JP2019159315A - Toner binder and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder and a toner excellent in low temperature fixability, glossiness, hot offset resistance, heat storage stability, charge stability, image strength, document offset property and durability. A toner binder containing a crystalline resin (A) containing an alcohol component (X) and a carboxylic acid component (Y) as essential constituent monomers, and the total number of moles of the carboxylic acid component (Y). Based on the above, 90 to 99.49 mol% of the linear aliphatic dicarboxylic acid (y1) having a carboxylic acid component (Y) of 2 to 12 carbon atoms and 0. It contains 0.5 to 9.0 mol% of an aliphatic monocarboxylic acid (y3) having 01 to 1.0 mol% and 22 carbon atoms, and the toner binder is heated for the second time by a differential scanning calorimeter (DSC). In the process, a toner binder characterized by having at least one peak top temperature of a heat absorption peak derived from the crystalline resin (A) in the range of 40 to 100 ° C. is used. [Selection diagram] None

Description

  The present invention relates to a toner binder and a toner.

In recent years, there has been a strong demand for improvement in low-temperature fixability of toners from the viewpoint of energy saving, that is, reduction of energy consumption in the fixing process as well as promotion of downsizing, high speed and high image quality of electrophotographic apparatuses.
As a means for lowering the toner fixing temperature, a technique for lowering the glass transition point of a binder resin (toner binder) is generally used.
However, if the glass transition point is too low, the resistance to hot offset decreases and the powder tends to agglomerate (block), so that the storage stability of the toner decreases. This glass transition point is a design point of the binder resin, and a toner that can be fixed at a lower temperature cannot be obtained by a method of lowering the glass transition point.

  Among them, a toner composition containing a polyester-based toner binder that is excellent in both low-temperature fixability and hot offset resistance is known (see Patent Documents 1 and 2). However, in recent years, there has been an increasing demand for storage stability and compatibility between low-temperature fixability and hot offset resistance (fixing temperature range), which is still insufficient.

As another method, it is known that the use of an amorphous resin and a crystalline resin in combination with the binder resin improves the low-temperature fixability and glossiness of the toner due to the melting characteristics of the crystalline resin.
However, if the content of the crystalline resin is increased, the resin strength may decrease, and the crystalline resin becomes amorphous due to the compatibilization of the crystalline resin and the binder resin during melt kneading, resulting in a glass transition of the toner. When the point is lowered, problems arise in hot offset resistance and toner storage stability similar to those described above.

In contrast, a method of regenerating the crystallinity of the crystalline resin by performing a heat treatment after the melt-kneading step (Patent Document 3), a long-chain monoalcohol having 8 to 62 carbon atoms or a long monomer as a monomer used in the crystalline polyester A method of reproducing crystallinity using a chain monocarboxylic acid (Patent Documents 4 to 7) and the like have been proposed.
Such a method can ensure the low-temperature fixability and glossiness of the toner, but the hot offset resistance, the fluidity of the toner, and the pulverization property during pulverization are reduced, and the durability is particularly insufficient.
In addition, a method of coating with a shell layer obtained using a melt suspension method or an emulsion aggregation method has been proposed (Patent Documents 8 to 10), but the crystalline resin is compatible with the core binder resin. Further, since the reprecipitation of crystals is insufficient in a short time, the image strength after fixing and the bending resistance are still insufficient.

JP 2005-77930 A JP 2012-98719 A JP 2005-308995 A International Publication No. 2015/170705 JP 2008-241845 A JP-A-2015-118310 JP 2016-212399 A JP 2011-197193 A JP 2011-186053 A JP 2006-251564 A

  An object of the present invention is to provide a toner excellent in low-temperature fixing property, glossiness, hot offset resistance, heat-resistant storage stability, charging stability, image strength, document offset property and durability, and a toner binder used therefor. .

As a result of intensive studies to solve these problems, the present inventors have reached the present invention.
That is, the present invention relates to a toner binder containing a crystalline resin (A) having an alcohol component (X) and a carboxylic acid component (Y) as essential constituent monomers, and the total mole of the carboxylic acid component (Y). Based on the number, the carboxylic acid component (Y) is 90 to 99.49 mol% of the linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms, and 0 is the aliphatic monocarboxylic acid (y2) having 20 carbon atoms. The toner binder contains 0.5 to 9.0 mol% of an aliphatic monocarboxylic acid (y3) having 0.01 to 1.0 mol% and 22 carbon atoms, and the toner binder is secondly increased by a differential scanning calorimeter (DSC). A toner binder having at least one peak top temperature of an endothermic peak derived from the crystalline resin (A) in the temperature process in a range of 40 to 100 ° C .; and a toner containing the toner binder.

  According to the present invention, it is possible to provide a toner and a toner binder excellent in low-temperature fixing property, glossiness, hot offset resistance, heat resistant storage stability, charging stability, image strength, document offset property and durability.

The present invention is described in detail below.
The toner binder of the present invention is a toner binder containing a crystalline resin (A) having an alcohol component (X) and a carboxylic acid component (Y) as essential constituent monomers, and is a total of carboxylic acid components (Y). Based on the number of moles, the carboxylic acid component (Y) is 90 to 99.49 mol% of a linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms and an aliphatic monocarboxylic acid (y2) having 20 carbon atoms. The toner binder contains 0.5 to 9.0 mol% of an aliphatic monocarboxylic acid (y3) of 0.01 to 1.0 mol% and 22 carbon atoms, and the toner binder is the second measured by a differential scanning calorimeter (DSC). In the temperature raising process, at least one peak top temperature of the endothermic peak derived from the crystalline resin (A) is in the range of 40 to 100 ° C.

The toner binder of the present invention is a toner binder containing a crystalline resin (A). In the present invention, “crystallinity” means that in the differential scanning calorimetry (also referred to as DSC measurement) described below, the DSC curve has a peak top temperature [Ta] of an endothermic peak. The ratio [Tm / Ta] of the softening point [Tm] of the crystalline resin to the peak top temperature [Ta] of the endothermic peak is preferably 0.8 to 1.55. Even if the resin is a block body having a crystalline resin block and an amorphous resin block, if the resin has an endothermic peak in differential scanning calorimetry (DSC), this is also a crystalline resin.
<Measurement method of peak top temperature [Ta] of endothermic peak>
Measurement is performed using a differential scanning calorimeter {eg, DSC Q20 manufactured by TA Instruments). The crystalline resin is heated for the first time from 30 ° C. to 180 ° C. under the condition of 10 ° C./minute, then left standing at 180 ° C. for 10 minutes, and then cooled from 180 ° C. to 0 ° C. under the condition of 10 ° C./minute. Then, after standing at 0 ° C. for 10 minutes, the top of the endothermic peak in the second temperature raising process when the temperature is raised from 0 ° C. to 180 ° C. under the condition of 10 ° C./min is shown. Let temperature be the peak top temperature of the endothermic peak of the crystalline resin.
<Measurement method of softening point [Tm]>
Using a constant test force extrusion type flow tester {“CFT-500D” [manufactured by Shimadzu Corporation]}, a 1 g measurement sample was heated at a temperature rising rate of 6 ° C./min. Apply a load, extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger drop (flow value)" and "temperature", corresponding to 1/2 of the maximum plunger drop The temperature to be measured is read from the graph, and this value (temperature when half of the measurement sample flows out) is defined as the softening point.

The crystalline resin (A) contained in the toner binder of the present invention is a crystalline resin having an alcohol component (X) and a carboxylic acid component (Y) as essential constituent monomers, and the carboxylic acid component (Y) Based on the total number of moles, the carboxylic acid component (Y) is an aliphatic monocarboxylic acid (y2) having 90 to 99.49 mol% of a linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms and 20 carbon atoms. In an amount of 0.01 to 1.0 mol% and an aliphatic monocarboxylic acid (y3) having 22 carbon atoms in an amount of 0.5 to 9.0 mol%.
Examples of the crystalline resin (A) contained in the toner binder of the present invention include crystalline polyester resin (a11), crystalline polyurethane resin (a12), crystalline polyurea resin (a13), and crystalline polyamide resin (a14). From the viewpoint of low temperature fixability, the crystalline polyester resin (a11) is preferable. In addition, these crystalline resin (A) may be used individually by 1 type, or may use 2 or more types together.

Based on the total number of moles of the alcohol component (X) and the carboxylic acid component (Y) in the crystalline resin (A), the linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms is converted to 90 to 99.99. 49-mol%, C20 aliphatic monocarboxylic acid (y2) 0.01-1.0 mol% and C22 aliphatic monocarboxylic acid (y3) 0.5-9.0 mol% The crystalline polyester resin (a11) having the carboxylic acid component (Y) as an essential constituent monomer will be described.
Examples of the linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms (including carbon of the carbonyl group) include, for example, a linear saturated aliphatic dicarboxylic acid having 2 to 12 carbon atoms {oxalic acid, malonic acid, succinic acid , Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid}, linear unsaturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms {maleic acid, fumaric acid, etc. } Etc. are mentioned. As dicarboxylic acid (y1), 1 type may be used and these 2 or more types may be used together.
Among (y1), from the viewpoint of the crystallinity of (A) and the charging characteristics of the toner, it is preferably a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms, more preferably succinic acid, adipic acid, or azelaic acid. Sebacic acid and dodecanedioic acid, more preferably azelaic acid, sebacic acid and dodecanedioic acid. As (y1), 1 type may be used and 2 or more types may be used together.

Examples of the aliphatic monocarboxylic acid (y2) having 20 carbon atoms include arachidic acid, linear unsaturated aliphatic monocarboxylic acid (such as gadoleic acid, eicosenoic acid, and eicosadienoic acid). Arachidic acid is preferable from the viewpoint of the charging characteristics of the toner.
Examples of the aliphatic monocarboxylic acid (y3) having 22 carbon atoms include behenic acid, linear unsaturated monocarboxylic acid (such as erucic acid and docosadienoic acid), and the like. From the viewpoint, behenic acid is preferred.

In the carboxylic acid component (Y) constituting the crystalline resin (A), the linear aliphatic dicarboxylic acid (y1), the aliphatic monocarboxylic acid (y2) having 20 carbon atoms, and the 22 carbon atoms are included. As components other than the aliphatic monocarboxylic acid (y3), other monocarboxylic acid component (y4), dicarboxylic acid component (y5), and trivalent or higher carboxylic acid component (y6) may be included.
Other monocarboxylic acid components (y4) are those other than (y2) and (y3), saturated aliphatic monocarboxylic acids having 1 to 19, 21 and 23 or more carbon atoms, and aromatics having 7 to 12 carbon atoms. Aliphatic monocarboxylic acids and unsaturated monocarboxylic acids having 3 to 15 carbon atoms, such as saturated aliphatic monocarboxylic acids {linear saturated aliphatic monocarboxylic acids (methanoic acid, ethanoic acid, propanoic acid, butanoic acid, Pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid Tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, tri Contanic acid and the like}}, aromatic monocarboxylic acids (benzoic acid, naphthalene acetic acid, cinnamic acid, etc.), unsaturated monocarboxylic acids {(meth) acrylic acid [“(meth) acrylic” is acrylic or methacrylic. means. ], Crotonic acid, and isocrotonic acid, etc.}. As the other monocarboxylic acid component (y4), one kind may be used, or two or more kinds thereof may be used in combination.

  Of the (y4), from the viewpoint of the crystallinity of (A) and the heat-resistant storage stability of the toner, saturated aliphatic monocarboxylic acids having 2 to 19, 21 and 23 or more carbon atoms, (meth) acrylic acid and benzoic acid are preferred. More preferably, it is a saturated aliphatic monocarboxylic acid having 16 or more carbon atoms (excluding those having 20 or 22 carbon atoms) and 30 or less, (meth) acrylic acid and benzoic acid, more preferably octadecanoic acid and (meth) acrylic. Acid and benzoic acid.

  Examples of the other dicarboxylic acid component (y5) include linear aliphatic dicarboxylic acids having 13 or more carbon atoms (including carbon of the carbonyl group) (for example, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1, 13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,15-pentadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid and 1,19-nonadecanedicarboxylic acid), branched aliphatic dicarboxylic acids (for example, citracone Acid, decyl succinic acid, dodecenyl succinic acid, pentadecenyl succinic acid, alkenyl succinic acid such as octadecenyl succinic acid), alicyclic dicarboxylic acid having 6 to 40 carbon atoms [eg dimer acid (dimerized linoleic acid) Etc.], an aromatic dicarboxylic acid having 8 to 36 carbon atoms (for example, phthalic acid, isophthalic acid, Phthalate, t- butyl isophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyl dicarboxylic acid, etc.) and the like. As (y5), 1 type may be used and these 2 or more types may be used together.

  Of (y5), from the viewpoint of the crystallinity of (A), a linear aliphatic dicarboxylic acid having 13 or more carbon atoms is preferable, and a linear aliphatic dicarboxylic acid having 13 to 20 carbon atoms is more preferable.

  Examples of the trivalent or higher carboxylic acid component (y6) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexane tricarboxylic acid). Acid), vinyl polymer having unsaturated carboxylic acid as an essential constituent monomer [preferably number average molecular weight (Mn): 450 to 10,000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer) And a styrene / fumaric acid copolymer). As the trivalent or higher carboxylic acid component (y6), one kind may be used, or two or more kinds thereof may be used in combination.

  Of these, trimellitic acid and pyromellitic acid are preferable from the viewpoint of hot offset resistance.

  The content of the aliphatic dicarboxylic acid having 2 to 12 carbon atoms (y1) is 90 to 99.49 mol% based on the number of moles of the carboxylic acid component (Y) that is a constituent monomer of the crystalline resin (A). However, from the viewpoints of crystallinity, heat-resistant storage stability, charging characteristics, and the like, preferably 91.1 to 99.39 mol%, more preferably 92.2 to 99.29 mol%, and even more preferably 93.3. 99.18 mol%, most preferably 94.4 to 99.07 mol%. When the content of (y1) is less than 90 mol%, the crystallinity of (A) is lowered, so that low temperature fixability, heat-resistant storage stability and charging characteristics become problems, and if it is more than 99.49 mol%, (A) Recrystallization is slow, and document offset and durability become problems.

  The content of the aliphatic monocarboxylic acid (y2) having 20 carbon atoms is 0.01 to 1.0 mol based on the number of moles of the carboxylic acid component (Y) that is a constituent monomer of the crystalline resin (A). However, from the viewpoint of heat-resistant storage stability, document offset property, durability and the like, preferably 0.01 to 0.9 mol%, more preferably 0.01 to 0.8 mol%, and still more preferably 0.00. It is 02-0.7 mol%, Most preferably, it is 0.03-0.6 mol%. When the content of (y2) is larger than 1.0 mol%, the crystallinity of (A) is lowered, so that low temperature fixability and charging characteristics are problematic. Crystallization is slow, and heat resistance and durability are problematic.

  The content of the aliphatic monocarboxylic acid (y3) having 22 carbon atoms is 0.5 to 9.0 moles based on the number of moles of the carboxylic acid component (Y) that is a constituent monomer of the crystalline resin (A). %, Preferably from 0.6 to 8.0 mol%, more preferably from 0.7 to 7.0 mol%, still more preferably from the viewpoint of heat resistant storage stability, document offset property, durability and the like. It is 8 to 6.0 mol%, particularly preferably 0.9 to 5.0 mol%. When the content of (y3) is larger than 9.0 mol%, the crystallinity of (A) is lowered, so that low-temperature fixability, heat-resistant storage stability and charging stability become problems, and if it is less than 0.5 mol% Recrystallization of (A) is slow and durability becomes a problem.

The crystalline polyester resin (a11) is a linear aliphatic dicarboxylic acid having 2 to 12 carbon atoms (y1), an aliphatic monocarboxylic acid having 20 carbon atoms (y2), or an aliphatic monocarboxylic acid having 22 carbon atoms. In addition to acid (y3), other monocarboxylic acid component (y4), other dicarboxylic acid component (y5) and trivalent or higher carboxylic acid component (y6), sulfonic acid (salt) group, sulfamic acid (salt) group And a dicarboxylic acid (y1 ′) having at least one group selected from the group consisting of a phosphoric acid (salt) group (hereinafter referred to as a dicarboxylic acid having a functional group) may be used as a constituent monomer. As dicarboxylic acid (y1 ') which has a functional group, 1 type may be used and 2 or more types may be used together.
By using dicarboxylic acid (y1 ′) having these functional groups as a constituent monomer, the charging stability and heat-resistant storage stability of the toner are improved.
The content of the other monocarboxylic acid component (y4), the other dicarboxylic acid component (y5), the trivalent or higher carboxylic acid component (y6), and the functional dicarboxylic acid (y1 ′) is crystalline, low temperature fixing. From the viewpoint of stability and heat-resistant storage stability, 5 mol% or less is preferable based on the number of moles of the carboxylic acid component (Y) which is a constituent monomer of the crystalline resin (A).
The “acid (salt)” in the present invention means an acid or an acid salt.

  Examples of the alcohol component (X) that is a constituent monomer of the crystalline polyester resin (a11) include a diol component (x1), a trihydric or higher alcohol component (x2), and a monoalcohol component (x3).

  Examples of the diol component (x1) include linear aliphatic diols (having 2 to 20 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1 , 13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol and 1,20-eicosanediol), branched aliphatic diols (having 3 to 18 carbon atoms, such as propylene glycol) 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-hepta Diol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 1,2-octadecanediol, and the like. 36 alkylene ether glycols (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), C4-C36 alicyclic diols (1,4-cyclohexanedimethanol, Hydrogenated bisphenol A, etc.), alkylene oxides of the above alicyclic diols (hereinafter “alkylene oxide” is abbreviated as AO) [ethylene oxide (hereinafter “ethylene oxide” is abbreviated as EO), propylene oxide (Hereinafter, “propylene oxide” is abbreviated as PO), butylene oxide (hereinafter, “butylene oxide” is abbreviated as BO), etc.] adducts (preferably having an average addition mole number of 1-30); bisphenols (bisphenol A) , Bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adducts (preferably an average addition mole number of 2-30); polylactone diol (poly ε-caprolactone diol, etc.); polybutadiene diol, etc. . Two or more of these may be used in combination.

  Among these diols, linear aliphatic diols are preferable from the viewpoints of crystallinity, low-temperature fixability and heat-resistant storage stability. More preferred is a linear aliphatic diol having 2 to 36 carbon atoms, still more preferred is a linear aliphatic diol having 2 to 20 carbon atoms, and particularly preferred are ethylene glycol, 1,3-propanediol, 1,4. -Butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol.

  The linear aliphatic diol content is preferably 80 mol% or more, more preferably 90 mol% or more based on the number of moles of the diol component (x1) used from the viewpoint of crystallinity.

  Similarly, the content of the diol component (x1) is preferably 80 mol% or more based on the number of moles of the alcohol component (X) that is a constituent monomer of the crystalline resin (A) from the viewpoint of crystallinity. More preferably, it is 90 mol% or more.

Examples of the trihydric or higher alcohol component (x2) include trivalent or higher valent polyhydric aliphatic alcohols having 3 to 36 carbon atoms [alkane polyol and intramolecular or intermolecular dehydrates thereof (for example, glycerin, trimethylolethane, Trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.]], saccharides and derivatives thereof (for example, sucrose and methylglucoside), trisphenols (trisphenol PA, etc.) AO adducts (preferably added moles) 2-30), AO adducts (preferably 2-30 added moles) of novolak resins (phenol novolak, cresol novolak, etc.) and acrylic polyols [copolymers of hydroxyethyl (meth) acrylate and other vinyl monomers, etc. ] Etc. are mentioned. As a trivalent or more alcohol component (x2), 1 type may be used and these 2 or more types may be used together.
Among these, from the viewpoint of hot offset resistance, a trivalent or higher valent polyhydric aliphatic alcohol and an AO adduct of a novolac resin are more preferable, and an AO adduct of a novolac resin is more preferable.

  The content of the trivalent or higher alcohol component (x2) is 10 mol% or less based on the number of moles of the alcohol component (X) that is a constituent monomer of the crystalline resin (A) from the viewpoint of crystallinity. Is more preferable, and 5 mol% or less is more preferable.

  Examples of the monoalcohol component (x3) include monoalcohols having 1 or more carbon atoms, such as primary alcohols {methanol, ethanol, linear saturated aliphatic monoalcohols (n-propan-1-ol, n-butane). -1-ol, n-pentan-1-ol, n-hexane-1-ol, n-heptan-1-ol, n-octane-1-ol, n-nonan-1-ol, n-decane-1 -Ol, n-undecan-1-ol, n-dodecan-1-ol, n-tridecan-1-ol, n-tetradecan-1-ol, n-pentadecan-1-ol, n-hexadecan-1-ol N-heptadecan-1-ol, n-octadecan-1-ol, n-nonadecan-1-ol, n-icosan-1-ol, n-henecosan-1-o N-docosan-1-ol, n-tricosan-1-ol, n-tetracosane-1-ol, n-pentacosan-1-ol, n-hexacosan-1-ol, n-heptacosan-1-ol, Branched saturated aliphatic monoalcohols (2-methylpropan-1-ol and n-octacosan-1-ol, n-nonacosan-1-ol and n-triacontan-1-ol and mixtures thereof (such as policosanol) 3-methylbutan-1-ol, etc.}, secondary alcohols (propan-2-ol, butan-2-ol, pentan-2-ol, hexane-2-ol, heptan-2-ol, 2-methylbutane-1 -Ol and cyclohexanol) and tertiary alcohols (2-methylpropan-2-ol, 2-methylbutane) 2-ol, 2-methylpentan-2-ol, 2-methylhexane-2-ol, 2-methylheptan-2-ol, 3-methylpentan-3-ol, 3-methyloctane-3-ol, etc.) In addition, as commercial products of higher monoalcohol having 23 or more carbon atoms (one-terminal primary alcohol of linear saturated hydrocarbon), Unilin 350 (26 carbon atoms), Unilin 425 (33 carbon atoms) , Unilin 550 (carbon number 39), Unilin 700 (carbon number 50) (all manufactured by Baker Petrolite Co., Ltd.), etc. As the other monoalcohol component (x3), one kind may be used. Two or more of these may be used in combination.

  Of the (x3), from the viewpoint of the crystallinity of (A) and the heat-resistant storage stability of the toner, primary alcohols (including commercial products of higher monoalcohols having 23 or more carbon atoms) are preferable, and 16 carbon atoms are more preferable. Primary alcohols (particularly preferably linear saturated aliphatic monoalcohols, including commercially available products of higher monoalcohols having 23 or more carbon atoms), more preferably n-octadecan-1-ol, n- Docosan-1-ol, Unilin 350 and Unilin 425.

  The content of the monoalcohol component (x3) is preferably 10 mol% or less based on the number of moles of the alcohol component (X) that is a constituent monomer of the crystalline resin (A) from the viewpoint of crystallinity, More preferably, it is 5 mol% or less.

The crystalline polyester resin (a11) comprises a carboxylic acid (salt) group and a sulfonic acid (salt) in addition to the diol component (x1), trivalent or higher alcohol component (x2) and monoalcohol component (x3) exemplified above. A diol (x1 ′) having at least one group selected from the group consisting of a group, a sulfamic acid (salt) group and a phosphoric acid (salt) group (hereinafter referred to as a diol having a functional group) It is good. As the diol (x1 ′) having a functional group, one type may be used, or two or more types may be used in combination.
By using the diol (x1 ′) having these functional groups as a constituent monomer, the charging stability and heat resistant storage stability of the toner are improved.
The content of the functional group-containing diol (x1 ′) is based on the number of moles of the alcohol component (X) that is a constituent monomer of the crystalline resin (A) from the viewpoints of crystallinity, low-temperature fixability, and heat-resistant storage stability. 5 mol% or less is preferable.

  Examples of the diol (x1′-1) having a carboxylic acid (salt) group include tartaric acid (salt), 2,2-bis (hydroxymethyl) propanoic acid (salt), 2,2-bis (hydroxymethyl) butanoic acid ( Salt) and 3- [bis (2-hydroxyethyl) amino] propanoic acid (salt).

  Examples of the diol (x1′-2) having a sulfonic acid (salt) group include 2,2-bis (hydroxymethyl) ethanesulfonic acid (salt), 2- [bis (2-hydroxyethyl) amino] ethanesulfonic acid ( Salt) and 5-sulfo-isophthalic acid-1,3-bis (2-hydroxyethyl) ester (salt).

  Examples of the diol (x1′-3) having a sulfamic acid (salt) group include N, N-bis (2-hydroxyethyl) sulfamic acid (salt) and N, N-bis (3-hydroxypropyl) sulfamic acid (salt). ), N, N-bis (4-hydroxybutyl) sulfamic acid (salt), N, N-bis (2-hydroxypropyl) sulfamic acid (salt), and the like.

Examples of the diol (x1′-4) having a phosphoric acid (salt) group include bis (2-hydroxyethyl) phosphate (salt).
The salts that make up the acid salts include ammonium salts, amine salts (methylamine salts, dimethylamine salts, trimethylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, propylamine salts, dipropylamine salts, tripropylamine salts, butylamines. Salt, dibutylamine salt, tributylamine salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, N-methylethanolamine salt, N-ethylethanolamine salt, N, N-dimethylethanolamine salt, N, N- Diethylethanolamine salt, hydroxylamine salt, N, N-diethylhydroxylamine salt, morpholine salt, etc.), quaternary ammonium salt [tetramethylammonium salt, tetraethylammonium salt and trimethyl (2-hydroxyethyl) Ammonium salts] and alkali metal salts (sodium salts and potassium salts, etc.).

  Of the diols (x1 ′) having functional groups, diols (x1′-1) and sulfonic acid (salt) groups having a carboxylic acid (salt) group are preferable from the viewpoint of charge stability and heat-resistant storage stability of the toner. Diol (x1′-2) having

Next, alcohol component (X), (y1) 90-99.49 mol%, (y2) 0.01-1.0 mol%, and (y3) 0.5-9.0 mol% are included. The crystalline polyurethane (a12) having the carboxylic acid component (Y) as a constituent monomer will be described.
As the crystalline polyurethane resin (a12), the crystalline polyester resin (a11) and diisocyanate (v2) as constituent monomers (a121), and the crystalline polyester (a11) and the alcohol component are used. Examples thereof include (a122) having (X) and diisocyanate (v2) as constituent monomers.
The crystalline polyurethane resin (a121) having the crystalline polyester resin (a11) and the diisocyanate (v2) as constituent monomers can be obtained by reacting the crystalline polyester resin (a11) and the diisocyanate (v2). .
The crystalline polyurethane resin (a122) having the crystalline polyester resin (a11), the alcohol component (X) and the diisocyanate (v2) as constituent monomers is composed of the crystalline polyester (a11), the alcohol component (X) and the diisocyanate (v2). ).

  Further, since the crystalline polyurethane resin (a12) further contains the diol (x1 ′) having the functional group as a constituent unit as a constituent monomer, the charging stability and heat resistant storage stability of the toner are easily improved. preferable.

  As the diisocyanate (v2) which is a constituent monomer of the crystalline polyurethane resin (a12), an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), and having 2 to 18 carbon atoms. Aliphatic diisocyanates, modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups and oxazolidone group-containing modified products) and two or more of these And the like.

  Examples of the aromatic diisocyanate having 6 to 20 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diene. Isocyanates (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI) and crude diaminophenylmethane diisocyanate (crude MDI) Etc.

Examples of the aliphatic diisocyanate having 2 to 18 carbon atoms include a chain aliphatic diisocyanate having 2 to 18 carbon atoms and a cyclic aliphatic diisocyanate having 3 to 18 carbon atoms.
Examples of the chain aliphatic diisocyanate having 2 to 18 carbon atoms include linear aliphatic diisocyanates (ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, etc.), branched aliphatic diisocyanates (2,2 , 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2, 6-diisocyanatohexanoate etc.) and mixtures thereof.

  Examples of the cycloaliphatic diisocyanate having 3 to 18 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis ( 2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate and mixtures thereof.

  As the modified product of diisocyanate, a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group and / or an oxazolidone group is used. Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof (for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)).

  Among these diisocyanates (v2), from the viewpoint of hot offset resistance and durability, preferred are aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms, and more preferred. TDI, MDI, HDI, hydrogenated MDI and IPDI.

Next, alcohol component (X), (y1) 90-99.49 mol%, (y2) 0.01-1.0 mol%, and (y3) 0.5-9.0 mol% are included. The crystalline polyurea resin (a13) having the carboxylic acid component (Y) as a constituent monomer will be described.
Examples of the crystalline polyurea resin (a13) include those containing the crystalline polyester resin (a11), the diamine (z), and the diisocyanate (v2) as constituent monomers.
Such a crystalline polyurea resin (a13) can be obtained by reacting a crystalline polyester resin (a11), a diamine (z), and a diisocyanate (v2).

Examples of the diamine (z) include aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms.
Examples of the aliphatic diamine having 2 to 18 carbon atoms include a chain aliphatic diamine and a cyclic aliphatic diamine.

Examples of chain aliphatic diamines include alkylene diamines having 2 to 12 carbon atoms (such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine and hexamethylene diamine) and polyalkylenes (preferably having 2 to 6 carbon atoms) polyamines [diethylene triamines. , Iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.
Cycloaliphatic polyamines include alicyclic diamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene dianiline) and 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like} and a heterocyclic diamine having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.] and the like.

  The aromatic diamine having 6 to 20 carbon atoms has an unsubstituted aromatic diamine and an alkyl group (an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group). An aromatic diamine etc. are mentioned.

  Examples of the unsubstituted aromatic diamine include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenylsulfone, benzidine, thiodianiline, bis (3 , 4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, naphthylenediamine and mixtures thereof.

  Examples of the aromatic diamine having an alkyl group (an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group) include 2,4- or 2,6-tolylenediamine, Crudetolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl- 2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4- Diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-to Ethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5- Diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2, 6-dibutyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetraisopropylbenzidine, 3,3 ′, 5,5′-tetra Methyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraisopropyl 4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetrabutyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,5 -Diisopropyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3' , 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4 , 4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone and mixtures thereof Thing etc. are mentioned.

  Preferred as the diisocyanate (v2) are aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms, and more preferred are TDI, MDI, HDI, hydrogenated MDI and IPDI.

Next, alcohol component (X), (y1) 90-99.49 mol%, (y2) 0.01-1.0 mol%, and (y3) 0.5-9.0 mol% are included. The crystalline polyamide resin (a14) having the carboxylic acid component (Y) as a constituent monomer will be described.
Examples of the crystalline polyamide resin (a14) include those containing the crystalline polyester resin (a11), the diamine (z), and the dicarboxylic acid (y1) or (y5) as constituent monomers.
Such a crystalline polyamide resin (a14) can be obtained by reacting the crystalline polyester resin (a11), the diamine (z), and the dicarboxylic acid (y1) or (y5).

  The toner binder of the present invention may contain a crystalline resin (A ′) other than the crystalline resin (A) having the alcohol component (X) and the carboxylic acid component (Y) as constituent monomers. . As the crystalline resin (A ′), the constituent monomer is not limited as long as it is a crystalline resin other than the crystalline resin (A).

  Examples of the crystalline resin (A ′) include the following crystalline polyester resin (a′11), crystalline polyurethane resin (a′12), crystalline polyurea resin (a′13), and crystalline polyamide resin (a′14). ), And a crystalline polyvinyl resin (a′15). These crystalline resins may be used in combination, or may be a crystalline resin copolymerized with a resin containing these crystalline resins.

The crystalline polyester resin (a′11) is a crystalline polyester resin other than the crystalline polyester resin (a11), and includes, for example, an alcohol component (X) and a carboxylic acid component (Y ′) as constituent monomers. A crystalline polyester resin, wherein (Y ′) contains less than 90 mol% (y1) or more than 99.49 mol%, contains less than 0.01 (y2) or 1.0 mol % And (y3) less than 0.5 or more than 9.0 mol% of crystalline polyester resin (a′111), (Y ′) is 90 to 99 (y1). Polyester resin (a′112), (Y ′) containing 90 to 99.49 mol of (y1) containing .49 mol% and (y2) of 0.01 to 1.0 mol% and not containing (y3) % And (y3) 0.5-9.0 mol%, The polyester resin (a′113) not containing (y2), and the polyester resin (a′114) in which (Y ′) contains 90 to 99.49 mol% of (y1) and does not contain (y2) and (y3) ) Etc.
As alcohol component (X) which comprises crystalline polyester resin (a'11), the same thing as crystalline polyester resin (a11) can be used, and as alcohol contained in alcohol component (X), it is crystalline. The same thing as illustrated with the polyester resin (a11) can be used.

  Examples of the crystalline polyurethane resin (a′12) include a crystalline polyurethane resin containing the crystalline polyester (a′11), the alcohol component (X), and the diisocyanate (v2) as constituent monomers.

  Examples of the crystalline polyurea resin (a′13) include crystalline polyurea resins containing the crystalline polyester (a′11), the diamine (z), and the diisocyanate (v2) as constituent monomers.

  Examples of the crystalline polyamide resin (a′14) include a crystalline polyamide resin containing the crystalline polyester (a′11), the diamine (z), and the alcohol component (X) as constituent monomers.

As the crystalline polyvinyl resin (a′15), a polymerizable carboxylic acid which is a carboxylic acid component (Y ′) [maleic acid and fumaric acid described in 2 to 12 linear aliphatic dicarboxylic acid (y1), monocarboxylic acid Polymer obtained by homopolymerizing or copolymerizing ester (e) of (meth) acrylic acid described in acid (y4) and alkenyl succinic acid described in other dicarboxylic acid (y5)] and alcohol component (X) Etc.
Preferred examples of the ester (e) serving as a constituent monomer of the crystalline polyvinyl resin (a′15) include 3-methoxy-propyl (meth) acrylate, 5-methoxy-pentyl (meth) acrylate, and 7-methoxy. -Heptyl (meth) acrylate, 9-methoxy-nonyl (meth) acrylate, 11-methoxy-undecyl (meth) acrylate, 13-methoxy-tridecyl (meth) acrylate and the like.
Specific examples of the monomer copolymerizable with the ester include esterified products of vinyl alcohol and aliphatic monocarboxylic acid (vinyl acetate, vinyl propionate, vinyl butyrate, etc.), allyl alcohol and dicarboxylic acid. Esterified product (diallyl phthalate, diallyl adipate, etc.), esterified product of 2-methylallyl alcohol and aliphatic monocarboxylic acid (isopropenyl acetate, etc.), vinyl methacrylate, esterified product of vinyl alcohol and aromatic monocarboxylic acid (vinyl) Benzoate, methyl-4-vinylbenzoate, etc.), esterified product of alicyclic alcohol and methacrylic acid (cyclohexyl methacrylate, etc.), esterified product of aromatic (aliphatic) alcohol and (meth) acrylic acid (benzyl (meth) acrylate) , Phenyl Meth) acrylate, etc.), vinyl methoxyacetate, ethyl-α-ethoxy acrylate, alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (Meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicosyl (meth) acrylate, stearyl (Meth) acrylate and behenyl acrylate, 3-methoxy-propyl (meth) acrylate, 5-methoxy-pentyl (meth) acrylate, 7-methoxy-heptyl (meth) acrylate, 9- Toxi-nonyl (meth) acrylate, 11-methoxy-undecyl (meth) acrylate and 13-methoxy-tridecyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight chain having 2 to 8 carbon atoms, Branched or alicyclic groups), dialkyl maleates (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) Allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.) and other polyalkylene glycol chains and polymerizable double bonds Monomer having [polyethylene glycol (eg Mn = 300) mono (meth) acrylate, polypropylene glycol (eg Mn = 500) mono (meth) acrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) of polyhydric alcohols Acrylate: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.]. These can be used as long as the crystallinity of the crystalline resin (A) is not impaired.

  The crystalline polyvinyl resin (a′15) is composed of the following monomers other than the above monomers (w1) to (w9) in addition to the above monomers as long as the crystallinity is not impaired. It can be copolymerized as a body.

  Examples of the hydrocarbon having a polymerizable double bond as the monomer (w1) include the following aliphatic hydrocarbon having a polymerizable double bond (w11) and an aromatic hydrocarbon having a polymerizable double bond: (W12).

  Examples of the aliphatic hydrocarbon (w11) having a polymerizable double bond include the following chain hydrocarbon (w111) having a polymerizable double bond and cyclic hydrocarbon (w112) having a polymerizable double bond. Can be mentioned.

  Examples of the chain hydrocarbon having a polymerizable double bond (w111) include alkenes having 2 to 30 carbon atoms (for example, isoprene, 1,4-pentadiene, 1,5-hexadiene, and 1,7-octadiene). The cyclic hydrocarbon having a polymerizable double bond (w112) includes mono- or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinylcyclohexene, ethylidenebicycloheptene, etc.) and mono or 5 to 30 carbon atoms. And dicycloalkadiene [for example, (di) cyclopentadiene and the like] and the like.

  Examples of the aromatic hydrocarbon (w12) having a polymerizable double bond include styrene and styrene hydrocarbyl (alkyl, cycloalkyl, aralkyl or alkenyl having 1 to 30 carbon atoms) substituted products (for example, α-methylstyrene, vinyl). Toluene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc.) and vinyl naphthalene, etc. Can be mentioned.

Examples of the salt of the monomer (w2) having a carboxyl group and a polymerizable double bond include alkali metal salts (sodium salt and potassium salt), alkaline earth metal salts (calcium salt and magnesium salt). Etc.), ammonium salts, amine salts and quaternary ammonium salts.
The amine salt is not particularly limited as long as it is an amine compound. For example, primary amine salts (such as ethylamine salts, butylamine salts and octylamine salts), secondary amines (such as diethylamine salts and dibutylamine salts), tertiary amines ( Triethylamine salt and tributylamine salt). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, and tributyllaurylammonium salt.

  Specific examples of the salt of a monomer having a carboxyl group and a polymerizable double bond include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monoester maleate. Examples include potassium, lithium acrylate, cesium acrylate, ammonium acrylate, calcium acrylate, and aluminum acrylate.

  As the monomer (w3), a monomer having a sulfo group and a polymerizable double bond, and a salt thereof, an alkene sulfonic acid having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid, and Methyl vinyl sulfonic acid and the like), styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfonic acid, C 5-18 sulfo (hydroxy) alkyl- (meth) acrylate [for example, sulfopropyl (Meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, etc.], carbon number 5-18 sulfo (hydroxy) alkyl (meth) acrylamide [eg 2- (me ) Acrylylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, etc.], alkyl (having 3 to 18 carbon atoms) ) Allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2-ethylhexyl-allylsulfosuccinic acid, etc.), poly [n (degree of polymerization; the same applies hereinafter) = 2 to 30] oxyalkylene (oxyethylene, oxypropylene) And oxyalkylene may be used alone or in combination, and when used together, the addition form may be random addition or block addition.) Mono (meth) acrylate sulfate ester [eg poly (n = 5-15) oxyethylene Monomethacrylate sulfate Este And poly (n = 5 to 15) oxypropylene monomethacrylate sulfate and the like] and salts thereof.

  In addition, as a salt, what was illustrated as a salt which comprises the salt of the said monomer (w2) which has a carboxyl group and a polymerizable double bond is mentioned.

Monomer (w4) phosphono group and monomer having a polymerizable double bond and salts thereof include (meth) acryloyloxyalkyl phosphoric acid monoester (alkyl group having 1 to 24 carbon atoms, for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxyalkylphosphonic acid (the alkyl group has 1 to 24 carbon atoms, for example, 2-acryloyloxyethylphosphonic acid) Etc.).
In addition, as a salt, what was illustrated as a salt which comprises the said monomer (w2) which has a carboxyl group and a polymerizable double bond is mentioned.

  Monomers (w5) having a hydroxyl group and a polymerizable double bond include hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene Glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol , 2-hydroxyethyl propenyl ether, sucrose allyl ether, and the like.

Examples of the nitrogen-containing monomer having a polymerizable double bond that is a monomer (w6) include a monomer (w61) having an amino group and a polymerizable double bond, and an amide group and a polymerizable double bond. Monomer (w62) having a nitrile group and a polymerizable double bond (w63), a monomer having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond And body (w64).
As the monomer (w61) having an amino group and a polymerizable double bond, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N- Aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole and these Salts and the like.

Monomers (w62) having an amide group and a polymerizable double bond include (meth) acrylamide, N-methyl (meth) acrylamide, N-butylacrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N , N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like It is done.
Examples of the monomer having 3 to 10 carbon atoms (w63) having a nitrile group and a polymerizable double bond include (meth) acrylonitrile, cyanostyrene, and cyanoacrylate.
Nitrostyrene etc. are mentioned as a C8-C12 monomer (w64) which has a nitro group and a polymerizable double bond.

  Examples of the monomer having 6 to 18 carbon atoms having a polymerizable double bond and an epoxy group as the monomer (w7) include glycidyl (meth) acrylate and p-vinylphenylphenyl oxide.

  Examples of the monomer (w8) having 2 to 16 carbon atoms having a polymerizable double bond with a halogen element include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichloromethane. Examples include styrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene.

Examples of the monomer (w9) ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond include carbon number having a polymerizable double bond. 3-16 ether (w91), C4-C12 ketone having a polymerizable double bond (w92), C2-C16 sulfur-containing compound having a polymerizable double bond (w93), and the like. .
Examples of the ether having 3 to 16 carbon atoms having a polymerizable double bond (w91) include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2- Examples include methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, acetoxystyrene, and phenoxystyrene.
As a C4-C12 ketone (w92) which has a polymerizable double bond, vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, etc. are mentioned.
Examples of the sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond (w93) include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide. .

In the toner binder of the present invention, the endothermic amount based on the endothermic peak when the temperature is increased in DSC (also referred to as differential scanning calorimetry) preferably satisfies the following relational expression (1). That is, in DSC, the endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the first temperature raising process at the time of temperature raising, cooling, and temperature raising is defined as S ₁ , and the crystal of the second temperature raising process. When the endothermic amount based on the endothermic peak derived from the conductive resin (A) is S ₂ , it is the low temperature fixability that the endothermic amounts S ₁ and S ₂ of the endothermic peak at the time of temperature increase satisfy the following relational expression (1): It is preferable from the viewpoints of heat-resistant storage stability, document offset property and durability.
(S ₂ / S ₁ ) × 100 ≧ 35 (1)

In the present invention, the temperature raising / cooling conditions when measuring S ₁ and S ₂ by DSC are raised from 30 ° C. to 180 ° C. under the condition of 10 ° C./min (first temperature raising process). Next, after standing at 180 ° C. for 10 minutes, it is cooled to 0 ° C. under the condition of 10 ° C./min (first cooling process). Next, after standing at 0 ° C. for 10 minutes, the temperature is raised to 180 ° C. under the condition of 10 ° C./min (second temperature raising process).

S ₂ / S ₁ is an index of the easiness of precipitation of the crystals (A) in the toner binder upon cooling after heat fixing. The larger the value, the easier the crystals of (A) are precipitated during cooling. It means that stability can be improved. More preferably, it satisfies the relational expression (1-1), more preferably satisfies the relational expression (1-2), and particularly preferably satisfies the relational expression (1-3).
99 ≧ (S ₂ / S ₁ ) × 100 ≧ 40 (1-1)
97 ≧ (S ₂ / S ₁ ) × 100 ≧ 50 (1-2)
96 ≧ (S ₂ / S ₁ ) × 100 ≧ 60 (1-3)
In order to satisfy the relational expression (1), the ΔSP value of the crystalline resin (A) and the amorphous polyester resin (B), which is an optional component described later, and the molecular weight, acid value, and hydroxyl value of each are adjusted. Design is possible.
Specifically, when it is desired to increase S ₂ / S ₁ , the ΔSP value of the crystalline resin (A) and the amorphous polyester resin (B) is increased, and the molecular weight of the crystalline resin (A) is increased. It can be controlled by reducing the acid value and hydroxyl value of (A) and the amorphous polyester resin (B).

In the DSC measurement of the toner binder, when there are two or more endothermic peaks derived from the crystalline resin (A), both S ₁ and S ₂ are calculated by the total area.
Further, when the endothermic peak derived from the crystalline resin (A) overlaps with an endothermic peak not derived from the crystalline resin (A), it is decomposed into each peak to obtain the endothermic peak area derived from the crystalline resin (A). Of the raw materials further blended into the toner binder, crystalline raw materials such as a release agent may exhibit an endothermic peak.
The endothermic amount of the endothermic peak is calculated by drawing a line perpendicular to the base line at the peak valley and using the area divided by the dividing line.
If the peak can be identified, DSC may be measured with toner instead of toner binder.

  The endothermic amount (J / g) based on the endothermic peak derived from the crystalline resin (A) in the second temperature raising process by a differential scanning calorimeter (DSC) is preferably 1 to 45 J / g, more preferably 1 to 30 J. / G, more preferably 2 to 25 J / g, particularly preferably 3 to 20 J / g. From the viewpoint of low-temperature fixability and gloss, the endothermic amount of the endothermic peak derived from the crystalline resin (A) is preferably 1 J / g or more, and preferably 45 J / g or less from the viewpoint of hot melt resistance. The endothermic amount of the endothermic peak derived from the crystalline resin (A) in the temperature raising process is measured by DSC.

The peak top temperature [Ta] of the endothermic peak derived from the crystalline resin (A) is 40 to 100 ° C. from the viewpoints of heat resistant storage stability of the toner, image strength after fixing, and document offset property.
Moreover, from a viewpoint of low temperature fixability and heat-resistant storage stability, Preferably it is 45-90 degreeC, More preferably, it is 50-85 degreeC, More preferably, it is 55-80 degreeC.
Note that the peak top temperature of the endothermic peak refers to the temperature at the deepest portion of the recess of the endothermic peak of the DSC chart.
And when there are two or more endothermic peaks derived from the crystalline resin (A), the temperature indicating the peak top of at least one endothermic peak may be in this range.

The acid value of the crystalline resin (A) is preferably 10 mgKOH / g or less, more preferably 7 mgKOH / g or less, still more preferably 5 mgKOH / g or less, and particularly preferably 3 mgKOH / g from the viewpoint of heat-resistant storage stability and charging characteristics of the toner. g or less.
In the present invention, the acid value can be measured by a method defined in JIS K0070.

The hydroxyl value of the crystalline resin (A) is preferably 70 mgKOH / g or less, more preferably 3 to 60 mgKOH / g from the viewpoints of low-temperature fixability, heat-resistant storage stability, charging stability, image strength and document offset property. More preferably 5 to 50 mgKOH / g, and particularly preferably 7 to 45 mgKOH / g.
In the present invention, the hydroxyl value can be measured by a method defined in JIS K0070.

  The weight average molecular weight of the crystalline resin (A) (hereinafter, the weight average molecular weight may be abbreviated as Mw) is 5,000 to 100,000 from the viewpoints of low-temperature fixability, glossiness, and heat storage stability. More preferably, it is 8,000-80,000, More preferably, it is 10,000-60,000, Most preferably, it is 12,000-50,000.

Mw and number average molecular weight (also referred to as Mn in this specification) are obtained by dissolving the crystalline resin (A) in tetrahydrofuran (THF), and using it as a sample solution, using gel permeation chromatography (GPC). And measured under the following conditions. Mw and Mn of the non-crystalline polyester resin (B) and non-crystalline vinyl resin (C) to be described later are also measured under the following conditions as in the case of the crystalline resin (A).
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSKgel (registered trademark) GMH6 [manufactured by Tosoh Corporation]
Mobile phase: THF
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Injection amount: 100 μL
Flow rate: 1 ml / min
Detection apparatus: Differential refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

  The toner binder of the present invention preferably further contains an amorphous polyester resin (B) from the viewpoints of hot offset resistance, charging stability, image strength, document offset property and durability.

If the amorphous polyester resin (B) used in the toner and toner binder of the present invention is an amorphous polyester resin having an alcohol component (x) and a carboxylic acid component (y) as essential constituent monomers, the resin The composition of is not particularly limited.
“Amorphous” in the present invention means that there is no peak top temperature of an endothermic peak when the transition temperature of a sample is measured using a differential scanning calorimeter.

  As the alcohol component (x) of the amorphous polyester resin (B), a diol {an alkylene glycol having 2 to 12 carbon atoms, an alkylene oxide adduct of bisphenols (hereinafter, "alkylene oxide" may be abbreviated as AO). (Preferably average added mole number 2-30) [For example, AO adduct of bisphenol A (average added mole number 2-30) etc.]} Polyhydric aliphatic alcohol and novolak resin having a valence of 3 or more Polyoxyalkylene ethers (preferably 2 to 30 as the number of oxyalkylene units) and the like, and examples of the carboxylic acid component (y) include those similar to the carboxylic acid component (Y).

Of the alcohol component (x) used in the amorphous polyester resin (B), from the viewpoints of low-temperature fixability and hot offset resistance, an alkylene glycol having 2 to 12 carbon atoms and an alkylene oxide adduct of bisphenols ( Average addition mole number 2-30) and polyoxyalkylene ether of novolak resin (preferably 2-30 as the number of oxyalkylene units), more preferably alkylene glycol of 2-6 carbon atoms and alkylene oxide of bisphenol A An adduct (average number of moles added 2 to 5), particularly preferably an alkylene oxide adduct of ethylene glycol, propylene glycol and bisphenol A (average number of moles added 2 to 3).
In order to obtain an amorphous resin, the content of the linear aliphatic diol is preferably 70 mol% or less, more preferably 60 mol% or less of the diol component used. Moreover, it is preferable that a diol component is 90-100 mol% in the alcohol component (x) which comprises an amorphous polyester resin (B).

  In addition, the alcohol component (x) of the amorphous polyester resin (B) is the same as the alcohol component (X) used in the crystalline polyester (a11) in addition to the above alcohol component as long as the amorphous property is not inhibited. Can be used.

  The carboxylic acid component (y) is preferably an aromatic carboxylic acid having 8 to 36 carbon atoms (benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, t- Butyl isophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4′-biphenyldicarboxylic acid), aliphatic carboxylic acid 2-50 alkanedicarboxylic acid (adipic acid etc.), C9-20 aromatic polycarboxylic acid Acids (such as trimellitic acid and pyromellitic acid) and combinations thereof. Further, anhydrides of these acids and lower alkyl (C1-4) esters (methyl esters, ethyl esters, isopropyl esters, etc.) may be used, or these carboxylic acids may be used in combination.

The glass transition point (Tg) of the amorphous polyester resin (B) is preferably from 40 to 75 ° C, more preferably from 45 to 72 ° C, further preferably from the viewpoint of low-temperature fixability, heat-resistant storage stability and document offset property. Is 50-70 degreeC.
In addition, Tg is measured by the method (DSC method) prescribed | regulated to ASTMD3418-82 using DSC.

The Mw of the amorphous polyester resin (B) is preferably from 2,000 to 200,000, more preferably from 2,500 to 180, from the viewpoints of low-temperature fixability, gloss, heat resistant storage stability and document offset. 000, more preferably 3,000 to 150,000.
Mw and Mn of the amorphous polyester resin (B) are determined by GPC in the same manner as the crystalline resin (A) described above.

The acid value of the amorphous polyester resin (B) is preferably 30 mgKOH / g or less, more preferably 2 to 2, from the viewpoints of low-temperature fixability, heat-resistant storage stability, charging stability, image strength and document offset property. 28 mg KOH / g, more preferably 3 to 25 mg KOH / g, and particularly preferably 4 to 22 mg KOH / g.
In the present invention, the acid value can be measured by a method defined in JIS K0070.

  The method for reducing the acid value of the amorphous polyester resin (B) is not particularly limited. For example, the molecular weight is increased, or the amount of trimellitic anhydride added to the terminal is decreased (specifically, production examples described later) In this method, the amount of trimellitic anhydride to be reacted at 180 ° C. is reduced), the end is capped with a monoalcohol or the like, a trifunctional or higher functional acid or alcohol is used for the crosslinking reaction, and the alcohol is adjusted by adjusting the ratio of acid and alcohol. And the terminal functional group is converted to alcohol.

The hydroxyl value of the amorphous polyester resin (B) is preferably 50 mgKOH / g or less, more preferably 3 to 3, from the viewpoints of low-temperature fixability, heat-resistant storage stability, charging stability, image strength and document offset property. It is 45 mgKOH / g or less, More preferably, it is 5-40 mgKOH / g or less, Most preferably, it is 7-38 mgKOH / g or less.
In the present invention, the hydroxyl value can be measured by a method defined in JIS K0070.

  The method for reducing the hydroxyl value of the amorphous polyester resin (B) is not particularly limited. For example, the molecular weight is increased, the end is capped with a monocarboxylic acid or the like, and the crosslinking reaction is performed with a tri- or higher functional acid or alcohol. And adjusting the ratio of the charged acid and alcohol to make the acid a little excessive to make the terminal functional group an acid.

  The softening point (Tm) of the amorphous polyester resin (B) is preferably 80 to 170 ° C, more preferably 85 to 165 ° C, still more preferably 90 to 160 ° C, and particularly preferably 95 to 155 ° C.

  The amorphous polyester resin (B) may be used in combination of two or more types having different Tm, and a combination of those having a Tm of 80 ° C. or more and less than 110 ° C. and those having a Tm of 110 ° C. or more and 170 ° C. or less is preferable. Is a combination of those having a temperature of 85 ° C. or higher and 105 ° C. or lower and those having a temperature of 115 ° C. or higher and 160 ° C. or lower. By using two or more kinds of amorphous polyester resins (B) in the above range, low-temperature fixability, hot offset resistance, heat-resistant storage stability and image strength are improved.

The method for mixing the crystalline resin (A) and the amorphous polyester resin (B) is not particularly specified. For example, the crystalline resin (A) and the amorphous polyester resin (B) are mixed with a melt kneader. And a method of dissolving and mixing with a solvent and then removing the solvent, and a method of mixing the crystalline resin (A) during the production of the amorphous polyester resin (B). The mixing temperature is preferably 100 to 200 ° C from the viewpoint of resin viscosity, and more preferably 110 to 190 ° C.
The toner binder of the present invention can be obtained, for example, by mixing the crystalline resin (A) and the amorphous polyester resin (B) as described above.

  The weight ratio (B / A) between the amorphous polyester resin (B) and the crystalline resin (A) is preferably 50/50 from the viewpoints of low-temperature fixability, hot offset resistance, charging stability and document offset. It is -95/5, More preferably, it is 60 / 40-92 / 8, More preferably, it is 70 / 30-90 / 10. A mixture containing the amorphous polyester resin (B) and the crystalline resin (A) in the above ratio is preferable as the toner binder of the present invention. That is, the weight ratio (B / A) between the amorphous polyester resin (B) and the crystalline resin (A) in the toner binder of the present invention is preferably within the above range.

  As the toner binder of the present invention, other resins (C) other than the crystalline resin (A) and the amorphous polyester resin (B) may be used. Examples of the other resin (C) include an amorphous vinyl resin (C1), an amorphous epoxy resin (C2), and an amorphous urethane resin (C3).

As the amorphous vinyl resin (C1), for example, a polymer of a styrene monomer alone, a copolymer of a styrene monomer and a mono (meth) acrylic monomer, a polymer of a styrene monomer alone and the amorphous polyester Examples thereof include a resin obtained by binding a resin (B) and a resin obtained by binding a copolymer of a styrene monomer and a mono (meth) acrylic monomer and the amorphous polyester resin (B).
Examples of the styrene monomer include styrene and alkyl styrene having an alkyl group having 1 to 3 carbon atoms (for example, α-methyl styrene and p-methyl styrene). Styrene is preferred.

Mono (meth) acrylic monomers that can be used in combination include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. An alkyl mono (meth) acrylate having 1 to 18 carbon atoms in the alkyl group; a mono (meth) acrylate having a hydroxyl group having 1 to 18 carbon atoms in an alkyl group such as hydroxylethyl (meth) acrylate; dimethylaminoethyl (meth) C1-C18 amino group-containing mono (meth) acrylates of alkyl groups such as acrylate and diethylaminoethyl (meth) acrylate; acrylonitrile, methacrylonitrile, alkyl groups having 2-18 carbon atoms in methacrylonitrile Replaced nitrile group-containing mono (meth) acrylic compound and (meth) acrylic acid.
Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid; and a mixture of two or more thereof are preferable.

If necessary, other vinyl ester monomers and aliphatic hydrocarbon vinyl monomers may be used in combination with the amorphous vinyl resin (C1).
Examples of vinyl ester monomers include aliphatic vinyl esters (4 to 15 carbon atoms such as vinyl acetate, vinyl propionate and isopropenyl acetate), unsaturated carboxylic acid polyvalent (2 to 3 valent) alcohol esters {8 to 200 carbon atoms. For example, polyfunctional (meth) acrylate (ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1, 6-hexanediol diacrylate and polyethylene glycol di (meth) acrylate, etc.)}, aromatic vinyl esters (C9-15, such as methyl-4-vinylbenzoate) and the like.
Aliphatic hydrocarbon vinyl monomers include olefins (2 to 10 carbon atoms such as ethylene, propylene, butene and octene), dienes (4 to 10 carbon atoms such as butadiene, isoprene and 1,6-hexadiene) and the like. Can be mentioned.

  The Mw of the amorphous vinyl resin (C1) used in the present invention is Mw 100,000 to 300,000, preferably 130,000 to 280,000, more preferably from the viewpoint of the fixing temperature range. 150,000-250,000.

  Further, the ratio (Mw / Mn) of Mw and number average molecular weight (Mn) of the amorphous vinyl resin (C1) is preferably 10 to 70, more preferably 15 from the viewpoint of the fixing temperature range. It is -65, More preferably, it is 20-60.

  Mw and Mn of the amorphous vinyl resin (C1) are determined by GPC in the same manner as the crystalline resin (A) described above.

  It is preferable to use two or more types of amorphous vinyl resins (C1) having different molecular weights from the viewpoint of the fixing temperature range.

  Amorphous epoxy resin (C2) includes polyepoxide ring-opening polymer, polyepoxide and active hydrogen-containing compound {water, polyol [diol and trivalent or higher polyol], dicarboxylic acid, trivalent or higher polycarboxylic acid, polyamine. }, A polyepoxide ring-opening polymer and the amorphous polyester resin (B), and a polyepoxide and active hydrogen-containing compound polyaddition and the amorphous polyester resin (B). ) And the like.

  As the amorphous urethane resin (C3), the diisocyanate (v2), the monoisocyanate (v1) and / or the tri- or higher functional polyisocyanate (v3), the amorphous polyester resin (B), and as necessary. What reacted with chain extension agents (diamine etc.) etc. are mentioned.

  As monoisocyanate (v1), phenyl isocyanate, tolylene isocyanate, xylylene isocyanate, α, α, α ′, α′-tetramethylxylylene isocyanate, naphthylene isocyanate, ethyl isocyanate, propyl isocyanate, hexyl isocyanate, octyl isocyanate Decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, cyclobutyl isocyanate, cyclohexyl isocyanate, cyclooctyl isocyanate, cyclodecyl isocyanate, cyclododecyl isocyanate, cyclotetradecyl isocyanate Nates, isophorone isocyanate, dicyclohexylmethane-4-isocyanate, cyclohexane Ren isocyanate, methyl cyclohexylene diisocyanate, norbornane diisocyanate and bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, and the like.

  Further, the trifunctional or higher polyisocyanate (v3) is not particularly limited as long as it is a compound having three or more isocyanate groups. Examples thereof include compounds containing chemical structures of triisocyanate, tetraisocyanate, isocyanurate and biuret. It is done.

  The glass transition point (Tg) of the other resin (C) is preferably 40 to 75 ° C., more preferably 45 to 72 ° C., and still more preferably 50 to 50 ° C. from the viewpoints of low-temperature fixability, heat-resistant storage stability and document offset property. 70 ° C.

  The weight of the other resin (C) contained in the toner binder is preferably 30% by weight or less based on the weight of the toner binder from the viewpoints of low-temperature fixability, hot offset resistance, charging stability and document offset. It is.

  The toner binder of the present invention contains a crystalline resin (A), and may further contain an amorphous polyester resin (B) and other resins (C). As long as the above is not impaired, a crystalline resin (A ′) may be included as necessary. A toner binder containing a crystalline resin (A) and an amorphous polyester resin (B) is preferable.

  The toner of the present invention contains the toner binder of the present invention.

  In addition to the toner binder of the present invention, the toner of the present invention may contain one or more known additives selected from a colorant, a release agent, a charge control agent, a fluidizing agent, and the like, if necessary.

As the colorant, all of dyes and pigments used as toner colorants can be used. The colorant preferably contains one or more selected from the group consisting of a black colorant, a blue colorant, a red colorant and a yellow colorant.
Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin 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, Orazole Brown B, Oil Pink OP, etc. Or 2 or more types can be mixed and used.
Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant.

The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the total amount of the toner binder.
When magnetic powder is used, the amount is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight with respect to 100 parts by weight in total with the toner binder. Above and below, parts mean parts by weight.

  As the release agent, those having a softening point [Tm] of 50 to 170 ° C. by a flow tester are preferable, and aliphatic hydrocarbon waxes such as polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and oxides thereof. , Carnauba wax, montan wax and deoxidized waxes thereof, ester waxes such as fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and mixtures thereof.

The softening point [Tm] of the release agent by a flow tester was measured under the following conditions.
<Measurement method of flow softening point [Tm]>
Using a constant test force extrusion type flow tester {“CFT-500D” [manufactured by Shimadzu Corporation]}, a 1 g measurement sample was heated at a temperature rising rate of 6 ° C./min. Apply a load, extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger drop (flow value)" and "temperature", corresponding to 1/2 of the maximum plunger drop The temperature to be measured is read from the graph, and this value (temperature when half of the measurement sample flows out) is defined as the softening point.

  Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And low-molecular-weight polypropylene, low-molecular-weight polyethylene, low-molecular-weight polypropylene-polyethylene copolymer), oxides of olefin (co) polymers with oxygen and / or ozone, olefin (co) heavy Maleic acid modified products of a compound [for example, maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.) modified products], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid And maleic anhydride, etc.] and / or not Copolymers with Japanese carboxylic acid alkyl esters [alkyl (meth) acrylates (alkyls having 1 to 18 carbon atoms) esters and alkyl maleates (alkyls having 1 to 18 carbon atoms) esters, etc.], sazol wax, etc. Is mentioned.

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

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

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

  Examples of the fluidizing agent include hydrophobic silica, alumina powder, titanium oxide powder, calcium carbonate powder, and the like.

The method for producing the toner of the present invention is not particularly limited.
The toner of the present invention may be obtained by any known method such as kneading and pulverization, emulsion phase inversion, and polymerization.
For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying, the volume average particle diameter (D50) is preferably 5 to 20 μm and then mixed with a fluidizing agent.
The volume average particle diameter (D50) and particle size distribution (volume average particle diameter / number average particle diameter) are measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Beckman Coulter, Inc.)]. The
When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified for production. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.
When a toner is obtained by a polymerization method, a dispersion in which the crystalline resin (A) is finely dispersed in advance in an organic solvent and a component constituting the toner excluding the fluidizing agent are dissolved or dispersed in the organic solvent. You may manufacture by mixing and removing an organic solvent. The method for dispersing the crystalline resin (A) in the organic solvent is not particularly limited. For example, the crystalline resin (A) may be crystallized in the organic solvent and then finely dispersed by a disperser (for example, a bead mill or a colloid mill).
Further, it is produced by a method using organic fine particles described in JP-A No. 2002-284881 and JP-A No. 2014-80586 and a method of dispersing in carbon dioxide in a supercritical state described in JP-A No. 2007-277511. May be.

  The toner of the present invention may or may not contain carrier particles. When carrier particles are contained, iron powder, glass beads, nickel powder, ferrite, magnetite, and resin (acrylic resin, silicone resin) are included as necessary. Etc.) and mixed with carrier particles such as ferrite whose surface is coated and used as a developer of an electric latent image. The weight ratio of toner to carrier particles is preferably 1/99 to 100/0 for toner / carrier particles. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

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

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

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

<Production Example 1> [Synthesis of Crystalline Resin (A-1)]
In a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer and a nitrogen introduction pipe, 422 parts by weight of 1,6-hexanediol (x1-2), 674 parts by weight of sebacic acid (y1-4) ( 97.9 mol%), 2 parts by weight (0.2 mol%) of arachidic acid (y2), 22 parts by weight (1.9 mol%) of behenic acid (y3) and 1.5 parts by weight of tetrabutoxytitanate as a condensation catalyst And reacted for 8 hours at 170 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-1).

<Production Example 2> [Synthesis of Crystalline Resin (A-2)]
In a reaction vessel equipped with a cooling tube, a heating / cooling device, a thermometer, a stirrer and a nitrogen introducing tube, 380 parts by weight of 1,6-hexanediol (x1-2) and 708 parts by weight of dodecanedioic acid (y1-5) (97.8 mol%), 10 parts by weight (1.0 mol%) of arachidic acid (y2), 13 parts by weight (1.2 mol%) of behenic acid (y3) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst The reaction was allowed to proceed for 8 hours at 170 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-2).

<Production Example 3> [Synthesis of Crystalline Resin (A-3)]
430 parts by weight of 1,9-nonanediol (x1-3), 578 parts by weight of dodecanedioic acid (y1-5) in a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer, and a nitrogen introduction pipe (91.0 mol%), 0.2 parts by weight (0.02 mol%) of arachidic acid (y2), 85 parts by weight (9.0 mol%) of behenic acid (y3) and tetrabutoxy titanate as a condensation catalyst. 5 parts by weight was added, and the reaction was carried out for 8 hours at 170 ° C. in a nitrogen stream while distilling off the generated water. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-3).

<Production Example 4> [Synthesis of Crystalline Resin (A-4)]
In a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer and a nitrogen introduction pipe, 541 parts by weight of 1,10-decanediol (x1-4), 546 parts by weight of sebacic acid (y1-4) ( 99.0 mol%), 4 parts by weight (0.5 mol%) of arachidic acid (y2), 5 parts by weight (0.5 mol%) of behenic acid (y3) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst And reacted for 8 hours at 170 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-4).

<Production Example 5> [Synthesis of Crystalline Resin (A-5)]
In a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer and a nitrogen introduction pipe, 585 parts by weight of ethylene glycol (x1-1), 27 parts by weight of fumaric acid (y1-2), adipic acid (y1 -3) 811 parts by weight (98.4 mol%), arachidic acid (y2) 2 parts by weight (0.1 mol%), behenic acid (y3) 30 parts by weight (1.5 mol%) Butoxytitanate (1.5 parts by weight) was added and reacted at 170 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 210 ° C., the mixture was reacted for 4 hours while distilling off the water produced under nitrogen flow, and further reacted under reduced pressure of 0.5 to 2.5 kPa. The acid value was 2.0 mgKOH. When it reached / g, it was taken out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-5).

<Production Example 6> [Synthesis of Crystalline Resin (A-6)]
788 parts by weight of ethylene glycol (x1-1), 748 parts by weight of succinic acid (y1-1) (97.9 mol) in a reaction vessel equipped with a cooling pipe, heating / cooling device, thermometer, stirrer and nitrogen introduction pipe %), 1 part by weight (0.05 mol%) of arachidic acid (y2), 45 parts by weight (2.0 mol%) of behenic acid (y3) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst, The reaction was carried out for 8 hours while distilling off the water produced under a nitrogen stream at ° C. Next, while gradually raising the temperature to 210 ° C., the mixture was reacted for 4 hours while distilling off the water produced under nitrogen flow, and further reacted under reduced pressure of 0.5 to 2.5 kPa. The acid value was 2.0 mgKOH. When it reached / g, it was taken out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-6).

<Comparative Production Example 1> [Synthesis of Crystalline Resin (A′-1)]
In a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer and a nitrogen introducing pipe, 424 parts by weight of 1,6-hexanediol (x1-1), 686 parts by weight of sebacic acid (y1-1) ( 99.0 mol%), 12 parts by weight (1.0 mol%) of behenic acid (y3) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst, and the generated water was distilled at 170 ° C under a nitrogen stream. The reaction was allowed to proceed for 8 hours. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A′-1).

<Comparative Production Example 2> [Synthesis of Crystalline Resin (A′-2)]
In a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer and a nitrogen introducing pipe, 451 parts by weight of 1,6-hexanediol (x1-1), 661 parts by weight of sebacic acid (y1-1) ( 99.6 mol%), 4 parts by weight (0.4 mol%) of arachidic acid (y2) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst, and the generated water was distilled at 170 ° C under a nitrogen stream. The reaction was allowed to proceed for 8 hours. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A′-2).

<Comparative Production Example 3> [Synthesis of Crystalline Resin (A′-3)]
In a reaction vessel equipped with a cooling tube, a heating / cooling device, a thermometer, a stirrer, and a nitrogen introduction tube, 382 parts by weight of 1,6-hexanediol (x1-1) and 690 parts by weight of dodecanedioic acid (y1-2) (96.5 mol%), arachidic acid (y2) 15 parts by weight (1.5 mol%), behenic acid (y3) 21 parts by weight (2.0 mol%) and tetrabutoxy titanate 1.5 parts by weight as a condensation catalyst The reaction was allowed to proceed for 8 hours at 170 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A′-3).

<Comparative Production Example 4> [Synthesis of Crystalline Resin (A′-4)]
In a reaction vessel equipped with a cooling tube, a heating / cooling device, a thermometer, a stirrer, and a nitrogen introducing tube, 360 parts by weight of 1,6-hexanediol (x1-1) and 639 parts by weight of dodecanedioic acid (y1-2) (89.9 mol%), 15 parts by weight (1.5 mol%) of arachidic acid (y2), 90 parts by weight (8.6 mol%) of behenic acid (y3) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst The reaction was allowed to proceed for 8 hours at 170 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A′-4).

<Comparative Production Example 5> [Synthesis of Crystalline Resin (A′-5)]
In a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer and a nitrogen introduction pipe, 359 parts by weight of 1,6-hexanediol (x1-1) and 649 parts by weight of dodecanedioic acid (y1-2) (90.8 mol%), arachidic acid (y2) 0.9 parts by weight (0.09 mol%), behenic acid (y3) 96 parts by weight (9.1 mol%) and tetrabutoxy titanate as a condensation catalyst. 5 parts by weight was added, and the reaction was carried out for 8 hours at 170 ° C. in a nitrogen stream while distilling off the generated water. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa. The acid value is 1.5 mgKOH. When it became below / g, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A′-5).

  Table 1 shows the physical property values of the crystalline resins (A-1) to (A-6) and (A′-1) to (A′-5).

<Production Example 7> [Synthesis of Amorphous Polyester Resin (B-1)]
In a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer and a nitrogen introduction pipe, 733 parts by weight of propylene glycol, 2 parts by weight of an ethylene oxide 2-mole adduct of bisphenol A, 2 moles of propylene oxide of bisphenol A 1 part by weight of adduct, 671 parts by weight of terephthalic acid, 38 parts by weight of adipic acid, 34 parts by weight of benzoic acid, 53 parts by weight of trimellitic anhydride and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added at 220 ° C. under pressure. The reaction was carried out for 20 hours while distilling off the generated water. Subsequently, the pressure was returned to normal pressure while gradually releasing the pressure, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 129 ° C., the resin (b-1) was taken out using a steel belt cooler. The removed propylene glycol was 353 parts by weight.

  In a separate reaction vessel equipped with a cooling tube, a heating / cooling device, a thermometer, a stirrer, and a nitrogen introduction tube, 583 parts by weight of propylene glycol, 1 part by weight of an ethylene oxide 2 mol adduct of bisphenol A, and propylene oxide of bisphenol A 2 parts adduct 50 parts by weight, terephthalic acid 623 parts by weight, adipic acid 8 parts by weight, benzoic acid 47 parts by weight, trimellitic anhydride 58 parts by weight and tetrabutoxy titanate 3 parts by weight as a condensation catalyst, The reaction was carried out at 220 ° C., and the reaction was carried out for 10 hours while distilling off the produced water. Subsequently, the pressure was returned to normal pressure while gradually releasing the pressure, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 100 ° C, the pressure was returned to normal pressure and cooled to 180 ° C. 17 parts of trimellitic anhydride was added and reacted for 1 hour. It cooled to 150 degreeC and took out resin (b-2) using the steel belt cooler. The removed propylene glycol was 234 parts by weight.

  Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.] so that the weight ratio (b-1) / (b-2) of the obtained resin (b-1) and resin (b-2) is 50/50. To obtain an amorphous polyester resin (B-1).

<Production Example 8> [Synthesis of Amorphous Polyester Resin (B-2)]
In a reaction vessel equipped with a cooling pipe, a heating / cooling device, a thermometer, a stirrer and a nitrogen introduction pipe, 320 parts by weight of bisphenol A ethylene oxide 2 mol adduct, 421 parts by weight of bisphenol A propylene oxide 2 mol adduct, 274 parts by weight of terephthalic acid and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added, reacted at 220 ° C. under pressure, and reacted for 10 hours while distilling off the generated water. Subsequently, the pressure was returned to normal pressure while gradually releasing the pressure, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 90 ° C, the pressure was returned to normal pressure and cooled to 180 ° C. 41 parts by weight of trimellitic anhydride was added and reacted for 1 hour. It cooled to 150 degreeC and resin (b-3) was obtained using the steel belt cooler.

  In a separate reaction vessel equipped with a cooling pipe, heating / cooling device, thermometer, stirrer and nitrogen introduction pipe, 168 parts by weight of bisphenol A ethylene oxide 2-mol adduct, bisphenol A propylene oxide 2-mol adduct 130 weight Part, 466 parts by weight of propylene oxide 3 mol adduct of bisphenol A, 184 parts by weight of terephthalic acid, 53 parts by weight of trimellitic anhydride, and 3 parts by weight of tetrabutoxytitanate as a condensation catalyst are reacted at 220 ° C. under pressure. The reaction was carried out for 10 hours while distilling off the generated water. Subsequently, the pressure was returned to normal pressure while gradually releasing the pressure, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 110 ° C., the pressure was returned to normal pressure and cooled to 180 ° C. 51 parts by weight of trimellitic anhydride was added, the temperature was raised to 210 ° C., and the reaction was further proceeded under reduced pressure of 0.5 to 2.5 kPa. When Tm reached 144 ° C., a resin (b-4) was obtained using a steel belt cooler.

  In Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.] so that the weight ratio (b-3) / (b-4) of the obtained resin (b-3) and resin (b-4) is 50/50. To obtain an amorphous polyester resin (B-2).

<Production Example 9> [Synthesis of Amorphous Polyester Resin (B-3)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 315 parts by weight of propylene glycol, 400 parts by weight of a PO2 molar adduct of bisphenol A, 462 parts by weight of terephthalic acid, 61 parts by weight of benzoic acid Then, 2.5 parts by weight of titanium diisopropoxybistriethanolamate is added as a polymerization catalyst and reacted for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream, and then 0.007-0. The reaction was performed for 1 hour under a reduced pressure of 026 MPa. Subsequently, it cooled to 180 degreeC, 27 weight part of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and amorphous polyester resin (B-3) was obtained. The removed propylene glycol was 161 parts by weight.

  Table 2 shows physical property values of the amorphous polyester resins (B-1) to (B-3).

<Production Example 10> [Preparation of precursor (M-1) solution]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 680 parts by weight of bisphenol A ethylene oxide 2-mole adduct, 82 parts by weight of bisphenol A propylene oxide 2-mole adduct, terephthalate 275 parts by weight of acid, 7 parts by weight of adipic acid, 22 parts by weight of trimellitic anhydride and 2 parts by weight of dibutyltin oxide were added and subjected to a dehydration reaction at normal pressure and 230 ° C. for 5 hours. A dehydration reaction was performed for 5 hours under a reduced pressure of 03 MPa to obtain a polyester resin corresponding to the amorphous polyester (B).
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, 350 parts by weight of a polyester resin, 50 parts by weight of isophorone diisocyanate, 600 parts by weight of ethyl acetate, and 0.5 parts by weight of ion-exchanged water are put in a sealed state. Reaction was performed at 90 ° C. for 5 hours to obtain a precursor (M-1) solution having an isocyanate group at the molecular end. The urethane group concentration of the (M-1) solution was 5.2% by weight, and the urea group concentration was 0.3% by weight. The solid content was 45% by weight.

<Production Example 11> [Production of fine particle dispersion]
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe, 690 parts by weight of water, sodium salt of polyoxyethylene monomethacrylate sulfate “Eleminol RS-30” [Sanyo Chemical Industries Co., Ltd. )] 9 parts by weight, 90 parts by weight of styrene, 90 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate and 1 part by weight of ammonium persulfate, and stirred for 15 minutes at 350 rpm, a white emulsion was obtained. was gotten. Next, the temperature was raised to 75 ° C., and the reaction was carried out at the same temperature for 5 hours. Further, 30 parts by weight of a 1% by weight ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and a vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide addition) corresponding to the amorphous vinyl resin (C1). A fine particle dispersion of a sodium sulfate ester copolymer) was obtained. The volume average particle size of the particles dispersed in the fine particle dispersion was measured using a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.). there were. When a part of the fine particle dispersion was taken out and Tg and Mw were measured, Tg was 65 ° C. and Mw was 150,000.

<Production Example 12> [Production of Colorant Dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 557 parts by weight of propylene glycol, 569 parts by weight of dimethyl terephthalate, 184 parts by weight of adipic acid and tetrabutoxytitanate 3 as a condensation catalyst A part by weight was added, and the reaction was carried out for 8 hours while distilling off the methanol produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. The recovered propylene glycol was 175 parts by weight. Next, the mixture was cooled to 180 ° C., 121 parts by weight of trimellitic anhydride was added, reacted for 2 hours under normal pressure sealing, reacted at 220 ° C. and normal pressure until the softening point reached 180 ° C., and polyester resin (Mn = 8 , 500).
Into a beaker, 20 parts by weight of copper phthalocyanine, 4 parts by weight of a colorant dispersant “Solsper's 28000” [manufactured by Avicia Co., Ltd.], 20 parts by weight of the obtained polyester resin and 56 parts by weight of ethyl acetate were added and stirred uniformly. After the dispersion, copper phthalocyanine was finely dispersed by a bead mill to obtain a colorant dispersion. The volume average particle diameter measured with “LA-920” of the colorant dispersion was 0.2 μm.

<Production Example 13> [Production of modified wax]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a dropping cylinder, 454 parts by weight of xylene, low molecular weight polyethylene “Sun Wax LEL-400” [Tm: 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.] 150 Part by weight was added, and after nitrogen substitution, the temperature was raised to 170 ° C. with stirring, and at the same temperature, 595 parts by weight of styrene, 255 parts by weight of methyl methacrylate, 34 parts by weight of di-t-butylperoxyhexahydroterephthalate and 119 parts by weight of xylene. Part of the mixed solution was added dropwise over 3 hours, and the mixture was further maintained at the same temperature for 30 minutes. Subsequently, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax. The modified wax had a graft chain SP value of 10.35 (cal / cm ³ ) ^1/2 , Mn of 1,900, Mw of 5,200, and Tg of 56.9 ° C.

<Production Example 14> [Production of release agent dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, paraffin wax “HNP-9” [Maximum heat of fusion peak temperature: 73 ° C., manufactured by Nippon Seiki Co., Ltd.] 10 parts by weight, production example 1 part by weight of the modified wax obtained in 11 and 33 parts by weight of ethyl acetate were added, the temperature was raised to 78 ° C. with stirring, the mixture was stirred at the same temperature for 30 minutes, and then cooled to 30 ° C. over 1 hour to obtain paraffin wax. Crystallization was performed in the form of fine particles, and further wet pulverized with Ultraviscomil (manufactured by Imex) to obtain a release agent dispersion. The volume average particle diameter was 0.25 μm.

<Production Example 15> [Production of Resin Solution (L-1)]
In a reaction vessel equipped with a stirrer, 10 parts by weight of crystalline resin (A-1), 90 parts by weight of amorphous polyester resin (B-3), 30 parts by weight of colorant dispersion, and release agent dispersion 40 Part by weight and 153 parts by weight of ethyl acetate were added and stirred to obtain a resin solution (L-1).

<Production Example 16> [Synthesis of curing agent (β-1)]
Into a reaction vessel equipped with a stirrer, heating / cooling device, cooling tube and thermometer, 50 parts by weight of isophorone diamine and 300 parts by weight of methyl ethyl ketone are charged, and after 5 hours of reaction at 50 ° C., the solvent is removed and the curing agent (Β-1) was obtained. The total amine value of (β-1) was 415 mgKOH / g.

<Comparative Production Example 6> [Production of Resin Solution (L′-1)]
In a reaction vessel equipped with a stirrer, 10 parts by weight of crystalline resin (A′-1), 90 parts by weight of amorphous polyester resin (B-3), 30 parts by weight of colorant dispersion, release agent dispersion 40 parts by weight and 153 parts by weight of ethyl acetate were added and stirred to obtain a resin solution (L′-1).

<Examples 1-7, 9-10> and <Comparative Examples 1-5>
Using the crystalline resin (A) and the amorphous polyester resin (B) obtained in Production Examples 1 to 8 and Comparative Production Examples 1 to 5, according to the blending ratio (parts by weight) in Table 3, Toner binders (N-1) to (N-7), (N-9) to (N-10), (N′−) containing the crystalline resin (A) and the amorphous polyester resin (B) by the method 1) to (N′-5) are obtained, and a toner material containing a toner binder and an additive is converted into a toner by the following method, and toners (T-1) to (T-7) and (T-9) are obtained. ) To (T-10) and (T′-1) to (T′-5).
Carbon black [MA-100 manufactured by Mitsubishi Chemical Co., Ltd.] as the colorant, polyolefin wax [Biscol 550P manufactured by Sanyo Chemical Industries, Ltd.] as the release agent, and Eisenspiron black [preservation] as the charge control agent T-77 manufactured by Tsuchiya Chemical Co., Ltd.] and hydrophobic silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] was used as a fluidizing agent.
First, after adding a crystalline resin (A), an amorphous polyester resin (B), a colorant, a release agent, and a charge control agent, and premixing using a Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.] The kneading was performed using a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and the particle size D50 is 7 μm toner particles were obtained. Next, hydrophobic silica was mixed with 100 parts by weight of toner particles in a sample mill so that the mixing ratio shown in Table 3 was obtained, to obtain a toner.

<Example 8>
In a beaker, 170 parts by weight of ion-exchanged water, 0.3 parts by weight of the fine particle dispersion, 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of “doleminyl MON-7”, “ELEMINOL MON-7” [Sanyo Kasei Co., Ltd. ) Made] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly. Next, the temperature was raised to 50 ° C., and while stirring the TK auto homomixer at 10,000 rpm at the same temperature, 11 parts by weight of a precursor (M-1) solution of an amorphous urethane resin (C3) and a curing agent (β -1) 5.5 parts by weight and 63 parts by weight of the resin solution (L-1) were added and stirred for 2 minutes. Next, this mixed solution was transferred to a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, and ethyl acetate was distilled off at 50 ° C. until the concentration became 0.5% by weight or less. A-1) Toner containing amorphous polyester resin (B-3), amorphous urethane resin (C3) which is a reaction product of precursor (M-1) and curing agent (β-1) An aqueous resin dispersion of particles was obtained. Next, it was washed and filtered, and dried at 40 ° C. for 18 hours to obtain a toner (T-8) of the present invention with a volatile content of 0.5% by weight or less.

<Comparative Example 6>
A toner (T′-6) was obtained by reacting in the same manner as in Example 8 except that the resin solution (L-1) was changed to the resin solution (L′-1).

[Evaluation methods]
For toners (T-1) to (T-10) and comparative toners (T′-1) to (T′-6), low-temperature fixability, glossiness, hot offset resistance, and heat resistant storage stability are as follows. Evaluation was made on charging stability, image strength, document offset property, and durability test. The results are shown in Table 3.

<Low temperature fixability>
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 from which the heat fixing machine was removed was used. Other methods may be used as long as the powder can be uniformly loaded with the above-described weight density.
Measures the low temperature fixing temperature, which is the temperature at which cold offset occurs when this paper is passed through a pressure roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ^2. did.
The lower the low temperature fixing temperature, the better the low temperature fixing property.

<Glossiness>
The fixing evaluation was performed in the same manner as the low temperature fixing property. White cardboard was laid under the image, and the glossiness of the printed image was measured at an incident angle of 60 degrees using a gloss meter (“IG-330” manufactured by Horiba, Ltd.).

[Criteria]
◎: 20 or more ○: 15 or more and less than 20 △: 10 or more and less than 15 ×: Less than 10

<Hot offset resistance (hot offset temperature)>
Fixation was evaluated in the same manner as the low-temperature fixability, and the presence or absence of hot offset on the fixed image was visually evaluated.
The temperature at which hot offset occurred after passing through the pressure roller was defined as hot offset resistance (° C.).

<Heat resistant storage stability>
The toner was allowed to stand in an atmosphere of 50 ° C. for 24 hours, the degree of blocking was judged visually, and the heat resistant storage stability was evaluated according to the following criteria.
[Criteria]
○: Blocking has not occurred.
X: Blocking has occurred.

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

[Criteria]
◎: 0.8 or more ○: 0.7 or more and less than 0.8 Δ: 0.6 or more and less than 0.7 ×: Less than 0.6

<Image intensity>
Load of 10 g from right above the pencil in which the test paper used for measuring the low temperature fixing temperature (the paper on which the image is fixed obtained by the evaluation of the low temperature fixing property) is fixed at an angle of 45 degrees according to JIS K5600 A scratch test was conducted, and the image strength was evaluated from the pencil hardness without scratches.
Higher pencil hardness means better image strength.

<Document offset property>
Two sheets of A4 paper on which images obtained by evaluation of low-temperature fixability were fixed were overlapped on the fixing surfaces, applied with a load of 420 g (0.68 g / cm ² ), and allowed to stand at 65 ° C. for 10 minutes. .
The document offset property was evaluated according to the following criteria for the state when the stacked papers were pulled apart.

[Criteria]
○: No resistance △: Crisp sound but image does not peel off from paper ×: Image peels off from paper

<Durability>
Using toner as a two-component developer, continuous copying was performed using a commercially available monochrome copying machine [AR5030, manufactured by Sharp Corporation], and durability was evaluated according to the following criteria.

[Criteria]
◎ No change in image quality and no fogging after 10,000 copies.
○ Fogging occurs after 10,000 copies.
Δ: Fog is generated after copying 6,000 sheets.
X: Fog occurs after 2,000 copies.

  As is apparent from the evaluation results in Table 3, the toners containing the toner binders of the present invention of Examples 1 to 10 were excellent in any performance evaluation items. On the other hand, the toner of Comparative Example 1 containing the crystalline resin (A′-1) not using the aliphatic monocarboxylic acid (y2) having 20 carbon atoms has poor heat storage stability and durability, and the carboxylic acid component The toner of Comparative Example 2 containing the crystalline resin (A′-2) in which the content of (y1) and (y3) in (Y) is out of the range is heat resistant storage resistance, hot offset resistance, document offset property. In addition, the toner of Comparative Example 3 containing a crystalline resin (A′-3) that has poor durability and the content of (y2) in the carboxylic acid component (Y) is out of the range is low-temperature fixability and charged. The toner of Comparative Example 4 containing the crystalline resin (A′-4), which has poor stability and the contents of (y1) and (y2) in the carboxylic acid component (Y) are out of the range, is fixed at low temperature. Property and charging stability are poor, and (y in the carboxylic acid component (Y) The toner of Comparative Example 5 containing a crystalline resin (A′-5) whose content is outside the range is poor in low-temperature fixability and charging stability, and has a carbon number of 20 as in Comparative Example 1. The toner of Comparative Example 6, which contains a crystalline resin (A′-1) that does not use an aromatic monocarboxylic acid (y2) but has a different toner production method from that of Comparative Example 1, was poor in durability.

  The toner binder and toner of the present invention are excellent in low temperature fixability, glossiness, hot offset resistance, heat resistant storage stability, charging stability, image strength, document offset property and durability, electrophotography, electrostatic recording, electrostatic It is useful as a toner for developing a magnetic latent image or electrostatic image used for printing or the like.

Claims (6)

  A toner binder containing a crystalline resin (A) having an alcohol component (X) and a carboxylic acid component (Y) as essential constituent monomers, based on the total number of moles of the carboxylic acid component (Y), The carboxylic acid component (Y) is 90 to 99.49 mol% of a linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms and 0.01 to 1 .1 of an aliphatic monocarboxylic acid (y2) having 20 carbon atoms. The toner binder contains 0.5 to 9.0 mol% of an aliphatic monocarboxylic acid (y3) having 0 mol% and 22 carbon atoms, and the toner binder has crystallinity in the second temperature rising process by a differential scanning calorimeter (DSC). A toner binder having at least one peak top temperature of an endothermic peak derived from the resin (A) in a range of 40 to 100 ° C.   The toner according to claim 1, wherein the aliphatic monocarboxylic acid (y2) having 20 carbon atoms in the carboxylic acid component (Y) is arachidic acid, and the aliphatic monocarboxylic acid (y3) having 22 carbon atoms is behenic acid. binder.   The toner binder according to claim 1 or 2, wherein an endothermic amount based on an endothermic peak derived from the crystalline resin (A) in the second temperature raising process by a differential scanning calorimeter (DSC) is 1 to 45 J / g. The toner binder according to claim ₁ , wherein the endothermic amounts S ₁ and S ₂ based on the endothermic peak at the time of temperature rise satisfy the following relational expression (1).
(S ₂ / S ₁ ) × 100 ≧ 35 (1)
However, S _{1 is} the endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the first temperature raising process when the temperature of the toner binder is raised, cooled, and the temperature rises, and the second temperature raising crystal. sex resin (a) endothermic quantity based on an endothermic peak derived from the S _2.   The toner binder according to any one of claims 1 to 4, wherein the toner binder further comprises an amorphous polyester resin (B) having an alcohol component (x) and a carboxylic acid component (y) as essential constituent monomers.   A toner containing the toner binder according to claim 1.