JP2018189955A - Toner binder and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder and a toner which are superior in heat proof keeping quality, electrification stability, image intensity and document offset quality of the toner while balancing low temperature fixity, glazing characteristics and hot offset quality.SOLUTION: A toner binder contains crystalline resin (A) and a cyclic ester compound. Structure raw material of the crystalline resin (A) and the cyclic ester compound are alcohol component (x) and carboxylic acid (y) respectively. The alcohol component (x) contains normal aliphatic diol (x1) that carbon number is odd number and 3-11. Total content of the (x1) forming the crystalline resin (A) is not less than 50 mol% on the basis of mole number of the alcohol component (x) forming the (A). The cyclic ester component is contained 0.01-0.9% by weight on the basis of the weight of the toner binder.SELECTED DRAWING: 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 (also referred to as a toner binder) is generally used.
However, if the glass transition point is too low, the hot offset resistance is lowered. 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 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, the same hot offset resistance and toner storage problems as those described above occur.

On the other hand, a method of regenerating the crystallinity of the crystalline resin by performing a heat treatment after the melt-kneading step (Patent Document 3), a method of changing the monomer component to be used (Patent Documents 4 to 6), and the like have been proposed.
Such a method can secure the low-temperature fixability and glossiness of the toner, but has a problem that the hot offset resistance, the fluidity of the toner, and the pulverization property during pulverization are reduced. Furthermore, they have a problem that the amount of cyclic ester compound produced as an impurity when synthesizing a crystalline resin is large, and heat resistance storage stability and charging stability at high temperature and high humidity are lowered.
A method of coating with a shell layer obtained using a melt suspension method or an emulsion aggregation method has also been proposed (Patent Documents 7 to 10). However, the crystalline resin is compatible with the binder resin of the core and is short. Due to insufficient time for reprecipitation of crystals, image strength after fixing and bending resistance are still insufficient.

JP 2005-77930 A JP 2012-98719 A JP 2005-308995 A JP 2012-8371 A JP 2007-292816 A International Publication No. 2015/170705 JP 2011-197193 A JP 2011-197192 A JP 2011-186053 A JP 2006-251564 A

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

As a result of intensive studies to solve these problems, the present inventors have reached the present invention.
That is, the present invention is a toner binder containing a crystalline resin (A) and a cyclic ester compound. The crystalline resin (A) and the cyclic ester compound comprise an alcohol component (x) and a carboxylic acid component (y), respectively. As a constituent raw material, the alcohol component (x) contains a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms, and the total content of (x1) constituting the crystalline resin (A) is A toner binder containing 50% by mole or more based on the number of moles of the alcohol component (x) constituting (A) and containing 0.01 to 0.9% by weight of a cyclic ester compound based on the weight of the toner binder. And a toner containing the above-mentioned toner binder.

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

The present invention is described in detail below.
The toner binder of the present invention is a toner binder containing a crystalline resin (A) and a cyclic ester compound. The crystalline resin (A) and the cyclic ester compound are an alcohol component (x) and a carboxylic acid component (y), respectively. And the alcohol component (x) contains the linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms, and the total content of (x1) constituting the crystalline resin (A) The amount is 50 mol% or more based on the number of moles of the alcohol component (x) constituting (A), and the cyclic ester compound is contained in an amount of 0.01 wt% to 0.9 wt% based on the weight of the toner binder. .

The toner binder of the present invention is a toner binder containing a crystalline resin (A). In the present invention, “crystallinity” means that the ratio [Tm / Ta] of the softening point [Tm] and the endothermic peak top temperature [Ta] measured by the following method is 0.8 to 1.55. Means. “Non-crystalline” and “non-crystalline” means that the ratio [Tm / Ta] between the softening point and the endothermic peak top temperature is greater than 1.55 or there is no endothermic peak top temperature [Ta]. Means.
The resin in which the crystalline resin and the amorphous resin are combined has a clear endothermic peak in the differential scanning calorimetry (DSC), and the softening point [Tm] and the maximum peak temperature of the heat of fusion [Ta]. When the ratio [Tm / Ta] is 0.8 to 1.55, a crystalline resin is used.
<Tm measurement method>
Using a Koka flow tester {for example, “CFT-500D” [manufactured by Shimadzu Corporation]}, a 1 g measurement sample is heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa is applied by a plunger. Is drawn from a nozzle having a diameter of 1 mm and a length of 1 mm, and a graph of “plunger lowering amount (flow value)” and “temperature” is drawn, corresponding to 1/2 of the maximum value of the plunger lowering amount. The temperature is read from the graph, and this value (temperature when half of the measurement sample flows out) is defined as Tm.
<Ta measurement method>
It is measured using a differential scanning calorimeter {for example, “DSC210” [manufactured by Seiko Instruments Inc.]}.
The sample used for the measurement of Ta was measured with a differential scanning calorimeter (hereinafter abbreviated as DSC) at a rate of temperature increase of 20 ° C./min to measure the endothermic change. The endothermic peak temperature at 20 to 100 ° C. observed at this time is defined as Ta ′. When there are a plurality of peaks, the peak temperature having the largest endothermic amount is defined as Ta ′. Finally, the sample is stored at (Ta′−10) ° C. for 6 hours, and then stored at (Ta′−15) ° C. for 6 hours.
Next, the sample was cooled to 0 ° C. at a temperature decrease rate of 10 ° C./min by DSC, and then the temperature was increased at a temperature increase rate of 10 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak is defined as the endothermic peak top temperature (Ta).

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 constituent materials, and the alcohol component (x) constituting the crystalline resin. ) Contains 50 mol% or more of the linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms based on the number of moles of the alcohol component (x). The crystalline resin (A) is preferably an acyclic crystalline resin.
The crystalline resin (A) contained in the toner binder of the present invention contains 50 mol% or more of a carboxylic acid component (y) and a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms. It includes a crystalline polyester resin (a11), a crystalline polyurethane resin (a12), a crystalline polyurea resin (a13), a crystalline polyamide resin (a14), and the like that contain an alcohol component (x) as a constituent raw material, and low temperature fixability From the viewpoint of the above, the crystalline polyester resin (a11) is preferable, and these preferably have an acyclic structure. In addition, these crystalline resin (A) may be used individually by 1 type, or may use 2 or more types together.

Of the crystalline resin (A), a carboxylic acid component (y) and an alcohol component (x) containing 50 mol% or more of a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms are constituted. The crystalline polyester resin (a11) used as a raw material will be described.
Examples of the linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms include 1,3-propanediol, 1,5-pentanediol, 1,7-heptanediol, 1,9-nonanediol, Examples include 1,11-undecanediol and 1,13-tridecanediol.
Among (x1), 1,3-propanediol, 1,5-pentanediol and 1,9-nonanediol are preferable from the viewpoint of crystallinity and charging characteristics.

The alcohol component (x), which is a constituent material of the crystalline polyester resin (a11), may contain 50 mol% or more of the linear aliphatic diol (x1) based on the number of moles of the alcohol component. A component (x2), a trivalent or higher valent alcohol component (x3), and a monoalcohol component (x4) may be included.
Other diol components (x2) include linear aliphatic diols (for example, those having an even number of carbon atoms, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, etc., and those having an odd number of carbon atoms of 13 or more 1,13-tridecanediol, 1,15-pentadecanediol and 1,19-nonadecanediol, etc.), branched aliphatic diols (for example, 1,2-propylene glycol and 1,2-butanediol, 2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octane All, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol and 1,2-octadecanediol), alkylene ether glycols having 4 to 36 carbon atoms (for example, Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols having 4 to 36 carbon atoms (for example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.) , An alkylene oxide of the above alicyclic diol (hereinafter, “alkylene oxide” is abbreviated as AO) [ethylene oxide (hereinafter, “ethylene oxide” is abbreviated as EO), propylene oxide (hereinafter, “propylene”). Xide ”is abbreviated as PO), butylene oxide (hereinafter,“ butylene oxide ”is abbreviated as BO), etc.] adducts (addition moles 1-30), bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adducts (addition mole number 2-30), polylactone diol (polyε-caprolactone diol etc.), polybutadiene diol and the like. Two or more of these may be used in combination.

  Of (x2), from the viewpoint of crystallinity, a linear aliphatic diol is preferable, a linear aliphatic diol having 2 to 36 carbon atoms is more preferable, and a linear fat having 2 to 20 carbon atoms is particularly preferable. Most preferred are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol and 1,12-dodecanediol.

  Examples of the trihydric or higher alcohol component (x3) include polyhydric aliphatic alcohols having 3 to 8 or more carbon atoms having 3 to 36 carbon atoms [alkane polyols and intramolecular or intermolecular dehydrates thereof (for example, glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan and polyglycerin etc.)], saccharides and derivatives thereof (eg sucrose and methylglucoside), trisphenols (trisphenol PA etc.) AO adducts (preferably Addition mole number 2-30), AO adduct (preferably addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.) and acrylic polyol [hydroxyethyl (meth) acrylate and other vinyl monomer copolymerization Etc.]. 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, preferred are polyhydric aliphatic alcohols having a valence of 3 to 8 or higher and AO adducts of novolac resins, and more preferred are AO adducts of novolac resins. It is.

  Examples of the monoalcohol component (x4) 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), etc. As the other monoalcohol component (x4), one kind may be used, Two or more of these may be used in combination.

  Of (x4), 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 preferred, and 16 carbon atoms are more preferred. Primary alcohols (particularly preferably linear saturated aliphatic monoalcohols, including commercial products of higher monoalcohols having 23 or more carbon atoms), most preferably n-octadecan-1-ol, n- Docosan-1-ol, Unilin 350 and Unilin 425.

  The content of the linear aliphatic diol (x1) is 50 mol% or more based on the number of moles of the alcohol component (x) that is a constituent raw material of the crystalline resin (A). In view of the above, it is preferably 70 mol% or more, particularly preferably 90 mol% or more. When the content of (x1) is less than 50 mol%, the content of the cyclic ester compound is increased, so that the heat resistant storage stability and charging characteristics may be problematic.

  The content of the other diol component (x2) is preferably 30 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 20 mol% or less, and most preferably 5 mol% or less.

  The content of the trivalent or higher alcohol component (x3) is 5 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 preferably 3 mol% or less, and most preferably 0 mol% or less.

  The content of the monoalcohol component (x4) is 15 mol% or less based on the number of moles of the alcohol component (x), which is a constituent monomer of the crystalline resin (A), from the viewpoint of heat-resistant storage stability and document offset property. Preferably, it is 7 mol% or less, and most preferably 5 mol% or less.

The crystalline polyester resin (a11) comprises an alcohol component (x) containing 50 mol% or more of a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms, a carboxylic acid (salt) group, a sulfone group. A diol (x1 ′) having at least one group selected from the group consisting of an acid (salt) group, a sulfamic acid (salt) group, and a phosphoric acid (salt) group may be used as a structural unit.
By using the diol (x1 ′) having these functional groups as a structural unit, the chargeability and heat resistant storage stability of the toner are improved.
The “acid (salt)” in the present invention means an acid or an acid salt.
The diol (x1 ′) having a functional group may be used alone or in combination of two or more.

  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, alkali metal salts (sodium salts and potassium salts, etc.).

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

  Examples of the carboxylic acid component (y) which is a constituent raw material of the crystalline polyester resin (a11) include dicarboxylic acid (y1), trivalent or higher carboxylic acid component (y2), and monocarboxylic acid (y3).

  As the dicarboxylic acid (y1), an alkanedicarboxylic acid having 2 to 50 carbon atoms (including carbon of the carbonyl group) {alkanedicarboxylic acid having a carboxyl group at both ends of a chain saturated hydrocarbon group (succinic acid, adipic acid, Sebacic acid, azelaic acid, dodecanedioic acid, 1,18-octadecanedicarboxylic acid, etc.), alkanedicarboxylic acids having a carboxyl group in addition to the end of the chain saturated hydrocarbon group (decylsuccinic acid, etc.)}, 4 to 50 carbon atoms Alkene dicarboxylic acid (alkenyl succinic acid such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, etc.), alicyclic dicarboxylic acid having 6 to 40 carbon atoms [dimer Acid (dimerized linoleic acid, etc.)], aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid) , Terephthalic acid, t- butyl isophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyl dicarboxylic acid, etc.) and the like. As dicarboxylic acid (y1), 1 type may be used and these 2 or more types may be used together.

  Examples of the trivalent or higher carboxylic acid component (y2) include polycarboxylic acids having a valence of 3 to 6 or higher. Examples of polycarboxylic acids having 3 to 6 or more valences include, for example, aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic tricarboxylic acids having 6 to 36 carbon atoms. (Hexanetricarboxylic acid etc.), vinyl polymer of unsaturated carboxylic acid [number average molecular weight (Mn): 450-10,000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, and styrene / fumarate) Acid copolymer, etc.). The number average molecular weight (Mn) is determined by gel permeation chromatography (GPC).

Examples of the monocarboxylic acid (y3) include those other than the above (x1′-1), and unsaturated monocarboxylic acid {for example, (meth) acrylic acid [“(meth) acrylic” means acrylic or methacrylic. . ], Crotonic acid, isocrotonic acid, cinnamic acid and the like} and saturated monocarboxylic acids (for example, behenic acid, stearyl acid and benzoic acid). As monocarboxylic acid (y3), 1 type may be used and these 2 or more types may be used together.
Of the monocarboxylic acid (y3), behenic acid is preferred from the viewpoint of crystallinity and heat-resistant storage stability.

Among these carboxylic acids, dicarboxylic acid (y1) and monocarboxylic acid (y3) are preferable from the viewpoint of crystallinity of (A), low-temperature fixability of toner and heat-resistant storage stability, and alkanedicarboxylic acid having 2 to 50 carbon atoms. And aliphatic dicarboxylic acids and saturated monocarboxylic acids having 4 to 50 carbon atoms of alkene dicarboxylic acid are more preferable, and dicarboxylic acids and saturated monocarboxylic acids having carboxyl groups at both ends of the chain saturated hydrocarbon group are particularly preferable. Most preferred are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and behenic acid.
Moreover, what copolymerized aliphatic dicarboxylic acid and / or aromatic dicarboxylic acid (Terephthalic acid, isophthalic acid, t-butylisophthalic acid, and these lower alkyl esters) is preferable from a charging viewpoint.

  The content of dicarboxylic acid (y1) is preferably 80 mol% or more based on the number of moles of carboxylic acid component (y), which is a constituent monomer of crystalline resin (A), from the viewpoint of crystallinity. More preferably, it is 90 mol% or more, and most preferably 95 mol% or more.

  The content of the trivalent or higher carboxylic acid component (y2) is 5 mol% or less based on the number of moles of the carboxylic acid component (y) which is a constituent monomer of the crystalline resin (A) from the viewpoint of crystallinity. Preferably, it is 3 mol% or less, more preferably 0 mol% or less.

  The content of monocarboxylic acid (y3) is 15 mol% or less based on the number of moles of carboxylic acid component (y), which is a constituent monomer of crystalline resin (A), from the viewpoint of heat-resistant storage stability and document offset property. Preferably, it is 7 mol% or less, and most preferably 5 mol% or less.

Next, a crystalline polyurethane comprising a carboxylic acid component (y) and an alcohol component (x) containing 50 mol% or more of a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms as constituent materials. (A12) will be described.
Examples of the crystalline polyurethane resin (a12) include those containing the crystalline polyester resin (a11) and the diisocyanate (v2) as constituent materials, and the crystalline polyester (a11), the alcohol component (x), and the diisocyanate ( and v2) as constituent materials.
The crystalline polyurethane resin (a12) using the crystalline polyester resin (a11) and the diisocyanate (v2) as constituent materials can be obtained by reacting the crystalline polyester resin (a11) and the diisocyanate (v2).
The crystalline polyurethane resin (a12) comprising the crystalline polyester resin (a11), the alcohol component (x) and the diisocyanate (v2) as constituent materials comprises the crystalline polyester (a11), the alcohol component (x) and the diisocyanate (v2). Can be obtained by reacting.

  Further, it is preferable that the crystalline polyurethane resin (a12) further includes the above-described diol (x1 ′) having a functional group as a constituent raw material because the chargeability and heat-resistant storage stability of the toner are easily improved.

  The diisocyanate (v2) which is a constituent raw material of the crystalline polyurethane resin (a12) is an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic having 2 to 18 carbon atoms. 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 mixtures of two or more thereof Etc.

  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. Isocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), 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, 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, a crystalline polyurea comprising a carboxylic acid component (y) and an alcohol component (x) containing 50 mol% or more of a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms as constituent materials. The resin (a13) will be described.
Examples of the crystalline polyurea resin (a13) include those using the crystalline polyester resin (a11), the diamine (z), and the diisocyanate (v2) as constituent materials.
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, a crystalline polyamide comprising a carboxylic acid component (y) and an alcohol component (x) containing 50 mol% or more of a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms as constituent materials. The resin (a14) will be described.
Examples of the crystalline polyamide resin (a14) include those using the crystalline polyester resin (a11), the diamine (z), and the dicarboxylic acid (y1) as constituent materials.
Such a crystalline polyamide resin (a14) can be obtained by reacting the crystalline polyester resin (a11), the diamine (z) and the dicarboxylic acid (y1).

  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). For example, the crystalline polyester resin (a′11) includes an alcohol component (x) and a carboxylic acid component (y) as constituent monomers. A crystalline polyester, which is a polyester resin, wherein the total content of the linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms is less than 50 mol% based on the number of moles of the alcohol component (x) Resin (a′111) or the like.
As the carboxylic acid component (y) constituting the crystalline polyester resin (a′11), the same one as the crystalline polyester resin (a11) can be used, and the alcohol contained in the alcohol component (x) can be crystalline. The same resin as exemplified for the conductive polyester resin (a11) can be used.

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

  As the crystalline polyurea resin (a′13), those containing the alcohol component (x), the diamine (z) and the diisocyanate (v2) as constituent monomers, and the crystalline polyester (a′11) Examples include those having the diamine (z) and the diisocyanate (v2) as constituent monomers.

  The crystalline polyamide resin (a′14) comprises the alcohol component (x), the diamine (z), and the dicarboxylic acid (y1) as constituent monomers, and the crystalline polyester (a′11). And those containing diamine (z) and dicarboxylic acid (y1) as constituent monomers.

As the crystalline polyvinyl resin (a′15), a polymerizable carboxylic acid which is a carboxylic acid component (y) [an alkenedicarboxylic acid having 4 to 50 carbon atoms and a monocarboxylic acid (y3) described in dicarboxylic acid (y1)]. (Meth) acrylic acid etc.] and an ester of the alcohol component (x) {preferably containing 50 mol% or more of a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms}. The polymer which homopolymerized or copolymerized e) is mentioned.
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 products of alicyclic alcohol and methacrylic acid (cyclohexyl methacrylate, etc.), esterified products of aromatic (aliphatic) alcohol and (meth) acrylic acid (benzyl methacrylate, phenyl ( Meta) 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, 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-methoxy- Nyl (meth) acrylate, 11-methoxy-undecyl (meth) acrylate, 13-methoxy-tridecyl (meth) acrylate, etc.], dialkyl fumarate (the two alkyl groups are linear, branched, having 2 to 8 carbon atoms) A dialkyl maleate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxy Alkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.), etc., single units having a polyalkylene glycol chain and a polymerizable double bond Mer [polyethylene glycol (Mn = 300) mono (meth) acrylate, polypropylene glycol (Mn = 500) monoac Relate, methyl alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like]. These can be used as long as the crystallinity of the crystalline resin (A) is not impaired.

  The crystalline polyvinyl resin (a′15) is used in combination with the following monomers (w1) to (w9) as constituent monomers in addition to the linear alkyl (meth) acrylate as long as the crystallinity is not impaired. Can be polymerized.

  The monomer (w1) is a hydrocarbon having a polymerizable double bond, and examples of the hydrocarbon having a polymerizable double bond include the following aliphatic hydrocarbon (w11) having a polymerizable double bond: An aromatic hydrocarbon (w12) having a polymerizable double bond is exemplified.

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).
Examples of the cyclic hydrocarbon (w112) having a polymerizable double bond include mono- or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinylcyclohexene and ethylidenebicycloheptene) and mono- or dicyclocarbon having 5 to 30 carbon atoms. Alkadiene [for example, (di) cyclopentadiene etc.] etc. are mentioned.

  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, vinyltoluene). 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 It is done.

The monomer (w2) is a monomer having a carboxyl group and a polymerizable double bond and a salt thereof. Examples of the salt constituting the salt of the monomer having a carboxyl group and a polymerizable double bond include: Examples include alkali metal salts (such as sodium salt and potassium salt), alkaline earth metal salts (such as calcium salt and magnesium salt), ammonium salt, amine salt and quaternary ammonium salt.
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.

  The monomer (w3) is a monomer having a sulfo group and a polymerizable double bond and a salt thereof, and examples of the monomer having a sulfo group and a polymerizable double bond and a salt thereof include carbon Alkene sulfonic acids of 2 to 14 (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid), styrene sulfonic acid and its alkyl (2 to 24 carbon atoms) derivative (for example, α-methyl styrene sulfonic acid) C5-C18 sulfo (hydroxy) alkyl- (meth) acrylate [for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyloxyethane Sulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, etc.], having 5 to 18 carbon atoms Rufo (hydroxy) alkyl (meth) acrylamide [eg 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2 -Hydroxypropanesulfonic acid, etc.], alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2-ethylhexyl-allylsulfosuccinic acid, etc.), poly [n (degree of polymerization; hereinafter the same). ) = 2-30] Oxyalkylene (oxyethylene, oxypropylene, oxybutylene and the like. Oxyalkylene may be used alone or in combination. When used together, the addition type may be random addition or block addition.) Mono (meth) acrylate Sulfate ester [Example For example, poly (n = 5 to 15) oxyethylene monomethacrylate sulfate and poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.] and salts thereof.

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

The monomer (w4) is a monomer having a phosphono group and a polymerizable double bond and a salt thereof. Examples of the monomer having a phosphono group and a polymerizable double bond 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) and (meth) acryloyloxyalkylphosphonic acid (of alkyl group) C1-C24) (for example, 2-acryloyloxyethylphosphonic acid etc.) etc. are mentioned.
Examples of the salt of the monomer having a phosphono group and a polymerizable double bond include those exemplified as the salt constituting the monomer having a carboxyl group and a polymerizable double bond of the monomer (w2). .

  The monomer (w5) is a monomer having a hydroxyl group and a polymerizable double bond. Examples of the monomer having a hydroxyl group and a polymerizable double bond include hydroxystyrene and 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-butene Examples include -1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, and sucrose allyl ether.

  The monomer (w6) is a nitrogen-containing monomer having a polymerizable double bond. Examples of the nitrogen-containing monomer having a polymerizable double bond include a monomer having an amino group and a polymerizable double bond. Monomer (w61), monomer having amide group and polymerizable double bond (w62), monomer having 3 to 10 carbon atoms having nitrile group and polymerizable double bond (w63), polymerization with nitro group C8-C12 monomer (w64) etc. which have an ionic double bond.

  Examples of the monomer (w61) having an amino group and a polymerizable double bond include 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.

  Examples of the monomer (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, etc. Can be mentioned.

  As a C3-C10 monomer (w63) which has a nitrile group and a polymerizable double bond, (meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc. are mentioned, for example.

  As a C8-C12 monomer (w64) which has a nitro group and a polymerizable double bond, nitrostyrene etc. are mentioned, for example.

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

  The monomer (w8) is a C 2-16 monomer having a halogen element and a polymerizable double bond, and a C 2-16 monomer having a halogen element and a polymerizable double bond is Examples thereof include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene and chloroprene.

  The monomer (w9) is an ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond. Examples of the ketone having a heavy bond and the sulfur-containing compound having a polymerizable double bond include, for example, an ether (w91) having 3 to 16 carbon atoms having a polymerizable double bond, and 4 to 4 carbon atoms having a polymerizable double bond. 12 ketones (w92), a sulfur-containing compound having 2 to 16 carbon atoms 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- Examples include 2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, acetoxystyrene, and phenoxystyrene. .

  Examples of the ketone having 4 to 12 carbon atoms having a polymerizable double bond (w92) include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.

  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. Can be mentioned.

  The toner binder of the present invention contains 0.01% to 0.9% by weight of a cyclic ester compound having the alcohol component (x) and the carboxylic acid component (y) as constituent materials based on the weight of the toner binder. To do. The cyclic ester compound comprising the alcohol component (x) and the carboxylic acid component (y) as constituent raw materials is more preferably 0.01 wt% to 0.5 wt%, still more preferably 0.01 wt% to 0.3 wt%. %, Particularly preferably 0.01% to 0.2% by weight, and most preferably 0.01% to 0.1% by weight. If it exceeds 0.9% by weight, the heat resistant storage stability and charging characteristics may deteriorate.

The cyclic ester compound is a cyclic compound in which a total of 2 to 20 alcohol components (x) and a carboxylic acid component (y) are polycondensed, and the alcohol component (x) and the carboxylic acid component (y) It is an oligomer component produced as a by-product when the crystalline resin (A) is synthesized using as a constituent material. The cyclic ester compound is distinguished from the crystalline resin (A) by the number of constituent monomers constituting the cyclic structure (that is, the total number of the alcohol component (x) to be polycondensed and the carboxylic acid component (y)). . In the present invention, the cyclic compound obtained by polycondensation of a non-cyclic compound and a total of more than 20 constituent monomers is referred to as crystalline resin (A).
If the cyclic ester compound, which is an oligomer component, is present in an amount of more than 0.9% by weight based on the weight of the toner binder, the heat resistant storage stability and charging characteristics are adversely affected.
Two or more kinds of alcohols that use, as a constituent raw material, an alcohol component containing 50 mol% or more of a linear aliphatic alcohol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms, which is an alcohol component of the crystalline resin (A) The by-product amount of the cyclic ester compound is suppressed by either using the component (x) in combination, using two or more carboxylic acid components (y) in combination, or using a monoalcohol or monocarboxylic acid as a constituent raw material. And can have a predetermined content. This is because the produced cyclic compound is easily decomposed because it is thermodynamically unstable.

Examples of the cyclic ester compound include compounds in which the alcohol component (x) and the carboxylic acid component (y) are condensed in equimolar amounts in the range of 1 to 10 to form a cyclic ester.
Specifically, a cyclic ester compound of an alkanedicarboxylic acid having 4 to 32 carbon atoms and an alkylene glycol having 2 to 30 carbon atoms (adipic acid: 1,2-propylene glycol = 1: 1 molar cyclic condensate, sebacic acid: 1,2-propylene glycol = 1: 1 molar cyclic condensate, adipic acid: ethylene glycol = 2: 2 molar cyclic condensate, succinic acid: 1,2-propylene glycol = 3: 3 molar cyclic condensate, adipic acid: 1,2-propylene glycol = 5: 5 mol cyclic condensate, and sebacic acid: 1,2-propylene glycol = 10: 10 mol cyclic condensate), and aromatic dicarboxylic acid having 8 to 20 carbon atoms and carbon number Cyclic ester compounds with 2 to 30 alkylene glycols (phthalic acid: 1,2-propylene glycol = 1: 1 molar cyclic condensate, phthalic acid: , 2-propylene glycol = 1: 1 molar cyclic condensate, isophthalic acid: 1,2-propylene glycol = 2: 2 molar cyclic condensate, terephthalic acid: 1,2-propylene glycol = 3: 3 molar cyclic condensate, Terephthalic acid: 1,2-propylene glycol = 5: 5 mol cyclic condensate, sebacic acid: 1,6-hexanediol = 1: 1 mol cyclic condensate, sebacic acid: 1,6-hexanediol = 2: 2 mol Cyclic condensate, sebacic acid: 1,6-hexanediol = 3: 3 mol cyclic condensate, sebacic acid: 1,6-hexanediol = 4: 4 mol cyclic condensate, sebacic acid: 1,6-hexanediol = 5: 5 mol cyclic condensate, and terephthalic acid: 1,2-propylene glycol = 10: 10 mol cyclic condensate).

  Among the cyclic ester compounds, examples of the cyclic ester compound having the linear aliphatic diol (x1) and the carboxylic acid component (y) as constituent materials include cyclic esters of a linear aliphatic alcohol and a linear aliphatic carboxylic acid. Compound (1,9-nonanediol: dodecanedioic acid = 1: 1, 1,9-nonanediol: dodecanedioic acid = 2: 2, 1,9-nonanediol: dodecanedioic acid = 3: 3, 1,5 -Pentanediol: sebacic acid = 1: 1, 1,5-pentanediol: sebacic acid = 2: 2, 1,5-pentanediol: sebacic acid = 3: 3) and the like.

  The content of the cyclic ester compound in the toner binder can be measured by liquid chromatography (hereinafter abbreviated as LC), and was measured under the following conditions.

The apparatus used was the following manufactured by Shimadzu Corporation.
LC: LC-30 Nextera
Ion source: ESI
MS: LCMS-8030
<LC measurement conditions>
Mobile phase: A; 10 mM aqueous ammonium acetate solution / methanol = 80/20
B; Methanol LC time program: A / B = 25/75 → 5/95 (v / v%)
B liquid ratio 75% (0 minutes), B liquid ratio 95% (10 minutes), B liquid ratio 95% (31 minutes), B liquid ratio 100% (32 minutes), B liquid ratio 100% (35 minutes), B liquid ratio 75% (36 minutes), STOP (40 minutes)
Flow rate: 0.3 mL / min Autosampler: Injection volume 1 μL, sample cooler 25 ° C.
Column: Inert SustainSwift (GL Science Co., Ltd., particle diameter 1.9 μm, inner diameter 2.1 mm, length 50 mm)
Column oven: 40 ° C
<MS measurement conditions>
Ionization mode: ESI (+)
Analysis mode: SCAN m / z 100-1500
Interface temperature: 350 ° C
DL temperature: 250 ° C
Nebulizer gas flow rate: 3L / min Heat block temperature: 400 ° C
Drying gas flow rate: 15L / min

<Sample solution preparation method>
(1) 0.96 g of toner or toner binder is put in a screw bottle and dissolved with 8.64 g of tetrahydrofuran (hereinafter THF).
(2) After dissolution, 28 g of LC / MS methanol is added to the screw bottle to precipitate the insoluble matter.
(3) Using a centrifuge, sediment the insoluble matter at 2000 rpm × 5 minutes.
(4) The supernatant obtained in (3) is filtered using a syringe and a membrane filter, and taken in a dedicated vial to make a sample solution.
(5) LC / MS measurement is performed on a part of the sample solution.

<Calculation method of cyclic ester compound amount>
(6) The THF / methanol mixed solution soluble matter is calculated from the solid content concentration of the sample solution of (5) and the resin sample amount.
The solid content concentration of the sample solution is determined by the following method.
About 2.00 g of sample before drying is weighed and dried at 150 ° C. for 45 minutes. After the dried sample is taken out and cooled in a desiccator, the weight is measured to the second decimal place, and the solid content concentration is calculated from (weight of sample after drying / weight of sample before drying) × 100.
(7) The ratio of the cyclic compound is calculated from the LC / MS area ratio.
(8) Multiply the THF / methanol mixed solution soluble component by the area ratio of the cyclic compound to obtain the amount of the cyclic ester compound in the toner or toner binder.
Amount of cyclic ester compound = "THF / methanol mixed solution soluble component" x "peak area of all cyclic compounds" ÷ "peak area of all compounds"
In addition, the peak area of the total cyclic compound here is the total amount of the area derived from the cyclic compound in the peak measured under the present conditions, and the peak area of the total compound is the total amount of the peak area measured under the present conditions. It is.

For example, when the linear aliphatic diol (x1) is 1,6-hexanediol and the carboxylic acid component (y) is sebacic acid, the content of the cyclic ester compound is calculated as follows.
Sebacic acid: 1,6-hexanediol = 1: 1 molar cyclic condensate has a molecular weight of 302, sebacic acid: 1,6-hexanediol = 2: 2 molar cyclic condensate has a molecular weight of 587, and sebacic acid: 1,6 -Hexanediol = 3: 3 The molecular weight of the cyclic condensate is 871, and the total peak area of the molecular weights derived from the cyclics as described above detected by LC-MS is divided by the total area of the toner binder. Is required.
When two or more alcohol components (x) and carboxylic acid components (y) are used in combination, the respective peak area values are summed with respect to the molecular weights of the possible combinations of cyclic compounds. It is obtained by dividing by the area.

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 , the low temperature fixability is that 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): From the viewpoint of heat resistant storage stability and document offset property.
(S ₂ / S ₁ ) × 100 ≧ 35 (1)

In the present invention, the temperature rise / 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), further preferably satisfies the relational expression (1-2), and most preferably satisfies the relational expression (1-3).
99 ≧ (S ₂ / S ₁ ) × 100 ≧ 35 (1-1)
95 ≧ (S ₂ / S ₁ ) × 100 ≧ 37 (1-2)
90 ≧ (S ₂ / S ₁ ) × 100 ≧ 40 (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 resin (B) is increased, the molecular weight of the crystalline resin (A) is increased, and the crystalline resin ( It can be controlled by reducing the acid value and hydroxyl value of A) and the amorphous resin (B).

When there are two or more endothermic peaks derived from the crystalline resin (A) in the above-described toner binder DSC measurement, 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 in the toner binder, a crystalline raw material such as wax may exhibit an endothermic peak.
The endothermic amount based on the endothermic peak is divided by drawing a line perpendicular to the base line at the peak valley, and is calculated 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 is preferably 1 to 30 J / g, more preferably 2 to 25 J / g, still more preferably 3 to 3. 20 J / g. From the viewpoint of low-temperature fixability and glossiness, the endothermic amount based on the endothermic peak derived from the crystalline resin (A) is preferably 1 J / g or more, and preferably 30 J / g or less from the viewpoint of hot offset resistance. The endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the temperature raising process is measured by DSC.

The endothermic peak top temperature (Ta) derived from the crystalline resin (A) is preferably 40 ° C. or higher from the viewpoints of heat-resistant storage stability of the toner, image strength after fixing, and document offset property. From the viewpoint, it is preferably 100 ° C. or lower.
The range of Ta (° C.) is preferably 40 to 100 ° C., more preferably 45 to 95 ° C., and particularly preferably 50 to 90 ° C.
The endothermic peak top temperature (Ta) refers to the temperature at the deepest portion of the recess of the endothermic peak.
When there are two or more endothermic peaks derived from the crystalline resin (A), the temperature indicating the endothermic 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, particularly preferably 5 mgKOH / g or less, and most 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 weight average molecular weight of the crystalline resin (A) (hereinafter, the weight average molecular weight may be abbreviated as Mw) is preferably 5,000 to 100,000, more preferably from the viewpoint of low-temperature fixability and gloss. Is from 8,000 to 80,000, particularly preferably from 10,000 to 60,000, most preferably from 12,000 to 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. The peak area having a molecular weight of 1,000 or less, Mw and Mn of the amorphous resin (B) to be described later are also measured under the following conditions in the same manner as 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 resin (B) from the viewpoint of hot offset resistance, charging stability, and thermal stability of a fixed image.

The composition of the amorphous resin (B) used in the toner and toner binder of the present invention is not particularly limited as long as it is an amorphous resin.
Preferred examples of the amorphous resin (B) include an amorphous polyester resin (B1), an amorphous vinyl resin (B2), an amorphous epoxy resin (B3), and an amorphous urethane resin. (B4) etc. are mentioned. Of these, the amorphous resin (B) is preferably an amorphous polyester resin (B1).

  As the alcohol component (X) of the amorphous polyester resin (B1), a diol {an alkylene glycol having 2 to 12 carbon atoms, a polyoxyalkylene oxide adduct of bisphenols (hereinafter, “alkylene oxide” is abbreviated as AO). (Preferably 2-30 added moles) [for example, AO adducts of bisphenol A (added moles 2-30), etc.]}, polyvalent fats having a valence of 3 to 8 or more Polyoxyalkylene ethers of group alcohols and novolak resins (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 components used in the amorphous polyester resin (B1), from the viewpoint of low-temperature fixability and hot offset resistance, an alkylene glycol having 2 to 10 carbon atoms and an alkylene oxide adduct (addition mole) of bisphenols are preferable. 2-5) and polyoxyalkylene ethers of novolak resins (2-30 of oxyalkylene units), particularly preferably alkylene glycols having 2-6 carbon atoms and alkylene oxide adducts of bisphenol A (addition moles). 2-5), and most preferred are alkylene oxide adducts of ethylene glycol, propylene glycol and bisphenol A (added mole number: 2 to 3).
In order to obtain an amorphous resin, the linear aliphatic diol content 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 alcohol component (X) which comprises an amorphous polyester resin (B1).

  Further, as the alcohol component (X) of the amorphous polyester resin (B1), the alcohol component (x) used in the crystalline polyester (a11), in addition to the above-described alcohol component, as long as the amorphous property is not inhibited. Similar ones can be used.

  As the carboxylic acid component (Y), aromatic carboxylic acids 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. Moreover, anhydrides and lower alkyl esters of these acids may be used.

The glass transition point (Tg) of the amorphous polyester resin (B1) is preferably 40 to 75 ° C. from the viewpoints of low temperature fixability, glossiness, heat resistant storage stability, image strength after fixing, and document offset property. Preferably it is 45-72 degreeC, Most preferably, it 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 (B1) is preferably from 2,000 to 200,000, more preferably from the viewpoints of low-temperature fixability, glossiness, heat resistant storage stability, image strength after fixing, and document offset property. It is 2,500 to 180,000, particularly preferably 3,000 to 150,000.
Mw and Mn of the amorphous polyester resin (B1) are determined by GPC in the same manner as the crystalline resin (A) described above.

The acid value of the amorphous polyester resin (B1) is preferably 30 mgKOH / g or less from the viewpoints of low-temperature fixability, glossiness, heat resistant storage stability, charge stability, image strength after fixing, and document offset property. More preferably, it is 2-28 mgKOH / g, More preferably, it is 3-25 mgKOH / g, Most preferably, it is 4-22 mgKOH / 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 (B1) is not particularly limited. For example, the molecular weight is increased, the amount of trimellitic anhydride added to the terminal is reduced (specifically, the production described later) In the example, the amount of trimellitic anhydride to be reacted at 180 ° C. is reduced), the end is capped with a monoalcohol or the like, and a crosslinking reaction is performed with a trifunctional or higher acid or alcohol, and the acid and alcohol ratio is adjusted. For example, the terminal functional group may be converted to alcohol by slightly adding alcohol.

The hydroxyl value of the amorphous polyester resin (B1) is preferably 50 mgKOH / g or less, more preferably 3 to 45 mgKOH, from the viewpoints of low-temperature fixability, heat-resistant storage stability, charging stability, image strength and document offset property. / G or less, more preferably 5 to 40 mgKOH / g or less, and most preferably 7 to 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 (B1) is not particularly limited. For example, the molecular weight is increased, the terminal is capped with a monocarboxylic acid or the like, and the crosslinking reaction is performed with a trifunctional or higher acid or alcohol. And the like, adjusting the ratio of the acid such as urethane and the alcohol ratio to make the acid a little excessive to make the terminal functional group an acid.

  The molecular content of the amorphous polyester resin (B1) having a molecular weight of 1,000 or less is determined by gel permeation chromatography from the viewpoint of heat-resistant storage stability, charging stability, image strength and document offset property. When expressed by the peak area when the molecular weight of the polyester resin (B1) is measured, it is preferably 17% or less of the total peak area, more preferably 10% or less, still more preferably 6% or less, Especially preferably, it is 4% or less, Most preferably, it is 2% or less.

In the present invention, the amorphous polyester resin (B1) has a molecular content of not more than 1,000 in the chromatogram obtained by measuring the molecular weight of the amorphous resin (B) by GPC as follows. Obtain by processing.
(1) A retention time at which the molecular weight becomes 1,000 is determined from a calibration curve with the molecular weight and the retention time as axes.
(2) Obtain the total peak area (Σ1).
(3) The peak area after the retention time obtained in (1) (peak area with a molecular weight of 1,000 or less) (Σ2) is obtained.
(4) The content of molecules having a molecular weight of 1,000 or less is determined from the following formula.
Content of molecules having a molecular weight of 1,000 or less (%) = (Σ2) × 100 / (Σ1)

  The method for reducing the content of molecules having a molecular weight of 1,000 or less in the amorphous polyester resin (B1) is not particularly limited. For example, the molecular weight of the amorphous polyester resin (B1) is increased, and the terminal is monocarboxylic. For example, a crosslinking reaction may be performed with a trifunctional or higher functional acid capped with an acid or the like.

  The softening point (Tm) of the amorphous polyester resin (B1) is preferably 80 to 170 ° C, more preferably 85 to 165 ° C, and particularly preferably 90 to 160 ° C. The softening point (Tm) of the amorphous polyester resin (B1) of the present invention was measured by the same method as described above.

  The amorphous polyester resin (B1) 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 more preferably a combination of 85 ° C to 105 ° C and 115 ° C to 160 ° C. By using two or more kinds of amorphous polyester resin (B1) in the above range, the low-temperature fixability, hot offset resistance, heat resistant storage stability and image strength are improved.

An amorphous vinyl resin (B2) can also be used as the amorphous resin (B) in the present invention.
Examples of the amorphous vinyl resin (B2) include, for example, a polymer of a styrene monomer alone, a copolymer of a styrene monomer and a (meth) acrylic monomer, a polymer of a styrene monomer alone, and the amorphous resin. And a copolymer of a styrene monomer and a (meth) acryl monomer and the amorphous polyester resin (B1).
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.

Examples of monomers that can be used in combination include alkyl such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Alkyl esters having 1 to 18 carbon atoms, hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms such as hydroxylethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) ) Alkyl group-containing (meth) acrylates of alkyl groups such as acrylate, etc. (meth) acrylates, acrylonitrile, methacrylonitrile, nitrile groups containing methyl groups of methacrylonitrile replaced with alkyl groups of 2-18 carbon atoms ( Meta) Acu Le compounds and (meth) the acrylic acid.
Among these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic acid are preferable. As a monomer, 1 type may be used and 2 or more types may be used together.

If necessary, other vinyl ester monomers and aliphatic hydrocarbon vinyl monomers may be used in combination with the amorphous vinyl resin (B2).
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.
Examples of the aliphatic hydrocarbon vinyl monomer include olefins (having 2 to 10 carbon atoms, such as ethylene, propylene, butene, octene), dienes (4 to 10 carbon atoms, such as butadiene, isoprene, 1,6-hexadiene, and the like). It is done.

  The Mw of the amorphous vinyl resin (B2) 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. Is 150,000-250,000.

  Further, the ratio (Mw / Mn) of Mw and number average molecular weight (Mn) of the amorphous vinyl resin (B2) is preferably 10 to 70, and more preferably from the viewpoint of the fixing temperature range. It is 15-65, Most preferably, it is 20-60.

Mw and Mn of the amorphous vinyl resin (B2) are determined by GPC in the same manner as the crystalline resin (A) described above.
The molecular content of the amorphous vinyl resin (B2) having a molecular weight of 1,000 or less is determined by gel permeation chromatography from the viewpoint of heat-resistant storage stability, charging stability, image strength and document offset property. When expressed by the peak area when the molecular weight of the styrene (co) polymer and its polyester-modified resin (B2) is measured, it is preferably 17% or less of the total peak area, more preferably 10% or less, More preferably, it is 6% or less, particularly preferably 4% or less, and most preferably 2% or less.
The content of molecules having a molecular weight of 1,000 or less in the amorphous vinyl resin (B2) in the present invention is determined by treating in the same manner as in the amorphous polyester resin (B1).

  It is preferable to use two or more types of amorphous vinyl resins (B2) having different molecular weights from the viewpoint of the fixing temperature range.

  As the amorphous epoxy resin (B3), a ring-opening polymer of polyepoxide, polyepoxide and active hydrogen-containing compound {water, polyol [diol and trivalent or higher polyol], dicarboxylic acid, trivalent or higher polycarboxylic acid, Polyamine etc.}, polyepoxide ring-opening polymer and non-crystalline polyester resin (B1) -bonded polyaddition product of polyepoxide and active hydrogen-containing compound and non-crystalline polyester resin ( B1) and the like are exemplified.

Mw and Mn of the amorphous epoxy resin (B3) are determined by GPC in the same manner as the crystalline resin (A) described above.
The molecular content of the amorphous epoxy resin (B3) having a molecular weight of 1,000 or less is determined by gel permeation chromatography from the viewpoint of heat-resistant storage stability, charging stability, image strength and document offset property. When represented by the peak area when the molecular weight of the epoxy resin (B3) is measured, it is preferably 17% or less of the total peak area, more preferably 10% or less, still more preferably 6% or less, Especially preferably, it is 4% or less, Most preferably, it is 2% or less.
The content of molecules having a molecular weight of 1,000 or less in the amorphous epoxy resin (B3) in the present invention is determined by processing in the same manner as in the amorphous polyester resin (B1).

  As the amorphous urethane resin (B4), the diisocyanate (v2), monoisocyanate (v1) and / or trifunctional or higher polyisocyanate (v3), the amorphous polyester resin (B1), What reacted with the chain extender (diamine etc.) as needed is 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.

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

Mw and Mn of the amorphous urethane resin (B4) are determined by GPC in the same manner as the crystalline resin (A) described above.
The molecular content of the amorphous urethane resin (B4) with a molecular weight of 1,000 or less is the toner fluidity, heat-resistant storage stability, charging stability, grindability, image strength after fixing, folding resistance and document offset. From the viewpoint of safety, when expressed by the peak area when the molecular weight of the amorphous urethane resin and its polyester-modified resin (B4) is measured by gel permeation chromatography, it is preferably 17% or less of the total peak area. More preferably 10% or less, still more preferably 6% or less, particularly preferably 4% or less, and most preferably 2% or less.
The content of molecules having a molecular weight of 1,000 or less in the amorphous urethane resin (B4) in the present invention is determined by treating in the same manner as in the amorphous polyester resin (B1).

A method for mixing the amorphous resin (B) and the crystalline resin (A) is not particularly defined. For example, a method of mixing the amorphous resin (B) and the crystalline resin (A) with a melt kneader, a solvent For example, there are a method in which the solvent is removed after being dissolved and the like, and a method in which the crystalline resin (A) is mixed during the production of the amorphous 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 resin (B) as described above.

  The weight ratio (B / A) between the amorphous resin (B) and the crystalline resin (A) is the viewpoint of toner fluidity, heat resistant storage stability, grindability, image strength after fixing, low temperature fixability, and glossiness. To preferably 50/50 to 95/5, more preferably 60/40 to 92/8, still more preferably 70/30 to 90/10. A mixture containing the amorphous resin (B) and the crystalline resin (A) in the above proportion is preferable as the toner binder of the present invention. That is, the weight ratio (B / A) between the amorphous resin (B) and the crystalline resin (A) in the toner binder of the present invention is preferably in the above range.

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

  The toner of the present invention may contain the toner binder of the present invention, but may contain a colorant. 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.

As the colorant, all of dyes and pigments used as toner colorants can be used.
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 of the total amount of the toner binder. Above and below, parts mean parts by weight.

In addition to the toner binder and the colorant, the toner of the present invention contains one or more additives selected from a mold release agent, a charge control agent, a fluidizing agent, and the like as necessary.
As the release agent, those having a softening point [Tm] of 50 to 170 ° C. by a flow tester are preferable, polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms and these. A mixture etc. are mentioned.

  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 olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Copolymers of maleic acid alkyl (having 1 to 18 carbon atoms in the alkyl) esters, etc.] or the like, and Sasol wax.

  Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax. Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid.

  As the charge control agent, nigrosine dye, triphenylmethane dye containing tertiary amine as a side chain, quaternary ammonium salt, polyamine resin, imidazole derivative, quaternary ammonium base-containing polymer, metal-containing azo dye, copper phthalocyanine dye, Examples include salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, and halogen-substituted aromatic ring-containing polymers.

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

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) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
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 may be produced by a method using organic fine particles described in JP-A No. 2002-284881 or a method of dispersing in carbon dioxide in a supercritical state described in JP-A No. 2007-277511.

  The toner of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.) as necessary to cause an electrical latent. Used as an image developer. The weight ratio of toner to carrier particles is 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.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Production Example 1
[Synthesis of Crystalline Resin (A-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 545 parts by weight of 1,3-propanediol (x1-1) (100 mol% based on the number of moles of the alcohol component), 825 weights of dodecanedioic acid 170 parts by weight (98 mol% based on the number of moles of carboxylic acid component), 17 parts of behenic acid (2 mol% based on the number of moles of carboxylic acid component) 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 reaction is performed for 4 hours while distilling off the water and 1,3-propanediol produced under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became 2 or less, it was taken out. The removed 1,3-propanediol was 259 parts by weight. 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 stirrer and a nitrogen introduction tube, 387 parts by weight of 1,5-pentanediol (x1-2) (100 mol% based on the number of moles of alcohol component), 723 parts by weight of sebacic acid (98 mol% based on the number of moles of carboxylic acid component), 18 parts by weight of behenic acid (2 mol% based on the number of moles of carboxylic acid component) 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 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. It was taken out when it became. 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)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 353 parts by weight of 1,9-nonanediol (x1-3) (100 mol% based on the number of moles of alcohol component), 743 weights of dodecanedioic acid Parts (98 mol% based on the number of moles of carboxylic acid component), 20 parts by weight of behenic acid (2 mol% based on the number of moles of carboxylic acid component) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst, The reaction was carried out for 8 hours at 170 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. It was taken out when it became. 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 tube, a stirrer and a nitrogen introduction tube, 211 parts by weight of 1,9-nonanediol (x1-3) (60 mol% based on the number of moles of alcohol component), 1,6-hexane Diol (x2-1) 159 parts by weight (40 mol% based on the number of moles of alcohol component), 723 parts of dodecanedioic acid (98 mol% based on the number of moles of carboxylic acid component), 19 parts by weight of behenic acid (carbon 2 mol% based on the number of moles of the acid component) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were 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 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. It was taken out when it became. 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 tube, a stirrer and a nitrogen introduction tube, 335 parts by weight of 1,9-nonanediol (x1-3) (99 mol% based on the number of moles of alcohol component), 15 parts by weight of behenyl alcohol ( 1 mol% based on the number of moles of alcohol component), 769 parts by weight of dodecanedioic acid (100 mol% based on the number of moles of carboxylic acid component) 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. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the water produced under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. It was taken out at the time. 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)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 348 parts by weight of 1,9-nonanediol (x1-3) (98 mol% based on the number of moles of the alcohol component), 22 parts by weight of behenyl alcohol ( 2 mol% based on the number of moles of alcohol component), 135 parts by weight of sebacic acid (20 mol% based on the number of moles of carboxylic acid component), 614 parts by weight of dodecanedioic acid (80 based on the number of moles of carboxylic acid component) Mol%) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were allowed to react at 170 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. It was taken out when it became. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-6).

Production Example 7
[Synthesis of Crystalline Resin (A-7)]
395 parts by weight of 1,9-nonanediol (x1-3) (100 mol% based on the number of moles of alcohol component), 710 parts by weight of sebacic acid in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube (98 mol% based on the number of moles of carboxylic acid component), 22 parts by weight of behenic acid (2 mol% based on the number of moles of carboxylic acid component) 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 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. It was taken out when it became. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-7).

Production Example 8
[Synthesis of Amorphous Resin (B-1)]
In a reaction vessel, 734 parts by weight of 1,2-propylene glycol, 1 part by weight of EO2 mole adduct of bisphenol A, 1 part by weight of PO2 mole adduct of bisphenol A, 670 parts by weight of terephthalic acid, 38 parts by weight of adipic acid, benzoic acid 34 parts by weight of acid, 53 parts by weight of trimellitic anhydride, and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added, reacted at 220 ° C. under pressure, and reacted for 20 hours while distilling off the generated water. Next, 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 130 ° 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, 581 parts by weight of 1,2-propylene glycol, 1 part by weight of EO2 mole adduct of bisphenol A, 49 parts by weight of PO2 mole adduct of bisphenol A, 625 parts by weight of terephthalic acid, 8 parts by weight of adipic acid , 49 parts by weight of benzoic acid, 58 parts by weight of trimellitic anhydride, and 3 parts by weight of tetrabutoxytitanate as a condensation catalyst were reacted at 220 ° C. under pressure, and reacted for 10 hours while distilling off the generated water. . Next, 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 105 ° C., the pressure was returned to normal pressure and cooled to 180 ° C. 14 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 resin (B-1).

Production Example 9
[Synthesis of Amorphous Resin (B-2)]
In a reaction vessel, 322 parts by weight of an EO2 molar adduct of bisphenol A, 419 parts by weight of a PO2 molar adduct of bisphenol A, 274 parts by weight of terephthalic acid, and 3 parts by weight of tetrabutoxytitanate as a condensation catalyst were placed under pressure. The reaction was carried out at 0 ° C. and the reaction was carried out for 10 hours while distilling off the water produced. Next, 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. 42 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, 167 parts by weight of EO2 mol adduct of bisphenol A, 128 parts by weight of PO2 mol adduct of bisphenol A, 468 parts by weight of PO3 mol adduct of bisphenol A, 184 parts by weight of terephthalic acid, trimellitic anhydride 53 parts by weight and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added and reacted at 220 ° C. under pressure, and the reaction was carried out for 10 hours while distilling off the generated water. Next, 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. 52 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 145 ° C., a steel belt cooler was used to obtain a resin (b-4).

  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 resin (B-2).

<Production Example 10> [Synthesis of Amorphous 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, 404 parts by weight of a PO2 molar adduct of bisphenol A, 459 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, 27.3 weight part of trimellitic anhydride was added, and it was made to react under a normal pressure for 1 hour, and amorphous resin (B-3) was obtained. The removed propylene glycol was 161 parts by weight.

<Production Example 11> [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, 681 parts by weight of an EO2 molar adduct of bisphenol A, 81 parts by weight of a PO2 molar adduct of bisphenol A, 275 parts by weight of terephthalic acid Then, 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 after dehydration reaction at normal pressure and 230 ° C. for 5 hours, the pressure was reduced to 0.01 to 0.03 MPa. The polyester resin corresponding to the amorphous polyester (B1) was obtained by performing a dehydration reaction for 5 hours.
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 12> [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 performed 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 the vinyl resin corresponding to the amorphous vinyl resin (B2) (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide addition) 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 13> [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).
In a beaker, 20 parts by weight of copper phthalocyanine (C-2), 4 parts by weight of a colorant dispersant “Solsper's 28000” (manufactured by Avicia), 20 parts by weight of the obtained polyester resin and 56 parts by weight of ethyl acetate are charged. After stirring and uniformly dispersing, 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 14> [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 15> [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 melting heat peak temperature: 73 ° C., manufactured by Nippon Seiki Co., Ltd.] (D-2) 10 Part by weight, 1 part by weight of the modified wax obtained in Production Example 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. Then, the paraffin wax was crystallized into fine particles, and further wet pulverized with Ultra Viscomil (manufactured by IMEX) to obtain a release agent dispersion. The volume average particle diameter was 0.25 μm.

<Production Example 16> [Production of Resin Solution (L-1)]
In a reaction vessel equipped with a stirrer, 15 parts by weight of crystalline resin (A-2), 85 parts by weight of resin (B-3), 30 parts by weight of colorant dispersion, 20 parts by weight of release agent dispersion and acetic acid 153 parts by weight of ethyl was added and stirred to obtain a resin solution (L-1).

<Production Example 17> [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 added, and after 5 hours of reaction at 50 ° C., the solvent is removed and the curing agent is removed. (Β-1) was obtained. The total amine value of (β-1) was 415 mgKOH / g.

Comparative production example 1
[Synthesis of Crystalline Resin (A′-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 427 parts by weight of 1,6-hexanediol (x2-1) (100 mol% based on the number of moles of alcohol component), 696 parts by weight of sebacic acid (100 mol% based on the number of moles of the carboxylic acid component) (manufactured by Toyokuni Seiyaku Co., Ltd.) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were added, and the water produced was distilled off at 170 ° C under a nitrogen stream. The reaction was continued 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. It was taken out when it became. 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)]
149 parts by weight of 1,9-nonanediol (x1-3) (40 mol% based on the number of moles of alcohol component), 1,6-hexane in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube Diol (x2-1) 253 parts by weight (60 mol% based on the number of moles of alcohol component), 702 parts by weight of sebacic acid (98 mol% based on the number of moles of carboxylic acid component), 20 parts by weight of behenic acid (carboxyl 2 mol% based on the number of moles of the acid component) and 1.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were 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 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. It was taken out when it became. 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> [Production of Resin Solution (L′-1)]
In a reaction vessel equipped with a stirrer, 15 parts by weight of crystalline resin (A′-1), 85 parts by weight of resin (B-3), 30 parts by weight of colorant dispersion, 20 parts by weight of release agent dispersion, and 153 parts by weight of ethyl acetate was added and stirred to obtain a resin solution (L′-1).

The temperature (Ta) showing the endothermic peak top of the crystalline resin (A) was measured by a differential scanning calorimeter (DSC) by the following method.
Apparatus: Q Series Version 2.8.0.394 (TA Instruments)
The pattern of temperature rise, cooling and temperature rise is as follows:
(1) Temperature rise from 30 ° C. to 180 ° C. at a rate of temperature increase of 10 ° C./min. (2) Hold at 180 ° C. for 10 minutes and then cool to 0 ° C. at a rate of temperature drop of 10 ° C./min. Then, the temperature was raised again to 180 ° C. at a rate of temperature rise of 10 ° C./min. An aluminum empty pan was used as a reference. At this time, the temperature at the deepest part of the recess of the endothermic peak of the crystalline resin (A) in the temperature raising process (second temperature raising process) of (3) was defined as a temperature Ta indicating the endothermic peak top. In the case where there are two or more endothermic peaks of the crystalline resin (A), the temperature showing the highest endothermic peak top among them is defined as Ta.

Tg (Tg1) of the amorphous resin (B) is determined by a method (DSC method) defined in ASTM D3418-82 using DSC (Model Q Series Version 2.8.0.394 manufactured by TA Instruments). It was measured.
The acid value and hydroxyl value of the crystalline resin (A) and the amorphous resin (B) were measured by the method defined in JIS K0070.

The molecular content of the amorphous resin (B) having a molecular weight of 1,000 or less was determined by data processing of the measurement results of each resin by GPC as follows.
(1) The retention time at which the molecular weight was 1,000 was determined from a calibration curve with the molecular weight and the retention time as axes.
(2) The total peak area (Σ1) was determined.
(3) The peak area after the retention time determined in (1) (peak area with a molecular weight of 1,000 or less) (Σ2) was determined.
(4) The content of molecules having a molecular weight of 1,000 or less was determined from the following formula.
Content of molecules having a molecular weight of 1,000 or less (%) = (Σ2) × 100 / (Σ1)
The content (%) of molecules having a molecular weight of 1,000 or less determined as described above was described as “content of molecules having a molecular weight of 1,000 or less”.

Examples 1-10 and Comparative Examples 1-2
Using the crystalline resin (A) and the amorphous resin (B) obtained in the production example and the comparative production example, the crystalline resin (A) and, if necessary, amorphous, according to the blending ratio (parts by weight) shown in Table 1. Toners (N-1) to (N-10) and (N'-1) to (N'-2) containing a functional resin (B), and further containing a toner binder and an additive The raw material was converted to toner by the following method to obtain toners (T-1) to (T-10) and (T′-1) to (T′-2).
Carbon black [MA-100 manufactured by Mitsubishi Chemical Corporation] as the colorant (C-1), polyolefin wax [Biscol 550P manufactured by Sanyo Chemical Industries, Ltd.] as the release agent (D-1), charge Eisenspiron black [T-77 manufactured by Hodogaya Chemical Co., Ltd.] was used as the control agent (E-1), and colloidal silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] was used as the fluidizing agent (F-1).
First, after adding a colorant, a release agent, and a charge control agent, and premixing using a Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.], a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.] Kneaded. 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, 100 parts by weight of toner particles and colloidal silica were mixed in a sample mill to obtain a toner.
Table 1 shows the toner evaluation.

  Using the crystalline resin (A) and the amorphous resin (B) obtained in the production examples and comparative production examples, a toner binder containing the crystalline resin (A) and, if necessary, the amorphous resin (B) ( N-11) and (N′-3) are obtained, and a toner material containing a toner binder and an additive is converted into a toner by the following method to obtain toners (T-11) and (T′-3). It was.

<Example 11>
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 the precursor (M-1) solution of the amorphous urethane resin (B4), the 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-2), toner particles containing amorphous resin (B-3), amorphous urethane resin (B4) which is a reaction product of precursor (M-1) and curing agent (β-1) An aqueous resin dispersion was obtained. Next, the product was washed, filtered, and dried at 40 ° C. for 18 hours to obtain a toner (T-11) of the present invention containing a toner binder (N-11) with a volatile content of 0.5% by weight or less. Table 2 shows the analytical values.

<Comparative Example 3>
A toner (T′-3) containing a toner binder (N′-3) was obtained by reacting in the same manner as in Example 11 except that the resin solution (L-1) was changed to a resin solution (L′-1). .
Table 2 shows the analytical values.

When the toner binder is heated, cooled, and heated, the endothermic peak area derived from the crystalline resin (A) in the first heating process measured by DSC is S1, and the second heating process is crystallized. The endothermic peak area derived from the conductive resin (A) was S2, and S1 and S2 (endothermic peak area at the time of temperature increase) were measured as follows.
About 5 mg of a mixture of the crystalline resin (A) and the amorphous resin (B) blended in the proportions shown in Examples, Comparative Examples or Table 1 is precisely weighed and placed in an aluminum pan. DSC measurement was performed under the conditions.
Apparatus: Q Series Version 2.8.0.394 (TA Instruments)
The temperature was raised from 30 ° C. to 180 ° C. under the condition of 10 ° C./min (first temperature raising process), then left at 180 ° C. for 10 minutes and then cooled to 0 ° C. under the condition of 10 ° C./min (No. 1). First cooling process), and then allowed to stand at 0 ° C. for 10 minutes, and then heated to 180 ° C. under a condition of 10 ° C./min (second heating process).
DSC was measured from the beginning of the first temperature raising process (30 ° C.) to the end of the second temperature raising process (180 ° C.).
Tables 1 and 2 show the value of (S2 / S1) × 100. Further, the endothermic heat amount (J / g) derived from the crystalline resin (A) in the second temperature raising process measured by DSC is shown as “endothermic amount (J) / g derived from (A)” in Table 1 and Table 1. It is shown in 2.

[Evaluation method]
The following describes the low-temperature fixability, glossiness, hot offset resistance, heat-resistant storage stability, charge stability, image strength, document offset test measurement method, evaluation method, and judgment criteria of the obtained toner.

<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. The low temperature fixing temperature (° C.) of the toner is shown in Table 1 and Table 2 as the low temperature fixing property (° C.).

<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 △: 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 the image obtained in the evaluation of the low-temperature fixability was fixed were overlapped with each other on the fixing surface, 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 △: Sounds crispy but image does not peel off from paper ×: Image peels off from paper

  The above evaluation results are shown in Tables 1 and 2.

  As is clear from the evaluation results in Tables 1 and 2, all of the toners of Examples 1 to 11 of the present invention were excellent in performance evaluation. On the other hand, Comparative Examples 1 to 3 which do not contain 50 mol% or more of (x1) based on the number of moles of the alcohol component (x) were poor in some performance items such as heat resistant storage stability and charging characteristics.

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

Claims (10)

A toner binder containing a crystalline resin (A) and a cyclic ester compound;
The crystalline resin (A) and the cyclic ester compound are composed of an alcohol component (x) and a carboxylic acid component (y), respectively.
The alcohol component (x) contains a linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms,
The total content of (x1) constituting the crystalline resin (A) is 50 mol% or more based on the number of moles of the alcohol component (x) constituting (A),
A toner binder containing 0.01 to 0.9% by weight of a cyclic ester compound based on the weight of the toner binder.   The linear aliphatic diol (x1) having an odd number of carbon atoms and 3 to 11 carbon atoms is at least one selected from the group consisting of 1,3-propanediol, 1,5-pentanediol and 1,9-nonanediol. The toner binder according to claim 1. 3. 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 increase satisfy the following relational expression (1).
(S ₂ / S ₁ ) × 100 ≧ 35 (1)
[However, using a differential scanning calorimeter, the toner binder is first heated from 30 ° C. to 180 ° C. under a condition of 10 ° C./min, and then cooled to 0 ° C. under a condition of 10 ° C./min. Subsequently, the endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the first temperature increase process when the second temperature increase is performed from 0 ° C. to 180 ° C. under the condition of 10 ° C./min is expressed as S _1. , an endothermic amount based on the second round of the endothermic peak derived from the crystalline resin (a) of the heating process and S _2. ]   The toner binder is first heated from 30 ° C. to 180 ° C. under the condition of 10 ° C./min, then cooled to 0 ° C. under the condition of 180 ° C./10° C./min, and then from 0 ° C. to 10 ° C. The endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the second temperature raising process when the temperature is raised to 180 ° C. for the second time under the conditions of 1 / min is 1 to 30 J / g. Item 4. The toner binder according to any one of Items 1 to 3.   The toner binder is first heated from 30 ° C. to 180 ° C. under the condition of 10 ° C./min, then cooled to 0 ° C. under the condition of 180 ° C./10° C./min, and then from 0 ° C. to 10 ° C. The endothermic peak top temperature derived from the crystalline resin (A) in the second temperature raising process when the temperature is raised to 180 ° C. for the second time under the condition of / min is at least 1 in the range of 40 ° C. to 100 ° C. The toner binder according to claim 1, wherein the toner binder is contained.   The toner binder according to claim 1, wherein the acid value of the crystalline resin (A) is 10 mg KOH / g or less.   The toner binder according to claim 1, further comprising an amorphous resin (B).   The toner binder according to claim 7, wherein the weight ratio (B / A) of the amorphous resin (B) to the crystalline resin (A) is 50/50 to 95/5. In the chromatogram obtained by measuring the molecular weight of the amorphous resin (B) by gel permeation chromatography, the peak area of the amorphous resin (B) having a molecular weight of 1,000 or less is 17% or less of the total peak area. The toner binder according to 7 or 8.
[Gel permeation chromatography measurement conditions]
Column: TSKgel (registered trademark) GMH6 2 Mobile phase: THF
Measurement temperature: 40 ° C   A toner containing the toner binder according to claim 1.