Toner binder

Abstract

To provide a toner binder excellent in dispersibility, low temperature fixability, chargeability, heat resistant storage stability and image intensity.SOLUTION: A toner binder includes a crystalline polyester resin being a polycondensate of an alcohol component (x), a carboxylic component (y) and a fluorine compound (z). A fluorine compound including the alcohol component (x) including a 2-24C aliphatic diol; the carboxylic component (y) including 2-24C aliphatic dicarboxylic acid and / or 8-20C aromatic dicarboxylic acid; and the fluorine compound (z) having a hydroxyl group and / or a carboxyl group is used as the toner binder.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a toner binder.

Background Art

[0002] In recent years, with the promotion of miniaturization, high speed, and high image quality of electrophotographic apparatuses, improvement of low-temperature fixability of toner has been strongly demanded from the viewpoint of energy saving such as reducing energy consumption in the fixing process. However, generally, when attempting to improve low-temperature fixability, heat-resistant storage stability decreases, and when attempting to improve heat-resistant storage stability, low-temperature fixability decreases. Therefore, low-temperature fixability and heat-resistant storage stability are in a trade-off relationship, and development of a toner binder that enables both low-temperature fixability and heat-resistant storage stability has been demanded. For example, for the purpose of achieving both low-temperature fixability and heat-resistant storage stability, a toner composition containing a polyester-based toner binder that can improve low-temperature fixability while maintaining heat-resistant storage stability from the melting characteristics of a crystalline resin by using an amorphous resin and a crystalline resin in combination in a binder resin has been proposed (see Patent Documents 1 and 2). However, the toner using the above crystalline resin does not have sufficient charge amount necessary for coping with high-speed printing during development, and improvement thereof is desired. In addition, a toner composition containing an amorphous polyester bonded with fluorine has been proposed for the purpose of improving chargeability (see Patent Document 3). However, it is difficult to solve these problems simultaneously by any method.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a toner binder excellent in dispersibility, low-temperature fixability, chargeability, heat storage stability, and image strength.

[0005] As a result of intensive studies to solve these problems, the present inventors have reached the present invention. That is, the present invention is a toner binder containing a crystalline polyester resin which is a polycondensate of an alcohol component (x), a carboxylic acid component (y), and a fluorine compound (z), wherein the alcohol component (x) contains an aliphatic diol having 2 to 24 carbon atoms, the carboxylic acid component (y) contains an aliphatic dicarboxylic acid having 2 to 24 carbon atoms and / or an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and the fluorine compound (z) is a fluorine compound having a hydroxyl group and / or a carboxyl group.

Advantages of the Invention

[0006] According to the present invention, it has become possible to provide a toner binder excellent in dispersibility, low-temperature fixability, chargeability, heat storage stability, and image strength.

Embodiments for Carrying Out the Invention

[0007] Hereinafter, the present invention will be described in detail.

[0008] The toner binder of the present invention contains a crystalline polyester resin which is a polycondensate of an alcohol component (x), a carboxylic acid component (y), and a fluorine compound (z). In addition, the "crystallinity" in the present invention means that in differential scanning calorimetry (also referred to as DSC measurement), the DSC curve has a peak top temperature (Tm) of an endothermic peak. The measurement method of the peak top temperature of the endothermic peak of the crystalline polyester resin will be described below. Measure using a differential scanning calorimeter (for example, DSC Q20 manufactured by TA Instruments Co., Ltd.). The first heating of the crystalline polyester resin is carried out from 30°C to 180°C at a rate of 10°C / min, followed by cooling from 180°C to 0°C at a rate of 10°C / min, and then the second heating from 0°C to 180°C at a rate of 10°C / min. The temperature indicating the top of the endothermic peak in the second heating process is defined as the peak top temperature of the endothermic peak of the crystalline polyester resin.

[0009] The crystalline polyester resin of the present invention is a crystalline polyester resin which is a polycondensate of an alcohol component (x), a carboxylic acid component (y), and a fluorine compound (z). The alcohol component (x) contains an aliphatic diol having 2 to 24 carbon atoms as an essential component, and the carboxylic acid component (y) contains an aliphatic dicarboxylic acid having 2 to 24 carbon atoms and / or an aromatic dicarboxylic acid having 8 to 20 carbon atoms. The fluorine compound (z) is a fluorine compound having a hydroxyl group and / or a carboxyl group. From the viewpoints of dispersibility and crystallinity, the fluorine compound (z) is preferably bonded to the terminal of the crystalline polyester resin.

[0010] The alcohol component (x) is an alcohol component excluding those containing fluorine. In addition to the aliphatic diol having 2 to 24 carbon atoms which is an essential component, it may contain a diol (x1) other than the aliphatic diol having 2 to 24 carbon atoms, a monoalcohol, and a polyol having a trivalent or higher valence.

[0011] As the aliphatic diol having 2 to 24 carbon atoms, a linear aliphatic diol having 2 to 24 carbon atoms is preferred. Examples of the linear aliphatic diol having 2 to 24 carbon atoms include 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-eicosanediol. From the viewpoint of low-temperature fixing property, a linear aliphatic diol having 2 to 12 carbon atoms is preferred, and ethylene glycol, 1,9-nonanediol, and 1,12-dodecanediol are more preferred.

[0012] Examples of the diol (x1) other than the aliphatic diol having 2 to 24 carbon atoms include an alicyclic diol and / or an aromatic diol having 6 to 36 carbon atoms.

[0013] Examples of the alicyclic diol having 6 to 36 carbon atoms include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 5-norbornene-2,3-dimethanol, hydrogenated bisphenol A, spiroglycol, isosorbide, and an alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as "AO") adduct of the above alicyclic diol.

[0014] Examples of the alkylene oxide adduct of the above alicyclic diol include an ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as "EO") adduct, a propylene oxide (hereinafter, "propylene oxide" may be abbreviated as "PO") adduct, and a butylene oxide (hereinafter, "butylene oxide" may be abbreviated as "BO") adduct of the above alicyclic diol. The average number of moles of addition of the above alkylene oxide is preferably 1 to 30, and more preferably 2 to 5.

[0015] Examples of the aromatic diol include 1,3-benzenedimethanol, 1,4-benzenedimethanol, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A, 2,2'-diethylbisphenol F, and alkylene oxide adducts of the above aromatic diols.

[0016] Examples of the alkylene oxide adducts of the above aromatic diols include EO adducts, PO adducts, and BO adducts of the above aromatic diols. The average number of moles of the added alkylene oxide is preferably from 1 to 15, more preferably from 2 to 5.

[0017] Examples of the polyol having a valency of 3 or more include polyhydric aliphatic alcohols (alkane polyols and their intramolecular or intermolecular dehydrates, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin), saccharides and their esterified products, such as sucrose and methyl glucoside, alkylene oxide adducts of trisphenols (such as trisphenol PA) (the number of added moles is preferably from 2 to 30), alkylene oxide adducts of novolak resins (including phenol novolak and cresol novolak, etc., and the average degree of polymerization is preferably from 3 to 60) (the number of added moles is preferably from 2 to 30), and acrylic polyols [copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers, etc.].

[0018] Examples of the monoalcohol include linear or branched alkyl alcohols having 1 to 30 carbon atoms (such as methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol).

[0019] When the alcohol component (x) contains a component other than aliphatic diols having 2 to 24 carbon atoms, from the viewpoint of heat storage stability, a monoalcohol is preferred, and a linear or branched alkyl alcohol having 1 to 30 carbon atoms is more preferred.

[0020] From the viewpoint of low-temperature fixability, the content of the aliphatic diol having 2 to 24 carbon atoms in the alcohol component (x) is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and still more preferably 100 mol% based on the number of moles of the alcohol component (x) which is a constituent component of the crystalline polyester resin.

[0021] The carboxylic acid component (y) is a carboxylic acid component excluding those containing fluorine, and in addition to the aliphatic dicarboxylic acid having 2 to 24 carbon atoms and / or the aromatic dicarboxylic acid having 8 to 20 carbon atoms which are essential components, polycarboxylic acids having trivalent or higher valences and anhydrides of these acids and lower alkyl (having 1 to 4 carbon atoms) esters (such as methyl ester, ethyl ester and isopropyl ester) and the like described below can be mentioned. Further, a monocarboxylic acid may be used for the carboxylic acid component (y) if necessary.

[0022] As the aliphatic dicarboxylic acid having 2 to 24 carbon atoms, a linear aliphatic dicarboxylic acid having 2 to 24 carbon atoms is preferred. Examples of the linear aliphatic dicarboxylic acid having 2 to 24 carbon atoms include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid and 1,18-octadecanedicarboxylic acid. From the viewpoint of low-temperature fixability, a linear aliphatic dicarboxylic acid having 2 to 12 carbon atoms is preferred, and more preferably adipic acid, sebacic acid and dodecanedioic acid.

[0023] Examples of the aromatic dicarboxylic acid having 8 to 20 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid. From the viewpoint of chargeability, an aromatic dicarboxylic acid having 8 to 14 carbon atoms is preferred, and more preferably terephthalic acid and isophthalic acid.

[0024] Examples of polycarboxylic acids having a valency of 3 or higher include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), aliphatic tricarboxylic acids having 6 to 36 carbon atoms (such as hexanetricarboxylic acid), and vinyl polymers of unsaturated carboxylic acids [number average molecular weight (Mn): 450 to 10,000] (such as styrene / maleic acid copolymers, styrene / acrylic acid copolymers, and styrene / fumaric acid copolymers). Further, anhydrides or lower alkyl esters of these acids may also be used.

[0025] Examples of monocarboxylic acids include aromatic monocarboxylic acids having 7 to 37 carbon atoms (such as benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), aliphatic monocarboxylic acids having 2 to 50 carbon atoms (such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, behenic acid, (meth)acrylic acid [“(meth)acrylic” means acrylic or methacrylic], crotonic acid, isocrotonic acid, and cinnamic acid, etc.).

[0026] When the carboxylic acid component (y) contains a component other than an aliphatic dicarboxylic acid having 2 to 24 carbon atoms and / or an aromatic dicarboxylic acid having 8 to 20 carbon atoms, from the viewpoint of heat-resistant storage stability, a monocarboxylic acid is preferred, and an aliphatic monocarboxylic acid having 2 to 50 carbon atoms is more preferred.

[0027] The content of the aliphatic dicarboxylic acid having 2 to 24 carbon atoms and / or the aromatic dicarboxylic acid having 8 to 20 carbon atoms in the carboxylic acid component (y) is preferably 80 to 100 mol% based on the number of moles of the carboxylic acid component (y) which is a constituent component of the crystalline polyester resin, more preferably 90 to 100 mol%, and still more preferably 100 mol% from the viewpoint of low-temperature fixability.

[0028] The fluorine compound (z) is a compound containing a fluorine atom, and is not particularly limited as long as it is a fluorine compound having a hydroxyl group and / or a carboxyl group. Examples thereof include fluorinated monoalcohols, fluorinated phenols, fluorinated polyols, fluorinated monocarboxylic acids, fluorinated polycarboxylic acids, and the like. The fluorine compound (z) may be used alone or in combination of two or more kinds.

[0029] The fluorinated monoalcohol is not particularly limited, and examples thereof include fluoroalkyl alcohol and fluorobenzyl alcohol. Examples of the fluoroalkyl alcohol include alcohols having 1 to 41 fluorine atoms and 1 to 20 carbon atoms {for example, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, pentafluoroethanol, 3-fluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 2-trifluoromethyl-2-propanol, 2,2,3,3-tetrafluoro-1-propanol, pentafluoropropanol, 1,1,1,3,3,3-hexafluoro-2-propanol, heptafluoropropanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 4,4,4-trifluoro-1-butanol, 2,2,3,4,4,4-hexafluoro-1-butanol, heptafluorobutanol, nonafluoro-tert-butyl alcohol, 4,4,5,5,5-pentafluoro-1-pentanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H,1H-nonafluoro-1-pentanol, nonafluoropentanol, 1H,1H-undecafluoro-1-hexanol, 1H,1H,7H-dodecafluoro-1-heptanol, 1H,1H-tridecafluoro-1-heptanol, tridecafluorooctanol, 1H,1H-pentadecafluoro-1-octanol, 1H,1H,2H,2H,3H,3H-tridecafluoro-1-nonanol, 1H,1H,9H-hexadecafluoro-1-nonanol, 1H,1H-heptadecafluoro-1-nonanol, heptadecafluorododecanol (1H,1H,2H,2H-heptadecafluoro-1-decanol), 1H,1H,11H-eicosapentafluoro-1-undecanol, and 1H,1H-tricosapentafluoro-1-dodecanol, etc.} and the like. Examples of the fluorobenzyl alcohol include benzyl alcohols having 1 to 41 fluorine atoms and 7 to 20 carbon atoms {for example, α-(trifluoromethyl)benzyl alcohol, 2-(trifluoromethyl)benzyl alcohol, 4-(trifluoromethyl)benzyl alcohol, 3,5-bis(trifluoromethyl)benzyl alcohol, 1-[3,5-bis(trifluoromethyl)phenyl]ethanol, 2-fluorobenzyl alcohol, 3-fluorobenzyl alcohol, 4-fluorobenzyl alcohol, 4-fluoro-α-methylbenzyl alcohol, 2,3-difluorobenzyl alcohol, 2,4-difluorobenzyl alcohol, 2,5-difluorobenzyl alcohol, 2,6-difluorobenzyl alcohol, 3,4-difluorobenzyl alcohol, 3,5-difluorobenzyl alcohol, 4,4-difluorocyclohexanol, 4,4'-difluorobenzhydrol, 2,4,5-trifluorobenzyl alcohol, 2,3,5,6-tetrafluorobenzyl alcohol, 2,3,4,5-tetrafluorobenzyl alcohol, 2,3,4,6-tetrafluorobenzyl alcohol, 1-(pentafluorophenyl)ethanol, pentafluorobenzyl alcohol, etc.} and the like.

[0030] The fluorine-containing phenol is not particularly limited. For example, phenols having 1 to 41 fluorine atoms and 7 to 20 carbon atoms {such as bisphenol AF, octafluoro-4,4'-biphenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 4-fluorocresol, 4-fluoro-4'-hydroxybiphenyl, 2,3-difluorophenol, 2,4-difluorophenol, 2,5-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2-fluoro-5-(trifluoromethyl)phenol, 3,5-bis(trifluoromethyl)phenol, 3-hydroxybenzotrifluoride, 2,3,4-trifluorophenol, 2,3,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, 2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenol, and pentafluorophenol, etc.} can be mentioned.

[0031] The fluorine-containing polyol is not particularly limited. For example, polyols having 4 to 40 fluorine atoms and 1 to 20 carbon atoms {such as 2,2,3,3-tetrafluoro-1,4-butanediol, hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol, and 1H,1H,10H,10H-hexadecafluoro-1,10-decanediol, 1H,1H,12H,12H-icosapentafluoro-1,12-dodecanediol, 1,3-bis(hexafluoro-α-hydroxyisopropyl)benzene, and 2,3,5,6-tetrafluoro-1,4-benzenedimethanol, etc.} can be mentioned.

[0032] The fluorine-containing monocarboxylic acid is not particularly limited. For example, fluoroalkyl carboxylic acids and fluorobenzoic acids, etc. can be mentioned. Examples of the fluoroalkyl carboxylic acid include carboxylic acids having 1 to 41 fluorine atoms and 1 to 21 carbon atoms {for example, 1-(trifluoromethyl)cyclobutanecarboxylic acid, 4-(trifluoromethyl)cyclohexanecarboxylic acid, 4,4-difluorocyclohexanecarboxylic acid, flurbiprofen, 4'-(trifluoromethyl)biphenyl-2-carboxylic acid, difluoroacetic acid, trifluoroacetic acid, 2-fluorophenylacetic acid, 3-fluorophenylacetic acid, 4-fluorophenylacetic acid, 2-(trifluoromethyl)phenylacetic acid, 3-(trifluoromethyl)phenylacetic acid, 4-(trifluoromethyl)phenylacetic acid, 2,3-difluorophenylacetic acid, 2,4-difluorophenylacetic acid, 2,6-difluorophenylacetic acid, 3,4-difluorophenylacetic acid, 3,5-difluorophenylacetic acid, 2,4-bis(trifluoromethyl)phenylacetic acid, 3,5-bis(trifluoromethyl)phenylacetic acid, 2,4,5-trifluorophenylacetic acid, pentafluorophenylacetic acid, pentafluoroethanoic acid, 2,2-difluoropropionic acid, 3-(3-fluorophenyl)propionic acid, 3-(4-fluorophenyl)propionic acid, 3-(3-trifluoromethylphenyl)propionic acid, 3-[4-(trifluoromethyl)phenyl]propionic acid, 3,3,3-trifluoropropionic acid, 3,3,3-trifluoro-2,2-dimethylpropionic acid, 2,2,3,3-tetrafluoropropionic acid, pentafluoropropanoic acid, 4,4,4-trifluorobutyric acid, heptafluorobutyric acid, perfluoropentanoic acid, nonafluorofluorohexanoic acid, undecafluorohexanoic acid, tridecafluoroheptanoic acid, tridecafluorooctanoic acid, pentadecafluorooctanoic acid, heptadecafluorononanoic acid, nonadecafluorodecanoic acid, 2H,2H,3H,3H-heptadecafluoroundecanoic acid, heneicosafluoroundecanoic acid, heptadecafluorododecanoic acid, and tricosafluorododecanoic acid, etc.} and the like. Examples of the fluoro benzoic acid include benzoic acids having 1 to 41 fluorine atoms and 7 to 20 carbon atoms {for example, 2-fluorobenzoic acid, 2-(trifluoromethyl)benzoic acid, 3-fluorobenzoic acid, 3-(trifluoromethyl)benzoic acid, 4-fluorobenzoic acid, 4-(trifluoromethyl)benzoic acid, and 2-fluoro-3-methylbenzoic acid, 2-fluoro-4-methylbenzoic acid, 2-fluoro-5-methylbenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid, 2,5-difluorobenzoic acid, 2,6-difluorobenzoic acid, 2-fluoro-3-(trifluoromethyl)benzoic acid, 2-fluoro-5-(trifluoromethyl)benzoic acid, 2-fluoro-6-(trifluoromethyl)benzoic acid, 3-fluoro-4-methylbenzoic acid, 3,4-difluorobenzoic acid, 3,5-difluorobenzoic acid, 3-fluoro-4-(trifluoromethyl)benzoic acid, 3-fluoro-5-(trifluoromethyl)benzoic acid, 3,5-bis(trifluoromethyl)benzoic acid, 4-fluoro-2-methylbenzoic acid, 4-fluoro-3-methylbenzoic acid, 4-methyl-3-(trifluoromethyl)benzoic acid, 4-fluoro-2-(trifluoromethyl)benzoic acid, 4-fluoro-3-(trifluoromethyl)benzoic acid, 5-fluoro-2-methylbenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,4,6-trifluorobenzoic acid, 3,4,5-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, 2,3,5,6-tetrafluorobenzoic acid, 2,3,5,6-tetrafluoro-4-methylbenzoic acid, and pentafluorobenzoic acid, etc.} etc.

[0033] The fluorine-containing polycarboxylic acid is not particularly limited, and examples thereof include carboxylic acids having 1 to 40 fluorine atoms and 1 to 21 carbon atoms (for example, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 3-fluorophthalic acid, tetrafluorophthalic acid, tetrafluoroisophthalic acid, tetrafluoroterephthalic acid, tetrafluorosuccinic acid, hexafluoroglutaric acid, octafluoroadipic acid, hexadecafluorosebacic acid, dodecafluorosuberic acid, etc.).

[0034] Among the fluorine compounds (z), fluorine-containing monoalcohols, fluorine-containing phenols, and fluorine-containing monocarboxylic acids are preferred because they are easily introduced into the terminal of the crystalline polyester resin and have good dispersibility. More preferably, they are fluorine-containing monoalcohols and fluorine-containing monocarboxylic acids. Even more preferably, they are fluoroalkyl alcohols, fluorobenzyl alcohols, and fluoroalkyl carboxylic acids. Particularly preferably, they are monoalcohols having 1 to 41 fluorine atoms and 1 to 20 carbon atoms, benzyl alcohols having 1 to 41 fluorine atoms and 7 to 20 carbon atoms, benzoic acids having 1 to 41 fluorine atoms and 7 to 20 carbon atoms, and most preferably pentafluorobenzyl alcohol and / or 1H,1H,2H,2H-heptadecafluoro-1-decanol. In addition, from the viewpoint of chargeability, the fluorine compound (z) used in the present invention is preferably a compound containing at least two or more fluorine atoms, and more preferably a compound containing five or more fluorine atoms.

[0035] From the viewpoint of achieving both low-temperature fixability and chargeability, the weight ratio of the fluorine compound (z) is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and even more preferably 1 to 5% by weight based on the total weight of the alcohol component (x), the carboxylic acid component (y), and the fluorine compound (z).

[0036] The reaction ratio of the alcohol component (x), the carboxylic acid component (y), and the fluorine compound (z) is preferably 1 / 2 to 2 / 1, more preferably 1 / 1.3 to 1.5 / 1, and even more preferably 1 / 1.2 to 1.4 / 1, expressed as the molar ratio of the hydroxyl group to the carboxyl group {[OH] / [COOH]}. When the fluorine compound (z) is a compound having a hydroxyl group, the above hydroxyl group is the total of the hydroxyl groups derived from the alcohol component (x) and the fluorinated compound (z). When the fluorine compound (z) is a compound having a carboxyl group, the carboxyl group is the total of the carboxyl groups derived from the carboxylic acid component (y) and the fluorine compound (z).

[0037] In the present invention, the crystalline polyester resin can be produced in the same manner as the known polyester production method, except that the fluorine compound (z) is used. For example, the components containing the alcohol component (x), the carboxylic acid component (y), and the fluorine compound (z) can be reacted in an atmosphere of an inert gas (such as nitrogen gas) at a reaction temperature preferably of 150 to 280°C, more preferably 160 to 250°C, and even more preferably 170 to 235°C. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, 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 end of the reaction.

[0038] At this time, an esterification catalyst can also be used as needed. Examples of the esterification catalyst include tin-containing catalysts (such as dibutyltin oxide, etc.), antimony trioxide, titanium-containing catalysts [such as titanium alkoxide, potassium titanate oxalate, titanium terephthalate, titanium alkoxide terephthalate, catalysts described in JP-A-2006-243715 {titanium diisopropoxybis(triethanolamineate), titanium dihydroxybis(triethanolamineate), titanium monohydroxytri(triethanolamineate), titanyl bis(triethanolamineate) and their intramolecular polycondensates, etc.}, and catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.), etc.], zirconium-containing catalysts (such as zirconyl acetate, etc.), and zinc acetate, etc. Among the esterification catalysts, from the viewpoint of low-temperature fixing property, a titanium-containing catalyst is preferable, and more preferably, the catalysts described in JP-A-2006-243715 and JP-A-2007-11307.

[0039] In the present invention, the crystalline polyester resin is subjected to the first temperature increase from 30°C to 180°C at a rate of 10°C / min using a differential scanning calorimeter, then cooled from 180°C to 0°C at a rate of 10°C / min, and then subjected to the second temperature increase from 0°C to 180°C at a rate of 10°C / min. Preferably, the peak top temperature (Tm) of the endothermic peak in the second temperature increase process is 40 to 125°C, more preferably 60 to 85°C. When it is 40°C or higher, the heat-resistant storage property becomes good, and when it is 125°C or lower, the low-temperature fixing property becomes good.

[0040] In the present invention, from the viewpoint of low-temperature fixing property, the endothermic amount in the endothermic peak having the above peak top temperature (Tm) of the crystalline polyester resin is preferably 40 to 130 J / g, more preferably 50 to 130 J / g.

[0041] In the present invention, the acid value of the crystalline polyester resin is preferably 0 to 20 mgKOH / g, more preferably 0.1 to 5 mgKOH / g, from the viewpoints of chargeability and heat-resistant storage stability.

[0042] In the present invention, the weight average molecular weight (Mw) of the crystalline polyester resin in gel permeation chromatography (GPC) is preferably 10,000 to 30,000, more preferably 10,000 to 20,000, from the viewpoints of low-temperature fixability and image strength.

[0043] The toner binder of the present invention contains the above crystalline polyester resin as an essential component. The crystalline polyester resin may be used as the toner binder as it is, or if necessary, various additives such as known other binder resins for toners, colorants, release agents, charge control agents, fluidizing agents, etc. may be mixed and used as a toner. The content of the crystalline polyester resin in the toner binder is preferably 1 to 50% by weight, more preferably 3 to 20% by weight, and still more preferably 5 to 15% by weight.

[0044] As the binder resin to be mixed with the above crystalline polyester resin, an amorphous resin is preferable, and examples thereof include resins such as amorphous polyester resins, amorphous vinyl resins, amorphous epoxy resins, amorphous polycarbonate resins, and amorphous polyurethane resins. As the binder resin, an amorphous polyester resin is preferable from the viewpoint of low-temperature fixability.

[0045] The composition of the amorphous polyester resin is not particularly limited as long as it is an amorphous polyester resin which is a polycondensate of an alcohol component (X) and a carboxylic acid component (Y). In the present invention, "amorphous" means that when measuring the transition temperature of a sample using a differential scanning calorimeter, there is no peak top temperature of the endothermic peak.

[0046] As the alcohol component (X) of the amorphous polyester resin, examples include alkylene glycols having 2 to 12 carbon atoms, polyhydric aliphatic alcohols having a valence of 3 or more, alkylene oxide adducts of bisphenol A (the number of added moles is preferably 2 to 30), and alkylene oxide adducts of novolak resins (the number of added moles is preferably 2 to 30). As the carboxylic acid component (Y), examples include aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, and terephthalic acid) and aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). Further, as the carboxylic acid component (Y), anhydrides of these carboxylic acids, lower alkyl (having 1 to 4 carbon atoms) esters (such as methyl ester, ethyl ester, and isopropyl ester) may be used, or the anhydride or lower alkyl ester and the above carboxylic acid may be used in combination.

[0047] Among the alcohol components (X) used in the amorphous polyester resin, from the viewpoints of low-temperature fixability and image strength, preferably, an EO adduct of bisphenol A (average number of added moles 2 to 3) and a PO adduct of bisphenol A (average number of added moles 2 to 3). Among the carboxylic acid components (Y), from the viewpoints of low-temperature fixability and image strength, preferably, terephthalic acid, adipic acid, and trimellitic anhydride.

[0048] The amorphous polyester resin used in the present invention includes a linear polyester resin (B1) and a non-linear polyester (branched or crosslinked polyester) resin (B2), which may be used alone or in combination of two or more. Further, the linear polyester resin (B1) and the non-linear polyester resin (B2) may be mixed and used. In addition, from the perspective of achieving both low-temperature fixability and hot offset resistance, the amorphous polyester resin preferably consists of a linear polyester resin (B1) and a non-linear polyester resin (B2). The weight ratio of the linear polyester resin (B1) to the non-linear polyester resin (B2), ((B1) / (B2)), is preferably 10 / 90 to 90 / 10, more preferably 15 / 85 to 85 / 15, still more preferably 20 / 80 to 80 / 20, and particularly preferably 30 / 70 to 70 / 30, from the perspective of achieving both low-temperature fixability and hot offset resistance.

[0049] The glass transition temperature (Tg) of the amorphous polyester resin is preferably 40 to 75 °C, more preferably 45 to 72 °C, and still more preferably 50 to 70 °C.

[0050] The acid value of the amorphous polyester resin is preferably 30 mgKOH / g or less, and more preferably 2 to 25 mgKOH / g.

[0051] The hydroxyl value of the amorphous polyester resin is preferably 60 mgKOH / g or less, and more preferably 1 to 55 mgKOH / g.

[0052] The Mw of the amorphous polyester resin is preferably 4,000 to 150,000, and still more preferably 5,000 to 15,000.

[0053] The 1 / 2 drop temperature of the amorphous polyester resin is preferably 80 to 170 °C, and more preferably 95 to 150 °C. Two or more amorphous polyester resins having different 1 / 2 drop temperatures may be used in combination. A combination of those with a 1 / 2 drop temperature of 80 °C or higher and less than 115 °C and those with a 1 / 2 drop temperature of 115 °C or higher and 170 °C or lower is preferred, and a combination of those with a 1 / 2 drop temperature of 85 °C or higher and 115 °C or lower and those with a 1 / 2 drop temperature of 120 °C or higher and 160 °C or lower is more preferred.

[0054] The weight ratio of the crystalline polyester resin to the amorphous polyester resin of the present invention is preferably 3:97 to 30:70.

[0055] It is preferable to contain one or more selected from the group consisting of a black colorant, a blue colorant, a red colorant, and a yellow colorant as the colorant. As the colorant, all dyes, pigments, etc. used as colorants for toner can be used. Specifically, carbon black, iron black, Sudan black SM, Fast Yellow G, benzidine yellow, solvent yellow (such as 21, 77, and 114), pigment yellow (such as 12, 14, 17, and 83), Indofast Orange, Irgasin Red, paranitroaniline red, toluidine red, solvent red (such as 17, 49, 128, 5, 13, 22, and 48:2), disperse red, carmine FB, pigment orange R, lake red 2G, rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, solvent blue (such as 25, 94, 60, and 15:3), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, Orazol brown B, oil pink OP, etc. can be mentioned. Further, if necessary, magnetic powder (powders of ferromagnetic metals such as iron, cobalt, and nickel, compounds such as magnetite, hematite, and ferrite) can be contained while also serving as a function of the colorant. The content of the colorant is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight in total of the crystalline polyester resin and the binder resin 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 100 parts by weight in total of the crystalline polyester resin and the binder resin.

[0056] Examples of the release agent include natural waxes (such as beeswax, carnauba wax, and montan wax), petroleum waxes (such as paraffin wax, microcrystalline wax, and petrolatum), synthetic waxes (such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oxidized polyethylene wax, and oxidized polypropylene wax), and synthetic ester waxes (such as fatty acid esters synthesized from fatty acids having 10 to 30 carbon atoms and alcohols having 10 to 30 carbon atoms). It is preferable to contain one or more selected from the group consisting of these release agents. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and still more preferably 1 to 10% by weight based on 100 parts by weight in total of the crystalline polyester resin and the binder resin of the present invention.

[0057] From the viewpoint of low-temperature fixing property, the melting point of the release agent is preferably 40 to 90°C, more preferably 45 to 85°C, and particularly preferably 50 to 80°C.

[0058] From the viewpoint of low-temperature fixing property, the kinematic viscosity of the release agent at 100°C is preferably 3 to 20 mm 2 / s, more preferably 4 to 19 mm 2 / s, and particularly preferably 5 to 18 mm 2 / s.

[0059] As the charge control agent, either a positive charge control agent or a negative charge control agent may be contained. For example, nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salts, polyamine resins, imidazole derivatives, polymers containing a quaternary ammonium base, metal-containing azo dyes, copper phthalocyanine dyes, metal salts of salicylic acid, boron complexes of benzoic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, etc. may be mentioned. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 7.5% by weight based on 100 parts by weight in total of the crystalline polyester resin and the binder resin of the present invention.

[0060] Examples of the fluidizing agent include silica, titania, alumina, fatty acid metal salts, silicone resin particles, and fluororesin particles, and two or more of them may be used in combination. Silica is preferred from the viewpoint of the chargeability of the toner. Further, the silica is preferably hydrophobic silica from the viewpoint of the transferability of the toner. 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 100 parts by weight in total of the crystalline polyester resin and the binder resin of the present invention.

[0061] In addition, the total weight of additives such as a colorant, a release agent, a charge control agent, and a fluidizing agent may be 3 to 70% by weight, preferably 4 to 58% by weight, more preferably 5 to 50% by weight, based on the toner weight. By setting the composition ratio of the toner within the above range, it is possible to easily obtain a toner having good charging characteristics.

[0062] The volume average particle diameter (D50) of the toner is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 7 μm.

[0063] There are no particular restrictions on the method for producing the toner, and known kneading and pulverizing methods, suspension polymerization methods described in Japanese Patent Publication No. 36-10231, Japanese Patent Laid-Open No. 59-53856, and Japanese Patent Laid-Open No. 59-61842, emulsion polymerization methods typified by a soap-free polymerization method in which a monomer is directly polymerized in the presence of a water-soluble polymerization initiator to produce a toner, interfacial polymerization methods such as microcapsule production methods, in site polymerization methods, coacervation methods, association polymerization methods in which at least one or more fine particles are aggregated as disclosed in Japanese Patent Laid-Open No. 62-106473 and Japanese Patent Laid-Open No. 63-186253 to obtain those having a desired particle size, dispersion polymerization methods characterized by monodispersity, or those obtained by a dissolution suspension method in which resins necessary for a water-insoluble organic solvent are dissolved and then tonered in water may be used, or it may be produced by a method of dispersing in supercritical carbon dioxide.

[0064] For example, when obtaining toner by the kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended using a Henschel mixer, Nauta mixer, Banbury mixer, etc., and then melt-kneaded using a continuous mixing device such as a twin-screw kneader, extruder, continuous kneader, and three-roll mill. After that, it is roughly pulverized using a mill or the like, and finally atomized using a pneumatic pulverizer or the like, and the particle size distribution is adjusted using a classifier such as an elbow jet. After obtaining fine particles with a volume average particle size (D50) of 4 to 12 μm, it can be manufactured by mixing a fluidizing agent using a mill or the like.

[0065] For example, when obtaining toner by the dissolution and suspension method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent to form an oil phase, and then fine atomization is performed by mixing the water phase containing a surfactant and the above oil phase. Further, the organic solvent is removed from the mixture of the oil phase and the water phase, and then the toner particles are separated and classified. Finally, it can be manufactured by mixing a fluidizing agent.

[0066] The toner using the toner binder of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, printer, etc. to be a recording material. As a method for fixing on the support, known heat roll fixing methods, flash fixing methods, etc. can be applied.

[0067] The toner using the toner binder of the present invention can be preferably used for developing an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording, electrostatic printing, etc. More preferably, it can be used for developing an electrostatic charge image or a magnetic latent image for full color.

Examples

[0068] Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, "parts" means parts by weight.

[0069] Regarding the physical property values of the crystalline polyester resin, amorphous polyester resin, toner, etc., they were measured by the following methods.

[0070] <Measurement method for peak top temperature of endothermic peak of crystalline polyester resin (A)> Measurement was carried out using a differential scanning calorimeter {“DSCQ20” [manufactured by TA Instruments Co., Ltd.]}. The first heating of the crystalline polyester resin (A) was carried out from 30 °C to 180 °C at a rate of 10 °C / min, followed by cooling from 180 °C to 0 °C at a rate of 10 °C / min, and then the second heating from 0 °C to 180 °C at a rate of 10 °C / min. The temperature indicating the top of the endothermic peak in the second heating process was defined as the peak top temperature of the endothermic peak of the crystalline polyester resin (A).

[0071] <Heat absorption amount at the endothermic peak of crystalline polyester resin (A)> With the DSC curve of the second heating process observed under the same measurement conditions as the measurement of the peak top temperature of the above endothermic peak, a straight line was drawn connecting the point on the baseline closest to the peak below the endothermic start temperature (T0) of the endothermic peak and the point on the baseline closest to the peak above the end point temperature of the endothermic peak, thereby calculating the heat absorption amount at the endothermic peak having the peak top temperature of the above endothermic peak.

[0072] <Measurement method for weight average molecular weight (Mw)> The measurement of the molecular weight was carried out by dissolving the polyester resin in tetrahydrofuran (THF), filtering the insoluble matter with a glass filter, using the resulting solution as a sample solution, and measuring under the following conditions. Apparatus: HLC-8120 manufactured by Tosoh Corporation Columns: Two TSK GEL GMH6 [manufactured by Tosoh Corporation Measurement temperature: 40 °C Sample solution: 0.25 wt% THF solution Solution injection volume: 100 μl Detector: Refractive index detector Reference material: 12 standards of standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh Corporation (molecular weights: 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)

[0073] <Acid value and hydroxyl value> Measured by the method specified in JIS K0070. However, the measurement solvent for the acid value was a mixed solvent of acetone, methanol, and toluene (acetone: methanol: toluene = 12.5:12.5:75), and the measurement solvent for the hydroxyl value was THF.

[0074] <Half-drop temperature> 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, applying a load of 1.96 MPa to the plunger, extruding from a nozzle with a diameter of 1 mm and a length of 1 mm, drawing a graph of "plunger drop amount (flow value)" and "temperature", reading the temperature corresponding to 1 / 2 of the maximum value of the plunger drop amount from the graph, and taking this value (the temperature when half of the measurement sample has flowed out) as the half-drop temperature.

[0075] <Measurement method of glass transition temperature (Tg)> Measured by the method specified in ASTM D3418-82 (DSC method) using a differential scanning calorimeter (manufactured by TA Instruments, DSC Q20) under the following conditions. (1) Heating from 30 °C to 150 °C at a rate of 20 °C / min (2) Holding at 150 °C for 10 minutes (3) Cooling from 150 °C to -35 °C at a rate of 20 °C / min (4) Holding at -35 °C for 10 minutes (5) Heating from -35 °C to 150 °C at a rate of 20 °C / min (6) Analyzing the differential scanning calorimetry curve measured in the process of (5) to obtain the glass transition temperature.

[0076] <Volume average particle diameter (D50) (μm), number average particle diameter (μm), and particle size distribution (volume average particle diameter / number average particle diameter) of toner> Measurement was performed using a Coulter counter [product 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, Inc.), which is an electrolytic aqueous solution. Further, 2 to 20 mg of the measurement sample was added, and the electrolytic solution in which the sample was suspended was subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Using a 50 μm aperture as an aperture, the volume and number of toner were measured with the above measurement device, and the volume distribution and number distribution were calculated. From the obtained distributions, 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.

[0077] <Production Example 1> [Synthesis of crystalline polyester resin (A-1)] Into a reaction vessel equipped with a condenser, a heating and cooling device, a thermometer, a stirrer, and a nitrogen inlet tube, 447 parts (48.5 mol%) of 1,9-nonanediol, 607 parts (50 mol%) of dodecanedioic acid, 40 parts (1.5 mol%) of 1H,1H,2H,2H-heptadecafluoro-1-decanol, and 1.5 parts by weight of titanium dihydroxybis(triethanolaminato) as a condensation catalyst were placed. The reaction was carried out at 170 °C under a nitrogen stream for 8 hours while distilling off the generated water. Then, 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. Further, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa and taken out when the acid value reached 0.2 mgKOH / g. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a crystalline polyester resin (A-1). The weight average molecular weight (Mw) of the crystalline polyester resin (A-1) was 20,000, the peak top temperature (Tm) of the endothermic peak was 72 °C, the endothermic amount at the endothermic peak was 107 J / g, and the acid value was 0.2 mgKOH / g.

[0078] <Production Examples 2 to 5> [Synthesis of crystalline polyester resins (A-2) to (A-5)] Crystalline polyester resins (A-2) to (A-5) were obtained in the same manner as in Production Example 1, except that the raw materials described in Production Examples 2 to 5 of Table 1 were used. The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, and acid value of the obtained crystalline polyester resins are shown in Table 1.

[0079] <Comparative Production Examples 1 to 2> [Synthesis of Crystalline Polyester Resins (AR-1) to (AR-2)] Crystalline polyester resins (AR-1) to (AR-2) were obtained in the same manner as in Production Example 1, except that the raw materials described in Comparative Production Examples 1 to 2 of Table 1 were used. The weight average molecular weight (Mw), peak top temperature (Tm) of the endothermic peak, endothermic amount at the endothermic peak, and acid value of the obtained crystalline polyester resins are shown in Table 1.

[0080] The blending parts and resin physical properties of the crystalline polyester resin (A) of the present invention obtained in Production Examples 1 to 5 and the crystalline polyester resin (AR) obtained in Comparative Production Examples 1 to 2 are shown in Table 1.

[0081]

Table 1

[0082] The details of the raw materials used in Tables 1 and 2 are as follows. Ethylene glycol [manufactured by Nippon Shokubai Co., Ltd.]. Propylene glycol [manufactured by ADEKA Corporation]. 1,9-Nonanediol [manufactured by Kuraray Co., Ltd.]. 1,12-Dodecanediol [manufactured by Nippon Aerosil Co., Ltd.]. Behenyl alcohol [manufactured by BASF, STENOL 1822 80 PAST]. Sebacic acid [manufactured by Toyo Kosan Co., Ltd.]. Dodecanedioic acid [manufactured by Ube Industries, Ltd.]. Terephthalic acid [manufactured by Mitsui Chemicals, Inc.]. Adipic acid [manufactured by Asahi Kasei Corporation]. Trimellitic anhydride [manufactured by Mitsubishi Gas Chemical Company, Inc.]. Benzoic acid [manufactured by Emerald Kalama Chemical, BV]. 1H,1H,2H,2H-Heptadecafluoro-1-decanol [manufactured by Tokyo Chemical Industry Co., Ltd.]. Pentafluorobenzyl alcohol [manufactured by Tokyo Chemical Industry Co., Ltd.]. 4-(Trifluoromethyl)benzoic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]. 1H,1H,10H,10H-Hexadecafluoro-1,10-decanediol [manufactured by Tokyo Chemical Industry Co., Ltd.].

[0083] <Production Example 6> [Synthesis of Amorphous Polyester Resin (B-1)] In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 193 parts (14.6 mol%) of bisphenol A·PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P"), 539 parts (35.4 mol%) of bisphenol A·PO 3 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-3P"), 173 parts (26.7 mol%) of terephthalic acid, 67 parts (11.8 mol%) of adipic acid, 86 parts (11.5 mol%) of trimellitic anhydride, and 3.6 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were placed, and the reaction was carried out at 220°C while distilling off the generated water for 20 hours. Further, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa, and when the 1 / 2 drop temperature reached 150°C, it was taken out using a steel belt cooler. The taken-out resin was pulverized and granulated to obtain an amorphous polyester resin (B-1). The 1 / 2 drop temperature of the amorphous polyester resin (B-1) was 150°C, the glass transition temperature (Tg) was 60°C, the acid value was 23 mgKOH / g, the hydroxyl value was 1 mgKOH / g, and the weight average molecular weight (Mw) was 130,000.

[0084] <Production Example 7> [Synthesis of Amorphous Polyester Resin (B-2)] In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 324 parts (20.0 mol%) of bisphenol A·PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P"), 443 parts (30.0 mol%) of bisphenol A·EO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BPE-20"), 280 parts (47.7 mol%) of terephthalic acid, and 3.0 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were placed. While heating up to 230°C under a reduced pressure of 0.5 to 2.5 kPa, the reaction was carried out while distilling off the generated water until the acid value became less than 2 mgKOH / g. Then, it was cooled to 180°C, 14 parts (2.3 mol%) of trimellitic anhydride was added, and the reaction was carried out for 1 hour under normal pressure and then taken out. After the taken-out resin was cooled to room temperature, it was pulverized and granulated to obtain an amorphous polyester resin (B-2). The 1 / 2 drop temperature of the amorphous polyester resin (B-2) was 97°C, the glass transition temperature (Tg) was 58°C, the acid value was 8 mgKOH / g, the hydroxyl value was 55 mgKOH / g, and the weight average molecular weight (Mw) was 5,000.

[0085] <Production Example 8> [Synthesis of Amorphous Polyester Resin (B-3)] In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 649 parts (50.0 mol%) of propylene glycol, 673 parts (42.0 mol%) of terephthalic acid, 32 parts (2.3 mol%) of adipic acid, 52 parts (2.8 mol%) of trimellitic anhydride, 34 parts (2.9 mol%) of benzoic acid, and 2.5 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were placed and reacted at 220°C, and the reaction was carried out for 20 hours while distilling off the generated water. Further, the reaction was advanced under a reduced pressure of 0.5 to 2.5 kPa, and when the 1 / 2 drop temperature reached 130°C, it was taken out using a steel belt cooler. The taken-out resin was pulverized and granulated to obtain an amorphous polyester resin (B-3). The 1 / 2 drop temperature of the amorphous polyester resin (B-3) was 130°C, the glass transition temperature (Tg) was 64°C, the acid value was 2 mgKOH / g, the hydroxyl value was 25 mgKOH / g, and the weight average molecular weight (Mw) was 65,000.

[0086] <Production Example 9>[Synthesis of Amorphous Polyester Resin (B-4)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 583 parts (48.5 mol%) of propylene glycol, 49 parts (1.5 mol%) of bisphenol A·PO 2 mol adduct (manufactured by Sanyo Chemical Industries, Ltd., "Hymer BP-2P"), 627 parts (40.8 mol%) of terephthalic acid, 8 parts (0.6 mol%) of adipic acid, 58 parts (3.3 mol%) of trimellitic anhydride, 49 (4.4 mol%) of benzoic acid, and 2.5 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were added. The reaction was carried out at 220°C, and the reaction was carried out for 20 hours while distilling off the generated water. Further, the reaction was advanced under a reduced pressure of 0.5 to 2.5 kPa. When the 1 / 2 drop temperature reached 105°C, the pressure was returned to normal pressure and cooled to 180°C. 17 parts (0.9 mol%) of trimellitic anhydride was added, and the reaction was carried out for 1 hour and taken out using a steel belt cooler. The taken-out resin was pulverized and granulated to obtain an amorphous polyester resin (B-4). The 1 / 2 drop temperature of the amorphous polyester resin (B-4) was 114°C, the glass transition temperature (Tg) was 64°C, the acid value was 10 mgKOH / g, the hydroxyl value was 24 mgKOH / g, and the weight average molecular weight (Mw) was 13,000.

[0087] <Production Example 10>[Synthesis of Amorphous Polyester Resin (B-5)] An amorphous polyester resin (B-5) was obtained in the same manner as in Production Example 7 except that the raw materials described in Production Example 10 of Table 2 were used. The 1 / 2 drop temperature, glass transition temperature (Tg), acid value, hydroxyl value, and weight average molecular weight (Mw) of the obtained amorphous polyester resin are described in Table 2.

[0088] The compounding parts and resin physical properties of the amorphous polyester resin (B) obtained in Production Examples 6 to 10 are shown in Table 2.

[0089]

Table 2

[0090] <Example 1>[Production of Toner (T-1)] 10 parts of crystalline polyester resin (A-1), 27 parts of amorphous polyester resin (B-1), and 63 parts of amorphous polyester resin (B-2) were premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Machinery Co., Ltd.] after adding 8 parts of carbon black "MA-100" [manufactured by Mitsubishi Chemical Corporation] as a pigment as a colorant, 4 parts of paraffin wax "HNP-9" [manufactured by Nippon Seiro Co., Ltd.] as a release agent, and 1 part by weight of charge control agent "T-77" [manufactured by Hodogaya Chemical Co., Ltd.], and then kneaded with a twin-screw kneader [PCM-30 manufactured by Ikegai Corporation]. Subsequently, after finely pulverizing using a supersonic jet mill Labojet [manufactured by Nippon Pneumatic Mfg. Co., Ltd.], it was classified using an air classifier [MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.] to obtain resin particles having a volume average particle diameter of 5 μm and a particle size distribution of 1.2. 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 using a sample mill to obtain toner (T-1).

[0091] <Examples 2, 3, 5> [Manufacture of Toners (T-2), (T-3), (T-5)] Toners (T-2), (T-3), and (T-5) were obtained in the same manner as in Example 1 except that the crystalline polyester resin (A-1) in Example 1 was replaced with (A-2), (A-3), and (A-5).

[0092] <Example 4> [Manufacture of Toner (T-4)] Toner (T-4) was obtained in the same manner as in Example 1 except that the crystalline polyester resin (A-1) in Example 1 was replaced with (A-4), 27 parts of (B-1) was replaced with 50 parts of (B-3), and 63 parts of (B-2) was replaced with 50 parts of (B-4).

[0093] <Comparative Examples 1 to 2> [Manufacture of Toners (TR-1), (TR-2)] Toners (TR-1) and (TR-2) were obtained in the same manner as in Example 1 except that the crystalline polyester resin (A-1) in Example 1 was replaced with (AR-1) to (AR-2).

[0094] <Comparative Example 3> [Manufacture of Toner (TR-3)] A toner (TR-3) was obtained in the same manner as in Example 1, except that the crystalline polyester resin (A-1) of Example 1 was not used.

[0095] <Comparative Example 4> [Production of Toner (TR-4)] A toner (TR-4) was obtained in the same manner as in Example 1, except that the crystalline polyester resin (A-1) of Example 1 was not used, and 27 parts of (B-1) and 63 parts of (B-2) were replaced with 100 parts of (B-5).

[0096] [Evaluation Method] The measurement methods, evaluation methods, and judgment criteria for the dispersibility (maximum particle size and average particle size of the crystalline polyester resin), low-temperature fixability, chargeability, heat-resistant storage stability, fixing strength, and image strength of the toner binder obtained below are described.

[0097] <Dispersibility> (Maximum Particle Size and Average Particle Size of Crystalline Polyester Resin) The crystalline polyester resin (A) and the amorphous polyester resin (B) were preliminarily mixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Machinery Co., Ltd.] in the blending parts described in Table 3, and then kneaded using a twin-screw kneader [PCM-30 manufactured by Ikegai Corporation]. Using the obtained toner binder, a cross-section of the toner binder observed with a transmission electron microscope (TEM) was prepared as follows. The obtained toner binder was embedded with a visible light-curable embedding resin (D-800, manufactured by Nisshin EM Co., Ltd.), cut to a thickness of 60 nm using an ultrasonic ultramicrotome (EM5, manufactured by Leica), and ruthenium staining was performed using a vacuum staining apparatus (manufactured by Filgen). Thereafter, using a transmission electron microscope (H7500, manufactured by Hitachi High-Technologies Corporation), the dispersion state of the crystalline polyester resin was observed from the cross-section of the obtained toner binder at an acceleration voltage of 120 kV. The major axis of the crystalline polyester resin having the largest major axis among the entire observed image was defined as the maximum particle size. Also, for an arbitrarily selected enlarged image (×1000), image processing was performed using the free software "image J" according to the following procedure, and the calculated "mean feret" was defined as the average particle size of the crystalline polyester resin. In the toner binders of Comparative Examples 2 to 4, the dispersion of the crystalline polyester resin could not 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 measurements → Feret diameter)

[0098] <Low-temperature fixability> (MFT) The toner was uniformly placed on the paper surface so as to be 0.6 mg / cm 2 At this time, as a method of placing the powder on the paper surface, a printer with the heat fixing unit removed was used. Other methods may be used as long as the powder can be uniformly placed at the above weight density. This paper was passed through the pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm 2 under the conditions of a heating roller temperature in the range of 90 to 230 °C in 5 °C increments. Next, the presence or absence of cold offset in the fixed image was visually observed, and the temperature (MFT) at which the occurrence of cold offset disappeared was measured. The lower the occurrence temperature of the cold offset, the better the low-temperature fixability. Under this evaluation condition, it is generally preferable that MFT is 125 °C or lower. The low-temperature fixability of the toner is shown in Table 3 as MFT (°C).

[0099] <Chargeability> (Charge amount) (1) 0.5 g of toner and 10 g of ferrite carrier (manufactured by Powdertech Co., Ltd., F-150) were placed in a 50 ml glass bottle, and this was conditioned at 23 °C and a relative humidity of 50% for 8 hours. (2) Stir and mix at 90 rpm for 2 minutes using a Turbler Shaker Mixer. Load 0.2 g of the mixed powder after stirring into a Blow-off Powder Charge Measurement Device equipped with a 20-μm stainless steel wire mesh, and measure the charge of the remaining ferrite carrier under the conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa. Calculate the charge (μC / g) of the toner by a standard method. Note that for toner, the higher the negative charge, the better the charging characteristics, and it is preferably -15 μC / g or less. The Blow-off Charge Measurement Device [manufactured by Toshiba Chemical Corporation] was used for the measurement.

[0100] <Heat-resistant storage stability> (Degree of aggregation) Mix 1 g of toner and 0.013 g of Aerosil R8200 (manufactured by Evonik Japan Co., Ltd.) with a shaker for 1 hour. Put the mixture into a sealed container, leave it standing for 48 hours in an atmosphere of 45°C and 80% humidity, measure the degree of aggregation with a Powder Tester, and evaluate the heat-resistant storage stability. The lower the numerical value of the aggregation test obtained by the following method, the better the heat-resistant storage stability. Under these evaluation conditions, it is preferably 3% or less. Device: POWDER TESTER model PT-X (manufactured by Hosokawa Micron) Mesh size of the sieve: 355 μm, 250 μm, 150 μm Vibration amplitude: 1 mm Vibration time: 30 seconds Operation method: Set the sieves on the vibration table of the Powder Tester in the order of 355 μm for the upper sieve, 250 μm for the middle sieve, and 150 μm for the lower sieve. Place 1 g of toner on the upper sieve and vibrate it for 30 seconds with a vibration amplitude of 1 mm, then measure the weight of the toner remaining on each sieve. Degree of aggregation: Calculated from the weight of the toner used in the measurement and the weight of the remaining toner after sieving. Degree of aggregation (%) = (U / N + M / N × 3 / 5 + L / N × 1 / 5) × 100 U: Weight of the upper sieve, M: Weight of the middle sieve, L: Weight of the lower sieve, N: Weight of the sample (1 g)

[0101] <Fixing strength> (Tape peeling) The fixing strength of the fixing image at the MFT fixed in the above evaluation of low-temperature low-adhesion property was evaluated by a tape peeling test. After attaching a tape (Scotch Mendin Tape manufactured by 3M) to the fixing image, the tape was peeled off, and the image density (ID) of the image attached to the tape was measured with a reflection densitometer (product name: X-Rite model 404, manufactured by X-Rite). The smaller the image density (numerical value) of the attached image, the higher the fixing strength. Under this evaluation condition, it is preferably 0.2 or less.

[0102] <Image strength> (pencil hardness) The fixing image at the MFT fixed in the above evaluation of low-temperature low-adhesion property was subjected to a scratch hardness test by the hand-drawing method in accordance with JIS K5600-5-4 (1999) so that a load of 10 g was applied from directly above a pencil fixed at an angle of 45 degrees, and the image strength was evaluated from the pencil hardness without scratches. The higher the pencil hardness, the better the image strength. Generally, it is preferably HB or higher.

[0103] The above evaluation results are shown in Table 3.

[0104]

Table 3

[0105] As is clear from the evaluation results in Table 3, all of the toners (T-1) to (T-5) containing the crystalline polyesters (A-1) to (A-5) according to Examples 1 to 5 obtained excellent results in all performance evaluations. On the other hand, some performance items of the toners (TR-1) to (TR-4) according to Comparative Examples 1 to 4 were poor.

Industrial Applicability

[0106] The toner binder of the present invention can be suitably used as an electrophotographic toner used for developing a latent image formed in electrophotography, electrostatic recording, electrostatographic printing, etc. Furthermore, it is suitable for uses such as a paint additive, an adhesive additive, and particles for electronic paper.

Claims

1. A toner binder containing a crystalline polyester resin which is a polycondensate of an alcohol component (x), a carboxylic acid component (y), and a fluorine compound (z), wherein the alcohol component (x) is an aliphatic diol having 2 to 24 carbon atoms, the carboxylic acid component (y) is an aliphatic dicarboxylic acid having 2 to 24 carbon atoms, the fluorine compound (z) is a fluorine compound having a hydroxyl group and / or a carboxyl group, and the fluorine compound (z) is pentafluorobenzyl alcohol and / or 1H,1H,2H,2H - heptadecafluoro - 1 - decanol.

2. The toner binder according to claim 1, wherein the fluorine compound (z) is a fluorine - containing monoalcohol and / or a fluorine - containing monocarboxylic acid.

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