JP2019215527A - Toner binder - Google Patents

Abstract

To provide an excellent toner binder that contains, as a main component, a polymer containing a monomer having an ethylenically unsaturated bond as a constituent monomer, and is excellent in low-temperature fixability, hot offset resistance, storage stability, and charge stability.SOLUTION: A toner binder contains a vinyl resin (A) containing a monomer (a) as an essential constituent monomer; the monomer (a) is (meth)acrylate having a chain hydrocarbon group and having 21 to 40 carbon atoms and/or a vinyl ester having a chain hydrocarbon group and having 21 to 40 carbon atoms; the melting point of the vinyl resin (A) is 40 to 80°C; the dielectric constant ε' of the vinyl resin (A) is 2.5 to 4.0; the amount of water contained in the vinyl resin (A) is 500 to 10000 ppm; the polymerization ratio of the vinyl resin (A) is 20.1 to 99.9 weight%; the polymerization ratio of the monomer (a) is 15 to 90 weight%.SELECTED DRAWING: None

Description

  The present invention relates to a toner binder.

A toner binder for a heat fixing method, which is generally used as an image fixing method in a copying machine, a printer, and the like, is required to have both low-temperature fixing property, hot offset resistance, storage stability, and the like. For this reason, the toner binder has a high storage elastic modulus at a temperature lower than the fixing temperature, a low storage elastic modulus in a short time at a temperature at which fixing is started, and maintains a constant storage elastic modulus up to a high temperature. It is required that the storage modulus changes to an appropriate value before and after the fixing temperature.
In order to achieve the above-mentioned appropriate change in storage modulus, a conventional toner binder uses polyester as a main component (for example, see Patent Documents 1 and 2).
However, compared to a polymer of a monomer having an ethylenically unsaturated bond, the toner binder containing a polyester as a main component and the toner composition using the same have a lower charging characteristic due to a decrease in volume resistivity due to moisture absorption. Is deteriorated. In the case of producing a chemical toner using a toner binder containing a polyester as a main component, a solution suspension method other than emulsion polymerization or suspension polymerization using a monomer having an ethylenically unsaturated bond (for example, Patent Document 1) 3) or a special emulsification technique such as an emulsion aggregation method (for example, see Patent Document 4).
On the other hand, a conventional toner binder containing a polymer of a monomer having an ethylenically unsaturated bond as a main component instead of polyester has a low intermolecular cohesion force as compared with polyester, so that low-temperature fixability and hot-resistance are low. It is difficult to balance offset properties.
In order to solve this problem, a technique using a combination of low and high molecular weight components (for example, see Patent Document 5), a technique using a site having high cohesion as a constituent unit (for example, see Patent Document 6), and the like However, there is a problem that the low-temperature fixability is insufficient with an increase in storage modulus in the fixing temperature range.
Therefore, it is possible to improve the low-temperature fixability by using a crystalline acrylate resin or a copolymer of a crystalline acrylate resin and other copolymerizable monomers among polymers of a monomer having an ethylenically unsaturated bond. (For example, Patent Documents 7 and 8) have been proposed.
However, these techniques have a problem that storage stability is deteriorated due to introduction of an acid value into a crystalline acrylate resin and deterioration of hygroscopicity due to use of a copolymer with a copolymerizable monomer having a hydroxy group. is there.
The techniques described above are insufficient to satisfy both low-temperature fixability, hot offset resistance, storage stability and charging stability.

Japanese Patent No. 4493080 Japanese Patent No. 2105762 Japanese Patent No. 3596104 Japanese Patent No. 3492748 JP-A-11-327210 Japanese Patent No. 321860 Japanese Patent No. 4677909 JP 2004-163956 A

  An object of the present invention is to use a polymer having a monomer having an ethylenically unsaturated bond as a main component as a main component, and to provide a low-temperature fixing property, hot offset resistance, storage stability and charge stability. And to provide an excellent toner binder.

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 the monomer (a) as an essential constituent monomer, wherein the monomer (a) has a carbon number having a chain hydrocarbon group. It is a vinyl ester having 21 to 40 carbon atoms having a (meth) 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 vinyl resin ( A) has a relative dielectric constant ε ′ of 2.5 to 4.0, a water content of the vinyl resin (A) of 500 to 10000 ppm, and polymerization of the vinyl resin (A) based on the weight of the toner binder. Wherein the proportion of the monomer (a) is from 15 to 90% by weight based on the total weight of the monomers constituting the vinyl resin (A). It is a binder.

  According to the present invention, a toner binder having excellent low-temperature fixability, hot offset resistance, storage stability, and charge stability can be provided.

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 a monomer (a) as an essential constituent monomer, wherein the monomer (a) has a chain hydrocarbon group. It is a (meth) acrylate having 21 to 40 carbon atoms and / or a vinyl ester having 21 to 40 carbon atoms having a chain hydrocarbon group. The vinyl resin (A) has a melting point of 40 to 80 ° C by DSC measurement, The resin (A) has a relative dielectric constant ε ′ of 2.5 to 4.0, the vinyl resin (A) has a water content of 500 to 10000 ppm, and the vinyl resin (A) is based on the weight of the toner binder. Is from 21 to 99% by weight, and the polymerization rate of the monomer (a) is from 15 to 90% by weight based on the total weight of the monomers constituting the vinyl resin (A). Toner binder.

In the present invention, “(meth) acryl” 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 36 carbon atoms and vinyl esters having a linear alkyl group having 18 to 36 carbon atoms are preferable from the viewpoint of the storage stability of the toner. More preferred are (meth) acrylates having a straight-chain alkyl group having 18 to 34 carbon atoms and vinyl esters having a straight-chain alkyl group having 18 to 34 carbon atoms, and particularly preferred are straight-chains having 18 to 30 carbon atoms. (Meth) acrylate having an alkyl group and vinyl ester having a linear alkyl group having 18 to 30 carbon atoms, most preferably octadecyl (meth) acrylate, myristyl (meth) acrylate, and behenyl (meth) acrylate. .
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 18 to 80% by weight, more preferably 20 to 80% by weight based on the total weight of the monomers constituting the vinyl resin (A). ７０70% by weight, particularly preferably 25-65% 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) of the present invention may further contain a monomer (b) other than the monomer (a) as a constituent monomer. The monomer (b) is a monomer other than the monomer (a), and has a hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of preferably 5.0 or more and 15.0 or less, more preferably 6 or less. Any monomer may be used as long as it is at least 11 and at most 11.
When the hydrogen bond term (dH) of the monomer (b) exceeds 15.0, charging stability and storage 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 (meth) acrylate (b1) having a chain hydrocarbon group having 1 to 3 carbon atoms, methyl acrylate (the value of the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) is 9.4, Are the same in parentheses), ethyl acrylate (6.5), propyl acrylate (6.5), 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).
Examples of the vinyl ester (b2) having a hydrocarbon group having 1 to 3 carbon atoms include vinyl formate, vinyl acetate, vinyl propionic acid, and isopropenyl acetate.

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.

  Examples of the hydroxyl group-containing (meth) acrylate (b7) include hydroxyethyl methacrylate (13.4), hydroxypropyl acrylate (13.7) (2-hydroxypropyl ester, and 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 And hydroxybutyl acid (11.7).

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

As the monomer (b), one type may be used alone, or two or more types may be used in combination.
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. A compound having a carboxyl group having 1 to 9 carbon atoms and a vinyl group, and a (meth) acrylate having a hydroxyl group.
More preferably, (meth) acrylic acid, methyl methacrylate, vinyl acetate, vinyl propion, (meth) acrylamide, acrylonitrile, methacrylonitrile, vinylpyrrolidone, (anhydrous) maleic acid, hydroxyethyl (meth) acrylate and (meth) acrylate And hydroxypropyl acrylate.

  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. From 10 to 85% by weight, more preferably 15 to 80% by weight, particularly preferably 18 to 75% by weight, based on the total weight of the monomers constituting the vinyl resin (A). is there.

  The weight ratio of the monomer (a) to the monomer (b) constituting the vinyl resin (A) {(a) :( b)} is preferably 98: 2 from the viewpoint of low-temperature fixability and storage stability. １５15: 85, more preferably 70:30 to 15:85.

The vinyl resin (A) is other than (a) as a constituent monomer, and may contain a monomer (c) other than (b). 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 other than the monomer (b). And alkyl styrene (e.g., α-methylstyrene and p-methylstyrene), ethyl methacrylate, propyl methacrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, vinyl butyrate, and vinyl isobutyrate. Can be Of these, styrene is preferred from the viewpoint of storage stability when used as a toner.

  When the monomer (c) is included in the monomer constituting the vinyl resin (A), the weight ratio of the monomer (c) is determined from the viewpoint of storage stability that the amount of the monomer constituting the vinyl resin (A) is It is preferably from 0 to 40% by weight, more preferably from 0 to 35% by weight, particularly preferably from 0 to 30% by weight, most preferably from 0 to 25% by weight, based on the total weight of the body. .

  The vinyl resin (A) in the present invention may be a known monomer composition containing a monomer (a) and optionally a monomer (b) and / or an optionally used monomer (c). It can be produced by polymerization by a 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 1,000, from the viewpoints of low-temperature fixability and hot offset resistance of the toner. And particularly preferably from 50,000 to 500,000. The weight average molecular weight of the polymer (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 through a 1 μm aperture PTFE filter)
Mobile phase: tetrahydrofuran (does not include polymerization inhibitor)
Solution injection volume: 100 μl
Detector: Refractive index detector Reference substance: 12 points of standard polystyrene (TSK standard POLYSTYRENE) (weight average molecular weight: 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 28900000) [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 80 ° C, more preferably from 55 to 70 ° C.
When the melting peak temperature Tm 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, 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 melting point can be increased by a method such as increasing the weight average molecular weight of the number of carbon atoms in (A). 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 DSC measurement in the present invention is a value measured under the following conditions using a differential scanning calorimeter {DSC210, etc., manufactured by Seiko Instruments Inc.}.
<Measurement conditions>
(1) Hold at 30 ° C. for 10 minutes (2) Heat up to 150 ° C. at 10 ° C./min (3) Hold at 150 ° C. for 10 minutes (4) Cool down to 0 ° C. at 10 ° C./min (5) 10 ° C. at 10 ° C. (6) The temperature is raised to 150 ° C. at 10 ° C./min. The above operations (1) to (6) are continuously performed in order, and each endothermic peak of the differential scanning calorimetry curve measured in the process of (6) Is analyzed.

  The relative dielectric constant ε ′ of the vinyl resin (A) is 2.5 to 4.0, preferably 2.7 to 3.9, and more preferably 3.0 to 3.9. This makes it possible to transfer the charged toner particles more efficiently during image formation.

  The relative permittivity 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 15%, the relative dielectric constant falls within the above range by setting the acid value to 0 or more.

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
Ando Electric Co., Ltd. TO-198 type thermostatic bath solid electrode: SE-70 solid electrode 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 water content of the vinyl resin (A) is 500 to 10000 ppm, preferably 600 to 6000 ppm, and more preferably 750 to 3000 ppm. If it is less than 500 ppm, the charging stability will be poor, and if it exceeds 10,000 ppm, the storage stability will be poor.

The amount of water contained in the vinyl resin (A) can be adjusted by the type, composition ratio, and acid value of the monomers constituting the vinyl resin (A). Specifically, (meth) acrylate (b7) having a hydroxyl group is used as a monomer constituting the vinyl resin (A), and the weight ratio of the monomer (b7) constituting the vinyl resin (A) is increased. The amount of water contained in the vinyl resin (A) can be increased by a method such as increasing the acid value of the vinyl resin (A). For example, when hydroxyethyl methacrylate is used as the monomer (b7) constituting the vinyl resin (A) and the weight ratio of the monomer (b7) is 4%, the acid value of the vinyl resin (A) is 19. When the content is 9 mgKOH / g or less, the water content of the vinyl resin (A) falls within the above range.
The moisture content of the vinyl resin (A) is measured by a Karl Fischer moisture measuring device combined with a moisture vaporizer [for example, trade name: VA-100 (Mitsubishi Chemical Analytech) (vaporization temperature: 190 ° C)].

  The weight ratio of the vinyl resin (A) is 21 to 99% by weight, preferably 40 to 95% 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 21% by weight, the low-temperature fixability deteriorates, and when the weight ratio of the vinyl resin (A) exceeds 99% by weight, the charging stability deteriorates.

  The acid value of the vinyl resin (A) is preferably 19.9 mgKOH / g or less, more preferably 0 to 15 mgKOH / g, and particularly preferably 0 to 10 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 the method described in 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 (2).

HO-Ar-X-Ar-OH (2)
[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, preferred are aliphatic diols having 2 to 4 carbon atoms and alkylene oxide adducts of bisphenol A, more preferably 1.2-propylene glycol and bisphenol A 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 viewpoints of low-temperature fixability and hot offset resistance, alkanedicarboxylic acids having 4 to 36 carbon atoms, alkenedicarboxylic acids having 4 to 36 carbon atoms, and aromatics having 8 to 36 carbon atoms are preferable. Aromatic dicarboxylic acids and aromatic polycarboxylic acids having 9 to 20 carbon atoms, more preferably adipic acid, fumaric acid, terephthalic acid and trimellitic acid.

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

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 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 point of the amorphous polyester resin (B) is preferably 45 to 80C, more preferably 50 to 80C. The glass transition point 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 point of the amorphous polyester resin (B) is 45 ° C. or higher, storage stability is good, and when it is 80 ° C. or lower, low-temperature fixability is good.

The glass transition point of the amorphous polyester resin (B) is measured by a method (DSC method) specified in ASTM D3418-82 using DSC20, SSC / 580 manufactured by Seiko Instruments Inc.
Specifically, 5 mg of the sample is heated at a rate of 20 ° C./min to a temperature about 30 ° C. higher than the end of the glass transition, and cooled at a rate of 60 ° C./min to a temperature about 50 ° C. lower than the glass transition temperature. Heat at 20 ° C per minute to a temperature about 30 ° C higher.
From the data obtained by the above measurement, draw a graph with the vertical axis representing the amount of heat absorption and heat generation and the horizontal axis representing the temperature, and a straight line that extends the low-temperature baseline to the high-temperature side, and a step-like change in the glass transition. The temperature at the intersection with the tangent drawn at the point where the slope of the curve becomes maximum is 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 15,000, more preferably from 4,000 to 12,000, particularly preferably from 4,000 to 12,000, from the viewpoint of low-temperature fixability and storage stability. Preferably it is 4,500-10,000. 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). The weight average molecular weight of the amorphous polyester resin (B) can be measured by the same method as the measurement of the weight average molecular weight of the vinyl resin (A).

  The acid value of the amorphous polyester resin (B) is preferably 1 to 30 mgKOH / g, more preferably 1 to 25 mgKOH / g, and particularly preferably 1 to 20 mgKOH / g. When the acid value of the amorphous polyester resin (B) is 1 mgKOH / g or more, the charging stability is good, and when it is 30 mgKOH / g or less, the storage stability is 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 softening point of the amorphous polyester resin (B) is preferably from 90 to 144 ° C, more preferably from 95 to 130 ° C, and further preferably from 95 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 the resin composition contains the amorphous polyester resin (B), the weight ratio of the vinyl resin (A) to the amorphous polyester resin (B) is preferably 99/1 to 21/79, and more preferably 95/5 to 5/5. 40/60. If the ratio is 99/1 or more, the charging stability deteriorates, and if it is 21/79 or less, the low-temperature fixability deteriorates.

The toner binder of the present invention is obtained by uniformly mixing the vinyl resin (A) and the amorphous polyester resin (B) by simply using a known mechanical mixing method (for example, a method using a mechanical stirrer or a magnetic stirrer). And a method in which the vinyl resin (A) and the amorphous polyester resin (B) are dissolved in a solvent at the same time to homogenize the mixture, and then the solvent is removed.
When the mechanical mixing method is used, the mixing temperature is preferably 50 to 200 ° C. The mixing time is preferably 0.5 to 24 hours.
In the case of using a method of dissolving in a solvent, the solvent is not particularly limited, and any solvent may be used as long as it can suitably dissolve all polymers constituting the toner binder. Examples include toluene and acetone.
The temperature at which the solvent is removed is preferably 50 to 200 ° C., and the removal of the solvent can be promoted by reducing the pressure or exhausting air as necessary.

  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.
Above and below, parts mean parts by weight.

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 , Sasol waxes and their deoxidizing waxes, ester waxes such as fatty acid 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 heat-reduced polyolefins] (eg, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer), oxides of (co) polymers of olefins with oxygen and / or ozone, (co) weights of olefins Unified maleic acid modified products [maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate and dimethyl maleate, etc.)], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid And maleic anhydride, etc.] and / or unsaturated And alkyl esters of alkyl (meth) acrylates (alkyl having 1 to 18 carbon atoms) and alkyl maleates (alkyl having 1 to 18 carbon atoms) and sasol wax. Can be

  Among them, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, carnauba wax, ester wax and amide wax are preferable from the viewpoint of low-temperature fixing property 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, alumina, calcium 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>
The autoclave was charged with 30 parts of toluene, the atmosphere was replaced with nitrogen, and the temperature was raised to 170 ° C. Then, at the same temperature, 64 parts of behenyl acrylate as the monomer (a), 18 parts of styrene as the monomer (c), 18 parts of acrylonitrile as the monomer (b), and 0 parts of di-t-butyl peroxide. A mixed solution of 0.7 parts and 10 parts of toluene was added dropwise at the same temperature over 3 hours, and further kept at the same temperature for 1 hour to obtain a toluene solution of the vinyl resin (A1). Next, in the obtained toluene solution, toluene was removed at 1 kPa or less, and after confirming that the toluene in the resin was 100 ppm or less by gas chromatography and taken out, a thermo-hygrostat at a temperature of 40 ° C. and a humidity of 80% was used. For 48 hours to obtain a vinyl resin (A1).
The hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the used monomer (b), the weight average molecular weight, the melting point, the relative permittivity, the water content and the acid value of the vinyl resin (A1) are shown in Table 1. .

<Production Examples 2 to 10>
Vinyl resins (A2) to (A10) were obtained in the same manner as in Production Example 1 except that the monomers and other raw materials shown in Table 1 were used as specified parts by weight. The physical properties are shown in Table 1.

<Production Example 11>
2040 parts of behenic acid, 2067 parts of vinyl acetate, 0.044 parts of palladium chloride, 0.10 parts of lithium bromide, and 0.984 parts of tribasic sodium phosphate were placed in a four-necked flask equipped with a stirring and reflux cooling device and a thermometer. After charging and reacting at 70 ° C. for 40 hours with stirring, 1527 parts of vinyl behenate was obtained by distillation under reduced pressure.

<Production Example 12>
The autoclave was charged with 30 parts of toluene, the atmosphere was replaced with nitrogen, and the temperature was raised to 170 ° C. Next, at the same temperature, 68 parts of the vinyl behenate obtained in Production Example 11 as the monomer (a), 18 parts of styrene as the monomer (c), 18 parts of acrylonitrile as the monomer (b), A mixed solution of 1.1 parts of -t-butyl peroxide and 10 parts of toluene was added dropwise at the same temperature over 3 hours, and further kept at the same temperature for 1 hour to obtain a toluene solution of vinyl resin (A11). . Next, in the obtained toluene solution, toluene was removed at 1 kPa or less, and after confirming that the toluene in the resin was 100 ppm or less by gas chromatography and taken out, a thermo-hygrostat at a temperature of 40 ° C. and a humidity of 80% was used. For 48 hours to obtain a vinyl resin (A11).
The hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the used monomer (b), the weight average molecular weight, the melting point, the relative permittivity, the water content and the acid value of the vinyl resin (A11) are shown in Table 1. .

<Production Example 13>
An autoclave equipped with a stirrer was charged with 100 parts of xylene, 100 parts of behenyl acrylate as the monomer (a), and 1.5 parts of thioglycolic acid, and the atmosphere was replaced with nitrogen. . 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 monomer. The white solid monomer had a weight average molecular weight of 6,000 and a melting point of 65 ° C. The weight average molecular weight and the melting point were measured in the same manner as for the vinyl resin (A).
Next, 30 parts of toluene was charged into another autoclave, the atmosphere was replaced with nitrogen, and the temperature was raised to 170 ° C. Then, at the same temperature, 64 parts of a white solid monomer, 18 parts of styrene as monomer (c), 18 parts of acrylonitrile as monomer (b), 0.7 part of di-t-butyl peroxide and 10 parts of toluene Was added dropwise over 3 hours at the same temperature and further maintained at the same temperature for 1 hour to obtain a xylene solution of the vinyl resin (A12). Next, in the obtained toluene solution, toluene was removed at 1 kPa or less, and after confirming that the toluene in the resin was 100 ppm or less by gas chromatography and taken out, a thermo-hygrostat at a temperature of 40 ° C. and a humidity of 80% was used. For 48 hours to obtain a vinyl resin (A12).
The hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) used, the weight average molecular weight, the melting point, the relative permittivity, the water content and the acid value of the vinyl resin (A12) are shown in Table 1. .

<Production Example 14>
An autoclave equipped with a stirrer was charged with 100 parts of xylene, 100 parts of acrylonitrile, which is a monomer (b), and 1.8 parts of thioglycolic acid, and the mixture was purged with nitrogen. 1.05 parts 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, 1.9 parts of hydroxyethyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), which is a monomer (b), was added into the reaction vessel, and the temperature was raised to 55 ° C. 3.1 parts of 4-methylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.1 parts of t-Bu hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 20 parts of chloroform Was added dropwise over 1 hour. Thereafter, stirring was further performed at 55 ° C. for 5 hours. Thereafter, the mixture was cooled to 35 ° C. and purified by a methanol precipitation method. The obtained solid was dried under reduced pressure to obtain a white solid monomer. The white solid monomer had a weight average molecular weight of 9,300 and a glass transition point of 55 ° C. The weight average molecular weight and the melting point were measured in the same manner as for the vinyl resin.
Further, another autoclave was charged with 30 parts of toluene, and the autoclave was purged with nitrogen, and then heated to 170 ° C. Then, at the same temperature, 64 parts of behenyl acrylate, 18 parts of styrene as monomer (c), 18 parts of white solid monomer as monomer (b), 0.7 parts of di-t-butyl peroxide and 10 parts of toluene Of the mixed solution was added dropwise over 3 hours at the same temperature, and further maintained at the same temperature for 1 hour to obtain a xylene solution of the vinyl resin (A13). Next, in the obtained toluene solution, toluene was removed at 1 kPa or less, and after confirming that the toluene in the resin was 100 ppm or less by gas chromatography and taken out, a thermo-hygrostat at a temperature of 40 ° C. and a humidity of 80% was used. For 48 hours to obtain a vinyl resin (A13).
The hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) used, the weight average molecular weight, the melting point, the relative permittivity, the water content and the acid value of the vinyl resin (A13) are shown in Table 1. .

In Table 1, 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).
Further, (dH) of the monomer (b) composing the vinyl resin (A) described in the physical property column is, if only one kind of the monomer (b) was used, the (dH) was simply used. When two or more types of the monomer (b) were used, the average value of (dH) of the used monomer (b) calculated based on the weight ratio of the monomer (b) was described.

<Comparative Production Examples 1 to 5>
Vinyl resins (A'1) to (A'5) were obtained in the same manner as in Production Example 1 except that the monomers and other raw materials shown in Table 2 were used in the specified parts by weight. The physical properties are shown in Table 2.

<Production Example 15>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 365 parts of EO 2 mol adduct of bisphenol A, 339 parts of PO2 mol adduct of bisphenol A, 266 parts of terephthalic acid, 8 parts of adipic acid, trimellitic anhydride 29 parts of an acid and 2.5 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst are added, and the mixture is reacted at 230 ° C. for 4 hours while distilling off generated water under a nitrogen stream to obtain 0.5 to 2.5 kPa. After reacting under reduced pressure for 5 hours, the mixture was taken out to obtain an amorphous polyester resin (B1). Table 3 shows the physical properties.

<Production Example 16>
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe, 752 parts of a PO2 mole adduct of bisphenol A, 313 parts of terephthalic acid, 1 part of fumaric acid, 1 part of trimellitic anhydride, and titanium diisopropane as a condensation catalyst After adding 2.5 parts of propoxybistriethanolaminate and reacting at 230 ° C. under a nitrogen stream while distilling off generated water for 4 hours, and then reacting under reduced pressure of 0.5 to 2.5 kPa for 5 hours, It was taken out to obtain an amorphous polyester resin (B2). Table 3 shows the physical properties.

<Example 1> [Preparation of toner (T-1)]
80 parts of a vinyl resin (A1) as a toner binder, 9 parts of an amorphous polyester resin (B1), 6 parts of carbon black [MA-100, manufactured by Mitsubishi Chemical Corporation] as a coloring agent, and carnauba wax as a releasing agent [ 4 parts of Carnauba wax manufactured by Nippon Wax Co., Ltd., and 4 parts of Aizen Spiron Black [T-77, Hodogaya Chemical Co., Ltd.] as a charge control agent were added to form a toner by the following method. First, after preliminarily mixing using a Henschel mixer [FM10B manufactured by Nippon Coke Industry Co., Ltd.], the mixture was kneaded with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using an air-flow type pulverizer [KJ-25 manufactured by Kurimoto Iron Works Co., Ltd.], classification was performed using an elbow jet classifier [EJ-L-3 (LABO) type manufactured by Matsubo Corporation]. Toner particles having a volume average particle diameter (D50) of 8 μm were obtained.
Then, 99 parts of the toner particles were mixed with 1 part of hydrophobic silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent in a sample mill to obtain a toner (T-1) of the present invention.

<Examples 2 to 19>
[Preparation of Toners (T-2) to (T-19)]
Toners (T-2) to (T-19) were obtained in the same manner as in Example 1 except that the vinyl resin (A) and the amorphous polyester resin (B) shown in Table 4 were used in the specified parts by weight. Was.

<Comparative Examples 1 to 7>
[Preparation of Toners (T'-1) to (T'-7)]
Toners (T'-1) to (T'-7) in the same manner as in Example 1 except that the vinyl resin (A) and the amorphous polyester resin (B) shown in Table 5 were used in the specified parts by weight. Got.

[Performance evaluation]
The low-temperature fixability, storage stability, hot offset resistance, and charge stability of the obtained toner were measured, evaluated, and evaluated by the following methods. The results are shown in Tables 4 and 5.

<Low temperature fixability>
The toner is uniformly placed on the paper surface at 0.8 mg / cm ² . At this time, the method of placing the powder on the paper uses a printer with the heat fixing machine removed. 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, 125 ° C. or less is generally required.

<Storage stability>
The toner was allowed to stand for 15 hours in a dryer conditioned at a temperature of 50 ° C. and a humidity of 80%, 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 is evenly placed on the paper at 0.6 mg / cm ² . At this time, the toner was placed on the paper using a printer without the heat fixing device. 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, 180 ° C. or higher is generally required.

<Charging stability>
0.5 g of the toner and 20 g of a ferrite carrier (F-150, manufactured by Powder Tech) are placed in a 50 ml glass bottle, and the relative humidity is adjusted at (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.
Under this evaluation condition, a numerical value of 0.40 or more is generally required.

  As is clear from the evaluation results in Tables 4 and 5, the toner using the toner binder of the present invention (Examples 1 to 19) has a lower low-temperature fixability than the comparative toner (Comparative Examples 1 to 7). The result that the hot offset resistance and the charging stability were remarkably good while obtaining both the storage stability was obtained.

  The toner using the toner binder of the present invention has excellent low-temperature fixability, hot offset resistance, and storage stability, and is therefore useful as a toner for developing an electrostatic image used in electrophotography, electrostatic recording, electrostatic printing, and the like. .

Claims (4)

A toner binder containing a vinyl resin (A) having a monomer (a) as an essential constituent monomer, wherein the monomer (a) has a chain hydrocarbon group and has 21 to 40 carbon atoms ( (Meth) acrylate and / or a vinyl ester having 21 to 40 carbon atoms having a chain hydrocarbon group,
The melting point of the vinyl resin (A) measured by DSC is 40 to 80 ° C,
The relative permittivity ε ′ of the vinyl resin (A) is 2.5 to 4.0,
The water content of the vinyl resin (A) is 500 to 10000 ppm,
The polymerization ratio of the vinyl resin (A) is 21 to 99% by weight based on the weight of the toner binder,
A toner binder, wherein the polymerization ratio of the monomer (a) is 15 to 90% by weight based on the total weight of the monomers constituting the vinyl resin (A).   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 2. The toner binder according to claim 1, which has a value of 5.0 to 15.0.   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.