JP2019214706A - Toner binder - Google Patents

Abstract

To provide a toner binder that satisfies hot off-set resistance and charging stability while achieving both of low temperature fixability and storage stability.SOLUTION: A toner binder contains a vinyl resin (A) having a monomer (a) as an essential constituent monomer. The (a) is a C21-40 (meth) acrylate having a chain hydrocarbon group and/or a C21-40 vinyl ester having a chain hydrocarbon group. The (A) has a melting point by DSC measurement of 40-80°C. The (A) has a relative dielectric constant ε' of 2.5-4.0. The (A) has a volume resistivity of 4.5×10-6.3×10Ω cm. Based on the weight of the toner binder, the weight ratio of the (A) is 20.1-99.9 wt.%, and based on the total weight of constituent monomers of the (A), the weight ratio of the (a) is 15-90 wt.%.SELECTED DRAWING: None

Description

  The present invention relates to a toner binder.

2. Description of the Related Art In recent years, in a printing apparatus such as a copying machine and a printer using an electrophotographic technique, low temperature fixing of toner has been demanded from the viewpoint of environmental load and high speed.
In the electrophotographic process, an electrostatic latent image formed on a photoconductor is developed with toner, the formed toner image is transferred to a recording medium such as paper, and then fixed by heating to form an image. In this process, the toner must have charge stability, storage stability that does not stick in the developing tank, hot offset resistance at high temperatures, and the like.
As a technique for fixing toner at a low temperature from the viewpoint of environmental load and high speed, lowering the glass transition temperature of amorphous polyester or styrene-acrylic resin used as a binder resin can be cited. There is a problem that stability is deteriorated.

Therefore, in recent years, a method of improving low-temperature fixability by using a crystalline resin having excellent sharp melt properties as a binder resin has been proposed.
It is known that low-temperature fixability is improved by using a crystalline vinyl resin containing crystalline alkyl acrylate and / or crystalline alkyl methacrylate as a constituent resin as the binder resin. (Patent Documents 1 to 5)
However, for example, in Patent Document 1, when the vinyl resin has low crystallinity, the melting point is low, and the storage temperature exceeds 50 ° C., the storage stability of the toner is extremely deteriorated. In Patent Document 2, the sharp melt property is impaired due to the low weight ratio of the vinyl resin in the toner binder, and the low-temperature fixability is not satisfactory. In Patent Literature 3, the weight ratio of the alkyl acrylate and alkyl methacrylate constituting the vinyl resin is high, and the crystallinity is high. Hot offset resistance deteriorates. In Patent Document 4, since a monomer having high hygroscopicity is used, the volume specific resistance of the resin under high temperature and high humidity is reduced, and the chargeability is deteriorated. In Patent Document 5, since the vinyl resin has a high acid value and a high hygroscopic property, the volume specific resistance of the resin particularly under high temperature and high humidity is reduced, and the charging stability is deteriorated.

  As described above, there has been no toner binder that satisfies hot offset resistance and charging stability while achieving both low-temperature fixability and storage stability.

JP-A-6-175394 JP 2011-94136 A JP-A-11-44967 JP 2004-163956 A JP 2007-193069 A

  An object of the present invention is to provide a toner binder that satisfies hot offset resistance and charging stability while achieving both low-temperature fixability and storage stability.

The present inventors have intensively studied to solve these problems, and as a result, have reached the present invention.
That is, the present invention relates to a toner binder containing a vinyl resin (A) containing a monomer (a) as an essential constituent monomer, wherein the monomer (a) has a carbon number of 21 having a chain hydrocarbon group. (Meth) acrylate and / or a vinyl ester having a chain hydrocarbon group and having a carbon number of 21 to 40. The vinyl resin (A) has a melting point of 40 to 80 ° C. measured by DSC, and the vinyl resin (A) )), The vinyl resin (A) has a specific volume resistivity of 3.0 × 10 ^{10 to} 6.3 × 10 ¹¹ Ω · cm, and the toner binder The weight ratio of the vinyl resin (A) is 20.1 to 99.9% by weight based on the weight of the monomer (a), and the monomer (a) is based on the total weight of the monomers constituting the vinyl resin (A). A weight ratio of 15 to 90% by weight. Is underground.

  According to the present invention, it is possible to provide a toner binder that satisfies hot offset resistance and charging stability while achieving both low-temperature fixability and storage stability.

Hereinafter, the present invention will be described in detail.
The toner binder of the present invention is a toner binder containing a vinyl resin (A) containing the monomer (a) as an essential constituent monomer, wherein the monomer (a) has a carbon atom having a chain hydrocarbon group. A vinyl ester having 21 to 40 carbon atoms having (meth) acrylate and / or a chain hydrocarbon group, having a melting point of 40 to 80 ° C by DSC measurement of the vinyl resin (A); The relative dielectric constant ε ′ of (A) is 2.2 to 4.0, the volume resistivity of the vinyl resin (A) is 3.0 × 10 ^{10 to} 6.3 × 10 ¹¹ Ω · cm, The weight ratio of the vinyl resin (A) is 20.1 to 99.9% by weight based on the weight of the toner binder, and the monomer (a) is based on the total weight of the monomers constituting the vinyl resin (A). ) Is 15 to 90% by weight. It is a toner binder.

In the present invention, “(meth) acrylic acid” means methacrylic acid or acrylic acid.
In the present invention, “(meth) acrylate” means methacrylate or acrylate.

The toner binder of the present invention contains a vinyl resin (A) containing the monomer (a) as an essential constituent monomer.
The monomer (a) is a (meth) acrylate having a chain hydrocarbon group having 21 to 40 carbon atoms and / or a vinyl ester having a chain hydrocarbon group having 21 to 40 carbon atoms.
As the (meth) acrylate having a chain hydrocarbon group and having 21 to 40 carbon atoms, a (meth) acrylate having a linear alkyl group having 18 to 36 carbon atoms [octadecyl (meth) acrylate, nonadecyl (meth) acrylate, Eicosyl (meth) acrylate, heneicosanil (meth) acrylate, behenyl (meth) acrylate, lignoceryl (meth) acrylate, ceryl (meth) acrylate, montanyl (meth) acrylate, myristyl (meth) acrylate, dotriaconta (meth) acrylate, etc.] and (Meth) acrylates having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth) acrylate and the like] may be mentioned.
Examples of the vinyl ester having a chain hydrocarbon group having 21 to 40 carbon atoms include vinyl esters having a linear alkyl group having 18 to 36 carbon atoms [for example, vinyl stearate, vinyl behenate, vinyl tricontanate and hexa And vinyl esters having a branched alkyl group having 18 to 36 carbon atoms.
Of these, (meth) acrylates having a linear alkyl group having 18 to 30 carbon atoms and vinyl esters having a linear alkyl group having 18 to 36 carbon atoms are preferable from the viewpoint of storage stability of the toner. More preferred are (meth) acrylates having a linear alkyl group having 18 to 24 carbon atoms and vinyl esters having a linear alkyl group having 18 to 24 carbon atoms. As the monomer (a), one type may be used alone, or two or more types may be used in combination.

The weight ratio of the monomer (a) is 15 to 90% by weight, preferably 30 to 80% by weight, more preferably 40 to 80% by weight based on the total weight of the monomers constituting the vinyl resin (A). ７０70% by weight.
When the weight ratio of the monomer (a) is less than 15% by weight, the low-temperature fixability deteriorates, and when it is more than 90% by weight, the hot offset resistance deteriorates.

The vinyl resin (A) is 15 to 90% by weight (preferably 30 to 80% by weight, more preferably 30 to 80% by weight, based on the total weight of the monomers constituting the vinyl resin (A)). The content of the vinyl resin (A) of the present invention is not particularly limited as long as the monomer (b) contains the monomer (b) other than the monomer (a). The monomer (b) is a monomer other than the monomer (a), and the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) is preferably 5.0 or more and 15.0 or less, More preferably, it is 6.0 or more and 13.0 or less.
When the hydrogen bond term (dH) of the monomer (b) exceeds 15.0, storage stability and charging stability deteriorate, and when it is less than 5.0, storage stability deteriorates.

  The Hansen solubility parameter is obtained by dividing a solubility parameter introduced by Hildebrand into three components, a dispersion term (dD), a polarity term (dP), and a hydrogen bond term (dH), and is represented in a three-dimensional space. Things. The dispersion term (dD) indicates the effect by the dispersive force, the polar term (dP) indicates the effect by the dipole force, and the hydrogen bond term (dH) indicates the effect by the hydrogen bond force.

  The definition and calculation of the Hansen solubility parameter is described in Charles M. Hansen, "Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007)". Further, by using the computer software “HSPiP 4.1.0”, it is possible to estimate the Hansen solubility parameter from the chemical structure of a monomer whose parameter value is not described in the literature. In the present invention, for a monomer whose parameter value is described in the literature, the value is used. For a monomer whose parameter value is not described in the literature, the parameter value estimated using HSPiP is used.

Examples of the monomer (b) include a (meth) acrylate (b1) having a hydrocarbon group having 1 to 3 carbon atoms, a vinyl ester (b2) having a hydrocarbon group having 1 to 3 carbon atoms, and an amine (meth). A) amide with acrylic acid (b3), compound having a nitrile group and a vinyl group (b4), compound having a lactam ring and a vinyl group (b5), compound having a carboxyl group and a vinyl group (b6), a hydroxyl group And (meth) acrylate (b8) having an aldehyde group. As the monomer (b), one type may be used alone, or two or more types may be used in combination.
Hereinafter, the value of the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) is described in parentheses following the compound name of the monomer (b).

  Examples of the (meth) acrylate (b1) having a chain hydrocarbon group having 1 to 3 carbon atoms include methyl acrylate (9.4), ethyl acrylate (6.5), propyl acrylate (6.5) and Methyl methacrylate (5.4) and the like.

  Examples of the vinyl ester (b2) having a hydrocarbon group having 1 to 3 carbon atoms include vinyl acetate (6.8), vinyl butyric acid (6.2), and isopropenyl acetate (6.2).

Examples of the amide (b3) of an amine and (meth) acrylic acid include a monomer obtained by reacting ammonia and an amine having 1 to 8 carbon atoms with acrylic acid and methacrylic acid by a known method.
Specific examples include acrylamide (12.8), methacrylamide (11.6), N-methylacrylamide (9.7), N-ethylacrylamide (8.7), and the like.

  As the compound (b4) having a nitrile group and a vinyl group, a compound having a nitrile group having 1 to 5 carbon atoms and a vinyl group (for example, acrylonitrile (6.8), methacrylonitrile (8.5), Pentennitrile (5.7), 5-hexenenitrile (5.2), α-chloroacrylonitrile (5.2) and the like can be mentioned.

  As the compound (b5) having a lactam ring and a vinyl group, a compound having a lactam ring having 4 to 8 carbon atoms and a vinyl group (for example, vinylpyrrolidone (5.9), N-vinylpyrrolidone (6.3) N-vinyl-3-methylpyrrolidone (5.7), N-vinylpiperidone (5.7), N-vinyl-4-methylpiperidone (5.5), N-vinyl-caprolactam (5.5) and N- And vinyl-2-pyridone (6.8).

As the compound (b6) having a carboxyl group and a vinyl group, a compound having a carboxyl group having 1 to 9 carbon atoms and a vinyl group [for example, methacrylic acid (13.4), crotonic acid (14.4), cinnamic acid (10.9), maleic acid monomethyl ester (12.7), fumaric acid monomethyl ester (12.7), itaconic acid monomethyl ester (13.7), citraconic acid monoethyl ester (13.9), 3-butene Acid (14.1), 4-pentenoic acid (12.7), 5-hexenoic acid (11.6), 6-heptenoic acid (10.4), 7-octenoic acid (9.9), 8-nonene Acid (9.2), 9-decenoic acid (8.6), 10-undecenoic acid (7.9) and 11-tridecenoic acid (7.8)].
In the present specification, the number of carbon atoms in the compound having a carboxyl group and the structure does not include the number of carbon atoms contained in the carboxyl group portion.

  As the (meth) acrylate (b7) having a hydroxyl group, any one of hydroxyethyl methacrylate (13.4), hydroxypropyl acrylate (13.7) (2-hydroxypropyl ester, 2-hydroxy-1-methylethyl ester) Or a mixture thereof), hydroxypropyl methacrylate (12.2) (any of 2-hydroxypropyl ester and 2-hydroxy-1-methylethyl ester or a mixture thereof), hydroxybutyl acrylate (13.0) and methacrylic acid Hydroxybutyl (11.7) and the like.

  Examples of the (meth) acrylate (b8) having an aldehyde group include acrolein (7.0) and methacrylolein (5.8).

Among the above-mentioned monomers (b), (meth) acrylates having a hydrocarbon group having 1 to 3 carbon atoms and hydrocarbon groups having 1 to 3 carbon atoms are preferable from the viewpoint of compatibility between low-temperature fixability and storage stability. A vinyl ester having 1 to 8 carbon atoms, an amide of an amine having 1 to 8 carbon atoms and (meth) acrylic acid, a compound having 1 to 5 carbon atoms of a nitrile group and a vinyl group, and a lactam ring having 4 to 8 carbon atoms and a vinyl group. And a compound having a carboxyl group having 1 to 9 carbon atoms and a vinyl group.
More preferably, methyl methacrylate, vinyl acetate, vinyl propion, (meth) acrylamide, acrylonitrile, methacrylonitrile, vinylpyrrolidone, (anhydrous) maleic acid, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, etc. is there.

  When the vinyl resin (A) contains the monomer (b), the weight ratio of the monomer (b) in the monomers constituting the vinyl resin (A) is determined based on the low-temperature fixing property and hot offset resistance. Therefore, the amount is preferably 5 to 80% by weight, more preferably 10 to 40% by weight, based on the total weight of the monomers constituting the vinyl resin (A).

  When the vinyl resin (A) contains the monomer (b), the weight ratio of the monomer (a) and the monomer (b) constituting the vinyl resin (A) {(a) :( b)} Is preferably from 98: 2 to 15:85, more preferably from 90:10 to 50:50, from the viewpoint of low-temperature fixability and storage stability.

The vinyl resin (A) may contain a monomer (c) other than (a) and (b) as a constituent monomer. As the monomer (c), one type may be used alone, or two or more types may be used in combination.
The monomer (c) is not particularly limited as long as it is a monomer other than the monomer (a) and the monomer (b). For example, styrene, alkyl having 1 to 3 carbon atoms in the alkyl group. Examples include styrene (eg, α-methylstyrene and p-methylstyrene), hydroxyethyl acrylate, maleic acid, fumaric acid, and itaconic acid. Of these, styrene and maleic acid are preferred from the viewpoint of storage stability when used as a toner.

  From the viewpoint of storage stability, the weight ratio of the monomer (c) in the monomer constituting the vinyl resin (A) is preferably based on the total weight of the monomers constituting the vinyl resin (A). It is 0 to 40% by weight, more preferably 0 to 25% by weight.

  The vinyl resin (A) in the present invention contains a monomer composition containing a monomer (a) and optionally a monomer (b) and / or a monomer (c) optionally used. It can be produced by polymerizing by a known method (for example, radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, living cationic polymerization, etc.). For example, a method described in JP-A-5-117330 (a method in which the monomer is reacted with a radical initiator (azobisisobutyronitrile or the like) in a solvent (toluene or the like) and synthesized by a solution polymerization method), And a method of polymerizing by the method described in JP-A-10-326026.

  The weight average molecular weight of the vinyl resin (A) in the present invention is preferably from 10,000 to 3,000,000, more preferably from 50,000 to 500,000, from the viewpoints of low-temperature fixability and hot offset resistance of the toner. It is. The weight average molecular weight of the vinyl resin (A) can be adjusted by a polymerization temperature, a radical polymerization initiator amount, a chain transfer agent and the like.

The weight average molecular weight of the vinyl resin (A) is measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
Apparatus (example): HLC-8120 [manufactured by Tosoh Corporation]
Column (one example): 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25% by weight of tetrahydrofuran solution (use insoluble matter filtered with a PTFE filter having a pore size of 1 μm)
Mobile phase: tetrahydrofuran (does not include polymerization inhibitor)
Solution injection volume: 100 μl
Detector: Refractive index detector Reference substance: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (weight average molecular weight: 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000) (manufactured by Tosoh Corporation)

In the present invention, the melting point of the vinyl resin (A) measured by DSC is from 40 to 80 ° C, preferably from 45 to 75 ° C, more preferably from 55 to 70 ° C.
When the melting point is lower than 40 ° C., the storage stability deteriorates, and when it exceeds 80 ° C., the low-temperature fixability deteriorates.

  The melting point of the vinyl resin (A) by DSC measurement can be adjusted by the type, composition ratio, weight average molecular weight, and the like of the monomers constituting the vinyl resin (A). Specifically, the number of carbon atoms of the monomer (a) constituting the vinyl resin (A) is increased, and the weight ratio of the monomer (a) constituting the vinyl resin (A) is increased. The melting point can be increased by a method such as increasing the weight-average molecular weight of the number of carbon atoms in (2). For example, when the number of carbon atoms of the monomer (a) is 22 and the ratio of the monomer (a) is 40% by weight, the weight average molecular weight is 5,000 or more, so that the above range is obtained.

  The melting point of the vinyl resin (A) is measured using a differential scanning calorimeter (for example, DSC20 manufactured by TA Instruments Co., Ltd.). The first temperature rise of the vinyl resin (A) is performed from 20 ° C. to 150 ° C. under the condition of 10 ° C./min, and then cooled from 150 ° C. to 0 ° C. under the condition of 10 ° C./min. The temperature at the top of the endothermic peak in the second heating process when the second heating is performed to 150 ° C. from 10 ° C./min is defined as the melting point of the vinyl resin (A).

  The relative permittivity ε ′ of the vinyl resin (A) is 2.2 to 4.0, preferably 3.0 to 3.9, and more preferably 3.0 to 3.7. This makes it possible to transfer the charged toner particles more efficiently during image formation.

  The relative dielectric constant ε ′ of the vinyl resin (A) can be adjusted by the type, the composition ratio, and the acid value of the monomer constituting the vinyl resin (A). Specifically, increasing the carbon number of the monomer (a) constituting the vinyl resin (A), increasing the weight ratio of the carbon number of the monomer (a) constituting the vinyl resin (A), The relative dielectric constant can be increased by a method such as increasing the acid value of (A). For example, when the weight ratio of the monomer (a) is 40%, the relative dielectric constant falls within the above range by setting the acid value to 0 or more.

The volume specific resistance value of the vinyl resin (A) is from 3.0 × 10 ^{10 to} 6.3 × 10 ¹¹ Ω · cm, preferably from 4.0 × 10 ^{10 to} 3.0 × 10 ¹¹ Ω · cm. Yes, more preferably 4.0 × 10 ^{10 to} 1.3 × 10 ¹¹ Ω · cm. Thereby, the charging stability is improved.

  The volume specific resistance value of the vinyl resin (A) can be adjusted by the type, composition ratio, acid value, and the like of the monomers constituting the vinyl resin (A). Specifically, the vinyl resin (A) may be reduced in carbon number of the monomer (a) and the vinyl resin (A) may be reduced in the weight ratio of the carbon number of the monomer (a). The volume resistivity can be increased by a method such as lowering the acid value of (A). For example, when the weight ratio of the vinyl resin (A) is 40%, by setting the acid value to 20 or less, the volume specific resistance falls in the above range.

The volume resistivity and the dielectric constant of the vinyl resin (A) were measured under the following conditions.
Apparatus: Ando Electric Co., Ltd. TR-1100 dielectric loss automatic measurement device
TO-198 type constant temperature bath manufactured by Ando Electric Co., Ltd. Electrode for solid: SE-70 type electrode for solid Measurement environment: 23 ° C, 50% RH
1.5 g of vinyl resin (A) is put into a molding ring (made of PVC, φ25 mm, height 5 mm), pressed with a press machine at 98 kN × 10 seconds, and molded into a cylindrical shape having a thickness of about 2.3 mm and φ = 25 mm. did. The molded product was left at 23 ° C. and 50% RH for 30 minutes or more, removed from the molding ring, and the thickness of the molded product was measured with a micrometer (D, unit μm). The measurement was performed at 1 kHz between the main electrode and the counter electrode, and the CONDUCTANCE (Gx, unit nS) and the capacitance (Cx, unit pF) were recorded. By substituting the obtained numerical values into the following equation (1) or (2), the volume resistivity and the dielectric constant were calculated.
Volume specific resistance = 3.14 × (0.9) ² / (G × D × 10 ⁻¹³ ) (1)
Dielectric constant = (14.39 × Cx × D) / 32400 (2)
The relative dielectric constant of the vinyl resin (A) is determined by the ratio of the calculated dielectric constant to the specific dielectric constant of air 1.000585.

  The weight ratio of the vinyl resin (A) is 20.1 to 99.9% by weight, preferably 50 to 90% by weight, and more preferably 70 to 90% by weight based on the weight of the toner binder. When the weight ratio of the vinyl resin (A) is less than 20.1% by weight, the low-temperature fixability deteriorates.

  The acid value of the vinyl resin (A) is preferably 19.9 mgKOH / g or less, more preferably 0 to 15 mgKOH / g. When the acid value of the vinyl resin (A) is 19.9 mgKOH / g or less, the storage stability is good because of low hygroscopicity.

  The acid value of the vinyl resin (A) can be adjusted by adjusting the acid value of the monomer and the content of the monomer having the acid value. The acid value of the vinyl resin (A) is measured by, for example, a method such as JIS K0070.

  The toner binder of the present invention may contain an amorphous polyester resin (B) having an alcohol component (x) and a carboxylic acid component (y) as essential constituent monomers. The amorphous polyester resin in the present invention is a polyester resin having no endothermic peak top temperature when a transition temperature of a sample is measured using a differential scanning calorimeter.

  Examples of the alcohol component (x) of the amorphous polyester resin (B) include aliphatic diols (x1) having 2 to 4 carbon atoms, alkylene oxide adducts of bisphenol A (x2), and other than (x1) and (x2). Examples thereof include diol (x3), trivalent or higher polyol (x4) and monol (x5).

  Examples of the aliphatic diol having 2 to 4 carbon atoms (x1) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and diethylene glycol.

Examples of the alkylene oxide adduct of bisphenol A (x2) include an alkylene oxide adduct of bisphenol A (an average addition mole number is preferably 2 to 30).
The alkylene oxide to be added to bisphenol A is preferably an alkylene oxide having 2 to 4 carbon atoms, and specifically, ethylene oxide, propylene oxide, 1,2-, 2,3-, 1,3- or iso- Butylene oxide, tetrahydrofuran and the like.

The diol (x3) other than (x1) and (x2) includes alkylene glycols having 5 to 36 carbon atoms, alkylene ether glycols having 4 to 36 carbon atoms, alicyclic diols having 6 to 36 carbon atoms, and 6 to 36 carbon atoms. And 36 alkylene oxide adducts of alicyclic diols and dihydric phenols.
Examples of the alkylene glycol having 5 to 36 carbon atoms include neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol.
Examples of the alkylene ether glycol having 4 to 36 carbon atoms include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.
Examples of the alicyclic diol having 6 to 36 carbon atoms include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the alkylene oxide adduct of an alicyclic diol having 6 to 36 carbon atoms include alkylene oxide adducts of an alicyclic diol having 6 to 36 carbon atoms (the average addition mole number is preferably 2 to 4).
Examples of the dihydric phenol include monocyclic dihydric phenols (for example, hydroquinone) and alkylene oxide adducts of bisphenol compounds other than bisphenol A (preferably having an average addition mole number of 2 to 30).

  The alkylene oxide adduct of a bisphenol compound is obtained by adding an alkylene oxide (hereinafter, “alkylene oxide” may be abbreviated as AO) to a bisphenol compound. Examples of the bisphenol compound include those represented by the following general formula (4).

HO-Ar-X-Ar-OH (4)
[In the formula, X represents an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S— or a direct bond. Ar represents a phenylene group in which a hydrogen atom may be substituted by a halogen atom or an alkyl group having 1 to 30 carbon atoms. ]

  Bisphenol compounds include, for example, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A, and 2,2′- Diethyl bisphenol F and the like.

  Examples of the trivalent or higher polyol (x4) include a trivalent or higher aliphatic polyhydric alcohol having 3 to 36 carbon atoms (alkane polyol and an intramolecular or intermolecular dehydrate thereof, for example, glycerin, trimethylolethane, trimethylolpropane, Pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol), saccharides and derivatives thereof (for example, sucrose and methyl glucoside), and AO adducts of the above-mentioned aliphatic polyhydric alcohols (the average number of moles of addition is preferably 1 to 30) , An AO adduct of trisphenols (such as trisphenol PA) (the average addition mole number is preferably 2 to 30) and a novolak resin (phenol novolak and cresol novolak), and the average degree of polymerization is preferably 3 to 60. ) AO adduct (average number of moles added is preferred) Ku can be mentioned 2 to 30), and the like.

  Examples of the monol (x5) include alkanols having 1 to 30 carbon atoms (such as methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol).

As the alcohol component (x) of the amorphous polyester resin (B), one type may be used alone, or two or more types may be used in combination.
Among these alcohol components (x), from the viewpoint of low-temperature fixability, an aliphatic diol having 2 to 4 carbon atoms and an alkylene oxide adduct of bisphenol A are preferable, and 1.2-propylene glycol and bisphenol A are more preferable. Of ethylene oxide and propylene oxide of bisphenol A.

  Examples of the carboxylic acid component (y) of the amorphous polyester resin (B) include a monocarboxylic acid (y1) and a polycarboxylic acid (y2).

Examples of the monocarboxylic acid (y1) include aliphatic (including alicyclic) monocarboxylic acids and aromatic monocarboxylic acids.
Aliphatic (including alicyclic) monocarboxylic acids include alkane monocarboxylic acids having 1 to 30 carbon atoms (formic acid, acetic acid, propionic acid, butanoic acid, isobutanoic acid, caprylic acid, capric acid, capric acid, lauric acid, myristylic acid) And alkene monocarboxylic acids having 3 to 24 carbon atoms (such as acrylic acid, methacrylic acid, oleic acid and linoleic acid), and the like.
Examples of the aromatic monocarboxylic acids include aromatic monocarboxylic acids having 7 to 36 carbon atoms (benzoic acid, methylbenzoic acid, pt-butylbenzoic acid, phenylpropionic acid, naphthoic acid, and the like).

  Examples of the polycarboxylic acid (y2) include a dicarboxylic acid (y21) and / or a trivalent or higher polycarboxylic acid (y22).

  Examples of the dicarboxylic acid (y21) include alkanedicarboxylic acids having 4 to 36 carbon atoms (eg, succinic acid, adipic acid and sebacic acid), and alicyclic dicarboxylic acids having 6 to 40 carbon atoms [eg, dimer acid (dimerized linoleic acid)] Alkene dicarboxylic acids having 4 to 36 carbon atoms (eg, alkenyl succinic acids such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid), and aromatic dicarboxylic acids having 8 to 36 carbon atoms (eg, phthalic acid, isophthalic acid) Acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and their ester-forming derivatives [lower alkyl (C 1-4 of alkyl group: methyl, ethyl, n-propyl, etc.) esters and acid anhydrides; The same applies to derivatives. And the like.

  Examples of the trivalent or higher polycarboxylic acid (y22) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid) and aliphatic polycarboxylic acids having 6 to 36 carbon atoms (hexanetricarboxylic acid). And their ester-forming derivatives (such as esters with acid anhydrides and lower alcohols).

As the carboxylic acid component (y) of the amorphous polyester resin (B), one type may be used alone, or two or more types may be used in combination.
Among these carboxylic acid components (y), from the viewpoint of low-temperature fixability and hot offset resistance, preferably, alkanedicarboxylic acid having 4 to 36 carbon atoms, alkenedicarboxylic acid having 4 to 36 carbon atoms, and 8 to 36 carbon atoms. Aromatic dicarboxylic acids and aromatic polycarboxylic acids having 9 to 20 carbon atoms, more preferably adipic acid, fumaric acid, isophthalic acid, terephthalic acid and trimellitic acid.

  The reaction ratio between the alcohol component (x) and the carboxylic acid component (y) is preferably 1/2 to 2/1, more preferably 1/1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 0.3 to 1.5 / 1, particularly preferably 1 / 1.2 to 1.3 / 1.

In the present invention, the polycondensation of the alcohol component (x) and the carboxylic acid component (y) can be performed using a known esterification reaction. As a general method, for example, the reaction temperature is preferably 150 to 280 ° C, more preferably 180 to 270 ° C, particularly preferably 200 to 260 in an inert gas (nitrogen gas or the like) atmosphere in the presence of a polymerization catalyst. The reaction can be carried out at a temperature of about 10 ° C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.
It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

As the polymerization catalyst, from the viewpoint of reactivity and environmental protection, it is preferable to use a polymerization catalyst containing one or more metals selected from titanium, antimony, zirconium, nickel and aluminum, and it is more preferable to use a titanium-containing catalyst. .
Examples of the titanium-containing catalyst include titanium alkoxide, potassium oxalate titanate, titanium terephthalate, a catalyst described in JP-A-2006-243715 [titanium dihydroxybis (triethanolaminate), titanium monohydroxytris (triethanolaminate). ) And their intramolecular polycondensates] and the catalysts described in JP-A-2007-11307 (such as titanium tributoxy terephthalate, titanium triisopropoxy terephthalate and titanium diisopropoxy diterephthalate).
Antimony-containing catalysts include antimony trioxide.
Examples of the zirconium-containing catalyst include zirconyl acetate and the like.
Examples of the nickel-containing catalyst include nickel acetylacetonate and the like.
Examples of the aluminum-containing catalyst include aluminum hydroxide and aluminum triisopropoxide.

  It is desirable that the addition amount of the catalyst is appropriately determined so that the reaction rate is maximized. The amount added is preferably 10 ppm to 1.9% by weight, more preferably 100 ppm to 1.7% by weight, based on all raw materials. The addition amount of 10 ppm or more is preferable in that the reaction rate is increased.

The glass transition temperature of the amorphous polyester resin (B) is preferably from 50 to 80C, more preferably from 55 to 70C. The glass transition temperature of the amorphous polyester resin (B) can be adjusted by the weight average molecular weight, the structure of the alcohol component (x), the structure of the carboxylic acid component (y), the composition ratio, and the like. As the adjustment factor, a generally known method can be used.
When the glass transition temperature of the amorphous polyester resin (B) is 50 ° C. or more, storage stability is good, and when it is 80 ° C. or less, low-temperature fixability is good.

The glass transition temperature (Tg) of the amorphous polyester resin (B) was measured by a method (DSC method) specified in ASTM D3418-82 using DSC20 manufactured by TA Instruments. The conditions for measuring the glass transition temperature are described.
<Measurement conditions>
(1) Heating from 30 ° C to 150 ° C at 20 ° C / min (2) Holding at 150 ° C for 10 minutes (3) Cooling to -35 ° C at 20 ° C / min (4) Holding at -35 ° C for 10 minutes (5 ) Temperature rise to 150 ° C. at 20 ° C./min. From the differential scanning calorie curve obtained by the above measurement, draw a graph with the vertical axis representing heat absorption and heat generation and the horizontal axis representing temperature. The temperature at the intersection of the straight line extending to the side and the tangent drawn at the point where the slope of the curve of the step change portion of the glass transition becomes maximum was defined as the glass transition temperature.

  The weight average molecular weight of the amorphous polyester resin (B) in the present invention is preferably from 3,000 to 300,000, more preferably from 5,000 to 50,000, from the viewpoint of low-temperature fixability and storage stability. . The weight average molecular weight of the amorphous polyester resin (B) in the present invention can be adjusted by adjusting the charging ratio of the alcohol component (x) and the carboxylic acid component (y), and the weight average molecular weight of the amorphous polyester resin (B). Can be measured in the same manner as the measurement of the weight average molecular weight of the vinyl resin (A).

  The THF-insoluble content of the amorphous polyester resin (B) is preferably 0 to 50% by weight, more preferably, 0 to 50% by weight based on the weight of the amorphous polyester resin (B), from the viewpoint of low-temperature fixability and hot offset resistance. 0 to 35% by weight.

The THF-insoluble portion of the amorphous polyester resin (B) was determined by the following method.
50 ml of THF is added to 0.5 g of the sample, and the mixture is stirred and refluxed for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter, and the resin content on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The insoluble content is calculated from the weight ratio of the dried resin component on the glass filter to the sample.

  The acid value of the amorphous polyester resin (B) is preferably from 0 to 30 mgKOH / g, more preferably from 5 to 30 mgKOH / g, and particularly preferably from 10 to 15 mgKOH / g. If the acid value of the amorphous polyester resin (B) is 0 mgKOH / g or more, the charging stability becomes good, and if it is 30 mgKOH / g or less, the storage stability becomes good.

  The acid value of the amorphous polyester resin (B) can be adjusted by adjusting the acid value of the monomer and the content of the monomer having the acid value. The acid value of the amorphous polyester resin (B) is measured, for example, by a method such as JIS K0070.

  The hydroxyl value of the amorphous polyester resin (B) is preferably 0 to 60 mgKOH / g, more preferably 1 to 50 mgKOH / g, and particularly preferably 2 to 30 mgKOH / g. When the hydroxyl value is 60 or less, the charge stability and storage stability when used in a toner become better.

  The hydroxyl value of the amorphous polyester resin (B) can be adjusted by adjusting the hydroxyl value of the monomer and the content of the monomer having the hydroxyl value. The hydroxyl value of the amorphous polyester resin (B) is measured, for example, by a method such as JIS K0070.

  The softening point of the amorphous polyester resin (B) is preferably from 90 to 144 ° C, more preferably from 100 to 120 ° C, from the viewpoint of storage stability.

The softening point of the amorphous polyester resin (B) in the present invention is measured under the following conditions.
Using a flow tester (for example, CFT-500D, manufactured by Shimadzu Corporation), while applying a load of 1.96 MPa with a plunger while heating 1 g of the measurement sample at a heating rate of 6 ° C./min, a diameter of 1 mm , Extruded from a 1 mm long nozzle, draw a graph of "Plunger descent (flow value)" and "Temperature", and read the temperature corresponding to 1/2 of the maximum value of the plunger descent from the graph This value (the temperature at which half of the measurement sample flows out) is defined as the softening point.

  When containing the amorphous polyester resin (B), the weight ratio between the vinyl resin (A) and the amorphous polyester resin (B) is preferably 99/1 to 20/80, and more preferably 90/10 to 10/80. 40/60. If the ratio is larger than 99/1, the charging performance deteriorates, and if it is less than 20/80, the low-temperature fixing performance deteriorates.

In the present invention, the melting point of the toner binder is from 40 to 80C, preferably from 45 to 75C, and more preferably from 55 to 70C.
When the melting point is 40 ° C. or more, the storage stability becomes good, and when it is 80 ° C. or less, the low-temperature fixability becomes good.
The melting point of the toner binder is measured under the same conditions as the melting point of the vinyl resin (A).

The acid value of the toner binder of the present invention is preferably from 0 to 30 mgKOH / g, and more preferably from 1 to 20 mgKOH / g. When the acid value of the toner binder is 0 mgKOH / g or more, the charging stability becomes good, and when it is 30 mg or less, the storage stability becomes good.
The acid value of the toner binder is measured by, for example, a method such as JIS K0070.

  The toner binder of the present invention is not particularly limited as long as it contains 20.1 to 99.9% by weight of the vinyl resin (A). For example, the vinyl binder (A) and the amorphous polyester resin (B) are used. Can be mixed by a known method. Examples of the mixing method include powder mixing, melt mixing, and solvent mixing. Further, the vinyl resin (A), the amorphous polyester resin (B) and the additives used as required may be mixed simultaneously with the production of the toner. Among these methods, a melt-mixing method that mixes uniformly and does not require solvent removal is preferred.

Examples of a mixing device for mixing powder include a Henschel mixer, a Nauta mixer, and a Banbury mixer. Preferably, it is a Henschel mixer.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous type mixing device. In order to mix uniformly at an appropriate temperature in a short time, a continuous mixing apparatus is preferable. Examples of the continuous mixing device include a twin-screw kneader, a static mixer, an extruder, a continuous kneader, and a three-roll mill.

  As a method of mixing the solvent, the vinyl resin (A) and the amorphous polyester resin (B) are dissolved in a solvent (ethyl acetate, THF, acetone, etc.) to homogenize (A) and (B), and then the mixture is removed. A method of pulverizing with a solvent or a method of dissolving (A) and (B) in a solvent, dispersing the solvent solution of (A) and (B) in water to uniformly disperse (A) and (B), and then removing There is a method of using a solvent.

  When the toner binder of the present invention is used as a toner, it may contain a colorant, a release agent, a charge control agent, a fluidizing agent, and the like, if necessary.

As the colorant, any of dyes, pigments and the like used as colorants for toner can be used. For example, carbon black, iron black, Sudan Black SM, Fast Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Pigment Red, 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, pigment yellow, oil yellow GG, kayaset YG, orazol brown B, oil pink OP, and the like. Can be used alone or in combination of two or more. If necessary, a magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, and nickel or a compound such as magnetite, hematite, and ferrite) can be contained as a colorant.
The content of the colorant is preferably 1 to 40 parts, more preferably 3 to 10 parts, based on 100 parts of the toner binder of the present invention. When using magnetic powder, the amount is preferably 20 to 150 parts, more preferably 40 to 120 parts.

As the release agent, those having a softening point of 50 to 170 ° C. are preferable, and aliphatic hydrocarbon waxes such as polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax and oxides thereof, carnauba wax, montan wax And their deoxidizing waxes, ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like.
The softening point of the release agent is measured under the same conditions as the softening point of the amorphous polyester resin (B).

  Examples of the polyolefin wax include (co) polymers of olefins (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof), and those obtained by (co) polymerization. (Including low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer), oxides of olefin (co) polymers with oxygen and / or ozone. , Maleic acid-modified olefin (co) polymers [maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate and the like) and the like], olefins and unsaturated carboxylic acids [( Meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or A copolymer of an unsaturated carboxylic acid alkyl ester [(meth) (C1-18 alkyl) acrylic acid alkyl esters and maleic acid alkyl (C1-18 alkyl) esters, etc.] and the like.

  Examples of the microcrystalline wax include Hi-Mic-2095, Hi-Mic-1090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, and Hi-Mic- manufactured by Nippon Seiro Co., Ltd. 1045, Hi-Mic-2045 and the like.

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

  Examples of the Fischer-Tropsch wax include Sasolwax C80 manufactured by Sasol.

  Examples of carnauba wax include refined carnauba wax No. 1 manufactured by Kato Yoko Co., Ltd.

  Examples of the ester wax include fatty acid ester waxes (for example, Nissan Elector WEP-2, WEP-3, WEP-4, WEP-5, and WEP-8 manufactured by NOF Corporation).

  Examples of the higher alcohol include aliphatic alcohols having 30 to 50 carbon atoms, such as triacontanol. Fatty acids include fatty acids having 30 to 50 carbon atoms, such as triacontancarboxylic acid.

  Examples of the fatty acid amide include Diamid Y and Diamid 200 manufactured by Mitsubishi Chemical Corporation.

  Among the above, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, carnauba wax, ester wax and amide wax are preferable from the viewpoint of low-temperature fixability and hot offset resistance.

  As the charge control agent, any of a positive charge control agent and a negative charge control agent may be contained, and a nigrosine dye, a triphenylmethane dye containing a tertiary amine as a side chain, and a quaternary ammonium Salt, polyamine, imidazole derivative, quaternary ammonium base-containing polymer, metal-containing azo dye, copper phthalocyanine dye, salicylic acid metal salt, boron complex of benzylic acid, sulfonic acid group-containing polymer, fluorine-containing polymer, and halogen-substituted fragrance Ring-containing polymers and the like can be mentioned.

  Examples of the fluidizing agent include silica, titania, calcium aluminate carbonate, fatty acid metal salt, silicone resin particles and fluororesin particles, and two or more kinds thereof may be used in combination. Silica is preferred from the viewpoint of toner chargeability. The silica is preferably hydrophobic silica from the viewpoint of transferability of the toner.

When the toner binder of the present invention is used as a toner, the composition ratio of the toner is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, and particularly preferably, the toner binder of the present invention is based on the weight of the toner. 45 to 92% by weight.
The colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, and particularly preferably 0.5 to 50% by weight based on the weight of the toner.
The release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight, based on the weight of the toner.
The charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.5 to 7.5% by weight based on the weight of the toner.
The fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, particularly preferably 0.1 to 4% by weight, based on the weight of the toner.
The total content of the additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, and particularly preferably 5 to 50% by weight, based on the weight of the toner.
When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

The method for producing the toner when the toner binder of the present invention is used as a toner is not particularly limited, and may be any of a kneading and pulverizing method, an emulsion phase inversion method, an emulsion polymerization method, a suspension polymerization method, a solution suspension method, and an emulsion aggregation method. May be obtained by the above method.
Among these production methods, the kneading and pulverization method and the dissolution suspension method are preferred from the viewpoints of productivity, low-temperature fixability and storage stability.

For example, when a toner is obtained by a kneading and pulverizing method, components constituting the toner excluding a fluidizing agent are dry-blended with a Henschel mixer, a Nauter mixer, a Banbury mixer, and the like, and then a twin-screw kneader, an extruder, a continuous kneader and Melt and knead with a continuous mixing device such as three rolls, then coarsely pulverize with a mill, etc., and finally make fine particles using a pneumatic fine pulverizer, etc., and further reduce the particle size distribution with a classifier such as an elbow jet. By adjusting the volume, fine particles having a volume average particle diameter (D50) of preferably 5 to 20 μm can be produced, and then mixed with a fluidizing agent. The volume average particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
Specifically, 0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 to 150 mL of ISOTON-II (manufactured by Beckman Coulter), which is an aqueous electrolytic solution. Further, 2 to 20 mg of a measurement sample was added, and the electrolyte in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the measurement device used a 50 μm aperture as an aperture to obtain a volume of toner particles. , The number is measured, and the volume distribution and the number distribution are calculated. From the obtained distribution, the volume average particle size (D50) (μm), the number average particle size (μm), and the particle size distribution (volume average particle size / number average particle size) of the toner particles are obtained.

  When a toner is obtained by an emulsification phase inversion method, it can be manufactured by dissolving or dispersing components constituting the toner except for a fluidizing agent in an organic solvent, emulsifying by adding water, and then separating and classifying. The volume average particle diameter of the toner is preferably 3 to 15 μm.

  As the emulsion polymerization method and the suspension polymerization method, known methods [methods described in JP-B-36-10231, JP-B-47-518305, JP-B-51-14895, etc.] can be used.

  As the dissolution suspension method and the emulsion aggregation method, known methods [methods described in Japanese Patent No. 3596104, Japanese Patent No. 3492748, etc.] can be used.

  The toner used in the toner binder of the present invention may be, if necessary, carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic polymer, silicone polymer, etc.). And used as a developer for an electric latent image. The weight ratio between the toner and the carrier particles is from 1/99 to 100/0. Further, instead of the carrier particles, friction with a member such as a charging blade can be performed to form an electric latent image.

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

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, parts are by weight unless otherwise specified.

<Production Example 1>
After charging 17 parts of xylene in an autoclave and purging with nitrogen, the temperature was raised to 140 ° C. in a sealed state with stirring. 50 parts of behenyl acrylate (manufactured by NOF Corporation, the same applies hereinafter), 50 parts of styrene (manufactured by Idemitsu Kosan Co., Ltd., the same applies hereinafter), 25 parts of monomer (a) (B) acrylonitrile [manufactured by Nakarai-Tex Co., Ltd .; the same applies hereinafter] 23.5 parts, methacrylic acid monomer (b) [manufactured by Nacalai-Tex Co., Ltd., the same applies hereinafter] 1.5 parts, perbutyl D [Di-t-butyl peroxide, NOF CORPORATION, the same applies hereinafter] A mixed solution of 0.15 part and xylene 17 parts was added dropwise over 3 hours while controlling the temperature in the autoclave at 140 ° C., and polymerization was carried out. Was done. After the polymerization was completed at the same temperature for 2 hours to complete the polymerization, the solvent was removed at 170 ° C. to obtain a vinyl resin (A1). Table 1 shows the weight average molecular weight, melting point, volume resistivity, relative dielectric constant and acid value of the vinyl resin (A1).

<Production Examples 2 to 10>
Vinyl resins (A2) to (A10) were obtained in the same manner as in Production Example 1 except that the respective monomers and the radical initiator were used in the specified parts by weight based on the composition of the monomers shown in Table 1. The analysis values were as shown in Table 1, respectively.

<Production Example 11>
An autoclave equipped with a stirrer was charged with 100 parts of xylene [manufactured by Nacalai Tex Co., Ltd .; the same applies hereinafter], 100 parts of behenyl acrylate as the monomer (a), and 1.5 parts of thioglycolic acid. The temperature was raised to 85 ° C. in a sealed state with stirring. 0.80 part of di-t-butyl peroxide [Azo V65, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd .; the same applies hereinafter] was charged, and polymerization was carried out for 3 hours while controlling the temperature in the autoclave at 85 ° C while maintaining the same temperature. Was done. Thereafter, the temperature was further raised to 105 ° C, and the mixture was stirred at 105 ° C for 1 hour and then cooled to 30 ° C. After cooling, 2.5 parts of hydroxyethyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a monomer (b) was added to the reaction vessel, and the temperature was raised to 55 ° C. 4 parts of 4-methylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.1 parts of t-Bu hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 20 parts of chloroform. The resulting mixture was added dropwise over 1 hour. Thereafter, stirring was further performed at 55 ° C. for 5 hours. Thereafter, the solution was cooled to 35 ° C., and the dissolved matter excluding the solid content was purified by a methanol precipitation method. The obtained solid was dried under reduced pressure to obtain a white solid macromonomer. The white solid macromonomer had a weight average molecular weight of 6,000 and a melting point of 65 ° C.
Further, another autoclave was charged with 17 parts of xylene, and the autoclave was purged with nitrogen, and then heated to 170 ° C. Then, at the same temperature, 64 parts of a macromonomer as a white solid, 30 parts of methyl methacrylate (manufactured by Nacalai Tex Co., Ltd., the same applies hereinafter) as a monomer (b), and methacrylonitrile as a monomer (b) [ A solution of 16 parts of monomer (b), 4 parts of methacrylic acid, 0.15 part of perbutyl D and 17 parts of toluene was added dropwise over 3 hours at the same temperature to carry out polymerization. Was done. After the polymerization was completed at the same temperature for 2 hours, the solvent was removed at 170 ° C. to obtain a vinyl resin (A11). Table 1 shows the weight average molecular weight, melting point, volume resistivity, relative dielectric constant, and acid value of the vinyl resin (A11).

<Comparative Production Examples 1 to 3>
Comparative Production Examples 1 to 3 were vinyl resins (A′1) to (A′1) to (A′1) in the same manner as in Production Example 1 except that the respective monomers were used in the specified parts by weight based on the composition of the monomers shown in Table 1. A'3) was obtained. The analysis values were as shown in Table 1, respectively.

  In Table 1, the parentheses following the compound names of the monomers (b) and (c) indicate the hydrogen of the Hansen solubility parameter (HSP) of the monomers (b) and (c) in parentheses. The value of the bond term (dH) is described.

<Production Example 12>
[Production of amorphous polyester resin (B1)]
In a reaction vessel, 164 parts of a 2 mol adduct of propylene oxide of bisphenol A, 577 parts of a 3 mol adduct of propylene oxide of bisphenol A, 260 parts of terephthalic acid, 24 parts of trimellitic anhydride and titanium diisopropoxybistriethanol as a condensation catalyst After adding 2.5 parts of aminate and reacting at 230 ° C. under reduced pressure of 0.5 to 2.5 kPa, and reacting for 10 hours while distilling off generated water, the acid value becomes 1 mgKOH / g or less. Cooled to 180 ° C. 21 parts of trimellitic anhydride were added and reacted for 1 hour. After cooling to 150 ° C., an amorphous polyester resin (B1) was obtained using a steel belt cooler. The analysis values were as shown in Table 2.

<Example 1> [Production of toner binder (C1)]
85.0 parts of vinyl resin (A1) and 15.0 parts of amorphous polyester resin (B1) are mixed and supplied to a small twin-screw kneader [IMC-IADA type manufactured by Imoto Seisakusho] at 45 g / min. , 100 ° C and 180 rpm. The resultant was cooled to room temperature to obtain the toner binder (C1) of the present invention.

<Examples 2 to 18> [Production of toner binders (C2) to (C16)]
The vinyl resin (A) and the amorphous polyester resin (B) in the parts by weight shown in Table 3 were mixed, and the toner binders (C2) to (C16) of the present invention were obtained in the same manner as in Example 1. .

<Comparative Examples 1 to 3> [Production of Toner Binders (C'1) to (C'3)]
The vinyl resins (A ′) and amorphous polyester resins (B) in the parts by weight shown in Table 3 were mixed, and the toner binders (C′1) to (C′3) were mixed in the same manner as in Example 1. Obtained.

  Table 3 shows the analysis values of the toner binder.

The melting point of the toner binder was measured by the following method.
The melting point of the toner binder was measured using a differential scanning calorimeter ("DSC20 manufactured by TA Instruments". The first temperature rise of the toner binder from 20 ° C. to 150 ° C. at 10 ° C./min. At 150 ° C. to 10 ° C./min and then to 150 ° C. at 0 ° C./10° C./min. The temperature indicating the top of the endothermic peak derived from the vinyl resin (A) was defined as the melting point.

  The acid value of the toner binder was measured by a method specified in JIS K0070. However, the solvent for measuring the acid value was a mixed solvent of acetone, methanol and toluene (acetone: methanol: toluene = 12.5: 12.5: 75).

<Example 17><Production of toner composition (Ts1)>
[Production of wax dispersion 1]
15 parts of carnauba wax and 85 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a thermometer, and a stirrer, and heated to 80 ° C. to dissolve. The wax was crystallized into fine particles, and wet-pulverized with “Ultra Viscomil” (manufactured by Imex) to prepare (Wax Dispersion 1).

[Production of fine particle dispersion liquid 1]
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of sodium salt of a methacrylic acid ethylene oxide adduct sulfate [Eleminor RS-30, manufactured by Sanyo Chemical Industries, Ltd.], 139 parts of styrene, 138 parts of methacrylic acid Then, 184 parts of butyl acrylate and 1 part of ammonium persulfate were charged and the mixture was stirred at 400 rpm for 15 minutes to obtain a white emulsion. The mixture was heated to a temperature in the system of 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and the aqueous solution of vinyl polymer (copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-ethylene methacrylate ethylene oxide adduct) was obtained. A dispersion (fine particle dispersion 1) was obtained. The volume average particle diameter of the (fine particle dispersion liquid 1) measured with a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) was 0.15 μm.

[Manufacture of pigment masterbatch]
1200 parts of water, 40 parts of carbon black (manufactured by Cabot Corp., Regal 400R) and 20 parts of the toner binder (C1) produced in Example 1 were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture was used using three rolls. After kneading at 90 ° C. for 30 minutes, the mixture was rolled, cooled and pulverized with a pulperizer to obtain a pigment master batch (MB1).
[Production of aqueous phase s1]
955 parts of water, 15 parts of (particulate dispersion liquid 1), and 30 parts of an aqueous solution of sodium dodecyldiphenyletherdisulfonate [Eleminol MON7, manufactured by Sanyo Chemical Industries] are charged into a container equipped with a stirring rod, and a milky white liquid (aqueous phase s1) is added. Got.

[Production of Toner Composition (Ts1)]
191 parts of toner binder (C1), 25 parts of pigment masterbatch (MB1), 67 parts of (wax dispersion liquid 1), and 124 parts of ethyl acetate are put into a beaker, and dissolved and mixed uniformly to obtain (oil phase s1). Was. 600 parts of the (aqueous phase s1) was added to the (oil phase s1), and a dispersion operation was performed at 25 ° C. for 1 minute at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The solvent was removed by an evaporator under the conditions of a reduced pressure of -0.05 MPa (gauge pressure), a temperature of 40 ° C. and a rotation speed of 100 rpm for 30 minutes to obtain an aqueous colored polymer dispersion (X1).
The process of centrifuging 100 parts of the aqueous colored polymer dispersion (X1), further adding 60 parts of water, centrifuging, and performing solid-liquid separation twice was repeated, followed by drying at 35 ° C. for 1 hour. (Elbow Jet, manufactured by Matsubo Co., Ltd.) Remove and color fine powder and coarse powder so that fine powder of 3.17 μm or less is 12% by number or less and coarse powder of 8.0 μm or more is 3% by volume or less. Polymer particles (Cs1) were obtained.
Next, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] was added to 100 parts of the colored polymer particles (Cs1) of the obtained colored powder, and the peripheral speed was changed to 30 m / sec. Five cycles of mixing for 1 second and resting for 1 minute were performed to obtain a toner composition (Ts1).

<Examples 18 to 32 and Comparative Examples 4 to 6><Production of Toner Compositions (Ts2) to (Ts16) and (Ts'1) to (Ts'3)>
Except that (C2) to (C16) and (C′1) to (C′3) were used in place of the toner binder (C1), [oil phase s2] to [oil phase s2] to [C] were respectively used. [Oil phase s16] and [Oil phase s'1] to [Oil phase s'3] are obtained, and the toner compositions (Ts2) to (Ts16) and (Ts'1) to (Ts'1) have the compositions shown in Tables 4 to 6. Ts'3) was obtained.

[Performance evaluation]
The low-temperature fixability, storage stability, hot offset resistance, and charge stability of the obtained toner binder were measured, evaluated, and evaluated by the following methods. The results are shown in Tables 4 to 6.

<Low temperature fixability>
The toner composition was uniformly placed on the paper surface at 0.8 mg / cm ² . At this time, as a method of placing the powder on the paper, a printer without a heat fixing machine was used. Other methods may be used as long as the powder can be uniformly placed at the above weight density.
The temperature (MFT) at which a cold offset occurred when the paper was passed through a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² was measured.
The lower the temperature at which the cold offset occurs, the better the low-temperature fixability. Under these evaluation conditions, 140 ° C. or lower is generally required.

<Storage stability>
The toner composition was allowed to stand in a dryer conditioned at 50 ° C. and a humidity of 80% for 15 hours, and the presence or absence of blocking was visually determined, and the storage stability was evaluated according to the following criteria.
[Criteria]
：: Blocking has not occurred ×: Blocking has occurred

<Hot offset resistance>
The toner composition is uniformly placed on the paper so as to be 0.6 mg / cm ² . At this time, the toner composition was placed on the paper using a printer without a heat fixing machine. The hot offset temperature was measured when the paper was passed through a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 5 kg / cm ² . Under these evaluation conditions, 140 ° C. or higher is generally required.

<Charging stability>
0.5 g of the toner composition and 20 g of a ferrite carrier (F-150, manufactured by Powder Tech) are put into a 50 ml glass bottle, and the humidity is adjusted at a relative humidity of (1) 50% (2) 85% for 8 hours or more.
The mixture was friction-stirred with a tumbler shaker mixer at 50 rpm × 10 and 60 minutes, and the charge amount was measured at each time. A blow-off charge amount measuring device [manufactured by Toshiba Chemical Corporation] was used for the measurement. The saturated charge amount was defined as the charge amount for 10 minutes with a friction time of 50% relative humidity. In addition, “a charge amount of friction for 60 minutes at a relative humidity of 85% / a charge amount of 60 minutes for a friction time of 50% of relative humidity” was calculated and used as an index of charge stability.
[Evaluation criteria for charging stability]
◎: 0.6 or more ：: 0.5 or more, less than 0.6 Δ: 0.3 or more, less than 0.5 ×: less than 0.3

  As is clear from the evaluation results in Tables 4 to 6, the toner compositions using the toner binder of the present invention (Examples 17 to 32) had lower temperatures than the comparative toner compositions (Comparative Examples 4 to 6). The results showed that the hot offset resistance and the charging stability were remarkably good while satisfying both the fixing property and the storage stability.

  The toner binder of the present invention is a toner for developing an electrostatic image used in electrophotography, electrostatic recording, electrostatic printing, etc., because it has excellent hot offset resistance and charging stability while satisfying both low-temperature fixability and storage stability. And as a toner binder.

Claims (4)

A toner binder containing a vinyl resin (A) containing a monomer (a) as an essential constituent monomer, wherein the monomer (a) has a chain hydrocarbon group and has a carbon number of 21 to 40 (meth) A) a vinyl ester having 21 to 40 carbon atoms having an acrylate and / or a chain hydrocarbon group, the melting point of the vinyl resin (A) measured by DSC is 40 to 80 ° C., and the relative permittivity of the vinyl resin (A) ε ′ is 2.2 to 4.0, the volume resistivity of the vinyl resin (A) is 3.0 × 10 ^{10 to} 6.3 × 10 ¹¹ Ω · cm, and based on the weight of the toner binder. The weight ratio of the vinyl resin (A) is 20.1 to 99.9% by weight, and the weight ratio of the monomer (a) is 15 to 10% based on the total weight of the monomers constituting the vinyl resin (A). 90% by weight of a toner binder.   The vinyl resin (A) has a monomer (b) other than the monomer (a) as a constituent monomer, and the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) is 6 2. The toner binder according to claim 1, which has a value of not less than 0.0 and not more than 13.0.   3. The toner binder according to claim 1, wherein the vinyl resin (A) has an acid value of 19.9 mg KOH / g or less.   The toner binder contains an amorphous polyester resin (B) containing an alcohol component (x) and a carboxylic acid component (y) as essential constituent monomers, and the softening point of the amorphous polyester resin (B) is 90 to 90. The toner binder according to claim 1, wherein the temperature is 144 ° C. 5.