10
A polyester A10 was obtained in the same manner as <Polyester Production Example 1> except that the raw materials described in Example 10 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 11 Synthesis of Polyester A11
A polyester A11 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 11 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 12 Synthesis of Polyester A12
A polyester A12 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 12 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 13 Synthesis of Polyester A13
A polyester A13 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 13 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 14 Synthesis of Polyester A14
A polyester A14 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 14 in Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

Example 15 Synthesis of Polyester A15
A polyester A15 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Example 15 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

<Comparative Example 1> [Synthesis of Polyester A'1]
A polyester A′1 was obtained in the same manner as <Polyester production example 1> except that the raw materials described in Comparative Example 1 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

<Comparative Example 2> [Synthesis of Polyester A'2]
A polyester A′2 was obtained in the same manner as in <Example 1 of producing a polyester> except that the raw material described in Comparative Example 2 of Table 2 was used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

<Comparative Example 3> [Synthesis of Polyester A'3]
Polyester A'3 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Comparative Example 3 of Table 2 were used. Table 2 shows the Tm, acid value, hydroxyl value, Tg, Mw and Mp of the obtained polyester.

In addition, the raw material used for manufacture of polyester is as follows.
・ Bisphenol A • PO2 molar adduct (BP-2P) [Sanyo Chemical Industries, Ltd.]
-Bisphenol A · PO 3 mol adduct (BP-3P) [Sanyo Chemical Industries, Ltd.]
-Bisphenol A · EO 2 molar adduct (BPE-20) [Sanyo Chemical Industries, Ltd.]
・ Trimethylolpropane (TMP) [Mitsubishi Gas Chemical]
-Terephthalic acid [Mitsui Chemical]
・ Isophthalic acid [Mitsubishi Gas Chemical]
Anhydrous trimellitic acid [Hyakukawa Chemical Co., Ltd.]
-Titanium diisopropoxy bis triethanolaminate [Organics TC-400 manufactured by Matsumoto Fine Chemicals Co., Ltd.]

<Method of measuring Tm of polyester resin (A)>
A load of 1.96 MPa is applied by the plunger while heating a 1 g measurement sample at a heating rate of 6 ° C./min using a high-rise flow tester [CFT-500 D, manufactured by Shimadzu Corporation], and the diameter is From a 1 mm long and 1 mm long nozzle, draw a graph of “Plunger drop amount (flow value)” and “temperature”, and graph the temperature corresponding to 1⁄2 of the maximum drop amount of the plunger This value (temperature at which half of the measurement sample flowed out) was taken as Tm.

<Method of measuring acid value and hydroxyl value of polyester resin (A)>
It measured by the method prescribed | regulated to JISK0070 (1992 version).

<Method of measuring Tg of polyester resin (A)>
It measured by the method (DSC method) prescribed | regulated to ASTMD3418-82 using Seiko Instruments Inc. make DSC20, SSC / 580.

<Method of measuring Mp and Mw of polyester resin (A)>
Device (example): Tosoh Corp. HLC-8120
Column (one example): Two TSK GEL GMH6 (made by Tosoh Corp.)
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Injection volume: 100 μl
Detector: Refractive index detector Reference material: Tosoh Co., Ltd. product standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500 1,050 2,800 5,970 9,100 18,100 37,900 96,400 190,000 355,000 1,090,000 2,890,000)
For measurement of molecular weight, a polyester resin was dissolved in THF, and the insoluble matter was filtered off with a glass filter to obtain a sample solution.

  Using the polyesters A1 to A15 obtained in the examples and A'1 to A'3 obtained in the comparative examples, toners were formed in the following procedure and evaluated.

  First, 100 parts of polyester, 6 parts of colorant, 7 parts of wax and 3 parts of wax dispersant were preliminarily mixed using a sample mill, and then they were kneaded by a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, after finely pulverizing using supersonic jet crusher Labojet (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), it is classified by an air flow classifier (MDS-I manufactured by Japan Pneumatic Mfg. Co., Ltd.), and particle diameter D50 is Toner particles of 7 μm were obtained. Subsequently, 100 parts by weight of the toner particles and 0.5 parts by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) were mixed by a sample mill to obtain a toner composition for evaluation of each polyester.

The colorant, wax and wax dispersant used in preparation of the toner composition are as follows.
Colorant: "Carbon Black MA-100" (Mitsubishi Chemical)
Wax: "FNP 0090" [Nippon Seiwa]
Wax dispersant: "Hymer WDA-1BE" [Sanyo Chemical Industries, Ltd.]

  With respect to the toner composition obtained by the above method, the low temperature fixability, the hot offset resistance, the heat resistant storage stability, and the image quality stability at the time of continuous copying were evaluated by the following methods. The evaluation results are shown in Table 2.

[Evaluation method]
[1] Low-Temperature Fixing Properties An unfixed image developed by using a commercial copying machine (AR 5030; manufactured by Sharp) using the above toner composition is evaluated using a fixing machine of a commercial copying machine (AR 5030; manufactured by Sharp) did. The fixing roller temperature at which the residual ratio of the image density measured with a Macbeth reflection densitometer RD-191 (manufactured by Macbeth Co., Ltd.) after rubbing the fixed image with a pad is 70% or more is defined as the lowest fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixability.
Judgment criteria
○: minimum fixing temperature 120 ° C. or less Δ: minimum fixing temperature 120 ° C. to 130 ° C.
X: Minimum fixing temperature 130 ° C. or higher

[2] Hot Offset Resistance The fixation was evaluated in the same manner as the above-described low temperature fixation evaluation method, and the presence or absence of the hot offset on the fixed image was visually evaluated. The fixing roll temperature at which the hot offset has occurred is taken as the hot offset generation temperature. The higher the hot offset occurrence temperature, the better the hot offset resistance.
Judgment criteria
○: Hot offset occurrence temperature 180 ° C. or more Δ: Hot offset occurrence temperature 160 ° C. to 180 ° C.
×: Hot offset occurrence temperature 160 ° C. or less

[3] Heat-Resistant Storage Properties The toner was allowed to stand in an atmosphere of 45 ° C. for 24 hours, the degree of blocking was visually judged, and the heat-resistant storage properties were evaluated according to the following judgment criteria.
Judgment criteria
○: no blocking occurred
Fair: Blocking has occurred in part.
X: Blocking has occurred on the whole.

[3] Stability of Image Quality in Continuous Copying 30 g of the toner composition and 800 g of a ferrite carrier (P-150, manufactured by Powdertech Co., Ltd.) were uniformly mixed to obtain a two-component developer. An unfixed image developed by using a commercial copying machine [AR 5030, manufactured by Sharp Corp.] using this developer, using a fixing unit of a commercial full color copying machine [LBP-2160, manufactured by Canon Inc.] , Fixed at a process speed of 80 mm / sec.

[Evaluation criteria]
○: good image even after continuous copying of 8,000 sheets Δ: slight deterioration in image quality (dirt on white background) observed after continuous copying on 8,000 sheets ×: after continuous copying on 8,000 sheets, in addition to white background dirt The image quality is clearly seen such as white streaks on the image

  As is clear from the evaluation results of Table 2, all the toners of the examples of the present invention obtained excellent results in all the performance evaluations. On the other hand, the polyester (A'1) of Comparative Example 1 using an alkenyl succinic acid having a carbon chain length of 12 has poor low-temperature fixability, and the polyester of Comparative Example 2 using an alkenyl succinic acid having a branch number of 1 Polyester (A'3) of Comparative Example 3 in which the low-temperature fixability, the heat-resistant storage stability, and the image quality stability during continuous copying are poor in (A'2), and the molar ratio of alkenylsuccinic acid in carboxylic acid is 55% In the case of 2.), the hot offset property, heat resistant storage stability, and image quality stability at the time of continuous copying were poor.

The toner binder and toner composition of the present invention are capable of achieving both low temperature fixability and heat resistant storage stability, and have excellent image quality stability in continuous copying, electrophotographic toner, electrostatic recording toner, electrostatic printing toner, etc. Can be provided.

Claims (3)

A toner binder comprising a polyester resin (A) which is a reaction product of a polyol component (x) and a polycarboxylic acid component (y),
The polycarboxylic acid component (y) has a branched alkyl group (r1) and has an alkylsuccinic acid (y10) having 15 to 32 carbon atoms (r1) and a branched alkyl group (r2), (r2) Have a C15-32 alkylsuccinic anhydride (y11), a branched alkenyl group (r3), and a (r3) C15-32 alkenyl succinic acid (y20) and a branched alkenyl group (r4) And (r4) an alkenyl succinic anhydride (y21) having 15 to 32 carbon atoms, a mono- or di-ester of (y10) and an aliphatic monoalcohol having 1 to 4 carbon atoms, and the above (y20) And at least one member selected from the group consisting of mono- or diesters of C1-C4 aliphatic monoalcohols, (r1), (r2), (r3) and (r4) each having a methyl group of 2 More than one ,
A toner binder, wherein the total number of moles of (y10), (y11), (y20) and (y21) is 3 to 50 mole% based on the total number of moles of (y).   The toner binder according to claim 1, wherein the softening point of the polyester resin (A) is 90 to 150 ° C., and the acid value is 7 to 21 mg KOH / g. A toner composition comprising the toner binder according to claim 1 and a colorant.